The Chemistry of Diazonium and Diazo Groups.

The Chemistry of Diazonium and Diazo Groups
Edited by Saul Patai

Copyright 0 1978 by John Wiley & Sons Ltd. All rights reserved.
The chemistry of
diazonium and diazo groups
Part I
Edited by
SAULPATAI
The Hebrew University, Jclxsaleni
1978
JOHN WILEY & SONS
CHICHESTER- NEW YORK - BRISBANE - TORONTO
At1 Ititet-science co Aiblicarioti
Copyright @ 1978 by John Wiley R: Sons Ltd
Reprinted February 1979.
All rights reserved.
No part of this book may be reproduced by a n y means,
n o r transmitted, nor translated into a machine language
without the written permission of the publisher.
Library of Congress Catalog Card No. 75-691 3
ISBN 0 471 99492 8 (Pt. 1)
ISBN 0 471 99493 6 (Pt. 2)
ISBN 0 471 99415 4 (Set)
Printed in Great Britain by Page Bros (Norwich) Ltd,
Mile Cross Lane, Norwich.
Contributing authors
W. Ando Chemistry Dcpartmcnt, The University of Tsukuba, Niiharigun,

Ibaraki 3 0 - 3 1 , Japan
D, A. Ben-Efraim The Weizrnann Institute of Science, Rehovot, Israel
C. F. Cooper Department of Chcmistry, University of Missouri-Rolla, Rolla,
Mo. 65401, USA
A. J. Fry Wesleyan University, Middletown, Connecticut, USA
A. F. Hegarty Chemistry Department, University College, Cork, Ireland
E. S. Lewis Department of Chemistry, Rice University, Houston, Texas, U S A
G. Linstrumelle Equipc de Recherche No. 12 du CNRS, Laboratoire d e Chimie,
Ecole Normale Supdrieure, Paris, France
J. F. McGarrity Institute of Organic Chemistry, University of Lausanne,
Lausanne, Switzerland
J. 6. Moffat Department of Chemistry, University of Waterloo, Waterloo,
Ontario, Canada
H. M. Niemeyer Institute of Organic Chcmistry, University of Lausanne,
Lausanne, S\vitzerland
M. Regitz Department of Chemistry, University of Kaiserslautern, D-6750,
Federal Republic of Germany
K. Schank Fachbereich 11.1 Organische Chemie, Universitat des Saarlandes,
D-6600 Saarbrucken, Germany
R. S h a w 1 I62 Quince Avenue, Sunnyvale, California 94087, USA
P. J. Smith Department of Chemistry and Chemical Engineering, University
of Saskatchewan, Saskatoon, Saskatchewan, Canada
S. Sorriso Istituto di Chimica Fisica, Universiti di Perugia, 06100 Perugia,
Italy
V. St6rba Organic Chemistry Department, Institute of Chemical Techno-
logy, 532 10 Pardubice, Czechoslovakia
K. C. Westaway Department of Chemistry, Laurentian University, Sudbury,
Ontario, Canada
D. Whittaker Dcpartment of Organic Chemistry, University of Liverpool,
England
D. S. Wulfman Department of Chemistry, University of Missouri-Rolla, Rolla.
Mo. 65401, USA
V
Foreword
The present volume, ‘The Chcniistry of Diazonium a n d Diazo Groups’ is, on the
whole, organized and presented according to the gencral lines described in the
‘Preface to the Series’, printcd on t h e following pages.
Some difficulty arose in the prcsentation owing to t h e fact that while the two groups
treated, i.e. the diazo group and the diazonium group, are closely related and even
occur in equilibrium with each other, thcir chemical behaviour and chnracteristics
differ from each other considerably. Moreover, thc material which had to be covered
proved to be much more extcnsivc than originally surmised. For thesc reasons,
some of the subjects had t o be divided into two or more chapters; for instance, the
synthetic applications of diazonium and diazo groups arc treated in two separate
chapters and even so each of these turned o u t to be very large. Similarly, the
syntheses of thc diffc‘erenttitle compounds are discussed in three separate chapters.
The plan of the present volume also included a chaptcr on ‘Biological and
Pharmaceutical Effects’ which, howcver, failed to materialize. It is hoped that this
will appear i n one of the supplementary volumes to t h e series.
Jerusalem, February 1977 S A U L PATA?
vii
T h e Chemistry of Functional Groups
Preface to t h e series
T h e series 'The Chemistry of Functional Groups' is planned to cover in each volume
all aspects of thc chemistry of one of the important functional groups in organic
chemistry. The emphasis is laid on the functional group treated and o n the effects
which i t exerts on the chemical and physical properties, primarily in the immediate
vicinity of the group in question, and secondarily on the behaviour of the whole
molecule. For instance, the volume The Clronistry of the Eilier Litikc~gedeals with
reactions in which the C-0-C group is involved, as well as with the effects of the
C-0-C group o n the reactions of alkyl or aryl groups connected to the ether
oxygen. It is the purpose of the voluine to give a complete coverage of all properties
and reactions of ethcrs in as far as these depend on the presence of the ether group but
the primary subject matter is not the whole molecule, but the C-0-C functional
group.
A further restriction in the treatment of the various functioml groups in these
volumes is that material included in easily and generally available secondary or
tertiary sources, such as Chemical Reviews, Quarterly Reviews, Organic Reactions,
various 'Advances' and 'Progress' series as well as textbooks (i.e. in books which are
usually found in the chemical libraries of universitics and research institutes) should
not. as a rule, be repeated in detail, unless i t is necessary for the balanced treatment
cf the subject. Thercfore each of t h e authors is asked tiot to give an encyclopaedic
coverage of his subjcct, but to concentrate 011 the most important recent de\:clop-
ments and mainly o n material that has not been adequately covered by revie\\?s or
other secondary sources by the time of writing of the chapter, and to address hiniself
to a reader who is assumed to be at a fairly advanced post-graduate level.
With these restrictions, i t is realized that no plan can be devised for a volume that
would give a cotiipletc coverage of the subject mfith t i 0 overlap between chapters,
while at the same time prescrving the readability of the tex!. The Editor set himself
t h e goal of attaining rcwsotrnhle coverage with ttiorlerate cverlap, \ r i t h a minimum of
cross-references between the chapters of each volume. I n this manner, sufficient
freedom is given to each author to produce readable quasi-monographic chapteis.
The general plan of each v o l u ~ includes
i~ t h e following main sections:
(a) An introductory chapter dealing with t h e general and theoretical aspects of

the group.
(b) One or more chapters dealing with the formation of the functional group in
question, either from groups present in the molecule, or by introducing the new group
directly o r indirectly.
(c) Chapters describing the characterization and characteristics of the functional
groups, i.e. a chapter dealing with qualitativc and quantitative methods of deter-
mination including chemical and physical methods, ultraviolet, infrared, nuclear
ix
X Preface to the series
magnetic resonance and mass spectra: a chapter dealing with activating and
directive effects exerted by the group and/or a chapter o n the basicity, acidity or
complex-forming ability of the group (if applicable).
(d) Chapters on the reactions, transformations and rearrangements which the

functional group can undergo, either alone o r in conjunction with other reagents.
(e) Special topics which d o nct fit any of the above sections, such as photo-
chemistry, radiation chemistry, biochemical formations and reactions. Depending
on the nature of each functional group treated, these special topics may include
short monographs on related functional groups on which no separate volume is
planned (e.g. a chapter on ‘Thioketones’ is included in the volume The Chemistry
of tlie CGrbotiyl Group, a n d a chapter o n ‘Ketenes’ is included in the volume The
Cliernistry of Alkenes). I n other cases certain compounds, though containing only
the functional group of the title, may have special features so as to be best treated in
a separate chapter, as e.g. ‘Polyethers’ in The Cfiemistry of the Ether Linkage, or
‘Tetraaniinoethylenes’ in The Cfiemistryof the Amino Group.
This plan entails that t h e breadth, depth and thought-provoking nature of each
chapter will differ with the views and inclinations of the author a n d the presentation
will necessarily be somewhat uneven. Moreover, a serious problem is caused by
authors who deliver their manuscript late or not a t all. I n order to overcome this
probleni at least to some extent, it was decided to publish certain volumes in several
parts, without giving consideration t o the originally planned logical order of the
chapters. If after the appearance of the originally planned parts of :: volume it is
found that either owing to non-delivery of chapters, or to new developments in the
subject, sufficient material has accumulated for publication of a supplementary
volume, containing material o n related functional groups, this will be done as soon
as possible.
The overall plan of the volumes in the series ‘The Chemistry of Functional
Groups’ includes the titles listed below:
Tfie Cliemistry of A l k n e s (two volumes)

The Clietxistry of the Carbonyl Group (two volumes)
Tlie Chemistry of the Ether Linkage
Tfie Cliertiistry of the Amino Group
Tfie Cfiemistryof the Nitro and Nitroso Group (two parts)
Tlie Chemistry of Carboxylic Aciak and Esters
The Chemistry of tlie Carboi?-Nitrogen Double Bond
The Chemistry of the Cyario Group
The Clieniistry of Amides
Tlie Clicmistry of tlie Hydroxyl Group (two ports)
Tlie Chemistry of the Azido Group
The Chemistry of Acyl Halides
The Cfietnistry of the Carbon-Halogen Bond (two parts)
The Cliemistty of Qiiitio:!oid Compounds (two parts)
The Cliemistry of the Thiol Gvoiip (two parts)
The Cfietnistry of Aniidines arid Irnidates
The Cliertiistry of the Hydrazo, Azo and Azoxy Groiips
The Cfietnistry of Cyanates and their T h o Derivatives
The Chemistry of Diozoriiicm atid Diazo Groups
Supplemetit A: The Chemistry of Double- Bonded Fiitictioiial Groiips ( t w o parts)
Prefacc tc) the series xi
Titles in press:
The qliernistry of the Carboti-Carbon Triple Bond
Siippletnent B: The Clictnistry of Acid Dcricativcs
Future volumes planned include:

The Cliernistry of Ciimiiletres atid iietcrocitrniilcries
The Clreniisfry of Orgariomefallic Cornpoirtrds
The Chemistry of Siilplriir.-co,itaitiitrg Cotnpoiiticls
Sirpplemerit C: The Chemistry of Triple-borided Ficirctiorial Grorips
Siipplemetit D: The Chemistry of Halides atid Psciido-halides
Siipplemetit E: The Chemistry of -NIT,, - O N , atid -SH Groirps atid thzir
Derivatives
Advice or criticisin regarding the plan and execution of this series will be welcomed
by the Editor.
The publication of this series would never have started, let alone continued,
without the support of many persons. First and foremost among these is Dr Arnold
Weissberger, whose reassurance and trust encouraged me to tackle this task, and who
continues t o help and advise inc. The efficient and patient coopcration of several
staff-members of thc Publisher also rcndered me invaluable aid (but unfortunately
their code of ethics does not allow me to thank them by name). Many of my friends
and colleagues in Israel and overseas helped mc in the solution of various major
and minor matters, and my thanks are due to all of them, especially t o Professor
Z. Rappoport. Carrying out such a long-range project would bc quite impossible
without the non-professional but none the less essential participation and partnership
of my wife.
T h e Hebrew University SAUL PATAI
Jerusalem, ISRAEL.
Contents
1. General and theoretical aspects of the diazonium and diazo groups 1
J . B. Moffat
2. Diazonium-diazo equilibrium 71
V. Stgrba
3. Structural chemistry 95
S. Sorriso
4. Thermochemistry of diazo compounds and organic azides 137
R. Shaw
5. Detection and determination of diazo and diazonium groups 149
D. A. Ben-Efraim
6. Basicity, acidity and hydrogen bonding 179
J. F. McGarrity
7. Complex formation 231
H. M. Niemeycr
8. Synthetic applications of diazonium ions 247
D. S. Wulfman
9. Photochemistry of the diazonium and diazo groups 341
W. Ando
10. The electrochemistry of the diazo and diazonium groups 489
A. J. Fry
11. T h e influence of the diazo and diazonium groups 499
E. S. Lewis
12. Kinetics and mechanisms of reactions involving diazonium and diazo
groups 511
A . F. Hegarty
13. Rearrangements involving the diazo and diazonium groups 593
B. iL'hit t a ker
14. Preparation of diazonium groups 645
K. Schank
15. Synthesis of diazoalkanes 659
M . Regitz
16. Preparation and uses cf isotopically labelled diazonium and diazo
compounds 709
P. J. Smith and K. C . Westaway
xiii
xiv Contcnts
17. Carbonyl, phosphoryl and sulphonyl diazo compounds 751
M. Regitz
18. Synthetic application of diazoalkanes, diazocyclopentadienes and
diazoazacyclopentadienes 82 1
D. S . Wulfman, G . Linstrumelle and C. F. Cooper
Author Index 977
Subject Index 1045
CHAPTER 1
6eneral and theoretical
aspects of the diazsnium
and diazo groups
J. B. MOFFAT
Department of Cheinistry, University of Waterloo,
Water!oo, Ontario, Canada
I. INTRODUCTION. 2
11. DIAZO COMPOUNDS . 4
A. The Prototype, C N N . 4
B. Diazomethane (H,CNN) . 6
1. Introduction . 6
2. Thcoretical studies . 6
3. Thennochemical properties . 9
C. Isomers of Diazomethane . . 10
1. Nitrilimine . . 10
2. Diazirine and derivatives . . . 12
a. Spectra, structure and therrnochemistry . . . 12
b. Theoretical studies . . 14
3. Substituted diazirines . . 19
a. Spectra and structure . . 19
b. Kinetics of thermal decomposition . . 24
111. DIIMIDES (DIAZENES) . . 30
A. The Prototypes, N2H+and N,H . . 31
B. Diimide (Diazene) . . 32
1. Introduction . . 32
2. Spectroscopy and structure . . 33
3. Theoretical studies . . 36
C. Disubstituted Diimides . 45
1. N2F, . . 45
a. Theoretical studies . . 45
b. Spectra and structure . . 49
c. Thennochemical properties . . 52
d. Kinetics of isomerization . . 53
2. Tetrazene . . 53
D. Monosubstituted Diimides . . 53
1. Introduction . . 53
2. Spectra and structure . . 54
3. Theoretical studies . . 54
IV. DIAZOMUM COMPOUNDS. . 58
A. Introduction . . 58
B. Crystal Structure and Spectroscopic Data . . 58
C. Theoretical Studies . . 60
V. ACKNOWLEDGEMENT. . 64
VI. REFeI2ENCE.S . . 64
1
2 J. b. MolTaf
1. INTRODUCTION
In discussing the chemistry of molecules containing the N N bond and, in darticular,
in this first chapter, the general and theoretical aspects of such molecules, it seems
reesonablc to establish the scenario by comparing and contrasting such groups with
other groups of importance in organic chemistry.
One would be hard pressed to find more logical candidates for comparison with
molecules containing the N2 group than those of C 2 and C N . Indeed such a
ubiquitous trio of organic chemistry involving two homonuclear and one hetero-
nuclear bond, the latter formed from t h e two different clenients of the former,
almost invite sociological comparison with parents and offspring. The C2, C N and
N2 groups contain 12, 13 and 14 electrons, respectively, and the hierarc!iy of bonding
can be conceived as beginning with the so-called single bond, so that we have as the
simplest example for each group:
The first line of Table 1 compares average bond lengths for t h e central bonds o f
each of these nlolecules, and, not surprisingly, in view of the extra proton in the
nitrogen nucleus as compared to carbon, the bond lengths decrease as one passes
from the C-C to the N-N bond.
1. Average bond lengths (A) in molecules containing

TABLE
C C , C N and NN groups
Bond label CC CN NN
Single 1.537 1472 1451
Double 1.335 1-32 1*25
Triple 1.202 1.157 1.098 (N,)
1.312 (C,) 1-172 (CN)
Removal of a hydrogen atom from each of the central atoms in the molecules
above produces the trio of molecules with central double bonds,
H H H H H
\ / \ / /
F=C /"=" ?="
\
H' H H H
Again the same trend in bond lengths (line 2, Table 1) is observed a s in the case of
the corresponding single-bonded molecules. However, in addition, in all cases
shown, formation of the double bond results in a decrease in the bond length.
Continuation of the dehydrogenation process yields
H-C=C--H H-C=N N=N
with the same gradation in bond lengths being maintained from C=C to N=N, as
well as a further decrease in bond length in each case on formation of the triple
bond. Extraction of thc remaining hydrogen atoms from acetylene and hydrogen
cyanide produces a n increase in bond length, signalling a discontinuity in electronic
structures. However, for cach type of bond (single bonded, ctc.) i t is clear from the
table that the N N bond length is, in each case, the lowest of the three shown.
The foregoing comparison may be cxtendcd to encompass bond encrgics, and
average values for these arc given in Table 2. Examination of the table shows t h a t the
two loivest bond energies listed are 37 and 61 kcal/niol, those for the N-N a n d N = N
bonds respectively, while the highest value is 225 kcal/niol for the dissociation of the
nitrogen molecule. In fact, with the exception of CO which has a dissociation energy
of 256 kcal/mol, N, has the highest dissociation energy of any diatomic molecule.
2. Average bond energies (kcal/rnol) of CC,

TABLE
CN and NN bonds
Bond label CC CN NN
Single 83 73 37
Double 1.16 I12 61
Triple 200 213 225 (N,)
144 (C,) 188 (CN)
Consistent wi; h these experimental observations are the conclusions derivable

from siniple molecular orbital theory for the electron configurations of Cp, C N and
N,, and their singly-ionized forms (Tablc 3). The dilference between the number of
bonding orbitals and the number of antibonding orbitals, sometimes called the
bond order, can bc seen to increase from C: to N,, thercby suggesting that the
strength of the bond in N2 should not be unexpected.
TABLE
3. Electron configurationsa of C.,. CN and N, molecules and their singly-ionizcd forms
N ~1ni ber
of Lowcst Differ- 0:
electrons Molecule electron configuriition State Pb Pa ence (volts)
15 N;
Pb = Number of bonding electron pairs.

P,, = Number of antibonding electron pairs.
DE = Dissociation energy.
a G . Herzberg, Spectra of Diafotnic Molecules, 2nd ed., D. Van Nostrand Co. Inc.
Princeton, N.J. (1950).
Energy and geometry parameters relating to the ionization of the diatomic species
C2, N, and C N are given in Table 4. Again, although limited data are availablc, a
consistent pattern is followed, N, is observed to have a high ioaization energy and
would be predicted t o have a relatively high electron affinity.
4 J. B. Moffat
4. Energy and geometry parameters" for ionized forms of
TABLE
q,N2and CN
Ionization Electron Bond lengths (A)
energy affinity
Molccule (kcal/mol) (kcal/mol) XY- XY XYf
c2 71.5 1.24
CN 348.9 88.1 1.07 1.18 1-17
N 2 359.3 1.10 1-12,
a K. Watanabe, T. Nakayama and J. Mottl, J . Quanr. Specr. and
Energy Tramfer, 2, 369 (1962).
T h e theoretical aspects, and related physicochemical properties of molecules

containing the N = N bond will be developed, in the following sections, by con-
sidering individual molecules and their substituted derivatives, each representative
of a particular type of azo or diazo compound. The simplest relatives of N 2 will be
considered first, C N N being taken as a hypothetical precursor of diazomethane, a n d
N,H+ and N2H being considered as prototypes of the diimide bond. The discussion
on C N N is followed by sections on diazomethane itself and the two of its structural
isonieric forms, nitrilimine and diazirine, which contain the N = N bond. Relevant
information on substituted diazirines is also included.
Section I11 discusses the results of theoretical studies of diimide and its mono-
ar,d di-subs!i!u!ed ferms 2s -w!! ' s being concerned with related experimental work
on these molecules. Although not strictly within the bounds of the title of this volume,
diimides have been included here both for completeness and purposes of comparison
in discussions of the N N bond.
In all cases, where available, spectral dnta and the results of theoretical calcula-
tions are given, together with some thermocheniical and kinetic data, particularly
where the latter may assist in understanding the structure and properties of t h e
molecule. I n general each section is developed historically, in order to permit the
appropriate assessment of the data to be made by the reader wishing to use them, and
also to indicate to the researcher topics which require further study.
II. DIAZO COMPOUNDS

A. The Prototype, CNN
Molecules containing two nitrogen atoms joined together and with one of these
nitrogen atoms attached to a single carbon atom are referred to as diazoalkanes
(R,CNN). A number of extensive reviews of this subject'. have been published in
the previous decade, i n addition to several since 1970, some as recent as 19723-c.
There has been much interest in diazoalkanes for many years, particularly because
of their usefulness as intermediates, and more recently as a consequence of work on
the reactivity and structure of carbenes (R,C:), which are intermediates in the
photolysis and thermolysis of diazoalkanes.
The parent species of the diazoalkanes can be viewed, at least from the theoretical
point of view, as diazoniethylene, CNN. Robinson and McZarty, Jr', following the
photolysis of diazomethane in a krypton matrix, observed a featurc in the spectra a t
4240 A and tentatively suggested that this might be assigned to C N N or to H C N N .
At about the same time, Goldfarb and PimentcP observed features at 4182 a n d
3968 A, following the photolysis of diazome!hane isolated in a nitrogen matrix,
I . General and theoretical aspects or the diazonil1r.i :itid diaro groups 5
which they too considered must be duc to a reactive species, presumably C N N ,
since these fcatures vanished when the sample was warmcd. I n I966 thc rcsults of the
first complete spectral study o n C N N , prepnrcd by tlic pliotolysis or matrix-isolated
cyanogen azide with 2100-2800 8, radiation, were reported by blilligan and J ~ C O X ~ .
They first suggested the following mechanism for the production of di:tzomethylel1c
from cyanogcn azidc :
N,CN+hv (hc2800 A) ____> N;+-CN (1)
N;+-CN M,NC (2)
NSNC >- 2 N,+C (3a)
N,NC -+ N,+CNN (3b)
However, observations on the systems containing IsN Icd thcm to modify thcir
conclusions to suggest that the principal mode of forniation of the C N N is by the
attack of a carbon atom on a nitrogen nioleculc.
Diazoniethylene was deduced to possess a triplet clcctronic ground state \,:it11 a
linear structurc. T h e carbon-nitrogen bond was round to linvc approximately
triple-bond character and the nitrogen-nitrogen bond approximntcly double-bond
character, with the length of the former being estimated as 1.15 A, and t l i n t of the
latter as 1.25 A.
Morc rccenily, C N N was prepared by trapping carbon atoms i n a pure N,
matrixlo a n d medium-intcnsity bands of '?CN2 (in a N2 matrix) v..erc observcd at
2858, 1253 and 394 cm-', which shifted to 2836, 1232 and 392 C11i-l when I3C was
vaporized. Stretching force constants of 19.5 and 14.7 nidyn/A w r c calculated for
the CN a n d N N bonds, respectively.
What appears t o be the only theoretical work done on C N N \vas rcportcd by
Thornson11 in 1973. Using the !inear niolccules program ALCHEI\/IY'2 he pcrformcd
restricted Hartrce-Fock calculations for thc C N N configuration, 3X-,( I G ) ~ ( ? G ) ~ -
( ~ 0 ) ~ ( ~ c ) ~ ( ~ c 1)X
~ )(,6' (~
~G) *)(~ ( ~ XCalculatcd
)'. cnergics, gcomctries and atomic
populations are reported in Table 5 .
5 . Calculated energies' and structure of CNNl'
TABLE
.rota1 atomic
populations
Basis set Energy R(NN) R(CN) C N N
Double zeta - 14659091 2.565 7.220 5.71 743 6.s5

Doublezetafpolarization - 14668096 2.530 2.190 6.12 6.91 6 96
a Energies are in hartrees and bond lengths in bol1l.s: 1 hartrec = 627.7 kcalimol;
1 bohr = 0.529 A.
I n addition a dissociation energy (to atoms) of 0.198 hartrec and a dipolc momcnt
of 1.022 D were calculated for C N N , with the convcntion that thc right-hand
nitrogen atom is positive.
The calculated bond lengths are in reasonable agreenicnt with the estimates of
Milligan a n d Jacox9. The atomic populations arc seen to bc particularly scnsitivc to
the size a n d nature o f t h e basis set. Thomson also cakulated the dissociation energies
for NCN, NCC a n d C N C to be 0.212, 0.270 and 0.273 hartrecs, respectively. As
expected t h e calculations suggest that C N N is less stable than any of thcse lattcr
three species.
6 J. B. MolTat
B. Diazornethane (H,CNN)
1. Introduction
Diazomcthane is the simplest diazoalkane and as such has served as the prototype
for many studies, both experimental and theoretical. From a classical point of view
it may be considered as a resonance hybrid of a variety of planar forms:
- +
CH,-NzN (4
-
CH,-N=N + (b)
CH,-N = N - (C)
+
CH,=N=N- (4
Hence it is not unreasonable to expect diazomethane t o be capable of assuming the
properties of a carbene source, or an acid or a base, or an electrophile or a
nucleophile, or a 1 ,3-dipoleJ.
For many years there was considerable controversy concerning the structure of
diazorncthane until electron d i f f r a ~ t i o nand
' ~ microwave spectroscopic experinientsll
showed the arrangement of carbon and nitrogen atoms to be linear and the overall
structure to be planar. I n 1960 the chemical evidence for the linear structure of
diazoniethane was provided by P a u I s ~ n and ~ ~ , Schmitz and OhrneIGin the form of
independent syntheses of the first diazirines,
/N
F\NI
8\
R'
which are isoelectronic with their corresponding diazoalkanes.
2. Theoretical studies
T h e first calculation^^^ of the electronic structure employed the simple Hiickcl
molecular orbital method to calculate a resonance energy of 0.6p and, at least within
the assumptions of the method, values of the bond lengths and dipole moment in
reasonable agreement with experiment. Hoffmann18 some years later applied his
extended Huckel technique to calculations o n the excited states of diazoniethane.
Yoshida and Kobazashi have calculated the electronic spectra of diazomethane by
the ASMO-LCAO-SCF-CI l9 and INDO-SCF-MO-CI 2o methods. BrintzingerZ1
has suggested a qualitative description of the chemical bonds in diazoniethane.
What appears to be the first ab itiitio study of diazoniethane was that performed by
AndrC and coworkers2?. ApFarently, hoj.::evcr, an error in geometry unfortunately
~ ~ done CNDO calculations
invalidates the results. Bastide and H e n r i - R o u ~ s e a uhave
to examine the transition between the linear and a bent form of diazomethane, thc
CNN angle in the latter was take11 as 75". A rotational barrier of 22 kcal was
calculated and a n interpretationc4 of orientation effects in 1,3-dipolar addition
reactions was proposed. Hartzs suggested that sevcn isomers of diazomethane are,
in principle, possible, and carried out ob irtirio calculations using the LW [533; 31
Gaussian lobe basis set, o n five of these structural isomers, diazomethane itself being
included. Caballol and coworkersztiemployed the I N D O technique to obtain wave-
functions for the 'Al, 'A" and 3A" states of diazomethane. T h e ground-state
I . General and theoretical rtspcc~sof the diazonium and dinro groups 7
geometry was taken from Herzberg?' and the excited state geometries were obtained
from the ground-stnte geometry by bending the CNN angle in the molecular and
bisector planes. Thc: planar structures were found t o bc more stable and the CNN
angle was found to be 158" and 152" for the first excited singlet and triplet state,
respectively. Two minima of depth - 14.9 and - 13.9 kcal/mol were found in the
electrostatic potentials for ground-state diazomethane, the former at the carbon end
and the latter at the nitrogen end of the molecule. These authors argue that this
agrees with the experimental results which suggest a carbon attacks. In the case of
the first excited 'A" singlet state, protonation is predicted t o occur within the
molecular plane with a single minimum ( - 23.6 kcal/mol) appearing in the neigh-
bourhood of the terminal nitrogen. Electrostatic potential results for diazomethane
in the triplet state are quite similar t o those for the singlet state, the well depth being
- 24-4 kcal/mol in the triplet case.
Leroy and SanaZ8have employed the Gaussian - 7 0 prsgramme of Hehre and
coworkers29and a variety of basis sets to calculate the electronic structure and some
thermodynamic properties of this compound. With the contracted Gaussian basis
of Clementi, a total electronic energy of - 147.18569 hartree, and bond energies of
103 and 181 kcal/mol for th:: CN and N N bonds, respectively, were obtained. I n
these calculations the geometry of diazomethane determined experimentally by Cox
and coworkers30 was employed. With a 4-31G basis set, Leroy and Sana2*calcu-
lated the dipole moment t o be 1-52 D to be compared with an experimental value
of i -40 D 30, and a total electronic energy of - 147.60552 hartree.
T h e energy of formation at 0 K was obtained by the use of the equation
AEr (0K ) = E,D = AEth + 4 2 / I t > ,
t
where A 4 " , the theoretical energy of formation was taken to be that calculated with
t h e 4-31G basis set, and the v i are the frequencies or the nine normal modes for
which the values from Moorc and P i n i e n t ~ Iwere~ ~ employed. The energy of
formation at 25 "C
AEf (298.16 K) = Eo = €00 (Eo- E:)+
was then obtained by using the previously calculated value for E,O, together with the
value of E n - E E found by Moore and Pimente13'. The heat of utomizaticn (AH,)
at 298.16 K was calculated from the experimental values of the heats of atomization
of the e l ~ m e n t s ~ ~ .
In addition Leroy and Sana2*calculated values for the thermodynamic functions
mentioned above by another method, namely that proposed by Hehre and co-
t v o r k e r ~i n~ which
~ use is made of reactions and their calculated energies i n which
the niolccule of interest, in this case diazoniethane, is involved either as a reactant
or as a product. T h e two such reactions selected by Leroy and Sana are
2 CH,N,+ NH, = (CH,),NI-I +2 N,
AEtb= - 145,260 kcal
CH,N,-;NH, = CH,NH,+N,
AE'"= - 72,064 kcal
So that correlation effects could be considered to cancel out, both the C-H and
N--H bonds had to be assunled equivalent, as well as t h e C-N bonds in all
molecules in which they were present. l h e energy of formation of diazoniethane can
then be obtained from
A P = k , N , AEf,
8 J. B. Moffat
or, more specifically for each of the reactions (a) and (b)
(a) AEth = 2AE~P(N2)+AEfXp[(CH3),NH]
- AE,"'D(NH,) -2AGh(CH2N2)
(b) h E t h = AEfxp(N,) + AEPP[(CH,)NHJ
- AE,e'P(NH,) - 4Efh(CH,N,)
where AEfW is an energy of formation referenced to 0 K and corrected for the zero
point energy. Table 6 reports the values obtained by Leroy and Sana for the thermo-
dynamic functions of diazomethane. A value of 78 kcal/niol was also found for the
CH bond energy. Thc calculated value for the heat of formation of diazomethane at
298.1 6 K (63.5 kcal/niol) may be compared with that obtained experimentally
(51-60 k ~ a l / m o l ) ~ ' also Table 8).
(see
6. Calculated thcrrnodynamic properties of diazomethane (kcal/mol)28.
TABLF
Reproduced by permission of Springer-Verlag
At?:'' A& (0 K ) AEf (298.16 K ) A H , (298.16 K)

Mcthod 1 55.26 55.85 6 I -74 440.56
Method 2
Equation (a) 57.45 6 1.03 63.91 438.39
Equation (b) 60.26 62.83 65-72 436.58
Average value 57.66 60.90 63.79 438.5 1
Leroy and Sana h a w also performed geometry optimizations within the STO-3G
basis. Thcir results togcther with those for the force constants ar e compared with the
experimental values of Moore and Pimentel in Table 7.
7. Nuclear configuration a n d force constants of diazomethane (dyne/cm and erg/rad2).

TABLE
Reproduced by permission of Springer-Verlag
CN NN CH HCH Reference
Calculatcd length (A) 1.282 1.189 1.078 121.7 28
or angle (deg)
Experimental (1.300) (1.139) (1.075) ( I 26.0) 31
Force constant
Calculated 12.53 x lo5 17.48 x lo5 - 3.60 x lo-" 28
Experimental 8.3 x 105 16.9 x 1 0 5 - 0.63 x lo-" 31
Leroy and Sana, in discussing the significancc of their ab inifio calculations in

respect of the structurc a nd bonding of diazornethane, note that the C-N a n d N--N
bonds in diazomethane have the characteristics expected of a double and a triple
bond respectively, and hence the molecule behaves as one possessing six x electrons.
F o u r of these six clcctrous form a i; bond extending over three centres, while the
remainin2 two arc essentially Iocalizcd on the two nitrogen atoms. These authors
concludc that the most important structural forms are those labelled (a) a n d (d) in
Section 11.13.1.
~ ~ very rccently reported on the results of ab initio
Walch and G ~ d d a r c lhave
generalized \fnlrnce bond (GVB) a nd configuration interaction (CI) calculations
(using n double-zeta basis) o n the ground and low-lying excited states of diazo-
methane. All calculations employed thc experimental geometry for the ground state
as found by Cox, Thomas a n d Sheridan30: Rcn = 1.077 A, Rm = 1.300 A,
Rm = 1.139 A and LHCH = 126.1". In contrast to the conclusion of Leroy and
Sana, Walch and Goddard conclude that the calculated wavefunction is basically
that of a singlet biradical with strong bonding between the radical x orbitals o n the
C and terminal N resulting from the interaction with the x pair on the central N:
H'
Further, Walch and Goddard suggest that the GVB model of diazomethane would
support a mechanism based on a biradical attack in the 1,3-addition of diazomethane
t o olefins, analogous t o that in ozone rather than the usual mechanism dependent
on the dipolar nature of diazomethane.
Results of theoretical studies, in which both diazomethane and diazirine are
considered, a r e discussed in the section on diazirine.
3. Thermochemical properties
~ ~ concluded that the proton affinity (PA) of diazo-
Foster a n d B e a ~ c h a m phave
methane can be ordered with that of ammonia, azomethane and methylanline in the
following way:
PA(NH,) c PA(CH,N,) c PA(CH,N=NCH,) < PA(CH,NH,)
Consequently they place the heat of formation of diazomethane as greater than

64 kcal/mol but less than 73 kcal/mol.
Table 8 summarizes the various values suggested for the heat of formation of
diazomethane.
8. Heat of formation of diazornethane

TABLE
AH, (25 "C)
Mcthod (kcallrnol'r Reference
+
~ ~~~ ~
Kinetics 67 a
Thermochemistry 64-11 b
Group additivity 71 C
Appearance potential 49 d
Photodissociat ion 51 + e
Proton affinity 64-73 f
Theoretical 64 g
D. W. Setser and B. S . Rabinovitch, Can. J .

Chwt., 40, 1425 (1962).
J. C. Hassler and D. W. Setser, J. .inter. Client.
Soc., 87, 3793 (1965).
S. W. Benson, F. R. Cruickshank, D. M. Golden,
G. R. Haugen, H. E. O'Neal, A . S. Rodgers, R. Shaw
and R. Walsh. Cizern. Rev.,69. 279 (1969).
G . S. Paulett and R. Ettingcr, J . Cltenz Pltys.,
39, 825, 3534 (1963); 41. 2557 (1964).
A . H. Laufer and H. Okabe, J . Anter. Clzent.
Soc., 93. 4137 (1971).
1 Referencc 36.
0 Reference 28.
10 J. B. M oK at
C. Isomers of Diazomethane
As Hart25 has pointed out, diazomethane is unique among small molecules in
having six known or suspected structural isomers.
H,CNN HCNNH
Diazomethane Nitriliminc
(iso d iaz o m e t h ane)
H
\
CNNH, N-CfN
1
lsocyanamide H'
Cyanamide
H-N=C=N-H
Carbodiimide
Diazirine lsodiazirine
Of these isomers, diazirine a n d cyanamide have been prepared, and are stable
molecules a t room temperature. Derivatives of isodiazomethane, carbodiimide and
isocyananiide are known and there is some evidence that isocyanamide has been
prepared37*38. Carbodiimide a n d isodiazirinc have apparently not yet been prepared.
Isodiazomethane, although not stable at room temperature, has been prepare~l~~-.'I.
Only the diazo isomers, namely isodiazomethane, diazirine a n d isocyanamide, will
be discussed here.
1. Nitrilimine
Investigations of the reaction of triphenylmethyl sodium on diazoniethane by
Miiller a n d coworkers in 193430led to the discovery of this isomer of diazomcthane.
Anselmea2has summarized the properties of isodiazomethane as they were known in
1966. T h e preparation involves the acidification at -SO "C of a n ether suspension of
diazomethyl anion ([CH-N=N]-M+), with a n aqueous solution of potassium
dihydrogen phosphate or ammonium chloride, as in
H,CNN . LiCEIJ
on-
[HCNN]M+
*I
HCNNH
+
where M f may be Li+, Na+ (C6H&PCH3. Isodiazoniethane, a palc yellow liquid, is
then obtained by evaporation of the solvent at - 50 "C it! UOCIIO. Decomposition
I . General and thcoretical nspccts or the diaronium and diazo groups 11
begins to occur at 1 5 "C and the compound explodes at 35-40 "C 'O. A maximum
occurs at 247 nm in the ultraviglet spectrum, compared to absorption at 412 rim and
321 nm with diazomethane and diazirine, respectively. No infrared spectra have
yet been reported, but it appears from niolecular weight determinations in benzene
that isodiazomethane is monameric4'. The formation of isodiazomethane by acidic
hydrolysis of [CH-N=Nl-M+ may be explained through the assumption of a
kinetically controlled reaction, by which protonation occurs rapidly at the more
nucleophilic nitrogen (presumably the terminal nitrogen) to give the thermodynamic-
ally less stable isomer.
Apparently the only theoretical work which has been done on isodiazomethane is
that by Hart2Smentioned previously. Results of calculations on isocyananiide were
also reported at that time. The total electronic energies were obtained as - 147-2425,
- 147.2868 and - 147-3386 hartree for isodiazomethane, diazomethane and iso-
cyanamide, respectively. This would imply that isocyanamide is more stable than
isodiazomethane or diazomethane by approximately 63 and 34 kcal/mol,
respectively. Indeed, Muller, Beutler and ZeehJ3 now suggest that the compound
previously labelled isodiazomethane may in fact be isocyanamide. I f this be so i t is of
interest to seek out any evidence for the existcnce of nitrilimine. Mills and
Thompson", in a report in 1954 o n the vibration-rotation bands of diazomethane,
note that a peculiarity in the results for t h e band near 2100cm-1 leads to the
suggestion that this may be d u e to nitrilimine. On the other hand, Moore and
PimentelP5,10 years later, find n o evidence for any tautomcric form of diazomethane.
More recently however, OgilvieJ6, again on the basis of an unexplained infrared
band observed at 2169 cm-' in the photolysis of diazomethane (gas phase and a n
argon matrix), has postulated the existence of nitrilimine.
Hartzs has calculated the total electronic energy of the anions [HCNNI- and
[CNNHI- a: - 146.6485 and - 146.6389 hartree, respectively, making the former
[HCNNI- more stable than [CNNHI- by approximately 6 kcal/mol. Calculations,
assuming the entropies of these anions are equal, yield a value of 2.3 x 10' for the
equilibrium constant K for the equilibration of the two anions. Hart has calculated
electrostatic potential maps for the two anions. For [CNNHI- there are niinima
of -225.0 and - 187.0 kcal/mol in the region of the nitrogen and carbon lone
pairs, respectively, while for [HCNNI- the corresponding valucs are - 191.0 and
- 229.0 kcal/mol. These results suggest that protonation of [CNNH-1 is more
likely t o occur at the nitrogen atom to give isocyanamicic 3s the product whik
protonation of [ H C N N I - should occur a t the carbon atom to give diazomethane.
These values indicate that t h e dilference in proton affinity for nitrogen over carbon
in [CNNHI- is exactly reversed in [HCNNI-. Protonation at the 'secondary'
nucleophilic site in each anion gcneratcs a common intermediate, llitrilimine. Hence
-
i t is conceivable that a feasible tautomeric pathway could involve a q!!ickly attained
equilibrium (involving proton gain and loss) through nitrilimine a s a n intermediate:
ti+
CNNH 7EI+
-It
HCNNH
+ -H+
HENN
A hypothetical reaction mechanism for the production of isocyanamide from

diazomethane can then be constructed as shown in Figure 1. The anion tautomerism
could occur through nitrilimine or directly as a single step (broken line). Unfor-
tunately there is very little experimental evidence to support any mechanism. Of
course a variety of different possibilities for such a mechanism exist. The formation
of a dianion (CNN2-) intermediate or the formation of a cyclic transition state
involving a water molecule cannot be excluded. With the suggestion from Walch
12 J. I3. MoFSat
a diradical structure for diazomethane, various mechanisms
and G ~ d d a r dof~ ~
involving radicals become more reasonable. As HartzS points out, although his
calculations suggest that isocyanamide is more stable than diazomethane, the
experimental evidence suggests that diazomethane is thermodynamically the more
stable. Since geometry optimization was performed with isocyanamide but not
diazomethane, it is probable that the energy of the latter is not at the minimum
value.
-
L
0
1
lu
H,C NN
FIGURE 1. Total electronic energy changes in a hypothetical reaction mechanism for the
production of isocyanarnide from diazomethane. Reproduced by permission of the
Atrstraliatt Joitrtml of Clternistry.
2. Diazirine and derivatives

a. Spectra, strttctiire and thermoclteniist~y.The cyclic isomers of diazoalkanes
(diazirines) were first prepared in !960 independcntly by P a ~ I s e n a n~d~Schmitz and
O h ~ n e ~Studzinskii
~. a n d K o r o b i t ~ y n a . 'have
~ briefly considered the subject of
diazirines a s part of a review on aliphatic diazo compounds. Shortly thereafter
the molecular structure, dipole moment and quadrupole coupling constants of
diazirine were deteriiiinedjOfrom t h e rotational spcctruni in the frequency region
7.8-4: GHz. Measurements on H , ' T N , and H2C IJN 16N permitted interatomic
distances of 1.238, 1.483, and 1.09 8, to bc calculated for N N , CN and CH, respcc-
tively. T h e H C H , N C N and NCH angles were given as 117", 48'57' and 118'24' and
the dipole inornent as 1.59 debye.
Schmitz and Ohmcsl and Grahams2rcport the syntheses, by two different methods,
of diazirinc itself. Diazirinc is a colourless gas at room tempcratiire and has a
boiling point of - 14 'C. Graham"2 reports a numbcr of sharp, regularly spaced
peaks between 282 and 324 nm in the gas-phase ultraviolet spectrum and remarks on
the striking similarity in shape of the spectrum with that of 2,3-diazabicyclo[2.2.1]-2-
hepteneS3. The proton n.ni.r. spectrum in carbon tetrachloride solution at 0 "C is a
singlet a t + 241 Hz (relative to external benzene), a relatively high-field absorption
for methylcne protons, which is consistent with a strained three-membercd ring
structure. In the infrared spectrum of diazirine, Ettingers' found strong absorption
in t h e 1600 cni-' region, which he assigned to double-bond N N stretching. I n
comparison, Le Fkvre and coworkersS5~ concluded that the -N=N- linkage, in
a simple cnvironment found i n a series of azo compounds, has a charactcristic
frequency about 1580 cm-'. Valucs of the thermodynamic functions for diazirinc
(ideal gas, 1 atni) as calculated by EttingerS4are given in Table 9. I n a brief prc-
liniinary note, Merrittsi has reported on the ultraviolet spectrum of diazirine under
1. General and theoretical aspects of the dinzonium and diazo groups 13
high dispersion, and finds the 0-0 band at 30,964 cm-I. A number of frequencies in
the ground and upper state a r e also found and tentatively identified.
The mass spectra and appearance potcntials of diazirinc and diazomethane have
been detcrniined58and the heat of formation of diazirinc estimated to be 79.3 kcal/niol
a s coniparcd with 49.3 kcal/mol for diazoniethane. By the us2 of bond encrgies the
strain energy associated with the diazirine ring structure was estimated to be about
22 kcal/mol. T h e heats of formation of the ions CH,N; and CHN: wcre also
estiniatcd to be 314 and 355 kcal/mol, respectively.
9. Thermodynamic functions (cal mo1-I dcg-l) for diazirinc"' (ideal

TABLE
gas, 1 atm)
7(K) -(GO-H:)/T c:: So (ff"-ll~)/T
~
298 IC 45.43 10.19 56.S7 s.43

400 51.01 12-39 60.17 9.16
600 55.05 15.94 65.9 I 10.S7
so0 58.39 18.35 70.85 1245
1000 61.32 20.04 75. I4 13.51
That t h e cyclic isonier is morc stablc than thc lincar isomer is rcadily secn from thc
dilference in the estimated heats of formation, approxiniatcly 30 kcal/mol. The
difference is also evident in tlie reaction chemistry, the diazoalkancs bcing some of
the most reactive substances known in organic chcmistry \vhile diazirincs arc much
more stable. Grahams* notcs that diazirine is decomposed relatively slowly by
sulphuric acid with liberation of a molecule of nitrogen. I t is stablc to 1-butoxidc ion
in t-butyl alcohol and, although storable i n glass, is decomposed by ultraviolet
radiation. Apparently i t can be handlcd safcly at room tempcraturc as a liquid or a
gas although, as a consequence of the lack of agrccnient on this point, i t is advisable
to take suitable precautions.
Bellss has suggested that a different set of assumptions concerning thc processes
occurring in the mass spectrometer ion source will yield values of A H f diffcring froni
those of Paulctt and EttingerSs but more i n accord with the resalts of other cxperi-
ments. The production of CH: from CH2N2(either diazirine or diazonicthane) can
bc expressed by
A(CH:) = AHf(CH:) - AHf(CH2N.J
where A(CH:) is the appearance potential of CH: from thc particular isoincr under
consideration. Hence AHf(CH,N,) can be obtainctl from the expcrirncntal appear-
ance potential if a value for AH,(CH:) is available. Bell argues that thc valuc of
333 kcal/molGoused by Paulett and Ettinger for AHl(CH;) is an older onc, and in a
previous applicatiorP has led to tile conclusion that the major product in an ion-
inoleculc reaction is fornied via an Ciidothel'nii; process, whcrens i f the valuc
suggested by Bell is uscd the process bcconics exothermic. Thc ionization potcntial
of CII.,(3?=c)to give CH:(%), probably tlic ion ground st:lte, is 240 kcal/niol c 2 . Bell
suggests that a very probable value for A H l of CH,('A,) is S5 kcal/mol, on the basis
of kinetic and thcrniocheniical experimentsG3-". Jordan and Loiigiict-HiggiiisG"have
calculated a valiie of 10 kcal/mol for tlie separation of thc CH2('X,) state from the
ground state CH,("i). Hcncc Af/l[CH2(3E;)] = 75 kcal/mol and AHl[CI-I,+('I~)] =
315 kcal/mol. If a correction of 40 kcal/inol is applied to allow for thc possibility
that CH: will not be formed in the O z state in elcctron-impact experi11ients~'but
rather in thc higher energy 4X; stateG2,then AHl[CH,i('S;,)] is 355 kcal/lnol. Table 10
14 J . B. MofTat
summarizes Bell's values, with two heats of formation for each of CH2N,, CH,N:
and CHN: from each isomer, calculated on the assumption (i) that A(CH:)
corresponds to a process yielding CH:(JC;), o r (ii) that A(CH:) corresponds to a
process giving CH$(*xj.
10. Appearance potcntinls and calculated thcrrno-
TABLE
chemical valuesSo(kcal/mol)
~~ ~ ~~
Diazorncthane Diazirine
A(CH2) 58 284 254
A(CH,N:) 511 208 '35
A(CHN:) 5 8 34 I 327
hHr(CH,N?) (1) 71 101
(ii) 31 61
AHf(CH2N;) (i) 279 336
(ii) '39 296
AH,(CHNl) (i) 3 60 176
(ii) 320 336
Differentiation between values labelled (i) and ( i i ) i s
riven in tlic tcxt.
Bell favours the value of 71 kcal/niol for AHf (dimomethane), since kinetic
s t u d i e P suggest that the vaiue shouici be greater than 67 kcal/mol, a n d the value of
61 kcal/mol for A H , (diazirinc) zil :hc basis that t h e value of 101 kcal/mol would
cause the reaction to yield CH, and N, to be 16 kcal/mol exothermic, and this would
secni to conflict ivith the expcrimenraiiy known relative thermal stability of diazirine
compared to diazornethane.
Paulett and Ettinger", in their reply to Bell, argue that his estimate of 75 kcal/mol
for the hcat of formation of the ground state of methylene is too low and present
evidence t o support a value of 9 5 5 5 kcal/niol. They present values of 104 and
134 kcal/mol for t h e heats of formation of diazomethanc and diazirine. respectively,
in the casc where the A(CH:) corresponds to proccsses in which CH: is generated
i n an excited state.
LauG8has rcported an absorption maximum of 30,989 cni-' for diazirinc, and
notcs a red shift whcn the spectra of derivatives of diazirine were obtained i n
solution, which leads him to sugsest that the electronic transition is a x*-x transition.
Following up on his earlier note, Merritt'O providcs further dctails of his \vork on
the electronic absorption spectra of n-diazirine, Ni5-diazirine, d,-diazirinc a n d
&diazirine. Merritt notes that, as in diimidc, t h e diazirine molecule contains two
adjacent nitrogen atoms, each with a lone pair of electrons. Hence a splitting of the
degeneracy in the electronic spectrum resulting from the perturbation of the lone-
pair electron orbitais wouia be expected. Mcrritt reports two systems. separated by
approximately 220 cm-I, at 30,970 cm-' and 31,1S7 cni-', both of w h i c h are present
at 14K.
b. Thorctictll studies. What appears to be the first quantum chcmical study of
diazirine was done by i?~lf::;an'~
using his extended Hiickel calculations (EXH). T h e
experimentally determined geomctry of Pierce and Dobyns5" was employed to
calculate that diazomethane is 70 kcal/niol niorc stable than diazirine and t h a t the
ionization potentials of diazorncthane and aiaiirine arc 11.96 a n d 12.78 e\',
respectivcly, compared with the Paulett and E t t i n g e P experimental values of 9.03
and 10.18 eV, respectively. The iciativc simplicity of the EXH nicthod must, of
course, be kept in mind. Frey and Stevens7?and Amrich and have shown that
the major primary photochemical reaction in the 3200 A photolysis of diazirines is
probably direct elimination of nitrogen to form a carbene, while a minor pathway is
rearrangement to form the diazo compound.
The b, orbital is C-N, and C-N2 bonding but N,-N2 antibonding. The anti-
bonding a 2 orbital is only N,-N2 antibonding. Hence the a, t b, excitation (to
which the 3200 A transition is assigned) weakens the C-N, and C-N, bonding more
than that of N-N, and the breaking of one o r both of these bonds is consistent with
the known photochemistry of the molecule.
In a study of the photolysis of diazirine in a nitroger? matrix, Moore and
P i ~ n e n t e showed
I~~ that the product diazomethane was formed from the reaction of
methylene ( f r o n diazirine) and matrix N2. No diazomethane was found in the gas
phase photolysis of diazirine. Hoffmann employed calculations on two simple
models to obtain information on the path of the isomerization. Starting with
diazirine geometry, a simple C-N, bond lengthening, keeping C-N, and N,-N,
constant was studied. In addition, using the diazomethane structure, and holding all
bond lengths fixed, combinations of changes in CN,N, and HCN, bond angles were
considered, but with N1 and N, constrained to remain in the original plane of the
ring. A number of features wcre observed from the results of the calculations. The A 2
excited state of diazomethane prefers to be planar, and correlates with the B,
excited state of diazirine. T h e A, excited state of diazcmethane h2s a lower relative
energy with a bent C N N skeleton. The results of photochemical e x p e ~ i m e n t s ~ ~
appear to require the involvement of more than one excited state of diazomethane
in the rearrangement. Hoffmann suggests that one possible pathway then involves
t h e conversion of some of the excited B, diazirine into the second excited state, A,,
of diazomethane, and return from that excited state to the ground state without
internal conversion to the A? excited state. T h e application of Woodward-Hoffmann
rules to the concerted decomposition of diazomethane and diazirine to methylene
a n d N 2 leads to the conclusion that the first excited state of diazirine (B,) and that
of diazomethane (A2) may decompose only to an A, or B, methylene and a n
electronically excited nitrogen molecule.
Snyder and B a ~ c h ' ~a ,s part of a paper in which heats of reaction are calculated
from self-consistent field energies of closed-shell molecules, have included diazo-
methane and diazirine among the many molecules considered. Table 11 summarizes
11. Calculated and experimental data for diazirine and diazo~nethnne~~

TABLE
Diazirine Diazoniet hanc
EDZ(hartree) - 147.7287 - 147.7702
- V/2T(hartree) 0.99960 1.00006
(hartree) 0.0321 " 0.0306
Evib
ET (hartree) - 147.6938 -147.7368
Ecorr-intm (hart reel -0.7014 - 0.707 1
A H : (298 K) (kcal/mol) [ + 1011 59 [+71Is9
Expcri- Experi-
Reactions Theory mental Theory mental
AHgpg (2 CH,+ CHZNZ C2Hs + CHj + N2) - 97.2 [ - 103.31 -69.8 [ - 73.31
(kcal)
16 J. B. MofTat
their various results for these two molecules, with experinicntal geometries einployed
throughout. To facilitate the calculations it was assumed that the sum of the
electronic correlation energy and the difference of the electronic energy in the
Hartree-Fock and the double-zcta basis did not change in a reaction having closed-
shell reactants and products. The second set of values given for the complete
hydrogenation reaction i n Table 1 1 results from the inclusion of estimates for
interatomic and intraatoniic correlation energy.
Kochanski and Lehn"j employ the IB MOL programme for nb itzirio SCF-LCAO-
MO calculations using a basis set of gaussian functions on diazirinc in its experi-
mental configurationzo. Table 12, column 1, contains some of their calculated
12. Calculated and experimental dataa for diazirine

TAULE
Kochanski
and L e l ~ n ' ~ Lombardi, Robin and coworkers77.78
T 147.6529
vm 63.8985
vn, -472.6353
Vee 113.3859
Ebt - J4769SO - 147.7287
[ - 148.34691'
Overlap and type

___-__
- 15.7283 - 15.6895
- 15.7266 - 15.6879
- 11.3530 - 11.3193
- 1 '5467 - 1.5253
- 0.952 1 - 09385 + 0.205 N - N a
0.205 C - H,,,a and
- 0.8744 - 0.8540 - 0.809 N-NG
- 0.7 1 1 2 ( ; ~ ) - 0.6970 f0.210 C- H1,,;5
- 0.6776 - 0.6687 +0.186 N-I<G
- 0.5897 - 0.5777 +0.057 C-NG and -0.001 N-N 1.p.
- 0.5 I 1 I(x) - 0.4920 +0.352 N-N?;
- 0.4347 -0.4180 - 0.228 N-N 1.p.
+ 0.0937
Total atomic populations
N,, N, 7.163 7.054
C 6.188 6.301
H,, H, 0.743 0.795
Binding 0.223
energy [0.67191b
Dipole 2.47 D 2.34 D
moment [1.59 D]
Ionization 11-83eV
potential [lO.lS eV1
All energies in hartrees.

* Estimated from lieat of f o r i i ~ a t i o n . ~ ~
I . General an d theoretical aspects of t h c diazoniuin and diazo groups 17
results. The MO’s 2b2, 6a, and 3b2 which are strongly localized on t h e nitrogen
atoms contribute a t the same time weakly to the C-N bonds and strongly to the
nitrogen lone pairs. Both 2b2 and 6a, contribute strongly to the description of the
lone pairs.
T h e C and N atoms have the following charge distributions:
c: ]sl.’B 2sl.2z 2pa1’7’3 2pn1.?5
N: 1~1.08 2~1.89 2pa?.32 2pn0.97
F r o m this it may be concluded that the N atoms are o acceptors and very weak ;i
donors, while C is a x acceptor. Overlap populations show that the C-N bonds in
diazirine are much weaker than the C-C single bonds in cyclopropene. T h e N = N
bond is weakly G antibonding and ;ibonding (MO’s l b , and Zb,) so that the N=N
double bond is weak. The low-lying 2b, M O results from the antisymmetric mixing
of two nitrogen lone pairs mostly N(2s) in character. 6a, is weakly N-N bonding
which contradicts the result from overlap population which implied that 6a, was of
weakly N-N antibonding character. 3b2 contributes to the nitrogen lone pairs as
well as to the C-N bonds. There is n o pure lone pair MO. All MO’s contributing
to the lone pairs also contribute to some extent to the ring bonds.
A n experimental study of the lower n -P x * excitation in difluorodiazirine, F,CN,,
has been performed by Lonibardi and coworkers7’ and a supporting calculation on
both diazirine and FpCN2 has been done7*. Calcu1a:ion.s were performed using a
gaussian-type orbital (GTO) basis set, using a total of 125 primitive GTO’s which
were contracted to 50 gaussian-type functions. This basis is equivalent to a so-
called Double Zeta basis, in which each A 0 is represented by two Slater-type
orbitzls. Hencher and Bauer’s structural dataa7were employed.
for F2CN2are given in Table 13. T h e two MO’s 9a, and
T h e calculated res1.11t.s~~
4b, represent the two ‘non-bonding’ orbitals conventionally assigned t o the azo
group, but mutual interaction separates them by 3.8 eV. The t z + x* transition
originates at 4b,, and terminates at the x* MO, 2a,. The computed singlet-singlet
and singlet-triplet excitations are 3.99 and 3.07 e V , rcspectively, compared t o the
observation of the excited singlet at 3.7 eV. Analysis of the MO’s involved in the
transition shows that ti is nearly equally distributed among the C-N-N atoms of
the ring, but that *; is completely localized on the N atoms. Consequently the t v x *
+
excitation involves the transfer of about electron from thc CF2 group to the N = N
group of difluorodiazirine.
T h e results of the ab initio calculation by Robin and coworkers7Eon diazirine are
included in Table 12 for convenience i n comparison with the earlier work of
Kochanski and Lehn7G.In addition, Tables 12 and 13 also include some of the results
obtained in comparison with photoelectron spectral data of bot!l diazirine and
F,CN,. The agreement between their observed and calculated (using 92% of the
Koopmans’ Theorem value) ionization potentials for both these molecules was
found to be quite acceptable.
Bloor and Maksicso calculated dianiagnetic susceptibilities and quadrupole
moments of diazirine using the CNDO/ZD and SCC (self-consistent charge) semi-
empirical methods. T h e molecule was oriented as shown :
YA
18 J. B. MofTat
TABLE
13. Calculated and cxperiniental data for difluorodia~irinc'~
~ ~~~~~~ ~~ ~
Total energy (a.u.) - 345-3999

- V/2T 0.9996 1
Orbital encrgies
la1 - 27.3726
lb, - 27.3726
2a L - 15.7494
1 b, - 15.7483
3% - 11.5465
4a, - 1.7715
2bz - 1.6915 Overlap and type'e
5a1 - 1.5702 ___---
3bl - 0.9790 -0.581 N-NO
6a 1 -0.9763 +0.158 N-NG
3b2 -0.8569 +0.100 C-FG
7% - 0.8437 +0.195 N-No
3b1 - 0-7741 -0'207 N-"G
1a2 -0.7306 -0.042 F-F
8% - 0.7 107 +0.081 N-NG
4b, -0.7017 -0.145 F-F
9% - 0.625 1 +0.039 N-N 1.p. and -0.071 C-Fl,2a
5b2 - 0.5800 ( x ) +0.354 N-NK
4b1 - 0.485 1 -0,255 N-N 1.p.
2a2 +0.0221 ( x * )
5b + 0-2568
108, + 0.2705
6bl + 0.2970
Dipole moment 0.082 D
Quadrupole coupling constantsfl
x, (N) -0.614
.rep (N) - 2,457
x,, (N) + 3.066
It 0.599
Net charges
C + 0.544
N -0.018
F - 0.255
Second moments of the electronic charge
(.?> 4 1.432 3
< Y2> 97.293 1
<Z2> 136.2211
Values in Mc/sec computed in the principal axes system using a nuclear

quadrupole moment of Q(14N) = 1.60 x cm2.
* z is the two-fold rotation axis, x is perpendicular to z in the CN, plane
and y is perpendicular to the CN2 plane.
Tables 14 and 15 list the electronic second moments and the molecular quadrupole
moments calculated by the two methods and compare these with the a6 initio resultssl.
Unfortunately there d o not appear to be any experimental d a t a for diazirine with
which to compare the calculated values. However, with other molecules where such
experimental data are available, agreement between such data and calculated values
is very good for the second moments, but not a s satisfactory with molecular
1. Gencral and theoretical aspects of the diazonium and diazo groups 19
quadrupolc momcnts, the former agreement being ascribed by the authors m o r e to
the insensitivity of the quantities mentioned than to the high quality of the calculated
wavefunct ions.
TAULE14. Second moments of the electronic-chargc

e cm?) of dinzirineso
distribution (10--lG
CNDO/2D SCCMO nb itzifioA1
<s?> 15.8 I 15.60 15.48

<Y?> 9.27 9.47 9.62
<:?> 4.94 4.89 5.08
<ra> 30.02 29.96 30.22
TABLE
15. Molecular quadrupole moments Fr cm2)
(Fr = C.S.U. of chargc) of diazirinc*O
CNDO/2D SCCMQ ab itiifioR1
QZZ - 0.8 1 0.54 2.01

Quu - 2.44 - 4.02 - 4.76
Q*L 3.25 3.48 2.75
T h e results of MINDO/2 and EXH calculationss2#83 on diazirine a n d its dimethyl

derivative are shown in 'Table 16. Haselbach a n d coworkersa2 note that the orbital
sequence for diazirine calculated b y the MINDO/Z technique differs from that
obtained by Robin a n d in the order of the orbitals a,(n+) and al(G), a n d
point o u t that it is known that for unsaturated systems MINDO/2 yields o orbitals
with somewhat high energies. Hence the positioning of al(o) between bl(x) a n d
al(n+) in Table 16 should be considered a consequence of the use of the MINDO/2
method.
TABLE16. MINDO/2 calculated orbital energies

(hartrees) for diazirine and 3,3-dimethyldiazirine
Diazirincs2 3,3-Dimethyldiazirincs3
0.5751 b,(x) 0.3572 b2(tz-)

0.4943 al(ti+) 0.3862 b , ( x )
0.4322 a l ( ~ ) 0.4212 al(c)
0.4105 bl(z) 0.4392 a l ( t z + )
0.3838 b2(n-) 0.4502 bl(z)
T h e vertical ionization potentials Z\(J) of dirnethyldiazirine as determined by

photoelectron spectroscopy*? are given as 9.76, 12.11 and 13.31 eV, or 0.3587,
0.4450 and 0.4891 hartrees.
3. Substituted diazirines
a. Spectra mid sfriictiive. Although earlier workersa7- bs had proposed
518
methods for the preparation of diazirine a n d substituted diazirines, i t appears that

Mitsche4 was the first to prepare perfluorodiazirine (F,CN,), a precursor of CFs. H e
2
20 J. B. Momat
and his coworkers subsequently nieasureds5 the infrared spectrum of F,CN, from
4000 to 250cni-l and the Ranian spectrum from 2700 to 100cm-I in order to
cstablish its structure. T h e frequencies of the infrared and Ranian bands for the
fundamental modes expected for the diazirine a n d diazomethanc structures werc
calculated and t hcse were compared with the measured fundamental vibration
frequencies of F,CN,, shown in Table 17. T h e match bcttveen those values predicted
for the diazirine structure and those observed is quite convincing.
TAULE 17. Summary of funda-
nicntal vibration frequencies of
F2CNZas.Rcprintcd, with permis-
sion, from Hciicher and Baucr, J .
Afncr. Chcni. S O C . , 1186(1965).
~~,
Copyright by the American
Chemical Society
Frequency
Symmetry (c rn- I )
A, v, 1563
v2 1252
v3 805
v4 502
A, 19; 451
B, v6 1248
v7 481
B, v8 1091
1'9 544
Simmons a n d coworkers8Gstudied the ultraviolet absorption spectrum of CF,N2

in the 3750-3000 8,region under high resolution and confirmed the conclusions from
the infrared a n d Raman works5, t h a t the molecule did indeed possess a cyclic C2v
structure. The results of the two studies agree quite \veil, as can be seen from Table 18,
except for v 3 . u1 and v4 may be described as the symmetric N N stretch and symmetric
CF, d e f a m z t i o n , respectively. Hence i t appears that the most significant change in
geometry between the two electronic states is a stretching of the nitrogen-nitrogen
bond which expands t h e ring and alters the F C F angle.
IS. Comparison of thc vibrational assignment for the A , specics in CF,N, as
TABLE
found from the infrared85, R a n i a ~ and
i ~ ~ ultraviolets6 spectra
Ultraviolct (vapour)
Infrared (vapour) Raman (liquid) -_______
Vibration (cm-I) (cni-I) u" (cm-I) v' (cni-I)
VI 1563 1560 1564.0 1436.9

V? 1282 1280 1282.9
"3 805 804 715.0 643.3
v4 592 500 500.2 5 16.6
Hencher and BaueP' completed the puzzle by providing interatomic distances and
bond angles from electron diffraction experiments o n the vapour. They confirmed
the C2v symmetry in which the planes of CF, a n d CN,! are mutually prrpendicular
with C-F = 1 . 3 1 5 & C-N = 1.426A, N = N = 1.293 A, L F C F = 111.84",
L N C N = 53.95". Comparison of these values for perfluorodiazirine with those for
diazirine shoivs that the C-N distance is shorter ( 1 4 2 6 vs 1.482 A) and the N = N
1. Gcncral a n d ihcorctical aspects of the diazonium and diazo groups 21
distancc is longcr (1.293 vs 1.228 A) i n the former than i n thc latter by about 0.06 A.
These arc sunilnarizcd in Table 19. Hcncher and Rauer comixire thc C-F distance
and the L F C F for F,CN,, 1.315 A and 1 1 1.84", rcspectively, with thosc found for
perfluorocarbciic (F,C:) *I, 1.300 A and 104.9", respectivcly, and rationalize the
differenccs on the basis of the greater extent of tielocalization of the carbon valence
electrons in thc radical. In addition, the compression of the chargc density around the
carbon atom and hence the shortening of adjacent bond Icngths when F is substitutcd
for H o n a carbon a t o m has Secn observcd with many other molecules. The introduc-
tion of F a t o m affects not only thc adjacent C-1: bond lengths. but also adjacent
bonds are shortened, as is observed in the prescnt examples, where the C-N distance
in F,CN2 is smaller than in H,CN2. The longer N = N bond in F2CN2than in H,CN,
cannot be d u c priniarily to thc prescncc of a three-atom ring since the C-C distance
in cyclopropene is 1.525 A*9, close t o that found in cyclopropancgO,while C=C is
1.256 A, less than the C = C distance in ethylene. To be consistcnt with thcsechangcs,
i t would be anticipated that the N = N distance i n F2CN2(1.293 A) would be lcss
than that in N,F, (1.224 A)S1, which i t is not.
19. Nuclcar con5guration of dinzirinc and

TABLE
perfluorodinzirine
Para rncici' F,CN, yi I-I,CN2 so
C-- F 1.315 8,
c- ti I .09 A
C-N 1.426 A 1.4s2 A
LNCN 53.95" 48.9"
L FCF 1 1 1.84"
L HCH 117" ( i2)
N=N 1.293 8, 1.228 A
F . . . 1- 3.178 8,
N...F 2.374 A
Robertson and Illerritty2,continuing the work on diazirincs already begun i n their

laboratory, obtained thc ultraviolet abscrption spcctra, at high resolution, for
3-bronio- a n d 3-cliloro-3-n?ethyldiazirine. These compounds were prepared by the
incthod of Graham"'. Two clectronic systcms are found for these two substituted
diazirincs, separatcd by 63 cni-' in 3-bromo-3-niethyldiazirine (BMD) and 137 cm-l
in 3-chloro-3-iiictliyIdiazirinc (CM D), again providing evidencc for the splitting of
the degeneracy of the lone-pair nitrogen clectrons as obscrved with diazirinc:O. T h e
strong progression is the symmctrical N N stretching frequency a t 1412 mi-l in
R M D and 1454 cni-l in C M D . Spectra of solutions of B M D and C M D i n benzenc,
ethanol and chlorobcnzene showed a blue shift of approximately 30 cm-I as the
-
solvent was changed from less polar to more polar, which indicatcs that the transition
is T;* ti.
Thc vapour-phase infrared spectra of B M D and CIMD \vcre measurcd in thc
250-4000 cni-' region by Mitchell and Mcrritt". Thc N = N stretching vibrations in
B M D and C M D a r e 1571.3 and 1573.4 cni-', respectively, litrle changed from
1626 cii1-l i n diazirine5' and 1563 cm-' in difluorodiazirine". Thc symmctric a n d
antisymrnetric C-N stretching vibrations wcre assigncd a s 991 and SO7 cn1-l in
diazirine", a n d 1282 a n d 1091 i n difltiorodiaziriiiebs, a considcrable shift.
klitchell and Mcrritt assign the symmetric C-N srretching \.ibration to 1071.6 cm-'
in C M D and 1090.9 cni--l i n B M D and thc antisymmctric vibration to S5S a n d
868 cni-l i n BMD a n d C M D , respcctively.
22 J. B. hloffat
Since Hencher and Ijauersi had found that the C-N a n d N = N bond lengths of
F,CN, differ by an unexpcctedly large amount (0.06 A) from their corresponding
values in H,CN2, then i t might be expcctcd that other substituents would alter the
ring geometry but to a lesser degree. Hence Wollrab a n d coworkersg4observed the
rotational spectra for diinethyldiazirine to test this hypothesis. Their nieasured
structural parameters are given in Table 20. The N = N and C-N distances in
diazirine and D M D are quite similar, indicating that methyl sr;bstitution has little,
if any, effect on the ring structure. A dipole moment of 2.19 D ( 20.07) was obtained
from the Stark shift. The internal rotation splittings for (CH,),CN, yield a barrier
to internal rotation of 1129 f 20 cal/mol and an angle of 120.4 f 0.4" between the
top axes. The quadrupolc coupling constants (MHz) are xaa = - 0.94k 0.8,
Xbb = 3-2020.4, xcc = -2.2720.4, with the a axis being that passing through the
ring carbon atom and bisecting the N = N bond, the C axis passing through the ring
carbon atom a n d running parallel to the N = N bond.
TABLE 20. Structure parameters of dimethyldiazirinc (DMD) 'I, difluorodiazirine

(DFD) *', diazirine (D) tio methyldiazirine (MD) Oi and 3-chloro-3-methyldiazirinc
(CMD) 8G
~~
Bond DMD DFD D MD CMD

Bond length (A)
c-c 1.499 1.501 1.498
C- N I -490 1.426 1.482 1.481 (1.467)
N=N 1.235 1.293 1.728 1.235 1.24I
C- H, 1.080
l.0g8 ] (1.09)
C-Ha 1.100 1 -09 1.096
Bond angle
LNCN (48.9")' 53.95" 48.9" 49.3" 50.2"
LNNC (65.So)a
LCCC 119.7"
L FCF 1 1 1,s"
L HCH 117"
-
aAssumed from the structure of diazirinc5".
H,, Ha: symmetric (in-plane) and asymmetric (out-of-plane) hydrogen positions,
respectively.
Continuing their examination of the effect of substituents on the diazirine ring,

Scharpen and obtained the rotational spectra of CH3CHN2 and
CD3CHN2(methyldiazirine). Their results are shown in Table 20 for convenience in
comparison of the values of the various parameters. T h e N = N bond length is the
same a s that found in dimethyldiazirine although the C N bonds may be slightly
shorter. The internal rotation splittings gave a methyl group rotation barrier of
773.9 cal/mol. Quadrupole coupling constants (MHz) of xaa = +0.48 i-0.8,
+
X b b = - 2.53 f 0.4 and xcc = 2.05 k 0.4 were obtained with the a axis along the CN
bond and the b axis parallel to the N = N bond. A dipole moment of 2.03 2 0.07 D
was calculated.
A third paper, this time o n C M D , was published by Wollrab and Scharpenge,and
the structural parameters a r e a d d x i to Table 20 for convenient comparison. T h e
N = N bond length is only slighrly lrirgcr than the same parameter in the methyl-
substituted diazirinesg4. T h e barrier to internal rotation of the methyl group is
1. General and theoretical aspects of the diazoniuni and diazo groups 23
1689 k 10 cal/mol. The chlorine quadrupole coupling constants (MHz) are
xaa= -66.51, X b b = 32.91 and ,yrc = 33.60 with the nh plane being the molecular
symmetry plane containing the two carbon atoms, thc chlorine atom and H,. The
L: axis is normal to this plane.
Mitchell and Merritte7 measured the vapour and solid-phase infrared spectra for
3,3-dimethyldiazirine and 3,3-dimethyl-~~-diazirincin the %SO-4000 cm-' region.
T h e N N stretching frequency (solid phasc) was 1556 cm-I, while the symmetric and
antisymmetric C-N strctching vibrations wcre assigned to 1136 and 788.1 cm-l,
respectively.
Lombardi, Klemperer, Robin, Basch and Kuebler (LKRBK)" carried o u t both
a n experimental and theoretical study of the lower tz -> x * excitation in difluoro-
diazirine, F,CN, (DFD). They note that n o microwave spectrum has been observed
for D F D which may be due to a vanishingly small ground-state dipole moment.
Using the results of Henchcr and Bauers7 they are able to establish the changes in
the N-N and F-F distances on excitation, and hence thc molecular structure of
F,CN, in the ri -P x* excited state. Such changes are given as + 0.060 k 0.005 and
- 0.034 2 0.005 8, for N N and F F , respectively, yielding 1.343 8, and 2.144 A,
respectively, for the rz ;i*excited state bond distances. These authors point out
--f
that since the spectrum is sensitive only to the change in the N = N distance on
excitation, their results cannot confirm or deny the large value previously found8' by
electron diffraction for the N = N bond length in D F D . LKRBK estimate a value of
p' = 1.5 kO.2 D for the n -> x* excited-state dipole moment of I I F D and a value
of cnly 0.082 D for that in the ground state. Discussion of the tl:eoretical studies
of LKRBK on D F D has been given in the appropriate section of this chapter.
However, it may be desirable to summarize those portions of their theoretical
results which relate particularly to their experimental work. The orbital energies
are summarized in Table 13 of t h e theoretical studies section (II.C.2.b) to which
reference may be made. Orbitals 4bl and 9a,, the highest occupied and the third
highest occupied, have energies of - 0.455 I and - 0.625 1 hartrees, respectively, and
represent the two 'non-bonding' orbitals associated with thc - N=N- group. As
has been observed repeatedly experinicntally in the diazirines, thcir mutual interaction
separates them, in this case by 0.14 hartrees or 3.5 eV. The 12 + x* transition involves
the passage of an electron from 4b, to the z* molecular orbital, 2a2. Using the virtual
orbital approximation yields a calculated singlet-singlet tz z* excitation encrgy of
--f
3-99 eV compared to their observcd value of 3.7 eV.

LKRBK note that the electronic spectrum of a polyatoniic molecule is normally
severely blue-shifted on substituting the hydrogens by fluorine, and hcnce i t is
surprising to find the t i - P r * band of F,CN, (3.7 eV) to the red of that of H,CN,
(3.95 eV). Ho\vevcr their calculations predict the correct rclntivc ordering of the
rr -> ;i*barids of diazirine (4.17 el!) and difluorodiazirine (3.99 eV).
T h e bond length changes on excitation may be rationalized by examining thc
nature of the niolccular orbitals (MO). The 9a, MO tcnds to draw the two nitrogen
atoms togcther while the 4b, MO acts i n a n opposing fashion. Hence, in an rz -> x*,
the promotion of an electron from the 4b, M O \vould be expected to cause the N = N
distance to shorten, but promotion occurs to the 2 a 2 x * MO which is more N = N
antibonding than 4b,. Consequently the increased N = N distance in the upper state
can be rationalized.
LKRBK also argue that the sccond band systcm obscrved in the vibronic spectra
o f diazirines by themselves and othersv' could not be the sccond ti + x * transition
(9a, --> 2a2) for two reasons. One, their b1O energies would have the two ti -> x*
transitions scprirntcd by approximately 20,000 cm-', a value of the order of 100-
times larger than that observcd experimentally. Secondly, symmetry considerations
24 J . R. Momat
would suggest that tlic second ! I -p z* transition is forbidden. L K R K B tentatively
assign the second system i n the diazirines to thc x -' =* triplct state.
Robertson and Merritts* measured the higft-resolution electronic absorption
spectrum of 3,3'-dimcthyldiazirine (DMD), and two superimposed electronic
systenis \yere again observed, the weak second origin is 176 ern--' to the red of the
strong origin of the allowed singlet-singlct x * 11 system. In addition, a third
d-
elcctronic system was obscrvcd in the 390tb4200 A region, which these authors take
as the triplet-singlet *; i-I Z transition. The N = N stretching vibration is again the
most prominent fcatiire in all systcnis. Thc high-resolution electronic absorption
spectrum of 3-methyldiazirineg9was also obtained. Results soniewhat similar to those
for D M D werc obtaincd, the two electronic systcnis again being observed, this time
separated by 92 cni-I. The N = N stretching vibration \vas again prominent near
1499 cni-'.
Correlations of bond strctching frequencies, bond lengths and dissociation
energies, as advanced by BernsteinIOO, have bcen pursued by McKean and co-
workers101 for a large variety of niolecules among which are the diazirines. CH
dissociation energies (D!LJ of 110.8 and 98.4 kcal \vere predicted for diazirine and
dinietliyldiazirine, respectively.
The 3920 A absorptioa spectrum of difluorodiazirine \vas reinvestigatcd by
I-iepburn and Hollas102and changes in structural parameters for the ground lo the
excitcd state were calculated as 0.036 and -0.038 8, for the NN and FF bond
lengths, respectively, which may bc compared to t-0.06 and -0.034 8, for N N and
FF, respectively, as found by LKRBK". Hepburn anc! Hollas also conclude that
there is no positivc evidence for a second electronic system in thc 3520 8, region.
Accurate valiics of the 14N nuclcar quadriipole coupling constants (MHz) have
been measured by Pochan and fly gar^'"^, as xna = + 0 . : 9 6 , xbb = - 3.010,
xcc = +2.814, all 2 0.150, wlicre the n axis is coincident \ v i t h the molecular symmetry
axis and h is in the plane of the moleculc. These valucs are in fair agreement with tlie
calculated results of LKRBK:', xaa = -0.S MHz, xbb = - 1.S8 MHz, xrc = +2.69
MHz. Walsli orbitals having sp orbitals in the plane of thc ring (one pointing away
from the N and containing a lone pair of electrons; the other entering into a C-N
G bond) werc used \vith unhybridized p: and p v orbitals to dcscribe the 14N field
gradients.
b. Kinctics of ~ I I C I ~tlecoiuposi/ion.
III~/ Relativcly little work had bcen donc on the
thermal decomposition of aliphatic diazo coinpounds, presumably because of their
instability, u n t i l tlie discovery of convcnicnt preparative proccdurcs for various
substitutcd diazirincs. Since thesc cornpounds appeared to be more stable than the
corresponding diazo cornpounds, there followed a substantial amount of work on
their decomposition. This section will deal primarily with tlic physicocheniical
aspccts of such dccornpositions.
Frev and Stcvens'u4 havc investigated the thermal dcconiposition of dimethyl-
diazirine (DhlD) in the teniperatitrc rangc from 123 to 173 " C ,and havc found this
reaction, producing properic and nitrogen, to be homogeneous and first order. Below
100 torr, the first-order rate colistant decreases with pressure, but a t 100 torr i t
has essentially attaincd its high-pr'essiire limit. At an initial pressure of 4 torr, the
measured first-order ratc coiistants yield an activation energy of 33.2 kcal!niol. At
this pressure and 145.1 "C, k := 3.47 x lo-' sec-I. At suficicntly high pressures the
riitc const;int of a iininiolccular rcnction should bc indcpendcnt o f pressure, and
conscqucntly tlic aiithors propose that t h i s reaction is probably unimolecular.
Furthcr, no depart tire from lirst-order kinctics \vas observed eve11 in runs carried
to iiiorc than SO'): decomposition. Sincc propcne is known to bc an intiibitor of
1. General and thcorctical aspects of tlic diazoniuni and diazo groups 25
radical-chain reactions, and since the rate of decomposition of dimethyldiazirine
is not affected by the accumulation of propene in the system, it was concluded that
i t was unlikely that any chain reaction is involved. Hence it was presumed that the
decomposition is a true unimolecular reaction. These authors considered two
possible mechanisms, first, a 1,2-hydrogen shift and a C-N scission to form a
diradical as a n intermediate, followed b y a breaking of the remaining CN bond and,
second, a concerted mechanism in which N2 is released and diniethylcarbene is
formed as an intermediate, followed by the rearrangement to propenc. The authors
argue that thc first mechanism is unlikely on energetic grounds.
Boltomley and Nyberg'O' have also investigated thc gas-phase thermal decomposi-
tion of DMD, but in the temperature range 60-70 "C and at pressures of 200 torr, at
very slow rates using precision gas-volumetric techniqtics. Their rcsults a n d those
of Frey and Stevens'o', aftcr adjustmcnt for pressurc differcnces, fit a single Arrhenius
activation energy cquation. They also concliidc that the reaction is homogeneous.
Bottoniley and NybcrglOs argue for a mechanism in which dirncthyldiazomcthanc is
formed as a n intermediate, since the high value of the pre-exponential factor (loll)
is taken to indicate a transition state considerably 'looser' (i.e. highcr entropy) than
the initial configuration, espccially whcn a rigid cyclic structure is broken.
The thermal decomposition of difluorodiazirine (DFD) yields primarily nitrogen.
tetrafluoroethylenc, hexafluorocyclopropnnc and perfliioro-2,3-diaza-l,3-butadienc,
with traces of other fluorinc-containing compoundsq4.IoG.
The reactions may be represented a s a serics of competitive consecutive steps:
By decomposing at a partial pressure of 50 torr in the presence of a 3-molar cxcess of

C,F4, the side reactions were mininiizcd and decomposition occurred primarily to
form difluorocarbene and nitrogen. Such primary dccoiiiposition appcarcd to bc
uniinolecular and hornogencous in the tcmperature range of 123-170 "C and total
prcssurc of 100-800 torr. 'The rate constant was prcssurc dcpendcnt in this range.
At a total initial pressure of 200 torr and 141.0 "C the rntc constant was 1.27 x lo-'
scc-.'. At the same prcssurc the pre-exponential factor ivas nnd the activation
energy 32.2kcal/niol. Neuvar and ivlitschl"' also prefer a nicchanism involving
difluorodiazoinctliane as a n intcrmcdinte prior t o loss of nitrogcn.
I n order to determine the elycct of the clcctronegativc chlorine atom o n the
decomposition of diazirines a n d to confirm that the dccoiiiposition w a s unimolecular,
by follo\ving the rcaction in the fall-off region. the tlierninl decomposition of 3-chloro-
3-mcthyldiazirine (CMD) i v m iiivcstigatcdl"y. I n tlic tempcrntilrc region of 106-
170 "C, C h l D undergoes a lirst-ordcr dccoinposition. \vhich is probably unimolccular,
t o form vinyl chloride and nitrogcn. N o other products wcrc detected. Lo\v-prcssiirc
cxperimcncs \ v e w porformcd at ;ti1 initial rcict;int prcssurc of 4 torr and at nine
tcnipcrntiires ranging from 107 1 0 170 OC'. At 117 " C the rate constant \vas
3.50 x scc-l, thc pre-exponential factor lo"", and the activation energy
27.2 kcal/mol. I n ordcr lo study thc effcct ol' pressurc pcrfluoropropane tvas added
26 J . B. Moffat
a s an inert gas. For a reaction mixture which consisted initially of 50 torr of C M D and
300 t o n of perfluoropropanc, and temperatures between :I0 and 148 "C, a n
Arrhenius expression was obtained for k , which contzincd as a pre-exponential
factor and 31.1 kcal/mol as a n activation energy. These authors retain their belief
that the decompositions proceed via the formation of a carbenc. Substitution in the
3-position of a chlorine atom should lead to some stabilization of the resulting
carbene as compared with its hydrogen or alkyl analogue. T h e energy of activation
for D M D was 33.2 kcal/mol(4 torr) which probably could be adjusted to 34 kcal/mol
to correspond to k,. The difference between this value and that of 31 kcal/mol
obtained from C M D would suggest a significant stabilizing effect of the chlorine
atom. Bridge and coworkerslO* take the pre-exponential factor of 10lJ'las indicating
that the decomposition has a relatively small entropy of activation, and hence that
in the transition state no new free rotations have developed. They consequently
favour a cyclic intermediate in which both C-N bonds a r e weakened and N = N
strengthened.
T h e thermal decomposition of 3,3-tetramcthylenediazirine, 3,3-pentamethylene-
diazirine and 3,3-diethyldiazirine was also investigated by Frey and Scapiehornlo9.
T h e decompositions may be represented as follows :
3,3-Tetramethylenediazirine
k = 1013.40
exp ( - 30,50O/RT) sec-l
Pi,renctont
= 7 torr
3,3-Pentamethylenediazirine
k = 1 013.3'
exp ( - 30,87O/RT) sec-'
pi. reoctant = 5 torr
3,3-Diethyldiazirine
EtCH =CHMe
/
Et\ /N cis and irans (118-149 "C)
c II
Et' \N \ E t T
k = exp (- 3 1,89O/RT) sec-'

Pi. rc.irt?nt = 10 torr
In all cascs the reactions \vcre homogeneous and first order, and probably uni-
ni olccu lar .
1. Gcneral and theoreiical aspects of the diazonium and diazo groups 27
Although it does not properly fall under the heading of kinetics of thermal
decomposition, nevertheless it seems appropriate to take note of a study of the
polymerization of difluorodiazirine (DFD)"O bccause of the information which such
work may provide concerning possible reaction intermediates. Pyrolysis or ultra-
violet pyrolysis of difluorodiazirine in the presence of boron trifluoride produced
polydifluoromethylene. Unlike Frey, Ogden and M itschllofavour the formation of a
linear intermediate rather than the concerted clirnination of nitrogen i n the de-
composition of DFD. Under certain conditions tetrafluoro-2,3-diazabuta-l,3-dienc,
tetrafluorethylcne and perfluorocyclopropanc arc formed from the decomposition
of DFD:
/N A F
F,C II -f F\/c=c\ / -I- /CF,
\ + F,C=N-N=CF,
\N F F F,C-CF,
Tetrafluoro-2,3-diazabuta-l,3-dienecould be derived from reaction of difluoro-

carbene with the linear intermediate or by insertion of difluorocarbcne into the
difluorodiazirine double bond, followed by rearrangement :
However, Ogden and Mitschllo could find n o examples of insertion of difluoro-

carbene into a n N = N bond, and consequently favoured the linear intermediate.
Continuing their studies of the thermal decomposition of diazirines, Frey and
Liulll investigated 3-chloro-3-ethyldiazirine,3-chloro-3-n-propyldiazirine,3-chloro-
3-isopropyldiazirine and 3-chloro-3-r-butyldiazirine.T h e overall decomposition
reactions are given below:
3-Chloro-3-ethyldiazirine
Me\ H
Et\
c
/N
II
__ ,CI
+ Me\ /
+ Nz
CI/ \rd ' H/'=' \H H'c=c \c I
k = 10'3~8R5exp ( - 30,45O/RT) see-'
(20 torr of diazirine and 60 torr of n-butane; 103-145 "C)
-
3-Chloro-3-m-propyldiazirine
n-Pr\ /N Et\ / CI Et, /H

C I I + ,C=C, + N,
C1/ \N H/c=c\ H H CI
k = I013.9R exp ( - 30,98O/XT) scc-'

(10 torr diazirine and 20 torr butane; 105-149 " C )
28 J. B. Moffat
-
3-Chloro-3-isopropyldiazirine
i-Pr, /N Me, /C=C / H + N,

c II \
CI’ \N Me CI
k = exp ( - 30,59O/RT) sec-’
(10 torr diazirine and 20 torr butane; 107-145 “C)
3-Chloro-3-t-butyldiazirine
k = 1 0 1 3 . 3 6 exp (- 29,500IRT) sec-l

(4 torr diazirine; 105-148 “C)
T h e values of the free energy of activatioi? (AG*) for decomposition of all the
alkylchlorodiazirines fall within the range 28.75 k 0.3 kcal/mol and the authors
again interpret this as supporting the intermediate formation of a carbene by a
concerted elimination of nitrogen.
T h e thermal decomposition of 3-chloro- and 3-bromo-3-phenyldiazirines (BPP)
has been investigated in several solvents over the 60-1 10 “C temperature range"?.
In this temperature range, 3-chloro-3-phenyldiazirine(CPD) decomposes uni-
molecularly to yield nitrogen and the corresponding carbene. This carbene can
either rcact with diazirine t o give dimeric product or with the solvent t o yield the
appropriate compounds. T h e average activation energies for CPD and BPD are
27.8 and 27.4 kcal/mol respectively, the former being averaged over that obtained in
three different solvents. The former value represents a decrease in activation energy
of about 3 kcal/mol from that found for 3-chloro-3-methyldiazirineL08a n d this is
suggested to reflect the resonance stabilization effects of the phenyl group on t h e
transition state of diazirine decomposition. T h e pre-exponential factors in both
cases are approximately lolo, suggesting a typically unimolecular reaction with a
relatively tight transition state. T h e results of Liu and Toriyama112 also show that
the rate of decomposition changes very little as the solvent is varied, which appears
to indicate that the transition state of the rate-determining step is likely t o bc more
radical than ionic. Further, the substituent effects are interpreted as supporting a
radical intermediate such as
I n a sccond paper Liu and Toriyama3l3have examined the cffect of porn sub-
stituents on the thermal decomposition of a series of 3-chloro-3-aryldiazirinesin
various solvents. A summary of their results, together with those of previous workers,
is given in Tablc 21. They find, in agrcement with the data previously discussed in
this section, that thc thermal decomposition of diazirines is uniniolecular with a pre-
exponential factor of approximatcly Each of the solvents used (cyclohexene,
diethyleneglycol monoethyl ether and dirncthyl sulphoxide) gave similar organic
products and all t h e free energies of activation are approximately 26.0 ~f:0.3 kcal/mol.
I . General and theoretical aspects of the diazonium and diazo groups 29
TADLE
21. Summary of kinetic data for the thermal dcconiposition of substituted dia~irines"~
Reproduced by permissiotr of the Natiofial Research Council of Canada from thc Caiindjori
Jortriial of Chemistry, 50, 3009-3016 ( I 972)
As+
E (cal mol-I
Reference X Y State log A (kcal/mol) de2-I)
-~
107 Fluoro Fluoro Vapour 13.40 32.50 0.5
109 Ethyl Ethyl Vnpour 13.73 3 1.89 2.0
10s Chloro Methyl Vapour 14.14 3 1.07 3.9
111 Chloro Ethyl Vapour 13.99 30.45 3.2
111 Chloro ti-Propyl Vapour 13.98 30.95 3.2
111 Chloro i-Propyl Vnpour 14.01 30.59 3.3
111 Chloro I-B u t y I Vapour i3.36 29.50 0.3
112 Chloro Trich I o r o met h y I CCI, 1330 29.20 2.3
112 Chloro Phenyl Cyclohexene 13.57 25.00 2.6
113 Chloro p-Met hoxyphenyl Cyclohcxene 13.41 26.49 0.5
113 Chloro p-Tolyl Cyclohexene 13.94 27.Y7 2.9
113 Chloro p-Chlorophen yl Cyclohexene 13.81 27.72 2.3
1I 3 Chloro p-Nitrophenyl Cyclohcxene 13.80 27.Y5 2.3
112 Brorno Phcnyl Cyclohexenc 13.75 27.36 2.1
Although the substituent effects on the rates of reaction are small, nevcrtheless the
following order can be discerned: p-CH,O>p-CH,>p-Cl> Hgp-NO?. Liu and
Toriyama employ these results in an attempt to select one of
R+
(1) (W (111)
as the most likely transition state. The order of substituent effects would be expected
to be the reverse of that observed if the charge separated transition state I1 is
invoked. Further, the lack of solvent effects renders I1 unlikely as a transition state
i n the thermal decomposition of diazirines. I n view of the suggestion of SchmitzI1'
that a mechanism passing through transition statc I would require thc carbon atom
in that state to tend towards a sextet, a n d consequently that such a transition cannot
be stabilized by withdrawal of electrons, Liu and Toriyama conclude that the order
p-CH,O >p-CH, > H >p-CI > p - N O , would be expected, t h u s ruling against state I
in the present case. Liu and Toriyama as a result conclude that transition state 111
is most probable a n d consider three possible structures for that state:
\- \+ \- +
/C-N=N ,C-N-G /C-N=N
(Illa) (Illb) (Ilk)
State LIIc is believed t o be unlikely in view of t;ie known relative electroiiegati\.ities
of nitrogen and carbon atoms. The free radical form may be classified as ail S
radical11gi n which the observed properties are shifted in tlic same direction with
donor 2nd acceptor substituents. T h e likely order of contribution of different
30 J. B. Moffat
substituents to structure I n b would, however, be identical to the observed order.
Consequently these authors believe that the transition state of 3-chloro-3-p-
methoxyphenyldiazirine would be stabilized through both structures IIIa and b,
and hence might be expected to exhibit t h e most rapid decomposition. Since 3-
chloro-3-p-tolyl-phenyldiazirinehas less resonance ability, both transition states
IIIa and b will be involved to a lcsscr extent. With 3-cliloro-3-p-clilorophenyld~a~~~-
rinc, LlIa would then be the expected transition state, and its rate would be expected
to be lower. Although structure IIIa is relatively equally stabilized by the p - N 0 2 as
by the p-CH30 substituent, since p-NO, is strongly clectronegative ILlb is not likely,
and the stabilizing effect from IlIa may be largely erased so that the obscrvcd rate
is similar to that of the unsubstitiited compound. Liu and Toriyania conclude that
the most likely mechanism is one involving the breaking of one of the C-N bonds
leading to a diradical (IIIa) and a diazomethane (IIlb) intermediate, the contribution
of the latter probably being small due to t h e lack of solvent effects. As has been noted
earlier in this chapter (Section II.B.2) Walch and G 0 d d a 1 - d obtained
~~ wavefunctions
for diazomethane which lead them to suggest a singlet biradical structure for the
ground state of diazomethane.
Although thc recent calculations by Tschuikoiv-Roux and Jung116 on a three-
centre decomposition reaction for perfluorodiazirine might be included in the section
on theoretical studies of diazirines, they a r e included here because results of such
calculations d o provide information on a possible decomposition mechanism.
These authors begin with the stable configuration for perfluorodiazirine, that is,
with t h e N C N plane pcrpendiciilar to the FCF plane. The molecule is then perturbed
within one of three models where the L N C N bending niodc is used as the reaction
coordinate. In model I, the C-N bonds a n d the N-N bond are taken to have
half-bond orders and bond order 2.5. respectively. The C-F bond distance and the
LFCF remain unchanged from the initial state. I n model 11, the total bond order is
taken as fixed, the C-N bonds and N-N bond then have half-bond orders and
bond order 3, respectively. The L F C F is chosen as the average of that in perfluoro-
diazirine and the CF, radical. The CF, bond distance is unchangcd from the initial
value. Model I11 retains the assumption of conservation of total bond order but
postulates that the fractional decrease i n bond order of a bond bcing partially
broken is equal to An = 1/3, the fraction of the number of bonds undergoing
changes in the ring opening. Consequently, 2/3 and ,9/3 bond orders are assigned to
the C-N and N-N bonds, respectively. T h e C F bond lengths and L F C F are used
as in model 11. Basically what is then required is the minimum energy corresponding
to each of these sets of constraints, and these are calculated as 60.3, 75.6 and
32.7 kcal/mol, for models I, 11, and 111, respectively, compared to the cxpcrimental
activation energy of 32.2 kcal/niollo'. Model 111 apparently is the most appropriate
and in support yields a calculated pre-exponential factor in reasonable agreement
with the experimental value. I t should be emphasized, ho\vever, that ho\vever
interesting such results rnay be, they d o not provide sufficient information to permit
a discrimination between a thermal decomposition mechanism involving a linear
intermediate and one involving ;I concerted elimination of nitrogcn. However, the
weight of evidence prescnted in this section appcars to favour a linear intermediate
i n the decomposition of diazirines.
111. DIIMIDES (DIAZENES)

As indicated in the introduction to this chapter, although not strictly speaking \tithin
t h e purview of this chapter, diimides have bccn included for purposes of comparison
and completeness. Rcfcrencc should also bc madc to the chapter by Dr M. B. Robin
1. General a n d theoretical aspects of the diazoniuni and diazo groups 31
o n 'Electronic Structiircs' ivhich appcared in the volume on Tlrc Clrcmis/ry of /he
Hydrazo, Azo r r ~ dAzosy Grmrps in the present series. I t is hoped that the present
discussion will supplcment, rather than duplicate, the information given in the
chaptcr nicntioncd above.
A. The Prototypes, N,H+ and N,H

T h e molecular ion, N,H+, may quite reasonably be considered as representing the
simplest azo or diazo compound. I n 1974 Turner"' reported the discovery of three
closely spaced new interstellar lines near 93.174 GHz. Green and coworkersll*
suggested the molecular ion N,H+ to be an excellcnt candidate for the carrier of
Turner's !ines and, assuming the ion to be linear, have performed a6 initio calcula-
tions, using a double-zeta basis sct, as a function of r ( N N ) and r(NH), the nitrogen-
nitrogen and nitrogen-hydrogen bond lengths. The minimum energy was found when
r(NN) = 1.099 A and r(NI1) = 1.041 A, and the frequency of the J = 1 - 0
rotational transition was calculated to be 92.2 f 1.8 GHz, i n good agreement with
the observed value given previously. Similarly the quadrupole coupling constant for
the outcr nitrogen, deduced from observations as - 5.7 hlHz, was calculated to be
- 5.3 2 0.5 MHz, while that for the inner nitrogen was calculated as - 1.2 k 0.5 MHz,
a contribution to thc hyperfine structure too small to be resolved in the sourccs so
far observed. However, the agreement between the aforenientioncd experimental
a n d calculated values seeins to provide rather good evidence for the association of
Turner's lines with N,H+.
Even more recently, Hillier and Kendrickllg have extended the previous calcula-
tions on N,H'. Restricted Hartree-Fock (RHF) calculations of the electronic
ground state of N,H+ were performed with inclusions of nitrogen d and hydrogen p
polarization func t ions.
Large-scale configuration interaction calculations were then performed including
single and double excitations from the R H F configuration and again assuming the
molecule to be linear. Values of 93.1 GHz, -4.70 MHz and -1.00 MHz were
obtained from the calculations for the frequency of the J = 1 -P 0 rotational transi-
tion (actually Be rather than Bo was calculated), the quadrupole constant for the
outer nitrogen and that for the inner nitrogen, respectively. Quite obviously the
agreement of the first value Lvith experiment is considerably improved, while that of
the second suffers some degradation. The inclusion of correlation alters other
calculated values, of course, and - 109.414325 hartrees, 1.097 A and 1.031 8, are
found for the total electronic energy, r(NN) and r(NH), respectively, as compared
with - 109.163339 hartree, 1.065 A and 1.023 A, respectively, obtained with the
R H F calculations.
Vasudevan and co~.vorkers'?Ohave carried out extensive calculations on N,H+.
Their calculated equilibrium values compared with those mentioned previously and
~ provided in Table 22. Vasudevan and coworkers
with those of Forsen and R O O S I ?are
performed calculations as a function of N H and N N distances as well as the H N N
angle, and found N 2 H - 10 be linear in its ground state.
A6 irritio molecular orbital calculations have also been performed'?? on :!iC free
radical H N N , using the restricted open-shell method of R o ~ t h a a n ' ?with ~ the
extended 4-3 1 G basis set of Pople and Standard molecular exponents
were used for HNN. and N2, but the energy used for the H atom was that obtained
with optimum atomic exponents. The internuclear separations of N N and N H were
calculated as 1.1s and 1.020 A , respcctively, and the H-N-N angle was obtained
a s 1 IS". The H N N . radical was calculated to bc less stable than an H atom and an
N2 molecule in thcir ground states, the radical having a dissociation energy of
33- J . B. MoKat
22. Calculatcd equilibrium parameters for N,H+
TABLE
NH
Stretching Total Proton
force electronic Dissociation affinity
r(NH) r(NN) constant energy encrgy (kcal/
(A) (A) (mdyn/A) (hartrce) (ev) mol) Referencc
1.041 1.099 - - - - 11s
1.031 1,097 - - 109.414325 (CI) - - 119
1.023 1.065 - - 109.163339 ( R H F ) - - 119
1.026 1,093 7.1 - 109.0738 (SCF) 5.4s 126.5 120
1.027 1.093" 4.9 - 109.2443 (CI) 5.46 126.0 120
1.024 1.093'' - - 108.967 - 127.7 121
- 1.077 - - 109.157* - 123 121
Assunled.
With d-type polarization functions.
- 9.0 kcal/mol. The activation energy for the decomposition of H N N * to N, and H

was found as 22.6 kcal/mol.
Very recent nb hilio SCF and CI calculations125on the ground and excited states
of the H N N radical, using a bond length for N-H of 1.058 A and either 1.093 A or
1.199A for N-N, predicted the ground state t o be non-linear with a H-N-N
angle of 124" and a binding energy of 2.2 kcal/mol.
B. Diirnide (Diazene)
1. Introduction
Although the molecular ion, N2H+,may be taken as the simplest representative of
the class of molecules containing the N N bond, the molecule H-N=N-H,
diiniide (or diazene) is perhaps a more appropriate candidate for this position, since
i t is the simplest uncharged molccule of this type. Like diazomethane, as discussed
earlier, diimide has a number of possible isomers, the cis and t r a m form, and 1 , l -
+
dihydrodiazine (H,N=N). Diiniide is the parent molccule of the azo compounds.
The unsymmctrically substituted diazenes, of which 1 ,I-dihydrodiazine is the parent
compound, are both important and interesting molecules. Lemallk8has pointed out
that these unstable isomers of azo compounds might be expected to lose molecular
nitrogen with ease and hence scrve as a n important method for producing carbon-
carbon bonds, as azo compounds do. However, a s a consequence of their instability,
other reactions appear to occur preferentially. Nevertheless, the properties ana
reactions of 1 ,I-disubstituted diazenes rcniain of importance in chemistry. Un-
fortunately, discussion of these compounds would lead us too far afield of the
intention of this volume. Hence, attention m i l l be limited to 1,I-dihydrodiazine
itsclf for comparison with the cis a n d fratis forms of diiniide. A comprehensive
review of nitrcncs of which Reference 126 is a part has been published previously.
The nomcnclature unfortunately presents some difficulty. Lema1126has pointed
O u t that N,H2 is a n aniinonitrene, but prefers to label R2N2.whcre the two R atoms
or groups arc attached to the same nitrogen, as I,]-disubstituted diazene, or simply
diazcncs. Hunip and suggest that the systematic name diazene would be
appropriate if N H was analogously named 'azene'. They employ diimine in prefer-
ence to diiniide on the basis of less ambiguity and continued association with the older
literature. In the present article, diimide and diazene will be employed interchange-
ably where n o confusion can arise.
*Although a number of workers believed that they had direct or indirect chemical
evidence for the existence of diimide, it was not until 1958 that Foner and Hudson128
first detected diimide by mass spectrometry as a n mle 30 peak during the decomposi-
tion of hydrazoic acid or hydrazine in a n electric discharge under reduced pressure.
A fast-flow system was used and the diimide was detected downstream from t h e
discharge. Foner and Hudson also showed that N2H2could be trapped a t - 196 "C
as a yellow solid consisting of ammonia and N1H2, and regenerated in the gas phase
on warming. Thermal decomposition of anthracene-9,10-biimine a t 100 "C in U U C I ~ O
at the inlet of a mass spectrometer also apparently produces diimidelZg,thereby

suggesting a relatively high thermal stability for diimide. In contrast, diimide cannot
be detected during the thermal decomposition of hydrazine in argon a t 1470-
2770 O P o .Photodecomposition of hydrazine131 with vacuum ultraviolet radiation
and the combustion of hydrazine at low p r e ~ s u r c ~ ~ *also led to the observation
has
of diimide.
2. Spectroscopy and structure

The various nuclear configurations which are, in principle, possible for N,H2 are
shown below:
H
+/
H--h=N-H N=N
\
linear H
H H H
\ / \
N=N N=N
\
planar, cis H
planar, trans
H H
\ .:
N=N
n o n-pla na r
One of the prime tasks of the spectroscopists was not only to determine in which of
these forms diimide exists in its most stable form, but also to elucidate the nature of
the electronic states, and in particular the electronic ground state. T h e next section
attempts to trace the development of the answers for these and other questions, and
to indicate those r.lhich remain unanswered a t this time.
W a l ~ h ' in , interesting and far-reaching semi-quantitative predictions of shapes,
~ ~his
spectra, and the electronic orbitals of polyatomic molecules, suggested that diimide
would possess a planar non-linear structure. Wheland apd Chen13' assumed N H and
N N distances to be 1-014 8, and 1.23 A, respectively, and calculated, using simple,
34 J. B. Momat
semi-empirical, LCAO-MO theory with overlap integrals neglected, a value of 100"
for the most stable N N H angle. With the assumption that the cis-lrnns isonierization
passes through a planar interincdiate in which one N N H anglc is 180". whereas the
other is allowed t o take on whatevcr value leads to the most stable configuration, an
activation energy of 33 kcal/mol was calculated for an activated complex in which
the N N H angle that is not equal to 180" has the value of 76".
Blau aiid c o ~ o r k e r sn6
~ ~obtained
~. the infrared spectrum of solid diirnide between
350 and 4900cm-l and that of t h e gas in the 3200 to 1300cm-' regions by de-
composition of hydrazine with a microwave discharge. Infrared bands were observed
at 3205, 3095,2898, 1521, 1495, 1406 and 1362 cm-l. They deduced that the solid a t
liquid nitrogen tcmperatlire has a planar structure and that the molecule appears t o
be primarily in the cis form, with molecular parameters of N H , N N and L H N N ,
being assumed as 1.014 A, 1.230 8, a n d IOO", respectively. Unfortunately, the struc-
ture of the molecule in the gaseous state could not be unambiguously determined
from the spectrum.
Dows and coworker^'^' investigated spectra of glow discharge decomposition
products of H N 3 aftcr condensation at 90 K and during slow warming. Absorptions
a t 860 a n d 3230 cm-' were attributed to N2H.?. Three prominent absorptions at
1290, 1325 and 30SO cni-' obscrved in the photolysis of NH, in solid nitrogen were
attributed13* to intermediates D, E a n d F, respectively, possibly corresponding to
NH,, N,H, and N H , respectivcly. I t was e ~ t a b l i s h e d ' that
, ~ species D contained two
hydrogen atonis but i t was not possible to distinguish between the amine radical,
cis- and tram-diimide, or NH,N3. h'lilligan and Jacox140proposc that D and E may
be N,H, o r H N = N - N = N H . Emission features near 3000 cm-' from an amnionia-
oxygen flame'." \\.ere interpreted as d u e to NH,, but with N,H, a s a n a!!ernate
possibility. Rosengren and Pimentel14? produced diimide by photolysing hydrazoic
acid, both unlabelled and labelled with deuterium and lSN, in solid nitrogen a t
20 K . To trans-diiniide the following features were positively assigned: 1285.8 cm-I
( H N N H ) , 1480.5 and 1058 cni-l ( H N N D ) , 946.2 cm-l (DNND). The only other
absorptions which displayed isotopic frequency patterns appropriate to diimide
were bands at 1279 and 3074 cm-' which they assigned to cis-HNNH.
Trombettila3 examined the infrared spectrum of N,H, vapour in the 3100 cm-l
region and the vacuum ultraviolet spectra of both N,H, and N,D,, and concluded
from an analysis of the former spectrum that N,H, in the ground state has a planar
iratis conformation with r x - x = 1.238 and LN-N-H = 109', assuming r S - H to be
between 1.05 and 1.08 A. Trombetti attributes five bands to diimide in the discharge
products (77 K) of N2H, (3095, 2950, 2900, 1404 and 1359 cm-I) and N z D 4 (2521,
2291, 2199, 1032 and 999 cni-l). Trombetti interpreted his results in terms of a tram
structure only, assigning the three infrared active fundamentals of trans-N,H, a t
3095, 1404 and 1359 cm-I (2291, 1032 and 999 cm-I for N,D,). The remaining bands
were tentatively assigned a s combinations involving unobserved Raman-active
fundamentals which were deduced to be 1552 and 1496 cm-' (1498 and 1167 cm-1
for N2D2). Trombetti also observed two electronic band systems near 3500 and
1730 8, and, from intcnsity variations in the 1730 8, system, decided that the ground
state is a triplet PB,) and that the first excited state may have a B, symmetry.
TrombettiIJJ has also measured the infrared spectra of solid N,H, and N z D 2 from
600 to 4000 cm-I at liquid nitrogen temperature. For both compounds five bands
were observed and tentatively assigned to the three allowed fundamentals (N,H,:
1359, 1404, 3095; N2D2: 999, 1032, 2291 cm-') and to two combination bands
(N,H,: 1496, 1552; N,D,: 1167, 1498 cm-') of trans-diimide.
Bondybey and Niblerl'j have preparcd N2H, as a discharge product of N,H, and
have studied the infrared and Raman spectra for both solid and matrix isolated
I . Gcnetal and thcoretical aspects of thc diazoniiim and diazo groups 35
kINNH, H N N D and D N N D . Thc five in-plane vibrations of isolated Irans-HNNH
have all been dc[eimincd: Raman A, modes, 3128, 1583 and 1529 cni-I; infrared
B,, modcs, 31 31 and 12S6 c n - ' . Isotopic substitution establishcd the characteristic
N N stretch as thc I529 cin-' band. The A, out-of-plane torsion was not definitcly
assigncd but could be a weak infrared feature observcd al 832 cm-'. N o evidence of
cis-diimide was dcteclcd. Dilution studies of the solid discharge products showed that
a nunibcr o f hydrogcn-bonded complexes form bctrveen H N N H and NH3, and
Rondybcy and Niblcr suggest thac thcir work indicates that the car!ie: iz!cYpiC:Z-
tions13G, 1 4 3 of the solid spcctra i n ternis of 'isolated' tram- and cis-diiniide must be
discountcd. Thesc authors also concludc that thcir results are not inconsistent with
Tronibetti's conclusion that tlie elcctronic ground state of N2H2is a triplet.
The infrared absorption spectrum of diimide ia ttle 3.2 pm rcgion has bcen re-
examined at higher resolution than previously and that of dideutero-
diiinide (N,D,) at 4.3 [mi was also obtaincd for the first time. The following
geomctrical paranictcrs werc obtained for the planar t r n m conformation of diimidc:
r,y-n = 1,028 A, ~'x-_g= 1.252 A, LN-N-H = 106'51'. I t is interesting to notc
that this N-N bond distance is thc same as in azoniethane, while LN-N-H is
lower than LN-N--C in the same niolecule by approximately 5 degreesIai. l J 8 .
Carlotti and coworkers14Gargue that the evidence provided on line intensities agrees
with the intensity alternation which would bc expectcd for an A, or A,, ground state.
This disagrees with the earlier conclusions of Trombettila3,whose spectral data were
recently confirmed by Willis and Back1i9.Hence Carlotti and coworkcrs offer the
possibility that the ultraviolet and the infrared spectra may not have the same lower
state. They speculate that it may be possible that planar trans-diimide converts
slowly to a less stable cis form which absorbs in the ultraviolet, so that an explanation
for the apparently long lifetime of the ultraviolet absorption could be provided.
Back and coworkers150have exainincd the absorption spectra of N2H2and N z D 2
in the gas phase in the region 3000-43OOA. The spectra were attributed to the
'B, + lAg (x* t n,) transition of trnrzs-diimidc, which the authors suggest may be
allowed as a consequence of vibronic interaction. From Franck-Condon calculations
the H-N=N angle in the upper state was calculated t o be 132", or 25 degrees larger
than the ground-state value a n d the increase in tlie N = N bond length was L' w e n as
approximately 0.05 A. As these authors point out, it might be expected that diimide
becomes non-planar in its first excited singlet state. However, if the excited state of
diimide were non-planar, progressions in the spectra corresponding to excitation of
the LJ; torsional vibration should be observed, but there are n o unassigned bands
of significant intensity.
The near-ultraviolet absorption spectrum of diiniide in liquid ammonia at - 50 "C
has been measured151. At this temperature the diiniide and ammonia should exist as
a pale yellow liquid. Compared with the gas-phase spectrum, the absorption of
diimide in aminonia is shifted to the red by approximately 500 A, broadcned
considerably, and the sharp vibrational structure found for the gas phase essentially
disappears. These effects are attributed to a strong interaction between ammonia and
diimide, possibly through hydrogen bonding. A complementary experiment with
diazomethane, in which a much smaller shift to the red was observed, leads Back and
Willis to conclude that the bonding of the diimide hydrogens to the NH, lone pairs
is much more important than the bonding of the NH, hydrogens to the lone pairs of
azomcthane or diimide, which niight be expected from the strong intramolecular
interaction between the t i v o lone pairs in azo compounds which make them less
available for intermolecular interactions.
A brief surnrnary of this section may be both appropriate and useful. The evidence
would appear to favour the planar trans configuration of diiniide as its most stable
36 J. B. Moffat
structure with values for the geometrical parameters as shown:
H
The electronic ground state appears to be a singlet and the first excited state
apparently possesses a planar structure with an N=N-H angle widened to 132".
The first theoretical studies of diimide were those of W a l ~ h and
I ~ ~Wheland and
C h e ~ ~The l ~ results
~. and conclusions of these authors have been briefly described in
the previous section and only brief additional references will be made to them here.
In 1953, W a l ~ h predicted
'~~ from the number of electrons in the molecule for the
then unknown N,H2, a planar bent ground state, existing in either a cis or a trans
form. Whelar~d'~' could not distinguish between the cis and trans forms because of
the assumptions made in his calculations, but he did find the most stable N N H
angle to be about 100" and a n activation energy of 33 kcal/mol for the cis-trans
isomerization.
T h e spectroscopic studies in the mid-60's o n the structure of diimide prompted
Alster and Burnel11S2to carry out extended Hiickel (EXH) calculations on the
cis-trans thermal isomerization of NzHz.They considered three possible activated
complexes: (i) a n asymmetric bent structure in which one N N H angle was held a t
180" while the other N N H angle was varied to produce the most stable configuration
(lowest electronic energy), (ii) a 90" twisted structure in which one N N H bond is
held a t 90" to the second N N H bond and both angles are varied to minimize the
energy, (iii) the linear N2HZstructure. The N N and N H bond distances were held
fixed at 1.22 and 1.03 A, respectively. Values of 128" in the cis, trans and asymmetric
bent geometries and 143" in the 90" twisted structure for the N N H angle were found
to minimize the energy. Energy differences from the cis form, which these calcula-
tions predicted to be of lowest energy, are 8.5, 11.6, 16.6 and 20.6 kcal/mol for the
trans, asymmetric bent, 90" twist and linear forms, respectively. Hence the 8.5 kcal/
mol corresponds to the cis-rratzs transition energy and the remaining values t o the
predicted activation energies for the isomerization of the cis form.
Very shortly after, Robin and coworkers1s3published the results of their work on
t h e electronic states of azoalkanes. They performed ab inirio calculations in a
Gaussian-type orbital (GTO) basis with limited configuration interaction, and, in
addition, measured the electronic spectra of a series of trans-azoalkanes,
R-N=N-R, where R was CH,, Co_Hs,(CH,),CH and (CH,),C, also trans-
difluorodiazirine and one cis-azoalkane, 3-methyl-l-pyrazoline,
/" =N\
H,c,~,CHCH,
H*
In their calculations, cis- and tratzs-HN=NH were taken to have planar structures
with L N N H = 112"39', D(N-H) = 1.021 A a n d D(N=N) = 1.240 A. Two basis
1. General and theorelical aspects of the diazoniuni a n d diazo groups 37
sets wcre employed, a conventional 'energy-niininiized' gaussian basis and a n
augmented GTO basis. The authors note that it appcars that the energy-minirnizcd
basis yields excited states of unusually high cncrgies due to a ncgkct of thc rails of
the wavefunctions. It is predicted that in the case of tmri.s-diirnidc, the lowest cxciteti
triplet state will lie below the singlet ground state when calculatcd in the energy-
minimized basis, but 2 eV abovc it when calculated in thc augmcntcd basis.
Consequently their calculations primarily employed the augmented basis. Ionization
potentials of 10.97 and 10.46 eV were calculatcd for cis- a n d /rcrns-diimide, rcspcc-
tively, compared to t h e Foncr a n d valuc of 9.S5 eV.
Gordon a n d FisherISJ, as part of a study of the isomerization mcclianism o f
diazacumulenes using the INDO mcthod, examincd diiniide and difluorodiimide.
I n both cases the cis form was found to be tlicrniodyiianiically more stable thari thc
tram form by 4.5 and 4.1 kcal/mol for diimide and difluorodiimidc, rcspectivcly.
Activation energies of 46 and 72 kcal/niol arc predicted for inversion and rotation
o n one nitrogen, respcctively, if o n l y singlet states a r e involved \vith diimide. A
triplet isomerization proceeding by a rotation around the double bond has ;i
calculated activation energy of 40 kcal/mol for diiniide. For difluorodiimidc the
calculated singlet a n d triplet activation energies are 6S and 52 kcal/iiiol, i~:spcctivdy.
SCF-LCAO-MO calculations using Gaussian functions and cmploying the
I BM O L program with a basis set consisting o f 9s and 5p for N and C and 4s for Fl
were reported by Lchn and Munsch15S.The bond Icngths or diiniide were takcn from
the results of Blau a n d H ~ c h h e i n i e r 'and
~ ~ the N N H bond angles \vcrc optimized.
T h e result:; a r e given in Table 23. T h c lrnrrs form is found !o be niorc stable t h a n the
cis by 10.5 kcallmol. Thermal tram-to-cis isorlicrization by inversion ;it onc nitrogen
(activation energy of 50 kcal/rnol) is predictcd, thc activation encrgy for rotation
around the N = N bond being substantially higher a t 54.1 kcal/niol. Veillard. Lchn
and MunschISGh a d pointed out earlier that nitrogen invcrsion is accompanied by a
2s --f 2p electronic population transfer at the inverting nitrogen atom. With diimidc
a decrease of approximately 0.3 a n d 0.1 elcctron was observed for tlic nitrogen 2s
and hydrogen (OR the inverting nitrogen) 1s populations, respectively. Sinitiltancously
the population of the nitrogen 2p orbital lying in the direction of the lone pair
increases by 0.47 electron. From a comparison of population changes on inversion
in other molccules the authors conclude that a high inversion barrier corresponds to
a large population transfer.
23. Coniputed angles and encrgics for diiniide'"~

TABLE
0p t i ni i zcd
Symmetry NNH Total energy ' Energy barriers
groups Conformation anglc (ha rtree) (kcal/mol)
____--- _____
CZh tram 70" - l09.9X240
CZv cis 63" - 109.907558 ris-tmri.~= 10.5
ch bent (b) 68" - 109.844374 b-traris = 50.1
linear (I) 0" - 109.137979 I-tmtrs = 116.9
C, perpendicular (perp) 56" " - 109.790331 perp-fruits = 54.1
~~ ~
a Angle not optimized.
Scliaad and Kinser (SK)Is7 point out that diiniidc gives cis addition of hydrogcn
to a double bond, which is usually interpreted i n ternis of a cyclic transition state,
which seems to imply a cis structure for diimidc or pcrliaps an easy intcrconversion
between the cis and trnris forins. With this in mind, calculations were done employing
38 J. B. Moffat
a minimal basis of Slater-type orbitals (Is for each hydrogen and Is, 2s, 2p,, 2p,, 2pz
for each nitrogen and carbon atom) expressed in terms of normalized gaussian
functions. In their calculations o n the various f o r p s of diimide, SK optimized bond
angles and bond lengths. The same conformations of diimide as those studied by
Lehn and Munsch1K5were also considered by Schaad and Kinser, except that in
place of the perpendicular form, a twisted form with a variable out-of-plane angle
was employed. Only the closed-shell singlet states of the electronic configurations
were considered.
Table 24 shows the results of Schaad and Kinser for the various configurations.
When the configurations yielding the lowest energies had been found, the bond
lengths and angles were varied to minimize the energy of that configuration. The
lowest energy configurations found were:
cis: (lal)2(lb2)'(2al)'(2b~))?(3a,)'(4al)~(1
b1)?(3b2)'
tram: ( I a,)?( 1 b,)2(2ao)2(2bU)?(;a,))?~3bU)?(
1 aU)?(4as)?
Table 24 summarizes the values of the total electronic energy and bond angles and
lengths for the optimum geometries. The table indicates that the trans structure is
7 . 6 kcal/mol lower in energy than that of the cis and the lowest energy path for the
tratis-cis isomerization involves the bent conformation with a n activation energy
of 7 2 . 4 kcal/mol. These authors employ group frequencies to calculate statistical
mechanical values of various thermodynamic functions. I t turns out that the hG,,,
value for cis-tram isomerization is 7.5 kcal/mol yielding a value of 2.7 x lo5 (25 "C)
for the equilibrium constant, K = [ t r a m l / [ c i r ] ,which implies that approximately
2.2 x lo1*molecules of cis isomer are piesent per mole. Hence, double bond reduction
could take place only with the cis isomer which is replenished through equilibrium
with the trans form.
TABLE
24. Total electronic energy and geometrical parameters for
conformation of N2H,lS7
Electronic Bond lengths (A) Bond angles
energy -
Conformation (kcal/niol) NN NH NNH 4'
cis - 66,844.1 1.27 1.13 112" 0'
lrans -66,851.7 1.28 1.13 104" 180"
linear - 66,654.9 2.28 2.77 180" -
twisted -66,767'6 2.53 1.24 105" 90"
bent - 66,779.1 2.42 1 ;::; 115"
180") -
Wong and performed LCAO-IMO-SCF calculations employing a

basis set of Gaussian lobe atomic wavefunctions on trans-diimide, cis-diimide and
1, I-dihydrodiazine in the expected closed-shell, ground-state, electronic configuration
with full geometry optimization. I n addition they made additional calculations for
a n open-shell configuration using one of Trombetti's experimentally measured
geometries for trans-diimide. A summary of their results is given in Table 2 5 . The
itz sir(( adjusted Gaussian lobe function calculations referred to in the table involve
the determination of t h e long-range components of the 2s and 2p groups of nitrogen
by the SCF procedure. The extended Gaussian lobe function caiculation makes use
of a basis in which a one-component s orbital and three one-component p orbitals
centred at the middle of the NN axis have been added as supplementary functions.
1. General and theoretical sspects of the diazonium and diazo groups 39
Examination of the wavefunctions and coefficients of the molecular orbitals (MO)
shows that the first two MO's a r e nitrogen 1s orbitals, a n d the remainder could
approximately represent one GNN bond, two G ~ sp'H bonds, two sp2 lone pairs, and
one pure P, N N bond.
25. Results of Wong, Fink and

TABLE for diimide
Bond lcngths
-_.
Bond angle Em.
Basis sct Structure " N Ii HNN (liar t ree)
SCF-LCAO-GLO trails" 2.370 1.90 102.5" - 109.93017

in sifrr adjusted cis" 2.353 1.91 1 15.5" - 109.92913 -
H,Ne=N-b 2.403 1.89 122" - 109.92233
Extcnded GLO trans 2.260 1.90 102.5" - 109.95274
cis 2.353 1.91 1 1 5.5" - 109.94423
H,N+=N- 2.423 1.90 122" - 109.94145
Open shell /rails 2.340 2.01 109"
l B, - 109.79297
=BI7 - 109.81556
Closed shcll Irons 2.340 2.01 109"
lAK - 109.9340
Samc elcctronic configurations as given by Schaad and KinserX5'.
( I .4,)'(2A,)?:3A,)?(4A1)~( 1 B2)?(5Alj2(1B,)2(2B,)2.
It is instructive t o examine the ground-state molecular-orbital symmetries and

order of occupancy. The 'B, of H2N+=N- a n d cis-N2H2.lA, of fmns-N,H, are all
2p, z bonded molecular orbitals. T h e 2B2 in H2N+=N- is a pure 2p, bonded with
hydrogen atoms. In 3B2 of cis-N 2 H2 ,4A, of truns-N,I-12, t h e molecular orbitals are
hybrid orbitals mixing 2p,, 2p,, 2s, Is of nitrogen and bonded to hydrogen atomic
orbitals.
T h e theoretically predicted ionization potentials for trans-diiniide, cis-diimide and
1 ,I-dihydrodiazine are 10.87, 10.84 a n d 9.95 eV. respectively, which may be compared
with the experimental value of 9.85 eV Use of the relation
E(binding) = E ( t o t a l j - 1 Ei (atom)
I
where zi E , (atom) = - 109.77432 hartree for N,H, yields binding energies of 4.55,
4.62 a n d 4.55 eV for !rwris-diiinide, cis-diirnide and H,N+=N-, respectively. Hence
all these species are predicted by Wong and coworkers to be possible, although
diimide is thermodynamically unstable with respect to N,-t H,, as shown by Schaad
and Kinscr'". F r o m Table 25 i t is readily seen that the calculated order of stability
places rrcitu-diimidc first, followed by cis-diimide, then H,N4-=N-- followcd by the
f r o m form i n the triplet state. Hence a planar, f rom structure for a 'Ag clectronic
ground state is favoured.
Tinland15sapplicd the CNDO/S to the cis and frxm forins of diimide
with the geometries of Robin and coivorkers1":'. T h e computed ionization potentials
of cis- and trorrs-diimide are 12.61 and 11.96 eV, respectively. and i t is predicted
that the fratis form is more stable than thc cis forin by 0.47 e V . The general features
of the shape of diimide, molecular cnergy levels a a d simplc molecular orbital
40 J. B. MoFi'at
picturcs as dctcrmined by estcndcd Hiickel calculations are presented by GimarclG1.
Giniarc also makes usc of syrnnictry arguments in discussing probable cis-trans
isomcrization mcc!ianlsms. Ir. thc /rotis isomer of N2H2, the highest occupied
orbital is 3 4 whilc in the cis isomcr it is 2b,. O n rotation from trans t o cis through
thc non-planar transition state, the /ram 3aL orbital moves much higher in energy to
bcconic a? in thc cis form. On the other hand, the lowest unoccupied orbital in the
/ r u m form is />: which falls in energy to become 2b, in the cis form on rotation from
/ r m s to cis. Hencc the orbitals cross, and consequently the electrons in the highest
occupicd orbital ( 3 4 ) of /rms-diimide, o n rotation from Irons to cis through t h e
non-planar transition statc, would have t o transfer to the b orbital, which falls
during rotation. to avoid moving to the higher energy. As Gimarc points out, this
would be a violation of the principles of conservation of orbital symmetry1G2.I n the
C, pathway the a, b synimctry is lost and 3aL can be convcrted directly to 2b2. Hence
thc planar C, transition state for the N2H, isomerization is strongly favoured since
thc linear state can be excludcd on cncrgetic grounds and the non-planar rotation
by symmetry conditions.
The II x* transition cnergies and one-electron orbital energies for the cis and
-&
I r n m forms of diiniide, as obtained from ab itiitio minimal basis SCF-CI calculations,

arc rcported by Ditchfield and coworkers1G3.The niininial basis set of Slater-type
atomic orbi!als (STO) is replaced by a sum of four gaussian-type functions, one
such stin1 for cacti STO. Wavefiinctions, +:. describing singly excited configurations
are fornicd from tlie ground-state wavefunction by promoting electrons from
doubly occupied orbitals (lli to virtual orbitals 4 ~ Mixing ~ . of configurations represcnt-
ing dinercnt singly cxcitcd virtual states is then performed. Thcse authors calculate
that the t r v i m isomcr should be more stable than the cis for the ground states.
Since the azo group contains two pairs of non-bonding electrons, there are two
possibic I I --> ;T* transitions, although only one low-energy U.V. band is generally
observed. I f diirnidc exists in the fratis form, thcn a relatively strong interaction
bctwcen the lone pairs will occur, and consequnntly a large splitting in the energies
of thc two I I orbitals, and finally two 11 -> z* transitions of quite different energies.
Ditchficld and cou-orkcrs find a splitting between the two ) I orbitals of approxi-
ti-
mately 5-6 eV and 2.5-3.5 eV in thc trotis a n d cis compounds, respectively. The two
K * transitions in the /ram compound are separatcd by about 6 eV, but only
2 eV in tlic cis compound. Valucs reported for the transition energies for diirnide
arc 4.37 and 3.37 eV for cis and /rotis forms, respectively, to be compared with
Trombctti's cxpcrimcntal \slue of 3.55 eV for the /rnns structure.
Genson and Clirisioffc'rseii'", continuing their work o n ab irii/io calculations by
a techniquc employing molecular fragnicnts and employing the floating spherical
gaussian orbitals of Chit and FrostlG5as basis functions, applied this inethod
to a numbcr 01' nitro_scn-containing moleculcs, including diimide. Bond lengths of
2.30 and 1.91 I bohr for N-N and N-H bond distances, respectively, were used.
They too find that thc frn/rsform is the more stable with energy of - 93.56754 hartree
comparcd to - 93,5604s hartree for the cis form. Thc value of E(c-is)- E(/rons) was
calc1rlntcd a s 4.5' kcal/mol.
/ { / I irririo calculations were pcrformcd with tlie IBMOL-5 program, using a
gaussian-type basis, on I , I -dihydrodiazine and on cis- and /ram-diiniides by
\VaSnicrc";". Tlic gcameiry of Robin and c ~ w ~ r k was e r ~employed,
~ ~ ~ namely
I.(") = 1.240 K , /.(NH) = 1.021 A, L(NN1I) = 112"39'. Calculations involved
t \ v o lxisis scis ( I nnil I l ) , onc n i t h 1 Is and 7p on nitrogen and 6s on hydrogen
contracicd 1 0 a ( 5 , 3/2) sct, tlic othcr (11) i v i t h the same contractcd basis, augmcnted
by pol:irizaiion func~ionsi n 11ic plane of tiic ~iioleculc,pz and pv, o n each hydrogen
iitotii, a i i d by dili'usc s, I>=, pv, pz functions on each nitrogcn atom. Thc lowest
1. Geceral and theoretical aspects of t h e diazonium and diazo groups 41
energies were, of course, obtained with basis set I1 and are listed below for the
lowest closed-shell state:
cis-Diimide - 109.96639 hartree
trans-Di i m ide - 109.98092 hartree
1,l-Dihydrodiazine - iO9-95317 hartree
Calculations by Wagniere'"" on the excited states of the three molecules showed that
the 3A, state of 1,l-dihydrodiazine lies 0.090 eV in energy below that of the closed-
shell state lAl (basis set 11).
Hariharan and Pop1el6' have carried out a6 irzitio calculations intended to examine
the influence of polarization functions on molecular orbital hydrogenation energies,
and in so doing have used a 4-31 G basis set, a 6-3 1G basis set and a 6-31G basis set
with polarization functions added. The 4-31G set has an s inner-shell function which
is a linear combination of four s-type gaussian functions and a valence shell (s and p)
represented by inner (three-gaussian) and outer (one-gaussian) parts. For hydrogen,
similar (31) s-type functions are used. The 6-31G basis set differs from the 4-31G
set in improvement of the inner-shell function. Then a set of six single (uncontracted)
d-gaussian functions is added t o the 6-31G set for heavy atoms, the hydrogen
functions being unmodified. This set is labelled 6-3 1G*. The basis set called 6-31G**
is arrived at from the 6-31G* set by adding three p-polarization functions on each
hydrogen atom. Bond lengths of 1-25 8, and 0.99 A for N N and N H , respectively,
109.47" for the N N H bond angle, and the rrms conformation, were employed for
diimide. Total energies as follows were calculated with the various basis sets
(hartree):
6-31G - 109.92792
6-31G* - 109.99123
6-31G** - 109.99768
-
These values may be compared with - 109.81102 and - 109.79320 hartree for zrans-
and cis-diimide obtained earlier with the 4-3 1G setlG8.For the complete hydrogen-
ation reaction
HN=NH+P H, 2 NH,
they calculated the following energies (kcal/mol) :

4-31G - 90.7
6-31G -91.0
6-31G** - 81.4
Hence these authors suggest that the addition of d-functions (6-31G -+ 6-31G*)
produces a n energy lowering per N atom (in N,H2) or 19.9 kcal/mol while the
inclusion of p-functions on hydrogen (6-31G* + 6-31G**) lowers the energy per
hydrogen atom by 2.0 kcal/mol (for N,H,).
Baird and Swenson160have used the closed-shell SCF-LCAO-MO method with a
minimal basis of Slater-type orbitals each represented by a linear Combination of
three gaussian-type orbitals (STO-3G) to calculate various properties of diirnide in
the ground, l ( n , x * ) , 3(n, x*)and "(x, x*)states. I n their work all N-H bond lengths
were taken as 1.01 8, and the two H-N-N angles were assumed t o be equzl, while
the N-N distance, the H-N-N bond angle, a n d the dihedral angle between the
two N-H bonds were taken as variables. An absolute minimum is claimed for
the trans conformation, with the cis isornx 5 kcal/mol highcr in energy. Optimizcd
geometries were obtained for the trans, cis, bent and twisted forms and these are
42 J . B. Momat
shown in Table 26. A value of 98" was found for the dihedral angle of the twisted
form at the maximum in their potential energy curves. Activation energies of 60 a n d
84 kcal/mol \vere found for the /ratis to cis isomcrization through the planar a n d
rotational transition states, rcspectivcly. These authors note also that the N--N
bond lengths i n thc planar excited states, I(n, x * ) and 3(n, r*),d o not differ Sreatly
from those in the ground state, and attributc this t o the fact that thc highcst occupied
molecular orbital (HOMO) in both cis and frtrtis diiinide is N-N antibonding, SO
that removal of a n electron from the n - M O of cis diimide increases the N-N
ovcrlap population by 0.21, which almost cornpcnsatcs for the decrease of 0.29 d u e
to single occupancy of the 7;* M O . As they also point out, ionization of the lcast
tightly bound electron would be expected to producc a dccrease i n the central bond
distance for diimide a n d azo conipoccds, an effect not often observed in polyatoniic
molecules.
TABLE 26. Optimized geometries (A and degrees) for diimidcr69.Rcprodticed by permission
of the National Research Council of Canada from the Catmdim Jorrv/ra/ of C/renris/ry,51,
3097-3101 (1973)
/mns cis Twisted Bent
- -
Angle Angle Angle Anglc
State N-N H-N-N N-N 13-N-N N-N 11-N--N N-N H-N-N
~~ ~~ ~ ~
Ground 1.21 109 1.2: 115 1.24 124 1.21 110

l(n, x + ) 1.26 121 I .22 I33 1.22 127 1.24 116
3(tr, nu) 1.26 120 1.22 132 1.26 1 I7 1.14 118
Yx. z*) 1.42 10.5 I .42 1 I4 1.36 128 1.35 I05
I t is interesting to note. that Back, Willis and R a m ~ a y ' ~ "from , their absorptiGn
spectral data and Franck-Condon calculations, predicted that the l(tr, x * ) state of
diimide would have a n N-N bond length increased by 0.05 8, and an H N N angle
25" larger than the ground-state value, for the /rotis form. Baird and Swensonlo9
calculated 0.058, a n d 12" for the corrcsponding increases, providing reasonably
satisfactory agreement.
Calculations show that / i ~ ~ tot i scis isomcrization through a rotational nicchanisni
is preferred far both the :I(ir, x * ) a n d ' ( t i , x * ) slates of diimide with the activation
energies being zero for both states, compared to 25 and 23 kcal/mol, respectively,
for passage through t h e planar transition state. Rotational isomcrization for thc
3 ( x ,T ; * ) state should be symmetry-forbidden, and the /ratis to cis barricrs a r c
calculated to be 71 and 65 kcal/rnol for the rotational and planar transition statcs,
respectively.
In the course of analysing the photoelectron spcctra of a number of a m compounds,
Brogli and coworkcrs170 have perfornicd some extended Hiickel and M I N DO/2-
type calculations o n cis- and /rotis-diiruide. From the latter type of calculations they
have shoivn that the splitting for the nitrogen lone-pair orbital encrgies passcs through
a maximum at about 120" for the N-N-I-I angle i n the / r n m form bui n :nininiuin
at about 100" for the ci.y form. This appears to bc supportcd, in part, by tlicir spectral
data. GimarclG1argued that such behaviour in cis-azo groups is duc to a 'through-
bond' interaction of the ti+-orbital with n lower lying N-N ci-orbital.
Merenyi and coworkersi71used the program REFLECT, which employs a bilsis
set of gaussian orbitals, in this case four s-type orbitals on cach hydrogen atom and
sevcn s - ~ y p cand tlirce p-typc on cnch nitrogen atom, to calculate barricrs to rotation
and inversion for cliimidc and its protonatcd form. The ycoinetry of Lclin and
Munsch'j5 was used. Thcir rcsults a r e surninarized i n Table 27. \!'ill1 both diiinidc
1. Gcncral and thcorctical aspccts of the diazonitin? and diazo groups 43
and protonated diimide the inversional barrier is lower than the rotational barrier
for isomerization, but the corresponding barriers for the protonated form are l o w r
than those for thc unprotonated form.
TABLE 27. Effect of protonation o n the encrgics and

barricrs to rotation and invcrsion of d i i n ~ i d e ” ~
Total
encrp Barrier
Form (hnrtrec) (kc3l/rnol)
~ ~~
H-N=N-H
trails - 109.8175
CiS - 109.5033 8.9(c-r)
planar bcnt - 109.7348 51.9”
twisted - 109.7044 71.0
H,N ’ =NH - 1 IO.13GO
planar bent - I10.0580 30. I
twisted - 110.0325 64.9
Rclative to the cncrgy of the t r m s isomer.
An extensive study172by mcans of ab iiiitio SCF and CI methods has been carried
out on both the ground and excited states of diirnide for the purpose of investigating
the ultraviolet spectrum of this nioleciile. The N N and N H distances were held fixed
at 1.238 8, a n d 1.065 A, respectively’”, and the N N H bond angle was varied from
90” to 170” for a variety of electronic configurations. A n absolute minimum was
obtained for the t r a m form with an energy of - 109.9345 hartree, first ionization
potential of 10.78 eV and cis-/mns energy difference of 12.6 kcal/niol. A barrier to
isomerization of 109 kcal/mol was calculated for the ground state by employing a
linear configuration for the transition state.
The most recent reports of theoretical studies on diimide appear to be that o f
Vasudevan and coworkers’72, mentioned previously, and that of Winter and
P i t z e ~ ’ ~I n~ .the latter work, both N H and N N bond distances and the N N H bond
angle were varicd to achieve a geofiietry optimization to 0.01 bohr and 0.3” for thc
bond distances and angle, respcctivcly. Hartree-Fock calculations employed the
9SSP/4S gaussian basis set of Huzinaga”.‘ contracted to a [4s3p/Zs] basis by
DunningIi5. A summary of geometries, energies and energy difTcrenccs for all
calculations of these and previoas workers is shown in Table 28.
Ahlrichs and Staeninilcr17Chave published the rcsiilts of nb iiiitio calculations on
the structure and geometry of thc three isomers of N,H?. including 1.1-dihydro-
diazine, a n d using gaussian basis sets with polarization functions. Thesc authors
refer to the work of Carlotti and coworkersIJG and Frost and c o ~ v o r k e r sas ~~~
establishing experimentally that diiniide possesses a singlei ground state in a planar
t m n s configuration. T h e latter authors have studied the photoelectron spectrum of
N2H,and conclude that they are probably observing the molecule in the singlet
ground statc.
The calculations of Ahlrichs and Staeinr?iler, thc rcsults of which are sunimnrized
i n Table 25, account for clectron corrclation by means of a configuration intcrnction
(CI) computation bascd on the pair natural orbitals ( P N O ) of the respective pair
correlation functions ( P N O CI). This trcatmcnt is stated by these authors to bc
essentially cquivalcnt 10 ;i configuration interaction calculation in \vhich all doubly
substituted configurations have bccn included with thc l-lartree-fock function. I n
TABLE
28. Geometries and energies for cis- and trorrs-diimide P
P
Eact
AE (kcalimol)
RSN RXII 8Nslr E (kcalimol) (froin trotis
Author (A) [A) (degs) (liartree) (cis-irorrs) form) Reference
W licl nn d 100' 33 i34
Alstcr and 13urncllc 1.22 1.03 128* 8.5 12 152
Robin. Hart and Kucbler I ,210 1.021 I I2.7* 153
Gordon a n d Fisher 4.5 4G (i); 72 (r) 154
Lelin and blunsch cis I .230 1.014 117* - 109.9076 10.5 50 (i); 53 (r) 155
trolls 1.230 1.014 I lo* - 109,9242
Schnnd and Kinscr CiS 1.27* 1.13* 1 I?* - 106.5745 7.6 7 2 (i) 157
[rails I .28* 1.13* IO4* - 106.5365
W o n g , Fink and Allen cis 1.245* 1.011* I15.5* - 109.929i 0.7 158
lrorrs I .251* I .005* 102.5" - 109.9302
\Vong, Fink and Allen cis I .245* 1.011* 1 I5.5* - 109.9442 5.3 4
frnrrs 1.196* 1.005* 102.5" - 109.9527
Ti 11I n nd 1.230 I .07 1 112.7 10.8 159 ?
Gcnsnn o n d CIi r i s t o ffcrscn cis 1.217 1.01I - 93.5605 4.5 164 z0
troiis 1.217 1.011 - 935675
\Vn g nicre cis 1.240 I 4 21 112.7 - 109.9664 166 CI
2
trails 1.240 1.021 112.7 - I099809
Rntlom, I-lchre and Pople cis 1.25 0.99 109.5 - 109.7932 11.2 168
[rnIIs 1.25 0.99 109.5 - 109.81 10
Hariharan and Pople trails 1.25 0.99 109.5 - 109.9977 167
Baird and S w n s o n cis 1.21 1.01 115 - 108.5595 5 GO (i); 84 (r) 169
traris 1.21 1.01 109 - 108.5678
blcrinyi, Wcttermnrk and Roos cis 1.230 1.014 117 - 109.8033 8.9 52 (i); 71 (r) 171
fraiis I .230 1.014 I10 - 109.8175
cis 1.238 1 .OG5 Ill* - 109.9144 12.6 109 (linear 172
froris state)
trotis 1,238 1.065 Ill* - 109.9345
Winter and Pitzer cis 1.235* 1.025 * 1 l6* - 109.9301 8.2 173
fratis 1.239* 1.017* 110' - 109,953I
Alilriclis and Staeminlcr traits 1.207* 1.0'1* 109* - 110.3755 5.8 55 176
cis 1.207* I .032* 11.1" - 110.3665
~~~ ~ ~~~ ~~ ~
I = inversion; r = rotation; * = optimized variable.

i . Gencral and theoretical aspects of thc dinzoniuni and diazo groups 45
addition, thc coupled electron-pair approximation was ernploycd to approximate
the effect of unlinked cluster terms arising from the doubles (CEPA). The energy
values given in Table 28 are those arising through the use of CEPA. Not included
in the table arc their values for H,NN which are 1.221 A, 1.012 A, and 122.3" for
the N N and N H distances and N N H angle, rcspectively. Their bcst energy for ttic
triplet (ground) state of H R N N is - 110.3341 hartrec (CEPA).
Ahlrichs and Staemmler find the lratls isorner lo bc the most stable isonier \vitIi
the cis isomer and H,NN approximately 5.8 and 26.0 kcal/mol above thc t/.ntls
forni. In addition thcir CEPA calculations yield a value for A E of 59.6 kcal/mol for
the reaction
N,H, (frans) - ? H+N,+H
so that the isomerization apparently competes with this process. Further, thcir
value of 5 5 kcal/niol for the barrier to the / / ~ n n s - c i sisomerization suggcsts that such
isomerization is unlikely to be the first step of the decomposition of N,H2
2 N,H, -> N,H,+N,
Unpublishcd work from this laboratory*78, in which a variety of molcculcs

containing the N N bond have been compared using a11 STO-3G basis, will be
referred to in more detail later. While not yielding cnergy values of Hartrec-Fock
quality, such calculations d o have the advantage of being rclatively inexpciisively
extended to larger molecules, thus permitting a comparison of a larger numhcr of
molecules possessing the N N bond. With this method, an energy of 7-3 kcal/niol
was calculated for the tmm to cis isonicrization, with the ivntrs possessing the lower
energy of the two forms.
C. Disubstituted Diimides
1. N,F,
a. T/ieot.eficnlslrrdies. Next to diimide itself, probably the most studied diimidc,
froin the point of view of theoretical calculations, has bcen difliiorodiiiiiidc.
Extended Hiickcl calculations were employed by Kaufman and coworkers179to
examine some properties of molecules containing nitrogen and fluorine, among
them being cis- and Irntis-N,F,. The values given by Simborn1s8for thc structural
parameters \yere used. Calciilatcd N-F overlap populations of 0.33 and 0.32 for thc
trotis and cis forms, respectively, and 1.09 and 1.16 for that of the N = N bond in
the t v m s and cis forms, respectively, indicated that the N-F distance in /t.ntis-N,F,
should be shorter than that in cis-N,F,, while the N = N distance i n cis-N,F, should
bc shorter than that in ttwtzs-N,F,. I n addition, thcir calculated total elcctronic
energies suggested that thc cis form should be niorc stable than tlic lrntis.
Ray and N a r a ~ i n i I i a n have
~ ~ ~ utilized cxtendcd Hiickel theory to study the
transition state in thc isornerization of frntis-N,F, to cis-N,F,. Thc structural data
of Rohn and Ikiuer201were employed i n the calculations. Configurations gcncratcd
by rotating one N F bond around ttic N N axi s were considered. Two typcs of f r o m
configurations were cxariiined, one (T) i n \vhich the esperimentally observcd bond
kngtlis and angles of thc I t x m form ivcre uscd, and the othcr (T') in which thosc of
the cis form (C) \rere employed. Like\vise C' refcrs to a hypothetical cis forni in
\vhich the /r.otis bond Icngths and angles arc uscd. Lincar configurations. LT and
L c , tvere also considered, i n the former thc N--N and N-1: bond lengtlls of
Iratis-N,F, tvcre used, wtiilc in ttic latter those of the cis forin w r c cmploycd.
46 J. B. Moffat
Table 29 summarizes t h e calculated values of electronic energy. The calculated
binding energy for fratis-N,F,, 255.4 kcal/mol is in good agreement with the
experimental value 07 2 4 4 . 3 kcal/mol 193. The cis ( C ) configuration is predicted to be
more stable than the rratls(T) by approximately 15 kcal/mol, compared with 3 kcal/mol
found exprrimcntally (Armstrong and Marantz). The T' and C' configurations have
TAnLE 29. Total electronic cnergics for N,F, as found by EXH

met hod IHa
Binding cnergy (kcnllrnol)
Total encrgy
Configuration (eV Calculntcd Obs~rved'~~.
--
T - 539.4168 255.41 243.3
C - 540.0626 270.33 247.3
T' - 539.1941
C' - 539.6203
LT - 531.7076
LC - 531.8146
higher energies than the respective T a n d C forms. Barrier heights in the isomeriza-
tion of rrans- to cis-N2F, are shown in Table 30. According to the results of
exteilded Huckel calculations, of t h e three transition-state configurations considered,
that achieved by a rotation around the N = N bond possesses the lowest energy.
TABLE 30. Barricr hcights for fratrs -> cis isonier-

ization of N,F, '""
Transition state Barricr height (kcal/niol)
rotation 47
LT 178
LC I76
Gordon and FisherlSJhave utilizcd the C N D O and I N D O methods of Pople and

coworkersl*I to calculate energies and structural paramcters for N,F,, the latter
being obtained by minimizing the energy. As can be seen from Table 31, thc iratis
form is found to be 4.1 kcal/rnol higher in energy than that of the cis form, in good
agreement \vith thc expcrirnentally derived value of 3.0 kcal/mol found by
Armstrong and Marantz1D3.I f o n l y singlet states are involved in t h e isonierization
of cis- to fraris-N,F,, then activation cncrgies of 65 and S5 kcal/mol for inversion a n d
rotation on onc nitrogen, respectively, a r e found. I f the transition form esists in a
triplct statc, then i t is prcdictcd that thc lowest activation energy, 52 kcal/mol, will
be achieved through rotational isonierization. I n the singlet and triplet rotational
transition states, dihedral angles of 100" and 70". respectively, wtrc calculated.
C N D O / 2 calculations have also bccn perfornicd on N2F, by Hcrndon and
co\vorkers'". Geometry optimization was also employed and gave 1.26 A for the
N-F distance in both the cis and fratis forms (experimental: cis, 1.41 A; r ~ m i ~ ,
1.40 and 112" and 109" for the F N N angle in the cis and f m i s molecules
respectively (experimental: cis, 114"; f r a t i s , 106°20').In vicw of these results, these
I . General a n d thcoretical aspccts of thc diazonititn and diazo groups 47
3 I . Total relative electronic cncrgies and energy-optimizcd structural parameters
TABLE
for N,F, as found with the C N D O and I N D O niefhodsIsa
Geomctrical paratnctcrs
-~
Bond angles
Bond lengths (A) (degrees) Rclat ive
- - cnergy
Statc Form N-F N=N LFNN Di ticdral (kcal/mol)
Singlet linear 1.25 1.20 - - 143.8
Triplet lincar 1.25 1.20 - - 128.6
Triplet cis 1a23 1.30 111 0 98.5
Triplet bcnt 1-25 I .2G 115 - 94.0
(1.23)O
Singlet lratis I -24 1.24 132 100 85.0
Singlet bent 1*24 1.22 114 - 67.7
(1.23)O
Triplet fratis 1.24 1,27 119 180 66.7
Triplet trans 1.24 1-30 113 70 52.0
Singlet fratis 1.25 1.25 109 180 4.1
Singlet cis 1.25 1.24 116 0 0.0
a Bond lengths in bracicts refer to the N - F lengths at the N - F which is bending.
workers varied the value of the /3 constant for fluorine in the CNDO method to bring
the experimental and theoretical N- F distances for the traits into coincidence.
Table 32 summarizes their results, which d o not differ greatly from those of Gordon
and Fisher1sa except in predicting a n activation energy of 81.1 kcal/mol for the
inversion mechanism.
Girnarc'"' applied the extended Huckel method to N2F, and discussed the results
primarily from the point of view of the molecular orbitals involved and the shapes
of the molecule. For molecules like N,F, which possess 24 valence electrons, the
highest occupied orbitals for linear geometry would be the doubly degenerate upper
32. C N D O / 2 results for N,F,

TABLE using adjusted / 3 ~
value of 14.07
Gcometrical parametcrs
Bond angles
Bond lengths (A) (degrees) Relative
energy
Form N-F N=N LFNN Dihedral Symmetry (kcal/mol)
trails 1.40 1.19 143 180 C:h 155.2 (max)

linear 145 1.15 180 - DoDh 106.8
tram 1.40 1.23 110 95 c
2 85.70 (max)
fratis 1.393 1.19 112, 1 so cs 81.10 (max)
185
rratis 1.40 1.23 110 90 c, 79.65
bent 1.393 1.19 112 - c, 75.40
(1.393)
1,l-Difluoro 1.40 1.19 133 - C,, 39.0 (min)
fratis I .395 1.22 105 1 80 c,h 3.14 (min)
cis 1.40 1.21 114 0 C2" 0.00 (min)
38 J. B. Momat
xu orbitals, zR(.v) and xE(y).These arc completely antibonding, being composed of p
atomic orbitals antiparallel to each other, and each would contain a single electroil
only. The c!egeneracy of thcse xg(x)and z&) orbit'ils is removed when the molecule
bends, the two levels becoming a? and b, for cis, and V; and afc for trarzs bending, and
tliese four orbitals can now contain p: and s atomic orbitals as well as pz or pv.
When cis bending occurs, thc energy of t h e a, level changes very little from that of
the x C ( y ) ,but the energy of the b, level decreases substantially below that of the
linear xC(x),because the lower lobes of the F atom pz atomic orbitals move from
antibonding positions into favourable bonding positions with respect to the
ncighbouring N atom pz orbitals. On the other hand, when irons bending occurs,
bz remains similar in energy to K&), but the a; level is lower in energy than zc(.t-),
since the pz orbitals on the F atoms niovc into bonding positions with respect to
their ncighbouring N atoms. As Giniarc points out, it is then the b,(cis) and a;(tmns)
encrgy levels which give cis and trotis shapes to N,F,.
In discussing the isonierization of N,F2, Girnarc notes that the rotational
niechanism involves the crossing of highest filled and lowest unoccupied a and b
orbitals. The principle of conservation of orbital symmetry consequently forbids
the rotational mechanism. In the inversional mechanism the highest-filled (1; orbital
can convert into b2 because a,b symmetry is lost.
has used the C N D O theory to calculate the total electronic energies of
t h e cis and I ~ N I Z Sforms of N,F, as a function of bond angle between 90" and 125".
Minimum energies of -78.6953 and -78.6958 hartree were found at 110' and
105" for the cis and trotis forms, respectively. Within the limits of error of the
calculation the energies zre the same. The calculated rotational barrier (trans --> cis) is
S5.l kcal/mol. Turner suggests, since no significant change occurs in the population
analysis in passing from the frnns to the cis form, that the origin of the barrier is
probably not d u e to any alteration i n chemical bonding but is simply an atom-atom
rep u 1s i on.
T h e method and results of nb itzitiu minimal basis SCF-CI calculations performed
by Ditchfield and c o \ v o r k e r ~on~ ~
diirnide
~ have been discussed in a previous section.
T h e same paper reported - 11.4 and 5.67 eV for the energies of the n and z * orbitals
of cis-N2F2,and - 10.05 and 5.S7 e V for the corresponding orbitals of fmns-N,F,,
yielding vertical singlet rz -? x * transition energies of 5.75 and 4.22 ev' for the cis
and [ r a m forms, rcspcctively.
Brundle and have employed photoelectron spectroscopy and ab
itiifio gaussian orbital calculations to study the cfl'cct of the substitution of Fluorine
for hydrogen i n a planar molecule, which has been shown, at least in some cases, to
have a much larger stabilizing effect on the G MO's than on the z MO's. There is
some difiiculty i n studying diirnide and difluorodiiniide for this purpose, as these
authors point out, since there are no photoelectron data for trans-diimide and the
photoelectron spectrum of t t ~ ~ n s - N , F ~ contain bands due to an isomeric
may
impurity. Ho\vever, Table 33 summarizes their calculated and experimental ioniza-
tion potentials for these two molecules. The highest M O in N,F,, 7a,, contains some
N-F c-antibonding character in addition to the N-N antibonding lone-pair
component. The agreement bet\vecn the calculated encrgy of 13.92 eV and the
experimental, 13.4 cV, is quite good. What the authors refcr to as the perfluoro
shift, or simply the change i n orbital energies on substitution of fluorine for hydrogen,
is + 3.6 eV f o r the 4a,-7a, orbital p i : . The la, z MO of N1H2 i: calculated to
possess an energy of 13.07 eV, which correlates with the 2a, level of N,F, at
14.23 eV (calc.). The la,-2a,, shift then is approximately + 1 . 1 eV.
Companion and €4sia'*s havc employed a biccntrically rescaled, energy-
partitioned, version of the CNDO/2 method in a study of atomization of a variety
1. Gcncral and theoretical aspccis of the diazoniuni and diazo groups 49
of nitrogen fluoride molecules, including N,F,. T h e geometrical d a t a of Bohn and
Bauer'O' were employed. Calculated values for the heats of atomization were 217.1
and 216.0 kcal/niol for the trntrs and cis forms respectively, which may bc compared
with the experimental v a l u c ~of ~ 1.6 and 254.9 kcal/mol for the t r a m and cis forms.
' ~25
respectively. The elcctron affinity and first ionization energy werc calculated as
2.00 and 14.62 c V for N,F2.
TABLE 33. Observed and calculated ionization potentials (eV) for N2H, and
fratrs-N,F, la'. Reprintcd, with pcrniission, from Brundle and coworkers, J .
Atner. C/ietn. Soc., 93, 1451 (1972). Copyright by the Anicricnn Chemical Society
N,H, N,F,
Adiabatic Vertical
Orbital 0.92 K.T.= Orbital 0.92 K.T.O IP IP
4% 9.84 13.92 12.8 13.4
1a, 13.07 14-24 13.65 14.1
3bu 15.97 16.60
3ag 17.42 17.50
2bU 23.93 18.57
2% 34.80 19.80 18.0 18.70
1 bU 39 1.4 20.20 13.80
1 ak7 39 1* 5 20.39 21.0
24.06 22.3 72.7
35.8
42.4
43.5
396
396
66 1
66 1
(I 0.92 K.T. refcrs to 920/, of the valuc as given by Koopmans' theorem.
b. Spectra arid striictrrre. The elcctron diffraction pattern of a sample of NzF2

~ ~ , assumed a SO-SO% mixture of cis and trails
was determined in 1947 by B a ~ e r ' who
isomers, and fitted the data with N-F and N = N bond lengths of 1 4 4 and 1-25 A,
respcctivcly, and F N N bond angle 115". S a n b ~ r n prepared
*~~ large amounts of N,F,
by maintaining a n electric discharge in a strcam of nitrogen trifluoridc in the
presence of mercury vapour. Two fractions were obtained by gas chromatographic
separation on a silica-gel column held at a low temperature, each with a molecular
weight of 6G, but with quite different cheniical reactivity. One fraction reacted with
mercury and explosively with diborane, while the other did not, and the infrared
spectra of the two fractions were different. Sanborn, from his infrared data, decided
that the inactive form was rrnns-l,2-difluorodiazine (r-I,2-DFD) arid the activc
form was suggested to be 1,I-difluorodiazine (1,I-DFD). For the fraction suggested
to be .r-1,2-DFD, three fundamental vibrations (an-') of synimctry A, (1010;
N-F symmetric stretch; 1636, N = N stretch; 592, N = N - F synimetric bend), one
of A, (360,torsion) and two of Bu (989, N-F asymmetric stretch; 421, N=N--F
asymrnctric bcnd) \vece identified. On thc other hand, 1 , I - D F D gave three A,
fundamentals (896, N - F symmetric stretch; 1524, N = N stretch; 552, F-N-F
symmetric bend), one B2 (737, out-of-plane bend) a n d two B1 (952, N - F
asymrnctric stretch ; 573, F-N-F symmetric bcnd). Sanborn provided chemical,
50 J . B. Mom31
mass spectral, dipole nionient and infrared spcctral evidence for thc identification
of liis ‘active’ fraction of N2F, as 1.1-DFD and not cis-1,2-difluorodiazine.
Ettinger and agrced with Sanborn that t h e less active (lower boiling,
- 11 1.4 “C) isomer was the trans configuration, but argued that the structure of the
more active (higher boiling, - 105.7 “ C )isomer was much inore in doubt, for a variety
of reasons. They provided alternative interpretations for Sanborn’s experimental
data and, in addition, noted that n.m.r. spcctra of both the high- and low-boiling
isomers showed only one nitrogen resonance, while two nitrogen resonances might
be expected for I l l - D F D . They noted also that the dipole moment change for the
N = N stretching mode is not along the axis of the least moment of inertia, but is
along an axis of intermediate moment. Consequently, a cis isomer a s well as a
I ,I-isomer could show only PR structure. Sanborn190while conccding that the shapes
of the infrared bands did not preclude a cis isomer, insisted that the infrared band
at 737cm-’ in ‘active’ N,F, must be a fundamental vibration, and can only be a
bending fundamental, which would be, he argued, out of position for a cis isomer,
but fitting perfectly for 1.1-DFD.
Herron and Dibelerlgl, in their mass spectrometric study of NzFZ,nieasured t h e
appearance potentials of N,F+, N,F+ and NFi from the trans isomer a s 13.1, 13.9
and 17.0 eV, respectively, while those from what they considered to be the cis isomer
were, for N,F+ and NF’, 14.0 and 16.9 eV, respectively. The cis isomer apparently
does not produce a parent ion. Hence the appearance potentiais of the normal
fragment ions N 2 F + and N F + are identical withl:i experimental uncertainty
(kO.2 eV) for both cis- and trans-N,F,. Herron and Dibeler reasoned that this
information suggested a similarity in molecular structure and hence favoured the
identification of the ‘active’ isomer as cis-l,2-DFD rather than 1,l-DFD. Heats of
formation for the cis and frntrs isomers were reported as 16.4 and 19.4 kcal/mol,
respectively with associated bond dissociation energies D(FN=NF) a s 106 and
103 kcal/mol, respectively.
Measurements of the ’OF chemical shifts and splittings for the two isomers of
N s F z were reported by Noggle and coworkers’s2. An analysis of the 19F-(14N}13
double-resonance spectra for the reactive isomer indicated that both nitrogens in the
molecule have the same chemical shift, thus providing strong evidence in favour of
the cis structure for the ‘active’ isomer. Calculated and observed spectra agreed
quite well when the cis and rratu structures were assumed.
T h e heats of formation of the two isomeric forins of N2Fz were measured
calorin~etricallyby Armstrong and MarantzIQ3,by reacting the N2Fpwith ammonia.
N,F,(g)+8/3 NH,(S) = 2 NH‘F(C)+4/3 N,(g)
Mean heats of reaction of 21 1.7 and 209.2 kcal/niol were measured for the tram
and ‘active’ isomers, respectively. The difference in the heats of reaction of the two
samples, adjusted for the purity of the samples, yields a heat of isomerization
( a c t i v e 2 trans), AH/O?g8= 3.0 kcal/mol, indicating that the ‘active’ form is more
stable thermodynamically than the f r o mform. Use of AH/0208[NH,(g)]= - 11.04 kcal/
m0Iig4, and AH,?,,,[NH,F(c)] = - 1 1 1.0 kca1/nio1185, produces values of 19.4 and
16.4 kcal/tnol for AH,029s of the f r m u and ‘active’ isomers of N,F2, respectively.
Arnistrong and Marantz calculate the total binding energy of tratis-N,F, to be
244.3 kcal/mol, which, with the use of 107.9 kcal/mol for E ( N = N ) , yields a value of
68.2 kcal,/mol for E(N-F).
The microwave spectrum of the ‘active’ isomer of N,F, was measured by
Kuczkowski and Wilson1eG,who concluded that the structure was planar and cis
with NN and N F bond lengths of 1.214 and 1.384 A, respectively, and F N N angle
I . General a n d theoretical aspects of the diazoniuni a n 3 diazo groiips 51
01' 114.5 '. A dipolc iii~iiicnto l ' O . 1 6 D \\'as obtninccl from thc rotational Stark clTect.
Thus, by 1963, the evidencc in favour of the cis structurc for the 'active' isomer
seemcd strongly to outweigh any other previously hcld conclusion.
Thc gas-phase infrarcd and liquid-phase Raman spectra of irom-N,F, has been
measured by King and Overend'!'', \vith the following vibrational assignments:
VXS = 1 5 2 2 , s ~ =~1010,s8~,-17
~ = 600, i i v ~ 1 . -= 990, a 8 ~ 1 =
. ' 423 and torsion = 363.5
cm-'. Thcse authors note that their assignment of thc infrared spcctrum is essentially
the samc as that of Sanborn'". I n a subsequent thesc same authors re-
studied sonic of the bands at higher rcsolution to obtain cstirnates of the rotational
constants, which values are consistent with the values of Bauer18' from elcctron
diffraction nieasurcnients.
T h e Ranian spcctrum of gaseous troiz.7-I ,2-dilluorodiazine has been reportcd by
Shaniir and Hyman139.The three symmctric vibrations were obtained and assigncd
as 101s cm-', N-F symmetric stretch; 1523 cm-l, N = N stretch, and 603 cm-',
N = N - F symmetric bend, which agree quite wcll with thosc found by King and
Overend19' for thc liquid, whcre in all cases the liquid-phasc values are lower than
those in the gas phase, as might be cxpected.
T h e Raman spectrum of cis-N,F, was also measured by King and 0verend2"".
A summary of their data, together with that of othcr workers, is givcn i n Table 34.
33. Vibrational assignnient of cis- and tr.crits-N,F,

TABLE
cis-N, F, (gas)?"O traits- NLF,
-~
Frequency (crn-I)
Frcquency
(cni-I) Description Liquid19y C n l ~ . ' " Descriplion
~
__-
A, VI I525 "NS A, v1 1523 I522 1636 VK.U
V? 896 vN1: v2 lois 1010 1010 vx1:
1'3 34 I &: v3 603 600 592 8h.l..
A, 1e4 (550) Torsion A, v4 362 363.5 360 Torsion
Bl v5 952 VIi F B, v5 990 990 989 ~ ~ 1 7
VG 73 7 SS F vg 420 423 421 8x1:
Bohn and Bauer201 have determined the structures of cis- and irons-I ,2-difluoro-
diazine from electron diffraction nieasuremcnts, using sectored-niicrodcnsitoinetcr
data. The gcometric configurations and interatomic distances werc found to be
essentially the same as those previously estimated on the basis of the visual tecliniquc.
Table 35 records the structural paramcters from the work of Bohn and Bauer?O1and
Kuczkowski and \Vilson196.T h e X = N and N--F distances as obtained by Bohn and
Baucr2O1 are similar to those expected for other molecules with N = N and N--F
bonds. However, in the traits isomer, L N N F = 105.5" is surprisingly small. With t h e
cis compound there is agreement between the two sets of data shown in Table 35
for the N = N bond distance and L N N F but not for the N-F bond distance. R u t
the major structural difference between the cis and trails isomers is the larger
L N N F in the former compound. This can be rationalizcd on the basis of a repulsion
between the two F atoms in the cis isomer which are about 1 Angstrom closer
together than in the trails form. T h e N = N bond lcngth is also somewhat shorter i n
the cis form, while the N-F distance is slightly longer in the cis form.
Calculations of vibrational coupling effects and potential functions of both the
cis and trans isomers have been made by Pearce and Levinzo2who cniployed the
3
52 J . B. Moffat
structural paramcters of Bohn a n d Bauer201, a n d compared their calculated rcsults
with t h e expcriniental Io3. Calculatcd a n d obscrved frequencies agreed
q u i t e well in all cases.
35. Structural parameters for cis- and fratzs-N,F,

TAULE
fmtu-N,F, c~s-NZF,
___
Bohn and Bnucr201 I3ohn and Bsucr2"l Kuczkowski and Wilson196
N = N (A) 1.230 1.211 1.214

N-F (A) I .396 1.410 1.384
N
F -- -- --
F (A)
F (A)
LNNF(deg)
3.093
3.339
105.5
2.209
2.38 1
114.4 114.5
c. Tliertnochcmicnl propcrlies. Cot burn a n d c o w o r k c r ~ ' "were~ t h e first t o report o n

t h e properties of N,F,. Their values for a variety of physical properties a r e givcn in
Tablc 36. F o r comparison purposes the table is augmented by t h e d a t a given in t h e
review paper of Pankratov'"'. Colburn a n d coworkers203considered t h e cis isomer
to be chemically more rcactib'e, yet Lustig2"j found that the isonierization of t h e
[ratis t o the cis isomer took place below 100 "C nearly quantitativcly in a static
system. LustigZospoints o u t that this isonierization is consistent with t h e heats of
f o r m a t i o n of A r m s t r o n g a n d MarantzIe3 (see T a b l e 36), which indicates that t h e
cis isomer is thcrrnodynamically m o r c stable.
TABLE
36. Physical propertics of cis and fratis difluorodiirnideZo3
rra,ls-Difliiorodiimidc cis- Di fl uorodi i mide

-~
Vapour pressure log Pmrr = ( - 7 4 2 . 3 / T )+ 7.470 log Ptorr= ( - S03.OiT)i-7.675
Boiling point ("C) - I 1 1.4 - 105.7
Heat of vaporization 3400 3670
(cal/mol)
Critical temperature ("C) - 13 -1
Critical pressure, 55 70
estimated (atm)
Melting point ("C) - 172 below - 1 9 5
Heat of isomerization 27.5 +_ 5.0 ( c s ~ ) " ~
(kczl/rnol)
Heat of formation AH," 19.4 l g 3 16.4
(kcal/mol) 25.3 ?OI
20.5 ( - 105 "C)
Pankratov?"' has determined the heat of forination of the 'active' cis isomer o f
N,F, from reaction with acid potassium iodidc solution. He obtained
25.3 +_ 2.0 kcal/mol a t 25 "C a n d 20.5 t 2.0 kcal/mol a t - 105.7 "C (for t h e liquid
isomer). Pankratov calculates a dissociation energy of 97.5 kcal/mol for t h e N= N
b o n d in the cis isomer by using 61.14 kcal/mol for t h c heat of f o r m a t i o n o f N F a n d
his value f o r N2F2.
1. Gcncral snd thcorcticrl aspects of the dinzoniuni and diazo groups 53
d. Kiiictics of isoti~crizatiot~.
Binenboym and coworkers2nGhave carried out
experiments designed to provide information on the cis-tram isomerization of
difiuorodiiniide under homogeneous conditions. As has been mentioned, the
isornerization is catalysed by heated metal reaction vessels, and diiluorodiimide also
attacks glass at elevated temperatures. In the study by Binenboym and coworkers,
N2F2, highly diluted i n argon was heated i n a single-pulse shock tube. Since the
tube walls remain cold, the reaction can be studied under homogeneous conditions.
T h e isomerization was studied between 297 and 342 "C and at pressures u p to
1.6 atm. Vapoti; phase chromatography was employed to calculate cis and trans
concentrations. The isornerization was identified as first-order with rate constants
given by
k = lo" C X P ( - 32,20O/KT) SCC-'
These authors point out that the pre-exponential factor is high and similar to that
found with the carbon-carbon double-bond Howcver, their calculations
of the energy required to decouplc the x-bond overlap yielded 84 kcal/mol, much
higher than their experimental value of 32 kcaljmol. Hence they conclude that the
isomerization cannot take place by rotatiori and a decoupling of the ;r-bond overlap
so that the transition state presumably retains its double-bond character. They
tentatively suggest that a linear configuration in the transition state may be consistent
with their results.
Apparently no further work on the fratis-cis isomerization was done until, in 1974,
Vedeneev and reported on experiments done in a Teflon reactor
from 100 to 150 "C and at initial /raris-N,F, pressures of 15, 25 and 32 torr. They
report that a n autoaccelerated reaction begins ivhen the first trace of cis-N2F2 is
formed. Values of A H = -207Ok 145 cal/mol and A S = - 1.55 2 0 . 3 7 e.u. were
obtained .
2. Tetrazene
Wiberg and coworkers have recently reported on the preparationzogof tetrazcnc,
N4H4,and its photoclectron spectruni210resulting from their earlier work on azo
compounds."' Discussion of the work contained in thc latter reference Lvould lead
us too far outside the domain of this volume.
These authors believe that N,H, is l-I,N-N=N--NH2, probably, at least with
their methods of preparation, in the trnns form. Thcrmal decomposition produces
N, and hydrazine by one route or alternative rearrangcment to ammonium azide
NH: N,, the former in about 75% yield and the latter 35%. Gaseous tetrazene is
unstable a t room temperature, whereas decomposition of solid tetrazene begins at
approximately 0 "C. Their assignments of the bands of the photoclectron spectrum,
plus CNDO/S calculations lead to the following orbitals and energies: ~ ~ ( 8 . 5eV),
1
n+(10.13eV), ~ ~ ( 1 1 . eV),
6 7 rt-(13.92eV) and ~ ~ ( 1 4 . eV).
44
D. Monosubstituted Diimides
1. Introduction
Relatively little work, of either theoretical o r experimental nature, had been
reported on the physicocheniical properties o f the interesting molecules,
R-N=N-H, until quite recently. A has been published in 1971 by
Kosower. He states that, up to 1965, there \yere no reports of the direct observation
of a monosubstituted diiniidc, although there were many descriptions of reactions
in which R-N=N-H had becn invoked as an intermediate. Monosubstituted
54 J. B. Moffat
diiniides (i) are oxygcn sensitive, ( i i ) disappear via bimolecular reaction and (iii)
react (often) with base. I t is claimcd that mctliyldiiniide is tlie only monosubstituted
diiniide that can bc readily isolated in purc form.
2. Spectra and structure

Absorption data are reported by Kosowcr for thc nionosiibstituted diirnides. The
ti + x * bands fall bctwcen 3490 and 3750 8, for unconjiigated systcnis and between
4030 and 4175 8, for conjugated compounds. Kosower notes that the absorption
coetllcients are all vcry low, between 18 and 100, thus implying a trans structure for all
diirnides listed. The tz --i ;* transition for trans CH,N=NCH3 appears at 3430 A2I2,
while that for CH,N=NH is given as 3610 A, thus suggesting that alkyl substitution
for hydrogen may decrcasc the tz+-tz- splitting.
Steinmetz213has rneasurcd the niicrowavc spectrum of CH,NND, the deutcrated
species being used because of its higher stability than rhe hydrogen species. The
deuterated species can be stored at liquid nitrogen temperature wi!hn.t decomposi-
tion, whereas the hydrogen species will still decompose at this temperature. To
obtain a structure thc H C N angle and C H bond length were assumed to be 109.5"
and 1.09 A, respectively and values of 1.24, 1.47 and 1.014 8, wcrc taken for the N N ,
C N and N H bond lengths, after consideration of other similar compounds. This
pcrniitted angles C N N and N N H to be calculated as 112 and 1 lo", rcspcctively. A
methyl group rotational barricr of 1665 k 40 cal/mol was also calculated.
Ackernian and coworkers214-215have rncasurcd tlic infrared spectra (4000-
200 cni-') of mcthyldiimide and its deutcrated forms, in the gas phasc, condensed
phase (77 K ) , and in nitrogen matrices (20 K), and have made thc following assign-
ments (deuterated species in brackets): N-H strctch at 31 30 (2320), N = N stretch
a t 1575 (1550) and tlie N-H out-of-plane bend a t 544 crn-1 (662). The N-H stretch
agrees with that found for trotis diiniideIJ3. I t is intercsting to note, however, that
the N-H out-of-plane bends in diiniide itself have been assigned at 1359 crn-l
(N,H,) and 999 ciii-l (N2D,)l1', much higher than those for thc nionosubstituted
molecules.
Tentative assunipt ions"4 of geomctrical paramctcrs for met hyldiiniide were :
N-H 1.014A LNNH 110"
C-H 1.093 A LHCH 109.5"
C-N 1.470 8, LHCN 109.5"
N=N 1.240A LCNN 110"
By comparing their rcsiilts \\it11 those for from-diazene, Ackerrnan and
coworkers214-215 concludcd that tlie frotis form can be cxpccted to be the most stable
structure of met li y ldii m idc.
Very few calculations of any type have bcen reportcd in the literature for rnono-
substituted diirnidcs. This is sonie\vliat surprising since sornc relatively simple
monosubstituted diimides, whosc existcncc has not yet been verified experimentally,
could be studicd with advantage from a thcorctical point of view. Of course the
experimentally kno\vn monosubstituted diimidcs inay still be too large for inexpensive
theoretical work.
I . Gcncral and thcorcticnl aspects of I h e diazoniuni a n d diazo groups 55
Ditchfield and c ~ \ v o r k e r s in ~ , work discusscd in an earlicr section, have
~ ~their
calculatcd the t i and x * orbital energies and singlet n -> x * transition energies for a
number of monosubstituted diirnides. Their results are summarized in Table 37.
Using thcir standard geometry, Ditchficld and coworkcrs found that the t r a n s
isomer should be more stable than the cis in the ground state. with the encrgy
difference between the two forms decreasing in the order CH,> H > NH,> OH > F.
TABLE3'7. ti, x* Orbital cnergics and singlet i f -> x * transition
encrgies (eV) for IZN=NH 1nolecu1es~~~
A.E(,r --z x*)
0bscrved
R E-. Ca Ic ula ted (Ld
CH, (cis) -9.30 6.68 4.63
N!.12 (cis) - 9.92 6.83 5.72
HO (cis) - 10.05 6.42 5.54
F (cis) - 11.14 5.67 5.75
CH, ( t r a m ) - 8.64 6.88 3.58 3.45-3.55 *I2
NH, ( t r a n s ) - 9.98 6.32 4.37
F (tram) - 10.05 5.87 4.22
HO (/rmrq) - 9.98 6.32 4.37
I n both the cis and trntls monosubstituted diimides, the tz --> z* transition (the
lowcst of two is reportcd) is sliiftcd to higher energy in order C H 3< HO < NH, c F
for the cis, a n d CH, < F < HO < NH1 for the fratis, although the differences for the
highest three encrgies in the trotis series is small. As Ditchficld and coworkcrs point
out the changcs of thc ti and x * orbital energics resulting from ri withdrawal are
more important than the x-donating effects.
Again, as with diimide itself, the cxistence on thc azo group of two pairs of non-
bonding electrolis gives rise to [\YO possible ti --> ;5* transitions. However, only one
low-cnergy U.V. band is usually observcd. 11' the niolcculcs have a t r a m structure, a
strong interaction will exist betwecn thc lone pairs, which gives risc to a large splitting
i n the cnergies of the t\vo 11 orbitals, and conscquently two I I -> z* transitions of
very JifTercnt energies. Ditchfield and collaborators find the splitting between the
two t i orbitals to be approxiinatcly 5-6 and 2.5-3.5 eV in thc [ratis and cis isomers,
respectively, thus supporting this explanation. The t\ro 11 -+ z* transitions are
separated by approxiniatcly 6 and 2 CV in the t r a n s and cis compounds. Consequently,
i t \vould be expected that thc second iz --> x d transition in the / r m i s isorncrs will bc in
a much dimerent region of the U.V. spcctruni.
McrCnyi and coworkers171, in their work describcd in a previous section, have
performed ab iriirio calculations 011 CH,N=NH and its protonated form for the
purpow of obtaining barriers of rotation and of inversion. Their results arc repro-
duced in Table 38. In addition, a proton aflinity of 212.5 kcal/mol and n z-orbital
energy of -0.468 hartrec were calculatcd for thc /rotis form. The high valucs for the
barrier of inversion with CH,N=NH arc attributed to the orbital associated with the
lonc pair of electrons.
I n this laboratory21c.we have employed the Gaussian 70 programme2Dand a
minimal STO-3G basis set to calculate the total electronic encrgies of a number o f
niono- and di-substituted Jiiniidcs in thcir cis and f r m i y configurations. I n all cases
tlie nuclear configurations were optimized to t 0.001 A for bond lengths and k 0.1
for bond angles. Tablc 39 summarizes [lie optimized values for the various bond
56 J. B. Moffat
TABLE 38. Total electronic cncrgies of CI&,N=NH a n d CH,N=NH,f in various
c~nfgurations"~
Total cncrgy Barrier
Molecule Configuration (hart rcc) (kcal/rnol)
1
~~ ~~
CH3N=NH trails
CH,N=NH cis - 148.7907
148.8032 7.8
CH3N-NH Jnvcrtomcr - 148.7 193 52.6 (from frutzs)
( H inverts)
C H3N=N H Invertomer - 148.7297 46.1 (from frarzs)
(CH3 inverts)
CH,N=NH; - 149.1419
CH3N=NH: Invert omcr - 149.1030 24.4
CH,N=N H: Ro tamer - 149.0371 65.8
TABLE 39. Cnlculatcd structural parameters" of m o n o - and di-substituted diimidcs

Bond lengths Bond angles
~ _ _ _
Molecule NN NX X I4 NNX NCH HCH
~-
H N N H (trarrs) 1.267 1,061 105.3
H N N H (cis) 1.7-63 1,064 111.4
H N N H (invcrt) 1.246 1,082 108.0
1,006" (1 83.0)
H,C-N=N--CH, ( I ) 1.268 1.514 1.089 109.6 109.8 109.3
H,C-N=N-CH,, (c) 1.264 1.513 1.088 1 19.2 109.8 109.0
H,C-N=N-CH3 ( i ) 1.247 1.549 1.088 11 1.4 11O.U 109.0
1.432" I .096 ( 1 82.0) 110.2 109.1
CH,-N=N-H (I) 1.265 1.060 ( N H ) 104.8 ( N N H )
1.515 (NC) 1.089 (CH) 109.9 (NNC) 109.6 109.6
C H , - N ~ N - - H (c) 1.263 1.066 (N H) IIl.O(NNH)
1.517 (NC) 1.089 (CH) 115.6 ( N N C ) 109.5 109.5
CH,-N==N-H (i) 1.250 I.OS2 (NH) 1.096 (CH) 107.6 ( N N H ) 109.5 109.5
on CH, 1.436 (NC)' (183.0) ( N N C )
F-N=N-F (1) 1.287- 1.371 ( N F ) 106.1 ( N N F )
F-N=N-F(c) 1.277 1.373 ( N F ) I 1 1.5 ( N N F )
F-N=N-F (i) 1.250 1.398 (NF) 109.2 ( N N F )
1.351 (NF)* (1S2.0) ( N N F )
NC-N=N-H (I) 1.277 1.062 (NH) 104.2 ( N N H )
1.446 (NC) 109.5 (NNC)
1.159 ( C E N ) 109.5 (NNC)
NC-N=N-H (c) 1.373 1.064 (NH) 1 1 1.9 ( N N H )
1.447 (NC) 115.3 (NNC)
1.159 ( C = N )
I .270 1.056 (N tl) 104.0 ( N N H )
1.370 ( N F ) 107.4 ( N N F )
F--I\I=N-H (c) 1.264 1.065 ( N H ) 105.7 ( N N H )
1.377- ( N F ) 110.6 ( N N F )
NC-N=N-CN (I) I.2Sl 1.441 (N-C) 109.1 ( N N C )
1.160 ( C = N )
NC-N=N-CN ( c ) I.2SI 1,440 (N-C) 117.3 (NNC)
1.160 (C..N)
" Bond Icnplhs in A a n d bond angles ir. degrees.

(' Bond Icngth of inverting NX.
1. General and theoretical aspects of thc diazonitim and diazo groups 57
lengths a n d angles. As can be seen froni the table, in the cases of diimide a n d
dimethyldiirnidc calculations were a h performcd on the invertoniers. By bcnding
one of the NX bonds where X is either I-I or CHn. the bend angle corresponding to
the top of the encrgy barrier was located. Optimization of the nuclcar geometry was
then d o n e with this bend angle (normally approximately 180") held fixed.
T h e total clectronic energies (including nuclear repulsion) and the transition
energies for the cis to t r a m isonierizations a r e gi\'en in T abl e 40. I t can be seen t hat
these calculations predict that t he rrans (singlet) form will be the m ore stable of the
two, cis a n d trans, for all thc molecules examined except N2F,. I n the case of N2F2,
although other d a t a a r e not entirely coriclusivc, nevcrthcless the evidence available
points to the cis isomer as the inorc stable form (see Section 1Ii.C.l.a-c). However
the calculated isomerization energy given in Table 40 is suspiciously small. W e used
the optimized N2F2geometry f r o m Table 39 a n d calculated, using a n extended basis
(6-31G), for the cis and fratis forms of N,F2, energies of -307.441691 a n d
- 307.44078 1 hartree, respectively, corresponding t o an isomerization energy of
ab o u t 0.6 kcal/mol. This is still much smaller than the 3.0 kcal/mol value of
Arrnstrong a n d mar ant^'^^ or t h e 2.1 kcal/niol obtained by Vedeuecv and co-
workers2O8. T h e calculated inversion energy of 62.1 kcal/mol is also m uch higher
th an th e experimental value of 32.2 kcal/mo120G.
40. Calculated electronic encrgics for mono- and di.substituted

TAULE
d i i mi des
Transition energies
Molecrile Energy (harfrcc) (kcal/niol)
H NNH ( / m / t s ) - 108.55696 ( i r n m to cis)
+ 7.3
HNNH (cis) - 108.54525
I-INNH (invert) - 108'45 100 (66-5),+1
CH,NNCH, ( 1 ) - 185'72658 + 6.8
CH,NNCH3 ( c ) - 185.71578
CH,NNCH3 (i) - 185.62767 (67.1 ) ( + I
CHn-N=N-H (t) - 147.14214 + 5.7
CH,-N=N-H (c) - 137.13388
CH,-N=N-H (invcrl on CH,) - 147.04272 (62'4),+i
F-N=N-F (/) - 303.44058 -0.1
F-N=N-F (c) - 303.44 I02
F-N=N-F(i) - 303.30685 (S4.2)c-i
NC-N=N-H (I) - 199.09309 +6. l
NC-N=N-H (c) - 199,08341
F-N=N-H (I) - 206.00450 f 1.1
F-N-N-H (c) - 206.00?S 1
NC-N=N-CH (1) - 2S9.62759 i 6.6
NC-N=N-CH (c) - 789.61 703
T h e results of o u r calculations for mcthyldiimidc predict that the frrrns isomer is

more stable than the cis by appr oxi n~ at cl y5.2 kcal/mol which a g c c s reasonably well
with the conclusions of Mcrenyi a n d con.orkers allhough their total elcctronic
energies reflect t he higher quality of their \\zvefunctions. However, their C H 3
invcrsion energy of 36.1 kcal/niol is much lowcr than o u r 67.4 kcal,'mol.
T h e results of w r y similar calculations have just bcen publishcd by H O W C I I a n d
Kirsclienbauni?" and, as cxpected, o u r rcsults agrce quite \\ell witti thc results of
these authors.
58 J . B. Moffat
IV. DlAZONlUM COMPOUNDS
A. Introduction
A number of books concerned, at least partially, with diazoniuni compounds have
appeared in the last 25 years. Of thcse. two, one by Saunders2lS,and the other by
Zollinger', were published prior to 1965. More rcccntly, Overberger and colleagues?,
have discussed organic compounds \vith nitrogen-nitrogen bonds and have included
a section on diazoniuni salts. A chapter on carbonium ion formation from diazonium
ions, ivritten by Friedmanz1O, is contained in the series on carbonium ions by Olah
and Schleyer.
The reactivity and stability of arencdiazonium ions have been reviewcd recently
by Zollinger220,and the diazotization of heterocyclic primary aniincs has been
discussed by Butler?21. Porai-Koshits' summarized the current state of the problem
of the structure and reactivity of aromatic diazo compounds.
Most textbooks refer to diazoniuin salts as ionic compounds in which the diazo
group is bonded to an aromatic residue, so that the diazonium ion is the appropriate
cation. I t was originally belicvcd' that aliphatic diazoniuin salts are incapable o f
existence. There are, however, evidences that stable non-aromatic diazoniuni salts
can be prepared?" and olefin diazoniurn compounds are also r e p ~ r t e d ~ ' ~ .
For the purposcs of the present discussion we will consider that any cation of the
form RN; may be properly considcrcd as a diazonium ion. Consequently, the ion
N.;H:, discussed previously in section III.C, qualifies as the simplest diazonium ion.
Ho\vever most of the siibseqiicnt discussion will be concerned with benzcne-
diazonium salts, and cation and monosubstituted forms, since most of the theoretical
work has dealt with thcse conipounds.
B. Crystal Structure and Spectroscopic D a t a

What appcars to be the first crystal structurc information on diazoniuni salts was
reported in a preliminary short note by Ramming i n 1959'?'. This was followed by
more-conipletc data in I963"j . A single crystal of benzenediazonium chloride
(CGH5N2CI)was examined by X-ray methods. The crystals are orthorhombic, space
group C222, with u n i t cell dirnensions: n = 15.152 A ; /I = 4.928 A ; c = 9,044 A.
The shortest C1- to N distance is 3.325 A. Thc space group requires the
N,,,-N,,,-C,,,...C,,, atoms to be situated o n a ttvo-fold axis of symmetry so the
distances between these atoms could be found from one projection normal to this
axis. Planes containing chloride ions bisect the N-N bond o f the diazoniurn ions,
and every (N=N-)>. group is surrounded by four chloride ions i n a planar arrange-
ment normal to the N-N axis, two of then1 are at a distance of 3.184 A and two at
a distance of 3.51 1 A from this axis. The distances from the formcr chloride ions,
the connecting line of which runs nearly normal to the planc o f the benzcnc ring, to
the N,,, and N , , , are 3.225 A and 3.237 A, respectively, \\here N , , , rcfers to the
nitrogen atom attached to C , , , .T h e corresponding distances from the other set of
chloride ions to the N,,, and N,,, atoms arc 3.545 8, and 3.559 A. The latter chloride
atoms arc approximately i n thc plnnc of the benzcnc ring and arc scparatcd from
the H,?, atoms by only 2.5 A. As Romming points out, this is half a n ingstroni less
than the suni of the van der Waiils radii, so that a strong interaction is presumed to
exist bctwcen thesc atoms.
Classical valence concepts suggest that the N , , , atom is equivalent to rhc nitrogen
atom of an ammonium ion and should carry the positive charge. In the structurc
studied by Romniing, thc distances from the N,,, atom to thc chloride ions arc nearly
equal to, but slightly smallcr than, those from the N ( , ) atom to the chloride ions.
1. General and theoretical aspects of thc diazoniuni and diazo groups 59
Further, in the case of benzenediazonium chloride, i t niight be expected that some
shift of electron density from Nor !o N c I ,might occur. If the shift is substantial
enough, the two nitrogen atonis niight then share the positive charge, thereby
resulting in the approximately equal separations of the two nitrogen atonis from a
chloride ion.
Table 41 summarizes the internuclear distances and angles found by Kamniing for
the benzenediazoniuni ion. The N N bond length is approximately that found for
gaseous nitrogen. The N ( l l - C ( I ) bond is O.OS5 A shorter than the aliphatic N-C
bond. The carbon-carbon bonds are all found to be shorter than those in benzene
(1.397 A). T h e perturbation of the C C C angles is not unexpected as a consequence
of the inductive effect of the N: group. Interestingly, however, the distortion in the
diazoniurn case is more substantial than that found with benzonitrile2"G.thereby
demonstrating the stronger inductive efT'ect of t h e N: g r o u p when compared with the
nitrile group. Of course, i t is well to note that the bcnzonitrile data to which reference
is made were measured in the gas phase.
41. Internuclear scparations and angles in the benzencdiazoniirni

TABLE
ion??.'
Bond Lcngth (A) Bond Anglc (degrces)
A t about the same time, Andresen and R ~ n i r n i n greported

~~~ on tlie crystal
structure of benzenediazoniuni tribroniide. The compound crystallizes in the
monoclinic system with space group C2/c. The tribromide ions are situated i n
centres of symmetry and the benzcnediazoniurn ions on two-fold axes. The Br-Rr
bond Icngrli is 2.543 .A, ar?d the N-I\ and N-C bond lengths in the dinzonium ion
a r e 1 . 1 1 and 1.41 A, respcctively, the latter two agreeing reasonably well with the
results found for the chloride. The tribromide ion is centrosymmetric. The bromine-
benzene plane separation is 3.68 A which is approximatcly 0.10 8, less than thc s u m
of the van der Waals radius for bromine and the half-thickness of the benzene
molecule. The shortest distance between a central bromine and a nitrogen atoin is
4.34 A . However, the shortest distance from any broniinc atom to any nitrogen atom
is 3.31 A, where the nitrogcn atom is N(?,, that is, an outer nitrogen, and the
particular Br here is bclievrd to carry the negativc charge. This suggests that N,,,
carries a substantial positive charge, again i n agreement with Roniining's conclusions
for benzcnediazoniiim chloride.
Ksmming and Waerstad?2Risolatcd [lie crystalline, orangr-red complex of a
diazoniuni sait and cuprous halide obtained from ;1 Sandmeycr reaction at low
temperature and in concentrated sollition, and found i t to consist of normal
benzenediazoniuni ions and (Cu, Br;) ions. Each of the 'inner' nitrogen atollis, N,,,,
is surrounded by four broniini atoms lying in a plane approximately. pcrpendicular
to the C-N-N direction with a nitrogcn to bromine distance of 3.65 A .
Although cxtcnsion of the prescnt discussion to so-called doublc dia7oniiini salts
(Ar N,X* MXn) may lic outside the intended scope of this chapter. sonic mcntion
of these compounds should be madc for tlie sakc of complcteness. Porai-Koshits
a n d coworkers have published the structure of thc double salt of ferric
60 J. B. Moffat
chloride and o-methoxybenzenediazonium chloride229 and of p-N,N-dimethyl-
aminobenzcnediazonium c h l o r o ~ i n c a t e ~In~ ~the
. former case t h e ionic structure
[o-CH30CGHIN,]+.[FeCI,]- was shown to apply a n d it was suggested that the
positive charge lies primarily on the terminal nitrogen atom, N l n , .The length of the
C(ll-N(ll bond was measured as 1.48 A, substantially larger than that found by
Rermming for the chloridezz5or the bromidezz7.Howevcr the NIII-Nln) length of
1 - 1 1 8, was in agreement with the earlier values. T h e average distance between
chloride ion and nitrogen atom was found to be 3.36 and 3.53 A, for N l t 1and
respectively, again suggesting a concentration of positive charge o n the terminal
nitrogen atom, N(,,.
In the case of p-N,N-dimethylaminobenzenediazonium c h l o r o ~ i n c a t e ~the ~~,
structure was found to consist of planar cations [(CH,),NC,H,N,l+ and tetrahedral
[ZnCl,l2- anions. In this case no evidence was found for the shortening of the
Co)-C13, or CIsI-C(B)bonds in the benzene ring, although the c[G)-c[II-c[?)
angle is reported as 130". Again, although a division of electron density was not
possible, the results were interpreted as suggesting that NI2,posscsses a positive
charge.
C. Theoretical Studies
What appears to be the first calculations done on any diazonium ion wcre reported
by Schuster and P o l a n ~ k y in ? ~1965.
~ n-Bond orders and electron densities as calcu-
lated by the Huckel method were given for a number of diazonium ions including
that of methyl and phenyl. In a l l cases for RN:, the nitrogen atom adjacent to the R
group had a calculated z density of approximately + 0.8 to + 0.9 while that on the
neighboilring nitrogen atom was approximately + 0.1 to +0.2. Klasinc and
S c h u l t e - F r ~ h l i n d eperformed
~~~ the same type of calculation on a variety of
substituted phenyldiazonium ions and established correlations between the rate
constants for thermal decomposition of the diazonium ions and thc C-N bond
orders, and a quantity labelled ( A H ) , which is related to the difference betwcen the
x-electron energies of the diazonium and corresponding carboniurn ion.
Russian were also among the first to calculate properties of
diazoniurn ions using Hiickel theory. Correlations between absorption energies and
t h e differences in energies between the highest occupied and the lowest unoccupied
orbitals wcre developed.
Evleth and measured the visible-ultraviolet absorption spectra of benzcne-
diazonium, 2-, 3-, 4-methoxybenzcncdiazoniurn, 2,4-, 2 5 , 2,6-, 3,4-dimethoxy-
benzenediazonium. and 2,3,5-, 2,4,5-, 2,4,6-, 3,4,5-trinicthoxybenzenediazonium
cation in the 200-450 nm region. Hiickel theory was employed to calculate transition
energies which correlated well with those measured experimentally. The so-called
Coulomb and resonancc parameters wcre adjusted to proLide the bcst fit with the
first two electronic transitions in t h e benzencdiazoniuni cation. ;;-Electron densities
of 1.34 and 0.71 were calculated for the adjacent and terminal nitrogen atoms ot'
this cation.
The results of experiments and calculations on the electronic absorption spectra
of the benzencdiazonium cation and its p - and it~-substitutedforms werc reported by
Sukigarn and K i k u ~ h i ? The ~ ~ . ncar-ultraviolct absorption spectrum of bcnzene-
diazonium fluoroboratc in cthanc! solution produced two peaks at wavclengths 259
and 395 nm, and molar extinction coefficicnts 5640 a n d 1160, respcctivcly, \vhilc i n
q u c o u s solution the peaks appear at 263 and 298 nm. From their observed
fluorescence cniission and cxcitation spectra, thesc authors concludcd that the
radiative transition occurs from the same excited state, when the system was excited
1. General and theoretical aspects of the dia7oniiini and diazo groups 61
to the lowest excited singlet state. No emission was observed Lvlicn the diazonium
salt was excited by 259 nm light. T h e phosphorcscence emission spectrum (77 K )
was observed only when the diazonium salt solution was excited by a 295 nm light.
On the other hand, an e.s.r. signal (77 K, methanol solution) was obtained only when
the diazoniurn salt was irradiated by a 259 n m light. T h e observed c.s.r. spectrum
resembled that obtained for the phenyl o-radical.
Sukigara and Kikuchi23Gused the earlier X-ray structural d a t a of
in their Pariser and P a r P ' calculations on the benzenediazonium cations. Values
of -2-39 and -2.42 CV were taken for / 3 ~ ac n d /3m, respectively, where
/3m and w (the T;, clcctron density on t h e nitrogen atom attached to the carbon
atom and x is the direction in t h e plane of the ring and perpendicular to the N N
axis) were taken as adjustable parameters whose best values were -3.10 eV and
1-05, respectively. Sukigara and Kikuchi ascribe the 295 nm and 259 nm absorption
bands to the 'A1-lBI and 'A,-'A, transitions respectively, the calculated transition
energies (experimental in brackets) being 4.1 8 (4.20) and 4.75 (4.79) cV, respectively.
They also deduce from thcir results that the nitrogen atom adjacent to the ring
bears almost all of the positive cl?srge of the benzenediazoniurn cation and that the
N N bond order is apprcximately ::wee.
Sukigara and Kikuchi conclude that two processes occur from the excited IB,
state, namely, radiative transition to the ground state and intersystem crossing to a
phosphorescent state. N o detectable photochemical decomposition occurs after the
lA1-lB1 transition. Since neither fluorescence nor phosphorescencc was detected
after the IA,-lA, transition, n o radiative process occurs from the excited 'Al state
and no internal conversion or intcrsystem crossing to a radiative state occurs.
From this excited state t h e molecule presumably decomposes rapidly to givc phenyl
c-radical.
In their second paper, Sukigara and K i k u ~ h i ?measured
~~ the visible and near-
ultraviolet absorption spectra of p-fluoro, p-chloro, p-bromo-, p-iodo, p-methoxy
and p-dimethylamino-benzenediazoniumcations and applicd the P P method in their
calculations. Table 42 summarizes their cxpcriniental results.
TAULE 42. Observed peak wnvclengths and
molar extinction coeficicnts for pam-substi-
:utcd benzenediazoniiirn cations (aqueous
solution)236.Rcproduced by pcrniission of the
Chemical Socicty of Japan
Substituent Amas (nn1) log cm:is

___--
F 267 4.229
CI 28 1 4.195
Br 293 4, I 78
I 327.5 4.036
OCHR 315 4.283
N(CH,)a 350 4.118
In their P P calculations 011 the p-substituted cations, Sukigara and Kikuchi use
the electron affinity of the electron-acceptii1g group -C,;lI,hT~ anti the core
resonance integrals, &s, where X = F, CI, Br, 1, 0 or N , a s adjustable parameters.
These authors conclude that thc strong absorption i n the visible and near-
ultraviolet regions can be assigned to the lA,-'A, transition, and that the weak
62 J. B. Motrat
absorptions of the 'A1-'B, transition are hidden in t h e largc absorption bands of
the 'A1-'A, transition. T h e calculations also show the large stabilizing eKect that a n
electron-donating group at the para position exerts on the lowest excited 'Al
electronic state. Evidence is also presented to support the contention that the strong
absorption bands of thc p-iodo-, p-mcthoxy- and p-dimcthylamino-benzene-
diazoniuni cations have the character of intramolecular charge-transfer bands,
while the strong bands of the p-fluoro-, p-chloro- and p-brorno-benzenediazonium
cations are associated with local excitation within the benzenediazoniuni franie-
work.
In addition, i t was shown that the vibrational frequency of the N N group
increased linearly with the N-N bond order. Further the N-N bond order
decreases and the contribution of charge transfer to the ground statc increases with
an increase in the electron-donating capability of the substitilent group. This
suggests that the contribution of a resonance structure
*O&
becomes larger in the ground state a s the electron-donating capability of thc para
substituent increases. This had previously been predicted by Zollingerl.
F-inally, Sukigara and Kikuchi examined the electronic structures and electronic
absorption spectra of m-fluoro-, m-chloro-, m-bromo- and twinet hoxy-benzene-
diazoniurn cations. A summary of their cxperimcntal rcsults is given in Table 43.
TAULE 4 3 . The obscrved peak wavelengths and

molar extinction coefficients for uir/o-substitutcd
benzencdiazoniiim cations?". Rcproduced by
pern~issionof thc Chemical Society of Japan
Siibst i t i x n t )0113s (nm) 10s f!ll3\

F 262 4.160
305 3.457
CI 266 4.000
317 3.299
Br 268.5 3.625
323 7.972
OCH,, 273.5 3.982
34s 3.475
Treiger and coworkers238also applied the PP method to the benzencdiazonium

was taken as an adjustable parameter whosc best valuc \vas found
cation. Again f l s ~
to be -4.50 eV. T h e nitrogen atom adjacent to the carbon atom w a s calculated to
posscss a charge of + O . S S , while that on thc rcmaining nitrogen atom \\'as -t 0.27
in semi-quantitative agreement \vith the rcsults of Huckcl c;llciilations'~J:'.l h e s c
authors notc that, i n the transition to the cxcitcd state with an cncrgy of 4.04 eV
(A, -* B1), clectron density is transferred from the orflio and the Iiic*/cc positions of
the benzcnc ring to the diazoniuni group, resulting i n a decrease in bond order of
the N-N bond and the positive chargc on thc dinzonium group, while in the case
of the transition with an energy of 4.77 CV ( A , . > A,) [tic transfer occurs from the
p m n position of the benzene ring.
I . General and theoretical aspects of the diazonium and diazo groups 63
Treiger and Baga12::9applied the Pariser-Parr i i i c t l ~ o dto~a~ series
~ of substituted
benzencdiazonium cations in their ground and lowest excited states. As i n the work
of Sukigara and Kikuchi'JC, values of adjustable parameters were obtained by
fitting to experimental data for the bcnzcnediazoniuni cation. A linear correlation
was established betwcen the frequcncics (2250-2305 cm-l) of the strctching
vibrations of the N-N bonds and the calculated values of the z-electronic orders
of these bonds for the various substituted benzencdiazonium ions. However, the
largest deviation from this linear correlation was displayed by those molecules
containing elcctron-donating substituents in the orrho and p n m positions, particularly
in thc. case of the niethoxy group. The authors suggest that the method of calculation
employed is unsuitable when the resonar,ce struc!ure contributes substantially to
char gc t ran sfcr .
Treiger and B a g a P 9 also calculated values for some of the electronic transitions
and found reasonably good agreement ( k 0.04eV) with the expcriniental values in
most cases. These authors conclude that the absorption due to charge transfer in
the para derivatives proceeds from the 4.71 eV band of the unsubs!ituted compound,
while for the r m / n and orrho derivatives i t can be referred to the 4-18cV band.
Quite recently240low- and high-energy photoelectron spectroscopy and ab itiifio
molecular orbital calculations have been applied to diazocyclopentadiene (CSH,Nz).
I t appears that this is the first report either of such experiments or of such
calculations on any diazo compound of the form R N N where R is larger than CH2.
Single determinant, all-electron, SCFMO calculations employing a basis of gaiissian
functions fitted to three Slater-type orbitals were perfornied on diazocyclopentadiene
and its singly ionized states. Bond lengths of 1.130,1.340,1.431 and 1.104 8, were
taken for N-N, C-N, C-C and C-H, respectively.
Table 44 summarizes the calculated charge distributions of diazocyclopentadiene
where C,,, is attnchcd to N,]). T h e diazo group in this molecule is essentially neutral.
However, the nitrogen atom attached to the carbon a t o m of the ring shows a net
increase in its ;i population compared to t h a t of the nitrogen atom in the nitrogen
molecule. This increase is balanced by a decrease in 2s and 2po density from that
found in No. The four remaining carbon atoms not attached to nitiogen each have
approximately the sanie negativc charge which is approxiniately balanced by the
positivc charge on the attached hydrogen atom. The carbon atom, C , , , , attached to
nitrogen, has a sinall net positive charge, a n d more ;i but less G density than the
TAULE 44. Calculated charge distribution of diazocyclopentadiene240.Reproduced, with

permission, from Aarons and coworkers, J . Chon. Soc., Furaduy Tratrs. 11, 6 , 1106 (1974).
NU) No, G I , CO) c,,, H(2, H(3) N (in N?)
IS 1.995 1.997 1.993 1.994 1.994 0.710 0.714 1.997
2s 1.48 I I.SIS 1.161 1.287 1.299 1.766
2I)G 1,093 1.139 1.547 1.909 1.966 1.236
2p;i 1.192 1.261 1.255 1.093 1.053 2.000
( I ,289)" (0.740)
Atomic
charge -005 0.05 0.05 -0.28 -0.31 0.19 0.29 0
x-bond overlap populations
N,I)--N,2) c , l ) - N , l ) C(I,--COl co,-c,:,, c,,,-c,,, N-N (in N,)
0.32 0.2 1 0.13 0.40 0.18 O.5Ob
Valucs in brackets are for the nitrogen 2p orbital in thc molecular plane and are not
included in the ::ovcrlap populations.
* For onc ;;orbital only.
64 J. 13. Moffat
other four carbon atonis. The N-N x-bond overlap population is much smaller in
this diazo molecule than in N,, and the authors interpret the C-C T;-bond overlap
populations as suggesting that a dicnc-type structure may be more appropriate than
a delocalizcd one. Finally they regard the bonding as resulting from a n initial
c -> xlI electron promotion in N2 followed by x bonding with the fivc-membered
cyclopentadienylidene ring.
Some calculations have been performed in this laboratory2J', using the Gaussian
70 p r ~ g r a m n i ewith~ ~ a n STO-3G basis, to obtain more information on the
diazonium cation. The calculations were done on the benzenediazonium cation
and on the same cation with a fluorine substituted at the ot-rho, rnefa or para
positions of the ring. R ~ m i i i i n g ' s ?geometry
~~ was employed in all cases. The
energy decreased as the fluorine was removed from the orrho t o the mefa to the
para position, although as total decrease was only 3 kcal/mol this may not be
significant, given the approximate nature of the calculations. What is more interesting,
however, is the observation that the charge o n the nitrogen atom N,,, attached to
the carbon atom is +0.09, while that on the remaining nitrogen atom, N12,,is
+0.25. The carbon atom C,,, itself carries a charge of +0.10. N o significant change
i n this distribution of charge is observed *;;hen fluorine is attached at any one of the
o r f b , t w ! a 3r para positions. In addition, the calculations show that the c electrons
yield contributions to the total charges of N t l l and NC2)of f-0.43 and +0.10,
+
respectively while the x electrons produce - 0.34 and 0.18, respectively, suggesting
that N I 1 ,has a deficiency of c electrons but a surplus of ;i electrons. Hence in all
cases greater than 50% of the positive charge is distributed around the benzene
ring, most of i t rcsiding on the hydrogen atoms.
For comparison purposes similar calculations were performed on several diazo
compounds, some of which may be hypothetical in the sense that they have not yet
been synthesized. Atomic charges obtained are as follows:
"11 N(2, G I ,
Difluorodiazomethane -0.15 0.00 + 0.36
Fluorodiazomethane - 0.10 - 0.01 +0.13
Diazoacet oni trile -0.02 +G.O4 - 0.02
In these cases the charge on the nitrogen atom N,,,
attached to the carbon atom
is much more dependent on the groups attached to the carbon atom.
V. A C K N O W L E D G E M E N T
The financial support of the National Research Council of Canada is gratefully
acknowledged.
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222. H. Reinilingcr, Atrgew. Cherir. 1/11. E d . , 2, 482 (1963); K . 13011, Arrgeiv. Cherrr. / I / [ . Ed.,
3, 804 (1964); K. Bolt, Arrgew. Clrorr. f i r / . € d . , i 3 , 821 (1971).
223. K. Bolt, Chern. Ber., 108, 402 (1975).
224. Chr. Rsrnming, Ac/u Chern. Scarrd., 13, 1260 (1959).
225. Chr. Romming, Acra Cherii. Scurrd., 17, 1444 (1963).
226. B. Bak, D. Christensen, W. B. Dixon, L. 1H:inscn-Nygaard and J. Rastrup-Andcrscn,
J . Clrerri. Phys., 37, 2027 (1962).
227. 0. Andresen and Chr. Rmnming. Acla Cherrr. Scarrd., 16, 1882 (1962).
228. Chr. Rsmming and K. Waerstad, Chcrrr. Cotrrriir~.,299 (1965).
229. T. N. Polynova, N. G. Bokii and M. A. Porai-Koshits, Zh. S~rirkr.Khirr~.,6, 878 (1965).
230. Ya. M. Nesterova and M. A. Porai-Koshits, Z/r. Stritkt. Khirri., 12, 108 (1971).
231. F. Schuster and 0. E. Polansky, Morra/slr., 96, 396 (1965).
232. L. Klasinc and D. Schulte-Frohlinde, Z . Physik. Cherrr. A’crie Folge, 60, 1 ( 1 968).
233. D. A. Bochvar, N. P. Gnnibaryan, V. V. Mishchcnko and L. A. Kazitsyna, Dokl.
Akad. Narrk SSSR, 175, 829 (1967).
234. L. A. Kazitsyna, N. B. Dzegilenko, A . V. Upaldysheva, V. V. Mishchenko and
0. A. Reutov, Izv. Akad. Nuitk S.S.S.R., Ser. Khirn., 1925 (1967).
235. E. M. Evleth and R. J. Cox, J . Phys. Clierrr., 71, 4082 (1967).
236. M. Sukigara and S. Kikuchi, Bull. C/rorr. SOC. Japaii, 40, 461, 1077, 1082 (1967).
237. R. Pariser and R. G . Parr, J . Clrerri. Plry.~.,21, 466 (1953).
238. V. M. Treiger, I. L. Bagal and B. A. Porai-Koshits, Zh. erg. Klrirn., 6, 2535 (1970).
239. V. M . Treiger and I. L. 62gaI. Z/r. Org. Khirri., 10, 2494 (1974).
240. L. J. Aarons, J. A. Connor, I. H. Hillier, M. Schwarz and D. R. Lloyd, J . Chenr.Soc.
Furaday Trarrs. I / , 6, 1106 (1974).
241. J. B. Moflat (lo be published).
CHAPTER 2
Diazonium-d iazo eq u iI ibri um

VOJESLAV STERBA
Organic Clieniistry Depnrttiictit, Itlsiitlrie of Cheinicnl Teclrnology,
532 I0 Pcliditbice, Czechoslooakiu
I. INTRODUCTION. 71
11. D I A Z O N I U M - D I A Z O EQUILIURIUM DIAZOCOhiPOUNDS .
OF ALIPHATIC 72
111. ARENEDIAZONIUM ION+DIAZOI~YDROXIDE+DIAZOTATE
EQUILIURIA. . 72
A. Development of Ideas Regarding the Reaction A r N + + O H - . 73
B. EKect of Benzene Ring Substitucnts on thc Diazonium Ion+-?syu-Diazotate
Equilibrium . 74
C . Kinetics a n d Mechanism of the Rcactions: Diazonium Ion+.~yu-Diazo-
hydroxide~~).n-Diazotate . 76
D. Kinetics and Mechanism of syn-mri Isomerizations . 79
E. Some Conclusions from the Results on syti-anti Isomcrization . 83
Iv. DIAZONIUM-DIAZO EQUILIURIA OF HETEROCYCLIC DIAZONIUMIONS . 84
v. REACTIONS OF DIAZONIUM I O N S W I T H OTHER NUCLEOPHILES. 86
A. Arenediazocthcrs 86
B. Arenediazoaniino Compounds (Triazcnes) . 87
C . Areiiediazosulphonates . 89
D. Arenediazosulphoncs . . S9
E. Arenediazothioethers . . 90
F. Arcnediazocyanides . 91
VI. REFERENCES. 92
1. INTRODUCTION
Diazonium ions RNf (R = substituted arcne, alkcne, hetcrocyclic c o n i p o u d , alkane,
etc.) a r e strong Lewis acids. They form covalent bonds with a number of bases with
formation of diazo compounds, c.g. benzenediazonium ion with OH- gives benzene-
diazohydroside C,H,N=NOH. Diazo c o m p o u n d s differ from azo compounds, such
a s azornethane C H , N = N C H , , in that the base is bound to nitrogen by a n a t o m
other t h a n carbon (diazocyanides, A r N = N C N , a r c a n cxccption). In principle therc
is of c o u r s e n o diffcrencc between t h e diazo conipound, for example a diazohydroside
o r a diazocyanide, a n d the a z o compounds, such a s azobcnzcne'.
T h c diazoniuni ions which havc a hydrogen a t o m at the cu-carbon (or an acidic
hydrogen at s o m e other position, see Section IV) may also react with bascs a s
Broinsted acids, yiclding diazo compounds, e.g.
+ -
C,H,O,CCH,N: +B 7C,H,O,CCH=N=N+BH+ (1 1
T h e present c h a p t c r discusses t h c kinetics a n d mechanism of reversible formation

of d i a z o c o m p o u n d s from diazoniuni ions a n d nucleophilcs. The main emphasis is
on t h e reaction of arenediazoniuin ions Lvith hydrosidc ions.
71
72 Vojeslav Sterba
II. DIAZONIUM-DIAZO EQUILIBRIUM O F ALIPHATIC
D I A Z O COMPOUNDS
The equilibrium system diazoalkane + alkanediazonium ion + alkanediazotate
(equation 2) cannot be studicd, because alkanediazonium ions are not stable and
usually decompose2 imniediatcly with formation of nitrogen and compounds
derived from the cation R C H f :
RCH,N:+OH- 7RCH,N=NOH RCH,N=NO-+H+ (2)
RCH =N,
Existence of the diazonium ion can be infcrred, in some cases, from the structure of
products and the presumed reaction mcchanism. When R is strongly electron with-
--
drawing, a diazo compound is formed on nitrosation of the amine under suitable
conditions?.n:
noxo -011-
C,H,O,CCH,NH, ----+ C,H,O,CCH,N=NOH
-n +
C2H,02CCH2N: C2H,02CCH=N2 (3)
In strongly basic media, the primary alkanediazotatcs RCH,N,O- are transformed
into a mixture of diazoalkane and the products derived from RCHZ (Reference 4).
Obviously the diazoalkane is formed by action of base on RCH,N: which is present
in a very slight amount, according to the equilibrium shown in equation (2).
The instability of alkanediazonium ions is further demonstrated by acid-catalysed
decomposition of diazoalkanes. The decomposition of diazodiphenylmethane is a
general acid-catalysed rcaction5, which means that the decomposition of the dia-
zonium ion is faster than the splitting off of the proton.
I1 + x-
(C6H5)2CN2 (C6HJ2CHN: (C,HJ2CHX+N2 (4)
Some substituted alkenediazoniiini ions can exist in thc form of salts with anions
of strong acids as SbF, (Reference 6) for example. The increased stability is d u e to
rcsonance of the diazonium group with p a n d n electrons. Nucleophiles rcact with
the activated double bond which results either in substitution (if halogens are present
-
instead of RO), or in addition of H 2 0 or R O H giving an alkanediazonium ion which
-
is immediately decomposed6.
+
Ro\c=c / H Ro\+ /
H
Ro\ /
H
\
c-c /c-c
FiO/ \
Nt RO/ \N, RO N2
111. ARENEDIAZONIUM I O N + DIAZOHYDROXIDE =:

D IAZ OTATE E Q UILI BRIA
I n contrast to alkancdiazonium ions, arenediazonium ions are usually quite stable
in aqueous solutions in the form of salts with anions of strong acids. This stability is
duc to rcsonaiicc intcraction of thc diazonium group with ring T; electrons (and
elcctrons of substitucnts in certain cases) a n d to the fact that t h e bond between
nitrogen and a sp'-hybridized C atom is stronger t h a n that with the sp3-hybridized C
atom.
2. Diazoniuni-diazo equilibrium 73
Substituted arenediazonium ions can react with nucleophiles in three ways' which
are schematically represented below for the reaction of 4-hitrobenzenediazonium ion
with hydroxyl ion (the first reaction proceeds by the SNI mechanism, and the water
molecule is the real nucleophiles). The first and second reactions are practically
irreversible, the third o n e is reversible and much faster except for diazonium ions
having strongly activated rings such as 2,4-dinitrobenzenediaz0nium iong or 1,4-
+ +
benezenetetrazonium ionlo, N2CGH4N2, for which the rates of the second and third
reactions are comparable.
A. Development of Ideas Regarding the Reactions ArN: -k OH-

I n IS58 Griess described the preparation of a diazonium salt by action of nitrous
gases on picramidel'. When studying the reactions of further similarly prepared
diazonium salts he found" that benzenediazonium salt is transformed by action of
potassium hydroxide into a crystalline potassium salt, the reaction being reversible.
Development of azo chemistry and its application in thc dyestuff industry was
influenced in a n important way by investigations of Schraube and Schmidt13 pub-
lished in 1594. The sodium salt prepared by action of sodium hydroxide on p-nitro-
benzenediazonium compounds did not couple with aromatic hydroxy compounds,
and on acidification it slowly gave the original diazonium salt. Similarly, while the
potassium salt prepared from benzenediazonium salt coupled readily with alkaline
2-naphtholate, it rearranged on heating for several hours with concentrated potas-
sium hydroxide into a stable, non-coupling isomer. Since the sodium salt prepared
from the 4-nitrobenzenediazonium salt gave 4-nitro-N-methylnitrosan1inc by
reaction with methyl iodide, the authors13 presumed that the isomers not capable of
coupling were salts of derivatives of nitrosamine, and that the reactive isomcr was a
diazotate. Hantzsch, who studied the stereochemistry of aromatic oximes several
years earlier, came to the conclusion that on the basis of analogy between both types
of compounds the matter was stereoisomerism in this case, too''. Is. Hc ascribed the
syn structure to the reactive form and the nnri structure to the Eon-reacting one.
74 Vojcslav Strrba
The existence of two stereoisoniers was proved later in the case of the structurally
similar azobenzenelG.l7 and substituted benzenediazocyanides'Y. 1 9 ; thc i.r. spectra
of substituted syn- and m/i-benzenediazotates were also intcrpreted?O on the basis of
t he structures suggested by Hantzsch.
Ar 0- Ar
\ / \
N=N N=N
\
0-
Syli anti
Two equivalents of hydroxyl ions are consumed in tlie transformation of a dia-
zoniuni ion into the respective diazotate. Hnntzsch follo\ved this reaction con-
ductonietrically?', and assumed that the reaction proceeds in two separate steps, as
with other dibasic acids, and he even described thc isolation of the presumed diazo-
hydroxide and the measurement of its dissociation constant.
Wittwer and Zollinger22measured the diazoniiim ;r diazotatc equilibrium with
threc substituted benzenediazoniuni salts and found that the neutralizatim curve
showed but one step, even though two equivalcnts of base were consumcd for one
equivalent of diazonium ion. This case was similar to that described before by
Sch\varzcnbacli23. The diazonium ion reacts with the hydroxyl ion as a Lewis acid.
The equilibrium constant K , of this rcaction is smaller than thc equilibrium constant
X2 of the rcaction of the formed diazoliydroxide (ivhich is a Bronsted acid)
with a further OH- ion. Therefore, the diazohydroxide is transformed quickly into
the diazotate ion, so that the concentration of thc former is slight throughout the
measurement. This result was confirmed also by spcctral dctcrniination of the
diazoniiim ion s diazotate equilibrium i n a series of substituted bcnzencdiazoniurn
ions?'. Only the absorption bands corrcsponding to the starting diazoniuni ion and
final diazotate ion wcrc found in tlie spectra. The slopes of thc dcpendence of
iog[ArN~],/[ArN,O-](calculated from the nbsorbances) o n pH had the value - 2.
This means that the diazoniiim ion reacts practically at oncc with two equivalents of
-
OH- ion, and the diazohydroxidc concentration is negligible.
ArN:+OH- ArN,OH K, (6)
ArN,OH+OH- 7ArN,O-+H,O K, (7)
6. Effect of Benzene Ring Substituents on the Diazonium / o n ..+ syn-Diazotate

Equilibrium
I n alkaline aqueous medium the following rcversiblc rcactions of diazonium ions
take place'j. 2 5 :
ArN:+OH- . k,
k-,
syn- A r N,O H K, (6)
syn-ArN,OH+OH- 7syn-ArN,O-+H,O K, (7)

k,
syn-ArN,OH ~ anti-ArN,OH K, (8)
k-8
syn-ArN,O- . k'
f - ,
anti-ArN,O- K, (9)
anti-ArN,OH+OH- 7 .
anti-ArN,O-+H,O K, (1 0)
2. Diazoni u m-d inzo cq ti il i br iu m 75
Benzenediazonium ions which have a hydroxyl group in thc oivllo or p n m position
split off the proton even in mildly acidic medium; the py2 value of 4-hydroxy-
benzenediazoniuni ion is 3.40 27. Thc diazo compounds formed are only slightly
reactive and do not form diazotates evcn i n a strongly alkaline medium.
Besides these reactions, irreversiblc substitutions of the nitrogen or substituents in

the orrho or para positions by O H - group (equation 5) and decomposition rcactions
of diazohydroxides (leading to formation of hydroxy compounds and othcr, often
polymeric, substances) may be significant. These side-reactions make determination
of equilibrium constants difficult. For example, ,n-nitrobcnzenediazoliydroside
decomposes so rapidly that at a pH of about 9 (the region of its maximum concentra-
tion) practically all the diazonium salt is transformed into the dccomposition products
within less than a minute.
With most substituted benzenediazoniuni ions the rate of syn-on/i isonierization
is many orders of magnitude slower than that of the reaction of the diazoriium ion
with OH-, SO that i t does not interfere with the determination of tlie ArN: + syn-
A r N 2 0 - equilibrium. Diazoniuni ions which have strong - M type substituents (e.g.
nitro groups) in ortlio or para positions form an exception.
The transformation of diazoniuni ions into syn-diazotates can also bc expressed
by the following equations:
7
-
ArN:+H,O syn-ArN,OH+H+ K,, (12)
syn-ArN,OH syn-ArN,O-+H+ K,, (1 3)

Equilibrium constants of t h e overall reaction of the cases described by equations
(6)+(7) and (12)+(13) respectively arc given by the relations:
K = K,.K, = [ArN,O-]/[ArN:] [OH-]’ (1 4)
KA = KA~.K,, = [ArN,O-] [H+]’/[ArN,+] = K.K:, (15)
where K,v = [H+] [OH-].

As the determination of a n equilibrium does not dcpend on the path by which i t
has been reached, both methods are correct. I n fact practically all arenediazoniuin
ions are transformed into diazohydroxidcs by reaction with liydrosyl ions. The
reaction of diazoniuni ion with water in alkaline medium is slower by n a n y orders
of magnitudc. Also diazohydroxide rcacts far quicker with hydroxyl ion than with
water in tlie p H region used for measurements of equilibrium constants of this
reaction (except perhaps for the most reactive diazonium ions). On the contrary, the
use of equations such as (13) and (14) is more usual and more convenient for acid-
basc equilibria; on introducing logarithms into eqiiation (15) w c get the relation:
This means that @rC,, +pK.\\,)/? equals thc p1-i of the niediuni i n \vhich [ A r N i ] =
[ArN,O-] (as in t h e case of pK., of tlie Bronstcd acids). This p H was cnllcd pH,,, by
Lc\\ is and Suhr?’ (Table 1).
The ratio [ArN:]/[ArN,O-] changes a hundrcd times on changing pH by unity,
hence at pH = (pH,,,+ 1) the rcaction mixtiire contains 1% diazonium ion and 99%
diazotate ion. Concentration of diazohydroxide is negligibly low (except for very
76 VojcsIav Sterba
reactive diazonium salts) in the whole pH range, being maximum at pH = pH,.
The equilibrium constants K depend on ionic strength and thcy increase about ten
times on changing the ionic strength from 1 M to 0.1 M ? I .
TABLE 1. Equilibrium constants K and pH, values of

the reaction XC,H,Nf + 2 OH-+XC,H,N,O-+ H,O
KO
x
K b
(12/nio12) (I'/nio12) PHm
4-NOZ 1.3 x 109 2.0 x 10'0 9.44

4-CN 2.9 x los 3.9 x 109 9.77
3-CI 4.0 x 10' 1.9 x 1 0 7 10.70
4-CI 3.s x 10' 6.7 x 10' 11.21
H 1 . 6 10'
~ 3.8 x 10' 11.90
4-CH3 6.6 x 10' 2.2 x 103 12.59
Refcrence 24: room temperature, ionic strength
1.0 M.
Reference 28: 23 "C,ionic strength 0.004-0.03M.
Dependence of log K on the Hamniett u constants is linear with the slope p = 6.3
G . 5 8 2 8 or G*6G'g. T h e p valiics found are unusually high. One of the reasons
for this is that K is a product of two equilibrium constants, so that the final value is a
sum of pl and pr characterizing the formation and dissociation2' of diazohydroxide,
respectively. Similarly i t is also possible to correlate pH,, with the u constants; in
this case the p value is negative and half that from cquation (17).
+
log ( K / K , ) = pa = log ( K , / K Y ) log ( K J K ; )
= p l a + p , u = (pl+pZ)a (1 7)
It is impossible to determine the values of K , and K 2 or of p1and p2 separately by
measuring the concentrations or the pH of the equilibrium system; sincc K , > K ,
only the overall constant K is accessible. For dctcrniination of the constants of both
reaction steps i t is necessary to determine the rates of t h e reactions considered; in
this case only t h e rcaction of diazoniuni ion with hydroxyl ion and the reverse
decomposition of diazohydroxide are suitable for nicasurement.
C. Kinetics and Mechanism of t h e Reactions: Diazonium Ion + syn-Diazo-

hydroxide + syn-Diazotate
The rate of thc reaction of diazohydroxide with hydroxyl ion (equation 7) is far
greater than that of the dccornposition of diazohydroxide into diazoniuni ion and
Iiydroxyl ion (in neutral and alkaline mcdia). Thercfore, the rate-limiting step of the
transforniation of diazoniuin ion i n t o syn-diazotate consists in the reaction of
diazonium ion \viIti hydrosyl ion (equation 6). whereas the ratc of the reverse
reaction (transformation of diazotatc into diazoniiim ion) is Iiniitcd by thc splitting
of t h e diazohydroside.
-4
v = k,[ArN:] [OH-]
c
Y = k-,[ArN,OHl (19)
At a pH coniparablc w i t h pH,,, or Iiighcr (thc conditions suitable for dcterrnination
of k , ) [ArN,OH]e[ArN,O-], and cquation (20) can be written for the rate of the
2. Diazoniuni-diazo cquilibriurn 77
revcrse reaction
c
Y = k-,[ArN,O-]/K,[OH-] = k,[ArN,O-J/K,K,[OH-I
4
The rate of formation of diazotate ion ( u ) increases linearly with concentration of
hydroxyl ion, a n d , on the contrary, the rate of the reverse reaction decreases linearly
with [OH-]. T h e observed rate constant kobs is a sum of t h e constants in both
directions (equation 21) a n d has its minimum at pH = pH,, (Figure 1, curve a)
k o b = kt[OH-l+kt/K, K,[OH-] = kt([OH-]+l/K[OH-]) (21 1
when the concentrations of diazonium and diazotatc ions are, after reaching the
equilibrium, the same. Logarithms of the rate constants measured by spectro-
photometric stopped-flow methodz8.2g correlate with u constants (equations 22, 23).
log k l = 2-61a+ 3-72 (Reference 28) (22)
log k l =: 2.06 2 a + 3.97 (Reference 29) (23)
--
3 7
FIGURE 1. The pM dependence of log kobs of the reaction 3-nitro-4-chlorobcnzcnediazoniurn

ion+syn-diazohydroxide+syn-diazotate at 20 "C.(a) Transformation of diazoniuni ion
into the diazotate; (b) transformation of diazohydroxidc (in equilibrium with diazotatc)
into diazoniurn ion.
In spite of OH- ion being a much stronger base than the anions of C-acids (aceto-
acetanilide, acetylacetone) and naphtholate ions, the rate constants found arc
generally lower than those of coupling reactions with the anions mentioned by
several orders of magnitude30. At the same time the respcctivc p value (2.06) is lower
than those of the coupling reactions (3-4), too. This fact is inconsistent with thc
rule31 (which often is not fulfilled) that the more selcctive a reagent is, the more
slowly it reacts. T h e reason is probably that the O H - ion is strongly solvated in
water, and partial desolvation must take place bcforc the N - 0 bond can be formed.
This process necessitates considerable cncrgy and is obviously thc main cause of the
relatively lower reactivity of the O H - ion. The N - 0 bond formation proceeds very
quickly, and this step is little selcctivc. Since the substitiicnts in the benzcnc nucleus
of diazonium ions have small effect on the desolvation of t h e OH- ion, the overall
influence of substitiicnts is relatively small which makes itself fclt in the low value of
the p constant. O n the contrary, thc naphtholatc ions and the anions of C-acids are
far less solvatcd, a n d the carbon ;itonis which are involved in (he reaction d o not
form any hydrogen bonds, so that the predoniinant part of the activation energy is
consumed in the coupling reaction (formation of C-N bond).
78 Vojeslav StEtrba
Under the conditions suitable for determination of k , i t is possiblc to obtain only
the complex constant k - , / K , (equation 20) for the reverse reaction. The determina-
tion of k-, (and K.J neccssitates starting with syn-diazotate and following the reaction
at lower p H values when a considerable part of the diazotate is transformed into
diazohydroxide in a rapid pre-equilibrium. The reaction proceeds practically only
i n onc direction, and kobs is defined by equation (24).
kobs = k-+/(l SKJOH-I) = k-,[H +]/(KA+[H 'I) (24)
With increasing proton concentration log ko~,s increases gradually more and more
slowly eventually becoming pH independent (Figure 1, curve b) when almost all the
diazotate has been transformed into diazohydroxide in a rapid pre-equilibri~ini~~.
In diluted hydrochloric acid /robs again increases with increasing proton concentra-
tion, and the same is true in chloroacelatc buffer for increasing concentration of
chloroacetic acid; this means that the transformation of diazohydroxide into
diazonium ion is a general acid-catalysed reaction3?; the value of the Bronstcd
coeficient is about 0.2:
k o b ~= k-1 +kn+ [H +I+k,,[HAI (25)
Logarithms of the ratc constants k-, and dissociation constants K.t2 (Table 2)
corrclate with u constants:
2. Rate and equilibrium constants of the rcaction

TABLE
arenediazonium ion + OH- . t,
k-,
% sjw-diazohydroxidc . 1C.h
. syn-diazotate+ 13.'.
at 30 "C a t ionic strength 0.25 %I
kl a k-, ArN,OI-I
Substituents (I mol-l S C C - ~ ) (sec-1) Kl P KA2 (%)
3-NOz-4-CI 7.4 x 1 0 3 1.95 x 102 3.8 x l o 3 6.90 2.05
3,5-Br2 3.6 x lo5 4.96 x 10' 7.3 x 1 0 2 7.00 0.79
3,5-CI, 3.8 x los 6.03 x lo2 6.3 x 10' 7.05 0.90
3-NOZ 4.5 x 1 0 5 5.34 x 102 10'
8 . 4 ~ 7.15 1.1 I
3.4-CIZ 1.3 x 10s 3.0 x lo3 4.5 x 10' 7.30 0.28
~~~ ~~
Reference 29.
" A t pH = pH,,.
The equations (23). (26) and (27) describe quantitatively the reaction of substituted
benzenediazonium ions ivith O H - ion and the subsequent dissociation of syn-
diazohydroxide to syri-dinzotate. From thc values K, a n d K2 i t is also possible to
calculatc the maximum conccntration of s?,/i-dinzohydroxidc (at p H = pH,,,). T h c
conccntrations are slight, in accordance with the predictions of Zollingcr"', and they
increase with increasing value of u constants, because K , increases with increasing
D value niuch fasler than K , does ( p , > p s ) . Thc constant p , of thc reaction (6) can be
calculated either from the difference of the p constants derived froin the equilibrium
constants K and K.,2 or from thc rate constan(s k , and k - l . The average valuc of p ,
is 5.4.
The reaction of diazonium ion with hydroxyl ion produces first the diazohydroxide
which then partially isonicrizes to nitrosamine ArNHNO. The proton transfer
between nitrogen and osygen (be i t inter- or intrn-molecular) rcprcsents a reaction
several orders of magnitude faster than thc splitting off of hydroxyl i o n from diazo-
hydroxide, so that the rcaction produces an equilibrium mixture of both tautolners.
The extent of this isorncrizalion is not known. T h e p constant of l o g K ~of sub-
stituted phenols33 is 2.23; tlie inserted N = N group diminishes t h e p constant by a
factor of about 0.4 so that for diazohydroxides we obtain p= I . For dissociation
constants of substituted f ~ r n i a n i l i d e s ~(which
' are strticturnlly similar to nitros-
arnines) thc cxperimental p value was 1.53. The difTcrence is relatively small, and thc
value 1.3 (equation 27) is almost in thc middle, so that, from this point of view, i t is
impossible to decide whether the compound is a diazohydroxide, a nitrosamine or
a mixture of both.
Splitting of diazohydroxides is subject to general acid catalysis, hence the reverse
1 I*
reaction of diazoniuni ion with water niust be subject to general base catalysis,
ArNf 4- H 2 0 f X- ArN;..O, I:,. ArN,OH + HX (28)
1 'X J
where X stands for H,O, RCO; or cven OH-, although in the last casc there is a
possibility that OH- reacts directly with the nitrogen atom of the diazoniuni ion.
Wittwer and Zollinger?' found that the dcpendence of l o g k on pH for the reaction
of diazotized nietanilic acid with the dianion of 2-hydroxynaphthalenc-6-sulphonic
acid at pH > I 2 is lincar with a slope of - 2. The rate-limiting step is tlie reaction of
the dianion \vith the diazonium ion which is present in a rapid pre-equilibrium with
diazotate in- \ t thc given pH, niore than 99% of !he clectrophile is present in the
r.
.. 1\120-,and concentration of ArN: depends linearly on [H+]?. I n the case
_ . ,'cry reactive diazonium ions and with thc use of sufficient conccntration of
coupling component (e.g. substituted naphthol) the coupling rate becomes greater
than the rate of reaction of diazoniuni ion with hydroxyl ion?s. The splitting off of
OH- ion from diazohydroxide is rate limiting. Thc reaction rate is directly propor-
tional to the first power of [H+]and independent of the concentration of the coupling
component (nap h t ho la te) .
D. Kinetics and Mechanism of syn-anti lsomerizations
syn-Arenediazotate ions formed by reaction of diazonium ion and hydroxyl ion
isorncrize into m/i-diazotate ions. Isomcrization of symdiazohydroxidcs, which in
alkaline solution arc present in a substantially smaller concentration, takes place to
a very small extent. New equilibria are established, e.g.
syn-ArN,OH 7anti-ArN,OH syn-ArN,O- 7anti-ArN,O-
and the acid-base equilibrium

anfi-ArN,OH - anti-ArN,O-+H+,
and hence also a new overall equilibrium
ArN: + 2 OH - 7%
anfi-ArN,O + H,O-
In t h e case of the substituted benzenediazonium ions this equilibrium is usually
established \r.ithin a fraction of a second. The syn-miti isomerization procecds
slowly (except for diazotate ions with - M type substituents in the parc~or ortho
80 Vojeslav Sterba
position), e.g. the isoiiicrization half-life of benzenediazotate ion is 38 niin at 80 "C 2 4 .
In all the cases known u p to now the rate constant k , of the reaction of diazoniuni
ion with hydroxyl ion is greater than k4 of isomerization (equation 9) at least by
several orders of magnitude, so t h a t the two reactions can be followed separately.
T h e effect of substituents on t h e isomerization rate was determined with 4- and
5-substituted 2-nitrobcnzenediazotate ions35 whose isornerizations are, due to
activation by the o-nitro group, rapid enough even at room temperature. The
respective logarithms of the constants k4 correlate with a and u- accord-
ing to equation (29)3G.syiz-2-Nitrobenzenediazotateion is the basic member of the
series.
logk4 = 2 . 1 [ ~ + 2 . 4 ( ~ - - 0 ) ] - 2 . 8 3 (29)t
I n contrast t o thc syn diazotates \vhich split off hydroxyl ion within a half-life
of several msecond o r less, the anti-diazohydroxides are much morc stable. Their
dissociation constants Kiis (equation 10 but with H20as the reagent) can be deter-
mined by usual methods, e.g. potentiometric titration of anti-diazotates with a ~ i d s ~ ~ , ~ '
o r from the p H dependence of the transformation of anli-diazotate into diazonium
ion39. 38 (Table 3).
37s
Thc other rate and equilibrium constants (Tables 3 and 4) were determined by
the reverse 37-30.. anti-diazotate was injected into a solution of acid or
TABLE 3. Rate constants of isomerization of substituted benzene-

diazotate ions (k,) and diazohydroxides ( k - J and dissociation
consunts of anti-diazohydroxides at 20 "C35
Substit ucnt k, (sec-') k-, (scc-l) PKAS
H 2 x 10-6 a ] .5x 10-2 b. c 7.29
4-NOZ 5.4 x 10-2 * 4.8 x 10-3 b 6.13
2-NO2 1.5 x 10-3 1.9 x 6.1 5
2-NOt-S-CI 1.0 x lo-' 4.0 x 5.60
2,4-diN02 20.9 5.0
~~~~ ~ ~ ~
Reference 40, 25 "C.

Reference 37, 25 "C.
Rate constant of splitting of atrfi-diazohydroxide.
4. Rate and equilibrium constants of syti-anti isornerization of
TAULE
substituted benzenediazotate ions at 20 "C 34
Substituents k, (sec-l) k - 4 (sec-*) K,
GOO
~~
4-NOz 5.4 x 10-2 a

2-N02-4-CH3 7.8 x 10-4 4.2 x 18.5
2-NOZ 1.5 x 10-3 8.3 x 18.0
2-NOZ-4-Cl 4.3 x 10-3 3.7 x 10-4 11.5
2-N02-5-C1 1.0 x 10-2 8.3 x 10-4 12.0
2-CI-4-NOZ 3 . 2 lo-'
~ 9.2 x 10-5 3 50
2,6-CIZ-4-N02 5.5 x 10-3 1.8 x 10-5 3.0
2- N 0,-4,6-C12 0.70
a Reference 40, 25 "C.
Reference 26.
Reference 35.
+ +
t The generalized equation is: log k = p [ a r(u- - o) log ko. The constants p, u and u-
have their usual meaning; thc reaction constant r has been interpreted as the ratio of
conjugation in a particular reaction series to that in the limiting cases requiring a-.
ArN:
1
SCHEME
L kHA[HA)
buffer containing a sufficient a m o u n t o f reactive coupling component. T h e diazonium

i o n thus formed reacted rapidly with t h e coupling c o m p o n e n t to form t h e rcspective
a z o c o m p o u n d , so that t h e overall reaction was p s e u d o first order. T h e reaction
course is represented in Scheme 1, a n d the dependence of log kobs on p H is given in
Figure 2 f o r benzenediazotate ion a n d its 2-nitro-4-chloro a n d 2.4-dinitro derivatives.
Anti-syn isomerization of bcnzenediazotate is very slow24,the main reaction p a t h
being t h e splitting of hydroxyl ion from anfi-diazohydroxide (Scheme 2t) ; from t h e
-1 -
-2 -
-x
-z.3 ~
-4 -
- 5 0 ; ; i ; 5
GH
6 ; 8 9 1 0 1 ' 1
2. pH-Dependence of log kobe of the conversion of unsubstituted (U), anti-2-nitro-

FIGURE
4-chloro- ( A) and anri-2,4-dinitrobcnzenediazotate( CB) into diazonium ion.
t As with syti-diazohydroxides, in this case also, two tautomeric forms arc possible:
diazohydroxide and nitrosamine. The diazohydroxide is, without doubt, the form which is
split into diazonium ion and hydroxyl ion. Neithcr from the splitting ratc nor from the
pH dependence of log k , , ~ ,is
~ it possible to determine the population of the both tautomers.
The constant kU;" is a product of the rate constant of the splitting of anfi-diazohydroxidc
and of the molar fraction of the diazohydroxide in the mixture of the two isomers. The
same is truc also of the constant k-l of the splitting of syn-diazohydroxides.
82 VojesIav Sterba
dcpcnclencc of log k " ~ on , ~ pH at pH > 6 and from ttic pH-indcpendciit rcgion thc
constanls K , , and /;?'it' (thc rate constant of splitting o f o,r/i-diazoliydr.oxide) were
dctermiiicd, respectively (Table 3). At pl3 < 3 the acid-catalyscd splitting of atiti-
diazohydroxide begins to bc significant. Logsrithnis of k:;ll of bcnzencdiazotatc ion
and its 4-mcttiy1, 4-cliloro and 3-chloro derivatives corrclatc wir ti the u constants
according to cquation (30):
log k'i"' = - 2 . 6 -
~ 1-89 (30)
The p value -2.6 is comparablc with that (-3.4) found for splitting of syn-diazo-
hydroxides3?.
J"l,
H+ + anii-~,~,~,~- ~~~;-c,H,N,oH C,H,N:
2
SCHEME
With increasing valucs of the substitucnt constant u the splitting rate of diazo-
hydrosidcs decreases and simultaneously thc isornerization rate incieases. With the
2-nitro-4-chloro derivativeas the splitting of the anti-diazohydroxide is slotver than
isornerization of thc diazotate and diazohydroxidc, and the subsequent splitting of
syn-diazohydroxide; these bcconic the main reaction paths. At the highest p H values
thc reaction proceeds according to Scheinc 3. Splitting of spz-diazohydroxide is the
anfi-ArN,O- - syn-ArN,O- ~
SCHLXIE
3
+rr +
.L syn-ArN,OH
1; -,
+ ArN:
rate-limiting step, and thc dependence log /cobs us pH has a slope of - 1 (Figure 2)
With increasing proton conccntration the transformation of sjwdiazotatc into
diazoniuiii ion becomes more and niorc rapid. Thc airti-syu diazotate isomeriza-
tion bcconies the rate-limiting stcp, and the rcaction rate becomes independent of
p H ? . Further increase in the proton concentration results in the increase of con-
centration of anti-diazohydroxide whose isomerization becomes the main reaction
path and, at the same time, the rate-limiting step (Schcme 4). The reaction rate,
which at first increases again, finally becomcs pH indcpendent when almost all
-
diazotate ion has changcd into anti-diazohydroxide. Thc acid-catalysed splitting of
-
mti-diazohydroxide becomes significant at pH about zero.
k- 3
H++anfi-ArN,O- anti-ArN,OH ___> syn-ArN,OH ArN+
SCHEME 4
Further increase in the electron-withdrawing ability of substituents results in an

evcn greater decrease in the syn-diazohydroxide splitting rate a n d an increase in the
isomerization rate. The splitting of syn-diazohydroxide becomes rate limiting in a
broader pH range and the reverse is true of thc rate-limiting transformation of anti-
into syrz-diazotate. In the case of the 2,4-dinitro derivative3* (Figure 2) the non-
catalysed splitting of syz-diazohydroxide ( k - , ) is rate limiting u p to p H about 4.5,
a n d the reaction rate is directly proportional to the anti-diazohydroxide concentra-
tion. Further lowering of pH causes the proton-catalyscd splitting ( k n + ) to become
more and more significant. At pH < 1 the rate of the proton-catalysed splitting of
syn-diazohydroxide is substantially greatcr than that of the revcrse isonicrization to
anti-diazohydroside. The transformation of anri- to sy-diazohydroside becomes
rate limiting, and log k is p H independcnt.
t The reaction rate docs not beconic completely pH indcpendent, because the individual
reaction paths overlap.
2. Dinaoniiiin-diazo cqtiilibrium 83
E. Some Conclusions f r o m t h e Results on syn-anti lsomerizotion
Isonierization rates of siw-diazotates to outi-diazotatcs depend strongly on polar
effects of the substitiicncs, especially on thcir - effect. The valuc r = 2.4 in
equation (29), which dcscribcs thc rclative importancc of the mesonieric effect, is
probably the highest given in the literature up to now. The atiii : syiz diazotatc
concentration ratio is practically indcpendent of thc polar effects of substituentsc0*35
but i t rapidly increases wiih increasing stcric rcquirements of substituents i n ortlio
positions3s (Table 4). This nieans either that the syn and atiti derivatives have (in
contrast to all other published interpretations) thc configuration trans and cis,
respectively, or that the / r m s configuration is stabilized by substituents in ortho
positions. A similar case is described in connection with the study of sytz-anti
configuration of substituted N-alkyl-N-nitrosoanilinesJ'where the ortho substitution
shifts the equilibrium in favour of isomer 1:
(11
The isomerization rate of utzti- to syn-diazohydroxides (Table 3) depends generally

much less o n polar effects and especially on the - M effect (equation 31) than the
isomerization of diazotate ions, and i t is usually far quicker. It can be presumed that
log k4 = 1 .O[U + 0 . 6 5 ( ~ -- u)] - 1.8 (311
the isomerization mechanism is different for t h e two cases. Two mechanisms can be
considered for diazotate ions", either rotation about the N-N bond in 2 or inver-
sion at the N atom positively charged in the transition state 3. The rotation about
the N-N bond of the nitrosarnine tautonier is the most probable mechanism for
diazoanhydrides.
-0 0-
N=N
-0' N=O
A reaction mechanism, according to which an anti-diazotate would be formed

directly by reaction of hydroxyl ion with the diazoniuni ion which is in equilibrium
with syn-diazotate, is untenable, since in alkaline solution the isomerization rate is
independent of hydroxyl ion c ~ n c e n t r a t i o n ~The
~ . mentioned mechanism would
necessitate L' = [ArN:][OH-], and the isomerization rate would have to be inversely
proportional to [OH-], because [ArN;] decreases with the square of [OH-].
Substituted anti-benzenediazohydroxides are by about one order of magnitude
stronger Bronsted acids than sy,r-diazohydroxides. Direct comparison is possible
only in the case of the tn-nitro derivativesz6* 32, but i t obviously holds also for the
other n7cfa- and para-substituted diazohydroxides, because the constants of the
acid-base reactions are approximately the same: 1.3 for syn3' and 1.17-1.45 for
37. Hence i t follows that the ratio atiti : syn will bc by about one order of
atzfi2e.
magnitude smaller for diazohydroxides than that for diazotate ions. These con-
clusions do not hold for ortho-substituted diazohgdroxides.
4
84 Vojeslav Stcrba
For the majority of substituted bcnzenediazoniuni ions i t is possible to determine
the equilibrium constant K of thc reaction ArN: syrz-ArN,O- by direct nieasurc-
ments o n solutions in the pH range near pH,,,. I f tlic absorbances and the pH values
of the reaction mixtures are measured after establishing the cquilibrium of the
s.v)z-o)z/I'isornerization, i t is possible to determine tlic equilibrium constant of t h e
reaction ArNf e m f i - A r N 2 0 - . As irreversible side reactions take place simul-
taneously, the values obtained are usually w r y inaccurate, or not accessible at all
(e.g., with the rrz-nitro derivative). In the case of the diazoniiim ions having strong
- M type substitucnts i n ortho and ~ J positions
M (e.g. 2,4-dinitrobenzenediazoniuni
ion) the rate of syri-ariti isonierization at p H close to pH,, is greater than the rate
of the reversc transformation of spz-diazohydroxide to the diazonium ion, so that
the equilibrium constant of the rcac!ion ArNg + syn-ArN,O- cannot be determined
by tncasureiiieiits".
IV. D l A Z O N l WM-DIAZO EQUILIBRIA OF HETEROCYCLIC

DlAZONlWM IONS
Diazotization of heterocyclic primary aniines can bc exprcssed b y the following
reaction sequence4?:
-11+
HArNH, ___- z HArGH,NO HArNHNO HArN=NOH
-us
.
A
113
HArN:X- ~
-
ArN: <- Ar=N,
SCIIEhll. 5
I n this Scheme (contrary to general usage in this serics) the symbol Ar represents a
hetcroaroniatic ring minus iicw hydrogcn atoms a n d the synibol HAr represents a
heteroaryl group.
If the aromatic ring contains a n acidic hydrogen atom, the diazo compounds
Ar=N, along with the corresponding diazoniuni ions are usually thc main reaction
products. The equilibrium HArNp $ A r = N , t H+ was measureda3 in a series of
azols in aqueous solutions at 0 "C. The acidity of the diazonium ions increased with
the number of ring N atoms. In principlc, the reaction is similar to that in the
aliphatic series (alkanediazoniuni ion e diazoalkane + H+).
H H H
pK* 445 2.6 0.3
H H
-0.4 - 5.2
If the five-nicnibered ring does not contain any acidic Iiydrogcn atom, the product
of nitrosation of the amine in diluted mineral acid is usually a mixture of the nitros-
atnine, the diazohydroside and the diazonium cation. The tendency to form nitros-
aniines and diazohydroxidcs usually incrcascs with increasing nurnbcr of ring
2. Diazoniiini-diazo eqiiilibriuni 85
heteroatonis. High yiclds of nitrosamincs were obtained Lvitll substituted triazoles
and tetrazolesJ1.Js, thiadiazoles4'. J 6 , and oxadiazoles.". The situation is not quite
clear, e.g. substituted 5-amino-I ,3,4- and -1,2,4-thiadiazoles (4, 5 ) give high yields
of nitrosamineslJ~J", however, the 5-substituted-3-arnino-1,2,4-thiadiazolc (6)
forms only a relatively unstable diazoniuni saltJ8..19 Commonly, the structure and
yield of the isolated product depend on various factors such as the solubility of
products, the rates of the substitution reactions \vith the nucleophilcs present and of
decomposition react ions.
F r o m i.r. (in solid state) and n.1n.r. spectra i t follows." that the products currently
denoted a s nitrosamines are, in fact, iiiixtures of thc nitrosaniinc and thc tauto-
meric diazohydroxide. I n alkaline mcdiiim thcse are transformed into anti-diazo-
tatesJO.Dissociation constants were measured" in the case of triazole derivatives (7);
the pKA values wcre between 3.54 and 3.13 for X varying from 4-CH3 to 4-N02, i.e.
far lower than those of substituted bcnzencdiazohydroxides (Tables 2 and 3).
C,H,X
(4) (7)
Increasing proton conccntrations causes gradual transformation of the nitros-
ainine into the diazonium ion; the position of no such cquilibrium as as yet
measured. In one case the extent of transforination was followed1Gby measuring the
coupling rate of the formed 3-1iiethyl-l,2,4-thiadiazo-5-diazoniuni ion with 2-
naphthol in dilute sulphuric acid. Under thcse conditions 2-naphthol rcacts in its
undissociated forni, so that the change of the coupling rate expresses thc change of
the equilibrium concentration of the diazoniuni ion. The reaction rate increased
steeply u p to the highest sulphuric acid concentration used (1.65 hf), which means
that the nitrosarninc predominated all the time i n the reaction niixturcs.
T h e extraordinary stability of five-membered heterocyclic nitrosamincs (and
diazohydroxides) coniparcd with the carbocyclic aromatic diazohydrosidcs is due,
first of all, to the strong clcctron-withdrawing effcct of heterocyclic rings. This effect
increases the reactivity of the diazonium ion and the stability of the nitrosaniinc in
the same way as in substituted benzcnediazoniuni ions (Table 2), but to a greater
extent. 1,2,4- and 1,3,4-Thiadiazole-5-diazoniumions are far more reactive than
2,4-dinitrobcnzenediazoniuni ionS0(towards 2-naphthol). T h e isolated nitrosaniines
a r e obviously present in the form of thc more stable ( m / i )isomer. Although so far
n o data have been published about syti-unti isonierization of hcterocyclic nitros-
arnines, it can be presumed from analogy with substituted benzencdimohydroxides
that the isomcrization half-lives will be shortcr than 1 sec in most cascs. Another
factor given by Butler4? is the stabilization by intramolccular hydrogen bonding in
the case of the diazohydroxidc 8. However, this form is, according to spcctral
analyses4J,far less populatcd than the nitrosaniine and the isomeric diazohydroxide 9.
..'H ' o
X- X- N
(8) (9)
All these effects should be present in six-membered heterocyclic diazoniuin ions,
too. However, up to now n o stable nitrosarnine derived from a six-membered
86 Vojcsla\? Sti.i.ba
heterocyclic amine has been isolated. By acidification of pyridine-2- and -4-dia-
zotates"' and 9-alkylpurinc-G-diazotate52( 1 0 ) solutions were prepared @robably
containing the respective Nn/i-diazohydroxides tii trosamines. T h e pH dcpendence
of log k of their transformation into the corresponding diazonium ion (or the
products derived from the Inttcr) has a similar c h a i x t c r as that of thc substituted
benzencdiazoliydroxides, and t h c reaction is subject to general acid catalysis, too.
A rather substantial dilf'erence is encountered with pyridine-4-diazohydroxide,
which at pH < 4 becorncs protonated to give the less reactive conjugated acid (11).
V. R E A C T I O N S O F DIAZONIUM I O N S WITH O T H E R
NU C L E O P H I L E S
Arenediazoniuni ions react with a number of nucleophiles to give diazo com-
pounds'. G3-i5. The free electron pair for the bond formation can be supplied by a
carbon, oxygen, nitrogen, sulphur or phosphorus aton1 of the nucleophile. In the
first case azo compounds are formed which are usually very stable, although the
reaction with CN- ions (forming arenediazocyanides) is reversible. The other
adducts are called diazo compounds, however some of them (e.g. those containing
N-P bonds) are dcnoted as azo compounds.
Some diazo compounds are veiy unstable, e.g. diazoethers formed by reaction of
diazonium ions with substituted phenolate ions; here it is questionable whether the
nucleophile and the azo group arc connected by a covalent or a n ionic bond. I n
other cases, the primarily formed diazo compound is rapidly transformed to other
more stable compounds. Reaction of diazonium ions with azide ion Ny produces
unstable diazoazides which, in a subsequent (as a rule rate-limiting) step, either
decompose to give nitrogen and a n aryl azide or isomerize to arylpentazoles which
are also unstableSe.Some diazo compounds are formed in other ways than from the
reaction of arenediazonium ion with nucleophile.
T h e following discussion is limited to diazo compounds for which i t was possible
to determine the equilibrium constant of t h e reaction of at least some derivative of
arenediazonium ion with the nucleophile.
A. Arenediazoethers
Reaction of diazonium ions with alkoxide ions is analogous with the first reaction
step of that with hydroxyl ion. Very reactive heterocyclic diazonium salts, e.g.
3-phenyl-I ,2,4-thiadiazol-S-diazoniunifluoroborate, give high yields of diazoethers
even on reaction with pure methanol5'. For preparation of substituted benzenediazo-
ethers i t is more convenient to alkylate silver diazotates with methyl i ~ d i d e ~ ~ - ~ ~ ;
alkylation of a sodium or potassium salt produces the aryl derivative of N-methyl-
nit rosamine13.
Reaction of 4-nitrobenzenediazonium ion with methoxide ion in methanol
produces, in a rapid reversible step, the diazoether probably having the cis con-
figurationc1; it is transformed to the more stable trans isomer and to nitrobenzene in
2 . Dinzoniiini-diazo cquilibritim 87
about equal amounts"(Sclierne6). Thc isomcrization rateconstant is7.23 x 10-3 sec-1
at 0 ° C .
Rate constants of formation of the syri isomers were measured at 23 "C by the
stoppcd-flow methodfi1for 4-nitro- and 4-cyano-bcnzenediazoniuni ions (3.0 x 108
and 2.0 x 10' 1 niol-I SCC-I,respectively), and cquilibriuni constants wcrc determined
for 4-nitro- (5.6 x 10' I/niol), 4-cyano- (3.6 x loGI/mol) and 3-chloro (4.2 )I: lo5 I/mol)
derivatives6l. Both k , and K are by scveral ordcrs of magnitude greater than the
corresponding values of the rcaction with hydroxyl ion in watcr. The half-life of the
decomposition of 4-nitrobenzcncdi~zoethcrto diazonium ion and methoxide ion
is 130 niscc, i.e. two orders of magnitude greater than that for 4-nitrobcnzenediazo-
hydroxide i n water.
SCHEXII: 6
6. Arenediazoarnino Compounds (Triazenes)

Diazoniuni ions give a number of compounds by reactions with nucleophiles
containing an H N < g r o ~ p The ~ ~ most
~ ~ iniportant
~ . and most studied are arene-
diazoaniino compounds (triazenes) &liich arc formed by reaction of diazonium ions
with primary and secondary aliphatic and aromatic (or heterocyclic) amines
I-INRIRS (R' is Iiydrogcn o r alkyl, R2is alkyl or aryl):
+
ArN:+HNR'R2 ~ '' ArN=NNHR'Rz ArN=NNR'RZ+Hf (32)
I..-,
So far it has not been possible to prove ci.7-trans isornerism of thcse reaction products
such as, for cxample, that of diazotatesG396 1 Measurcments of dipole moments
indicateG3that the substances measured arc from isomers.
The rcaction with aromatic aniines can result eithcr in a reversible reaction at the
amino nitrogen to give a triazene or i n an irrcversiblc coupling reaction at a ring
carbon atom to give an azo compound. Coupling at carbon is negligible in thc case
of aniline in neutral and slightly acidic mediaGs:i t is of minor importance with
alkylanilinesc6, but i t represents the main reaction in the case of more reactive
aromatic amines such as substitutcd naphthylamincs. I n more strongly acidic
media t h e rcvcrse reaction of the triazcne becomes incrcasingly important and thc
content of azo compounds in reaction products increases.
The reaction \vith primary amincs involves a further complication bccalrsc two
tautomcric forms are produced, the second being split into compounds other than
the original diazoniuni salt and arnine (Scheme 7). I f R is aryl, thc triaienes are
split predominantly into the lcss reactive diazonium salt and lcss basic ainineG7.I f R
is alkyl, the splitting produccs thc aroriiatic aniine and alcohol", t h c amount of the
diazonium salt bcing ncgligibleG9.
The cquilibriuni const;int for rcaction ( 3 1 ) has not yct been dctcrmined i n any casc.
An attcnipt 10dctcrrnine the cquilibriurn concentration i n thc rcaction with dicthyl-
aniine (Lvherc thc reaction is not coinplicared by C-coupling or by decoinposition to
88 VojesIav Strrba
products different from the starting substances) was made impossible by simultaneous
decomposition of the diazoniuni salt7".
T h c equilibrium constant can be calculated from the rate constant of formation of
triazene and from that of the reverse reaction in those cases where two tautomeric
forms of triazene are not formed.
ArN=NNHR ArNNH=NR
-
.
LI+
ArNH,+RN: (R = Aryl)
I u+, 11,o
ArNH,+N,+ROH (R = Alkyl)
SCHEME
7
T h e kinetic equations (33) and (34) are prcsumed for formation and decomposition
of triazenesG5* 6G- [R1R2NHJ represents the concentration of the non-protonated
amine. K A is the dissociation constant of thc protonated triazcne; its value has not
-
yet been determined in any casc.
v = k,[ArN+ 3 [R'R'NH] (33)
c +
v = k-,[ArN=NNHR'R'] = k-,[H+I/I(.~[ArN=NNR'R']
= k a + [ H + ][ArN=NR'Rz] (34)
K = [ArN=NNR'R,] [H+]/[ArN:] [R'R'NH] (35)
T h e rate constants of forniation7?and reverse r ~ a c t i o n of
' ~ triazenes were measured
for the reaction of t m f n - and parn- substituted benzencdiazonium ions with dimethyl-
arnine in water at 25 and 20°C.
T h e observed p constants of the formation and the reverse reaction of triazenes
are 3.47 and - 3.5, rcspectively. The resulting p = 7.25 for the equilibrium constant
(equation 35) is only slightly higher than that for the reaction of diazonium ions with
hydroxyl ionz8.23. The calculated rate constant k , of the rcaction of benzenediazoniurn
ion with dimethylamine is 450 I niol-' sec-'; the kH-l constant of the reverse reaction
can only be roughly estimated to be 10-20 1 mol-l scc-l. The slope of the dependence
of log k on pH in the measured pH range 1-3 was (instead of the expected - 1 ,
according to equation (34). provided that only minute amounts of tlie triazene are
protonated) only about - 0.75. The calculated K value is about 30. For the sake of
comparison with the equilibrium constant of the reaction of benzenediazonium ion
with hydroxyl ion, which is equal to 2.0 x 10' 12/mo1?(Reference 26) the above value
must be divided by the ionic product of water K,,. (which corresponds to a change of
equation (32) i n thc scnse that thc protonated triazenc loses its proton by reaction
\vitIi hydroxyl ion). Thc resulting value, about 3 x I O l 5 12/mo12is about 1 1 orders of
magnitude greater than that for thc formation o: diazota!!: This difference is due,
first of all, to thc far grcatcr acidity of tlie protonated triazcne as comparcd with
benzenediazohydroxide. Obviously hcre K A is close to unity whereas i t is lo-* for the
diazohydroxide".
T h e above-mentioned valucs, cspecially those for tlic reverse rcaction and for the
equilibrium constant, must be accepted with rescrve. I t cannot be excluded that
isonierizntiont takes place side by side with the reaction and that the rate-limiting
stcp cliangcs with pH.
t Ritsliic'" studied thc reaction kinetics OT 4-chlorobenzcnediazoni~imion with diethyl-

amine and observcd a slowcr subsequcnt reaction independent of diethylamine concentration.
2. Diazonium-diazo equilibrium 89
C. Arenediazosulphonates
Thc formation of diazosulphonatcs was described i n 15697a and has been much
studied because of its technical importance. The rate of formation of diazosulphonate
is directly proportional to the concentration of arenediazoniuni ion and SO:-; the
diazonium ion docs not react with HSO; 4 0 , i ' J . In thc first, very rapid, step a product
is formed which was called sywsulphonate by HmtzschiG, and i t is transformed
slowly into the other isomer (nnri):
The log K valucs of formation of syn-sulphonates (Tablc 5 ) correlate with the u

constantsao;the p value is 5 . 5 . The syn-sulphonates are very reactivc and are rapidly
decomposed into the starting substances. Half-life of the reverse reaction of 4-chloro
d ~ r i v a t i v e 'is~ 15 msec. On the contrary, the anti isomcrs a r e extraordinarily stable.
The values given fcr the 4-methoxy dcrivativc are lo7 for K 3 = [mrti]/[syn]and
lO-*sec-' for the rate constant of the nnfi to syn transforniation".
5 . Rate and equilibriiini constants of the reaction of sub-

TAULE
stituted bcnzcncdiazoniurn ions w i t h sulphitc ions
Substitucnt K (l/mol) k, " (I rnol--' SCC-l) k , (scc-l)
4-NOZ 3.2 x 10' 4.5 x 1 0 s 1 - 8x 10-3
4-CN 1.1 x 108 4.3 x 10'
4-CI 2.7 x I@' 2.4 x I 0 7 0.5 x 10-3
H 3.6 x 10' 1.9 x 10-3
Reference 40, ionic strcnglh 1 hf.

Reference 70, ionic strength hi.
At 0 "C.
D. Arenediazosulphones
Arencdiazosulphones are formed by reaction of diazonium salts with anions of
sulphinic usually the rcaction is carried out in slightly acidic aqueous
medium70. Only one isomer was provcd i n the reaction so. The dipole
moments founds1 suggest t r a m structure of the products. T h c prcscnce of the single
isomer is explaineds2 by lowering of the rotation barrier about t h c N = N bond by
contribution of cxpandcd octet structures such as 12b, c:
ArN:+f?SO; . k-,
ArN=NSO,R (37)
(1 2 4 (12b) (12c)
Sincc the watcr-solubility of the products is very low, t1:c rcaction kinctics of
substituted benzencdiazonium ions with bcn7cnesulphinic acid \vcrc measured i n
90 Vojeslav Sterbn
methanol". In contrast t o the reactions of diazonium salis with most other iiuclco-
philes, the diaznsulphone is formed so slowly that the reaction can be followed by
usual spectrophotometric mcthods. The dcpcndencc of the l o g a r i t h m of the rate,
and equilibrium constants on thc u constants is expressed by equations (38) to (40):
+ 5.26
log K = 3 . 7 6 ~ (38)
l o g k , = 2.40u+2.52 (39)
log k-1 = - 1.360 - 2.74 (40)
I n spite of anions of sulphinic acids being Tar weakcr nuclcophiles than the sul-
phite anion, the k- , values are more than four orders of magnitude lower than those
for the diazosulphonates. Obviously this is caused by thc reverse reactions of diazo-
sulphonates involving the more stable trotis isomer. This fact also influences the
values of the equilibrium constants. The small p observed for the diazosulphone
equilibrium is cxplaineds2 by the contribution of structurcs such as 12b where a
partial charge remains localized o n the nitrogen.
E. Arenediazothioethers
Arenediazothiocthers are formed very easily and rapidly by reaction of dia-
zonium salts with thiols. They are very unstable and decompose, evcn explosively
in some cases, to give nitrogen and the corresponding sulphidc". I n contrast to
aromatic hydroxy compounds the reactions with thiophcnols, thionaphthols and
even dithioresorcinol d o not lead to coupling in the rings4.
TABLE6. Rate and cquilibrium constants for the rcaction

XC,H,N: + C,H,S- . x',
syn-XC,H,N=NSC,H, anti-XC,H,N=NSC,H,
in nicthanol at 23 "C
X k , (I niol-l sec-I) K (I/mol) k , (scc-l)
~~ ~~ ~ ~
4-NO2 8.7 x 109 1.9 x 10" G4x lo-"

4-CN 7.0 x 10' l.s x 10'0 66x 10-2
3-CI 5 . 2 : < 103 1.4 x lo-'
4-CI G Ox 10' 3.7 x 10-1
H 1.4 x lo3
4-CH30 5.7 x 103
T h e reaction of bcnzenediazoniuni ions with thiophcnoxidc ion was followcd by

the stopped-flow mcthod i n methanolic buffers"'. At relatively high concentrations of
thiophenoxide ion the reaction of diazonium salts having a positive u value for the
substituent (4-chloro- to 4-nitro-) proceeds in two clearly separated steps. T h c initial
rapid reaction is probably the formation of a s),ii-diazotIiioetlier, and the slower
reaction is syii-onti isomerization. With thc unsubstituted, 4-methyl and 4-mcthoxy
derivatives the reactions followed first-ordcr kinetics over the entire course of the
reaction. Thc formation of syw-diazothioether was probably thc rate-limiting step
followed by a rapid s)*ii-mti isonicriuation. D u c to the isomerization, reliable values
for the equilibrium constant could be oblainecl for the 4-nitm and 4-cyano deriva-
tivcs o n l y (Table 6 ) :
A, 1,
-2
9
ArN: -I-C,H,S- syn-ArN=NSC,H, ___ -> anti-ArN=NSC,H, (41)

k-,
2. Diazoniiini-diazo equilibrium 91
The k l values approach the valucs for diffusion-controlled reactions; the influence
of substitucnts is far smaller than in the other reactions studicd and decreases with
increasing value of (3 constant. Equilibrium constants arc about threc orders of
magnitude higher than those for rcactions w i t h CHJO- ion.
F. Arenediazocyanides
Substituted benzenediazonium ions rcact vcry rapidly and reversibly with cyanide
ions to form syn-diazocyanides8.i which are slo\vly transformcd (half-life of one to
several hours at rooni tcmperaturc) into ~ti/j-(iiazocyanidesa~. I-Iantzschs5suggested
cis and trnns configuration for tlie sj'n and otiti isomers, rcspcctively, which agrees
with the nicasured dipole moments and i.r. spcctra of the two 19:
ArN': + CN- . k.
k-,
Ar-N,
N
--+ Ar-N+
N-CN
(42)
I
CN
Equilibrium constants of formation of tlie syti isonicr wcre measured by the tise of
convcntional spectrophotomeiric methodsqGand by the stopped-flow technique2q.
The latter method affords niore accurate rcsults, because the detcrmiiiation of the
equilibrium constant is not disturbcd by slowcr subscquent reactions". The effect
of the ring substituents on the equilibrium and rate constants, determined also by
the stopped-flow method, was quantitatively expressed by the Hanimett equation:
log K = 3.530+ 1.82 (43)
logk, = 2.31of2.32 (44)
The relativcly small p value 3-53 is (analogously to diazosulp5onates) duc to t h e
partial positive charge on the nitrogen atom of the diazo group caused by the s:rong
+
- M effect of tlic C N group (niesomeric structure Ar-N-N=C=N). Tlic strong
- M effect of the C N group is obviously also responsible for thc fact that electron-
withdrawing substituents slow down the i s o i n c r i ~ a t i o n ~ ~ .
TABLE 7. Rate and equilibrium constants for the reaction of stibsti-
tuted benzeriediazonium ions with cynnidc ion i n water at 33 "C 3
Substituent K (I/mol) k , (1 Inol-' sec-1) k - , (sec-1)
____
4-NO2 6 . 0 ~
10' 1.7 x 10' 0.28
4-CN 1.4 x 10' 7 4 x 103 0.53
(2.3 x 107) = (1.2 x 106) = (0.1) =
4-Br 3.7 x 10' 6.5 x 10' 1.75
(3.2 x lo9) ( 1 . 6 ~10") (0.05)
4-CI 4.5 x 10: 6.5 x 10' 1.5
(2.5 x 109) b (1.5 x 10') (0.06)
4-CH3 1.5x 10 9.0 x 10 6.0
(1.4 x 103) (3.5 x 107) ' (0.27) '
(1 I n methanolc1.
b I n diinetliyl sulpIioxicleq8.
The rcaction of some substittitcd beiizencdiazunitiiii ioris \ \ i t 1 1 cyanidc ion was

rneasured in watcr, i n iiiet1i:inoP' and dimethyl sulpliuxidc'q. T h e cquilibritini
constants arc three aiid s x c n orders of mngnitudc grcater in iiictlianol and dimethyl
sulphoxide, rcspectivcly (Table 7). The influence of tlie medium is dccisivc in the case
92 Vojeslav Sti.rba
of k,, w h e r e a s t h e reverse reaction s h o w e d a relatively l o w e r decrease. A large
i n c r e a s e in t h e e q u i l i b r i u m c o n s t a n t a c c o m p a n y i n g a c h a n g c f r o m a p r o t i c to p o l a r
aprotic solvent is typical for reactions w i t h sniall, negatively-charged, nucleophiles“.
VI. REFERENCES
1. H. Zollingcr, Azo arid Diazo Clronisrry, Intcrscience Publishcrs, N e w York, 1961, p. 39.
2. I-. Friedman, in Carborriton Ions, Vol. 11 (Ed. G. A. Olah a n d P. von R . Schleyer),
J o h n Wiley & Sons, Inc., 1970, Chap. 16.
3. P. Gricss, Client. Ber., 16, 2025 (1883).
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5. J. D. Roberts and W. Watanabe, J . Arner. Chem Soc., 72, 4869 (1950).
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7. Reference 1, Chaptcr 7.
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9. 0. MachiEkova, V. StErba a n d K. Valtcr, Coll. Czech. Chetii. Cotmiitri., 37, 2197,
(1 972).
10. E. S. Lewis a n d M. D. Johnson, J. Amer. C/ier?r.SOC., 82, 5399 (1960).
11. P. Griess, Anu. Chent., 106, 123 (1858).
12. P. Gricss, Ann. Cltettr., 137, 54 (1866).
13. C. Schraube a n d C. Schmidt, Cheni. B e r . , 27, 514 (1894).
14. A. Hantzsch and A. Werncr, C h n . Ber., 23, I 1 (1890).
15. A. Hantzsch, Chem. Bet.., 27, 1702 (1894).
16. J. M. Robertson, J. J. Lange a n d J. Woodward, J. Chin. Soc., 237 (1939).
17. G . C . Hsnipson and J. M. Robertson, J . C/twr. Soc., 409 (1941).
18. R . J. L. LeFcvrc a n d H. Vine, J . Cheui. Soc., 431 (1938).
19. D. Anderson, R. J . L. LcFevre and J . Savage. J . Chem. Soc., 445 (1947).
20. R. Kiiblcr and W. Liittke, Ber. Drimetrges. pltysik. Chern., 67, 2 (1963).
21. W. B. Davidson and A. Hantzsch, Chem. Ber., 31, 1612 (1898).
22. C . Wittwer and H. Zollinger, Helo. Chint. Acru, 37, 1954 (1954).
23. G. Schwarzcnbach, Helu. Chim. Acra, 26. 418 (1943).
24. E. S. Lewis a n d H. Suhr, Chetn. Ber., 91, 2350 (1958).
25. C. D. Ritchic a n d D. J. Wright, J . Arner. C/tem. Soc., 93, 2425 (1971).
26. J. S. Littlcr, Tram. Faraduy Soc., 59, 2296 (1963).
27. E. S. Lewis and M. D. Johnson, J. Arner. Chetn. Sor., 81, 2070 (1959).
28. C . D. Ritchie a p d D. J. Wright, J. Anrer. C/teut. Soc., 93, 6574 (1971).
29. V. Beranek, V. StCrba and K . Valter, CON.Czech. C h i n . Cot?tmin., 38, 257 (1973).
30. V. Stcrba a n d K . Valter, CON. Czech. C/ton. Conmutt., 37, 1327 (1972).
31. M . G. Evans and M . Polanyi, T r a m . Farttduy Soc., 34, 1 1 (1938).
32. J. Jahclka, 0. MachZkovri a n d V. Sterba, Coll. Czech. Chon. Cotttmirr., 38, 706 (1973).
33. A. J. Biggs and R. A. Robinson, J. C h m . Soc., 388 (1961).
34. J . Kavalek a n d V. StZrba, Coll. Cxclt. Chmr. Conwtrirr.,40, 1176 (1975).
35. J. Jahelka, 0. MachiEkovl, V. Sterba a n d K. Valtcr, C d / . Czech. Cltetri. Commor.,
38, 3290 (1973).
36. M . Yoshito, K. Hamarnoto a n d T. Kubota, Btrll. Chenr. Soc. Jopcrn, 35, 1723 (1962).
37. E. S. Lewis and M. 1’. Hanson, J . Artier. Clion. Soc., 89, 6268 (1967).
38. 0. M a c h X k o v a and V. St6rba, Coll. Cieclr. C/reur. Comirrirt., 37, 33 13, 3467 (1972).
39. E. S. Lewis and H. Suhr, J . Anter. Chenr. Soc., 80. 1367 (1958).
40. E. S. Lewis and H. Suhr, Cltetn. Ber., 92, 3031 (1939).
41. J. T. D’Agostino a n d H. H. Jaffc?,J. Org. C/renr.,36, 992 (1971).
42. R. N. Butler, C/renr. Rev., 75, 241 (1975).
43. J. Villarrasss, E. Melendez a n d J . Elgiiero, Terraltcdrorr Leri., 1609 (1974).
44. R. N . Butlcr, T. M . Lambe, J. C . Tobin a n d F. L. Scott, J . C/ropr. Soc. Perkin I , 1357
(1 973).
45. H . Gchlen and J . Dost, A m . Chetx, 655, 144 (1963).
46. J. Goerdcler and K. Deselacrs, C/te/tr.Bcr., 91, 1025 (1958).
47. J . Gocrdcler and M . Roeglcr, C h m . Bet-., 103, 112 (1970).
48. J. Gocrdcler and A. Fincke, Cheni. Ber., 89, 1033 (1956).
49. J. Goerdeler and P. Mertens, Cheni. Ber., 103, 1085 (1970).
50. J. Goerdeler and H. Haubrich, C/ieni. Ber., 93, 397 (1960).
51. C. A. Bunton, M . J . Minch and B. B. Wolfe, J . Anicr. Chem. SOC., 96, 3267 (1974).
52. C. A. Bunton and B. B. Wolfc, J. Airier. Cheni, Soc., 96, 7747 (1974).
53. Reference 1, Chapter 8.
54. R. Putter in Hoitben- IVeyl's Met/ior/en der otgariischeii Chemie (Ed. Eugen Mullcr),
Vol. X/3, 4th ed.. Georg Thieme Verlag, Stuttgart, 1965, pp. 551-626.
55. C. Suling, Reference 52, pp. 699-743.
56. J. Ugi and R. Huisgen, Chcm. Ber., 90,2914 (1957).
57. A. Ginsberg and J. Goerdeler, Clicni. Om., 94,2043 (1961).
56. A. Wohl, Cltern. Ber., 25, 3631 (1892).
59. E. Bambcrger, Cheni.Bey., 27,917 (1894.)
60. A. Hantzsch. Cheni. Ber., 27, 1857 (1894).
61. C. D. Ritchie and P. 0. I. Virtmen, J . Anier. Chein. SOC.,94, 1589 (1972).
62. W. J. Boyle, T. J . Broxton and J . F. Bunnett, C h o n . C o m m n . , 1469 (1971).
63. R. J. L. LeFevre and T. D. Liddicoet, J. Clreln. Soc., 2743 (1951).
64. H. C. Freeman and R. J. L. LeFcvre, J. C h n . SOC., 2932 (1952).
65. V. Bcrinek and M. VeEeia. Coll. Czech. Chent. C o m n i i n . , 35, 3402 (1970).
66. V. BerAnek, H. Koiinkovi, P. Vetclnik and hi. Vci.e?a, Coll. Cieclt. Clicni. Commit.,
37, 282 ( 1 972).
67. German Patent 535670 (1928).
68. 0. Dimroth, Chew. Ber., 38, 670 (1905).
69. V. ZvCiina, M. RemeS, J. Divi9, J. Marhold and M. Matrka, Coll. CiecA. Clrerri.
C o m nt m . , 38, 251 (1973).
70. C. D. Ritchie and P. 0. I. Virtanen, J . Auier. C/ieui. Soc., 95, 1882 (1973).
71. T. Yamada, Bid/. C/ieni. SOC.Japart, 42, 3565 (1969).
72. M. Remel, 3. DiviC, V. ZvPiina and M. Matrka, Coll. Czccli. Cheni. Cotnmoi., 38, 1049
(1973).
73. V. Zveiina, J. DiviS. M. RenicS and M. Matrka, Cheni. p r h . , 22, 454 (1972).
74. R. Schmidt and L. Lutz, Cheni. Ber., 2, 51 (1869).
75. R. Dijkstra and J . de Jonge, Rcc. Tirau. Chiin. Pays-Bas, 77, 538 (195s).
76. A. Hantzsch, C h e n ~Eer.,
. 27, 1726 (1894).
77. L. K. H. van Beek, J. Helffcrich, H. Jonker and Th. P. G . W. Thijsscns, Rec. Trau.
Chini. Pays-Bas,86,405 (1967).
78. W. Konig, C/iem. Bcr., 10, 1531 (1877).
79. H. v. Pechnian. Cheni. Ber., 28, 861 (1895).
80. A. Hantzsch and M . Singer, Chenr. Bcr., 30, 312 (1897).
81. H. C. Freeman, R. J. L. LeFtvrc, J. Northcott and J. Youhotsky, J . Clietii. SOC.,
3381 (1952).
82. C. D. Ritchie, J . D . Saltiel and E. S. Lewis, J . Aiiicr. Clrem. S O C. 83,
, 4601 (1961).
83. H. 13. Szmant and G . Lewitt, J . A met. Cheni. Soc., 76. 5459 (1954).
84. J. Pollak and E. Gebauer-Fulncgg, Moriaisli. Chcni., 50, 31 5 (1928).
85. A. Hantzsch and 0. W. Schulze, C/teni. Ber., 28, 666 (189s).
86. E. S. Lewis and H. Suhr. Clioti. Ber., 92, 3043 (1959).
87. R . J. L. L.eFcvre and J . Northcott, J . C h m . SOC., 944 (1949).
88. C. D. Ritchie and P. 0. I . Virtanen, J . A / m r . Chem. Soc., 94, 4966 (1972).
89. A. J. Parker, Quart. Reu., 16, 163 (1962).
CHAPTER 3
Structural chemistry
S . SORRISO
Isriirito di Chimica Fisiui, UiiiccrsitLj cfi Perrigia, 06100 Pcrirgia, Italy
I. INTRODUCTION . 96
A. General . 96
B. Usefulness and Errors in a n X-Ray Examination 1 ; 96
11. D ~ A Z O N I USALTS
M . 97
A. Outer Diazonium Salts . 37
1. Structural data . 97
a. Benzenediazonium chloride . 97
b. Benzenediazonium tribromide . 97
c. p-l\r,iV-Dimethylarninobenzcnediazoniumtet;achlorozinc(ii) . 99
d. o-Methoxybenzencdiazoniuni tetrachloroiron(1n) . . 99
c . p-Benzenebisdiazonium tetrachlorozinc(ii) . 99
f. 1: 1 Complex benzenediazonium chloride-acetic acid . 100
2. Discussion . 100
3. Effect of thc anion on the structure of diazonium cations . 102
B. Inner Diazoniiim Salts . 103
1. 2-Diazonium-4-phenolsulphonatemonohydrate . 103
2. p-Benzenediazonium sulphonate . 104
111. DIAZOTATES . 105
A. Isomerism . 105
B. Structure of Potassium-s~ir-methyl-diazotate . 106
I\'. DIAZOALKAKES. 106
A. General . 106
B. X-Ray Data . 107
1. 2-Bromodiazofluorene . 107
2. Phenyl(triphenylsilyl) diazoniethane . 108
V. AROMATIC DIAZOCYANIDES . 109
A. Synthesis . . 109
B. Structures . 109
1. p-Chlorobenzene-ad-diazocyanide . 110
2. a-Broniobenzene-atiri-diazocyanide . 110
3. o,p-Dibromobenzene-miti-diazocyanide . 110
4. p-Chlorobenzene-anri-diazoimidoglyoxynitrilc . 111
C. Isomerism . 111
VI. DIAZOKETONES. 113
A. Isomerism . 113
1. General . 113
2. Ultraviolet/visible and infrared spec'tra ; 115
3. Nuclear magnetic resonance . . 117
4. Electric dipole moments . 120
5 . M O calculations . . 120
6. Conclusions. . 123
B. Configuration and Wolff Rearrangement . 123
95
96 S. Sorriso
C. Structures . 124
1. 1.4-l~isdi~zo-?,3~bc1lancdionc
. . . 125
2. 5-Diazo-6-1netliox~-6-hydrouracil . . 125
3. 2'-Deos~-S-diazo-G-hy~ro-Oc,5'-cyclouridine . 12s
V I I . D I A Z O OXIDES . . 126
A . Gcneral . . . 126
B. Electronic Striistiirc . . . 128
C. X-Ray Data . . 130
I . 3,6-Bisdiazocyclohesanctetra~nc . . 130
2. 2,6-Dichloro-4-diazo-2,S-cyclohexadicn-l-one . 130
V l I I . REFERENCES . . 131
1. INTRODUCTION
A. General
It is normal in a chapter on stiuctural chemistry to discuss bond distances and
angles i n molecules containing the characteristic group, and to explain the modi-
fications undergone, or induced, by the latter. In the case of diazonium a n d diazo
groups this is not sufficient because the structural data are often lacking. This
makes necessary recourse to other kinds of results to discuss at least the possible
configuration.
T h e configuration of diazo compounds has been the object of much work since
their discovery about a hundred years ago'. Nevertheless, many problems still
remain not completely solvcd. For example, due to thc instability of the molecules
examined, the type of isomerism present in some covalent diazo compounds and
the reasons for its existence are still objects of discussion.
T h c book written by Zollingcr' in 1961 covers the configurational aspects of the
present groups. Therefore, with very few exceptions, work carried out before this
year will not be covered since i t has been revicwed at length in that book. A historical
introduction to the configurational problems in the diazonium and diazo groups
may be found in the book by Saunders".
Strictly structural results are relatively recent and they have not been reviewed
previously. These, which have been obtained exclusively from X-ray measurements,
will be treated cxtensivcly in the present chapter.
B. Usefulness and Errors in an X-Ray Examination

X-Ray data in chemistry give information on the molecular configuration and
thus they are very helpful in indicating uncquivocally the type of isomerism present.
Besides, the rcfincnient of the structiirc by means of modern computational methods
often allows information to be obtained also on the hybridization of the atoms and
on the bond order.
T h e reliability of a n X-ray crystallographic determination is usually indicated
by the R factor, the residual error index or discrepancy index, and by u, the standard
deviation3#
The R factor is a function of the observed (Fo) and calculated (F,) structurc
factors:
H does not have a prccisc theorctical meaning and depends greatly on temperature
factors, the coniplesity of the structure and the aniount of data collected. T h e lowel.
the value of I(, tlic lower is tlic discrepancy between observed and calculated structure
factors. CoIisec111ci1tly. i t is also useful to the crystallographer for follon,ing the
progress of structure rcfincnient. Initial K values of 0.50 and final oncs of 0.10 :ire
normal1. At present, with niodcrn computer techniques, R values between 0.08
and 0.03 arc being reported for the most reliably determined structures$. The f<
fnctor is a function of the intcnsitics. Therefore, when heavy atoms arc present,
they niay dominate thc structure factor calculation. Consequently, t h e bond lengths
involving hcavy atoms will be more precisely determined than those involving
light ones.
T h e standard deviation in bond lengths and angles is generally 0.002 A a n d
0.2-1.5". respectivcly, in more rcccnt bvork. Howevcr for the former, given the
possibility of systematic errors, i t is reasonable to assign a value of 0.01 A, even i f
account is takcn of thermal motion (corrected value). For lighter elements, the
standard deviations in bond distances are usually higher. In fact, since X-rays are
diffracted by electrons, they give statistically the position of the centroid of negative
charge rather than that of the nucleus. This means that while for hcavy atoms the
centroid of electron cnargc and that of the nucleus are statistically coincident, i n
light atonis there is a certain difference. For example, for hydrogen the difference5
between the two is -0.1 A, which for lithium decreases to -0.01 8,.
Caution is necessary in interpreting the crystallographic data in ternis of the
electronic structure and bond order. I n fact, the standard deviation in bond length
niay be subject to different errors, such as the inadequacy of the atom-form factors,
of thc crystal model and of the temperature factors. Tlicse may become so important
as sometimes to render the experimental data suspect, even if u values arc excellent.
I I . BlAZONlUM SALTS
A. Outer Diazoniurn Salts
I . Structural data
chloride, PhN,CI (1). This molecule has been examined i n
a. Bci~zciic~ia-.otiirrt~i
two studies. In the first studyc. the measurements were performed at room
temperature. T h e compound is conipletcly ionized; R = 0.06; standard deviations
0.006-0.010 8, and 0.6-0.7". The second stlidye was performed at - 160 " C ; R not
specified; standard deviations 0.002 8, and 0.2". Each diazoniuni group' is surrounded
by four CI- ions situated in a plane perpendicular to the N-N axis. Two of the CI-
ions lie at 3,184 and the other two at 3.51 1 8, to this axis. The fornicr chlorine ions
lie 3.225 and 3.237 A away from N t 2 ,and N,,,. respectively, and the others at 3.545
and 3.559 A. The separation between the latter and the Ho, atom (see Figure I ) is
only 2.5 8,.Because this distance is half an Angstrom less than the sum of the van
der Waals' radii, a strong interaction must be present between these two atonis'.
tribrotiiidc, PhN,Br,
b. Betiieticr~i~inzorrirrtil (2). Completely ionized ; Rok2= 0.08,
Rllho= 0.073 and Khol = 0.073 (where 11, k and I are used to indicate the plane
referred to); estimated standard deviations 0.04-0.05 8, and 3-4". The spatial
arrangement of tribromide ions about the diazo cation is shown in Figure 2. T h e
C,II-N-N arrangement is linear. The shortest distances between the bromine
atonis and N , , , and N t s ,are 3.46 and 3.31 A, respectively.
98
FIGURE
I . The layer of chloride a n d benzenediazoniurn ions. Rcprinted, with permission,
from Romming, Acrn Client. S c a d . , 17, 1444 (1963).
Uncorrected bond lengths and angles
Reference Refercnce Rcference Refercnce
7 8 7 8
N(,)-N(2) 1,097 8, 1.093 8, G,)--N(I)--N(?l 180' -
N(,l-C(ll 1.385 8, 1.410 8, C(l)-C(sj-C(s, 117.6" 1 1 5.9"
C(ll-C(2) 1.374 8, 1.396 8, C(2)-C(3)-C(dj 119.8" 120.6"
C(2)-C(3) 1.383 A 1.392 C(,)-C(dI-C(;) 121.7" 121.1"
C(3)--C(4) 1.376 A 1.395 8, C(e)-CI11- Col 124.8" 126.1"
(1)
FIGURE 2. Arrangement of tribrornide ions about a benzenediazonium ion. T h e lines

Br:ll-Br:!; and Br:i;-Brj3"; form angles of about 85" and 35" with the plane of the
benzene ring, respectively. Reprinted, \vith permission, f r o m Andresen a n d RrJmrning
A c ~ nCheni. S c a d . , 16, 1882 (1962).
Uncorrected values
3. Structural cheriiistry 99
C. p-N,N- Di~~l~/lrylnt~ii/i~be,l;ewcc(itr-.oriir/r)i
~ c i ~ a c l ~ l o r o z i r i c((p~-iFffe2NCGH.,N2)2.-
)
ZnCI, (3). Ionic structure; R = 0.141 ; only the atomic coordinates havc bcen
i ~ p o r t e duncerlainty
; in atomic coordinates has n o t been specificd. From thesc data
we have extracted the following bond distances and angles:
IG9.9"
1 10.9"
108.9"
128.3"
1 16.7"
118.3"
1 17.3"
129.8"
17-2.8"
119.5"
120.0'
A
The chlorine ions form a tetrahcdron about thc Zn atom (CI-Zn-CI 106-110'
and Zn-CI 2.28-2.35 A). The shortest distances between Cllll and N ( l ) and N 1 2 ,
are 3.672 and 3.435 A, respectively, and those between CI,,, and N ( l l and N,,,
3.701 and 3.420 A.
d . ~ - ~ ~ c / h o . u y b e t ~ i e t i c d i n z o/c/i.nchlo,.oirmi(iiI),
niri~~i o-MeOC,,H4N2.FeC1, (4).
Ionic structure. R = 0.13; standard deviation 0.01-0.02 A. The chlorine ions form
A
a tetrahedron around the Fe atom (CI-Fe-CI 107.5-113.2" a n d Fe-Cl 2.165-
2.230 A). All the atoms C, N and 0 are coplanar. T h e shortest distances between
the chlorine and the two nitrogen atoms are CI-N(ll 3.51 and CI-N(21 3.36 A.
Uncorrected
1.11 A 179"
1.48 8, 118"
1.38 A 119"
1.40 8, 114'
1.41 8, 126"
1.41 A 174"
149 A 103"
1.48 8, 134"
1.36 8, 117'
1.45 A 120"
(4)
e. p-Ben:enebisdia;oniuni fefr.aclr/orozitzc(Ii), p-N2C,H,Nz.ZnCI, l 3 (5). Ionic

structure; R = 0.065; standard deviations 0.012-0.017 A and 0.8-1.2". The
Uncorrected
N(ll-N(21 1.09 8, C(Z)-C(il- C(61 128.2"

C(ll-N(ll 1.42 8, clll-c(21-c[31 115.9"
Nq,)
n
O
(,) co,--~z, 1.37 A
C,,,-C,,) 1.47 8,
Cl,l-Col 2.62 A
Co)-C(51 2.85 8,
(5)
100 S. Sorriso
p-benzenebisdiazonium ion is, within the accuracy of the measurements, planar
and the N-N-C-C-N-N arrangement is lincar. The diazonium group is
surrounded by four chloride ions situated in a plane perpcndicular t o the N-N axis.
Thc shortest distances betwecn t h e chlorine and nitrogen arc CI-N(,, 3.26 and
CI-N,,) 3.43 A. These values are almost equal to the van der Waals' separation
between these two atoms (3.3 A). Thus i t is not possible to draw any conclusion as
10 the charge distribution in the diazonism group from the geometrical parameterst.
f. I : 1 Coniplcx heti,.et~c~inzotiiiiIncldorirlc-ncetic acid, PhN2Cl.M e C 0 2 H (6).

R = 0.075; standard deviations 0.006-0.016 8, and 0.5-1.2". The crystals a r e built
up of benzenediazonium ions, chloride ions and acetic acid molecules. The distance
between the oxygen and chloride ions (3.01 A) may indicate the presence of a
hydrogen bond". 15, O(.,,-. H,,,-CI-.
~ , )N(2) f:
'(5) '(6)
Uncorrected Corrected Uncorrected Corrected

N(I)--N(Z) 1.093 A 1.09s A C(ll-N(l)-N[z) 177.5"
C(l)-N[l) 1.418 A 1.425 A c[l)-c(21-c(3)1lS.I)" 1 17.3"
C(I)-C(2) 1.384 A 1.398 A c(2)-c(31-c(4)121.1" 121.0"
C(2)-C(3) 1.356 A 1.363 8, c(3)-c,,)-c(,, 119.3" 119.7"
C,J)-C(,) 1.396 A 1.413 8, C(il-C(5)-C(6) 120.7" 120.5"
C(4)-C15) 1.402 A 1.417 A C(5)-C(G)-C(l) 117.5" 117.3"
Ct5,-C(,,) 1.360 A 1.368 A C(G)- C(11- C,,) 123.6" 124.0"
C(G)-c(,) 1.389 A I .406 8,
C(71-C(8, 1.470 A
C(7)-O(1) 1.216 A
C(7)-O(21 1.326 A
Csp*- H 1.01-1.08 A
OI3-H 1.05 A
(6)
2. Discussion
The results reported in Section II.A.1 leave no doubt as to the structure of the
diazonium group. It may be seen that, with thc exception of the compound 5, in all
the compounds examined the N-N distance lies in the range 1.09-1.1 1 A, virtually
the same as that observed in dinitrogen (1.097 &IG, which indicates that in the
ground state thc extreme form 7 clearly predominates over 8 and 9. The presence of
(7) (8) (9)

an essentially triple N-N bond has also been arrived at from the value of the
frequency of the N-N stretching vibration band (-2290 cm-')''-?' which is between
the Raman frequency of dinitrogen (2330 and the stretching vibration
frcquency of the C = N group ( - 7,255 cm-I for PhCN)23.Also in agreement with this
iSee Note Added i n Proof, p. 135.
3. Structtiral chemistry 101
suggcstion are thc theoretical calculations carried out, using different methods,
by Sliuster and I'olansky?' and, more extensively, by Bochvar and co\vorkcrs?"
and by Sukigara and Kikuchi2GG-ZR.
'The fact that the N-N bond is virtually a triple bond suggests that the positive
charge of the benzenediazoniuin ion, according to the valence theory, is localized
mainly on the nitrogen atom which is bonded to the phenyl ring. Scvcral authors", ?O
d o not agree with this conclusion. They base their opinions on the fact that for most of
the diazoniurn salts above, the shortest distance Hal-N,,, is always shorter than, or
of the same order as, the distance Hal-N,,,, which suggests that the positive charge
of the diazo cation is slightly more localized on the terminal nitrogen or, a! least,
equally distributed over both nitrogen atonis. We feel that this shorter Hal-N,,,
distance probably does not depend cxclusively o n the electrostatic interaction
between the nitrogen and the halogen ion, but also on that between the latter and
the hydrogen ortho to the phenyl ringz9. This suggestion might be supported by the
fact that in benzenediazoniurn chloridc' (Figure I) the distance between the H,?)
atom and CI- ion is 2.5 A, about 0.5 8, smaller than the sum of the van der Waals'
radii.
X-ray data for t h e complexes o-MeOC,H.,N,.FeCI, and [p-Me,NCcH,N2]2.ZnCI,,
together with results of MO calculations, havc been used by some authors?5 to
suggest the presence of a 'bcnzenoid zone' and of a 'quinoid' one in niethoxy- and
amino-diazo cations. We shall now scc how far this suggestion is supported by the
experimental results.
o-fvleOC,H,N,~FeCI, : The bond lengths in the diazoniuni group d o not indicate
the presence of conjugation with the rest of the molecule. In fact, the N-N bond
(1.11 A)13 is virtually the same as that in benzenediazoniurn chloride ( - 1.09-
1.10 A). In addition, the C,,,-N,,, bond ( 1 4 8 A) is noticeably grcater compared
to the same bond i n 1 (1.385-1.410A), whercas i t should, of course, be shorter
according to the canonical forms 7-9.In agrecmcnt with these results, the niethoxy
group does not support the presence of conjugation with the diazoniuni group.
In fact, the O-Csl,? distance (1.36 A) is of thc same ordcr as that in similar niolecules,
e.g. 1,4-dimethoxybenzene (1.36 A)30 and p,p'-dinietlio?cybenzophenone (1.37
[p-Me?NCGH,Ns]..ZnCI,: For this molecule the fact that the N-N distance is
sensibly longer (1.18 A) than i n benzenediazonium chloride may be an indication
that there is a n increase in the contribution of the extreme forms 8 compared to
that i n the parent cornpound 1, i.c. strong conjugation between the substituent and the
diazonium group. l n agrcenicnt with this, the N,31-C,I,: distance (1.35 A) is shorter
than that observed in 2,s-dichloroaniline (1.40 A)32 arid p-tolaidiiie (1.43 A):13,and
a)3'
is similar to that found in p-nitroaniline ( I .37 and N,N-dimethyl-p-nitroaniline
(1.35 A)3s, for which conjugation between the nitro and aniino groups is accepted.
These points, important for defining the structure of this compound, unfortunately
are doubtful because the C,Il-C,2) and C , 6 1 - C ~ ldistances
l are very different
(1.53 and 1.36 A, respectively) whereas they should be cqual (within experimental
error, which is less than 0.1 A)1o-l l . Furthermore, thc prescnt results are uncertain
since thc autliorS'0. 11 d o not rcport the exact standard deviations in the atomic
coordinates. To conclude, the above discussion on the coniplexcs 3 and 4 shows
that the present structural parameters cannot be used to prove thc existencc of a
'quinoid zone' about the arnino group and a 'benzenoid zone' involving the
diazoniuni grollp"'. O n thc other hand, in this case, the theoretical calculations's
cannot be invoked to support this suggestion since for the benzenediazonium
cation they are very sensitive to the input parameters used. I t s e e m obvious that,
given the utility of X-ray 111easurements, amine coniplexcs with different anions
should be examincd before definite conclusions can be drawn.
102 S. Sorriso
Further information on thc electronic structure of diazo cations substituted in the
phenyl ring with electron-donor groups has been obtained using other techniques.
I n din'ercnt solvents, good correlations have been found", ly. 211, 3G-36 between the
frequency of the stretching vibration band ( U S N ) , its integrated band intensity, the
N-N bond order and the Haminett up values3!' for diazoniuni cations
p-XC,H,Ni (X = H, Me, CI. Br, NO2, SO,NH,, I , F, OMe, CO,Et, O H, 0- or
SO;). For p-OH-, p-OMe- and p-Me,N-derivatives u+ h u e s have been used instead
of u,, ones. This procedure led to thc result that the points for the first two derivatives
were on a straight line but that for the aniine compound was noti7. This indicates
further polar conjugation between the substitucnt and the diazonium group, which
is much greater in the amine derivative.
Many workers have shown interest in the electronic structure of the latter
compounds. In the spectral zone characteristic of quinones some similarity has been
observeda0 between the U.V. spectra of p-aniino-, p-methylamino- and p-dimethyl-
amino-benzenediazonium cations and that of diphcnylquinoniethane, which has a
quinoid structure (10). This led to the suggestion that these molecules have a n
analogous structure (1 1). There are many possible criticisms of this suggestion and
it certainly appears that a completely quinoid structure for all three of the above
derivatives cannot explain the other experimental results. In fact, if this were indeed
the structure, there should be no appreciable variation in t h e electronic con-
figuration of the diazo cation on introducing two methyl groups in place of the
amine hydrogens. The opposite is the case, because on passing from the amino to
the dimethylamino derivative, uss goes from 2183 to 2166cm-I and the band a t
357 goes t o 352 mi indicating an increase in quinoid character. Also, the N-N
integrated band intensities (12.6 and 13.5 mol-I cni-? x 10' respectively, for
p-NH2CoH.,N2CIand p-Me2NCGH,N2C1)18 show the same difference between these
two compounds. Very probably the present amino derivatives also arise from a
resonance hybrid between the canonical forms 7 and 8. However, there is a noticeable
contribution from 8 which, instead, in these compounds becomes 11. This resonance
form would account not only for the frequency and integrated intensity of the N-N
stretching vibration band but also for the fact that for dimethylamino derivative
even the u+ value does not lie on the v_\;sversus uI) plot. Form 11, further, would
explain the much higher stability and the colour of these conipounds as compared
with the other diazonium salts of simple anions, the great majority of which are
col~urless~~.
3. Effect of t h e anion on t h e structure of diazonium cations

Much information on this niatter has been obtained from infrared measurements.
These have been confined to the study of the N-N stretching vibration band in
complex molecules and to comparison with spectra of diazonium salts of simple
anions. I t is not appropriate to underline the various contributions, which are very
a ,chapter on structural chemistry. However, a concise discussion
n u m e ~ o u s ' ~ -in~ ~
of the results available may be useful.
3. St r uct u ra 1 chemis t ry 103
Independently of the physical state, all the diazonium salts studied to date show
one absorption band in the N = N region. Some authorss0 report two N-N bands
in this region only in p-dialkylamino derivativcs. Of these bands t h e niore intense,
-
at -2170crn-', is assigned to the N-N stretching vibration and the other, at
-2250 cm-', appears to be the first overtone of the band at 1100 cm-', assigned
to t h e C-N vibrations of the alkylamino groups. Instead, other authors4S-4S. sG
have also observed a complex band, usually with two peaks, for many diazonitini
salts, indcpendently ofsubstitution at the phenyl ring. The rcason for the appearance
of a complex N-N band is not clear. In most cases i t is probably due to solid-
state lattice effects, since there is only a single peak on regrinding thc mullso. To
interpret the prcsence of cor,ii;Iex N--N bands as caused by weak bonding between
the diazoniuni group and the anion secms hazardous, although i t cannot entirely
be excluded. On the other hand, X-ray data on the complex diazonium salts examined
above when compared to those for PhN,CI d o not indicate the presence of this bond.
Nuttall and coworkerS"O observed that the salts of the very strong complex fluoro
acids show a VKS valuc higher than that in other complex diazoniuin salts. For thcse
authors this fact indicates that the former are completely ionic, while the latter have
il weak covalent bond between the empty orbital of the diazonium group and the
halogen lonc pair, or bct\veen the z orbital of the diazonium group and the metal
atom of the anion. The first suggestion might be prcferred"O for the follo\ving reasons.
I n complex diazoniuni salts with p-dimethylarnino substituted cations, in which the
diazonium group is less positive than in other derivativcs, the v g value~ does not
show the clcar diffcrcnce between the fluoro derivatives and thc others.
To conclude. the extensive spectroscopic results together with X-ray data suggest
that the electronic structure of the diazo cation in diazoniuni salts of complex
anions is substantially the same as that in the analogous simple salts.
5. Inner Diazoniurn Salts

I. 2-Diazonium4phenolsulphonate monohydrate
N , C 6 H 3 S 03 . 0 H . H 260o (12): R = 0.125; standard dcviation 0.01-0.02 A. The
compound has a zwitterionic structurc; the water molecules connect t hcse zwittcr-
ions by nieans of hydrogen bonding.
104 S. Sorriso
2. p-Benzenediazon iurn sulphonate
N2C,H,S03 (13): The structure of this molecule has been determined twice. I n
the first study61, R = 0.13, standard deviations were not reported. According to the
authors, the dimensions of the phenyl ring indicate that the molecule is quinoid i n
character. The second studyzg has, R = 0.052. standard deviations 0-002-0.004A
and 0.1-0-3". The C-H bond lcngth is 0.91-0.99 A 28.
3
N(1) "2)
Reference
61 Reference 29 Uncorrected
Un- U n- Reference Reference
corrected corrccted Corrected 61 29
N(I)-N(Z) 1.14 A 1.091 A 1,091 A G I 1-N (1 ,--No, 178" 179.6"

C(,)--N,,, 1.39 A 1.410 A 1.412 A N,l)--C,l,--C(2) 117" 1 16.2"
C(1)-C(Z) 1.45 A 1.390 A 1.398 A c(,,--c(2l--co, 114" 116.3"
Cl2)-C(,) 1.38 A 1.371 A 1.374 A Cl2I-C(3)-C(.,) 125" 120.4"
C(3)-ClI) 1.41 A 1.392 A 1.399 A C13)-C(41-C(J) 119" 121.0"
C(41-C(5) 1.44 A 1.376 A 1.384 A col--col-~~c, 121 120.7"
C(,)-C(,) 1.37 A 1.380 A 1.382 A clJl-~o~--col 118" 116.1"
C(G)-C(1) 1.45 A 1.377 A 1.384 A COl- C(,) -Ct2) 124" 125.4"
S--co, 1.75 A 1.798 A 1.801 A c,3,--c,4,--s 121" 1 18.7"
S-011) 1.47A 1.449A 1.457 A c,4 )-s-o(, I 107" 105.4"
S-Ol,l 1.48 A 1.438 A 1.451 A c(,,--s-O(2, 106" 105.9"
s-00, 1.42A 1.450A 1.459 A cI., -s-0( 3 106" 104.7"
00,--s--012, 112" 1 13.9"
0 1 1 )-S- O(3) 112" 1 12.2"
ow -s- 0( 3 ) 114" 1 13.7"
(13)
There has bccn discussion as to whether p-bcnzenediazonium sulphonate has a
quinoid structure (14) o r a benzenoid one, of the predominant extreme form (15).
(14) (15)
T h e data available suggest that this molecule, and also 12, has a zwitterionic
structure although, according to some a small contribution froni canonical
form 14 cannot be entircly excluded from the spectroscopic results. In fact, the
N-N strctching band frequcncy lies at 2296 cm-' (in pctro!eum ctlier)'O in benzene-
diazoniuni chloride and at 2254 cni-l in p-benzenediazonium sulphonate. Instead,
in p-diazo oxide, OCJ-I,Nt, for which a prevalent quinoid structure is now believed
to exist, vhx (in CI-IC13)lies at 208s c n - ' . On the other hand, the structural data d o
not appear useful in this case since a small participation of canonical form 14
could cause a variation i n the bond lengths of tlic same order as that of the experi-
mental errors.
I n agreement with a zwitterionic structure, the N(,,-N12, distance (1.08 and
1.09 A, respectively, in 2-diazonium-4-phenolsulphonate monohydrate and in
) the same order as that found in most
p-bcnzenediazonium ~ u l p h o n a t e ~is~ of
diazonium salts (1.10-1.1 1 l’. In turn, the C I I ) - N c l ) bond length is 1.40-
1.41 A and compares very favourably with the values observed for unsubstitutcd
diazonium salts (1.39-1.42 A). Finally, these results are confirmed by the value of
the C - S bond length, which is very near to that found in similar moleculesG2* G3.
111. D!AZOTATES
A. isomerism
Addition of a strong base to a n aqueous solution of a diazonium salt leads to
rather complex transpositions, which have been of interest for a long time’. The
reaction scheme which is presently agreed on’. G4-72 IS
. the following:
slow
ArN:+OH- syn-ArN,OH
+ 7syn - A r N,O - + H,O

fa9t
syn- A r N ,O H 0H - (2)
filou.
syn-ArN,O- -A anti-ArN,O- (3)
ArN: +OH- 7anti-ArN,OH (4)
anti-ArN,OH anti-ArN,O-+H+ (5)
There is kinetic evidence only for the participation of syn-diazohydroxide in the
reaction’s 6 3 * ‘l, while anti-diazohydroxide has bcen identified spectroscopically but
not isolated iri the pure state’. ‘j4.
The existence of two diazotate ions in aqueous solution at appropriate pH,
which is now accepted by most workers‘, was in doubt until very recently72.i3.
Their existence now seems definitely established evcn for the syn-isomer of p-nitro-
phcnyldiazotate, which could not be detected previously becaiise of its high
labi I i t ~ ’ ~ .
The problem of t h e type of isomerism present in diazotate ions has been widely
studied’. However, since the techniques available were unsuitable, the results
obtained were never conclusive. Most workers’, O-O agreed that the isomerism present
in diazotates is geometrical isomerism (equation 6). However, the evidence put
forward to support this claim was essentially based on the analogy with similar
compounds or on kinetic results. Direct confirmation has been obtained only
recently, via the three-dimensional X-ray structural analysis of potassium-syiz-
methyl-diazotate’j. T h e results obtained, which are reported in Section III.B, may
be extended, so far as this type of isomerism is concerned, to the corresponding
phenyl derivative (PhN20K), since Muller and found that both corn-
pounds are prepared in the same way and have similar properties.
/N=N
Ar
\
0-
cis ( s y n )
--
- __f
/N=N
Ar
I
0-
trans ( a n f i )
The problem of the configuration of the syrz and anti isomers is now largely
clarified and will not, therefore, be treated at length.
106 S . Sorriso
B. Structure of Potassium-syn-methyl-riiazotate
MeN,O-K (16): This is thc only diazotatc for which structural paranicters are
available; R = 0.054; standard deviations 0.005-0.01 A and 0.5". The C-N and
N-N bond lengths in 16, (1.477 a n d 1.246 A, respectively) arc of the same order
as those observed in azornethane (1.474 a ~ 1.244
d A, rcspcctively)". By contrast,
the N-0 distance (1.306 A) is shorter than that observed usually (l.39-1.41)7s.
Uncorrected
N[,)-N,,) 1.246 8, C-N[,l-N,2) 116.2"

C-No, 1.477 A N[1,-N[.,)-O 119.8"
N,,,-O 1.306 A
NW NO) N:,1 0 2.205 A K 0 2.650-2.785 A
K N,?, 2.900 A K N,,) 2.914-1.957 A
(16)
These results may be explained by invoking the participation of the extreme forins
17a and 17b to the resonance hybrid, with the prcdorninance of the former. T h e
data reported for 16 exclude the altcrnative theory on the configuration of
diazotates'. according to which the stable isomer (n,iti) has the sanic con-
figuration as that p u t forward by Hantzsch, whilst the labile one (syn) has thc
structurc 18.
(?7b)
IV. DIAZOALKANES
A. General
T h e structures of only a few diazoalkanes not containing othcr characteristic
groups (diazoniethane, 2-bromodiazofluorene and plienyl(triplienylsilyl)diazo-
methane) have been determined. T h e structural pararnetcrs for diazornethane have
been reviewed previously's M 283~ and will not bc reported herc.
In the diazoalkanes examined to date, the C-N bond Icngth (1.28-1.32 A) is
greater than that observed for a Csp'=N bond (1.23-1.26 A)34.At the same time, the
N-N distance (1.12-1.13 A) is greater than that found for dinitrogen and for
bcnzenediazoniuni chloride (1.09)8*lG. Jn agrccincnt with most workers""-32, this
evidence suggests that the =CN, group is a resonance hybrid beliveen thc canonical
forms 19 and 21. Form 21 is commonly not reported sincc its contribution is very
small compared to that of 19 and 20, as i t possesses fewcr covalent bonds and there
is a largcr charge separation.
R' R' R'
\C=N=fi
+ \- + \- +
/
R'
< t
/
R'
C-NEN 7
/C-N=N
R'
(19) (20) (21 1
Tlie participation of the t\vo extreinc forins 19 a n d 20 to tlie I'csonaiice hybrid

is confirmed by the infrared spectra. I n fact, tlic frcqucncy of llie N-N strctching
vibration band (3058 cm-' in ether and in CCI, for the rnolecl1le CH,N2)RY. 'J3 is
3. Structural chemistry I07
smaller than that observed for the p-dimcthylarninobenzenediazoniuin cation
(2166 cm-I, in petroleum ether)?", for which a relevant contribution of a quinnid
form is now proved.
There has been some work on the relative contributions of forms 19 and 20 by
means of n.m.r. and electric dipole moment measurements.
Interpretation of the n.m.r. spectra was based on the observation that in form
19 the electron density on the carbon atoms a and p to the diazo group is different
from that in 20. Consequently, the chemical shift of the protons bonded to these
carbon atoms should give some indication as to the participation of the two
canonical formsg4.95. TO this purposc, Ledwith and Friedrichsg determined the
nuclear magnetic resonance shielding parameters for the following compounds :
H2CN2, IvieCHN,. C H K H C H N , , EtOCOCHN,, MeOCOCIIN,, PhCHN2,
Ph,CN2, (p-MeOCGH,),CN,, diazocyclopentadiene and 9-diazofluorene. For these
molecules a greater shielding than that for similar compoundsg6~ O7 was found.
According to the authorseg this may be due to a considerable participation of form

20 and/or t o the presence of diamagnetic anisotropy in the diazo group analogous
to that observed for acetylenes and nitrilesgs.
It now appears that the high shielding found in n.ni.r. spectra is due in t h e niain
to the presence of diamagnetic anisotropy. In fact, rroni the observed moments for
the molecules Ph2CN2 (1.27-1.42 D)'O0.Io1, (p-ClC,H,),CN, (0.65 D)'O0.Iol and
t +
using p(C,,,-CCI) = 1.59 D lo?, a value of p(CN2) of c. 1.0 D, having the direction
indicated1o3, is obtained. Taking into consideration the fact that the theoretical
moment of form 19 is smaller than that of 20 (5.46 and 6.24 D, respectively, for
diaz~methane)~ we~ , deduce that the first predominates over the second. In t h i s
context it is worthy of note that for diazomethane 19 and 20 are present i n the
ratio 66/34", in agreement with a n independent estimate of 70/30 obtained from
microwave quadrupole measurements'o4.
B. X-Ray Data
I . 2-Bromodiazofluorene
CI,H,N,Br 105 (22): R = 0.09; standard deviations 0.031-0.040 8, and 1.8-2.8".
All the atoms lie in the same plane apart from Br, C171
and No,, which arc slightly
shifted from this plane.
Uncorrectcd
... ___-
108 S. Sorriso
Uncorrected
1.501 A 1.456 8,
1-384 8, 1-393 8,
1.349 A 1.362 8,
1.404 8, 1.876 A
1.124 8, 1.323 8,
121.1" 120.8"
121.7" 1273"
1 18.6" 109.9"
119.6" 125.9"
122.7" 117.9"
115.9" I 17.8"
108.7" 126.2"
104.8" 102.5"
112.9" 178.2"
104.4" 1 18.5"
109.0" 120.3"
133.4" 131.2"
2. Phenyl(triphenylsily1) diazomethane
Ph(Ph3Si)CN2'OB (23): R = 0.117; standard deviations 0.0164020 A and
0-5-1.4". T h e C-H bond length is 1.05-1.08 A. T h e molecule is monomeric. T h e
structural parameters of the CN, group a r e very close to those found for diazo-
methane1Sa2* The Si-C bond distance (1.865 A) is similar to that observed for
tetraphenylsilane (1.872 The present data d o not suggest the participation of
- +
a form =Si=C-N--=N, involving 3d orbitals, to the resonance hybrid.
Uncorrected
1.882 8, 1.468 8,
1.863 8, 1.280 8,
1.871 A 1.130 8,
1.846 8,
1.366 8, 1.380 8,
1.375 8, 1.372 8,
1.347 8, 1.353 A
1.358 A 1.380 8,
1.364 8, 1.392 8,
1.413 A 1.391 8,
Uncorrccted
1.383 A 1.359 A
1-386 8, 1.374 A
I .360 A 1.342 a
1.369 8, 1.353 8,
1.381 8, 1.415 A
1.357 8, I .393 A
108.3" 110.7"
109.2" 125.7"
107.1" 115.3"
112.1" 1 18.8"
109.2" 178.1"
120.6" 124.5"
122.3" 122.0"
119.0" 119.9"
123.4" 119.9"
122.0" 120.6"
1 18.6" 1 19.3"
1 17.7" 118.2"
121.8" 1 17.0"
1 19.6" 121.9"
127.8" 124.7"
118~1" 118.3"
121.0" 120.2"
119.0" 121.5"
122.7" 1 18.0"
I 16.4" 116.8"
173.9" 171.0"
V. AROMATIC DIAZOCYANIDES
A. Synthesis
T h e following isomers of these compounds have been isolated : the addition
product PhN,CN.HCN and the two isomeric forms, sytz and m r i , of the diazo-
cyanide. The former is labile and the latter stable. The addition product is prepared
in acid medium and in excess of cyanide108-111. T h e other two compounds are also
prepared in acid medium, but the cyanide is added slowly and is always in less than
molar ratio with respect to the diazonium salt and the I f the reaction is
carried out a t - 5 "C and in sufficiently Concentrated solution, the labile form
precipitates a s a crystalline compound. At room temperature, the labile isomer
slowly isomerizes to the stablc one. Finally, if the reaction is carried out by adding
a neutral solution of the diazonium salt to a concentrated solution of potassium
cyanide in a water-alcohol mixture at - 20 "C. the compound obtained is
completely different from those mcntioned above1o8* On X-ray evidence116 this
compound has been assigned the formula ArN,C(NH)CN.
B. Structures
T h e structural parameters of the stable isomer of the diazocyanides have been
determined in threc works. Unfortunately, because of their low stability, no structural
110 S. Sorriso
study has been carried out o n the labile sytz isomers. Even qualitative data on the
latter would have allowed definite conclusions to be arrived at regarding the
type of isomerism present i n diazocyanides. This has bcen much discussed (see
Section V.C).
The bond distances in the an/i-diazocyanides fall in t h e following ranges:
C,,r-N, 1.29-1.42 A ; N-N, 1.25-1.32 A; N-CC,,, 1.36-1.41 A and C = N 1.14-
I .! 5 A. Comparison of these distances with those for rrntrs-azobenzenc and its
symmetrical derivatives gives useful information on the electronic structures of
diazocyanides. I n ~ ~ n t i ~ - a z o b e n z e n Cfr~tis-4,4'-dichloroa~obenzcnc~~~,
"~, trntis-
4,4'-azodiphenetole1~!',frmrs-4-plienylazoben~ene1zo the bond distances are: Csp:- N ,
1.43-1.46 A, and N-N, 1.23-1.25 A. T h e presence of some dclocalization in thc
azobenzenes (bond order 1.9 for N-N and 1 . 1 for Csp2-N)9J has been suggested
by comparison with the aliphatic analogues. For the diazocyanides, which have no
symmetry elements, this delocalization increases since the C,,I-N bond length is
shorter, and the N - N greater, than those of rmtis-azobenzenes.
I. p-Chlorobenzene-anti-diazocyanide
CIC,H,N,CN (24): R = 04282; standard dcviations 0.007-0.030 8, and
0.7-1.9". The molecule is planar.
2. o-Bromobenzene-anti-diazocyanide
BrC,H,N,CN 132 (25): R = 0.059; the standard deviations are 0.006-0.011 8,
and 0.7". The molecule is almost planar.
3. o,p-Dibromobenzene-anti-diazocyanide
Br,C,H,N,CN (26): R = 0.168; almost planar.
(26)
Uncorrected
1.153 A
1.414 A
1.322 8,
1.285 8,
1.406 8,
1.366 A
1.322 A
1.469 A
1.337 A
1.511 A
1 ,850 A
1.915 A
Uncorrected Uncorrected Corrected LTncorrected
-
174.7' 172.5" 170.5"
108.0" I 1 3.0" 1 13.9"
116.6" 1 13.6" 1 13.2''
120.9'' 125.7" 128.3"
122.1" 1 17.6" I 15.8"
1 18.9' 137.0" 125.6"
118.1" 1 19.0" 1 12.2"
122.6" 119.9" 124.6"
120.2" 119.7" 122.4"
117.9" 120.8" 1 17.9"
122.0"
121.4" 122.0"
112.3"
4. p-Chlorobenrene-anti-diazoimidoglyoxynitrile
ClCoH4N2C(NH)CN'lo (27): R = 0.09; standard deviations 0.007-0.014 A and
0.5-0.8". Other bond lengths: C-H, 0.90-1.05 8, ( f. 0.1), and N-H, 1-05( L- 0.1I).
T h e molecule is essentially planar. The structure of the CBHPN2group is very
similar to that observed in the other anti-diazocyanides.
119.1"
1 19.3"
1 19.5"
1 19.6"
121.6"
I 19.4"
1 18.3"
121.7"
124.4"
113.9"
112.9"
111.2"
114.5"
119.1"
126.6"
177.2"
C. Isomerism
Since there are n o literature data on the structure of the syn isomers of diazo-
cyanides, it may be useful to coniment on the type of isomerism present in these
.pounds.
112 S. Sorriso
On thc basis of the structural results obtained fgr the ben-~r,,o-nrtti-diazocyanijes
seen above there are t\vo possibilities for the isomerism of diazocyanides:
ArN=NNC r z A:N=NCN (7)
CN
/
N=N
\ t-
, N=N
/
Ar CN Ar
syn (cis) anfi (Irans)
T h e disagrcemcnt as to the significance of the chemical evidence, which has occupied
several shows that i t cannot constitute conclusive proof for either of
the possibilities (7) and (8). The only physical results currently available have been
obtained from dipole moment and infrared spectra measurements.
Tlie electric dipole moments of sonic diazocyanidesllJ, measured in benzene, are
shown in Table 1. What conclusions can be drawn from these d a t a ? Since the group
nioments for nitrile and iso-nitrite are very similar131, information on the con-
figuration niay be from a n examination of several members of the series
rather than by treating each singly. The situation (7) leads virtually to the same
difference in obscrvcd dipole moments in each pair of syn/an/i isomers. Since, a s
seen from Table 1 , this is not the case, this possibility may be excluded. The
possibility remains of a geonietrical isomerism (8). W e can try to verify this as
follows. Tlie group moment p(2,4,6-Br,CBH,N)may be assumed equal, to a good
d
approximation, to p(PhN), which is c. 2.0 D I14. Using this value, from the moment
observed for 2,4,6-tribromobcnzene-anri-diazocyanide, p(N-C=N) is estimated
to be c. 2.0 D llJ. With this value and the usual bond and group moments'02, the
following theoretical inoments (palc) for the an/i isomers of XCBH,N2CNniolccules
are then deduced (X, pC,lc,p,,bs): 4-C1, 2.4, 2.73; 4-Br, 2.4, 3-75; 4-N02. 2.0, 1.47.
T h e discrepancy between observed and calculated moments d o not allow con-
clusions to be drawn as to the presence of geometrical isomerism.
1. Observed dipole moments (D) for some aromatic
TABLE
diazocyanidcs"'
Compound Pwn Panti Psvn-Pant,
/+CIC,H,N,CN 2.93 3.73 - 0.80

p-BrC,H,N,CN 2.91 3.78 - 0.87
o- Br C, H.]N,CN 3.79 5.32 - 1.53
p-N OZC, H.1N ZCN 2.03 1.47 +0.57
o,w,p-Hr,C,H,N,CN 2.5 4.0 f 1.5
Interpretation of the i.r. spcctra is based o n the assumption that two geometrical
isomers should have C=N stretching bands very close t o one another in frequency
l ~ . This is observed, for example, in l - ~ y a n o - l - p r o p e n e ~
( v ~ h , ) l 133. which
~ ~ , gives V C N
a t 2221 cn1-l for the cis isomer and at 2223 for the trans isomer. By contrast, the
difference between the vm values for a pair of structural isomers is of the order of
100 ci1i-I 115, 135, 13G. Several authors have used these observations to obtain infor-
mation on the type of isomerism present in diazocyanides. The results obtained are
shown in Table 2 . T h e data in this table rcveal some disagreement among the
various workers. A difference in the vcx values between the labile and the stable
isomers has been found only by some authorsllS. I t seems hazardous to use this
evidence alone as suficient to indicate the presence of structural isomerism. In fact,
the integrated intensity of the C = N stretching vibration is greater in the stable
isomer (nitrilic) than in the labile one (isonitrilic) while an isonitrile usually shows a
more intense C E N band than t h e corresponding nitrilellss 13% 13G. Jn addition, the
difference in the v r n values is much smaller in a pair of diazocyanidcs than between
nitrileisonitrile pairs. Some workers explain this fact115 by invoking a strong
/-9
Ar-N=N-CeN conjugation, which would not only lower the frequency for this
-3
isomer but would also lead t o an almost linear -NNCN group. This explanation
is discounted by thc X-ray structural parameters obtained for the benzene-anti-
diazocyanides (see Section V.B). In fact, these molecules have a non-linear structure
with a C = N bond equal to 1-14 A, which is of the same order, if not lower, a s that
found in most nitriles studied to date137.
2. Frequency ( q ? and
TABLE ~ ) intensity of absorption ( A ) of the C=N
stretching vibration band for some aromatic diazocyanidcs
~ ~ ~~~~
Compound lsomcr Y (cm-I) A x lo-' inol-' I)
p-MeOC6H,N,CN syI1 21 50" 0.1 1

atiti 2190 0.47
p-CIC, Ha N2CN syn 2187b
atir i 2187
p-BrC,H,N,CN syn 2154" 0.026
2187b
2185'
atiti 2192" 0.17
2187b
2185'
sytl 2 161" 0.037
2187b
anti 2 193" 0.064
2187b
o,tn,p-Br3C,H,N2CN syri 21 87c
anti 2185
a In CCI, l15.
In CCI, 132.
I,
' ?'he tribromo compounds were examined in CHCIJ and CS, solutions
and the monobromo one in nujol
To conclude, the results of Kazitsyna and also d o not constitute
proof that situation (7) is present. On the basis of indirect evidence, i.e. by analogy
with similar compounds, we tend, like most workers', toward isomerism of geo-
- .rical type (8).
VI. DIAZOKETONES
A. Isomerism
1. General
Different diazoketones may be obtained, depending on the position of the carbonyl
group with respect to the diazo group. Most work has been centred on the
a-derivatives because they are the easiest to prepare and have also numerous
applications in organic syntheses'. 138-141.
114 S. Sorriso
The configurations adopted by z-diazoketones depend on the conjugation betwem
the diazo group, which in this case acts with a + M effect, and the carbonyl group,
which exerts a - M effect. The atomic orbital scheme involved in this delocalization
is shown in Figure 3. For the only niolccular structure of .x-diazoketones solved to
A
date, 1,4-bisdiaz0-2,3-butanedionc"~,the following values were obtained: C N N
A
176.8", CCN 116.5". These results indicate that in the a-diazoketones the carbon
aloni C(?, (Figure 3) is essentially sp? hybridized and both nitiogen atoms have sp
hybridization. The x , orbitals are localized on the latter two atoms, which each
furnish a n electron t o the bond formed between them. Instead, the x, orbitals a r e
delocalized over several atoms (e.g. five in the case of diazoacetone, MeCOCHN,) to
different extents depending on the nature of the substituents R' and R2.The nitrogen
atom N,,, donates two electrons to this molecular orbital and all the other atoms
donate one each. The delocalization of the x, electrons on the atoms of the molecular
skeleton causes the central C(,,-C(,, bond to become partially double bonded.
It follows that two rotational isomers may exist, each having the COCN, group
more or less planar (Figure 3) depending on the electronic, steric and electro-
static effects exerted by R' and R2.
Apart from this geometrical isomerism, a-diazoketones may also, in theory,
show structural isomerism due to the transposition of the hydrogen atoms a to the
carbonyl group. Depending on whether the hydrogen migrates to the carbonyl
oxygen or to the terminal nitrogcn there will be keto-enol or diazo-isodiazo
isomerisin, respectively.
Identification of the type of isomerism present becomes more difficult since
diazoketones may form an intcrrnolecular hydrogen bond with another diazo-
ketone molecule o r with a iiydroxylic cornpouiid'43--"5. This explains why early
results, although experimentally valid, often led to incorrect conclusions.
We now examine the theorctical and experimental evidence for the type of
isonicrism prcsent in 3-diazoketones in cliffcrent mcdia.
2. Ultraviolet/visible and infrared spectra

The ultraviolct/visible spectra of u.-diazoketones in mixtures of non-polar and
hydroxylic solvents show a charactcristic behaviour. The -COCN, group has a n
intense band at c . 245-250 nm, which becomes weaker with increase in the
hydroxylic/non-polar solvent ratio, and another band at 270-290 nm which a t the
same time increases in There are n o shifts in the bands on going
from one solvent to the othcr. I n almost all the cases studied to date the curves show
a n isosbestic point which seeins lcss clear the lower is the availability of the carbonyl
oxygen lone pair, i t . the higher is the frequency of the C=O stretching model".
T h e presence of an isosbestic point suggcsts that two species exist i n solution in
equilibrium with one another15'. There are four possibilities for our niolccuies:
the keto-enol equilibrium

OH
I
OH
I
RCH=CCHN,
(28)
the diazo-isodiazo equilibrium
0
0
II
RCH,-C-CHN,
0
+
y
II +
R E H - C-CH=N=N-H
the conformational equilibrium

cis 7frans
(30)
and, finally, the presence of a hydrogen bond (31).
The existence of an isosbestic point does not necessarily mean that situations 28
or 29 are present since it is also observed for molecules which d o not contain
transposable hydrogen l J 0 . The same may be said of the conformational
5
116 S. Sorriso
equilibrium, 30, since a siiiiilar dependence on solvent and an isosbestic point are
also found i n the spectra of compounds for whicli this isomerism is not possible,
e.g. 2-diazocyclohe~anone~~~, 3-diazonorcamphor and 3-diazocamplior'".
For a variety of reasons, we favour the possibility (31). In agreement with F a h P
i t is our opinion that in mixed solvents there is formation of a hydrogen bond
between the diazo compound and the hydroxylic solvent. The evidence for this
conclusion is derived from t h e fact that the isosbestic point becomes more evident
the greater is the availability of the oxygen lone pair to form this type of bond. The
presence of the latter is proved by the behaviour of t h e 0 - H stretching vibration
band of phenol in the presence of various a - d i a z o k e t o n e ~ ~
This
~ ~ . interpretation
explains why the same behaviour in mixed solvents is observed for molecules for
which two conformers are possible and those for which they are notia9. lS3. In
agreement with this, for diazoacetonc, MeCOCHN,, and diazoacetophenone,
PhCOCHN,, it was observed that the band due to the T ; +it* transition in the cis
isomer overlaps that in the tmns isomer.153
As to the infrared spectra of a-diazoketones in mixed solvents, Foffani and
observed that integrated intensities and frequencies of the N-N
stretching vibration band are almost invariant for diazoacetone, diazoacetophenone
and benzoyl(diazo)phenylmet hane on varying the ratio between non-polar and
hydroxylic solvents. Morcover the C=O stretching band at 1662 cm-l in diazo-
acetone decreases in intensity, in C2C14 as solvent, with increasing quantity of
phenol. At the same time the peaks at 1633 and 1633 cm-I, which are very weak
in intensity in non-polar solvents, became more intense with increasing phenol
concentration. These phenomena may be due to the presence of hydrogen bonding
between the carbonylic compound and the hydroxylic solvent, which stabilizes one
conformer more than the other. According to this, for molecules having two con-
formers, one peak in the N-N stretching band disappears in the presence of
hydroxylic soIventsiS4.This interpretation, which reconciles the U.V. and i.r. results,
appears plausible but requires further experimental justification.
The atoms involved in the hydrogen bond may, in theory, be the terminal
nitrogen, the carbon of the diazo group and the carbonyl oxygen. Involvement of
the nitrogen o r of the carbon atom may be excluded since the i.r. spectra of phenol
in the presence of diphenyldiazomethane (0.004M) in CCI, show no evidence for
its presence145.The only atom available is thus t h e carbonyl oxygen.
The formation of a n intermolecular hydrogen bond between two diazoketone
molecules has recently been established1l4#Ia5 for RCOCHN, compounds. N.m.r.
measurements were carried out in weakly accepting solvents such as CCI, and
d,-benzene at a temperature at which interconversion between possible rotamers is
very fast and it was found that the chemical shift varies regularly with the con-
centration of the diazo conipound14S.
The possibility that two rotamers exist in equilibrium in apolar solvents, foreseen
by Foffani and c o w o r k ~ r s * ~ has
~ , recently been established by Sorriso and
lS6 by examining the N- N stretching vibration band in CCI,. This
band is suitable for our purpose because i t falls in a frequency range in which other
groups present in the molecule do not absorb. 'The molecules CH,CICOCHN,,
CHCI,COCHN,, r-BuCOCf-BUN,, PhCOCHN? a n d PhCOCMeN, show a single
N-N stretching band, while MeCOCHN,, MeCOCMeN, and PhCOCPhN, give
split N-N bands (Figure 4). Since rotaniers stabilized by a sufficiently high-energy
barrier to interconversion have different i.r. spectra, the splitting of the diazo band
indicates the presence of two conformers.
Insight into the reasons for the existence of t w o rotamers in a-diazoketones comes
also from an examination of the frequencies of the carbonyl and diazo stretching
vibrations, which fall around I650 and 2080 cni-l. respcctivelyR8,03, 1r+'.5fl. These
frequencies are clearly shifted compared to those in the corrcsponding
and d i a z o h y d r o c a r b o ~ i s93;
~ ~vc0
~ moves to lower frequency and V X X to higher
frequency. This indicates that in these molecules the carbonyl group has lcss double-
bond character than i t does in ketones, while the N-N bond is of higher order than
4. Profile of N-N stretching vibration band observed in CCI, for: (a) diazoacetone
FIGURE
McCOCHN,; (b) I-acetyl-I-diazoetliane, McCOCMeN,; (c) benzoyl(diazo)phenyl-
methane, PhCOCPhN2; (d) diazoacetophenone, PhCOCHN,,.
in diazohydrocarbons of the same order of substitution. 111 other words, a third
limiting form, 34, which occurs at the expense of form 33, is i n addition to the
canonical forms 32 and 33 also present in diazohydrocarbons. The participation of
the form 34 gives the central C-C bond a partial double bond character. T h e
contribution of forms of type 33 and 34 is higher the higher the frequency of the
diazo band and the lower its intensity. The oppcsilc: holds for contribution of forms
of the type 32 93. 160.
(32) (33) (34) (35)

When R 1is a phenyl group, forms of the type 35 may also
3. Nuclear magnetic resonance

One of the most important applications of n.m.r. spectroscopy is in structural
studies by means of the chemical shift (8) and coupling constant ( J ) para-
meters86, 87, 161, 162 . The chemical shift and coupling constant, which give comple-
menlary structural information, are directly connected to the electron distribution
about the nucleus and t o the type of bond between the nuclei, respectively. Both
parameters change with change in the molecular environment. Thus, the use of the
technique in studies of the type of isomerism present and determination of thermo-
dynamic parameters for isomer equilibrium is understandable.
a-Diazoketones of general formula RCOCHN, have been widely studied using
p.m.r.Id4. Some results of this study are shown in Table 3. Temperature-dependent
p.m.r. spectra have been observed for the molecules IICOCHN,, MeCOCHN,,
EtCOCHN,, PhCH,COCHN,, MeOCOCHN, and EtOCOCHN,. At room
temperature there is a single sharp peak which broadens and splits into a doublet
on lowering the temperature (Figure 5). Only a single peak is observed in the
11s S. Sorriso
t-butyl derivative (r-BuCOCHN,) and in aryldiazoketones (PhCOCHN,, p-NO&-
H,COGHN, and p-MeOC,H,COCI-IN,) the inteilsity of which remains constant
at different tempcratures. A s for analogous cases1G3-1G5 this indicates that two forms
are present in equilibrium i n the first six compounds, whilst the aryldiazoketones
give only a single peak and thus only a singlc spccics, or else two in rapid inter-
conversion or coincidentally having the same chemical shift. Given the steric effects
present, the r-butyl dcrivative almost certainly exists i n a single, very distorted, form.
TABLE 3. Fractional populations ( P ) , equilibrium constants ( K e g ) and standard free-energy

dilferences ( A F ) of the cis snd t n r m forms of diazoketoncs (RCOCHN,), 40% w/w solution
in deuteriochloroforni. Reprinted with permission from Kaplan and Meloy, J . Amer. Chew.
Soc., 88. 950 (1966). Copyright by the Amcrican Chcniical Society
Ha 0.69 +O.0Zc 0.31 +0.02 0.149( - 2 0 ) 0.40 ( - 20)

Me 0.924 i: 0.008 0'076 f0.008 0.082 ( - 40) 1.16 (-40)
Mcb 0 9 0 3 -1- 0.002 0.097 2 0.002 0 . I SO ( - 40) 0.79 ( - 40)
f-C,H, > 0.99 <0.01d
PhCH, 0.962 If: 0.002 0.035 f0.002 0,040 ( - 40) 1 '49 ( - 40)
McO 0.535 0.004 0,462 2 0,004 0.859 ( - 50) 0.07 ( - 50)
EtO 0.54 +0.01 0.36 20.01 0.840 ( - 50) 0.08 ( - 50)
Values of energy of activation (E:,), frequency factor ( A ) , free energy of activation (AF')
and temperature of coalesccnce (T,) for hindered internal rotation about the C-C central
bond in diazoketones (RCOCHN,), 40% w/w solution in deuteriochloroform
trniis -+ cis
Ea E2 fw,,I<
R (kcal/niol) log A (kcaljmol) log A (kcal/niol) T, ("C)
_- ~-
Me +
15.5 0.9c 12.5 15.4 1 5 . 5 f0.9" 13.9 13.9 12.s
M ee 15.9 f0.6 15.0 154 15.9+_0.6 16.1 14.1 13.5
Et +
16.1 0.6 13.6 15.3 16.2 f 0.6 14.8 13.5 6.5
PhCH, +
15.2 0.6 14.9 15.3 18.2 f 0.6 16.3 13.4 1.0
Me0 +
12.5 0.9 12.6 12.8 +
12.5 0.9 12.7 12.7 - 25.0
Eto 9.0 f0.8 9.7 13.3 9.020.5 9.8 13.2 - 32.5
~~
Concentration unknown.
a
20% w/w solution in deuteriochloroforni.
b
Average deviation involving at least two separate samplcs.
The [runs resonance line was not observed.
Errors represent the prccision of the Arrhenius plots. The free energies of activation
were calculated from the relationship SF;. = 2.303 XT log (T+ KkT/h). The transmission
coefficients, K , are assumed to be unity.
For the compounds which give doubling of the methine proton peak at low
temperatures, attempts have been made to assign struct urcs. Kaplan and Meloy144
considered the possibilities: keto-enol (28) and diazo-isodiazo (29) structural
isomerisms; geometrical isomerism (30) (Figure 3). Tautonieric equilibria (28) and
(29) may be excluded since the I3C- EI coupling constant for high-temperature time-
average species is the same as that of the species predominant at low temperature
( J = 199 c.P.s.) for McCOCHN,, EtCOCI-lN, and EtOCOCI-lN,. If structural
3. Structural clicmistry 119
isonicrs had been present, the time-averaged species at high temperature would
have been expected to show coupling co~istanlsdiffcrcnt from those of the species
predominant at low temperature, sincc the two species have different C-13
environments.
1 A
34 "C -13°C
i
y' c
A- 43°C
FIGURE 5. Tcmperatiire dependence of thc n.m.r. spcctrum of thc methine proton of methyl
diaioacetate (MeOCCCI-IN,). Rcprintcd, \vith pcrniission, from Kaplan and Meloy,
J . Amev. Chem. Soc., 88, 950 (1966). Copyright by the American Chemical Society.
Having assigned the two pcaks to the two conforiiicrslGG-'", the thermodynamic
parameters for the cis 2 frn~rsequilibrium have been calculatcd by integrating the
peaks (Table 3). The values listed in this table show that the ratio of the two con-
formers does not depend only on stcric factors.
The cnergy barriers to intcrconvcrsion between the two rotnmers fall in the range
9-18 kcal/mol. The IoLver values are obtained for diazo esters, in \vhich diazo-
carbonyl conjugation is lower and hence thc double-bond character of the C - C
central bond is lower.
The 13C-H coupling constant ( J == 199c.p.s.) indicates144that the C-H bond
has high s charac:er (41%,), which suggests that the rnethine hydrogen m a y
participate in hydrogen bonding.
T h e p.m.r. evidence leaves little doubt that the isomerism present in
a-diazoketones is geometrical isomerism. Furthcr conformational studies are thus
airned niore at obtaining insight into the cffect of thc R' and R 2 groups on thc
cisltrotrs ratio and into the theoretical aspects of this isomerism rather than proving
its existence.
120 S. Sorriso
4. Electric dipole moments
The usefulness of electric dipole moments in conformational studies has been
known for some 170-17,. For a-diazoketones this technique has been used to
determine the relative contribution of the two rotainers and to study t h e effect of
the R 1 and R? groups. The observed dipole moments, in benzene, at 25 "C and
assuming f3 = 0, are (compound, dipole moment in debye): MeCOCHN,, 3.37;
CH,CICOCHNz, 2.80; CHCI,COCHN,, 2.65 ; CCI,COCHN,, 2.46 lo3; PhCO-
CHN?, 3.66; p-MeCeH4COCHN2, 4.01 ; p-CIC,H,COCHNz, 3.08 ; p-BrC,H,CO-
CHN,, 3-11 ; p-MeOC,H,COCHN,, 3-73; PhCH,COCHN,, 3.31 ; Ph(CH2),-
COCHN?, 3.39 l i 3 ; BzCPhN?, 2.77 ; VI-CICCHJCOCHNZ, 3.34; o - C I C ~ H ~ C O C H N ~ ,
3.56 l o l ; MeCOCMcN,, 2-45; Y-BUCOC~-BUN,,1.98; PhCOCMeN,, 2.75;
p-CIC6H4COCMeN,, 2.05 ; o-CIC,H,COCMeN,, 3.18
The observed moments indicate that whilst MeCOCHN,, PhCH2COCHN,,
Ph(CH,),COCHN,, BzCPhN,, o-CIC6H4COCHN2, MeCOCMeN,, p-CICeH4-
COCMeN,, PhCOCMcN, and o-CIC,H,COCMeN, may be two rotamers, only
one species, the cis one, is present in halogen derivatives of diazoacetone.
Presumably there is a strong electrostatic effect by t h e halogen atom on the diazo
group.
The aryldiazokctones are almost entirely present as the cis conformer. This
result agrees with the X-ray data175a n d with the fact that only a single sharp peak
for the methine proton is observed in the n.m.r.l" and the N-N stretching vibration
band is single in CC14Is.-'.
Finally, the t-butyl derivative gives only a single rather distorted structure with
an angle of c. 140' between the CCO and CCN planes.
5. MO calculations
MO calculations on a-diazoketones have essentially two aims: to see if there is
theoretical justification for the rotational isomerism found experimentally, and to
obtain information on the molecular conformation of rather complicated coni-
pounds, information not obtainable by other means.
~ ~ ~performed MO calculations on diazoacetone
Csizniadia and c o ~ o r k c r shave
and diazoacetophenone using Hoffniann's extended Hiickel met hod. The scheme
used and the results obtained are shown in Figures 6 and 7. From Figure 6 i t may
be seen that two conformers, cis and fmm. both with almost the same energy and
the COCHN, group planar, are possible for diazoacetone. The energy barrier
height to interconversion between the two species (- 14 kcal/mol) is of the same
order as that determined cxperimentdly from n.1n.r. spectra in CDCI, ( - 16 kcal/
mol)*4t.As expected, variation in the angle 4 has an almost negligible effect on the
relative energies of the two rotamers and on the barrier height.
By contrast, the effect on changes in angle 4 in diazoacetophenone is con-
siderable (Figure 7). At y = 120" and C#I = 0" there is only a single isomer, the cis
form. Instead on varying the angle 4, i.e. on rotating the pheny! group out of the
molecular planc, diazoacetophenone gives two conformers having similar energies
and a barrier height of the order of 14 kcal/mol. This result is not in agreement
with the i.r. and n.ni.r. spectra and the dipole moments, which suggest only one
isomer, the cis one. The discrepancy betlveen theoretical and experimental evidence
may be due to solvation and/or to entropic factors's3.
Sorriso and coworkers have studied the molecules CH,CICOCHN,,
MeCOCMeN, PhCOCPhN2 and PhCOCMeN, by the C N D 0 / 2 method
using the structural parameters of Figures 6 and 7. The calculated energies suggest
1.07
1.32
1.12 i
116.5'
r +-
. -13555.6 -135695 I
T + O '
30"
+
- 13555.4
Oo 30" 60" 90" 120° 150" 180"

cis Barrier trans
Angle 8
(b)
e
N
1.
c
FIGURE6. Geometrical parameters (a) and energy surface for diazoacctone, MeCOCHN, ( y = 120").Numbcrs oil surface
refer to energy in kcal/mol ; (b) contour diagram, (c) pcrspcctive view. Reprinted, with permission, from Csizmadia,
Houlden, Meresz and Yates, Tetrahedron, 25, 2121 (1969).
?
CIS Barrier trans

Angle 8
(b) (4
~ ' I G U W 7.
Geonlctrical parameters (a) and energy surface for diazoacetophenone, PhCOCHN, ( y = 120'). Numbers
on surface rerer to cnergy in kcal/mol; (b) contour diagram, (c) pcrspective view. Reprinted, with permission, from
Csi./madin. Houldcn, Meresz and Yates, Terrulrcdrorr, 25, 2121 (1969).
3. Structural chcniistry 123
that two conformers were present in equilibrium ir? MeCOCMcN, and PhCOCPhN,
and only one, the cis, in the chloro derivative. Finally, two forms in rapid inter-
conversion exist for PhCOCMeN,.
For PhCOCMeN, and PhCOCPhN,, as for the diazoacetophenone, there is
concerted rotation of the phcnyl and the methyl groups about the bond with the
nioleculdr skeleton during the interconversion bet\cecn the two rotamers.
The phenyl group bonded to t h e carbonyl coiijugates with it, in agreement with
experimental resultsss*l i 9 . In addition, in PhCOCPhN, the phenyl bonded to the
diazo group conjugates with it. Dcspite this, diazo-carbonyl conjugation prc-
dominates over the others.
6. Conclusions
T h e results obtained to date show that the isomerism present in a-diazokctoncs
is geometrical isomerism. As mentioned in Section V I . A . 1 , this arises because of
conjugation between diazo and carbonyl groups, which makcs the central C-C
bond partially double-bonded. This suggcstion is supported by the frequency of the
N-N and C - 0 stretching vibrations compared with those in diazohydrocarbons
and ketones. T h e presence of t w o conformers is confirmed by the low-tcmperaturc
doubling of the methine proton in n.m.r. specira of several diazoketones of the
type RCOCHN, and the doubling of the N-N stretching vibration band. M O
calculations using two different methods also show that, if hindrance of all kinds
is absent, thc configuration preferred by the COCN, group is a planar one.
T w o factors seem to control the cis f r o m equilibrium in a-diazoketones
R'COCR2N,. T h e first is diazo-carbonyl corijugation, which is responsible for the
energy barrier height to interconversion between the two conformers. The latter
increases -if R1 is electron attracting and decreases if i t is a n electron donor. By
contrast, it is lowered if R' is electron attracting since such a group involves the ;i
system of the diazo group, lowering thc conjugation of the latter \\,it11 the carbonyl.
T h e second factor is the influence of steric and clectrostatic elfccts excrted bct\veen
R', R2, the carbonyl group and the diazo group. This factor causes variations i n
both the height and relative energy of the two conformers and therefore in thcir
population.
Finally, for most of the molecules of general formula RCOCHN,, the cis con-
former is preferred to the from one. This may be due to two reasons. The first is the
fact that the diazo group is larger than the hydrogen and thercfore repulsion between
i t and R is greater than that betnrecn the hydrogen and R . The second is the
through-space interaction between the carbonyl and the diazo group. The latter
may be related to the presence of a fraction of negative charge on the c x b o n y l
oxygen and of one of positive charge on N , l , \vhich \vould attract one another, or
to a n interaction bet\vcen the ::systems of the diazo and t h e carbonyl groups. That
a certain stabilizing action is present i n the cis form is shown by the clear pre-
dominance of the cis species over the / m r s one in diazoacetaldchyde, HCOCHN,.
N .m.r. measurements lead to a cis/fr.rrm ratio of 7/3 for this molccule14.1.In the
absence of the stabilizing effect, the trotis form would havc been favoured, as shown
by models constructed using van der Waals' radii.
B. Configuration and Wolff Rearrangement

Knowledge of the configuration of a-diazoketones allows suggestions to be made
regarding the nieclianism o f thcir dccomposition1a4.Howevcr, i n order that the
products obtained may be correlated with thc structures of the starting molecules,
124 S. Sorriso
it is necessary that the rate of interconversion between the two rotamers be lower
than their rate of decomposition (36). This is not the case for diazoacetone'J4, for
which a first-order rate constant of 1.65 x sec-l has becn calculated for the
decomposition in f-butanol at 80 "C, and the cis -* trans interconversion has a rate
.I
constant of lo3 sec-*.
ka
cis + frans
k-= I
Products
(36)
I t is known that the decomposition of a-diazoketones (37) under appropriate

conditions, leads to cc,P-unsaturated ketones (38) and ketenes (39). The photolytic
and silver-oxide catalysed decomposition of a-diazoketones at room temperatures
gives mainly 38 and at high temperature 39. For PhCOCMeN, and (Me,C)COC-
(CMeJN,, the dipole moment d a t a allow a semiquantitativc analysis of the results.
0 0
II II
R'CC(CH,R')N, R'CCH=CHR' R'R'CH,C=C =O
(37) (38) (39)
If two conformers with COCN, group planar are present for these molecules, t h e
following cisllrans ratio would be expected : PhCOCMeN,, 44/56 and (Mc,C)COC-
(CMe,)N,, 7 / 9 3 . These values are of the same order as the ketenc/unsaturated
ketone ratios obtained experimentally. In fact, for thc unsaturated ketone, for de-
composition of PhCOCMeN, catalysed by Ag,Olin we obtain a ratio of 72%, and for
decomposition of (Me,C)COC(CMe,)N2 (pyrolysis, irradiation or acid-catalysed
~ obtain 80-90%. This evidence suggests that there is some
~ e a r r a n g e m e n t ) " we
dependence of the mechanism of decomposition o n the conformation of a-diazo-
ketones. This would mean that the decomposition occurs not through an intermediate
carbene radical but, rather, via a concerted migration process of an alkyl or aryl
group and loss of a nitrogen molecule14p.The cis form presents the more suitable
situation for this mechanism, which would also cxplain the effect of tctnperature o n
the nature of the decomposition products. I n fact, increase in temperature favours
the higher energy rotamers (for the two molecules concerned, the cis form) and with
this the formation of the ketene, exactly as observed experimentally.
FI~ially,the fact that the two molecules PhCOCMeNa and (Me,C)COC(Me,C)N,
are not planar means that t h e mechanism describing the Wolff rearrangement is
most facilitated in the cis conformer and impeded in the f r m s one and that there are
intermediate situations between these two extremes.
C. Structures
The molecules of a-diazoketones for which X-ray crystal structures have been
reported are not, unfortunately, the more representative ones. It is, therefore, not
possible to deduce general conclusions for this class of compounds nor to describe
their clectronic configuration from the present structural results.
I . I ,QBisdiazo-2,3-butanedione
C4H2N402 (40): R = 0.029, standard deviation = 0.001 A. T h e molecule is
planar with a centre of symmetry and has a cis conformation for both COCN,
groups. As pointed out by the authors'"?, these results appear to be contradictory.
In fact, thc C - 0 distance, of the sanic order a s that commonly observed for
and thc N-N bond, virtually the same as that for diazoniuni salts (sce
Section II.A.I), suggest a structurc of :hc 'diazo oxide' type 32 and 33, in which the
triple-bonded N-N type 33 predominates, as in unsubstituted diazonium salts.
In contrast, the values above indicate a significant double-bond character in the
bonds C-N and CO-CN, which may be rationalized by invoking a sensible
contribution by the canonical forms 32 a n d 34, respectively, to the resonance
hybrid.
Uncorrected
176.8"
116.5"
1 16.3"
125.2"
1 14.0"
(40)
As mentioned previously (Section VI.A.2), the formation of an intraniolecular

hydrogen bond between the methine hydrogen and the oxygen of the carbonyl
group in solution has been reported by several workers. For the niolecule treated
here, there seems to be little evidence for such a bond in the solid state as t h e
minimum 0 - H distance (2.66 A), even considering the usual X-ray displacement
of the hydrogen atom, is slightly higher than the commonly observed value of
2-52 A
3. 2'-Deoxy-5-diazo-6-hydro-0~,5'-cyclouridine
CgHIONdOL180 (42): R = 0.052; standard deviation G0.007 A. Only the bond
distances have been reported.
I26 S. Sorriso
Uncorrected
N(51-Nlil 1.120 A C(fil-O[s 1 1.415 A
C 1 5 1 - N 1 5 ) 1.308 A O(,.,-C[, 1 1.433 A
C(s,-C(I, 1.431 A C(s*]--Ctd,) 1.519 A
C o l - O l l ~ 1.234 A C(,*,-O(,,1 1.449 A
C t 4 , - N ( 3 1 1.361 A Ct,,,-O(,*) 1.404 8,
N131-C(21 1.381 A C,,,,-Nl,, 1.486 8,
C111-O15) 1.219 A C(,.)--C[2,I 1.529 A
N(l,-Cp, 1.319 A C(?,,-C(,.) 1.519 A
C ( G , - N , , , 1.457 C,,~,-O,,~, 1.431 A
CtS)-CIGl 1.484 A C(3.,-C(d.) 1.522 A
(42)
The bond distances observed for 41 and 42 suggest that as for thc other diazo-
ketones. the COCN, group in these niolecules is a resonancc hybrid between the
canonical forms 43-45. Thc other parts of thc molecule d o not conjugate with
COCN, group.
VII. D I A Z O OXIDES
A. General
When alkali is added to or/lro- and porn-hydroxy-substituted diazonium salts
and the mixture heated, compounds of !he type 46 arc obtained:
(46)
T h e nature of thc bonding present and the character of the six-membered ring are
the subject of t h i s section.
These substances are of some interest as they arc uscd as interniediatcs in the
laboratory and in industry and bccause they can be viewed, theoretically, as
reprcsenting a situation intcrmediate between the diazoniuni salts and the diazo-
alkancs.
Various names Iia\-e been suggested for these compounds: diazoquinoncs, diazo-
anhydrides, diazo oxides and quinonc diazides. For t h e derivatives of benzene and
naphthalene, the nnmcs diazophenols and diazonaphthols, respcctively, have also
becn used. In thc prcscnt chaptcr for most cascs \vc will adopt the name diazo oxides.
Scveral suggestions have been p u t fonvard as to rhc structure of diazo
oxides1H'-1s9,47 and 48. Sonic of thcse are now unacceptablc on the basis of modern
electronic thcory. Othcrs, such as thc cyclic structures, may be escluded o n the basis
of thc X-ray dsta (Section V1I.C) and of thc frequencies of the N-N and C-0
stretching vibration bands, some of which are slio\\n in Table 4. As can be seen
3. Structural clicniistry 127
f r o m this table, these frequencies a r e foiind in regions characteristic of absorptions
b y a N-N bond intcrmediate betwccn a d o u b l c a n d a triple b o n d and by a C-0
b o n d slightly lower than a doublc b o n d .
4. Values of the stretching vibration frequencies V S N and vco for some diazo oxides
TABLE
a"
Solvent o r
Subst it uent physical state VSX (cm-') vco (crn-') Reference
Diazophenols: oriho derivatives

N2
Unsubstituted K Br 2175 2140 I620 190

5-Me K Llr 2175 2130 1613 190
4,5-h?e2 K Rr 3,170 2120 1625 190
4,5-Me2 CHCI, 2150 2100 I625 191
5-Bu-I CHCI, 2182 2160 1618 190
3,5-( B u - ~ ) , CHCI, 2135 2124 1625 190
5-Me0 CHCI, 2128 1620 190
3,G-MeO CHCI, 2135 2087 1613 190
S-PhCHZO CHCI, 2150 1620 190
5-CI CHCI, 2205 2158 1613 190
6-CI CHCI, 2195 2158 1610 190
4,5-CI, CHCI, 2 IiiO 1613 190
3,5-Br2 Parafin mulls 21 10 1582 192
4-NOz Parafin mulls 2157 1562 192
4-NOZ Parafin mulls 2153 2150 41
4.64 NOJ, KBr 2235 193
4-COOH K Br 2215 193
Diazophenols: para derivatives 0-J--(-2N
Unsubstituted CHCI, 2080 191

Unsubstituted Paraffin mulls 2109 41
2,6-Me2 CHCI, 2090 1615 191
2,G- M e3 Dioxane 2060 1600 194
2,5-Me, CI-ICI, 2070 191
2,6-CI, K Br 2140 193
~ - M c 6-COOH
, K Br 2225 193
2-CCOH, 6-NOZ KBr 2225 193
Dinzonnpht hols
1,2-Naphthaquinonc-l- CHCI, 2132 2096 1671 195
diazide
4-Nitro-1.2-naphtha- Parafin mulls 2015 1642 193
quinone-1 -diazide
1,2-Napht haquinonc-2- CHCI, 2155 2114 1621 195
diazide
1,2-NaplitIiaquinone-2- Parafin mulls 2148 1610 1618 192
dinzidc
1,4-Naphthaquinonediazide Paraffin mulls 2014 1618 197
For the values of the stretching vibration frequencies reported for other diazo oxides
see Reference 196.
128 S. Sorriso
The problem of the elec1ronic structure of diazo oxides may at prcscnt be put i n
these terms: should these compounds be considered quinoid (483) or benzenoid
(48b) i n character, or a resonancc hybrid between both extreme forms 48? We will
attempt a reply to this question in Section VI1.B.
N
B. Electronic Structure
Some time ago, Sidgwick and suggested that the diazo oxides could
better be represented by a resonance hybrid between the two forms 48. This idea
was later accepted by other lg0. Anderson and RoedellB9found that the
visible and ultraviolet spectra of some diazophenols and diazonaphthols were very
similar to those of the corresponding quinones a n d inferred that the former must
have a quinoid structure. Le Ftvre a n d coworkers'"* O o 0 , from dipole moment
measurements and i.r. and U.V. spectra, concluded that the diazo oxides are a
resonance hybrid between the canonical forms 48, the quinoid form clearly pre-
dominating. The electric dipole moments, determined in non-polar solvent, are
reported in Table 5. Vector analysis of the moments of this table may give the
5 . Electric dipole moments observed for some
TABLE
quinone diazides"
Corn po und P (D)
3,5-Dibrorno-l,2-benzoquinonc-2-diazide 1.9
1 ,',-Naphthaquinone-I-diazide 4.0
1 ,Z-Naphttiaquinone-2-diazide 3.5
4-Nitro-] ,2-naphthaquinone-l-diazide 4.6
1,4-Naphthaquinonediazidc 4.2
p-Benzoquinonediazide 5 .o
In benzcne. at 3-5 "C.P:, = 0.
following qualitative information. As the monient observed for phcnanthraquinone

+ '
is 3.0 D and p(C=N=N) is c. 5.4 D200, theoretical moments of c. 2.4 D are
for the quinoid form 48a of 1,4-naphthaquinonediazideand 1,4-benzo-
quinoncdiazidc, which are much lower than the values observed for these compounds
(4.2 and 5.0 D, respective1y)"O. The calculated moments become equal to the
observed ones if i t is assumed that the diazo oxides are a resonance hybrid between
the two forms 48, in which, however, the contribution of the zwitterionic form must
be very small as it has a rather high theoretical moment (27.4 D ?O0.
The dipolc moment evidence is supported by i.r. measurements. In fact, Le Ftvre
a n d coworkcrs observed that the frequency of the C-0 stretching vibration band,
which is much lower than in t h e quinone analogues, indicates that in the diazo
oxides an extreme form is present in which the C-0 bond is a single bond’”.
Results i n agreement with these have also been obtained by Whetsel and
coworkers4’.
The presence of a structure intermediate between the benzenoid and quinoid
types was also suggested by Vaughan and Phillips2o1 from thermal stability
measurements.
Unusual results on the electronic structure of diazo oxides have been obtained by
Kazitsyna and 2 0 2 . These authors performed M O calculations, using
the Hiickel approximation, on 0- and p-diazo oxides having different substituent
groups. I t was found that the C - 0 bond order is slightly lower than double and the
negative charge on the oxygen atom is slightly higher than that usually calculated
for a carbonyl oxygen. I n the molecule 49 the bond order for the bonds C(4,-C(3)
0 0 No)- N(?,
(49)
a n d C(J)-Cls)is very closc to that for a quinoid structure. However, on going from
the atoms C12)and CtG) towards the diazo group the situation changes. In fact, the
bond order of C(,)-C(sI and C,8,-C(1, is noticeably higher than that for a quinoid
structure and the C-N and N-N bonds are almost entirely single and triple bonds,
respectively. In addition, the fraction of positive charge is localized on the two
nitrogen atoms, which rationalizes the tendency of diazo oxides to undergo diazo
coupling reactions. According to Kazitsyna and coworkers, the electronic structure
of the present compounds is better described if the forms 50 are present, in addition
to 48. The participation of these caconical forins to the mesomerism of diazo oxides
0-k - (two forms) O O N-NA
(50)
might account for the above-mentioned C - 0 , C-N and N-N bond orders and
also for the fact that the negative charge is greater on the oxygen atom and on the
atoms C l l ) ,C(3)and CIS,.Finally, i t was found that the distribution of electrons on
the molecule is very sensitive to the parameters used. Although this result is further
evidence that the electronic system of the diazo group is very mobile it also induces
caution in the interpretation of results from such calculations.
W e cannot conclude this examination of the literature data without underlining
the similarity in i.r. behaviour between the diazo oxides and the a-diazoketones.
I n both types of compounds the v X and ~ vco values are noticeably shifted compared
to those in the corresponding diazohydrocarbons and ketones: V ~ Nto higher
frequency and i*c0 to lower frequency. From the evidence discussed above we come
to the conclusion that this behaviour has a single cause: conjugation between the x
system of the diazo group and the T; electrons of the C-0 bond. Consequently, at
the present stage of work on these compounds, the most likely situation seems that
of a resonance hybrid having the main extreme forms 48, with the quinoid form
being predominant.
130 S . Sorriso
C. X-Ray Data
The two diazo oxide structures dctermincd to date are not rcprcscntativc of this
class of compounds, and the data rcported hcre cannot give insight on the clcctronic
:;:_:
structure of thcse moleculcs.
I. 3,6-Bisdiazocyclohexanetetraone
C,N,O, ?03 (51): R = 0.079; standard deviations 0.010 A and 0.7-0.9". T h e
molecule is planar. T h e N--N bond length (1.10 A) is of the same order as that of
diazonium salts (see Section II.A.I), while it is slightly shorter than that found in
diazoalkanes (1.12-1.13 A). This would indicate that the form having a triplc N-N
Uncorrccted
NIl)-N,Z) 1.107 A C,,,-N,,,-N,,, 177.9"

0 C,I)--N,,)1.357 A C,,)-C,,,-N,,) 114.4"
C[l)-C[2> 1.433 A ClG)-Cll)-C12) 129.1"
C(?,-C[3) 1.541 A C ( l ) - C ~ 2 1 - O ~ l )123.8"
0
6 C(3) C,3)-C,4)
C,2)-Oll)
1.437 A
1.214 A
C131-Olz) 1.208 A
C,,,--Ci,,-C,,,
C,,)--C,,)-O,,)
CI2)-Cl3)-C,,,,
114.9"
119.2"
115.9"
N
(51)
ON
bond is predominant, as in diazonium salts which arc not substituted in the benzene
ring. Instead, the fact that the C-0 bond length (1.21 A) is practically the same as
that found in 1,4-bcnzoquinone (1.22 A) ?05 may in part
" ' 8 be explained by
remembering that t h e two diazo groups conjugate with four CO groups, which
decreases the conjugation efTect in the CO's. Finally, the CO-CO bond length i s
1.54 A, indicating the presence of a single bond, while thc CO-CN, bond (1.43 A)
is slightly longer than for an aromatic bond (1.39 A). The above cvidcnce is sufiicient
to allow the conclusion that the electronic structure of this niolccule may be
described by a resonance hybrid betwecn several extreme forms, the most important
of which are those of 52. The distance between molccular planes in the crystal (not
c 2.90 A) indicatcs that thcre are no intermolecular contacts.
rJ -
I1 I+
N
O
0 N+ O - ' -"I0 N+
I\ 111
N- N
(52)
2. 2,6-Dichloro4diazo-2,5-cyclohexadien-l-one
C,H,CI,N,O ?OG (53): R = 0.105; standard deviations 0.013-0.018 8, and
0.10-0.14".
3. Structural chcmistry 131
178.7"
115.1"
125.9"
117.6"
124.2"
114.0"
I 17.0"
123.0"
117.9"
123.9"
(53)
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187. E. Bamberger, Ann. Clrern., 390, 154 (1912).
1%. L. Wolff, A m . Clietn., 312, 119 (1900).
189. L. C. Anderson and M. J . Roedel, J . Ariter. Cltern. Soc., 67,955 (1945).
190. L. Horner and W. Diirckeimer, Cliern. Ber., 95, 1206 (1962).
191. Y. K . Stille, P. Cassidy and L. Plummer, J . Anter. Clrern. SOC.,85, 1318 (1963).
192. R. J. W. Le Fcvre, J . B. Sousa and R. L. Werner, J . Cltetn. Soc., 4686 (1954).
193. W.Reid and H. Appel, Z . Nnirtrforsclt., 15b, 684 (1960);A m . Clrcrn., 616,83 (1961).
194. T. Kunitake and C. C. Price, J . Artier. Clrern. Soc., 85,761 (1963).
195. P. Y a k s and E. W. Robb, J . Arner. Cltern. SOC.,79, 5761 (1957).
196. L.A. Kazitsyna, B. S. Kikot' and A. V. Upadysheva, R i m . Climi. Rev., 35,388 (1966).
197. N. V. Sidgwick, T. W. Taylor and J . W. Baker, The Oiparric Clretnistry of Nitrogen,
Clarendon Press, Oxford, 1937,p. 423.
198. L. R. Modling a n d A. Burger, J . Arner. Chern. Soc., 63, 1115 (1941).
199. A. M. Simonov, Zlt. obsltclt. Klrint., 10, 1220 (1940).
200. J. D. C. Anderson, R. J. W. Le Fkvre and I. R. Wilson, J . Cltern. SOC.,2082 (1949).
201. J. Vaughan and L. Phillips, J . Cltetn. Soc., 1560 (1947).
203. L. A. Kazitsyna and N. D. Klyueva, Izvesl. Akad. Natrk S.S.S.R., Ser. kltirn., 1, 192
(1970).
203. G. B. Ansell, J . Cltern. SOC.,B, 729 (1969).
204. J. Trotter, Acia Cryst., 13, 86 (1960).
205. J. Bernstein, M. D. Cohcn and L. Leiscrowitz, in The C1reuiisir.y of rlre Quittonoid
Cornpoiinds (Ed. S. Patai), Intersciencc, London, 1974, Part 1, p. 40.
306. C . Travis Presley and R. L. Sass, Acltr Crysf., B26, 1195 (1970).
Note Added in Proof
T h e zinc atom is nearly tetrahedrally surrounded by chlorine atoms, with the
A
CI-Zn-CI angles o f 105.8" a n d I 17.0", both with a n estimated standard deviation
of 0.2".T h e Zn-CI distance is 2-238 A (e.s.d. 0.002 A), i n agreement with the results
obtained by Nesterova a n d coworkers1' for p-N,N-ditncthylaniinobenzenediazonium
tetrachlorozinc( 11) (3).
I n the present molecule you can obscrvc a m o r e accentuatcd shortening of the
distance ClI,-C14, found in benzencdiazonium chloride (1) a n d in o-methoxy-
benzencdiazonium tetrachloroiron (4). This effect, qualitatively cxplanable by a
diminution in the p character of orbitals C,,, in the links C(II-C12)a n d Co)-C161
a n d by a n increase in the character p along Cll,-N121, has been attributed to the
presence of the diazonium group'J.
T h e m oc he m ist ry of
diazo compounds and
organic azidest
ROBERTSHAW
1162 Quince Avenue,
Siinnyvale, California 94087, U S A
11. DIAZOCOMPOUNDS . 138
A. Diazomethane . I38
B. Diazoethane . 138
9 C. Diazopropylene . 140
D. Diazotoluene . 140
111. ORGANIC AZIDES . 141
A. Hydrogen Azide . 141
B. Methyl, Ethyl, Vinyl and Phenyl Azidcs . 141
IV. SUMMARY OF THERMOCHEMICAL PROPERTIES 01:
DIAZO COMPOUNDSAND ORGANIC
AZIDES . . 145
v. VALUES FOR ESTIMATING THERMOCHEMICAL .
ADDITIVITY
PROPERIlES BY GROUP 146
VI. ACKNOWLEDGEMENTS. 146
.
VII. REFERENCES 146
1. INTRODUCTION
A search of t h e literature has revealed n o infmmation o n diazoniutn compounds and
very little in the way of experimental data on diazo compounds and azides, so the
emphasis of this chapter is on estimation. The literature searched included Clter~iicaf
Abstracts, IUPAC's Biillefin of Tlie~niocliernistryand Tlierrtiodytiamirs, and the two
classic monographs's ?, Stull. Westrum and Sinke's The Cliemical Thermodynamics
of Organic Compounds and Cox and Pilcher's Tlrevniochenristry of Organic arid
Orgartometallic Conipounds.
T h e methods of estimation are based on additivity techniques developed by
Benson and his It would not be appropriate t o give a detailed dis-
cussion of additivity principles here because they have been adequately covered
previously, in earlier volumes in this seriesG,'. Nor would it be appropriate in a
review article of this size t o estimate the thermodynamic properties of all possible
t Since the volume The Chcnlistry of the Azido Groicp (1971) did not contain a chapter
on thermochernistry, it was decided to annex the material available on the azido group
to this chapter.
137
138 Robert Shaw
compounds of interest. The main emphasis here is on the methyl, ethyl, vinyl, and
phenyl derivativcs in the hope that thcy will form a basis for further work. A few
other compounds are included.
The thermochcniical properties discussed hcre are the heat of formation, the
entropy and the hcat capacity for the ideal gas state at a temperature of 298.15 K
(25 "C). F o r the sake of brevity, t h e terms molar, gas and 295.15 K will be omitted
from the therniochemical symbols. Otherwise, the nomcnclature will be that
recommended by IUPAC8. F o r example, the symbol for the hcat of formation of
methyl azide in the ideal gas state at 298.15 K is denoted herc by &H"(CH,N,).
Since the unit of cnergy recommended by IUPAC is the joule, all heats of formation
will be in uni:s of kJ/mol, followed by a value in thc prcviously accepted unit,
kcal/mol. The conversion factor is cal = 4.15 J. The symbol for the standard molar
entropy is S 8 (chemical compound) and that for the standard molar heat capacity
is c: (chemical compound). The units for all entropies and heat capacities will be
J/(mol K). As with the heats of formation, the value of the entropy and heat capacity
in the previously acceptcd unit cal/(mol K) will also be givcn.
Most of the measurcments reported in this rcvicw arc good to +_ 10 kJimo1,
2 kcal/mol, for the heat of formation and ? 5 J/(mol K), 1 cal/(mol K), for the
entropy and hcat capacity. Most of the estimates are good to k 20 kJ/mol, 5 kcal/nioi,
for the heat of formation and k 10 J/(niol K), 2 cal/(mol K), for thc entropy and
heat capacity.
I I . DIAZO COMPOUNDS
A. Diazomethane
Diazomethanc is thc only diazo compound for which experimental results have
been reported. Langcr, Hipple and Stcvenson9 obtaincd a value of 1 9 5 2
25 kJ/mol, 4 6 k 6 kcal/niol, for the heat of formation of diazornethane from thc
appearance potential of CHf in the mass spcctrum of diazoniethane. Moorc and
Pimentel'O calculated thc entropy to be 242.4 J/(niol K), 55.0 cal/(niol K), and the
heat capacity to be 52.7 J/(mol K), 12.6 cal/(niol K), from statistical mechanics
and the infrarcd spectrum of diazomethane.
B. Diazoethane
No measured thcrmochemical data have been rcportcd for diazoethanc. The heat
of formation, entropy and heat capacity of diazocthane may be estimated by
assuming that the dilrcrencc betszcn diazoethanc and diazoniethane is thc same as
thc differcncc bctwcen ethylacetylene and niethylacetylenc, equation (1).
CH,(CHN,) - H(CHN2) = CH,(CH,C=CH) - H(CH,C=CH) (1 1
From eqmtion ( I ) , i t folloivs that

CH,(CHN,) = H(CHN,)+CH,(CH,C=CH) - H(CH,C=CH) (2)
By using equation (2). inserting values for diazomcthanc from the previous scction
and valucs for cthyl- and methyl-acetylene from Stull, Wcstrum and Sinkel, I
estimatcd thc hcat of formation of diazoethane to be 172 kJ/niol, 41.2 kcal/mol,
the entropy as 255 J/(mol K), 65.2 cal/(mol K), and the heat capacity as
73.5.J/(nioI K), 17.6 cal/(mol K). The results are summarized in Table 1.
f
4
5
3
0
TABLE
1. Estimation of the standard molar hcat of formation, cntropy and lieat capacity of diazocthane, diazopropylene and diazotoluene 2
in the idcnl gas state at 298.15 K (75 "C) 3
-.
- 2
-I
Y
At H e SO
4 0,
-.
a
Conipountl kJ/mol kcal/mol Ji(mol K) cal/(mol K) J/(mol K) cal/(mol K) Method of estimation u
sn
Diazoet ha ne 172-2 41.2 285.1 68.2 73.5 17.6 CH3(CHN2) - H(CHN,) =
CH3(CH,CsCH) - H(CH,C=CH)
5
-0
0
Diazopropylcne 277.1 663 309.9 73.9 93.6 22.4 CH,=CH(CHNJ - H(CHN2) =
c5
CH,=CH(CHpCH=CH,) - H(CH,CH=CH2)
W
=I
Diazotolucne 284.2 68.0 408.0 97.6 115.0 27.5 Ph(CHN,) - H(CHN2) = a
Ph(CHzCH=CH,) - H(CH,CH=CHZ) 4
03
W
3,.
n
L
W
W
140 Robert Shaw
C. Diazopropylene
No experiments have been reported on the thermochemical properties of diazo-
propylene. Values may be estimated by assuming that the difference between diazo-
propylene and diazomethane is the same as the difference between 3-vinyl-I-propyne
a n d propyne, equation (3).
CHz=CH(CHN,) - H(CHN2) = CH,=CH(CH,C=CH) - H(CH,C=CH) (3)
From equation (3), it follows that
CH,=CH(CHNJ = H(CHNZ)+CH,=CH(CH,C=CH) - H(CH,C=CH) (4)
Unfortunately, neither Stull, Westrum and Sinkel nor Cox and Pilcher2 list
thermochemical properties of 3-vinyl-I-propyne. Furthermore, it is not possible t o
estimate values using group additivity because one of the groups, namely the
(C-Cd,Ct,H2)t group, has not been evaluatcd4.
Another solution is to assume that the difference between diazopropy!ene and
diazomethane is the same as the difference between 1,4-pentadiene and propylene,
equation (5).
CH,=CH(CHN,) - H(CHN,) = CH,=CH(CH,CH=CH,) - H(CH,CH=CH,) (5)
From equation (9,
it follows that
CH,=CH(CHN,) = H(CHN,)+CH,=CH(CH,CH=CH,) - H(CH,CH=CH,) (6)
By using equation (6), inserting values for diazomethane from the previous section
and values for 1,4-pentadiene and propylene from Stull, Westrum and Sinkel, I
estimated the thermochemical properties of diazopropylcne. The results are given
in Table 1.
D. Diazotoluene
No experimental values have been reported for the thermochemical properties of
diazotoluene. Valucs may be cstimated by assuming that the difference between
diazotoluene and diazomethane is the same as the differexe between 3-phenyl-
propyne and propyne, equation (7).
Ph(CHN2) - H(CHN2) = Ph(CH,C=CH) - H(CH,C=CH) (7)
From equation (7), it follows that
Ph(CHN,) = H(CHN,)+Ph(CH,CECH) - H(CH,C=CH) (8)
Unfortunately, neither Stull, Westrum and Sinke’ nor Cox and Pilcher2 list the
thermochernical properties of 3-phenylpropyne. Furthermore, it is not possible to
cstimatc values using group additivity because one of the groups, namely, the
(C-CU,C~,H,)S group, has not been evaluated$.
Another solution is to assume that the difference between diazotoluene a n d
diazomethane is the same as the difference between 3-phenylpropylene a n d
propylene, equation (9).
Ph(CHN,) - H(CHN,) = Ph(CH,CH=CH,) - H(CH,CH=CH,) (9)
t Wherc Cd is a double-bonded carbon atom and CLis a triple-bonded carbon atom.

Wherc CB i s a benzenoid carbon atom.
4. Therrnochcrnislry of diazo compounds and organic azides 141
From cquation (9), i t follows that
Ph(CHN2) = H(CHNz)+Ph(CH,CH=CH,) - H(CH,CH=CH,) (10)

Although n o values for 3-phenylpropylene are known'*2,it is possible to estimate its
thermochemical properties using group additivity bccausc all the groups are avail-
able4. (While i t is not noted in the text of Reference 4, i t is probable that thc values
for the group (C-Cn,Cd,H,) are assigned, that is, estimated by analogy with a
similar group.) The results are given in Table 1.
111. ORGANIC AZIDES

A. Hydrogen Azide
The thermochemical properties of hydrogen azidc have becn measured experi-
mentally1l-I5. They are listed in Table 2 along with similar data for organic azidcsIG-l9.
Experimental work on the heat of formation of hydrogen azide has bcen reviebved
by Evans, Yoffe and GrayI3. (The reference for the heat of formation of hydrogen
azide in another reviewJ is wrong.) Dows and Pimentel'5 used statistical mechanics
to calculate the entropy and heat capacity of hydrogen azide from its infrared
spectrum.
B. Methyl, Ethyl, Vinyl and Phenyl Azides

No thermochemical properties have been measured for methyl, ethyl, vinyl and
phenyl azides, but they can be estimated with reasonable accuracy using additivity
techniques3&,as follows.
T h e heats of formation of cyclopentyl azide, cyclohexyl azide and 2-hydroxyethyl
azide have all been measured in the liquid state (see Tablc 2). Fagley and
measured the surface tension of cyclopentyl and cyclohexyl azides and, from a n
empirical correlation of surfacc tension with heat of vaporization, estimated the
heat of vaporization of cyclopentyl azide to be 41.8 kJ/mol, 10 kcal/mol, and that
of cyclohexyl azide to be 46.0 kJ/mol, 1 I kcal/niol. Thus the heat of formation in
the ideal gas state of cyclopentyl azide is 220.7 kJ/niol, 52.5 kcal/mol, and that of
cyclohexyl azide is 154.2 kJ/mol, 36.9 kcal/mol.
Fagley, Klein and Albrechtl8 measured thc heat of formation of 2-hydroxyct hyl
azide in the liquid state (see Table 2). The heat of vaporization of ethyl azido-
acetate may be estimated as follows. The boiling point of ethanol' is 352 K and that
of cyclohexane' is very similar at 354 K . Therefore i t may be assumed that the hcat
of vaporization of 2-hydroxyethyl azide is ihe same as that for cyclohexyl azidc,
namely, 46.0 kJ/mol, 11 kcal/mol. Thus the heat of formation of 2-hydroxyethyl
azide in the ideal gas state is 140.0 kJ/mnl, 33.5 kcal/mol.
All three compounds, namely cyclopentyl, cyclohexyl and 2-hydroxyethyl azides,
contain the group (C-C,H,,N,). Furthermore, for all three compounds, valucs are
known' for all the additional groups that make up each molecule. For exanlple,
2-hydroxyethyl azide is made up of the groups (O-C,kI), (C-C,H,,O) and
(C-CC,H2,N3).Thus from the known value of the hcat of formation of 2-hydrosy-
ethyl azide and from the known values of the (0-C,H) and (C-C,H,,O) groups, a
value is obtained for the (C-C,H,,N,) group. Similarly, values for thc (C-C,H,,N,)
group may be obtained from cyclopentyl and cyclohexyl azides. T h e results are
given in Table 3. The results show that there is reasonable agreement between the
two values from the cycloalkyl compounds, but that thcre is poor agreement with
TABLE
3. The standard inolar heat of Torination, enlropy and heat capacity or azides that h a w been determined experimentally at
298.15 K ( 2 5 "C)
IIO 4 -
SO
Coriipotird Slate kJ/mol kcal.'mol Rcfcrcnce Ji(rnol K) cnl/(rnol K) Rcfcrcncc J/(mol K ) cal/(mol K) Reference
1-1 N, I 269.1 64.37 1-13

2 '99.5 7 1.66 1-13 238.6 5 7.08
9 293.8 70.3 4 -
g 296.8 71.0 238.7 57. I 43.5 10.4 Selected
value 2
77.5
IIOCI I,Ctl,N, I 94.0 L- 6
C3 k1.,"3 s 915.4 219 13, 17
N,,CH,COOC,Hj I 139.1 33.3 13, 18
c).c/(I-C,~I,NJ I 178.9 42.8 2, 13, 19
PhN, I 3344 82.3 13, I8
c)~c/o-C,
1-1 I ,N, I 108.3 25.9 2, 13, 19
4. Thermochcinistry of diazo compounds and organic azidcs 143
thc valuc derived from 2-hydroxycthyl azide. I n selecting the group value to be used
in further calculations, I ignored the value from 2-hydroxycthyl azidc and obtained
an average valuc from thc other two compounds.
TAIILE 3. Hcat of formation in the idcal gas state

at 7-98.15 K (25 "C) for the (C-C,H,,N,) group,
detcrniined from values for the heats of formn-
tion of 2-hydroxyethy1, cyclopentpl and cyclo-
hexyl azidcs, and from other known' group
values
Compound kJ/rnol kcal/mol

HOC H2CH2N, 332.3 79.5
C , H ION,
C~C/O- 277.1 66.3
H 1 1 N3
c~c/o-C, 257.5 61.6
Selcctcd value 267.5 64.0
Ethyl azide is made up of two groups, namely, the (C-C,H,) group and the
(C-C,H2,N3) group. The value of the heat of formation of the (C-C,H,) group is
knownJ to be -42.2 kJ/mol, - i O . 1 kcal/mol, giving the heat of formation of ethyl
azide as 225.3 kJ/mol, 53.9 kcal/mol, as shown in Table 4.
The heat of formation of phenyl azide has bcen measured in the liquid statc (see
Table 2). The heat of vaporization may be estimated as follows. The boiling point
of benzene' is 353 K and that of cyclohcxane is 354 K. Therefore it may be assumed
that the heat of vaporization of phenyl azide is the samc as that of cyclohcxyl azide,
namely, 46.0 kJ/niol, 11.0 kcal/mol, giving the heat of formation of phenyl azidc
in the ideal gas state as 385.8 kJ/mol, 92.3 kcal/niol, as shown in Table 4.
No expcrimental results have bcen reported for thc heat of formation of methyl
azide. Ho\vever, i t may be estimated as follows. From the above discussion on ethyl
and phenyl azidcs, the difference in the hcats of formation of ethyl and phenyl azide
is - 160.5 kJ/mol, - 3S.4 kcal/mol. From the literature4, the difference between t h e
heats of formation of ethyl and phcnyl chlorides is - 159.7 kJ/mol, - 35.2 kcal/mol.
I t is therefore a good approximation to say that
A, He(EtN,) - A, N '(PhN,) = Af Ho(EtCI)- Af IIo(PhCI) (11)
I t may bc assumed then that

A, He(MeN3)- 3, H'(EtN3) = At H'(MeC1) - A, He(EtCI) (1 2)
I t follows from equation (12) that

Af He(kleN3) = hf H O(EtN,) + At If e(MeCI) - Af Ho(EICI) (13)
From equation (13) and known values for the heats of formation of ethyl azide
(Table 4) and methyl and ethyl chlorides', the heat of formation of methyl azide is
246.6 kJ/mol, 59.0 kcal/mol. This value is in very good agreement with an earlier
estiniate of 238.3 kJ/mol, 57.0 kcal/mol, by Evans, Yoffe and GrayI3.
Similarly, the heat of formation of vinyl azide \vas estimated from equation (14)
At H'(CH,=CHN3) = Ar Ho(EtN3)+ Af Ho(CH2=CHCI) - AfH'(EtC1) (14)
TAULE
4. Estimation of the standard molar heat of formation, entropy and heat capacity of methyl, ethyl, vinyl and phenyl azidcs in the
ideal gas state at 298.15 K (25 ‘C)
A* H e SO
Compound kJ/inol kcal/mol J/(mol K) cnl/(mol K ) J/(mol K) cal/(mol K ) Method of estimation
Methyl azide 238.3 57.0 From cycloalkyl azidesI3 ;a

246.6 59.0 MeN3 - EtN, = MeC1- EtCl 0
d
283.0 67.7 67.7 0
1
16.2 MeN, = MeNCO -
242.4 58.0 283.0 67.7 67.7 16.7, Selected value
i?
m
Ethyl azide 225.3 53.9 Group additivity, see text €
322.3 77.1 90.5 21.6 EtN, = EtCI
Vinyl azide 366.6 87.7 CH,=CHN, - EtN, = CH,=CHCI - EtCl
295.5 70.7 75.7 18.1 CHz=CHN, = CHz=CHCI
Phenyl azide 385.8 92.3 PhN,-EtN, = PhCI- EtCl
357.0 85.4 102.4 24.5 PhN, = PhNCO
4. Thermochemistry of diazo compounds and organic azides 145
N o measurements have been reported for the entropies or heat capacitics of methyl,
cthyl, vinyl or phenyl azides. However ccrnparison of the values for hydrogen azide,
HN3, with those for hydrogen isocyanate, H N C O (see 'Table 5 ) , suggest that i t
would be a good approximation to assume that the entropy and heat capacity of
methyl azide is equal to t hos e for methyl isocyanate, cquations (15) a n d (16).
So(MeN,) = S '(MeN C0) (1 5)
c;(MeN,) = cE(MeNC0) (1 6)
Values f o r the entropies a n d heat capacities of ethyl, vinyl and phenyl azides were
estimated similarly to those f or methyl azide.
TABLE 5. Comparison of the standard molar entropy and heat capacity of hydrogen azide,
hydrogen cyanate and hydrogen isocyanate in the ideal gas state at 298.15 K (25 "C)
S9 4
Compound J/(mol K) cal/(mol K) Reference J/(mol K) cal/(mol K) Reference
HN3 238.7 57.1 15 43.5 10.4 15

HOCN 230.3 55.1 20 44.3 10.6 20
HNCO 237.8 56.9 20 45.1 10.8 20
IV. S U M M A R Y OF T H E R M G C H E M I C A L PROPERTIES O F
DIAZO C O M P O U N D S A N D O R G A N I C A Z I D E S
F o r convenience, t he measured and estimated heats of formation, entropies and
heat capacities discussed in t h e previous sections have been collected in Table 6.
TABLE 6. Measured and estimated standard molar heats of formation, entropies and heat
capacities of diazo-methane, -ethane, -propylene and -toluene, and of hydrogen, methyl,
ethyl, vinyl and phenyl azides in the ideal gas state at 295.15 K (25 "C)
4
~~~~~~~ ~
A, H e
- --SO
kJ/ kcall J/ cal/ J/ cal/
Compound rnol rnol (rnol K) (mol K) (rnol K) (mol K) Table
Diazo-
-methane 195 46 242.4 58.0 52.7 12.6 Text
-ethane 172.2 41.2 285.1 68-2 73.5 17.6 1
-propylene 277.1 66.3 308.9 73.9 93.6 22.4 I
-toluene 284.2 68.0 408.0 97.6 115.0 27.5 1
Azides
hydrogen 296.8 71.0 238.7 57.1 43.5 10.4 2
methyl 242.4 58.0 283.0 67.7 67.7 16.2 4
ethyl 225.3 53.9 322.3 77.1 90.5 21.6 4
vinyl 366.6 87.7 295.5 70.7 75.7 18.1 4
Dhenvl 385.8 92.3 357.0 85.4 102.4 24.5 4
I46 Robert Shaw
V. VALUES FOR ESTIMATING THERMOCHEMICAL
PROPERTIES BY GROUP ADDITIVITY
T h e principles a n d use of group additivity have been dcscribed in considerable
detail elsewhere3-'. 21. A simple example was given earlier in the discussion of ethyl
azide.
Values of the thermochemical properties of the groups a r e summarized in Table 7.
TABLE7. Group values for estimating the thermochemical properties of diazoalkanes and
organic azides
A, H e
Source
molecule kJ/mol kcal/mol kJ/mol kcal/mol kJ/rnol kcal/niol
C H,C H N, 214.4 51.3 158.0 37.6 47.6 11.4

CH,=CHCHN, 222.4 53.2 166.8 39.9 53.5 12.8
PhCHN, 191.4 45.8 199.8 474 62.3 14.9
EtN, 267.5 64.0 195.2 46.7 64.4 15.4
CH,=CHN, 340.2 8 1.4 180.2 43.1 54.3 13.0
PhN, 316.8 75.8 116.2 27.8 34.7 8.3
VI. ACKNOWLEDGEMENTS
I am pleased t o t h a n k Theodore Mill, Dale G . Hendry, David M. G o l d e n a n d t h e
Stanford Research Institute for the use of their libraries, Eileen Fellows for typing,
a n d K i t t a Reeds for editing the manuscript.
VII. REFERENCES
1. D. R. Stull, E. F. Westrurn and G. C. Sinke, The Chemical Tlicrtnodytiatnics of Organic
Cotripoioids, John Wiley, New York. 1969.
2. J. D. COXand G. Pilcher, Tfiert,iochet?iistryof Orgaiiic atid Organotnefallic Conipounds,
Academic Press, New York, 1970.
3. S . W. Benson and J. €1. Buss, J . Cheni. Phys., 29, 546 (1958).
4. S. W. Benson, F. R. Cruikshank, D. M. Golden, G. R. Haugen, 14. E. O'Neal, A. S.
Rodgers, R. Shaw and R. Walsh, Chem. Rev., 69, 279 (1969).
5. S. W. Benson, Tlierrnochemical Kitietics: Methods for rlie Esriniafion of Tlierniocheniical
Data and Rate Paranietrrs, John Wiley, New York, 1968.
6. R. Shaw, 'Thermochemistry of Hydrazo, Azo, and Azoxy Groups'. in Chemistry of
Hydraio, Azo, and Azoxy Groups (Ed. S. Patai), John Wiley, New York, 1974.
7. R. Shaw. 'Estimation of the Therniochernistry of Imidic Acid Dcrivatives', in Chemistry
o f / m i d i c Acid Dericatives (Ed. S . Patai), John Wiley, New York, 1975.
8. M. L. McGlashan, A m . Rev. PIiys. G'iem., 24, 51 (1973).
9. A. Langer, J. A. Hipple and D. P. Stevenson, J . Clietti. Pliys., 22, 1836 (1954).
10. C. B. Moore and G. C. Pimentel, J . Cherri. Pliys., 40, 312 (1964).
1 1 . P. Gray and T. C. Waddington, Proc. Roy. SOC.(Loridon), A2-75, 106 (1956).
12. P. Gunther, R. Mayer and F. Mullcr-Skjold, 2.Pliysik. C h e m , 175, 154 (1935).
13. B. L. Evans, A. D. YofTe and P. Gray, Clirtn. Xcu., 59, 515 (1959).
14. D. D. Wagnian, W. H. Evans, V. B. Parker, I. Halow. S. M . Bailey and R. H. Schurnm,
'Selected Values of Chemical Thcrmodynamic Properties', Utiireti States h'atiotial
Burerrir of Standards Teclitiical Note 270-3 (1 968).
15. D. A. 1)ou.s and G. C. Pimentel, J . Chetti. Phys., 23, 1258 (1955).
4. Therniochemistry of diazo compounds and organic azides 147
16. T. F. Fagley, E. Klein and J. F. Albrecht, Jr, J . Attier. Cltem. Sac., 75, 3104 (1953).
17. H. Muraour, Bid/. Soc. Chirrr. Frurtce, 51, 1 I52 (1932).
18. W. A. Roth a n d F. M d l c r , Urcttt. Ber., 62, 1188 (1929).
19. T. F. Fagley and H. W. Myers. J . Artter.. Chem. Soc., 7 6 , 6001 (1954).
20. R. Shaw, 'Thermocheniistry of Cyanatcs, Isocyanatcs, and their T h i o Derivatives',
in Cheniistry of Cyartutcs, lsocyatiatcs, a d tlwir T h o Dcriuafives (Ed. S . Patai), John
Wiley, New York, 1977.
21. H. K. Eigenmann, D. M. Golden and S . W. Benson, J . Pltys. C/te/rt.,77, 1687 (1973).
G
CHAPTER 5
Detection and determination of

diazo and diazonitum groups
DAVID
A. BEN-EFRAIM
The IVciztiinriti Itislitirte of Scicwcc, Rclrouot, Isrnrl
--
BY CIlEhllCAL METIIODS.
I. DETECTION i50
A. Diazoalkancs, a-Diazoketones and cu-Diazocsters . 150
B. Arencdiazonium Salts . 151
C. Triazencs. . 151
11. DETERMINATION HY CHEMICAL METHODS . 151
A. Elerncntal Analysis . 151
13. Diazoalkanes and Related Compounds . 151
1. Reaction with acids . 151
2. Gravimctric dcterniination . 152
3. Colorinietric dctcrniination . 152
4. Gasometric determination . 152
C. Diazoniuni Salts, Diazophcnols and Diazotates . 152
1. Reductometric titrations . 152
a. Titanous chloride . 152
b. Cliromous chloride . 153
c. Vanadium(rr) sulphatc . 153
d. Sodium hyposulphitc . 153
c. Hydriodic 3cid. 153
2. Coupling reactions . 153
3. Gasometric methods . 154
4. Miscellaneous mcthods . 155
D. Triazcnes and Tctrazenes . 155
1. Gasomctric methods . 155
2. Misccllancous methods . 155
E. Other Diazo Conipounds . . 156
111. POLAROGRAPIiY . 156
1V. SEPARATION A N D CHROMATOGRAPHIC MLTHODS. . 158
A. Diazoalkanes, cu-Diazokctoncs and a-Diazoestcrs . . 158
B. Arenediazoniuni Salts and Diazotates . 158
C. Triazcncs and Tetrazenes . 159
V. INFRARED A N D RAMAN SPECTROSCOPY . 159
A. Diazoalkanes, a-Diazoketones, cu-Diazoaldelipdcs. cr-Iliazoestcrs, Diazo-
cyclopentadienes and Rclated Conipouiids . 159
B. Diazonium Salts, Diazophenols, Diazotatcs, Diazosulphonatcs and
Diazoethers . 161
C. Diazocyanidcs and Diazoisocyanides . . 167
D. Triazcncs and Tetrazcncs . . 163
VI. ELEc-rRoNIcSPECTKOSCOI>Y,FLUORESCESCE ASL) P l ~ O S P k f O I < ~ S C E S C E . 163
A. Diazoalkancs, Diazocyclopcni;idienes, cx-Diazoaldchydcs, cu-Diazoketoncs
and cu-Diazoestcrs . 163
149
I50 David A . Ben-Efraim
B. Arenediazoniuni Salt:, Diazophcnols, Diazotates, Diazosulphones and
Diazosulphonntcs . I65
C. Diazocynnides and Diazoisocyanides . . 166
D. Triazcncs and l’ctrazenes . 166
VII. NUCLI:AR M A G W T I C R ~ S O K A S C FSPECTROSCOPY
. . . 167
A. Diazoalkancs, a-Diazokeioncs, a-Diazocstcrs, a-Diazosulphoncs and Dinzo-
cyclopcntadienes . 167
B. Diazonium Salts and Diazotates . 168
C. Triazenes . I69
VIII. MASSSPECTROMETRY . 169
A. Diazoalkanes, a-Diazoketones and a-Diazoesters . 169
B. Diazophcnols . 170
C. Triazenes. . 170
IX. ELECTRONSPIN RESOSANCE SPECTROSCOPY A N D CHEMICALLY
INDUCED
D Y S A M NUCLEAK
~C POLARIZATIOS . 171
X. ELECTRON SPECTROSCOPY 172
XI. DIPOLE MOMENTS. 172
XII. REFEREXES. 173
This chapter covcrs diazoalkanes, diazoketones, diazoesters, diazonium salts and

diazoaniino compounds (triazenes, tetrazenes), as well as related compounds of the
general formula R N = NX, such as diazotates, diazocyanides, diazosul.zhonates,
etc. ; azo compounds, however, arc excluded. T h e arenediazonium salts and the
aromatic diazoamino compounds play a major role in the manufacture of azo dyes.
Diazoalkanes and diazoketones are also important reagents and intermediates,
respectively, in organic synthesis. Many of these compounds are rather unstable,
a n d are conveniently handled in solution. Consequently spectroscopic methods as
well as effective chemical methods of analysis arc of great significance i n the elucida-
tion of their structures and in their detection and determination.
1. DETECTION BY CHEMICAL METHODS

Nitrogen in diazo compounds cannot be detected by the usual method of niclting
the sample with potassium to yield potassium cyanide which is subsequently con-
verted to Prussian blue, because under the reaction conditions, even at low tempera-
tures, the diazo conipounds decompose with nitrogen evolution’.
A. Diazoalkanes, a-Diazoketones and a-Diazoesters

Diazoalkanes can be detected by the vigorous liberation of nitrogen when treated
in the cold \vith dilute hydrochloric or sulphuric acid. Nitrogen evolution also takes
place on heating with water. E-Diazoketoncs similarly liberate nitrogen when heated
with acetic acid?. The stability of aliphatic diazo compounds towards trichloroacetic
acid is of interest in this conncction and has been found to bc in the following order:
-
diazoalkanes < diazoketones < diacyldiazoniethanes < diethyl diazon~alonate~.Ali-
phatic diazo compounds can also be identified by the p r o d u c k they yield with
-
various reagents (equation I)?.
- \
RCHN,+HCI RCH,CI+N,
RCHN,+ArOH RCH,OAr+N,
(1 1
R’CHN,+RZCO,H R’CH,OCOR’+N,
R’COCHN,+R’CO,H ___z R’COCH,OCOR*+N,
Dctcction and dctermination of diazo and diazonium groups 151
Diazoalkancs (1-50 nig), as ~ v e l las diazoketones and diazoesters, are detectcd by
reaction with aqueous 4-(4-nitrobenzyl)pyridinium perchlorate, followed b y dilution
with alkali, which precipitatcs blue-black crystals of N-alkyl-4-(J-nitrobenzylidene)-
I ,4-dihydropyridincs, which in various solvents havc charactcristic absorpiion
maxima in the visible rcgion4.
5. Arenediazonium Salts
Arenediazonium salts generally libcratc nitrogen on heating w i t h water or with a
dilute mineral acid2. Some of tlicm, such as those derived from aminoanthra-
quinones, are very stable under thesc conditions2. With AuCI, or PtCI, they furnish
complex salts, such as [ArN,J+AuCI,; and [ A r N , ] ~ + P t C I ~whercas
- with ZnCI,,
CaCI, or SnCI, they yield slightly soluble double salts?. When arenediazonium
bromides are treated with brominc i n a potassium bromide solution, they precipitate
crystalline perbromides [ArN,]-'-Br; which scrvc in their detcction and characteriza-
tions. Their most sensitive method of detection, howcver, involvcs coupling with a
phenol in a Na,CO, solution, or with an aroniatic aniine i n dilute acetic acid? to
yield azo dyes'.
When a weakly acidic solution of an arcnediazoniuni salt is added to a n alkaline
solution of resorufin (9-hydroxy-3-isophcnoxazonc),the fluorcscence of the latter
is quenched as soon as the niixturc becomcs acidic. Addition of a Na,CO, solution
to the above mixture precipitates bro\vn dyestutfs if diazonium ions a r e present,
otherwise the red fluorescence is restoredG.
C. Triazenes
-
Aromatic triazenes behave chemically in similar fashion to arenediazonium salts,
but they are more stable and liberate nitrogen only when treated with strong mineral
acids (equation 2)'.
LIS
Ar'NHN=NArZ Ar'NH,+ArzN;X- ArzX+N, (2)
In contrast to arenediazoniurn salts which coiiple with m-plicnylenedianiine in
ethanolic solution t o yield azo dyes, aromatic triazenes do so only on addition of
acetic acid'.
Various 3-ligdroxytriazcnes have bccn detected by a spot test which involves
treatnicnt with I-naphthylaniine i n acetic acid, giving at once a pink or red-brown
colour, which intensifies on gentle heatings.
II. D E T E R M I N A T I O N BY CHEMICAL M E T H O D S
A. Elemental Analysis
The Kjcldalil method for the elemental dcterminntion of nitrogen cannot be
applied to diazo compounds, in particular not to a-diazoketones, since addition of
hydriodic acid rcsults in nitrogen evolution evcn i n the cold3. Zinneke has howcvcr
modified the Kjeldahl method in siich a manner that the total nitrogen evolved
could be trapped and iiicasured in a specially built nitrometer'".
B. Diazoalkanes and Related Compounds

1. Reaction with acids
Diazoalkanes easily alkylnte carbosylic acids and phcnols to the corresponding
S early as 1910
methyl esters and methyl cthers, respsctivcly (cqtiation I ) . T ~ U as
diazomcthane and diazoethane \\crc detcrinincd by adding thc diazonlkane i n
152 David A. Ben-Efraim
anhydrous ether at 0 "C to an ~ X C C S Sof a solution of p-nitrobenzoic acid in ether,
and after :I short timc titrating tlie exccss acid with a standard 0.1 N-Ba(OH),
solution to a phcnolphthalcin end-point". Later diazoalkanes (CH,NP, McCHN,,
EtCHN,) wcre similarly cstiniated in anhydrous ether at 0 " C , using benzoic acid,
and back-titrating the exccss acid with a 0.1 N-NaOH o r K O H solution and phenol-
phthalein12.The nicthod was modificd to the micro scalc, using excess benzoic acid,
0.01 N - N ~ O H
solution as titrant anti phenolphthalein':'. Recently diazoinethane was
detcrniined by reaction Lvitli benzoic acid and tlie resulting mcthyl benzoate was
mcasured by vapour phase chromatography". The dcutcriuni contcnt of CD,N,
was obtained by its reaction with PhC0,D i n anhydrous cther, followed by deter-
mination of the deutcriuni contcnt i n tlic formed riicthyl benzoate, eithcr by n.ni r.
o r by mass spcctronietry15.
2. Gravimetric determination
Diazoalkancs (CH,N,, MeCHN,, EtCHN,) were also determined by adding a n
aliquot of an ether solution of the diazoalkane to a cold solution of 3,s-dinitro-
bcnzoic acid. E k e s s acid was removed by base and aftcr conventional work-up and
cvaporation to dryness, the diazoalkanc was estimated by the weight of thc resulting
methyl ester, and the latter's purity was asscssed by a melting-point
3. Colorimetric determination
Colchiccinc aflords, with fcrric chloride, a dccp green colour, not given by its
metliylated dcrivativc colchicine. This reaction scrvcs in thc determination of diazo-
methane. TIic solution of diazonicthane is added to a known amount of colchiceinc,
and the excess of unrcacted colcliiccine is estirnatcd aftcr addition of FcCI, by
colorimetric comparison w i t h colchiccinc-FeCI, solutions of known concentration.
T h e method givcs results in good agrccnient with tliosc obtaincd by the titration
method with bcnzoic acid"j.
The dctcction of diazoalkanes by tlie colour reaction with 4-(4-nitrobenzyl)-
pyridinium perchlorate has already bcen nient ioncd4. I n its quantitative version
diazoalkanes R C H N 2 ( R = Me, Et, ti-Pr, ti-Bu, allyl) give with this rcagent on
addition of piperidinc a rcd-violet colour. hlcasureiiicnt of its ahsorbancc at 545 n n i
and comparison \vitli a calibration curve yiclds the concentration of the diazoalkane'.
4. Gasomet ri c determination
Aliphatic diazo compounds on trcntmcnt will1 dilute su:phuric acid liberate
nitrogen which is incasurcd i n a nitromctcr (cquiition 1)". The method uses u p to
I-g samplcs, but has been adapted to tlic micro scalc, making L I S ~of tlie liydrazino
apparatus of Ma and hlattcila.
C. Diazonilsni Salts, Diazophenols and Diazotates

The most coninionly wed iiicthods in tlie determination of diazoniunl salts
include reductometric titrations, coupling titrations and gasomctric and colorimetric
met hods.
1. Reductometric titrations
Most of thcsc rcdtictionc iiiust bc carried out i n the abscnce of oxygcn.
a. Ti/f//iouscliloridL.. Kncclit and Thompson t i t ra tcd bcnzcned iazoni 11111 chloride
with a TiCI:, solution in cold dilute liydrocliloric :icid. using 14 acid (S-ainino-l-
acid) as an csterrial indic'itor (equation ,)I9.
naplitliol-3,6-disiil~~l1~1iic The titration
-
Dctection and determination of diazo and diazonium groups 153
can also be carricd out by adding an excess of a TiCI, solution, and back-titrating
the excess with a standard acid green solution in the presence of sodium tartrate'o.
2 PhN:CI-+4 TiCI,+2 HCI PhN=NNPhNH,+4 TICI, (3)
The method was modified to the micro scale by adding an excess of the TiCI,
solution to 3n acetate-buffered solution of the sample at room temperature, and
back-titrating the excess TiCI, with a ferric alum solution, using ammonium thio-
cyanate as an indicatoro0.It should be pointed out that this method is also applicable
to azo groups and to nitroarylhydrazines. Siggia has also described this procedure
in detail as a mcthod for the analysis of azo and nitro groups as well as hydrazines
and diazonium salts2'.
-
b. Cltroniorts chloride. With this reducing agent diazonium salts are quantitatively
reduced to the corresponding hydrazincs (cquation 4). Excess CrCI, solution is
ArN,+CI-+4 CrC1,+4 HCI ArNHNH,.HCl+4 CrCI, (4)
added to a weakly acidic or neutral solution of the diazoniuni salt, and back-titration
of the excess CrCI, is accomplished potcntionictrically with a standard ferric alum
solution??. This reduction method has certain advantagcs over the popular coupling
(Section II.C.2) and gasometric (Scction II.C.3) methods becausc i t is fast as well as
quantitative. I t is. howcver, also applicable to nitrobenzcnes and hydrazines.
c. Vonodirrni(rr)sri/p/io/e. Diazophcnols and diazonaphtliols containing CI, CO,H
or SO,H groups \verc determined titrimetrically in an inert atmosphere by reduction
of their acid solutions with excess VSO,, and back titration of the esccss reducing
agent with a fcrric alum solution, using safraninc as indicator. The rcaction requires
two equivalents of reducing agent per molc of didzo compound, and is accompanied
by a quantitativc libcration of iiitrogcn2J.
d. Sodirtill hyposit/p/ti/c. This reagent also served in the quantitative reduction of
diazoniuni salts to arvlhydrazines i n HCI solution at 0 "C. Esccss reagent was used
and its excess was back-titrated with a standard acid grecn solution".
e. Hyrlriodic acid. A sample of 20-30 mg diazoniuni salt is reduced with 57% HI
--
in a sealed tubc betwcen 100 anti 300°C (equation 5 ) and the liberated iodine is
back-titrated with a sodium thiosulphatc solution and a starch indicatorZ4.
ArN:CI-+2 HI N,+ArH+HCI+I, (5)
2. Coupling reactions
This method is bascd upon tlic coupling of arencdia7oniuiii salts with aromatic
aniines or phcnols to yield azo dyes (equation 6). Thc method is very selective
ArN:X- + PhOH -- A r N = N e O H + HX
because only 1 . c ~othcr compounds coiiplc w i t h thcse reagents. The dcterinination

is carricd out l~clow0 "C by adding the sample to an cxccss of coupling agcnt,
usually I-phcnyl-3-mcthyIpyrazolin-5-onc o r 2,4-dianiinotoluene in acidic solution,
154 David A. Ben-Efrairn
o r R-salt (sodium 2-naphthol-3,6-disulphonate) in a Na,CO, solution, and back-
titrating the excess reagent with a standard 0.1 N-benzcnediazoniuni chloride
solution or a 0.1 N-/??-nitrobcnzenediazoniunichloride solution, using an external
indicator (H acid or resorcinol in basic solution). The accuracy aiid precision of the
method are lower than those of the gasomctric method (Section II.C.3) because of
the slow rate of coupling and the dificulty in observing the end-point25.
Traces of diazonium salts were determined by coupling the salts with R-salt in
aqueous solution o r with phloroglucinol or naphthol in etlianolic solution. Tenths of
a p.p.ni. o f the formed azo dye were then dctermincd spectrophotonietrically26.
Additional colorinietric determinations bascd on tlie coupling method were also
reportcd2?.
The isomeric nitrobenzenediazoniuni salts i n mixtures of azo coupling products
\vere determined by coupling them with 2-naphthol. The products were chromato-
graphed on alumina to separate the orrho isomer from the niixture of the nwin and
para isomers ; the ortho isomer \\us deteriiiined spcctropliotomctrically and the
nwfa and para isomers were determined by differential spectrophotometry at two
different wavelengths. Each isomer was detcrmined with an accuracy of 2-5Xz8.
3. Gasometric methods
Gasometric methods are the most general and most specific for measuring diazo-
nium salts and are widely used in industry. An accuracy and precision of about 1%
are obtainable, but the procedure is tedious a n d time consuming. A single analysis
may take up to I hour.
Solutions of aliphatic and aromatic diazonium silts readily decompose on heating
with mineral acids to furnish phenols and nitrogen. When heated with acid and
cuprous chloride, chlorobenzenes and nitrogen arc obtained. T h e nitrogen is
qmntitatively liberated in these reactions and is determined volumetrically in a
nitrometer. Thc method is very selective since few compounds liberate a gas under
the above reaction conditions. Siggia has described in detail a general procedure and
nitrometer for the determination of diazonium salts by decomposition in tlie presence
of cuprous chloride in concentrated hydrochloric acid".
A simple apparatus, bascd on nitrogen evolution, has been described for the
determination of aliphatic and aroniatic diazonium salts, stabilized salts, diazotates
and triazenes. Nitrogen evolution is cmected by boiling the sample with 30% H,SO.,
and 0.75% C U , C I , ~ ~Recently
. another apparatus \\'as devised for the rapid volu-
metric determination of the nitrogen evolved by I-ICI-Cu2Cl2from diazonium salts
and diazoamino compounds. Thc reproducibility of the method is 2 0.3% and the
maximum error is k 1.0% 31.
Siggia and coworkers used a graphical kinetic approach to nnalyse mixtures of
diazoniiim compounds, which is based on t h e first-order rates of decomposition in
the presence of cuprous chloride. The nitrogen evolved is measured in successive
time intervals. I n the case of a mixture of two diazonium salts a plot of log (100-x)
versus f (where 100 is the total diazo nitrogen and s is the ?< diazo nitrogen evolved
i n time I ) is a straight line as soon as most of the faster-reacting component has been
decomposed. By extrapolating to t = 0, the composition of the mixture can be
obtainedn2.
Diazo compounds were determined gasonietrically on a seinimicro scale by
dcconiposing samples by light irradiation in a special apparatus containing a
nitrometer. The method had a standard deviation of L 0.077< and tlic whole pro-
cedure rcqiiircd 30-35 ixin. I t has been applied to diazonaplitliols \vliich cannot be
easily determincd by thc coupling incthod:'J.
Detection a n d deterinination of diazo and diazoniunl groups I55
4. Miscellaneous methods
Tzrent'ev and Tubina describcd three niethods for the detcrmination of arene-
diazonium salts. T h e first method involves a direct titration of a solution of a
secondary aliphatic amine (hcxamcthylcnimine, piperidine, diethylaminc) containing
sodium carbonate with the solution of tlie diazoniuin salt at 15-20 "C until the
colour formed \\it11 a 1% solution of sodium 4-arnino-5-hydroxynaphthalcnc-2,7-
disulphonate persists for about 30 SCC. The second method is based upon the reac-
tion bet\veen the diazonium salt and an cxccss of a secondary aliphatic amine,
making t h e reaction mixture basic, and distilling the excess aniine into aqueous 4%
boric acid and titrating it with 0.1 K-HCI. The third method involvcs reaction
between t h e diazoniuni salt a n d excess nz-toluidine, making thc solution basic, and
steam-distilling thc excess amine, which is then brorninated and tlie excess bromine
is titrated with sodium thiosulphate and starch as indicator3'.
Arenediazonium salts dissolved in non-aqueous solvents (pyridine, dirnethylform-
amide) were determined by potentionietric titration \vith 0.1 N-sodiuni methoxide i n
-
benzene-methanol, using a saturated calomel electrode and a glass electrode. A
probable reaction (equation 7) has been suggested. The error was less than & 1.8% 3i.
ArN: Br-+ MeONa ArN,OMe+NaBr (7)
D. Triazenes and Tetrazenes

I. Gasometric methods
-
Aliphatic triazenes are readily decomposcd by mineral acids, liberating nitrogen
(equation S), whereas aromatic triazenes require, in addition, heating in order to
libeiate nitrogen (equation 2). Aliphatic and aromatic triazenes were determined
R'N=NNHR2+ HCI R'CI+ N,+ R'NH, (8)
gasonietrically by conventional procedures after boiling samples with concentrated

HCI 36 (see also Section II.C.3). Pierce and Rising described a micro-scale niodifica-
tior, of the above procedures and an apparatus for tlie detcrixinntion of aromatic
t r i a ~ e n e s ~ Lohr
'. has obseiwd that the method of Picrcc and Rising gave excellent
results with pure aryl-substituted triazenes but was not rcadily adapted to samples
which were solutions, slurries or H e niadc thc nicthod applicable to samples
in any physical state, using cuprous chloride in cmcentratcd HCI to catalyse the
quantitative liberation of nitrogen. Two other similar proccdurcs \vhich are applic-
able to triazenes as \veil as to diazonium salts have already been mentioned"*3 1
(Section II.C.3). T h e deterinination of 1 -nryl-3,3-dimctliyltriazencs by the above
procedures (Cu,CI,-HCI) has also been rcported".
2. Miscellaneous methods
If the aromatic aniinc produccd on hydrolysis of an aromatic triamic (equation 2)
can be broniinatcd, this can serve as a method for the determination of aromatic
triazenes. The triazene is dissolved in glacial acetic acid. HCI and KBr solutions are
added, and the niixturc is titrated with a 0.5 N-KBr-KBrO, solution, using KI-starch
paper ;is indicator'".
Small amounts of I-aryl-3,3-dialkyltriazcnes\vere dctemiincd by hydrolysis to
furnish arenediazonium cations (equation 2) which werc couplcd w i t h :\'-elliylnaph-
thylamine. The absorbance of the obtained dye was ineasurcd spcclropliotometrically
at the absorption maximum. The accuracy of the method was within 5% and it has
been shown that the rate of hydrolysis of the triazenes depends on the pH and on the
electronic character of the substituents on the benzene ring4'. Similarly, triazenes
stabilized with aliphatic amines were hydrolysed with aqueous acetic acid, and those
stabilized with aromatic amines were hydrolysed with dilute HCI, and the resulting
diazonium ions were coupled with excess I-phenyl-3-methylpyrazolin-5-one, and the
excess of the latter was back-titrated with 0 * 5 ~ - N a N 0T~h.e error was less than
2 2% and a determination took up to 1 houra2.
I-Aryl-3,3-dialkyltriazenes were also determined by their hydrolysis with 0.1 N-
H2SOI to furnish a dialkylamine which reacted with the acid, and the excess acid was
titrated potentiometrically with 0.1 N-NaOH. This procedure was modified in the
case the compound contained functional groups, such as carboxyl groups, which
interfered with the determination. In that case the reaction mixture was made basic
and the dialkylamine formed was steam-distilled into an excess of standard acid and
was then d e t e r r ~ i i n e d ~ ~ .
4-Amino-l-(5-tetrazolyl)-l-tctrazenehydrate was determined by hydrolysis with
sulphuric acid to give amidinohydrazine which was estimated by oxidative titration
with 0.1 N-KBrO,, using iodine as indicator's. Tetramethyl-2-tetrazene was deter-
mined by titration with boron trifluoride etherate, perchloric acid in acetic acid,
aluminium chloride in chloroform, o r sulphuric acid in acetic acid, using crystal violet
as indicator. The titration gave sharp, yet fading, colour changes at a molecular ratio
of 1 : 1 4 5 .
E. O t h e r Diazo Compounds
p-Mcthoxyphenyl diazothio(2-naphthyl) ether was determined as follows: hydro-
lysis i n alkaline solution yielded p-methoxybenzcnediazoniuin ions and 2-naph-
t halenethiol. T h e diazonium ion was couplcd with 2-naphthol and the dye formed
was determined spectrophotonietrically. Thc thionaphthol was determined ampero-
metrically by reacting i t with excess silver nitrate and back-titrating the excess of the
latter with a standard ethanolic n-dodecyl mercaptan solutionPe.
111. POLAROGRAPHY
The anodic half-wave potentials of several aryl-substituted diazoalkanes, such a s
4-RC6H,CN,Ph, 4-02NCGHJCN2Rand 4-R1CsHaCN,CeH,R2-4. r-diazoketones,
4-RCGIJICN,COPh, and a-diazoesters, 4-RC6H,CN,CO,Et, have been recorded at
rotating platinum elcctrodes and their shifts with change in R have been correlated
with substituent constantsJ7. Polatographically reduced a-diazoacetophcnoncs gave
three waves \vhich have been attributed to three reactionsJ8.
Arencdiazoniiini salts are reduced at a dropping-mercury electrode. Two half-
waves have been observed arid tabulated, but they have only qualitative significance
-
since the shapes of the waves are irregular. I t has been suggested that the product of
reduction is an arylhydrazine (equation 9). In spite of the fact that the waves are too
ArN: +4e- +3H + ArNHNH, (9)
complex, their hcights vary directly with the concentration. T h c first wave has a
Iialf-wnvc potential of less than - 0 . 3 V. I t is thcreforc possible to determine arene-
diazonium salts at - 0 . 3 V vcrsus SCE, using a dropping-inercury electrode. The
difTusioi1 current ineasurcd is then compared with a calibration curve of diffusion
current asainst diazonium salt conccntrationaO.
Detection and determination of diazo and dinzonium groups 157
Another observation is that the first half-wavc of thc arenediazonium group
occurs at a potential well below that of the azo group. This finding has becn utilizcct
in the determination of diazoniuni salts by a coupling titration in an ainperonietric
titration cell equipped with a dropping-mercury electrode and operating at -0.3 v
versus SCE. A known aliquot of 1-phenyl-3-nicthylpyra~olin-5-onein tlie ccll is
titrated with the diazonium salt solution. As long as coupling occurs no rcduction
of t h e diazoniiim salt takes place and n o current flows. As soon as the pyrazolinone
has been consumcd, the end of the titration is indicated by a current flow which is
directly proportional to the concentration of excess added diazoniiirn salt. This new
technique is more generally applicable than cither the gasonietric o r colorimetric
methods of determination of diazonium saltS"O. IB.
Diazonium salts derived from aniline and froin the threc isomcric aminobenzoic
acids exhibit two polarographic waves i n the range of 0 V to - 1.5 V versus SCE.
At a single pH the diffusion currents are proportional to the coiiccntrations of the
diazoniurn salts.s1 Two distinct waves were obtained i n a series of arenediazoniiim
salts and the half-wave potentials of the first wave wcre tabulated at different p H
values together with the diffusion current pcr unit of conccntration"".
A German patent describes a n apparatus containing a polarographic analyser
for the continuous determination of diazoniiim salts i n reaction mixturcs, and for
the automatic regulation of diazo couplings3.
Aromatic triazenes are reduced at thc dropping-mercury elcctrodc at much highcr
voltages than arencdiazonium salts. As a result, i t is possiblc to measurc the rate of
formation and hydrolysis of triazenes by following the ratc of increase o r dccreasc
in diazcniuni ion concentration, using the technique described abovc13. 1-AryI-3,3-
dialkyltriazenes have been determined by reduction at a dropping-mercury clcctrodc,
giving well-defined waves at pH 5-7 ( E * = - 1.0 vcrsus SCEI). Results of the polaro-
graphic analysis were reliable and compared well with those of other methods':'.
A positive shift of 0.18 V has becn observed in the half-wave potentials of triazenes
o n their polarographic reduction in the presence of tetraalkylaninioniurii ions, i n
contrast to negative shifts observed in the reduction of other conipounds".
The polarographic method has becn used to cstimate 1.3-diphcnyltriazenc i n tlie
atmosphere, which accumulates there during prodaction of cellular rubbcr. Particles
collected froin the air were extracted with ethcr and thc residue obtaincd o n evapora-
tion of the solvent was nitrated. The triazene in the product was determined polaro-
graphically by recording the wavc starting from 0.8 V versus SCE and comparing it
with a calibration curvc of difTiision current against triazenc concentration55.
Measurement of polarographic half-wavc potentials of isomeric diazosulphonatcs
indicates that the isonicrs form an intcrconvcrtiblc sytz-mti pair 1 ar,d 2 , rather than
Ar-N Ar-N ArN =N -0S0,K

II 1
I
K0,S-N N-SO,K (3)
(1) (2)
a diazosulphonate (2)-diazosulphite (3) pair. The niorc stable m / i isomers 2 arc

reduced at a more negative potential than the labile cis forms 1".
The polarographic reduction of azodicarbonitrilc (4) to thc azodicarbonitrilidc
radical anion ( 5 ) is a reversible one-electron process at Ei + 0.40 V versus SCE 5 7 .
NCN=NCN NCN=NCN-
(4) (5)
IV. SEPARATION A N D CHROMATOGRAPHIC METHODS
The aliphatic diazo group, in view of its instability, is not expected to occur in
nature. Nevertheless several antibiotics containing this group have been isolated.
Thus azaserine (O-diazoacetyl-L-serine)js and G-diazo-5-oxo-~-norIcucine~~ were
isolated and purified by chromatography on pretreated alumina, followed by
chromatography o n carbon columns and recrystallization from aqueous ethanol or
methanol. Azaserine w.as also analysed by Craig countcrcurrcnt distribution betwcen
water and phenol, and t h e norleucine derivative was analysed by paper chroniato-
graphy and paper ionophoresis. Alazopeptin [~-alanyl-(6-diazo-5-oxo)-~-norleucyl-
(6-diazo-5-oxo)-~-norleucine] has been isolated from fermentation broths of
SII-cptamyccs gi.iseoplmrrs by crystal I iza t i o n 6 0 .
Bicyclic a-diazoketones were purified by chromatography on basic alumina and
recrystallization61. Several unsaturated a-diazoesters were separated from their
reaction mixtures by chromatography on Florisil and rccrystallization, whereas
other similar esters decomposed on chromatography o n t h e same adsorbent"?.
Diethylphosphonodiazornethane was purified by distillation (69-70 "C at 0.35 miii)c3.
0. Arenediazonium Salts and Diazotates

Arenediazonium salts are relatively rarely isolated and are generally handled in
solution because of their instability and tendency to explode in the solid. They can,
however, be isolated free of inorganic salts when diazotization is carried out \vith
organic diazotizing agents. such as aniyl nitrite in ethanol, and are then precipitated
by ether. They should be dried and haiidlcd carefully in small quantities only.
Nowadays the solid diazonium salts used in industry have been superseded by the
so-called stabilized diazonium salts, as \yell as by the diazotates, and, above all,
by the diazoamino compounds. They can also be stabilized as coniplcx salts with
inorganic salts".
Stabilized arenediazonium salts were separated by paper chromatography using
as solvent a mixture of 95% EtOH-concentrated HCI-distilled H 2 0 (30 : 0.5 : 43.5),
and the spots were developed with Naphthol AS. R , valucs and colours of spots \yere
report~d~~.
Arenediazoniuni chlorozincates and fluoroboratcs were scparaied by t h i n layer
chromatography on silica gel G plates. The best solvcnt mixtures \\ere ivle,SO-
MeC02H-H,0 ( 6 : I : 1 ) and ivIc,SO-SS% HC0,H-CHCI,-dioxanc (25 : 1 : 5 : 20).
Spots were developed with a blue-dye-forniing coupler (7,3-dihydroxynaptitlialenc),
followed by trcatnicnt with ammonia. Thc diazoniurn salts ncrc also rccovcrcd
p r cpar a 1i vel y from thick p t a t es""
Arenediazonium salts \vere analysed by pyrolysis gas chromatography on Chronio-
sorb 103 at temperaturcs betueen 160 and 300 "C. The pyrolysis products \yere
identified by infrared or lascr Ranian spectroscopy of the trapped peaks. For routinc
analysis thc samplcs were pyrolysed at 160 "C and the nitrogen from ihe pyrolysis
was eluted o n a column of Molecular Sieve 5A and determined quantitatively by
coniparison of nitrogcn peak arcas wiih calibration curvcs of injected nitrogen
samples. Prccision and accuracy of thc met hod \\.ere comparable to those of analyscs
by other methods":.
mii-Diazoiatcs are obtained by adding solutioiis of diazoniiim salts to liin,lily
concentrated solutions of alkali Iiydrosidcr; a t rooiii or hiqlier tempcraturcs. They
arc thcn isolatccl by either salting o t i t or precipitation with ethanol';'.
Detcciion and dctcrminniion of diazo and diazonilim groups 159
C. Triazenes and Tetraxenes
Aromatic triazenes arc light yellow solids when pure but upon precipitation from
a reaction mixture are often orange to deep red in c 0 1 o u r ~ ~I n. earlier years mixed
mciliyl- and dimethyldiazoa~i~inobenzenes’~ and nitrodiazoanliriobe~.~zenes~~ have
been precipitated in pure form by cadmium hydroxide in methanol. illore recently
chromatography on alumina has bcen recommended for purificationcg. Thus
bisthiadinzolyltriazcnes have been separated quantitatively o n alumina by elution
with pyridine-glacial acetic acid (92 8)’?.
Various aromatic triazenes were separated by paper chromatography. Thus diazo-
aminobenzcnes substituted in the benzene rings73 and para-substituted l-aryl-3,3-
dimethyltriazenes‘J were separated using a variety of solvent systems and detecting
agents. Rr values n-erc given.
Several phenyltriazenes and nitrophenyltriazenes found as contaminants in
1 -phenyl-3,3-diinethyltriazene and in l-(p-nitrophenyl)-3,3-dimethyltriazene were
separated from these two compounds by thin layer chromatography on silica gel
using xylene and benzene as solvents, and ultraviolet detectionis.
Mixtures of various tetraalkyl-2-tetrazenes were quantitatively separated a n d
recovered a s pure compounds by gas chromatography on polyethylene glycol on
firebrick at 70 “C. A linear relationship was found between peak area and amount of
compound injected7G.
V. INFRARED A N D RAMAN SPECTROSCOPY

A. Diazoalkanes, a-Diozoketones, a-Diazoaldehydes, a-Diazoesters, D i a r o -
cyclopentadienes and Related Compounds
All the bands in the infrared spectra of gaseous CH2N2,CHDN, and CD,N, have
been recorded and assigned7’. The strongest band in these spectra is the stretching
vibration of the NN bond, which appears in the vapour phase a t 2102cm-1 in
C H 2 N n ,at 2097 cm-l in CHDNa and at 2096 cm-1 in CD,N, ’’”. I n CC14 solution
this band occurs in CH2N2at 2075 cm-I The assignments of the major bands of
t h e above three compounds have been tabulated7g. The infrared spectrum of
CH,N”N has also been
The spectra of several nionoalkyl-, alkylaryl- and diaryldiazomethanes in CH2CI,
display their strongest band, naniely thc stretching vibration of the NN bond in the
2070-2010 cni-’ regionys. 4-Diazooctane displays the N N stretching vibration i n
CCI,, at 2050 cm-1 whereas in diazopropyne i t appears at 2075 Bis-
(trifluoromcthyl)dia17.omethane and bis(perfluoroethy1)diazornethanc exhibit this
band at 21 37 and 21 19 crn-I, respcctively’”. Dicyanodiazornethane displays the band
at 2140 cm-’ which indicates considerable contribution from the diazonium methylid
structure 6. The high symmetry of this molecule is reflected i n the simplicity of the
spectruni \vhich contains only four bands in K B r at 2225,2140, 1240nnd 1215 cm-’ 83.
Three 5-nitro-2-fury1 diazo compounds were shown to display the NN band in the
region 21 10-2070 cm-’ 81. Mcrcury derivatives of diazoinethyl compounds 7 exhibit
160 David A . Ben-Efrairn
the N N band in the region of 2080-2037 cm-', whereas germanium, tin and lead
substituted diazoniethancs show it in the 2050-1950 cn1-I regions5.
RCHgCR
II II
N, N,
(7)
s ~ ~Fahrsc tabulated the infrared spectra of a large number

Yates and c o ~ o r k e r and
of a-diazoketones and compared them with those of related types of compound.
T h e a-diazoketones show a mutual interaction between the carbonyl and diazo
groups, which can be represented by resonance contributions from structures of
0-
I +
RC=CHN=N
(8)
type 8. This leads to lo\ver carbonyl frequencics and to higher values of the N N diazo
frequency, which by now possesses some triple bond character. Thus diazoketones
of type RCOCHN, (R groups may be alkyl or aryl) display a strong band in the
region of 210&2050 cm-', whereas those of type R1COCR2N, cxhibit a strong band
in the range of 2075-2050 c n - l . The intense carbonyl band for both types of diazo-
ketone occurs in the rangc of 1645-1605 crn-I, with the exception of diazocainphor
a n d diazoacenaphthenoric which have this band around 1680 cm-I. The cc-diazo-
ketones also exhibit a very intense band in thc 1390-1380 cm-1 region which in some
compounds is a composite band and in others is composed of two strong bands.
F a h r also discussed the mutual interaction of the diazo and carbonyl groups in the
infrared spcctra of bisdiazo compounds, N,CHCO(CH,),COCHN,, and in analogous
compoundsYi. I t hzs also been found that with increasing contribution from dict-
zonium structures 8 the integrated intensity of the N N stretching band decreasessa.
a-Diazoketoncs also display a strong band between 2.356p i and 2.444pm which is
attributed to the first overtone of the asymmetric diazo stretching vibration".
T h e diazo stretching vibration of cc-diazoaldehydes, RCN,CHO (where R is
alkyl), falls i n the region of 2100-2OSO cni-', and the carbonyl band appears around
1690-1650 c n - ' . Both bands are split, which may be due to the presence of cis-trans
conformers, resulting from the partial doiible bond character of the bond between
thc carbon attachcd to thc diazo group and t h e carbonyl carbong0.
T h e NN stretching frequencies of many other a-diazoketones have been tabu-
liltedgoa.8 5 . Ill, as wcll as those of 2-diaz0-1,3-dikctones~~,
a-diazo-p-oxophosphonyl
compoundsg1and mercury dcrivalivcs of diazonicthyl compounds (7,when R is acyl
or aroyl)". The NN strctching vibration of u,$-unsatiiratcd a-diazokctones occurs
in thc region of 2101-2066 c n - ' ns. Thc diazo and carbonyl bands of 2-0x0-I-diazo-
cyclnalkancs uere tabulated"". 16-Diazoandrostan-3~-ol-17-one exhibits bands at
2075, 1650 and 1324 c n - I 91. whereas the bands of diazoisofenchone occur at 2092,
1698 and 1335 cni-l The absorption frequencies of several cyclic 2-diazo-1,3-
dicarbonyl compounds were also recorded and these display two bands around 2180
a n d 21.10 c n - ' D'i.
Thc interaction bctwcen diazoketoncs and hydroxylic solvents was investigated
by infrarcd spcctroscopy". Infrared studies showed that diazoketones. RCOCHN,,
donate and accept protons i n Iiydrogcn bondinggJ.T h c conformations of hindered
cc-diazoketones wcre derived from infrared spectra and dipole niotnentsg9.
Dctcction and determination of diazo and diazoniiim Sroiips 161
u.-Diazoesters exhibit the N N stretching frequency practically in the same region
as a-diazoketones and a - d i a z o a l d e h y d e ~8’0~R .~l o o ~ I o l , 6 2 ~ H 5 .
T h c N N stretching frequency of diazoniethylcne sulphones occurs in the range
of 2 145-2109 cm-I 9 1 and that of phosphonyl- and phosphono-diazonicthanes falls
in the range of 21 32-2075 m i - I 35.
T h e strongest band in the infrared spectra of diazocyclopentadiene i n CCI, lies at
2082 cm-I I o 3 , lo4. T h e NN stretching frequency of many substituted diazocyclo-
pentadienes has bcen reportedlo‘. Io5. A complete vibrational analysis has been made
for diazocyclopentadiene and its perdeuterated analogue106. The diazo band of
a-diazoanthrone lies at 2070 cm-I and that of the carbonyl group at 1647 cm-l lo’.
B. Diazonium Salts, Diazophenols, Diazotates, Diazosulphonates and

Diazoethers
Arenediazonium salts in Nujol mulls exhibit the N N stretching frequency around
2260 f 20 cm-’ lo8, occasionally in the range of 2295-21 10 cm-I log. It is observed
that changes in the anion produce only negligible shifts in this band, whereas changes
of substitution in the benzene ring result in a marked effect on the frequcncy of the
band1OB.T h e infrared spectra of benzenediazonium tetrafluoroborate, tetracliloro-
borate and tetrabromoborate have been rccorded1I0. A systcmatic relationship
between the N N stretching frequency of met hoxy-su bst i t uted benzened iazoni um
cations and o+ constants has been observed, which is useful in the identification and
classification of these cornpounds’l’. The N N stretching frequencies of several sub-
stituted arenediazonium and of several o-dialkylaminobeiizencdiazonium
have been recorded. T h e infrared spectra of 20 pnm-substituted benzene-
diazonium cations measured a s solid [14gC14]2-salts indicated that electron-donating
pnra-substituents caused increase in the Ar-N stretching frequency at 1400-
1300 cm-I and decrease in the N N stretching I’requency, whereas electron-attracting
substituents were less effective in causing such shifts. A linear correlation was also
found between these frequencies and Hamniett u p values”‘.
T h e lsN=I5N stretching band of the ’SN,-benzenediazonium ion in a KBr pellet
was observed at 2227.5 cm-’, i.e. shifted 74.5 cm-’ from the respective 14N=-”N
frequency. Its C6HS-15N stretching fundamental was at 1478 ctn-l and the band
due to the in-plane bending of the C - ~ ’ ” N E ~ ~moiety
N was found at 51 I cm - I .
The corresponding bands in the unlabelled compound were at 1500 and 518 ciii-l,
respectively115.
T h e N N stretching frequencies of fourteen substituted ethylenediazoniuni salts
were observed116to occur in the range of 2260-21 10 cm-’.
Diazobenzenes with hydroxyl groups in orflro or porn position, the so-called
diazophenols and diazonaphthols, exhibit their N N stretching frequency in tlic range
of 2175-2015 cm-l, whereas their carbonyl frequency occurs in the range of 1640-
1560 cm-I, the latter being close to the carbonyl frequency of simple tropolones.
This indicates that they exist as a resonance hybrid 9ll’. With increasing contribution
from the diazonium structure 9a the diazo frequency is shifted to highcr
(9a) (9b)
T h e infrared spectrum of potassium syn-methanediazotate has been recorded in a
Nujol mull: i t has strong bands at 1393, 1335, 1140 and I 1 15 cni-l, and additional
I62 David A. Ben-Efrairn
bands at 1600, 1587, 1013, 935 and 777 cm-’ ll0. Potassium syn-l-phenylethane-
diazotate has in a Nujol mull bands at 1600, 1490, 1375, 1160, 1150, 1057, 758 and
697 mi-’, whereas the anti-diazotate has bands at 1600, 1490, 1410, 1300, 1166, 1079,
1015, 760, 695 and 61 1 cm-’ I Z o .
I n earlier years Le Fevrc a n d coworkers recorded and tabulated the infrared
spectra of potassium s y ~ -and nrrri-benzenediazotatc, sodium p-nitrobenzenediazo-
tate, and potassium p-methoxybcnzenediazotate in the 1800-600 cm-l region.
These authors were however unable to make definite spectral assignments for the
N N stretching vibration’?’. The infrared spectra of two crystalline modifications of
potassium syn-benzenediazotate and of two crystalline modifications of potassium
syn-p-toluenediazotate were recorded and tabulated“?. A very thorough infrared
study of syir- and nnfi-arenediazotates has been made by utilizing lSN-labelled
compounds. I t has been found in this study that the intense N N stretching vibration
occurs around 1350 cm-l in the sytr compounds and around 1375 cm-’ in the anti
compounds. The band is shifted by substituents o n the benzene ring but the metallic
cations have no effect on its location. The N O stretching vibration in these diazotates
displays two close and strong bands in the region of 1200-1120cni-1. It has been
concluded that in both tlie syn- and anti-diazotates the bond order of the N N bond
exceeds markedly that of the N O bond, and that the anti-diazotates have a planar
frnrrs structure with respect to the N N bond, while the syn-diazotates possess a non-
planar distorted cis ~ t r u c t u r e ’ ~ ~ .
The infrared spectra of several arenediazosulphonates were recorded and tabu-
lated but no definite N N band assignments could be made’?’. The infrared spectrum
of p-nitrobenzenediazo methyl ether, p-O,NC,H,N=NOMe, was recorded and
tabulated’23: the N N stretching vibration occurs as a shoulder at 1508 cm-’ and the
N O stretching vibration as an intense band at 995 cm-’.
C. Diazocyanides and Diazoisocyanides

The infrared spectra of several cis- and tra,rs-arenediazocyanides were re-
ported124.’?’ and the band occurring around 2170 cm-’ was assigned to the C=N
stretching vibration’“. It has however been claimed that the assignments in
Reference 124 were erroneous a n d that the stable and labile forms of arenediazo-
cyanides were actually nitrile-isonitrile isomers125.Recently the original conclusions
that the labile and stable pairs of arenediazocyanides were geometrical stereoisomers
have been Thus i t has been shown that the unstable cis isomers
exhibit the cyano stretching vibration at 2175-2150 cm-I, which shifts to 2195-
2190 cm-’ as they isonicrize to the more stable t r n m isomers. The diazo stretching
vibration occurs in thc cis isomers at 1480-1420cm-1 and in the t r a m isomers at
1460-1390 cm-’ The above-mentioned band at 2195-2190 cm-l in the lrans
isomers of p-chlorobenzenediazocyanide and in p-bromobenzcnediazocyanide,
which is absent in the cis isomers, has bcen used to determine them in solution during
their formation in the isonierization of the cis i~oniers’~”.
Azodicarbonitrile (4) and its stable radical anion 5 exhibit infrared bands at 2217
and 21 65 cm-’, rcspectivelyj’.
The spectra of p-chlorobenzencdiazoisocyanide and p-bromobenzenediazoiso-
cyanide have been reported. Their most intense band is split, and its two parts
occur in the ranges of 2135-2130 cm-I and 2100-2095 cm-’. This band has been
assigned to the N C isocyanide stretching vibration while a band occurring a t
1440 cni-’ has been assigned to the N N diazo stretching vibration. Several other
bands have bcen tentativcly assigned and resonancc contributions to the structure
of the diazoisocyanides havc been discussed’28.
Detection and determination of diazo and diazonium groups 163
D . Triazenes and Tetrazenes
Diazoaniinobenzcne displays its bands at 3.1, 3.3, 6.2, 6.6, 6.8, 6.9, 7.0, 8.0, 8.3,
8.5, 9.3, 11.2, 13.0, 13.3 and 14.5 uni The infrared spectra of several triazenes
have been reproduced and tabulaced in the 1800-600 cm-I region, and tentative
band assignments have been madc, thc N N diazo band presumably occurring around
1400 cm-I and/or 1600 cm-I I ? * . The spectrum of the diazoaminothiadiazole I 0 has
(’10)
been recorded. This compound and its analogues show a strong broad band in the
2700 cm-I region, indicating strong hydrogen bonding’?.
Tautorneric equilibria of triazenes substituted in the benzene rings have been
calculated by comparing integrated intensities of 14NH and ISNH bands in the
3300 cm-I region in specifically labe!led compounds130.
Infrared group frequencies of triazenes, ArN=NNHAr, have been assigned by
laser Raman spectroscopy. Thus the band in the range of 3500-3300(w) cm-I was
assigned to the N H stretch; the band at 1522(m) cm-1 to the N H bend; and the band
at 1178(m) cm-1 to the C N
In a study of infrared spectra of compounds of high nitrogen content, the spectrum
of 1 -guanyl-4-nitrosoarninoguanylisotetrazene (11) was obtained. A band at
HN=CNHNHN=NC=NH
I I
NH, NHNHNO
(11)
1062 cm-1 was assigned to the N N diazo stretching vibration. Other assignments
were also made132.
VI. E L E C T R O N I C SPECTROSCOPY, F L U O R E S C E N C E A N D
PHOSPHORESCENCE
A. Diazoalkanes, Diazocyclopentadienes, a-Diazoaldehydes, a-Diazoketones
and a-Diazoesters
The spectra of diazomethane and diazoethane were recorded in t h e vapour
phase133.Their spectra as well as the spectrum of 1-diazopropane were also recorded
in hexane and in other Their absorption begins around 550 nm, displaying
a broad and diffuse maximum in the 450 nm region, which is of very low intensity
( E 3-10). Alkyl substitution shifts the band slightly bathochroniically, whereas aryl
substitution causes a largc shift. This is manifested in the change in colour from the
yellow diazomcthane, to the yellow-red ’-diazopropane, and to the blue-red diphenyl-
. wavelengths shorter than 300 nm a second region of rapidly
d i a ~ o n i e t h a n e ~ ”At
increasing absorption is found133.The vacuum ultraviolet absorption spectrum of
gaseous diazoniethane and deuterated diazomethane were obtained in the 135-
200 n m region’3G.
The concentration of diazoniethanc in ether solution has been determined spectro-
photometrically at 410 nni from t h e molecular extinction coefficient, E 7.215.
164 David A. Ben-Efrairn
The ultraviolet spectra of three 5-nitro-2-fury1 diazo compounds have bcen
tabulated and recordedsJ. The ultraviolet spectrum of dicyanodiazomctllane in
acetonitrile shows absorption at 241 and 313 nni ( E 12,400 and 1 0 7 p . The spectra of
several diaryldiazomctlianes wcrc recorded137.
Crystalline diazocyclopcntadiene (1n.p. -23 to -22 "C) is yellow but is red as a
liquid. Its electronic spectrum in isooctanc displays a maximum a t 298 nm
(log E 4.17) and a long tailing absorption into the visible, the latter being responsible
for its red c 0 1 o u r ~ ~ ~ .
The ultraviolet and visible absorption spectra of diazocyclopentadiene and several
of its substitution products were tabulated. As with other aromatic compounds,
substitution with conjugating substituents on the diazocyclopentadiene ring rcsul ted
in bathochromic shifts'O'. The ultraviolet spectra of several polyphenyldiazocyclo-
pentadienes were reported and rcproduced'a5C.d.
The ultraviolet spectra of seven cx-diazoaldehydes have been tabulated. They
exhibit two short wavelength bands at approximately 250 and 280 nni ( E - l o J and
5 x 103-105),in addition to a long wavelength band of low intensity in the region of
360-400 nni (E-40). As with a-diazoketones there is a markcd influence of solvents
on the relative intensities of thc short wavelength bandsoob.
T h e ultraviolet spectra of numerous a-diazoketones belonging to several classes
have been tabulated13'. Conjugation of the diazo and carbonyl groups shifts the long
wavelength weak band hypsochromically relative to this band in diazoalkanes, while
the short wavelcngth intense band is bathochromically shifted. 1-Diazo-2-butanone
absorbs a t 247, 269 and 360 nm ( 6 7650, 7110 and 21) and a-diazoacetophenone
absorbs a t 250 and 294 nni (E 12,300 and 13,500). Substituted diazoacetophenones
have two bands in the 240-270 and 270-300 nm regions with molecular extinction
coefficients, E 10c3 x 10% 13'. T h e ultraviolet spectra of several cyclic 2-dirizo-l,3-
dicarbonyl compounds were reportede6. 16-Diazoandrostan-3~-ol-17-one has in
ethanol bands at 250 and 297 nni ( E 4139 and 3592)94.a-Diazobenzyl phenyl ketone
absorbs at 267, 317 and 417 nni ( E 19,953, 5012 and IOO)l3".
The ultraviolet and visible spectra of numerous diazoacctoyiicnones in several
solvents have been reported. They all show maxima at approximately 210, 250 and
290 nm, a n d a low-intensity band a t about 400 nm. The hypsochroniic shift of the
long wavelength band in polar solvcnts may result from a n tz + *; transition, due to
the diazo group?39.Thc interaction of diazocarbonyl compounds with hydroxylic
solvents has been investigated, and it has been concluded that their behaviour in the
ultraviolet and infrared are reasonably consistcnt with the possible intervention of
conformational isomeric forms97.140. In fact, it has been shown quantum-niechanic-
ally that the ultraviolet spectra of u-diazokctones, such as diazoacetone and a-diazo-
acetophenone, can be interpreted satisfactorily if i t is assumed that they exist in cis
and f r o m confortmttions"'.
Ethyl diazoacetate absorbs in ethanol at 249 and 377.5 nm ( E 10,050 and 16)'42;its
spectrum in water has been Azaserine, another a-diazo cster, exhibits
niaximum at 250.5 niq (E 19,700) at p H 7 in water". The ultraviolet spectra of the
following esters have been reported: 12 (in ethanol) has niaxima at 213 and 248 nm
(E 4860 a n d 16,200); 13 (in ti-hexane) a t 220 and 245 n m ( E 7850 and 12,650), and 14
N,=CHCO,CH, H
\
/c=c\/
H Me
N =CH CO, N,=CHCO,
H H
Dctcction and dctcrmination of diazo and diazonium groups 165
(in n-hexane) at 217 2nd 245 nni ( E 8100 and 12,700)62.Scveral %-substituted or-diazo-
esters have two bands in ethanol in the regions of 262--264 and 360-415 nm. Thus
ethyl benzyldiazoacetate absorbs at 263 and 4 15 nii1102. Gicthyl diazoinalonate
absorbs in cyclohexanc at 252 and 352 niii ( E 7400 and 23), and dimethyl diazo-
malonate absorbs in cyclohexane a t 225(sh), 250 and 352 nni (& 7300,7900 and 22)'OO.
B. Arenediazonium Salts, Diazophenols, Diazotates, Diazosulphones and

Diazosulphonates
Arencdiazonium clilorides in 0.1 N-HCI display maxima in the 220-300 nm r-g' ,- ion
(E 104-2 x loa), which are strongly dependent on ring substituents and their position.
The unsubstituted benzenediazoniuin chloride absorbs at 262 nm ( E 1 2,390)14'.
Benzenediazor.ium fluoroborate in acetonitrile absorbs at 261 and 296 nm (log E 4.09
and 3*28)145.Its spectrum and that of several mono and polyniethoxy derivatives
have been recorded in the 200-450 nm region and assignments of electronic transi-
tions were made by means of molecular orbital theory145.T h e electronic spectra of
para- and meta-substituted benzenediazonium fluoroborates were rccorded and
tabulated. The para series has a single band in the range of 260-350 nni (log ~ > 4 . 0 ) ,
and the meta series has two bands around 270 nm (log E - 4 . 0 ) and in the range of
300-350 nni (log E c. 3.5). As indicated before, the niaxinia are strongly dcpcndcnt
on substituents and their positions. Molecular orbital calculations were made to
correlate these transitions with substitiicnts14G.T h c electronic spectra of several
o-dialkylaniinobenzenediazoniurn tctrafluoroborates show two bands at about 275
and 440 nm (log E - 3.75 for both
Stabilized arencdiazoniuni salts as their zinc chlorides have been accurately
determined spectrophotometrically by thcir maximum absorbance a t 380 nm. The
method does not require pretrcatment and compares favourably with results
obtained by the gasometric method. Seer's law is followed a t 380 nrn for aqueous
solutions of 1-10 p.p.ni. concentrations. T h c method can be applied t o other
substituted benzenediazonium salts with maxima in the 350-400 nrn region, since
decomposition products and other impurities d o not absorb in this region1".
I t has been reported that several arenediazoniuni salts exhibited fluorcscence at
room temperature and phosphorcscence at liquid nitrogen teniperatures1I*.
T h e ultraviolet spectra of diazophenols and diazonaphthols have been reported.
I t has been argued from these spectra and from dipolc moment nieasuremcnts that
these compounds are resonance hybrids with contributions from quinonoid reson-
ance structures 9b149sI5O. A similar conclusion has bcen rcached from thc electronic
spectra of p-aminobenzencdiazoniunl salts, which should be assigned the quinonoid
structure 15151.
T h e ultraviolet spectra of syn- and anti-diazotates in aqueous alkalinc solution

differ markedly. The anti isomers have absorption maxima between 270 and 280 nm
(log E c. 4.1), whereas the syn isomers show a very broad inflexion in that region, the
centre of which has log E c. 3 Is*. The ultraviolct spectra of scveral syn- and anti-
diazotates obtained on alkaline equilibration of diazonium salts have been tabulated.
I t is observed that the spectral shifts on going from the diazonium salts to the diazo-
tates depend strongly on the substituents and their positions. The ultraviolet spectra
166 David A. Ben-Efraiin
indicate that in strong alkali the predominant species in these equilibria is the iso-
diazohydroxide1J4.The ultraviolet spectra of the components in equilibrium (equa-
tion 10) in the alkaline solution of p-nitrobenzenediazonium ions have bcen obtained
T--%
011- O H --
p-O,NC,H,N: (p-O,NC,H,N=N-OH) p-O,NC,H,N=NO-+H,O (10)
by computation. Whereas the diazoniuni salt exhibits maxima at 260 and 31 1 nm

(log E 4.14 and 3.24), the corresponding nnri-diazohydroxide, and the syn- and anti-
diazotates display their maxima at 3 15, 305 and 332 nni (log E 3.70, 3.92 and 4.10),
re~pectively'~~.
T h e electronic spectra of several diazosulphones, Ar1N=NS0,Ar2, have been
recorded, and it appears from these spectra that the diazo group has the trans
c o n f i g u r a t i ~ n ' ~Benzyl
~. benzenediazosiilphone has maxima at 290 and 438 nni
( E 14,200 and 129) in c y c l ~ h e x a n e ~ ~ ~ .
T h e electronic spectra of ten pairs of alkali salts of isomeric diazosulphonates
have been recorded. In aqueous solution the sytr- and anti-o-chlorobenzenediazo-
sulphonates exhibit maxima at 238, 300 and 448 nm (log&3.7, 3.2 and 2.3), and at
228, 292 and 428 nm (log E 3.8, 3.9 and 2.3), respectively. Small differences only are
found in the ultraviolet spectra of each pair15s.The electronic spectra of numerous
ortho-, tnetn- and para-substituted anti-benzenediazosulphonates have been tabu-
lated. The unsubstituted isomer absorbs at 219, 255, 290 and 416 nm (log& 3.93,
3.14, 4.07 and 2.25). The two long wavelength bands have been assigned to the
-+ ;i*and n --> T;* transitions, respectively. The effects of substitution on the
spectra have also been
C. Diazocyanides and Diazoisocyanides

Electronic spectra of five pairs of isomeric cis and trans halo- and nitrobenzene-
-
diazocyanides have been obtained. They display three bands in the regions of 220-
270, 300-340 and 390-480 nm (log E 3, 3-4 and 4). The difference between the
spectra of each pair is The spectra of cis- and rrmis-p-chlorobenzenediazo-
cyanides have been reported. They are quite similar but the maxima of the t r a n s
isomer are bathochromically shifted and are of somewhat higher intensity as coin-
pared with those of the cis isomer. This indicates that the cis isomer has steric
~ . electronic spectra of cis- and trntis-diphenyl-
hindrance, inhibiting r e ~ o n a n c e ' ~The
4-diazocyanides have been recorded. They are very similar but not identical, and
show the differences expected of geometrical isomers1s9. Azodicarbonitrile (4) and
its radical anion 5 display maxima in acetonitrile at 240 and 445 nni ( E 7830 and IS),
and a t 222, 372 and 525 nm ( E 5270, 4560 and 120), rcspectively".
T h e ultraviolet spectra of p-chlorobenzenediazoisocyanide and its p-bromo
analogue have been reported. They indicatc that the rigid. semipolar-bonded iso-
cyanidc group (N+=C-) is non-chromophoric in character128.
D. Triazenes and Tetrazenes

T h e electronic spectra of 19 substituted derivatives of 1,3-diphenyltriazenes have
been determined. They all display three bands, in the rcgions of 230-240, 280-300
and 340-360 nm ( E - 2 x lo', 10' and 2 x loa).N O conclusions could be drawn from
this study about thcir structure in solution'Ga.T h e spectra of I-aryl-3,3-dimethyl-
triazenes display the same bands as the above series, but it was concluded here that
the coinpounds possess a rtwm configuration about the - N = N - bond"". Elcc-
tronic spectra of numcrous triazencs have been recorded, such as those of ArN=
Dctcction and dctcrmination of diazo and diazonium groups 167
NN(Ph)X (Ar == p-anisyl, I-naphthyl; X = H, Me, Ac)l6=; h'o2C6H,N=
N N H C G H ~ X(X = H, Me, Ph, CI, MeO, NHAc, N 0 2 Y b ; ROZCC6H4N=
NNHC,HIX (R = 14, Me; X = H, Me, Ph, CI, MeO. NtIAc, CO,H, CO,Me,
isomcric chlorophenyltriazenes1G2d,and polysubstituted diazoamino-
I-Aryl-3,3-bis(2-hydroxyethyl)triazenes, uscd in dyeing and printing, were

analysed spcctrophotometrically. Their ultraviolet spectra in ethanolic or aqueous
solution exhibit maxima froni 220 to 245 nm and from 315 to 390 nm, occasionally
also a masimuni in the 250-295 nni region. I n acid solution, a band corresponding
to a diazonium cation is observed. T h e conversion of these triazenes to the diazonium
salts is accompanied by an isosbestic point, indicating a quantitative relationship
betwcen tlic triazencs and the diazoniuin compounds. The dissociation products of
the triazenes (a diazonitim salt and a n aniine) d o not interfere in the determination
I\ hen the long wavelength absorption band is usedIG3. l-Aryl-3,3-dialkyltriazenes
have bcen determined in concentrations down to 50 p i (in 96% EtOH) by absorb-
ance mcasurcrnents at wavelengths between 317 and 380 nm IG1.
T h e ultraviolet spectra of tetraniethyl-2-tetrazene and tetraethyl-2-tetrazene in
ethanol display maxima at 277 nin ( E 5300) and at 2S5 nm ( E 7600), respectively.
'The tetrazenes are basic i n nature and can act as proton acceptors, affording in
proton donor solvents a ncw band around 240 nnia5. The purity of tetra-alkyl-2-
tetrazenes, which were separated by gas chromatography of their mixtures, was
deterniined from thc ratio of their absorbance in basic aqueous solution at 248 and
377 11111 i r , .
VII. NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

A. Diazoalkanes, a-Diazoketones, a-Diazoesters, a-Diazosulphones and
Diazocyclopentadienes
Diazomethane in CCI, displays a singlet at 6 3.20 p.p.m. 165 As compared with
allcnes ant1 ethylenes this is a large upfield shift which may be due to resonance
structures with a negative charge on the carbon. This is also manifested in the nucleo-
philic character of c!iazoinethanc'cG. T h e cheniical shifts of several diazoalkanes have
been tabulated'". The chemical shifts of the a-protons fall in the range of 3.0-
5.0 p.p.m., and it can be seen that they are shifted downfield when the negative
cliargc on thc x-carbon can be stabilized by appropriate substituents, as, for example,
i n phcnyldiazomcthane (6 4.55) or in ethyl diazoacetate (6 4.96) IG7.
The 'H chemical shifts of several 5-nitro-2-furql diazo compounds have been
rcportcdXJ,as were also t h e 19F chemical shifts of bis(trifluoroinethyl)diazomethane
and bis(perfluoroetIiyl)di37.omethanefi?. Tri~luoroiiiethyldiazomethanecxhibits a
quartet in the IH spectruni at 4.6 p.p.ni. (CDCI,, J H F 4.0 Hz) and a doublet in
the 19F spectrum at - 5 4 4 5 p.p.rn. (in CDCI, solution, with CFCI, as external
standard)'".
I n the *H spectrum a-diazoacetone cxhibits t h e niethine singlet at 5.18 p.p.ni. and
the methyl singlet at 2.00 p.p.m. I G 9 The a-mcthine protons of a,?-unsaturated
a-diazoketoncs resonate in the range of 5.2-5.7 p.p.m. y 2 I t has been shown that the
mcthine proton of aryl a-diazoketones resonates in CCIJ at about 5.8 p.p.ni., i n
benzene at about 4-9 p.p.m. and in (CD,),SO at about 6.9 p.p.111. ''
Nuclear magnetic resonance at diffcrent temperatures has demonstrated that
~~-cliazoaldeliydes, u.-diazoketones and a-diazocstcrs exist as equilibrium mixtures of
cis and / r f / i i . sconformers. In dinzoacctone the lroirs-methine proton resonates around
5.2 p .p .m ., ctbout 0.5 p.p.ni. upfield froni the cis-niethine"O.
The methine protons of methyl and ethyl diazoacetate resonate at 4-96 p.p.m. 167
T h e same proton in srvcral other similar a-diazoesters was found to display singlets
in the region of 4.6-4.7 p.p.m. 6 2 The methine proton of a-diazo-N,N-diethyl-
acetamide resonates at 2-40p.p.m. The methyl group o n the double bond of
ethyl 2-methyldiazoacctate resonates at 1 * 5 5 p.p.m. lol, whereas the methylene of the
benzyl group of ethyl 2-benzyldiazoacetate resonates at 3-61 p.p.m. Io2
The methine protons of m-tolyldiazosulphone and of r-butyldiazosulphone resonate
in CCI, at 5-07 and 4.79 p.p.m., respectivelye3. In diethylphosphonodiazomethane
this proton resonates at 4-23 p.p.m. (Jpcn 1 1 Hz) 03.
The aromatic protons of diazocyclopentadiene exhibit two multiplets centred at
6-7(a-protons) and 5.8 p.p.m. (F-protons)104rlG7.It has been concluded that diazo-
cyclopentadiene has very little contribution from structure 16, but that it possesses
almost complete carbanion character in the ring as indicated in structure 17Io7.
R N+
II
N'
The 'H chemical shifts of 9-diazofluorene have been r e p ~ r t e d ' ~ 'T. h e lH chemical
shifts of several nitro- and iodo-substituted diazocyclopentadienes" and of poly-
phenyl-substituted diazocyclopentadienes105c~have also been reported.
B. Diozonium Salts and Diazotates

The first example of IH and 19Fn.ni.r. spectra of an alkyldiazonium ion has been
reported'68. Trifluoromethyldiazoniethane in fluorosulphonic acid exhibits at
- 6 0 ° C in its 'H spectrum a quartet at 6.3 p.p.rn. ( J ~ 6.1
F Hz), which has been
assigned to the methylene group of the 2,2,2-trifluoroethyldiazoniurn ion (18). In
C F,C H, N
(18)
the 19Fspectrum it exhibits the CF, signals as a triplet at - 64.58 p.p.m. from CFCI,
( J I I F6.1 Hz).
The l H n.m.r. spectra of p-methoxy-, p-methyl-, p-chloro- and p-nitro-benzene-
diazonium salts in D20were reported. The chemical shifts of the aromatic protons
are in the region of 7-7-9.2 p.p.m., and the ortho coupling constants are about 9 Hz.
T h e effects of the substitiients o n the IH chemical shifts in the diazonium ions and
in the corresponding aniines and ammonium salts are in the same direction. The
chemical shifts are also closely related to the Hammett u c o n ~ t a n t s " ~The
. aromatic
multiplets of several o-dialkylaminobcnzenediazoniuni fluoroborates fall in the
region of 6.5-8-2 p.p.m.
The methyl singlets of potassium syrt- and mri-methanediazotates occur at 3.1 8
and 3.70 p.p.ni., respcctively172.lG5. The mcthinc, methyl and aromatic protons of
potassium syri-1 -phenylethancdiazotate resonatc at 1 .I9 (doublet), 5 . 5 8 (quartet) and
7.05-7.43 (multiplet) p.p.111. (.Jcn-cll, 6.S Hz),whereas those of the orzti isomer have
their signals at 1.36 (doublet), 4.79 (qiiarlet) and 7.09-7.44 (broadened singlet) p.p.ni.
(Jcu-cu, 6.8 Hz)"".
Detcction and detcrrnination of diazo and dinzoniurn groups 169
C. Triazenes
T h e triazene 19 exhibits in its ‘OF n.m.r. spectrum a doublet centred at 4.27 p.p.m.
(J 8 Hz), upfield from CFCLCFCI,; its ‘H n.m.r. spectrum contains a septet a t
8 4.13 (1H) ( J 8 Hz) and two singlets at 3.40 p.p.m. (4H) and at 1.35 p.p.m. (6H) a*.
(C F, ),CH N = N
H 9)
-N
3
T h e methyl chemical shifts of several 1 -aryl-3,3-dimethyltriazenesoccur in
CDCI, in the 3.5 p.p.m. region. These triazmes exhibit hindered rotation about the
N12)-N13, bond because of its partial double bond charactcr, as concluded from
low temperature n.m.r. ~ t u d i e s ” ~In. a series of papers Wiberg and Prachtl’‘ studied
silyltriazenes 20. They have tabulated ’H chemical shifts of numerous s u b ~ t i t u e n t s ~ ~ ~ ~
R2
/
R’N=NN
\
R’
(20)
and have shown by variable temperature n.m.r. that where R *= R 2 = Me and
R3 = SiMe,, SiEt, and SiMeEt,. only a single methyl singlet appears and that this is
due to fast fluctuations of the silyl group R3 between N t l , and N ( R 174R.
, b. The same
authors also applied low temperature n.m.r. to demonstrate that silyltriazenes,
where R 2 = R3 = SiMe, and SiMcEt,, exist as cis-frairs isomers, which can be
isolated at low temperatiires1‘4C.Finally thcy have shown that in the last-mentioned
group of triazenes hindered rotation occurs about the N N single bond, a s evidenced
from low temperature n.ni.r. studies174d.Values of free energy of activation were
presented for the different processes reported in these studies.
VIII. MASS SPECTROMETRY

T h e mass spectral peaks and rclative intensities of diazomethane have been
tabulated. Its strongest peaks are due to CH2N,+,N: and CHC, the relative intensitics
being 96.5, 50.0 and 100.0, respectively. The spectrum is to a large extent similar to
that of diazirine, with the exception that the CH,N: and N: peaks are more intense
in d i a ~ o m e t h a n e ” ~ .
T h e more abundant peaks of several x-diazoketones and their rclative intcnsilics
were schematically presented. These peaks arc listed below for each of the diazo-
ketones and the most abundant peak of each spectrum is undcriined:
PhCOCHN2: - -
PhCOCHN:, PhCOCH+, PhCO+, C7H,+,Ph+, 52,
CHN;, N
:
;
CCI,COCHN,: CCI,COCHN:, CCI,CO”, CCl;, COCHN;, CHN’, N l ;
CH2CICOCHN,: CH,CICOCHN:, CH,COCHN:, CH,CICO+, COCHNZ,
CH,CICH+, CH2Clf, CHNC and COCH+, N f ;
McCOCHN, : McCOCHNC, COCHN;, MeCOCI-Ii, McCOf, COCH +
and CHN;, NB. Me+.
From the above it is seen that all of these molecules have molecular peaks as well as
N? and CHN; peaks. Ionization potentials and bond dissociation energies of these
compounds were also presented, and it was concluded that fragmentation in the
mass spectrometer involved a competitive intervention of a mechanism of direct
electron impact at the diazo compound, and a process of primary ionization of the
carbonyl fragment formed on thermal cleavage17c.
T h e mass spectral peaks and relative intensities of several diazo-I ,3-dicarbonyl
compounds were tabulated. The molecular ions are of low abundance, but the
compounds give peaks at [M-N,]+ and [M-N2-CO]+, the latter being due to an
electron-impact induced WolrT rearrangement. A 13C-labellcd compound was used
to investigate the migration mobility of substituents in this ~ e a r r a n g e m e n t ' ~In~ .a
study of the major fragmentation patterns of diazoketophenanthrenes i t was observed
that the more abundant ions were M + , [M-N,]+, [M-N,-COI+, [M-N2-CO-
HI+ and [M-NN,-CO-HC==CH]+ 178.
T h e mass spectral peaks of diazoesters 12-14 were reported. Molecular peaks are
absent in their spectra but they exhibit [M-N,]' and CHN' peaksG2.The mass
spectral patterns of several 2-diazo-I ,3-ketoesters wcre tabulated but, in contrast to
the diazo-] ,3-dicarbonyl compounds mentioned above, the fragments [M-i\l,]+ d o
not give a Wolff rearrangement'".
B. Diazophenols
T h e zwitterions of diazotized o- and p-aminophenol are volatile and give intense
molecular ions and strong [M-N,]+ and [M-N,-CO]+ peaks, which are formed
via the quinonoid structures of these molecules. By contrast, the meta isomer which
cannot be stabilized through a quinonoid structure yields a complex mass spectrum.
The zwitterions of diazotized anthranilic acid and diazotized sulphanilic acid did not
afford molecular ion peaks178.
C. Triazenes
The mass spectra of four diaryltriazenes 21 (R' = H or alkyl) givc molecular ions
of low abundance, presumably because of their rapid central cleavage to the abun-
dant ions 22 and 23. The tautomerisrn in triazenes 21 (R' = H) is also reflected in
N=N-N
I
their mass spectra, but i t is n o t known \r.hcthcr the tautoiiicrs arc formed before o r
after electron impact. Elimination of nitrogen as (M-N2)+ or (M-R'N)+ peaks is
also common in these triazenes18".
IX. ELECTRON S P I N RESONANCE SPECTROSCOPY A N D
CHEMICALLY I N D U C E D D Y N A M I C NUCLEAR POLARIZATION
Many diazo compoilnds a r e unstable and decompose easily with evolution of
nitrogen. Until recent years only chemical and indirect physical methods were
available to the chemist to study which of the reactions of diazo compounds proceed
b y a free-radical mechanism. With the emergence of the powerful spectroscopic
methods of this section, it has beconie possible to probe into this problem in a
straightforward manner. This section, however, will be restricted only to those cases
where the diazo compounds themselves become free radicals, leaving out the
majority of cases where the primary reaction products are free radicals.
On shaking diazofluorene with sodium in ether solution it yields a deep blue,
oxygen-sensitive free radical, 24, which has been detected by e.s.r. Diphenyldiazo-
methane behaves similarly, yielding a free radical, which probabiy has a contribut-
ing structure 2S".
Ph -
\C/kN ,-
Ph'
124) (25)
I n the diazo coupling between a n arenediazoniurn fluoroborate and methanolic
sodium phenoxide which yields a p-hydroxyazobenzene, it has been shown by
CIDNP that the first step of the reaction involves a reversible electron transfer
reaction (equation 1 I ) to give two free radicals which then combine to yield the azo
(11)
compound. This was proved by using a diazonium salt, lSN-labelled at both posi-
tions, and detecting not only enhanced absorption of the azo product, but also
enhanced absorption and ernission of t h e first formed aryldiimine radical 2618'.
This reaction was also studied by and lSN CIDNP, which as above showcd not
only polarization of formed products, but also enhanced absorption of the and
I5N resonances of the original diazonium ion. A mechanism was proposed for this
reaction, involving d i a ~ o e t h e r s ' ~In~ .similar fashion I3C C I D N P of p-methoxy-
benzenediazonium ions (labelled with 13C a t Ccl,)showcd, on addition of a sodium
hydroxide solution, not only emission from the formed anisole but also enhanced
absorption which has tentatively been attributcd to C ( l l in the original diazoniurn
ion. This indicates participation by the above !ype of aryldiiminc radical (26)IR4.
A phenyldiazotate u radical 27 has been observed by e.s.r. in the dccomposition of
N-nitrosoacetanilide'89.
lSN C l D N P of the thermal decomposition of labelled diazoaminobcnzene shows
in addition to polarization of the formed products also enhanced absorption of the
starting material, but only in thc central nitrogen atom. This presumably originates
from recombination of free radicals 28 and 29. Radical 28 must however be very
ditrerent from radical 26, generated in tlic deconiposition of arenediazonium

fluoroboratcs in alkaline ~ o l u t i o n IR3,
' ~ ~bccause
~ in tlie latter, atoms C,,,, N,,, and
No, are equally polarized, whereas in the diazoaniinobenzcnc only the is
pol a r i zed Ia8.
X. ELECTRON SPECTROSCOPY
Electron spectroscopy is used to study the sequence of molccular orbitals a n d their
energies in molecules. I t has also found analytical a n d structural applications, but
as yet it has presumably not bcen used i n the analysis of diazo compoundsIJi.
The ultraviolet photoelectron spectra of 2-diazopropane and diazocyclopcntadicnc
have been obtained. Froin these spectra it has been possible to conclude that in these
two compounds, as well as in diazonicthanc itself, the highest occupied orbital is a
non-bonding b2(z)
The X-ray photoelectron spectrum (ESCA) of benzcnediazonium fluoroborate
displays two nitrogen Is pcaks with a pcak separation of 1 . 3 cV. I t has becn con-
cluded that tlie higher binding energy pcak is associatcd \\ith t h e nitrogen atom
directly attached t o the phenyl group'".
XI. DIPOLE MOMENTS

Dipole moments have contributed to structural, configurational and conformational
assignments of organic molecules.
Dicyanodiazomethane has a dipole moment of 3.8 D, which indicates a consider-
able contribution from tlie diazonium niethylid structure 6 to the ground state of
the molccule".
Thc dipolc momcnts of diazoacetonc and its three chloromethyl dcrivatives have
bcen detcrmined, ant! from thcsc valucs i t has been inferred that tlic molccules
possess a rigid planar COCHN, structurc, whcre the C O and CN, groups may have
either thc cis or ~rntzsconformation. Diazoacctone itself exists in both conformations,
but i n the chloro derivatives only the cis conformers are present. Comparison of
experimental a n d thcoretical dipole nioinent values for CH,CICOCHN, and
CHCI,COCHN, Icd to angles of 150" and 40°,rcspcctivcly, bctwcen the niolecular
plane containing thc COCHN, grouping. and t l i c plnnc defined by C(carbony1)-
C(alky1)-X (X = CI in thc forincr niolccule, X = H in thc latter nioleciile)'qo.
Dipole niomcnts of pnra-substitutcd phcnyldiazokctoncs showcd that the cis-/raris
cquilibrium at tlie COCHN, grouping is almost entircly shifted to the cis conforma-
tion, in contrast to dinzoncctoiic'!''. Dipole nioiiieiit nic;istirciiicnts of hintleixxi
diazoketoncs also point to occiirrcncc o f t \ v o psciido cis-rrn/i.r (distorted) confornia-
tions". Dicthyl diazoi1ialon;itc has ;I dipolc iiiomcnt of 2.66 D I " ' .
O f t h e configurational pairs o f arenediazocyanides, the stable forms have thc
larger dipole m o m e n t and therefore possess t h e fratis configuration, whereas the
labile forms h a v e t h e cis onf figuration^^^^ 159.
121ae
T h e dipG!c m o m e n t s o f 1 -aryl-3,3-dimethyltriazenesindicate t h a t they prcsuniably

have a irarrs configuration a b o u t the -N=N- G912.
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I62b. P. Graiiiiiinticakis, Bull. Soc. Chint. Frarice, 129 (1957).
162c. P. Granimaticakis, Bitll. SOC.Cltiitt. Fra/tcc, I39 (1957).
167-d. P. Grammnticakis, C. R . Acrid. Sci. Paris, 245, 1252 (1957).
162c. V. 0. Lukashcvich and E. S. Lisitsyna, Dokl. Akari. Naitk S.S.S.R.,160, 129 (1965)
[Cltcitt. Abstr., 62, 1171 Ic (1965)l.
163. V. K. Kruglov, A. P. Ershov, 2nd A. A . Kharkliarov, Iic. Vyssltikh Ucltcbtt. Zaccdertii
Khitn. i Khim. Tc.k/ritol.,9, I05 ( 1 966) [ Cl!eut. Absrr., 65, 820 I f ( 1 966)].
164. V. Zveiina, V. Chmltal, I . Junkova, J . DiviJ and M. Matrka, Cheut. Prrtrt!., 20,
231 (1970) [Clron. Ahstr., 73, I16171 (197U)l.
165. H. Stihr, Cltoti. Ber., 96, 1720 (1963).
166. D. F. Koster and A. Danti, J . Cltem. Pltys., 41, 582 (1964).
167. A. Lcdwith a n d E. C. Friedrich, J . C/tem. Soc., 503 (1964).
168. J. R. Mohrig and K. Kcegstra, J . Attier. Chon. Soc., 89, 5492 (1967).
169. 14. D a h n , A. Donzel, A. Mcrbach a n d H . Gold, fielu. Chirit. Acta, 46, 994 (1963).
170. F. Kaplan and G . K. Mcloy, J . Anrcr. Cl~eni.SOL..,88, 950 (1966).
171. H. Suhr, Bcr. Bitriscrtges. Plrys. Chem., 66, 466 (1962).
172. E. Miillcr, W . Hoppe, H . Hagenmaicr, 14. Haiss, R . Huber, W. Rundcl a n d H . Suhr,
C k m . Ber., 96, 1712 (1963).
173. M. H. Akhtar, R. S. McDanicl, hl. Fcscr and A. C. Oehlschlagcr, Terral!edrotr, 24,
3899 (1968).
174a. N. Wibcrg a n d H . J. Prncht, Chent. Be,., 105, 1377 (1972).
174b. N. Wibcrg a n d H . J. Praclit, Cltettt. Ber.. 105, 1388 (1972).
174c. N. Wibcrg and H. J . Pracht, Chert!. D o . . , 105, 1392 (19721.
174d. N. Wibcrg and H. J . Pracht, Cltent. Be,., 105, 1399 (1977).
175. G . S. Paulctt and R. Ettingcr, J . Chem. Phys., 39, 825 (1063).
176. A. FofTani, S. Pignataro, B. Cantone a n d F. Grasso, ~ ‘ ~ ~ [ J L YCimejito,
I 29, 918 (1963)
[Client. Absrr., 60, 9Sh (1964)l.
177. K.-P. Zellcr, t i . Meier arid E. Mullcr, Ann. Chettt., 749, 178 (1971).
178. P. Kinson and B. M. Trost, Terrdicr/rort Lcfrcrs, 1075 (1969).
179. K. Undhcini, 0. Thorstad and G . Hvistcndahl, O q . Alnss. Spcctro~?!., 5 , 73 (1971).
180. R. A. W. Johnstone, D. W. Payling, P. N. Preston, H. N. E. Stevens a n d M. F. G .
Stevens, J . C h n . Soc. C, 1338 (1970).
181. T. Kauffmann and S. M . Hagc, Attgew. Chetn., 75, 348 (1963).
182. N. N. Bubnov, K. A. Bilcvitch, L. A. Poljakova and 0. Yu. Okhlobystin, J. Cheut. Soc.
Clwtti. Cottrincoi., 1058 ( 1 972).
183. E. !.ippniaa, T. Pchk, T. Saluvere a n d M . MSgi, Org. Afagn. Resorturtce, 5 , 441 (1973).
184. S. Bcrgcr, S. Hauff, P. Nicdercr and A. Rickcr, Tefrdedrott Letters, 2581 (1972).
ISS. J. 1. G. Cndogan, R . M. Paton a n d C . Thonison, Chetn. Cultttir!t/t., 614 (1969);
J. I. G. Cadognn, Accoiinrs Client. Res., 4. 186 (1971).
186. E. Lippillan, T. Saluvere, T. Pchk and A. Olivson, Oi-g. Alngrt. Rc.sottnttce, 5,429 (1973).
I78 David A. Bcn-Efraim
187. D. T. Clark, in Annual Reporfs on the Progress of Cheniistry, Vol. 68 (1971). Section B,
The Chemical Society, London, 1972, pp. 91-101 ; D. T. Clark, in Annrral Reports 011
the Progress of Chemistry, Vol. 69 (1972), Section B, The Chemical Society, London,
1973, pp. 66-83.
188. E. Hcilbronncr and H.-D. Martin, Chem Ber., 106, 3376 (1973).
189. P. Finn and W. L. Jolly, Inorg. Chem., 11, 1434 (1972).
190. G . Piazza, S. Sorriso and A. Foffani, Tetrahedron, 24, 4751 (1968).
191. S. Sorriso, G . Piazza and A. Foffani, J. Chern. SOC.B, 805 (1971).
192. R . J. W. Le Fkvre and H. Vine, 1. Chem. SOC.,431 (1938); R. J. W. Le Fkvre and
J. Northcott, J. Clieni. Soc., 333 (1949).
CHAPTER 6
Basicity, acidity and hydrogen
bonding
J. F. MCGARRITY
Institiile of Organic Clrertiistry, UtiiuersiIy of Laiistintic, Lmsotitic, Switzcrlund
11. BASICITY
OF ALIPHATIC DIAZOCOMPOUSDS . . 180
A. Gas Phase Basicity of Diazoalkanes . . 180
B. Solution Basicity of Diazoalkanes . . 182
1. Site of protonation in 'super-acid' media. . 182
2. Thermodynamic basicity of diazoalkancs . . 183
3. Acid-catalysed hydrogen-deuterium exchangc . . 185
4. Basc-catalyscd dcconiposition of N-nitrosourcthanes and ureas . . 185
5. Acidic species alkylated by diazoalkancs . . 190
6. Kinetic basicity of aliphatic diazo coinpounds . . . 191
111. LEWISBASICITY O F ALIPHATIC DIAZO COMPOUNDS . . 201
A. Kinetics of Elcctrophilic Addition . . 201
B. Reactions with Elcctrophilic Carbon . . 203
1. Reactions with esters . . 203
2. Reaction with aliphatic diazoniurn ions . . 204
C. Site of Electrophilic Attack . . 204
1. Reaction with aromatic diazoniiim ions . . 204
2. Reactions with carbenes . 205
Iv. PROTON ACIDITYO F DIAZOALKANES . . . 206
V. LEWISACIDITYOF DIAZOA N D D I A Z O N ~ U GROUPS
M . . 210
A. Coupling of Aromatic Diazoniurn Ions . . 210
1. Introduction . 210
2. Reactions with nucleophilic carbon. . 210
3. Reactions with heteronucleophilcs . . . 211
B. Coupling of Aliphatic Diazoniurn Ions . . 212
1. Stable aliphatic diazonium ions . . 212
2. Trapping of aliphatic diazoniiim ion intcrmediatcs . . 213
C. Coupling of Aliphatic Diazo Compounds . . 214
VI. HYDROGEN BONDING . . 218
A. Diazoalkanes as Proton Acceptors . . 218
B. Diazoalkanes as Proton Donors . . 220
VII. ACIDITYA N D BASICITY OF AROMATIC DIAZOCOMPOUNDS . . 221
A. Diazohydroxides . . 221
1. Introduction . 221
2. Dissociation of syn diazohydroxidcs . . 222
3. Dissociation of anti diazohydroxides . . 222
4 . Reaction of atiti diazohydroxides with acids . . 222
5 . Reaction of sytr diazohydroxides with acids . . 223
B. Diazophenols . . 223
C. Triazenes . . 223
VIII. ACKNOWLEDGEMENTS. . 224
IX. REFERENCES . . 224
179
7
1 so J. F. McGarrity
1. ! N T R B D U C T I 0 hl
The clcctron distribution in priniar y diazoulknnes is oftcn reprcsentcd by resonance
forms la-Id.
+ R R
R\ C=N=N-
+ R,-
C-NrN
\-
C-N=N
+ \+
C-N=N-
H’ H’ H’ H’
(1a) (1 b) (1c ) (1d)
Forms l b and l c dictate thc reactivity of diazoalkanes to acids and electrophiles,

with forms l a and Id playing a minor role. Proton abstraction by bases is governed
by form l a whereas reactions with nucleopliiles arc best rationalized by considera-
tion of forms 1b and lc. I n the equations that follow, the choice of representation
will depend on the reaction in question, arid docs not imply a prcdcminance of that
form in the overall electron distribution.
The structurc of the discussion follows largely that of the classic review of Huisgen’.
Emphasis is howevcr placed on quantitativc evaluation of basicity and acidity. Whcn
tlierc is a lack of thcrinodynamic data, as is oftcn the case for t h e compounds dis-
cussed, kinetic results are examined. Qualitative examples are presentec! a s illustra-
tions of specific points, and d o not represent a cornpletc covcrage of the subject.
Extensive refcrencc is made to comprchcnsivc?. and more recentJ. reviews.
II. BASICITY OF ALIPHATIC DIAZO C O M P O U N D S

A. Gas Phase Basicity of Diazoolkanes
In contrast to its elusive beliaviour in solution, the iiietliancdiazoniiini ion (2) can
be directly observcd and induced to rcact i n the gas phase.
-
The most unequivocal methods of formation are by nucleophilic displacement
processcs‘, and by fragmcntation of the azomethane niolccutar ion: :
+
N,+CH,FH CH,N:+HF (1 1
(2)
I
[CH,N=NCH,]+ A CH,-N=N+-CH, (2)
This latter nieans of generation of the nicthanediazoniuni ion lends itself admirably
to the study of subsequent proton transfer rcactioris forming diazoniethanes, by ion
cyclotron resonance spectroscopy*. Thus at 13 eV (4.3 e V above the appearance
potential of thc mcthanediazonium ion), an increase i n the pressure of azomethane
results in its protonation by the diazoniuni ion:
+
CH,N: +CH,N=NCH, > CH,N,+CH,NH=NCH, (3)
As is often thc casc for the chemistry of alkyl diazoniuni ions in solution, the loss of
a proton is accompanied by compctitive loss of nitrogen. T h e species so formed are
characteristic fragments of the trinietliyIdiazeniitm ion (3), initially produced by a
nucleophilic displacenicnt of nitrogen.
6. nnsicity, acidity arid hydrogen bonding 181
The proton aflinity (P.A.) of diazomcthanc, shown to be inferior to that of azo-
nicthane by observation of the rcaction &en by equation (31, was found to be
-
intcrnicdiate bct\vcen those of mcthylamiiic and ammonia, by tlic rcactions obscrvcd
upon in:;oduction of cach of thcse bascs into thc azomethane system, (equations
54).
+
CH,N:+CH,NH, (CH,),NH,+N, (5)
CH,N: +NH, -X+ CH,N,+ + NH, (8)

Hcnce
P.A. (NH,) c: P.A. (CH,N,) <P.A. (CH,N=NCH,)<P.A. (CH,NH,) (9)
-
T h e existence of the niethancdiazoiiiuin ion in thc gas phase, as a n intermediate or
part of a transition statc, in the reaction of !iydrogcn halides with diazomethane
(equation lo), is much less evident.
CH,N,+HX C.H,X+N, (1 0)
T h e estimated uppcr limit of 24.5 kJ/mol for the activation encrgy of this reaction
involving hydrogen iodidc was considercd to be cornpatiblc!' with a simple polar
transition statc such as 4.
8- fif s- 8-t
HI+CH,N, ~ > 1- - _ _H _ _ - -CH,-N=N >- CH,I+N, (1:)
(4)
T h e extreme rapidity of these reactions even at -75 "C limited thc measurements
of rate constants i n this study to ratios based on conipetitivc experiments. Thus at
300 K :
k l l l l r = g t 2 -k -
rrl - 4 k 2 k111
- = 50-+15
k U((1 kHnr k1rc1
Rate constants for the rcactions of hydrogen chloridc and hydrogen bromide with
diazomethane have, ho\vcvcr, becn determined'":
kncl = (7.0 +_ 1.0) x 10' ctn3 niol-l SCC-I,
k n n r = (3.0 -+ 1.0) x loc cm3 mol-' SCC-'
The significance of thcsc figures is obscured by tlic contribution of a wall reaction,
providing a n experimentally-obscrved ncgative activation energy of - 1.6 kJ/niol.
Experiments with deuterium chloride and diazornethane provided evidence that t h e
first associative step is rcversiblc". All thrcc deuteratcd species of the product methyl
chloride were obtained. Whcn deutcriuni chloride \vas injected \vith a n excess of
diazomethane, which was subsequently quenched with hydrogen broniidc, there was
20% deuteration of the methyl bromidc. This hydrogcn isotopic exchange was
considered to be impossible via an intermediatc complex of thc form 4. The alter-
native complexcs postulatedll did not include 5, which nevertheless merits considcra-
tion as it allows for both competing substitution and dcprotonation reactions, with
a minimum of structural rcorganization.
H
..' +
H-CLNEN
&-C,--gS+
(5)
182 J. F. McGarrity
6. Solution Basicity of Diazoalkanes
1. Site of protonation in 'super-acid' media
Of the two potentially basic sites in simple diazoalkanes, reaction a t one-the
carbon in limiting structures (lb) and (1c)-leads to the habitually observed products
of reactions with acids12. T h e alternative site-the nitrogen of limiting structures
(la) and (Id)-is not apparcntly involved. An earlier postulate of N-protonation13
was subsequently revised in t h e light of more extensive data". Is.
Protonation of 2,2,2-trifluorodiazoetlianein fluorosulphonic acid-deuteriochloro-
form gave a solution of the carbon-protonated species16 indicated by the 'H and
IyF n.m.r. spectra.
H\- + CDCI, +
C-NEN + FSO,H t F,C-CH,-NEN + FSO, (1 2)
F,C'
8~ = 4.6 p.p.m., q J = 4.0 Hz 8~ = 6.3 p.p.m., J = 6.1 Hz

=
8 ~ x 9 + 54.45 d 8 p e = +64.58, t J = 6.1 HZ
T h e principal evidencc for this protonation site was the presence of a triplet in the
FI9 spectrum. Analogous C-protonated diazonium ions were formed from 1,1,1,3,3,3-
hexafluoro-2-diazopropane at - 70 "C in FS03H-CDCI, and for 1 -phenyI-2,2,2-
trifluoro diazoethane at - 60 "C in S02-HFSORIn.From the spectral data presented
for these examples, a n N-protonated species cannot be so rigorously excluded.
When the diazo group is adjacent to a carbonyl group, another potential site of
protonation is introduced. Thus on admixture of diazoacetone with HF-SbF, in
SO2 at - 80 "C, protonation occurs on the carbonyl oxygen, to give a mixture of Z
and E diazonium ions, ( 6 ) and (7), in the ratio 4 : 1 19.
ii
N+
111
(7) N
For 6 :
~ C H ,= 2.19, 8c.u = 6.1, J = 1 Hz, 8 0 =

~ 9.29 p.p.ni.
T h e observation of geometrical isoincrs renders improbable protonation on
carbon or nitrogen as in 8 and 9 respectively.
Thc difference in coupling constants betwcen the inethine proton and that derived
from the acid in 6 snd 7 tends 10 confirm 0-protonation. In FSO,H-SbF,-SO, a t
-60 "C neither this H-H coupling nor, indeed, the resonance of thc OH proton
could be observed due to its rapid exchange with the solvent protons.
(8) (9)
Protonation on oxygen was also observed for a series of aryl primary diazo-
ketones of general formula ArCOCHN, and for alkyl diazoketones, primary?O and
s e c ~ n d a r y ' ~T.h e p.ni.r. spectra of ?-diazo cholestan-3-one dcrivatives in FS03H-
CDCI,-SO, at - 70 "C were interpreted as indicating protonation on carbon?'.
T h e principal evidcnce cited as argument against oxygen protonation, i.e. t h e dis-
similarity of the cheniical shift of the acidic proton at 8 = 9.3 p.p.m. to that for
protonated ketones, is, i n the light of subseqiicnt values for oxygen-protonated
diazoketoneslg,of 6 = 8.2 - 9.3 p.p.rn., probably invalid. Thc rapid proton exchange
with the solvent, on warming the solution, is also more compatible Lvith 0 rather
than C protonation.
2. Thermodynamic basicity of diazoalkanes

For direct observation of alkyl diazonium ions in solution, they must possess
features protecting then1 against spontaneous decomposition into molecular nitrogen
and carbocations, and must bc able to cxist in weakly nucleophilic media. In the
examples cited abovc, the first criterion was fulfilled by strongly electron-with-
drawing groups diminishing the stability of possible carbocationic products. The
second was assured by the extrcmcly feeble nucleophilicity of t h e counterions
SbF, and FSO,, cxtrapolatcd from their extrcmcly weak basicity?". Thcse conditions
have so far prevented thc establishment of a dircctly observable equilibrium. In the
highly acidic rnedin mentioned above, the diazo compounds studied were com-
pletely protonated; i n more basic solutions thc cqiiilibriuni concentrations of the
diazonium ions are too low. Thas thc protonation eqiiilibriuni prcccding the rate-
determining loss of nitrogen. i n the hydrolysis of ethyl diazoacetate'R-25(10) (equa-
tion ls), cannot be directly observcd, evcn in 2.5-molar aqueous perchloric acidzG.
0 N, 0 :N 0 OH
It 1
I II I p,
II I
ROC-CHI-H,~ +
%
-- ROC-CH, ROC-CH, (1 5)
k-, uzo
(10, R = C,HJ
The overall rate constant for this reaction is given by equation (16):
Furtherniorc, as in this case k , e k -1
where K = k l / k - l .
154 J. F. McGnrrity
Thus thc observed rate cons!ant contains the protonation equilibrium constant K ,
multiplied by k,, thc rate constant for thc displacement of nitrogcn, which has been
shown to be nucleophilc assisted for this substratez7. Although the value of k , is
inaccessible directly, its sensitivity s to the strength of the participating Ilucleophiie
i f , as expresscd by thc Swain-Scott cquation28, has been dcter~nined~'. Identical s
values for two nucleophilic substitutions indicate a common sensitivity of the
transition statcs to reactant properties. This is equated by the Lemer postulate2S.30,
to a common position of the transition states along the reaction coordinate, the
position being governed by thc difference in free energy between reactants and
products. The activation frce energy is determined by this energy difference and a
nunibcr of factors, including stcric, solvational and entropy changes dependent on
the transition-state structure. I t has bccn proposed that sutstituent effects on
structurally related diazoniuni ions are s~iiall'~. I f one accepts this proposition, i t
follows that thc reactions of water with structurally related diazonium ions, dis-
playing similar sensitivity to substitution by otllcr nucleophiles, should havc similar
activation cncrgies. This rescmblancc in transition state structures (with idcntical
entering and lcaving groups) implies similar free cnergics of reaction dominated by
the frce energy of formation of molecular nitrogen, and common interactions unique
to the transition state. Hence thc s values for thc hydrolysis of 10 and diazoacetonc
(11) of 0.3 and 0.4 O7 imply approximately equal values of k , for nitrogen displace-
mcnt. Consequently, comparison of the overall second-order hydrolysis rate con-
stants of 10 and 11 givc a mensurc of the relative acidity of their corresponding
diazonium ions.
log kol,,( 11) - log kO1,,(10) = - pK(10) + pK(11) = 1.3 (1 8)
This type of comparison cannot bc justifiably cstendcd to the hydrolysis of

primary aryldiazosulphoncs ArS02CN,H. which although following the same
mechanism have a sonicwhat highcr s value?'.
An estimate of the acid dissociation constants of alkancdiazoniuni ions can be
made in some cascs, wherc the deprotonation is lcss rapid than the compctitivc loss
of nitrogen. This situation is characterized by rate-determining protonation. When
k,>k-,, equation (1 6) bccomcs:
A n increasing concentration of additional base may, Iiowevcr, sufficiently accclerate

the deprotonation, so as to make tlic sccond stcp partially rate dctermining, i.c. the
dependence of thc observed rate constant on acid concentrations may change. This
situation was rcalized in the hydrolysis of diazoacctatc anion (12) i n thc presence of
hydroside ion3', and i n tlic hydrolysis of '-diazo butan-3-one (13) and ethyl diazo-
~ ~ in thc prcscnce of acetic acid/acetate buffers.
p r ~ p i o n a t e(13)
0 Nz 0 N2 0 N2
II I1 II II II II
H,C,O -C- C -R H,C-C-C-R 6-C-C-H
(10) R = H (11) R=H (12)
(13) R = CH, (14) R = CH,
Analysis of t h e kinetic data3', 3 1 providcs valucs for k-,/k,, whicl , with ccrtain
approximations, allo\v cstimatcs of k - , . Combinatioii \vitli tlic known k, value gives
limi!ing valucs of A'< 10" mol/l, K < 5 x lo3 niol/l and K < 1 molil for the proto-
nated forms of 14, 13 rind 12, respectively, i.e. p K . = - 5, p K < -3.7 and p K < O .
6. Basicity, acidity and hydrogcn bonding 185
A more involved analysis of kinetic data for general acid-catalyscd hydrolyses of
diazo compounds can Icad, in principle, to an estimate of thc p&'s of the conjugate
acids. The significance and limitations of this approach will be discusscd in
Section II.B.6.
3. Aci d-catal ysed h yd rogen-deuteri u m exchange

Primary deactivated diazoalkancs of t h e form R C H N , whcre R = -CO2Rz3. '.I,
-OR 35-38, - S 0 2 R 39* 4 0 , -CF, .'I, establish an acid-basc equilibrium with
aqucous acid, prior to nitrogen loss. This equilibriuiii is principally dcmonstrated by
a kinetic isotope efTcct kllto//iJ,,o~ 0 . I4? , o r by Iiydrogcn-deutcrium eschange in a
deuteratcd solution, cithcr in tlic diazo compounds o r products derivcd therefrom.
For sirnplc diazoalkanes, precise kinetic ineasiirciiieiit is difficult d u e to their
cxtrerne acid lability, and so the second probe is rnorc often uscd.
In t h c casc of diazonicthanc, thc rcsults obtaincd appcar somewlint confusing.
Whercas i t undergoes exchangc in a t\vo-phase systcni of alkaline IILOand dibutyl
cther o r t c t r a h y d r o f i ~ r a n,I1,~ ~i n~ a system of chloroform--D,O thcrc is no cschangc
unless catalytic quantitics of a weak acid, such ;IS phenol, ammonium chloride o r
benzoic acid, are addctiI5. I n diosanc-D,O. reaction of Jiazoiiiethanc \\.itti an acid
or phenol gives the trideutcrntcd cstcr or etlicr respectivcly15. hlonotleuteration on
carbon is observed i n dcutcratcd acetic acid.'G,whilc it pre-eqiiilibriiirn is reported to
be cstablishcd with bcnzoic acid iii toluene4:. In strong aqucous a.:id solution, only
one deuterium is incorporated", ,Iq.
That the exchange occiirs via tlic conjugatc base of diazomcthanc (SCCSection 1V)
cannot bc escludcd (1 pr.iori. However, t!ic implication o f ncidic catalysis by wcak
acids, but not by D:,O-, susgests that thc tlctcrmining factor is the strength of the
conjugatc base of tlic catalyst. Ccrtain di;iLocarboiiyl compounds, I 2 3c, 14 lgand
bcnzoyl p1ieiiyldiazouictli;iii~( 15)'neJ 1 have bccn shown to iindcr9.o protonation by
water and. at lcast i n the lirst ~ N Y ) c;ises, subsequcrit regcneration b y ttic hydrosidc
ion. F o r bases stronger than water, dcprotonatioii is I'avoLircd over nucleophilic
substitution. I n support of this argument, the mctlianol isolated afier t h e hydrolysis
of diazomcthanc i n dioxane-D,O is mono~leirterateclon carbon \vhen the hydrolysis
is carried out at pI-1 3, tridctiteratctl for pt-l 13. and contains a mixture o f i11oiio-,
di- and trideutcratcd species when tlic rcaction is performcd bctwccn pl.1 6 and 7 "'.
The siimc plienoiiienon has becn more prccisely detinccl b y a study of the incthano-
lysis of di:izobiiianc'33. I n neutral or acidic Jetiterated solution tlicrc is no cschaiigc,
Iiowevcr i n strongly basic solutions (tip to I.S hi-NaOMc) exchnngc is obscrvcd to
thc estcni of S7y/,. Thc approsiriiatc i:i\:crsc propurtionality of t l i c obscrvcd ovcrall
rate to mctliosidc ion coiiccntrittioii (csccpt a t coiiceiiti.;ilioiis I .O M ) siggcsts
establishiiicnt of a partial prc-cquilibriiim clcpciiclcnt oii base coilcentration. The
alternativc interpretation of base-catalyscd cschangc may bc supported by the
dcviation from linearity of tlic rLitio CD,HOMe : C D t l , C k l e against [OMe-1 at
base concentrations of approuimatcly 1.5 .ft At thesc concentrations. Iio\\~cvcr.i t is
difficult to dccic!c \\,hat confidence can be placed i n kinetic equations, not corrected
for variations i n the activity of the siibstratcs'".
4. Base-catalysed decomposition of N-nitrosourethanes and ureas

T h c alkaiicdiazoniilm ion--1liazoalkanc cquilibi.i[ini in baSic solution caii be
established by prcliminary forriiation of the acic!ic specks by anotlicr rcaction
scquencc. This situation is rcalizcd, in principle, by the decomposition i n basic
solution of ,~'-nitrosourctlianes""(16) a n d iireas'G(17).
186 J. F. McGarrity
T h e implication of diazotates (18) as intermediates in t h i s scheme follows from
their isolation in the reactions of differently substituted N-nitrosourethanes in
ethereal 5 7 , and their subsequcnt convcrsion into previously obtained
products in basic prctic solvents. The exact status of the diazohydroxide (19) and
N-
+;
II
- -
-H,O
0H-
N
Ill+
N
I
CHRR'
II
N
, CHRR' RR~HC;~
0YN
-': I
,'/R R' (19) (18)
N//O
I
-H'
-d
$7 / - HNCO
RR'HC-N, /NH, NY NH
C RR*HC/ 'C~U
II II
0 0
(17)
the diazonium ion, either frcc or in an ion pair, as precursors of the diazoalkane
will be discussed later. T h e reactions of the diazohydroxide leading to the formation
of the diazoalkane compete with its decomposition to nitrogen, solvated hydroxide
ions and carbonium ions. Thus the yields of substitutcd diazoalkancs will be depen-
dent not only o n the substituent effect o n their stability, but also on that of the
.H.
J (20)
I H
O C / ' + C H
\\ I
t-- DLc,q'-N j@+c0cH2
+
X N-N X I H X I
I H H
H
J.
X = m-NO,,p-CI, H, p-Me Products
alternative carboniurn ions. For examplc, in the formation of p y r a ~ o l e sderived
from d i a ~ o a l k e n c s ~the
" , observed effect o f electron-withdrawing groups of incrcasing
the pyrazolr: yield is compatible with destabilizing thc incipicnt carboniuni ion, o r
in facilitating development of thc ncgativc charge in the transition state for diaio-
alkane formation. The cffccts of alkyl substituents, coniplerncntary in stabilizing
carboniuni ions and inductively destabilizing the diazo group, are evident for
examples 20, 21, 22, 26 and 27 of Table 1.
1. Yields of diazoalkancs from basic hydrolysis of the corresponding

TABLE
diazotates
ICR'CN, R R' [OH-I Yield (x) Reference
20 H H u n k now n I00 51
21 ti- Pr )I 3 ht GO 53
22 ,I-Octyl I4 3 !I. 31 53
23 Cyclopropyl H 3 hl 0 59
24 Ph H u 11known 100 57
25 Vinyl H 3 hI I00 53
25 ti-Hexvl 3 hl 3 3 ti0
27 Cyclohexyl 3 XI 0 53
28 3 hf 100 53
From dcuterium-incoiporation expcrirnents.
Separation of the two cffects can apparently bc made for examples 23. 24, 25 and
28. T h e stability of the cyclopropyl carbinyl cationG1accounts for its prefercntial
formation, and, o n the contrary, the relativc instability of the cyclopropyl cation6"
allows the establishment of the diazo compound 28 as a n intcrinediate in the reaction.
The stability conferred to alkyl carbonium ions by substititent phenyl or a l k y l groups
dot's not, howevcr, dctcrmine the dircction of reaction of the diazohydroxides. T h e
quantity of phenyl- and vinyl-diazomcthane formed may rather bc due to a dominant
stabilization of the transition state in thc base-catalysed elimination, reflecting a
conjugative stabilization of the product diazo group. The abovc arguments3 is
entirely dependent on thc assumption that the benzyl a n d ally1 cations are as rcadily
formed in water as is thc 2-octyl cation which is generated in prcfcrcnce to 2-diazo-
octanc. Solvolysis rates in nucleophilic solvents, \\,here the bimolecular contribution
to the ratc-deterrnining step is unknownG3,offer debatable support to this thesis.
+
Gas-phase heats of formation from the corresponding alkancsc' ( 3 H f Ph-CH, =
= 906 kJ) in thc absence of
i.
854 kJ, H2C=CH-CH, = 940 kJ, C,H,-?-CH,
I
H
solvational energies offcr a support only for the bcnzyl cation. For this particular
example the alternative diazoalkanc product was obtained at unspccified base
concentration ('five- to six-fold excess'); at a Iowcr, cqually unspecified base con-
centration, there was minor formation of benzyl alcohol.
That the diazoalkane lbrrnation is dependent on base concentration and strength
is supported by the observation that when cyclohexane diazotate is quenched in
IS8 J. F. McGarrity
methanol rather than water, providing a more basic medium, diazocyclohexane is
observed". It is worth noting, in this respect, that cyclopropyldiazomethane (23).
completely by-passed in the aqueous diazotate hydrolysis, is prepared by reaction of
t h e corresponding N-nitrosourethane with a concentrated solution (2 M) of sodium
triethylene glycolate in triethylene glycol at - 25 "C 59. For the octane-2-diazotate
system, the inferred yields of diazooctane increased from 3% to 15% with increasing
base concentration60. The effect of base on the partition between the two reactions in
methanol was examined by Kirmse for a series of c y ~ l o p r o p y l66,
~ ~6 7. and alkenylas
substituted diazoalkanes.
/ 'CONH,
\/
I
\
1
-phv+
phvoMe +
+
Ph-CH-CH-CH,
(30)
Ph-CH=CH-CH,OMe Ph-CH(0Me)-CH=CH,
The yield of allene 30, derived from diazoalkane 29, increased from 0.52% to 80%
for both cis and tram starting ureas (28) with increasing base strength. T h e impor-
tancc of the diazonium ion, either free or in a n ion pair as the immediate precursor
of the diazoalkane, as depicted above, is controversial. As regards secondary alkyl
diazotates, i t has been established from results with optically pure and labelled sub-
strates that carboniurn ion products are not derived from diazoniurn ions, but rather
from a solvated diazotate speciescg
/NN
' NGN
/"=N\o- R+
R
\ -
0 + SV-H * R
~
/
0-
SV-H' -SV.-- H
R = 2-Octyl, 1-phenylethyl ROH SVR

SV-H = Solvent HOR RSV
Thc influcnce of diazo group and carbonium ion stability on the reaction course
implies that both sets of products are formed from a common intermediate-the
diazotate species favoured by M O S P or free diazoniuni ion preferred by Kirmse"G.70.
6. Basicity, acidity and hydrogen bonding 1 S9
An alternative explanation is that a n equilibrium between the two intermediates is
established rapidly relative to the two competing product-forming reactions
R\ Ease R\ R\+
C=N, t--- CH-N=N-OH -+ CH N, -OH
R'/ R'/
R'/
or
R\ R\ R\
C=N, t CH-N"+
/
-OH 3 /
CH-N=N-OH
R'
/
I
R' R'
(24)
+
R'RCH + N?
18-Oxygen labelling experiments showed, a m o n g other things, that this equilibrium
is not established i n secondary diazotate hydrolysisG9. As the benryl and alkyl
cation-forming processes are presumed to have activation cnergies lower than, or
equivalent to, those for secondary cations. the equilibriuin must also be excluded in
these cases (assuming equivalent diazonium ion stability). This conclusion is in part
supported by the observed base catalysis. The equilibrium will be di5placed to the
diazohydroxide form by increasing base concentration. This, conlbinccl Lvith the
expected first-order dependence of thc proton abstraction rcact ion on base, would
give an ovcrall zero-order dependence for diazoalkanc formation, which is not
observed. T h e irrefutable evidence, from trapping expcrimcnts7" for frce diazoriium
ions in the systems, is restricted to cyclopropyl diazoniurn ions, whish may arise
from diazocyclopropane rather than diazohydroxide prccursors.
The partition of the two reaction scqiienccs appears to occur at thc diazotate-
diazohydroxide stage. T h e mechanism for thc basc-cntalysed cliniination of watcr
has been formulated as a two-step process"'.
This however would appear to present n o advantngcs over n concertcd scheme

similar, in essence, to that proposed for the base-catalyscd cleavagc of 15 ".
It should be noted that whcn diazoalkancs are decomposed in basic alcohol
~ ~ l ~ i t i o ndiazoniuni
sS3 ions, and not dinzotic estcrs analogous to 19, arc tlic car-
bor,iuni ion precursors. This follo\vs from the inverse-order dependence of reaction
rate on base concentration (rather than zero order).
R,- +
C-NEN + R'OH
R\
CH-NEN
/
+
+
-
OR" e-
R\
CH-NzN-OR'
/
R" R'
R' I I
190 J . F. McGarrity
In conclusion the partition of diazotatcs in basic solution, between diazoalkane
and carboniurn ion products, appears to be dominated by t h e base strength, and
substituent effects on the carboniuni ions, rather than by diazoniurn ion acidity.
5. Acidic species alkylated by diazoalkanes

The acid strength and reaction conditions necessary to protonatc diazoalkanes
vary largely with their substitucnts. Whereas diazoniethanc rncthylatcs rcadily and
smoothly carboxylic acids and phcnols, their reactions with diazoesters and diazo-
ketones require gentle warming. Likewise, dialkyloxoniuni salts are eficiently
methylated in d i c h l o r o r n e t h a n ~according
~~ to :
In contrast, the efficicncy of quaternization of protonated amines, by diazoaceto-

phenone (31) in alcohol, varics apparently as a function of the acid strength as
indicated in Table 2.
TABLE 2. Efiicicncy of quatcrnization of

pyridiniurn salts by 3 1 (equation 28)
Acid pK," (%)
a See discussion in Scction II.B.6.
Diazoincthane reacts at room temperature with alcohols75,the efficiency and rapidity

of reaction incrcasing with substitution of electron-\+ithdratving groups in the latter.
Reduction of the already feeble acidity of tlic IiyJroxyl group by solvation may
prevent reaction; thus trichlorocthanol is mctllylalcd in hcptane but not in c t h ~ r ' ~ , .
6. Basicity-, acidity and hydrogen bonding 191
On the other hand, incrcasc of the proton acidity by prior complexation of the
hydroxyl oxygen with a n clcctrophilic species draliiatically incrcases the efficiency
of the procc'ss7:s-7 7 .
H CH,
Similar catalysis, preferably by boron trifluoride, renders aniines sufficiently acidic
to iindcrgo this rcaction7y.7 7 .
Whcreas certain carbon acids such as acetylacctonc react with diazoalkanes
through tlicir enolic f o r ~ i i (equation
s~~ 30), sufficiently acidifying but non-enolizable
substitiicnts such as sulp1ioneq0~ and nitroR2groups allow direct methylation on
carbon.
minor
6. Kinetic basicity of aliphatic diazo compounds

In coriirast to the paucity of thermodynamic data related to diazoalkane basicity,
thcre exists a wealth of relevant kinetic data. This results from the facility of rate
mcasurements by following the evolution of nitrogen, o r currently by monitoring
thc diazo ultraviolet absorptions. A comparative analysis of the data is not, however,
as straightforward as thcir measurement. The second-order rate constant may be
simply a nicasure of the protonation rate (equation 19) as for a n AS& reaction.
Alternativcly, for A-2 and A-1 mechanisms, i t may be expressed by equation (17)
wherc k 2 is rcspcctively dependent on or indcpendent of the nature and concentra-
tions of nucleophiles present. Examplcs of all thrce kinetic fornis and intermediate
situationsR?.33. b3 have been found for acid-catalysed diazoalkane hydrolysis'?.
Consequently in the ignorance of the exact mechanism, caution should be exercised
in drawing conclusions as t o structure/reactivity relationships. For example, in the
reaction of protonatcd pyridines with 31 (Table 2 ) , the reduced yield for the 2-pico-
linium ion relative to the pyridiniuni homologue [nay represent not only its inferior
acidity, but also a diminished nucleophilicity of its conjugate base due to steric
hinderance. Independent evidence suggests that this diazo compound hydrolyses by
a n A-2 mechanism", although a conflicting opinion has been expresseds4.
T h e increasing reactivity in the order diazomethane-diazoethane-diazopropane
towards phenol in toluene*s [nay not only be a reflection of increased basicity, but
also of more rapid nitrogen loss from the intermediate diazonium cation. The
inertness of a diazo compound to acid, for example diazonialonitrile to sulphuric
acid in anhydrous acetonitrilesGallows no extrapolation to its behaviour in a protic
nucleophilic medium.
Similarly, the acidity scale developed on the basis of reaction rates of a series of
- ~ ~ , as 32 and 33, in chlorinated hydro-
acids with weakly basic d i a z o a l k a n e ~ ~ 'such
carbon solvents, is not necessarily a function uniquely of acid strength. Such a
situation would be realized only if the protonation of the diazoalkanes i n question
lvere rate determining, or if the decomposition of the diazonium ion formed were
unassisted. In the first case the observed rate constants would indeed be measures of
kinetic acidities; in the second, in that they would depend on t h e equilibrium con-
ccntration of the diazonium ion, they would be measures of thermodynamic acidity.
I n view of thc quantitative convcrsion of 1 , I , I ,3,3,3-hcxafluorodiazo-2-propane
(34)
i n t o its conjugate acid in highly acidic nicdia”. and the subsequent Sx2 type dis-
placement of nitrogen from the latter by the fcebly nuclecphilic fluorosulphonate
anion, both these possibilities scem to be unlikely. It should be noted that the
observed linear log kobs-pKsi plot^^^-^^ are consistent also with the remaining A-2
type mechanistic possibility. Both the thermodynamic strength of the acid, and the
kinetic nuclcophilicity of its conjugate basc which are included i n the rate constant,
can be related to the aqucous acid strength by linear free energy relationships.
The data in Table 3, and the subsequcnt discussion, refer to hydrolysis of diazo-
alkanes where protonation by the hydrated proton has been shown to be rate
detcrmining. For several substrates, data for various sets of reaction conditions are
included as minor differences in the latter can significantly affect the former.
T h c rcactivity of differently substituted stabilized diazo compounds within the
same class towards strong acids in non-nucleophilic solvents has been correlated with
the N = N stretching frcquency in the i.r. The hydrolysis rates for series
of primary diazoketoncs and sulphones have been similarly correlated108. Generally,
the higher thc absorption frequency, the more the electron distribution described by
the form C-k=N is predominant in the ground This is favoured by
clcctron-withdrawing groups attached to the carbon; ips0 facta, these decrease the
acid lability. For reactions that proceed by a rate-dctermining protonation step
there is a gencral trend in this sense1OB,but extrapolation from one class of com-
pounds to another allows only qualitative of ground-state effects by
this means.
In the series PhCN,R the protonation rate decreases in the order R = H, Ph, CN,
0 0
II II
CF3, Si(Ph),, (EtO),PO--, (I’h)2PO-, R’O-C-, -R‘C-. This variation repre-
sents well thc expected different degrees of stabilization of the ground state, by
clectron withdrawal (except for the triphenglsilyl substituent which may also provide
a steric retardation of the reaction).
It is interesting to note that for the unique series whcre the effcct on the protona-
tion rate of an alkyl group relative to a hydrogen substituent has been directly
measurcd, the protonation of 1 -p-nitrophenyldiazoethaneis slower by a factor of
almost 10 than that of p-nitrophenyldiazoinethane.The substitution of a methyl
group has apparently less effect for diazoketones. Whereas protonat ion rates of
primary diazoketones are normally inaccessible, that of diazoacetone has been
lneasured by hydrogen isotopic exchange rates’O’. Furthermore, in the hydrolysis
of 7-(2’-diazo-)acetyl-bicyclo[2.2.l]hept-2-ene( 3 7 , the protonation is rate deter-
mining due to acceleration of the subsequent nucleophilic displacement of nitrogen
by participation of t h e neighbouring double bondloo. In both cases, protonation is
TADLE
3. Kinetic parameters for proton transfer from H 3 0 + to diazoalkanes
Substrate Solvent T ("C) Pa k, (I rnol-' sec-') kij,O/kD,O AH* A# Reference
A 25 1.1 x 10-1 6.5 & 1 x 10' 3'

B 0 2 . 0 10-3
~ 7.5 x 10 2.64 90
B 0 2.0 x 10-3 2.4 90
B 20 2.0 x 10-3 1.3 x 10 * 2.81 56.6 - 39.1 90
C 20 4.0 x 10-4 8.3 C, d 3.8 91 a!
C 20 2.0 x 10-3 9.1 x 10-1 d cI 2.70 91 W
C 20 2.0 x 10-3 5.5 x 10-1 c, d 92 E.
8.
C 20 0 5.4 x 10-1 * 92 5
D 1.9 x lo-' 7 . 5 2 0 . 2 ~10-I 93 %
-.
E 29.5 1.4 x 3.8 x 10 3.4 1 94 a
E 29.5 1.0 x 10-4 2.8 x 10 ' 2.28 95 G
0,
7
a
zr
Y
F 25 5 x 10-2 6.1 x lo-' c* 1.37 76.2 -2@+_6 96 1
a
0
NZ
(36) 0-
5
0
C 20 5 x 10-2 3.5 x 10-2 C, d 92 a
C6H,CN2CF3 B 25 9 x 10-2 1.3 x 10-1 2.13 61.3 - 67 18
a
GI
a
C,H,CNZCN A 25 5 x 10-1 2.5 x 10-3 2.2 97
CH3COCN,CH3 A 25 5 x 10-2 7.4x 10-1 2.5 98
G 25 1 x 10-2 3.1 x lo-' 2.5 67.2 - 33 99
CH3COCN2C,H, G 25 1 x 10-2 2.4 x 10-1 2.4 99
CH3COCN,Pr-i G 25 1 x 10-2 4.8 x lo-' 2.6 99
B 25 1 x 10-2 4.2 x lo-' 2.0 99

c.
W
3 (cm.)
TABLE P
Substrate Solvent T("C) Pa k2 (1 mol-l sec-I) k u , ~ / k ~ , ~A H * AS' Reference
G 25 5 x 10-3 2.4 1.9 99
c
7
B 25 I x 10-1 1.67 I .8
i.
-
Y
(37)
CH,COCNzH A 0 1x 10-1 101
C,jH,COCNICH3 C 20 1x lo-? 2.42 102
p-NOzC6HdCOCN2CH3 C 20 1x 10-2 2.3 102
B 25 5x 10-1 2.0 99
C 2.0 Ix 10-2 2.3 103
p-N OZC6H,COCN,C, H, C 20 Ix 10-2 2.4 103
p-NOzC8H,COCN2Pr-f~ C 20 Ix 10-2 2.4 103
p-NOzC8H,COCNzPr-i C 20 I X 10-2 2.4 103
G 25 5 x 10-2 1.8 99
TAULE
3 (corrf.)
Substrate Solvent T ("C) Po k2 (I mol-1 sec-*) ku,olk~,o AHf AS' Reference
C 20 92
C 20 2 x 10-1 1.4 92
C 20 1 x 10-1 83
A 25 2.6 81.5 -29 so
C 20 1x 10-1 I .5 83
A 25 1x 10-3 2.5 98
A 25 sx 10-2 98
B 25 5x 10-1 1.6 104
C 20 1x 10-1 105
C 20 8x 10-I 83
C 20 1x 10-1 2.5 I06
C 20 Ix 10-1 2.3 84.0 -25 105
C 20 5 x 10-2 9.0x 10-3 c, fJ 1.7 82.3 -29 10s G

0
3
Solvent: A, water; 9, dioxancwater 60-40 V/V; C, dioxanc-water 2-1 v/v; D, dimethylsulphoxide-water 4-1 w/w; E, water 2.2 hi in G!
acetonitrile; F, ethanol-water 93.8% w/w; G,dioxane-water 40-60 V / V ; H, toluene.
a Ionic strength mol/l.
* Extrapolated from Arrhenius plot.
Measured wiih one acid concentration only.
Reaction followed by nitrogen evolution.
Value extrapolated from data for differing salt concentrations.
f The acid added, p-toluene sulphonic acid may not be completely dissociated in this system.
0 Measured by hydrogen isotopic exchange.
196 J. F. McCarrity
three- to four-times more rapid than for methyl-substituted diazoketones measured
under the same conditions. This behaviour contrasts with the accelerating influence
of alkyl substitution on the overall reaction of diazoalkanes with phenol in tolueneas.
The stabilizing effect of benzoyl relative to carboethoxy groups is dependent on
the nature of other substituents present. Thus the effcct of their different electron-
withdrawing capacity is diminished by introduction of an additional stabilizinggroup:
The more rapid proton-deuterium exchange of primary arylsulphonyldiazo-

methanes relative to the corresponding diazokctones'O, though not a direct measure
of protonation rate, indicates a superior stabilization provided by the carbonyl group.
T h e variation o f protonation rate with nuclear substituents in several series of
aryldiazoalkanes give normally good correlations with Hammett u values (Table 4).
T h e rho ( p ) values derived therefrom are generally in the range - 1.5 to - 1.8,
indicating a large sensitivity to electron availability. The ccrrelation in the diazo-
fluorene"' (36)examples with Hammett parameters modified as by Taftll' is indica-
tive of the non-benzenoid nature of the aromatic substituent site rather than any
peculiarity of the proton transfer. On the other hand, the correlation for diaryl-
diazoketoness3 with the u+ parameters of is inconsistent with the simply
visualized C-protonalion mechanism. It should be noted however that as the rate
constants for the hydrolysis of these compounds arc successfully correlated with
those for aryldiaLophosphonate esters1o5, which are themselves correlated with
ordinary u values, there appears to be a lack of sensitivity to t h e constants used.
Likewise while the one electron oxidation potentials of several series of aryl-
substituted diazo compounds correlate with u+ 'l4* l l i , for diaryldiazoalkanes they
a r e also proportional to the logarithms of the protonation rates, themselves
dependent o n u.
Other traditional indices of transition-state structure in relation to reactants and
products are not immediately definitive. It is a commonly held thesis that primary
hydrogen isotope elfects for proton transfer attain their maximum value for approxi-
mately 'symmetric' transition states, with a continuous decline for increasingly exo-
or endo-energetic reactions116. One might then expect decreasing overall solvent
isotope effects for increasingly 'uphill', hence slow, reactions for a series of related
compounds. This is not apparent from the d a t a presented, although within a series of
substituted aryldiazoketones there is some relations3. With specific reference to
3-diazobutan-2-one (14) and ethyl diazopropionate (13), despite a difference in
reaction rate of 28, the measured solvent isotope effects are 2.5 and 2.46
respectivelys8.
Furthermore, an analysis of this global isotope effect, from experiments in
H,O-D,O for transfer to the two substrates respectively, produces
almost identical fractionation factorsllR, = 2.1 k 0.03 x lo-' and 2.08 x lo-', and
+ 2 = 7-78 +- 0.04 x lo-' and 7-85+_ 0.12 x lo-', for the proton 'in flight' and residual
protons of thc lyonium species. The latter results give values of a,,a parameter
describing the position of the transition state along the reaction coordinate, of
0.27 and 0.29, surprisingly close to that of 0-30 for the much more reactive diazotate
anion"' (12). This similarity is cxtended to the values of the exponent L Y ~in the
Bronsted relation
+
log k u = C y g log ICm c (32)
Here Kit\ is the dissociation constant of a n acid, whose reaction with a substrate
has a rate constant k l ~ , ,and ~ r g describing
, the sensitivity of the latter to the former,
4. Hammett rho (p) values for diazoalkane protonations
TABLE
Substit uent Number of
Acid Reference p'
Substrate series constant Solventa substituents P
W
PI
XCGHdCNpH 0 B 3 -1.6 H30 90 L".
E.
C,H,CN2C,H,X U D 4 - 1.10 H30+ 93
0 D 4 - 1.43 HCClzCOzH 93 p3
9
0 D 4 - 1.34 H jCCOzH 93 0.
U D 4 - 1.36 GF5OH 93 I?:
0 D 4 - 1.30 3,4,5-CI,C6H,OH 93 G
CI
0 E 11 - 1.99 H30f 95 =I
a
0 H 11 - 1.57 C6H;C0,H 110 I
CH3CN,COCtiH.,X 0,
C 4 - 1.0 H30+ 102 u'
C,,H,CN,COCoH,X up+ N o p +- US) C I -0.812 H30+ 83
e
0
XCoHaCN2COC,H:, U P+ C 6 - 2.05 H30+ 102
UD
83
XCeHICN2PO(OC2H,,2 C 5 - 1.641 105
0-
H30
XC,H4CN2CF, UD B 4 - 1.74 H30+ 18 0
3
(361 c3
(or+aaR) F 11, 11, 13b -1.63--2.1b H,Of 111 m
~
O Solvent index given in Table 3.

Data for three series of substituents in positions 2, 3 and 4.
198 J. F. McGarrity
has been interpreted in the samc fashion a s a i above. The values in question, for
reaction with carboxylic acids, arc 0.61 k 0.03, 0.59 f 0.04 and 0.5 1 k 0.03 for 14, 13
and 12 respectively. The identity of these values, within expcrirnental error, for thc
diazoketone and ester is surprising in vicw of their reactivity difference and the valucs.
reflecting the degree of proton transfer in the transition state, appear incompatible
with such a therinodynamically unfavourable reaction. (The acid dissociation con-
stants of the diazoniuni ions formed are c lo5, c 5 x lo3, < 1, whereas K , I of~ ~the acid
catalysts < 6 x The disparity between the values of an and u., is a result of the
greater acid strength of the hydronium ion relative to carboxylic acids. For proton
transfer from the stronger acid, the transition state is expected to be niorc 'rcactant
like', in the oft-quoted terms of the Hammond postulate"!' or its niore quantitative
formulation2g.30, and to be characterized by a lower value of cr.
A more refined free energy of activation-free energy of reaction relationship
derived by Marcus'?O, equations (34) and ( 3 9 , has met with some success in the
analysis of diazoalkane protonation data. For the reaction
AF&, = Wr (35)
AF& is the free encrgy of activation observed for the proton transfer from H A to
S, i.e. from state ( I ) to state (IV).
Wr is the energy that must be supplied to form the 'reactant complex', i.c. state
(11) from state (I), and involves diffusion, desolvational energy and distor-
tion of bonds, if ncccssary to allow the proton to be transferrcd.
AFfc is the standard free-energy difference within the reaction ccmplex, i.e.
AFO state (111) - A F o state (11) and is ostensibly equal to I ~ F , " ~ , - A F { ~ , . .
AFo* is the activation free-energy within the reaction complcx for the case where
A F i = 0.
From this equation, the rate of change of a \vith differing A F i is inversely propor-
tional to AFu* which measures the inherent reactivity of the system. The data for
the hydrolysis of 12 catalysed by phenols for which a = 0.74, carboxylic acids where
o = 0.51 lZ1, and a series of protonated aniines displayed in Figure 1 12?, allowed
calculation of AFO*, and hence the other parameters of equation (35).
T h e corresponding parameters could be calculated from the data for hydrolysis of
13 and 14, with inclusion, however, of t h e data for catalysis by H 3 0 i 3 4 , and for
hydrolysis of diphenyldiazomcthane ( 3 9 , catalysed by carboxylic acids and phenolsg3.
The collected parameters are listed in Table 5 .
T h e first points of note are the values of AF&+, i.e. the free energies of the
reactions:
SH++H,O S+H,O+ (37)
In all cases they are unacceptably large: for 14 and 13 they correspond to dissocia-
tion constants 10'' lnOl/l and 10" mol/l, respectively, coniparcd to independently
estimated values of < lo5 mol/l and < 5 x lo3 mol/l (Scction B.2). Furthermore, t h e
variation o f the values derived for protonated diazoacetate anion indicates that
these values d o not have an absolute thermodynamic significance. Their significance
I I I I I 1 I I
0
4 - 0
8
0
-
- d
2 - -
- -
-
a 0 -
*= - -
cn
0
-6
-16 -14 -12 -?@ -8 -6 -4 -2 0 2
log KHA
FIGURE 1. Predicted and experimental relations between log k l l ~for the hydrolysis of 12,
and log K,.l,, of the cntalysing acid. The @ arc points for oxygen acids, the x for protonated
amincs. The solid lines are predicted from cquation (35) by inscrtion of the parameters
listed in Table 5 . Reprinted with permission from M. M. Kreevoy and S . Oh, J . Amer.
Cllem. Soc., 95, 4805 ( 1 973). Copyright by the American Chemical Society.
is rather in thc context of the reaction complex, in that differently organized reactant
complexes, in solvational and hydrogen-bonded terms (state II), may be formed with
different types of acids. Such a variation with acid type should dictate a variation in
AF'* and, more obviously, in I+'*. Although the values of AFo* obtained by t h e
5. Pnrarncters of the Marcus formalism for dinzonlkane hydrolysis
TABLE
Acid H A Base A P * (kJjmol) W' (kJ/niol) AFZH+ (kJ/mol)
~~
R1R?R3NH+ 12 5.9 58 - 28.5

RCO,H, A r O H 12 17.0 34 - 14.7
RC02H, H,O+ 14 s.0 71 - 24.8
RCO,N, H30+ 13 s.0 GO - 19.8
RCO,H, ArOH 35 5.5 72.3 -2522
above analyscs are probably underestimated d u e to simplifications made in t h e

algebraic derivation123,12% their significance, relative to the term Wr for related
compounds, is nevertheless a valid point of comparison.
The magnitude and variation of the values of W' are the most significant features
of the data in Tablc 5. They are markedly superior t o the free energies estimated for
the diffusion together of substrate and acid, a n d desolvation of the latter, i.e.
betwecn 37.2 kJ,hnol l2I and 42 kJ/mol The diffcrence in hydrolysis rate for 13
and 14 is sccn thus to stem primarily froin thc different work terms Wr. It is also
this term that represents the stabilizing elfcct of the aryl groups in 35. The major
200 J. F. McGarrity
-0 7
In
0
el c9
\+= ''0
0
I I
-0
I
a H
I
0 '0 0 0
\ / % /
a3 +z
+
2
+I \ I
I-v x..;v,
\
(L
=. \ =
c
w
,I
i
0 -
i=J H H
k6~au3
6. Basicity, acidity and hydrogen bonding 20 1
kinetic consequence of these large work terms is that n o matter how thermodynamic-
ally favoured be the proton transfer, depending on the acid strength, the rate can
never approach the diffusion limit1z2.Differing interpretations of the high values of
W' in terms of hydrogen bond formation in the reaction complexs3. lZ2, and non-
equilibrium solvated specie$' appear to be complementary. Evidence for the former
is derived from a n analysis of the Hamrnett p values for solvolysis of 35. This value
can be separated by use of certain approximations into p Wr a n d pc termss3, the
latter referring t o the actual proton trsnsfer, state (11) + state (111). It was found that
the p W' term was by far the more important, indicating that the aryl substituent
effects are primarily felt in the H-bond formation. The differencesin hydrolysis rates
of 12, 13 and 14 can be attributed t o difleering degrees of electron delocalization from
the diazo group into the adjacent carbonyl substituents. T h e reflection of these
differences in the work terms W'and not AFO', for the same acid types, implies that
this electron delocalization is reversed before the proton transfer occurs34.
This interpretation demands a n intermediate with negative charge located on the
diazo carbon, but available for hydrogen bonding, and with a consequently re-
arranged solvation sphere. The energy changes along the reaction profile are illus-
trated schematically in Figure 2.
A corresponding energy diagram for nitroalkane deprotonation is included. This
represents the same electron reorganization phenomenon, but in a reversed sense in
that the tetrahedral carbanionic species (state 111) formed by proton transfer,
relaxes into the x-delocalized anion126. In this case, kinetic evidence for the schemc
includes substituent effects of different magnitude on the transition state, leading to
the carbanionic structure (111) and on the final statc (IV) of the nitronale anion.
This behaviour leads to values of an > I and < 0, inexplicable conventionally126*
in terms of 'degree of proton transfer'. Similar results of anomalous (Y values for
diazoniuni ion deprotonation would be expected, but are as yet unobtainable.
The above diagram shows how differing diazo compounds, despite differences i n
overall rcactivity towards acids, can have identical indices of transition-state position
along the reaction coordinate within the 'reaction complex'.
111. LEWIS BASICITY OF ALIPHATIC DIAZO COMPOUNDS

A. Kinetics of Electrophilic Addition
T h e problems involved in defining a basicity scale for diazoalkanes towards Lewis
acids a t e niore complex than those conccrning proton basicity. As before, instability
of the adducts formcd preclude direct determination of their equilibrium concentra-
tions. Kinetic measurcnients may be subject to specific solvational effects. Un-
certainty may exist a s to the nature of the rate-determining step, or even of the
electrophilic specics. Whereas the effective catalytic species in the CuI1 (CF3C02)?-
catalysed decomposition of diazoalkanes has bcen to be Cul, a contrary
conclusion has been drawn concerning catalysis by Cu'[P(OR),], complexes124.
HgC12 reacts with diphenyldiazomethane (35) more rapidly than HgI, in a n ether-
hexane solution12g,but less rapidly than HgBr, in tetrahydrofuran, and does not
react at all in ether12g. A qualitative order of reactivity of a series of elcctrophiles
towards 35 in ether-hexnne or acetonitrile has becn established and is reproduced in
Table 6 .
T h e comparative reactivity o f differently substituted diazoalkanes towards a
single clectrophile appears to follow their reactivity tonards proton sources. Intro-
duction of a p-methoxy substituent increases the rcaction rate of diphenyldiazo-
mcthane (35) with HgCll in tetrahydrofuran, and, whereas 35 is unaffected by the
202 J. F. McGarrity
less electrophilic alkylmercury chlorides, diazomethane reacts readily in their
presence130. Decomposition of p-toluyldiazomethane by zinc(r1) halides is more rapid
than that of p h e n y l d i a ~ o r n e t h a n e ' ~ ~ .
TABLE 6. Relative rates of catalysed diphenyldiazomethane decomposition in ether-hexane

or acetonitrile solution. Reprinted with permission from D. S. Crumrine, T. J. Haberkamp
and D. 3. Suther, J . Org Clrem., 40, 2274 (1975). Copyright by the American Chemical
Society
Rate" Catalyst
~~ ~~~~~~~ ~~~ ~~~ ~~~~~ ~ ~
Very fast AICI,, TiCI,, SnCI,, BF,.O(Et),

Fast HgCI,. Hg(N03)~.CuBr,, FeCI,, Znl,, CuIP(0Pr-i),, CuCNIMeCNlb
Moderate HgI,, ZnCI,, CuCl[etherl, CuCI2.2H2O, SnCI,.H,O, Hg,CI,[MeCNl
Slow CuCN, CrC1,.6H,O, AIC1,.6H20
No reaction Hg2Cl,[ether], CdCI,, Zn(CN),, Cr(OAc),.6H20, NiC1?.6H20,
Co(NOJ2.6H2O, CoC1,.6H20, MgCI2.6HZO,CaCI,, LiCI, LiBr, NH,CI
" Very fast, reacts completely in less than 1 min. Fast, reacts in :ess t h a n 15 niin.
Moderate, reacts in less than 4 h. Slow, reacts while standing for 24 h.
Brackets indicate solvents in which the reactivity order dilftred. Taken from Reference
129.
-
T h e related zinc(n) halide-catalysed decomposition of diphenyldiazornethane and
diazofluorene in acetonitrile, proceeds by a rate-determining association132(equa-
tion 38)
slow mpld
Ph,CN,+ZnX, Ph,CN:Zn-X, ~
f [Ph,C+Zn-Xz] (38)
--N I
-
In contrast, the adducts formed by each of these two substrates with copper(1i)
-
bromide are in equilibrium with the reactants before
slow
Ph,CN,+CuBr, Ph,CN:Cu-Br,
-XI
[Ph,C+Cu-Br,] (39)
For the former reaction (equation 38 where X = Cl), i t is intercsting to note that
the Hammett p values for diazofluorene and diphenyldiazonlethane substituents are
quite dissimilar (- 2.45 a n d approximately - 1 .O), despite the minor (7-fold)
difference in rate. Also striking is the observation that the order of kinetic catalytic
efficiency, ZnCI, < ZnBr, 4ZnI,, does not follow the equilibrium Lewis acidity
(towards diben~acridine'~?).
A situation somewhat lcss complicated kinetically was eticoiintered in thc rcaction
of diphenyldiazomethane with peroxybenzoic acid'".
T h e effect of substituents in the aryl groups of the diazoalkane on the reaction
rate, as reflected by theio p value of - 0.96, is less marked than o n the corresponding
proton transfer reaction. That the electrophilic attack was indeed by oxygen and not
by a proton, was supported by the similarity af the kinetic isotope effect k ~ o ~ ~ /
k ~ = 10- 3 3 ~a n d ~of lhe solvent dependence of reaction rate to those of other
peroxide oxidations. A similar mechanism is probably operative for the reaction of
peroxybenzoic acid with d i a ~ o k e t o n e s Other
~ ~ ~ . examples of electrophilic oxygen
attack on diazoalkanes are provided by the reactions of ozone136 and singlet
oxygen137.
6. Reactions with Electrophilic Carbon

1. Reactions with esters
The reactions of diazoalkanes with electron-deficient carbon centres in carbonium
ions3, acid and carbonyl groups3. 138. l J 0 have been reviewed fre-
quently. In the last-mentioned category, there exist few examples of reaction with
the carbonyl group of esters. Whenever electron-withdrawing substituent groups
such as t r i h a l o n ~ e t h y l lo~r ~nitro“? are attached, the reactivity of the carboxyl group
is sufficiently enhanced to allow addition and subsequent cpoxide formation as for
ketones.
Me H
Me
Me
Addition of diazo groups to esters may be favoured by other circumstances, for

example the close proximity of the two groups i n the same n i 0 1 c c u I e ~ * ~ - ~ ~ ~ ~ .
1C0,Me
As these reactions werc llowevcr carried out in the presence of base, necessary for
the initial nitrosolactam dccomposition, the possibility of nucleophilic catalysis, by
attack on the terminal diazonitrogen146,cannot be cxcluded (see Section V.C).
2. Reaction with aliphatic diazonium ions

Similar intramolccular proximity can lead to the rcaction of 311 aliphatic dia-
zoniuin ion with a n unprotonated diazo lay.
Another diazoalkanc-diazonium ion r c x t i o n h a s Sccn proposcd to expl;iin azine

formation from dipotassiuni diazomethnnc disulplionatc in \vatcr'13. Therc arc.
howevcr, significant dilferenccs bct\vecn tliis csample and the above. Here the
alkyl diazonium ion is prcsumed to react intermolcciilarly \\ ith the diazo group ( i n
water), and through nitrogen rather than carbon as thc elccfrophilic site. Thcre
exists ample precedent, howcver, for the formation of azines by dircct rcaction of
two diazo compounds (Section V.C).
C. Site of Electrophilic Attack

1. Reaction with aromatic diazonium ions
Aromatic diazonium ions are well cstablishcd iis clectrophilic partncrs i n dinzo-
alkane reactions'". Whcrcas. as is usually observcd, the majority of products
iiriplicatc carbon as thc nucleophilic site (cquation 47), in the case of diazomethnne,
the formation of a tetrazole by-product indicatcd attack at nitrogen (equation 45).
Ar-N=N
+P-
CHz-N,
+ Ar-N=N-CH,-N,
f++ + A r - NH -N=CHCI
%
CI- CI - (46)
+ CI-
1
c1-
(47)
H
\
C=N
It has, however, been pointed that this product could be generated by a

1,3-dipolar cycloaddition of diazomethane to the arenediazochloride, in equilibrium
with t h e separated ions.
Ar
\
N-N
2. Reactions with carbenes

The only unequivocal examples of electrophilic attack at the terminal nitrogen of
diazoalkanes involve carbenes. The formation of azincs in thc thermolysis of diazo-
alkanes does no1 nccessarily involve the prior formation of a cal-benc. Indeed, the
singlet carbene from phenyldiazocthnrle fornis styrcne rather than the azine observed
as the major thermolysis product1S'. The dirncrization could result from an excited
state-grouiid state interactionlS3, or from a n clectrophilic attack of OIK diazo group
206 J. F. McGarrity
o n another (Section V.C.) Kinetic evidence exists, however, t h a t the formation of
benzophenone azine from diphenyldiazoniethane is in part due to a carbene
r n e ~ h a n i s r n ’ ~and
~ , in part to diinerizationlss.
Carbenes with d i h a 1 0 - l ~and ~ a variety of otherlS7substituents react preferentially
a t the nucleophilic carbon site of diazoalkanes, including diphenyldiazomethane and
diazofluorene. A n increase in the bulk of the substituents at this carbon, however,
may direct reaction to the nitrogen terminus.
7. Variation of product distribution, with increasing bulk

TAULE
of aryl substitucnts, in reaction ( S O )
P tl H s5.0 0
Ph a-Napht hyl 52.0 7.0
a-Naphthyl a-Napht hyl 6.1 14.5
This is i1lustr;ited by the results in Table 7, for the influence of cr.-napthyl sub-
stituents on the distribution, bctwecn olefin (40) and azine (41) products, for the
reactions of diaryldiazoalkanes with dihalocarbenes (equation 50).
/
CI
N- N=C,
CI
(411
Accordingly, reaction of plicnyl-~-iiaphthyl-methylenewith its diazo parent yields

~ . steric hindrance to reaction at carbon could well
azine rather than ~ l e f i n ’ ~Thus
explain the preferential formation of azine in t h e reaction of diphenyldiazonlethane
with its corresponding carbene, and especially carbenoid, species132.Compilation of
reactions of diazoalkancs with electrophilcs with subscquent retentior?, or of
nitrogen exist, and will not be repeated hcre. Thc rapidly developing area of sub-
stitutjon at a nietallatcd diazo carbon5, where the mechanism is IG1,
will also be left untreated. Discussion of these rcactions and of interactions of diazo
compounds with metals in general will be found i n Chapter 7 on ‘Complex Fornia-
tion’ in this volume.
IV. P R O T O N ACIDITY O F DIAZOALKANES
-
D i azoniet ha nc is d ep ro t o n a I cd by t r i phe n y I met h y 1sod i 11nil‘?, inc t h y I I i t h i 11ni o r
p h e n y l l i t h i ~ n i ’in~ ether
~ at 0 “C to form the corresponding alkali metal salts.
H,C=G=N-+(Ph),C- NaC HC=&=N- Na4 +(Ph),CH (51 1
Whereas hydrolysis of these salts with alcohol-water at room temperature produces
a 35% yield o f diazornethane, hydrolysis at -15°C with a concentrated, weakly
acidic buffer solution (of ammonium chloride or potassium dihydrogen phosphate)
yields a colourlcss diazomethane isomer. This ‘isodiazornethane’, originally con-
sidercd to possess a nitrilirninP‘. 165 structure (42), is now idcntified as an N-amino-
isocyanide (43) on the basis of spectroscopic1o6and ~ h e m i c a lc8 l ~evidence.
~~~
7
--It+
H,c=~=N-
Diazomethane is re-formed immediately and quantitatively by treatment of

‘isodiazomethane’ with solid potassium hydroxide in ether163. Reaction with a
buffered aqueous neutral solution, however, generates forniylhydrazine and hydra-
zine’”. T h u s ‘isodiazomethane’ is the kinetically controlled product of protonation
of the diazomethane anion, while under equilibrating conditions diazomethane is
favoured. T h e possibility that the experimental conditions of the isornerization,
involving the presence of a heterogeneous basic system, rnag upset the equilibrium
i n favour of diazomethane (20) is unlikely as 20 is in part reformed from 43 in a
basic aqueous buffered solution1G3.SCF-MO calculations using r\ LW [533 ; 31
gaussian lobc basis set do not reproduce the energctics of t h e above situationx6@.
Thus 43 is calculated to be 136 kJ more stable than 20.
Substituted diazomethanes d o not form isolable salts, but evidence of their
deprotonation by organonietallics is to be found in the reaction products. Diazo-
ethane o n treatment with methyllithiurn yields acetaldehyde N-niethylhydrazone
(44), and 4,5-dimethyl-l,2,3-triazole(45)170. The corresponding triazole is the
unique isolable product of the reaction of phcnyldiazornethane with biphcnylyl-
phenyl-ketone disodiuni*62.
H
(45)
The hydrazone product is readily visualized as arising from nucleophilic attack
of the base on the terminal nitrogen of the diazo system. This process, also observed
t o the extent of 15% for the diazonlethancmethyllithium will be discussed
in Section V.C. Thc triazole product has been postulated to bc the result of the
nucleophilic attack of the diazoethyl anion o n its conjugate however a
1,3-dipolar cycloaddition of diazoethane onto the hydrazone formed concurrently is a
more appealing possibility.
As would be expected, ethyl diazoacetate is more acidic than simple diazoalkancs
in that it can be lithiated with butyllithium at - I10 "C The salt formed is, now-
ever, thermally unstablet at temperatures above - 50 "C 173 as witnessed by previous
unsuccessful attempts at preparation173. Below this temperature it is suficiently
reactive to undergo metal exchange with trimethylsilyl a n d tributyltin chloride and
to condense with ketone carbonyl groups.
Y7
H-C-C-OEt
BuLi
--65"c+
Nz 0
I1
LiC-C-OEt
II (CH,),SiCI
f (CH,),Si-C-C-OEt
N,
II
0
I/
(54)
HO N, 0
I II II
R' R'C -C-C-OEt
This latter reaction can be conveniently effected by treatment of a mixture of

diazoester and ketone with butyllithium at - 65 "C. Similar types of condensations
occur under the influence of weaker bases, but with more electrophilic carbonyl
bonds. Thus ethyl diazoacetate condenses with aldehydes in ethanolic potassium
hydroxidc solution at room temperature17J.These conditions are unsuitable for the
corresponding reactions with ketones, due to the unfavourable equilibrium estab-
lished between reactants and product adduct. Reaction does proceed, however, with
small ring or a-carbonyl ketone^'?^. Metallation of ethyl diazoacetate with Grignard
reagents occurs a t - 70 "C whereas at 0 "C, only nucleophilic addition to the
terminal nitrogcn is observed.
Ethyl diazoacetate has long been known to dimerize in ethereal potassium
alkoxide The most reasonable mechanism proposed' involves its reaction
as Bronsted and Lewis acids at carbon and nitrogen centres respectively.
+
RO,CC=N =N-
+ N=N-sHCO,R
--+ RO,CC '
\
N'N
N2
CHCO,R
/
--- RO,CC
-/
\
N=N
+
N=N)
CHCO,R
/
J
RO,CC '
N-N-
\
N'N
'CHCO,R
/
K+
- RO,CC
-/
\
N=N
NN
'
\
CHC0,R
/
(55)
(46)
t The formation of thermally stable, metallated diazoesters, where the metal is Ag or

Hg ctc., which do not proceed by initial proton abstraction, is discussed in Chapter 7 on
Complex Formation'.
I’rimary a-diazoketones display a similar balance of rcactivity as acids and
clcctrophilcs towards bases. 2,4,6-Trimethyl-w-diazoacetophcnone(47) undcrgoes
base-catalysed proton deutcriuni exchange rapidly in alcoholic as d o
primary diazos~~lpliones~’~.The reaction product Lvith niethoxidc in methanol is the
tetrazine (48)”’, analogous to 46, however with r-butoxide in r-butanol the tetrazole
dimer (49) is Both types or dinier are also produced by diazoacetophenone,
but with potassium hydroxide in dimethylsulphoxide and with potassium /-butoxide
in r-butanol, rcspcctively17J. The influence of different bases and conditions o n the
reaction course has not bcen clarified as both of the above dimers c m be considered
to arise from initial proton abstraction or nucleophilic addition by the base.
0 Nz
II I/
Ar-C-C-Q
?
Ar-C-C-H
;
2 MeOH
T ~* II
N/N,C/COA‘
I
(47) ArOC’
C
‘z’
NH
i56)
KOBu-I
L-BuOH
4,
N-N
N \\
ArOC-C, ,N
N
I
CH,COAr
Dimerization subsequent to proton abstraction is also observed in the reaction

of diazoketones with lithium diisopropylamidc at - 70 “ C , however if a ketone is
also present, condensation occurs to form the cc-hydroxy d i a ~ o k e t o n e ’ ~For
~ . this
reaction butyllithium is a n unsuitable metallation reagent as it competitively adds
to the terminal diazo
Base-catalysed condensation of diazoketones, diazophosphonate esters and diazo-
~ ~ ~carbonyl groups is observed under mild conditions if the
p h o s p h i n e o ~ i d e swith
latter are sufficiently activated, c.g. in isatin derivativcs180,or held in thc immediate
vicinity of the diazo grouplsl. This condition allows even attack at a carboxyl
function.
..
R’ = H,Me R” = OEt, Ph, Me R
210 J. F. McGarrity
It should finally be noted that the presence of an a-diazo group does not exclude
tcHNz
normal base-catalysed reactions, e.g. intramolecular alkylation1S3, or Darzens
condensat ion183
eN2
(CHNZ NaOH
0-5 “C , (60)
CI
C I A
0 N , + PhCHO t
OH- p h a z h 0 (61 1
HO 0
V. LEWIS ACIDITY OF D I A Z O A N D D l A Z O N l U M GROUPS

A. Coupling of Aromatic Diazonium Ions
I. Introduction
T h e reactions of the aromatic diazonium group with nucleophiles can be con-
sidered as substitutions or additions. The former class does not provide an index of
the Lewis acidity of the group and, as it has recently been reviewed181, will not be
considered further here. General considerations of terminal addition to t h e diazo-
nium group by nucleophiles, such as hydroxide, alkoxide, phenoxide, cyanide,
azide, thiolate and bisulphite anions, phosphites, phosphines, ammonia and sub-
stituted amines, have been extensively Quantitative thermodynamic
aspects of these reactions are presented elsewhere in this volume. T h e coverage of the
literature on azo-coupling to aromatic’8c and aliphatic carbon n u c l e o p h i l e ~ ~ * ~ - ~ ~ ~
will not be repeated. T h e following discussion will be limited to more recent results,
which may define the relative ‘kinetic acidity’ of several classes of nucleophiles.
2. Reactions with nucleophilic carbon
-
Generally the principal factor influencing the ease of coupling with aliphatic
carbon bases is the nature of the substituents in the base, rather than in the diazo-
niurn salt.
+
ArN=N+-CHR, ___+ ArN=N-CHR, Ar-NH-N=CR, (62)
6. Basicity, acidity at?d hydrogen bonding 21 1
The rate constants for hydrazone formation for the anions of n i t r ~ e t h a n e aceto-
~~~,
acetanilidelD1,acetylacetone'"' and acetoneIQ3with a series of diazoniuni salts have
beer? determined. Furthermore, good correlations of rcaction rates for each anion
with Hanimett's u parametcrs were obtained. As was noticed for coupling to aro-
matic nuclci, the most reactive diazoniuni ions have negative deviations from this
relation as :hi diffusioii rate limit is approached. This phenomenon was ascribed to
lack of additivity of substituent constants rather than to incursion of diffusion
control (with one exception), or to a change of p values with decreasing activation
free energylgJ. Such a change in p with the overall reactivity of each anion type
was however observed. Coupling to the highly reactive anion of acetone ( p K n = 19-
20) was associated with a value of 1.89, compared to a value of 3.45 for acetyl-
acetone. In fact the p values ivere observed to decrease regularly with increasing
rate constant, even when data for coupling to aromatic nucleophiles were included,
although the correlation was better when restricted to substrates of similar struc-
tural typeIg5. Such a n analysis of the Hamniett p values in terms of selectivity-
reactivity relationships is, however, subject to severe limitations and has recently
been criticizedlQB.T h e uncertainty in extrapolating this sort of comparison to
substrates of different charge type is typified by the similar p values of 4.0 and 4-15,
for the coupling reactions to 1-naphthol and its anion respectively, despite the
greater reactivity of the latter by a factor of 10' l g 7 . Such a difference in reactivity
between a nucleophile in its protonated and unprotonated forms is common t o
enols, naphthols, pyrazolones, naphthalene sulphonic acidslg2, pyrroleslss and
3-methylind0le'~~.
3. Reactions w i t h heteronucleophiles
T h e rate constants for coupling of aromatic diazoniuin ions with nitrogen in
amines appear to decrease in the series h'-metliylaniline~OO, dimethylamine2"',
anilinezoz.This decrease is not reflected by a systematic change in the values of p
3.94, 3.47 and 3.90, respectively. The effect of variation of aromatic substituents on
-
the coupling rate with methylamine is difficult to assess, since electron-donating
substituents encourage further reaction of the initially-formed triazene with the
-
diazonium ion to generate a p e n t a ~ a d i e n e ? ~ ~ .
ArN: +CH,NH, Ar-N=N-NHCH, 7ArNH-N=NCH, (63)
ArNH-N=NCH,+ArN: ArN=N-NAr-N=NCH, (64)
T h e kinetic resul!s for this system have so far defied analysis20'.

Coupling with hydroxyl, cyanide, bisulphite and azide ions leads initially to the
cis-azo compounds, despite t h e fact that the f r o m isomers are thermodynamically
favouredZo5.The syn diazohydroxide formed when the nucleophile is hydroxyl ion
is extremely rapidly deprotonated to the S ~ I diazoate?OG.
I ?Oi (see Section VI1.A). The
aryldiazoazide formed with azide ion decomposes into aryl azide and nitrogen, o r
cyclizes to an arylpentazole, prior to nitrogen evolution2oa.
Ar-N=N+
I
+ - N=N=N- -.Ar-N=N-N=N=N-+ (--t Ar-pJ=N-N-N=N-
J
212 .I. F. McGnrrity
For several solwnts the kinetic nuclcophilicity of anions is in thc order C,H,S-<
N; < CN- '"!'. A n exccptioii to this sequence is providcci by the reaction of azide with
diazonium ions (other than with p-nitroben7ciicdi~~/oniLiill~ in watcr"". In these
particular cases the rate-dctcrriiiniri~step is assumed to bc dccomposition of the
aryldiazoazidc2*1.Tlic abovc-mciitioncd reactivity order is maintained towards
triarylnicthyl and tropyliuiii ions and is regarded a s following the relative ease of
desolvation of the iiucleopliilcs'2"3.Conscqucritly, ii considcrable part of thc activa-
tion cncrgy f o r thcse rapid rcactions is iinaffcctcd by the reactivity of the diazoniuni
ions. Hcnce there does not exist even an approximate relation between Harnmett p
values and ovcrall reactivity as found for azo-coupling rcactions. The p values in
qucstion for -OH,ll>o,= 2.16 ?12, 2. I ?I3, -CN,ll,o, = 2.3 1 "', N,chf,orrl = 2.83 m
are considerably smaller than thosc for azo-coupling to carbon nucleophiles whcre
p = 4.0, despitc the fact that these lattcr rcactions are much more rapid. The
coupling ratc of 2,6-dichloro-4-nitrobcnzencdiazoniu1ii ion with I-naphtholate
anion is IO:'-tinics t h a t with hydrosidc ion, despitc the greatcr basicity of the lattcr
by a factor of loG'.I5. The similarity of the p values of azo-coupling to carbon to
those of diazoniun-diazo cquilibria \\it11 the above anionic nucleophiles, i.e. 3.2 <
p < 5.2. may indicatc that the transition states for thcse azo-couplings are 'product
like' l a 4 . On the other hand, the smaller p values for reaction with anions (after their
desolvation) imply a less sclectivc reaction, with 'rcactant likc' transition state.
T h i s rcasoning*Jl is consistcnt with formation of cis products for 'carly transition
state' rcactions, and direct forniation of ~ v n r r sproducts with amines, phenols and
aromatic tertiary amines.
B. Coupling of Aliphatic Diazonium Ions

1. Stable aliphatic diazonium ions
Stablc, isolable aliphatic diazonium salts (i.e. those froni which spontaneous
nitrogLn evolution would lead to vcry u n s ~ a b l e v i n y l cations) d o not undergo
reactions analogous to azo-coupling. This is due to preferred reactions with nuclco-
philcs at alterriativc sites. T ~ Uolefin
S diazonium s a l t s undergo substitution at the
electrophilic olefin positions rather than addition at thc tcrininal nitrogen216.
The .j-pyridiiiyl-sLibstitute~i tiiazonium ion (50) is deprotonatcd by triethyl-
aniine217. The dinzoniiim-substituted acetyl-acctone complex (51) normally
6. Basicity, acidity a n d 'iydrogcn'bonding 21 3
experiences substitution of thc diazonium group by nucleophilcs, but does show
colouration, indicative of coupling \villi nnpli~liol"'.
(511
2. Trapping of aliphatic diazonium ion intermediates
Coupling products havc bcen isolated froni reactions involving aliphatic clia-
zonium ion internicdiates. I n all cases the ions could be trapped due to nitrogen
l o s s becoming unfavourable, assisted or unassisted, by position either on a Sridge-
head219or on a cyciopropyl ring'". :?'I.
(52) 30%
Undcr the same conditions as the cyclopropyl diazoniiim ion (52) expericnccs
terniinal addition, the isobutyl and methyl analogues prcfer nitrogen
A bridgehead position is not in i1sclf suficient to pcrmit diazonium ion trapping.
The polychlorinated liomocubane diazonium ion (53) gave products typical of
radical decomposition of an intcrinediatc addition specics (54), and also couplcd
with ~-naphtho1?21.I n contrast, its hydrogenated analogue yiclded only normal
hydrolysis products in the same reaction conditions"'.
7-
1
IINO?
R-NH, >- R-N,' R--N=N-OH ____> R-N=N-ON0
(53)
(54) (71)
R-+N,+.ONO
R=
214 J. F. McGarrity
T h e less stabilized methane??3-?Zaand ethane d i a ~ o n i u m ?ions
* ~ can be trapped by
their counter-ions co-generated in ion pairs.
OOH
-.CH,Nb G 5 ! = N - c H ~ ~ n!=N-CH,
0' 0
' 0
I I I
CH, CH, CH,
C. Coupling of Aliphatic Diazo Compounds

Generally the reactivity of diazoalkanes towards nucleophiles increases with
increasing contribution of limiting forms (lb) and (Ic) to their overall electron
distribution. Diazoalkanes lacking electron-withdrawing substituents require more
reactive nucleophiles.
Trialkyl- or triaryl-phosphines, though more feeble nucleophiles than amines
toward many metal ions228,form, unlike amines, stable addition complcxes with
most d i a z o a l k a n e ~ even
~ ~ ~ ,d i a z ~ m e t h a i i e This
~ ~ ~ .unique reactivity results from the
-
ability of phosphorus to stabilize the betaine thus formed (55) by z-acceptance into
its empty d orbitals.
- +
R,C-N=N++P(Ph), R,C-N=N-P(Ph), a+
R,C=N-N=P(Ph), (73)
(55)
When the delocalization is diminished by hydrogen bonding, for example in the
a-hydroxyphosphazine (56), the thermal stability of the adduct diminishes corre-
~ . this case dissociation into reactants occurs at 70 " C , whereas
s p ~ n d i n g l y ' ~In
normally higher temperatures are reqcired for pyrolysis231.
\
C0,Et
(56)
Although the addition reaction is subject to acceleration by electron-releasing

substituents in the phosphine aryl groups23' ( p = - 1.03), the limitations of the
extent of reactions seem to be primarily ~ t c r i c ~ Thus
~ ' . diazocyclopentadiencs sub-
stituted with alkyl or aryl groups in both the 2- and 5-positions fail to react with
triphenylphosphine. Reaction does proceed with the less hindered and more nucleo-
philic tri-n-butylphosphine, or if the 5-substituent is replaced by a hydrogen,
chlorine or nitro In the latter two cases the electron-\vithdrawing sub-
stituents would be expected to stabilize both the diazonium reactant and also the
product-contributing form 55. The increased importance of this form has been
invoked to explain the more ready hydrolyses of the phosphazines containing these
substituents, by nucleophilic attack at Trialkylphosphites also form
phosphazine adducts, b u t examples are scarce234.235.
Iliazoalkanes disubstituted with strongly electron-withdrawing groups, such as
-CN 8 6 , -CF, 23G, - S 0 2 R 2 3 7 , react with phosphines or Grignard reagents at or
below room temperature. In certain cases such compounds, e.g. a-nitro ethyldiazo
acetate (57) can also serve as 'diazo-transfer' reagents238.
(74)
/-
A
N? + NO,CHCO,Et
Bisarylsulphonyldiazoniethanes also react readily with car bani on^'^^ (equation

75), and bismetliylsulphonyldiazon~etlianes can experience terminal nucleophilic
attack by enamines?40s? J 1 (equation 76)
+ S0,Ph Ph s02, -9 (JSOZPh
"
PhSO, \- -/
,C-N, + HC, > ,C-N=N-CH

PhSO, S0,Ph PhSO, 'S0,Ph
PhSO,, /H
,C=N-N=C \
PhSO, SO, Ph
1
Products
216 J. F. McCnrrity
Electron-rich olefins also react with elcctrophilic z-dicarbonyl diazoalkanes?J2and
. ~ form
d i a ~ o f l u o r e n e ?to ~ azines. b
Ph Ph 0 Ph Ph
I I 1 I I
+ ,C-- R’
+ N=N-E
\
/ \
rHR
I I 4-
Ph Ph 0 Ph +N Ph
\ I
R R’
A n alternative route to azine products from diazofluorene and 58, via prior dis-
sociation of the latter to nuclcophilic carbcnes, has bcen 21:’.
--
Ph Ph
I
IN>-+
tL+ + R‘ +NJ p ,R’
C-N=N-C
(58) - 2 N=N-C~R “1 L-‘ R
I I (78)
Ph PI1
V
I
(59)
T h e diazo carbon of diphcnyldiazoniethane is sufficiently nuclcophilic to form

azines with stabilized diazoalkanes without passing through a carbcne inter-
mediateqc~ xC
Ph\-
C
,-
+
N
N=N-C,
N
S0,Ph
S0,Ph
- Ph,
Ph
C
,?
\
C N+- N
N=N,
t-c,
,SO,Ph
S0,Ph
(79)
,SO,Ph
Ph, ,N =C,
C, =N S0,Ph
Ptl
T h e more nucleopliilic diazoethane carbon reacts similarly with p-nitro-w-diazo-

acetophcnonc and less rcadily with u.-diazopropioplienone, whereas diazomethane
does not react under thc satlie conditions”‘# ?.In.
6. Basicity, acidity nrld liydrogcn bonding 21 7
-
The normal course of reaction of d i a z o k e t o n e ~ ~ ~d.i‘a, z o e ~ t e r s ” ~
or aryldiazo-
-
alkancs249-251with carbanions from organomctnllic 2.’1 leads to a hydra-
-
zone after hydrolysis.
- -
Ph,C-N=N+ +PhMgBr Ph,C-N=N-Ph Ph,C=N-i-Ph
Ph,C=N-NHPh (80)
The initially-formed, azo-couplcd products from diazodiketoncs and enolate ions

may be isolated as such242.2 5 ; or may cyclize to substitutcd p y r a z o l e ~ ~ ~ ~ ,
The addition products of diazoalkanes and triphenylphosphoranes fragment to

form the mixed a ~ i n e ~ ~ ~ .
R = Ph; R‘=Ph,CH,,Ph,H; V
I (82)
R” = CO,Et, CO,Et, Ph, Ph 0

II
H, ,C=N-N=C, ,CR’
+ (Ph),P
R R”
Less-nuclcophilic phosphoranes whcre R = Ac, Bz or C0,klc failed to react.

N-Tcrminal attack 011 dinzokctoncs by cyanide and bisiilphite anions, and by
amino groups, is evident from thc isolation o f tlie corrcspoiiding addition products’.
These reactions involving nminc and sulpliidc nuclcopliilcs arc usually restricted to
intramolecular cyclizations’, although pipcridirlc forms a linear triazene w i t h tlie
sufficiently rcactivc 1,1,1,3,3,3-Iiexafluorodiaz0-7-propane‘~~.
F o r other nucleophiles the evidence of reaction is less obvious. The extcnt of
hydrogen-deuterium exchange in 2,4,6-tri1i~etl~yl-c3-dia~o~cetophenone in deutcrated
methanol, catalysed by halide salts, depends on the nucleopliilicity rather than o n
the basicity of the Thc proposcd exchange mechanism is given in equa-
tion (84).
H 01) I! 0-
RCOCH-N=N--B RCOCHD-N=N-B RCOCD-N=N-B etc.
(83)
The products of rcactions of diazokctones in the prcsencc of hydrosidc or alkoside
ions are consistcnt \ v i t h intcrmcdiatcs of the abovc typc. Similarly, nuclcophilic
218 J. F. McCiarrity
rather than basic catalysis has bcen invoked to explain the interaction of diazo-
carbonyl groups with adjacent electrophilic functions’IG.
0
II
T h e formation of /ratis cinnaniic esters from aryl-2-diazopropionic esters in basic

could well involve such an intermediate, instcad of the original diazo-
ester, as an acidic spccies.
x 0 7-50
C H =C‘-I-C \
OR
X
On the other hand, t h e reaction of diazoketones in ethanol-sulphur dioxide

mixtures255is not neccssarily thc result of a nucleophilic attack of ethanol o n the
diazo group. A sufficient increase of acidity of ethanol, due to coordination with the
Lewis acid SO2, to pcrmit protonation, would be a n equally acceptable explanation.
Finally, azo-coupling with aromatic substrates is limited to the very reactive
1,3,5-!rihydroxybenzenc for diazokctoncs, ethyl diazoncetatc and d i a ~ o n i e t h a n e ~ ~ ~ ,
although dicyanodiazoincthane couples with the 4-position of N,N-dimethyl-
anilinesG.
VI. H Y D R O G E N BONDING
A. Diazoalkanes a s Proton Acceptors
The formation of a hydrogen bond, betwen a n acid and a diazo carbon atom, has
been shown to account for a considerable part of the activation energy of the overall
proton transfer (Section I I.B.6). I n non-polar solvents, complexes so formed n i n y
have a lifetime sufficicntly long to pcrmit an alternntivc reaction with the solvent.
6 . Basicity, acidity and hydrogen bonding 219
Thus CIOSS~~' has proposed a carbenoid transition state (59) for thc trifluoroacetic
acid-catalysed formation of cyclopropanes froin phenyldiazonietliane in olefinic
solvents.
+
,c=c,
\ /
T h e evidence for such a transition state includes stereospecificity of cyclopropane

formation and partial deuterium incorporation from deuterated catalysts, as opposed
- - -
t o monodeuteration of the carbonium-ion-derived products.
A similar hydrogen-bonded intermediate was originally proposed to explain the
product distribution in the alkylation of tautomeric acid s y s t e m P .
A-H+CH,N, A-H-..CH,N, N,+A--H.*-CH, A-CH,
(87)
Collapse of intimate o r solvent-separated ion pairs would currently be a more
acceptable explanationis. 2G8.
Hydrogen-bond formation to diazoalkanes from is indicated by the
The nuclcophilicity of the
function of the former as transesterification catalysts260-2G2.
alcohol hydroxyl group is sufficiently raised by hydrogen bonding to t h e weakly
basic diazomethane to allow attack on a carboxyl group.
+ + + t
ROH + -
CH,N, -+- R-O--H.-CH,N~ --+ R-o-H-CH~N,
R',l
,C- OR"
R
; -0
R"O0 =O
I
,
R"
o=c, + R"OH + CH,N,
OR
It is significant in this respect that dicthyl oxalate is transesterified under condi-

tions which leave the less electrophilic diethyl malonate The catalytic
function of diazomethane is supported by the lack of formation of methyl acetate, in
the reaction of phenyl acetate with
220 J. F. McGarrity
Similar mechanisms are proposed for the catalysis by diazoalkanes of the addition
of alcohols to electrophilic double and of isocyanates o r isothiocyanates
to o-hydroxybenzoate estersze5(equation 90).
R'
Y=C=N / Y T"C /R'
I ... H: +._.C H R" N
0
&-o - H -CH R- N,
CO,R
1 (89)
qy:R, -I- CHR"N,
Catalytic efficiency for this reaction increases in the order diazoethane, diazo-
methane, phenyldiazomethane, which is the inverse of the order of their rates of
reaction with phenols. F o r the most efficient catalyst, phenyldiazomethane, 0.1-
0.01 molar equivalents are sufficient to ensure complete The inter-
mediacy of proton-bridged rather than discrete diazoniuni ion intermediates was
demonstrated by the lack of incorporation of deuterium into the products, when
molar equivalent quantities of deuterated diazoalkanes were used a s catalystP6#?'j7.
B. Diazoalkanes as Proton Donors

i n solution, primary o.-diazosulphones"" and a - d i a ~ o k e t o n e scan
~ ~ ~function as
hydrogen-bond donors, either to themselves or to solvent molecules. This is revealed
by a downfield progression of chemical shift of the proton bonded to the diazo group
in a series of solvents following the basicity of the solvent. It should be noted that in
the solid phase n o evidence of hydrogen bonding was to be found in the determination
of the crystal structure of 1,4-bisdiaz0-2,3-butadione~~~.
On the basis of solvent dependence of chemical shift, diazosulphones are
apparently better hydrogen-bond donors than are diazoketones. The latter possess,
however, a better acceptor site i n the carbonyl group as compared to the sulphone
group268.
The difference in hydrogen-bond donor ability between the two classes of com-
pound has been invoked to explain the alkylations of diazosulphones (60), but not
of diazokctones by enamines?'l. Formation of the hydrogen bond to the enamine
apparently increases its immonium ion character (62), and hence its susceptibility to
attack by the nucleophilic diazo carbon.
.4 close parallel to the above behaviour cxists in the chemistry of diazodiphenyl
phosphine oxides (61). The p.m.r. spectrum displays a similar, solvent-dependent,
chemical shift for the proton attached to the diazo and furthermore
6 . Basicity, acidity and hydrogen bonding 23-1
61 adds elcctrophilically to enamines in exactly t h e same manner as do diazo-
sulphone~?~~.
(60) X = RS02- (62)

(61) X = (Ph)lPO-
VII. ACIDITY A N D BASICITY O F AROMATIC D!AZO

COMPOUNDS
A. Diazohydroxides
1. Introduction
T h e investigations of acid-base equilibria involving diazohydroxidcs are com-
plicated by two major features. Firstly, both thc diazohydroxides and their conjugate
bases display geonietrical isomerism bctwecn the syn and the more stable arifi forms,
interconversion of which may be acid catalyscd. Sccondly thc SJW diazohydroxide is
itself a component of a Lewis acid-base equilibrium, with arenediazonium and
hydroxide ions. As the equilibrium constant for this reaction is usually much
inferior to the dissociation constant of the sytr diazohydroxide, the latter, when
formed from diazonium ions, is almost totally deprotonatcd by the hydroxide ions
present274.This behaviour, summarized in equation (9 l ) , prccludes a direct measure
of the acid dissociation constant K:,from equilibrium concentrations.
ArNf f H,O
ArNf + -OH
OH
, / 0-
,N=N N=
Ai
Analysis of kinetic data for conversion of diazonium ions into .syii a n d ririri diazotatcs
(65)and ( 6 6 ) , s n d (:iceEL’I’SO, alloivs separation of dissociation coilstants ( K , and A’.,)
for syri and m f i diazohydroxidcs ( 6 3 ) and (64). I n soine c:ises, the rntcs of reaction
of 63 and 64 with acids have been determined.
222 J. F. McGarrity
2. Dissociation of syn diazohydroxides
2,6-Dichloro-4-nitrobenzenediazohydroxide is exceptional in that, for a certain p H
range, it may be present in considerable concentrations in equilibrium with the other
species in equation (91)215. This is in part due to the instability of thc corresponding
diazonium ion, which results in an increase in K , , and also to diminution of the iso-
merization equilibrium constant Kis0. The dissociation constant K , was calculated
from that of the equilibrium mixturc of syii and atiti diazohydroxides and the
isomerization constants Kiso and K{w, to bc equal to 1.55 x Solutions of syn
diazotates can be prepared by reaction of hydroxide ion with diazonium ions where
substituents a r e not niesornericnlly electron withdrawing, and hence d o not favour
syn-onti isomerism275. Quenching of these solutions immediately after formation
with buffer solutions reforms the benzenediazonium ion with a rate dcpendent on
the concentration of the syri diazohydroxide p r c ~ e n t Hence,
~ ~ ~ . the variation of rate
with the p H of the buffer solution employed allows determination of K?. The Harn-
mett p value for the dissociation constants of such a series of diazohydroxides was
found to be 1.3.
3. Dissociation of anti diazohydroxides

The rates of conversion of atiti diaz.otates (66) to the corresponding diazoniuni ions
in solutions of high p H ( > 7) are directly proportional to the equilibrium concentra-
tions of the anti diazohydroxides (64). Thus the variation of rate with p H readily
gives the appropriate dissociation constants K 3 ?06. Such an analysis has been applied
to the reactions of pyridine?”, purine278, di-“O and trisubstitutedZ1’”
anti
diazotates. The values of p K , thus established vary from 4.65 for 2,6-dichloro-4-
nitrobenzenediazotate to 7.40 for 4-toluenediazotate. In the series of mono-
substituted substrates, the dissociation constants give a Hanimett correlation with
p = 1.45 27B (or 1.15 ?07 as measured by potentionietric titration). The magnitude of
these values and those for the syti isomers, both being much less than for phenol
ionization, exclude, as expected, the possibility of localization of the chargc formed
o n the nitrogen o r oxygen.
4. Reaction of anti diazohydroxides with acids

The rate of conversion of mono-substituted atiti diazohydroxides into diazonium
ions has a first-order and a second-order :
- d[ArN,OH]
dt
= k,[ArN,OH] + k,[ArN,OH][H,,O+]
The first-order component, with rate constant k l , is a composite of dircct dissocia-
tion into A r N c and O H - (for which the Hanimett p = -2.6) and an uncatalysed
(or \vater-catalyscd) isonierization atiti-.~yti27”.The rate constant k, of the second-
order component represents an acid-catalysed isonierization of m t i - . y y t i diazo-
hydroxides, and is associatcd with a p value of -2.4. In thc conditions where
k,[ArN,OH][H,O-‘] is significant, generally at p1-I < a , the scission of the syti diazo-
hydroxide is more rapid than thc reversc isomerization. I n the pyridine 4-diazo-
hydroxide system a water-catalysed reaction, possibly corrcsponding to an anti-syti
isonicrization, is significant o n l y at pH c I , in which region the aromatic ring
nitrogen i s already protonated. Acccleration of the reaction of 2,6-dichloro-4-nitro-
bcnzenediazoliydrositic and 2,4-dinitrc~benz~ncdiazotiydro?tide‘~~ i n this rcgion of
p H , with increasing acid conccntration, Cali also be ascribed to acid catalysis of the
6. Basicity, acidity and hydrogcn bonding 223
rate-determining atiii-syti conversion. The existence of such an acid catalysis term
does not resolve the question of whether the ntiti diazohydroxides exist as such in
solution or are better represented as their N-nitrosoamine tautomers2E2.Protonat ion
of either tautomer could facilitate overall conversion to diazonium ion, either by
reduclion of the isomerization energy barrier or by improving the leaving group in
the direct scission reaction.
H
H,I H //O
N -N
Ar’+
-
!I-.-
0 H,
H,
L
,N-N
A r’
N-N@
Ar *o *,,N=N ‘OH
#
H‘ ,OH
N=N
Ar ’
5. Reaction of syn diazohydroxides with acids
Arenediazotates with 2.6-dichloro-4-nitro- and 2,4-dinitro- substituents generate
their relatively reactive diazonium ion counterparts by a rate-controlling scission of
the syn diazohydroxide at p H 4.5. In this pH region, the scissions are general acid
catalysed281.This was found also to be the case for syti diazohydroxides generated
by quenching a solution of syn d i a ~ o t a t e s ~The
’ ~ . Bronsted a values could be measured
for the catalysis in both experimental approaches. Those of substrates with the
electron-withdrawing substituents were greater (0.34, 0.31 as opposed to 0.19).
8. Diazophenols
Arenediazonium ions with 0- or p-hydroxy substituents react with only one
equivalent of base to form t h e corresponding phenolate ion, often named a diazo-
phenol :
T h e pKn value of 3.19 283 is inferior to that of 2,4-dinitrophenol (4.1 1) as expected

from Hammett siibstituent constants for the diazonium group.
C. Triazenes
A comprehensive review of the acid-catalysed rearrangements of 1,3-diaryl-
triazenes to p-aniinoazobenzenes has been given elsewliercsyJ.3-Alkyl-1 -aryltriazenes
react readily with acids to form the corresponding anilines, nitrogen- and carbonium-
8 ~ . decomposition prevents direct determination of their
ion-derived p r o d u ~ t s ~ This
2 24 J. F. McGarrity
basicity. Protonation rates are also inaccessible from t h e kinetic d a t a accumulated
to date. Either there exists a rapid acid-base equilibrium, with rate-determining
scission of the conjugate acid in water286,o r the rate-limiting protonation is con-
sidered to be coupled \vith simultaneous departure of a carbonium ion fragment in
~ ~ . acid-catalysed scission of 1,5-dipheiiyl-3-rnethyI-1,4-penta-
~ I i l o r o f o r r n ~ The
zadiene in water proceeds by a mechanism comparable to t h e formerza8, with its
consequent limitations of cvaluation of protonation r a t e constant.
VI II. A C K N O W L E D G E M E N T S
The a u t h o r ivould like to express his gratitude t o Professor H. D a h n a n d t o Mr T.
Srnyth for helpful discussions throughout t h e preparation of this chapter.
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249. G . H. Coleinan, H. Gilnian, C. E. Adams and P. E. I’ratt, J . Org. Chctn., 3, 99 (1938).
250. E. M. Kaiser and C . D. Warncr, J . Orgnttcimct. C/tem., 31, C17 (1971).
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254. N. Takamura, T. Mizoguchi and S . Yamada, Chetit. Pharttt. B I I //.,23, 299 (1975).
255. M. Tanaka, K. Katayama, T. Nagai and N. Tokura, Tctrnhcdro/t Lett., 3355 (1973).
256. T. Sevcrin, Angew. Chcni., 70, 745 (195s).
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258. F. Arndt, B. Eistert, R. Gomppcr and W. Walter, Chetn. Ber., 94, 2125 (1961).
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2104 (1975).
CHAPTER 7
Complex formation
HERMANNM. NlEblEYER
lnstitirfe of Organic Chemistry, University of Lausantie,
Lniisnntie, Switzerlntid
I. INTRODUCTION. . 231
11. COMPLEX FORMATION BY DIAZOALKANES . 232
A. Carbon Coordination . . 232
B. Nitrogen Coordination . . 237
C. 'Side-on' Coordination . 238
111. COhlPLEX F O R h l A T I O N BY DIAZONIUM
IONS . 238
A. Structure . . 238
B. Synthesis . . 239
C. Spectroscopic Properties . . 240
1. Infrared spectroscopy . . 240
2. N.m.r. spectroscopy . . 242
D. Chemical Properties . . 242
IV. ACKNOWLEDGEMENTS . . 244
V. REFERENCES. . 244
1. INTRODUCTION
T h e structure of diazoalkanes may be described in the valence-bond formalism i n
terms of the canonical structures 1, 2 and 3, and their reactions may be classified
on this basis. T h u s diazoalkanes may react as 1,3-dipoles (3) o r as nucleophiles

through carbon (1) or through the terminal nitrogen (2). In addition, the un-
saturated nature of these compounds renders possible the formation of x-type
complexes.
Diazonium ions on the other hand may be described as 4 and 5, and they react
normally as electrophiles through the terminal nitrogen (5).
R - ~ ~ N : R-N=N:
.. +
(4) (5)
The possibility of certain metal derivatives acting as Lewis acids and bases
enables them to form complexes with diazoalkanes and with diazonium ions. Few
complexcs have been isolated wherc a diazoalkane molecule as such is present as a
231
232 Hcrmann M. Niemeyer
Jigand, but their presence a s reactive intermediates has been invoked in numerous
occasions. Consequently most of the evidence presented is of an indirect nature.
O n the other hand. diazoniuni ions have yielded numerous stable complexes with
transition metal derivatives. While this manuscript was in preparation, a n
authoritative review appeared in this field'. Hence, the emphasis will be on the
most recent developments.
II. COMPLEX FORMATION BY DIAZOALKANES

The number of stable coniplexcs of diazoalkanes reported in the literature is
severely limited. Nevertheless in the few examples described the metal has been
proposed to bind the diazoalkane in three different ways. Hence, metal-carbon,
metal-nitrogen and 'side-on' bonding have been suggested.
A. Carbon Coordination
There is a wealth of reactions in which diazoalkanes are thought to act towards
metal derivatives as nucleophiles through the diazo carbon to give intermediates of
type 6 (Scheme 1) but their direct observation has been limited to two reports.
L,MCHN, + HX
Y
L L,MtCH, -t N ,
I
X
(7b)
SCHEhlE 1
Upon treatment of 8 with diphenyl diazomethanc at - 75 "C the observed colour

changc from red to brown was attributed to the formation of a complex whose
structure has been assigned as 9 on the basis of chemical evidence?. Furthermore, the
less stable diazornethane apparently forms with 8 a n analogous coniplex at lower
temperatures?.
I t has bcen postulated that a similar complex is formed in the reaction of AIEt,
with diazoniethane, which at - 7Y "C yields a colourless solution without nitrogen
evolution3. Spectroscopic and othcr mctliods to probe further into the nature of
the bonding in these complexes have not been used.
T h e intermediate 6 may suffer a variety of reactions which lead to the formation
of different types of products. Thus i t is often the case that compounds of Groups
IVb a n d Vb which possess a basic or potentially basic group react with diazoalkanes
possessing a n a proton to give a heterosubstituted diazoalkane as in path (a). Some
transition metal derivatives of Groups l b and I I b have also been shown to react
in this fashion but more often these dcrivatives induce the decomposition of diazo-
alkanes. Products of formal insertion of the diazo carbon into the bond between
the metal and o n e of its substituents (by loss of nitrogen and 1,2-migration of a
metal substituent t o the former diazo carbon) are commonly observed with the
normal elements and also with transition elements, the intermediacy of species 7a,
an 'invcrse' metal ylide, or 7b, a metal-carbcne complex, often being postulated.
These species have available other reaction paths such as polymerization via
successive attack o n 7 by diazoalkane and 1,2-migration of the growing alkyl chain,
attack by the terminal nitrogen of another diazoalkaiic molecule to form an azinc,
attack by the carbon of another diazoalkane molecule with forination of olefin.
I n addition it may react with compounds such as olefins to give products of formal
carbene insertion and/or of carbonium ion-type rearrangements.
T h e factors that govern the path chosen by the reaction are not well understood
at present. We shall examine some evidence that bears on the question of stability
of intermediates 6 and 7.
-
Reaction (a) (Scheme 1) has been widely applied in the synthesis of a-hetero-
substituted diazoalkanes4-l3,a s !he examples given below testify.
2 Me,SnNMe,+CH,N, (Me,Sn),CNz+2 HNMe, (1)"-'6
+
MeAs (NMez), 2 H CCO 0Et ___> MeAs(CCOOEt),+2 HNMe, (2)"
II
N,
M[N(SiMe,),],+2 HCCOOEt ___f M(CCOOEt),+P HN(SiMe,), (3)"
I1
N2
M = Zn, Cd, Hg
-
Hg(OAc),+4 HCCOOEt -t Hg(CCOOEt),+P Nz+2 AcOEt (4)'O
II II
N2 N2
-
Hg0-l-2 HCCOOEt Hg(CCOOEt),+H20
II II
Nz NZ
2 AgOAc+2 CH,N, AgzCN,+2 AcOMe+N, (6)z2
The mechanism of the reaction of metal amide derivatives such as equations ( I )

and (2), has been t h e subject of several discussions'o. A recent proposal12, appealing
in its simplicity, involves a rate-determining nucleophilic attack of the diazo carbon
on the metal with formation of a 4-centred transition state of structure 10, in which
interaction also takes place betwcen the diazo hydrogen and a basic ligand in the
reactant.
L"M--NRZ
N,C -H
I
H
(10)
234 Herrnann M. Nienieyer
The rcactions of diazoalkanes with transition metal derivatives, such as those
shown in equations (4), (5) and (6), have not bcen studied from a mechanistic vicw-
point. In the formation of disilverdiazoniethane (cquation 6), acetate may be replaced
by other anions provided that they give silver salts soluble i n the solvent employed.
Yiclds are better with anions deriving from weak acids. Added base helps the
rcaction, presumably by partially bonding a n outgoing proton and/or the terminal
nitrogen in the diazoalkane thus rendering thc carbon more nucleophilic.
Spectroscopic studies on a-hcterosubstituted diazoalkanes provide somc S a s k
f o r judging factors that contribute to their stability. In !he i.r. sllcctrum, these
compounds present a band ii; ihe region 2150-1950 cm-l attributed to a n N-N
stretching vibration, sensitive to the naiure of the substituent.
For compounds 11, the vt", values decrease with progression down the Periodic
Me,MCCOOEt M = C, Si, Ge, S n , Pb
, I1
N2
(11)
Table. This trend may be interpreted by invoking the increasing electron-donating

effect in the series partially compensated, in particular, i n the case of the silicon
compound, by p,,-d, resonance interaction??.
The possibility of the metal in a metal-substituted diazoalkane expanding its
valence shell has also been shown for compound 12. In its reaction with crotyl
bromide, an 85/15 mixture of 13 and 14 is obtained pointing to the intermediacy
of a n ion pairz3.
N,
I1
CH,CH=CHCH,CCOOEt
N, (13)
II
AgCCOOEt + CH,CH=CHCH,Br
(12) N,
I1
CH,=CHCHCCOOEt
I
c H,
(14)
T h e intermediacy of nietal-carbene complexes?a."-' or 'inverse' metal ylidcs has

been invoked in numerous mctal derivative-catalysed decompositions of diazo-
The nature of thc rate-determining step of the reaction has been
established by kinetic measurements in only a few cases. In the reaction of diphenyl-
diazomethane catalysed by ZnCI, or ZnBr, to yield, after work up, mixtures of
benzophenone and benzophenone azine, the kinctics and product proportions arc
+ -
consistent with rate-limiting formation of the complex PhlCZnX2 3G. Whcn CuBr,
is employed as catalyst, a copper complex which may have diphcnylmethylcne as a
ligand is fornied in a rapid first step, the further consumption of diazoalkane
occurring at a slower rate32.
Correlations have becn found betwecn the ratcs of decomposition of diazoalkanes
and their basicity and the strength as Lewis acid of the metal compound. Thus,
while diphcnyldiazomctliane shows R O reaction with ZnCI, bclow - I5 "C, phenyl-
diazomethane reacts at - 50 "C. T h e decreased basicity of the former compound
7. Complex fornintion 235
may be attributed to inductive electron withdrawal and to t h e additional steric
hindrance of the second phenyl ring3". On the other hand, in the presence of the
typically strong Lewis acids AICI, and SnCI,, 0.1 nimol of diphenyldiazoniethane
reacts completely in air in less than 1 minute while t h e reaction takes hours in the
presence of the weaker acids ZnCI, or SnCI,
In the decomposition of diphenyldiazornethane aidcd by different metal salts
the observation was made that the products wcre related to the reduction potential
of the salt in H,O 3 R . Thus, when TI"'(OAc), ( E = + 1-21 V) or Cu"(OAc),
( E = +0.15 V) was used the products resulted from a two-electron or one-electron
transfer with formation of TI'OAc and Cu'OAc respectively, whereas when
Cr1I1(OAc), ( E = -0.41 V) was employed n o reduction of the metal ion took place.
T h e mechanism proposed involves internal acetate transfer within a metal-carbene
complex38.
In a very limited number of cases stable metal-carbene complexes have been
isolated from the reaction of metal derivatives and diazoalkanes (equations 7
8 31 and 9 9.
F,C CF,
\ /
Me PP h ," '
(1 5)
FLY,
[WPPh,)2(CH,=CH,)I [Pd(PPh,),(Fl)]+CH,=CH2
(16)
FI = 9-Fluorenylidene
Mn,
OC20 CArZ
On the other hand, methods different from path (b) (Scheme 1) have been used to
synthesize numerous complexes, most of which possess oxy, thio, seleno or amino
substituents on the carbene carbon a!oii~'~.O:. These complexes may be said to
originate from nucleophilic carbenes.14el5 and their bonding is interpreted in terms
of t h e limiting structures 18, 19 and 20. complexes 15, 16 and 17 would thus con-
stitute exceptions by being electrophilic carbene complexes. Presuniably the electron-
withdrawing character of t h e carbene substituents induces strong =-back donation
from the metal and hence produces a strong h.1-C bond.
236 Hermann M . Niemeycr
The methylene insertion reaction has bccn the subject of several structure-
reactivity studies that have confirmed that a nucleophilic attack on the metal is
involved in the rate-determining stepa6.47. The data availablc d o not distinguish
cither between a stepwise and a concerted process o r betwecn a zwitterionic inter-
rncdiate such as 213 and an ion pair intermediate such as 21b.
[L,MCH,N,+] [L,MCH,N:]X-
I
X (21b)
(21 4
In general i t is found that organic substitution in the Group I V a halides tends to

decrease the reactivity of the M-X bond towards diazomethane. Thus, while
SiCl, reacted rapidly with CH,N2 in ether even a t -50 "C to give CICH,SiCI,,
further methylenation was found to be incrcasingly dificult. Et,PbCI, on the other
hand, did react to give Et,PbCH,CI in high yield4G.A quantitative study of the
substituent influence upon t h e reaction of 22 with CH,N2 has produced a p value
of 2.3 0 6 . These data show that more electrophilic character in the metal favours the
react ion.
An initial association of diazoalkanes to the metal has also been proposed for
their reaction with Group Illa derivatives. The adduct rcacts further to give either
methylenation products3. or/and polymerizat ion of thc diazoalkanc". 53.
Qualitative expcrimcnts have led to the conclusion that the rate of thc reaction
depends o n the Lcwis acidity of the metal derivative. Thus, while BEt, reacts
vigorously with CH2N, at room temperature to give polymethylene, B(OEt),
requires hours under the same conditions3.
The fate of the intermediate adduct has been found to depend on the Lewis
acidity of t h e metal dcrivative as well, weakcr acids favouring polymerization over
insertionso. Thus higher proportions of polynierization over insertion are found for
boron derivatives as coniparcd with analogous aluminium ones, for derivatives
-
substituted with O R groups rathcr than R, I-l or X , and for reactions in which
additional donor molccules have been addedR.A mechanistic interprctation may bc
givcn (cquation 10). Intcrmediatc 23 bchaves as a strong elcctrophile and can add
L,,MX+CH,N, ___> L,M c CH,N, L,M <- CH, (1 0)
I I
X X
(23)
further diazonicthanc to form 24. However, the stronger the intcraction bctween
the metal and the diazo carbon, the more effcctive will be the cornpctition of M-X
bond rupture and migration of X to carbon"'.
L ,,Mc H,; H,
I
X
(24)
0. Nitrogen Coordination
The reaction of diphenyldiazomethane with dodecacarbonyltri-iron and also its
irradiation in the presence of pentacarbonyliron in benzene leads to two com-
p o u n d ~5 ~8 , ~whose
. structures have been determined by X-ray studies to be 25 5 5
A:,C
v
Ar,C=N H N
\ .-. I *,?
N‘ *.,$
oc, co,:
Fe- Fk
/r r\
oc E : co
oc co
(25)
and 266fi. The N atoms in both complexes show angles characteristic of sp3
hybridization and the N-Fe bond lengths are close to those found in other com-
plexes known to contain N(sp3)-Fe bonds.
A single case has becn reported where a diazo compound as such is bonded to a
metal through its terminal nitrogen5”, as shown in equation (1 I). T h e product of
the reaction is stable up to 80 “C, diamagnetic, and it liberates the diazomalonate
ester upon treatment with PPh:, under irradiation or with C O .
I + N,C(COOEt), THF 2. I
OC%\THF (11)
R = H, Me 1:
COOEt
(27)
T h e structure proposed may be compared with those determined by X-ray studies

for aryldiazenato complexes (see SectiGn III.A), the basis for t h e comparison being
the importance of limiting structure 28 in the ground state of the diazoester.
COOEt
4-
N= N-c:/., -
Y-
COOEt
(28)
Complexcs 27 show i.r. absorptions at 2025, 1952 and 1951 cm-l ( R = H) and
2022, 1979 and 1943 cm-l (R = Me). By analogy with [M(x-C,H,)(CO),(N,Ar)]
(M = Cr 5 R , M o ‘*9-c1 or W G 2 , G3), the first two bands niay be assigned to v ( ~ 0and
,
the last to v , s s l . T h c high value of V , S S , points to 3 ligand with an N N C anglc
close to 180” (see Section 1II.C.l).
238 Hermann M. Niemeyer
C . ‘Side-on* Coordination
A series of complexes of Ni and Pd have been synthesized in which a diazoalkane
ligand is claimed to be bonded ‘~ide-on’~’. They have the general composition
‘ja.
[ML’L2(diazoalkane)] (29) with t h c ligands being 1-BuNC, PPh, o r 1 ,:~cyclo-

octadiene and the diazoalkanes, 9-diazofluorene or diphenyldiazoniethane. These
complexes have been synthcsized via addition reactions to [ML1L2]G5 or ligand
substitution reactions with [ML1L‘(CH,=CH2)], a s shown in thc examples (12)
and (13).
R&V-
[ML’Lz] - [ML’L’(R,CN,)]
(29)
PhyC’S,
[Ni (f- Bu N C),] [Ni(f-BuNC),(Ph,CN,)] (1 2)
[Pd(PPh,),(CH,=CH,)] ~
1”“
’ [Pd(PPhJz(FINz)I (1 31
FI = 9-Fluorenylidene
The complexes 29 present an i.r. absorption attributed to v(”) between 1550
and 1450 cm-I; a linear end-on coordination involving the terminal nitrogen would
presumably show in the region around 2000cm-1 and a coordination through
carbon presumably still higher. Furthermore, the trends observed in the i.r. spectra
upon changing the metal, the ligands and t h e diazoalkane parallel the trends found
upon similar changes in complexes containing an alkyne ligand, which is known t o
be bonded ‘ ~ i d e - o n ’ ~ ~ .
The structure of the ketenimine complex [Ni(r-BuNC),{r-BuN=C=C(CN),}]
has been determined by X-ray studies to involve a ‘side-on’ coordination in which
the Ni a t o m is nearly equidistant to the N and the adjacent C ‘j6. A similar proposal
has beerr made for the bonding in t h e diazoalkane coniplexes, whcre the orbital
picture would involve the donation from an occupied x orbital localized between
the nitrogen atoms to the metal and ;i back donation from the metal into the
corresponding unoccupied ~ i orbital.
* ‘Side-on’ coordination has also been suggested
for analogous derivatives with dicyanodiazomethanc as ligand”.
111. COMPLEX F O R M A T I O N BY DlAZONlUM IONS

Since the first synthesis of an aryldiazenatot complex of a transition metal in
1964 this area of chemistry has been continuously expanding both in the quantity
and in the scope of t h e research carried out in i t . Among the transition metals
belonging to Groups Vlb, VlIb and VIII, there only remain to be isolated coniplcxes
of Tc, Ni and Pd. O n the other hand, the vast majority of the coniplexcs reported
involvc the aryldiazenato ligand, only a handful of alkyldiazenato complexes having
been characterized.
A. Structure
The terminal aryldiazcnato ligand has becn observed in two geometrical forms:
singly bent and doubly bent. In the first instance t h e bonding is described as
c-donation from a n sp hybrid orbital on the terminal nitrogcn w i t h z back donation
from d orbitals of the rnctal into a p orbital on the terminal nitrogcn ( N , l , ) .A simple
valencc bond description of this type of complex has becn given (structure 30)“’.
Evidcnce exists to show that lipon reaction of an arencdiazoniuni salt to form a
t The following nomenclature will be uscd’: diazcne ( H N = N H ) , nryldinzcnc ( A r N = N H ) ,
;Iryldiazenato (ArN2-- 01’ ArN,<) a n d ;1rcnedi:17oniuiii(ArN:).
complex \\,here t!?e aryldiazenato ligand is coordinated in this fashion, the oxidation
statc of the metal suffers n o change. Hence, the ligand may formally be regarded as
an 1b-N; two-electron donor ligand.
The doubly bent terminal ligand has been described as having a single bond by
overlap between a n sp2 orbital on N(’) with a hybrid orbital on the metal, as shown
in structure 31 87. In this case, the evidence available indicates that when an arene-
diazonium ion becomes coordinated as a doubly bent ligand, the metal suffers a
formal two-electron oxidation. The bonding may hence be formally described a s
that between a two-electron donor ArN; ligand and a doubly oxidized metal.
The X-ray studies reported’. 03- 6 9 for complexes containing a singly bent Iigand’O. 7 1
show that the NNC angles lie within the range 118-124”, the only exception being
[RuCI,(PPh,),(p-N,C,H,Me)l, with a value of 137”. It has been suggested that
slight back donation from the metal into *; orbitals o n the aryldiazenato moiety
leaves the N-N bond largely as a triple bond and the NNC angle close to 180”
(hypothetical linear terminal diazenato ligand)’, whereas stronger back donation
as described above predicts this angle to be 120”. Intermediate values of the angle
might be expected depending upon the relative iniportance of the linear and singly
bent formalisms to the electronic structure or, equivalently, upon the degree of the
metal to ligand electron transfer processB7(see Section Ill.C.1). Detailed discussions
on the electronic structure of the isoelectronic nitrosyl ligand have been
reported7?.7 3 .
B. Synthesis
The most frequently used reagents for preparing aryldiazenato complexes have
been diazonium salts, either as such or as compounds that generate them in sitrr.
The complexes are produced via ligand substitution, oxidative adGition or Lewis
base association reaction^^^.
A general mechanism has been proposed’, which has received additions and
partial confirmation from comparative electrochemical studies o n nitrosyl and
aryldiazenato complexesi5; i t is shown in Scheme 2. The nature of t h e products
has been observed to depend on the metal and its ligand, but with the exception
mentioned above:> no quantitative studies have yet been reported.
Complexcs between diazonium ions and transition metal derivatives havc been
postulated as reactive intermediates i n the Sandnieyer7G-78
and relateds0 reactions,
but structural proofs are not available.
Several other methods have been used to prepare aryldiazenato complexes
including’ apparent inscrtion of diazonium ions i n t o metal-hydrogen bonds
240 Hermann M. Niemeyer
followed by deprotonation of the aryldiazene coniplex formedR1,reaction of co-
ordinated nitrosyl with aromatic amines, reaction of metal complexes with aryl-
hydraziness2, organodiazenes or diazoalkaness3, and modification of complexes
already containing an aryldiazenato ligandsl.
2
SCHEME
C. Spectroscopic Properties
I . Infrared spectroscopy
Infrared studies have provided a useful tool for examining the interaction of the
aryldiazenato ligand with the transition metal to which it is bonded and with other
ligands present in the complex. Several studies have shown that although overlap
of Y ( K N ) with t h e absorption of other groups in the complex and coupling between
the N-N stretching vibration with aryl vibrational modes occurG1. the
isolation of v , ? ; ~is, possiblc by mathematically decoupling the interacting bands
which shift upon ?H or ISN substitution8;.
T h e N-N stretching vibration is found within the broad region defined between
c . 1340 and 2100 cm-’. This wide range is a reflection of the different coordination
modes of the aryldiazenato ligand, i.e. 30 and 31.High values of v , s ~(>, c. 1650 cm-I)
can generally be attributed to the occurrence of complexes of type 30, whereas low
valucs of Y ~ S N ,( < c . 1500 cni--’) can be generally identified with complexes of
type 31. With values i n the intermediate ovcrlap region, the assignment is not
trustworthy.
A method has been proposed’O which brings the V , S S ) values to a common scale
and rcduces the region where the ligand structiirc assignment is doubtful, the basis
of i t being the variations expected in Y , S N , upon changing the nature of the metal
and its ligands.
The mutual influence of the aryldiazenato ligand and other ligands present in the
same coniplcx can be studied in CO-containing complexes, since V , C O , is a n easily
identifiable absorption. An increase in V , C O , implies an increase in the C - 0 bond
order, a consequence of diminished d,-p, back donation by the metalco. This effect
may be induced by substituents in the aryldiazenato ligand. Thus, in coniplcxes 32,
[Fe(PPh,),(CO),(p-N,C,H,X)J’ BF; X = NO2, F, CI, H, Br, OMe, OH
(32)
7. Complex formation 24 1
the bettcr clcctron-withdrawing substituents produce the highest V , C O , and the
lowest v(xxl of the series"', pointing to electron flow from the CO groups to the
aryldiazenato ligands.
T h e complexes of the heavier metals prcsent lower vtxS) values (or/and lower
v m , values when appropriate) indicating that they are bettcr electron donors than
the lighter oncs. Thus for example, [ R L I B ~ , ( P P ~ , ) ~ ( ~ - N , C ~ H ~ M =
~ )IS95
] , cm-I,
may bc compared with [ O S B ~ , ( P P ~ , ) ~ ( ~ - N , C ~ HvIxh',
~ M ~=) ]1855
, cm-'
The electronic configuration of the metal influences its capability of back donating
electron density, a comparison of the V ~ X S ,values for the aryldiazenato com-
plexes reported showing that they exhibit a general trend in which L ~ ~ K Sdecreases ,
as the d " configuration of the metal increasesf18.Since the data available are rather
scarce, simultancous variations in the ligands, the charge and the metal are included
in the comparison.
TIic i.r. spectra of complexes 33 ( v l S N , = 1723, vlco, = 2030, 1978 cm-I) and
34 ( V , S N , = 16S9, v,co, = 2010, 1960 cni-') show that a positive charge, which
may be assumed to rcsidc mainly o n the metal", diminishes the electron density
available on the latter to share with the ligands.
[Fe~Co),(pph,),(PhN,)l BF; + [Co(CO),(PPh,),(PhN,)l

(33) (34)
-
T h e nature of the ligands influences the availability of electrons on the metal.
In equation (l4), replacement of CO by the relatively poorly accepting PPh3 ligand
[M o (CO),(x-C,H,PP h,)( A r N,)] + P Ph, [M o( C 0)(
x - C,H, P P h,) ( P P h,)( A r N,)]
(1 4)
[M o( CO),( OH) ( A r N,)], + Base ---+ [M o ( C O M 0 H <- Base) (A r N J I , (1 5)
results in an incrcased electron release from the metal a n d v l s N I and v t ~ 0 occur

, at
lower wave numbers in the productsg1. In equation (15) the lower v t n , and v t ~ o ,
values observed in the adductsg2may be related to incrcased electron release from
the metal caused by donation of electron density from the Lewis base to the O H
ligand through a hydrogen bond.
1. Correction parameters to
TABLE v c h ~(an-')
,
Coordination
hletnl Group Charge Ligrinds number
-
First row -50 VIb + 100 4-2 - 1-10 Third PPh, +20 4 + 50
Sccond row -30 Vllb +jO +: -YO Fourth PPh, +SO 5 , 6, 7 0
(Mo, -10) VlIl 0 0 0 HBPz; - 20
Third row 0 -1 +50 z-CjH,PPh, 4-60
-2 +140 H- + 20
-3 +200
Pz = 1-Pyrazolyl.
Table 1 collccts the suggested correction parameters which should be added

(or subtracted) to vthT) to obtaill a modified frequency Y , X S , . The magnitudes of
the corrections have bcen chosen so as to give the best agreement with data collected
from several hundred known complexes of t h e isoelectronic nitrosyl ligand.
24 Z Hcrninnn M. Nicineyer
T h e number of X-ray structure determinations being very limited, the V , N S ,
valucs provide a useful tool to predict confidently the type of ligand present in the
great majority of aryldiazenato complcxes, a value above 1550 cm-l indicating a
complex of type 30 and one below 1530 ciii-’ of type 31.
A relationship between electron back donation by the metal and i.r. spectra has
been demonstrated in complexes containing the mortohapro-dinitrogen ligandD3.B1,
isoelectronic with NO+ and with ArN; e5. In a series of these complexes, X-ray
photoelectron spectroscopy studies show that increasing electron density on the
N2 fragment, a s measured by the binding energy of its core electronseo,is coupled
with decreasing N N stretching frequencies”’.
2. N.rn.r. spectroscopy
Although the ‘H-n.m.r. spectra of many of the aryldiazenato complexes reported
have been determined, the information they yield is very unspecific and hence they
have been utilized as a n analytical tool rather than as a probe into the electronic
distribution in thecomplexes. On the other hand,18F-n.m.r.studies areseverely limited
in numberel~ ee, but they have yielded valuable information on the interaction at the
electronic level between metal, aryldiazenato ligand and other ligands in the
complex.
T h e most recent and complete studyG1has applied the technique of TaftlOo and
coworkers where the differences in chemical shifts between a para- and a mera-F
substituent are taken as a measure of the electronic effects acting on t h e ring that
holds these substituents. Thus, the more positive the value of 6,-6, is, the less
shielded the para-F is relative to the mera-F substituent, and hence the less electron
flow into the aryl ring has taken place.
Some results obtained are collected in Table 2. Comparisons among them lead
to the same conclusions concerning the influence of the metal and its ligands on the
aryldiazenato ligand, as reached o n the basis of i.r. spectra.
2 . leF-N.ni.r. data for aryldiazenato complexes“

TABLE
~~~~ ~~ ~
[Mo(x-C,H,)(CO)(PPh,)(N,Ar)] - 5.02
[W(HBPZJ(CO),(N,A~)]~ - 4.54
[ Mo(x-C,H,PPh,)(CO)(PPh,)(N,Ar)]’ BF; - 3.86
[ Mo( H BPz.J(CO)~( N,Ar)lb - 3.58
[ M o ( z - C ,H,)(CO),( N, A r )] - 2.30
[Mo(HCPz,)(CO),(N,Ar)] BF; + -2.11
[Mo(x-C,H,PPh,)(CO),(N,Ar)]+ BF; - 0.14
Chemical shifts for CH,CI, solutions and refcrred to external

hexafluorobenzcne.
Pz = 1-pyrazolyl.
D. Chemical Properties
N o quantitative study on the reactivity of aryldiazenato complexes has yet
appeared in the literature. Conclusions concerning the influence of the metal, of
the substituents on the aryldiazenato ligand and of the rest of the ligands o n the
reactivity of thc complexes have been based on a reaction failing to produce the
7. Complcs for mat i o n 24 3
expected product or not, or on the total time requircd for a complex to disappcar
under given conditions. Some of these data are discussed below.
I n general, the reactivily of the complex is very dependent upon tlie type of bonding
between the metal and the aryldiazenato ligand. Complcxes possessing structure
30, which present a n M-N bond with a substantial double bond character, are
found to be more stable towards N, loss than coinplcxes of type 31, \vherc the
M-N bond is cssentially single. Tlic N-N bond in conip1esc.s 30 presents a partial
triple bond character (see Section 1II.A) and is found to be more dificult to saturate
than t h e corresponding bond in complexes of structure 31, where i t is essentially a
double bond. Furthermore, tlie tendency t o react with acids of complexes 30,
which present a ligand impoverished in electrons, is found to be diminished as
compared with complexes 31, where the ligand is rich in electrons.
The nitrogen evolution from complex 35 according to equation (16) is fastest
when a NO, substituent is prcsent’O’, pointing to dccreased electron withdrawal
[Pt(PPh,),(p-N?C,H,X)]+ BF, ___> [Pt(PPh,),(p-C,H.X)]+ BF; +N, (16)
(35)
X = NEt,, NMe,, OMe, H, Me, F, NO,
by PtT1 in 35 and hence decreased Pt-N double bond character, when electro-
negative substituents are present. I n accord \rith this explanation, a negative slope is
observed for the correlation between the U . V . absorption corresponding to the
n-x* transition and Hamniett’s substituent parameters, ~7Io1. Furthermore, in the
complexes [Pt(PPh,,)l(L)(ArN,)]+ BF; the stability towards the decomposition
shown in equation (16) follows the ordcr NH, =pyridine> PEt, = R N C > CO,
!has para!leling the global electron-donat ing CTCC:~f thc figandyWL.
The complexes [M(PPh,),X,(ArN,)] ( M = Ru, 0 s ; X == C1, Br) exhibit i.r.
spectra consistent with structure 30 and are air-stable solids, resistant to protonation
or hydrogenation under mild conditionsR7.O n the other hand, the coniplexes
[Rh(PPh,),X,(ArN,)], presumably of structure 31, arc stable as solids, but when
dissolved in organic solvents they yield unstable solutions which react by
eliminating nitrogen or, when possible, by abstraction of HCI from the solvents7.
T h e complexes [Os(CO),(PPh,),(PhN2)]+ PF; are very reactive towards protona-
tion, slowly extracting protons from freshly distilled methanol or ethanol, while
their ruthenium analogues, although they can be protonated by acids, are stable in
the presencc of neutral alcoholsX7.A relationship has been established between
basicity of a complex and its V ( , Y S , frcquency. Thus, the following order in basicities
has been obtaineds1 for the d G complexes 36, 37 and 38: 36 [v(r,~,= 1455 cni-’]>
37 [vth%, = 1462 cn-1-~]>38[ v ( m , = 1470 cni-’I.
Not only the ease of protonation but also the site of protonation varies with t h e
structure of the aryldiazenato complex. Thus complexes 30 are expected to
protonate on N,,, while complexes 31 are expected to d o so at N(,,. These
9
244 Hcriiinnn M. Nicnicycr
expectations have been confirmed by X - r a y studics in the cascs of equations (1 7)Io3
and
H
I1 +
i
[RelCI,( PMe,P h),( NH,)( N,P h)] ~ f [RelCI,(PMe,Ph),(NH,)(N=NPh)]+ (17)
H
It+ i
[Pt 'I C I ( P E t 3)2( p - N C,H, F)] -- > [Pt"Cl(PEt,),(p-N=NC,H,F)] +
Finally, although the discussion has been centred o n aryldiazenato complexes,

most of i t should apply as well to alkyl, acyl a n d aroyl diazcnato complexes. Caution
should be eserciscd howcver in not extcnding the gencrality t o o far because the
stability o f the aryldiazenato as ligand is grcntly influenced by its capability t o
accept ; ; electrons from a inetal, a charactcristic not shared by alkyldiazenato
groups'0~.
IV. A C K N O W L E D G E M E N T S
T h e a u t h o r wishes to esprcss his gratitude to Professor H. D a h n for his encourage-
m e n t a n d advice a n d to Professor J.-C. Bunzli for helpful discussions.
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CHAPTER 8
Synthetic applications
of diazonium ions
D. S. WULFMAN
Di~pnrti?icritof Clrrmistry, Uiiiwrsity of Missoitr-i-Rolln, Rollu,
iMo 65401, U S A , a n d
Eqiiipe rlc Rcclierclre No. I 2 rlic CiV R S , Lnbor-utoire rlc Cliiitiic,
Ecole Norninle Sitpc'r-icitr-c,Paris, Fraricc
I. INTRODUCTIOS . . . 248
11. REAcnoNs OF ARYLD l ~ Z O ~ t u IONS hi . . . 250
A. Class A : Derivatives Formed by Substitution o r by Changes in the Sub-
stitueiits of the Aryl Nucleus . . 252
I . G r o u p 1 : Electrophilic substitution . 252
2. G r o u p 2 : Solvolysis of substituents o n the aryl nucleus . . 252
3 . G r o u p 3: Exchange of diazonium anions with substitucnts of t h e a r y l
nucleus . . . 255
B. Class B. Derivatives in which t h c Diazo Group is Involved but Remains
Functionallv Intact . . 256
I . G r o u p i : Metallic diazotates a n d diazoanhydrides. The use o f iso-
diazotates or nitrosaniines as stabilized diazo compounds . . 256
-.7 G r o u p 2: Diazocthers . . 258
3. G r o u p 3 : Diazocpanides. diazocarbouylic acids and related compounds 259
4. G r o u p 3 : The Diazosulphonates, their preparations, reactions a n d use a s
stabilized diazo compounds . . 260
5 . G r o u p 5 : Diazopcrhalidcs . . 260
6. G r o u p 6 : Diazosulphides. . . 260
C. Class C:'Dcrivativcs in which the Diazo Function Disappears but the Diazo
Nitrogen Atoms Remain in the N e w Molecule . 26 1
1. G r o u p 1 : Diazo-amino and -iinino compounds or triazenes . . 26 1
2. G r o u p 2: Oxidation products . . 266
3. G r o u p 4 : Reactions \virh nitrogen bases. T h e formation of aryl azides . 266
4. G r o u p 6 : Azo compounds formed by coupling reactions (C coupling) . 266
a. Coupling at active CH, and C H Groups . 268
( i ) Esters, acids and their derivatives . 2 69
( i i ) Nitriles, nitroparafins and sulphones . . 270
( i i i ) Kclones . . 270
(iv) T h c Japp-Klingeinann reaction . . 27 1
(v) Coupling with tropoloncs . . 273
5 . G r o u p 7: Complcxcs of aryl diazonium a n d alk1.l diazonium ions and
diazo compounds with transition metals . 274
D. Class D : Typc B Ring Compounds in which the Diazo Nitrogen has bccn
lost. T h c Pschorr Typc Syntheses . . 276
1 . Subclass a : Diazo nitrogen retained . . 277
a. G r o u p 1 : Cinnolincs . 277
b. G r o u p 2 : lndazoles . 278
c. Group 3: Benztriazolcs . 279
24 7
248 D. S . Wulfman
d. Group 4 : Benztriazines . 250
C. Group 5: Renzotliiadiazoles . . 285
2. Subclass b: The diazo nitrogen is lost . 285
a. Group 6: Thc Pschorr type synthesis and its hctcrocyclic analogucs . 285
E. Class E: Dcrivatives Formed by Replaccnicnt of the Diazo Group . 286
1. Group 1 : Replaccnicnt of the diazo group by hydrogen . 286
2. Group 2 : Replacement of thc diazo group by halogens including astatine. 288
a. Replaccmcnt by fluorine. . 288
b. Replacemcnt of the diazo group by chlorinc and bromine . 289
c. Rcplnccment of the diazo group by iodine and astatine . 290
3. Group 3 : Rcplacenient of the diazo group by nitrogen-containing
functions through formation of a ncw C-N bond . 290
a. The formation of nitro compounds . 29 1
b. The formation of azides . 29 1
4. Group 4 : Replacement of the diazo group by oxygen. Forniation of
phenols, phcnol cthers and phenol esters. . 292
5. Group 5 : Replaccnicnt of the diazo group with for'niatio'n of a' C-C bond 292
a. Formation of aryl cyanides . 292
b. Formation of symmetrical and asymmetrical biaryls . 293
c. Arylated quinones and other unsaturated species including hctero
aromatics and non-classical aromatic systems. The Meerwein reactions 294
6. Group 6: Rcplacement by groups in which attachrncnt occurs through
sulphur, selenium or tellurium . . 295
7. Group 7: Rcplacernent of the diazo group by arsenic, antimony and
bismuth. . 296
8. Group 8 : Replacement of the diazo group by mctals . . 297
111. ALKYLDIAZONUM IONS . 297
IV. BENZYNES, HETARYNES A N D OTHER DIDEHYDROAKOMATICS . 305
V. CYCLOALKYNCS 312
VI. REFERENCES. 313
1. INTRODUCTION
The treatments in this a n d the following chapter will in m a n y cases be rather
selective as a conscqucnce of thc sheer volume of material reported o n a n a n n u a l
basis a n d the large n u m b c r of reviews which have covered various aspects during
the past 20 years. (Reviews a r e marked with a n asterisk in the References.) In t h e
areas dealing with the alleged generation of carbcnes a n d carbenoids from diazo-
alkanes t h e a u t h o r has refrained from employing thcsc terms, f o r as Kirmse h a s
cautioncd655,a n d the a u t h o r has recently shown'3o'. l 3 l o , the assignment of rcactions
to thesc categories rcsts predominantly o n a house-of-cards. I n only a vcry few
instances can assignments be made with a n y degree of rigour.
N u m e r o u s cxaniples a n d studies have probably been ovcrlooked, f o r the species
a r e sufiiciently coninion a n d their reactions so frcquently eniployed t h a t t h e processes
have n o t been abstracted a n d a r e not detectcd by key word searches. I n these
instances the examples chosen reflect only a bias on the part of t h e writer for reading
literaturc related to his synthetic a n d pcdagogical needs a n d not a feeling that a
particular workcr's contribution is unworthy of enslirincment. T h e a u t h o r has tried
to cover all literature abstracted through Octobcr 1975 a n d all m a j o r journals
which were in his h a n d s by that date. I n addition he has tried to enlist thc aid of
many workcrs w h o h a d published in thc area d u r i n g thc preceding 2 years. Their
responscs arc too nuiiicrous to acknowledge fully but rcsults were m a d e available
to him prior to publication by Aracknl. Eistcrt, Doyle, Brokken-Zijp. Carrie, L. a n d
Y. Vo-Quang, Hubert, Woolsey, Marchand, Moss a n d Rossler. T h e i r kind aid is
8. Synthctic applications of diazonium ions 249
gratefully acknowledged along with that of S. Julia who made his extensive notes
on diazo alkane chemistry available to the author.
Thc origin of diazo chemistry dates from the initial gcncration of diazonium
succinamic acid from asparagine by Piria991wn 9 2 in 1849. I t had only a transient
existence and proceedcd to malic acid. Much chemistry has been performed on this
class of compounds which furnished onc of the major bases for thc foundation of the
modern chemical industry. Modern synthetic chemistry is normally assumed to bcgin
with the work of Johann Peter Griess4'G in IF58 when he undcrtook to clarify t h e
observations of Gerland12g(1853) that a red intermediate was formed i n increasingly
greater proportion at lower teniperatures whcn arninobenzoic acid was converted
to hydroxybenzoic acid by the action of nitrous acid. His studies, like Gerland's,
were undertaken at the suggestion of Kolbe and followed the earlier observation by
HuntzZ6in IS49 that treatment of aniline with nitrous acid generated phcnol. G r i c s P
modestly attributed his successcs to the fact that he operated at a lower temperature
than H u n t of Gerland. He studied thc reaction of nitrous acid with picramic acid (1)
and obtained the diazoxide (2) which he quickly rccognizcd as belonging to a new
class of compounds. He immediately procecded to subject many othcr amino
compounds to the same treatment. H e prepared the first azo coupling product in
1861-624s1. and by 1865-66 i t was being prepared on a large scale by Caro??G.
250 D. S. Wiilfnian
Griess continued his work for 3 years when he was Hofrnann’s assistant in London
and afterwards while working i n a brewcry for Mcssrs Allsopp, Burton-on-Trent.
He was faced with the need for CI-lN analyscs and overcame the problem by
developing a barter system with R. Schmitt in Dresden. Hempel’s account is of
interest: ‘Regelnirissig kainen von Burton an den Ufern des Trent die von Greiss
dargestellen neuen Korpcr in klcinen Packeten, um in Dresden a n der Elbe analysirt
zu werden. Per Fraclit kamen dann wohl gleichzeitig als willkomniene Beilage
F5sser von Allsopp’s beruhmten Pale Ale i n ausgesuchtester Qualitat.’ Griess’s
investigations were very thorough and he discovered many of the reactions of aryl
diazonium ions which had been observed up until the time of his death in 1891.
Thus, by 1908 (50 years aficr his initial work) chemists had a rather thorough
knowledge of the chemistry arid structure of aromatic diazoniurn ions although
work still continues in the area. The accuracy of many of the observations is all the
more impressive when i t is remembered that thcse progresscs were realized without
i.r. and n.m.r. spectroscopy, X-ray structure determination and only very crude
u.v.~O’. I3I3 and visible spcctra20 studies.
The first important studies in the aliphatic arca after Piria’s initial work occurred
in 1853 when Curtius prepared diazoacetic ester (4)275* 237. Diazomethane was
prepared by von Pechrnann1217in 1594. T h e use of copper salts with aromatic
diazoniiirn salts was examined by Sandrneyer1Og1.l:jaG in 1884, and GattermannllC
substituted finely divided copper powder for its salts in 1890.
A great resurgence in diazoalkane chemistry occurred i n t h e 1950’s when groups
led by Alder“ and D ~ e r i n g ” rcinvestigated
”~ the structure of the esters and acids
obtained by BuchnerlG9,?21- 222 from the decomposition of cthyl diazoacetate in
benzene(3-9). Further impetus was gained from the production of ‘evidence’ that
decomposition of diazoalkanes proceeds via ‘carbcne’ interniediatcs. Additional
interest arose from the increasing demand for sypthetic pathways for strained
hydrocarbons, the study of 1,3-dipolar cycloaddition reactions and studies related
to examining t h e reliability and validity of orbital symmetry calculations.
The chemistry of alkyl diazonium ions has long been the object of a variety of
mechanistic and synthetic studies with the synthetic efforts being primarily directed
towards exploiting rearrangements of the Tiffeneau-Deinjanov type (10 -’12) and
the rcplaceinent of amino functions by various substituents. Most recently, research
in this area has bcen directed towards the generation. isolation and use of diazotates
as synthetic interrnediatcs and the continued development of improved means of
changing amino functions to other functions.
II. REACTIONS O F ARYL DlAZONlUM IONS

Thc reactions of aryl diazoniuni ions have been systematically classified by
Saunders1Io3. His classification system Lvith minor changes is adequate and will be
used here. I t is summarized i n thc Table of Contentst for this chapter and is used
with thc permission of the publisher.
The formation of diazoniuni ions is the subject of another Chapter in this book
and will not be dealt with further. Saundcrs1103gives a very detailed discussion of
the subject with appropriate references.
The aryl diazonium ions are of varying stability. Their stability is strongly
influenced by the pH of the solution, temperature, the anions present, trace
contaminants such as transition metal ions and the presence or absence of water11o3.
Except for Class C, Group 3 (Reduction products) a nd Group 5 (S-azo products--

diazo-thioethcrs) which are treated in othcr sections.
8. Synthetic applications of diazonium ions 25 1
In the solid state some aryl diazoniurn salts exhibit appreciable stability whereas
others are quite brisant explosives. There would appear to be no basic guidelines
which predict stability without exceptions but it is possible to make some
generalizations. It is highly probable that diazonium salts where the counter-ion
is a reasonable oxidizing agent such as nitrate’I6, perchlorate1Io3,
chlorate1103,etc. will not exhibit a high degree of stability. Conversely siilphates
tend to be more stable as are the However, the bchaviour of
p-diazobenzene. sulphonate is notoriously fickle and some workers have found it
quite dangerous1I0. Diazonium ions which have a potential leaving group orrho to
the diazonium function are potentially dangerous because they can form ‘benzynes’
with the o-carboxy and o-SO,- compounds being at t h e extreme end of the scaIe5’0.
In these cases fragmentation furnishes two neutral molecules, N, and CO, or SO,,
all with high heats of formation. There are several diazo derivatives which have been
patented as explosives. Thus 4,6-dinitro-2,1 -diazoxidPI has been used as a
detonator which is less sensitive to friction than mercury fulminate o r lead azide
but equal or superior to both as a detonator. One should be suspicious of any
h I
0--
--
ul
W
0
z
I2
€ - Diazotates
Maximum i Range in which

stability I stabilization can
be reolized by using
stabilizers sulphona tes
Maximum
stability obtainable
with added sulphonates
- I-Diozotates
35
-
0 7 0 14 0
PH
FIGUREI . Reprinted (with permission) from Saunders, Thr Arornufic Diuzo Compouridr,
2nd ed., Edward Arnold, London, 1949.
252 I). S. Wulfman
compound having sufficient oxygen to convert more than half of t h e carbon atoms
present into CO and/or a C/N ratio c3. All dry diazonium salts should be con-
sidered suspect until clearly demonstrated a s being stable and then they should be
treated with respect. In aqueous solution decomposition of benzene diazonium ion in
strongly acidic media is independent of the anion (Cl-, Br-, SO:-, NO;)1128. 1130. 309, 5 0 6
and proceeds according l o t h e expression16e.221, 2 2 2 , In k = 35.6457 - 27025/RT.
C a i r ~ " ~found that the rate of decomposition fell a t very high pH values. The
overall trend in stability has been siimmarized by Saunders"03 in Figure 1. Snow1160
compiled a list of 32 diazonium chlorides arranged in order of their stability at
20 "C but there appears to be no obvious correlation of structure with stability.
It had been claimed that negative substituents increase stability"03 but the data d o
not support such a
Some metals form double salts with diazonium ions and retard their decomposition.
Similar effects occur upon addition of aryl sulphonic acids7so. and on the addition
of sodium chlorideso6,llD0, b o r a t e ~ ~ t~~'n~g,s t a t e s ' ?and
~ other neutral salts. Excess
nitrite and nitrate is as is the presence of colloidal
and of copper and its 133.
The diazonium ion salts of strong acids are essentially JOO% ionized and therefore
are comparable to K or N a salts in their degree of hydrolysis, but unlike these metal
ions they d o form stable covalent bonds with such nucleophiles as RS-, -OH and
-CN. The resulting products will be discussed under Class B reactions.
A. Class A: Derivatives Formed by Substitution or by Changes in t h e Sub-

stituents of t h e Aryl Nucleus
1. Group I : Electrophilic substitution
Although diazonium ions are of only moderate stability it is possible t o perform
some substitution reactions upon t h e aryl nucleus. This is facilitated by the fact that
the -N+ ion is the strongest electron-withdrawing group encountered in organic
chemistry and acts both inductively and mesomerically. i t is not surprising that in
the benzenoid systems t h e diazonium compounds most prone to electrophilic
substitution are the diazooxides which are formally neulral molecules. With poly-
annulated systems, electrophilic substitution occurs in a ring not bearing the -N:
function13G3(Scheme 2).
2
SCHEME
2. Group 2: Solvolysis of substituents on the aryl nucleus

When diazotization of an urrlru- or para-substituted aniine is carried out, there
is always the possibility of the solvent, normally water, replacing a labile substituent
to form an u- or p-diazoxidc. This can be prevented by operating in a highly acidic
medium where the activity of the water is greatly suppressed by protonation and if
the substituent is P chloride or bromide, by using HCI o r HBr. Meld~la'''~ and
colleagues examined these processes in great detail and found that normally two
electron-withdrawing functions should be present o n the initial amine and preferably
@""'-
in a n orrho and/or para relationship to the departing group. Under such conditions
HONO
OZN H*O
-02N6N
HONO
HOAc
N2
HONO
HOAc
OZNQ OCH, OZNQ OCH,
SCHEME 3
NO2 can leave a s nitrite ion. Anisoles can even be solvolysed in acetic acid to
furnish the diazo oxide. The failure to solvolyse in the last example is to be predicted
on the basis that none of the required Wheland intermediates (Scheme 4) for
replacement of NO, places charge (PMO analysis)?"~282 upon more than one
starred atom bearing a n electron-withdrawing substituent. With the replacement
of the OCH3, t h e required Wheland intermediate places N : on an unstarred position
and the driving force is not present. T h e rule appears to be that the leaving group
must be on a carbon which furnishcs a Wheland interrnediatc where the Ni and
one other strong electron-withdrawing substituent are present on starrcd atoms.
Such a treatment is equivalent to the rules of Meldola and Hay7*$.When NO, o r
254 D. S . Wulfman
OCH, can serve as a leaving group NO, is jost's5. An amusing feature of the displace-
ment of NO; is that once i t begins, the amines furnish the HONO needed to carry
out the diazotization.
Subsequent to formation of tlic diazonium ion, it is often possible to replace a
labile substituent which has withstood the initial reaction conditions. This can be
realized by employing a base such as an alkoxide or hydroxide. In these cases the
requirements for positioning electron-withdrawing substituents are not as stringent.
T h e processes are often quite rapid compared with othcr reactions. The attempted
reduction of I ,6-dinitro-2-naphthalenediazoniumion with alcohol under reflux
failed and furnished instead the 2,1 - d i a z ~ x i d c ' ~Sulphonic
~. acid groups can be
replaced114G and the yield is improved by oxidizing the resulting sulphite ion to
sulphatc with hypoch1oriteio6 or hydrogen p e r ~ x i d e (Scheme~ ~ ~ - ~5 )~. An
~ extensive
SO,H 0
SO,H SO,H
(24) (25)
"QBr H O1A c '
wNHz
wN2 Br
fir
(2)
(1) H,O
HONO/HOAc>
0
6r
(28) (29)
SCHEME
5
investigation was performed by O r t ~ n ~ ~who * - compiled
~~~' a table of the relative
degrees of completion under standard conditions. He found that Br was a better
activating and leaving group than CI, that the replacement of a halogen by NO,
improves the reaction and the total number of substituents in the 2 + 4 + 6 positions
should bc >, 2. The data nicely correlate with a simple PMO analysis. The study of
t h e resulting diazooxides from these displacement reactions has received con-
siderable attention because they undergo many coupling reactions to furnish
o-hydroxy-azo systems capable of forming metal ion complexes.
In a few cases i t is possible to replace carbon substituents on a n aromatic ring in
the course of, or immediately subsequent to, diazotization. E l i ~ n found~ ? ~ that the
usc of the Witt method of diazotization12g' led to t h c replacement of a carbonyl
function by a nitro group in a series of 3,5-dibromo-4-aminophenyl carbonyl
compounds and that bromine was replaced by nitro in 3,5-dibromo-2-aminobenzoic
(Scheme 6).
X
I
I I+
NH,F~o,
+ N:
(30) (311
X = CO,H, CHO or COCH,
SCHEME 6
3. Group 3: Exchange of diazonium anions with substituents of the aryl

nucleus
Hantzsch and othersJ9, 4 5 2 , 4.55-1.57, 493, 498, 501, 605, 5 5 3 , 1128 found that a few diazonium
salts were capable of exchanging anions betwcen the -N2 function and the aryl
nucleus. The process was not reversible. As in the case of solvolysis, Br- was a
better leaving group from t h e aryl nucleus than CI- and these are probably only
special cases of type A-2 reactions. Although one might write a concerted con-
version of 35 to 36, i t is not possible to account for 37 going to 38 in a concerted
fashion and a p-Claisen mechanism would be required for the transformation 39
to 40.
N,SCN $cl-
(35) (36)
+
bSCR
N,SCN N,Br-
Br J& ’ Br
(37) (38)
8 -8
+
N,SCN N,CI-
CI SCN
(39) (40)
7
SCHEME
356 D. S. Wulfinan
6. Class €3: Derivatives in which the Diazo Group i s Involved but Remains
Functionally lntact
1. Group I : Metallic diazotates and diazoanhydrides. The use of iso-
diazotates or nitrosamines as stabilized diazo compounds
The history of diazonium ion chemistry is not lacking in conflicting interpretations
of data and as such makes fascinating reading for anyone interested in the develop-
ment of bonding theory and structure elucidation. C u r t i ~ s noted
* ~ ~ in 1890 that a n
earlier structural assignment of Griess'sJ1e 4 2 where he postulated that acidification
of KON2C6H5furnished free diazobenzene, CGH,N2,was incorrect. The salt was
subsequently shown to be the so-called is0 S ~ I ! ' ~ (45) which is also known as the
stablc or artti salt. The normal salt (43) is also known as the syrz or labile salt. Their
early history is treatcd by Gain??' and the modern (i.e. present) interpretation is
summarized by Z ~ l l i n g e r and
~ ~ ? by
~ Laing'OO. The equilibria can be summarized
as in Scheme 8. In accordance with current nomenclature t h e isomers should
Z-Diazohy d r ox ide I-Diaz o t at e

8. Synthetic applications of diazoniiim ions 257
probably be classified as Z for syn and E for nnti. The question as to whether the
a,iti-diazohydroxide is a n azohydroxide or its tautomer, t h e nitrosamine, has not
been adequately answcred. There is reason to suspect that some assumed iso-
diazohydroxides are nitrosamines while others are anti-diazohydroxides.
T h e important synthetic features are: syn-diazohydroxidcs give the same typc of
coupling reactions as diazonium ions; anti-diazohydroxides are stable to coupling
but slowly cleave with acid to liberate the free diazonium ion. Clearly the position
of equilibria and the structure of the i s 0 compounds lie buried under a combination
of substituent and steric effects and should be resolvable.
Iso-diazotates are normally formed by one of thc methods given i n Scheme 9.
H
I
H
I
(50)
SCHEME
9
When diazonium salts or syn-diazotate solutions are neutralized to a pH range

5.5-7.5 the diazoanhydrides arc formed. These are highly explosive, are converted
by acids into diazonium ions and by bases into syn-diazotates.
258 D. S . Wulfman
CI
(55)
CH,CHO
(58)
ci
(57)
SCHEME
10
2. Group 2: Diazoethers
T h c diazoethers occasionally result from failed coupling reactions306 but they are
normally prepared by alkylation of syrz- or anti-diazotates. Since the ions are
ambidentate [ArN=N-6 ++ ArN=N-Ol it is not surprising that aralkyl-
nitrosamines are occasionally formed. T h e N a and K salts of the p-nitro compound
furnished the nitrosamide with methyl iodide whereas the Ag salt yields the
ether50, 6 2 , 182, 485, 487, 490, 1249.
8. Synlhetic applications of diazoniuni ions 259
3. Group 3: Diazocyanides, diazocarboxylic acids and related compounds
Two forms of diazocyanides arc known, E and Z . and the structural assignments
are probably correct since they are sufficiently stable to permit a variety of trans-
formations. A related isonitrile has been15!l, 224. 298. 500. 503. 7 2 2 , 728. 738, 1175, 1326 prepared
by a n 'unequivocal' synthesis. Thc synthesis requires the slow addition of the
cyanide solution of the diazo compound in excess acid while the temperature is kept
low. T h e Z isomer is formed first and this slowly rearranges to the E isornerpgD~ 5oos
In the prcsence of excess cyanide the formation of a n arcnediazoniumcyanide-

hydrogen cyanide complex occurs408.4 s g , I n some cascs the isomeric arylazo-
carbonimidoylcarbonitriles are
The Z isomer is normally lower melting than the E isomer. both are unionized,
coloured and water insoluble. T h e isornerization to thc E isomer occurs
spontaneously in the melt, in solution or in sunlight. T h e ease and extent of
isornerization are subject to steric and eixtronic effects. The 2 isomer couples
and in the presence of Cu furnishes the nitrile.
An earlier that one isomer was the isonitrilc was disproven1l0l,11'J2
through the synthesis of the isonitrile by generating i t from AgCN and by
dehydrating 1 -aryl-2-formyl triazencs with pyridine/SOCI, to form the isonitriles.
CN CO,H
I I
N N
y4 N4
H:O
-OH. H '
CONH,
I
0'
X'
(67)
SCHEhlE 13
260 D. S. Wulfrnnn
T h e E nitriles undergo hydrolysis of the CN function to furnish the related acids.
The CN function can also be converted into the CO,R and CONR, f u n c t i ~ n s ” ~ ~ .
T h e carbonamides react with H 2 0 2 to furnish the azoxy derivatives’ 9 8 4 - 9 8 6 and ‘ 9
cleave with alkali to furnish d i a z o t a t ~ s ~ ~ ~ ~ .

T h e aniides undergo a somewhat general process when treated with cold concen-
trated hydrogen halide in aqueous media. The halogen enters the pnrn position to
furnish a p-halophenylhydrazidocarbonylamide1’z90. The reaction occurs with other
groups of similar electronic character, e.g. 2-pyridy1, 4-pyridyl. 2-pyridyl-N-oxide,
4-pyridyl-IV-oxide, benzoyl, C(NH,)=NOH, C(OH)=NOH, C(CH,)=NOH,
C(NH2)=NNHBz, C(NHp},)=Nph 7 4 , 186, 259, 2 6 0 , 43R. 496, 617, 635, 976, 1029, 1030, 1290 but
does not occur with azobenzenes1290.
4. Group 4: The Diazosulphonates, their preparations, reactions and use

as stabilized diazo compounds
Ciazonium ions couple with N a 2 S 0 3to furnish both labile and stable derivatives
of the form ArN2S03Na with bonding through sulphur to the terminal diazo
nitrogen53, 5 4 . 5 8 , 157, 158, 2 2 1 , 299, 392, 3 9 3 , 1 8 3 . 4 9 0 , 1 8 8 , 4 9 1 , 4 8 7 , 499, 553, 5 5 5 , 6 6 5 , 7 2 7 , 1103, 1115, 1231, 1222
T h e reaction involves sulphite ions and not bisulphite280and if the pH is too high,
diazotates and other undesirable by-products are formed. If the medium is too
acidic, reduction occurs484.493. Both the Z and E isomers can be reduced to the
related hydrazines. T h e stable compounds do not couple but d o react with chlorine
and bromine to furnish the diazonium halides; thcy are also cleaved by lead nitrate
and silver nitrate. T h e originally formed labile isomers isomerize extremely rapidly
to the stable form but they can be isomcrized photochemically to the labile
formGIC, 1337, 1344, 1 3 4 7
I n a chemically similar reaction, aryl-sulphinic acids couple with diazonium salts
t o furnish sulphones (ArN: + Ar’S0,H --> ArSO,Ar‘+ H+) logo.Diazonium salts
also react with alkyl and arylsulphonamides to furnish ~ u l p h o n e 318; s ~ ~syn-diazo
~~
cyanides have also been found useful for this type of coupling with sulphinic acidsso0.
T h e mixed alkyl-aryl-diazosulphones decompose by a homolytic path in solvents
such a s benzene a n d hetcrolytically in highly polar medialo3. The product mixtures
from the honiolytic react ions were SOz,biphenyl, azobenzene and phenylazobenzene
(14 : 3 2 : 3 : 2). In polar media (acetonitrile) a 71% yield of acetanilide was
When thc benzyl derivative was employed in benzene, SO2,benzaldehyde
plienylhydrazone, IV-benzyl benzaldehydephenylhydrazone and biphenyl were
obtained (66 : 55 : 6 : Z)500. An earlier showed that phenyl benzene-
diazosulphone furnished primarily biphenyl, benzenesulphonic acid and only 5%
of the diphenyl sulphone.
5. Group 5: Diazoperhalides
Diazonium halides react with halogens and mixed halogens (e.g. ICI) to furnish
compounds of the type ArN2XX‘X” (X = halogen) ’Io3. These compounds contain
active halogen and are most probably of t h e form ArN:X;; as such, they are
reasonable halogenating reagents. Wher, boiled in alcohol they furnish the aryl
halide179. Treatment of the aryl diazonium perbromides with ammonia offers a
route to aryl azides4G3.
6. Group 6: Diazosulphides
As a conscquencc of extensive studies by Brokken-Zijp arid her Dutch
colleague^^^^^ much of the chemistry of this class of derivative is now clarified
and will probably serve as a foundation and model for studies on related systems.
van Beck'223has developed a general synthesis for a number of E and Z diazo-
sulphides. An alkanethiol was allowed to react with an equivalent amount of the
diazonium fluoborate in acetone at 0 "C and aqueous sodium hydroxide w a s added
over a period of 1 h. The isomers either crystallized from solution or were extracted
with benzene. Afler 2 h at 90 "C in isooctane, thermal equilibrium between E and Z
isomers was established. The correctness of the structure assignments have been
verified for some compounds by Br~kken-Zijp'~',who also examined the action of
light on both the E and Z isomers. Operating at 405 nm in methanol, pure E or
pure 2 lead to mixtures of both. At 300 nm, E isomers and decomposition products
(sulphides, disulphides) were obtained. Irradiation of the pure E isomer at 300 n m
generated only the Z isomer. The 4-cyano-, 4-nitro- and 3,5-dichloro-4-dimethyl-
amino benzene diazo-r-butyl sulphides and phcnyl diazo-r-butyl sulphides were
studied.
The term 'diazosulphide' as employed by S a ~ i n d e r swas ~ ~ by hiin to
~ ~ used
describe diazothioanhydrides (ArN,SN2Ar') and ArN,SR instead of only the latter
as employed in t h e current Iitcrature. T h e thioanhydrides arise from the reaction
of neutral diazonium salts with hydrogen sulphide. The thioanhydrides couple with
alkaline p-naphtlio15Gand furnish the biaryl upon heating in refluxing benzenes6.
Some of the thiodiazoanhydrides are cxtreniely unstable and even explode under
water at 0 "C 334, 561, '352.
T h e diazosulphides are inore stable than their oxygen analogues and fail to
couple or cleave with cold acids or bases. They d o decompose thermally via a
honiolytic process*225.
If H,S is passed into acid solutions of aryl diazonium ions, the main product is
the aryl-diazoniunithiol hydrosulphide (ArN,SH. H,S).
C. Class C: Derivatives in which the Diazo Function Disappears but the

Diazo Nitrogen Atoms Remain in t h e New Molecule
1. Group I : Diazo-amino and -imino compounds or t r i a z e n e ~ ~"03,
* ~ '326
*
The reactions of arene diazonium ions with amines date from Griess's initial
studiesJa8where he obtained 1,3-diphenyltriazene by reacting nitrous vapours with
a n excess of aniline. The process is favoured by neutral conditions and is suitable
(69) (70) (71)

SCHEME
14
for reactions with aromatic or aliphatic amines. With aromatic arnines in which
either aryl unit has a vacant para position, treatment with acid leads t o coupling
with the aromatic nucleus. In addition, equilibration is rapidly reached between both
isomers and with acid, cleavage to all possible diazonium and ammonium ions
results. Such a situation is simplified by blocking a para position.
This sensitivity to substituents is sufficiently great that nzeta-toluidine undergoes
C substitution rather than N c o u p l i ~ i g ~ ~ .
262 D. S . Wulfman
With primary aliphatic amines, bis coupling frequently occurs and 1 ,S-diaryl-
3-alkyl-pentaza-l,4-dienesresult. It is possible to generate the aryl alkyl triazenes
by adding a cold neutral solution of the diazonium salt to a cold solution of the
amine in the presence of sodium carbonate. The resulting triazenes are moderately
stable. In the case of the methyl and ethyl p-tolyl systems, useful reagents for
esterification of carboxylic acids result301.435, 764. D93-995* lzE1,
1z83.
This method of esterification offers some advantages over diazoalkanes. Most

notable is the ability to generate tertiary esters in modest yields. These are not
available from diazoalkanes. With secondary amines, only a very small degree of
rearrangement is observed.
In the course of decomposing the secondary derivatives, extensive alkylation of
the aromatic nucleus occurs. The process proceeds with a high degree of stereo-
specificity and retention of configuration even when the alkyl s o u p is a-phenethyl.
T h e simple monoaryl triazene, C6H,N,NH2, does not arise by the reaction of
the benzene diazonium ion with ammonia but is generated by reduction of phenyl
azide with stannous chloride in ether302.G r i e ~ s ' ~d82
* . obtained a n explosive substance
from ammonia and diazobenzene. Von P e ~ h r n a n n 'ran ~ ~ a~ similar reaction with
p-toluene diazonium ion and ammonia and obtained p-C,H,N,NHNpC7H,-p. The
structure was verified by methylation which gave the same compound obtained from
methylamine. I n Griess's original attempts he obtained C,,HSN2CsHpNH2.
(84)
16
SCHEME
H
I
-
- -
RNN=NAr A N,+R.+ArNH- Products
H
I A
ArNN=NAr Ar-N,+ArNH. Products
(90)
SCHEME 17
264 D. S. Wulfman
T h e reaction of the bis aryl triazenes with acids furnishes a phenol, nitrogen and
a n amine. T h e reaction gives two phenols and two anilines when asymmetric starting
materials are employed. In the presence of copper(1) salts and halogen acids, the aryl
halide is formed in place or partially in place of the phenol. T h e amino nitrogen is
sufficiently electron poor in bis aryl triazenes t o render the hydrogens acidic and the
sodium salts are known754.T h e systems also are sufficiently good ligands t o permit
formation of platinum465,~ u p r i cnickePO, ~ ~ ~ , mercury1271and palladium755complexes.
T h e bis aryl triazenes and alkyl-aryl triazenes decompose thermally by a homolytic
proce&O7, 638, 642, 820, 848, 851, 1024-10?Ue
T h e coupling of diazonium salts with hydrazines and hydrazones normally
-
leads to formation of tetraZeneS1Dg. 377, 378. 5 1 3 . 578. 761. 7 6 2 . 1113. 1337, 1304. A variety of
other triazene reactions is summarized by
RNHNH,+ArN: ArN=N-N-NH,
I
(911 R
(92)
H
I
R,C=NNAr+Ar’N: ___f R,C=N-N-N=N-Ar’
I
(93)
(95)
Y = Y N r -I- H,NNH, 1
N =N
)-N=N-y-y-N=N
N ,N-N H H N-N,
H H
(97) (98)
18
SCHEME
T h e diazo tetrazol (97) is reported to couple with hydrazine in a manner not

observed with the benzene diazonium ion to form the hexazadiene (98)572. 577.
Tetraryl hexazadienes can be prepared by oxidation of diary1 triazenes. T h e products
undergo slow decomposition to azobenzenes (99 -> 100 -+ 101).
When 1,3-diaryl tetrazenes are oxidized with permanganate ion, explosive com-
pounds believed to be octazatrienes are obtained (102 --z 103)1305,
1306. The chemistry
of nitrogen chains of three or more N atoms is reviewed in S i d g ~ i c k and ~ ~ lin
~
Smith115g. Lieber and Smith730 have discussed poly-aza systems derived from
aminoguanidines.
When diazonium ions condense with aryl or alkyl hydroxylamines, triazene
oxides or their tautomers the hydroxy triazenes result. These compounds undergo
both N and 0 alkylation.
6;'"acl ~
CI
CI
(99) (100)
If 4-substituted aryl diazoniuni salts are treated with methyl hydroxylaniine

hydrochloride and sodium carbonate a t 10 "C, l-aryl-3-hydroxy-3-methyl triazenes
(104 -+ 105). When ethyl anthranilate is diazotized and treated with
(1) aq. HCI

(2) NaNO,/H,O
(3) CH,NHOH. HCI/Na,CO,
I
N
\N
I
H,C
AOH
(105)
SCHEME
20
alkylamines, the related triazenes are generated. These in turn are converted smoothly
in refluxing ethanol or over basic alumina i n t o 4-0x0-3-alkyl t r i a z e n e ~ " ~
(106 --f 107 -+ 108).
0
(107)
SCHEME
21
266 D. S . Wulfmnn
This is in striking contrast with the results with diazotized anthranilic acid
(89 + 90).
The oxides also result from peracid oxidation of triazencs. This latter approach
leads to both possible isomers (1 and 3) when asymmetric triazenes are employed
although the presence of an electron-rich aromatic system favours the oxygen ending
o n the N adjacent to the electron-ric11 systcmSS,60. 61. 68, 69, 79. 131. 136, 31.1. 327. 805. 8 0 6 , ' 0 2 8 .
2. Group 2: Oxidation products

In addition to those oxidation processcs mentioned in earlier sections the
diazonium function can be oxidized. Both Z and E diazotatcs undergo oxidation
to furnish aryl nitroamines. Ferricyanide, hydrogen peroxide and permanganate
have all been used under alkaline conditions's~12', 373. lluG~ ,1'2s
3. Group 4: Reactions with nitrogen bases. The formation of aryl azides

Azides have been the subject of a monograph in this series"$. Diazonium per-
broniidcSJS9, plumbochlorides239 and i o d o ~ h l o r i d e s react
~ ~ ~ with ammonia to
furnish azides and diazonium salts react with azidc ion to furnish aryl azides,
presumably via intermediate pentazoles and pcntazatrienes.
A route to aryl azides known as the 'Dutt-M'armall Reaction' involves the action
of an aryl diazonium ion upon a sulphonamide such as p-tolucnc sulphonamide.
T h e method is theoretically only 50% eficient in aryl diazonium ion since a second
molecule couples with the liberated sulphinic acid1s1. 318. The reaction of azide
317s
ion with diazoniuin ions is treated as a Type E process.
4. Group 6: Azo compounds formed by coupling reactions (C coupling)

The coupling of aryl diazonium ions with phenols and aniines to furnish azo
dyes is not a majcr subject of this review but has bcen treated with a fair degree of
thoroughness in texts by Fieser3'0 and by Nollcrssu*'.
We shall therefore limit the trcatnient hcre to some of the lcss well-known
coupling processes and a brief treatment of the common coupling reactions.
Coupling to form C-azo derivatives received extensive attention from chemists
almost from thc time that diazonium salts were discovered and lead to the develop-
ment of the chemical industry in Germany with a heavy emphasis on thc synthcsis
of dyes. Almost all azo dyes are prcpared by the coupling process. The dyc-forming
reactions are normally performed in aqueous media and the reactions are p H
dependent. Many compounds will couple in acidic media as well. The general p H
limits are 3.5-7.0 for aryl amine substrate and 5.0-9.0 for phenols. An cxamination
of the stability graph for diazoniuni ions reveals that this is thc same p H range where
the stability is at a minimum. In gcncral coupling occurs \vith phcnols, aryl aniines
and activc niethylene compounds. lncludcd i n this group are such non-classical
aroniatic phenols as the tropolones and proteins.
The aromatic arnines couple in the para position byhen a n aniline is involved but
otherwise couple in thc position of maximum electron density and minimum AE=
as prcdicted by a simple P M O analysis'3'. Thus rJ-naphthyl amine couplcs i n t h e
I-position and not thc 3-position. Using the P M O analysis (Scheme 27) quickly
leads to an explanation of why 1,3-dianiino benzcnes are more reactivc than the
1.2-isomers or the aniltnes. The same analyses hold for phenols and polyhydric
phenols.
T h e reaction is obviously facilitated by net electron-donating groups (negative
Hammett u values) and hindered by those groups which are net elcctron withdrawing.
Since the anilines couple in the para position exclusively, the presence of substituents
at that position stops t h e reaction from occurring unless strong activation of an
ortho position is operating. With hetcrocyclic aniines such as aminopyridines,
coupling is not a very facile process because of the inherent inertness of pyridines
to elcctrophilic attack. The presence of a and 'x' amino substituents increascs the
activity of the y position towards attack. A PMO analysis would secrn to indicate
that (3 substituents should be more effective.
H2N
It
SCHEME
22
T h e coupling of aminoquinolines has been examined in some detai11°5' with

benzenediazonium ion as the electrophilc (Table 1).
TABLE
1
Coupling at Triazenc" C-4 N.R." -C-6, C-8 C-5 C-8 C-5

Amino function at C-2 c-3 c-4 c-5 C-6 C-7 C-8
aTriazcne = coupling w i t h the amino function of thc aminoquinoline. N.R. = no
react ion.
With aminophenols coupling can, in principle, be controlled by either functional

group since the pH dependence of the coupling reaction is different for phenols and
anilines. This can often be realized and a number of examples 367- 369- J20.
4 2 4 , 1061.
T h e coupling with proteins primarily involves the three amino acid units froni
tyrosine (117), histidine (118) and tryptophan (119). This phenomenon was behind
I
H
(117)
SCI4EXIE 23
a process employed for dycing silk. Thc obvious biochemical applications of the
reactions have not been overlooked. Since sevcral amino acids have functionality
capable of forming ArN,-X-R units (where X is a n aniino or thiol function)
coupling is not limited to proteins containing tyrosine histidine, tryptophan or
related units.
268 D. S . Wulfrnan
Unlike the anilines, phcnols can couple in the orrho position as well as the
normally more reactive para position. Occasionally the position of coupling in
naphthols is dependent upon t h e diazoniuni ion employed. Thus 1,Sdihydroxy-
naphthalene is attacked a t the 2-position (counter to t h e PMO analysis) by diazotizcd
o-aminophcnolsulphonic acid but a t the 4-position by diazotized anthranilic
a. Corcplirrg at actiue C H , and CH groicps. Therc is a large number of compounds

which possess active methylene groups and, not surprisingly, a large proportion
have been subjected t o diazonium-coupling conditions. Some examples include
acetoacetic ester"", nitroethancigi, malonic estcrig6, acetone dicarboxylic acid1244,
P - n i t r ~ a c e t o p h e n o n e ~ glutaconic
~~, acetoplienone-~-sulplionic acidgfiD,
many cyclic 7 3 5 , pyrazolines201,510, ll0I, 1233 and the nitroparaffins48.
361, 798, 709, 801,1??1.
The coupling products frequently exist as the hydrazones if the hydrogen replaced
is borne on a -CH2-- or CH,- unit. This point was the source of considerable
controversy6?. 172- l i 3 , 343, 611, 124J, and one should probably treat some of thc
7n6s
related literature with a degree of caution. The processes can be cxceedingly complex
and furnish a variety of products. Thus coupling of phcnyl diazoniuni ion with
nitromethane furnishes n o fewer than 12 33s. 362. , one of which
llP5 lolqs
results from rearrangcmcnt while recrystallizing from refluxing e t h a n 0 1 ~ ~~~

1145.
The overall processes can be conveniently subdivided into those occurring when
a hydrogen is replaced in a formal ~ n e t a t h c s i and
s ~ ~ those
~ ~ of the Japp-Klingmann
type where a radical is split off such as an acyl or carboxylate function1nJ4
(equations 1 and 29n1).The processes have been well studied and by 1958 ovcr
H
I
ArN,X+R-C-H I__- z ArNHNCR,+HX
I
R
H
I
ArN,X+R-C-R ----+ ArNHN=CR,+LX
I
L
700 pertinent rcfcrcnccs could be found@".g y l . The niajor determinant rclative to

whether a n aryl diazoniurn species will replace a hydrogen is the activity of t h e
hydrogen and not tlic nature of the diazoniuni spccics.
Normally the reaction will not occur w i t h ketones lacking some additional
activating group, and tvith attack on a methyl group there is a strong tendency
to generate a forniazyl ketoneio.p 7 . 124.16. Similar behaviour occtirs with nitro-
niethancS9?, 113'2,. 1115.
0 N,Ph
--
1
I I
CH,COCH,+P N: Ph > CH,C-C=N-NHPh i3)
CH,NO,+2 N+ Ph Ph-N=N-C-NO, (4)

II
N-NHPh
The forrnazans undergo ;1 fairly general cyclizatioii reaction whcn treated with
strong acids such as sulphuric acid. T h e process kno\vn as the 'Eaniberger Triazene
Synthesis' furnishes benzo-1 ,2,4-triazenes2. 02, 43m4 6 , . T h e chemistry of formazans
has been
Benzenediazonium chlorides couple with 2-benzoyl-2-cyano-thioacetanilidesin

aqueous ethyl alcohol to furnish 2-arylhydrazono-3-0~0-3-phenyl prop ion it rile^^^^.
(i) Esters, acids and their derivatives. Simple acids d o not generally undergo
condensation but a-keto acids (e.g. pyruvic) d o react. With pyruvic acid t w o molecules
of diazonium salt are consuinedP7in direct analogy with acetone and nitromethane.
9-Keto acids undergo loss of carbon dioxide a n d if an excess of diazoniuin ion is
used a second molecule will reactJ3. 610, 1055. Similar results accrue with acetone
dicarboxylic acid1244.
lZa8.
0 0
I
Ph
G o o d yields of the mono hydrazones can be obtained by employing the esters

and o n c equivalent of the diazonium salt but if 2 moles of diazonium salt are
employed with acetoacetic esters, a second diazo group enters with loss of the
2 70 D. S. Wulfman
acctyl group7G.
. A similar phenomenon occurs with diethyl oxalo-
1032, 1033. 1293
1033, 12g3, where the second mole of diazoniuni ion leads to ejection of a n
ethoxyalyl group. According to Parmerter these are the only t w o groups which a r e
susceptible to loss when attack is on methylene. Other leaving groups are of course
encountered with the Japp-Klingemann reaction (cide infin). Coupling also occiirs
with acetacetanilides and nialonimidesl4-17, 1%. '244, 36R, ,402, 1O:I. 1131, 1162, 1'281
It is not particularly surprising that malonic acid, like nitromethane, is capablc
of multiple reactions involving I , 2 or 3 moles of the elcctrophile with both tiiotzo
- -
and bis products resulting from the reaction with equivalent amounts of
with monosubstituted malonic acids, his substitution readily
occurs~os.1259.
CH,(CO,H), ArNHN=CHCO,H ArNHN=CH-N=NAr
(133) (134)
___j ArNHN=C(N,Ar),
(135)
SCHEME 27
A limited number of reports of arylacetic acids and esters reacting with diazonium
ions exists. The reaction goes moderately wcll with the 2,4-dinitrophenylacetic acid
a c d its derivatives (appareniiy as il consequcnce of [lie highly electron-\\~ithdrawing
aryl group). The acid reacts twice with loss of CO? whereas the ester consumes only
1 mole of diazonium ion.
(ii) Nitriles, nitroparaffins and sulphones. The cyano function also can serve as
an activating group and a variety of dinitriles, F-cyano-carbonyl compounds,
(3-sulphononitriles, (3-nitronitriles and (3-iminonitriles undergo attack by aryl
diazoniuln j o n s l 1 3 , 1.15. 2 5 0 , 273, 338, 311, 3 4 6 . 384, 7 0 5 , 738, ; : I , 1 1 1 4 , 1172, 1173, 1 2 1 1 , 1113. 1 2 d 0 , 1273
Sulphones33, 2 1 8 , 59'2, 1211, 1 2 1 3 and nitrOpar;lffinSJR,71. 19:. 4 3 4 , 580. 613. 907-1001 are also
quite reactive. Hydrazones are the normal products resulting from attack of a
methylene group. Subsequent attack of aldehyde hydrazones derived from activated
methyl groups are responsible for thc formation of his aryl diazo-derived products.
The reactions when carried out as two-step proccsscs are good synthetically and
furnish f o ~ n i a z a n s ~1317- " ~ l3l5.
- ~ ~ The
~ ~ aryl hydrazoncs of g,(%diketobutyric esters
and a-kcto-acids undergo attack by a second molecule of aryl diazonium salt in
processes formally analogous to the Japp-Klingeniann reactioiP. 73* 13$- (OG. 713.
1034, 1 0 7 4 .
Bcnzcnediazoniuni chlorides couple \v i l l i 2-benzoyl-2-cyano-thioacetanilides i n

aqueous alcohol 10 furnish 7--arylliydrazo1io-3-oxo-3-phcnylpropionitriles~~'~.
(iii) Ketones. Aryl diazonium ions attack ketones bearing an electron-\~,ithdra~~ing
group to the carbon (r to t h e carbony1 groupIU0, 101, 120, 111, 2 4 1 . 2 8 1 . 2 9 7 . 310. 599, 6Ou. 7 0 3 .
7 O G , 7 3 1 , i$D, 7 x 7 , 1057, 1 ' 5 1 , 1283, 1'294, I395. The reactions are o n occasion rather varied.
Thus t h e oxalylindene (136) undergoes simple while its benzo
analogue (138) undergoes a Japp-Klingemann reaction7O6 as does the pyridiiie
derivative (140) which furnishes a formazan1OS7.
ArN;
moEt
(1 40)
0
ArN:
Ar
SCHEME 28
(iv) T h e Japp-Klingemann reaction. T h e Japp-Klingeniann reactionuH1 has found

extensive synthctic application. The processes differ from those discussed above in
that only a single active hydrogen is replaced and a functional group attached to the
carbon atom being substituted is lost. The reaction strongly resembles formal
-
attack by + N O 1208. (This parallel occurs in transition metal chemistry as well,
uirlc itifrfm.)
R
I
ArN, + H-C-X ArN,CRR'
I
R'
29
SCHEME
272 D. S. Wulfman
The nicclianisni of both processes undoubtably involves initial generation of a
stabilized c a r b a n i o ~ i ~ ~ ~then
- attack by t h e diazonium ion to furnish a diazo
derivative which can then cleave by nucleophilic attack upon the potential leaving
group followed by ejection of the product, its tautomeric form or the stabilized
anion of the product.
Ar
I
The enhanced stability of both of t h e final products (the desired product plus the
final form of the leaving group) may serve as the driving force for the reaction117.17;*
190-202, 251, 300, 303-308, 336, 338, 3.13, 3 4 $ , 390, 512, 513, 515, 510, 6 8 2 , C20, 733, 8 0 2 , 1121, 1123, 1132, 1137.
1140s1115+ 1237. 1238, 1250. 1302. If we extend this general mechanism to the J a p p
Klingemann reaction using a general refinement suggested by DewarZgofor ester
hydrolysis, we obtain Scheme 30.
Normally the Japp-Klingemann reaction requires two or even three electron-
withdrawing substituents such as carbonyl, cyano, nitro or sulphonyl groups being
present. However, electron-deficient aromatic systems such as fluorene, pyridine,
quinoline and dinitrophenyl can scrvc as activating substituents as can the halogens.
Halogen rarely serves as the leaving group. Perhaps this is a consequence of the
fact that normally the leaving g o u p is attacked by a nucleophilc and with halogens
this requires a formally positive halogen. Hence one would predict that the tendency
for loss of halogen should be expected to occur in direct parallel with decreasing
electr~negativity~'~. 341. This interpretation accounts for the apparent anomalous
behaviour of 3-bromotriacetic lactone12*8 (148). Acetoacetic esters undergo the
0
PhN:+ fi r\H
+/
0
tN'
0
Bi:OH,
Ph
___f
(149)
SCHEME31
8. Synthetic applications of dinzoniuni ions 273
Japp-Klingcmann reactioii with the loss of the acetyl group and thc resulting
products are N-substituted derivatives of csters of dchydro amino acids. Reduction
offers a ready route to the amino acid esters and treatment under Fisher-indole
synthesis conditions furnishes indolesl, .la, 128, 174-176. 180, 321, 347-330, 352-351, 356-300, 525, 58.1,
610, G l l , 683, 734. 1136, 1185, 1 2 G O
With 1,3-diones, similar behaviour is observed and one has a route to a-amino
339. This approach is complementary to the use of p-tosyl azide in a diazo
transfer process which furnishcs the a-diazo ketone which can also be reduced to the
related a n i i n ~337, ~ ~I 3,l 1 .
T h e Japp-Klingemann reaction of 2-carboalkoxycyclanones offers a ready
source of o-carboxy a-amino acids and of 3-(alkyl-o-carboxy) indoles. Since the
starting materials are readily available by a Dieckmann cyclization or by reaction
of the cyclanone with diniethyl carbonate, this offcrs a very ready route to both
s y s t e r ~ i s 2BG,
~ ~ 355.
~e 51ae7 3 3 . A n interesting variant on this approach employs a 2-acyl-
butyrolactone. Subsequcnt ring opening can be performed with a variety of
*I6].
nucleophiles to furnish lactones, esters or hydroxy
\
COOEt
(v) Coupling with tropolones. T h e tropolones are prone t o coupling with

diazoniurn ions. T h e reaction is of sufiicient reliability to permit its use as a
diagnostic tool for the presence of a substituent at C-5. The processes offer rcady
routcs to 5-amino tropolones via subsequent reduction-“61, 308. 619-521, 639, 071, 910, 912,
274 I). S. Wulfmnn
013, 0 1 5 , 0 1 7 , 0 ? 1 - Y 5 , 9“. 930. U31, 9 3 4 , 937, 938, 1135,
I3l3. The reaction is somewhat sensitive
to steric cffects and both 4-isopropyl and 4-i-b~ltyltropolone fail to couple91y.
H H H
The presence of halogens a t positions 3 or 3 and 7 grcatly decrease^^^^. 926 the

reactivity of the tropolone. For the test to be fully valid, it is necessary to perform
the reduction step, for 5-met hyl, 5-hydroxy, 5-halo and 5-isopropyl tropolones
furnish coloured conlplexes which are cleaved by reduction without introduction
of thc amino f u n ~ t i o 0n1 3~. 9 2~G ,~030.
~ 935, 942. Several other 5-s~ibstitutedtropoloncs
fail to form y16, 0 3 0 .
5. Group 7: Complexes of aryl diazonium and alkyl diazonium ions and

diazo compounds with transition metals
Until relatively recent times o n c might have dismissed out of hand t h e possibility
of isolating and characterizing transition metal coniplexcs of diazoniuni ions or of
diazo compounds. This was a direct consequence of the fact that many transition
metals catalyse t h e decomposition of both diazo and diazonium ions. There are of
course a number of old examples \vhere aryl diazonium salts formed double salts
with coniulex ions of such metals as platinum and mercury, but in those cases the
diazonium ion was serving a rolc similar to that of a n alkali mctal cation. During the
past 1 1 years a sufficient number of aryl diazoniuni-transition metal complexes
have been isolated and characterized to warrant a review with over 100 references11g3.
With diazo compounds, the nunibcr of examples is somewhat more limited, but in
both cases well-documented examples now exist where the -N, function serves as
a ligand with bonding to t h e metal occurring through the terminal nitrogen. The
fact that bonding occurs through the nitrogen is probably the cause of their stability.
There is reason to believe that the loss of nitrogen from diazo alkanes in the presence
of metal catalysts proceeds via attack on the diazo carbon1312.
T h e nomenclature which has been used to describe these complexes in the
literature is not uniform. Thus the terms ‘arylazo’, ‘ a r y l d i a ~ o8G7,
’ ~ ~ ~ have
~ been
employed for the aryl complexes although the compounds can be named as
derivatives of d i i ~ n i n e ~diimideGo2
?~, o r d i a ~ e n e699.
~ ~Some
~ , workers have employed
the terms ‘hydrazido d i a n i ~ n ’ and
~ ? ~ ‘phenyl hydrazido dianion’;‘j6 to describe the
protonatcd complexes. It is perhaps unfortunate that ultimately the arrogance4O4
of Clrernicul Abstracts will probably dorninate1lQ3and the dinzene nomenclature will
be employed and the I.U.P.A.C. proposed term, aryl dinzennfo will not become
fixed in the literature. T h e use of dinzonnto (aryl or alkyl) would appear even more
logical and consistent with the fact that the term diuzo has been used for 11 1 years.
8. Synthetic applications of diazoniuni ions 275
This term has been in usc for at least a hundred years before the American Chemical
Society took upon themselves the rolc of final arbitrator for Chemical
N o r n e n ~ l a t u r e4~0 1~, 96".
~.
T h e coniplexes appear to fall into two basic classes: those in which the -N2
function formally furnishes thrce clectrons to thc mctal to satisfy the 18-electron
requirement of filling the valcnce shell, and those which formally furnish a single
electron to satisfy the IS-electron requirement. These groups can be identified by
X-ray crystallographic analysis of the M--N-N bond angle. The three-electron
donor situation leads to angles in the range 170-179" 29- 234. 3 1 3 , 59E, ' ~ 7 and
~ the
one-electron donor system leads to a bond anglc of 125.1" S ~ t t o n "has
~ ~discussed
the bonding theory which leads to predictions of 180" and 120".
There is a very limited number of alkyl-diazonato complexes and structural
analysis by X-ray is lacking. The spectroscopic parameters presented are totally
consistent with the claimed structures.
\
COOEt
(163)
35
SCHEME
T h e formation of the diazoiiato complexes is most commonly realized by direct

reaction of the diazo compound or the diazoniurn salt with a complex (ionic or
neutral) with or without the displacement of an existing ligand.
0c / YcoO-\Co
10
276 D. S. Wulfrnan
N,C(COOEf),
,Mo,
OC I N,C(COOEt),
co
- -
Pt(PPh,),+ArN,X ___t ArN,Pt(PPh,), X-
(178) (179)
PtHCI(PEt,),+ArN: ArNHNPt(PEt,),CI ArN,Pt(PEt,),CI+H +
(180) (181) (182)

SCHEME
36
T h e number of diazoalkane complexes with transition metals is small. For a

summary of the aryl diazonium based complexes readers should see S u t t ~ n " ~ ~ .
T h e aryl-diazonato complexes tend to be basic at the nitrogen adjacent to the
metal atom11Q3and undergo protonation o n nitrogen. However, since they are
prepared a s ends rather than intermediates, their chemistry is not well characterized.
D. Class D : Type 6 Ring Compounds in which the Diazo Nitrogen has been
lost. The Pschorr Type Syntheses
Detailed discussions of several of these classes of heterocycles have appeared in
the form of monographs and as such will be described only in terms of their syntheses
unless there exist additional diazo- or diazoniuni-type reactions. These reactions
a r e treated below. The chemistry of the members of groups in which the nitrogen is
lost are not of concern here and we shall only treat their generation from diazonium
compounds. There are obviously other means of obtaining many of the products
which d o not involve diazo or diazoniuni chemistry and standard references and
reviews cover most, if not all, alternate methods.
Y. Synthetic applications of diazonium ions 217
In recent years thc chemistry of aromatic systeins has increasingly been relegated
to the briefest of treatments in standard textbooks. This is perhaps a reflection of
t h e amount of research activity in the area or the simple increase in the total amount
of material covered. As a direct consequence t h e chemistries of diazonium ions
normally discussed in beginning texts are the reactions in Class E and coupling with
an occasional reminder that certain orrho-substituted anilines arc not suitable for
diazonium reactions. The chemical reason behind this bccomes evident when one
notes that the so-called 'forbidden' groups are potential nucleophiles ideally located
adjacent to electrophilic diazonium groups. This proximity effect means that
systems incapable of bimolecular reactions may well be capable of unimolecular
cyclization. The orflio function need not of itself be a nucleophile or have nucleo-
philic character if the conditions of the reaction can cause the substituent to generate
a transient intermediate capable of serving in that role. Thus a n enolizable ketone
can readily fulfil the role of an ethylene.
1. Subclass a: Diazo nitrogen retained

a. Group I: Cimolines. T h e presence of a vinyl group in the orrho position of an
aniline or other aromatic primary amine may lead to the formation of a
cinnoline378, 964, 1252. 127G upon diazotization. The configuration around the vinyl
group need not be cis for both cis and /ratis 1,2-disubstituted ethylenes can
participate'2H5.The basic reaction shown in Scheme 37 has some limitations which
HONO
E H 2 A
(1) HONO
(2) CH,NO,/cold dil. - O H R
I
CO,H OH
A
HONO
Ql$rco2H
278 D. S. Wulfman
have been detailed by Simpson128s.He has concluded that when R = H or C0 2 H
and R’ = aryl, the reaction does not occur. I f R = aryl, R‘ can be aryl also. When
R‘ = aryl, thcrc is a possibility that a Pschorr condsnsation will
289, 603, 6 2 1 (Scheme 38). This process is discussed in detail under Group E, Class 5 ,
R R
Q
(1 93) R’ =
R=
(194)
38
SCHEME
reactions. The synthesis of cinnolines from o-vinyl diazoniurn ions is known a s the
Widman-Stoermer SYntheSiS12, 25, 1 1 7 , 161, 102, 4 7 3 , 723, €344, Y65, 1120, 1123, l H 7 , 11PM. 1150, 1170.
1285; from o-acy] diazonium ions as the Borsch synthesis13. 28. 634-636. 683, 7 2 4 , 0 4 5 , 1117. 1122,
and from o-alkynyl diazoniurn ions as the Richter 1116s 1121, 1163, lZs2.
BaumgartenQohas modified the Borsch synthesis as shown (185 -+ 187 -+ 188).
b. Groicp 2: Induzoles. In certain cases a methyl, methylene or methine group is
rendered sufficiently acidic by substituents to make i t a potential C acid. When
this occurs adjacent to a potential diazonium ion, cyclization may occur to furnish
3-H-benzpyrazole which may if a hydrogen is at C-3 rearrange t o furnish the
1-H-benzpyrazole (indazole) (Scheme 39). T h e presence of electron-withdrawing
,:@R HONO
R’ @ NHz -
R6
(1 96)
SCHEME
39
groups as R1, R?,R3, R5 will facilitate the reaction65. 818, However,
there exists the possibility that the resulting indazole will be coupled to unreacted
diazonium compound if there is a n electron-withdrawing group a t C-6(R5) or
C-4 (R3)but not at C-5 or C-7 (e.g. Scheme 40).
I
H
The difference between the two substrates would appear to be a consequence of

the 6-nitrobenzpyrazole having a more basic C-3 due to contributions from the
anilino nitrogen. This would be strongly suppressed by electron-withdrawing groups
in the 5- or 7-positions.
c. Groirp 3: Borztrimoles. Bis-diazotization of ortho-diamino systems is extremely
difficult, and under a wide range of diazotization conditions they afford
triaZOleS7,148, 330, 330, PGR-470, 567, G32. i O R , 813. 815, 0 0 3 , IOiR. 1103, 1 1 2 7 , 1219, 1267, 1321, 1323, 1325
The reaction was discovered by Hofmann in 1860 when h e worked with nitro-o-
~ ~ . driving force is sufficiently great that acetylation of
p h e n y l e n ~ d i a m i n e ~The
one nitrogen does not prevent the reaction and mono-alkylation has no effect.
Asymmetrically substituted o-phenylene diamines may lead to t w o isomeric triazoles.
At the time of their discovery, a debate as to structure occurred between Griess
and his adherents and Kekule and his. Much research was directed towards
preparing and isolating both isomers. K e k ~ 1 e . sstructure ~~~ (204 a n d 205) would
lead to two products, Griess's to one (206) OG9.
280 D.S. Wulfman
Finally, Morgan and colleagues81J.815. 1321 prepared the two N-acetyl derivatives
of (204) and (205). The former was known as the a-isomeride and the latter the
P-isomeride. Unequivocal syntheses were employed and the argument was closed
by their hydrolyses to furnish the same ‘compound’ (mixture) which on
reacetylation furnished a mixture of the a and P acetyl derivatives with t h e
a-isomeride being predominant. They claimed that they were able to separate the
two triazoles which had slightly different absorption spectra and did not equilibrate
in organic solvents. The question of which tautomer is dominant in these systems
has been extensively examined using modern instrumental 7041 95’.
1003, llG3.
When or/ho-amino diphenylamines arc submitted to diazotization conditions,

they readily undergo conversion to benzotriazoles. The triazoles were shown to be
thermally unstable by Graebe and Ullmann and to offer a ready route to
carbazoles103. ??Q, 442.
(208)
SCHEME
42
e6:
d. Group 4: Benz[riuzities. Normally diazonium ions will not couple with a n amide
to furnish a triazene but ihe intramolecular process occurs with great
601. 7 0 0 , 1loR, 1202. 1?70 (Scheme 43) and with a wide range of substituents for
0 0R‘
R -p
N2 ”
(210)
(214)
SCHEME
44
(216)
SCHEME
45
.
1dil. H,SO.. 4
Q$H
., K O H
0
(219)
Ag+ and Na+

salts
SCHEME 46
282 D. S . Wulfman
R and R' to furnish 1,2,3-benzotriazines. Examples are known employing bis acyl
hydrazides as we]] as diamides37'. 372, 531, 700. 7 7 0 . 73:, 93% 983 (Schemes 44 and 45);
diazoaniine esters2Jo.7 7 0 (Scheme 46) ureasBol;diazonium salt esters (Scheme 46)l3I6,
amino benzpyrazoles63, 6 6 , 6 7 , 416, 6 5 5 , 1272, 1 3 0 9 , 1310 (Scheme 46); amino benzamide
oxirnes (Scheme 49)"O. 990; cyano hydroxylamines (Scheme 47Ic3,66. 07, ; amino
oxirnes (Scheme 47)6J. 7 2 s 7 7 8 , l l n e ; amino benzyl aryl hydrazines (Scheme 48)'88;
amino benzyl amides (Scheme 48)13a2190-1'J3, 1017s l x 3 ., amino t l ~ i o a m i d e s ~ ~ ~ ~ ,
1 ,g-diamino naphthalenes (ScheIne 49)7. 329. 1086, 112'. 1258. 1359, 1355 ; heterocyclic amino
carboxaniides618; amino oriho-2-pyrazoles and amino oriho-5-pyrazolcs, their
ben?opyrazole 1212 (Scheme 49) ; rearrangement of a benzpyrazolo-
diazenege7(Scheme 50). Additional leads to 1,2,3-triazines are given in References
ozN@NHoH HoNo'
NC CN NC
1 Alhalt 1 Zn/HOAc
R
(237)
0
HoNo
R=H
Ky\ u R
HONO
R=Ac’ R
284 D. S . Wulfman
37, 138, 366, 403, 527-530, 640, 687, 811-813, 901, 1087, 1352 and 1353 and for
1,2,4-triazenes see References 364, 842, 905, 966, 977, 1284, 1286 and 1307. The
reaction of a diazonium ion with a cyanamide (Scheme 51)987 or I-aryl diazo aryl
hydrazines42, 0 3 , 46, 73, 77, 268, 363, 436, 437, 779-781, 863-866, 1350, 1370. 1380 (Schemes 51 and 52)
offer a route to 1,2,4-benzotetrazines. Syntheses with aryl diazo aryl diazonium ions
open routes t o 1,2,3,4-benzotetrazinese7* 633, 1320* 13*?. 1324.
SCHEME
50
-
H H
NC0,Et Ar Nz
Xylene
+ ArN-N
Na,CO, J
0
I
H
(2W (265)
(266)
SCHEME
52
T h e products of the type 244 are not aromatic in the heterocyclic system and
undergo coupling with P-naphthol and other phenols. As such thcy can serve as
disguised and stabilized diazonium intcrmediates. In general, substituents o n N-3
render the triazine ring systems susceptible to use as diazonium ions at elevated
temperatures. A number of syntheses depend upon the triazines and triazine
N-oxides as intermediatcs.
e. Groirp 5 : Bctizothindiazolcs. When p-aniino thiophennls arc subjected to

diazotization conditions they couple through sulphur to furnish the 4,4’-bis-
(arnin~phenyl)disulphides~~~~.When the orrho isomers are subjected to the same
conditions, cyclization to furnish benzothiadiazoles results.115.5 6 6 , 583. These

compounds participate in some processes charactcristic of diazonium ions. Hence
the nitrogen can be replaced by treatment with carbon disulpliidesg3 and as such
offers a route to aryl 1,2-dithiols.
2. Subclass b: The diazo nitrogen i s lost

a. Group 6: The Pschorr type synthesis and its heterocyclic annlogrtes. Although
~ O ~ down t h e various processes into subgroups, many of the
S a ~ n d e r s ~brcaks
reactions in the group are formally identical to the Pschorr Phenanthrene
synthesis?**. T h e reaction proceeds well with a varicty of grogps X, c.g.
C H = C H 1007-1023 -CH2-CH2- 1081, - S - 2 G P 3 , -0- 289 , -NR- 538.2, -co- 4 4 1
-CH2- 381 -se- 1019 -so2- 299, -SO,- I1Os3. The processes are probably
9 9
mechanistically very similar. A possible exception is the bis-diazotizaton of

2 , 2 ’ - d i a m i n o b i p h e n y l ~lo1’*
~~~~~
T h e nature of the intermediate had been the subject of somc speculation but
quite probably involves a bis(benzo)triazapinc which readily loses niirogen.112.
S a ~ n d e r s ”had
~ ~ proposcd that the react ion involvcd the tetra-azotizcd systcm
losing hydrazoic acid from a partially reduced system but this seems unlikely on
thermodynamic and electronic grounds. Chauncy and Gchlcrt have successfully
replaced the copper catalyst in the Pschorr synthesis with N ~ i t ~ ~ : ~ .
256 11. S. Wulfnian
Although the Pschorr syntheses formally resemble the Gomberg-Bachmann-Hey
syntheses, they differ in terms of experimental conditions. The former are normally
carried out in acidic media whereas the latter are invariably performed in basic
media. T h e Pschorr processes are homogeneous because the attacking species is
part of the substrate whereas the Gomberg-Bachniann-Hey reactions are hetero-
geneous. Thus the Pschorr syntheses possess the inherent advantage of decreased
entropy requirement.
A C0.H
72%
SCHEhlE 55
When a rigid bridge is incorporated, the configuration must be cis for closure to
occur. DeTar has suggested that the ethylenic bridge is perhaps the best bridge
avaiiable as a consequence of its rigidityz8"; with Irons bridging other processes
occur1oE?. He also noted that electronic factors seem to be of secondary impor:ance28B.
With t h e presence of o-hydroxy and p-hydroxy substituents, difficulties occur which
lead to the formation of diazooxides. The presence of ether or amine functions in the
orrho position can lead to extensive tar formation1217. When substituents are present
at t h e 3'- and 5'-positions, two possible modes of attack operate unless one of t h e
2'- (6')-positions is blocked. Since the processes exhibit only a small degree of
sensitivity to electronic effects, one will invariably obtain mixtures of products
when the possibility exists. However, when appreciably different A E n values are
to be expected, the P M O analyses will correctly predict the product to be generated.
E. Class E : Derivatives Formed by Replacement of t h e Diazo Group

With the possible exception of the coupling of diazoniuni ions with aryl aniines
and phenols, Class E represents the most widely known class of aryl diazonium
reactions and is very sketchily presented in nearly every basic text on organic
chemistry. The emphasis is normally placed upon replacement by hydrogen and the
four halogens and is usually limited to the Mai-Kornblum reduction, t h e Sandmeyer
reactions and the Balz-Schiernann reaction. Many other replacement processes are
known which are of great synthetic utility and have bcen the siibjects of chapters
in Orgatric Reactions and a variety of reviews. Copper and its salts are encountered
with a large number of the replaceinent reactions described i n this section. Each
valence state has associated with i t a name, Cu(0) Gattermann, Cu(r) Sandmeyer and
CU(II)Korner-Contardi. I t seems quite likely that in this case a single valence state
is actually involved. The Merck Index groups all of the processes under thc name
Sandmeyer reactions11GM.
1. Group I : Replacement of the diazo group by hydrogen

Classically, diazonium ions were rcduccd with ethanol and G r i e ~ s rnadc
. ~ ~ ~the
original observation in 1564 \vhen he obtained benzene, dinitrophenol and
acetaldehyde from the reaction of ethanol with bcnzenediazoniuni nitratc.
8. Syniliciic applications of diazoniuni ions 281
The processes are rclatively sensitive to conditions and reduction is favoured by
the presence of water, use of the diazotate rathcr than diazoniurn ion and the
presencc of clectron-withdra\~ingsubstitucnts in thc ortho position such as nitro
o r halogens or hydroxy. Hodgson"'9 had suggested that thc grcatcr the positive
character of the diazonium carbon, the greater the ease of replacement by hydrogen.
T h e validity of such a statcment might appear qucstionable in the light of current
theory since thc substituents included above encompass + E , - E and - I but all
are capable of stabilizing homolytic processes. The reaction is often accompanied
by thc formation of appreciable quantities of thc aryl alkyl ether which is in direct
parallel with the formation of phenols from watcr. When diazonium halides are
employed, aryl halides can become important products. This problem was overcome
by Chamberlain2J8 who employed alkaline conditions which generated diazo-
hydroxides or diazotatcs which furnished no ethers. Unfortunately, even this
improvement frequently leads to only moderate yields of the hydrocarbon. Parsons
and found that copper bronze improved the reduction of 4-methyl-
azobenzene-4'-diazoniurn sulpliatc and other workers have successfully employed
Cu(0) prepared in a variety of ways to facilitatc reduction by alcohol^^^^^ 5 5 2 . 120G.
Under the best of conditions, reduction with alcohols is not a good reliable
method and this led to a search for alternative reducing agents. F r i e d I a n d e P ,
Bamberger and Mei~nberg'~, E i b n e F " . and Hantzsch and VockS0' investigated the
use of sodium stannite in aqueous media and found it effective. The E diazotates
d o not reduce with sodium stannites0'. As noted previously, acid reduction with
tin furnishes the hydrazine. Surprisingly, diazotized ethylamino gallate is reduced
by stannous chloride to ethyl gallatelOOJ. Two rarely used reduction techniques
which may actually have promise are alkaline sodium pyrosulphiteJJJ and hydro-
quin~ne~ B ~r e~w. ~ t e ravoided
~ ~ ~ the ether formation process and obtained good
yields in the naphthalene series. Other methods include the use of a l ~ m i n i u m ~ ~ ' ~
in ethanol solution and cuprous oxide in alcohol or formaldehyde G50,
7 4 0 , 1079
The most widely accepted reduction technique, the use of hypophosphorous acid,
is due to Mai7IGand has been rated by Adanis and Kornblum3 as the preferred
method. Yields range as high as 807< whcreas other methods rarely reach 60%
and are dependent to a large extent upon the ratio of diazonium salt to hypo-
phosphorous acid. Dificult reductions require as much as a 15-fold excess of
-
reducing agent even though the apparent proccss involves oxidation of 1 mole of
reductant to phosphorous acid.
ArN:+H,PO,+H,O ArH+H,P0,+H++N2 (5)
Cadogan?" has successfully replaced the amino function on a number of anilines

in a one-pot process involving treatment of the amine with excess pentylnitrite in
refluxing T H F or dioxan.
C,H,,ONO
A
'
Br Br Br 6 B r
288 D. S. Wulfmsn
2. Group 2: Replacement of the diazo group by halogens including
astatine
The replacement of the diazoniuni group by a halogcn has becn known since
1860417when Griess heated diazoaminobenzoic acid with concentratcd hydrogen
halides to obtain halobcnzoic acids. Gricss4"' later extended his studies to prepare
US
H0,C-ArN, HO,CArX+ N,+ R,N-ArCO,H+ R,NH,X (6)
representatives of all of the halogens by adding diazoniuni sulphates to concentrated

solutions of the hydrogen halide using rricta-carboxybenzencdiazonium sulphate;
he found that the yield was improved by incrcasing the halogen c ~ n c e n t r a t i o n ' ~ ~ .
This point was pursued further by others who added halide salts to furnish increased
Iialidc concentrations"'. 5 5 ' J . Cupric chloride was tlic additive of choice for preparing
p-chloronitrobenzcnc. Although the rcactions are normally run in concentrated
acidic solutions, Gricss45'. did observe that thermal decomposition of solid
salts such as the chloroplatinate and hexachlorostannate furnishcd the chlorides.
The most common solid salt decomposition is due to Schiemann and
Balzao. llU6, 1109- 11')0 which, with the improvements of Schwecten1131, provides a
331s
moderate scale route to aryl fluorides. The most widely known halogen and pscudo-
halogen replaccnient processes were developed by Sandnieyerlool-lloo.Sandmeyer
had been attempting l o prepare phenylacetylenc from copper acetylide and benzene-
diazoniuni chloridc and obtained some chlorobcnzene. He was able to show this
had ariscn from reaction with copper(]) chloridc. Subsequcntly, Gattcrmann4lG. 419
found that freshly prcpared copper powdcr (CuSO, + Zn) brought about the
formation of chlorobcnzene from bcnzenediazonium chloride. Ullmann121Gfound
that commercial copper bronze could also be cmployed.
T h e use of copper salts is not nceded for preparing aryl iodides and can
be accomplished by adding an alkali iodide to a diazoniuni sulphate or by using
H I 2 7 0 , 454, 466, ,467, 581, 626, 763, 1110, 1212, 1 2 9 1
a. Rcplacetmvit by fliioririe. AI though the gcaerally preferred method for intro-

ducing fluorine is the Balz-Schieniann reaciion ;,:id normally good to excellent
~ ~ ~ of
yields are obtained, i t is not free from d i ~ c u l t i e Some ~ ~these
. difficulties are
no! surprising, c.g. inadvcrtent rcplacemcnt of functional groups during the
diazotization step. A coniinon problem when solubilizing substituents such as OH
are present is difficulty in isolating the fluoroboratc salt. T o overcome this, other
pcrfluoro inorganic acids have becn examined and the hexafluorophosphates have
shown some promise bccause they arc extremely insoluble and PFS is a very weak
acidyoY3-I o a 4 . Thus the isolation of p-hydroxybcnzenediazonium fluoroborate is not
rcalizcd whilc the fluorophosphntc is obtained in over 75% yield. Unfortunately,
the thermal decomposition to furnish the fluoride is seldom better than the Balz-
Schieniann approach. Attempts to improve the decomposition of diazonium
fluoroborates have not becn overly successful. There is at least one report of tetra-
methylurea serving as the solvent of choice for decomposing diazonium hexa-
fluorophospliatcs1084.
Additives have been employed for a variety of reasons. Deconipositions of
nitro-aryldiazoniuni fluoroborates arc often difficult to control and neutral
diluents such as sand or even sodium chloride are often e m p l o y ~ d1063, ~ ~ llOG.
~,
Clearly thc use of salts with nucleophilic anions is a rishy approach since much of
the dccomposition occurs via heterolytic mechanisms. The use of alkali fluorides
c a n overcome the problem of additional nucleophiles but tends simultaneously to
- -
change the mechanism from heterolytic to homolytic by interchange of anionsgs.
ty
1
PhN,BF,+MF PhN,F+MBF,
(7)
PhN,F Ar-+F-+N, Products
The use of transition metal catalysts has also been claimed to lead to homolytic
processes. Copper(]) fluoride and chloride have been used witF some success when
there are n o highly polar substituents such as NOz, OH, C0,H. These are some of
t h e same substituents which lead to difficulties with uncatalysed reactions110.
Apparently the use of copper(1i) fluoroborate has not been examined even though
i t should be free from many of the objectionable characteristics of other systems.
The use of various solvents has been examined and the results arc frequcntly
consistent with a heterolytic process747-7so~ 878, 847, e.g. halobenzenes, nitrobenzene,
benzonitrile, diphenyl ether, trifluoromethyl benzene, acetophenone and methyl

benzoate. When benzenediazonium fluoroborate was decomposed in pyridine
solutions, the formation of 2- and 4-phenylpyridines were the dominant arylation
processes observed. These are most consistent with a homolytic process. In those
cases where homolytic processes appear to be occurring, the yields of fluorides are
always low.
When the Balz-Schiemann reaction is applied to diazonium ions to furnish
fluorides which are highly susceptible to nucleophilic attack, problems can arise in
workup. If a nucleophilic centre is already present, as in many nitrogen heterocycles,
t h e reaction can fail totallyg8.loBs* 1065. On occasion Pschorr-type cyclizations cause
considerzb!e difficulties3a6.
Danek, Snoble and Nouzova280succeeded in preparing the 0-,m- and p-fluoro-
phenols by diazotizing the aminophenols in 40% fluoroboric acid at - 10 " C . With
t h e 0- and p-diazonium salts the fluoroborates could be isolated in good yield and
decomposed t hermally as the dry salts, whereas the m-diazonium ion was destroyed
in solution (Scheme 57).
57
SCHEME
b. Replacement of thc diazo group by chlorine and bromine. T h e most frequently

employed method used to replace a diazo group by chlorine or bromine is due to
Sandmeyer and involves the diazotization of the related anilinium halide and
addition to the cuprous halide. There appears to be n o general trend in conditions
required and it is therefore necessary to optimize temperature and concentration for
t h e process under considerationz1. The best results are obtained when the diazonium
ion solution is run into the cuprous halide solution. This tends to minimize formation
of phenol and hydrocarbon coupling reactions. The diazonium ion appears initially
to form a complex with the copper salt which then loses nitrogen. The reaction with
cuprous chloride almost invariably gives excellent results when the conditions have
been optimized. A largs number of other metal chlorides have been investigated as
290 D. S. Wulfman
sG3 but coppcr appears to
alternative sources of halide ion and catalytic zctivityss4~
occupy a unique position in diazonium chemistry. Waters1269has ascribcd this to
the oxidation potential of copper(1).
CI
SCHEME 5 s
With bromine, the Sandmeyer processes are complemented by the use of a

complex double salt such as (ArN,),HgBr, 8 8 5 - 8 s 5 . which is thermally decomposed,
by hydrogen bromide decomposition of the diazonium bromide with or without
copper o r its salts being present, and by the decomposition of the diazonium
perbromides. Various copper([) complexes and salts have been used when troubles
have been encountered2GG- 2 i 1 . 272.
l ~ ~ salt pyrolysis is a n extension of Griess's earlier work and
S c h w e ~ h t e n ' s ~double
has been used to some advantage by Newman884.885 who recommends employing
twice a s much mercury salt as employed by Schwechten.
Griess used the perbromidesJS4.Q 6 4 to prepare the aryl bromides. The diazonium
perbromides were used with sodium carbonate and the products were distilled from
the mixtures. In some cases no diluent is neededli9. N e ~ m a has n ~ diazotized
~ ~ the
anilinium bromide in hydrobromic acid solution by adding nitrogen trioxide until
the solution remained dark coloured, and then heated until nitrogen was no longer
evolved.
C. Repplacemetit of the diazo group by iodine mid astatitie. GriessJSr,,06, 407

discovered that replacement of the diazonium group by iodine was extremely
facile either in hydroiodic acid o r upon addition of a n alkali iodide. Waters12R2.
ascribes the ease of the reaction to the fact that the redox potential is near that of
copper(1) and that the process involves generation of .I: Normally the reaction is
mild although 2-diaaodiphenyl has proceeded explosivelys81.
The element astatine can be introduced into a n aromatic nucleus via the diazonium
astinide. Thus, at - 5 "C, o-halobenzenediazonium ions form complexes with
astinide ion which are subsequently decomposed at 80 "C to furnish, as the major
radioactive product, the corresponding l-halo-2-astinobenzeneiB~.
3. Group 3: Replacement of the diazo group by nitrogen-containing

functions through formations of a new C-N bond
It is possible to replace the diazonium group by a number of groups which result
in new C-N bonds but the only ones of wide synthetic utility are the introduction
of t h e NO2 and N3 functions. It is o n l y of academic interest to convert a n arylamine
into itself by generating the diazoniuni ion and then allowing it to react with
hydroxylamine to furnish a mixture of azide and In some cases this can
be accomplished by reaction with ammonia, presumably via the diazoamines which
undergo prototropy t o furnish the aniline plus nitrogen47J.1?s5, . I t appears that
neither reaction has any promise as a route for introducing labelled nitrogen. A
possibly more promising way of introducing labelled nitrogen is via the replacement
of the diazonium group by N C O in the presence of copper salts417.41R. Synthetically
this offers no special advantage over treating the amine with phosgene if labelling
is not desired.
a. The fornzatiori of nitro cot~ipont~ds.

T h e replacement by NO2 can be realized by
several paths including the Sandmeyer reaction, and the Korner-Contardi reaction
and the Griess replacement.
A number of copper derivativcs have been employed including Cu,O, finely
divided copper 1166- copper(i1) sulphate in conjunction with cobalt
nitrite complexes555, cupric chlorides94-6saand cuprocupric s ~ l p h i t e ~ all
~ * ,in the
presence of excess nitrite. In a number of cases the diazonium fluoroborate has been
decomposed with a copper salt in the presence of nitrite 1167.
Double mercury salts of the type (ArN2)2Hg(N02)2(N03)2 have been de-

composed in thc presence of copper derivatives. In line with Newman's observations
on the double salts with mercury one might suspect that the use of the
diazonium nitrite with an additional equivalent of mercury salt would prove a more
useful process.
In a number of cases, the generation of diazmium ions in the presence of large
excesses of nitrite ion leads to formation of the nitro compound directly. This is
most readily realized if the aryl group possesses electron-attracting substituents in
the ortho and/or para positions. The substituents can be electron donating in the
mesomeric sense, thus bromo and nitro substituents are both effectivelB7-16a- 955+
1088, 1207.
C,H,-N-N
I
1535%
\\
+ 15
c,H,N=N-N=N=N
+
(294)
=N=N
I5 + N,
SCHEME
59
b. The formafie;!gf azides. T h e aryl azides were known a s azoimino compounds
-
well into the 20th century and a s such have appeared in the literature since 1864
when G r i e ~ s ~450' ~ .reported that benzenediazonium perbromide reacted with
ammonia to generate phenylazoimine.
PhN: Br;+4 NH, PhN,+3 NH,+3Br- (8)
292 D. S. Wulfrnan
The same compound results when benzenediazonium sulphate is treated with
-
h y d r ~ x y l a m i n e745, . diazotization of p h e n y l h y d r a ~ i n e 732
~ ~ ~by ~ ~ ~or
. reaction of
-
hydrazine with benzenediazonium sulphate.
I
PhN; HSO,+NH,OH PhN,+H,O+H,SO,
(9)
PhNHNH,+HONO PhN,+P H,O
A very general synthesis is known which proceeds in part via the unstable pentazole
which loses nitrogen to furnish the azide. The synthesis was developed by Noelting
and MichePoolin 1893 but it was not until 1954 that evidence was obtained indicating
the formation of an intermediate pentazole along with a diazonium a ~ i d e587,~ ~ ~ .
T h e pentazoles are extremely unstable substances and their chemistry has been
reviewed by Ugi12158(see Scheme 59 above).
4. Group 4: Replacement of the diazo group by oxygen. Formation of

phenols, phenol ethers and phenol esters
One of the earliest reactions observed with diazonium ions was replacement by
-OR (R = H, alkyl, acyl). The formation of alcohols is a common reaction of
alkyl diazonium ions and is often an annoying side-reaction when aryl diazonium
ions are formed.
T h e alkyl diazonium reaction was noted by Piriaggl.gg2 in 1848 when he treated
asparagine and aspartic acid with nitrous acid and obtained malic acid. The
formation of phenol by heating an aqueous solution of benzenediazonium sulphate
was reported by Griess in 18665G0. The reaction was employed by Fisher in 1878 to
help elucidate the structure of the triphenylmethane dye, rosaniline, which has thrce
aniino groups which he replaced with h y d r o ~ y l s ~The ~ ~ .reaction is generally
successful and works well with tetrazotized biphenyls. Substituents d o affect the
with which the reaction o c ~ u r s 1 7 1 . 223, 225, 526, 6 4 1 , 806, 907, 1329, 1335, 1348, 1365. Care
must be taken to avoid a n excess of nitrous acid or nitrate ion since under the
acidic conditions of the process, the resulting phenols are often prone to
nitrosation or nitrationgo2.
The forniation of ethers from alcohols and diazonium ions is in direct parallel
with the reaction with water. The reaction is frequently accompanied by reduction
to the hydrocarbon. T h e two reactions compete effectively and often prevent one
from obtaining a good yield of the desired product unless care is taken to employ
the anhydrous diazonium salt. (There is however some divergence of opinion on
this matter. Thus in at least one case, 15% water was found permissible1053.)When
this is done, the ethers are often obtained in excellent yields. T h e reactions are
usually performed in refluxing a l c o h 0 1 ' ~950, ~ ~ 970, 1051-1053, 1141 but operating in a
pressure vessel to permit a n increase in temperature has been efficacious in several
instances793.Q 5 0 . g70, *OS0. 1052, 1053. IoJ1.
The reaction does not work well with phenols
where yields of less than 20% are common and they are accompanied by large
quantities of arylated plicnols242v571.
5. Group 5: Replacement of the diazo group with formation of a C-C

bond
a. Formation of aryl cyanides. In Section II.B.3 we have discussed the formation
of diazocyanides and their rcactions. Sandmeyerdo2- Iog3 demonstrated that treat-
ment of a diazonium salt with KCN-CuCN furnished aryl cyanides. Subsequently
a large number of aryl nitriles have been prepared in this fashion and the reaction
is now recognized as a simple variant of the Sandmeycr reaction with
halides8, 691. 0 8 8 , 1075, 1U80, 1004. 1125. 1218, 1351, 1362 . The yields arc often only moderate
because the initially formed 'labile' diazocyanidcs rapidly isomerize to the 'stable'
isorners which d o not decompose to furnish the nitrilc. Unlike the Sandmcycr
reaction with halogens, other metal coinplcxes can be uscd, in particular tctra-
cyanatonickel(1i). A claim has been made that its use is to be prefcrred over bis-
cyanato copper(1) 402, G91. Potassium tetracyanatoamniine coppcr(i1) has also bcen
employed to avoid the potential hazard of gcncrating c y a n ~ g e n ' ~ ~ ' ~ .
b. Formation of sytnmetricol und asyimietrical binryls. Diazoniuni hydroxides

decompose in aromatic solvents to furnish biaryls. The rcaction, known as the
Gomberg-Bachmann r e a c t i o P , proceeds by a frce radical mechanism and is
strongly paralleled by the related Grie\,e-Hey-Heil bron syntheses using aroniatic
nitrosamides which are decomposed in the substrate aromatic solvent3'. 2 s ' - ""* 'I8-
539, l103, 1326. Both provide a route to unsyinnictrical biaryls (Schcrne 60) and are
QNo2 -
mechanistically similar. T h e reactions have been reviewed. These proccsses offer
one of the best routes to unsymmetrically substituted biaryls and furnish ready
access t o rneta-substituted biphenyl when substituents are to bc in only one ring;
the related substituted aniline is employed along with the aromatic hydrocarbon.
Unlike electrophilic substitution, t h c products from substratcs such as nitrobenzene
are para substituted. This is not particularly surprising if one reniernbcrs that the
corresponding Wheland intermediates (298, 299) will be more highly delocalized
with para or ortho attack than with mefo (300). With substrates such as pyridine all
possible isomers result. T h e related unimolccular process involving the formation ot'
phenanthrene and fluorcnes is known as a Pschorr synthesis and has been treated in
Section D.2.b. The Gomberg-Bachmann reaction furnishes yields in thc poor to
good range (60 + % but infrequently higher). The Pschorr reaction (actually
discovered previously by Graebe and Ullmann441~ l " and Fischer and Schmidt3M1)
294 D. S. Wulfinan
being an intramolecular process can be expected to furnish good yields, 70-90:<
not being unusual. It should not surprise anyone to find that isomer mixtures result
when the non-diazoniiim ring system is asymmetrically substituted. Obviously the
presence of an ot.flio ethylene bridge causes the rnolecules to undergo some or even
dominant closure to cinnolines and related heterocycles. Thus all three of these
related reactions are subject to the same liniitations as are othcr o-substituted
diazonium ions.
A fundamental limitation of both the Gomberg-Bachmann and the Grieve-
Hey-Hcilbron syntheses is the need to employ the substrate hydrocarbon in the
liquid state. When this is combined with the desirability of having t h e substrate
molecule as the most symmetrical portion of the biaryl to be synthesized, very
strong limitations in scope arise. Since the reactions are normally run below 3 0 "C,
many formal processes arc just not practicable in the laboratory. The use of solvents
is not particularly encouraging since the aryl radicals generated can attack the
solvent as well. Thus when chloroform or carbon tetrachloride are used, appreciable
quantities of the aryl diazoniurn compound end up as aryl With sub-
strates such as pyridine, the dry diazonium salt can be added to the pyridineso7 or
by the reaction of the sodium diazotate with pyridine-acetic anhydride3Ru.
Alternatively the nitrosoacetyl derivative can be heated in pyiidine ~ o l u t i o n 518.
"~~~
C a d ~ g a nhas
~ ~ smoothly
~ converted aryl diazoniuni fluoborates to dihalo-
diazobenzenes by deconiposing the diazonium salt in 10% acetone 90% benzene at
room temperature using copper powder. If 2 mol of water are present, the biphenyls
result (Scheme 58).
C. Ary fated qiiitiancs atid other iinsaturoted species incliiditig Iietcro aroniatics atid
non-classical aromatic systems. The Afcetwcitr reactions. I t is possible to arylate
quinones, u,F-unsaturated carbonyl compounds, vinyl nitriles and styrene using
aryl diazonium ions. In the case of quinones and quinone oximes they are frequently
dissolved in acetic acid or alcohol and the diazonium salt is added at room
temperature. The evolution of nitrogen is normally complete in 24 h ??, 137. 'Oi.
1393
759, l o i l . 1103. When olefins are uscd as substrates, copper salts are normally employed
as 1330. This process has become known as the Meerwein reaction1071.
With many substrates two possible products c a n arise in principle, but a simple
analysis on the basis of which intermediate radical will be most stable usually
suffices to predict the correct product.
A large variety of olefinic substrates can be used and these include, vinyl
halides269, 079, 9 4 4 , acrylonitriles163,2 9 3 , ,195, 6 7 0 - 6 8 ? . 717, 751, 752, 1332, phcnylacetylenes766,
phenylpropiolic acidi6', acetylenen4$, c o ~ n i a r i n ~ 1332, ~ ~ ~ cinnarnaldchyde~~"',
767p
cinnamyl estersG84,
7
767 acrylic acidS702, 6 4 4 . 1036 butadienes15?, 2 6 5 , 476, 8 4 4 , 107?, 1073 ,
2 i B , 6 7 9 . G 8 0 . 1039, vinyl 844- maleic acidslo3j, maleic and
fumaric eSters767, lloc, 1235, maleimideS'O6S. 1070 furanS1GO. 395. 396. 717, 9 4 6 and nitro-
Most of these reactions are straightforward but in some cases addition of aryl
halogen the double bond occu~slS?, 2 6 5 , 269. 283, 425. 476, 679, 680, 682. 71?, 751, 7 5 2 ,
7 6 7 , 8 4 4 , 8 4 7 , 1 0 ~ 8 1070.
. 1072, 1073. 1196. 1235. This is in part influenced by the reaction
conditions. Cinnamic acids and maleic acids are often accompanied by decarboxyl-
ation with the aryl group formally replacing the -CO,H 106-10*. z s 6 . 40;. 622, 716. 767,
771, 7 7 2 , 1035. This is somewhat dependent upon reaction conditions, with very low pH
apparently favouring retention of the carboxyl functionGz2.

The variety of less common unsaturated substrates also undergo the Meerwein
reaction. These include oximesg'. 93- 140s 62ze623* malonic esterJs0,nitromethanel*l',
ferrocenel55, 8 8 0 - 8 8 2 . 1275 and y-pyridines1031.
There seem to be few limitations upon the aryl diazonium compound used except
that t t very low pH values some lose nitrogen to form aryl halides which is facilitated
by the copper catalysts normally used. At higher pH resin formation can create
problems.
6. Group 6: Replacement by groups in which attachment occurs through

sulphur, selenium or tellurium
Many of the aryl diazo-sulphur derivatives mentioned previously are of extremely
limited stability and lose nitrogen explosively to furnish aryl-S derivatives.
Griess'Jo-.l6I prepared diplienyl sulphide by reacting benzenediazoniuni salt with
solutions of potassium sulphide. T h e same product occurred when the silver or gold
salts obtained from the diazonium hydroxide were treated with hydrogen sulphide.
Even in extremely small runs of these reactions, explosions occurred. The use of
cupric sulphide in analogy with a Sandmeyer-type process fails a n d furnishes only
The reaction with elemental sulphur furnishes phenyl sulphide and, in a
similar fashion, reaction with selenium furnishes the ~ e l e n i d e ~ ~
With
' ~ . tellurium
one obtains the diary1 dihalotelluride12i0.
When the hydrogen sulphide is replaced by alkyl mercaptans, the resulting aryl
diazoniuni alkyl sulphides can be readily (often explosively) decomposed into the
aryl alkyl ~ u l p h i d e I1'ja.
'~~~
Clearly this approach does not offer much attraction to cautious chemists and
approaches employing the sulphur atom in modified form are more desirable.
The safe generation of thiophenols and of aryl thioethers from diazonium salts
can be realized by the Leukart thiophenol reaction where the diazonium salt is
allowed to react with a potassium xanthate. If the ether is desired it is pyrolysed;
if the thiophenol is wanted it is subjected to alkaline hydrolysisi2".
ArSR
(304)
This process along with the somewhat similar approaches of Lustig7'0 and Clifford
and L i ~ h t y have
? ~ ~ fairly general appli~ability?~?. 5 7 4 . 59.1. l Z i 1 * 1340.
When aryl diazonium salts are added to solution of calcium or sodium poly-
sulphides, the bis(ary1) disulphides are generated and these can be subsequently
converted to the t h i o p h e n o l ~ 1'3~s 1~- 133R.
~~
The reaction of aryl diazonium ions with thioiireas generates aryl thioronium
salts which hydrolyse to furnish the thiophenols203. When the thiourea is un-
substituted, troubles can arise. Thus a diazonium anthrone furnishes the t h i 0 1 ' ~ ~ *
while thiophenol was not isolated from the reaction with benzene diazonium
ion?OR . Forrester and Wardell list only the Leukart synthesis for t h i o p h e n o l ~ ~ ~ ~
296 D. S. Wulfrnan
amongst the various syntheses given. T h e sulphides can also be prepared from the
rcaction of a dialkyl sulphide with benzyne and diary1 sulphides with differing
substituents can be obtained by copper-catalysed decomposition of the aryl
diazonium aryl s u l p I i i d e ~ 6oo.
~.~~-
Aryl diazonium ions react with thiocyanate and selenocyanate ions to furnish
the related aryl thiocyanate or aryl ~ c l e n o c y a n a t e 355.
~ ? ~415,
~ 421423, 6 8 8 , Subsequent
hydrolysis furnishes the corresponding phenol analogues. A large number of metal
and metal salt catalysts wcre examined in the thiocyanate case with ferric chloride
being the superior catalyst for conversion of o-nitrobenzenediazonium chloride at
15-20 "C (76%) and tungsten hexachloride being the best catalyst a t 60-70 "C
(69%)030. With mern-nitrobenzcnediazonium chloride, ferric ion was found to be the
best catalyst (80%)G89.
The aryl selenocyanides are convenient intermediates in aryl selenium
7. Group 7: Replacement of the diazo group by arsenic, antimony and

bismuth
In a footnote to a papcr, E;oenigPGnoted in 1890 that the benzenediazonium ion
gave a cherry-red colour with arsenite. This is a characteristic phenomenon observed
when aryl arsonic acids are prepared by the Bart reaction which was described in
1910 in the German, English and French patent literature1331-1342. 1356.
Prior to that time arsenite had been employed as a reducing agent in strongly
alkalinc solution. T h e Bart reaction is of general 963 furnishing the aryl
arsenic acids in fair to excellent yields", 8 8 . 91, 387. 801, 619. 625. 729. '383, 809. BJ8. 1111. 1263.
1 3 h i - l X 9 , 1366.
I t has been used to prepare heterocycliP- 230. 879, 115s, 1366 and
p o ~ y c y c ~ i c l . - ~ ' . l O R I ( , 1102. 11.1 arsonic acids. The reaction is strongly dependent upon
pH and is catalyscd by silver-, copper- and nickel-based catalysts. A modification,
-
known as tlic Scheller reaction, proceeds through the copper-catalysed decomposition
of the aryl diazonium tetrachloroarsenite which furnishes a n intermediate which
decomposes i n hot watcr to furnish the aryl arsonic acid'?''. 1364, 1367.
ArN,OH+Na,HAsO, ArAsO,Na,+N,+H,O
Elemental arsenic"", l Z G i and elemental a n t i n i ~ n y ' are

~ ~ ~attacked by aryl
diazonium salts when warmed in acetone and furnish the triaryl antimony dichlorides
or triarylarsenic dichlorides.
ArN,CI+Sb ~ + Ar,SbCI,
The aryl stibonic acids arc formed by trcating a strongly alkaline solution of the
diazo compound with an alkali nntimonatelllz~
1333, 1360. 1361. A modification employs
the aryl tli;i;lonium chloride-zinc chloride double salt (c.g. May's double salt).
This i5 decolnposcd i n thc prescnce of copper of copper(1) salts1112.1339, 1341 or zinc
diisth7*.AIyl bismuth cornpountis arc generated by decomposing the diazonium-
bismutli chloi.ide tioublc salt in ii solvcnt such as acetone. Mono-, di- and triaryl
bismuths arc formed in moderatc yiclds4:"- 433.
8. Synthetic applications of diazoniurn ions 297
8. Group 8: Replacement ofthe diazo group by metals
The aryl diazonium ions form a large number of double salts with a variety of
heavy metals. The decompositions of some of these offer routes to aryl metal systems
where a metal-carbon bond results. There is apparently only one example involving
a transition metal (Pt) l0*4.
(C,H,),P, ,
Ph
PhN,BF, + PtHCI[P(C,H,),], * PhN,PtCI[P(C,H,),l, _\7
cI/pt\
(306) (307) PK, H5 1,
(308)
SCHEME
62
This fact is rather surprising since a large number of aryl diazonium metal
complexes are known1103and many metals are capable of forming aryl-metal bonds.
One might expect to form aryl-metal bonds in some of the cases where the
decompositions of aryl diazonium ions are catalysed by transition metals and their
derivatives. The absence of such products may be a consequence of oversight rather
than thermodynamics.
With mercury, tin and lead it is possible to prepare the aryl derivative from aryl
diazonium ions. Nesmeyanov and coworkers have prepared a number of aryl-
-
mercurichlorides from the aryl diazonium chloride-mercuric chloride double salts
in the presence of c ~ p p e r " ~ -Alternatively,
~~~. one can react the diazonium salt
while strongly agitating the mercury 7J4.
Cll
ArN,CI.HgCI, 2 CuCI+N,+ArHgCI
Stannic halides also form double salts with aryl diazonium ions and these, when
reduced with zinc, copper or preferably tin in ethyl acetate solution, furnish
principally the bis(ary1)stannyl d i ~ h l o r i d e s ~ ~ ~ ,
2 ArN2CI.SnCI,+4 Sn ~ + Ar,SnCl,+2 N,+4 SnCI,
In acetone solutions, tin reacts directly to furnish the bis(ary1)dichloro stannane'266.
Decompositions of lead double salts in the presence of copper furnish poor
yield of triaryl chloro plumbane and biaryl dichloro plumbanes12GGs
When aryl diazonium fluoroborates are decomposed with copper powder, small
amounts of the aryl copper(1) derivatives are formed and these can be stabilized
by chelation with ~ y r i d i n e ' ~ ~.
1280.
111. ALKYL D l A Z O N l U M IONS

The known reactions of alkyl diazoniurn ions unlike those of the arenediazoniilm
ions are rather limited. It seems likely that many of the processes known for t h e
arenes will ultimately become known when suitable reactionconditions are developed.
Until fairly recently, alkyl diazonium ions have held the role of 'alleged intermediates'
in deamination reactions. The basic features with numerous examples have been the
of several reviews83, 115, 158, 183, 2 2 6 , 2 5 8 , 477, 478, 6 5 1 , 7 1 5 , 758, 8 2 5 , 8 3 6 . 09G. 1010, 1056,
l105, 1152, 1157, 1278. 1282. 1326 and we shall only conccrn ourselves here with the
synthetic uses of the nitrosation of alkyl amines and with species derived from acyl
nitrosamines.
One of the niore practical synthetic reactions of alkyl diazonium ions is the
Tiffeneau-Demjanov reaction where a n a-amino alcohol or a n amine is treated with
298 D. S. Wulfman
a nitrosating agent and rearrangement occurs with shortening or lengthening of the
carbon chain (usually a ring is enlarged or contracted). The processes often proceed
with excellent yields and in many instances provide routes which are competitive
with the Wolff rearrangements and homologations with diazoalkanes, both of
which are discussed in Chapter 18. An exhaustive review of both sets of processes
has recently been presented by Gutsche and R e d m ~ r e ~*040. ' ~ . The Demjanov
reactionzB5in a strict sense describes the rearrangement process of a nitrosated
amine and can lead t o a ring expansion or contraction.
4 CH,OH
(310)
9 LNH,
___,
HONO
4 OH
(311) (312)
SCHEME
63
OH
c+NH2- (319)
SCHEME 64
The Tiffeneau reaction (sometimes referred to as a semi-pinacolic rearrangement)
invo~vesthe nitrosation of a n a-amino alcoho1701.1 2 0 5 . Since such compounds are
readily attainable in good yield by a variety of routes from ketones, t h e process is of
considerable synthetic utility. The reaction does not always lend to ring con-
traction77sand thc behaviour is a function of ring size2'5. 2 6 7 , 271, s??. 323. s ~ ? .6 7 4 , 743.
118.1* ''09* "'O and, as indicated in the hypothetical case illustrated, is a functioll of
conformation.
The overall question of conformational effects on deamination in rigid systems
has been summarized by Kirk a n d HartshorneGdl.The course of Tiffeneau-
Demjanov reactions on a variety of aminocyclanols has been summarized according
to ring size by Gutsche and Redmorelo.*oand it is clear that conformational effects
are of great importance. The difficulties encountered are often a direct consequence
G f the lack of conformational regularity encountered in seven or more membered
rings. I n the case of hydrochrysenes (e.g. D-homosteroids) a careful analysis has been
niade1278. The migrating group is alwiys anli to the leaving diazonium
nitrogenc67. G i J .
With simple amines one encounters a variety of processes which are normally of
little synthetic utility. The diazotization process normally furnishes mixtures of
alcohols and olefins which, on occasion, prove to be rather complex as a consequence
of Wagner-Meerwein rearrangements. Several reviews dealing with various aspects
of the deamination via nitrosation have appeared.
Fairly recently, work originating primarily in t h e laboratories of MOSS^*^-^^^,
NewmanRse-sssand of K i r m ~ e " ~has ~ to the development of reasonable to
- ~ ~led
excellent synthetic schemes dependent upon the transient existence of alkyl diazonium
ions. T h u s Steinheimer116b-1171, upon discovering that diazo transfer to 7-amino-
norcarane proceeded in only moderate yield, was able to convert the same amine
via the 7-N-nitrosourea or urethane into the azide in excellent yield by employing
Kirmse's reaction64Gwith lithium azide. The reaction was followed by careful
therrnolysis to t h e I-azetidine and represents a general route to the formal 2 + 2
cycloaddition of hydrogen cyanide to an olefinll;O- l I 7 l . The process had been
postulated by him as proceeding through a diazonium ion and a p e n t a ~ o l e ~ ~ " .
Simultaneous work in Kirrnse's laboratory revealed this to be t h e case6"*663and
that it did not involve the highly improbable cyclopropyl carboniuni ion originally
Kirnise644~~6s4~ G5i-6G9 has subjected a variety of A'-nitroso urethanes to basic

conditions under which there appears 1 0 be a high probability that alkyl diazonium
ions and alkyl diazotate ions are formedfi". The reactions involve trapping these
species prior to formatior. of a diazoalkane. I t seems likely that similar behaviour
is occurring in the synthetic studies of Hogan5', Billett121-123
and
M o s s " ~ - - " R ~ . p 3 3 - 8 1 1 . Kirnlsc has employed several bases of which formate, niethoxide,
carboliatc and bicarbonate are dominant. Many of his reactions have been run in
methanol but in some cases ethers have been employed. The solvent and base
contribute markedly to the naturc and distribution of the final products. Thus the
6-cso-bicyclo[3.I .O]hex-2-ene furnishcs 90% + benzene with sodium carbonate/
nietlianol and 437; bcnzene, 23% 322 and 35% 323 whcn sodium forniate/methanol
is e m p l ~ y c d " ~ .
When the P-phencthyl system \ \ a s treated with NaBH,, t h e N, function was
removed t o furnish 61% ethyl benzene and a mixture of styrene and u- and
3-phenethyl methyl ethers (7 : 9 : 84) c . 4 7 . The reaction to furnish cyclopropyl
azidc646,6 G 2 , 663 has been studied using isotopic labelling and the reaction strongly
rcscmbles the related aromaiic series i v i t l i a mixed path rcsulting from pentazole
iind penfazcne interrnediatcs. This fact should not be particularly strrprising since
D. S . Wulfman
N=O
I
RCH,-N-COR RCH2-N=N-o RCH,N=NOH
+
RCHN, RCH,N,
I 23%
90%
*N=O
EtNH
MeOH
NH, CI
(334) (335)
66
SCHEME
cyclopropyl carbonium ions are virtually non-existent with only o n e other
substantiated example being known (334 --z 345)878. Thus the claim of Jacquicr of
having observed the conversion of 7-exo- a n d 7-endo-norcaranylamines to the
alcohols via nitrosation has been shown to be incorrect along with their subsequent
conversion to a common cyclopropyl ketone”$, GG9. What does occur is
’ ~ ~ Steinheimer1171 cycled the 7-exo-
conversion t o cyclohept-2-enyl a l c o h 0 1 ~ 669.
norcaranylamine (336)through the azide and back to the amine and found only the
exo-azide (338) was formed (t.1.c. a t both stages, with known endo-amine for
comparison). Kirmse obtained allylic systems in the absence of azide ion6”* G57, G59.
When Kirmse examined the behaviour of the 7-e.ro- and 7-cndo-norcaranylamines
in the absence of azide ion, he obtained 97 a n d 91% of the rmm-7-cyclohepteny!
methyl ether (MeOH/Na,CO,) and 94 and 98% norcarane with sodium boro-
hydridecZ1.
(339)
0 N=O
I1 !
R-C-N
(342)
(343)
SCHEhlE 61
302 D. S . Wulfman
When I,o-diamines are subjected to the basic Kirmse sequence (amide,
nitrosamide-baseaso), the nature of the final products was found to be a function of
the chain length. With I,3-diaminopropane, cyclopropyl methyl ether was obtained
in 50% yield, but with larger chains the dimethoxy ethers and c+methoxy-a-olefins
occurred (with MeOH/MeONa, the diethers were the major p r o d ~ ~ c t s ) ~ ~ ~ .
When propargylic and allylic amines are subjected to the Kirrnse series,
rearrangements occurGss~ 6 5 8 , G65-G67. The propargylic systems offer routes to
P-substituted propionic acids, alkoxy allenes and propargylic ethers (Scheme 68).
CH,CECCH, N:
(344)
CH,CECCH,OCH, + CH,CHC=CH + CH,-C=C=CH,

I I
(345) OCH, OCH,
(346) (347)
(348) (349)
OCH,
I
PhC=CCH,N$ PhC-CGC-H
I
/ (352)
HCEC-CHN;~
I
Ph
(353)
-
CH,C=CCH,N~ ___+ CH,C=CCH,OCH,
(354) (355)
HC=CCH,N: C,H,CO,CH,
(356) (357)
SCHEME 68
With allylic systems, ally1 ethers (mixtures of isomers) are obtainedGS4.
65s. When
cyclic substrates are employed (cyclopropyl and cyclopropyl carbinyl) rearrnnge-
rnents occur in good yicld. I n two of the exaniplcs, thc diazoniuin species was
generated by the addition of H?C)/-OH photochemically and the presence of
rearranged products n o t available via a carbene process can be taken as evidence
that reaction did involve a carbonium ion process"G'.
Moss821-e31.833-811 has examined the question of when does the action of base
upon N-nitrosourethanes lead to alkyl diazotates and when d o diazoalkanes
resultB2’.In thc first paper of the Moss series and in a review, one finds a good
summary of references to earlier work in the area by a numbcr of workersHz1. 83G.
The reaction of z-phenethyl diazotates at - 5 0 “C in CH,CI, with Et,6BF,

furnished the alkyldiazo ether which collapses to the a-phenethyl ether with 70%
retention of configurations2G.82d. Concurrent with 0-alkylation, o n e obtains varying
amounts of N-alkylation to furnish a z o ~ y a l k a n e s8~3 3~- 834.
~ . The yields are somewhat
better in HMPA solutions than in CH2C12.The reaction has been employed to
synthesize L-dihydroelaromycin (359). L-Elaroniycin (358) has been reported to be
a n antibiotic and a carcinogenR3’.
H
\ H
, CH,OCHl CH,OCH,
/c=c CH,
n-C,H,,
\
N=N-C-C,
- /
CHI
-
n C, H ,c H, c H, N =N- c -c/,,,,
-*
0d A ,!,“‘OH 4
0
/,/,OH
(358) (359)
SCHEME 69
When a-phenethyl diazotates are treated with hydrazineRae,a-phenethyl hydrazine
results with 54% net inversion. When ammonia is employeda335,inversion OSPXS
along with some racemization. Similarly treatment with Grignard reagents leads to
alkylation with some inversion. Maximum inversion was observed at the lowest
-
temperature employed, with phenyl Grignard and s-butyl diazotate in ether.
R’
RzA 0 R’ H
cNA0+ Et,SiH R2
XSiEt,
I
304 D. S . Wulfman
a-Terpineol 32.5%
HONO
13.7%
Limonene 9.6%
(375)
SA. HONO
Linalool
Nerol
Geraniol
2&7%
14.8%
51.0%
(376) (377)
XR'R'CH=NHNHTos
SbCI,
cc,, ' [R'RZC=CH N, ]+
(378) SbCl,-
(379)
SCHEME
71
Ethyldiazotates react with acyl anhydrides and halides in ether solutions to

furnish intermediate diazotate estcrs which collapse with loss of nitrogen leading to
R stereoselective synthesis of esters, e.g. 17--31% inversion with acetic a n h ~ d r i d e ~ ~ l .
The reaction procecds with little intermediacy of the carbonium ion for the cyclo-
propyl carbinyl system proceeds in -80% yield to the cyclopropyl carbinyl ester.
Moss"" has summarized a number of potential reactions of diazotate chemistry.
These include the use of allenic diazotates to generate aryl diaz01nethancs8Dg.900,
photolysis of epoxy diazotatcs to furnish oxadiazotenes9'j1.8G3 and the modification
of D-nor-steroids via diazotate-generated carbonium ions7'4. 7 i G .
Recently, Newman's g r o ~ p ' ~ (Scheme ~ - * ~ ~70) has expanded upon earlier work by
I - l ~ i s g e nand
~ ~ Mullcr8D8
~ involving treatment of N-nitroso lactams (in one instance,
oxazolidones) with bases to furnish several interesting systems (360 -> 362) and
(363 -+ 365). Related work by (see also Reference 886) is summarized in
Scheme 66 (360 -'362). Hassner has presented a detailed study of N-nitroso
oxazalidone cheniistryS1l.
The use of acidic nitrosation to dearninate amines has received considerable
attention in the past and a number of recent reviews have appeared. The reactions
far too frequently lead to vcry complex mixtures (see, for example, References 184,
255, 773, 1236) but on occasion are relatively
At 0 "C i t has been possible to preparc P,P-disubstituted vinyl diazonium salts
using P-halo-aldehyde-tosylhydrazonesand SbCI, in CCI, l S o .
The behaviour of 3 (or 7) amino tropoloncs towards diazotization is closer to
that of alkyl amines than i t is to the anilines but diazonium tropolones exhibit
reasonable stabilities at other ring positions and have been used in the Pschorr
synthesis with mixed success. It is therefore surprising that when the diazonium ion
is in t h e 3-position, collapse to o-hydroxybenzoic acids occurs with great ease even
though a n intermediate oxadiazole should in principle exhibit considerable
stabiIity9, 2 6 2 , 521. 672, 843. 8D7, 911, 8 0 , 927, 929. 932, 933. 030 by virtue of being a 1 k electron
system.
The oxadiazole ring system may of course be generated but under the acidic
conditions reverts to the diazonium ion (383) which might collapse to the hydroxy-
benzoic acid.
(383)
(382)
SCHEME 12
IV. B E N Z Y N E S , H E T A R Y N E S A N D O T H E R
DIDEHYDROAROMATICS
T h e generation and reactions of beiizynes and hetarynes (Schemes 73-77) have been
~ ~ ~a chapter in The C h c m i s f r ~of~ A ~ e f y l c n c ~ ~ ~ ~ .
the subject of a n i o n ~ g r a p l iand
This type of species is often treated concurrently with carbenes and nitrenes in
texts and Annitnl Reporfs of the Chemical Society, as a consequence of their high
306 D. S. Wulfmnn
reactivity and cheniistry and their exhibiting a valence state with carbon having
fewer than four formal bonds (in one resonance form one has a bis-1,2-carbene).
A number of syntheses involving benzynes start formally or actually with diazonium
compounds. T h e recent innovations using the Pbl" and I -chlorobenzotriazole
oxidation of N-aminobenzotriazoles (Schemes 73 and 77) both formally and
(385)
Qr+rNTos LI
A or hv
(393)
SCHEME
73
practically involves the chemistry of N=N-X systems. Workers at the Robert

Robinson Laboratories at the University of Liverpool have carried out a
prodigious amount of work in this area. Earlier work involving the destruction of
o-carboxydiazonium salts and benzothiadiazole S,S-dioxides has also furnished
entry into this important synthetic area. The arynes can insert into X - Y bonds,
act a s hot dienophiles and dirnerize to furnish biphenylenes. The ability of arynes to
participate in cycloaddition reactions is very well documented (Schemes 76 and 77)
and H ~ f f n i a n nhas
~ ~presented
~ a 25-page tabulation of products.
8. Synthctic applications of dinzonium ions 307
0
(394) \
(398) (399)
SCHEME
74
11
308 D. S. Wulfman
T h e arynes are not limited to 1,2-benzo-type systems. Photolysis of 3-carboxy-
benzenediazonium systems furnish the 1 ,3-arynes113. The oxidation of 1 -amino-
naphtho[ 1.8~.8.dc]-1,2,3-triazine
furnishes the 1,8-didehydro~naphtlialcne~~~~
6243, ’;‘ja.
(384)
a”+aoH co;
DMFt
CHO
DMSO
_ 3 -
SMe
(411)
>q
SCIIEhlC 76
0:
(384)
N,
R - C(N,)COR’
CO R’
I
The gas phase and flash photolysis of benzcnediazoniuni 4-carboxylate furnishes

the 1 ,4-didehydrobenzcne1”. Recs and his colleagues have performcd extensive
studies in this field as a conscquence of syntheses dircctcd towards preparing
.y,y-didchydroaromatic systems such as I ,8-didehydronaphthalene (385), 2,2’-
didehydrobiphenyl and related conipouiids (e.g. 4,5-didehydrophenanthrene,
4,5-didcliydro~uorerionc~~*~),as well as intermediates for preparing I-azabenzo-
cyclobutenesG and benzynes. Tetrazotization of 2,2’-diarninobiphenyI (415) in
2 N-HCI furnishcd six identifiable products (Schcnie 78). Oxidation of 389 furnished
384 and related products but n o 392. Work with the rclatcd fluorenonc systems was
unsucccssful. When the 2,2’-diaminobipheiiyl was tctrazotized and treated with
(422)
SCHEMC 78
ammonia, t h e triazcpine (428) w n s obtained in high yield. Similar results were

obtained employing I ,8-diaminonaphthnlenc which furnishes 429. When 428 was
treated with a variety of reagents i t was evident that the system was a masked
diazonium ion in much the same fashion as is observed with open chain triazenes.
When the tetrazotized biphenyl was allowed to react with methyl amine, 430
resulted.
T h e aziminc (418) is a potential 1,3-dipole and is generated thermally from the
triazipene. The carboxethoxy derivativc (435, R = C02Et) was found to be a good
1J-dipolar reagent935. The N-ethyl dcrivative (435, K = C2H,) behaves anomalously
310 D. S. Wulfrnan
with N-alkylimides and acetylenic esters1o38. The triazine (439) available from
tetrazotized 1,s-diaminonaphthalenc is unusual in that it behaves as a 1 , l I-dipole
towards dimethyl acetylenedicarboxylate1044.
T h e iminoazimines (441) are readily prepared from 418 by reaction with the
appropriate imidochlorides in acetonitrile solution in the presence of potassium
carbonate. They undergo thermal rearrangement with the alkyl case proceeding
slowly even at room temperatureno.
N=N,
N=N/
NH .
A
N=N
'N
N -NO
I
H
I I
ON2
I ..+
(423) (424)
Although the formation of benzotriazene derivatives has been known for many
years i t was only in 1971 that Rees and Storrs reported the preparation of the parent
compound. T h e syntheses grew out of their attempts (ultimately successfuls~6, to
prepare benzazetes. Since these syntheses involve cyclizations of azido diazoalkanes,
they will be treated in Chapter 18. An alternative route was through oxidation of
N-aminoindazoles.
When 4-phenyl-l,2,3-benzotriazinewas pyrolysed in the vapour phase at 420-
450 0C/IO-3Torr, the benzazete (445) was formed along with several other products.
T h e product was collected at -78 "C and on warming the dimer is formed. A
number of possible dimeric structures are reasonable and the structure is currently
unknown.
8 . Synthetic applications of diazonium ions 31 1
8
(433) SCHEME
80
Me0,CC a CC0,Me
$N
C0,Me
.NH
C0,Me
(435)
C0,Me
(1) HONO
(2) Hypophosphorous'
acid
(437) SCHEME
81
D. S. Wulfinan
cl'"
312
Me0,CC I CC0,Me
Me0,C CO,Me
(443)
82
-
SCHEME
&! N"
Dimers
V. CYCLOALKY N E S
Thc compound cyclononync is knowni29and is quite rcacti\'e. Smallcr ring systems
\vould be expected to be even iiiorc rcactive and to rescmble the aryr,es. Hence one
might expect to form o n a transient hasis such intcrmediates by eliniination of H X
from a I-halocyclonlkcnc by treatment \villi strong bnses12"9. The eliminations of
thc clcnieiit of bl-X from some mctallated haloalkcnes are extremely slow reactions
as a conscquence of thc strain i n a potcntinl alkyiie or thc high energy of thc
didehydro specicsiR"i.The formation of straincci cycloalkync can Iiowcvcr be reachcd
via 1,2-diazocycloalkancs and tticir subscquent clccoinposition and rclrited
systenls1311. - I * 2 7 8 , 310, .isi. 5 5 5 , ious. i 3 w . This probleiii will be trcatcd in Chapter I S
1:11. I I X . "-r.
under dimerization processes in \vhich two new C- C bonds aIc rormed.

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338 D. S. Wulfman
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Those patents lacking a Cliem. Abstr. reference havc not been abstracted therein and
were encountered in other rcfcrences (primarily 220 and 1103).
I2
CHAPTER 9
WATARUANDO
Clictnisfry Dcpartimwf, The Utiivcrsity of Tsrrkitba,
Niiliarigwt, Ibarnki 300-3 1, Japan
I. INTRODUCTION. . 342
A. Photochemical Encrgy . . 342
B. Photochemical Excitation . 342
11. PHOTOCHEMISTRY OF AROMATIC DiAZONIUM SALTS 344
A. Deamination through Diazonium Salts . . 344
B Substitution of the Diazonium Group by Fluorine . . 346
C. Substitution of the Diazonium Group by Chlorinc or by Hydroxy Groups . 349
D. Spectra and Excited States of Diazonium Salts . 350
E. Reaction Intermediates 356
1. Radical species and carbonium ions . . 356
2. Cis-tram isomerization . 360
3. Sensitized photolysis of diazoniuni salts . 361
111. PHOTOLYSIS OF ALIPHATIC DIAZOh'lUhl COhlPOUlUDS . 362
IV. PHOTOLYSIS or: DIAZOCOMPOUNDS . 366
A. Thc Structure of Carbenes .
B. Chemical Induced Dynamic Nuclear Polarization (CIDNP) Stu'dies
C . Spin Multiplicity and Reactivity of Methylene .
: 367
370
373
D. Photolysis of Aromatic Diazo Compounds in Olefins . 378
1. Phenylcarbene . 378
2. Diphenylcarbenc . 379
3. Fluorenylidene . 385
4. Cyclopropenylidene. cyclolieptatrienylidene and cyclopentndicnylidene . 388
E. Photolysis of Diazocarbonyl Conipounds in Olcfins . 3 92
1. Intermolccular addition reactions . 392
2. Intramolecular reactions . . 400
F. Photolysis of Diazo Compounds in Aromatic Compounds . 403
G . Insertion Rcactions .
1. C-H insertion of carbcnc in sa'turated hydrocarbons
2. C-H insertion of carbene in ethers . .
; : 408
408
412
H. Intramolecular Reactions . 415
Photolysis of Diazo Compour~dsin Compounds Containing Hetcro Atonis 424
1. Reaction with polyhalomethanes . 424
2. Rcaction with nitrogen compounds . 432
3. Reaction with oxygen compounds . 437
a. Molecular oxygen . 437
b. Reaction with alcohols . 439
c. Reaction with ethers . . 442
4. Reaction with sulphur coriipounds . 44 5
J. Wolff Rearrnngerncnt . . 455
1. Synthetic utility . 458
34 1
342 Wataru Ando
2. Tlic mechanism of the WolfT rearrangement . . 461
K. Bisdiazo Conipounds . . 476
V. REFERENCES . . 471
1. INTRODUCTION
Light can be transmitted, refracted, scattered or absorbed by a system. It is a
fundamental tenet of photochemistry that only the light absorbed can be effective
in producing chemical or physical changes in a molecule.
A. Photochemicol Energy’-5
T h e energy of light in kcal/mol is given by thc expression:
An energy of 1 kcal/mol corresponds to radiation of wavelength 286,000 8, o r

10* A/cm
1 kcal/niol = = 353cm-’
256,000 8,
in the infrared portion of the spectrum. When electromagnetic radiation of these
frequencies is absorbed, molecules are excited to higher vibrational states. Radiation
of shorter wavelength (higher frequency) contains more energy. Visible light has
a wavelength from 4200 8, (violet) to 7000 A (red), i.e. i t contains 6 8 4 1 kcal/mol.
Ultraviolet light of 2000 8, corresponds to an energy of 143 kcal/mol.
6. Photochemical Excitation
Light in the ultraviolet-visible region has energy sufficient to excite molecules to
higher electronic states. Consider now the potential energy curve for the ground
state ( E o ) and first excited state ( E , ) . According to the Franck-Condon principle
transitions occur between vibrational levels for which the nuclear configurations
are the same (I-’ = r ” ) , i.e. we have vertical excitation as shown in Figure 1. The
energy of the electronic transition is measured from yo of the ground state to yo of
the excited state, E,(v,) - Eo(v,) = A E = h v .
T h e major events that occur following light absorption may be summarized in
terms of a Jablonski diagram. The absorption of light raises the molecule from
So to S p , as shown in Figure 2. I n solution the excess vibrational energy of S2 will
be rapidly dissipated by radiationless processes. After conversion to S1 the molecule
may lose its energy by four important processes: (i) fluorescence, (ii) chemical
reaction, (iii) return to a highly vibrationally excited ground state (S,-So) and
(iv) intersystem crossing. Intersystem crossing (S, to T,) occurs between two excited
states of similar energy and is very important in photochemistry, because the
triplet state T1 picduced is even longer lived than S,. The lifetimes of TI are limited
by: (i) phosphorescence, (ii) chemical reaction and (iii) radiationless decay to So.
Furthermore, an excitcd moleculc may transfer its energy to another molecule;
if this occurs the excited or donor molecule returns to its ground state and the
acceptor molecule becomes excitcd. I f the donor molecule (D) was in the triplet
state at the time of its energy transfer, the acceptor rnolccule (A) gets promoted to
its triplet state, and similarly \ye cxpect singlet-singlet energy transfer.
9. Photochemistry of the diazoniuni and diazo groups 343
\ Antibondino
~~~ ~ ~~
Internuclear distance. r'

1. Potential energy curve for a n clectronically excited a n d ground-state diatomic
FIGURE
molecule.
kg
conversion
Internal crosslng
intersystem
I -
..
T2
Chemical
reactions T (triplet)
+<Chemical
Phosphorescence
react ions
FIGUKC
2 . Jablonslii diagrain. Typical cnergy diagram.
344 Wataru Ando
I I . PHOTOCHEMISTRY O F AROMATIC D l A Z O N l U M SALTS
-4t the end of the last century, Andressen' cstabiished that aqueous solutions of
diazo compounds dccornpose under the influence of light. The rncchanisni of the
photochemical decomposition is not completcly understood; i t appears that it is
largely determined by thc environment and by t hc chcmical specics present. The
effect of substitucnts on the light scnsitivity of diazo compounds has been studied
by many investigators'. 8 .
A. Deamination through Diazonium Salts

According to AndressenG, diazoniuni salts irradiated in aqueous solution are
decomposed into a phcnol a n d nitrogcn. 0r:on and coworkersD investigated the
photolysis of diazoniuni salts in aqueous solutions and found a noticcable increase
in the rate of decomposition as compared to that of the dark reaction. When para-
substituted benzenediazonium dcrivatives arc irradiated by ultraviolet light in
6 ax
methanol as the solvent, the formation of the phenol ethcr is rather a minor process,
while the main reaction is the substitution of hydrogcn for the diazo group'O.
N t CI-
+ ROH I, L
_ _ f +
X X
When 2,4,6-tribromobenzenediazonium sulphate was irradiated in aqueous
solution, Orton and coworkers obtained 2,4,G-tribromophcnol in quantitative
yielde. Whcn this reaction was carried out in acetic acid, 2,4,6-tribromophenyl
acetate was formed, whereas in formic acid o n l y 1,3,5-tribromobcnzene was
obtained .
OH
Br
"'@"'
N: X- OCOMe
I:.
-
Br Br
Br
9. I'hotoclieniistry of the diazonium and diazo groups 345
TADLE1. Photolysis of compounds
[RC,H,N,]+ CI- in niethanol solution
R Reduction (%) Ethcr (XI
p-NO, 60 0
p-CI 60 0
p-MC 40-50 20-30
p-OMc 40-50 20-25
I f the photolysis product is reactive enough, it can react under favourable

conditions with the non-decomposed diazonium compound and a dye is formed in
the exposed areas but not in the areas protected from light. T h e reactions taking
place can be expressed as follows:
N: CI- OH
I
Y V
OH OH
This process was first proposed by N'est'l and further explored by Feerl', A n d r e ~ s e n ' ~
and others.
When irradiating diazo conipounds in concentrated hydrochloric acid, Sus
obtained the corresponding p-halogenodiphenylamines. I-le also showed that the
action of light o n p - and a-dialkylaniinobenzcnediazoniunl compounds results, in
the case of para substitution, in the corresponding p-dialkylaminophenols, whercas
the ortho isoniers produce a considerable quantity of secondary amine, along
with the corresponding phenolsl4*lS.
OH
I
bN; bX
NR R ' NRR' NHR
x- 111 +
(2) X = OH (4 1
(3) x - CI
346 Wataru Ando
2. Photolysis of diazoniurn salts 1IG
TABLE
R R' Solvcnt 2(%) 3(%) 4(%)
la -(CH2)4- H,O (20 "C, lw) 51 0 0

lb Me Me H,O (20 "C, hu) 15 0 56
1 ~I-HCI(20 "C, h ~ ) S 10 48
1 h1-HCI (100 "C, 90 min) 5 16 44
H,O (100 "C, 90 rnin) 20 0 57
lc Et Et 1 M-HCI(20 "C, liu) - - 92
H,O (20 "C,Iw) - - 70
8. Substitution of the Diazonium Group by Fluorine

In the photolysis of crystalline diazonium fluoroborate and hexafluorophosphates,
t h e corresponding fluoroarenes were usually the only volatile product, as in
pyrolysis1'. In some cases, the yield of fluoroarenes was higher than that obtained
by pyrolysis of these salts (the Balz-Schiemann reaction), which remains the most
generally used means of introducing a fluorine substituent into an aromatic ringla.
Pure 4-substituted diphenylamine was isolated in 37% yield on the first attempt
when the corresponding diazoniurn fluoroborate was irradiated as a solid film at
30 "C with 3500 A light. Hexafluorophosphates sometimes gave better yields than
tetrafluoroborates in the Balz-Schiemann reactionlD:
hV
ArN: BF; (or PF;) 3500A P
ArF+N,+BF, (PFJ
Photolysis of aryldiazonium salts substituted with electron-withdrawing groups

gave much lower yields of fluoroarenes, perhaps because with a light source available
the products absorbed light about as well as the starting material and the competing
TABLE3. Photolysis of solid arenediazoniurn fluoroboratcs and

fluorophosphates, RCGHIN: X-
R X Irradiation time (h) Yield of RC,H,F (%)
4.539 53-55
4 72
94 74
17 55
19 69
24 37
2 34
8 10
2 29
12 40
54 19
reaction destroyed them. A n ionic intermediate or transition state of some sort
appears to be implicated in the photolysis of solid arenediazonium fluoroborates
a n d fluorophosphates. I f aryl radicals were intermediates, they would be expected
to abstract hydrogen atoms from other molecules of the starting material, especially
when side-chains with alkyl groups are present. However, n o reductive product
was produced in the photolysis of even the dimethyl- and diethyl-amino compounds.
I n contrast, when crystalline para-IV,N-dimethylaminobcnzenediazoniurnchloride
was irradiated, reduction to N,N-dimethylaniline (25%) competed strongly with
conversion to chloro-N,N-dimethylaniline(33%). These observations are in accord
BF,
Nkico2Et
N: C0,Et
HzNMCOzEt
NQH
NaNH,
*H H
N v N H
+
0-
N v N
t(1) ElOH
(2) MeS0,H
[i ;bH
N H, F
I I
1 LiAIH,
1
N a ' C(NtiAc)(CO,EI):
348 Wataru Ando
with the results of studies of isomer distribution in the phenylation products formed
when solid benzenediazonium haloborates are pyrolysed or photolysed in the
presence of a substituted benzenez0.
The lack of parallelism between fluoroarene yields for photolysis versus pyrolysis
makes it unlikely that these reactions proceed exclusively through a common
intermediate. Lewis and coworkers21 compared photochemical with thermal
reactions of diazonium salts in aqueous solution and concluded definitely that there
was no single intermediate common to both.
CH,CHCO,Me CH,CHCOOH
CH,CHCOOMe dCH,~t4~OOH
1A cy I a se
I -
NHAc
N
+/-H
NYNH
F
I
F
CH,CH,NHR Ar NMCH,CH,NHR
N-NH
-ArN;\
(PH 8)
""& + N v N H
NYNH
N,Ar
+ dC
NYNH
;;;
/=rHzcH2NHz
p\, t%
--- -
L ' 2 CH 2
dC
H2N 4
( 1 ) HNO.. HBF. OH-

(2) Ill
--+ NvNH
F
SCHEME
2
A wide variety of fluorinated analogues of biologically significant compounds

have been synthesized and studied as potential enzyme inhibitors and as therapeutic
agents".
Kirk and Cohcn studied synthetic approaches to fluoroimidazolesz3. Imidazole-
diazoniurn ions, prepared by diazotization of aminoimidazoles in tetrafluoroboric
acid solution and irradiated irz sifii, decompose with formation of fluoroimidazoles
in 3 W O % yield. This procedure has been applied to 2-fluoroimidazoles, 4-fluoro-
irnidazole and ethyl 3-fluoroimidazole-5-carboxylate. The ester, in turn, has served
as the starting point for various transformations, including the synthesis of 4-fluoro-
histamine and 4-fluorohistidine. To date, fluorinated imidazoles have been obtained
only by photochemical methods2'.
9. Photochemistry of thc diazonium and diazo groups 349
Irradiation of diazotized N-acetyl-L-histidine mcthyl ester in tetrafluoroboric
acid solution provides the 2-fluoroimidazole derivative in 32% yield ; 2-fluoro-
histidine is obtaincd after ester hydrolysis and enzymic deacylation of the lattcr
derivative. An analogous approach to 2-fluorohistarnine failed because of
dccomposition during acid o r alkaline hydrolysis of the A’-acetyl group. The
histamine analogue was obtaincd, howevcr, by use of the more labile trifluoroacetyl
group for protection of the side-chain amine. In contrast to the vcry high degree
of stability of 4-fluoroimidazoles, the 2-fluoro isorncrs are subject to fluorinc
displacement25.
C. Substitution of t h e Diazonium Group by Chlorine or by Hydroxy Groups

Solid anhydrous chlorides completely frce of polar influenccs were observed to bc
photolysed with a quantum efficiency of well over unity. These results can be
explained by considering the covalent diazo tautonier of the diazonium chloride,
which decomposes symmctrically in the first stepz6:
N: CI-
Free chlorine atoms and phenyl radicals so produced arc capablc of continuing the
original function of the utilized photon. For example,
CI
I
X x X X
T h e observed quantum yiclds were of the order of two.

Aromatic diazonium salts react with hydrochloric or with hydrobromic acid
undcr the influence of sunlight yielding halogenated aromatic conipout~ds?~.
In this
way, for example, 6 is converted to 7 or 8 , respcctivcly.
I I I
H H H
(9) (6) (7) x CI
(8) X == Br
350 Wataru Ando
The photoreaction of diazonium salts in very dilute sulphuric acid, like t h e
thermal decomposition of diazonium compounds in aqueous acid solutions, yields
hydroxy compounds.
The photoreaction proceeds very smoothly in niany cases, while the corresponding
thermal decomposition often leads to resin formation. 4-Anilinobenzenediazonium
sulphate (6) afforded 8, and 4-dimethylaniinobenzenediazonium chloride gave
4-dimethylaminophcno1. Huisgcn and Zahlcr have described the preparation of
fluoren-9-one (11) by irradiation of 10 in aqueous sulphuric acid?s:
0 0
(10) (11)
T h e photolysis of tetrazo conipounds of 1,5-di(o-aniinobenzoyInaphthalene)takes
place by means of a double Pschorr reaction to give 1,2,6,7-dibenzopyrene-3,8-
Q
quinone".
BF,- Nt'
-+
/I I
O J
D. Spectra and Excited States of Diazonium Salts

The spectra of diazoniuin salts are of interest here because thcy identify the
escitcd states \vhich arise i n t h e act of light absorption and arc potentially involved
in the photolyfic conditions. The siniplcst diazoniuin compounds absorb ultra-
violet radiation in the range 2200-3300 A, which is virtually non-cxistent in the
spectrum cmitted by conventional light sotirces. \Vhen dialkylamino, arylamino,
arylthio o r hydroxy groups are introduced into tlie niolccule in the orflio or para
positions with respcct to the exceptionally strong electron attracting diazoniuin
group, then tlie absorption is sharply movcd to longcr \vu\.elengths. Since most
substituted diazonitim compounds are yello\v and absorb in thc region 3600-
4500 A, they are sensitive to iicar ultraviolct and blue light, and are virtually
insensitive to rcd and grcen'". Figure 3 sho\\,s the absorption spectra change of
p-CGH,NHC,;H4N:HSO; i n water (pfi 4.6) during U.V. irradiation3".
I n aqueous solution, diazonium snlls stabilized by zinc chloride exhibited a major
absorption band i n thc region 350-390 nm and n minor band in t h e region 245-
260 n n i . The introduction of progressivcly Iargcr alkyl or phcnyl groups into the
para amino group causcs n slight ba~hochroniicshift i n the major band. With every
compound a minor band \\as obscrvcd in the rcginn 245-260 nin ' I .
9. Photoclicmistry of the diazonium and diazo groups 35 1
10
I
300 400 500
X (nm)
FIGURE 3. Absorption spcctral change of 4-C,H5NHC,H4N$ HSO, in water (pH 4.6)
during irradiation. Irradiation with a 500-\valt, high pressure Hg arc at about 30 cm.
Irradiation time (sec); (a) 0; (b) 1 5 ; (c) 20; (d) 30. [Reproduced, with pcrrnission, from
Inoue, Kokado and Shirnada, Nippot; Kagaku Kaislii, 12, 2272 (1974).]
4. Ultraviolet absorption maxima of

TABLE
R' R,
~~
h,,,, Molar extinction coefficient, E
H H 353 37,400
Me Me 375 38,900
Et Et 380 40,300
Me H 366 38,600
Et H 3 68 41,100
P 11 H 377 30,200
Ph Ph 388 74,100
Although t h e tz--;T* transition is observable in the absorption spectra of azo

compounds, it h a s not yet been observed with diazonium salts. T h e main absorption
b a n d with these salts is not greatly affected by solvents of different polarity a n d is
probably d u e to z-x* electron excitation. Bathochroniic shifts observed with
p-NH,-substituted derivatives also confirm this conclusion. I n aqueous solution n o
difference in spectra between p-aminobenzenediazoniurn chloride and its zinc
chloride d o u b l e salt was found, indicating that interaction between the cation a n d
zinc chloride w a s negligible.
352 Wataru Ando
T h e electronic states of t h e Scnzenediazoniiim cation wcre calculated by a method
similar to that of Pariser and O n the basis of the calculations, the 259 and
295 nni absorption bands were attributed to lA1-lA, and lA1-lB, transitions,
respectively. When the sample was irradiated in a n alcoholic solution by a 295 nm
light, no e.s.r. signal was detected, but fluorescencc and phosphorescence were
observed; the fluorescence and the absorption spectrum of the lAI-'BI transition
are niirror images of each other. On the other hand, upon irradiation by 259 nm
light, this sample showed an e.s.r. spectrum which was attributed to the phenyl
c-radical, but no fluorescence or phosphorcscence was observed. These results
5-
4 -
-?
0
x 3-
(u
2 -
<mot
1 - 1160
- 1
, \
A (nm)
FIGURE 4. Thc near ultraviolct absorption spectrum of benzenediazoniuni fluoroborate in
ethanol (* in water). [Reproduced, with permission, from Sukigahara and Kikixhi, Bid/.
Chetn. SOC.Japan, 40, 462 ( 1 967).]
show that thc electronically excited benzcnediazoniurn salt releases its excess
energy by the following processes: (i) There is radiative transition from the 'B, state
io the ground state and intcrsystein crossing to the phosphorcscent state, although
i t is a s yct uncertain whethcr 3B, or o t l x r !riplet stales a r e involvcd. The photo-
dccomposition does not procced from the excitcd 'B, statc. (ii) From the excited
lAl statc, neithcr radiative transition to the ground state nor a non-radiative
transition to any fluorescent or phosphorescent state occurs. The molecule
decornposcs rapidly to give a phenyl c-radical after cxcitation to this electronic state.
Electronic structures and absorption spcctra of p-halogeno-, p-methoxy- and
p-dinicthylaniino-bcnzenediazoniurn cations showed that when an electron-donating
group is introduced at the pmrn position, the lA1-'AI transition shows a very large
shift to longer wavelengths, while the lA,-'B, transition is not so much affected33.
Tsunoda and Yainaoka reported the relationship between the charge density
and the photolytic rate3'. I t was observcd that the benzcnediazonium cations having
elcctron-releasing groups such as - 0 M e and -NhIe, in thc prim position have
rclativcly largc quantum yields, \vhile electron-attracting groups, such as -NO2
and -Br, substituted in the porn or o r ~ h oposition lower the quantum yields. AS
- Emission spectrum
---- Excitation spectrum
250 300 350 400

X (nm)
FIGURE 5. The fluorescence emission and excitation spectra of benzencdiazonium fluoro-
borate. (Reproduced, with permission. from Sukigahara and Kikuchi, Bull. Clienr. SOC.
Japan, 40,462 (1967).]
I
FIGURE6. The e.s.r. spectrum of irradiated benzencdiazonium fluoroborate (at 77 K in
methanol). [Reproduced, with permission, from Sukigahara and Kikuchi, BUN. Cheni. SOC.
Japan, 40,462 (1967).]
the conjugated system extends, the peak of the absorption band is shifted to longer
wavelengths, but the quantum yield tends t o be lower. T h e tetrazonium cations also
have low quantum yields, which might be the effect of the strong electrophilicity
of two diazonium groups.
354 Wataru Ando
350 400 450 500

(nm)
FIGURE7. The phosphorescence spectrum of benzenediazonium fluoroborate at 77 K.
[Reproduced, with permission, from Sukignhara and Kikuchi, Biill. Cliern. Soc. Japan,
40, 462 (1 967).]
2x104 -
240 260 280 300 320 340 360 380 400 420
X (nm)
FIGURE8. The visible and near ultraviolet absorption spectra of the para-substituted
benzenediazonium fluoroborates. (A) p - F ; (B) p-CI; (C) p-Br; (D) p-MeO; (E) p-I;
(F) p-NMe,. [Reproduced, with permission, from Sukigahara and Kikuchi, Bull. Chem.
SOC.Japan, 40, 1078 (1967).]
T a b l e 6 shows t h e transition energy a n d the c h a r g e density of t h e ir-electrons

calculated by t h e Huckel theory. T h e charge density of, for example, t h e p-dimethyl-
aminobcnzenediazonium cation having a high q u a n t u m yield is m u c h greater than
that of, for example, the p-nitrobenzenediazonium cation with its low q u a n t u m
TAULE5 . Wavclength maxima and molar
extinction coefficients for pora-su bst i t uted
benzencdiazonium cations. [Reproduced, with
permission, from Sukigahara and Kikuchi,
Bull. Clieni. SOC.Japan, 40, 1078 (1967).]
Substituent Amax (nrn) log Emax

F 267 4.229
c1 28 1 4.195
Br 393 4.1 78
I 327.5 4.036
0Me 315 4.283
N Mc, 3 80 4.448
yield. A correlation between t h e q u a n t u m yield and the charge density of t h e

diazonium g r o u p also exists, even in t h e excited state. Figure 9 shows that the
diazonium cation w i t h a high charge density a t the diazonium g r o u p in t h e excited
s t a t e has a tendency to give high q u a n t u m yield. T h e ortho isomers do not follow
this tendency, because of steric hindrance.
6. Quantum yields and charge densities of diazonium cations,

TAQLE
[Reproduced, with permission, from Tsunoda and Yaniaoka, J . Plzoiogropkic Sci.

Japan, 29, 197 (1966).]
Charge density" Transition energy (eV)

Quantum
R A,, yield G E Calcd Found
H 264 0.38 2.0428 2.5590 4.81 4.70

p-c1 283 0.29 2.0485 2.5073 4.42 4.40
m-Cl 266 0.41 2.0424 2.5527 4.38 4.66
0-c1 269 0.18 2.0500 2.5395 4.40 4.60
p-Br 293 0.35 2.0522 2.5307 4.22 4-23
P-F 269 0.50 2.0606 2.5632 4.19 4.60
p-Me 279 0.23 2.0446 2.4795 4.67 4.44
nz-Me 279 0.35 2.0348 2.5288 4.69 444
o-Me 269 0.30 2.04 16 2.5 269 4.68 4.60
p-OMe 315 0.52 2.0534 2.5521 4.12 3.93
m-OMe 275 0.24 2.0417 2.1611 2.33 4.40
o-OMe 355 0.18 2.0550 2.5469 4.07 3.49
p-OH 350 0.54 2.0544 2.5854 3.32 3.54
p-N Me, 385 0.58 2.0662 2.5957 2.97 3.22
ni-NOZ 232 0.17 2.0426 1.9742 3.79 5.30
o-NO, 280 0.10 2.0434 2.0489 3.66 4.43
G = ground state, E = excited state.

356 Wataru Ando
Q+
09-
N=N
0 - 8- I
0.7 -
R
9' m-Meo-
"Me,
0.6 - p- NMe,
p-OH
0.5- PF p-OMe
d
.- I
/n-ct
-$ 0 4 - p-Me o
.B H
0.3- rn - OMe d p-Br
0 0 /O
,/o P-CL
0 . 2 - m-NO, 0~-N02,/ 0 0-CL
o----- o-OMe
/
01-
p-N02
I 1
19 2 0 2 1 22 23 24 25 2 6 2 7 2 8
Charge density of the diazo group in excited State
FIGURE9. The relationship between the quantum yield and the charge density of the
diazoniurn group. [Reproduced, with permission, from Tsunoda and Yarnaoka, J . Phoro-
graphic Sci. Japan, 29, 197 (1966).]
E. Reaction Intermediates
1. Radical species and carbonium ions
T h e products of the photodecomposition of p- and m-nitrobenzenediazoniurn
salts have becn studied in various solvents. It was found that the dominant primary
prccess in alcohol solution leads to nitrophenyl radicals, and the products are those
generally expected of a reaction involving a homolytic scission of the C-N bond.
7. Photolysis of p-NO&H,N:CI--
TADLE SnCI, in ethanolic solution
~~~ ~~ ~~~ ~
EtOH at 0 "C EtOH at - 10 "C EtOH +I, at 0 "C

Product (%) (%I (%I
~~~
Analysis not carried out but compound presumed present.

Nitrobenzene, a- and (3-arylethanol and butanediol are formed but 110 dinitro-
biphenyP5. Addition of 2,2-diphenylpicrylhydrazyl,halbgen or nitric oxide con-
firmed the importance of nitrophenyl radical formation in the pliotodccornposition.
However, all of the products cannot be explained on the basis of the one primary
process. T h e results are consistent with the occurrence of two primary processes,
( I ) and (2) :
O,NC,H,N: X-+hv O,NC,H,*+N,+X- (1 1
O,NC,H,N: X-1-h~ ___+ O,NC,H:+N,+X- (2)

where X- is CI-, SnC1,- or ion solvent dipole complexes, ctc. Presumably (1) is
followed by the secondary radical reactions which lead to the final products; in
ethanol solution the suggested secondary reactions are:
O,NC,H,*+CH,CH,OH ___t C,H,NO,+CH,CHOH (3)

O,NC,H,*+CH,CH,OH ____+ C,H,NO,+*CH,CH,OH (4)
OzNC,H,*+*CH,CH,OH
2 CHkHOH
-
- O,NC,H,CH,CH,OH
CH,CHCHCH,
OH
I I
O,N c,H,-+ CH,~HOH

-
--+
OHOH
CH,CH,OH+CH,CHO
C,H,NO,+ CH,CHO
I
O,NC,H,*+*CH,CH,OH -- C,H,NO,+CH,=CHOH
CH,CHO
The absence of dinitrobiphenyls in the reaction products suggests that the nitro-
phenyl radicals are converted primarily to nitrobenzene and other products via
-
reactions (3) and (4).
The second primary process (2) of lower probability was suggested to explain the
-
ether formation in the ethanol solutions:
O,NC,H:+CH,CH,OH
f
O,NC,H.OCH,CH,+H+ (5)
To test the mechanisms (2) and ( 5 ) , the diazoniurn salt was photolysed in the
-
presence of iodine. The amount of p-nitrophenetole was not essentially decrcascd
although the yield of nitrobenzene, which reflects the activity of the p-nitrophenyl
radical, was greatly decreased due to the very fast reaction (6) :
O,NC,H,*+I, OzNC,H,I (6)
358 Wataru Ando
There is a striking contrast between the products of the photodecomposition of
the diazonium salt in alcohol and in aqueous solution. Nitrobenzenc, the major
product in alcohol, is not detected in aqueous solution. Nitrophenol and nitro-
chlorobenzene dominate in water solutions. These results, coupled with product
8. Variation of product yield in the photolysis of p-N0,C,H4N:

TABLE CI-. 3 SnCI, in
various solutions
Solvent (%)
_ _ _ ~
5.3 hl- 9 hi- 4.3 M-

Product EtOH MeOH H,O NaCl(aq) HCl(aq) H,SO,(aq)
PhNO, 76.6 71.9 0.0 0.0 0.0 0.0
p-N02C,H,OR 5.3 3.5 0.0 0.0 0.0 0.0
p-NO,Cb H,lCI 0.0 0.0 7.4 30.2 61.6 0.0
p-NOZC,H4OI-I 0.0 0.0 73.5 50.8 23.2 84.3
Coupled product 0.0 0.0 4.1 5.2 0.0 0.0
studies with nitric oxide and hydroquinone, suggest that free radical formation is
unimportant in the photodecomposition of nitrobenzencdiazonium salts in aqueous
mlution. T h e results are consistent with the occurrence of a single primary photo-
-
decomposition mode, process (2), under these conditions. The product distribution
in solutions of varied chloride content results from the competition between Cl-
-
and H,O for the carbonium ion.
O,NC,H,++CI- O,NC,H,CI
O,NC,H,++H,O ON,C,H,OH:
ON,C~H,OH+H+
Boudreaux and B o ~ l e thave
~ ~ made magnetic measurements on the irradiated
aqueous solutions of p-dirnethylaminobenzenediazonium chloride. They have
suggested that the observed magnetism is due to the C1- radical and to the
Me,NC8H4* radical, 2nd they have estimated that the steady-state concentration
of radicals is about 1 x M. This conclusion seems untenable in view of the work
of Zandstra and E ~ l e t h Photolytic
~~. decomposition of p-diniethylaminobenzene-
diazonium chloride in aqueous solution at p H above 5 leads to the formation of a
paramagnetic species. The e.s.r. spectrum is the same as that obtained in air
oxidation of p-dimethylaminophenol in the same p H range. Hence the structure of
the photolytic radical could be established as the p-dimethylaminophenoxy radical.
Similarly, p-diethylarninobenzenediazonium chloride was photolytically decomposed
to yield the corresponding phenoxy radical.
!n the presence of chloride ion, aryl chlorides as well as phenols result from the
photolysis of arenediazonium salts in aqueous solution, as in the thermal reaction?'.
Benzenediazonium ion in aqueous sodium chloride yields just as much chloro-
benzene by photolysis as it does thermally at the same temperature, but thep-methyl-
and p-chloro-benzenediazoniunisalts give a significantly higher yield of the chloride
photochemically than thermally". A similarity, but not identity, of product-
determining steps is indicated. When p-MeCBH415N+=Nand p-MeOC,H41SN=N
9. Photochemistry of th: diazoniunl and diazo groups 359
9. Yield of aryl chloride from photo-
TABLE
lysis of diazonium salt, R O N : , in
aqueous sodium chloride

R NnCI ArCl(%>
~ ~~ ~
H 0.3 2.5 (2.5)O

1 .o 8.5
3.0 19-3
Me 0.2 3.2 (2-l)b
1 .o 1 1 *O(6.8)
3 .O 24.1 (16.6)
Cl 0.2 3.8 (2.5)'
1 *o 1 1.9 (7.7)
3.0 24.2 (1 8.7)
a Thermolysis at 3 "C.
a Thermolysis at 49 "C.
Tliermolysis at 80 "C.
are exposed to light insufficient to complete the photolysis, the residual diazonium
salt is in part rearranged to ArN+=lSN, significantly more than i n the corre-
sponding dark reaction. This allows us to reject the aryl cation as the only inter-
mediate. A simple mechanism adequate to describe all results is given below:
Reaction (7) conceals the complex process following the absorption of light and
leading to a state D* (uncstablished multiplicity) stable enough to undergo the
biniolecular reactions (10) and ( I 1 ) . Reaction (S) is included simply because i t
seems unreasonable that reaction (9) \vould occur without reaction (S). I t is attractive
to identify D* with the intermediate in t h e photolysis of thep-nitrobenzenediazonium
-
ion, which may participate in water reactions (10) and (11) as well as in ethano!,
-
reactions (12) and (13), to account for all the observed products:
D'+EtOH ArOEt+N,+H+ (12)
D'tEtOH Ar.+N,+CH,eHOH+H+ (13)
One may speculate that D* corresponds to the species observed by Lee, Calvert
and M a l ~ n b e r gin~ ~the low temperature irradiation of p-dimethylaminobenzene-
diazonium hexachlorostannate, for which the symmetric structure (12) was
tentatively suggested by Calvert and PitW9.
360 Wataru Ando
2. Cis-trans isomerization
T h e light-induced rearrangements of diazo compounds also give some information
for the reaction intermediate of diazonium salts, but only the diazosulphonates
ArN=NSO,Na and the diazocyanides A r N = N C N havc been studied in detail'.
It is assumcd that these exist in two forms: the unstable cis form, able to take
part in the reaction of azo coupling, and the stable, inactive, trans form which
cither takcs part in such a reaction only with great difficulty or not at all.
/I I. /
S0,Na
N=N, <- ,N=N
Ar ' S0,Na -+ Ar
C/s isomer. u n s t a b l e Trans isomer, stable
active forni inactive form
Hartlcy'O found that, when irradiated in a non-ionizing solvent (benzene), the

stable diazocyanide is convertcd to the unstable isomer which is in a state of
equilibrium with t h e stable form, and can be detected by its absorption spectrum.
While irradiating the stable diazocyanide in ethanol in the presence of silver nitrate,
Stephenson and Waters" showed that when the irradiation lasts a sufficiently long
time, silver cyanide precipitates quantitatively from the solution, and the diazo-
cyanide is convertcd to thc diazonium nitrate. When comparing these results with
the rcsults of Hartley, they arrived at thc conclusion that diazonium cyanide could be
obtained only as a result of the action of light on the labile form of diazocyanide,
sincc thcy wcrc ablc to show that the stable form of diazocyanide was unable t o
undergo this reaction in the dark and, consequently, no direct conversion of the
stable diazocyanidc to diazonium cyanide took place on irradiation. In non-polar
solvents the process of photostercoisomerization is confined, a s a rule, to the
formation of the unstable stereoisomer, whereas irradiation in polar solvents,
e.g. ethanol or acetone, results in the complete decomposition of the diazo group:
b;N ;fyN=N\ + b
S0,Na
/
N=N+
'. :- S0,Na __
+ SO;- + Na'
<~\
c,
Contrary to thc above \vork, d e Jonge and D i j k ~ t r anoticed
~ ~ that immediately after
irradiation of thc stable diazosulphonate in solution, the anion of sulphurous acid
and the diazonium cation are dctected, which slowly reacted with one another in
darkness, to givc the initial stable diazosulphonatc. The elimination of one of
the ions, for instancc the prccipitatioti of the SO:- anions with lead salts and/or the
conversion of the diazo cation to an azo dye, cuts short the dark reaction, and the
system does not revert to thc initial state. .4 short duration, high intensity irradiation
of neutral solutions of p-niethoxy- or o-chloro-p-methyl-benzenediazosulphonate
results in an intermittent increase i n the p H of the solution. After the light source
has been turncd oA', the solution reverts gradually to the original state, and the pH
decreascs to tlic initial value. This phenomenon becomes understandable if we
assume that, as a result of the action of light, there occurs at least partial
dissociation of diazosulphonntc according to the equation:
9. Photochemistry of the dizzoriium and diazo groups 361
Now, the solution of the initial diazosulphonate is neutral, but the product is a
salt of the weak sulphurous acid, and the p H of the solution therefore increases.
During more prolonged exposure the process becomes irreversible because of the
decomposition of the diazonium cation.
ArN:+H,O & ArOH+N,+H+
3. Sensitized photolysis of diazonium salts

The photolysis of diazonium salts in solution has been spectrally sensitized with
dyes in the presence of activators, such a s amine associates, thiourea a n d its
derivatives, and benzenesulphinate iona3. p-Anilinobenzenediazonium sulphate (13)
was photolysed in the presence of methylene blue and of 1,4-diazobicyclo[2.2.2]-
octane (DABCO) or sodium p-toluenesulphinate (STS). Figure 10 shows the
1.2
1.0
0)
g 0.8
n
0
5 0.6
n
a
0.4
0.2
400 500 600 700

X (nm)
10. Absorption spectra of solutions of 13 containing methylene blue and activator
FIGURE
under anaerobic conditions.
absorption spectra of the solution before and after irradiation. The quantum yields
were also p H sensi!ive. Figure 11 shows the variation in the quantum yields a s a
function of pH under aerobic conditions. It is seen that the p H for greatest dye
sensitization differs markedly between the two activators. I n the DABCO system,
the dye sensitization was restricted to a n alkaline range starting at about pH 7.
Lower pHs may accentuate the formation of the protonated form of DABCO
which results in a loss of photo-initiating activity.
T h e data given show clearly a greater range of activity in the STS system. T h e
quantum yield increased with a n increase in solution in the p H range below 7, and
decreased with greater alkalinity.
It may be inferred that the dye-sensitized photolysis of (13) does not take place
via the sulphonyl radical, which is formed from the dye triplet reaction with a
sulphinate ion, and which is a n efficient initiator for polymerization.
-
362 Wataru Ando
-
T h e reaction related to the sensitization may be written as follows:
Sens (G)+hu 5ens'
'Sens*+DABCO ___j (Sens - - - DABCO) Sens.+DABCO
Sens*+(ll) ___j Sens (G)+N,+Ar.
T h e key step of the sensitizing system may be the escape of Sens., semi-methylene
blue, from the dye-activator complex, Sens - - - DABCO, which is formed by
interaction of the excited triplet dye with unprotonated DABCO. The complex
undergoes collisional deactivation and dissociation to the semi-methylene blue
and a half-oxidized activator.
0.6
2
'u
0-5
x
0 4
cs 0 3
0
6 0-2
0-1
4 5 6 7 8 9
PH
11. Depcndence of quantum yields on solution pH under aerobic conditions.
FIGURE
111. PHOTOLYSIS OF ALIPHATIC D l A Z O N l U M COMPOUNDS

Photolysis of the sodium salts 14 and 15 of camphor and fenchone arenesulphonyl
hydrazone, respectively, gives both cso- and cndo-diazoniuni ions. In each case a
mixture of pinyl and tcrpinyl products is formed rogethcr with bornyl products
from 14 and fenchyl from 15, without any cross-over of thesc series. The ratio of
piny1 to terpinyl products recluircs that two isomeric, interconverting cations of
pinyl type 16 and 17 are formed. Similar results are reported for the apocaniphor
s c r i e P . On the other hand, the p-tolucnesulphonylhydrazone of norbornanone
protonates exclusively from the ordo face, atyording cso-2-norbornanediazonium
ion which gives nortricyclene and exo-3-norbornyl etlicrl>. Photolysis of the tosyl-
hydrazone (18) gives t h e tricyclo[3.2.1 .02~']oct-3-en-6-ylcation (19), which rearranges
reversibly to 20 at a rate competing with solvent attacka6.The tosylhydrazones, 21,
28 and 30, \vex prepared from 4-hydroxy-o~r/o-tricyclo[4.2.1 .02~5]non-7-e~i-3-one
and utilized in the deanlinative pinacol rearrangement to crrdo-tricyclo[3.2.1 .O 2,"
1-
oct-6-ene derivatives". The hydroxy compound 21 underwent ret roaldol cleavage

exclusively on irradiation in metlianol/NaOlLIe; 28 and 33 afforded the desircd
c~ndo-tricyclo[3.2.1.O 2~ i]oct-6-ene derivative, 29 and 32, rcspectively. Competing
processes such as double-bond participation i n the case of 28. arid hydride shift
i n the casc of 30, render these pinacol rcarrangeinents lcss cficicnt than the related
9. Photochcrnistry of the diazonium and diazo groups 363
- + Piny1 and
terpinyl
prod I: c I s
Na
NN
I Fenchyl
S0,PIl c_f
products
(1 5)
H
364 Wataru Ando
U
rz
-
' ,H
I - ii
fd eO
i 3
0
9. Photochcmistry of thc diazonium and diazo groups 365
Favorskii reaction. T h e bicyclo[4.2. Ilnona-2,4,7-trien-9-yl cation has invoked
interest because of its potential hon~oaromaticity.i8and bicycloaromaticity4Q. T h e
solvolysis of s~vz-bicyclo[4.2.1lnona-2,4,7-tricn-9-yl p-toluenesulphonate (33) afforded
exo-dihydrnindenyl acetate (34) and/or indene5'. 52, depending o n the reaction
conditions. Deamination, on t h e other hand, starting from the highly energetic
diazonium ion, passes its transilion state 'early' and without significant distortion
of nuclear positions (vertical ionization)". Consequently, deaniination may produce
cations of undistorted geometry which are by-passed in solvolysis (leading directly
to more stable bridged species). Photolysis of bicyclo[4.2.l]nona-2,4,7-trien-9-one
.A.---
tosylhydrazone (37) in MeOH-MeONa afforded sy~r-9-methoxybicyclo[4.2.1]-

nona-2,4,7-triene (40) and (35) as the major products. Minor products were endo-
dihydroindenyl methyl ether (41), indenyl methyl ether (42) and indene. Photolysis
of tosylhydrazone sodium salts generates diazo compounds which are protonated
by protic solvents t o give diazoniuin ions and products derived therefrom. Various
+ + + 36
OMe OMe
(35) (41 1 (42)
bicyclo[2.2.l]hcptcnyl (47) and bicyclo[3.2.0]heptenyl (SO) cations have been

generated by decomposition of suitable diazonium precursors (43 and 53). The
cations 47 and 50 d o not equilibrate, and their substitution pattern is largely
independent of the specific precursor5'.
366 Wataru Ando
NHNHTS
a NNHTs
H
I
H
IV. PHOTOLYSIS O F DIAZO COMPOUNDS

The photolysis of diazo compounds is an important route to the formation of
carbenes :
R R
\ \
C=N, -I- 111. ---+ C: + N,
/
R R’
Many rcvicivs and descriptions or carbencs are available55-M.5.
9. Photochemistry of the diazoniunl and diazo groups 367
A. The Structure of Carbenes
Two electronic configurations may occur: a singlet configuration (A) or a triplet
configuration (B).
The electronic spectrum of methylene produced in the gas phase by flash photolysis
of CH,N?, CHDN, and CD,N2 was recorded by Herzberg and Shoosmiths6. E.s.r.
spectra of methylene trapped in a xenon matrix at 4.2 X have been one of the most
recent achievements in this fielde7.Be.
The e.s.r. signal survived warming to 20 K but disappeared upon warming to
77 K. Analysis of thc results demonstrated the roduction of a linear or near-
linear species with a C-H bond length of 1.03 which absorbed U.V. radiation
at about 1414 A, and a bent species, bond angle 102-103", C-H bond length 1.12 A,
which absorbed radiation in the 5500-9500 A region. Moreover, in the presence
of a large excess of nitrogen, the absorption of the short wavelength, lincar CH2
increased at the expense of that of the long wavelength, bent CH,. This experiment
pointed to triplet CI-I, as ground state. The short-lived bent or singlet C H 2 was
being degraded through collisions with the moderator, nitrogen, and dropping to
the more stable species. Wasserman and coworkersae observed two species with
D = 0.6636 cm-I, E = 0.002 cm-' and D = 0.6844 cni-', E = 0.00347 cm-',
respectively. T h e value of D is related to the average l/r3 where r is the distance
between the two spins, so that a high value of D implies a large spin-spin inter-
action and a close proximity of the two spins. The value of E indicates qualitatively
the magnitude of the deviation of the spin-spin interaction from cylindrical symmetry.
The site with the lower D and E values in methylene is believed to allow greater
motional freedom; a bent molecule which rotates freely about the long axis will
have E = 0. Wasserman and coworkers arrived at a H-e-H angle of 136" in good
agreement with most theoretical calculations. Angles of 150-155" have beenestimated
for phenyl- and diphenyl-carbenes. I t was found that for diphenylcarbene the niagni-
tude of D = 0.4055 cm-I and E = 0.0194 cm-l shows a small dependence on the
nature of the host matrix:
[Reprinted, with pcrmission, from Trozzolo, Acroitnts Cliern. Res., 1, 329 (1968). Copyright
by the American Chemical Society.]
The higher D value of diphenylcarbene shows that two unpaired electrons are
largely localized on the divalent carbon atom*".
An orbital representation comparing a triplet ground-stare molecule with a
phosphorescent triplet state is given by Figure 12. Several carbenes have been
assigned a triplct ground state by e.p.r. experiment^^^-^^. Non-radical products of
photolysis of diazo compounds can not be determined by the e.p.r. technique, SO
368 Wataru Ando
that it became necessary to study the optical spectroscopy of the carbene species.
Ultraviolet spectroscopy, fluorescence excitation and absorption spectroscopy have
been used to study the carbene problem.
t
11 t 11
11 11 11
Singlet Phosphorescent Triplet
ground state triplet ground state
FIGURE12. Orbital representation of spin state. [Reprinted, with permission, from Trozzolo,
Accounrs Chem. Res., 1, 329 (1968). Copyright by the American Chemical Society.]
Closs and coworkers rcported the long-wavelength absorption band of diphenyl-

carbene oriented in single crystals of 1, l-diphenylethyleneQE.Moritani and coworkers
found two new absorption bands in photolysed solutions of diphenyldiazomethane,
by correlating e.s.r. studies, fluorescence, fluorescence excitation and absorption
spectroscopys7. Gibbons and Trozzolo reported the luminescence, excitation and
absorption spectra of d i p h e n y l c ~ b e n e T
~ h~ e. same spectrum was obtained for all
excitation wavelengths in the range 230-470 nm. The emission was identified as the
fluorescence of triplet ground-state diphenylcarbeneaa~ loo.
Excitation:
(b) 3 0 0 n m
0' I I I I I
300 350 400 450 500 550 600 650
Wavelenqt h ( n mi 1
FIGURE13. Luminesccnce of diphcnylcarbene. [Reprinted, with permission, from Trozzolo,
Accowirs Chen~.Res., 1, 329 (1968). Copyright by the Arncrican Chcmical Society.]
9. Photochcniistry OF the diazonium and diazo groups 3 69
T h e photolysis of other diaryldiazomethanes gave almost exclusively the corre-
sponding substituted diphenylniethylene which e.s.r. studies have shown to be
ground-state triplet molecules i n each case.
T h e maxima of both the absorption and emission bands were shifted to longer
wavelengths from those of diphenylcarbene; the short wavelength bands were more
intense than the visible range bands. The absorptions are considered to involve
x-x* transitions (Table 10). Moritani and coworkersg7~ lol have obtained the
TABLE10. Spcctra of diphenylmethylenes, R

0-e-0
in 2-methyltetrahydrofuran. [Reprinted. with permission, from
Trozzolo, Accoroifs Chew. Res., 1, 329 (1968). Copyright by the
American Chemical Society.]
R Absorption tnax. (nm) Emission max. (nm)
H 300. 465 480
CI 31 1, 475 487
Me 301,473, 487
OMe 335, 345 495
N 0, 265, 370, 555 No emission
Ph 355 555
electronic spectrum of 61 (Amnx 510 nm) by photolysis of the corresponding diazo

compound (60) in a variety of rigid matrices at 77 K and also in liquid paraffin a t
room temperature. The final product is the free radical dinier, and the decay of 61
I
V
Dimer ic
product
was assigned to the doublet free-radical 62. The e.s.r. spectra obtained by photolysis
of 3-bis(diazomethyl)benzene and 1,3-bis(cc-diazobenzyl)benzenc were much more
complex than those observed with triplet states1o2.lU3. The data have been analysed
in terms of the corresponding quintet ground states of the dicarbencs 63 and 64.
(63) (64)
I n a prim arrangenlent, resonancc interaction permits the ground state to be a

quinonoid triplet, rather than a quintet1o*.
370 Vt’ataru Ando
Quinonoid triplet Quintet
E.s.r. experiments also show that at 4 K or 77 K, such triplets as a-naphthylcarbene

can exist in two non-interconverting isomeric forms, which are possible since the
H H
11 c’ ‘ctt
I
triplet is not linear. Delocalization of o n e of the triplet’s electrons over the x-system
presumably provides enough double-bond character between the carbenic centre
and the ring to provide a barrier to rotational interconversion at 77 K Io5.
The spectrum of 9,9’-dianthrylcarbene (65) reveals that it is linear, however, with
two aromatic systems lying orthogonally. This structure permits extensive de-
localization through allenic resonance forms such as 65a Io8. The septet ground
11
-C
state is suggested for the tris-carbene (66)on the basis of its e.s.r.
Ph
=/
B. Chemical Induced Dynamic Nuclear Polarization ( C I D N P ) Studies

In the C I D N P method, the existence of a radical intermediate in a reaction is
implied through n.m.r. investigation of the product of that reaction a s it is being
formed. Polarization of the product by radical precursors may be observed experi-
mentally as enhanced absorption or as emission in the n.m.r. spectrum of the
productlO*. The observed signal directions are determined by the initial electron
spin multiplicity of the radical pair a n d of its p r e c ~ r s o r ~ A~ ~set- ~of~ ~simple
.
selection rules based on the radical pair model has been developed to permit
qualitative prediction of the effects11J.
Methylene has been the subject of extensive C I D N P investigation in its reactions
with alkyl halides and p ~ l y h a l o m e t h a n e s ~ ~ ~ - ~ ~ * .
Singiet methylene produced via direct photolysis of diazirine reacts with a
chlorine atom of CDCI, to give polarized CI,DC-CH,CI 'ID, probably through
the formation of a chloroniuni ylide which gives the polarized product via a radical-
pair intermediate. Similar reaction of diazirine forms a triplet radical pair by
deuterium atom abstraction from CDCI,; recombination of the resulting radical
pair then affords polarized CI&- CDCH, 'lS,
direct N sens.
tICH2 H,C:I/ t!CH,
1
N
CDCI,
+
c
1 CDCI,
I
1
I
[ C I,DC -C I - H, CI,C-.CDCH,
Radical pair
rccombination
V
Polarized CI,C -C DCH,
I Radical pair
recombination
Polarized C12DC-.CH,CI
T h e fundamental difference in the mechanism of reaction of singlet and triplet

methylene with toluene has been shown by a n investigation of the direct and
sensitized photolysis of diazomethane*18.Ethyl benzene is formed in both cases,
-
but direct photolysis gives methylene which inserts concertedly (no C I D N P signal
being observed) whereas the sensitized photolysis gives a signal consistent with a
mechanism involving energy transfer and triplet methylene (equations 14-1 7). The
Sens ( S o ) ___+
AY
Sens (S,)
-
-
Sens (T,)
Sens (S,)+RR'C=N,(T,)
-
Sens (T,)+RR'C=N,(S,) (14)
RR'C=N,(T,) RR'C:(T,)+N, (1 5)
RR'C:(T,)+SH RR+H+S- (16)
RR*~H+S. RR'CHS (1 7)
photosensitized decomposition of methyl diazoacetate was studied by examining the

effect of the diazoacetate on the C I D N P phenomena observed during the irradiation
of benzaldehyde and benzoin in deuterated cyclohexancbenzene solutions. The
CIDNP spectra generated by photolysis of benzoin were not changed significantly
by the addition of !he diazoacetate. I n contrast, the spectra observed during the
irradiation of benzaldehyde were suppressed by addition of diazoacetste and
replaced by C I D N P signals of products formed by reaction of diazoacetate with
benzaldehyde or with cyclohexane-d,,. These results show the energy transfer from
benzaldehyde to methyl diazoacetate leading to triplet carbornethoxycarbene121.
Photolytic decomposition of methyl diazoacetate in the presence of carbon
tetrachloride and deuterochlorofornl affords methyl 2,3,3,3-tetrachloropropionate
and methyl 3-deutero-2,3,3-trichloropropionate, respectively'?'. T h e slow decay of
13
372 Wataru Ando
hv PhCHO
PhCHO ---+ JPhCHO P h k 6 -I- H-ePh
1 1
OH
N,CHCOOMe
0 OH
II I
1
PhC-CHPh
'XHCOOMe PhCHO
[PhtO + -CH,COOMel
1Vdt2 1
CH0,COOMe + 1p t- Q+ .CHDCOOMe
0
II
PhC-CH,COOMe
the observed emission signals due to these polarized products suggested that the
products of the reaction were being formed after irradiation ceased. Primarily o n
the basis of this observation, a free radical chain mechanism was forwarded for the
reactions of carbomethoxycarbene with carbon tetrachloride and deuterochloroform.
However, this conclusion has recently been reconsidered in the light of the radical-
pair theory of C I D N P which does not allow spin polarization in a radical-induced
recombination The preferred mechanism t o account for the formation of
-
the methyl propionates involved carbene attack at halogen with consequent ylide
formation124:
I
1-
R- C -CI +:CH CO 0R'
I
[ :+
R-C-CI-EHCOOR' .CHCICOOR'
The recombination of geminate pairs formed presumably by homolysis of a

I
RC-CHCICOOR'
I
chloronium ylide is the more likely mechanism. The I3C C I D N P patterns are in
accord with the cage recombination of radical pairs, but inconsistent with a radical
chain m e c h a n i ~ r n ' ~ ~ .
Closs compared the photolysis of diphenyldiazomethane in toluene solution'"
and the thermal o r photolytic decomposition of the azo compound 67. Both
reactions afforded the same products 68-70, but the ratio of unsymmetrical to
9. Pliotocheniistry of the diazoniiim and diazo groups 373
symmetrical products 68/(69+70) was higher in the reaction of 67 (ratio 1.5 : 1)
than in the diphenylcarbene reaction (ratio 1 : 1). T h e n.m.r. spectra obtained
from the two reactions showcd opposite polarization in confirmation of theoretical
predictions for radical pairs of different multiplicity. Since there is little doubt that
acyclic azo compounds decompose through the singlet state"', this experiment
assigns triplet multiplicity to the radical pairs intervening in the diphenylcarbene
reaction.
Pt i ,C HN= NCH,P h Ph,CN, + PIICH,
(67)
P h?CH 11C H,Ph Ph,CH t t CH,Ph
Ph,CHCH,Ph + Ph,CHCHPIi, -I- PhCH,CH,Ph

(68) (69) (70)
C. Spin Multiplicity and Reactivity of Methylene

A principal aim in the photochemistry of diazo compounds is to correlate thc
observed chemistry with the multiplicity, singlet or triplet, of the carbenes formed.
-
Two typical reactions are observed: insertion into a C-H bond and addition t o a n
unsaturated bond :
/I 1'
I
N,CH, __f :CH, I R--C-CH,--H (insertion)
R-C--H I
I
\ /
c-c
NzCHz _ _ f
/I I.
:CH,
/
1 'C' \ (addition)
/c = c \ / \
H H
-
Singlet methylenc 'CH, gencratcd by the photolysis of diazomethane inserts into the
C-H bonds of alkanes with nearly random statistical preferences. An example is
provided by the liquid phase photolysis of diazomethane in 2 - m e : h y l b ~ t a n e ~ ~ ~ :
'CH,+CH,CHCH,CH, H-CH,CH,CHCH,CH,
I I
CH,
CH,-H
I
CH,CHCHCH,+ CH,CHCH,CH2-CH2-H+CH,CCH,CHl
I I I
CH, CHl CH,
1.22
_.
1a 0 5
- -
1*5l/bond
374 Wataru Ando
Only slight prefercnces for the tertiary hydrogen (1.5 I ) and the secondary hydrogen
(1 *22)appear.
One may ask whether the CH, insertion is direct or whether some intermediate,
such as a radical pair, is involved. Doering and Prinzbach'?' photolysed diazo-
methane in the Dresence of 2-niethyl[ I-*4C]propencand studied the distribution of
the radioactive label within 2-methyl-I -butene, the product of allylic C-H insertion.
*
,C=CH,
H,C
V
I
CH~?H,
\
,C=CH,
H,C
(72)
I n the liquid phase less than 2% scrambling occurred, whereas 8% of 72 was
obtained in the vapour phase.
Studying the configurational relationship between substrate and insertion product,
Franzen reported that methylene reacted with the tertiary carbon-hydrogen bonds
in the trans diacetate (73)with However, generally the insertion of
(73)
carbene has been shown to proceed with retention130.Optical activity is maintained
in the reaction with the rnethoxy~arbonylcarbene~~~ and methyl-( -)(S)-2-methoxy-
propionate and silicon-hydrogen bond131,13'..
Ho and Noyes had shown that the reactior. of triplet methylene with propane
involved a b ~ t r a c t i o n ' ~since
~ , dimeric products, hexanc and 2,3-dimethylbutane,
were isolated :
.'H3- + 'v + C- LH3p +
Average values for the relative rates of abstraction by triplet carbene are: primary/
secondary/tertiary = 11217.
Incisive information concerning the chemical characteristics of singlet and triplet
carbenes comes from study of addition reactions involving carbon-carbon double
b0nd~'~j-l~~.
As in C-H insertion, singlet methylene adds stereospecifically in a concerted
step: both bonds of the cyclopropanc are formed simultaneously since such a step
may occur with spin conservation. The additions of 'CH2 (from photolysis of
diazomethane in liquid phase) to cis-2-butene and trans-2-butene yield only cis-
1 ,Zcyclopropane and trans- 1,2-dimethylcyclopropane,respectively. These additions
are stereospecific; the geometrical relationship of the olefinic substituents is preserved
in the products:
\=/ + 'CH, -. v
\ + 'CH, + b
This behaviour has been taken as evidence hat t h addition of 'CH, D a n olefin
is a direct reaction and n o diradical intermediate intervenes. Triplet methylene
generated in the gas phase by the mercury photosensitized decomposition of ketene
adds to olefins with greater discrimination: e.g. its addition to butadiene is
6.6 times faster than to isobutene; the corresponding ratio with singlet methylene
is 3.2. The increased preference of T H 2 for butadiene can be attributed to the
11. Relative rates of mcthylene addition to
TABLE
~lcfins'~~
0.91 0.96
1.07 0.64
1 -0OC 1 .ooc
0-5s 0.33
0.65 0.3 1
3.20 6.64
0.87 0.56
0.72 0.35
0.68 0.35
a From photolysis of ketcne with 2600 A.
* From mercury photosensitizcd reaction of
kctene with 2537 A.
C Standard.
radical character of this addition, which presumably involves a diradical intermediate

somewhat stabilized by allylic resonance:
376 Wataru Ando
T h e addition of triplet methylene to cis- and trans-2-butenes is an indirect, two-
step reaction and takes place non-stereospecifically. Both cis- and trans-
1,2-dimethylcyclopropanesare formed from eithe; starting olefin. This phenomenon,
which is now believed to be diagnostic for triplet carbene additions, is most readily
understood in terms of the Skell-Woodworth hypothesis.
Skell argued that the addition of a triplet carbene to an olefin would generate a
triplet trimethylene intermediate, in which rotation about t h e single C - C bonds
would be at least as rapid as thc spin inversion needed before formation of the final
cyclopropane C - C bond could occur. The addition of a triplet carbene to cis-
or trans-2-butene should then yield both cis- and trans-I ,2-dimethylcyclopropanes.
O n the other hand, addition of a singlet carbene could l x.stereospecific, since there
would be no spin restriction on the simultaneous formation of both cyclopropane
C - C bonds.
H
'XR +
H
'CH, _j
+ H %%:
R R
V
I
R
H'v,; \d'H
H
d
SCHEME
3
Dilution with a 200-fold excess of inert perfluoropropane induces some inter-

system crossing in either the diazoniethane, or more likely in the methylene itself,
as the following product distributions l40:
I1 I .
N,CH, + +
None (%) 47.5 0.4 0.2 0.3 0.0 39.1 12.5

Excess(%) G0.4 13.3 61 1.9 7.1 9.3 1.9
SCHEME
4
Methylene produced by irradiation of diazomethane in the vapour phase in the
presence of high pressure inert gases gives non-stereospecific addition to
2-butenelW 1.1:
-----3
Olefins
Benzophenone-photosensitized decomposition of diazomethane induces a limited
non-stereospecificity in the addition reaction142. The sensitized reactions should
Ph,C=O + hi* ‘Ph,C=O ’Ph,C=O
’Ph2C=0 + N,CH, Ph,C=O + ’N,CH,
’CH, +
JN,CH,
w
- -
__f ’CH,
(1.9)
+ N,
(1 1
’CH, + \==, >- (trace) (mainly)
5
SCHEME
produce triplet methylene, while direct irradiation is known to produce the singlet.
I n the presence of an inert gas or in inert solvents, singlet methylene may decay to
the triplet before reacting with the unsaturated substrate.
A number of factors can influence the stereospecificity of the addition, notably
solvent cage effects or unusual rapid intersystem crossing. In spite of some diffi-
culties, Skell’s criterion appears to work well in practice in distinguishing between
singlet and triplet carbene species.
Theoretical justification has been forthcoming, through Extended Huckel Theory
(EHT) calculation^^^^-^^^.
A theoretical analysis of the addition of ’CH, to ethylene suggests initiation of the
reaction as in 74, a ‘x-approach’ in which the vacant p orbita! of the carbene begins
to overlap with the x-system. As reactants move along the reaction coordinate
towards product geometry, the x-approach goes over to a ‘ o - a p p r o a ~ h ” Transfer
~~.
of electron density from the olefin’s x-system to the carbene’s p orbital occurs;
this is an electrophilic addition131*147-1aQ.
n
(74) (75)
=-approach c-approach
378 Wataru Ando
More recent calculations suggest that ;;-approach 743 is energetically preferable
to x-approach 74b in the addition of singlet methylene. Addition of CF2 is calculated
to follow a similar course, with less charge transfer from olefin to carbene in the
transition statelso. Related calculations for additions of CH, and CF2 to isobutene
(744 (74b)
again suggest that 74a is preferred to 74b, but only by a small energy difference.
The results of these calculations must be treated cautiously, a s a guide t o thought
rather than as firm conclusions.
D. Photolysis of Aromatic Diazo Compounds in Olefins

I. Phenylcarbene
The ground state of phenylcarbene has been designated as triplet on the basis of
matrix isolation15*,which has been extended to 4 K Is*, and of its emission
and by extended Huckel calculation15J.
The chemical behaviour of phcnylcarbene generated by photolysis of phenyl-
diazomethane appears to be substantially singlet rather than triplet. Gutsche
p2 b, gl
reported only about 3% non-stereospecificity in the addition of phcnylcarbene to
Me R ' Me R' Me Rz
PhCHN, + "QR' 5 -t 4-
RZ
R' = H, R' = M e
R' = Me, R' = H
Pk
97%
2.5%
--
P I1
(svn)
51.1%
3%
Ph
(ant!)
46.4%
13. Relative rates of addition of arylcarbencs to olefins

TABLE
/I I'
CHN, d
R R
~~ ~
H 1.02 1.80 1.oo 0.9 1 3.3

rt1-a 1.27 I .79 1.oo 1.2 -
p-CI 1.14 I .9 1.oo 1.1 _-
P-MC 0.84 1.78 1.oo 0.83 2.4
p-OMe 0.70 1.6 1 .oo 0.77 -
frans-2-butene and about 2.5% non-stereospecificity in its addition to cis-2-butene lS5.
CIoss reported corresponding values of 0.5-1% and 3-5%156. T h e high stereo-
specificity can be takcn as support for a singlet statc of the reactive i n t e r m ~ d i a t e l ~ ~ .
The results could be consistent with triplet phenylcarbene addition if there was a
very fast ring closure allowing only incomplete rotanicr equilibration in the inter-
mediate triniethylene diradical. Moss and Doelling have presented evidence that
the properties of triplet phenylcarbene are quite different from those of the singletlS7.
These authors find that irradiation of a frozen solution of phenyldiazomethane in
cis- o r trans-2-butene yields not only cyclopropanes but products of abstraction-
recombination reactions as well. They suggest that triplet phenylcarbene reacts
largely by hydrogen abstraction.
PhCHN, +
0-c 2.1 92.7 1.4 0.4 3.5

-196 “ C 3.2 43.9 18.5 4.9 29.0
6
SCHEME
3PhCH: + \=/ ---+ P h i H , u >

- PhkH, r/
/ ! /
+
Y
Ph
Ptl Ph
SCHEME
7
-Y
2. Diphenylcarbene
In the photolysis of diphenyfdiazomethane in the presence of olefins the major
reaction path with cis- and trms-Z-butene is hydrogen abstraction from the allylic
positions, followed by recombination of the radical fragments. More highly substi-
tuted olefins give even greater percentages of abstraction-recombination :
Ph,CN, +
+ W C H P h Z
Ph Ph Ph Ph CHPh, 45.4%
380 Wataru Ando
With less substituted olefins cyclopropanes predominate, and with isobutene and
propene only cyclopropanes result. Clearly the mode of reaction ofdiphenylcarbene
(Table 13) depends intimately upon the olefinl6*:
F
Ph Ph
TABLE
13. Mode of reaction of diphenylcarbene with olefins
Cyclopropane Abstraction-Recombination
Olefin (%) (%)
L 100 0
100 0
3 87
74
13
26
52 48
22 78
8 92
0 100
Closs reports that cis-2-butene gives a cis : trans ratio of either 87 : 13 lS9 or 77 : 23 '"
-
and that frans-2-butene gives a trans : cis ratio 96 : 4 lS0.Thus they must be formed
mainly from the singlet state:
U W
Ph,C:
)( i- )( Total yield(%)
Ph Ph Ph Ph CyclopropaneOlefin
J
-/ 77% 23% 10 90
\ 4% 96% 10 90
There is a growing conviction that singlet and triplet diphenylcarbene a r e in

equilibrium, thus leading to reactions of both spin states occurring at the same
time:
'Ph,C: 7 SPh,C:
From cis-p-deuterostyrene and diphenylcarbene roughly 65% cis and 35% lrans
adducts were formed1SR:
Ph,C: + Ph D -+ yD+ phyD

Ph
Ph Ph Ph Ph
cis 65% l r a n s 35%
Obviously, in systems in which triplet abstraction is the primary reaction, the cyclo-
propanes will be formed largely from the singlet. This appears to be the case with
the 2-butene.
The stereospecificity increases at lower temperatures, for example, at - 10 "C
with cis-2-butene, cis- a n d trans-J ,2-dimethyl-3,3-diplienylcyclopropanes are
formed in a ratio of 3.2, while the corresponding ratio with tlmu-2-butene is only
0.04; at - 66 "C the product ratio obtained from cis-2-butene is 9.0.
The cis : t r m s cyclopropane ratio can be affected by addition of hexafluoro-
benzene, a molecule inert to diphenylcarbene158. With 80-95% hexafluorobenzene,
there c a n bc no more than 12% singlet reacting. Presumably unreactive collisions
allow diphenylcarbene to approach equilibrium more closely and the ground-
state triplet is naturally favoured. The presence of oxygen docs not change the isomer
ratio although the total yield of cyclic and acyclic hydrocarbons is greatly
diminished and approaches zero for high oxygen concentration.
TABLE 14. Addition of diphenylcarbene to styrene

in the presence of added hexnfluorobenzene
C , F, Cis adduct Tram ndduct

(mot .-%, (73 (YJ)
0 65 35
36 60 40
50 59 41
80 56 44
90 55 45
95 56 44
All these observations are most consistent with a mechanistic scheme as outlined
in below :
'Ph,C:
Ph Ph
A
382 Wataru Ando
It is postulated that intersystem crossing is much faster than any other reaction.
Furthermore, it is assumed that the reverse crossing is also very fast so that both
electronic configurations a r e effectively in equilibrium.
One might well expect a triplet to be more likely to undergo 1,4-addition than a
singlet, since the intermediate diradical might not be restricted to 1,2-closure. Even
with triplets, however, acyclic dienes yield only 1 , 2 - a d d u ~ t s ' l6I.
~~.
Ph,C=CHCH=C(CH,), +
b n
Ph Ph
Triplet diphenylcarbene reacts with alkynes by addition and abstraction, and each
of the reactions is a two-step process. With monosubstituted acetylenes, indenes
are the sole products as shown. Addition of diphenylcarbene to the less substituted
Ph,C: + HCrCR +
a: R = Me
b: R = I-Bu
C: R = Ph
R
I
end of the acetylenes generates 76, which may or may not be initially the triplet
carbene shown, but in any event it should quickly relax to yield 77.In t h e reaction
of diphcnylcarbene with dimethylacetylene, the main products are the cyclopropene
(79) and the allene (80). Compound 80 is probably the product of hydrogen
9. Photochemistry of the diazoniuin and diazo groups 383
abstraction reflecting the unavailability of a n unsubstituted end of the acetylene for
attack by diphenylcarbene. Howcvcr, both 78 and 79 are formed through addition
to give 81. T h e added methyl group causes a new effect: the most obvious diflerence
between 81 and 76 involves the methyl-aromatic ortho-hydrogen interaction
dpz
indicated in 81.
PhaC: + CH,CECCH3 ----f + C y " ' + H,C=C=C /

CHPh,
1
Ph Ph c H,
(78) 2%
(79) 75% (80) 25%
I *--/\.\
__f 79
Ph Ph
(81 1 (82)
Competition between cis-P-deuterostyrene and methylacetylene for the irradiation

product of diphenyldiazomethane gave mainly addition to styrene and only traces
of indene. This is reasonable, since styrene is a much better triplet trap than propene.
Phenylacetylene competes more successfully and 25% of the products in a com-
petition reaction with styrene are derived from addition to the acetylene.
PhZC: + PhCH=CHD + CH,C-CH - py

Ph Ph
cis/frans = 59/41
(Dimethoxyphosphory1)phenylcarbene (84), produced photolytically from 83,

reacts with alkynes 10 give satisfactory yields of dimethyl I -phenyl-2-cyclopropenyl-
phosphonates (85) 16*. With monosubstituted alkynes, ring closure to dimethyl-
3-indenylphosphonates (88) competes with the formation of 85. The carbene 84
II
N,
II
0
Ph-C-P(OCH,),
(83)
hv
__f
0
II
Ph-c-P(OCH,),
(84)
R'C-CR'
___f
RY
Ph P(OCH,),
I1
0
(85)
R' = R' = Ph, 61%
R' = R y = Me, 55%
R1 = Ph, R' = M e , 41%
R' = Me, R' = H, 59%
apparently attacks the unsubstituted alkyne carbon atom with formation of the
diradical 86 which yields first 87 and then 88.
Wataru Ando
84 -1 RCGCH
VI
O= P(0C H, )? O=;P(OCH,), O=P(OCH,),
(86) R
(87)
R = Ph, 18% O=P(OCH,),
R = Me, 38%
R
(88)
Moritani and c o ~ o r k e r s found
l ~ ~ that cyclopropanes were not formed by attack
of 89 on 2-butene but that some products of abstraction-recombination could be
found. The similarity between carbene 89 and diphenylcarbene may seem odd since
89 appears flat, at least on paper, and diphenylcarbene has been shown'"* lo be
bent and twisted. Carbenes 90 and 91 are even less flexible and both give products
+ + +
of addition t o olefins1e6~
k i
lGG. Remarkably the cyclopropanes are formed in a stereo-
specific fashion. Carbene 90 gives a spectrum of products which seems to implicate
a mixture of spin states. Irradiation of diazoanthrone in cyclohexane again led to
products of hydrogen abstraction, with no cyclopropane being formed167. Olefins
not containing allylic hydrogen did form adducts, however1e8.
o w
0 0.0 0 . 0
11% 23%
2%
b 2%
ft
70%
R'
R' R'
R' r- R' = H, 39yo
R' = Ph, R2 = H,93%
3. Fluorenylidene
Fluorenylidene, generated by photolysis from 9-diazofluorene. unlike diphenvl-
carbene, adds t o x-systems without the complication of large amounts of hydrogen
abstraction. Fluorenylidene adds easily to a variety of ole fin^'^^. With cis-Zbutene
as the solvent, cis-dimethylspirocyclopropane-9-fluoreneand its trans isomer are
formed in a ratio of 1-95, while irradiation in trans-Zbutene gives the same products
in a ratio of 0.06. This memory effect becomes much smaller when the reaction
mixture is diluted with hexafluorobenzene as a n inert solvent. At the highest dilution,
Cyclopropane
Cis adduct
-
Trans adduct
67% -33%
- 0% -100%
356 Wataru Ando
TAOLE
1 5 . Relative rates of fluorenylidene
addition to olefins
~ ~~~~~~~~
Olcfin 90% C,F, Pure olcfin
0.37 0.66
I .oo 1 .oo
A
1.70 0.47
0.86 0.38
3
<
0.40 0.43
J
069 0.56
K 9.00 3.5
h
when the solution was approximately 0.1 M in olefin, the corrcsponding ratios were
0.25 a n d 0.14. These observations f i t a mechanism involving stereospecific addition
of a metastable singlet fluorenylidene and a competing addition from thc triplet
ground sta1c occurring with complete loss of stereospecificity.
It is possible selcctivcly to filter out the triplet state by allowing i t to rcact with a
triplet trap such as butadiene, with which the triplet seems to react particularly
fast. As can be seen from Table 16, the more butadiene is added, the more stereo-
specific the addition beconics. Of course at high butadiene concentrations vcry little
product is observed from the reaction with the 2-butcne, and precisc numbers become
very difficult to obtain.
16. Reaction of fluorenylidene with cis-2-butene in

TAULE
thc presence of I ,3-butadiene
Cislrrans ratio
Butadiene (mmol) cis-2-Butene of cyclopropane
0 10.0 2.1
3.0 6.0 10.1
11.5 3 .O 49
Fluorenylidene was found to add t o cyclopcntadiene to give only 92 and t o add to

cyclohexadiene to give 95. N o trace of the hypothetical 1,4-adducts 93 and 96 could
be found. Diphenylcarbene also gives 1,2-adducts with cyclopentadienel'O. The
reactions of fluorenylidene and ~yclopentadienylidene~~~~ 17? with cycloocta-

tetraene are normal and no 1,4-addition products are found. The further rearrange-
ments of the initially formed adducts 97 and 98 have been studied.
%
388 Wataru Ando
+ --+
4. Cyclopropenylidene, cycloheptatrienylidene and

cyclopentadienylidene
For cyclopropcnylidene (99)and cycloheptatrienylidene (loo), i t was hoped that
the singlet carbcne would derive important stabilization from the aromaticity
expressed by the resonance hybrids which are shown below :
Important contributions by these forms would be shown by nucleophilic behaviour

and, indeed, only olefins with electron-poor it-bonds have proved to be suitable
substrates for these systems173.
ROOC
Ph COOR
Ph Ph Ph COOR
When tropylidcne is generated at lower temperatures, heptafulvalene is the only

product. It is not captured by simple alkenes, but it does add stereospecifically t o
electron-poor olefins such as dimethyl fumarate or maleate, and to mizture of
para-substituted styrenes in such a way that p can be deduced to be + 1.05. These
findings suggest that tropylidene is a nucleophilic singlet, the electron-donating
character being imparted by resonance contribution form 100.
-8+m
9. Photochemistry of thc diazoniurn and diazo groups 389
0:+
MeOOC COOMe
MeOOC
+
COOMe
-
/
47% 10%
NC
u CN
98% 2%
The ground state of cyclopentadienylidene is known to be a triplet in which one

unpaired electron is localized in plane sp? orbita:. while the other electron is in the
~ . singlet state of the carbene may be expressed as the resonance
i t - s y ~ t e r n ’ ~The
hybrid 101. Recent calculations indicate that the configurations (101a) and (101b)
are within 0.2 eV 175; the resulting extensive configuration interaction will lead to
mixing a n d the singlet is therefore best represented as the entire resonance hybrid
101.
(101a) (101 b) (101c)
Photolysis of diazocyclopentadiene in trans- a n d cis-4-methyl-2-pentene led to

spiro[2.4]heptadienes 102 and 103, respectively, in good yields. T h e addition is
nearly, b u t not completely, stereospecific. Addition of either hexafluorobenzene or
* 98% 2%
390 Wataru Ando
perfluorobutane has little effect on the stereochemistry. The reacting state seems to
be the singlet, although the ground state is known to be the triplet.
R'
-
7
)$q R' R'
RzQN2 R' J=)2R

-
R' R'
%+R'kk
R' R'
(104)
a: R' = RZ = ph, R3 = R4 = H
b: R' = R' = R3 = R' = Ph
R' R'
A variety of phenyl-substituted cyclopentadienylidenes has been examined. The

properties do not seem much changed by phenyl s u b ~ t i t u t i o n ' ~Norbornadiene
~.
gives a n initial adduct whish rearranges further on ph~tolysis'~'.Alkynes give
cyclopropenes which though isolable rearrange
17. Relative rates of addition of carbenes

TABLE
106 and 107
Olefin Carbene 106 Carbene 107
0.29 1.23
1.00 1.00
1.35
2-
0.19
0.2 1
- 0.24
1.25 0.21
0.93 3 .O
4
hh
h v .
A Ph
Ph Ph I
I
Ph Ph Ph Ph
Ph \ P h
Ph ROOCC=CCOOR Ph
tI L. O
R
&
:P
h COOR
COOR
-
Ph Ph Ph Ph
T h e photolytic addition of 105 to the double bond of cis-4-methyl-2-pentene

proceeded non-stereospecificallyl*o. The properties of 106 can best be described as
arising from the triplet state. The steric requirement of 106 is quite large and hence
Br Br
Br Br
+
Br Br Br Br
Br Br
40% 60%
(106)
might allow many non-reactive co isions to occur. and 1.ius give the carbene t me
to undergo intersystem crossing. In addition, heavy atoms are known to enhance
the probability of spin-forbidden transitions through coupling of spin and orbital
angular momenta.
4,4-Dimethylcyclohexadienylidene undergoes additions similar to that of the
five-membered ring compoundl"l (Table 17).
392 Wataru Ando
E. Photoiysis of Diazocarbonyi Compounds in Olefins
1. Intermolecular addition reactions
Diazo esters react with olefins by two distinct paths to produce cyclopropanes.
Diazoacetic ester might lose nitrogen under the influence of heat or light to produce
a carboalkoxycarbene which adds to the olefin or to the acetylene giving a cyclo-
propane or cyclopropene carboxylate.
N, 1- :CHCO,R
hs.
v
N,CHCO,R
~
+ :CHCO,R
CO,R
PATHA
Alternatively, the diazoacetic ester might react with the olefin to form a pyrazoline
which loses nitrogen to produce the cyclopropane carboxylate. In non-photochemical
reactions of double or triple bonds conjugated with a carbonyl, imine or nitrile
group, 1,3-dipolar addition of the diazo group usually occurs to give a pyrazoline
or pyrazole which is stable under the reaction conditions.
N,CHCO,R +
-
N
4-4
“’CHC0,R *pc CO,R
PATHB
Carboalkoxycarbenes are involved in reactions above 100 “C and in photo-

chemical reactions. Carboalkoxycarbenes behave as electrophilic species. With
cis- and rrans-2-butene, photochemically produced carboalkoxycarbene adds in a
stercospecifically cis manner. Thus, Doering and Mole1*? showed that methyl
diazoacetate and cis-2-butene gave a mixture of two meso cyclopropanecarboxylic
esters, whereas rra~s-Zbutenegave only the corresponding racemic mixture:
-+ N,CHCO,CH, -
I I
CO,CH, CO,CH,
9. Photochemistry of the diazoniurn and diazo groups 393
Addition to cyclic or asymmetric double bonds gives the less hindered a d d u ~ t ~ ~ ~ - ~ ~ ~
72% 18%
An attempt t o compare singlet and triplet states of photolytically generated
carboalkoxycarbenes has been made by Jones and his collaborators'86.
Direct photolysis of dimethyl diazomalonate has been shown by these investigators
t o afford a reactive intermediate whose chemical properties differ markedly from
those of the corresponding species produced via benzophenone-sensitized photo-
decomposition of the same diazo ester. It is thought that the reacting species pro-
duced in the direct a n d sensitized photodecompositions are singlet and triplet
biscarbomethoxycarbenes, respectively. The results with cis- and trans-4-rnethyl-
2-pentene are shown in Table 18. Since the addition is only 90-92% stereoselective,
(cis) rather than 100% stereospecific, it is possible that in the direct photolysis the
carbene is not formed exclusively in one spin state, but predominantly in one state
TABLE18. Product distribution in the reactions of dimethyl diazo-
-%
malonate with cis-4-rnethyl-2-pentene and rruns-4-methyl-2-pentene
N,C(COOMe),
+
MeOOC COOMe
(108a)
%
MeOOC COOMe
(108b)
Conditions 1083 (%) 108b (%) Yield (%)
+ 6
--&
hv 92 8 39.8
hv+ 10 90 24.3
+ Ph,CO
+&
hv
lo 90 43.0
hv + Ph2C@
14 86 -
394 Wataru Ando
and to a lesser extent in t h e other. In a n attempt to induce intersystem crossing
from the singlet to the triplet, the photolysis of methyl diazomalonate in cis-4-methyl-
2-pentene was studied in varying concentrations of hexafluorobenzene. Only when
very large amounts of hexafluorobenzene are added does the amount of trons-
cyclopropane increase significantly. Indeed, initially, the amount of cis-cyclo-
propane increases s!Ight!y. A likely source of this increase is excited methyl diazo-
malonate, which could produce trans-cyclopropane by addition to the double bond
followed by loss of nitrogen. As hexafluorobenzene is added fruitless collisions
could deactivate the excited diazo compound to the ground state, producing more
cis-cyclopropane until enough has been added so that all excited diazo compound
has been deactivated a n d intersystem crossing begins.
0
O O 0
0 20 40 60 80 100
Hexofluorobenzene (mol - O h )
FIGURE 14. Addition of dimethyl diazomalonate to cis-4-niethyl-2-pentcne in hcxafluoro-

benzene. [Reprinted with permission from Jones, J . Ainer. Chcni. Soc., 94, 7469 (1972).
Copyright by the American Chemical Society.]
I n a recent study of t h e benzophenone-sensitized photolysis of dimethyl diazo-

nialonate in the presencc of cis-4-methyl-2-pcntene, the ratio of products (10Sa)/
(10Sb) was larger in t h e presence of dimethyl sulphide than in its absence’88. Singlet
carbenes generally act as electrophiles, although the bulkier ones are subject to
steric hindrance. In contrast to the large amount of data reported o n singlet relative
rates, only fragmentary information is available for triplets. Diphenylcarbene is
rcported to add to 1,3-butadiene and 1,l-diphcnylethylene 100-times faster than to
~ i s - 2 - b u t e n e This
~ ~ ~ .comparison is unsatisfactory since diphenylcarbene reacts with
cis-2-butene primarily by hydrogen abstraction, not addition’”. Table 19 shows
that i n the sensitized photolysis there is a three- to four-fold increase in the relative
rate of addition to dienes over nionoolefins, and there is a dccrease in the relativc
ratcs of addition to certain olefins, e.g. to 2,3-diniethyl-2-butene and to cis-4-methyl-
2-pent em.
TABLE
19. Relative rates of addition of carbenes
produced in direct and sensitized photolysis of
dimethyl diazomalonate
Olefin Direct Sensitized
0.88 0.33
1-00 1.00
0.47 0.46
0.48 0.48
0.55 0.15
0-13
1-3 4.4
Relative rate constants for addition of several carbenes to a series of allylic

compounds were determined by means of competitive experimentsIg1. Results
summarized in Table 20 show that polar selectivities of carbenes are generally low
but correlate with the polar nature of substituents in the carbenes. The selectivities
of singlet carbenes were even lower than those of the corresponding triplet carbencs.
These facts strongly support a mechanism of addition with singlet carbenes which
does not involve any rate-determining process leading to polar intermediates, but
involves transition states having slight contributions from polar structures.
20. Competitive reaction of carbene with allylic compounds, CH,=CHCH,R
TABLE
R
Carbene Mode of
precursor decomposition SiMe, n-Pr OMe C1 CN
N,CHCOOMe hv 2.07 1.47 1.23 1.00 0.97

N,CHCOOMe hv+ Ph,CO 2-55 1.55 0.95 1-00 0-66
N,C(COO Me), kv 1.85 1.5C 0.93 1.00 0.66
N,C(COOMe), hv + Ph,CO 3.66 2-15 1.25 1.00 1.13
N,CH Ph hY 1.13 1.06 1.00 - 0.80
IfV 1-99 1.79 1.20 1.00 0.92

N 2 4
NaOH + CHCI, 80.14 14.04 3.44 1.00 0.75
396 Wataru Ando
However, Wulfman102, recently tried to establish the existence of bismethoxy-
carbonyl carbenoids by analysing the activation parameters for both catalytic and
photolytic processes, but the data cast strong doubt on the existence of free carbenes
during the cyclopropanation of olefins and during insertions into the allylic C-H
bonds by the alleged singlet carbene. They are forced to conclude that a free singlet
3-CH Insertion 4-CH Insertion

Teniperature
Conditions ("C) Cyclopropane Cyclopropane
Pure 0 0.47 0.05
54 0.46 0.1 1
90 mol.-% 0 0.46 0.23
CliF, 54 0.47 0.39
Sensitized 0 0.13 0.1 1
Ph2C=0 54 0.19 0.10
carbene is not an intermediate during the non-sensitized photolysis of dimethyl

diazomalonate. The cyclopropane and the allylic C-H insertion products may be
formed via the photoexcited diazo compound forming a complex with the olefin.
An alternative criterion was proposed recently by Shimizu and Nishida103, who
used 1,I-dicyclopropylethylene(109) as the substrate. Here addition of a singlet
carbene can proceed in the usual concerted manner to afford 110, whereas the
existence of a triplet carbene is revealed by the observation of rearranged products
111 and 112 as shown below.
Unsensitized decomposition of dimethyl diazomalonate in allene gives 113 as the
only isolable product186.One might have speculated that the sensitized reaction,
proceeding through a triplet, would lead to trimethylenemethane (114), and then to
113 and 115. A similar scrambling of label has been seen in the gas phase addition
of dideuteromethylene to allene but the likely explanation for the scrambling involves
hot molecule rearrangements, not spin state. The sensitized decomposition gave
only 113 and 1.1-diphenylethylene in the ratio 12 : 1. The latter product probably
arises via the oxetane (116). Hendricklg4 has observed furan formation in the
N,C(COOMe), + CH,=C=CH, ---+

hu
MeOOC COOMe
Ph,C=O, hv (113)
reactions of triplet biscarbomethoxycarbene with alkynes. The direct photolysis of

methyl diazomalonate in 2-butyne afforded the expected cyclopropene 118 in 36%
yield. Only trace amounts of other products, assumed to be insertion products,
-
were detectable.
+ COOMe
h I.
N,C(COOMe), RCECR’
COOMe
(117) R
(118)
a: R = R ’ = Me Ph,CO, h ~ ,
b: R =n-Bu, R’ = H
C : R = R’ = n-Pr
d : R = Me, R‘ = H R’ COOMe
Ph.C-0
>-
I1 Y
R
398 Wataru Ando
R”
I n sharp contrast, sensitization of the photolysis in 2-butyne with a n equimolar

amount of benzophenone gave as the major product the furan 119 in 43% yield,
accompanied by only 9% yield of 118. The course of the triplet carbene reaction can
be ascribed to cyclization of t h e diradical 120. It is interesting to note that the
substitution of bulky groups o n the acetylene results in increased closure to cyclo-
propene but not nearly so dramatically as in the case of diphenylcarbene.
TADLE 21. Relative yields of 118 and 119 from de-

compositions of diniethyl diazomalonatc in acetylcnes
117a4
117 Mode of decomposition 118 119
Av 99 1
h v + Ph2C0 16 84
I1 v 99 1
+
IIV Ph,CO 10 90
hV 99 1
h v + Ph,CO 25 75
CuS04. reflux 99 1
+ Ph,CO
liv 1 99
In the photolyses of the diazo compound 121, related to Meldrum’s acid, direct
irradiation in olefins produced very little product of any kind, while in the sensirized
decomposition adducts can be isolated in relatively good yields. The stereochemistry
of the sensitized decomposition is exactly what one would expect from a triplet
intermediate. These results are summarized in Table 22
Photolysis of ethyl bromo-, iodo- and chloro-diazoacetate affords the bromo-,

iodo- and chloro-ethoxycarbenes, which add cis stereospecifically to olefins and
insert to C-H bonds of alkanes, though less readily than the carboethoxy-
carbene. The pliolosensitizcd decomposition of ethyl bromo- and chloro-
diazoacetate in olefins leads to addition products with essentially complete cis-
stereospecificity (97%)lg5.
2 2 . Decomposition of 121 in olefins
TABLE
Olefin Conditions Yield (%) Cis (%) Trarrs (%)
IIV 2 - -
Irv+I’h,CO 26 14 86
hv+Ph,CO 26 15 85
Very small - -
-L hv+Ph2CO 17 4 96
Very small - -
hv+Ph,CO - 6 94
23. Relative yield of dicyanocarbene addition

TABLE
Olefins Addition/Insertion Dilution cis-Cyclopropane (%) rraits-Cyclopropane (%)
LJ 9218 Neat 92 8
LJ 9416 1 : 100 60 40
9812 1 : 100 70
L-/ 30
88/12 Neat 6 94
9416 1 : 10 22 78
9812 1 : 100 30 70
400 Wataru Ando
Addition of dicyanocarbene to olefins is largely but not completely stereo-
specific. Addition of cyclohexane as diluent evidently induces intersystem crossing
since the stereochemistry of addition becomes independent of the configuration of
the starting 2-butene at 100 : 1 (cyclohexane : olefin).
Addition to acetylenes gives cyclopropenes, and the carbon-hydrogen insertion
reaction is common (tertiary/secondary/primary = 12/4.6/1) lg6.
2. Intramolecular reactions
Intramolecular reaction of diazoketones also give cyclic compounds. 3-Diazo-
methylketocyclopropenes (122) are the only unsaturated ketones so far where light-
effected intramolecular addition produces the tricycle[ 1.l. 1.O *, 6]pentane skeleton1"'.
(122) 0
Ph 0
II Ph Me
\C=CH-C-P(OMe),
/ II
Me N,
Ph
c. 0
0
II
Me P(OMe1,
\ II
C=CH- ?-P(OMe),
/
Me
Me
Ph 0
\ II
C=C=CH -P(OMe), (Reference 198)
/
Me
The intermediate diazoketone (123) obtained in the photolysis of 1,Zdiazine

N-oxide has two competitive pathways open to itlQ9.One pathway is the intra-
molecular 1,3-dipolar cycloaddition resulting in the formation of benzoyl-5-phenyl-
pyrazole (127) via the tautomeric 3H-pyrazole (126); this thermal isomerization is
expected to be even faster than the known isomerization of vinyldiazomethane to
pyrazoIe200.The other pathway involves photodecomposition of the diazoketone to
a carbene which reacts intramolecularly to yield 2,Sdiphenylfuran. Since there are
competing thermal and photochemical reactions it would be expected that irradiation
9. Photochemistry of the diazonium and diazo groups 40 1
with more intense light source or lowering the temperature during irradiation would
increase the photochemical reaction, i.e. the conversion to 2,5-diphenylfuran.
0
I1
Ph
flNc-ph
y
Irradiation of pyridazinium dicyanornethylylide gave 3-(2,2-dicyanovinyl)-

pyrazoles (128) and 3-(2,2-dicyanovinyl)cyclopropenes (129) *01, probably through a
mechanism similar to that operating in the photolysis of pyridazine N-oxide.
Photolysis of 3-acylpyrazolines yields an a,P-unsaturated ketocarbene, which
rearranges mainly into ketene. However, intramolecular addition of the a,p-
ethylenic ketocarbene has been observedzo2.
1
CN
R
\ R
C= C( CN) ,
p
\
C=C(CN )*
R f i R --+ R q R -
I
H NC CN NC CN R
402 Wataru Ando
0
1 0
II
R - C - C=C=C
/
\
R’
Ph Ph
h I. RI? “2 ). (Reference 203)
PI] Ph
R2
R R
I
V
/
4 - Rr
R
P
&Lf R I
(Reference 204)
F. Photolysis of Diazo Compounds i.n Aromatic Compounds

Photolysis of diazocyclopentadiene in benzene solution afforded a crystalline,
rather sensitive, adduct of a spironorcaradiene structure. Thermal rearrangement
of 132 !ed to 133, while a mixture of phenylcyclopentadienes resulted from acid-
catalysed rearrangement205.Hexafluorobenzene gives an adduct of a spiro cyclo-
heptatriene structure2OB.Similarly, a norcaradiene-type adduct was isolated from the
+ $"
photolysis of I-diazo-4,4-dimethylcyclohexa-2,5-dienein benzenezo7.Photolysis of

dicyanodiazomethane in benzene gave, as the sole product in 82% yield, 7,7-
dicyanonorcaradiene?O8.p-Xylene afforded two isomeric products, 135 and 136. The
14
404 Wataru Ando
photolysis of diazofluorenylidene in benzene afforded the equilibrating norcaradiene-

cyclohept at riene systemzog.Tet raphcnylcycl opentadienylidene reacts with benzene
to give a product, presumably the norcaradiene, which rearranges further t o (140)
and (141). T h e final product (141), which arises via ring expansion of the five-
membered ring, is somewhat unusual, since ring expansion of the seven-membered
ring usually occurs21o. Spironorcaradienes 138 (in equilibrium with their valence
isoniers 139) can be isolated if the photolysis is carried out with a long wavelength
filter ( A > 360 nm).
With pyrex filter ( h > 290 nm) the mixture 138 + 139 rearranges to benzocyclo-
heptatrienes (141) and their 5H isomers. Two possible mechanisms have been
proposed for this rearrangement?ll; a symmetry-allowed [1,7]-sigmatropic shift
(to 143), or a di-x-methane rearrangement (to 143). The successful isolation of
142, provides strong evidence for the intermediacy of novel bisnorcaradiene (143).
7-Phenylcycloheptatriene was obtained by photolysis of phenyldiazomethane in
benzene solution212. Similarly, 1,4-bis(diazornethyl)benzene was converted into
1,4-bis(cy~loheptatrienyl)benzene~~~. Benzene also acts as a n acceptor for bis-
carbomethoxycarbene, a report to the contrary notwithstanding21*. Photolysis of
methyl diazomalonate in bcnzene gave 146 and 147 in a ratio of 2.7 : 1. T h e photo-
sensitized reaction gave the same two products in the ratio of 1.6 : 1. The increased
amount of the phenylmalonate (147) is consistent with a mechanism involving a
diradical which can either close to the norcaradiene related t o 146 or undergo
hydrogen shift to 147 lB6, 215. Photolysis of ethyl diazoacetate by means of pyrex-
filtered light afforded 148 in reasonable yield and SO-SO% purity216,217. Short wave-
length U.V.irradiation caused extensive isomerization of 148 to cycloheptatriene-3-,
-4-carboxylate and bicyclo[3.2.0], and t2.2. llheptadiene carboxylate218. A Hammett
treatment showed that the reaction was a n electrophilic aromatic attack. The p
value of -0.38 suggested that not much positive charge had developed in the ring
a t the tran~ition"~.
9. Photochcmistry of the diazoniuni and diazo groups 405
di--r-methane
I' r car r an g cm en t
(144) (143)
1 I
Y
5'
Rl&
R"
(142)
(141) (142) (140)

406 Wataru Ando
+ N,CHCO,Et --
"+" 0 CHC0,Et + o\ C O z E t
+ N2CHCOzEt A
Me
C0,Et C0,Et C0,Et
Photolysis of 2-diazoacenaphthen-I -one in benzene gives spiro[acenaphthen-

1,7'-cis-norcara-2',4'-diene]-2-one (149) which rapidly isornerizes to 2-phenyl-
acenaphthen-I -one (150) under silver perchlorate catalysiscz0,and gives acenaphtho-
[1,2-b]benzofuran (151, X = H) in the presence of dicyanobenzoquinone. Other
aromatic receptors give similar
8
/
A-
00
@
NZ
(Dimethoxyphosphoryl)(methoxycarbonyI)carbene (153) and benzene afford

products that depend on the duration of the irradiation222.If the photolysis of 152
is interrupted before the reaction is complete, the equilibrium system 154 + 155 is
produced. More prolonged irradiation leads next to a sequence of shifts of ester
groups and of H atoms, producing the cycloheptatriene 157. On still further
irradiation, the photostable bicyclo[3.2.0]heptadiene (156) is formed from 157 by
electrocyclic ring closure223.
0
II 0
MeOOC P(OMe), MeOOC 11
MeOOC
1
408 Wataru Ando
G. insertion Reactions
The term ‘insertion’ is rescrved for reactions where cleavage of the A-B bond
and formation of the A-C and B-C bonds occur in concert. The alternative
I
A. . B Y
stepwise process, abstraction followed by recombination, may afford insertion type
products via diradical processes:
X X
A-B +:CXY -’ [A. + I
-C-B] ->
I
A-C-B
I I
Y Y
When B is a heteroatom containing one or more unshared pairs of electrons, a third
mechanistic possibility may be operative involving intermediate ylide formation:
A-B + :CXY
m-
A-6-C
IX
\
__f
X
I
A-C-B
I
Y Y
1. C-H insertion of carbene in saturated hydrocarbons

The insertion of singlet methylene into hydrogen has been subjected to a very
detailed analysis2’.’. T h e results indicate that insertion can take place over a wider
range of initial conditions and by a much more complex pathway than static
‘minimum energy path’ analysis would suggest. Thc reaction of methylene with
hydrogen has also becn the subjcct of other calculationszo5.
EHM calculations for concertcd insertion of singlet niethylcne into a C-H bond
of methane2z6indicate a nearly linear transition state, thc niethylene approaching the
C-H bond in the direction shown in 158. The hgdroger. is transferred from methane
to methylene while the C-C distance (2.5 A) changes little; this is then followed by
collapse to give ethane, with no evidence for a discrcte radical intermediate in the
process.
n
MlNDO/2 calculations on the reaction of singlet and triplet methylene with

methane predict2” that the singlet can approach along the axis of a C-H bond of
methane, either i n an eclipsed (159) or i n a staggered conformation (160). T h e triplet
can also approach along thc C-13 axis, or midnay between two C-€3 bonds of
methane; thc latter approach is prcdicted to lend to insertion by thc triplet. Insertion
of methylene has been analysed by Zinirnerman, using his ‘MO following’
Doering and KnoxZ2Q proposed the charge separation hypothesis for the
r a t h a l i z a t i o n of the selectivity of various substituted carbenes toward primary,
I I
-C-H + :CH, -* -C-CH,
I I
\
H
\+
-C H
\
-C-
/ ...C.: C-J / -d 4--+ 1 4.4H
/ \ / \ / \
R R R R R R
secondary and tertiary carbon-hydrogen bonds, a s well as for the selectivity

sequence (CH,OOC),CN, > CK,OOCCHN, % CH,N,.
TABLE
24. Relative insertion rates of carbenes into C-H bonds under photolytical
conditions
Carbene precursor Alkane Secondarylprimary Tertiary/primary
N,CH,
h 1.2 1.5
N&H, 1.2
-
NZCHCFS -
t
-
NZCHCFS - 1.3
7-3
N,CHPh 6.3
N,CHPh 8.3
N,CHCOOMe t - 3.1
N,CHCOOMe
X -
-
2.9
N,CHCOOMe w 2-3
N2C(COO Me), * 4.8 -
N,C( COO M c ) ~
H -
8.4
13.1
-
N,C(C03Et),
NZC(COOEt),
X - 12.5
N,C(COOEt), t - 21.1
410 Wataru Ando
Evidence supporting the postulated charge separation in the transition state
comes from the reactivity of bridgehead hydrocarbons. Methylene reacts with
bicyclo[2.2.l]heptane to give all of the possible C-H insertion products in essentially
statistical amounts23o.The product mixtures obtained with methoxycarbonylcarbene
and biscarbomethoxycarbene, however, reflected lower reactivities for the bridge-
head positions. The bridgehead C-H bonds of nortricyclene were found to be even
less reactive toward et h o x y ~ a r b o n y l c a r b e n e ~ ~ ~ .
25. Relative rates of reaction with bicyclic hydrocarbons

TABLE
Diazo compound Hydrocarbon 1 -Position Ail others Tertiary/secondary
N,CHCO,R 1 .o 6.7 0.7
N,C( COOR), 1.o 27.3 0.2
6.0 1-0
6.7 0.7
2,5/bond 1.o 0.9 CH,CO,R
Generally, the sensitized decomposition of diazomalonate affords a slightly more

selective intermediate than does direct photolysis. Yields of insertion products are
much lower in the sensitized decomposition. Rough composite values for the
-
26. Relative rate of insertion of biscarbomethoxycarbene into
TABLE
carbon-hydrogen bonds186
Hydrocarbon Ratio Singlet Triplet
~ ~~ ~ ~~ ~
Secondary/prirnary 5.4 6.9

Secondar ylprimary 4.8 5.2
t Tertiary/primary 39 52
Tertiary/primary 13 20
9. Photochemistry of the dinzoniuni and diazo groups 41 1
tertiary-secondary-primary ratios of singlet and triplet biscarbomethoxycarbcnes
are 15-40 : 5 : 1 and 20-50 : 6 : 1, respectively. This fits in general the data of Ring
and R a b i n o ~ i t c h233
~ ~ on
~ . the abstraction of hydrogen by triplet methylene,
although the effects seem to be smaller. A hydrogen abstraction-recombination
process would be expected to give new products derived from t h e radicals generated
by abstraction. Such products d o appear as shown below, with the yields of the
sensitized reaction shown in brackets:
t
( 1- N,C(COOMe),
CH(COOMe)? + + CH,(COOMe),
38% (11%) 8% (2%) trace (2304)

CH(CO0,Me)
+ I
CH(CO0,Me)
trace (38%)
Direct irradiation produces only insertion products while the sensitized

decomposition gives more of the products expected from free radical dimerization
and hydrogen abstraction.
The photolysis of methyl diazoacetate in trimethylcthylsilane gave three major
T h e rates show that an a-secondary C-H bond (2.5) is more reactive
than a primary a-C-H bond (1.0), which in turn is less reactive than a primary
6-C-H bond (1.2). T h e differenccs may be explained by steric hindrance to
carbene insertion. A competition reaction showed that the reactivitics of C- H
Me,SiCH,CH,+N,CHCO,Me *” >
Me,SiCH,CH, + Me,SiCHCH, + Me,SiCH,CH,CH,CO,Me
I I 6%
CH,CH,CO,Me CH,CH,CO,Me
17% 9%
bonds towards carbomethoxycarbene insertion are higher in trimethylethylsilane

than in 2,2-dimethylbutane [k(Si)/k(C) = 1.81, possibly as a result of the inductive
effect of the silicon substituent.
The relative rate of the carbcne insertion into the primary y-C-H bond in
trimethyl(tt-propy1)silane and in trimethyl(iso-buty1)silane showed it to be less
reactive than that of the primary P-C-H bond of trimethylethylsilane, probably
because of the diminished effect of the silyl group.
The photolysis of mcthyl diazoacetate and diniethyl diazonialonatc in 1,1 -dimethyl-
1-silacyclopcntane (162) gave carbene insertion products into the secondary a.- and
P-C-H bonds as well as into primary C-H bonds in comparable cxtent.
The 1.eaction of I , 1,3,3-tetranietliyl-1,3-disilacyclobutane (163) gavc carbene
insertion into the Si-C bond, as has becn observed with d i c h l o r o c a r b e ~ i eas~ ~\vcll
~
a s insertion into primary and secondary C-H bonds in comparable rates.
412 Wataru Ando
(sl, +
M\"
(162)
Pe
N,CRR' 4 4 +Q
RR.cfi
Me Me
\ /
+
Me Me
\ /
CHRR'
Me CH,CHRR'
\ /
R = H, R' = C0,Me 1.6 2.0 1.O/ bon d

R =: R' = C0,Me 74 11.9 1 .O/bo n d
Me,Sii
L Sirvle, + N,CRR' ''"t
(1 63)
CHRR'
M e , SA
qiMe, + Me,Si-( + Me,Sil
LSiMe, LsiMe
R R' I
CH,CHRR'
R = H, R' = C0,Me 14% 33% 55%
R = R' = C0,Me 5% 50% 45%
2. C-H insertion of carbene in ethers

T h e insertion of singlet methylene into the C-H bonds of ethyl ether was reported
as long ago a s 1942, but the intervention of an ylide niechanism was ruled out only
recently. Thus, attack of 14C-labelled rnethylene on ether gave only end-labelled
propyl ethyl
'CH, + CH,CH,OCH,CH, *CH,CH,CH,OCH,CH, + CH,CHOCH,CH,

*I
r+ CH,
9. Photochcniistry of the diazonium a n d diazo groups 41 3
'3--
Thus, methyl etlicrs often arc obtained probably from ylides in decomposition of
ethereal solutions of dia~omethane~36:
ROCH,CH, + :CH, -+ t
R-OJ ROCH, -+ CH,=CH,
- 1-
CH, H
T h e oxygen atom of aliphatic ethers has a small promoting effect o n methylene
insertion which is accompanied by minor side reactions which may be explained by
an at tack of methylene on oxygen. Triplet met hylene abstracts liydrogen almost
exclusively from the a position, giving rise to products of apparent c c - i n s ~ r t i o n ~ ~ ' - ~ ~ ~ :
C H3C H,O C H, C Hj +C H N, A
2 C H 3C HZOC H C H ,+ CH 3C H 2 0 (C H 2) ZC H3
I
CH,
1*23 1*oo
(in liquid phase)
CH,OCH,CH,+CH,N, z CH,0CHCH3+CH,0(CH,),CH~+CH,CH,0CH~CH,
I
CH3
I n gas phase 1.49 1-00 1-13
I n liquid phase 1.30 1-00 1a00
The small preference for insertion into the a-C-H bonds of ethers was rationalized
in terms of polar resonance structures of the transition state.
In contrast t o expectations based on this conccpt, the 0-CH,-0 hydrogens of

methylal were found to be less reactive than the C H 3 - 0 hydrogens. T h e reverse
relation holds with 1,3-dioxolanc. Tlicsc results suggest that t h e conformation of
ethers and acetals may be a n important factor in determining the relative rates of
methylene insertion?'O.
9,
Me-0-CH,CH,
0.72 10
too
Insertion of carboalkoxycarbene into the C-H bonds of ctliers competes less

efficiently with cleavage a t the 0-alhcl bond than does the insertion of methylcne.
When methyl diazoacetate was photolysed'41 in the presence of diethyl ether,
methyl ethoxyacetate, methyl F-ethoxybutyrate and y-ethoxybutyrate were pro-
duced in the ratio of 4 : 4 : 1.
hv
CzH,OC,H,+N,CHCO,Me ___+
C,H,OCH,CO,Me+ C,H,0CHCH3+ C,H,OCH,CH,CH,CO,Me

I
C0,Me
4 4 1
hv
C,H,OC,H,f N,C(COOMe), >-
C,H,O CH (C OOMe), + C, H,CH C (CO 0Me), (Reference 242)
I
CH,
39% yield 27% yield
414 Wataru Ando
Cyclopentadienylidene inserts into both a-C-H and p-C-H bonds of diethyl
ether, producing 164 and 165 in 27 and 2% yields, respectively. The correction by
statistical factor shows that the reaction occurred 19-times faster at a n a-C-H
bond than at a p-C-H bond243.Competition experiments, in which mixtures of an
C - 0 insertion Z-C-H insertion 2-C-H insertion

(164) (165)
ether and either cyclohexane or 2,3-dimethylbutane were allowed to react with
cyclopentadienylidene, gave some indication that both resonance a n d inductive
effects of the oxygen atom influenced the rate of the insertion reaction of the carbene.
As in the other carbene reaction, cyclopentadienylidene inserts i n t o C-H bonds
most favourably when a partial positive charge on the carbon atom involved can be
stabilized. The inductive and resonance effects of the alkoxy group can be seen in
the results shown in Table 27.
27. C-H
TABLE insertion in the photolysis of diazocyclopentadiene in
ethers
.-
a-C-H P-C-H Y-C-H
Ether insertion insertion insertion
0.9
'"Y 2.7 0.58
Go 4.2 1.3
t
( 1.0 (standard, primary C-H insertion)
3.9 (secondary C-H insertion)
-
A variety of phenylcarbene precursors gave the same E-C-H insertion in alkyl
-
hv
PhCHN,+ C,H,OC,H, C,H,OCHCH,
I
CH,Ph 15% yield
hv
PhCHN,+PhCH,OR PhCHOR
I
CH,Ph 2030% yield
With allylic ethers, diphenylcarbene prefers insertion into the allylic C-H bond
over addition to the C=C double bond by about 1.5-1-7 to 1, and with benzyl
alkyl ethers, i t inserts readily into the benzyl C-H bond.
Photodecomposition of diphenyldiazomethane in the presence of aldehyde
afforded the insertion product of diphenylcarbene into the aldehyde C - H bondcds.
Ph,CN, + &OR -!!&
H. Intramolecular Reactions
Alkyl and dialkylcarbenes react predominantly by self-insertion into @- and
y-C-H bonds to give olefins and cyclopropanes.
The photolysis of diazoethane in the gas phase produced ethylene and acetylene
a s the major products. The ratio of ethylene to acetylene increased linearly with
pressure246.The photolysis of CD,CHN, showed that acetylene is formed from
excited ethylene and not from CD,CH:. Ethylcarbene illustrates two
common reactions of alkylcarbenes, 1,2-shift and 1,3-C-H insertion248.
CH,CH,CHN, -t
h I.
CH,CH,CH: -t A + A
88% 12%
Carbon- 14-labelled diazo-n-propane decomposes into nitrogen and singlet n-propyl-

c a ~ b e n e which either to butene or to methylcyclopropane, both
~ ~ ~ ,rearranges250-2s2
in a vibrationally excited state. The latter either decompose or are collisionally
deactivated. The radical produced may recombine to give stable products. The yield
of the product formed by collisional stabilization of 'hot' species should increase
with increasing pressurc as indeed was observed while the fragmentation products
(ethane, hexa-l,5-diene) should show opposite behaviour.
The 1 ,2-hydrogen shift in methylcarbene was subjected to detailed analysiszs3.
In conformation 166, the hydrogen atoms adjacent to the vacant p orbital can
migrate with little or n o activation, but movement of the third hydrogen is much
less favourable; in cases where rotation about the carbon-carbon bond is inhibited,
416 Wataru Ando
$1:
+ CH,CH,CH='CH,
CH,. + * ; Z . ~ ~ , ~ ~ = = ' / 2 ~ ~ ,
[CH,CH,CH=*CH,]
+CH,CH=CHCH,
/ H e + CH,CHCH=CH,
CH,CH,CH;CHN, AL z CH,CH,CH,'CH:
r+CH,-C(CH,),
[*/*IJ-L
\
A
+ CH,CH-CHCH,
CH,CH,"'CH== ' "CH,
2 .CH; -- , CH,CH,
CH,. 1-* I ? . CH,CH-;"'CH, -, CH;!'CH,CH=',~CH?
2 ^ ' ? . C H , C H = = * / ? C H , -- , CH,=CH *"CH,CH=
*/? *!'cH,
SCHEME
8
for example, the axial hydrogen atom adjacent to the centre should migrate
preferentially :
T h e 1,3-shift insertion can be formulated as follows:
T h e photolysis of 167 led to formation of the butadiene (168) arid as major product,
the vinylcyclopropane (169) 251.
Hydrogen migration is a very eficient intramolecular trapping process for phenyl-

~ . proposed that in the photolysis of 170 migration of the
m e t h y l ~ a r b e n e ~I t~was
phenyl group takes place in the triplet carbene, whcreas hydrogen migration occurs
9. Photochemistry of the diazoliiuni and diazo groups 417
exclusively in the The diazo compounds 170 and 171 give the same ratio
of stereoisomers of 1,2-diphcnylpropene (172 and 173) by migration of different
groups: this points to the existence of a common intermediate. It is suggested that
..
/\
hr
PhC H - C=N2 + PhCH-e-Ph PhCH-C-Ph
I I I I
(170)Ph
Me Me
Singlet Trii'et
Me
Ph migration
Ph,C-CHN, "* Ph,C-CH:
Me
I I
Me \
(1 711 Intermediate Ph,C=CHMe
ph..w
Me
Ph
Me
\
,c=c
PI1
/
\
H
Ph
\
/c=c\
Me
/
Ph
H
this intermediate might best be formulated as the phantom singlet state 174 of
a-methylstilbene. 1,2-Alkyl shift (C-C insertion) can also :
51.6%
Clearly, the more complicated the alkyl substituents in alkylcarbenes, the more
products are expected from intramolecular insertion. A rclatively simple example is
the following:
54% 36.5% 5.5% 4%
Kirmse and G r a ~ s r n a n nfound

~ ~ ~ that 1,2-hydrogen shift dominates in alkyl-
carbenes. Some intramolecular cycloaddition may arise from decomposition of
176, but this was slow compared to that of 175. Saturated bicyclic systems undergo
ring expansion as well as C-C insertion. Ring expansion also occurs in spiro
systems and some unusual olefins have been synthesized by Kirmse and P00kZs8and
418 Wataru Ando
@NFaN
(176)
1.1%
\?\
later by WibergZGo.
It seems remarkable that no hydrogen shift was observed:
-NTs
Masamune and coworkers isolated the ring-expanded product 178 o n the photolysis
of 177 261. Photolysis of cis- and rrans-3-diazomethyIbicyclo[3.1.Olhexane gave a
variety of products of carbon-hydrogen insertion but little ring expansion2G2:
47%
Photoirradiation of the sodium salt of 2,3-homotropone p-toluenesulplionyl-
hydrazone in tetrahydrofuran afforded a hydrocarbon (180) as the sole product in
70% yield, which is a dimer of 1,2,4,6-cycl.~octatetraene
(179) 283. The compound 180
+ N- N
/Lo
/
0 4
N
(179) I
reacted smoothly with N-phenyltriazoline-l,4-dioneat room temperature to afford,

probably via 181, the 1,l-adduct 182 in 65% yield. T h e intramolecular insertion of
(2-n-buty1phenyl)diazomethane (183) was found to proceed with fairly indiscriminate
attack o n the a,p, y and 6-C-H bonds, both when the irradiation is effected directly
or via photosensitization26J.This is interpreted in terms of a n equilibrium between
the singlet 191 and the triplet 192, equilibration being more rapid than the ensuing
processes leading to intramolecular insertion (ix. 184-187), intermolecular C- H
insertion (Le. to form 188) and hydrogen migration (i.e. to form 189 and 190).
Kirmse studied reactions of methoxy alkylcarbenes.
+a+q-+ I
420 Wataru Ando
Intramolecular C - H insertion
-. Intern\olecular C - H insertion
---+ Olefin formation
A methoxy group accelerates the shift of adjacent groups while itself being slow
to move compared to hydrogen and also to alky12G5,
260.
t
CH,O
h CH,O
CHN, -?-+
CH,O OCH,
53- 62% 6% 17-25% 16%
CH,O+CHN, A”
+
OCH,
+ )_JOCH’+ CH,O
4-
OCH,
23-25% 5% 22% 43-55%
Substitution in the y-position by a variety of groups X makes insertion more

difficult. The data indicate a largely inductive effect of X. Stabilization of partial
charge by resonance does not appear to be a n important The small
contribution of resonance suggests concerted hydrogen transfer and C- C bonding
in the y-C-H insertion.
X =: OMe 1.5% 60-80% 15-35%

x = NMe, 6-8% 92-94%
X :
.: ph 9-1 3% 60-700/,
Direct irradiation of 193 and the tosylhydrazone anion 194 gave C-H insertion
and vinyl group migration. Rearrangement of 195 might afford diphenyldimethyl-
9. Photochemistry of the diazoniurn and diazo groups 42 1
butadiene268.Hydrogen shift was shown to be favoured over fluorine or Ruoroalkyl
shift269:
cy,
CHN, A CH,=CHCF,C,F,
/
C,F,CFz
P-C-H insertion and alkyl migration predominate with alkyl(alkoxycarbonyl)-

carbene~?'~. In contrast to p,P-dirnethyl-a-diazobutyrate, r-butyl phenyl-
diazomethane prefers self-insertion to give cyclopropane rather than methyl shiftc7'.
)-iCO,Me
Nz
LL
' >-,,,,,
+ $CO,Me I1 I'
' )=(CO,Me + d C0,Me
NZ
62% 38%
Photolysis of ethyl diazoacetate, even in the vapour phase, did not produce
+
butyrolactone. t-Butyl and t-amyl diazoacetate, however, affordcd small amounts
of lactones o n photolysis in c y ~ l o h e x a n e ~Diethyl
~~. diazomalonate gave both
intermolecular and intramolecular reactions in the presence of t h i o b e n ~ o p h c n o n e ~ ' ~ .
$H,CO,C Me, 0
N,CHCO,CMe, +
90.5%
95%
v 27% 44%
+ Dimer
29%
422 Wataru Ando
Several diazoamides were found to undergo Intramolecular insertion into
p-C-H bonds of the N-alkyl groups with formation of f 3 - 1 a c t a m ~ ~ This
’~~~~~.
method was applied in a synthesis of methyl 6-phenylpenicillanate.
S N
* Me C0,Me
M e + (
II
‘COCPh s+O
N Z
Ph
The 1,2-alkyl shift in carbenes has been used to generate highly unstable olefins
a s transient intermediates. a-Silylcarbene (196) rearranges in alcohols t o the ester
(197)containing an unstable silicon+xirbon double bond which is then attacked by
the When trimethylsilyldiazomethane was photolysed with a high
C0,Et
/
Me,SiCCO,Et l ’ hMe,Si?CO,Et d Me,Si=C
II \
N? (1 9 6 ) Me
/
OEt OR
I I
Me,Si-C-CO,R
II
+ Me,SiCCO,R
I
D D
?R
M e,Si CD C 0, E t
OR I
I Me
1- Me,SiCCO,Et
I
D
pressure mercury lamp in various alcohols, two major products are obtained.
Product 198 may be produced by a nucleophilic attack of alcohol on the silicon
centre to release the diazomethane. T h e photolysis of silyldiazomethane in ethanol-d,
showed that the deuterium \vas only introduced into the a-carbon of the ethyl group.
-
T h e formation of 199 might be accounted for by 1,2-methyl migration producing a
silicon--carbon double bond followed by addition of alcohol to the latter. While
AV ROD
Me,SiCHN, ~
> Me,SiCH: Me,SiOR+Me,SiCHDCH,
I
OR
(198) (199)
niethoxy(trimethy1)silane is the major product in methanol, 1,2-methyl migration

becomes more rapid in r - b u t a n 0 1 ~ 272.
~~.
28. Photolysis of trimethylsilyldiazomethane
TABLE
in alcohols
ROH 198 (%) 199 (%) Total yield (%)
MeOH 83 17 96
EtOH 47 53 96
i-PrOH 35 65 66
t-BuOH 0 100 45
Similarly, the photolysis of diniethylphenyl- and dimethylbenzyl-silyldiazomethane

in methanol gave three major products, 200, 201 and 202. Relative yields of 201
and 202 indicate that the migratory aptitude of the methyl group is larger than that
of the phenyl or the benzyl group, even though statistical factors are considered.
This tendency is quite different from that observed in cases when the migrating
groiip is bound to carbon and not to
Me,SiCHN,
I
R
- -hv
Me,SiCH:
I
R
MeOH
OMe
I
Me,SiOMe+MeSiCH,CH,+hrie,SiCH,R
I
R
I
R
OMe
I
(2W (2011 (202)

R = Ph 52% 39% 9%
R = CH,Ph 49% 43% 8%
Photolysis of 203 in 204 gives 206 and 207, which probably arise from the inter-
mediate 205 278.
424 Wataru Ando
1. Photolysis of Diazo Compounds in Compounds Containing Hetero Atoms
In this section we treat especially attacks by carbenes at C--X bonds where X is
a substituent having a lone-pair of electrons. This mechanism involves intermediate
ylide formation prior to abstraction-recombination.
1. Reaction with polyhalomethanes

T h e reaction of diazomcthane with polyhalomethanes in the liquid phase proceeds
by a radical chain mechanism, which is initiated by halogen abstraction. The fast
migration of chlorine in the intermediate radical is thought to prevent chain transfer
at a n early stage, and to produce 208, the major product from carbon tetrachloride.
T h e high quantum yield and the inhibiting effect of radical scavengers provide
-
further support for the chain mechanism"O. T h e course of free radical reactions of
--
-- -
:CH,+CCI, *CH,CI+.CCI,
-CCI,+CH,N, -----+ N,+.CH,CCI, CICH,~CI,
CICH,~CI,+CH,N, N,+.CH,CCI, (CICH,),~CI
I
CH,CI
(CICH,),ECI+CH,N, N,+.CH,C(CH,CI), ~ > (CICH,),C*
I
-
CI
(C I CH,) ,C .+ CH,N, > .CH,C(CH,CI),+N,
.CH,C(CH,CI),+CCI, (ClCH,),C+*CCI,
(208)
diazoniethane with polylialoalkanes depends upon the reactivity of the organic
halide, the stability of the interrnediatc and on thc reaction conditions. With un-
rcactive halidcs, polymethylene is t h c dominant product (cf. 2-chloro-2-methyl-
propanc"O); with halides of low reactivity (cf. bromochloromethane), mixtures of
products of the general formula CICH2(CH2),Br are obtained281.The highly reactive
polybromo- and polyiodo-methanes give dibronio- or diiodo-methane and related
alkenes via F-elimination of bromine or iodine atoms from intermediate radicals282,
while the light-promoted reaction of halides of comparable reactivity give products
of attack of intermediate free radicals upon the polyhaloalkanes:
CBr,+2 CH,N, hy 2 N,+CH,Br,+Br,C=CH,
HCBrCI,+CH,N, *" > BrCHCH,CI+(CICH,),CHBr+(CICH,),CHCH,Br

I
CI
7% 13% 15%
Br C (C I) ,Me + CH,N, hv CI CH,C CI Br M e +(C I CH,),C BrMe +(CICH,),C Me
I
CH,Bi
10% 20% 4 3%
B r C C I, + CHIN, hr.C I CH,C C 1, B r +(C1C 9,) ,C CIBr +(C I CH,),C +
Br (C ICH,),C CH,B r
atI5-15 "C 1% 16% 15% 14%
at 40-70 "C 13% 26% 18% 0
T h e following is the postulated mechanism in the reaction of diazomethane with
bronlodichloromethane:
CH,NZ+~U ~ > :CH,
:CH,+HCCI,Br ----+ .CH,Br+*CHCI,
H~CICH,CI+HCCI,Br ---+ HCCICH,CI+H~CI,

I
Br
T h e gas-phase reactions of methylene with methyl chloride and methylene chloride

take place predominantly by chlorine and hydrogen abstraction. i n the case of
methyl chloride, both abstraction processes give rise to the same intermediates,
methyl and chloromethyl radicals. At higher pressures the major products are
29. Reaction products of :CH, with CH,CI

TABLE
Yield (%)
C2H.j CZHSCl CZHdCIZ CZH, CZHSCI

-
150 29 45 26 - -
76 28 44 28 trace -
32 31 31 26 12 tracc
12 34 13 25 26 2
4,8 32 5 24 33 G
0.9 17 - 13 50 20
ethane, chloroethane and 1,2-di~hloroethane?~~.

These products a r e consistent with
-
the following set of reactions:
:CH,+CH,CI ___j *CH,+*CH,CI
*CH,+*CH, C,H,
*CH,+.CH,CI ----+ CH,CH,CI
.CH,CI+*CH,CI ~ > CICH,CH,CI
T h e products above could also be consistent with C-H abstraction as the initial
reaction of :CH,. This possibility was checked by experiments with dichloromethane
where C-H abstraction would yield cthane, 1,l-dichloroethanc, 1,1,2-trichloro-
ethanc, chloroethane and I ,1,2,2-tetrachloroethanein addition to 1,2-dichloro-
ethane. Only 1,2-dichloroethane was produced in significant quantities. Further
evidence for the abstraction mechanism was obtained by adding a small percentage
of oxygen, when ethane, chloroethane and 1,2-dichloroethane were virtually
eliminated from the reaction products. Mechanisms involving the formation of a n
ylidc intcrniediate, however, cannot be eliminated :
426 Wataru Ando
Doering has found that the reaction of methylene with the carbon-chlorine bond of
optically active 2-chlorobutane proceeds with a high degree of racemizationZs4:
+ :CH, -- F T
CI CH,CI
(90% racemic)
These experiments indicate the possibility of a n ylide intermediate followed by
radical cleavage and recombination. More recently, the use of CIDNP has implicated
the singlet state in chlorine abstraction and the triplet state in hydrogen
abstract 288.
It was suggested that reactions of alkyl diazoacetates with polyhalomethanes may
proceed via a free radical chain mechanism2s7. Urry and Wilt found that photolytic
reaclions of methyl diazoacetate with chloroform, carbon tetrachloride and bromo-
trichloromethane produced the corrcsponding methyl polyhalopropionates28s*
A free radical chain mechanism was postulated on the basis of the identity of the
products and by analogy to the reaction with diazomethane. Recently, arguments
N,CHCO,R :CHCO,R
-
:CHCO,R+CCI,-X ---+ ~CI,+-CHCO,R
I
X
-
*CCI,+N,CHCO,R CI,C~HCO,R+N,
CI,C~HCO,R ---+ CI,~CHCICO,R
CI,~CHCICO,R+CI,C-X *CCI,+CI,CXCHCICO,R
(X = CI,Br or H)
against the operation of a radical chain mechanism in the photolytic reaction of
diazoacetate with carbon tetrachloride, chloroform and methylene chloride have
appeared. When ethyl diazoacetate was decomposed in each of these substratcs in
the presence of radical chain initiators (such as benzoyl peroxide), different products
were obtained from those reported earlier by Urry and Wilt. These results suggest29o
that the photochemical decomposition of ethyl diazoacetate affords a different
species than that produced when the diazo ester is decomposed in radical fashion.
The preferred inechanism to account for the formation of the methyl propionates
involves carbene attack at halogen with consequent ylide formation, followed by
-----
SNi type displacement of the halogen involved in ylide formation:
I 1 , -
1
I
-c-CI+:CHCO,R ---+ -c-CI-CHCO,R
I I
I
-C-CHCIC0,R
I
The pliotolysis of ethyl trimcthylsilyldiazoacetatc in polyhalomethanes afforded
ethyl acrylate derivatives?”, considered to be formed froni a chloronium ylicie
intermediate followed by cleavage and recombination.
30. The photolysis of diazo ester in polyhalomethanes
TARLE
~~
Diazo ester Halide Products Yicld (%)

N,CHCO,Et CCI, CCI,CHCICO,Et 42
CHCI, CCI,HCHCICO,Et 58
CICH,CO,Et 15.2
CHZCI, CCIH,CHCICO,Et 42.4
CICH,CO,Et 3.7
N,C(CO,Me), CCI, CCI,CCI(CO,Me), 49.8
(MeO,C),C= C(CO,Me), 13-2
CH C1, CHCI,CCI(CO, Me), 43.3
(MeO2C),C=C(C0,Me), 8.6
H,C(CO,Me),, H ClC(CO,Me), trace
CH,CI, CH,CICCI(CO,Me), 44.5
(MeO,C),C= C( CO,Me), 4.6
H2C(C0,Me)2 4.9
HCIC(C0ZMe)Z 5.1
/
N &\
SiMe,
+ CCI, * CI,C=C
/
\
CI
CO, Et C0,Et
87%
1 T
-
-CtSiMe,
CI SiMe, CI SiMe,
I 4- -/ I I
-c-CI-c -c-CCI
I \ I I
C0,Et C0,Et
SiMe, CI
/
/
N2C\ + CHCI,
/I,.
+ CICH=C
\
CO, Et C0,Et
46%
SiMe, CI
/
NzC\/ 1- CH,CI, "" H,C=C
\
C0,Et C0,Et
40%
CIDNP studies have confirmed the cage recombination of radical pairs from the
decomposition of halonium ylide intermediate, but are inconsistent with radical
chain mechanism2982-2".
Photolysis of diethyl mercurybisdiazoacetate with chloroalkanes may yield
chlorocarboethoxycarbene (Cl-?-CO,Et) by chlorine abstraction, with the
resulting products then arising from reaction of either carboethoxycarbene or
chlorocarboethoxycarbene with the ~ h l o r o a l k a n eHowever,
~~~. the marked differences
428 Wataru Ando
in reaction products from diethyl mercurybisdiazoacetate as compared with those
from ethyl diazoacetate give strong support for the absence of carboethoxycarbene
-
in the photolysis of the mercurybisdiazoacetate. T h e results suggest that carbyne
209 may be produced from mercurybisdiazoacetate in yields from 63 to 83%:
hV
CCI,+Hg(N,CO,Et),
CI
,CI I
CI,C=C\ +CI,CCCO,Et+CI,CCCI,
C0,Et I
-
CI
41% 12% 52%
hV
MeCCI,+Hg(N,CO,Et),
CI
,CI I
MeC=C' +MeCCH(CI)CO,Et+CH,=CCI,
\CO,Et I
CI
35% 37% 18%
MeCCI,+ N,CHCO,Et hy MeC=CHCO,Et

I
CI
40%
By analogy with the suggested mechanism for the carbon-halogen insertion reaction
of carbenes, one can speculate about a novel ylide-radical intermediate (210) in
the reaction of 209 with chloroalkanes:
-
Hg(N,CCO,Et), hy 2 N,+Hg+2 *?CO,Et
(209)
I I + -
-C-C1+209 -C-CI--C-CO,Et
I I
(210)
Halogen abstraction and recombination of the radicals thus produced appears
to be the major path of diarylcarbene reactions with polyhalomethanes2Q0~ '"'.
On the other hand, ylide formation plays a n important part in the formation of
Ar,CN, + CX, A f A r , C X * -t * C X , --+ Ar,CCX,
I
.I,
Ar,C=CAr2
diphenoquinones by photolysis of 211 in the presence of halogen compounds2Q8. The
isolation of the bromonium salt 212 lends support to the ylide intermediate which is
converted into the diphenoquinone 213 by triethylamine.
T h e reaction between singlet diphenylcarbene and bromotrichloromethane

could also lead t o the formation of the transition state 214 which could then
eliminate bromine chloride to give 215.
BrCCl
Ph,CN, Ph,C=CCI, 4- Ph,CzN-N ;CPII, -I- Ph,C=CPh,
+
Ph,~-Br-CCI, Ph,k-Br .CCI, - > Ph,CCCI,
I
Br
(21 4) (215)
Generally, alkyl halides appear to react whenever possible with carboalkoxy-

carbene to give olefins via H X elimination, when there is a P-carbon-hydrogen
bond present a s indicated below:
R,C=CH, -t XCH,CO,R + N,
y T
Y.
-xL
*<
R,CH-CH,X + N,CHCO,R
R,CHCH,CHXCO?R -f- N,
I n neopentyl bromide, carbon-bromine insertion prcdorninates over carbon-

hydrogen insertion by a f x t o r of 4. I t is especially interesting to note that no
430 Wataru Ando
:
rearranged products were observed in this reaction2gB
Me,CCH,Br+N,CHCO,Et hy Me,CCH,CHCO,Et+Me,CCH,Br
I I
Br CH,CH,CO,Et
Product ratio 4 1
This argues against the operation of a mechanism whereby an intermediate ylide
breaks down to form the carbon-bromine insertion product via dipolar abstraction
of bromine with subsequent recombination of ionic fragments. T h e reaction is
therefore envisaged as a n initial attack of singlet carbene on the halogen atom to
-
give an ylide intermediate 216 followed by p-elimination. Insertion into the C-CI
.. + rc
Brf
H,C ’d C
‘ H /
OH
+
H,C-CH,Br:
.. :CHC-OEt
d
-> I
H,YJ
(-7-I
II
C-OEt
BrCH-C
\
OEt
CH,=CH,
0 I
(216 )
BrCH,CO,Et
bond of chlorotetramethylsilane by singlet biscarbornethoxycarbene or carboethoxy-
carbene may proceed via a chloronium ylide which undergoes homolytic fission a t
the original C-Cl bond and r e c o m b i n a t i ~ n ~ ~ ~ :
Me,S iC H,CI +N,C (C00Me), hv M e,Si CH, CCI(C00M e),
Me,SiCH,CI+N,CHCO,Et & Me,SiCH,CHCICO,Et+Me,SiCHzCl
I
CH,CH,CO,Et
24% 8%
A chloronium ylide intermediate has recently been suggested to account for the
reactions of carboethoxycarbene and biscarbomethoxycarbene with allylic halides.
Direct photolysis of dimethyl diazomalonate yields singlet biscarbomethoxycarbene
which reacts with allyl chloride t o give 53% of allyl chloromalonate and 23% of
t h e cyclopropane derivative301. With y-methylallyl chloride the formation of
a-methylallyl chloromalonate and the cyclopropane was observed, but n o y-methyl-
ally1 chloromalonate was observed. T h e formation of ‘insertion’ products may be
explained by the formation of a halonium ylide followed by a symmetry allowed,
thermal [2,3]sigmatropic rearrangement3OC. With allyl bromide, a n excellent yield
CH,CH=CHCH,CI
+ CH,CH-CHCH,CI
\ C(COOMe),
/
N,C(COOMe), 15%
3%
HCf ~ c ?
I1 I ---+ CH,=CHCHCCI(COOMe),
C H’--C(C OOM e) , I
/ CH,
CH,
38%
9. Photochemistry of the diazonium and diazo groups 43 1
was obtained by the insertion of biscarbomethoxycarbene into the carbon-bromine
bond, whereas only a trace of addition product was formed (Table 31).
T h e most marked change between direct and sensitized photolysis is in the ratio
of the insertion and addition products.
3 1. The photolysis of diazocarbonyl compounds in allvl halides

TABLE
Diazo compound Halides Insertion (%) Addition (%)
DMo A C I 53 (5)d 23 (88)d
DM A C I 25 (trace) 22 (86)
DM -cl 38 (trace) 15 (49)
~ ~~ ~
Dimethyl diazomalonate.
Ethyl diazoacetate.
Ethyl trimethylsilyldiazoacetate.
Benzophenone sensitized decomposition.
The proposed mechanism for the formation of insertion products through

halonium ylide intermediates may be supported by the following evidence. In
direct photolysis, the insertion reaction with ally1 chloride was about 1-2.5 times
and with the bromide about 8 times faster than the addition. Since the reactivities
of the double bonds toward the attacking carbene species are not considered to be
very different in these two allylic substrates, the change in the ratio of insertion t o
addition may be d u e to the difference in nucleophilicity between chlorine and
bromine atoms. This consideration is also supported by results obtained in
competition experiments using pairs of allylic compounds (Table 32). From these
TABLE32. Competitive reaction of singlet and triplet biscarbomethoxy-

carbene with allylic compounds
Olefin Mode of product Singlet Triplet
-
Addition 1 .oo 1.00 (standard)
Insertion 2.3 0.07
Addition 1 .o 1.0
Insertion 8.5 0.3
Addition 1 -2 1 .o
Insertion 6.3 0.5
432 Wataru Ando
results it was concluded that singlet carboalkoxycarbene produced via direct
photolysis of diazo ester preferentially attacks the halogen atom in allylic halides to
afford predominantly C-X bond insertion products, whereas the corresponding
triplet carbenes generated by benzophenone-sensitized photolysis preferentially
add to the carbon-carbon double bonds in these substrates.
Support for this interpretation of the differing behaviour of the carboalkoxy-
carbenes produced via direct photolyses us sensitized photolyses of diazo ester was
obtained by the observation of a solvent effect on the insertion/addition ratio in
the photolytic reaction of dimethyl diazomalonate. It can immediately be seen
that the ratio of the insertion to addition products decreases with dilution with
methylene halides or c y c l ~ h e x a n e ~
This
~ ~ .was interpreted as indicating collision-
induccd conversion of singlet to triplet. In the heavily diluted runs the yields are
severely reduced, and the scavenging by methylene halide leaves a mixture of
carbenes richer in the triplet.
TABLE33. The effect of added solvents on the photo-

decomposition of dimethyl diazomalonate in ally1
chloride
Solvent Inscrtion/Addition Yield (%)
None 2-35 76
None + Ph,CO 0.056 93
CoHi:! 10% 3.39 64
50% 2.52 26
90% 1.95 5
CH,CI, 10% 2.38 60
50% 2-20 35
90% 1-17 10
CH,Br, 50% 1*60 14
90% 0.06 4
CH,T, 10% 1.94 27
2. Reaction with nitrogen compounds

Insertion into carbon-hydrogen bonds is the predominant reaction of methylene304
and of e t h o x y c a r b ~ n y l c a r b e n e308~ ~with
~ ~ triethylamine. Products possibly resulting
from j3-elimination within the hypothetical nitrogen ylide are formed only t o a
minor extent:
Et,N + N,CH, Et,NMe + Et,NCHMe,
Et,N -I- N,CHCO,Et ’”’ Et,N CHCH,CO,Et

I
+ Et,N(CH,), CO, Et
Me
-
45%
Et,N + N,C(COOMe), A +-1

Et,-N-CH
( Me 00C)
.:
CH,
I
Et,NC(COOMe),
I
H
+
CH,=CH,
a*a
Benzyldirnethylamine reacts with ethyl diazoacetate and with diazofluorene by
apparent insertion of the carbene into the N-benzyl bond307:
PhCH,NMe, +
II I+
N, P h CH,- N - Me,
PhH,C NMe,
PhCH,NMe, + N,CHCO,Et "" Z PhCH,CHNMe,

I
C0,Et
Most likely these products arise from a Stevens rearrangement of the ylide inter-
mediate.
Relatively little is known about the isolation of stable nitrogen ylides in these
reactions. Substituted pyridinium tetraphenylcyclopentadienylides were produced
pvtl
in almost theoretical yields on refluxing tetraphenyldiazocyclopentadiene in
pyridine, the picolines or 2,6-lutidine under a n atmosphere of nitrogen for
10 min 308-311 :
Ph
+ x 4
Ph Ph Ptl
N2 X+
Cyclopentadienylides of other hetero atonis were similarly~readilyobtainable by

decomposition of diazo compounds with reagents containing thcse elements.
The triphenyldiazocyclopentadiene was irradiated under nitrogen in the
2,5-dimethylpyridine with a high-pressure mercury lamp through a pyrex filter.
Recrystallization afforded the 2,5-dimethylpyridiniun~triphenylcyclopcnta~ieny~ide
in 48% yield312:
Ph
Ph Me Ph
N2
48% 26%
434 Wataru Ando
Pyridinium and isoquinolinium biscarbomethoxymethylides could be isolated from
the photodecomposition of dimethyl diazomalonate in pyridine and i s ~ q u i n o l i n e ~ ~ ~ .
Isoquinolinium carboethoxymethylide has also been obtained by photo-
decomposition of ethyl diazoacetate in the presence of i s ~ q u i n o l i n e ~ ~ ‘ .
mN
1- N,(COOMe), 4
h
-C(COOMe),
1- N,C(COOMe),
lhv
--q 1
m;-
m N -c(COOMe ),
(217) COOMe
(218)
m N + N,CHCOOEt
c Hc 0 0 E t
Isoquinoliurn dialkoxycarbonyl ylides (217) and dimethyl acetylene dicarboxylate
react in methanol to give the 1, IO-b-dihydropyrrole[2,1 -n]isoquinolines (217a);
217
QQ ‘C(C
-
OOM e ) ,
MeOOCC S C C O O M e
COOMe
COOMe
COOMe
(217a)
m N $ Y e -’ m N f - + (MeO),C=O
CHCOOMe
COOMe
qNbr
0 0
T F O O M e
MeOOC
\ 0 (217c)
(217b)
217 in methanol alone yields the more reactive monoalkoxycarbonyl ylide and
dialkyl carbonate, t h e former dimerizes to 217b or reacts in siru with olefins to
yield 1,2,3,10-b-tetrahydropyrroIo[2,1-a]isoquinolines (217c)316. The isolation of
stable pyridinium ylides suggests also the intervention of nitrogen ylides in reactions
in which one group bound to nitrogen is unsaturated. Here the ylide cannot be
isolated but rearranges in ~ i f t . 4 ~Very
~ ' . similar results were reported for the reaction
of carbomethoxycarbene with ally1 chloride and ally1 sulphides:
/
?<
CN'LC(COOMe)2
\
___f
I\
N.r' (COOMe),
The study of reactions of carbenes with nitrogen-hydrogen bonds is practically

virgin territory. In o n e such study, the reaction of carboethoxycarbene with
f-butylarnine has been reported to afford the nitrogen-hydrogen bond insertion
product along with a product resulting from WolfT rearrangement (see Section J)
of the ~ a r b e n e ~ ~ * :
I
f-UuNH
N,CHCGOEt :CHCOOEt ---A f-BuNHCH,COOEt
Wolff renrnrriurrnent
EtOCH=C=O f-BUNH-C-CH,OEt
II
0
The photolysis of a hydrazine or a hydrazone with w-diazoacetophenone in dry
tetrahydrofuran yields the corresponding phenylacctylhydrazine or phenylacetyl-
hydrazone in fairly good y i e l d P D ,probably via Wolff rearrangement. T h e benz-
hydrylamines produced from diphenyldiazornethane were accompanied by tetra-
phenylethane suggesting hydrogen abstraction as another p o ~ s i b i l i t y ~ ' ~ :
PhCOCHN? + RNHNH, -L PhCH,CONHNHR
(R = H , Ph, CH,Ph)
h I. , ~ N - N H C O C H , P h
PhCOCHN, +
RW!
H , K
The photolysis of ethyl diazoacctate and of ethyl diazomalonate in acetonitrile
gave oxazoles. It seems likely that the carboethoxycarbene formed by decomposition
of t h e diazo ester undergoes 1,3-dipolar addition to the nitrile to form the oxazole
219 directly. The photolysis of ethyl diazoacetate in the presence of benzophenone
gave an oxazoline incorporating the dements of carboethoxymethylcne, benzo-
phenone and acetonitrile, presumably by the addition of triplet carboethoxyrnethylene
IS
436 Wataru Ando
I1 8 .
R-C-C0,Et - R-G-CO?Et
I1
N,
I
'.'
OEt
(219)
to benzophenone and further addition of the diradical intermediate 220 to
a~etonitrile~~'.
phkl
Ph
I
Ph-C-01 M~c.-.N
HCC0,Et i- Ph,C=O -___
HC1 Et0,C
II Me .
C0,Et
(220)
Irradiation of diazoacetate (221) in acetonitrile gave the oxazole 222 initially
which in the presence of benzophenone rearranges to the isoxazole 224. The azirine
223 has been proposed as the intermediate but could not be detected. When molecular
oxygen, a triplet quencher, is introduced into the reaction vessel, the conversion of
222 to the isoxazole 224 is completely inhibited. The photolysis of trifluoroacetyl-
diazoacctate in acetonilrile gives 225 in 50% yield. T h e photolysis of thc latter
PhNHCO-C-CO,Et -r+
MeC-N Sens.
%ONHPh
I1 2537A Me C0,Et
N2
(223)
CONHPli
Me-
(224)
affords a 10% yield of the dimeric species 226 which is thought to arise from a
formal [2 + 21 cycloaddition of two oxazole rings. Weygand and coworkers have
CO-Et Et0,C C0,Et
(226)
developed a general procedure for preparing P-perfluoroalkylalanines from perfluoro-
alkyloxazole synthesized by the 1,3-dipolar addition of perfluoroalkyl diazoacetic
esters to acetonitrile. Over-all yields of 227 are 35-50% 322.
9. Photochcmistry of thc diazoniurn and diazo groups 437
(R,CO),O + N,CHCO,Et --> R,COCCO,Et

MeC-xN
I1
N*
Diphenyldiazomethanc and phenylisocyanate react under influence of U.V. light

to afford 2,2-diphenylindo~yI”~,presumably via diphenylcarbene addition to the
C=N bond and rearrangement of the a-lactam intermediate:
Ph 0
x
N-C
Ph,CN, + PhN-C=O +
11“
Ph Ph I
H
Irradiation of N-sulphurylaniline and diphenyldiazomethane gave N-diphenyl-
methyleneaniline as the major There is evidencc that S=O was evolved:
Ptl
\
N--S=O -50
+
I,
__ f
X
I
Ph,CN, PhN=S:-0 --+ Ph--N=CPh,
Ph Ph
3. Reaction with oxygen compounds

a. Moleciilur oxygcrt. The photolysis of diphenyldiazonietlianc in the presence of
oxygen afforded benzophenone, which became the major product under suitable
~ o n d i t i o n s ~ ‘T~h. e isolation of the cyclic peroxidc from t h e photooxidation of
diphenyldiazomethane suggests a carbonyl oxide as t h e i n t e r ~ n e d i a t e ~ ? ~ .
Experiments with la0,indicate that n o dccomposition of 230 to give oxygen a n d
benzophenone occurred under the conditions of the photooxidation. The processes
leading to benzophenone appear to proceed in a parallel fashion rathcr than
~ ~ . the photooxidation was carried o u t in t h e presence of
c o n s e c ~ t i v e l y ~When
I1 8 . 0, + +
Ph,CN, _?, Ph,C: --+ [Ph,C-0-0- ++-+ Ph,C-;O--O-]
I
I
-
VO ,
/ \
Radical reaction ph,t--O-O- Pti,C=O + O2 Ph,C
\
CPh,
/
(228) 0-0
(230)
acetaldehyde, propionaldehyde o r benzaldehydc, t h e ozonides of 1 , I -diphenyl-
propcne, 1 ,l-diphenyI-l-butene or triphcnylethylene, respectively, could be
In the last case, no dipcroxide was formed and the major product was
benzophenone. T h e ozonide is presumably fornicd from reaction of t h e carbonyl
oxide and the aldehyde, which reaction competes successfully with diperoxide
438 Wataru Ando
formation. Results to date indicate that ozonide formation is limited to diazo
compounds containing two aryl substituents.
Some saturated hydrocarbons are oxidizcd at room temperature when carbenes
are generated in them in the presence of oxygen329.The reaction seems to involve
TABLE
34. The oxidation products obtained from the photodecomposition of
a
various diazo compounds in cyclohexanc saturated with oxygen
Irradiation t i me Cyclohexanol Cyclohexanone
Diazo compound (min) (%I (%I
300 29 19 ( 5 5 ) O
Nz
None 300 1 1
Ph,CN2 58 21 13 (Sl)O
R
N,C(COOEt), 300 1 1
300 1 1
N 2
Yield of ketone from diazo compound by gas chromatography.

photolysis to give a triplet carbene which reacts with oxygen to give a diradical of
the type 228. The carbonyl oxide diradical then abstracts hydrogen from the alkane
to give an alkyl radical and R,?-O-OH; the alkyl radical may react with 228,
R C O O H or oxygen to give eventually alcohols a n d carbonyl compounds by steps
similar to those involved in other autooxidations of hydrocarbons.
(229)
0 0-0
II I \
Me,CHCH -k Me,CHCH 4- '0, -> Me,CH\ ,CHMe,
II 0
N*
55%
0-0
I \
PhCHN, -I- PhCHO + '0, -> PhCH ,CHPh
\0-
Triplet carbenes react with oxygen more readily than singlet carbenes, apparently
yielding a triplet carbene-oxygen adduct. This method has been extended to cases
where diazo compounds can be converted to ozonides by allowing them to react
with singlet oxygen in the presence of a n aldehyde330.This reaction is observed with
both aryl and alhcl diazo compounds. A possible mechanism involves attack by the
electrophilic singlet oxygen at a n electron-rich centre of the diazo compound. T h e
resulting intermediate 231 may decompose directly to give nitrogen and the zwitter-
ion 229 or it may cyclize first to the heterocycle 232.
The photochemical reaction of diazo ketones 233 with molecular oxygen in
aromatic solvents gave tetraphenylglycolide (2343) and 3,6-dimethyI-3,6-diphenyl-
glycolide (234b), respectively, instead of the peroxide (235) or diketone (236Y'.
0
fF[
!I
Ph 0-0 C--R
N,
II
(233)
PhCCOR --
l I I . 0,
0'
Ptl oKR
R-C
0
Y X
"
0-0
(235)
or
Ph
a : R = Ph (234) PhCOCOR
b: R == M e
a: 41% (236)
b: 49:L
By contrast, diazo ketones (237) afforded products resulting from 1,2-hydrogen
shift and 1,3-dipolar additicn of the keto-carbene intermediate.
F
MeC-COPh
11:. 0 ,
- CH:=CHCOPh -!-
Me
\
CHCOOH
/
Ptl
b. Reaction with alcoltols. W h e n diazomethclne and t-butanol mixtures were

photolysed, the major products were t-butyl mcthyl ether and 2-methylbutan-
2-01~~ From
~ . the amounts formed, the 0 - H bond of t-butanol is 10.9 times a s
reactive as a C-H bond. Competitive reactions with roughly equimolar mixtures
of alcohols gavc the following relative reactivitics of 0 - H bonds toward attack
by methylene :
hV
ROH+CH,N, ___j ROCH,+C-H insertion products
Reactivities of RO-H b o n d s for :CH,:
MeO-H EtO-H i-Pro-H 1-BuO--H
2.01 1a 9 5 1.37 1.00
This is the ordcr of decreasing acidity of the alcohols as well a s the order of
increasing steric hindrance. Photolysis of diphenyldiazomethane in methanol
afforded benzhydryl methyl ether in 70% y i ~ l d The
~ ~ ~quantum
. yields of the
440 Wataru Ando
photolyses in methanol and in nprotic solvents wcrc identical within experimental
error.334
Photolysis of diphenyldiazomethane in a methanolic solution of lithium azide
produced benzhydryl methyl ether and benzhydryl azide in virtually the samc ratio
a s that obtained in the solvolysis of benzhydryl chloride. These results suggested a
diphenylcarbonium ion intermediate, arising by protonation of diphenylcarbene:
Ph,CHOMe
*
Mc 0 3 ~
I1 I' McOH
Ph,CN, + Ph,C: -> Ph,CH+
Ph,CHN,
From studies of isotope effects it has bcen deduced that diphenylcarbene reacts
with the oxygen atom of ROH, giving a n ylide, subsequent rearrangernent of which
gives Ph,CHOR. T h e kinetics were rather c o ~ n p l e 33c.
x ~ With
~ ~ ~ i-propanol, hydrogen
abstraction to give diphenylmethane and acetone competed with formation of
benzhydryl i-propyl ether. If hydrogen abstraction and autooxidation are attributed
to triplet carbene, the kinetics require the reversible interconvcrsion of the singlet
and triplet states, indicating a delicate balancc of rncchanisms.
R'+/H
h I. ROH 0
Ar,CN, Ar,C: + I -+ Ar,CHOR
C-
Ar' 'Ar
T h e reaction of ally1 alcohol with biscarbomethoxycarbenc produced by direct

photolysis of dirncthyl diazomalonate afforded two principal products, that of
0-H insertion (238) and bicyclo[3.1 .O]lactonc (239). T h e product 239 is presumably
formed by lactonization with elimination of rncthanol from the initially formed
cyclopropylcarbinol arising by addition of the carbene to the double bond337.338.
35. Photolysis of dimethyl diazomalonatc in allylic

TALILE
alcohols
Direct (%)
Sensitized (%)
Alcohol (238) (239) (239)
R'R?C=CR'CR:OH + N,C(COOMe), % R'R?C==CR'CR;OCH(COOMe),
I,"
Y
(238)
R'RzC-CR'CR:OH __
\ /
C(COOMe),
0
(239)
Photolysis of ethyl diazoacetate in allylic alcohols gave similar products, 240
and 241, together with trans-cyclopropylcarbinol (242) and Wolff rearrangement
product (243). rrurJs-Cyclopropylcarbinol cannot be converted to bicyclo[3.1 .O]-
lactone. The most marked difference between direct and sensitized photolysis is in
R'RzC=CRJCR:OH+N,CHCO,Et > R'R3C=CR'R:OCH,C0,Et
(24)
R' CR:OH
I I
+ R'R'C-C-R'
\ /
+ EtOCH,CO,CR:CR'=CR'R*
CHC0,Et C H C0,Et (243)
0
(241 )
the relative ratio of t h e products of insertion and addition. The benzophenone-
sensitized photolysis of dimethyl diazomalonate gave bicyclo[3.1 .O]lactone, but no
0 - H insertion product. Similarly, the sensitized photodecomposition of ethyl
diazoacetate in allylic alcohols gave mainly the carbon-carbon double-bond
addit ion products.
The most probable mechanism of the 0 - H insertion involves an clectrophilic
singlet carbene attack on the oxygen atom of the alcohol to give an oxygen ylide
followed by the proton migration from oxygen to carbon. Distribution of the
products depends on the structure of the allylic alcohols and seems to be controlled
mainly by steric factors.
The photolysis of dimethyl diazomalonate in alcohols produced substantial
amounts of dimethyl malonate, and the efficiency of hydrogen abstraction varies
with the hydrogen donor properties of the
hv
N,C(COOMe)2 -t Me,CHOH -+ Me,CHOCH(COOMe)2
21 %
C0,Me
+ MeOCH
/
\
+ CH,(COOMe), + Me,C-CMe,
I I
C0,C H MeZ 41 % HO OH
12%
442 Wataru Ando
The formation of pinacol in i-propanol fits a scheme in which the triplet abstracts
hydrogen to give a radical pair followed by another hydrogen abstraction and
radical recombination. Both the photosensitized and benzoyl-peroxide-induced
decomposition of dimethyl diazomalonate in ethanol and in i-propanol gave
dimethyl malonate in 7480% yields.
N,C( C 00Me), + R R' C H0H + P h, C 0 hlr C H,( CO 0Me),
c. Reaction with ethers. The major reaction of methylene with ethers is nearly
random insertion into the various C-H bonds. T w o minor reactions are displace-
ment, leading to methyl ethers, and apparent insertion into the C - 0 bond. The
displacement reaction with methyl alkyl ethers resuits in the formation of dimethyl
ether and a n ~ I e f i n *It~ ~is. not suppressed by the presence of oxygen nor does it
occur when the methylene is produced by mercury photosensitization. The reaction
is therefore envisaged as resulting from the initial attack of singlet methylene on the
oxygen atom to give a n ylidc intermediate, followed by p-elimination.
RCH,OCH,CH,R' + ROCH,CH,CH,R ROCH, + R'CH=CH,

TABLE
36. The relative amounts of displacement and C-0 insertion of methylene
with ethers
Ethers Phase Displacemcnt ( x ) C-0 Insertion (%)
___-
Gas 4.0
Liquid 0
Gas 3.3
Liquid 0
Gas 10.0
5.6
/OMe {Gas 3.9 4.6

M e C,H Li q ti id 1.6 11.3
OMe
Photolysis of ethyl diazoacetatc in dicthyl ether Icd to 244 and 245 as t h e

. ' ~ . product 244 in the observation of CIDNP emission can
principal p r o d u ~ t s ~ The
be rationalized in tcrrns of oxygen ylide intermediate which then undergoes Stevens
rearrangements via a homolysis-recombination m c c h a n i ~ i n ~ ~Formation
'. of a
different ylide intermediate followed by Hoffman type F-elimination of ethylene by
a non-radical path is a reasonable explanation for the formation of 245. Many
substitutcd anisols and silyl-substituted methyl ethers gave rise to methyl elimination
products when trentcd with ethyl diazoacctate and diphenyldiazomethane. These
reactions may also bc rationalizcd by an oxygen ylidc intermediate from which,
EtOEt + N,CHCO,Et 4
n
+ I
Et-0-CH,CH,
I t l
EtO,C-C--
I
H __f EtOCH,CO,Et + CH,=CH,
4-
Et-0-CHCH, EtOCHCH,CO,Et
I _3 I
CH,CO,Et CH,
(244)
SiMe, Me
EtOEt + NzC\
/
-+ hs EltOCHSiMe,
I
C0,Et
+ I
EtOCHCHSiMe,
I
C0,Et C0,Et
50%
35%
after prototropy methylene, is split 0fP2:
+
ArOCH,+N,CHCO,Et hy Ar-0-CH, -+ Ar-b-eH,
I I
1
- CHC0,Et CH,CO,Et
:CH,+ ArOCH,CO,Et
Me,SiCH,OCH,+N,CHCO,Et hv Me,SiCH,OCH,CO,Et+MeOCH,CO,Et
+C-H insertion products
PhOCH,+PhRCN, ~
hV
Ph OCH RP h + Ph RC =N -N=CRP h
(R = H, Ph)
CH,OCH, + N,C(COOMe),
V!
H,C \ +c, H, COOMe H3C t CH3
0 I ‘0’
I --\
CH,OCCH,
Lt\
I
c, I
COOMe MeOOC
/
COOMe
MeOOC COOMe
(246)
SiMe,
SiMe, I
CH,OCH, -I- N,C \
/ -% CH,OCHSiMe,
I
+ CH,OCCH,
I
C0,Et C0,Et C0,Et
12% 18%
+ C H,OC H,C HSiM e,
I
C0,Et
8%
444 Wataru Ando
Insertion into the C-0 bond is the predominant reaction of ethyl trimethylsilyl-
diazoacetateZg1a n d dimethyl diazomalonate18* with dimcthyl ether. The insertion
reaction probably involves the formation of a n oxygen ylide intermediate. How-
ever, the sensitized reaction produces no such products. Apparently complexes of
the type 246 either are not formed or do not rearrange to products.
Similarly, C-0 bond insertion was observed in the reaction with carboethoxy-
carbene with cyclic ethers. T h e reaction of ethyl diazoacetate with 2-phenyloxirane
gave a n oxetane, styrene a n d g l y ~ x a l a t e 2-Phenyloxetane
~~~. produced a mixture of
17 1
cis- and rrans-2-ethoxycarbonyl-3-phenyltetrahydrofurans3".
Ph Ph
'\ + N,CHCO,R >
-
IIL
--f
RO,C
+ PhCH=CH,
-!-
0 L -CHC6, R
O=CHCO,R
Ph Ph
+ N,CHCO,R
I
35%
Addition of biscarbomethoxycarbene to the C=C double bond of allyl ethers was

accompanied by apparent 0-ally1 bond insertion products which can be considered
to form through the intermediate oxygen ylides by allylic r e a r r a ~ ~ g e m e n t ~The
~'.
bulky 1-butyl group on the oxygen atom seems to interfere with the formation of the
ylide. T h e corresponding reaction with ethyl trin~ethylsilyldiazoacetate~~~ results in
37. Yield of products from the photolysis of dimethyl diazomalonate in

TADLE
allyl ethers
-~ ~ ~ ~ ~~~~~~ ~ ~
Ally1 ethers Mode of decompositioc Insertion (%) Addition (%)

/Iv 31 20
/I v 37 17
hv 1s 38
Ifv 16 25
Iiv + Ph,CO trace 52
I1 v 1s 38
hv+ Ph,CO trace 62
If V 0 39
9. Photochcmistry of thc diazonium and diazo groups 445
the formation of a C - 0 insertion product via [2,3]-sigmatropic rearrangement of
the oxonium ylide a n d of addition products. However, no C-0 insertion product
was obscrvcd when diphcnyl diazomethane was photolysed in ally1 ether.
4. Reaction with sulphur compounds

Insertion of carbencs into the S-H bond of thiols has been achieved by the
photodccomposition of ethyl d i a z o a ~ e t a t e ~ and '~ of bis(phenylsulphony1)-
d i a ~ o r n e t h a n e ~Probably,
~~. singlet carbethoxycarbene reacts with the sulphur
N,CHCO,Et+EtSH hy EtSCH,CO,Et+EtOCH,COSEt
53% (247)
6%
atom to give a sulphur ylide intermediate, followcd by proton migration as with
alcohols. T h e product 247 involves the Wolff rearrangement of the carbene to a
ketene. T h e corresponding benzophenone-sensitized irradiation of ethyl diazo-
-
acetate in ethyl mercaptan gives products in similar yields. The radical mechanism
-
is probably involved in t h e S-H insertion even in direct photolysis as follows:
-
ELW
N,CHCO,Et :CHCO,Et CtS.+-CH,CO,Et
EtS.+ N,CHCO,Et N,+ EtStHC0,Et
EtSkHCO,Et+EtSH EtS*+EtSCH,CO,Et
T h c same radical reaction of ethyl diazoacetate can be achieved thermally by

employing azoisobutyronitrile (AIBN) a s a radical initiator. Radical-induced
decomposition of diazo compounds was also proposed by Horner and co-
~ ' . T h e formation of the S-H insertion product was rapid in the
w o r k e r ~ ~348.
presence of, and very slow in the absence of, the radical initiator. No other product
was found except a trace of diethyl disulphide:
EtSH + N,CHCO,Et+ AIBN

GO 'C
> EtSCH,CO,Et+(EtS),
97%
Since n o rearrangement product was detected in the aromatic thiol (Table 38),
the carbene may not be involved in these reactions, and the insertion into the
sulphur-hydrogen bond might occur only by radical chain reactions.
Dialkyl sulphides afforded stable sulphur ylides by adding carbenes with strongly
electron-withdrawing substituents. Biscarbomethoxycarbene, generated photo-
chemically from dimethyl diazonialonate, reacrs with alkyl and aryl sulphides and
sulphoxides to form stable sulphonium and sulphoxonium biscarbomethoxy-
350. T h e ability of sulphur to stabilize a n adjacent negative charge
111ethyIides~'~-
remains mi interesting phcnonienon.
446 Wataru Ando
38. Photodecomposition of ethyl diazoacetate in thiols
TABLE
~ ~~~~
Thiol Mode of dccornposition S-H insertion (%) Rearrangement (%)

EtSH hv 53
EtSH hv+ Ph,CO 70
i-PrSH hV 31
f-BUSH hV 35
PhSH hV 74
PhSH liv + Ph,CO 90
p-MeOPhSH hv 58
C o m p a r i s o n o f the sulphur ylides to nitrogen ylides indicates that factors beyond

electrostatic stabilization m u s t be involved. T h e simplest explanation involves
delocalization of electron density into low-lying d orbita!s of It has been
pointed o u t t h a t a combination of only s a n d p type orbitals can also a c c o m m o d a t e
+
N,C (CO 0Me),+ MeS Me Me,S -c(CO0M eja
(248)
0-
+ I
++ Me,S-C=C-OMe +--- Me,S=C(COOMe),
I (250)
-
COOMe
(249)
PhSO,,
R
,C=N,-tMeSMe
hl. PhSO,\-
R
,C- +
SMe,
R = PhCO, MeCO or PhSO,

s u c h a valence shell c x p a n ~ i o n(ylene
~ ~ ~ structure 250). A large shift (-110-
1 7 0 c m - I ) to lower energy in thc carbonyl stretching frequency in t h e infrared
spectrum of the biscarboniethoxyrnethylides c o m p a r e d to the analogous
sulphonium salts also demonstrates extensive delocalization of c h a r g e by s u c h
39. Formation of sulphonium ylides from bis(carbony1)diazo compounds and
TABLE
~ulphides~'~.
0
I1
( R = COOMc, R* = COOEI, R2 =1 COMe, R3 = PPh,)
Sulphides Ylidcs Melting point ("C) i.r. ( C = O ) Yicld (%)
+
Me,S M~~S-CR? 169-170 1625, 1675 ss
Et,S E&-CR, 150 1675, 1655 5:
Ph,S Ph,;--CR, 127-1 7s 1650, 1675 '1
Me$ Me,; - K c 134-1 35 1625, 1655 87
Me,S M& en: 166-167 1570, I600 5'
M~,&ER?R~ 157,
M ~ , S ~ C H , S M C ? ~ ~Me,SiCH,, + -
,S-CR, 132-1 34
Me
9. Photochemistry of the diazoniurn and diazo groups 447
carbanion stabilizing groups. An increase in the ylide carbon+arbonyl carbon
x-bond order accompanies the decrease in the ic-bond order of the carbonyl group
(betaine structure 249).
In the reaction of dimethyl diazomalonate with saturated cyclic sulphides, t h e
corrcsponding sulphonium ylides were also obtained as stable colourless solids.
Irradiation of dimethyl diazomalonate in pentamethylene sulphide gave 41% of
sulphonium ylide. Thiethane did not give sulphonium ylides because of its photo-
polymerizat i 0 n ~ :~ 4
0 S'
+ N,C(COOMe), *'. C&-E(COOMe),
+
es
High stereoselectivity is observed with 4-t-butyltetrahydrothi0pyran~~~
:
+ N,C(COOR), I1 I* ~ ' ' C S o O R L
Even v i n y l i ~ " ~and acetylenic s u l p h i d e ~ ~ thiophene

~', and b e n z ~ t h i o p h e n e ~in~ ~ ,
which the lone pair of sulphur is highly delocalized, may trap the carbene produced
in the photolysis of dimethyl diazomalonate. These ylides are quite stable at room
temperature:
PhC=CSEt -I! I
PK-C
Et
\-
S-
/
(COOMe l2
I! I
a
T a -% $i-C(COOMe12
The photolysis of dimethyl diazomalonate in AD-dihydrothiopyran317 gave the

sulphonium bis(carbon1ethoxy)methylide (251), which rearranged to 252 in 83%
yield on heating at 180°C for 30min. The ylidc 251 could be isolated and
rearranges only at higher temperatures, while ylides derived from open-chain allylic
sulphides gave rearranged products at room temperature. This l o w susceptibility
of the ylide (251) toward rearrangement is probably due to t h e transition state of t h e
concerted allylic rearrangement requiring the unfavoured boat form of the
dihydropyran ring bearing the COOMe group endo to the sulphur atom.
448 Wataru Ando
N,C(C 0 0Me) (COOMe),

I
- C(C OOMe),
(251 1
MeOOC,_,COOMe
A clear preference for the e m orientation was also seen in the rearrangement of
253 358.
Photolysis of diazocyclopentadiene in alkyl sulphides also gives stable cyclo-

pcntadienylides in high yields359. Dirnethylsulphoniurn cyclopentadienylide is
considered to be the resonance hybrid of the ylide structures 254, 255 and the
(254) (255) (256)

Ylide structure Ylene structure
ylene structure 256, with the ylide structures predominating3G0.Stabilized 0x0-

sulphonium ylides, unavailable by the direct condensation of sulphoxides and
a-halocarbonyl are suited for the carbene 3G2. Both
thermal methods and photolysis have been employed.
-k
Me,S=O+N,C(R)CO,R' hy Me,S-E(R)CO,R'
II
R = H or C0,Me 0
R' = Me, Et 3040%
+
Ph,S=O+N,C(COOMe), Ph,S--C(COOMe),
11
0
12%
T h e relative reactivity of the sulphur atom of dimethyl sulphide toward carbene
was estimated from the product distribution in the photolysis of dimethyl diazo-
malonate in mixture of cyclohexene and dimethyl ~ u l p h i d e I~t ~was
~ . suggested that
TABLE
40. Yields of products obtained from dimethyl diazomalonate
and dimethyl sulphide in the presence of an equimolar amount of
a second substrate
Second substrate Yield of ylide (%) Yield of adducts (%)
Cycl ohexene 61
2- Met hyl-2-butene 49
cis-4- Methyl-2-pentene 60
Cyclopentadiene 44
Methanol 78
Diethyl ether 73
a Mixture of 7,7'-dicarbomethoxynorcarane and 2-cyclohexenyl-

malonate in the ratio ol' 2.1 : 1.
* Olefin adduct only.
0 - H insertion product.
Ethylene elimination and C-1-l insertion products.
the biscarbomethoxycarbene reacts with dimethyl sulphide about 6 timcs faster
than with the double bond of cyclohexene. Similar high reactivity of sulphur toward
carbenes was also observed in the photolysis of equimolar mixtures of dimcthyl
sulphide and other nucleophiles.
Ethyl diazoacetate and aryl diazomethanes did not yield stable sulphonium
ylides, but afforded decomposition products of the latter363.364 :
R S R 4- N,CHCO,R' 5
R = Et, i-Pr, or t-Bu

T h e reactions of alkyl sulphides bearing a @-hydrogenatom with ethyl diazoacetate
yielded, by @-climination, alkyl thioacetates formed by thermal intramolecular
olefin elimination from the intermediate sulphonium ylides via a five-member
cyclic transition state.
Additional results concerning the behaviour of sulphonium ylides are available.
Thermal decomposition of biscarbomethoxymethylides gave dimethyl alkyl thio-
malonate in quantitative yield365. This supports the proposed ylide mechanism in
the reactions of carbethoxycarbene with hetcro atoms bearing @-hydrogens.
L;C, H
-% EtSCH(COOMe), + CH,=CH,
MeOOC COOMe
Photolysis of phenyl- and diphenyl-diazomethanes in diethyl and benzyl methyl
sulphides gave mainly a X - H insertion, with some @-elimination products, but
450 Wataru Ando
phenyldiazomethane with i-propyl and 1-butyl sulphides gave the p-elimination
The C-H insertion has been suggested to proceed via sulphur ylides
followed by benzyl or benzhydryl migration from sulphur to carbon.
Ph(R)C=N, + EtSEt h I.
R = H, Ph
EtSEt EtS-CHCH,
I I Et S -- CHCH,
-+
Ph
C-
/ \
R Ph
CH
/ \
R
t--,
- CH(R)P h
I-CH,=CH:
Et S C H( R) Ph EtSCHCH,
I
R = H, 4% CH(R)Ph
R = H, 35%
-MCC'H=CH~
CHMe,
(257) (258)
20% 15%
Such 1,2-shifts are forbidden in a concerted reaction mechanism. I n fact, the
accumulated evidence points to a diradical pathway3C6.A CIDNP enhancement of
the n.m.r. signal of the methylene group is observed if the reaction is carried out in
a n n.m.r.
Et 5 -c(C00Me), $
Et -?(C00Me), Et S -c(C 0C :.I e),
I
I ___f t----J
CH,COOMe -CH,COOMe .CH,COOMe
(259)
EtSC(COOMe),
I
CH,COOMe
9. Photochemistry of the dinzonium and diazo groups 45 1
Hence, C-S insertion of carber?es is considered to involve homolytic cleavage
of the sulphonium ylide yielding a radical pair, which collapses to the product.
Intervention of radical pair intermediates has been suggested in the reaction of
sulphonium salts with ~ ~ s c s ~ ~ ~ - ~ ~ ~ .
Stevens rearrangement was also observed in the photolysis of trimethylsilyl-
diazoacetate and trimethylsilyl@henyI)diazomethane in dimethyl, diethyl a n d
di-i-propyl sulphides at room
SiMe, SiMe, SiMe,

/ I /
N,C\
/I#-,
Room Icnip
R’SR’
R’SCR’ + R’SCH
\
I
R R R
Me,S 0
1 c
Me SiMe, R = Ph, COOMe

\+ - 1 R’ = Me, Et, i-Pr
s-c
/ \
Me R
85-00% yield
TAULE 41. Photolysis of ethyl trirnethylsilyl-

diazoacctatc and triniethylplicn~ldiazomethane
in alkyl sulphides nt room ternpcrnture
R R’ 260 (%) 261 (%)
COOEt Me 37 0
COOEt Et 43 G
COOEt i- Pr 31 25
Ph Me 30 4
Ph Et 15 25
Ph t-Bu 0 27
Me SR SiMe,
SiMe, SiMe,
/ I
Me SCH Me S-C-R
\ I \ + \ / I
/C=C
\
COOEt /c”c\ COOEt
Me H Me H
5-1 0%
R = Me, Et, or i-Pr

My /SCH(R)COOEt
/
c=c\
Me ‘H
16
452 Wataru Ando
The x-C-H a n d (3-elimination reactions were found to yield minor products.
A sulphonium ylide was also isolated when the reaction was carried out below
0 "C. However, this ylide does not rearrange to the C-S insertion product 260.
The corresponding reaction with the vinyl sulphide (261) affords 262 and 263;
product 263 results formally via carbene insertion into the C-S bond of 261. N o
addition product was Thermal decomposition of ethyl diazoacetate in
::p;;"
Me SCH,COOEt
150T
262 + N,CHCOOEt -__f
\
:="\
/
+
k
Me H
40% yield COOEt
Et A , = C H , 6% yield
Me .&LcHCOOEt
\ /
/C =c
\
Me H
RCrCSEt + N,CHCOOMe ++RC=CSEt

\c(,COOMe
iI I.
+
RCEC-S-Et
I - cn,=cH,
-CHCOOMe - d RC-CSCH,COOMe
vinyl sulphides a n d acetylenic sulphides gave mainly @-elimination products. No

C-S insertion product has been observed3sG.357. In the photolysis of diazocyclo-
pentadiene in di-r-butyl sulphide, C - S insertion, @-elimination and the C-H
insertion products were
CH,
In the photolytic reactions of diazo carbonyl compounds with dialkyl disulphides,

the products arising from thiocarbonyl elimination have been observed. Thus, the
reaction of dimethyl diazomalonate with dimethyl disulphide afforded dimethyl
y (264)
COOMe hb)
I
MeSCSMe MeSCH(COOMe),
I
COOMe (265)
(266) 44%
2.2%
9. Photochemistry of thc diazonium a n d diazo groups 453
methylthiomalonate (265) and dimethyl diniethylthiomalonate (266) via an ylide
intermediate (264)3 5 4 s 364.
,SiMe,
N,C, +RSSR RSCHSiMe,
‘COOEt I
COOEt
R = Me, 49%; R = Et, 95%
N,CPh,+MeSSMe hy MeSCHPh,
49%
Photolysis of diphenyl and phenyldiazomethanes in dimethyl sulphide led to
267,268 and 269. Product 267 can be rationalized in terms of Stevens rearrangenlent
of the intermediate sulphur ylide; products 268 and 269 d o not conform to this
scheme.. but rather to [2,3]sigmatropic rearrangement of sulphur ~ l i d e ~ ~ ~
(Sommelet-Hauser rearrangement).
+
I
CH,-S -Me
tI
UCHPh
Me+
,M
,e
Ph,CN, + MeSMe -% S
-I
CPtl, -->
(270)
. - S Me
C H,- 1 k,
Ph,CHCH,SMe t- .1‘
SCHPh,
OHPh
(267) qH,SMe
40%
OCHZP
The ratio of Sommelct-Hauser to Stevens rearrangement varied when the
photolysis of diphenyldiazornethane in dimethyl sulphide was carried o u t in different
PhCHN, + MeSMe k-
f tiCHzS (269)
20%
454 Wataru Ando
types of solvents. The striking result is the formation of a norrnal Sommelet-
Hauser type product (orbital symmetry-allowed [2,3]sigmatropic process) in polar
solvent conditions, whereas in non-polar conditions only a Stevens type product
(orbital symmetry forbidden process) is formed. Possibly, in the ylide 270, the
methylene catbanion attacks the benzene ring followed by proton migration-
hence, the necessity for a more polar medium. In non-polar solvents this require-
ment is not met, so that homolytic cleavage competes successfully with carbanion
attack (k,> k,) and the product is derived from the net orbital symmetry forbidden
1,2-shift.
TABLE 42. Solvent effects on the reaction

of diphenyldiazornethane with diniethyl
sulphide“
Solvents Product ratio, 2681267
Cyclohexsne 0.2
Benzene 0.3
Acetone 3.2
Mcsityl oxidc 3.5
Mole ratio of sulphidc to solvent
is 0.3.
1,2-Alkyl shifts of the trialkylsilyl group have also been reported in the reaction
of diazo compounds with silyl sulphides and silyl ethers”l. Carbethoxycarbene
produced in the photolysis of diazoacctate reacts with ct hyl thio(t rimethy1)silane
(271) to yield ethy! triniethylsilyl(cthylthio)acetate (273) in 38% yield and ethyl
ethylthioacetate (274) in 29% yield. The photolysis of diphenyl and phenyl-
diazomethanes in ethylthio(trimelhyl)silane afforded products similar to 273 and
E.,t -/R
Me,SiSEt+N,CRR‘ Az /s-c
(2711 Me,Si ‘R’
a: R = H, R’ = COOEt
b: R = H, R’= Ph
c : R = R‘= Ph
I (274)
R’
(273)
274. T h e formation of 273 may involve the sulphoniuni ylide (272) followed by
1,2-migration of the silyl group involving a geminate radical-pair intermediate
275, which collapses to 273. The radical 276 through hydrogen abstraction, yields
274. Whilc i t may account for the products, the geminate ion-pair mechanism has
never been established fcr !,2-n:igra!ion of :hc silyl group. A coi;certed 1,2-migration
of the trinicthylsilyl group might be involved since silicon may expand its valence
shell, and the decomposition of the sulphonium ylide via a concerted, five-member,
cyclic transition state could give 274 and Si=C, the fate of which is unknown372.3i3.
1,2-Migration of' a silyl group from the oxonium site to a carbon may also take
place in the reaction between carbenes and alkoxytriinethylsilanes (277).
OR
I
Me,SiOR+N,CHCO,Et hv Me3Si-6-R ~ > Me,SiCHCO,Et+ ROCH,CO,Et
I 2840y0 5-1 4%
-CHCO,Et
C-H insertion products

10-1 4%
Me,SiOMe+ N,CHPh A> rvie,SiCHOMe

I
Ph
25%
Since the carbene attacks a sulphur atom niore rapidly than the carbon-carbon
double bond, the reaction with allylic sulphides may also procced by attack on the
sulphur atom. The ylide may rearrange with complete allylic inversion as demanded
by 2,3-sigmatropic symmetry control. Thus, the photolysis of diniethyl diazo-
malonate in n-butyl ally1 sulphide gave 278 as the major and 279 as the minor
-
product :
,,, ~-BuSCH,CH-CH,
\ I
n-BuSCH,CH=CH, + N,C(COOMe), C(COOMe),
(279)
5
3
JhI.
J.
COOMe
I
<S-C(COOMe), -- f ~-BUSC-CH,CH=CH~
I I
n-Bu COOMe
(278)
In the bcnzophcnone-scnsitized photolysis, addition products were favoured

indicating that elcctrophilic singlet cnrhenc is capable of accepting the electron from
sulphur more easily than the triplet. Copper salt or coppcr powder catalysis, on the
other hand, yielded exclusively the products of tlic 3,3-sigmntropic process37a.
456 Wataru Ando
43. Product yields in the photolysis of dimethyl diazomalonate in
TABLE
allylic sulphides
Sulphide C-S insertion (%) Cyclopropane (%)
~~
A S E t
51 (18)" 10 (37)"
A S E t 46 (7) 12 (29)
-SEt 53 (31) 7 (1%
43 (19) 12 (27)
" Benzophcnone photosensitized reaction.
In the rcaction of allylic sulphidcs with ethyl diazoacetate, a greater lack of

specificity was In the photolysis of phenyl and diphenyldiazomethanes,
on the other hand. the C-S insertion product is observed in 20-30% yields, but
only a trace of cyclopropane or none at all was obtained30J:
N,CXY + MeCH=CHCH,SEt
X = H, Y = C0,Et
.*> CH,=CH-CH(Me)CXYSEt
19-23y0
+ Mk-
X
68%
Y
CH,SEt
X = H, Y = Ph 31% 4%
X=Y=Ph 36% 0
X = SiMe,, Y = C0,Et 60% 12%
Introduction of a bulky group at C(31leads to preferential formation of the

trans isomer a t the newly created double bond. Of the two orientations atthe
larger C(3) substituent should preferentially occupy the pseudo-equatorial
:
n-Bue
PhS
+ N,C(COOMe), --+
/II
Ph-S
<
n;-
I_ -I
C(C O O M e),
1 ,I--"
L C -SPh L
\
COOMe
90% 10%
Cyclopcntadienylidenc gavc, with allylic sulphides, iiiscrtion into the C - S bond

as well as addition. The former could arisc from an interincdiate sulphoniuin ylide
followed by 3,3-sigmatropic rearrangement3'":
458 Wataru Ando
Intramolecular carbene rcaction on the sulphur a t o m was also found. a-Ally1
and a-arylthioall:ylcarbenes generated by a modification of the Bamford-Stevens
method gave labile episulphonium ylides, which then rearranged to vinyl
s ~ l p h i d e s ~378.
’ ~ *The episulphonium ylides could be trapped by diethyl maleate or
dimethyl fumarate. An a-allylthioalkylcarbene generated by the photolysis of
allylthioacetophenone tosylhydrazone afforded a-allylthiostyrene. which gave a
smooth thio-Claisen rearrangement. 3-Thiabicyclo[3.1 .O]hexanc was obtained when
ally1thioacetophenone tosylhydrazone was decomposed photochemically in the
presence of bases.
I. Wolff Rearrangement
T h e Wolff rearrangement of x-diazocarbonyl compounds has received much
mechanistic attention. Thus, photolysis of a-diazo ketones in protic solvents yields
carboxylic acid derivatives. Ketenes (280) have been proposed as reaction inter-
mediates80- 85 . In aprotic media ketenes are often obtainable in preparative
811
N 2 R
II \
R-C-C-R’ -+
/I,.
c=c=o R’OH
-t R R’CHC0,R“
II /
0 R’
(280)
quantities. Many studies have attempted to determine whether loss of nitrogen

preccdes migration to give a n intermediate ketocarbene (281) and/or oxirene (282).
R
A R’
(2811 (282)
1. Synthetic utility
T h e reaction has considerable synthetic use, e.g. for chain Icngthening”:”:
RCOOH
SOCI,
t RCOCI
CH,IJ,
> RCOCHN, +>> RCH,COOH
E‘Sy
A. x;HMc
/I
RCH,COSEt RC H,CO N( Me)Ph
R a n e y h L/l(nlH,
RCH,CHO
In cyclic systems ring contraction occurs and thc reaction is useful i n synthesis of
strained small-ring compounds:
’0
c& 6
/I I.
__f
(Reference 381)
When 283 in benzene solution was irradiated a t room temperature, in the presence
of an alcohol, the product (284) was obtained via the Wolff rearrangen~ent~"?. The
photolysis of 285 gave in 65% yield a 2 : 5 mixture of $-lactam (286) and its
epimerization product (287). The reaction yiclds some compounds whose production
by other methods is either impossible or very difficult. For instance, the photolysis
of 288 is a convenient method of obtaining 6-aminoindene (289)3y5.Horner and
460 Wataru Ando
coworkers irradiated the 0-quinonoid diazoketone (290) in alcohol or in the presence
of aromatic amines, and separated derivatives of the corresponding ketene in the
form of esters or anilides of indenecarboxylic acid38e.In boiling xylene, the product
was an adduct of the ketene identified as 293. Diazokctoncs 294-296 undergo
smooth Wolff rearrangement, but only 2% ring contraction occurs with 296, presurn-
ably owing to a n increase of c. 50 kcal mol-' in strain energy.
d+-
%:
0 &0
(References 389,390)
Similarly pyridine and quinoline derivatives yield pyrrole- and indole-carboxylic
392. Photolysis of 298, through ring contraction, gives 2,5-dimethylpyrrole-
3-carboxylic acid (299) when the reaction is carried out at low temperatures.
Without cooling, 298 reacts with 299 to give the azo dye 300a which readily loses
carbon dioxide leaving the azo compound 300b 302.
(300)
(299)
a: R = COOH
b:R=H
Quinoline derivatives decompose similarly on irradiation:
rn H
I
This reaction can be used to obtain the corresponding indoles including the un-
substituted indole, the 5-chloro- and 5,6-dimethoxyindoles and their carboxylic
The photolysis of the diazo compound 301a gives 4-azaindole-3-carboxylic
acid which is characterized by a high stability and is incapable of decarboxylating.
Its isomer, the 6-azaindole-3-carboxylic acid from (301b), is very easily de-
~ ~ . rearrangement of a-diazoesters to
carboxylated, yielding 6 - a ~ a i n d o I e ~Wolff
alkoxyketenes, and products obtained from these were reported in a study of the
photolysis of diazoacetyl enzyme^^^^-^". A diazoester is attached at the active site
of the enzyme a n d subsequently reacts with neighbouring amino acid residues. In
particular, photolysis of diazoacetyl chymotrypsin presumably gencrates a carbcne
that reacts by a rearrangement analogous to that of diazo ketones, Lither by insertion
into water o r by insertion into amino acid residues. Histidine and tyrosinc residues
have so far been identified as sites of attack.
462 Wataru Ando
mNz
(301 a) H
-+H,O
/I 1, Q-J~
- co, ~ ~ ~
N / N’
I I
(301b) H H
T h e rearrangement encountered in these investigations was also illustrated with

~ ~ ~ , reacted in part as follows:
a z a s e ~ i n e which
0
II
HC-C-OCH,CH-COT
I
- Aw
0
II
:CHCOCH,CH-CO;
1
NH,’
4
I
NH: NH:
(303)
The product of photolysis of a diazothiolester protein derivative (304) in water,

after hydrolysis, gave 305 as derived by Wolff rearrangement of the thialkoxy
group307:
1
N,CHCOSCH,CHCONH-
Protein hy Rearranged compound
NHCO-
(304
1
8
0
I1
HOC-CH,SCH,CHCO;
I
i4;i
(305)
Ethyl diazoacctate (306), phenyl diazoacetate (307)and N-methyl diazoacetamide

(308) also give products from Wolff rearrangement when photolysed in protic
9. Photochcmistry of the diazonium and diazo groups 463
solvents. The major competing reaction is insertion into the 0 - H bond of :he
solvent.
MSOII
N,CHCO,R ROCH,CO,Me+MeOCH,CO,R
hv
(306) R = Et 20-25y0 75-80yo

(307) R = Ph 4540% 40-55y0
I
N,CHCONHMe hy :CHCONHMe A
no >
HOCH,CONHMe
(308) 70%
O=C=CHNHMe n*o z HO,CCH,NHMe

30%
The ketenes formed in the WolR rearrangement have been frequently subjected
- -
in sill4 to cycloaddition with C=C, C = N and N = N double 3q0:
hz
N,CHCO,R ROCH=C=O
. OR
\
PIiN=CHPh\
Horner obtained 309 from azibenzil a n d azobenzene, 310 from benzoyl diazo-
methane and azobenzene, 311 from diphenylketene and azodibenzoyl, and 312 from
azibenzil and a,a'-azotoluene 400, 401. There is no doubt that the a-diazocarbonyl
compounds used are first converted t o the corresponding ketenes which then react
with- the azo compounds to form the corresponding derivatives of 1 ,2-diazetidine.
R
\
C=C=O + R"-N=N-R" j
/
R' R/
N-N
'R"
(309) R = R' = R" = Ph
(310) R .= H, R' = R" = Ph (311) R = R' = Ph. R" = COPh
(312) R = R' = Ph, R" = CH,Ph
Photolysis of 5-acetyl-3,3-dimethyI-3H-pyrazole(313) gives rise to a ketene

intermediate 314, which reacts with 313 to produce the adduct 315 402. The ketene
464 Wataru Ando
0
MeC” COMe
L_,
Me Me
2c
(313)
MeMe
CNMe, Mc,NH +o d
313
Me Me Me
(31 4) Me Me 0
(315)
(Reference 382)
Ph 0
p h x , N - p h s
+ ph-$==N-Ph
Ph Ph
Ph Ph Ph
obtained from the photolysis of 283 reacts with azobenzene to give spiro com-
pounds3**. Ketenes formed by photolysis of diazoketones can also add to
azomethines to give P-Iactarnsao3:
The scope of this cycloaddition is limited above all by reaction of the starting
compound itself or its primary fragments (carbenes) prior to rearrangement. With
diazoketones intramolecular cycloadditions occur preferentially at the ketene stage
in the photochemical reactiondoJn,but at the carbene stage in the catalytic process404b.
Methy! 2iazoacetate upon photolysis in benzene affords two tetrameric isomers
316 and 317 (overall yield 55%)J0s, which apparently arise from dimerization of the
cyclopropane (319) formed by addition of methoxyketene (318) to carbomethoxy-
carbene.
Irradiation of a,P-epoxydiazomethylketones (320) in benzene afforded com-
pounds to which the butenolide structure 322 was attributedao7.
9. Photochcmistry of the diazoniuni and diazo groups 465
N,CHCO,Me -
h
z
I.
Me0,CHC MeXoIcHco’Me
+
0 X I
Me Me0,CHC
Me 0 CHCO’Me
Me
1 (31 6) (317)
MKJCO,Me
H
\
C=C=O + N,CHCO,Me ->
/ h t.
Me0 0
(318) (319)
466 Wataru Ando
T h e same reaction in the presence of an cxccss of mcthanol or ethanol yielded
y-hydroxy-a,P-unsaturated estersJn7.
R'. .OH
R'OH RZ-ORa
321 ->
R' 0
O n rearrangement of unsymmetrically-substituted 2-diazo-l,3-dicarbonyl com-

pounds, both R 1and R2 may migrate in the diacylcarbene providing a n indication
of the relative migration tendencies of various group^^^^--"'^.
TAULE
44. The relative migration tendencies of various
groups
Product ratios
-
Total yield (x)
R' R2 323 324 +
323 324
-
Et Me 51 49 84
Ph H 100 0 90
Ph Me 96 4 64
OEt Me 100 0 78
OMe Ph 100 0 88
Cyclic 2-diazo-] ,3-dicarbonyl conipounds can also be included in these

investigations. T h e arrows in structures 325 326 4 1 2 and 327 J 1 3 indicate the
centres of selcctive migratory aptitude.
The photolytic dccornposition of 6-diazo-2,4-cyclohexadien-l -one in methanol
affords a guaiacol (329), phenol, a dinier (330) o f methyl cyclopentadienecarboxylate
and a reddish pigment 331 ,111.
2. The mechanism of Wolff rearrangement

To date, the most thorough study of the Wolff rearrangement of diazo esters has
~ ~ " . thc photolysis of ethyl
been conducted by Strausz and c o w o r k e r ~ ~ ' ~ -From
diazoacetate in i-propanol they obtained 332 (9%), 333 (29%), 334 (25%) and 335
(12%). T h e ethoxy ether 333 results from ethoxy migration to form ethoxy ketene
which is trapped by i-propanol. T h e hydroxy ester stems from C-H insertion into
Me,CIIOH
N,CHCO,Et y,?Me,CCH,CO,Et+EtOCH,CO,CHMe,
I (333)
OH
(332)
+Me,CHOCH,COzEt+Me,CHOCH~COzCHMe,
(334) (335)
468 Wataru Ando
the solvent; the ether 334 arises from 0 - H insertion and may also be a product of
transesterification. Control studies indicated that the formation of 335 is a photo-
induced process which does not involve carbenes. Instead, a mechanism involving
light-induced heterolysis of the diazo ester was suggested :
RO
I
V V I
\
,c=c=o
H
The mechanism of the Wolff rearrangement of a-diazo ketones and esters in the
gas phase has been studied by ‘3C-labelling of diazo derivatives 336. T h e results are
attributed to the formation of two different ketenes 337 and 339, involving also an
oxirene intermediate 338. Franzen applied the lJC-labelling technique for the
photolysis of azibenzil (340). H e concluded that oxirene was not an intermediateJz0.
a RO--’~C=CH
0 0 0
II h 1. II Path 2 / \
N,CH-”COR --+ RO-.’TCH:
(336) (338)
1Path 1
-”c
11
-C ti0
I
O=”C==CHOR RO
(337)
1
Products
RO”CH=
(339)
c =O
Products
I-lowevcr, more recently, Strausz and coworkers found in the photolysis of

lT-labelled aziberlzil in cyclopentane that the isotopic composition of CO indicated
scrambling of the oxygen atom to a n extent corresponding to 54% oxirene
participation in t h e
0 N, 0
II
Ph-*C-C-Ph
I1 I, I
----+
I1
Ph--'C-C-Ph
.. 460,:
> Ph,C='C=O
Ph,'CH
c)
By t h e same technique, 28-32% oxirene participation (path 2) was indicated in the
gas-phase photolytic decomposition of methyl and ethyl diazoacetate (336).
Molecular orbital calculations suggest that ketene is more stable than the isomeric
oxirene o r formyl carbene by c. 70 kcal mol-l 421.
Ti 0
(1 "
C=CH
I
H
T
I
An experiment with IJC-labelled a-diazohornoadamanrnnonc (341) yielded only
the acid 342. N o radioactivity could be found in t h e carbon dioxide upon oxidative
decarbonylation, and hence the oxirene 343 did not intervene in any way in this
reaction4??. The photolysis of 2-dia~o-l-'~C-naphthalen-l(2H)-one (344) yields
470 Wataru Ando
indene-1-carboxylic acid containing all the label in the carboxy This result
shows that no isonierization of the oxocarbene 345 to 347 takes place. Compound
348 may be formed directly via Wolff rearrangement of 344 by concerted N2
expulsion and ring contraction.
A test for the transient formation of oxirenes was based o n the observation that
when a methylene group is adjacent to the diazo function, decomposition to the
oxocarbene is followed by a 1,2-shift to the carbene carbon atom, resulting in
formation of a n a,P-unsaturated ketone. Thus, for unsymmetrically substituted
diazoketones, different a,P-unsaturated ketones would form if the oxocarbene
initially produced equilibrated with a n oxirene i n t ~ r m e d i a t e ~ ? ~ .
/
L-
- *C
140 O
"COOH
Proof of oxirene formation that is completely independent of the Wolff rearrange-

ment was obtained with unsymmetrical a-diazo dialkyl ketonesaz5and some aryl
substituted a-diazo ketonesJz6.The trapping reaction yielding 349 strongly suggests
that oxirencs are true intermediates, and not transition state+!'.
Photolysis of dimethyl diazomalonate in the presence of methanol-d, affords
350 and 351 in the ratio 9 : 4. The absence of 352 suggests that n o oxirene inter-
mediate is involved, and the Wolff rearrangement to 351 proceeds with methoxy
-A
A-
57%
\
412 Wataru Ando
-
group migration, as indicated below0?*:
CD,OD C?
h I.
N,C(COOMe), :C(COOMe), __f C(COOMe),
/
H
-
(350)
MeO, MeOOC COOCD,

C=COOMe \ CD,OD I
\ / C=C=O MeOCD
0 / I
Me0 COOMe
\L (351 1
Me0 0
CD,OD I I1
Me0-?-COOMe ---+ DC-c-COOMe
I
CD,O
(352) Not observed
Photolysis of the diazoketone in the presence of sufficient benzophenone, so that
the latter absorbed > 95% of the light, yielded only traces of the enones obtained by
direct excitation. Thus, it can be assumed that triplet species do not rearrange via
oxirene intermediates. There seems to be general agreement that singlets must be
involved. Padwa and L a y t ~ n ~report
*~ that photosensitized decomposition of
diazoacetophenone in i-propanol results in a decrease in yield of Wolff rearrange-
ment product and an increase in reduced product as compared to direct photolysis :
0
II
P h -C -CH N,+ Me,C H OH hy P h C H,CO,CH Me,+ P h COMe
(A) (6)
A/B Directhv 2-5
Sensitized hu 0.003
Diazodibenzoylmethane (353) undergoes two primary photochemical processes
leading to 354 and to dibenzoylmethane (355)530. The formation of 354 is related to
the lowest excited singlet state of 353 and the formation of 355 is related t o the
lowest triplet state of 353. The quantum yields of both processes, (1)3s4 and (D355,
are strongly wavelength dependent. I t is unambiguously demonstrated that the
population of two excited states depends on the energy of the excited light, thus
causing a wavelength effect.
Photosensitized decomposition differs from photolytic decomposition of diazo-
t hiolacetate in that rearrangement is suppressed and products derived from radical-
?-ABLE 45. Wavelength effect on the photolysis of 353
Ratio
Wavelength of irradiation
(nrn. 297 K) 355 354
366 1 0.80
313 1 0.3I
z 54 1 0.17
Pyrex (77 K ) 1 20
Scnsitized (Michler ketone) 19 1
0
II
P h -C-CH-COOCHMe2
I
Ph
0 L : C H O H (354)
II
'S ----+ Ph-C-C=C=O
Y Ph
I
(353) s e h 0
.Ti 0
I1 8 . II II
*T ---+ Ph-C-C-C-Ph
11
4 ' .H.
Ph
H
(355)
like abstraction and insertion are Photosensitized decomposition of
diazothiolacetate (356) is a triplet process and the various reactions of triplet ethyl
a-diazothiolacetate (359) and/or triplet carbene (360) are summarized in Scheme 9.
H
h I. \ R'OtI
N,CHCOSE t c=c=o --f EtSCH,CO,R'
/
(356)
4tCHCOSEt - -eo S
I
Et
\ CH,COSEt
? ? Intersystem crossing
\
/" (361)
356 'N,CHCOSEt -+ -1fCHCOSEt

(359)
A Direct Sensitized
Product ralio 3581361 06.5,'3.5 19/81
SCHEME 9
474 Wataru Ando
It is apparent that there can be only minor intersystem crossing in the photo-
sensitized decomposition of 356. Nevertheless, Wolff rearrangement products (358)
are formed in photosensitized decomposition of 356. Jones and Ando
that aliphatic diazoketones such as diazocyclohexanone underwent Wolff rearrange-
ment on unsensitized irradiation. The corresponding carbene could not be trapped
with olefins. Photosensitized decomposition gave an intermediate that did give
Wolff rearrangement and was trapped by olcfins:
6
0
II
C0,Me
+ McOH ,
T h e sensitized decomposition of diazoacetone in olefins yields similar adducts

while none could be found in the unsensitized reactions:
0
II (1) /it w i t h Ph,CO a n d
Me-C-CHN, -(2)
MeOH
COMe
I t is tempting to describe these changes in the most simple terms, that is, singlet
carbenes a r e involved in the unsensitized and triplet in the sensitized decompositions.
The singlet finds a n accessible pair of electrons i n the adjacent carbon-carbon
single bond and reacts with these at a faster rate than with the more distant
x-electrons of the external olefin.
Carbcnes that a r e formed by photolysis of diazo compound 362 are rapidly
deactivated to their ground states, probably because of an internal ‘heavy atom
cffect’. This modifies their chemistry and provides a useful probe for determining the
spin multiplicity of the ground state433-435.
Use of methanoIda shows that it is the methyl group of the ether which comes
from the alcohol, a n d no product of Wolff rearrangement is cvident :
D
I
MeHgCCOOMe CDsoD’ > MeHgCCOOMe ‘”
I
II I
N, (362) OCD,
A,, Wolll‘renrranscment
D
MeO, I
,c=c=o ~
CD,OD
,MeHgCCOOCD, (Not observed)
MeHg I
OMe
Since photolysis of mercury-free diazoacetates in alcohol gives rise t o products of
oxygen-hydrogen insertion, carbon-hydrogen insertion, Wolff rearrangement and
‘exchange’ reactions, the presence of a mercury atom adjacent to the carbene site
enhances the selectivity of the intermediate430.
Irradiation of 363 in methanol leads to competition between the phosphoryl-
carbene and methylene phosphorane oxide rearrangement : 364-365-369, and the
equally possible classical Wolff rearrangement 364-368-372, the methyl esters 369
and 372 are formed in the ratio of approximately 4 : 1.
It is possible, however, to reverse this ratio by introducing a p-dimethylamino
group into the benzoyl group of 363. Furthermore, 364 reacts with methanol by
0-H insertion although the phosphorane oxide 366 cannot be isolated; it undergoes
intramolecular photochemical reduction of the carbonyl group to form the
diradical 370, which then cyclizes to the oxctane 371. Intermediate 365 afforded
dienes on reaction with conjugated ketonesa3’.
N?
II
R,P-C-C-R -+ /I I.
R,P-~-c-R
II II I1 I1
0 0 0 0
Y
/\ MeOH
4‘
OMe R
I \
R,P-CH-CR R, P -C H,CO R c=c=o
II II I1 /
0 0
0 R2;
(367) 0
(366)
(368)
.1
5%
McOH
R
V
R OH R
i
v
McOH
I I I \
O=P-CHCOR R,P- C H- C R CHCOOMe
II I /
I
OMe 0 O-eH, R2;
0
(369) (370)
“I
44% (372)
13%
OH
I
R ,P -C H--C R
II I I
0 0-CH,
(371)
137,
R’ R R 0
I 1 4
i- o=c R’
b
365 O=P-c R-P
\ / -----+ I I
c=c 0- C-R‘ R’
/
R’
\
R‘
R’
AR‘
476 Wataru Ando
K. Biodiazo Compounds
Bisdiazo compounds are potential intermediates for the synthesis of strained
cyclic olefins:
q
I I I I
/C=N, flu fC: TC
C"
\C=N,
-
-f C"
LC-6,
___f
c-7-
'C-N:
'
I I I I
Vicinal bisdiazo compounds yield a c e t y l e n c ~This
~ ~ ~route . led to the success-
~ ~ ~has
ful synthesis of a cycloheptyne and of c y c l o h e ~ y n 440.
e~~~~
In 1959, Kirmse reported the ring contraction of 2,6-bis(diazo)cyclohexanone
and interpreted the result o n the basis of a Wolff rearrangementaa1. Later studies
gave similar result^^^^-^^^. However, a recent alternative explanation is that in the
proposed carbene intermediate obtained from 373 the interaction of a carbanion
with a carbene centre should compete favourably with a-bond migration. While
374 may yield the ketene 375, the exceedingly low activation energy associated with
nitrogen elimination from aliphatic diazonium salts suggests that formation of the
cyclopropenonc could compete with o-bond cleavageaa5.A methanolic solution of
R R
(373)
(374)
R
0
- Products
373 was irradiated at - 40 "C t o yield methyl cyclopentene-3-carboxylatc (376,

15%), methyl cyclopentene-1 -carboxylatc (377, 61 "/,), methyl trans-2-methoxy-
cyclopentane carboxylate (378, 5%) and methyl cis-2-niethoxycyclopentane-
carboxylate (379,10%). Irradiation of (373)in toluene or furan at -40 "C or benzene
at 10°C containing a trace of water gave the ring-contracted cyclopentene-
1-carboxylic acid (380) and t h e corrcsponding anhydride (381) in a combined 65%
yield. Irradiation of I ,3-bisdiazo-l,3-diphenyl-2-propanonc (382) at - 40 "C in a
OMe
373 -
MeOH
11,.
->
(376) (377) (378,trans)

(379,cis)
,
4 : 1 methanol-tetrahydrofuran (vlv) solution gave methyl threo-2,3-diphenyl-

3-methoxypropionate (383, 41%). methyl eryt/rro-2,3-diphenyl-3-methoxypropionate
(384, I3%), methyl trans-2-phenylcinnamate (385, 5%) a n d diphenylacetylene (24%).
Irradiation of 382 under conditions at which diphenylcyclopropenone was photo-
stable, indeed resulted in the isolation of the latter. Photolysis of 387 a t -40 "C in a n
inert solvent such as toluene resulted in a 65% yield of the acetylene (386) as the
only characterized product.
Phxph
PhCH-CHPh
I I
+
+ PhCECPh
H C0,Me (386)
(383,fhreo)
.
,
A mZ H F (384, erythro) (385)
N, N,
(382)
M 2 y A
Ptl Apt, ""

Tolucnc
-
(386)
I n the photolytic decompositions, cyclopropenones a r e established as the major
[61 a+
primary products, at least in the acyclic cases. This also provides support for the
intermediacy of the cyclopropenenone 388 in the photolysis of 373.
373 I1 I ( Rearrangement
(388)
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407. P. M. M. van Haard, L. Thijs and B. Zwanenburg, Tetrahedron Lett., 803 (1975).
408. V. A. Nikolaev, S. D. Kotok and J . K. Korobitsyna, Zh. Org. Khim., 10, 1334 (1974).
409. K. P. Zeller, H. Mcier and E. Muller, Tetraltedrort, 28, 5831 (1972).
410. J. Horner and E. Spietschka, Chem. Ber., 85, 225 (1952).
411. W. D. Barker, R. Gilbert, J. P. Lapointe, H. Veschambreand D. Vocelle, Can. J. Chem.,
47, 2853 (1969).
412. B. Eistert and G . Heck, Liebigs Ann. Chent., 681, 138 (1965).
413. G. Lowe and D. D. Ridley, Chetn. Commun., 328 (1973).
414. M. Yagihara, Y.Kitahara and T. Asao, Chem. Lett., 1015 (i974).
415. T. DoMinh, 0. P. Strausz and H. E. Gunning, J . Amer. Chent. Soc., 90, 1660 (1968);
91, 1261 (1969).
416. I. G. Czsimadia, J. Font and 0. P. Strausz, J . Airier. Chent. SOC.,90, 7360 (1968).
417. D. E. Thornton, R. K. Gnsavi and 0. P. Strausz, J . Airier. Clretn. Soc.,92, 1768 (1970).
418. G. Frater and 0. P. Strausz, J . Attier. Cltetrt. Soc., 92. 6654 (1970).
419. T. DoMinh and 0. P. Strausz, J . Anter. C/tetn. Soc., 92, 1766 (1970).
420. V. Franzen, Jusltts Liebigs A m . Cltetn., 614, 31 (1958).
421. A. C. Hopkinson, J . Clte~tt.SOC.,Pcrkiri Traits. !I, 794 (1973).
422. Z. blnjerski and C. S. Redvanly, C ~ NC o.t ~ t t ~ t i ~694 n . ,(1972).
423. K . P. Zeller, Chetit. Corntttii~t.,317 (1975).
424. S. A. Matlin and P. G. Saninics, J . Chetn. SOC.,Perkilt Trans. I , 2623 (1972).
425. M. Regitz and J. Ruler, Clretn. Uer., 102, 3877 (1969).
426. K. G. Nogai, Disserrarion, Technische Univcrsitiit, Hannovcr, 1972.
427. H. Meicr, IVtIi IUPAC Sytitpositon, 1972, 163.
428. K. P. Zellcr, Chem. Ztg, 97, 37 (1973).
429. A. Padwa and R. Layton, Teiraltedron Lett., 2167 (1965).
430. N. Baumann, Helv. Chitrr. Acta, 5 5 , 274 (1972).
431. G. G. Orphanidcs, Ph.D. thesis, Ohio Srate Univcrsity, 1972.
432. M. Joncs, J r and W. Ando, J . A m ~ r .Cltcttr. Soc., 90, 2300 (1968).
433. P. S. Skcll, S. J. Valenty and P. W. HtIrller, J . Atiter. Client. Soc., 95, 5041, 5042
( I 973).
434. S. J. Valcnty and P. S . Skell, J. Org. C / / C I I 38,
I . , 3937 (1973).
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3276 (1961).
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440. G . Wittig, Aiigew. Chent. 1nr. Ed., 1, 415 (1962).
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CHAPTER 10
The ellectroch e n? ist ry

of the diazo
and diamoniurn groups
J. FRY
ALBEKT
IVcsleyati Utiivevsiry, Middctown, Contiecticrrt, U S A
~~ ~ ~
I . INTRODUCTION. . . 489
11. THEDIAZO GKOUP . . . 490
A. Reduction . . . 490
B. Oxidation . . . 493
111. THED I A Z O N l U h i G R O U P . . 496
IV. REFERENCLS . . 498
1. INTRODUCTION
This review includes a discussion of the clcctrochcniical oxidation and reduction
of diazo compounds (1) and diazoniuni salts (2), where R can bc any of a wide
variety of alkyl or aryl substituents, or, with 1 , hydrogen. Diazo compounds have
been both oxidized and reduced elcctrocheniically; on the other hand, the positive
charge in 2 inhibits anodic electron removal, and hence diazonium salts have only
becn rcduccd electrochemically.
R,CN, RN:X-
(11 (2)
Many mechanistic fcalures of the reactions to be discussed herein are similar to

thosc observed in the electrochemistry of a numbcr of other simple functional
groups. T h e rcadcr may wish to explore such analogies by referring to onc or more
reference works on organic clectrochemistry, of which there arc several
and revicw articlcsJ-' explicitly written for the organic chemist unfamiliar with this
area. The rcvicw by Fry and Reed' rcvicws elementary considerations involved in
interpreting the clectrocheniical behaviour of systems containing multiple bonds,
and much of \\hat is said therc could be applied in t h e present context. Most of
the rcferences cited above also elaborate upon the principles and techniques
employed in organic electrochcmistry, and hence the prcsent article \c.ill pre-
suppose a working knowledge of the appropriate concepts. The emphasis herein
is, ;It any rate, heavily upon the chemical reacticns undergone by 1 and 2 at elcctrodes,
rather than upon clectrochcmical details.
489
490 Albcrt J. Fry
II. T H E D I A Z O G R O U P
A. Reduction
Most studies of the electrochemical reduction of diazo compounds have been
carried out with diazocarbonyl compounds (3). Sincc they constitute t h e niechan-
istically best-understood class of diazo compounds, their elcctrochemical behaviour
will be discussed in some detail. It is probably true that many of the same con-
siderations can be applied to a n understanding of thc electrochemistry of simple
alkyl and aryl diazo compounds, but thcre are probably differences, as we shall see.
R’
I
RCOCN, C,H,COCHN,
(3) (4)
The electrochemical reduction of diazocarbonyl compounds is nicely understood

by reference to diazoacetophenone (4) This compound exhibits three polarographic
waves in aqueous buffer at p H 6. T h e heights of the three polarographic waves
correspond to uptake of six, two and two electrons, respectively, suggesting step-
wise reduction of 4 to a-aminoacetophenone (S), then acetophenone ( 6 ) and finally
a-phenylethanol (7) (Scheme 1).
C,H,COCHN, 6e-C,H,COCH,NH,
(4) (5)
5 se- C,H,COCH,
(6)
6 4 C,H,CHCH,
I
OH
(7)
SCtIELlE 1
Controlled-potential coulometry confirmed the numbers of clectrons consumed

in each stcp as six, t\vo and I\L‘O, respectivelyR, and the suggestion that t h e second
and third waves in thc polarogram of 4 correspond to reduction of intermediates 5
and 6 was supported by thc observation that 5 docs exhibit two polarographic
waves corresponding to the last two of 4, and that 6 exhibits a single wavc at the
potential of t h c third wave of 4 (or second wave of S)$. T h c reduction of 4 to 5
is clearly particularly complex in nature, involving as i t docs overall addition of
six electrons and six protons. Although onc could imagine a largc number of
sequences in which these electron and proton transfers could take place. other
investigations have thrown considerable light upon this conversion. For example,
diazocaniphor (8) also exhibits a six-electron wave over the pH range 6-8.5, and the
aniinoketone (9) (stereochcmistry iinccrtain) is the product of prcparative
electrolysis9. I n alkali, Iiowever, the six-clcctron wave of S splits into two wavcs, a
two-electron wave follou,ed by a four-electron (Scheme 2) 3 . Controlled-
potential elcctrolyscs at thc potentials of thc first and sccond waves of 8 in alkali
afford hydrazone 10 and aniinokctone 9, respectivcly. I’resumably 10 is also an
intermediate in the rcduction of 8 i n the p H range 6 4 . 5 . T h e conversion of 8 to
10. Thc elcctrochemistry of the diazo and diazonium groups 49 1
(1 0)
2
SCHEME
- -
10, like many other organic electrode processes, especially reductions of multiple
bonds', probably involves a n alternating sequence of electron and proton transfcrs
(Scheme 3), i.e. a so-called ECE process. One might imagine an alternate sequence
- -
-
e-
R,CN, R,C-N=N R,C-N=N.
(11 (11)
-
H+
11 R,C-N=NH
(12)
e- - El+
12 R,C-N=NH - > R,C=NNH2
(13)
SCHEME
3
to 12 involving initial protor? transfer (equation 1). A number of lines of evidence

favour Scheme 3, however: (a) diazo camphor is unstable in acid (pH < 6 ) 9 ; (b) the
radical anion (11) has been observed by e.s.r. spectroscopy in the reduction of
Li+ + C-
1 >- RzC-N=NH > 12 ~
(1 1
diazoacetophenone (although under quite different experimental conditions)lD;
and (c) diazoacetophenone (4) is reduced to acetophenone (6) in a rwo-electron
-
process a t p H 5 11, demonstrating that protonation of 1 leads to a different reduction
pathway involving protonation on carbon (equation 2).
H+ II+
-
C- C-
1 R,CHN: -S2 > R,CH* ~
R,CH- RZCHz (2)
The conversion of hydrazone 10 to amine 9 involves no ncw chemistry; i t is

known that hydrazones". 13, including those u- to a carbonyl group", are reduced
electrochemically in a four-electron step, and that this involves initial cleavage of
the N-N bond, followed by reduction of the resulting imine. Thus the overall six-
electron reduction of diazo conipounds 1 may now be seen to involve a sequence of
three two-electron reductions (equation 3). Each of the latter in turn presumably
is itself a n ECE process, analogous to the conversior. of 1 to 13.
2 e- 2 e- 2 e-
1 13 R,C=NH ~
2 H+ > R,CHNH, (3)

492 Albert J. Fry
T h e electrochemical behaviour of 3-diazooxindole (14) is very similar to that of 8.
In base @ H > 8 . 5 ) , a two-electron reduction to hydrazone 15 is observed, followed
by a four-electron reduction to aniine 16 at more negative potential^'^ (cquation 4).
mo
Of course, at lower pH a single six-electron step is observed. Ethyl diazophenyl-
acetate (17) is reduced cleanly to ethyl phenylacetatc in aqueous dioxane at p H 7
(cf the conversion of 4 to 6 in acid, already discussed) (equation 5 ) l o . More
0 (4)
N, NNH, NH,
a
(14) (15) (16 )
C6H5CR C6H5CH,R+N, (5)

II
NZ
[17: R = C0,Et; 18: R = P(O)(OEt),]
surprisingly, t h e diazophosphonate 18 is reduced in similar fashion in 90% yield

even in alkaline media, in contrast with the behaviour of 4, 8 or 14 under such
conditionslG.The reasons for this difference are not clear.
In the only study carried o u t to date ucder aprotic conditions, Elofson and
coworkers explored the electrochemical behaviour of several diazo compounds in
sulfolaneli. Like 17, ethyl diazoacetate suffered clean reduction to ethyl acetate and
nitrogen. Diazomethane was not reducible electrochemically. Reduction of diazo-
diphenylniethane (19) was more complex : diphenylmet hane (24, 20%) and benz-
hydrylamine (23, 2073 were the major products, but azodiphenylrnethane (22,
yield unspecified) could also be identified as a product by the use of mass
spectrometry. Formation of 22-24 was rationalized by the reactions shown in
Scheme 4. It would appear that successive electron and proton transfers to 21 should
-
(C6Hs)zCNz
e-
(c,H,),cN., A (c,H,),~HN,
(19) (20)
20 (C,H,),CH*+N,
(211
20+21 ~ > (C,H,),CHN=NCH(C,H,),
(22)
22- ’ (C,H,),CHNHz
rcfluction
21 -
1i-iib.itmction
(23)
(C,H,),CH,
(24)
SCHEME 4
be at least as likcly as hydrogen abstraction as a route to 24, and that 23 might be

formed by elcctrochemical rediict ion of 20, not 22, but the scheme seems essentially
sound. Judging from these results, the electrochemistry of diazo compounds in
aprotic mcdia differs considcrably from that in protic media. Further experimentation
to ciarify these differences would appear to be in order.
10. Thc electrochemistry of the diazo and diazonium groups 493
6. Oxidation
Anodic oxidation of a variety of diazo compounds, e.g. 25-27, in acetonitrile
has been shown to proceed by initial formation of a short-lived intermediate,
A r CAr' ArCCO Ar' ArCC0,Et
I1 II II
N? N? N,
(25) (26) 37)
presumably the corresponding radical cation1a-20.The oxidation potentials of each
class of compounds were found to be linearly correlated with Hammett u+ and
(3 1 R . 2 0 . Furthermore, the rates of reaction of members of a given class of diazo corn-
pound with benzoic acid were found to be linearly correlated with their oxidation
potentialsl8. 20. For example, the rates of reaction of substituted diazodiphenyl-
methanes (25) with benzoic acid were found to obey the following relationship
(equation 6) 18 :
log kit = - 6.1 3E!.1t 5.59 + (6)
where k~ and E ~ . are
R the rate of reaction and oxidation potential, respectively of
a given diazo compound. Similar correlations were observed for other classes of
diazo compounds, e.g. 26 and 27. The success of such correlations was ascribed to
the fact that both processcs occur at thc diazo group, the position of highest electron
density.
Inilinriori
-e -
19 (C,H,),CN:
(28)
Propogalion
19+28 -s' ' (C~H,)~C-~(W,),
I
N+
(29)
-S2
19+29 ~ > (c,H,),c=c(c6H,),+28
(30)
Tcv-t,iirintiort
-
28+H,O --
--
I1 &
+ '(C,H,),eOH
(311
29+31 30+(C,H,),C=O
OH
I
281-31 (C,Hs)zC-C(CoH,), --11+>
-" C,H,COC(C,H,),
I
'N
5
SCHEME
The radical cations from oxidation of diazo compounds decompose in complex

fashion. From diazodiphenylmet hane (19), for example, tetraphenylethylenc (30)
is the major product (SO:.; yield) but benzophenone, benzpinacolone and
494 Albert J. Fry
b e n z h ~ d r o l are
' ~ also formed. An important mechanistic clue was provided by coulo-
metric experiments, which demonstrate that the anodic process involves a chain
reaction: a t an initial concentration of 19 of 0.05 M , 25 molecules of 19 react for
every electron passed; when the initial concentration of 19 is 0.004M, only seven
molecules of 19 react per electron. T h e products were rationalized a s in Scheme 5 l e e 21.
Oxidation of 19 in the presence of ~~-propylamine, on t h e other hand, consumed
two electrons per molecule of 19 and afforded benzophenone ti-propyl imine (32)
(C,Hs)zC=NC,H,
(32)
as the product10. This reaction may have synthetic utility as a route to irnines
(Schiff bases). Other diazo compounds which were found to undergo electro-
chemical oxidation to afford the corresponding olefin include the following (yields
of olefin in parentheses)?':
NZ
45%
(R = H, 70%) (major product)

(R = CH,, 30%)
(R = C,H=, 60%)
A different anodic pathway appears to intervene when the diazo group is alpha
to a carbonyl group?? (33) or one of its phosphorus analogues'G (34). With such
compounds a complex set of products is formed, some of which apparently arise by
(33) (34)
R' = aryl or OR, R" = OR
coupling of two molecules of substrate a t the para position. This was established by
permanganate oxidation of the neutral fraction from the electrochemical reaction,
af;er removal of acidic materials. For example, anodic oxidation of benzoylphenyl-
diazomethane (35) in acetonitrile containing lithium perchlorate and sodium
bicarbonate afforded benzoic acid (27%), benzilic acid (trace), benzil (9%), benzoin
( ? %), benzaldehyde ( ? %) and a neutral fraction which afforded diphenic acid
( I 7%) and benzoic acid (35%) upon treatment with permanganate??. The coupling
was rationalized a s illustrated in Scheme 6 . All of the observed products can be
rationalized i n terms of intermediates 36 and 39 (which could also be written as a
quinoid structure), though other mechanisms could be imagined. (It should be
noted, incidentally, that there are many precedents for p o r n coupling of anodically
generated radical cationsz3.)T h e difference between the anodic behaviour of aryldiazo
10. The electrochemistry of the diazo and diazoniuni groups 495
compounds, e.g. 19, and species such as 35, appears to lie in the site at which
the corresponding radical cations couple: coupling of two 28 species OCCUI'S at the
diazo carbons, while with 36 coupling is between two para sites. Apparently the
electron-withdrawing carbonyl and phosphoryl groups in 33 and 34, respectively,
inhibit coupling at the diazo carbon.
C,H,COCN,C,H,
(35)
-- -e-
C,H,COCN,C,H:
-
(36)
2. 36 C,H,COC ~ ~ c o c b H S
I
N,f N,f
(37)
38 12)
(1) 40,
-e; c6H,,or !:ocbHs
-N,,
-H* (39)
SCHEME6
The anodic conversion of therdiazo group to an n-hydroxycarbonyl radical2*
(equation 7) (cf. the conversion of 38 to 39) can not only explain the formation of
N, 6 2 OH
II s- I I
-C--C-- -c-c- -Nz
H2° p -c-c- (7)
II II -H+ 1
I
0 0 0
benzoin and benzil from oxidation of 34, but also explains the anodic conversion of
diazoketone 40 to the dicarboxylic acid 43 (along with a trace of diketone 42Iz4.
$7j2 $-J
0 0 Nz;
-!!
-H +
0 OH
(40) (41)
(44
7
SCHEME
496 Albert J . Fry
40 appears to be the o n l y aliphatic diazokctone whose anodic electrochemistry h;l5
been examined. The generality of the conversion exemplified by 40 -? 43, and its
possible synthetic utility as a means of carbon-carbon bond cleavage alpha to the
carbonyl group of aliphatic ketones (via the corresponding diazoketones) remain to
be established.
Elofson and coworkers obtained N-niethylpyridinium perchlorate (44) by clectro-
chemical oxidation of diazoniethane in sulfolane in the presence of pyridine
(equation 8) 17. These workers suggestcd a mechanism involving successive generation
of diazomethane radical cation ( 4 9 , niethylene radical cation (46) and finally methyl
cation (equation 9). It is more likely that t h e product 44 derives from nuclcophilic
attack upon 45 (or possibly 46) by pyridine.
111. T H E DlAZONlUM G R O U P
Electrochemical reduction of arcnediazonium salts in aqueous media exhibits
some confusing features. Two polarographic \vaves arc observed, the height of the
first being controlled by adsorption. Microcoulometry at thc dropping mercury
electrode shows that the two waves correspond to uptake of one and four (overall)
electrons, respectively. The products of preparative electrolysis at a mercury pool
are either aryl mercury compounds or phenylhydrazines; which is formed depends
not only on the clectrode potential, but also thc rate of stirringzc.I n aprotic media,
- -
on the other hand, arencdiazonium salts arc electrochemically better behaved. A
one-electron wave is observed i n aprotic media, e.g. sulfolane or acetonitrile,
corresponding to the electrode process described by equation (10) 2 i . There is a
ArN:+e- ArN+. Ar.+N,
(47)
good linear correlation2’ between the polarographic half-\vave potentials of sub-
stituted benzenediazonium ions arid Hamnictt u substituent constants (+ . for para
substituents capable of donating electrons by rcsonnncc). Free phenyl radicals formed
by decomposition of intermediate 47 have been identified in several ways:
(a) electrolysis in the presence of v.-phenyl-N-c-butyl nitrone, a well-known radical
-
trap, affords radical 48 (equation 1 I ) which can be readily detected by e.s.r. spectro-
s c ~ p yand
~ ~ (b)
, isomer ratios, total ratc ratios and partial rate factors for arylation
+
C,H,*+C,H,CH=N--BU-f (C,H,),CHN--BU-~ (11)
I I
0- 0.
(48)
by electrochemically-generated phenyl radicals coincide with those for phenyl
radicals generated by thermolysis of benzoyl peroxide or N-nitrosoacetanilide,
indicating that there is no electrophilic coniponcnt to the arylation ( f r o n
10. The electrochemistry of the diazo and diazonium groups 497
decomposition of the parent diazonium ion) and that the phcnyl radical reactivity
is not influenced by the elcctrode surface29.Yields of phenylated products are some-
what lower than with benzoyl peroxide or N-nitrosoacetanilide, but the only radical
generated is the phenyl radical, unlike other routes. (Thus, benzoyl peroxide
thermolysis affords products derived from both phenyl and benzoyloxy radicals30.)
Other advantages of the electrochemical reduction of arene diazonium ions as a
Preparative route to aryl free radicals include the facts that aryl radicals may in
primiple be generated ovcr a wide tempcrature range, and that diazonium ions a r e
among the most easily reducible organic functional groups, so that a wide variety
of substituents may bt: accommodatcd in the aromatic ring. Elofson, Gadallah and
Schulz found n o t only that benzenediazoniuni tetrafluoroborate is converted to
phenylpyridines in 81% yield (a : (3 : y = 56 : 27 : 17) upon electrolysis in pyridine
a s solvent, but that metallic mercury alone can effect reduction of the diazonium
ion (87% yield of phenylpyridine~)~'.In fact, phenylation of pyridine could be
effected (though more slowly) by simply allowing the diazonium tetrafluoroborate t o
react directly with pyridine (92% yield of phenylpyridines). It was also found possible
to phenylate pyridine N-oxide with electrochemically generated phenyl radicals.
Yields of phenylpyridine N-oxides were better (35%, a : F : y = 89 : 1 : 10) than with
conventional methods of phenyl radical generation3'.
Elofson and Gadallah have shown that it is possible to effect electrochemical
cyclization of the appropriate diazonium a-phenylcinnamic acids in nearly quanti-
0
tative yield3? (equation 12). They also found it possible to efiect electrochemical
CO,H CO,H
R R---- - N z + + q - $ O Z H
R
(12)
cyclization of diazotized 2-aminobenzophenones (49) to fluorenones (51) (equation
13). Surprisingly, the same process was found to occur thermally, and it was suggested
that this occurs by intramolecular reduction of the diazonium group by the other
ring (an intramolecular charge-transfer process). Depending on the experimental
conditions, greater or lesser amounts of benzophenones (52) and diarylmercury
0
498 Albert J. Fry
compounds (53) accompanied products f r o m decomposition of 49. Yields o f 52
were highest i n aprotic solvents, where hydrogen abstraction by radical 50 is easiest ;
conversely, yields of fluorenones were best in protic media, or in aprotic
thermolyses of 49, which therefore apparently d o not involve radicals 50 as discrete
intermediates. Finally, reduction of 49 by iodide ion in aprotic media afforded
2-iodobenzophenones (54) in g o o d yield ; electron transfer f r o m iodide ion affords
50 and a n iodine atom, which then couple i n the solvent cage.
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24. L. L. Rodina, F. Pragst and W. Jugelt, J . Prokt. Cheni., 316, 286 (1974).
25. R. M. Elofson, Can. J . Clietn., 36, 1207 (1958).
26. P. Ruetschi and G . Trunipler, Helv. Chiin. Acta, 36, 1649 (1953).
27. R. M. Elofson and F. F. Gadallah, J . O r g . Climi., 34, 854 (1969).
28. A. J. Bard, J. C . Gilbert and R. D. Goodin, J . Atner. Chetii. Soc., 96, 620 (1974).
3-9. F. F. Gadallah and R. M. Elofson, J . O r g . Chem., 34, 3335 (1969).
30. D. F. DeTar, J . Atner. Clretn. SOC.,89, 4058 (1967).
31. R. M. Elofson, F. Gadallah and K . F. Schulz, J . Org. Ckeiii., 36, 1526 (1971).
32. R . M. Elofson and F. F. Gadallah, J . O r g . Clwrti., 36, 1769 (1971).
33. F. F. Gadallah, A. A. Cantu and R. M. Elofson, J . Org. Chetn., 38, 2386 (1973).
CHAPTER 11
The influence of the diazo and
diazoniurn groups
EDWARDS . LEWIS
Departnienr of Cliemis(ry, Rice Utiivcrsify,
Hoiisfon, Texas, U S A
1. INTRODUCTION. 499
11. INFLUENCE OF THE DIAZOG R O U P . 500
A. The Carbonyl Group as a Model . . 500
B. The Carbanion Model: Protonation . 501
C . The Carbanion Model: Electrophiles . 50 1
D. Acidity of Diazo Compounds . 502
E. Remote Efiects of the Diazo Group . 503
F. Effect of the Diazo Group on W-n.m.r. Spectra . 503
G . Special Diazo Structures . 504
111. THEDIAZONWhl I O N GROUP . 504
A. Coverage .
B. The Hammett Substituent Constants :
C. Electrophilic Substitution on Diazonium Salts .
504
505
506
D. Nucleophilic Substitution Activated by the Diazonium Group . 506
E. Chemistry of Bisdiazonium Salts . 507
IV. CONCLUSIONS . . 508
V. REFERENCES. 509
1. INTRODUCTION
A major interest in organic chemistry is the effect of structural change o n reactivity,
especially the effect of change in structure of one part of a molecule on reactivity
at some other part of the molecule. T h e influence of such a change in structure is
rathcr conventionally divided i n t o steric effects and electronic effects, although
these a r e neither totally suficient nor completely separable. A n example of the
insufficiency lies in the existence of secondary isotope effects, where the effect arises
exclusively from a difference in mass of two substituents having identical electronic
effects a n d sizes. A n example of the inseparability of steric a n d electronic effects
c a n be found in the efforts to understand the effect of orrho substituents on aromatic
side chain reactivity, where, despite strong efforts, n o reasonable and consistent
electronic effects have been found by incthods often capable of separating stcric
a n d electronic effects in other cases.
Wc c a n nevertheless begin to understand the electronic part of substituent effects
by combining qualitative considerations of inductive effects from electronegativities
a n d formal or real charges with resonance effects, alternatively estimated by various
molecular orbital methods, of which the semi-empirical methods now appear to be
499
500 Edward S . Lewis
the most quantitative. Similarly, steric effects can be related t o Van der Waals'
interactions by qualitative or quantitative methods.
O n these bases, the diazo (I) and diazonium ion (Xi) groups would be expected to
have very strong influences, because of the formal cliarges in the first, the real
positive charge in the second, as well as the unsaturation which gives the possibility
of extensive resonance interaction in both. The direction of the effect i s somewhat
equivocal in the diazo compounds, since even the sign of the charge nearest to the
rest of the molecule is uncertain, depending on the relative weights of contributing
structures Ia and Ib. Structure Ic is unimportant partly because it has the wrong
geometry. I n the diazonium ion the substituent effect is unequivocally that of electron
withdrawal; i t will be acid strengthening, it can be expected to have a positive
Hammett cr or Taft cq.
T h e experimental realization of these expectations is another problem. In order
to determine the effect of the diazo or diazonium groups on a reaction elsewhere in
the molecule, it is necessary to have such a reaction occur, leaving these nitrogen
functions untouched. The extraordinary reactivity of these two functional groups
makes all such studies difficult, for the majority of the reagents will attack these
very reactive functional groups before reacting elsewhere in the molecule. T h e low
thermal stability of diazo and diazonium compounds sometimes niakes i t uncertain
whether or not the loss of nitrogen has occurred before, after or in concert with a
reaction elsewhere. W e therefore lack the wide range of information on substituent
effects for t h e groups, and for the diazo groups there is virtually no quantitative
information. However, there are somc available data, mostly qualitative, and these
will be presented. T h e effect of the diazo group will be discussed first, then that of
the diazonium ion group. Three sourccs have been especially useful in this compila-
tion; the valuable book of Zollinger', the review on diazo compounds in acid by
More O'Ferrall?, and a review by Regitz3 which covers several reactions of diazo
compounds without loss of this functional group.
II. INFLUENCE O F T H E DIAZO G R O U P

A. The Carbonyl Group as a Model
T h e first question we can attack on the relative importance of structures Ia and
Ib is to ask whether a doubly bonded structure rather like a Schiff base or a ketone
is a better representation than a carbanion. We shall see that the carbanion structure
Ib is more descriptive of the behaviour than any carbonyl-like one. In fact, only
one reaction turned up to suggest the carbonyl-like structure. The reaction (equation
1) was postulated4 on the basis of the formation of PhCHOHCN,CO,Et and ethyl
-
N- N
II II
HO FI+ HO N
I II I I1
PhC--CCO,Et PhC-CCO,Et -t PhC0,Et
If
E t O-+ C =0
I
Ph
11. l'lic influence of the diazo and diazoniuni groups 50 1
benzoate from the attcmptcd condcnsation in basic ethanol of benzil with ethyl
diazoacetatc. Here the diazo group may have stabilized the intermediate carbanion,
111.
B. T h e Carbanion M o d e l ; Protonation
Thc analogy of dia7o compounds to carbanions is relatively better supported.
Diazo compounds rcact very generally with acids?, usually however giving diazonium
salts too unstable to allow the drawing of quantitative conclusions. Other electro-
philes also attack diazo compounds, and these reactions also contribute to our
inforniat ion.
One reaction sho\cing the protonation uncquivocally but casting little light on
-
the equilibrium constant is thc reaction of trifluorodiazoethane with fluorosulfonic
acid (equation 2). Thc conversion to the diazonium salt, which is stable a t - 60 "C
F,CCHN,+HO,SF F,CCH$,+-O,SF (2)
is quantitative'. Some other diazo compounds are acid stable to some extent, but
i t has not been establislicd whettier tlicse correspond to stable diazonium salts o r
very weakly basic diazo compounds. They include diethyl diazomalonate, stable to
niethanolic H,SO., G , and (RS0212CN2,which decompose a t rate slow enough to
incasiirc in chlorosulphonic acid'.
At a more familiar level ethyl diazoacctate hydrolysis rates correlate with H "
up to the fastest rates measureds. This suggcsts that the equilibrium extent of
protonation does not cxcecd a few percent i n the most highly acidic media used.
A
The rate of deprotonation of N,CH,CO,Et has not been measured, but the relative
rates of proton and nitrogen loss come out of studies on the acid-catalysed exchange
of tritiuni-labellcd diazoacetic csterg. One can attempt to estimate the acidity of
i
N,CI-I,CO,Et, either by using a substituent constant derived from the aromatic
scries (discusscd bclow), o r by correcting t h e pKn of N=C-CH,CO,Et for an
electronegativity and clcctrostatic changc. This leads, depending on how the various
corrections are applied, to pK, = - 7 k 5, a not very useful or firmly based number,
but at lcast consistent with the available data. Kreevoy'O has estimated from kinetic
+
coilsiderations based on the decomposition of diazoacetate ion that for N,CH,CO;-,
pK, 2 0.
The protonation of diazo compounds which d o not have these base weakening
and carboniuni ion destabilizing substituents is even more uncertain insofar as the
equilibrium constants arc conccrned. Thc details of protonation of diazo compounds
and the subseqitcnt reactions are discussed by More O'FerrallZ; in general, the
expected stability of t h e carbonium ion determines whether or not the protonation
is significantly reversiblc. Thus iindcr ordinary circumstances only diazomethane
sho\\Cs exchange in acidic D,O conipeting with nitrogen loss". Clearly R,CHN?+and
R,CN2 arc interconvertible, but we have not bcen able to establish a n equilibrium
constant even in one casc within orders of magnitude. In summary, the protonation
does occur, though hardly with the facility that would be associated with carbanions.
C. T h e Carbanion M o d e l ; Electrophiles
Diazo compounds also react with other electrophiles. Condensations using base
catalysis will be discussed later, but some react without any base catalysis. Ethyl
d iazoacet ate, d iazoacct oni t r ile, t ri fl uorodiazoet hane'? and ni trodiazomethaneI3 are
502 Edward S . Lewis
nitrated by N205, presumably by way of the stable but strongly acidic diazonium
salts (equation 3). Diazomethane is chlorinated14by t-butyl hypochlorite at - 100 "C,
XCHN,+N,O, - N0,
I
X-C-N:+NO;
H
I
7XCN,
N 0,
I
(3)
X = CO,Et, CN, CF,, NO,
here the presumed chloromethanediazonium ion is protected from decomposition
-
both by the low temperature and the very basic counter ion, f-BuO-.
A familiar electrophilic attack o n diazomethane and other diazo alkanes is the
reaction with acid chloride^'^ or anhydrideP, yielding diazoketones (equation 4).
RCOCI+P CH,N, RCOCHN,+ CH,CI+N, (4)
The extra mole of diazomethane is believed to serve as a sink for the proton of the
initial diazonium salt, RCOCH2N+, rather than as a base catalyst a t a n earlier stage.
T h e formation of polymethylene by the reaction of diazomethane with boron
fluoride" is also evidence for electrophilic attack on the diazo centre, even though
the immediate product is not observed. Similarly the reaction of diazo compounds
in the absence of basic catalysts, with ketones or aldehydes, is an example of electro-
philic attack, but with a non-isolable diazonium ion productlB.
D. Acidity of Diazo Compounds

Diazo compounds not only act a s bases but they are also pcrceptibly, although
not strongly, acidic. Diazomethane reacts with methyl lithium to give a lithium
derivativelo. Ionization is also possible with triphenylmethylsodium20, which puts
a lower limit on the acidity of diazomethane, since pKa of triphenylmethane = 33 21.
Ethyl diazoacetate has also been converted to the lithium salt??,and ionization under
relatively mild conditions is suggested by the facile hydrogen isotope exchange in
base9, compared to ethyl acetate which suffers hydrolysis much faster than exchange.
Furthermore, ethyl diazoacetate a n d other acyldiazo compounds undergo aldol
condensation with a variety of compounds with dilute ethanolic sodium hydroxide$.
Diazosulphones even add to e n a m i n e P , presumably via an initial proton transfer.
0
- I1
-
T h e perceptible stability of the arlions N2CCR is also indicated by reverse
condensations observed in a number of cases, mostly of diacyldiazornethanes
(equation 5). The mechanism is presumably that shown, and the diazo compound
XCY+RO- XCN,+ROY (5)
II I
N,
1
XCHN,
formed is often t h e one which would be expected to give the most stable anion.
A number of examples are listed by Regitz3, but cxcept for showing that acyldiazo-
methane anions have a stability comparable or greater than that of ordinary enolate
ions, quantitative conclusions are impossible.
11. The influence of the diazo and diazonium groups 503
The chemical evidence is then that the diazo carbon is definitely nucleophilic, and
is perceptibly, although not strongly, basic. It is also significantly more acidic than
a comparable methyl group, although the magnitude of the enhancement of acidity
is not known.
E . Remote Effects of the Diazo Group

Before going o n to physical evidence for the charge distribution about the diazo
compounds, i t is appropriate to comment briefly about reactivity more remote from
the diazo group. A n acid strengthening effect on the 12 carbon is suggested although
not convincingly demonstrated by the cleavage mentioned earlierJ. A few reactions
at positions remote from the diazo group have been observed, but without rate
measurements they are hard to interpret. Thus, potassium diazoacetate is prepared
by saponification of the ethyl by concentrated potassium hydroxide under
conditions which would also be expected to saponify ethyl acetate, but relative
rates are not known.
F. Effect of the Diazo Group on lJC-n.m.r., Spectra

A possible approach to electronic effects in diazo compounds is the chemical
shift in the n.m.r., for extensive electron withdrawal should reduce the nuclear
shielding, and supply should increase it. There are few proton spectra for diazo
compounds available, but a number of I3C spectra of diazo compounds have been
taken25. Several compounds, all diazo ketones or esters, are here presented, with
chemical shifts (in p.p.m. downfield from TMS), together with some model
compounds, taken from Breitmeyer and Voelter”.
0 0 0 0
55 1111-I 27.8 II 27.8 45.7 11 60.5 14.2 20 I1 59.8 0 . 8
N,CHCCH, CH,CCH, N,CHCOCH,CH, CH3COCH,CH,
I70
(VIII) (1 X)
R,COH
- 6 9 ( R f H)
These chemical shifts allow us to draw some conclusions, limited however by

the small size of the sample. The important effects a r e on the diazo carbon, on the
adjacent carbonyl carbon, and there is one example of a perceptible effect on thc
other carbon flanking the diazo group. More distant groups, as the ethyl group in
VI and VII, or the phenyl group in VIII and IX, seem to be relatively uninfluenced
(hcre dilferences of less than 2 p.p.rn. are ignored, largely because the author is not
competent to judge the sources of error in the various spectra). T h e carbonyl
frequency is uniformly at higher field for the diazo compound than for the models.
Since (in the one case of the tertiary alcohol, X, shown) the shift on the other side
504 Edward S. Lewis
of the diazo group is in the other direction, this is probably not a consequence of
a n inductive effect of the diazo group; instead i t probably represents a specific
conjugation similar to that in cc,p-unsaturated ketones, which also causes a higher
field shift of the carbonyl frequency. Alternatively, the extra shielding coitld be a
consequence of the formal negative charge on the diazo carbon (structure Ib).
The chemical shift of the diazo carbon is especially interesting; any model with
neutral carbon bonded with sp2 hybridization to carbon, oxygen or nitrogen would
predict chemical shift more than 100 p.p.m. from T M S . The observed shift of only
40-60 p.p.m. appears to require the addition of extra shielding, such as would bc
associated with a substantial negative charge associated with this carbon, for
example through the important contribution of Ib.
I n sum, the c.m.r. chemical shifts are in agreement qualitatively with the chemical
evidence, namely that diazo compounds have a significant partial negative charge on
carbon.
G. Special D i a z o Structures
Certain diazo compounds have such important contributions of diazoniuni-like
structures that they can really be thought of as members of one class as well 2s of
the other. These include the diazo oxides, XI, which are tlie cotijugatc bascs of
ortho- or para-hydroxydiazonium ions, which we shall consider briefly in a later
section. Another example is diazocyclopentadiene, XII, which appears to be virtually
an aromatic molecule, and undergoes electrophilic substitution with facility2’.
111. T H E DlAZONlUM ION G R O U P

A. Coverage
T h e effect of the diazoniunl ion group will hcre be liniited to discussion of aromatic
diazonium salts. T h e rclatively few aliphatic cases of any stability contribute little
to o u r knowledge. There are also sonie inorganic ‘diazonium salts’ of tlie form
L,MN2 o r metal nitrogen complexes, which share little of the chemistry of the
aromatic compounds; they will not be considered hcre.
Aromatic diazonium ions, ArN;, havc been extensively studied since their
discovery more than a hundred years ago. Nevcrthelcss, most of the chemistry
involves either loss of N2,and replacenlent by various groups (such as O H in the
hydiolytic dccomposition, halogen in the Sandmcyer reaction among many), or
alteration of the NZ group as in the reduction to phenylhyclrazine or coupling to
form ArN2X (where X may be carbon, oxygen, nitrogen. sulphur, phosphorus,
among others). With the one exception of partial reaction of tetrazotized aromatic
diamines, discussed below in Section 11I.E, all these reactions are outsidc thc scope
of this chapter.
1 I . The influence of the diazo and diazonium groups 505
B. The H a m m e t t Substituent Constants
Among the reactions suitable for discussing the effcct of t h c diazonium ion group
a s a substituent are acidities and basicities of acids and bases containing the N:
substituent, and the rates of various rcactions, including electrophilic and nuclco-
philic substitution o n the aromatic ring as long as the diazoniuni ion group remains
attached after the reaction. The diazonium ion group "as recognized as a powerfully
electron-withdrawing substituent for as long as that phrase has had meaning, but
the quantitative evaluation of the cffect was not attempted until a number of acid
strengths and reaction rates were measured with the goal ofestablishing the Harnrnett
substituent constant u Z 8 .Table 1 shows some of thc rcsults obtained for various
T A n L E 1. Substitucnt constants for the diazonium ion group2'

~~
Group Reaction urn 01, 01.

+N2CGH,0H Acid ionization < 2.1 3.03
+N,CGH,NH: Acid ionization 3-43
+N,Cs H,CO,H Acid ionization 1-76 1.91
+N,CGH,CH2C0,H Acid ionization 2.18
+N,C61-14COCH3 Brornination rate > 0.2 > 1.1
cases. Thc absence of entries or estimatcs of one limit only reflects experimental
problems, almost always due to side reactions which destroy the diasoniuni group.
T h e nature of the vzrious uncertainties is discussed in the original papcr.
The large difference between u and U - implics a large resonance interaction between
the N% and the p - 0 - (as shown in XI).This extra stabilization is confirmed by the
low reactivity of these 'diazo oxides' in coupling reactions23(among others), as well
as by t h e rather quinoid bond distanccs shown in XIII3O. The distances shown are
averages of cheniicnlly equivalent distances in two independent molecules.
-
CI
\
(XIII)
The very large substituent effect is also evident from the acidity of o-carboxy-
benzcnediazonium ion?', which has a pKa = 1-47; i t is almost ten times stronger
than the para isomer, but of course no substituent constant should be assigned.
In spite of the fact that the results in the Table weye determined more than 1 5 years
ago, there has been very little revision. T h e value for u,*= 1.76, based on a single
measurement, has been reported to be confirmed on the basis of studics of ionization
equilibria of some diazodiazoles itnd other I i ~ t e r o c y c l e A ~ . of the 'T-n.m.r.
~ ~study
of diazonium salts is reported3' to give chemical shifts simply related to u and
consistent with the old values.28 A study33 of the 35CInuclear quadrupole resonance
spectra of some chlorobenzenediazonium ions is reported to show substantial
electron withdrawal by N,+, but in the order o > ) n > p . This order is stated to be
consistcnt with the chemically detcrmined siibstituent effects since the nqr chemical
shifts are bclieved to be insensitive to resonance effects, but sensitivc to inductive
effects. A further confirmatory value of I J ~is presented in Section 1II.E.
506 Edward S. Lewis
The substitucnt cffects in the Table can be subjectively weighted to give 0, = 1.7,
an = 2 and a; = 3, but i t should be emphasized that they are only valid in aqueous
solution, sincc charged and uncharged substituents will behave differently as the
medium is changed. I t is nevertheless clear that thc N+ group has a more powerful
electron-withdrawing effect than any other single faniiliar group, and this is
reasonable, for i t combines the resonance effect of thc isoelectronic cyano group
( u p = 0.66) with the pure charge effect of the trimethylaninionium substituent
( u p = 0.82). It is perhaps the plausibility of the very large u values for N,‘ which
has led to a general acceptance of these values, rather than conviction from an
overwhelming mass of data.
C. Efectrophific Substitution on Diozoniurn Salts

Benzenediazonium ion has been nitrated with difficulty, and nitration occurs
mostly in the n z f o position. This is consistent with Hammett’s that
substituents with a,,>a,,, are niefn directing. There are n o direct data on the rates
of electrophilic substitution o n benzenzdiazoniuni ion, although the following,
rather flawed, argument suggests that in one case it may be slower than the attack
o n nitrobenzene. When benzenediazoniuni ion is decomposed in nitrobenzene,
rn-nitrobiphenyl is a n important product. When benzenediazonium fluoroborate is
~ ~ , 6% of the product is nitrobiphenyl,
heated in trifluoroethanol and n i t r ~ b e n z e n e only
but most of the remainder is the expected fluorobenzene and phcnyltrifluoroethyl
ether. If this electrophilic arylation had b e m able to attack benzcnediazonium ion
as easily as nitrobenzene, then fluorobiphenyl o r trifluoroethoxybiphenyl should
have been observed. T h e absence of these products is not convincingly demonstrated,
but again it is plausible and hence believable. The argument is somewhat
strengthened because arylation with dccomposing diazonium salts is believed to
be very unselective, as would be expected for the postulated phenyl cation inter-
mediate,? although a small discrimination among neutral organic solvents is
ob ~ e r v e d ~ ~ .
The much more facile electrophilic attack on diazocyclopcntadiene has been
mentioned above.
D. Nucleophilic Substitution Activoted by t h e Diozonium G r o u p

In contrast to the rare and difficult electrophilic attacks on diazonium salts there
are numerous examples of nucleophilic attack. Only those leaving thc diazonium
group intact, which still comprise a large body of data, arc relevant here. The
activation of nucleophilic aromatic substitution by a n o- or p-N: group had been
observcd very early, espccially by Hantzsch“ and by MeldolaJ”. Millcr41identified
the N l group as more strongly activating than ai:y other substitucnt. Quarititativc
studics on the rates of attack of thiocyanate orflio and porn to thc diazonium ion
group were undertakenaS. The reaction is facile for halogen and t h e second-order
ratc constants arc much faster in lower dielectric constant medium, as expccted for
this anion--cation reaction. The logarithm of the ratc constants correlated well with
t The actual interniediacy of the phenyl cation in the solvolysis of diazonium ions is
somewhat controversial and is complicated but illuminated by the sirnultnneous occurrence
of several reactions. The controversy centres around ~ h e t I i c r36 ~ ~or*not3’ nucleophiles arc
present in the rate-determining step, but there is n o controversy over the description of
all transition statcs as closely resembling the phenyl cation, and the consequcnt Linselcctivity
of the reaction, which discriminates poorly between halidc ions and w a t ~ r38, * allows
~ ~and
attack on very poor nucleophiles such as ~ h l o r o b c n z e n e fluoroborate
~~, ionlo or niolccular
nit rogcnJ’.
1 1 . Thc influcncc of the diazo and diazonium groups 507
the reciprocal of the diclectric constant for a range of aqueous f-butyl alcohol
solvents, and also correlated well with the solubility of p-chlorobenzenediazonium
fluoroborate in the same solvents. This strong and well-understood solvent
dependence emphasizcs the problem of a substituent constant for a charged group
and makes a direct comparison of the activation by N: with that of one o r more
nitro groups generally futile.
In the mostly aqueous systems usually studied, the diazonium group is, however,
very powerfully activating by comparison with any other group o r combination of
groups. In this qualitative vein, we note that in the reaction of thiocyanate ion with
p-nitrobenzenediazonium ion in aqueous 1-butyl a!cohol, the replacenient of nitro
is more important than that of the diazonium group4s,behaviour which it would be
unreasonable to attribute to the nitro group being a better leaving group. A similar
but even more striking observation is that 2,4,6-trinitrobenzenediazoniumion and
related substanccs suffer hydrolysis (at sufficiently high pH) with loss of nitrite by
attack on carbon orfho to one diazonium ion group, rather than losing nitrogen
by attack o n the carbon activated by as many as three nitro groupsJR.
It is necessary to be careful about t h e nature of t h e mechanism involved in these
substitutions. T h u s in apparent contradiction to the results with thiocyanate, at
higher temperatures p-nitrobenzenediazoniuni ion reacts with aqueous bromide ion
to give a mixture of p-nitrophenol and p-nitrobromobenzene. N o isolated product
was assignable to nitro group lossJ7.This behaviour is now believed36 to be associated
with the acidity-independent solvolysis rather than to an activated nucleophilic
attack. The perceptible acceleration4' by bromide ion is not niuch greater than that
observed with other diazoniuni salts, and has been explained36using transition states
strongly resembling the phenyl cation (see footnote above). Thus there is n o un-
equivocal evidence of nucleophilic substitution of N+ activated by a nitro group.
Substitution of N?f activatcd by a second N l group is, however, well established
and is discussed below.
E. Chemistry of Bisdiazoniom Salts

It was mentioncd in Section 1II.A that the vcry rich chemistry of aromatic
diazonium salts nearly always involved destruction of the N: group, and could not
therefore give information about the influence or substituent effect of this group.
This statement has t\vo exccptions. The first of these is that the reciprocal relation
between p and u first pointed out by H i m a 8 has been developed by Sager and
Ritchie,'9 to the point that the mcasurement of p for a reaction is rclatcd to the
change (in substituent enect) of the reaction sitc. Thus the rather cxtensive study
of substituent effects on diazoniuni salt cquilibria has been rendered understandable
by using a large positive u for the diazonium ion groupS". The second is that for
any reaction of the diazoniuni group, for example the conversion of N?+ to Y
(equation 6), o n e of the possible substitucnts X is a second diazonium group. This
XC,H,N: ~ _ _ XC,H,Y
f
allows a host of reactions to be studicd, subject only to the limitation that only
one o f thc two diazoniunl groups must react. This limitation is not very rcstrictive:
of the three most accessiblc tctrazonium salts, tetrazotized p-phenylcnedianline
allows in nearly all cascs thc isolatioli of the reaction of one group only; tetrazotized
I~I-phcnylenediamincis coniplexsl in its behaviour and has not becn extensively
studied, and tetrazotized bcnzidint. is, i n the dye industry, regularly coupled at one
cnd bcfore the others2, and \rould thcrcfore be suitable for quantitative study,
although i t has not yet been done.
508 Edward S. Lewis
Tetrazotized p-phenylcnediamine is subject to nuclcophilii displacenient of onc
diazonium ion group by CI-, Br- and SCN- 5 3 ; sccond-order kinetics arc followed
and the products, p-chlorobcnzenediazonium ion, etc., are quite stable under the
rcaction conditions. Iodide ion also reacts, but a vcry fast free-radical mechanism
is involvcd, and \ve can only say that the p-N: group accelerates thc nicchanism to
allow it to bc scen and to overwhelm nuclcophilic attack. Azide ion also attacks
very rapidly, but t h e mechanism probably docs not involvc carbon attack". The
powerful activating effect of the p-N: group is clearly illustrated, and the fact that
N?+ can be a leaving group in an activated nucleophilic substitution is also
demonstrated.
The tetrazonium salt is also convertible to a ~ n o n o d i a ~ o t a t Because
e.~~ this is
bclieved to have thc arzti configuration, the equilibrium is not readily compared to
t h e litcrature values 5 6 , 5 i for cquilibrium diazotate formation which involvc the
S ~ I Zisomers. Howcver, the protonation equilibrium bctiveen the monodiazotate
and its conjugate acid is directly comparable to mcasurenicnts of this reaction with
othcr anti-diazotates. One determination gives5* for this equilibrium p = 1.1 7,
another givcss9 p = 1.45, and combining these with the mcasurcd equilibrium
constants5 give then for u p the valucs 2.0 and 1.6 respectively. This is in reasonable
agreement with the substitutcd benzoic acid values prcsented above.
The facilc 'dediazonization' or hydrolysis of thep-phenylene-bis diazoniuni
is at first sight incompatiblc with thc cxtrcnic clcctron-witlidra\~ingcharacter of
the N: group, since electron-withdrau.ing substituents normally rctard the rate of
this phenol-forming rcaction. Ho\vcver, thc hydrolysis turns out to bc pH
d e p ~ n d e n t ~I n~ .fairly strong acidic nicdia this special mechanism is suppressed
and the tetrazonium salt now has thc expected high stability.
The tetrazonium salt shows several very facile free radical reactionsG1,notably
reduction by alcohols, and i t is clear (and not surprising) that the second diazonium
group facilitatcs one-electron rcduction of the first, although we have little to compare
this with quantitativcly, cspccially since in this reaction there is considerable net
reduction of both diazoniuni groups. The details of chain initiation and termination
proposed in this study of the alcohol reduction have been shoun to bc subjcct to
a more rcasonablc intcrprctation by introducing a new termination mcchanism".
Finally, \vc should interpret again the rathcr low u (1.3) derived from thc rate of
coupling of the tctrazoniuni salt with 2-amin01iaphtlialene-6-sulphonicacids8, based
upon the value of p for this coupling of +4.26 6 3 . Some coupling ralcs of diazoniuni
salts with various compounds havc given curvcd Hammett plots6', and this deviation
may correspond to the predicted concavc downward shape of sutliciently wide-range
Hammett plotsG5.The deviation may also arisc from a shift of rate-determining
step in this known two-step rcaction".
IV. CONCLUSIONS
The effect of the diazo group as a substitiicnt has been sho\vn to be not vcry large
and of ambiguous dircction, since i t is both acid strengthening and base
strengthening. The cffccts have not bcen detected cxcept very close to the diazo
group.
The effect of the diazoniuni ion group is quantitatively cstablishcd, i t has a very
strong acid-strengthening, clcctron-witlitlra\\..inS ellect. I t is, by virtuc of its chargc,
a substitilent wit11 a strong solvent dcpcndence of its substitucnt cflect and one
can therefore imagine soiiie efl'ccts of uiiprcccdentcd magnitude, but even in water
i t has more influcncc than a n y other kno\\n substitwilt.
11. The influcncc of t h c diazo a n d diazoniLlm groups 509
V. REFERENCES
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The Chemistry of Diazonium and Diazo Groups.

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The Chemistry of Diazonium and Diazo Groups

Edited by Saul Patai

W. Ando Chemistry Dcpartmcnt, The University of Tsukuba, Niiharigun,

(a) An introductory chapter dealing with t h e general and theoretical aspects of

(d) Chapters on the reactions, transformations and rearrangements which the

Tfie Cliemistry of A l k n e s (two volumes)

Future volumes planned include:

1. Average bond lengths (A) in molecules containing

2. Average bond energies (kcal/rnol) of CC,

Consistent wi; h these experimental observations are the conclusions derivable

Pb = Number of bonding electron pairs.

T h e theoretical aspects, and related physicochemical properties of molecules

II. DIAZO COMPOUNDS

Double zeta - 14659091 2.565 7.220 5.71 743 6.s5

At?:'' A& (0 K ) AEf (298.16 K ) A H , (298.16 K)

7. Nuclear configuration a n d force constants of diazomethane (dyne/cm and erg/rad2).

Leroy and Sana, in discussing the significancc of their ab inifio calculations in

Consequently they place the heat of formation of diazomethane as greater than

8. Heat of formation of diazornethane

D. W. Setser and B. S . Rabinovitch, Can. J .

A hypothetical reaction mechanism for the production of isocyanamide from

2. Diazirine and derivatives

9. Thermodynamic functions (cal mo1-I dcg-l) for diazirinc"' (ideal

298 IC 45.43 10.19 56.S7 s.43

11. Calculated and experimental data for diazirine and diazo~nethnne~~

12. Calculated and experimental dataa for diazirine

Overlap and type

All energies in hartrees.

Total energy (a.u.) - 345-3999

Values in Mc/sec computed in the principal axes system using a nuclear

TAULE14. Second moments of the electronic-chargc

<s?> 15.8 I 15.60 15.48

CNDO/2D SCCMQ ab itiifioR1

QZZ - 0.8 1 0.54 2.01

T h e results of MINDO/2 and EXH calculationss2#83 on diazirine a n d its dimethyl

TABLE16. MINDO/2 calculated orbital energies

0.5751 b,(x) 0.3572 b2(tz-)

T h e vertical ionization potentials Z\(J) of dirnethyldiazirine as determined by

methods for the preparation of diazirine a n d substituted diazirines, i t appears that

Simmons a n d coworkers8Gstudied the ultraviolet absorption spectrum of CF,N2

VI 1563 1560 1564.0 1436.9

19. Nuclcar con5guration of dinzirinc and

Robertson and Illerritty2,continuing the work on diazirincs already begun i n their

TABLE 20. Structure parameters of dimethyldiazirinc (DMD) 'I, difluorodiazirine

Bond DMD DFD D MD CMD

Continuing their examination of the effect of substituents on the diazirine ring,

3-99 eV compared to their observcd value of 3.7 eV.

By decomposing at a partial pressure of 50 torr in the presence of a 3-molar cxcess of

k = exp (- 3 1,89O/RT) sec-'

Tetrafluoro-2,3-diazabuta-l,3-dienecould be derived from reaction of difluoro-

However, Ogden and Mitschllo could find n o examples of insertion of difluoro-

n-Pr\ /N Et\ / CI Et, /H

k = I013.9R exp ( - 30,98O/XT) scc-'

i-Pr, /N Me, /C=C / H + N,

k = 1 0 1 3 . 3 6 exp (- 29,500IRT) sec-l