GIFT OF MICHAEL REESE

CHEMISTRY
OF THE

ORGANIC DYESTUFFS.
BY

B,

NIETZKI,

PH.D.,

PROFESSOR AT THE UNIVERSITY OF BASLE.

TRANSLATED, WITH ADDITIONS,

A.

BY

COLLIN,

PH.D., AND

W. RICHARDSON.

GFRNEY

&

LONDON JACKSON, 1 PATERNOSTER ROW.

:

(SUCCESSORS TO MB.

VAN

VOORST.)

MDCCCXCH.

PRINTED BY TAYLOR AND FRANCIS,

HBD LION COURT, FLEET STREET.

AUTHOE'S PREFACE.

ABOUT
'

three

years

ago

wrote

an

article

for

Ladenburg's

Handworterbuch der Chemie/ containing in a concise form an

This

exhaustive account of the history of the Organic Dyestuffs.

article

was also published separately, and

its

good reception
as

induced

me

to produce the present work,

which I have based

far as possible

upon the

earlier one.

The

article in question

was not complete in

itself,

and in the

present instance certain sections which came under other headings

in the
'

Handworterbuch

'

have been added.

New

material has

also been supplied

through the advances made in the coal-tar

colour industry and in our scientific knowledge of the constitution

of dyestuffs during the last three years.

Again, some subjects

have been dealt with at a greater length than was permitted by

the

somewhat limited space of the

'

Handworterbuch/

Conse-

quently, the subject-matter of the earlier work has been submitted

to a thorough revision, and the systematic classification of dyestuffs into

natural chemical groups attempted in the original book

has been carried out in a more complete manner, owing to the

advances

made

in our

knowledge of their constitution.

therefore be regarded
'

The present work cannot

edition of the article

as a second

from the

Handworterbuch/ and

as I have

sought to give the whole the form of a small chemical handbook,

vi

AUTHOR'S PREFACE.

dealing with dyestuffs from a scientific standpoint, I have selected

'

The Chemistry
In
this
laid

of the Organic Dyestuffs

'

as a suitable title.

work, as in the previous one, considerable weight has

been

upon the

relationships existent between the constitution

and

tinctorial properties of the dyestuffs.

it

I have thought

advisable to deal only with the principles

involved in the manufacture of individual dyestuffs, as details for

their technical production are unreliable,

owing to the continuous

developments taking place in the industry in question.

The application of
rather

with dyestuffs to textile fibres has been dealt

more

fully than in the earlier work, but not at a greater

is

length than

in accordance with the character of the book.

To

technologists
stuffs

requiring further details of the application of dye-

can

recommend Hummers

excellent

work on

'

The

Dyeing of Textile Fabrics/

Basle, October 1888.

TRANSLATORS' PREFACE.

LITTLE remains for us to add to Prof. Nietzki's account of the

design and character of his book.
appreciation in
lation
It has

met with very general

that a transfield

Germany, and

this

made us think

might be of service to English workers in the

which

the book covers.

Some time has

elapsed since the original appeared, and

we have

attempted as far as possible to bring the subject-matter up to date.

New

colouring-matters have been introduced without

altering

Prof. Nietzki's

method of

classification, a

method which has been

In some cases

very generally adopted

(Primuline, Thioflavine
;

since

its

appearance.

Pyronine, &c.) new sections might have

been desirable
original form.

we

preferred, however, to leave the book in its

The

figures in the text apply to the references given

on pages

273-288.

The

references have been left as in the original, with

the one exception that, wherever possible,

the English-Patent

number has been added.

Our thanks

are due to the Directors of the Farbwerke Hochst

(Meister, Lucius, and Briining)

and of the Farbenfabriken, vortnals

F. Bayer and Co., Elberfeld, for the ready kindness with which

they placed ample information at our disposal.

Paisley,

May

1892.

CONTENTS.
Page

INTRODUCTION
Colour, 1
;

1-22

Chromophors, Chromogens, 3 ; Theory of dyeing, 4 ; Constitution of chromogens, 7; Salt- forming groups, Auxochromic groups, 12 ; Acid and basic dyestuffs, 14 Mordants, lakes, 15 ;
;

Dye-trials,

16

History of

artificial colours,

17

Classification,

22.

CHAPTEE
NITRO-COMPOUNDS
General, 23
;

I.

23-27
Acid (Trinitrophenol), 24
;

Picric

Dinitrocresol,

24 ;

Dinitronaphthol, Dinitronaphtholsulphonic Acid, 25; Yellow, Tetranitronaphthol, Palatine Orange, Aurantia, Salicyl

Brilliant

Yellow, 26

Isopurpuric Acid, 27.

CHAPTEE
AZO-DYESTTJEFS
Introductory, 28-34.
I.

II.

28-79

AMIDOAZO-COMPOFNDS

35-43

Amidoazobenzene, 35

Amidoazobenzenemonosulphonic Acid, 36 ; ; Amidoazobenzenedisulphonic Acid (Acid Yellow), 36 ; Dimethylamidoazobenzene, Dimethylamidoazobenzenesulphonic Acid, 37 ; Phenylamidoazobenzene, Phenylamidoazobenzenesulphonic Acid

00), 38 ; Amidoazotoluenebenzene, Amidoazo39 ; Amidoazoxylenes, 40 Diamidoazobenzene (Chrytoluenes, Triamidoazobenzene (Bismark soidine), 40 ; Parazoaniline, 41
(Tropaolin
;
;

Brown), 42; Benzeneamidoazonaphthalene, Amidoazonaplithalene, 43.

CONTENTS.
Page
II.

OXYAZO-COMPOUNDS ...
;

44-59
Tropaolin 0, 45
;

Oxyazobenzene, Dioxyazobenzene, 44 benzenes (Azophenols), 45.

Naphtholazo-dyes, constitution, 46

Dioxyazo-

Azobenzene-a-naphthol, 53

; Naphtholsulphonic Acids, 48 Monosulphonic Acid (Orange I),

;

54

Azobenzene-/3-naphthol, Sulphonic Acids, 54 ; Disulphonic

Acids, Orange G, Crocei'n Orange, Scarlet 2 G, 55

;

; Azo-dyes from /3-naphtholdisulphonic acids, 55, 56 a-azonaphthalene-j(3naphthol, Monosulphonic Acid (Roccellerie, Fast Bed), 57;

Disulphonic Acids, Bordeaux B, Crystal Scarlet, Crocei'n Scarlet

3 Bx, Azorubin, 58
III. AZC-DYES

Silk-red, 59.

FROM DlAZO-CARBONIC ACIDS

59, 60

Dimethylamidobenzeneazobenzoic Acid, Phenolazometabenzoic Acid,

Resorcinazobenzoic Acid, /3-naphtholazobenzoic Acid, 59.

IV. AZO-DYES FROM CARBONIC ACIDS AND DIAZO-COMPOUNDS

....

(30-62

Azobenzenedimethylamidobenzoic Acid, Dimethylamidobenzoic Acidazobenzoic Acid,

Acid,
Acid,

Azo-3-diamidobenzoicacid-p-benzenesulphonic
Acid,

60

Azobenzenesalicylic

Azonaphthalenesalicylic

Dyes from

Nitrodiazo-compounds

and

Salicylic

Acid

(Alizarin Yellows), 61.

V. TETRAZO- OR DISAZO-DYESTUFFS
Introductory,

62-74

Phenoldisazobenzene, 62 ; Resorcinazobenzene, 63 ; Azo-dyes from Amidoazo-compounds, 63 Benzenedisazobenzene;

Monosulphonic and Disulphonic Acids, Biebrich Scarlet, 64; Crocein Scarlets, Archil Brown, Wool Black, 65 Azodibehzenephenylenediamine, 65 Azodibenzene toluylenediamine, 66; Table of dyes from Amidoazo-compounds, 66; Secondary
/3-naphthol,
; ;

and Tertiary azo-dyes from Nitrodiazocompounds, 67. Azo-dyes from Benzidine and analogous bases, 68-74.

Congo Red, 68 Sulphonic Acids of a.- and /3-naphthylamine, 6970 ; Azo-blue, Benzazurine, Tetrazostilbenedisulphonic Acid, 71 ; Table of direct dyes, 72, 73, 74 Azarin S, San Yellow,
; ;

Thiotoluidines (Primuline), 75 ; Erica, Thioflavine, 76 ; Direct production of Azo-dyes on the fibre, 77 Diamine Blacks, 79.
;

CONTENTS.

CHAPTER
OXYQTTINONES AND QlTlNONEOXIMES

III.

Page

80-95

Naphthazarin, 81. Anthraquinone-dyestuffs, 81-92.

;

Introductory, 80

Alizarin,

Technical formation, properties, 83 84 Mtroalizarin, Application, Turkey Red. 86 production, 87 Trioxyanthraquinones, Purpurin, 87 Iso- (Anthra*-) purAnthragallol, Alizarin Bordeaux purin, Flavopurpurin, 88; and Cyanines, 89 Alizarin Blue, 91 ; Alizarin Indigo-blue S and Green, 92 Styrogallol, 92.
;

82

Constitution,
;

Quinoneoximes, 93-95.
Introductory, Dinitrosoresorcin, 93
;

Fast Green, 94.

Naphthaquinoneoximes, 94; Gambine

Dioxine, 95.
.

R &

G, Naphthol Green,

CHAPTER
.

IV.

KETONEIHIDES AND HYDKAZIDES

Introductory,

96-101

96 Auramine, preparation, 98; salts, properties, Phenyl- and Tolyl-auramine, 99 ; Phenylhydrazides, Tartrazine,
;

100.

CHAPTER
TRIPHENYLMETHANE DYESTUFFS
Introductory, 102
;

Y.

102-145

Formation, 104.

A. Rosaniline Dyestuffs
Tetramethyldiamidotriphenylcarbinol (Malachite Green), 106
derivatives, preparation,
;

105-131
Salts,

107

Nitro-derivative,

108

Dichlorte-

tramethyldiamidotriphenylcarbinol
Tetraethyldiamidotriphenylcarbinol phonic Acids, Helvetia Green, 109

(Victoria

Green
Green),
S,

(Yictoria
;

B), Sul-

Light Green

Quinoline

Green, 110; Pararosaniline, 111; Methyl Violet, 112;

Manu-

XU

CONTENTS.
Page
facture,

113; Properties and composition, Acid Violets, 114; Hexamethylpararosaniline (Crystal Violet), 115 Hexaethylpara;

rosaniline (Ethyl Purple), Azo-Green, Methyl Green, 116; Rosaniline Magenta), 118 ; Formation, 119 ; Base, 120 ; Salts, Sulphonic

Acids (Acid Magenta), Tetrabromrosaniline, 121

Tetramethylrosaniline,

Trimethyl- and
(Iodine Green),

Pentamethylrosaniline

Hexamethylrosaniline,
Violet),

122

Triethylrosaniline

123;

Tetraethylrosaniline,
;

Acetyl,

Triacetyl-,
;

(Hofmann's and

Tribenzoylrosaniline,

124

123 Magenta residues, 123 Aniline Blue, 125 ; Monophenylrosaniline, 125 DiphenylManufacture, and Triphenylrosaniline (Aniline Blue), 126 Sulphonic Acids
; ;

of Aniline Blue, Alkali Blue,

Water
;

Blue, Cotton Blue, 126,

;

127

Diphenylamine Blue, 128

phenylnaphthylmethane dyestuffs,
Blue, 131.

DiAldehyde Green, 128 Victoria Blue B, 130 ; Night

B. Rosolic
Introductory,

Add
;

Dyestuffs

131-135

Pittacal, Eupittonic Acid,

134

Aurin (Pararosolic Acid), Rosolic Acid, 132 ; 133 Hexamethoxylpararosaniline, Aurintricarbonic Acid (Chrome Violet), 134 Dyestuffs
; ;

131

from Benzotrichloride
Rosamines, 135.
C.

and Phenols, 135; Resorcin-benzein,

Phthalems
;

136-143
;

Constitution, 136

Phenolphthale'm, 138

Ethers of

Eosin,

140

Spirit

Eosin,

Eluorescem, Eosin, 139 ; Iodine derivatives of

Fluorescem,

Lutecienne,

Erythrosine,

141

Phloxiue,

Rose

Bengal, 142; Rhodamine, 142; Pyronines, 143; Cffirule'in, 144 ; Glycerems, 145.

Gallem and

CHAPTER
QUINONEIMTDE DYESTUFFS
Introductory, 146.
1.

VI.
*

146-168

Indamines
;

149-151
Toluylene Blue, 150.

Phenylene Blue, Tetramethylindamine, 149

2.

Indophenols
;

151-153
Application, 152.

Preparation, properties, 151

CONTENTS.

xiii

Page

Indamines and Indophenols containing Sulphur .... 153-161 Introductory, 153; Lauth's Violet, 155; Methylene Blue, 155; Imidothiodiphenylimide, 158; Thionolines, Oxythiodiphenylimide, Thionol, 159 Methylene Red, 160 ; Methylene Green, 161. 4. Oxyindamine and Oxyindophenols (Oxazines) 161-165
3.
;

Naphthol Blue (Fast Blue), 161 Muscarine, 162 Nile Blue, Gallocyanine, 163; Gallamine Blue, 164; Prune, 165.
;
;

5.

Dichroines

165-168
167: Orcirufm, 168.

Resorufin, 165; Resazurine,

CHAPTER
AZINE DYESTTTFFS
Constitution and formation, 169.
1.

VII.

169-191

2.

Eurhodines (Amido-azines) Eurhodols (Oxy-azines)

3. Toluylene Red Toluylene Violet, Neutral Violet, 176.

172-174 175 175, 176

177-189
;

4.

Saffranines
;

Introductory, 177

Manufacture, 180

Phenosaffranine, 181

Diazo-

compounds, 182; a- and /3-dimethylphenosaffranine, Tetramethylphenosaffranine, Diethylsaffranines, 183 ; Acetyl and diazo-

compounds of Diethylsaffranines, 184; TetraethylphenosaffraTolusaffranine, 185 ; Methoxysaffranines, 186 ; nine, 185

;

Neutral Blue, 187 ; Saffranol, 187 188; Azine Green, 189.

5.
6.

Itidazine

M,

Basle Blue,

Magdala Red
Mauvei'ne

189
190, 191

CHAPTER
ANILINE BLACK

VIII.

192-199
194:
Technical

Formation, 192; Properties, 193; Constitution, Aniline Black, applications, 197.

CHAPTER
INDULINES AND NIGROSINES
Formation, 200
;

IX.

200-206
;

Azophenine, 201

Indulines B, 3 B, and 6 B, 202

Soluble Indulines,

203

Nigrosines,
;

Rosindulmes, Azocarmine, 205

204 r Applications, 205 Fluorindines, 206.

XIV

CONTEXTS.

CHAPTER
QUINOLINE AND ACRIDINE DYESTUFFS
Cyanine, Quinoline Red, 208
;

X.

207-218

Quinoline Yellow (Quinophthalon),

209; Elavaniline, 210; Berberine, 212; Chrysaniline, 212; Salts and derivatives, 213; Chrysophenol, 214; Synthesis of Acridine Yellow, Acridine Orange, BenzoChrysaniline, 214
;

flavine,

216.

CHAPTER XL
INDIGO DYESTUFFS
;
;

219-241

Indol, 219 Dioxindol, Indoxyl, 220; Indoxylic Acid, Oxindol 221 ; Isatin, 222 Isatic Acid, 223 Isatogenic Ether, DiisaPreparation and togen, Indoxanthic Ether, Indigo Blue, 224
; ;

properties of Indigo-blue,

225

226

Indigo- sulphonic Acids,

Dibenzoyl-indigo, Indigo-white, 227 Application of Indigo in

;

Indigo-dicarbonic Acid, purpurin, Indirubin, Indigo-red, 231.

dyeing,
;

228

Indoine, 229

Indigo-

Prom

Synthesis of Indigo-blue Indol and from Isatin, 231

;

231-236
;

Orthonitrophenylpropiolic Acid,

232

Synthesis from Orthonitrobenzaldehyde, 233 ; from Benzylidene-acetone, 234 ; from Bromacetanilide and from Phenyl-

of Indigo-disulphonic Acid, 236. glycocine, 235 ; Synthesis Constitution of the Indigo-group

236-241

CHAPTER
EUXANTHIC ACID AND GA LLOFLAVINE
Euxanthic Acid, Purree, 242
constitution, 244.
;

XII.

242-246
;

Euxanthone, 243

Derivatives

and

Synthetical Oxyketone Dyestuffs

245
(Ali-

Trioxybenzophenone zarin Yellow G), 245.

Ellagic Acid,

(Alizarin Yellow A), Grallacetophenone

245

Galloflavine, 246.

CHAPTER
CANAMNE

XIII.
,
,

247

CONTENTS.

XV

CHAPTER
MUREXIDE

XIV.
Page
...

248

CHAPTER XY.
DrESTUFFS OF UNKNOWN CONSTITUTION
Introductory, .249
;

249-271
; ;

Brazilin, 252 253 Young Fustic, Quercitrin, 254 QuerBrazilem, Morin, Rutin, Xanthorhamnin, Rhamnetin, 256 Luteolin, citin, 255 257 Bixin, 258 Chrysin, Curcumin, 259 Carotin, Orchil and Litmus, 260 Carthamin, 262 Santalin, 263 Alkannin, 263 Crocin and Crocetin, Lokao (Chinese Green), 264; Cochineal, 265 Carmine Red, 266 Carmine, 267 Lac-dye, 269 Tyrian
;
;

Hsematoxylin, Hsematei'n, 251

Purple, 269;

Catechu, 270; Cachou de Laval (Fast

Grey),

271.

REFERENCES

273-288

APPENDIX
INDEX
. .

289-306

307-313

ERRATA.

P. 9.

Phenazine formula, read

instead of

41.

No. 1 read Tropaolin P. 54, line 22, for Tropaolin P. 134. Formula for Chrome-Violet should be

For Symmetrical Amidoazobenzene read Symmetrical Diamidoazobenzene. OOO OOO No. 2.

/C H (OH)COOH C-C H (OH)COOH \0 8 o7

C 3 6 3
|

instead of

OH C-C H,(OH)COOH \C H (OH)COOH

6
6 3

/C,H,(OH)COOH

P. 136.

Kosamine formula should be

C/CX-N(CH

3) 2

C C H3 N(CH 3 ) 2 C1
instead of

C C H 3 N(CH 3 ) 2

INTRODUCTION.

CERTAIN chemical bodies possess the property of only transmitting or reflecting certain constituents of white light, while the others are absorbed. ' In other words,, such bodies have a particular
colour,

more or

less characteristic.

These bodies occur amongst

the so-called chemical elements, and the colour of the same element

be totally different according to the form and state of aggreCertain elements (e. g. chrogation under which it is observed.

may

mium) always form coloured compounds ; with others, again, the coloration of the compounds may be regarded as an exception, and if not caused by combination with a colour-giving element,
depends on the constitution of the compound. Coloured carbon compounds come under the
latter classification.

The number of organic compounds containing, besides carbon, hydrogen, oxygen, and nitrogen is very large, and by far the greater number of them are colourless. On the other hand, some compounds
of carbon with these elements possess colour which far surpasses that of any other element, both as regards intensity
"*

and character.
not at
all,,

The coloured carbon compounds often

differ little, or

from the colourless ones in their percentage composition, and it is this fact which renders it certain that it is the structure of the

compounds which causes in one case colour, in the other none. In the life-processes of plants and animals both colourless and
coloured carbon compounds are formed, and the latter have been employed since the earliest periods as dye-materials.

INTRODUCTION.

Natural dyes tuffs have for many years been the subjects of thorough chemical investigation, but their study has afforded little

knowledge as to the general nature of coloured carbon compounds ; and it is only since dyestuffs have been prepared synthetically
that

we have gradually come to understand greater number of these bodies.

Very
little is

the constitution of the

known

of the primary cause of colour in such

compounds, but our knowledge is so far advanced that colour is regarded as a characteristic property of whole classes of chemical compounds ; and the study of the constitution of such

compounds has shown that a their colour and their chemical

V

close relationship exists between

structure.

study of the carbon compounds shows that compounds of carbon with one or with several elements of equal valency are all colourless. For example, all hydrocarbons are colourless, and
derivatives obtained

by the introduction of monatomic elements

are also colourless.

Colour in coloured compounds depends on the introduction of compound radicals, mostly polyvalent ; but at the same time a
-

certain building-up of carbon atoms in the molecule

for production of a real colouring-matter.

is

necessary

For the

latter reason,

nearly

all

derivatives

organic dyestuffs belong to the aromatic series, and are of benzene, naphthalene, anthracene, or quinoline.

The

radicals

which possess

this

power of producing colour

in a

hydrocarbon
*

show a

characteristic

behaviour towards nascent

hydrogen. Nascent hydrogen possesses the property of converting coloured carbon compounds into colourless ones with greater or less facility ;
the reaction which takes place may, however, be widely different in various cases. The nitro-group is converted into an amido-

group, and on oxidation the nitro-group cannot be reproduced. The azo-group is converted in a similar manner into two amido-

com pounds

groups, but as an intermediate stage of the reaction hydrazoare formed.

as types of a class

These hydrazo-compounds may be regarded of colourless bodies, termed leuco-compounds.

large

number

INTRODUCTION.

of dyestuffs yield these leuco-compounds on reduction. These new bodies mostly contain two atoms of hydrogen more than the
dyestuffs,

and are converted into the

latter

on oxidation.

This circumstance was

made

i. p. 106) ; the presence of a bond between the colour-giving groups assuming in dyestuffs yielding leuco-compounds, corresponding to the linkage

Liebermann (Ber.

a subject of study by Graebe and and in 1867 a theory was advanced

of the oxygen atoms in quinone in the constitutional formula accepted at that period. In 1876 Otto N. Witt published a more

complete theory of the nature of colouring-matters, and this theory may be comprised in the following general laws (Ber. ix.
p. 522).

^ The colour of a

compound depends on the presence of

is

a certain

group of atoms, which

or chromophor.
v

therefore termed a colour-giving group

chromophor produces a more or less coloured body, which, however, is not a dyestuff; and intensely the dyestuffs are only formed by introduction of one or more
this

The introduction of

radicals capable of imparting salt-forming properties,

which

may

be acid or basic.

Witt terms compounds which only contain a

chromophor, chromogens.
Before proceeding it is necessary, however, to define the difference between a coloured body and a dyestuff somewhat more
clearly.

'A

real dyestuff is a

body which

possesses, besides colour,

the property of communicating colour to fibres, especially to animal fibres, doing this by reason of a certain peculiar affinity

betwixt the colouring-matter and the fibre. If a silk skein is placed in a solution of dyestuff, it gradually becomes dyed, while the liquid, if not too concentrated, finally loses the whole of its
colour.

The property of dyeing belongs principally to compounds It is possessing a more or less marked acid or basic character.
7

probable that these properties depend, at least in many cases, on a partly basic, partly acid character inherent in the fibre, which
in the

one case

is

developed by the colour- acid and in

tjie

other by

the colour-base.

B2

INTRODUCTION.

The exact relationship between a fibre and a dyestuff is not Dyeing processes are usually divided into two exactly known. 1) categories adjective, where the use of a mordant is necessary,,
:

^\nd
jbn

substantive, where

no third body

is

required to

fix

the dyestuff

the fibre.

Two

theories as to the nature of substantive dyeing have been

advanced, a chemical and a mechanical theory. The chemical theory of dyeing supposes that a chemical combination of dyestuff and fibre takes place, and this view is, to a
certain extent, supported

by experimental proof, the researches of

worthy of attention.

Knecht

in this direction being especially

According to the nature of a dyestuff, the fibre

part of an acid or of a base
fibre
:

may

act the

thus dyed fibres are

compounds of

and dyestuff constituted

like salts.

For example, rosaniline is a colourless base, forming red salts. If a skein of wool or silk be warmed in a colourless solution of
rosaniline,
it

sponding amount of a

becomes dyed red, and as completely as if a correThis salt of rosaniline had been employed.

behaviour is easily explained if we assume that the fibre plays the part of an acid, combining with the rosaniline to form a salt which, like rosaniline salts, has a red colour. It may, however, be
observed that the red colour of rosaniline
solution,
salts is

only evident in

compounds have a more or This point has been raised less marked bronze-green appearance. by upholders of other theories, that were a salt of rosaniline and
and in the
solid state these
fibre

formed, it might naturally be expected to possess the green colour of the solid salts of rosaniline.
as chemical processes, it is in applying salts of colour-bases, that these salts are probable,

If

we regard dyeing operations

decomposed in the dyeing process, the fibre combining with the base and the acid being set at liberty. Certain strong basic dyestuffs, such as methyl green, which (like all ammonium bases) forms very stable salts, are not capable of dyeing wool directly. If, however, ammonia is added to the dye-bath, the liberated colourbase combines with the wool and dyes it green. Silk, on the other

hand, evidently possesses a stronger acid character than wool, as

INTRODUCTION.
it

be dyed with methyl green without any assistance. Knecht has demonstrated by quantitative experiments that in dyeing wool with the salts of basic colours, the acid in combination with the

may

colour-base
if

is

liberated during the dyeing process.

For example,

wool

a solution of rosaniline hydrochloride (magenta) is treated with till all colour is extracted, the hydrochloric acid which was

in combination with the rosaniline remains in the colourless bath.

The behaviour
theory of dyeing.

of

some

acid dyestuffs also supports the chemical

a rule animal fibres are not capable of decomposing the salts of acid dyestuffs, and in dyeing the colour-acids have to be
set at liberty

As

by the addition of a stronger acid to the dye-bath. Certain colour- acids, for example the sulphonic acids of amidoazocompounds, have a different colour to that of their alkali salts. In
dyeing wool with such colour-acids, the shade produced
is

that of

the salts and not that of the colour-acid, so that in such cases

wool evidently plays the role of a base. In certain cases also there is evidence which points to the fact that definite molecular combinations of dyestuff and fibre exist.

In dyeing processes, from a practical standpoint, a certain quantity of dyestuff, seldom exceeding two per cent, of the weight
of the fibre,
is

found necessary to produce a

maximum

effect as far

as shade is concerned.

But

this

by no means expresses the limit

to the

amount

Knecht

of dyestuff which may be taken up by the fibre, as has found that wool is capable of extracting far larger
If a calculation be
is

quantities from concentrated dye-baths.

made
fibre,

based on the amount of picric acid which

it.

taken up by the

is

found that the

maximum amounts
violet

of naphthol yellow S,

tartraziiie,

and crystal

which may be combined with wool

closely approximate to molecular quantities.

Another conclusion which follows from the researches of the

same chemist,

is

that

many

cases of so-called substantive dyeing

are in reality adjective.

In the case of wool, for example, a comhas been isolated, called lanuguinic acid, and it has been pound found that this acid is capable of entering into combination with
dyestuffs, producing

compounds which, although amorphous, closely

INTRODUCTION.

resemble dyed wool in their properties. It is possible that in dyeing wool the action of boiling water liberates this substance,
the combination with the dyestuffs. In this hypothesis, the lanuguinic acid is supposed to be retained in the fibre in a state of solid solution.

which then

effects

different

theory of solid solution has been applied in a somewhat form by Witt to the substantive dyeing of wool, silk, and

skein of silk dyed with magenta is according to the chemical theory a combination of magenta and silk, and it requires
cotton.

pretty strong soaping to remove the dye.

But

if

the silk be treated

with alcohol, which is certainly capable of exerting only a solvent If water is effect, all the colouring-matter is quickly removed. added to the alcoholic solution, the dyestuff, however, returns to
This behaviour, unexplained by the chemical theory of In dyeing, may be cleared up by the "solid solution" theory. this especial instance of silk and magenta, we must suppose that
the
silk.

the essential constituent of the silk

solvent

fibre, fibroin,

has a greater

from

action for magenta than water, and thus withdraws it Alcohol having a greater solvent its aqueous solution.
fibroin,

power than the

removes the dyestulf from the fibre. Similar cases are frequent in purely chemical operations, and the extraction of magenta from its aqueous solution by silk is exactly

similar to the removal of resorcin

ether.

from an aqueous solution by

The

different behaviour of various textile fibres in dyeing

;

may

be explained by an assumption of different solvent power thus, silk dyes more readily than other fibres because the fibroin has a
Keratine again, the principle of the wool greater solvent power. fibre, possesses a greater solvent power than cellulose, which is
only capable of attracting and holding in solution a few dyestuffs, such as the tetrazo-dyes of the benzidine series, and in certain cases in this class the solvent power of the water in the dye-bath
has tu be decreased by addition of salt. The mechanical theory of dyeing is based on the assumption that the molecules of colouring-matter leave the dye-bath and are

mechanically deposited between the molecules of the fibre. Certain plant-fibres for example jute, the bast-fibre of Cor-

INTRODUCTION.
chorus

have the property of fixing dyestuffs directly, this being

due to the presence of an incrustation of foreign matter, present on

the fibre.

amongst which may be mentioned precipitated sulphur, gelatinous silica, and Kieselguhr, have the

Many amorphous

substances,

power of attracting basic

dyestuffs.

The properties of the so-called oxycellulose are also of interest On oxidation of vegetable fibre from a tinctorial standpoint.
with chlorine, chromic acid, or similar agents, it undera change, and becomes capable of fixing basic dyestuffs without goes a mordant.
(cellulose)

A consideration of the radicals capable of acting as chromophors shows that only two of these, the nitro- and nitroso-groups, are monatomic. If these groups are introduced alone into a hydrocarbon, the body produced possesses scarcely any colour.
is

coloured

body salt-forming group be also introduced, the latter probably forming a closed ring with the chromophor. The
case
is

formed

if a

similar

when

a valent chromophor

is

introduced into

several hydrocarbons, so that each valency is attached to a hydro-

carbon group not in linkage with any other. This is the case with the ketones, while the diketones (quinones) and simple ketones possessing a ring constitution (diphenylene ketone) are coloured

compounds. Azobenzene forms an apparent exception to

below)
.

this

rule

(see

The ketone group,

is

especially

when

it

occurs twice, as in the

one of the most important chromophors. The oxygen quinones, atom of the ketone group may be replaced by another diatomic
radical,

such as sulphur ; or the ketone carbon atom

may

enter

into combination with two valencies of a diatomic nitrogen

atom

the resulting groups

C=S

and

C=N in general possess

increased

As an example of this, it may be chromophoric properties. remarked that the derivatives of simple ketones are colourless, those of the thioketones, ketone-imides, and hydrazides being
coloured.

The ketone group

it

C=O appears only to act as a chromophor when

of a closed ring of carbon atoms.

occurs as a

member

large

INTRODUCTION.
of dyestuffs

number

may be

di-ketones (ortho- and para-quinones)

of the constitution of the quinones
is

regarded as built up similarly to the and as the present view ;

expressed by the following number of dyestuffs have to be

formula, the formula? of a large modified accordingly.

O
a

Quinone.

The indamines are derivatives of quinone-imide, and accordingly change from a tertiary to a secondary carbon atom must be

accepted in the constitutional formulae of these bodies.

NH

N-C H
6

NH

C 6H 4

NH

NH
Quinone- iinide (unknown).

NH
Indamine.

similar

constitution

may be

accepted for rosaniline and

rosolic acid.

C=(C

H NH
4

2)2

C=(C

H OH)
4

NH
Rosaniline.

Rosolic acid.

INTRODUCTION.

In these cases the oxygen of the ketone group

diatomic methane rest.

is

replaced by a

class of bodies closely

resembling the paraquinones are the

phenanthrenequinone are members of this class of compounds. From these a new class of compounds may be obtained, and these bodies,
orthoquinones,

for

example

/3-naphthaquinone

and

the azines, are in some respects analogous to the paraquinones.

If

atoms of the

an orthodiamine interacts with an orthoquinone, the oxygen latter are eliminated, and tertiary nitrogen atoms

new ring containing two nitrogen atoms and four carbon atoms being formed. The similarity of this ring
enter in their places, a
to the paraquinone ring exists in the fact that in the former tertiary

nitrogen atoms take the place of the chromophoric the latter.

C=O

groups of

This analogy

is

especially

marked

if

the constitutional formula of

anthraquinone is compared with that of the simplest aromatic azine.

CO

CO
Anthraquinone.

N
Phenazine.

and quinoline and acridine placed by nitrogen, and it

There are also certain points of resemblance between the azines here only one carbon atom is re:

is probably owing to this that the nature of these bodies is not so strongly marked as chromogenic that of the azines.

10

INTRODUCTION.
Generally speaking, the introduction of the simplest chromo-

phors gives rise to yellow dyestuffs, and when stronger and more complex groups are introduced the colour changes through red

For example, all quinoline and acridine dyestuffs are yellow, while only the simplest azines have this colour and become red and blue by introduction of salt-forming groups. In some other dyestuffs the presence of the lactone ring
to blue &c.

O is assumed, and here again the oxygen atom may be replaced by a primary nitrogen atom (indigo dyestuffs) It will be noticed, on examining the constitution of the chromo.

C=O

gens already treated

of,

that

most of them contain the chromodiffering

phor as

member

of

closed ring,

from the other

members

in valency and linkage.

For instance, compounds constituted on the quinone type contain two secondary and four tertiary carbon atoms. In cases
where four secondary carbon atoms are present, as in rhodizonic acid, C 6 (OH) 2 O 4 , the body is still coloured; but if all the six
carbon atoms of benzene become secondary, as in triquinoyl or
perquinone, C 6 O 6 , the colour disappears*. The same occurs if all the carbon atoms of quinone become tertiary, i. e. by reduction of
the quinone to hydroquinone.

attempt to explain the colours of all carbon compounds the existence of such rings possesses great interest, but it cannot by be denied that the necessary conditions are absent in numerous
dyestuffs, for example, thioketones, ketone-imides,

An

are such bodies,

i.

e.

and hydrazides tetramethyldiamidothiobenzophenone and

auramine,

(CH 3

) 2

N-C H -C-C H
6

N(CH

3) 2,

II

(CH 3

) 2

-N

C 6 H 4-C
II

C 6 H4-N(CH 3

2,

NH
in which the chromophors

CS and

CNH
make

are not present as a ring

but as an open chain.

*

The

researches of Hantsch (Ber. xx.)

is

of colour in triquinoyl and leuconic acid

it improbable that the absence due to hydration.

INTRODUCTION.

11

The nitre-compounds, which are almost the only class in which a monatomic group acts as chromophor, would also be difficult to
bring under the above ring classification.
there

There

is

no doubt,

however, that in amido- and hydroxyl derivatives of nitro-bodies

is

a certain relationship between the nitro-group and the

It is not improbable that the nitro-

hydroxyl or amido-group.
are

phenols possess a similar constitution to the nitrosophenols, which

The azo-dyegenerally regarded as quinoneoximes. stuffs are a class of bodies the properties of which are not in
accordance with their constitution, and this in the first member of the series, azobenzene.
is especially

now

marked

If a single hydrogen atom in a benzene ring is substituted, or if two rings are joined together by a diatomic radical, the bodies formed are colourless or only slightly coloured, while azobenzene
is

an intensely coloured compound and a powerful chromogen. This leads to the supposition that azobenzene does not act 6H5 according to the simple constitutional formula C 6 5

H N=NC

in certain

cases,

and other

facts

tend to speculation as to a

more complex formula. Azobenzene and its

derivative hydrazobenzene

may

be con-

verted into a derivative of diphenyl, benzidine; and the ease with which this reaction takes place seems to point to the existence of

an unstable linkage between the benzene rings.

This would be

most readily explained by the assumption that a change in the linkage (from double to single) between the carbon atoms in the
benzene chain takes place in a similar manner to the linkage in the

quinone formula.

The following formula would then express the

azobenzene
:

constitution of

12

INTRODUCTION.
Naturally such formulae are hypothetical, and only of interest in

attempting to regard
system.

all

dyestuffs as variations of

common
is

characteristic of

the radicals which act as chromophors

that they are never perfectly neutral groups, or in other words

their introduction confers a certain tendency towards basic or acid

properties to the bodies which they enter.

introduction of salt-forming groups these properties become strengthened in one or other of these directions. According to

By

their nature, therefore,

these chromophors

may be

classified as

basic or acid-forming.

The quinone group,

for example, possesses

simple hydroxyl derivative properties. of a hydrocarbon possesses weak acid properties, while the hydroxyl derivatives of the quinones have these properties in a far strong acid -forming

The nitro-group acts similarly. Chromophors higher degree. which contain nitrogen without oxygen tend to form bases.

We

have

still

to consider

more

closely the nature of the salt-

forming groups which have already been mentioned. These groups may act totally differently, and are divided into

two sharply defined

classes.

Certain radicals, generally acid, such as the sulpho-group, SO 3 H, and the carboxyl group, if introduced into a chromogen,
confer

upon

it

acid properties, but without increasing the colour

appreciably, indeed in

many

cases the dyeing

power

is

considerably

decreased.

Such bodies
effects the

act as acid dyestuffs,

fibre.

and the group introduced

animal
being

combination with the

Azobenzene, for example, has

perfectly neutral, while
its

no

affinity for

fibres,

weak

dyestuffs.

sulphonic and carbonic acids act as The influence of amido- and hydroxyl groups is

a totally different one. By introduction of these radicals the chromogen acquires basic or acid properties, and at the same time a considerable modification in the colour of the

body is produced. The colour generally becomes more intense; in many cases colour is only produced

when

these

groups enter.

Having regard

to

these facts the

" salt-forming/' groups (sulpho- and carboxyl) may be termed

INTRODUCTION.
while for

13

the latter Witt

has

recently suggested the

name

auxochromic (Ber.

xxi. p. 325).

The
it

relationship existing between these groups

and the chro-

mophors

In the case of the oxyquinones is not yet explained. has already been pointed out that the chromophoric quinone group confers strong acid properties on the auxochromic hydroxyl group.

The same

is

also observed in

the phthalei'ns and

These hydroxyl groups play at the same of salt-formers, and produce the necessary affinity time the part The auxochromic amido-groups exert a somewhat for the fibre.
rosolic-acid dyestuffs.
different

influence

behaviour

may

the base-forming amido-groups. This be explained by studying the basic triphenyleasily

on

methaiie dyestuffs, for instance rosaniline. Ilosaniline contains, besides the chromophor two auxochromic amido-

=C=R=NH,

groups.
It is certain that the imide group of this chromophor combines with the acid in the formation of the red monoacid

rosaniline salts, and

it

the fibre

is

effected.

by its means that the combination with The latter is deduced from the fact that
is

rosaniline dyes the colour of these salts, while the salts formed

by neutralising the two amido-groups are yellow. The amidoazines show this characteristic in a somewhat more
striking manner.

The

azines contain the

chromophor

N
and the simplest members of the series are weak bases forming salts which are mostly red or violet and only stable in presence of an excess of acid.

The amidoazines,

for

example toluylene red (diamidoazine), are

strong bases forming red monoacid salts, which, however, are stable. Here also the acid radical is combined with the azine group,

and the amido-groups only form

salts in

presence of an excess of

acid, the change being accompanied by a characteristic change of colour through blue to green.

14

INTRODUCTION.

In dyeing, toluylene red produces a red shade, and not a blue or green, so that the azine group alone enters into combination
with the
'It is
fibre.

easily seen that in these cases the

auxochromic amido-

groups tend to strengthen the basic character of the chromophor, At the same time the colour but do not act as salt-formers.

becomes more intense.

According to a rule which has been laid

down by Witt, the stronger of two similar dyestuffs is always that which possesses salt-forming properties in a higher degree.
be conceived that the simultaneous presence of a basic auxochromic group and an acid-forming chromophor, or
this it

From

may

vice versa, gives rise to a

case in point

they are

weak weak

dyestuff.

The

nitranilines

form a

dyestuffs, while on the other

hana
fully

the nitrophenols

have tinctorial properties much

more

developed. ^ From the foregoing reasons actual dyestuffs are divided into

two principal

classes

acid and basic.

Certain coloured bodies like indigo are neutral, and possess no Their dyeing is effected by precipitating affinity for textile fibres. on the fibre from a solution as in vat dyeing, or by converting
into a sulphonic acid, and thereby producing a capability to form
salts.

The

salts of certain

azosulphonic acids

may

be termed neutral

They may be directly fixed on vegetable fibres. dyestuffs. v basic and acid dyestuffs are fixed without aid by animal Most
fibres
;

vegetable fibres, on the other hand, require the interven-

tion of a special mordant.

Tannic acid

is

generally used along

salts

with basic dyestuffs, as

it

forms insoluble

with these com-

pounds. Cotton possesses the power of attracting a certain amount of tannic acid from solutions containing this body, and of retaining
it

even after washing. Cotton prepared in this manner may be In practice dyed with most basic dyestuffs just as well as wool.
the cotton treated with tannic acid
action of tartar emetic or insoluble salt of
is

further submitted to the

some other antimony compound. An tannic acid and antimony oxide is formed, and

INTRODUCTION.
this fixes basic dyestuffs

15

of the latter

method

is

with the greatest ease. The advantage that the shades produced are faster to

acid dyestuffs combine with metallic oxides, prosoap. insoluble lakes, different in colour to the original dyestuffs, ducing

Some

and varying considerably with the metallic oxide used.

property
is

This

much

used to effect the fixation of dyestuffs on the

Anthraquinone derivatives are always fixed in this manner, and numerous natural dyestuffs also. This peculiar property of dyeing on metallic mordants has as
fibre, especially

on cotton.

If cotton mordanted with yet had no satisfactory explanation. alumina or oxide of iron is placed in an alizarin bath, the lake is
precipitated and enters into intimate combination with the fibre. Many dyestuffs form insoluble lakes with metallic oxides, but

the property of combining with mordants on the fibre is peculiar Insoluble lakes may be obtained from the cosines and to a fe^.

from

all

oxyanthraquinones, but the former class of bodies can-

not be fixed on mordants, and of the latter only derivatives o

alizarin possess this property.
It is necessary that the lake

tion with the fibre

if not, it

produced forms a certain combinais only retained superficially, and is

removed mechanically during the dyeing process. It has been found that this capability of dyeing on mordants stands in close relationship to the constitution of the colouring-matter, and more
especially to the
relative

positions of the

substituting

groups

(compare quinone dyestuffs). The commercial value of a colouring- matter

;

is

best determined

by dye-trial numerous processes which have been proposed to determine

dyestuffs voluinetrically are

in fact this

is

the only trustworthy method, and the

influenced

by

untrustworthy, as they are readily the nature of the impurities present.

in dealing with a few dyestuffs which a pure state. come into commerce in For instance, alizarin is tested by a dye-trial, and then examined

Exceptions

may be made

after

washing carefully for the amount of which it contains.

solid

matter and ash

The testing of colouring-matters by means

of dye-trials

is

simply

16

INTRODUCTION.

colorimetric comparison of a dyestuff with a standard of

If equal quantities of

known

two samples of a dye are dyed quality. of wool or silk, a difference of two to five per upon equal weights cent, may be distinguished from the difference in shade observed
in the

two patterns.

By a second dyeing it is easy to determine the difference between the quantities of the two dyestuffs required to produce the same
shade, and a simple calculation then gives the value of the product At the same time an idea is tested, compared with the standard.

obtained of the relative purity of the shade of the dyestuffs and of the nature of the impurities which may be present.
In printing, both basic dyestnffs and acid ones capable of forming lakes with metallic oxides are employed.

The

principle of the fixation of

basic dyestuffs

in printing

depends on the insolubility of the tannin compounds. The tannates of all colour-bases are insoluble in water, but

The dyestuff is printed mostly dissolve in dilute acetic acid. with tannin and dilute acetic acid. The acetic-acid solution along
of the tannin lake penetrates the fibre, and subsequent steaming

removes acetic
shades
emetic.

acid, leaving

an insoluble lake on the

fibre.

The

may

be made faster to soap by passing through tartar

dyestuffs, like alizarin &c., are printed in the free state with the metallic mordants (aluminium, iron, or chromium along acetate) ; on steaming, acetic acid is driven off and the metallic

Acid

oxide combines with the colour-acid to a firmly adhering lake. Only a few natural dyestuffs (indigo, alizarin, and purpurin)

have been prepared synthetically, but the number of

dyestuffs
is

artificial

very large.

Some

of these, especially the phthalems

and

stitution,

seem to approach the natural dyestuffs in conbut the greater number belong to special classes, which are without analogue in either the animal or the vegetable kingdom.
rosolic acid,

Natural dyestuffs, with few exceptions (indigo, berberine), contain only carbon, hydrogen, and oxygen ; while many classes of artificial colouring-matters contain nitrogenous groups, often
of a decided basic nature.

Some

others again contain chlorine,

INTRODUCTION.
bromine, iodine, or sulphur.

17

The raw materials for the preparation

of these bodies are, at the present time, almost exclusively products of dry distillation, and the most important of these is coal-tar,

The discovery and

distillation

obtained as a bye-product in the manufacture of illuminating-gas. first preparation of artificial dyestuffs is there-

fore closely associated with the earliest studies

;

on products of dry and the development of the gas industry has, hand in

series of scientific researches appertaining therethe important colour-manufacturing industry into to, brought

hand with a

existence.

of preparing the first colouring-matters from of dry distillation belongs to von Reichenbach (pittacal products from wood-tar, 1832), and to Runge (rosolic acid from coal-tar,

The honour

1834) [1].

For a long time, however, the discoveries of these chemists remained in obscurity, and it was only after the knowledge of
products of dry distillation had been considerably advanced by later researches,, that the production of coloured derivatives again
attracted the interest of chemists.

Hofmaun,

Zinin,

and Fritsche were the

first

to

show the

aniline, phenol, &c. ; and the first explanation of the constitution of these products formed the foundation of the colour-industry.

relationship between benzene,

The

first

dyestuff prepared and applied on an industrial scale

was "mauve," introduced by Perkin in 1856. About the same period the formation of rosaniline was noticed by Nathanson,

who obtained

it

by heating aniline with ethylene chloride [2]

years later Hofmann [3] announced the discovery of a red product, obtained by the action of carbon tetrachloride on aniline.

Two

Hofmann and Nathanson,

pure aniline, must have hands.

if

their experiments

were made with

in
their

already

had pararosaniline

The next ten years were almost

entirely devoted to the scientific

study and technical development of rosaniline and its derivatives. The first patent was taken out by Renard freres and Franc, of

Lyons, on April 8th, 1859 [4], for the preparation of a red dyestuff,

18

INTRODUCTION.

according to a process discovered by Verguin, which consisted in the action of stannic chloride on aniline.

Numerous patents followed in England and France, depending on the action of other oxidising agents than stannic chloride. In some of these patents, however, it is not clear whether rosaniline
frcres

or some other dyestuff such as mauve is really produced. Renard introduced their products, still very impure, under the name " fuchsine."
of Gerber-Keller with nitrate of mercury is the one of any value (October, 1859) [5]. only In the following year, 1860, the application of arsenic acid as
oxidising agent was patented by

The process

simultaneously in
process was

Medlock and by Nicholson almost England [6]. A few months later the same

made

the subject of a French patent by Girard and

DeLaire

[7].
[8]

In 1861 Laurent and Castelhaz

patented the action of nitro-

benzene on iron and hydrochloric

first

acid, and this is evidently the of the nitrobenzene process. In the same year the opening of rosolic acid was effected by Kolbe and Schmitt [9] synthesis
.

The formation

of aniline blue

was also

first

observed in 1861

by Girard and De Laire ; and in the following year the process was further developed by Nicholson [10], by Monnet and Dury [11], who used acetic acid in the manufacture, and by "Wanklyn
[12],

who

applied benzoic acid.

from

In 1862 the composition of rosaniline, and its formation aniline and toluidine, was further explained by A. W.
[13].

Hofmann

Aldehyde green was also discovered in 1862 [14]. In 1863 the same chemist prepared ethyl- and methyl-derivatives of rosaniline, and showed aniline blue to be triphenylrosaniline [13].

Aniline black was

The

first

prepared in 1863 by Lightfoot [15]. azo-dyestuffs were introduced between 1864 and 1866.
first
first,

Amidoazobenzene [16] appeared phenylene brown [] 7]

.

and was quickly followed by

Caro and Wanklyn [18] demonstrated the relationship between

INTRODUCTION.
rosaniline

19

and

rosolic acid in

1866 ; and in the same year Keisser

green [19]
.

took the

first

patent for iodine

Diphenylamine blue was prepared by Girard and

De

Laire in

1867 [20]. In the same year methyl violet, which had already been noticed by Lanth in 1861, was manufactured on a large scale by Poirrier

and Chapat.

The composition of
Girard in 1869 [21]
;

iodine green was determined

by Hof mann and

and Rosenstiehl demonstrated the existence

.

of several rosanilines [22]

The

synthesis of alizarin was carried out

[23] in the

by Graebe and Lieber-

mann

same

year, this being of very great importance,

as the first synthesis capable of industrial application for production

of a dyestuff occurring in nature.

Hofmann and Geyger [24] examined induline and saffrathe latter a dyestuff which had appeared in commerce a nine,
In 1872

few years previously. In 1873 Hofmann published his researches on methyl and methyl green [25]
.

violet

In 1874 the phthalei'ns (eosine), discovered by Bayer and Caro, were introduced into commerce.

In 1876 pararosaniline was discovered by E. andO. Fischer, and the relation of this body to triphenylmethane demonstrated [26]
.

In 1877 Prud'homme discovered alizarin blue;

its

industrial

production was effected by Brunck in the following year. In the same year Caro [27] produced methylene blue, basing his process on the sulphuretted hydrogen reaction observed by

Lauth in 1876
was discovered

Almost simultaneously malachite green E. and O. Fischer [29] and by Doebner [30] ; by and O. N. Witt and Houssin introduced the synthesis of azo-dyes on a manufacturing scale, which proved afterwards to be of such
[28].

great importance.

In 1880 Bayer took out the

artificial

first

patent for the production of

indigo [31].
this

was followed by indophenol [32] and the cyanine of Witt and Koechlin.
In 1881

gallo-

20

INTRODUCTION.

In 1883-84 Caro and Kern [33] effected the synthesis of triphenylmethane dyestuffs by means of carbon oxychloride, and this

was applied to the production of auramine and Victoria blue. The constitution of numerous dyestuffs has been determined by been of great service purely scientific researches, and these have
in discovering

new

synthetical methods,

many

of which are applied

on a large scale. In 1886 an important development took place in the azo colourThis was based on an observation made by Griess (pat. industry. that certain azo-dyestu ffs derived from benzidine were 1884),
capable of dyeing vegetable fibres without mordant. As of this class of dyestuffs, which are very numerous,

members

may

be

mentioned chrysamine, congo red, benzo-purpurine, &c. In 1888 Witt explained the constitution of the saffranines by his classic researches on the azines; and not long afterwards,
Fischer and
of azines.

Hepp proved

that the indulines were also derivatives

The rhodamines, a

class of dyestuffs allied to the phthalei'ns,

were introduced in 1888.

The present requirements

are benzene and
lene,
its

of the colour-industry as raw materials

homologues (toluene and xylene), naphthaThe coal-tar of and anthracene, obtained from coal-tar.
is first

the gas-works

worked up in

tar-distilleries,

the above bodies

being obtained in a more or less impure state. The further purification is carried on in some colour-works ; but this generally
takes place in intermediate manufactories where the crude products are purified and worked up into a higher stage, benzene and its

homologues being made into

aniline, toluidine,

and xylidine, and

naphthalene into naphthylamine. The crude benzol is first submitted to a careful fractional distillation, and benzene, toluene,

and xylene are separated in

as pure a state as possible.

The

hydrocarbons boiling at a higher temperature find their principal application for solvent purposes, hence they are principally met with under the designation " solvent naphtha/' One purpose for

which

it

serves

is

the purification of

anthracene.

Benzene,

INTRODUCTION.
toluene,

21

and xylene are converted into aniline, toluidine, and xylidine by nitration and subsequent reduction. These bases are at present prepared by aniline-works in a state
of great purity ; for instance the aniline employed in the manufacture of blue (" blue oil ") is required to be chemically pure. The " red oil " used in the manufacture of rosaniline is a

mixture containing aniline, ortho- and para-toluidine in varying

proportions.

A classification
point
is

of the organic dyestuffs from a chemical stand-

Most respects a subject of great difficulty. text-books have adopted a division in which the dyestuffs are
in

many

classified

according to the hydrocarbon from which they are

this,

derived

however,

is

far

from natural,

as

by

its

means some

groups which are chemically well characterized, such as the azodyes, are divided ; and, on the other hand, dyestuffs of totally
different constitution are placed together.

In the following classification an attempt is made to group the colour ing- matters according to their chemical constitution,

In many cases this is rendered difficult, however, by the somewhat scanty knowledge of the relations existing between constitution and dyeespecial regard being paid to their colour-giving groups.
stuff character.

The

final class,

"

Dyestuffs of

unknown

constitution,"

is

still

a very numerous one.

of

This group comprises most natural dyestuffs the constitution some of these (alizarin and indigo) is known, and admits of
:

systematic classification with just as

artificial dyestuffs;

much

justice as the purely

and

it

would be reasonable to

treat of the

whole in a single chapter of natural dyestuffs. It must not be conceived that the constitution of all the colouringmatters here classified
it
is

is

completely explained, in

many

cases

deduced from analogy in formation to that of bodies of known constitution but as to the constitution of dyestuffs which
;

have not been prepared synthetically, we are altogether without

knowledge.

22

INTRODUCTION.

The organic colouring-matters may be grouped I. Nitro- Compounds. II. Azo-Compounds.

^*

as follows

III.

Oxyquinones and Quinoneoximes. IV. Ketone-imides and Hydrazides. V. Triphenylmethane Derivatives.

VI. Quinone-imide Dyestuffs.

-VII. Azine Dyestuffs.

VIII. Aniline Black.
IX. Iridulines and Nigrosines. X. Quinoline and Acridine Dyestuffs.

XI. Indigo Dyestuffs. XII. Euxanthic Acid and Galloflavine.

XIII. Canarine.

XIV. Murexide.

XV.

Dyestuffs of

unknown

constitution.

>

CHEMISTEY
OP THE

ORGANIC DYESTUFFS,

CHAPTER

I.

NITRO-COMPOUNDS.
and phenols are dyestuffs, of a pronounced character. The phenol derivatives have the greater tinctorial power, as the nitro-group is a chromophor which confers acid properties, and therefore possesses the power
nitro-derivatives of amines
less

THE

more or

of decreasing the basic properties of the amido-group. Indeed, in the case of certain bodies of only feebly basic properties, the introduction of several nitro- groups may produce an acid dyestuff,
for example, diphenylamine
is

a -body of this class.

Acid nitro-compounds are especially strongly coloured in the form of salts paranitrophenol, for example, is a colourless body,
;

yielding yellow

salts.

form colourless

salts

On the other hand, basic nitro-compounds with acids.

acid properties
like

The compounds produced when the

hydroxyl group are are colourless, for
instance,

of the
radical
nitro-

removed by introduction of an alcohol

nitroanisol behaves

derivative of a hydrocarbon. Those nitro phenols which

contain the nitro- group and the

hydroxyl group in the ortho position to each other, are as a rule the most strongly coloured.

The

close relationship existing

between the nitrophenols and

24

CHEMISTRY OF ORGANIC DYESTUFFS.

the nitrosophenols, and the assumption generally accepted, that the latter are quinoneoximes, render it probable that a similar structure may be ascribed to the nitrophenols, and that in the
latter there is a certain connection

between the nitro and hydroxyl

groups.

The number of coloured nitro-compounds is very large, and in the present place it is impossible to consider more than those which possess technical interest. They are all acid dyestuffs ; since the
introduction of the azo-dyestuffs their application has become

considerably

less.

Trinitrophenol (PICRIC ACID) [1,

2, 3].

C 6 H 2 (N0 3 3 OH.
)

Picric acid is formed by the action of nitric acid on phenol, and on many other organic bodies (indigo, xanthorrhoea resin, On a large scale it is obtained by the action of conaloes, &c.) centrated nitric acid on phenol-sulphonic acid. [2] In a pure state picric acid forms light yellow leaflets, M.P. 122* 5 C. It dissolves somewhat sparingly in water, more easily
. .

in alcohol.
It

forms well crystallized

salts
is

with

metallic

oxides

the

potassium salt, dyes wool and

C 6 H 2 (lST O 2 yOK,

difficultly soluble.

Picric acid

silk from an acid bath, a fine greenish shade of yellow being produced. Although this shade is not fast, it finds considerable application in silk-dyeing, and serves principally for

production of

compound

colours, especially for modifying green

and red dyestuffs.

Dinitrocresol.
TT

CHOH

The sodium salt of a dinitrocresol formerly came into commerce under the name " Victoria Yellow" or Saffron substitute [5]. It was probably obtained by treating crude creosol with nitric acid, partly also by diazotising crude toluidine and boiling the
compounds with nitric acid. It consists chiefly of a mixture of dinitroparacresol (CH 3 NO 2 NO 2 = 1 .4.3.5), M.P. 83-5, and dinitro-orthocresol (1.2.3.5), M.P. 85'8 [4]. It is now, however, almost out of the market.
resulting
:

OH

NITRO-COMPOUNDS.

25

RTIUS YELLOW).

C 10 H 5 (N0 3 3 OH.
)

Dinitro-a-naphthol was formerly obtained by boiling a-diazoat the present time it naphthalene [6] with dilute nitric acid is manufactured by the action of nitric acid on a-naphthol sul;

phonic acid (mono- or di-sulphonic acid) [7] Pure dinitronaphthol forms needles, which are sparingly soluble in water and difficultly soluble in alcohol, ether, or benzene. It
.

melts at 138, and forms salts which are moderately soluble in

water.

The commercial product is generally the sodium salt, though the It dyes wool and silk in an lime salt is occasionally met with. acid bath, a fine golden-yellow shade being obtained. The principal drawback in the use of this dyestuff is that it is volatile at a comparatively low temperature, and is therefore liable to mark off.
Another application of dinitronaphthol
is

for colouring con-

fectionery, as it does not possess the bitter taste peculiar to nitro- compounds.

most

^Dinitronaphthol Sulphonic Acid (NAPHTHOL YELLOW

S.)

C 10 H 4 (NO 2

)2

OH HSO

3.

By

the action of nitric acid on a-naphthol

mono- and

di-sul-

phonic acids (obtained by direct sulphonation), the sulpho-groups are replaced by nitro-groups, while on nitration of a-naphthol
trisulphonic acid, one sulpho-group remains intact [8], the other two being replaced by nitro-groups. The compound formed is a

monosulphonic acid of dinitronaphthol. This acid forms long yellow needles, which are easily soluble in water [9] The commercial product consists of the potassium salt, which is On wool and silk it dyes the same shades as sparingly soluble. Martius yellow, but is to be preferred as yielding much faster dyes. It may be distinguished from Martius yellow by treating its solution with acids ; Martius yellow is immediately precipitated, while naphthol yellow S gives no reaction.
.

26

CHEMISTRY OF ORGANIC DYESTUFFS.

Brilliant Yellow.
This dyestuff
yellow S, but
is

disulphonic acid of the Schollkopf Co.

little

prepared by the nitration of the a-naphthol It is an isomer of naphtLol is known of its dyeing properties.

Tetranitronaphthol [10].

C 10 H 3 (N0 2 4 6H.
)

tetranitrobromnaphTetranitro-a-naphthol It forms yellow needles which thalene by treating with an alkali. melt at 180. It gives fine orange shades on wool and silk, but
it is

is

obtained from

not fast to light, and has only obtained under the designation " Sun gold. "
1

slight appreciation

Tetranitrodiphenol.

of

This colouring-matter formerly came into commerce in form " Palatine its ammonium salt as orange," and was used in
It is formed by treating benzidine with nitrous and boiling the resulting tetrazodiphenyl with nitric acid.

paper-dyeing.
acid,

Hexanitrodiphenylamine (AUEANTIA) [11].

(N0 2 3C 6 H 2NHC 6 H 2 (N0 2

)

. ) 3

nitric acid

Hexauitrodiphenylamine is produced by energetic action of on diphenylamine. It forms yellow prisms, M.P. 238, and behaves like an acid, forming stable crystalline salts with the It dyes an orange shade on silk and wool, but since the alkalies.
is

introduction of the azo-dyes

scarcely ever used.

Salicyl Yellow (NITROBROMSALICYLIC ACID) [13].

The iiitro-compounds which are formed by treating monobromsalicylic acid

dyeing. their high price, renders

with nitric acid have been tried experimentally in They are very fugitive to light, and this, together with

them unsuitable

for technical application.

NITRO-COMPOUNDS.

27

Mononitrobromsalicylic acid dyes a very pure yellow on wool and silk from an acid bath, the dinitro- compound yields a more orange
shade.

Isopurpuric Acid.

C 8 H 5N5
The potassium
cyaminic
potassium
salt of this acid,

acid, is obtained

known as picroacid with solution of by treating picric

which
is

also

The ammonium salt obtained from the by double decomposition with ammonium chloride potassium was formerly used in dyeing under the name " Grenat soluble." It produces reddish-brown shades on wool and silk, but has now
cyanide.
salt

entirely disappeared.
is

Another colouring-matter which formerly occurred in commerce obtained from picric acid picramic acid, C 6 H 2 (NO 2 ) 3 2 OH,

NH

by

partial reduction.

28

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER

II.

AZO-COMPOUNDS.

THE

Azo-dyestuffs form a well- characterized group of compounds as chromophor. containing the azo-chain

N=N

This divalent group is always linked with two benzene rings or other aromatic hydrocarbon, and thus differs from the diazo-group, which is similarly constituted in other respects. The introduction
into hydrocarbons or bodies^cting similarly (anisol, phenetol) gives rise to the formaij^Bf coloured compounds, which, however, are not affinity for fibres
of the azo-group

dyestuffs.^^ie

is

only acquired

when groups

are introduced which confer acid or

basic properties to the azo-compounds.

Azobenzene, though intensely coloured, is not a dyestuff. Azobenzene-sulphonic acid possesses tinctoria^P^opj^p^ilthough only to a slight extent ; but if auxochrorrac groupl^uch as the

amido or hydroxyl groups, are present, the dyeing power is considerably increased, and at the. same time the shade is considerably
modified.
It is probable that in this class

of

compounds there

exists a certain linkage between the auxochromic and the chromogenic groups, this linkage being easily dissolved under certain

circumstances.

Liebermann deduced the following formula

benzene [1],

for /3-naphthol-azo-

C 6 H 5 -N-N
I

/U 10 M 6

from the fact that this body does not act as a phenol. In a similar manner Zincke ascribes one of the following formulae to the compound produced by the interaction of diazobenzene and /3-naphthylamine
[2]
:

AZO-COMPOUXDS.

29

C 6 H 5 -NH-N

pC
H
It

10

or

C6 H5 -

cannot be denied that

many

reactions of oxy- and amidoazo-

compounds, especially those of the ortho series, are easily explained on the assumption that these formulae are correct; but, on the other hand, amidoazo-compounds are capable of reacting as true
amines.

The above formulae show a

especially marked,
if

certain analogy to the quinones,

written slightly differently,

C 6 H 5 -NH-N=C 10 H 6 = O

and

C 6 H 5 -NH-N = C 10 H 6 = NH.

the bodies formed

important support for this theory is the circumstance that by the action of aromatic hydrazines on quinones are identical with those obtained from phenols and diazo-compounds. Phenylhydrazine, for example, reacts with

An

a-naphthoquinone, producing the same compound which is formed by combination of a-naphthol with diazobenzene [3j. The first method of formation renders the formula

C 6 H 5 -NH-N=C 10 H 6 =
probable, while the
latter affords just

as

good reason for the

formula

C 6 H 5 -N=N-C 10 H 6 -OH.
The compounds from hydrazines and ketones or quinones
(hydrazides) are so closely related to the azo-series, that one almost compelled to place them under the same classification. The property of forming combinations with sodium bisulphite
is

is

alike to azo-dyes, .ketones, and quinones [4] ence in the constitution of ortho- and para-derivatives cannot well be accepted, as the same reactions may be obtained with each,
.

common

differ-

though with varying degrees of ease. As has already been stated, the azo- compounds react like amidoor hydroxyl

compounds

in certain cases

azo-compounds yield diazo-compounds. forms exist in such cases, and that these react in one way or another according to circumstances.

It

for example, all amidois possible that two

30

CHEMISTRY OF ORGANIC DYESTUFFS.

The

pages, this being the general

older constitutional formulae have been used in the following method, and as there is just as much
is for

evidence in favour of the old formulae as there

the new.

simplest azo-compounds, simple constitution, have in general a yellow colour. By increasing the number of auxochromic groups, or by building-up of carbon atoms in the In many cases it goes molecule, the shade becomes deeper. red to violet, in others it becomes brown. Blue dyestuffs through of this class have only been obtained by introduction of several azo-groups in the molecule (dis- or tetrazo-dyestuffs). Azo-dyestuffs of a green colour have not yet been obtained, although many form green compounds with acids. The so-called u azo-green," although containing an azo-group,
its colour to the rest of triphenylmethane present. Dyestuffs which contain benzene and no higher hydrocarbon are mostly yellow, orange-yellow, or brown. By the introduction of a

The

like dyestuffs of

owes

violet dyestuffs are obtained if the

naphthalene group, red colouring-matters are formed, and blue and naphthalene ring occurs several
times.

of a radical of totally indifferent properties (as O the methoxyl group, 3) may produce a great alteration in the compound operated upon. the colour of

The introduction

CH

relative positions of the chromophor groups decided influence in this direction. The compound

The

have also a

(HS0

3) 2

0/^10 tL 4

JN

^6 tt 4

NC

-N 2<- lo

the azo-groups are in the para-position in the benzene ring, and red if in the meta-position. "1 The general rule that the depth of colour of a compound
is

blue

if

increases with the

number

of atoms constituting the molecule, does

not apply in all cases ; for example, the above dyestuff is redder, if the connecting benzene ring is replaced by a higher hydrocarbon.
colour-reactions on azo-dyestuffs give characteristic in strong sulphuric acid, and it is probable that in such dissolving cases the basic properties of the azo-group become apparent by the

Nearly

all

action of the strong acid.

stituted azo-dyes give the

It is worthy of notice that most subsame reaction with sulphuric acid as the

AZO-COMPOUNDS.

31

azo-hydrocarbon from which they are derived. Azobenzene dissolves in sulphuric acid with a yellowish-brown colour; and the same colour is obtained with its oxy- and amido-derivatives, although the latter are coloured red by dilute acid, a-azo-naphthalene, and its oxy- and amido-derivatives, give a blue coloration with concentrated sulphuric acid.

In mixed azo-compounds the presence of a sulpho-group may produce interesting changes according to its
/3-naphthol-azobenzene, for example,

position.

C 6 H 6 -NS -C 10 H 6 OH,
same which belongs
dissolves in sulphuric acid with a red-violet colour,, probably the to the mother substance,

C6 H5
The same colour
ring
;

C 10 H 7

is

obtained

if

a sulpho-group occurs in the benzene

while, on the other hand, if this group is in the naphthol, the compound dissolves with a yellow colour, the same as azobenzene.

These phenomena may be explained on the assumption that the sulpho-group exerts a salt-forming action with one nitrogen atom of the azo-chain ; and that in one case with the above compound,
the nitrogen atom attached to the benzene ring the other that combined with the naphthalene.
is

influenced, in

These colour- reactions become more complicated if several azogroups are present in the molecule. Substituted azo-compounds are generally prepared by the action
of diazo-compounds on phenols and amines. With the latter bodies the intermediate formation of diazo-amido compounds is

often observed.

Experience has proved that the azo-group enters in the paraposition to the amido- or hydroxyl-group if this is free; if this
point
already substituted, the linkage takes place in the orthoCondensations in the meta-position have till now not position. been observed.
is

Some azo-compounds may be

converted into easily oxidisable

all

hydrazo-compounds by cautious reduction, while posed by the action of energetic reducing agents.

are decom-

linkage between the nitrogen atoms is converted into an amido-group by addition of hydrogen. Azobenzene yields on reduction two molecules of aniline ; amidoazo-

In this case the dissolved, each atom being

32

CHEMISTRY OF ORGANIC DYESTUFFS.

benzene gives one molecule of aniline and one molecule of paraphenylenediamine,

This splitting up forms in many cases a means for recognition of azo-compounds and for determining their constitution. By far the greater number of azo-dyestuffs used technically are sulphonic
acids, while the

compounds

of

number weak basic

of basic azo-dyes is limited. Amidoazoare not easily fixed in dyeing ; properties

they yield, however, useful basic dyestuffs if a second amido-group is introduced into the ring, which already contains the auxochrome
it

group. Probably this second group does not act as an auxochrome ; has no connection with the azo-chain, and its function is appa-

If both rently to supply the necessary attraction for the fibre. are in different rings, the resulting compound acts amido-groups as a simple amidoazo-compound.

Chrysoidine,

C 6 H 5 -NS -C 6 H 3 (NH 2

) 2)

for example, is a strong basic dyestuff, while in an isomer parazoaniline,

NH C H -N -C H NH
2
6

2,

this property is absent.

Probably in the latter case both amido-

groups are influenced to a certain extent by the azo-chain, while with chrysoi'dine this is only the case with one group. The amido-groups acting as auxochromic groups are therefore
probably connected with the azo-group, and when combined with acids to form salts show a striking alteration in colour, while the amido-groups, which play merely a basic part, do not undergo
this change.

Chrysoidine, a case in point, forms stable salts with one molecule of acid, and their colour is little different to that of the base, while with an excess of acid a red di-acid salt is formed, which loses the

second molecule of acid on treatment with water. On the other hand, amidoazobenzene forms red salts which are decomposed by
water.
all probability contains two auxochromic shows different colours according as one or both of amido-groups, these groups are saturated. With acids it gives at first a green

Parazoaniline, which in

colour

in presence of excess, however, a red colour.

AZO-COMPOUNDS.

33

Certain facts render it doubtful whether the auxochromic amidogroups enter into combination with the acid radical in the formation of salts, and it is possible that the azo-group enters into

Amidoazobenzene, a weak base, retains its basic after acetylation, and forms red salts as before ; while properties the simple amines such as aniline, which possess much stronger
combination.
basic properties, yield on acetylation almost completely indifferent compounds. At any rate this fact strongly supports the assumption

a certain linkage between the azo- and amido-groups. sulphoriic acids of the amidoazo-compounds are interesting in this respect. Apparently they are incapable of existing in the
that there
is

The

free state, at least from their colour it appears that the formation of a salt takes place between the sulpho-group and the basic

group.

Amidoazobenzene in the

free state is yellow, while

its

sul-

phonic acids have the red colour of the amidoazobenzene salts. If, however, the sulpho-group is saturated by an alkali, the salt produced has again the colour of free amidoazobenzene.

These amido-sulphonic acids behave like acid dyestuffs, but in dyeing the fibre always takes the colour of their alkali salts or of the free amidoazo-base.

The conclusions naturally drawn from

group
effects

this are that the sulphofibre,

the combination with the

and that the acid

properties of the former are saturated

by the

latter.

This property

is still

more

striking with the sulphonic acid of

phenyl amidoazobenzene (Tropaolin OO) ; this body exhibits a colour- change from orange to violet. The azo-compounds, though long known, have attained most of
their importance in the last ten years, especially the scarlet-red The first shades, which have almost entirely replaced cochineal.

was triamidoazobenzene (phenylene Caro and Griess in 1867. by For ten years after this no particular progress was made in this field, and the first synthetical production of azo-compounds appears with the discovery of chrysoidine by Witt and Caro. ChrysoVdine was rapidly followed by the introduction of the acid dyestuffs, discovered almost simultaneously by Witt and Roussin, and which, since the introduction of naphthols, have
azo-dyestuff used brown) discovered
largely

attained great importance. ^ The manufacture of azo-dyes

is

in general very simple.

If a

34

CHEMISTRY OF ORGANIC DYESTUFFS.

diazo-compound has to be combined with a phenol,, the former is prepared by dissolving the amine or its sulphonic acid in water, or suspending them in as finely divided a state as possible, and adding to the liquid the calculated quantities of hydrochloric acid and sodium nitrite. After diazotisation is completed the liquid is allowed to run into an alkaline solution of the phenol or its sulphonic acid, care After some time being taken that the mixture remains alkaline. the dyestuff is salted out, and is generally filtered through a The combination of diazo-compounds with amines filter-press. is somewhat more Some of these, for instance complicated. metaphenylenediamine, combine with diazo-compounds in neutral
aqueous solutions; while others, like diphenylamine, are dissolved in alcohol, and a concentrated solution of the diazo-compound

In the manufacture of amidoazobenzene and compounds in which an intermediate formation of a diazoamido-compound takes place, a large excess of the amine has to be employed, to hold the diazoamido-compound formed in solution. Sulphonic acids are generally obtained by combination of diazogradually added.
all

sulphonic acids with phenols or diazo-bases with phenolsulphonic acids, in a few cases also by heating the azo-compound with

fuming sulphuric acid. The principal application of azo-dyestuffs is in wool-dyeing, and all acid azo-dyes may be directly dyed on animal fibres from an acid bath.

On

cotton they are generally incapable of complete fixation, as

real colour-lakes.

most of them form no

Exceptions to this rule

are certain tetrazo-compounds which dye cotton directly in the form of alkali salts of their sulphonic acids.

Basic azo-dyes (chrysoi'dine, Bis mark brown) are dyed like all colour-bases on vegetable fibres prepared with tannic acid. Their is in cotton-dyeing. principal application

much

uniform method of nomenclature for all azo-compounds is to be desired, but the strict application of such a principle, further than formation into groups, would lead to the necessity for

very long, and often unwieldy names, without insuring certainty in regard to position. For this reason such a method has been avoided, and the bodies
are in general described under the
discoverers.

names given them by

their

AMIDOAZO-COMPOUNDS.

35

I.

AMIDOAZO-COMPOUNDS.
Amidoazobenzene
(1)

[5, 6].
(4)

C 6 H 5 -N=N-C 6 H 4NH 2

Amidoazobenzene is formed by the molecular transformation which diazoamidobenzene undergoes when -brought in contact
with aniline hydrochloride, best in aniline solution. It is therefore the final product of the reaction which occurs when a salt of diazobenzene is treated with an excess of aniline, at a medium
temperature.
scale depends on this principle treated with such quantities of hydrochloric acid and sodium nitrite, that about a third is converted into diazoamidoIts
:

manufacture on a large
is

Aniline

aniline.

benzene, and that the latter remains dissolved in the excess of Further, the amount of hydrochloric acid is so calculated,

that after decomposition of the nitrite some aniline hydrochloride remains in the mixture. The conversion of the diazoamido-

benzene
filtered

is

excess of aniline

aided by warming gently, and, when complete, the is saturated with dilute hydrochloric acid, and

from

the

sparingly

soluble

amidoazobenzene

hydro-

chloride.

Free amidoazobenzene forms yellow needles melting at 127' 5, which may partly be sublimed without decomposition. * Its salts with acids are red and very unstable. They crystallise well, and possess a bluish reflex. They are decomposed by water, and are difficultly soluble in dilute acids, a red solution being With concentrated sulphuric acid, amidoazobenzene produced. a yellowish-brown solution. It is easily split up on reducgives aniline and paraphenylenediamine being formed. tion,

By
is

cautious treatment with zinc powder in alkaline solution

it

converted into amidohydrazobenzene, a colourless

compound

which oxidises rapidly on exposure to the air. 4 Amidoazobenzene itself is useless as a dyestufd, but is important as a starting-point for the manufacture of various dyestuffs.

36

CHEMISTRY OF ORGANIC DYESTUFFS.

isomer of amidoazobenzene, which contains the amido- and azo-groups in the ortho position, has recently been obtained by

An

Janovsky

[7].

Amidoazolenzenemonosulplionic Acid

[8, 9].

HSO C H 4 -N=N-C H 4NH

3 6
6

(1)

(4)

(1)

(4)

This acid is obtained with the disulphonic acid by treating It is formed in amidoazobenzene with fuming snlphnric acid. small quantities by the action of paradiazobenzenesulphonic acid on aniline hydrochloride. It may also be obtained by
cautious reduction of nitroazobenzenesulphonic acid. As obtained by decomposition of its salts with hydrochloric acid, it forms a gelatinous flesh-coloured precipitate, which after

some time changes

soluble

to needles.

Its salts

in cold water, but

salt

dissolve easily
leaflets.

throughout are sparingly in hot water. The

sodium

forms golden-yellow

Amidoazobenzenedisulphonic Acid
(1) (4)

[8, 9].

HS0
This acid
acid

C 6 H 4N=N-C 6 H 3NH 3 S0 3 H.

(1)

(4)

is produced by the energetic action of fuming sulphuric It forms shimmering violet crystals on amidoazobenzene. resembling chromic chloride, which on drying disintegrate. The acid is easily soluble in water, but separates on addition of a mineral acid. Its salts are yellow, very easily soluble, and

difficult to crystallise.

The sulpho-groups are present in both rings, and on reduction the body yields sulphanilic and paraphenylenediaminesulphonic
acids.

Both these sulphonic acids of amidoazobenzene, and especially the disulphonic acid, are valuable yellow dyestuffs, and the sodium salt of the latter comes into commerce as Acid Yellow or Fast Yellow. further application of these acids is in the preparation

of tetrazo-dyestuiFs, for example Biebrich- and Crocein-scarlets.

AMIDOAZO-COMPOUNDS.

37

Acetylamidoazolenzene [71],

C 6 H5
forms yellow
leaflets

N=N

C 6 H 4Np
/

v> 2-Ll- 3 v-'

Hn

chloric acid with a red colour,

It dissolves in hydromelting at 141. and is only saponified on boiling.

Dimethylamidoazobenzene [10].
(1) (4)

CH

Dimetlrylamidoazolenzenesulphonic Acid [11].

HS0 - C H 4 -^ =N-C H 4 -N(CH

3
6 6

(1)

(4)

(1)

(4)

3) 2.

Dimethylamidoazobenzene is obtained by action of dimethylon hydrochloride of diazobenzene, and if the latter be replaced by diazobenzeDesulphonic acid, the above monosulphonic
aniline

acid

is

formed.
leaflets

The base forms golden-yellow

hydrochloride, soluble in water.
to be increased
as

C 14,H 13 N 3 ,HC1, forms

The

melting at 115.
needles

Its

violet

sparingly

basic character of amidoazobenzene seems

radicals into the

by introduction of alcohol

amido-

the salts of dimethylamidoazobenzene are far more group, dilute solution of the stable than those of amidoazobenzene.

base becomes reddened by a trace of acid, and on this fact depends its application as an indicator in alkalimetry. Acetic acid

and amidosulphonic acids are without action on the compound. Dimethylamidoazobenzene is sometimes used for colouring butter and candles. The monosulphonic acid forms brilliant violet needles, which Its salts are yellow, and mostly well are sparingly soluble.
crystallised.

The calcium

salt is

obtained as a lustrous precipitate by adding

salt.

calcium chloride to a solution of the sodium

The sodium

salt of this

sulphonic acid has been used as

38

CHEMISTRY OF ORGANIC DYESTUFFS.

dyestuff under the names Tropaolin II, Orange III, and HeliIt gives fine orange shades on wool and silk, but owing anthine. to its sensitiveness towards acids has not met with great success.

Phenylamidoazolenzene [12],

C 6 H 6 -N=N-C 6 H 4 NHC
is

5,

amine.

formed by the action of diazobenzene chloride on diphenylIt crystallises in golden-yellow prisms or leaflets.

M.P. 82.
It is soluble in alcohol, ether, benzene,

and

ligroine, insoluble
violet,

in 'water.

Acids colour the alcoholic solution

the salts

being

precipitated as grey crystals.

It dissolves in concentrated

sulphuric acid with a green colour, changing through blue to violet on dilution with water. By action of amyl nitrite a nitros-

amine, M.P. 119'5,

is

obtained.

On

reduction

it

yields aniline

and paramidodiphenylamine.

Phenylamidoazolenzenesulphonic Acid [12].

(1) (4)

(TROPAOLIN OO, OEANGE IV.)

Is

obtained by action of p-diazobenzenesulphonic acid on an

The free acid forms alcoholic, dipheriylamine solution. needles resembling graphite, which dissolve sparingly in water with a red- violet colour. The salts are well crystallised, and, with the exception of the insoluble calcium and barium salts, dissolve
acid,

Concentrated water, less easily in cold water. sulphuric acid dissolves the compound, forming a violet solution. The sodium salt has a large application, and comes into commerce under the above designations. It dyes wool and silk a beautiful
easily in hot

orange.

An

isomeric

compound

sulphonic acid is yellower shades.

known

as

prepared from metamidobenzeneMetanil Yellow and dyes somewhat

AMIDOAZO-COMPOUNDS.

39

Yellow dyestuffs are also obtained by action of diazotoluenesulphonic acids on diphenylamine.

phenylamidoazo-compounds yield nitro-derivatives are carefully treated with nitric acid. into the diphenylamine, and certain bodies obtained in this manner are used under the names Azoflavine, Citronine, and Indian Yellow. They are distinguished from the original dyestufFs by their yellower shade. Experimental trials have also been made with higher sulphonic
Nearly
all

when their nitrosamines The nitro-group enters

acids of phenylamidoazobenzene.

Amidoazotoluenebenzene [1 3].

C 6 H 4 CH 3 - N = NC 6 H 4NH 2

(1)

(4)

(1)

(4)

From

paradiazotoluene
at

brown needles melting

and 147.

aniline.

Forms long

yellowish-

Amidoazotoluenes.
A.

C 6 H 4CH 3 -N=N-C 6 H 3 CH 3KH 3

(1)

(2)

(1)

(3)

(4)

[13]

Is obtained from orthotoluidine in a similar manner to amidoazobenzene from aniline. M.P. 100.

B.

C 6 H 4CH 3 -N = N-C 6 H 3 CH 3NH 2

(1)

(-4)

(1)

()

(4)

[13]

From paradiazotoluene and orthotoluidine.

C.

M.P. 127-128.
.

C 6 H 4CH 3 -N = N-C 6 H 3 CH 3NH 3

metatoluidine.
(1)

(1)

(3)

(1)

(2)

(4)

[13]

From
D.

M.P. 80.
(4)

C 6 H 4 CH 3 -N=N-C 6 H 3 CH 3 NH 2

d)

(2)

(4)

[13]

By
127.

the action of paradiazoamidotoluene on metatoluidine.

M.P.

E.

By
M.P.

[14] the interaction of paradiazoamidotoluene and paratoluidine.

C 6 H 4 CH 3 -N=N-C 6 H 3 CH 3 NH 2

(1)

(4)

(1)

(4)

(2)

40

CHEMISTRY OF ORGANIC DYESTUFFS.

These amidoazotoluenes, when treated with fuming sulphuric some of which are used as yellow
first

acid, yield sulphonic acids,

dyes tuffs.

The
group

in the para position to the azo-group.

four amidoazotoluenes, A, B, C, D, contain the amidoThey are all reddened

position

by acids, and yield paradiamidotoluene on reduction. The last compound, E, contains the groups in the ortho
it is

coloured green by acids, and yields orthodiamidotoluene on

reduction.

Amidoazoxylenes,
Seven isorneric amidoazoxylenes are known, but for a description must be made to the literature of the subject [15, 16].

reference

Generally speaking, their properties are similar to those of

amidoazobenzene and the amidoazotoluenes.

Diamidoazolenzenes [12, 13],

A.

Cliryso'idine [17, 18].

(i)

Chrysoidine is prepared by mixing equivalent quantities of of diazobenzene chloride and metaphenylenediamine. The base crystallises from hot water in yellow M.P.
solutions
needles,

117'5. It dissolves sparingly in water, easily in alcohol, ether, and benzene [18]. It forms two series of salts with acids [18] ; the monoacid salts are stable and yellow in the diacid salts are red and are solution,

decomposed by water. C 12 H 13 N4 ,HC1 is obtained in two forms according to whether it has been In the first case it crystallised rapidly or slowly. forms long red felted needles, and in the latter anthracite black
aggregates of octahedrons possessing a green reflex. With an excess of hydrochloric "acid, is obtained, a salt soluble with a red colour, but decomposed by water.

C^H^^HC!^

AMIDOAZO-COMPOUNDS.

41

On

reduction chrysoidine splits up, aniline and triamidobenzene

is

being produced.

C12H11N 4 (C8 HjP) 3

formed by warming chryscidine with

.

acetic anhydride ; forms yellow prisms, M.P. 250 [18] It yields a dimethyl derivative on warming with methyl iodide.

Tetramethylchrysoidine has been prepared by the action of diazobenzene chloride on tetramethylphenylenediamine. A sulphonic acid may be obtained by treating chrysoidine with

fuming sulphuric

acid, or

by allowing paradiazobenzenesulphonic

acid to react with metaphenylenediamine. Chrysoidine, which was discovered by Witt, is one of the few basic azo-dyestuffs, and like all basic colouring-matters dyes cotton

mordanted with tannic

dyeing, especially for

acid.

Its principal application is in cottonshading purposes. It gives a yellowish-

orange colour.
It is of historical interest, as being the first azo-dyestuff pre-

pared by a direct synthesis.

Symmetrical Jlmidoazobenzene [19, 20]

Parazoaniline,
(1)
(4)

(1)

(4)

formed by saponification of the acetyl compound described compound obtained by action of paranitrodiazobenzene on aniline. It forms long, flat, yellow needles. M.P. 140. It is sparingly soluble in water and benzene, easily in alcohol. The monoacid salts dissolve in alcohol with a green colour, while the diacid salts give a red solution.
is

below, and by reduction of the

Acetyl derivative [20], C 12 n 4 (C 2 3 O), is obtained by the interaction of aniline and paradiazoacetanilide in presence of a little hydrochloric acid. M.P. 212. Its salts dissolve with a red
colour.

H N

Di acetyl derivative, C^H^N^CgHsO^ is formed on reduction of paranitroacetanilide with zinc powder and alcoholic ammonia It forms yellow needles. M.P. 282. [19]
.

42

CHEMISTRY OF ORGANIC DYESTUFFS.

Tet ram ethyl derivative [21],
(1)

(4)

(1)

(4)

(Azyline),
aniline,

is formed by the action of nitric oxide on dimethyland by action of paradiazodimethylaniline on the same

amine [22]. Diphenine of Gerhardt and Laurent [23] and hydrazoaniline of Haarhaus [24] are regarded as hydrazo-compounds ; they are
probably diamidoazo-compounds, as they possess tinctorial properties in a marked degree, which is not usual in hydrazo-

compounds.

Triamidoazobenzene.
(1)
(4)

K ..

[2o]

(PHENYLENE BROWN, VESUVINE, BISMARK BROWN.)

Triamidoazobenzene forms brownish-yellow warty crystals, which dissolve sparingly in cold water, easily in hot water. M.P. 137. Acids colour the brownish-yellow solution reddish brown, and produce diacid salts. Triamidoazobenzene is formed along with other azo-compounds, on treating metaphenylenediamine with nitrous acid. Its hydrochloride forms the principal constituent of the dyestuffs known under the above names. (A more recent view is that Bismark

brown

consists partly at least of a

(i)

compound
2) 2

of the formula

rTJr

/N 2 -C 6 H 8 =(NH

which

is

to be regarded as a metaphenylenediamine disazometa-

phenylenediamine.) With the exception of chrysoidine, Bismark brown is the only basic azo-dyestuff in practical use. It is used in dyeing cotton and
leather.

Diamidoazotoluenes.

[See 26, 27.]

AMIDOAZO-COMPOUNDS.

43

Benzeneamidoazonaplitlialene [28, 29],

is

obtained by interaction of diazobenzene chloride and #-naph-

thylamine.

Sulphonic acids
sulphonic acid

may

be obtained by action of paradiazobenzene-

/3 naphthylamine. corresponding toluene compound has been prepared by action

.

on a and

of paradiazotoluene on a-naphthylamine [27] The dyestuff known as orchil substitute or orseilline

is

prepared

by action of paranitrodiazobenzene on naphthionic acid (a-naphthylaminesulphonic acid). It produces reddish-brown shades on

wool and
is

dyed from an acid bath [72]

Amidoazonaplithalene,

aC 10 H N=:N-C 10 H
7

NH

a [30],

is

formed by action of nitrous acid on excess of a-naphthylis best prepared by mixing a solution of two molecules of a-naphthylamine hydrochloride with one molecule of sodium nitrite. The base forms reddish-brown needles, which show a green reflex; it melts at 175, and is sparingly soluble in
amine, and
alcohol, readily in xylene. The salts dissolve in alcohol with

violet

colour,

and are

decomposed by water.

The azo-group
group.
.

is

present in the a para position to the amido-

Sulphonic acids of this compound are obtained by direct sulphonation, or by combination of diazonaphthalenesulphonic acid with
a-naphthylamine.
disulphonic acid of amidoazonaphthalene is obtained by action of sodium nitrite on naphthionic acid; its constitution differs from that of the above acids, as the second a-positijn
usually taken by the azo-group
is

occupied by the sulpho-group in

naphthionic
similar

acid.

The corresponding /3-amidoazonaphthalene is obtained in a manner from /3-naphthylamine ; it melts at 156, and is
Mixed amidoazonaphthalenes have
also been prepared.

a slightly weaker base.

44

CHEMISTRY OF ORGANIC DYESTUFFS.

II.

OXYAZO-COMPOUNDS.

Oxyazolenzene [31, 32, 33].

C 6H5

-N=N-C H OH.
6

(1)

(4)

(Phenoldiazobenzene.}

Oxyazobenzene

is

prepared by interaction of
is

diazobenzene

chloride and phenol-sodium [32], and

also

formed by action of

barium carbonate on
It

salts of

diazobenzene [31].

further be obtained by treating the isomeric azoxybenzene with sulphuric acid [34], and by the action of nitroso-

may

phenol on aniline [33]. It forms needles, M.P.

easily in alkalies

151;

it

is

slightly soluble in water,

and in alcohol.

Parasulphonic acid
(1)

(4)

(1)

may be

direct sulphonation, or by action of paradiacid on phenol-sodium. azobenzenesulphonic This compound was formerly in commerce as Tropaolin Y, but owing to its dull brownish shade was soon displaced. An isomeric

obtained

by

metasulphonic acid is formed by action of metadiazobenzenesulphonic acid on phenol-sodium [36]

.

Dioxyazobenzene [35].
a.

Unsymmetrical

-.

(i)

C 6 H 5 N = N-C 6 H 3<(3)

/OH

OH

This compound is prepared by action of diazobenzene chloride on resorcin in presence of an alkali. It forms red needles, M.P. 161 ; and is soluble in alcohol, ether, and alkalies.

OXYAZO-COMPOUNDS.

45

Parasulphonic Acid.

HS0 -C H 4 -N=N-C H
3

g.

(TKOPAOLIN O.)
This dyestuff is prepared by action of paradiazobenzenesulphonic
acid on resorcin [36, 37],

and

is

also

formed by sulphonation of

dioxyazobenzene [37]. The free acid forms needles, which appear almost black with a greenish lustre by reflected light, and red by transmitted light. It
is a strong acid, capable of liberating hydrochloric acid from a solution of common salt, thereby forming a sodium salt.

The salts are orange-yellow, and are only decomposed by concentrated hydrochloric acid or by dilute sulphuric acid. Tropaolin O is a strong dyestuff, producing a fine goldenIt yellow shade on wool and silk, being dyed from an acid bath.
was formerly used in silk-dyeing. The metasulphonic acid is obtained from metadiazobenzenesulphonic acid and resorcin [36]
.

/3.

Symmetrical dioxyazobenzenes (AZQPHENOLS) [38]

a.

Para-azophenol

is

formed on melting paranitro- or nitrosophenol with potash,

b. Ortho-azophenol

M.P. 204.

is

formed similarly from orthonitrophenol, M.P. 171.

Oxyazobenzenetoluene [33],

CH C H 4 -N=N-C H OH,
3

(Phenolazotoluene.)
is

obtained from nitrosophenol and paratoluidine, M.P. 151.

Cumeneazoresorcin^

(CH 3 3 C 6 H2 -N = N-C 6 H 3 (OH) 2

)

from diazocumene and resorcin

[39],

M.P. 199.

46

CHEMISTRY OF ORGANIC DYESTUFFS.

Amido-oxyazolenzene [40],

H NC H 4 -N = N-C H 4 (6H)
2
6

(M.P. 168),

is

obtained by saponification of the acetyl- compound

C2 H 3 ONH-C 6 H 4 -N=N-C 6 H 4 OH (M.P. 208),

which is prepared by interaction of phenol-sodium and the compound from monoacetylmetaphenylenediamine.
.

diazo-

Oxyazo-compounds are also obtained by action of diazo-compounds on the isomeric cresols [39, 41, 42]

a-Azonaplithalene-resorcin [46],

C 10 H

-N=N-C H
6

(OH) 2

forms red needles, M.P. about 200.

NAPHTHOLAZO-DYESTUFFS.
These dyes belong to the oxyazo series, and have within the last ten years attained enormous importance, on account of the beauty For these, of their shades and their strong tinctorial properties. and other reasons, they are worthy of being studied as a separate
class.

The isomeric naphthols combine with all diazo-compounds, producing azo-compounds, and with a-naphthol

the azo-chain enters into the second a-position of the substituted This is exactly analogous to the formation of the correring.

sponding compounds with benzene derivatives containing a free para position. The simplest a-naphthol azo-compounds are constituted as expressed by the following formula
:

OXYAZO-COMPOUNDS.

47

OH

/3-naphthol

has no free para position and the azo-group enters in the ortho
position, viz. in the adjacent a-position
:

case is different when these positions are already occupied other groups, for example, by the sulpho-group. With a-naphby tholthe azo-chain enters into the adjacent /3-position; for instance, with a-naphtholsulphonic acid azo-compounds of the general

The

formula

OH
3

N=N

are formed.

48

CHEMISTRY OF ORGANIC DYESTUFFS,

:

The formula with /3-naphthol

probably correct, but has not been proved to be absolutely In general, azo-compounds containing the chromophoric and auxochromic groups in the ortho position are far more valuis

certain.

able as dyes than their allies of the para-series. The latter have the undesirable property of altering their shade

much higher degree than This applies equally to oxy- and amidothe former compounds. azo-compounds,, especially those of the naphthol series.
on treatment with
alkalies or acids in a

For

this reason /3-naphthol gives

more useful

dyestuffs than a-

naphthol.

The

derivatives of the latter exhibit striking changes in colour

alkalies.

on treating with

in a-naphthol is substituted, as If, however, the para position in the a o-sulphonic acid, the azo-group enters in the j3- (ortho) are obtained. Diazo-compounds position, and stable and useful dyes
are capable of reacting on j-naphthol once, while a-naphthol, like In the phenol, reacts with two molecules of a diazo-compound.

resulting dis-azo bodies the second azo-group is probably in the @ 1 -position, as expressed in the following formula
:

OH

The naphthol azo-dyes

their sulphonic acids.

are almost exclusively applied in form of These may be obtained by combination of

OXYAZO-COMPOUNDS.

49

sulphonated diazo-corapounds with naphthols, or of diazo-com-

pounds with naphtholsulphonic acids. The sulpho-group of the diazo-compound has little or no influence in the shade of the dyestuff, but the isomeric naphtholsulphonic acids are capable of giving totally different dyestuffs with In most cases this may be attributed the same diazo-compound. Tt to the different positions of the azo-group already mentioned.
is

necessary for a correct comprehension of the following dyestuffs to consider the principal naphtholsulphonic acids somewhat more closely, for although our knowledge in this direction is incomplete,
researches have been

many valuable

made

in recent years, of

which

those of Armstrong are especially worthy of mention. At present three monosulphonic acids have been obtained from

a-naphthol, but the constitution of only one of these is known with any degree of certainty. This is the a a-acid prepared by Nevile and \frinther, and studied more closely by Witt. It is obtained by

decomposition of the diazo-compound of naphthionic acid with water, and from its method of formation is constituted according to the formula
:

OH

nature of the dyestuffs are totally different to the simple they a-naphthol dyes, as the azo-group enters in the /3 1 position and not in the a 2.

This formula agrees well with the

;

obtained from this acid

The
benzene

of the dyestuffs from a-naphthol and diazo-compounds series are orange or brown, while those from the a a-acid

are mostly of a beautiful ponceau-red tone. second acid was prepared by Schaeffer, in 1869,

who probably

obtained

it

mixed with the a a- acid.

is

obtained along with the latter acid by heating a-naphthol with concentrated sulphuric acid on the water-bath. It differs from the a a-acid by the sparing solubility of its sodiumSchaeffer' s acid
salt in alcohol, and more especially by the dyestuffs it yields. These are analogous to the corresponding a-naphthol derivatives, and therefore very probably para-compounds.

50

CHEMISTRY OF ORGANIC DYESTUFFS.

acid has probably the constitution expressed
:

The

by the follow-

ing formula

as it yields dinitronaphthol

on treating with

nitric acid,

and phthalic

acid on oxidation.

A third
its

acid has been prepared by

Baum, but

little is

known

of

constitution.

[Patent, 1883,

No. 3498,

Provisional Specifi-

cation.]

ascribe the constitution

tical

Glaus and Oehler have examined an acid [75] to which they a 2 , but it is doubtful whether it is iden-

with the Schaeffer or with the Nevile-Winther acid. It may be as well to take this opportunity of remarking that a method often used for determining the constitution of naphtholsulphonic acids appears not to be trustworthy, as molecular changes,

which occur so frequently in the naphthalene series, appear to take place here also. This is the method depending on the conversion of the acids into chloronaphthalenes by means of phosphorus Indeed the results so obtained often differ from pentachloride.
all

others.

The Schoellkopf Aniline Co. have patented an

acid obtained

by nitration of a-naphthalenemonosulphonic acid, reduction to amido-acid, and conversion into naphtholsulphonic acid by the
diazo-reaction.
It is so far characteristic as it gives a scarlet
its

with

diazotoluene, while

isomers give oranges.

[D.P. 15871.]

a-naphthol also yields a disulphonic acid (?), and a trisulphonic, which, however, have no importance in the manufacture of azodyes.

/3-naphthol, on treating with sulphuric acid, gives in the first instance three monosulphonic acids. One of these (the a-sulphonic acid or crocem-acid) is best obtained at a low temperature. By further heating with sulphuric

goes over into the /3- or Schaeffer' s acid, which was prepared by Schaeffer a long time ago. These acids are distinguished
acid
it

OXYAZO-COMPOUNDS.
principally

51

by the

different

solubilities

of their disodium com-

pounds

C io H 6<
The
basic salt of the a-acid

O Na
is

easily soluble in hot alcohol,

while that of the Schaeffer acid is almost insoluble. The third acid, which has only recently been identified by its conversion into the corresponding /3-naphthylaminesulphonic
acid, is identical with the
p. 721.]

F- or S-acid.

[Green

B. B. 1889,

From
in shade

the facts that azo-dyes from Schaeffer's acid differ but little and solubility from those obtained from /3-naphthol, and

that

simple /3-naphthol azo-compounds on sulphonation always yield derivatives of Schaeffer's acid, and never those of croce'inacid, it may naturally be concluded that the azo-group enters in

the same position both in /3-naphthol and in Schaeffer's acid. This is the a : position.

The behaviour of the a-acid is totally different. The dyestuffs do not resemble those from Schaeffer's acid and /3-naphthol in the Further, this acid may least, either as regards shade or solubility. easily be converted into a dinitro-compound with nitric acid, and this is not the case with either /3-naphthol or Schaeffer's acid. Another striking property of the a-acid is that its combination with diazo-compounds takes place with much more difficulty than is Its constitution is therefore experienced with Schaeffer's acid.

justifying the designation /3-naphthol-a-monosulphonic acid for this acid. The conversion of the corresponding /3-naph thylamine-

sulphonic acid into a-naphthalenesulphonic acid also shows that

it is

really an a-acid. Schaeffer's acid yields sulphophthalic acid on oxidation, showing that the hydroxyl and sulpho-groups are in different rings.

E2

52

CHEMISTRY OF ORGANIC
Noelting ascribes the following

DYESTUFtfS.

constitution

to

Schaeffer's

acid

OH
/3HS0 3

third sulphonic acid is that of Cassella and Co., prepared by heating naphthalene-a-disulphonic acid with caustic alkali. This acid is technically known as F-acid, and is identical with

the acid prepared by the diazo-reaction from Bayer's /3-naphthyl-

amine-8-sulphonic acid. Without doubt it has the constitution

SCXH

It is

Of the

without importance for preparing azo-dyes. /3-naphtholdisulphonic acids/ three are used in the

Two of these are formed by energetic colour-industry [73, 74]. action of sulphuric acid on /3-naphthol, and may be separated by taking advantage of the different solubilities of their sodium salts
in alcohol or in concentrated salt-solution.

and salt-solution (G-acid of Meister, and Briining, 7-acid of Cassella and Co.) behaves very like Lucius, ./3-naphthol-a-monosnlphonic acid (crocein acid), and must be regarded as a derivative of the latter, as it is formed quantitatively on further sulphonation of crocein acid. It may also be obtained from Schaeffer's acid (this is contradicted by some chemists), and Armstrong gives it the following formula

The

acid soluble in alcohol

HS0

HSO

OXYAZO-COMPOUNDS.

53

The azo-dyes from G-acid are yellowish and easily soluble, and are very similar to those from the a-monosulphonic acid. The disulphonic acid from the sodium salt, sparingly soluble in
alcohol and salt-solution (R-acid, Meister, Lucius, and Briining), gives dyestuffs of considerably bluer shade, and also more difficultly soluble.

They
is

are,

however, very important.

This R-acid
acid,

and

it is

best obtained by further sulphonation of Schaeffer's also stated that G-acid is converted into R-acid on

heating with sulphonic acid. expressed by the formula

:

The

constitution of the R-acid

is

SOHk
Another

/S

disulphonic acid, /3-naphthol-S- disulphonic acid is further sulphonation of the F-acid. It has the conprepared by
stitution

S(XH

/3-naphtholtrisulphonic acid is obtained by sulphonation of /3-naphthol with fuming sulphuric acid at a high temperature. It has been used for the preparation of azo-colours.

Azobenzene-a-napht7wl [1],

C 6 H 5 -N = N-C 10 H 6 OHa,
is

prepared by action of diazobenzene chloride on an alkaline

solution of /3-naphthol. It forms yellow leaflets, which dissolve in alkalies with a violet colour.

54

CHEMISTRY OF ORGANIC DYESTUFFS.

Monosulphonic Acid [11].

HSO -C H 4 -N = N-C H OH
3

(I)

(4)

10

a.

(ORANGE
This
is

I.

TEOPAOLIN

OOO

No.

1.)

dyestuff prepared by paradiazobenzenesulphonic acid on a-naphthol. The free acid forms almost black dissolve in concentrated leaflets, with a green reflex, which acid with a violet coloration. Its alkali salts are orangesulphuric

action

of

yellow,

and

dissolve easily in water.

The

solutions

become red
.

with excess of alkali (distinction from /3-naphthol dyestuffs) The sodium salt is used in dyeing under the above names.

It dyes wool and silk in an acid bath, producing an orange shade, which is somewhat redder and not so bright as that obtained with the corresponding /3-naphthol orange. The calcium salt is amorphous and insoluble. Owing to the sensitiveness which these

dyestuffs exhibit towards alkalies, the /3-naphthol derivatives are of

considerably

more importance.
Azobenzene-ft-naphtlwl [1].

C 6 H 5 N=N-C 10 H 6 OH.
Yellow
leaflets,

insoluble in alkalies.

Monosulphonic Acids.
i.

HS0 -C H 4 -N=N-C H
3

(1)

(4)

10

OH/3.

(ORANGE

II.

TROPAOLIN

OOO

No. %,)

From paradiazobenzenesulphonic acid and /3-naphthol. The The crystals acid forms orange-yellow leaflets, soluble in water. on drying lose water and fall to a powder resembling red lead.
The
alkali salts are similar to

the acid, and are unchanged by

excess of alkali

(distinction from calcium salt dissolves sparingly, the

barium

a-naphthol dyestufts). salt not at all.

Its

The
is

compound

dissolves in concentrated sulphuric acid with a

magenta-

red colour.

On

wool and

silk it gives a beautiful

orange, and

one of the most important azo-dyes.

OXYAZO-COMPOUNDS.

55

ii.

C 6 H 5 -N = N-C 10 H 5 OHHS0 3
(CKOCEIN OKANGE.)

From diazobenzene and

Schaeffer's /3-naphtholmonosulphonic

The shade of the dyestuff is somewhat yellower acid (/3-acid). than that of the former. It gives an orange-yellow solution with
concentrated sulphuric acid.

Disulphonic Acids.

C 6 H 5 -N=N-C 10 H4

XHS0
C.

3 ),

^ Uxi

ORANGE G.
/3-naphtholdisulIt is a soluble in alcohol). which gives an orange-yellow solution yellowish-orange dyestuff,
Is obtained

by the action of diazobenzene on

phonic acid

(the modification Gr,

with concentrated sulphuric acid.

SCAKLET 2 G.
This dyestuff is an isomer of the above, prepared by action of diazobenzene chloride on the R modification of /3-naptholdisul-

phonic acid.

Amidoazobfinzene-fi-naplitholdisulphonic Acid.
CD
(4)

(HSO

3) 2

May be obtained by saponificaticn of its acetyl derivative, ana by combination of /3-naphtholdisulphonic acid (R) with paradiazoaniline [44] (from paraphenylenediamine and one mol. 2 ).

HNO

forms brownish-yellow leaflets, which dissolve in alkalies with a violet colour, becoming red with excess of alkali.
It

Acetyl derivative

C2H 3

HN-C H -N -C H
6 4
2

'

10

ft

[43].

56

CHEMISTRY OF ORGANIC DYESTUFFS.

From
leaflets.

p-diazoacetanilid

and naphtholdisul phonic acid; forms red

Dyestuffs obtained by combination of the diazotoluenes and

their sulphonic acids with /3-naphthol also of technical value.

and

its

sulphonic acids are

AZO-DYES FROM /3-NAPHTHOLDISULPHONIC ACIDS AND THE HIGHER HOMOLOGUES OF DlAZOBENZENE [45].
It

has

already been remarked on p.

acids
of

53

that

the isomeric

disulphonic shades with

nucleus.

/3-naphthol give dyes of totally different This is probably caused by the diazo-compounds.

azo-group entering in a different position in the naphthalene This property is made use of in the colour-industry.
acid corresponding
to

The

the

sodium

salt

soluble in alcohol

(G-acid, Meister, Lucius, and Bruning) gives orange-yellow dyes with diazo-compounds of the benzene series, and scarlets with of the naphthalene series; while the R-acid (Meister, Lucius, and Bruning), from the sodium salt insoluble in alcohol, gives red dye-stuffs with the diazo-compounds of the benzene

those

series,

varying in depth according to the molecular weight of the

latter [45].

The R-acid, when combined with the diazo-compounds of the xylenes and higher homologues of benzene, gives rise to a series of scarlet dyes, which have a wide application in wool-dyeing
under the names Ponceau R, RR, RRR, and G. a-diazonaphthalene gives a deep claret-red (Bordeaux B). With diazonaphthalene" Amasulphonic acid and R-acid, a colouring-matter known as " ranth is obtained. Orthodiazoanisol and its homologues give fine

known commercially as Coccinines. The dyes from diazo-compounds of the benzene series (Ponceaux R, RR, RRR, and Coccinines) form scarlet powders, which dissolve in strong sulphuric acid with a red colour. They give
red dyestuffs
crystalline calcium salts
stuffs

which are soluble in hot water. Dyecontaining naphthalene rests on both sides dissolve in

sulphuric acid with blue or violet colour.

OXYAZO-COMPOUNDS.

57
dyestuffs

The following Table contains the most important

those prepared from the naphtholdisulphonic acids, excluding later belonging to the tetrazo class, which are mentioned
:

Ponceau 2

(Meister,

Lucius,

&

K-acid and diazobenzene.

Briining)

(Badische Aniline- und Sof.

R-acid and diazopara- and metaxylene (from coml. xylidine).

dafab.). 2 It (Actienges

Aniline)

3R
3

(Meister, Lucius,

& Briin-

R-acid and diazometaxylene (pure). R-acid and diazoethylnietaxy lene).

R-acid and diazopseudocumene.

ing)

(Bad. Aniline- und Sof.

.

dafab.).

4
2

R (Actienges Aniline) R (Meister, Lucius, & Briin.

Do. Do. R-acid and diazonaphthalene. R-acid and a-diazonaphthalene-sulph.

acid.

ing)

Bordeaux

(do.)

Amaranth

(Cassella

&

Co.)

Bordeaux S(Meister,Lucius,&Briining)
Coccinin (Meister. Lucius, Pheuetol Red (do.) Anisol Red (do.)

& Briining)

Do. R-acid and diazoanisol.

Do. and diazophenetol. Do. and homologues. G-acid and diazobenzene. Do. and diazopseudocumene. Do. and a-diazonaphtkalene.

Orange G (Meister, Lucius, & Briining) Ponceau 2 G (Bad. Anil. & Sodaf.) Crystal Ponceau (Cassella & Co.) ....
.

a.~Azonaphthalene~P"naphthoL

C 10 H 7
Is obtained

N N

C 10 H 6 OH

(0-,3-oxyazonaphthalene)

by interaction of a-diazonaphthalene chloride and

/3-

naphthol.

Monosutphonic Acid [47 J.

HS0 C H
3

10

~N=N-C H OH.
10
6

(FAST KED, ROCCELLINE.)

This
is

obtained by the action of a-diazonaphthalenesulphonic

acid on /3-naphthol. The acid and its sodium salt both form

brown needles, sparingly soluble in cold water, easily in hot, separating from the hot solution as gelatinous precipitates. The calcium and barium salts are insoluble and The compound possesses amorphous.

58

CHEMISTRY OF ORGANIC DYESTUFFS.

very strong tinctorial properties, dyeing wool and silk red. The shade is bluish and not particularly bright. It dissolves in concentrated sulphuric acid with violet colour, separating in brown
flocks

on

dilution.

Disulphonic Acids.
i.

C 10 H 7 N=N-C 10 H4

JI

fs03)2

[45].

a.

BORDEAUX B

(Meister, Lucius, and Briining).

From
acid.

diazonaphthalene.

/9-naphtholdisulphonic acid (insoluble in alcohol) and aGives a blue coloration with strong sulphuric

CRYSTAL SCARLET (Cassella & Co.). Obtained in a similar manner from a-diazonaphthalene and the G- or fy-disulphonic acid (soluble in alcohol). The sodium salt
1.

crystallizes very easily.

ii.

HS0 3 C IO H
.

-N=N-C H (
10 5

'

HSO

CROCEIN SCARLET 3 Bx.

From /3-naphthol-a-monosulphonic acid [48] and a-diazonaphthalenesulphonic acid. Is a beautiful scarlet dyestuff which dissolves in sulphuric acid with a reddish- violet colour.
Sulplioazonaphthalene-a-naphtholsulphonic Acid.

HS0 C H
3

10

-N=N-C

10

H,

(AZORUBIN.)
prepared by combination of a-diazonaphthalenesulphonic acid with the a-naphthol-a-sulphonic acid obtained from the former
is

This

acid by decomposition with water.

It

is

a fine bluish-red dyestuff.

sulphonic acids are also used in the manufacture of dyestuffs. Oxyazonaphthalene, obtained from /?" diazonaphthalene and /3-naphthol, is known as Carminnaphthe,"
its

/3-naphthylamine and

and

is used in colouring varnishes. /3-naphthylaminesul phonic acid (Bronner's acid), prepared by heating Schaeffer's /3-naphtholmonosulphonic acid with ammonia,

AZO-COMPOUNDS.
gives

59

when

diazotised

and combined with /3-naphthol, a dyestuff

used in silk-dyeing.

With a-naphthol-a-sulphonic

acid the dye

known

as Brilliant Scarlet is obtained.

dyestuff

known

as Silk-red, or Scarlet for Silk, is prepared

by sulphonating /3-naphthylamine and diazotising the resulting sulphonic acid and combining with /3-naphthol.

III.

AZO-DYES FROM DIAZOCARBONIC ACIDS.

Diazo-compounds combine with phenols and amines to form azocompounds. The tinctorial properties of these bodies are generally weak; becoming intensified, however, by converting the carbonic
acids into their ethers.

Dimethylamidobenzene-azO'benzoic Acid [50].

COOHC H 4 -N=N-C H N(CH

6 6

3) 2 .

Is obtained

from m-diazobenzoic acid and dimethylaniline.

Phenolazo-meta-benzoic Acid [49].

COOHC H -N = N-C H 4 OH.

6

From

diazobenzoic acid and phenol.

M.P. 220.

o-Sulphonic Acid.

From

o-phenolsulphonic acid and m-diazobenzoic acid.

Eesorcin-azo-benzoic Acid [49].

a)
3

OH

$-Na/phthol~azo-benzoic Acid [49].

COOHC H 4 -N:=N-C H OH.

6

(1)

(3)

10

M.P. 235.

Ethyl ether, M.P. 104

.

(from diazobenzoic acid

ether and /3-naphthol)

60

CHEMISTRY OF ORGANIC DYESTUFFS.

Monosulphonic Acid [49],

T

OH

acid and /3-naphtholmonosulphonic acid. and trisulphonic acids have also been prepared by Disulphonic action of m-diazobenzoic acid and its sulpho-acids on /3-naphthol-

From m-diazobenzoic

disulphonic acid.

Diazoanisic acid, as well as the paradiazocin-

namic

and its ethers [51], gives red azo-dyes [49] with acid and its sulphonic acids. naphthol
acid

IV.

AZO-DERIVATIVES FROM CARBONIC ACIDS AND DIAZO-COMPOUNDS.

to

Oxy- and amidocarbonic acids combine with diazo-compounds form azo-dyes, some of which possess the property of dyeing on

metallic mordants.

Azobenzene-dimethylamidobenzoic Acid [50, 39].

C H,
fi

7 N = N-CH SX N(CH
L

3) 2

COOH
acid.

From diazobenzene and dimethyl-m-amidobenzoic

125.

M.P.

Dimethylamidolenzoic Acid-azolenzoic Acid.

/COOH COOHC H 4 -N=N-C H/

6
6

[49].

By
acid.

action of m-diazobenzoic acid

on m-dimethylamidobenzoic

Azo-^-diamidolenzoic Acid-p-lenzenesulphonic Acid

[9].

HS0 -C H1 -N=N-C
3 6

H4^.

Is prepared

by action of p-diazobenzenesulphonic acid on &-di-

amidobenzoic acid.

AZO-COMPOUNDS.

61

Azolenzenesalicylic

Add
(1)

[52].

C 6 H 5N =N-C 6 H 3(
From diazobenzene and

/OH (2)
-

COOH

salicylic acid.

Monosulplionic Acid.

From p-diazobenzenesulphonic

acid and salicylic acid [36].

Azonaplithalene-salicylic
.,
.

Acid
.

[53],

C 10 H

/OH N=N-C H<

6

cooH

From
[54].

also been prepared

Dyestuffs have from salicylsulphonic acid and diazo-compounds Meta- and para-oxybenzoic acids [36], as well as oxy-

a-diazonaphthalene and salicylic acid.

naphthoic acids [55], give colouring-matters with diazo-compounds. The dyes prepared from salicylic acid mostly possess the property of dyeing on alumina, iron, and chromium mordants, in
a similar

manner

to alizarin.

is not met with in the meta- and paraseems to be connected with the ortho position, as oxy-derivatives, in the quinoneoxime dyes. These mordant-dyeing properties are found in a much higher

This property, which

degree in the bodies obtained by action of nitrodiazo-compounds on salicylic acid (Germ. Pat. 44170, 16 Nov., 1887). The dyestuff from metanitrodiazobenzene and salicylic acid comes into

Yellow G, and produces a fine yellow lake The pure dyestuff crystallizes from alcohol M.P. about 230. Its constitution may in light yellow needles. formula be expressed by the

commerce

as Alizarin

with chromium oxide.

C6 H 4N02 -N=N-C 6 H 3(
It

H
.

substitute

has been used to a certain extent in calico-printing as a for Persian-berry extract and fustic extract. An

62
isomeric

CHEMISTRY OF ORGANIC DYESTUFFS.

Alizarin Yellow

compound from paranitrodiazobenzene is known as R and gives more orange shades in dyeing. These compounds are also useful in wool-dyeing. The dyeing process is simple, as owing to the stability of these compounds the
mordanting with bichromate and the dyeing may be effected in one bath, a-oxynaphthoic acid combines with nitrodiazo-compounds, producing brown dyestuifs which possess the property, like the above, of dyeing on mordants.

V.

TETRAZO- OR DISAZO-DYESTUFFS.
differ

taining the azo-group

from the simple azo-compounds by conmore than once in the molecule. to their method of formation and constitution, these According The first of compounds may be divided into different classes. these classes, the type of which is phenolbidiazobenzene discovered by Griess, contain the two azo-groups and the auxochrome amidoThese bodies

N=N

These compounds or hydroxyl groups in one benzene nucleus. are obtained by the action of diazo-compounds on oxy- or amidoazo- compounds.

the auxochrome

second class contains only the azo-groups in one ring, while is in another. They may be prepared by acting

upon amines or phenols with diazoazo-compounds (from amidoazo-bodies), or by diazotisation of diamines and subsequent combination with amines or phenols [43, 46]. third class of tetrazo-dyestuffs includes those prepared from benzidine and its analogues. These contain two azo-groups in two

different

rings,

which are linked to each other.

i. e.>

Tertiary

and

those containing three and four quaternary azo-compounds, have also been obtained. azo-groups,

Phenoldisazobenzene (Phenolbidiazobenzene) [28, 56].

Is prepared by treating diazobenzene nitrate with carbonate of barium, or by the action of the former on oxyazobenzene. A homologue, M.P. 110, It forms brown leaflets, M.P. 131. be obtained from paradiazotoluene and oxyazobenzene [56] may
.

TETRAZO-COMPOUNDS.

63

Resorcindisazolenzene [46].

C 6 H 5 -N2 -C 6 H 2 (OH) 2 -N 2 -C 6 H 5

Two

isoraeric

compounds are formed by the action of diazoben-

zene chloride on metadioxyazobenzene. *. Soluble in alkalies, M.P. 215.

13.

Insoluble in alkalies, M.P.

222.

p-diazotoluene reacts with m-dioxyazobenzene, three isomeric resorcindisazotoluenebenzenes being formed [46].

Soluble in alkalies ("' (.! Ivl.Jr. <4<L Insoluble in alkalies /?. M.P. 198.
.

^^
may be

Various disazo-compounds of this

class

obtained from

azotolueneresorcin (from p-diazotoluene and resorcin) by action of diazobenzene and diazotoluene [46].

Amido-derivatives are produced by action of diazo-compounds on unsymmetrical diarnidoazobenzene (chrysoi'dine) and its homologues.

For example, chrysoi'dine and diazobenzene chloride react to form azobenzenephenylenediaminebenzene [57] M.P. 250.
.

C 6 H 5 -N = N-C 6 H 2 (OH 3
Homologues and carbonic
prepared [57, 58].

-N=N-C H
6

5.

acids of these bodies have also been

AZO-DYES FKOM AMIDOAZOCOMPOUNDS.

Amidoazo- compounds, of which the simplest representative
is

amidoazobenzene, are converted into the corresponding diazoazocompounds, which latter, like simple diazo-compounds, react with

amines and phenols, azo-dyes being formed. acids behave in the same way.

Amidoazosulphonic

Benzenetetrazolenzenephenol (Tetrazobenzenephenol) [59].

]

41

(4)

Is

formed by interaction of diazoazobenzene and phenol.

class.

It

may

be regarded as the simplest representative of this

64

CHEMISTRY OF ORGANIC DYESTUFFS.

Benzenedisazolenzene~fi-naplithol [60]
.

C 6 H 5 -N=N-C 6 H 4 -N=N-C 10 H 6 OH.

(

Tetrazobenzene-jS-naphth ol.)

Forms a brick-red /3-naphthol. It is insoluble in or brown leaflets with a green reflex. powder soluble in alcohol, easily in hot glacial acetic alkalies, sparingly

From diazoazobenzene and

acid.

It gives a

green solution with concentrated sulphuric acid.

acids of this

The sulphonic
sulpho-group.

compound come

into

commerce

as

Biebrich and Croce'in scarlets, according to the position of the

MonosulpJwnic Acid

[60].
13

HS0 C H 4N = N-C H
3 6 6

(1)

(4)

(1)

N=N-C H OH.
10
6

(4)

From diazoazobenzenemonosulphonic
sodium salt forms red needles or an

acid and /3-naphthol.

The

amorphous red powder which The in cold water, more easily in hot water. is sparingly soluble on cooling solidifies to a gelatinous mass. hot aqueous solution The calcium and barium salts are insoluble.
Disulphonic Acids.
A.

HS03C 6 H 4N = N-C

H HS0 N-N-C H OH
3

10

[60].

(BIEBRICH SCARLET.)
diazoazobenzenedisulphonic acids and /3-naphthol. The sodium salt is easily soluble, and forms a thick syrup with a
It

From

small quantity of water, becoming crystalline on long standing. may be crystallized from dilute alcohol in red needles. The

calcium and barium salts are insoluble. Commercial Biebrich scarlet is generally this disulphonic acid, sometimes it contains the monosulphonic acid also. Both give a

The shade green solution with concentrated sulphuric acid. obtained on wool and silk is a beautiful cochineal scarlet.
B.

HS0 -C H 4 -N=N-C H 4 N=N-C H OH HSO 3

3 6
6

10

The isomeric monosulphonic

acids of /3-naphthol react with di-

azobenzenesulphonic acid, producing dyes which, however, differ

Schaeffer's greatly according to the position of the sulpho-group. /3-acid gives dyes of a bluish shade and of little value, while the aacid gives dyestuffs the shade of which is much superior to that of

Biebrich scarlet.

TETRAZO-COMPOUNDS.

65

This body [61] is known as Crocem Scarlet 3B, and although Crocem not producing fast shades is used in cotton-dyeing. Scarlet 7 B is a dyestuff of somewhat bluer shade, and is obtained from orthoamidoazotoluenesulphonic acid in the same manner.

The tetrazo-dyes prepared from /3-naphthol-a-sulphonic

acid give soluble crystalline calcium salts, while those from the other acid give amorphous and insoluble calcium salts.

The G-disulphonic acid behaves similarly to the a- acid, and its combination with diazoazobenzene, known as Brilliant Crocein All the naph(Cassella & Co.), is closely allied to Crocem 3 B.

thol azo-dyes derived from amidoazobenzene and its homologues give a characteristic reaction on reduction, which readily serves for
their recognition.

On warming
its

powder, only the naphthol or

the alkaline solution with zinc sulphonic acid is split off ; the
this class is

amidoazo-compound being regenerated. Another characteristic property of the compounds of

that they exhibit a peculiar behaviour towards strong sulphuric acid. The sulphonic acids containing the sulpho-groups in the ben-

zene rings only react like the non-sulphonated azo-compounds, giving a green colour with concentrated sulphuric acid; if the

sulpho-groups are in the naphthalene ring, a violet colour is obtained ; while, if both rings are sulphonated, the colour is pure
blue.

On warming

the green solution of benzene-disazobenzene-

/3-naphthol in sulphuric acid, the colour gradually changes to blue, and the sulphonic acid formed is identical with the one from

diazoazobenzenemonosulphonic acid and /3-naphthol-/3-monosulphonic acid. a-naphthylamine reacts with diazoazobenzenedisulphonic acid to produce a brown dyestuff, which is known as Archil Brown, possessing, however, no great importance. The combination of diazoazobenzenedisulphonic acid with
paratolyl-/3-naphthylamine
is

known

as

Wool- Black.

Azodibenzenephenylenediamine [57].

C 6 H 5N=N-C 6 H 4 -N=NC 6 H 3 (NH 2 ) 2

Is

formed by action of diazoazobenzene chloride on metaphenyIt forms brownish-red needles, which melt at 185, and are easily soluble in chloroform, benzene, ether, and alcohol.
lenediamine.
F

66

CHEMISTRY OF ORGANIC DYESTUFFS.

Azodibenzenetoluylenediamine [57].

From
Forms

diazoazobenzene

chloride

and

metatoluylenediamine.

Sulphonic acids of this compound are formed by using diazoazobenzenesulphonic acids.

light

brown

needles.

Azobenzeneazoparacresol [42],

formed by action of diazoazobenzene chloride on paracresol. forms brown needles, M.P. 160, and dissolves in sulphuric acid with violet colour.
Is

It

The diazoazonaphthalenes combine with sulphonic acids of the naphthols to form dyestuffs, some of which are used on a large
scale.

Diazoazonaphthalenesulphonic

acid,

obtained by combination

of /3-naphthylaminesulphonic acid and a-naphthylamine, reacts

with naphtholsulphonic acids, producing deep blue dyestuffs. One of these comes into commerce as Blue-black or Azo-black, and dyes wool a shade similar to that with nigrosine [68]
.

Other dyestuffs derived from amidoazo-compounds are comprised in the following table
:

Dyestuff.

TETRAZO- COMPOUNDS.

67

phenols or amines ; the nitro-group is then reduced, and the resulting ami do-compound may be diazotised and again combined

with an amine or a phenol.

As an example of

the

method of

procedure the following is cited. Paranitrodiazobenzene combines with diphenylamine to pro-

duce

NO - C H 4 - N = N - C H NH - C H
2
6 6

5,

This body on reduction yields

This

may be
:

diazotised,

and on combination with /3-naphthol

yields

The

dyestuffs obtained in this

as those

manner belong to the same series with the diazo-compounds of paraphenyleneprepared

diamine.

The nitroazo-compounds obtained by combination of nitrodiazocompounds with primary amines may be diazotised and combined with phenols resulting nitrodisazo-compounds on reduction yield amido-compounds, which, when again diazotised and com;

bined with a

phenol, yield tertiary three azo-groups.

azo-compounds, containing

Paranitrodiazobenzene combines with a-naphthylamine, forming

:

N0 - C H N - N - C H NH
2
6

10

a.

This body, on diazotising and combining with /3-naphthol, yields

N0 -C H -N=N-C H -N=N-C H OH/5.

2
6

10

10

On

a diazo-compound
tertiary

reduction of the nitro-group, and treating with nitrous acid, is obtained, which with /3-naphthol yields a

azo-compound
10
6

HOC H

-N=N-C H N=N-C H -N=NC H OH/3.

6

10

10

Numerous
manner, and
article [6.2].

for these reference

azo-compounds were prepared in an analogous must be made to the original

68

CHEMISTRY OF ORGANIC DYESTUFFS.

AZO-DYES FROM BENZIDINE AND ANALOGOUS BASES.

The tetrazo-compounds obtained from benzidine and
similar

bases combine with phenols and amines to produce yellow, red, These have attained considerable blue, and violet dyestuffs.

importance on account of their remarkable property of dyeing form of alkali salts) on unmordanted vegetable fibres.

(in

The

remarked on
dyestuff
:

credit of this discovery belongs to P. Griess, it in his English patent (1884, No. 1099).

who

first

Tetrazodiphenyl combines with naphthionic acid, producing a

C 6 H 4 N2

C 10

which has considerable

application

under the name "Congo

Red"

[64].

The free sulphonic acid is blue, the salts are scarlet, and give the same shade on cotton. These shades, though fast to soap, are unfortunately turned blue by weak acids. This property is less marked in the dyestuff known as Benzopurpurine B. It is obtained [69] from tetrazoditolyl (obtained from o-tolidine and
nitrous acid) and the /3-naphthylaminesulphonic acid, obtained by Bronner from Schaeffer's /3-naphtholsulphonic acid and ammonia.
It will be of interest, before entering into the consideration of these dyestuffs, to examine the constitution of the naphthylamine-

sul phonic acids.

The sulphonic acids of a- and /3-naphthylamine are used for production of azo-dyes in general, their principal application being in the manufacture of the direct-dyeing cotton-colours.
They are produced technically by two methods, either by direct sulphonation of the naphthylamines or by heating the naphtholsulphonic acids with ammonia (i.e., a compound yielding ammonia
on heating).

TETRAZO-COMPOUNDS.

69

As the naplithylaminesulphonic acids are very numerous, only those of technical value will be considered here.
Only one of the sulphonic acids of a-naphthylamine, the
called naphthionic acid,
is

so-

of importance.

I.

Sulphonic Acids of u-naphthylamine.

acid,

Naphthionic

C 10 H 6 ^Q

i,,

NH.

This acid is prepared by heating one part of a-naphthylamine with three to five parts of concentrated sulphuric acid at 100, or

by heating a-naphthylamine sulphate to 180-200.

II.

Sulphonic Acids of p-naphthylamine.

the action of concentrated sulphuric acid on /3-naphthylfirst formed, /3-naphthylaminea-sulphonic acid (corresponding to the croce'm acid from /3-naph-

By

amine two monosulphonic acids are

thol),

and the ^-naphthylamine-7-sulphonic

acid.

are formed, the acid (Bronner's acid /3-naphthylainine-y8-sulphonic corresponding to the Schaeffer acid from /3-naphthol), and /3-naphthlyamineacids

At a higher temperature two other

F-sulphonic acid, corresponding to the F-acid from /3-naphthol. The ft- and F-acids are not products of direct sulphonation, but result from a molecular change in the a- and 7-acids, as both
these
acids, when heated with sulphuric acid, go over into a mixture of Bronner and F-acid. This mixture was termed S-acicl, and its discoverers, Bayer and Duisberg [76], and somewhat later Weinberg [77], showed that it could be split up into two acids the Bronner and the F-acids. These /3-naphthylaminesulphonic acids

may

also

be produced by heating the corresponding naphthol-

CHEMISTRY OF ORGANIC DYESTUFFS.

sulphonic acids with

on heating).

ammonia (i. e., a compound In this manner the crocei'n acid

yielding

ammonia

yields /3-napthyl-

/3-sulphonic acid, and the F-acid of sponding /3-naphthylamine F-acid.

amine-a-sulphonic acid, Schaeffer's acid yields /3-naphthylamineCassella yields the corre-

yet the /3-naphtholsulphonic acid corresponding to /3-naphthylamine-7-sulphonic acid has not been isolated from the acids

As

formed

in

sulphonating /3-naphthol.

The
:

constitutions of

the

acids, according to the

most recent researches, may be graphically

demonstrated by the following formulae

SO,H.

NH,

SOJ-I
a-acid.
/3-acid

(Bronner)

NH

SO,H

NIL

S0 3 H
y-acid.

F-acid.

/3- and F-acids produce fine red with tetrazo-compounds, while the a- and 7-acids give dyestuffs

Of

these sulphonic acids the

worthless yellow ones. As has already been stated, the /3-acid is used in the manufacture of Benzopurpurine B, and the F-acid serves, in combination

with o-tetrazoditolyl, for production of a sparingly soluble, bluishred dyestuff, known as Diamine-red 3 B. If a mixture of both acids (i. e. the so-called S-acid) is used, a
fine mixed dyestuff is produced, which contains one molecule of each acid linked to the benzene chains of the ditolyl. This body forms the principal constituent of the dyestuff known as Delta-

Purpurine 5 B. Mixed dyestuffs of this class are easily obtained, on account of a peculiar property of the tetrazo-compounds. The

TETRAZO-COMPOUNDS.

71

diazo-groups do not react simultaneously with the amine or

The second diazo-group combines with some difficulty, phenol. and indeed the action is frequently aided by warming. Some of these dyestuffs are commercial products.
acid both

/3-naphtholdisulphonic acid (R-acid) and a-naphthol-a-sulphonic combine with tetrazodiphenyl and tetrazoditolyl, forming

blue dyestuffs, which dye directly on unmordanted cotton.

The dyestuff from

acid
is

known
which

tetrazoditolyl and a-naphthol-a-sulphonic as Azo-blue, and produces reddish-blue shades on

cotton,

are,

however, fugitive to light [63]

more

stable dyestuff,
is

purer shade,

which possesses at the same time a obtained from dimethoxylbenzidine,

CH OC H NH
3 6

CH OC H NH
3 6 3

and a-naphthol-a-sulphonic

acid.

It

comes into commerce as

Benzazurine [70]. The combination of tetrazodiphenyl and

as

salicylic acid is known It produces on cotton a somewhat sad Chrysamine [66]. yellow, and serves principally for production of the cream shades

used as groundwork in calico-printing.

Tetrazostilbene
(obtained

by reduction

diazotisation of the resulting diamidostilbenej

acids yield numerous dyestuffs, Hessian Yellow, for example, industrial application.

and and its sulphonic some of which are capable of

of azoxystilbene
is

obtained

by combining tetrazostilbenedisulphonic acid with salicylic acid. The dyestuffs of this class have the property of acting to a
certain extent as

mordants

for basic dyestuffs,

if

and cotton dyed

with them acts with basic dyestuffs as

acid.

prepared with tannic

Frequent application of this property is made in practice. For instance, methylene blue, green, &c., may be dyed on a blue be modified at azo-dyestuff, and in this manner the shades may
will.

The following Table present in the market

:

comprises the principal

direct

dyes at

72

CHEMISTRY OF ORGANIC DYESTUFFS.

Dyestu/.

TETRAZO-COMPOUNDS.

73

TABLE
Dyestuff.

(continued).

Diazotised Base.

Combined with

Delta-Purpurine 7 13 Diamine lied 3 B Rosazurine B

.
. .

Orthotolidine.
.

2 mols. /3-naphthylamineS-monosulphonic acid. 2 mols. methyl-/3-naphthylamine-S-monosulphonic

acid.

1 niol. methyl-/3-naphthyl-

Rosaz urine

G
,

amine-8-monosulphonic
acid.

1 mol. /3-naphthylamine-Smonosulphonic acid.

Azo-Blue

2 mols. a-naphtholsulphonic

Toluylene Orange

acid N.W. mol. cresotic acid. 1 mol. metatoluylenedia1

Toluylene Orange R.

minesulphonic acid. 2 mols. metatoluylenediaminesulphonic acid. 1 mol. /3-naphthylaminedisulplionic acid R. 1 mol. naphthionic acid.

Brilliant Purpurine

Direct lied

Cotton

Red

Diarnidophenyltolyl. Orthometatolidine.

Sulphonazurine
Rosazurine

BB
.

Benzidinesulphone disulphonic acid. Benzidiuesulphone.

Ethoxybenzidine.
-

Diamine Red NO.

Diamine Yellow N

2 mols. naphthionic acid. 2 mols. naphthionic acid. 2 mols. phenyl-/3-naphthylamine. 2 mols. naphthionic acid. 1 mol. /3-naphthylaminesuiphonic acid B. 1 mol. /3-naphthylaminesulphonic acidF. 1 mol. salicylic The proacid, duct is then
1 mol phenol. ethylated. 1 mol. /3-naphthol-d-disul-

Diamine Blue

phonic acid.
1

mol.
mols.

a-naphthol-a-sula-naphthol-a-sul-

Diamiue Blue 3

R
.
.
.

phonic acid.
2

Diamine Black B.

phonic acid. 2 mols. y-amidonaphtholmonosulphonic acid. 1 mol. /3-naphthol-8-disulphonic acid. y-amidonaphtholsulphonic acid. 2 mols. naphthionic acid. 2 mols. /3-naphthylaminesulphonic acid B. 2 mols. a-naphtholsul1 mol.

Diamine Blue-Black E
Benzopurpurine 10 Rosazurine
.

Diauisidine.

Benzoazurine

phonic acid

N.W.

74

CHEMISTRY OF ORGANIC DYESTUFFS.

TABLE
Dyestuff.

(continued).

AZO-COMPOUNDS.

75

Azarin

[67].

The sodium bisulphite compound of an azo -dyestuff, prepared by combining dichlordiazophenol with /3-naphthol, comes into commerce under the above designation. This azo-dyestuff, which is insoluble, has a fine red colour, and
possesses the property of forming a lake with alumina.

By

treat-

ment with sodium

bisulphite

this body,

like all

yields an unstable sulphonic acid, which is If this compound is printed with aluminium acetate, and steamed, the sulphonic acid is decomposed, and the dyestuff combines with

azo-dyestuffs, only slightly coloured.

the alumina to a firmly adhering lake.

its principal application in calico-printing, and a fine red which, though fast to washing, is not suffiproduces ciently fast to light to compete with alizarin.

Azarin finds

obtained by combination of diazotised diamidooxysulphobenzide (phenolsulphone) with /3-naphthol. It is

Another azarin

is

also applied in

form of

its

bisulphite

compound.

Sun-Yellow.
Another dyestuff closely related to the derivative of the so-called azoxystilbene. dye cotton directly from an acid bath.
azo-compounds
Its
is

sulphonic acids

This yellow dyestuff is obtained by heating paranitrotolueneorthosulphonic acid with alkalies. It yields diamidostilbenesulphonic acid on reduction, but whether it is azoxystilbene or

whether a ring-formation between the methane-group and the azo- chain has taken place is doubtful [78, 79]. The compound in question is known as Sun-Yellow.

Thiotoluidines (PEIMULINE) [SO, 81].

By action of sulphur on paratoluidine, a base called thiotoluidine (C 6 3 3

Merz and Weith obtained

2 ) 2 S,

H CH NH
known

M.P. 103.

This

reaction takes place at 140; and if a higher proportion of sulphur and a more elevated temperature be employed, two new thiobases
are

formed, one of which

is

as

dehydrothiotoluidine

76

CHEMISTRY OF ORGANIC DYESTUFFS.

the other is the mother-substance of primuline. sulphonic acid of the latter come into commerce as Primuline, Polychromine,, &c. Primuline dyes unmordanted cotton directly from an alkaline bath, but its principal application is in

C 14 H 12 N2 S, and

The

salts of the

fact that primuline contains

This depends on the an amido-group capable of being diaThis was introduced technically by Green as zotised on the fibre. a method of producing insoluble azo-dyes direct on the fibre, the
connection with the so-called developers.

goods dyed with primuline being diazotised in a slightly acid bath with sodium nitrite, and then passed into the various yellow, red,
&c. developers, which consist of certain amines and phenols in suitable solvents.

Erica.
Metaxylidine gives similar compounds if treated with sulphur. of these, M.P. 107, possesses one amido-group capable of being diazotised, and certain of the azo-dyes prepared with it form the various brands of Erica. These dyestuffs have the remark-

One

able property of dyeing cotton

from a bath containing sulphate

of

soda, producing pleasing pink shades of considerable fastness. Erica B is the result of the combination of dehydrothiometa-

xylidine with a-naphthol-e-disulphonic acid.

Thiaflavine.
Thioflavines, although not azo-dyes, are closely related to Primuline, and may therefore be described here.

The

action of methyl chloride on dehydrothiotoluidine from the primuline melt, two compounds are formed, one of which comes into commerce in the form of its hydrochloride as Thioflavine T.

By

It is a basic dyestuff,

producing

fine

greenish shades of yellow.

The second product of the reaction, which is separated from the previous one by means of its sparing solubility in dilute hydrochloric acid, yields on treatment with fuming sulphuric acid a sulphonic It acid, a salt of which is sold under the name of Thioflavine S.
is

a substantive dyestuff applied to cotton from an alkaline bath. Thioflavine T is a dimethyldehydrothiotoluidine-methyl chloride

of the formula

AZO-COMPOUNDS.

77

CH
CH
3

Cl

C6H3<
is

/K ^C
\S^

C6H4

N(CH ) HC1
3

and Thioflavine S

dinesulphonic acid,

C 16 H 15 N2 S 2 O 3 Na.

a sodium salt of dimethyldehydrothiotolui-

DIRECT PRODUCTION" OF AZO-DYES ON THE FIBRE.

Azo-dyes prepared by interaction of a diazo-compound and a phenol are insoluble in water, and therefore of no practical value. For this reason a sulpho-group is introduced (see p. 84), and this
produces the solubility necessary for their application in ordinary dyeing processes. These sulphonated azo-dyes have a considerable
tetrazo-series)
silk, but (with the exception of those of the are not easily fixed on cotton. Cotton may be dyed with certain azo-dyes of the Crocem series, but the shades produced are not fast to washing.

affinity for

wool and

The

ease with which the combination of a diazo-compound and

a phenol takes place, and the purity of the resulting product, doubtless led to the idea that insoluble azo-dyes might be pro-

duced by direct precipitation on vegetable fibres. Messrs. Holliday were the first to make a practical application of the diazo-reaction in this direction, and in 1880 they patented processes whereby azo-dyes might be produced on vegetable fibres. Three alternative methods are prescribed
:

I.

The goods are impregnated with an alkaline solution phenol, and the colour produced by passage through a
tion of a diazo-compound.

of a
solu-

II.

The above
applied

process

is

reversed,

the diazo-solution being

first.

III.

The goods
alkali.

are impregnated with a mixture of diazo-compound and phenol, and the colour developed by passage through

Grassier, in the same year, brought out a process whereby the use of acid to develop the nitrous acid necessary for diazotisation

78
is

CHEMISTRY OF ORGANIC DYESTUFFS.

avoided.

A mixture of an amine, sodium nitrite, ammonium and a phenol is thickened, and the goods impregnated or printed with the mixture, and the colour developed by drying and steaming. A shade closely approaching Turkey red is obtained by using a mixture of xylidine and /3-naphthol. A process which has been used for silk-dyeing is similar to that of
chloride,

A diazo-compound in solution is neutralised by Messrs. Holliday. and a phenol (/3-naphthol) obtained in a fine state of division by precipitation is added. On working the goods in this mixture,
chalk,
is gradually developed and is fixed on the fibre. Messrs. Meister, Lucius, and Briining have recently modified the Holliday process, and adopt a method somewhat resembling

the colour

the last described.

It

was found that the presence of

free mineral

acid in the solution of the diazo-compound is disadvantageous, and that brighter and more even shades are obtained if the free acid is

neutralised by addition of chalk, or replaced by acetic acid, this The goods are being effected by addition of sodium acetate. worked first in the phenol dissolved in water in presence of two

of the

molecules of caustic soda, dried, passed into the prepared solution diazo-compound, and washed till the wash-waters are

colourless.

In general the theoretical proportions indicated by equation are adhered to in the preparation of the diazo-solutions ; certain bases, however, are not easily soluble, and are brought into commerce

amine and the amount of The diazo-solution is obtained by solution in the calculated amount of dilute hydrochloric acid. The red shades obtained by this process become duller on soaping, with the exception of those from the amidoazo-compounds. The shades obtained from amidoazo-compounds are also faster to The shades obtained with light than those from simple amines.
in pastes containing 25 per cent, of
nitrite necessary for diazotising.

/3-naphthol are bright orange-yellow to red, those from a-naphthol shade approximating to Turkey red is having a brown tone.

obtained from /3-naphthol and diazotised /3-naphthylamine. The above processes are purely mechanical, the goods being simply impregnated with the diazo-compound, or phenol. Another
is first

an important respect that the amine actually fixed, by dyeing, on the fibre. It has already been mentioned that primuline (an amine) may be fixed on cotton,
differs in

group of methods

AZO- COMPOUNDS.

79

diazotised on the fibre,

and new azo-colours produced by passage

through developers, i. e. solutions of amines or phenols capable of combining with the diazo-compound of primuIt is evident that this method must be more advantageous line. than those in which the diazo-compound is in mere mechanical incorporation with the fibre, shades produced by the latter process
of the goods

being more liable to rub.

Of

late a

new

class of direct-dyeing cotton -colours

has been

introduced.

These contain one or more free amido-groups capable of diazotisation, and are therefore suitable for direct production of azo-dyes on the fibre. Amongst these dyestuffs are Diamine BlueThese dyestuffs Black E, Diamine Black B and R (see Table). are combinations of diazotised bases of the Benzidine series with one or two molecules of an amidonaphtholsulphonic acid, and
these amido-groups, in the naphthol

compound remaining intact, be diazotised. may subsequently Cotton is dyed in a bath containing Glauber's salt and a little soap or soda, and the shades produced vary from dark blue to bluish black, about 6 per cent, of dyestuff being necessary to produce a maximum effect. The diazotising is effected by a bath of
nitrite acidified with hydrochloric acid. The developingbath varies according to the shade required. Resorcin, /3-naphthol, and phenylenediamine produce blacks of various shades ; blues are

sodium

obtained with naphthylamine ether

and mixtures of these deve-

lopers produce blacks of every conceivable shade. In all these processes depending on the use of diazo-compounds

the principal point

is

to

work

pounds decompose with a

as cold as possible. Diazo-comslight elevation of temperature, and are

unstable at ordinary temperatures, and therefore it is necessary to work as expeditiously as possible. In the Holliday and allied processes,

where a diazo-compound
;

is

used in solution, ice

is

frequently
is

necessary for its preservation

duced on the

fibre, this is

where the diazo-compound not of such great moment.

pro-

80

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER

III.

OXYQUINOKES AND QUINOKEOXIMES.

THE quinones belong to the most
this is equally true of

powerful class of chromogens, and both the para- and orthoquinones. They yield actual dyestuffs by introduction of auxochromic groups. The oxyquinones possess a specially marked dyestuff-character, as the quinone group belongs to the acid-forming chromophors, and the hydroxyl group introduced develops powerful acid properties. All the oxyquinones are coloured and form salts of still darker Most of them may be fixed directly on animal fibres, but colour. the shades obtained are weak and without value.

The true character of a number of these bodies only appears

their combinations with metallic oxides
;

in

" " quinones belong to the class of mordant-dyeing colouringmatters. They are especially distinguished fastness of their metallic lakes.

in other words, the oxy-

by the beauty and

An interesting property in connection with these bodies is that only such oxyquinones as have one hydroxyl group in the ortho-position to the quinone-oxygen possess this power of dyeing
on mordants, and that in general it is necessary to have simultaneously two hydroxyl-groups in the ortho-position to each other
[32, 33]. The rest of the

oxyquinones form coloured metallic

salts

which

are often insoluble, but which do not possess the essential property of adhering to fibre.

The oxyquinones of the benzene series contain at least one hydroxyl group besides the quinone-oxygen, and so far as they have been examined are capable of dyeing on mordants in a greater
or less degree.

and

nitranilic acid (dinitrodioxyquinone)

Tetroxy quinones, rhodizonic acid (dioxydiquinpyl) have great power in this

OXYQUINONES AND QUINONEOXIMES.

direction, while it is present to only a slight extent in and chlor- and bromanilic acids.

81

dioxyquinone
slight,

The

tinctorial

power of these bodies

is,

however,

and a

dyestuff of sufficient intensity and stability is only reached in the naphthalene series. This is naphthazarin, a dioxyquinone of un-

known

constitution.

The quinoneoximes closely resemble the oxyquinones in their properties. Only compounds derived from orthoquinones are Mono- or dioximes are formed capable of fixation on mordants.
by substitution of one or both quinone-oxygen atoms in an orthoquinone by the isonitroso-group NOH. Both may be dyed on metallic mordants, especially on iron or cobalt oxide. The mono-oximes, however, are more useful in this respect, and have for some time been applied technically.

Naphthazarin

Dioxynaphthoquinone).
2

C 10 H 4
This

(OH) 2

and

for

compound was discovered by Roussin in the year 1861, some time was thought to be alizarin. It is obtained by

heating a-dinitronaphthalene with concentrated sulphuric acid, fragments of zinc being added to the hot solution. It sublimes in

brown

It is sparingly soluble needles, with a cantharides lustre. in water, easily in alcohol and glacial acetic acid, with a red colour. It forms a blue solution with alkalies and a red one with strong

It combines with sodium bisulphite, and the comformed dissolves readily in water. Naphthazarin dyes pound excellently on mordanted fibres, giving a violet on alumina and a grey on chromic oxide. Naphthazarin has recently been introduced into commerce as The commercial product is the bisulphite comAlizarin Black. and finds its principal application in printing. For this pound, purpose it is mixed with chromium acetate. On steaming the bisulphite compound is decomposed, and the naphthazarin combines with the chromic oxide to form a firmly adhering lake.

sulphuric acid.

ANTHRAQUINONE DYESTUFFS.
its

Anthraquinone itself has only a slight yellow colour, while all hydroxyl derivatives have a more or less marked colour, gene-

rally orange-yellow to red.

The

solutions of the alkali-salts are

82

CHEMISTRY OF ORGANIC DYESTUFFS.

Certain of these bodies possess affinity for

generally red or violet.

and may be fixed like acid colours, but the shades have no practical value. produced The utility of these dyestuffs depends solely on their capability
animal
fibres,

of forming insoluble lakes with metallic oxides. These lakes may be firmly fixed on textile fibres, their colour varying according to

the nature of the metal.

Indeed the metallic compounds of these

bodies

may be

looked upon as so

many

different dyestuffs.

Of the numerous hydroxyl

those which have two

derivatives of anthraquinone, only hydroxyl-groups in the 1, 2-position to the

carbonyl-group of anthraquinone are capable of dyeing upon mordants. In other words, only alizarin and its derivatives possess
this property.

As

the

number

of anthraquinone derivatives

is

very

large, value.

we must

necessarily confine ourselves to those of technical

Alizarin [2,

3].

C 14 H 8 O4

Alizarin is one of the few natural dyestuffs which have been prepared synthetically, and is probably the only one which is preIt occurs pared artificially on the large scale. generally as a

C 26 28 O 14 [1, 2] in madder, the root of Rubia tinctorium, and also in some other plants. Ruberythric acid splits up by boiling with dilute acid, or by fermentation, glucose and alizarin being formed.
glucoside, ruberythric acid

C 26 H 28

14

+ 2H

=C H
14

+ 2C H 12
6

Alizarin crystallises in reddish-brown needles, which are almost insoluble in water, sparingly soluble in alcohol, more easily in hot It melts at glacial acetic acid, carbon disulphide, and glycerine.
C., and sublimes at a higher temperature in beautiful red needles. It dissolves in alkalies with a violet colour, and long the sparingly soluble acid salts may be precipitated from these solu-

289 to 290

tions

by carbonic acid. On oxidation with nitric acid it gives phthalic acid, and by heating with zinc powder anthracene is formed. With the oxides of aluminium, barium, calcium, iron, and
most of the heavy metals it gives characteristic coloured insoluble The red alumina lake, the maroon chromium lake, and the

lakes.

violet- black iron lake are of

The hydroxyl-groups

importance in dyeing. in alizarin are in the adjacent positions

OXYQUINONES AND QUINONEOXIMES.

to one carbonyl-group of anthraquinone, and its constitution be expressed by the following formula [4]
:

83

may

CO

OH

alcohol and acid radicals.

The hydroxyl-hydrogen atoms of alizarin may be replaced by The alkyl derivatives are easily obtained
alizarin with the requisite alkyl iodide in presence of Mono- and di- derivatives may be obtained in this

by heating

caustic alkali.

manner

[5, 6].

Acetic anhydride gives a diacetyl derivative, M.P. 160 C. [7]. Chlorine acts on alizarin, forming a monochloralizarin ; with

antimony pentachloride, dichlor-

maybe

obtained.

and finally tetrachlor-alizarin bromine derivatives have also Corresponding

[8]

been prepared

[8, 9,

10]

heating with ammonia in sealed tubes two isomeric alizarin amides (oxyamido-anthraquinones, C 14 6 O 2 (OH)NH 2 ) are The principal product of the reaction is the meta-comobtained. pound with a small quantity of the ortho.

On

met with

Sulphonic acids of alizarin have also been prepared, and are in commerce under the name of Alizarin Red S.

Alizarin may be prepared artificially by fusing dibromanthraquinone, nitroanthraquinone, or anthraquinonesulphonic acid with potash or soda [3] ; also by condensation of phthalic acid with

pyrocatechin [4], and by reduction of rufigallic acid [13]. Alizarin has only been prepared on an industrial scale from anthra-

quinone, and the artificial product has practically displaced madder in the course of the last twenty years.

was first effected by Graebe and These chemists had already observed the formation of anthracene from natural alizarin by heating with zinc powder, and recognizing alizarin as a derivative of anthraThis aim cene, attempted to convert anthracene into alizarin, was accomplished by fusion of bibromanthraquinone with potash. In the same year Graebe, Liebermann, and Caro [14] discovered
alizarin

The synthesis of Liebermann in 1869.

the formation

of

alizarin

by melting anthraquinonesulphonic

G2

84

CHEMISTRY OF ORGANIC DYESTUFFS.

This process, which is in use at the acid with caustic potash. was discovered almost simultaneously by W. H. present day,

Perkin [15]. Other processes have been proposed for the manufacture of alizarin, for instance by melting dichloranthraquinone or nitroanthraquinone [16] with caustic potash, but these processes have
never attained commercial importance. For a long time it was thought that the anthraquinonedisulphonic acids gave rise to the formation of alizarin, but this

assumption was based on an error.

is

The monosulphonic

acid alone

giving alizarin, while the disulphonic acids yield and flavopurpurin. This was already known to some isopurpurin technologists in 1871, but was first published by Perkin in 187(>
capable of
[17].

The formation of alizarin from anthraquinonesulphonic acid On the one does not appear to be due to any uniform reaction. is formed and becomes oxidised in the hand, oxyanthraquinone
alkaline

melt

to

nonesulphonic acid
alizarin

alizarin; on the other hand, oxyanthraquiis also a constituent of the melt, and yields
its

by replacement of

sulpho-group by hydroxyl.

Aliza-

It rinsulphonic acids are also often found in the alizarin melt. is not improbable that these different reactions are due to the

existence of several isomeric anthraquinonesulphonic acids. For the manufacture of alizarin on a large scale a very pure anthraquinone is required, and this is generally prepared by oxi-

dation of anthracene with sodium bichromate and dilute sulphuric The anthracene is generally a 50-per-cent. product which acid.

has oeen converted into a soft powder by subliming with superheated steam. The oxidation takes place in lead-lined vessels in which the mixture is heated by direct steam. By employing a

pure anthracene and a not too concentrated oxidation-mixture, the anthraquinone separates as soft grey powder, which is freed from The crude product is then dried, acid by washing with water. dissolved in concentrated sulphuric acid, and precipitated with water. A further purification is effected by sublimation with
superheated steam.

For production of monosulphonic acid a somewhat concentrated fuming sulphuric acid (containing 30 to 40 per cent, anhydride) is required, and the sulphonation should take place at as low a
temperature as possible.

OXYQUINONES AND QUINONEOXIMES.

85

acid is separated from the disulphonic acids formed by fractional crystallisation of the sodium simultaneously salts. By saturating the acid mixture with soda, the salt of the monosulphonic acid separates first. At present the sulphonation
is

The monosulphonic

carried out so as to produce as

much monosulphonic

acid as

possible with only a little disulphonic acid. As has already been stated, the reaction in the melt proceeds in two directions, viz., a substitution of the sulpho-group by hydroxyl

and a direct oxidation. In the older processes this oxidation was effected by air, and if the supply of this was insufficient, took place at the cost of some of the materials. To prevent this a large surface of the melt was
exposed to the air by melting in shallow pans. This process has been abandoned for about ten years, and the atmospheric oxygen is dispensed with by adding an oxidising agent (potassium chlorate), and operating in closed vessels under pressure.
is

This improvement is of great advantage, as the temperature easily regulated, even if the melt contains much water; while in

open vessels a certain concentration is necessary before the required temperature is reached. In place of the older melting process,
the sulphonic acids are

now heated with

concentrated soda-lye
'

under pressure.

The operation takes place in a horizontal

fitted

with a

stirrer.

cylindrical iron vessel Into this are introduced one part of anthra-

quinonemonosulphonate of soda, with about three parts of caustic soda and a certain amount of water and chlorate of potash. The mixture is then heated several days to 180-200. The melt is then dissolved in water and the sodium compound

The precipitate of decomposed by adding hydrochloric acid. alizarin is then well washed, and brought into commerce as a 10 to 20 per cent, paste. Its value may be ascertained by an estimation of the solid matter and ash, a dye-trial also being made. Blue and yellow shades of alizarin are known the former con;

of pretty pure alizarin, while the latter contain both the Alizarin trioxyanthraquinones isopurpurin and flavopurpurin.
sists

be fixed directly on wool, the shade produced being weak, and of the yellowish-red tone characteristic of free alizarin solutions. This shade has no value in dyeing, and the application of alizarin is solely in form of its brightly coloured aluminium, chromium, and

may

iron lakes.

86

CHEMISTRY OF ORGANIC DYESTUFFS.

Most of the

alizarin

made

is

used in cotton-dyeing and

printing,,

although a considerable amount is also used in wool- dyeing. Alizarin gives entirely different shades with different metals.
violet-black iron lake are almost exclusively used.

In dyeing and printing the beautiful red alumina lake and the Sometimes the

chromium lake

is

cotton, the latter is impregnated with the necessary metallic oxide, and brought into a bath containing alizarin in a fine state of suspension, the bath being gradually heated to boiling; although alizarin is so slightly soluble in water, its solubility is sufficient to effect its combination with

In order to dye

also applied. alizarin on

For test-dyeing with alizarins the metallic oxide on the fibre. This calico contains stripes of alumina and calico is used. printed
iron and mixtures of these, printed in different degrees of strength, and on dyeing in an alizarin-bath various shades are obtained.

In printing, a mixture of alizarin paste and aluminium or iron On steaming, the acetate is decomposed, and the acetate is used.
formation of the colour-lake takes place. In alizarin-dyeing, a great number of purely empirical operations
Brilliant especially in turkey-red dyeing. of turkey-red can only be obtained on alumina and The oil formerly used was a very rancid olive-oil, oil mordants. " Huile tournante," but this has been entirely replaced by the

are

common,

scarlet tones

This product is a ricinoleate of ammonia, oil. obtained by treating castor-oil with strong sulphuric acid, and It is probable neutralizing the separated fatty acid with ammonia. that the alumina forms double compounds with the fatty acids and
so-called turkey-red

with the alizarin, these compounds possessing a more brilliant colour than the simple alizarin lakes. The turkey-red process is very complicated, and comprises many operations which are not

For instance, treatment in a bath of cowproperly understood. dung and other similar processes.

Wool is mordanted with alumina, for alizarin-dyeing, generally by boiling in a bath of alum tartar. Chromium mordants are also used in connection with alizarin for production of maroon
shades.

The shades obtained with

alizarin are very stable.

They

resist

the action of soap and bleaching-powder, and are almost entirely unaffected by light.

OXYQUINONES AND QUINONEOXIMES.

Nitroalizarin [18, 19].

87

C 14 H 7 (N0 2 )0 4
Only the /3-nitro-compound

(of the constitution

OH OH NO

(1)

(2)

(3)

2)

It may be obtained by treating possesses technical interest. alizarin, suspended in toluene or nitrobenzene, with nitrous acid, or by cautious nitration of alizarin dissolved in glacial acetic acid

with nitric acid.

Pure
at
leaflets,

/3-nitroalizarin

forms orange-yellow needles, which melt

.

244, with

partial decomposition [19]

It sublimes in yellow

undergoing partial decomposition. It dissolves in benzene and glacial acetic acid, and gives a purple-red solution with The violet lime-lake is not decomposed by carbonic alkalies. acid. (Distinction from alizarin.) It forms a diacetyl compound, M.P. 218 [19]. Nitroalizarin dyes orange shades on alumina mordants, and reddish- violet on iron mordants. It comes into commerce in paste as Alizarin Orange, and is used in dyeing and printing, though its principal application is in the manufacture of Alizarin Blue.

TRIOXYANTHRAQUINONES.

C M H 5 (OH) 3
A. Purpurin

2.

[position i, 2, 4].

Purpnrin occurs with alizarin in the madder root [20], proIt may be obtained artificially from bably also as glucoside. alizarin by heating with manganese dioxide and sulphuric acid
[21], or arsenic acid; and also by melting an alizarinsulphonic acid (the so-called alizarin purpursulphonic acid) with potash

EH].
Purpurin forms long orange-yellow needles which contain one molecule of water. It dissolves pretty readily in alcohol, ether, and benzene, and is also much more easily soluble in water than It loses its water of crystallisation at 100, and sublimes alizarin.

M.P. 253. at a comparatively low temperature. The alkaline solutions of purpurin are reddish
rapidly become bleached on exposure to
light

violet,
air.

and

and

The

presence of certain metallic oxides produces a characteristic effect on the absorption-spectrum of purpurin solutions, and these may

88

CHEMISTRY OF ORGANIC DYESTUFFS.

.

Purserve for the detection of alumina and magnesia [22, 23] dissolves in boiling alum solution, forming a yellowish- red puriii fluorescent solution, from which the purpurin separates on cooling.

As alizarin is almost insoluble in alum solution, this method is used for the separation of these bodies. Although the alkaline solutions of purpurin are easily bleached by light, the alumina
lake
is

perfectly stable against this agency.

alumina mordants purpurin produces a beautiful scarlet much yellower in tone than that from alizarin, but its applired, cation is limited, as its price is much higher than that of isopurpurin.

On

B. Isopurpurin (Anthrapurpuriri) [24, 25, 26].

Isopurpurin
acid with
acid,

is

obtained by melting /3-anthraquinonedisulphonic

.

caustic potash, an isomer of alizarin, isoanthraflavic

being formed as a bye-product [26] In the first stage mono-oxyanthraquinonesulphonic

acids,

are formed, and these are oxidised to alizarins ulphonic acids, a small portion being converted into anthraflavic acids. These alizarinsulphonic acids yield the purpurins by exchange of a sulphof or

an hydroxyl group [42] It forms orange needles, which are soluble in alcohol but inIts M.P. is above 330 [25]. soluble in benzene. It yields no
.

phthalic acid on oxidation, and therefore probably contains the third OH-group in the second benzene ring. Isopurpurin is the

a fine scarlet red on alumina

little

It dyes principal constituent of the commercial alizarin for red. its iron lake is greyish violet, and of ;

value.

C. Flavopurpurin [26, 27].

OH
acid
;

T41

C H I C6H3
is

|[2]

CO M CO [m c H
[2] j

C(jH2

f [6]

OH
OH'

[5]

Flavopurpurin

obtained

anthraflavic acid, an isomer of alizarin,

from a-anthraquinonedisulphonic is formed as a bye-

OXYQUINONES AND QUINONEOXIMES.

product.

89

It forms golden-yellow needles, easily soluble in alcohol,

M.P. above 330 C. It dissolves with purple-red colour in caustic soda, and yellowish-red in ammonia and sodium carbonate. On alumina mordants it gives a red, which is still yellower than
Its principal application is in printing, that with isopurpurin. Anthraflavic acid and while that of isopurpurin is in dyeing. isoanthraflavic acid sometimes occur in the commercial products. They are entirely valueless in dyeing, and are produced in badly

conducted operations. Like isopurpurin, flavopurpurin contains the third hydroxylgroup in the second benzene nucleus.

D. Anthragallol [41].
is

This trioxyanthraquinone is not prepared from anthracene, but In obtained by condensation of gallic acid with benzoic acid.

anthragallol the three hydroxyl- groups occupy adjacent positions

[1: 2: 3]. It is prepared
gallic

acid

by heating equal molecules of benzoic acid and The following with concentrated sulphuric acid.
:

equation expresses the reaction which takes place

II

OH

CO

OH

Anthragallol has a brown colour, and dyes brown shades on alumina or chromic oxide. The commercial Alizarin Brown is a mixture of anthragallol with more or less rufigallic acid. The latter compound is hexaoxyanthraquinone, and is formed in a similar manner to anthragallol by condensation of gallic acid.
It belongs to the

mordant anthraquinone- derivatives.

Alizarin Bordeaux and Alizarin Cyanine [38, 39].

treating dry alizarin with a large quantity of sulphuric acid containing 70 per cent, anhydride, a peculiar ether of sulphuric acid
is

On

obtained, which on boiling with water splits

up

into a

uew

34

90
dyestuff,

CHEMISTRY OF ORGANIC DYESTUFFS. " Alizarin

is

Bordeaux

Bordeaux, and sulphuric acid. This alizarin a tetraoxyanthraquinone identical with quinalizarin Oil CO OH
:

OH

CO

This dyestuff produces fine Bordeaux shades on alumina mordants, and in colour-printing a blackish blue is obtained with a

chromium mordant. On wool a deep claret with a violet tone may be obtained. Alizarin Bordeaux crystallises from nitrobenzene in fine red needles which have a metallic lustre. It may be distilled,

undergoing only slight decomposition. Bordeaux be dissolved in concentrated sulphuric acid and treated with manganese peroxide or arsenic acid, oxidation takes place, a pentoxyanthraquinone being formed
If alizarin
:

OH

CO

OH

OH

CO

OH

This body comes into commerce as Alizarin Cyanine R or as Alizarin Blue CR. Alizarin cyanine crystallises from glacial
acetic

acid in beautiful

crystals,

and dissolves in concentrated

If sulphuric acid with a blue colour and a fine red fluorescence. dyed on cotton mordants with alumina, fine violet shades are produced, and chromium mordants give dark blues. In the pre-

paration of alizarin cyanine R, a sulphuric ether is formed as intermediate product, and on treating with ammonia this body
yields a dyestuff
it

which

differs

from

alizarin cyanine

R inasmuch as

produces considerably greener shades. It is also a commercial product, and is sold under the name Alizarin Cyanine G. Analogous series of reactions may be carried out with the isomers

" Bordeaux" and " Cyacorresponding to those described above may be obtained from purpurin, anthrapurpurin, flavopurpurin, and anthragallol.

and homologues of " nines

alizarin, for

example,

OXYQUINONES AND QUINONEOXIMES.

91

Alizarin Slue [28, 29, 30].

This dyestuff is prepared by heating /3-nitroalizarin with It is peculiar in so far that it glycerine and sulphuric acid. possesses the lake-forming properties characteristic of the alizarin
Alizarin blue was dyes, and is at the same time a weak base. discovered by Prud'homme [28], and the determination of its

by Graebe [29] led to the synthesis of quinoline by Skraup from glycerine, nitrobenzene, and aniline. Alizarin blue has the composition C 17 H 9 NO 4 and stands in the same relation to alizarin as quinoline to benzene. Its constitutional formula is as follows [29]
constitution
,
:

CO

OH

In the pure state (crystallised from benzene) it forms brownishviolet needles, insoluble in water and difficultly soluble in ether

and

alcohol.
It

It melts at

270, and sublimes, forming orange

dissolves in alkalies with a blue colour, an excess of alkali turning the solution green. Its salts with acids are of a

vapours.

reddish colour, and are decomposed by water.

On

distillation

C 1T H U N [29]. With chromium

lake.

with zinc powder

it

yields

anthraquinoline,

oxide, alizarin blue gives a stable indigo-blue

It is chiefly applied in the

latter

form of its bisulphite compound, the

being the principal constituent of the commercial Alizarin Blue S [3]]. This is a reddish-brown compound and is decom-

posed on heating, alizarin blue separating. The bisulphite compound is printed with acetate of chromium ; and, on steaming, the

The bisulof alizarin blue is fixed on the fibre. compound may be precipitated from its solutions by common phite salt, and comes into commerce as an easily soluble brown powder.

chromium lake

92

CHEMISTRY OF ORGANIC DYESTUFFS.

Alizarin Indigo-blue S, Alizarin Green S [40].

may be oxidised by action of fuming sulphuric the process being analogous to that used for the preparation acid, At 50 to 60 a dyestuff called Alizarin of Alizarin Bordeaux. is formed, and is best isolated in form of its bisulphite Blue-green compound. It is a monosul phonic acid of mono-oxyalizarin blue.
Alizarine blue
If the mixture be heated to 120, or if alizarin blue-green is heated with concentrated sulphuric acid to 120, an intramolecular change takes place, a new mono-oxyalizarin blue monosulphonic

This body acid being formed. known as Alizarin Green S.

If,

is

an

article of

commerce, and

is

finally,

the temperature of the reaction between sulphuric

to

acid and alizarin blue be raised to 200

is

210,

or if alizarin

green phuric acid, a third dyestuff, Alizarin Indigo-blue, is obtained. This body is a trioxyalizarin-blue. The commercial products are The shades propastes which contain the bisulphite compounds.

heated to the same temperature with concentrated sul-

duced in dyeing are sufficiently indicated by the names, being a The best dull indigo-blue and a dull bluish green respectively. results are obtained with chromium mordants.

Styrogallol [36, 37].

This

compound

is

obtained by heating gallic acid with cinnamic

It forms light yellow acid in sulphuric acid solution to 55. M.P. 350. It is insoluble in water, and sparingly needles.

soluble in alcohol, glacial acetic acid, and aniline. Its solution in alkalies is green, changing through violet to red

on warming.
red colour.
Styrogallol

It dissolves in strong sulphuric acid with a yellowish-

is

probably an o-dioxyanthracoumarine.

On warming
is

with acetic anhydride a diacetyl derivative,

M.P. 260,

obtained.

alumina mordants it dyes an orange-yellow shade, similar to alizarin orange, but owing to its high price has not been used
practically.

On

dibrominated dioxy-/3-methylcoumarine cially as Anthracene Yellow.

is

known commer-

OXYQUINONES AND QUINONEOXIMES.

93

QUINONEOXIMES.
These compounds are obtained by action of nitrous acid on but this phenols, and were formerly regarded as nitrosophenols ; assumption has gradually been abandoned. They may also be obtained by action of hydroxylamine on quinones, and yield
dioximes on further treatment with this reagent.
i. e.,

It is therefore

more probable that the nitrosophenols are really oximes of quinones, quinones in which one oxygen atom is replaced by the divalent

group

=N

OH.
O

NOH

O
Quinone.

O
Quinoneoxime
(Nitrosophenol).

The quinoneoximes,
possess
little tinctorial

like the quinones, are

power.

mostly yellow, but Certain oxime-derivatives of ortho-

quinones, however, like oxy quinones, are capable of combining with mordants (especially iron and cobalt), forming highly coloured
lakes

which may be fixed on

textile fibres.

of this latter class of quinoneoximes are described in as they have attained some importance as adjective dyedetail,
stuifs.

Some

Dinitrosoresorcin (Diquinoyldioxime) [32].

C6H2

(NOH) 2

This compound is obtained by treating an aqueous solution ot resorcin with nitrous acid (sodium nitrite and sulphuric acid). Dinitrosoresorcin crystallises from alcohol in yellowish-brown
leaflets,

acid,

which deflagrate at 115. It is a pretty strong dibasic and forms easily soluble salts with alkalies. Its constitution is probably expressed by the following formula

[33]

:_

CHEMISTRY OF ORGANIC DYESTU1TS.

dinitrosoresorcin is green, and the latter shades on cotton prepared with iron mordants. It produces green has been used for some time in cotton-dyeing under the name

The iron lake of

" Fast Green."

Naphthaquinoneoximes [34].

C 10 H 6 0(NOH).
/3-naphthaquinone yields two oximes, both of which are capable of dyeing on mordants, while this property is absent in the oxime of a-naphthaquinone (a-nitroso-a-naphthol),

NOH

/3-naphthol,

a-nitroso-/3-naphthol is obtained by action of nitrous acid on while a-naphthol under similar treatment gives

/3-nitroso-a-naphthol,

NOH

along with some a-a-compound.

Both derivatives of /3-naphthaquinone give intensely green lakes with ferric oxide, while their cobalt lake is dark red, being known

OXYQUINONES AND QUINONEOXIMES.

in

95

commerce as Gambine and respectively ; but they are not of great importance. The iron salt of a sulphonic acid of the a-/3-compound comes into commerce as Naphthol Green [38, 39]. The sulphonic acid is prepared by acting on Schaeffer's acid
with nitrous acid.

The iron compound of this acid is soluble and is fixed on animal fibres like the acid dyestuffs. water, Naphthol green is used to some extent in wool-dyeing.

in

The

dyestuff

known

as Dioxine

is

a nitroso-derivative of

T8

dioxynaphthalene.

96

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER

IV.

KETONEIHIDES AND HYDRAZIDES.

THESE
bodies, certain of which have been used as dyes tuffs, are derived from the simple ketones in the same manner as the quinoneimides and quinone-hydrazides from the diketones (quinones). Here, however, the chromophor occurs in an open carbon chain,

and
is

a weak character, requires a salt-forming The colour produced to develop the properties of a dyestuff. group
as it is only of

always yellow. It has already been remarked that the CO group, when it does not occur as a member of a closed carbon ring, cannot act as a

chromophor, and only becomes one when the oxygen is replaced by sulphur or by a nitrogenous group. So far as the present state of knowledge reaches, all benzophenone derivatives are On the other hand, thiobenzophenone yields coloured colourless. derivatives. Tetramethyldiamidothiobenzophenone [3]
:

(CH 3

NC H
6

for example, is intensely yellowish red, but is no dyestuff. If the sulphur in this compound be replaced by the imide-group

NH,

stuffs

auramine, the only representative of the ketoneimide dyeknown, is formed. The starting-point for the manufacture of auramine is tetra-

methyldiamidobenzophenone,

(CH 3

NC H/
6

This base was discovered by Michler [2]

in

1876, and has

KETONEIMIDES AND HYDRAZIDES.

recently

97
manufacture of

become an important product

for the

triphenylmethane dyestuffs. Tetramethyldiamidobenzophenone is obtained by action of carbon oxychloride or of perchlorformic ether on dimethylaniline. The analogous thioketone already mentioned is obtained in a similar manner from carbon sulpho chloride, CSC1 2? and dimethylaniline; it may also be obtained by treating the corresponding

oxygen ketone with phosphorus sulphide.

.

The two ketones are

similar in their reactions [3] By action of nascent hydrogen, tetramethyldiamidobenzophenone is converted into the corresponding benzhydrol [1]
:

(CH 3
(CH 3

) 2

NC H OH 4xc/ X NC H/ H
6
'

This compound combines with acids to form beautiful blue salts, which, like the dyestuffs of the rosaniline series, are deIt is probable that in these coloured colorised by excess of acid. salts the compound exists as an anhydride, as is the case with the
rosaniline salts.

The hydrochloride, for instance, has the

consti-

tution

(CH 3
(CH 3

)2

N-C H N-C H /C-H.

6

ci

71

The chloride obtained by treating tetramethyldiamidobenzophenone with a phosphorus chloride is probably not the simple
chloride

(CH 3

) 2

(CH 3
but, as
it

)2

N-C H >C=C1 N-C H/

6

possesses a deep blue colour,

:

is

constituted according to

the formula

(CH 3

)2

^ N-C H/- CL
6

ci

71

98

CHEMISTEY OF ORGANIC DYESTUFFS.

Auramine [1, 4, C 17 H 21N 3

H. Caro, and

5, 7].
.

This dyestuff was discovered simultaneously by A. Kern and is formed by action of ammonia on tetramethyl-

diamidobenzophenone. It is best prepared by melting this base with ammonium chloride and zinc chloride. The reaction is
expressed by the equation
:

C 17 H 20N 2
Another process
allowing

+ NH = C 17 H 21 N 3 + H O
3 2

for the

manufacture of auramine consists in

at

ammonia

to act on a mixture of tetramethyldiamidodi-

phenylmethane or tetramethyldiamidobenzhydrol with sulphur

180. Auramine

is

also prepared industrially as follows

is

Dimethylamidobenzoic chloride gene on dimethylaniline ;

produced by action of phos-

+ COC1 2 =C 6 H 4 -N(CH 3

CO 01
This chloride
is

treated with diphenylamine,

is

whereby dimethyl-

amidobenzodiphenylamine

formed

C 6 H 4 -N(CH 3

2
'

CO-N(C H
6

5) 2

Practically, the above reactions are

combined into one operation.

treated with a chloride of

The above condensation-product

is

phosphorus or phosgene, and the resulting chloride,

C6 H4 -N(CH 3) 2

C-C12 .N(C 6 H
C6 H4 .N(CH 3
XC
2

'

5) 2

condensed with dimethylaniline, and the compound produced

)

H 4 .N(CH

3) 2

.C1

heated with ammonia yields auramiiie and diphenylamine.

KETONEIMIDES AND HYDRAZIDES.

99

Auramine comes into commerce

HC1.
this

as the hydrochloride

C 17 H 21N 3

This salt

medium

easily soluble in water, and crystallises from in beautiful golden-yellow leaflets.

is

is decomposed by continued boiling with, water, especially in presence of free hydrochloric acid, tetramethyldiamidobenzo-

It

phenone and ammonia being regenerated. Platinum double salt, (C 17 H 2 iH 3 ,HCl) 2 ,PtCl 4, forms an orangered precipitate.
Picrate, soluble.

C 17 H 2 iN 3 ,C

(NO 2 3 OH, forms yellow

)
,

leaflets sparingly

Oxalate, (C 17 soluble in water.

H N
21

3) 2

C 2 H 2 O4

forms
is

yellow needles

sparingly

Leuco-auramine

[7],

C 17 H 23N 3

alcoholic solution of auramine with

colourless crystals, M.P. 135, with a blue colour (see under)
aniline

formed by reduction of an sodium amalgam. It forms

and
.

dissolves in glacial acetic acid

Phenylauramine and tolylauramine are obtained by action of and toluidine on auramine or on tetramethyldiamido-

benzophenone.

Auramine must be regarded as the imide of tetramethyldiamidobenzophenone, and accordingly has the constitutional formula
:

(CH 3

(CH 3

) 2

N C H 4X >C=NH. N-C H
6
6

The ring constitution accepted for tetramethyldiamidobenzhydrol cannot be present in auramine, as the elements of constiThe yellow colour of tutional water necessary are not present.
auramine also
is

against the assumption of a ring formula, the

benzhydrols being blue. On the other hand, a ring-formation is probably present in the blue salt formed by leucoauramine and acetic acid, and this Graebe
expresses by the formula
:
;

C 6 H 4N=

(CH,),'

An

objection to this
is

formula

is

that

till

now pentatomic

nitrogen

only known

in combination with an acid radical or

H2

100
hydroxyl.

CHEMISTRY OF ORGANIC DYESTUFFS.

Auramine and

known which belong

chromophor,

C=NH,

its derivatives are the only dyestuffs The to the class of simple ketoneimides. unlike that in rosaniline dyestuffs, occurs

in an open chain, and in this respect the hydrazides (Tartrazine) Auramine is one of are similar, and also have a yellow colour.

the few basic yellow dyestuffs, and owing to its easy fixation on tannin mordants has obtained a considerable importance in cottonIt produces a pure yellow shade. and

dyeing
Its

printing.

such as phenylauramine, have mostlv a brown colour, and have not been applied practically.
substitution-derivatives,

PHENYLHTDKAZIDES

[8].

Phenylhydrazine reacts readily with most compounds which contain the group CO ; the oxygen atom being eliminated in the form of water with two hydrogen atoms of the phenylhydrazine, the rest of the latter entering in the place of the oxygen. It is probable that the two hydrogen atoms which split off
belong to the amido-group, and therefore the hydrazides contain the group 6 5 That a close relationship exists between azo-compounds and

C= N NHC H

hydrazides is seen from the fact that certain oxyazo-compounds obtained from diazo-compounds and phenols are identical with the
hydrazides of certain quinones. Indeed all coloured hydrazides show a great similarity to the azo-compounds, and probably

Both classes of compounds, for example, belong to this class. behave similarly on reduction. The hydrazine group, like the azo-group, is split, yielding two amido-groups, one of which remains in combination with the phenyl group, the other with
the carbon atom. All the hydrazides

known

at present

have a yellow or orange

colour, like the simpler azo-compounds.

Tartrazine.
This dyestuff
is

sulphonic acid on dioxy-tartaric acid. hydrated condition has a formula

manufactured by action of phenylhydrazineThis acid, which in the

KETONEIMIDES AND HYDRAZIDES.

101

COOH i/OH V\OH

'/OH Son
COOH,
must be regarded
as the hydrate of a diketonic acid
:

COOH
CO CO
COOH.
It reacts according to the latter formula with hydrazines, two molecules of which enter into reaction.

The product obtained with two molecules of phenylhydrazine has a beautiful yellow colour; it is too sparingly soluble to be of use in dyeing,, but a valuble dyestuff may be obtained by introduction of sulpho-groups.

The commercial product known as Tartrazine is a sulphonic acid prepared by the action of two molecules of phenylhydrazinesulphonic acid (from sulphanilic acid) on one molecule of sodium
The constitution of dioxytartrate in hydrochloric acid solution. tartrazine is probably expressed by the following formula
:

COOH
C = N-NHC 6 H.S0 3 H

C=N-NHC H
6

SO 3 H

COOH.
forms a fine orange-yellow animal fibres from an acid bath, crystalline powder. producing a beautiful gold-yellow shade, which is valuable for its stability against light and milling.

The sodium

salt

of

tartrazine

It dyes

The application of higher hydrazines gives rise to dyestuffs of a redder tone.

102

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER

V.

TRIPHENYLMETHANE DYESTUFFS.
TRIPHENYLMETHANE
importance.
If amido- or hydroxyl- groups are introduced into triphenylmethane, in certain positions, colourless compounds, the leucoderivatives of dyestuffs, are formed. For example, if three amido-groups are introduced into the three benzene nuclei, in the para position to the methane-carbon

and

its

analogues are mother substances

of which are of great technical

of a series of dyestuffs,

many

atom, the compound

known
2

as paraleucaniline is formed,
4

H NC H4v >C H NC H/ H
6 2 6
|

C 6 H 4NH 2

On oxidation this compound loses two hydrogen atoms, and a condensation takes place between the nitrogen of an amido-group and the methane-carbon atom, pararosaniline being formed. [See
Introduction.]

H NC H4v ^C H NC H/
2
6 ' 2
6

C6 H 4

NH
free state takes

Pararosaniline only exists in the form of its salts, and in the/ up one molecule of water, triamidotriphenyl->

carbinol, a colourless

compound, being formed,

2

H NC H H NC H| OH
6

TRIPHENYLMETHANE DYESTUFFS.

103

This transformation into colourless carbinol-derivatives takes place with all basic triphenylraethane dyestuffs, and the carbinols
this

are for this reason regarded as the bases of the dyestuffs, although assumption is not altogether correct. Really both classes of

compounds have totally different constitutions, as in the dyestnffs a closed ring is present, while in the carbinols it is absent. In the triphenylmethane dyestuffs the chromophor EEC or

NH

=C O

always present, and generally effects the linkage between several aromatic nuclei. In most cases it occurs, howin one ring, occupying two para positions. For instance, ever,
is

pararosaniline contains the group

NH
N
II

which shows a certain analogy to quinones. The imido-group present in the chromophor also serves as saltforming group, and appears to effect a combination of the dyethe fibre. For instance, animal fibres may be dyed with tflff with the\ colourless carbinol bases, just as with the dyestuffs themselves. Apparently a salt is formed, in which the fibre acts as an
acid,

and combines with the imido-group.

The basic properties of the amido-groups present only become apparent under the influence of strong acids, or of the
haloid derivatives of the alcohol radicals.

These amido-groups, however, intensify the basicity of the imido-group. The formation of salts with these groups is generally attended by a striking alteration of the dyestuff character.
Basic triphenylmethane dyestuffs mostly form sulphonic acids ; these are generally acid dyestuffs, and when observed in the free state or in form of their acid salts have the same colour as the

104

CHEMISTRY OF ORGANIC DYESTUFFS.

and

Their neutral alkali salts are colourless, original dyestuffs. to be carbinol compounds. appear

The conversion

of basic carbinols into dyestuffs

is

generally

in many cases the formation of colourless salts of the gradual, and former may be observed. Tetramethyldiamidotriphenylcarbinol

malachite green) gives a colourless solution with (the base of dilute acetic acid, the formation of dyestuff only taking place on warming or after long standing.

Numerous methods

are employed for the production of tri-

phenylmethane dyestuffs. Substituted benzophenones

may

be condensed with tertiary

bases in presence of a dehydrating agent.

(CH 3

)2

(CH 3

)2

NC H V>iJ.o)o' ;CO + /V^V^ ~T C H N(CH NC H/

6
V^gJLJ.5.1^ 6 5
I

Tetramethyldiamidobenzophenone.

Dimethylaniline.

(CH 3
(CH 3

) 2

NC H /C~C H 4N(CH NC H/
6
4
6

3)2

Cl
Hexamethylrosamline.

similar manner.

The chloride of tetramethyldiamidobenzophenone reacts in a This compound has a blue colour, and probably
:

belongs to the diphenylmethane dyestuffs, which are analogous to It has the constitution the ros anilines.

Benzhydrol obtained by reduction of tetramethyldiamidobenzophenone (compare page 94), and which also in form of its salts behaves like a dyestuff, reacts with amines with the greatest ease.

In

this

reaction

the leuco-derivatives of

the dyestuffs

are

obtained.

TRIPHENYLMETHANE DYESTUFFS.

105

(CH 3

)2

(CH 3

N N

H 4v
Dimethylaniline.

C 6 H/

Tetramethyldiamidobenzhydrol.

' H )C-C H
4
i

H N(CH
4

3)

Hexamethylparaleucaniline.

Colouring-matters (rosaniline, methyl violet) of this class are also formed by oxidation of primary, secondary, or tertiary amines, which contain methyl groups in combination with nitrogen or carbon. Further, benzene-derivatives, which contain no methyl groups, yield dyestuffs if treated with compounds which at the same time are capable of withdrawing hydrogen and supplying carbon, such as carbon tetrachloride, oxalic acid, iodoform (rosolic acid, Another method consists in the direct diphenylamine blue).
introduction of

amido-groups into triphenylmethane. Again, aromatic bases or phenols yield triphenylmethane-derivatives by condensation with toluenes, chlorinated in the side chain, or with

aromatic aldehydes. In most of these cases leuco- compounds are The obtained, and are converted into dyestuffs by oxidation. a peculiar class of triphenylmethane dyestuffs, are prephthalei'ns,
pared by condensation of phthalic anhydride with phenols.

A.

ROSANILINE DYESTUFFS.

In the wider sense of the term, this class comprises all the basic from triphenylmethane and its homologues. As has already been remarked, the salts are the real dyestuffs,
dyestuffs obtained

while the so-called colour-bases are colourless carbinol derivatives. Up to the present, no suitable nomenclature has been applied to

the actual dyestuffs, rosaniline for example being generally called triamidotriphenylcarbinol, and this method has been adopted in
the present work;
little

although in reality the carbinol bases have

or nothing to do with the dyestuffs, so far as constitution is

dyestuffs are derivatives of

concerned.

The simpler basic triphenylmethane

106

CHEMISTRY OF ORGANIC DYESTUFFS.

diamidotriphenylmethane. This compound gives a violet dyestuff on oxidation, which has not been submitted to a close investigation [2]
.

It

is

probably a

member
:

of the class of

compounds in

question, and has the constitution

P TJ ~ n/ C H5

"NCANH
compound comes next

The tetramethyl
in the series, and
is

derivative of the above

a well- character]' zed substance.

Tetrametliyldiamidotriplienylcarbmol [3, 4, 5].

'

H N(CH
4

3) 2

OH
The base, separated from its salts by alkalies, forms a colourless or slightly grey powder. It crystallises from ligroin in shining colourless leaflets, or in round aggregates of crystals, M.P. 120. With acids the compound forms intensely green salts, water
replaceable scarcely probable that the hydrogen necessary for the formation of water is withdrawn from the methyl group, it may be accepted that the hydrogen atom is displaced from
split

being

off.

As the amido-groups contain no

hydrogen, and

as

it is

a molecule of the acid, and that the salt formed has a similar conAccordstitution to the salts of quaternary ammonium bases.
ingly the hydrochloride has the constitutional formula [3]
:

XC

H N(CH
4

3) 2

With

obtained.

a large excess of acid, the pale yellow diacid salt may be The monoacid salts are characterized by the ease with
;

tinctorial

which they crystallise power [5]

.

they are beautiful green dyestuffs of great

TRIPHENYLMETHANE DYESTUFFS.
Hydrochloride,

107

C 23 H 24N 2 ,HC1, forms easily soluble green leaflets.

Sulphate, C 2 3H 24 2 ,H 2 SO 4 , crystallises with one molecule of in brilliant green needles, or anhydrous in thick green 2O

prisms.
brilliant

Zinc chloride double salt, (C 23 24 green needles or leaflets.

H N ,C1) + 2ZnCl + 2H O, forms

2
8

Oxalate, in water.

2C 23 H 24 N 2 + 3C 2 H 2 O 4

large green prisms, easily soluble

Picrate sparingly soluble, crystallises in golden-yellow needles.

Ethyl ether,

C 6 H 5 C=[C 6 H 4N(CH 3 ) 2] 2

OC 2 H 5
obtained by heating the base with alcohol to colourless, and melts at 162.
is

110;

it

is

The methyl iodide

[5],

C 23 H 25 (OCH 3 )N 2 ,2CH 3 I + H 2 O,
is

alcohol.

formed by heating the base with methyl iodide and methyl It forms colourless needles.

Tetramethyldiamidotriphenylcarbinol, or more correctly its anhydride, is formed by oxidation of tetramethyldiamidotriphenyl-

methane

[3],

and by condensation of two molecules dimethyl-

aniline with one molecule benzotrichloride in presence of zinc chloride [4], It may also be obtained from benzoyl chloride

and dimethylaniline [3] by action of the air. The most recent method of preparation is by action of dimethylaniline on the chloride obtained by treating dimethylamidobenzophenone with phosphorus
trichloride.

X C 6 H 4N(CH 3

The salts of tetramethyldiamidotriphenylcarbinol come into commerce under numerous names, of which Malachite Green and Benzaldehyde Green are most usual. Malachite green has attained considerable importance ; it has almost treble the tinctorial power of the older methyl green, and possesses further the

108

CHEMISTRY OF ORGANIC DYESTUFFS.

The oxalate and the met with.

advantages of dyeing wool easily and resisting the action of heat. zinc-chloride double salt are most frequently

Malachite green was first prepared by E. and O. Fischer [3] by oxidation of tetramethyldiamidotriphenylmethane. Shortly afterwards Doebner obtained it by action of benzotrichloride on dimethylaniline, a process which was patented [4, 6] and used for the manufacture of the dyestuff. At that time Fischer's method of preparation was not practicable, as the necessary benzaldehyde could not be obtained. However, the difficulties encountered in the technical production of the latter were soon overcome, and now the benzotrichloride process, which gives very

At present unsatisfactory results, has been entirely abandoned. the manufacture of malachite green is carried out as follows
:

The leuco-base is prepared by heating one molecule of benzaldehyde with two molecules of dimethylaniline in presence of hydrochloric acid.

found to be unnecessary.)
theoretical

(Zinc chloride was formerly used, but has been The base is then dissolved in the
acid

quantity of hydrochloric

and

the calculated

amount of finely suspended lead peroxide added to the solution, which must be very dilute. The lead is removed as sulphate by adding sodium sulphate, and the dyestuff precipitated by adding zinc chloride and salt.

Nitro-derivatives of Tetrametliyldiamidotriphenylcarlinol
[3, 8].

The paranitro-compound

is

obtained by oxidation of nitro-

tetramethyldiamidotriphenylmethane

(from paranitrobenzaldehyde and dimethylaniline) and also by action of paranitrobenzoyl-chloride and atmospheric oxygen on dimethylaniline [3]
.

The
salts

base,

C 2 3H 25N2 O (NO 2

are green, and reduction a violet dyestuff (probably tetramethylpararosaniline) is formed ; complete reduction yields tetramethylparaleucaniline.

in yellow prisms. The ) , crystallises are decomposed by water. On partial

formed by oxidation of the nitrotetramethyldiamidotriphenylmethane obtained from metanitrobenzaldehyde and dimethylaniline. It is similar to the former compound, but does not yield a violet dyestuff on reduction.
[2, 8] is

The meta-compound

TRIPHENYLMETHANE DYESTUFFS.

109

DichlortetrametkyldiamidotripJienylcarUnol [11].

C 23 H 24N2 C1 2 O.
The salts of this compound come into commerce as Victoria It is prepared by condensaGreen 3 B or New solid Green 3 B. tion of dichlorbenzaldehyde with dimethylaniline and subsequent
oxidation of the leuco-base formed.
of malachite green.
Its shade is bluer

than that

TetraethyldiainidotriplienylcarMnol [7]

C 27 H 32N2 O.
The
Green.
salts of this

base

come

into

commerce under the names

Solid
,

Brilliant Green,

New

Victoria Green, Ethyl Green, and

most commonly met sulphate, The zincIt forms brilliant, gold shimmering needles. with. In dyeing chloride double salt forms brilliant green needles.

The

C 27 H 32 N 2 ,H 2 SO 4

is

brilliant green produces yellower shades

than malachite green.

Sulphonic Acids

[9, 10].

These bodies are in considerable demand, especially for wooldyeing, and numerous products are met with in commerce. They are generally prepared by sulphonation of the leuco-bases, and subsequent oxidation ; as the bases themselves do not give good
results

on direct sulphonation.
;

The sulpho-group

enters especi-

ally easily into benzylated bases ring of the benzyl group.

and probably enters the benzene

Helvetia Green.

C 23 H 25N2

SNa.

This dyestuff, which is obtained by sulphonation of leucomalachite green, and subsequent oxidation, is the oldest of its class ; but is not much used at present, as its acid properties are

only slightly developed.

110

CHEMISTRY OF ORGANIC DYESTUFFS.

Light Green S.

C 37 H3 5 N2
This dyestuff
is

10

S 3 Na.

known

also as

and Guinea-Green B, and

leuco-base used for

is

Acid Green, Light Green S F, the most important of this class. The

triphenylmethane, aniline and benzaldehyde.

its production is diethyldibenzyldiamidoobtained by condensation of ethylbenzyl-

and

oxidised.

The resulting body is sulphonated Green S F dyes wool and silk from an acid Light

bath (Friedlander, B.B. 1889,

p. 588). Certain blue dyestuffs which belong to this class have recently been introduced into the market. They are prepared by conden-

sation of dimethylaniline, diethylaniline, and ethylbenzylaniline with metaoxy- or meta-amidobenzaldehyde. The resulting leuco-

bases have the formulae

HC

/ C.H 4 OH(m)
\\[C 6

/C c H 4OH (m
or
2

H4N(CH )J
3

HC

\
known
as Patent

The commercial

dyestuffs

Blue

N and

Super-

fine are lime-salts of the sulphonic acids, obtained

by sulphonation and subsequent oxidation of the above leuco-bases. The shades produced are similar to those of indigo extract, and have the advantage of greater fastness and brilliancy (D. R. P. 46384,
48523; Chemikerz. 1889,
p. 1702). further dyestuff derivative of diamidotriphenylmethane is Quinoline Green [1], obtained by action of tetramethyldiamido-

benzophenone, its chloride, or its hydrol on quinoline. In the last case a leuco-compound is formed. The dyestuff is probably constituted according to the formula
:

(CH 3

)2

(CH

3) 2

=NC H =NC
6
6

H/|

Cl

and probably of dyestuff of similar properties, similar constitution to the above.

Acid

Violet

Nis a

TRIPHENYLMETHANE DYESTUFFS.

Ill

Triamido tripheriylcarbinol, Pararosaniline.

/ H NC H -C X
2
U

C 6 H 4 NH 2
'

H NH
4

The anhydride occurs only

in the hydrochloride
:

in the coloured salts

for example,

HN-^CH

/C

H NH
4
4

CH NHHC1
are in the para position to

The amido-groups of pararosaniline

the methane- carbon atom.
It
is

formed by heating two molecules

of aniline and one molecule of paratoluidine [11] with arsenic acid, mercuric chloride, or other oxidizing agents ; by partial reduction of trinitrotriphenylcarbinol with zinc powder and
acetic

acid

[12]

(paraleucaniline)

by oxidation of triamidotriphenylmethane by heating aurine with ammonia to 120 [12]

; ;

and by heating pure aniline with carbon tetrachloride, It may also be obtained by ethylene chloride, or iodoform. of paranitrobenzaldehyde [14], paranitrobenzyl- and benzoyl action chloride [15], or paranitrobenzyl- alcohol on aniline.
[12]
;

The base forms

form
salts

easily in hot water.

colourless leaflets sparingly soluble in cold, more It combines with one molecule of acid ta

of an intense red colour.

yellow triacid salts are formed,

With an excess of acid, which are decomposed by water.

On

reduction, pararosaniline yields paraleucaniline (triamido.

triphenylmethane) By heating with hydriodic acid in a sealed tube it splits up Pararosaniline was discovered by into aniline and paratoluidine. Rosenstiehl [16], and its constitution determined by E. and O.
Fischer [12].

The above
:

constitutional formula

is

deduced from

the following facts

treating with nitrous acid, pararosaniline gives a hexazocompound, i^ which all three nitrogen groups are present as diazoOn boiling with alcohol groups (probably carbinol compound)
.

On

this

diazo-compound yields triphenylmethane,

C 19 H 16

112

CHEMISTRY OF ORGANIC DYESTUFFS.

On partial reduction trinitrotriphenylcarbinol yields pararosaniline [12]; paraleucaniline being formed on further reduction. By action of paranitrobenz aldehyde on aniline in presence of
zinc chloride, nitrodiamidodiphenylmethane
.

is

formed; yielding
Its

paraleucaniline on reduction [12] Pararosaniline is present in most commercial rosanilines.

salts are similar to

those of the latter, but are in general somewhat more easily soluble in water. The synthesis of pararosaniline (from paranitrobenzaldehyde,

&c.) [14, 15, 17, 18] has until now not been carried out on a large scale, but it may be expected that in course of time the technical difficulties which stand in the way of these processes
will

be overcome.

Recently pararosaniline has been manufactured

by a synthetic process based on the following lines. Anhydroformuldehydeaniline, obtained by action of formaldehyde on aniline, is heated with aniline and aniline hydrochloride, whereby diamidodiphenylmethane
pararosaniline.
is

formed.

This latter compound, on heating

Avith aniline, aniline hydrochloride,

and an oxidising agent yields

Methyl Violet

[19].
this

The commercial products known under

thylaniline. ride of copper, acetic

name

are prepared

l)y oxidation of dimethylaniline sometimes containing

monome-

The dimethylaniline

of

common

salt.

mixed with sulphate or chloacid, potassium chlorate, and a large quantity more recent process consists in using phenol
is

in place of acetic acid the chlorate being generally dispensed the actual process the cupric chloride becomes rewith. During

duced to cuprous chloride, which oxidises again at the expense of the chlorate or by the atmospheric oxygen, thus acting as oxygencarrier. Cuprous chloride is capable of forming an almost insoluble double chloride with methyl violet, this property being absent in cupric chloride. Formerly the double compound was

decomposed by sulphuretted hydrogen, the soluble violet being At present the separated from copper sulphide by nitration. same end is attained by addition of ferric chloride, w).jich oxidises the cuprous salt to cupric chloride, which remains in the motherliquor after the violet has been salted out.

TRIPHENYLMETHANE DYESTUFFS.

113

The following will give an idea how the phenol process is carried out on a large scale. The operation takes place in a drum, which
is

jacketed, and connected with steam- and cold-water supplies.

Finely powdered salt and copper sulphate are stirred with phenol and a little water to a homogeneous mixture. Dimethylaniline is then added, and the whole heated to 55, with continual stirring, care being taken that the temperature does not rise above 60.
is removed, to allow the air to act, the temperature being maintained at 55. The process is ended in about 8 hours, and the melt is cooled by passing cold water into the casing of the drum. The melt is dissolved in water, and

After a few hours the cover

the base of the dyestuff precipitated, along with copper oxide, by addition of milk of lime, and the precipitate washed to remove soluble salts. It is then suspended in water, and treated with
sulphuretted hydrogen, whereby copper sulphide is formed, and being insoluble in hydrochloric acid, the violet may be obtained in solution by heating the precipitate with this acid. Finally, the
dyestuff

by

precipitated from the acid solution by salt, repeated solution and reprecipitation by salt.
is

and purified

older process, now abandoned, possesses interest from a theoretical standpoint. In this case no chlorine compound was the mixture consisting of dimethylaniline, copper sulphate, used, acetic acid, and sand. The violet is precipitated from the solution

An

of the melt as sulphate by sodium sulphate. The absence of chlorine prevents the formation of the insoluble double chloride, and the reduced copper compound is got rid of as insoluble suboxide.

The role played by the phenol in the modern process of manufacture has not been explained, but it is certain that its presence considerably increases the yield of the dyestuff. Methyl violet is produced by action of other oxidising agents
on dimethylaniline, such as iodine and chloranil. According to Brunner and Brandenburg bromine acts on dimethylaniline, forming a brominated methyl violet [21]. On the other hand, the dyestuff is not produced by oxidation of dimethylaniline in acid solution, with lead peroxide, manganese dioxide, or chromic acid.

As
group

yet,

understood.
is

the chemistry of the methyl-violet process is little According to E. and O. Fischer [12], a methyl partly oxidised, and the formic acid produced thereby

serves to link

necessary methane-carbon atom.

the benzene nuclei together, and to supply the As, however, the formation of
i

114

CHEMISTRY OF ORGANIC DYESTUFFS.

violet is difficult to follow, it is not easy to give

an explanation of

the reactions involved in

production. O. Fischer and Koerner have obtained hexamethylparaleucaniline quantitatively by action of the methyl ether of ortho-

its

In

fact

f ormic acid

aniline

The violet from dimethylon dimethylaniline [22] and chloranil is apparently identical with the ordinary one
.
.

obtained by the copper process [23] Methyl violet forms amorphous masses with a green lustre.
,is easily soluble a neutral bath.

It

in water,

and dyes wool and

silk violet

from

On

addition of a mineral acid, the solution of the

violet

becomes first blue, then green, and finally dirty yellow. The commercial product is a mixture, consisting chiefly of pentamethyl- and tetramethyl-pararosaniline with some hexamethylpararosaniline. If prepared from dimethylaniline containing monomethylaniline, the violet also contains lower methylated rosanilines.

As

the blue shade of the violet increases with the

number of

methyl groups, the bluest brands are richest in hexamethyl comBlue shades of violet are also obtained by action of pounds. benzyl chloride on the violet-base. According to Fischer the
benzyl group does not attack hexamethylpararosaniline, only the lower methylated products yielding benzylated violets [25]
.

The

dyestuffs

known

as acid-violets

are mostly sulphonic acids

of benzylated methyl violets. Methyl violet is difficult to convert into sulphonic acid by fuming sulphuric acid ; a better result is obtained by sulphonation, and

subsequent oxidation of the leuco-base.

ever; are

Benzylated

violets,

how-

form of their the sulpho-group probably entering the benzene leuco-bases, nucleus of the benzyl group. Other acid-violets are obtained by methylation and benzylation of acid magenta.
easier to sulphonate, especially in

much

Tetramethylpararosaniline [24]

This violet dyestuff was prepared by Fischer by oxidation of it is also obtained by tetramethyltriamidotriphenylmethane
;

partial reduction of paranitro-malachite green.

TRIPHENYLMETHANE DYESTUFFS.
Acetyltetrametliylpararosaniline [2 3],

115

formed by oxidation of acetyltetramethylparaleucaniline. It is a green dyestuff, and on treating with hydrochloric acid yields
is

tetramethylpararosaniline.

Pentamethylpararosaniline [25].
/ c eH 4N(CH 3 ) 2

The pure base

is

obtained by saponification of

its
is

vative with hydrochloric acid. of commercial methyl violet.

The hydrochloride

diacetyl deria constituent

DiacetylpentametJiylpararosaniline [25].

[(CH 3

) 2

NC H
6

4] 2

=C

C 6 H 4NCH 3 C 2 H 3 O
.

oa
May be obtained by treating the crude base of methyl violet with It is a colourless base, and gives a green salt acetic anhydride. with acetic acid. This fact is not easily understood unless under
the assumption that one acetyl group splits atom of the carbinol group is eliminated.
off,

and the oxygen

Hexamethylpararosaniline [23, 25, 26].

Cl
[

This dyestuff occurs in Methyl Violet.

aniline

(CH 3 2 NC 6 H 4] 2 = C C 6 H4N(CH 3 is known in commerce as Crystal

)

Violet,

and also

It is obtained

by action of dimethyl:

on tetramethyldiamidobenzophenone

(CH NC H
3) 2
6

CO

C 6 H 4N(CH 3

in presence of a dehydrating agent, according to the equation

C 17 H 20N 2 + C 8 H U N,HC1 = C 25 H 30N 3 C1 + H 2 O.

This
is
)

effected

on a large

scale

in one operation,

phosgene

(COC1 2

being allowed to act on dimethylaniline in presence of

116

CHEMISTRY OF ORGANIC DYESTUFFS.

zinc chloride, and further is formed by action of perchlormethylformiate on dimethylaniline in presence of aluminium chloride or zinc chloride. It is also produced by heating its methyl chloride or methyl iodide compound (methyl green) to 110-120.

The hydrochloride and

crystals.

zinc double salt

form lustrous green

The hydriodide and

picrate are sparingly soluble.

On

reduction

it

yields

hexamethylleucaniline,

which forms

leaflets,

M.P. 173.

Hexaethy lp ararosanilin e
r [(C 2 H 5 ) 2

-X-C H ]
-i

--^ -C-C
.

C1
5) 2 .

H 4-N(C 2 H

This dyestuff comes into commerce as Ethyl Purple, and is preIt dyes bluer pared by the action of phosgene on diethyl aniline. shades than Crystal Violet.

Azo-Grcen.

(CH 3 L-N

C 6 H4 -C /C H * V C 6 H4
|

--

N=N

C 6 H 3 / CO
8)

OH

JL

N (OH-2

this dyestuff are

is

Although containing an azo-group, the tinctorial properties of due to its derivation from triphenyl-carbinol. It obtained by combining the diazo-compound from metamidotetra-

It dyes methyldiamido-triphenylmethane with salicylic acid. shade. The corresponding chromed wool a bright greenish-yellow

paramido-compound gives a blue

dyestuff.

Metlnjl Green [19, 25].

6 6U /C 6 / * H 4N(CH 3 2 CH 3 C1
v

(Chlormethylate of Hexainethylpararosaniline Chloride.)

This chloride or the corresponding iodide is formed by the action of methyl chloride or iodide on commercial methyl violet. The tetra- and penta-methylpararosanilines are converted into hexamethylrosaniline
;

the latter adding on one molecule of methyl

is

chloride or iodide.

On

a large scale methyl chloride

used.

slow stream of the

TRIPHENYLMETHANE DYESTUFFS.
gas
to
is

117

passed through an alcoholic solution of methyl violet heated 40, and kept neutral by addition of soda. Autoclaves are un-

is sufficiently soluble in alcohol and no pressure is produced. The alcohol is then distilled off, and the residue dissolved in water, and unaltered violet precipitated by addition of soda or chalk and common salt. The pure zinc double salt of methyl green is then precipitated by adding zinc chloride the precipitate being sometimes washed with alcohol to remove any violet present. In commerce this zinc double salt is generally met with in the form of brilliant green leaflets. The iodide, C 26 H 33 N 3 I 2 forms green needles easily soluble in

necessary, as methyl chloride

water [18]. Thejozcr/e,C 26 H33N3[(C 6

)(NO 2 )3OH] 2

is

insoluble in water,

sparingly soluble in alcohol.

The
iodine

base,

C 26 H 35 TsT 3O 2

is

obtained by treating the chlorine or

oxide.
It is colourless, and its acidifying, the formation of The salts of methyl warming.

compound with

silver

alcoholic solution remains colourless

on

a green salt only taking place on

off,

green decompose at 110 to 120, methyl chloride or iodide splitting

violet residue of hexamethylrosaniline chloride. analogous green is the brom-ethylate obtained by the action of ethyl bromide on methyl violet. The composition of the com-

and leaving a

An

mercial zinc double salt (ethyl green)

is

probably
.

C 25 H 30 N 3 ClC 2 H 5 BrZnCl 2

An

advantage of this ethyl green is that its shade is yellower than that of methyl green. Methyl and ethyl greens dye silk directly, and cotton prepared with tannic acid. Wool cannot be dyed
directly, and is either previously mordanted with sulphur by a bath of thiosulphate of soda, or dyed in a bath of methyl green made alkaline with ammonia. Fibres dyed with these greens become

violet

on heating, and

this reaction serves for their identification.

At

present methyl and ethyl green are scarcely ever used, having been replaced by the cheaper and stronger benzaldehyde greens. The green colour of a compound appears to require the presence
of an

with an acid.

group, and an amido-group not in combination Benzaldehyde green, for example, fulfils these conditions. In methyl violet, an ammonium group and two methylated amido-groups are present, and as long as the latter are not in combination with an acid the compound is violet. When,,

ammonium

118

CHEMISTRY OF ORGANIC DYESTUFFS.

however, one of them is saturated by an acid, the colour changes to green, but the green salts are unstable, and are decomposed by water. Stable green dyestuffs are formed, if the acid is replaced
chloride, the same effect being produced by the introduction of an ethyl group. It appears, therefore, that the neutralisation of the basic properties of the third nitrogenous group has

by methyl

the same effect as

its

entire removal

would have.

TriamidodiplienyltolylcarUnol [12, 28].

(ROSANILINE, MAGENTA, FUCHSINE.)

OH
Rosaniline, a homologue of pararosaniline, is formed by oxidation of equal molecules of orthotoluidine, paratoluidine, and aniline. As oxidising agents, stannic chloride, mercuric chloride

or nitrate, arsenic acid, or nitrobenzene may be used. Mercuric arsenic acid, and nitrobenzene have been applied on a large nitrate, scale ; but at present the two latter are the only oxidants used
technically.
fitted

The

arsenic acid process

is

carried out in a boiler

Aniline above composition (aniline for red) and syrupy arsenic acid (containing about 70 per cent, arsenic anhydride) are introduced, and the mixture is heated to 170-180. Part of the aniline oil used distils over during the operation,
stirrer,

with a

and connected with a cooling- worm.

of approximately the

8 to 10 hours. As soon as the melt has it is allowed to flow out, and after It is then boiled with water in a closed cooling is broken up. vessel under pressure, the arsenic and arsenious acids being at

which generally

lasts

attained a certain condition,

the same time partly neutralised by addition of lime. After filtering, the rosaniline hydrochloride is separated from the filtrate by addition of salt. It is purified by recrystallisation. Magenta

prepared by this process generally contains arsenic. In the nitrobenzene process, aniline for red is heated with hydrochloric acid, nitrobenzene, and iron, the process being carried out in much the

same manner

as above.

The iron
is

forming ferrous chloride, which

serves to start the process, oxidised 'to ferric chloride

by by

the nitrobenzene, which latter salt in turn effects the oxidation of the aniline.

TRIPHENYLMETHANE DYESTUFFS.

119

Nitrobenzene appears to take no part in the formation of rosaniline, and simply acts as oxidant, being converted to dyestuffs of the induline class. When nitrobenzene is replaced by chlorrosaniline is produced, and not, as might be expected, nitroberizene, a chloro-derivative. Dyestuffs of the rosaniline series are formed

by oxidation of numerous bases in presence of aniline and paratoRosen stiehl and Gerber divide the homologues of aniline into three classes, according to their behaviour on oxidation with
luidine.

arsenic acid.

The first class includes bases which do not yield a magenta on oxidation alone, but do if oxidised in presence of aniline. These bodies are paratoluidine, asymmetric a-metaxylidine, cumidine, and amidotetra- and amidopenta-methylbenzene. The second
class comprises those bases

which yield no magenta

on oxidation with arsenic

acid, but do so if oxidised in presence of a base of the first class. These bases are aniline, orthotoluidine, and y-metaxylidine. The bases of the third class, metatoluidine

and /3-metaxylidine, do not yield magenta under any conditions. In the first class, one methyl group is in the para position to the amido-group, while in the second and third classes the para position is free. In the second class the groups are in the ortho position, and in the third class in the meta position to the amido-group. E. and O. Fischer's experiments have proved that, in the simplest
amido-groups are in the para position to the fundamental carbon atom. The complete analogy of the homologuous rosanilines with the first having been proved, it can be readily understood why the members of the first group, when oxidised by themselves or with each other, do not yield rosaniline, but do so in presence of aniline. In the bases of the second class, the para position is free, and one or two ortho positions are occupied. It is clear that these bases cannot yield rosanilines unless they are oxidised with a base
rosaniline, the three

of the

first group. Neither can the bases of the first class produce magentas, but no reasons yet given can explain why they should not be able to produce rosanilines, when oxidised with other

members of the

first class. The experiments of Monnet, Reverdin. and Noelting and O. Fischer and Koch have, however, confirmed this experiment. Noelting has recently extended our knowledge of the behaviour of the homologues of aniline in this direction. He examined bases in which both the meta and ortho positions are occupied, and found that such bases do not yield magenta under any

120

CHEMISTRY OF ORGANIC DYESTTJFFS.

conditions, and therefore belong to the third class. Metamethylated paratoluidines yield magenta on oxidation in presence of aniline, whether the ortho position be occupied or not.

The
follows
lidine,

investigations
:

on this subject are best summarised as All paramethylated anilines, paratoluidine, a-metaxy-

a-orthoxylidine, mesidine, pseudocumidine, isocumidine, the cnmidine of Noelting and Forel, isoduridine, phrenidine, and pentamethylamidobenzene yield magentas on oxidation with two
if

molecules of aniline, orthotoluidine, or v-metaxylidine, but do not oxidised with para free but methylated anilines as metatoluidine,

paraxylidine, v-orthoxylidine, s-metaxylidine, the cumidines of Edler and Mayer, and crystallised duridine. The commercial dyestuff is the hydrochloride of rosaniline ; the The free base is acetate, however, is also sometimes met w ith. also prepared for the manufacture of aniline blue.
r

Rosaniline-lase [28].

C 20 H 21N 3 0.
Free rosaniline crystallises in colourless
red on exposure to the
air.

leaflets,

which become

It is sparingly soluble in cold water, somewhat more easily in hot water, and still more easily in alcohol. It is sparingly soluble in ether.

Rosaniline
tion of

is

ammonium

capable of expelling ammonia from a boiling soluchloride, while in the cold rosaniline is preciits salts

pitated from a solution of

by ammonia. The base is obtained technically by boiling the hydrochloride (magenta) with the calculated amount of lime or caustic soda, and a large quantity of water. The filtered solution deposits the base on coobng, in form of colourless leaflets which become brownish
air.

on exposure to

By heating with water to 235, rosaniline decomposes, yielding phenol, ammonia, a base C 20 20 2 O 2 , M.P. 176, and an acid

H N

C 20 H 19KO 3
phenone

[25].

At 270

HO

C 6 H 4 COC 6 H 4

ammonia, phenol, and dioxybenzoHO are formed [26]

.

of rosaniline, like those of pararosaniline, are formed with a simultaneous elimination of water. The monoacid
salts [24]

The

salts

brown

have an intense red colour ; the diacid salts are yellowishThe salts are converted into a tertiary diazo[24].

compound by the

action of nitrous acid [12]. occurs as large octohedra Hydrochloride,

C 20 H 19 N 3 ,HC1 + 4H 2 0,

TRIPHENYLMETHANE DYESTUFFS.

121

or rhombic tables, which have a green metallic reflex. It is with difficulty soluble in cold water, easily in hot water and alcohol.

Acid

salt,

C 20 H 19 N 3 (HC1) 3
,

forms brownish-yellow

needles,
at

easily soluble in water,

and decomposed by an excess, or Platinum salt, (C 2 oH2oN 3 Cl 2 )(PtCl 4 )3. Hydro bromide, C 20 H 19 N 3 ,HBr, is sparingly soluble.

100.

Sulphate, (C 20 19 3 ) 2 2 SO 4 , sparingly soluble in water.

Acetate, C 2 oH 19 soluble in water.

H N H
3

forms

brilliant

green crystals,

N ,C H O
2

2,

forms large green crystals, easily

Pier ate,

C 20 H 19 N 3 ,C 6 H 2 (NO 2 3 OH,
)

forms

needles,

sparingly

soluble in water.

The tannate forms

a red precipitate insoluble in water.

Rosaniline and pararosaniline form colourless unstable compounds with sulphurous acid and bisulphites. These compounds
react with aldehydes, forming peculiar
dyestuffs

(Detection of

Aldehydes [29]).

Eosanilinesulphonic Acid [30],

(MAGENTA

S,

ACID MAGENTA.)

the action of strong fuming sulphuric acid on magenta at a sulphonic acid, probably the disulphonic acid, is formed. 120, This acid has an intense red colour, and the solutions of its salts

By

are not turned yellow

salts,

by acids like those of magenta. The neutral with the alkalies and metallic oxides, are colourless, the acid Both are
easily soluble in water,
it
is

salts

being red.

and

difficult to

crystallise.

From

the colour of the acid

sulpho- and amido-groups are combined to form a

colourless salts contain the carbinol group. Rosanilinesulphonic acid dyes wool and silk

probable that the salt, while the

from an acid bath,

and

finds extensive application in dyeing.

Tetrabromrosaniline [31]
is

less base,

formed by the action of bromine on rosaniline. forming violet salts.

It is a colour-

At
led to

present the researches of E. and O. Fischer and others have some confusion as to the exact composition of the methyl-

rosanilines

examined by Hofmann.

If methyl green

is

hepta-

122

CHEMISTRY OF ORGANIC DYESTUFFS.

methyl pararosaniline, iodine green is not penta- but heptamethylrosaniline, and the violet formed on heating is hexamethylrosaniline. The analytical results obtained by Hofmann scarcely admit of this interpretation. In the present work these bodies
are described under the older formulae, with the hope that further researches may elucidate the matter.

Trimethylrosaniline [2 8],

C 20 H 18 (CH 3

N 0.
3

The hydriodide, CosHogNgljis formed by heating rosaniline with methyl iodide and methyl alcohol. It is a violet dyestuff sparingly
soluble in water.

Tetramethylrosanilin e [28],

C 20 H 17 (CH 3
is

N 0,
3

obtained

C 24 H 28 N 3 I, forms

by heating

iodine green to long bluish-violet needles.

120.

The

iodide,

Pentamethylrosaniline [32].

(IODINE GKEEN.)
is

The

iodide,

C 2 oH 17 (CH3) 4N3l,CH 3 I + H 2 O,

prepared by heat-

ing rosaniline with methyl iodide and methyl alcohol to 100. It is freed from any violet dyestuff present in the same manner as

methyl green. The iodide forms metallic prisms heated to 100-120 methyl iodide

easily soluble in water.

splits
off,

When

leaving tetramethyl-

pararosaniline. The zinc double salt, C 25 31 3 Cl 2 ,ZnCl 2 , forms large green Its solutions are turned yellowish-green by acids. crystals.

H N

The picrate, C 25 H 29 N 3 C 6 H 3 (NO 2 3 O, forms prisms with a coppery

)

reflex,

which are insoluble in water and sparingly soluble in alcohol. Before the introduction of methyl green, iodine green was ex-

tensively used in dyeing.

Hexamethylrosaniline [32].

The iodide, C 20 14 (CH3) 6 3 I, is formed along with octomethylleucaniline by heating iodine green with methyl alcohol in a sealed tube to 100. It forms brownish-green needles, insoluble in water
and sparingly soluble in
alcohol.
It is a violet dyestuff.

TRIPHENYLMETHANE DYESTUFFS.

123

Triethylrosaniline [28].

(HOFMANN'S VIOLET.)
)

C 20 H 18 (C 2 H 5
The
iodide,

0.

C 26 H 35 N3 I2

is

obtained by heating rosaniline with

ethyl iodide and alcohol. It forms brilliant green needles, soluble in alcohol and sparingly so in water. It was formerly manufac-

tured on a large scale.

Tetraetliylrosaniline [28].

The iodide has the formula C2oH 16 (C 2 H 5 ) 4 N 3 L

Tribenzylrosaniline-metliyliodide^

C2oHi 6 (C 7
is

H N CH
7) 3
3

3 I,

iodide,

prepared by treating rosaniline with benzyl chloride, methyl and methyl alcohol. It forms green needles insoluble in

water [33].

Acetylrosaniline [34],
"

C 20 H 18 (C 2 H 3 0)N 3
is

formed when rosaniline hydrochloride

is

heated with acetamide.

violet salts.

It dissolves in alcohol with a red colour,

and forms

Triacetylrosaniline [35],

CsoHigNg (C 2 H 3 O) 3

and

Tribenzoylrosaniline [35],

C 20 H 16N 3 (C 7 H 5 0) 3
are obtained respectively

by the action of acetyl chloride and benzoyl chloride on rosaniline. They are colourless bases forming
of rosaniline with aldehydes have been described
cxl. p. 101).

orange

salts.

Compounds
II. Schiff

by

(Ann.

magenta obtained on a large scale by either of the processes already described is very poor, and seldom exceeds 33
The
yield of

per cent, of the weight of the bases employed. large quantity of bye-products is formed, and little is known as to their nature. constant product of the arsenic acid process is a small quantity

124

CHEMISTRY OF ORGANIC DYESTUFFS.

of chrysaniline. Besides this, various violet and bluish-black products are formed, some of which are soluble in water, some in
alcohol, dissolve

and others are totally insoluble. Some of these dyestuft's and remain in the mother-liquor of the magenta, but by
occur in the insoluble residue.

far the greater part

From the

latter
:

Girard, Delaire, and Chappotot [36] have isolated three bases, viz.

mauvaniline,

C 19 H 17N 3

C 21 H2iN 3

However,

violaniline, C 18 15 3 , and chrysotoluidine, sufficient analytical data are not forthcoming

,

H N

to support these formulae,

and

it is

doubtful whether the products

Possibly violaniline
is

examined were
identical

really chemical individuals.

with the simplest induline, and chrysotoluidine with chrysaniline, especially as dyes of the induline series occur in the

the magenta-residues (see Indulines).

Aniline Blue [37].

Aniline reacts with rosaniline at 180
organic acids,
in presence of certain

ammonia being

into the rosaniline molecule.

evolved, and phenyl-groups entering According to the number of phenyl-

groups introduced, the shade of the compound produced varies from violet to pure blue. It is not possible to introduce more than
three phenyl-groups into the rosaniline molecule. Acetic acid, benzoic acid, and stearic acid have been used technically, but at

present benzoic acid alone is used, as by its aid the best results are obtained both as regards yield and shade of blue (greenish). The action of organic acids in the blue process has not yet been explained.

Rosaniline heated with aniline without an organic acid a blue is, however, formed from rosaniline ; and paratoluidine. Only a minute quantity of benzoic acid is

does not yield a blue

required to effect the formation of blue, but in presence of a

larger quantity the results are better, and the process is more At the end of the reaction, benzoic acid remains in the rapid.

melt unaltered, tion with alkali.

and may be almost

entirely recovered

by extracis

The amount of
great importance.

aniline used in the manufacture of blue

of

In presence of a large excess of aniline the is more complete and rapid than when a small phenylation quanFor production of pure triphenyl rosaniline (green tity is used. shade of blue) a large excess of aniline is used (ten times the
theoretical

amount) along with a correspondingly large amount of

TRIPHENYLMETHAXE DYESTUFFS.
benzole acid.

125

The higher homologues of aniline, especially orthotoluidine, give redder shades of blue, and it is therefore necessary to use an aniline as pure as possible. It is required that commer" aniline for blue " should distil within one cial degree, and is thus almost chemically pure aniline. For the manufacture of a reddish shade of blue, smaller quantities of benzoic acid and aniline are On a large scale used, and a less pure aniline-oil is applicable.
aniline blue
is

prepared approximately as follows

The mixture of the requisite quantities of rosaniiine base, benzoic acid, and aniline is brought into a vessel fitted with stirrer and distilling arrangement, and heated to the boiling-point of the As the blue is contained in the melt in form of the aniline.
colourless base the progress of the reaction cannot be ascertained by simple inspection. For this purpose portions are removed from

time to time, and dissolved in alcohol and acetic acid, the operation being interrupted as soon as the test shows that the desired shade has been reached. According to the shade of blue required, the
process may last two to four hours, but if the heating some of the blue is liable to be destroyed.
is

protracted,

On

partly saturating the melt with concentrated hydrochloric

acid, the hydrochloride of tripheriylrosaniline separates out almost in a state of chemical purity, while impurities remain dissolved

in the concentrated solution of aniline in aniline hydrochloride. This latter is separated and saturated with dilute acid, and the
precipitate
is

worked up

for inferior blue.

This method of purifi-

cation has completely replaced the older process with alcohol. The salts of the lower phenylated rosanilines dissolve easily in
alcohol,
soluble.

while those of triphenylrosaniline are very sparingly A very large number of marks of blue come into com-

merce, the shades being influenced firstly by the degree of phenylation, and secondly by the number of sulpho-groups introduced for
the production of soluble blue. Other brands, again, are obtained from the lower quality of blue already mentioned.

i.

MonophenylrQsaniline.

C 20 H 20N 3 (C 6 H 5 )0.
The hydrochloride forms
brilliant

bronzy
.

crystals, soluble in

alcohol with a reddish- violet colour [39]

126

CHEMISTRY OF ORGANIC DYESTUFFS.

ii.

Diphenylrosaniline.

C 20 H 19 N 3 (C 6 H 5 ) 2 0.
This base forms bluish- violet salts [28, 38].
iii.

Triphenylrosanilme.
and

(ANILINE BLUE.)
)

C 20 H 18N 3 (C 6 H 5 3 0.
The
37, 38]
free base
.

is

colourless

easily soluble in alcohol

[28,

^hehydrochloride, C 20 17 3 (C 6 HJ 3 HC1, is the technical product obtained first in the fractional precipitation of the blue melt with
hydrochloric acid. In this state it forms brilliant green crystals, insoluble in water and sparingly soluble in hot alcohol. Aniline dissolves it somewhat more easily. The alcoholic solution has a pure

H N

blue colour.

of this product is used as " spirit-blue," but by far the greater quantity is used for the manufacture of soluble' blues. Triphenylrosaniline salts dissolve in sulphuric acid with a

Some

brown colour. The sulphate (C 20 H 16N 3 (C 6 H 5 ) 3 H 2 S0 4 )

alcohol.

is

almost

insoluble in

iv.

Sulplionic Acids of Triphenylrosaniline.

encountered in the sulphonation of rosaniline

The

difficulties

are altogether absent in that of the phenylated rosanilines. monosulphonic acid is formed by the action of concentrated sul-

phuric acid at a comparatively low temperature, while by a more energetic sulphonation two, three, and even four sulpho-groups may be introduced into the molecule.

From the foregoing it appears probable that the sulpho-groups enter the phenyl groups and not the rosaniline nucleus. The sulphonic acids are all amorphous, and possess a blue colour.
The
salts of

the acids are, on the contrary, colourless and probably

carbinol derivatives.

Monosulphonic Acid. C 38 H 30N 3 S0 3 H.

This
is

the

first

product of the action of sulphuric acid on

free acid is obtained
as a

aniline blue.

The

blue amorphous

TRIPHENYLMETHANE DYESTUFFS.
precipitate,

127

which
salt

is

insoluble in water.

nearly so, are easily soluble in water,

The sodium
This

forms the "

alkali

The salts are colourless or and cannot be crystallised. " of commerce. blue

salt, unlike those of other sulphonic acids, may be fixed on wool and silk from a slightly alkaline bath. It is probable that the basic groups of rosaniline effect this fixation. The shade ob-

tained

is

not strong, but on development with dilute acid, whereby

the free sulphonic acid is liberated, a good blue shade is obtained. Alkali blue finds its principal application in wool-dyeing.

Disulphonic Acid,

C 38 H 29 N3 (S0 3 H) 2
is

acid. acid,

a product of the further action of sulphuric acid on the above It is soluble in pure water, but insoluble in dilute sulphuric

and may therefore be precipitated from the sulphuric-acid

solution by water.

forms two series of salts with bases acid salts, which have a The acid reflex, and neutral salts, which are colourless. sodium salt is a commercial product, and is known as " water blue
It

coppery

for silk."

Tri-

and Tetra-sulphonic Adds.

at a

These bodies result by continued action of sulphuric acid

higher temperature. They are not precipitated from an acid solution by water^ and thus differ from the disulphonic acid. In order to isolate them,
the sulphuric-acid solution is neutralised with chalk, and the preThe solution of lime-salt cipitated calcium sulphate filtered off.
is

then converted into sodium-salt.

The dyestuff known

mixture of both
All the "

as

" soluble blue for cotton "

is

probably a

acids, or rather of their acid sodium-salts. " are soluble blues dyed on wool and silk

from a

bath containing sulphuric acid. Cotton is previously mordanted with alum and soap, or with tannin and tartar emetic.

Another blue is obtained by the action of aniline and benzoic acid on pararosaniliue. This product is valued for the pure greenish shade which it produces, and it has recently found extensive application, and appears to have almost displaced diphenylamine blue.

128

CHEMISTRY OF ORGANIC DYESTUFFS.

aniline blue have

Homologues of

been prepared by the action

They possess a dull reddish shade. are formed by action of the naphthylamines Naphthylrosanilines on rosaniline, but, like the above, possess no technical interest.

of toluidines on rosaniline.

Diphenylamine Slue.
Girard and Delaire (Jahresber. 1867,
p. 695).

Dyestuffs of a very pure blue shade are formed by the action of

oxalic acid or of hexachloride of carbon (C 2 C1 6 ) on diphenylamine. On a large scale diphenylamine blue is prepared by heating

The dyestuff diphenylamine with oxalic acid to 110-120. formed, which amounts to only 10 per "cent, of the diphenylamine employed, is purified by repeated treatment with alcohol. It comes
into
blue),

in the form of its higher sulphonic acids (soluble finds its principal application in silk- and cotton-dyeing. Similar dyestuffs, probably identical with diphenylamine blue,

commerce
and

are formed
as, for

by treating methyldiphenylamine with oxidising agents,

.

example, with chloranil [15] dyestuff named Bleu de Mulhouse was prepared by GrosRenaud and Schaeffer by the action of alkaline shellac solution on

rosaniline.

stuff by the action of

Persoz, Deluyne, and Calvetet obtained (1861) a soluble blue dyeanhydrous stannic chloride on aniline (pure ?)
.

The composition of

this

compound
.

is

not known, neither has

it

been applied in practice [41]

Aldehyde Green [43, 70, 71].

On

treating rosaniline with aldehyde and sulphuric acid, a blue

dyestuff is formed, which, on treatment with sodium thiosulphate For its' preparation, a in acid solution, yields aldehyde green.

mixture of rosaniline, aldehyde, and sulphuric acid

is heated, till It is then the product produces a blue-violet solution with water. into a very dilute solution of sodium thiosulphate. Sulphur poured and a grey compound separate, while the green remains dissolved.

It

may
;

soda
is

be precipitated by addition of zinc chloride or acetate of in one case a zinc double salt, and in the other a free base,

obtained.

The chemistry of the reactions taking place in the preparation of aldehyde green has been studied in detail with pararosaniline.

TRIPHENYLMETHANE DYESTUFFS.
In the
first

129

stages of the reaction a blue dyestuff, the so-called aldehyde blue., is formed, along with a green dyestuff. This blue has the composition of an anhydro-aldol-pararosaniline,

/ C H 4 -N=CH-CHo-CHOH-CH OH C-C H - N=CH - CHo"- CHOH - CH

6 6

3 3

incapable of yielding the green on treatment with a thioThe green dyestuff formed at the same time is a quinsulphate. aldine derivative of the above dyestuff, and has the constitution

and

is

^CH
N=CH-CH -CHOH-CH C H - N=CH-CH -CHOH-CH
f 4
4
2
2
6

;-N=C-CH -

3.

The thiosulphate employed

the green dyestuff into a
is

in the reaction enacts two functions.

It separates the above blue dyestuff,

and

at the

same time converts

new compound, containing sulphur, which

Two

and dyes a better shade than the original green. were originally in vogue for the production of aldeprocesses hyde green. The process of Lucius consists in treating the mixfaster to light

ture obtained by the action of aldehyde and sulphuric acid on rosaniline with sulphuretted hydrogen and then with sulphurous acid, while in that of Usebe the agent employed is a thiosulphate. The

green dyestuffs obtained in these processes are both derived from the above green, but differ in composition. The green obtained in Lucius's process contains two atoms of sulphur, while that of

Usebe only contains one.

following formulae
:

Their constitutions are expressed by the

CH = CH
/
I

C-OH
XC
6

H -NH-CH-CH -CHOH-CH<
4
2

S
s

C 6 H 4 -NH-CH-CH 2 -CHOH-CHLucius' s Green.

130

CHEMISTRY OF ORGANIC DYESTUFFS.

CH

C-OH
C 6 H 4 -N-CII-CH 3 -CHOH-CH 3
S

C 6 H 4 -N-CH-CH 2 -CHOH-CH 3
Usebe's Green.

Of course, the products obtained from rosaniline contain one methyl-group more than is expressed in the above formulae its position can only be a matter of speculation. Aldehyde green is a basic dyestuff, and was largely used before the introduction of iodine green. The zinc double salt came into commerce as a paste, or the green was prepared by the consumers. The tannate, obtained by precipitating the solution with tannic
:

acid,

was used in printing, being used with

acetic acid

and

fixed

by steaming.

Diphenylnaphthylmethane Dyestuffs

[1].

Certain derivatives of diphenylnaphthylmethane similar to the diphenylm ethane derivatives already described are in use as dyestuffs.

Compounds

of this class are obtained by the action of substi-

tuted naphthylamines on tetramethyldiamidobenzophenone in presence of dehydrating agents. In place of the latter compound its
chloride or the corresponding benzhydrol may be used. is the product of the action of phenyl-a-naphVictoria Blue

thylamine on tetramethyldiamidobenzophenone in presence of phosphorus oxychloride. The reaction is expressed by the following equation
:

H
H
2

O.

The

constitution of the dyestuff

is

represented by the formula

(CH 3 (CH 3

) 2

) 2

N-C H 4Xr N C H/
6
(

C 10 H 6

NHC H
6

_J\C1

Victoria Blue 4 R. This dyestuff is obtained by a -similar Its constitution is process with methylphenyl-a-naphthylamine.

TRIPHENYLMETHANE DYESTUFFS.

131

expressed by one of the following formulas,, the second being the more probable,, as it differs greatly in shade from Victoria Blue B.

(CH 3
I.

N-C H 4X
6

(CH 3

(CH 3 ) 2
II.

-N-C H/ -N-C H
6
6

;C
|

H 7 C6 5 C 10 H 6 N-CH 3 _J
\C1
/ C IO H T

Cl
Night
(

Blue

is

obtained

from

p-C 7 H 7 NHC 10 H 7 ) and tetramethyldiamidobenzophenone.

paratolyl-a-haphthylamine

These

dyestuffs come into commerce as hydrochlorides. They are beautiful blue dyestuffs, easily soluble, and dye cotton prepared with tannic acid similarly to methylene blue, but unfortunately

the shades produced are not very fast to light. In general their Alkalies reactions resemble those of the rosaniline dyestuffs.
precipitate a reddish-brown base, to yellow.

and acids turn the blue colour

Victoria blue B base cannot be crystallised. In a pure state it forms a brick-red powder M.P. 95. Victoria blue 4 B, base has also not been obtained in a crystallised state. It resembles the above in appearance, and melts at 77
;

[72].

B.

ROSOLIC ACID DYESTUFFS.

These dyestuffs are closely related to those obtained from rosaniline, and may be regarded as rosanilines in which the nitrogen
replaced by a group containing oxygen. The actual dyestuffs, like rosaniline salts, are anhydrides of a For example, aurin, C 19 14 O3, is the anhydride of an carbinol.
is

unknown

carbinol, trioxytriphenylcarbinol

HO
The compounds of these series have jan acid character, and in the free state are yellow, while the salts dissolve in water with a red colour. They cannot be fixed on textile fibres, and are con-

Some of the colour-lakes sequently almost useless in dyeing. are used in paper manufacture and for colouring tapestry. E V

132

CHEMISTRY OF ORGANIC DYESTUFFS.

Aurin, Pararosolic Acid [12].

(HO-C H 4 =C-C H 40.

6
)2

Aurin

is

prepared by heating phenol with oxalic acid

:

and

6 parts of phenol, 3 parts sulphuric acid, and sulphuric acid 4 parts of dried oxalic acid are heated for about twenty-four hours
to

120-130.
The melt
is

hot alcohol, and

extracted with water, and the residue dissolved in ammonia gas passed into the solution. The
is

boiled precipitate which forms Aurin is also acid [44, 48, 49].

with acetic acid or hydrochloric formed by condensation of

phenol with formic acid and zinc chloride [45], by boiling the diazo-compound from pararosaniline with water [12], by heating dioxybenzophenone chloride with phenol [46], and by action of in presence of concentrated sulphuric salicylic aldehyde on phenol
acid [47].

Aurin forms dark red rhombic

reflex.

crystals or

red needles with

a green metallic decomposes without melting. It in alcohol and glacial acetic acid with a yellowish-red dissolves It forms colour, and in alkalies with a magenta-red colour. double compounds with bisulphites of the alkalies. soluble
It

KHSO

,C 19

H O
14

posed by with hydrochloric

leucaurin (C 19

acids.

3 forms colourless leaflets, immediately decomAurin further forms a very unstable compound

acid.

Reducing agents
.

convert

aurin

to

16 3 ) (trioxytriphenyl methane) aqueous ammonia to 120 it yields pararosaniline [13] It is decomposed by heating with water, phenol and dioxybenzophenone being produced. For bye-products of aurin manufacture see the original
.

H O

On

heating with

article [49].

Eosolic Acid.

C 2oH 16 O

= OH \Q
CH/

OHC H
6

jj

\^ /C C 6 H 4 \/

niline

This body is formed on boiling the hexazo-compound of rosa(CaoH 19 3 ) with water [50], and may be obtained by

TRIPHENYLMETHANE DYESTUFFS.

133

heating a mixture of phenol and cresol with arsenic acid and sulphuric acid [49] The rosolic acid described by Runge (1834) as obtained from
.

the residue of crude phenol distillation is probably identical with the body at present under consideration. Rosolic acid forms infusible lustrous green crystals. It is almost insoluble in water, but dissolves easily in alcohol and
acetic acid with
red.
It gives colourless

in

its

an orange-red colour. Its alkaline solutions are double compounds with bisulphites, and behaviour closely resembles aurin. On reducgeneral

tion, leucorosolic acid (trioxydiphenyltolylmethane),

C 20 H 18

3,

is

formed.

Dioxyphenyltolylketon and phenol are products of

its

decomposition with water [31]. Two other products obtained from aurin have also been used
to

some extent

in practice.

Red
in

coralline

[52]

or Peonine

is

obtained by heating crude

aurin with

ammonia under

composition between obtained by action of aniline on aurin, and is probably an aurin This blue dyestuff was largely containing aniline groups [53] used before the introduction of aniline blue.
.

pressure, and! is probably intermediate aurin and pararosaniline. Azulin is

Pittacal (Eupittonic Acid).

The formation of this dyestuff was first observed by Reichenbach in 1835. He obtained it by treating certain fractions of
beech-tar creosote with baryta-water in presence of air [54] The formation of similar blue products has also been noticed by Graetzel, and the subject has been investigated by Liebermann and
.

by A. W. Hofmann. Liebermann gave to

his product the name Eupitton or Eupittonic acid, but it is not certain that this body is identical with ReichenThe constitution and method of formation bach's Pittacal [55].

of this

body were determined by Hofmann [56]

Eupittonic Acid, Hexamethoxylaurin [55].

C 19 H 8 (OCH 3
is

) 6

3.

obtained by action of carbon hexachloride on This compound solution of two molecules of pyrogalloldiraethyl ether an alkaline

134

CHEMISTRY OF ORGANIC DYESTUFFS.

and one molecule of methylpyrogalloldimethyl ether at 160-170. It is also formed by action of air on an alkaline solution of both
ethers [56].

Eupittonic acid forms orange-yellow needles, insoluble in water It is a dibasic acid and and soluble in alcohol and ether. ibrms salts which have a blue colour in solution. They may be The salts of the heavy metals precipitated by an excess of alkali. Like aurin, eupittonic acid are sparingly soluble blue lakes.

Dimethyl ether [56], C 25 H 24 O 9 (CH 3 ) 2 , is formed by action of methyl iodide on the sodium salt. It forms golden-yellow needles. M.P. 242.
Diethyl ether [56], Diacetate [56], C 25

gives unstable

compounds with

acids.

C H O (C H H O (C H O)
25

24

5) 2.

M.P. 202.

24

An analogous compound dation of pyrogalloldi methyl ether with methylpyrogalloldimethyl ether Tetraoxyethyldioxymethylaurin [56] ,
C 19 H 8 (OCH 3 2 (OC 2 H 5
)
)

yellow needles. M.P. 265. to eupittonic acid is obtained by oxi2

3 2,

3.

This compound forms brick-red needles, soluble in ether,

Hexamethoxylpararosaniline [25],

C 25 H 31N 3
is

=C H
19

13

(OC H 3 ) 6 N 3 0,

obtained by heating

under pressure to 160-170.

hair-like

eupittonic acid with aqueous ammonia The formation of this body is

analogous to that of pararosaniline from aurin.

colourless

The base forms

needles, which rapidly become blue on exposure to the air. It is decomposed on heating with water,

eupittonic acid being regenerated, while ammonia splits off. The monoacid salts of this base are blue and the triacid yellow.

The dyestuffs of this

class are

not of any technical value.

Aurintrwarbonic Acid (CHROME-VIOLET) [73].

/C 6 H 3 (OH)COOH C-C 6 H (OH)COOH

3

This

compound

is

obtamednSyoxidation of

salicylic

acid

and

methyl alcohol in concentrated sulphuric acid solution with sodium It forms a red powder with greenish reflex, and produces nitrite.

TRIPHENYLMETHANE DYESTUFFS.

135

The chromium lake is fast bright shades on metallic mordants. to soap. For the methyl alcohol may be substituted formaldehyde
or methylal, and homologous derivatives may be obtained by replacing the whole or molecular portions of the salicylic acid by
/3-cresotic acid.

DYESTUFFS FROM BENZOTRICHLORIDE AND PHENOLS.

Benzotrichloride, according to Doebner [57], acts on phenols The dyestuffs formed in a similar manner to dimethylaniline. are related to rosolic acid in their constitution ; they are deriva-

triphenylmethane and contain an oxygen atom linked to the methane- carbon atom and one benzene ring. Throughout, however, they contain one intact phenyl ring, the other two
tives of

containing oxygen. The simplest member of the class is formed by interaction of two molecules of phenol and one molecule of benzotrichloride,

and

is

called Benzaurin.

Benzaurin stands in the

relation to dioxytriphenylmethane as aurin does to trioxytriphenylmethane. Its constitution is accordingly the following
:

same

P 65 p/C H HO. TT ,\C H Q

6

4
.:

Benzaurin forms hard lustrous crusts. It is insoluble in water, soluble in alcohol, ether, and glacial acetic acid, with a yellow It dissolves in alkalies with a violet colour, and is precolour.
cipitated

from its alkaline solution by acids. It forms soluble double compounds with bisulphites. Benzaurin dyes wool and silk yellow from an acid bath. It on reduction. This compound yields dioxytriphenylmethane
crystallises
,

from alcohol in yellowish needles. Resorcinbenzem, C 19 H 14 O 4 is an analogous body obtained by With bromine it gives a action of benzotrichloride on resorcin. which dyes silk a shade similar to that tetrabrom-compound,
produced by eosine.
Basic derivatives of the above bodies have been recently described by

Heumann and Rey

[74]

These bodies, called Kosamines, are obtained by action of benzotrichloride on mono- or dialkyl derivatives of metamidophenol.

The new bodies

are beautiful red to violet dyestuffs.

One

of the simplest

members

of the series

tetramethylrosa-

136

CHEMISTRY OF ORGANIC DYESTUFFS.

mine is prepared by heating one molecule benzotrichloride with two molecules dimethylmetamidophenol in benzene solution, or mixed with sand, to about 60. The hydrochloride forms needles with a steely -blue reflex, and
dissolves easily in water with a beautiful bluish-red colour ; the solution exhibits a bright yellowish-red fluorescence. Its consti-

tution

is

expressed by the formula

Tetramethylrosamine dyes wool and silk in an acid bath, producing shades from pink to dark bluish red. The oxalate forms dark green needles and the nitrate steel-blue
needles.

By heating oxalic acid with resorcin and sulphuric acid, Baeyer obtained a yellow dyestuff, which is probably Euxanthone [58] According to Glaus and Andrese [59] it possesses the formula
.

C 13 H 8 O4
Kosicki

while

reaction, to both of

Gukassianz obtained two bodies in the same which he ascribes the formula C 14 H 8 O 5 [60]
.

[61] obtained a dyestuff isosuccinic acid and sulphuric acid.

by heating
Brasilei'n,

resorcin

with
is

This body, Resorcin-isosuc-

cinem, has the same composition as

similar in its properties.

C 16 H 14 O 5 and
,

C.

PHTHALEINS

[62].

The

phthalei'ns are derivatives of triphenylmethane,

and form a

group of dyestuffs which are sharply denned from the rosaniline and rosolic acid derivatives already described. In the latter the chromophorous groups are in para positions, while in the former two adjacent positions are taken up.

The chromophor

of the phthalems
II

is

the lacton ring

~~ C

CO/

TRIPHENYLMETHANE DYESTUFFS.
which occupies two adjacent positions in one benzene carbon atom being linked to another benzene ring.
ring,

137
one

there is a certain respect to the colour-giving group, these dyestuffs and those of the Indigo series, analogy between these latter being characterised by the lactam or lactim ring

With

CO

C-COH
or

-NH
The phthalems

-N

are all derivatives of phthalophenone, the inner

:

anhydride of triphenylcarbinolcarbonic acid

C 6 H5/

\C 6 H 4 COOH

C 6 H/
Phthalophenone.

Triphenylcarbinolcarbonic acid.

This acid is not capable of existing in a free state, but may be obtained in form of its salts. The relationship between phthalo-

phenone and triphenylmethane is

with alkalies
it

easily determined. By treatment yields triphenylcarbinolcarbonic acid, and this may be converted to triphenylmethanecarbonic acid by reduction with

On heating this latter compound, carbon dioxide forming triphenylmethane. Phthalophenone is not a dyestuff, the tinctorial character only becoming apparent on introduction of hydroxyl groups into both phenyl groups. The phthalems (hydroxylated phthalophenones) are almost exclusively obtained by action of phenols on phthalic anhydride. The position of the hydroxyl groups with reference to the methane carbon atom has considerable influence on the character
zinc powder.
splits off,

With simple phenols, as, for example, of the dyestuff produced. in the formation of phenolphthalem, the hydroxyl group is in the
para position to the carbon atom.
stuffs.

Compounds of this class are mostly of little character as dyeThey are colourless and only form coloured salts. Real

only obtained from phenols which contain two hydroxyl groups in the meta position, such as resorcin and pyrogallol. Probably here also the condensation takes place in a para position to one hydroxyl group, and is therefore ortho to the
dyestuffs are

138
other.

CHEMISTRY OF ORGANIC DYESTUFFS.

The condensation is generally attended of an anhydride between two hydroxyl groups.

by the formation

The
stuffs.

phthale'ins, with

exception of rhodamine, are acid dye-

The chromophor of the phthalems is of a strong acid character, and thus intensifies the acidity of the hydroxyl groups, and this
effect may be considerably increased by introduction of halogens or nitro-groups into the benzene rings. The halogens exert considerable influence on the shade of the dyestuffs.

The coloured phthalems are converted into colourless phthalins on reduction, these latter bodies being the corresponding derivatives of triphenylmethanecarbonic acid.

C 6 H/ '\C 6 H/

.2

C 6 H/

\C 6 H 4 COOH.

On
are

treating with energetic dehydrating agents, most phthalems converted into anthraquinone derivatives, one molecule of
split off

phenol being

during the reaction [62]

The phthaleins are very numerous, and only those of value

from a technical or theoretical point of view are considered
here.

Phenolphthale'in [62].

Dioxyphthalophenone,
4)2

(OHC

H =C O x
CO.

C 6 H4 /
This body
is

obtained by action of phenol on phthalic anhy-

dride in presence of strong sulphuric acid. forms colourless crystals, melting at about
alkalies with a red colour,

The

250;

free phthale'in it dissolves in

precipitate.

The

precipitated by acids as a white alkaline solution is decolorised by excess of alkali.

is

and

melting with caustic potash, it yields benzoic acid and dioxybenzophenone. On account of the change in colour occasioned by free alkalies (not carbonate or ammonia), phenolphthakm is useful as an indicator in titration.

On

TRIPHENYLMETHANE DYESTUFFS.
Fluoresce'in [62, 63].

139

HO

C6H3

CO
(Inner anhydride of resorcinphthalein.)

Fluoresce'in is obtained by heating an intimate mixture of two molecules resorcin with one molecule phthalic anhydride to 190

200.

The

materials used in the manufacture should be as pure

as possible, as impure fluorescein is difficult to purify. In the pure state it forms dark yellow crystals, sparingly soluble in alcohol,

more easily in glacial acetic acid. It is almost entirely insoluble in water, but dissolves in alkalies, forming a yellowish-red solution, which, when dilute, exhibits a bright green fluorescence. Acids
it from the alkaline solution as a yellow powder. Corresponding chlorofluorescei'ns are obtained by action of diand tetra-chlorophthalic anhydride on resorcin. These comare entirely different from those formed by direct chloripounds nation of fluorescein. In these the chlorine (bromine, or iodine) enters the resorcin-rest. The fluoresceins from the always

precipitate

chlorinated phthalic acids serve as starting-points for a series of very brilliant phthalein dyestuffs, which were first introduced into

somewhat redder shade than the corresponding fluoresceins which contain no chlorine.
Eosin.

the colour-industry by E. Noelting. The chlorinated fluoresceins have a

On

treating

fluorescein

with bromine, substitution of

the

The final hydrogen atoms in the resorcin-rests takes place. result is that four hydrogen atoms of the fluorescein are replaced by bromine, the product being tetrabromfluorescein, C 2 oH 8 O 5 Br4
[63].
tiful

latter, and also the lower brominated products are beaured dyestuffs, the shade being yellower with less, and bluer with more, bromine. Pure tetrabromfluorescein [63] crystallises

The

from alcohol
alkalies,

in yellowish-red crystals, containing alcohol. It is almost insoluble in water, but forms easily soluble salts with

which exhibit a beautiful green fluorescence in

solution.

140

CHEMISTRY OF ORGANIC DYESTUFFS.

From the alkaline solution, acids precipitate the colour-acid as a yellowish-red precipitate. The salts are only incompletely decomposed by acetic acid.
The
lakes.
lead, zinc, alumina, &c., salts are finely coloured insoluble

into

Tetrabromfluoresce'in and the lower brominated products come commerce as sodium or potassium salts, and form the various

brands of soluble eosins. On wool and silk they are dyed from a slightly acid bath and produce brilliant shades of red. Those on silk are noteworthy for
their peculiar yellowish-red fluorescence. Two of the four bromine atoms are contained in each resorcin

group, and on melting with potash eosin splits up into phthalic acid and dibromresorcin [64]. The bromine may be removed

by nascent hydrogen
less

on reduction with sodium amalgam colouris formed, and yields fluorescein on fluorescin, Various methods have been proposed for the brominaoxidation. For example, an alkaline tion of fluorescem on a large scale. fluorescein solution is mixed with the calculated amount of bromine dissolved in alkali, and on adding acid the fluorescein and bromine are liberated simultaneously and combination is thus This process does not, however, appear to be successful, effected. and at present bromination is carried out in alcoholic solution. Fluorescein in a finely divided state is suspended in alcohol, and the requisite amount of bromine added, the mixture being care;

C 2 oH 14 O 5

fully

cooled.
is

The hydrobromic

acid

developed

during the

reaction

by addition of potassium chlorate, which again In this manner a saving of bromine is liberates the bromine.
utilised
effected,

and only four atoms are necessary, while under ordinary conditions eight atoms are required, four being lost as hydrobromic
acid.

Ethers of Eosins [63].

treating the potassium salt of eosin with methyl iodide or chloride, or with ethyl bromide, monomethyl- and monoethylethers of eosin may be obtained, and these even surpass the eosins

By

in brilliancy of shade, their tone being in general somewhat bluer. They are monobasic acids, as one unaltered hydroxyl group is

The salts are insoluble in water and absolute alcohol, present. but dissolve with tolerable ease in alcohol of 50 per cent. The
solutions

show a magnificent fluorescence.

TRIPHENYLMETHANE DYESTUFFS.

141

The potassium

salt of

monoethyltetrabromfluorescem,

forms large ruby-red crystals with a fine green reflex. The ethyl ether, in form of its sodium or potassium salt, is " primerose a extensively used in silk-dyeing as spirit eosin or For use, the commercial product is dissolved in Falcool/' added to the dye-bath, which is acidified with spirit and gradually
acetic acid.

Colourless ethers of eosin also exist, and may be prepared by heating the silver salt of eosin with alcoholic iodides [63].

Iodine Derivatives of Fluoresce'in.

The commercial products known

as

"

"
erythrosin

are iodine

The alkaliderivatives of fluorescein corresponding to eosins. which are the commercial products, are soluble in water, and salts,
possess a much bluer tone than the corresponding eosins, and their solutions do not exhibit the fluorescence characteristic of

the latter bodies.

The commercial brands of erythrosin are of various marks, according to the amount of iodine they contain. On cotton they may be fixed in form of an insoluble alumina lake, and on this account are used somewhat extensively in cotton-dyeing, and also
to a certain extent in colouring paper.

Dinitrodibrowftuoresce'in.

C 20 H 8 Br2 (N0 2
This dyestuiF
is

[62].

formed by bromination of dinitrofluorescei'n or

by
is

nitration of di- or tetrabromfluoresce'm.

On

a large scale

it

prepared by treating dibromfluorescem with nitric acid in Pure dinitrodibromfluorescem forms yellow alcoholic solution.

It is a needles, sparingly soluble in alcohol and acetic acid. dibasic acid, and forms easily soluble salts with alkalies. strong The solutions of its salts are yellow if concentrated, red if dilute,

and do not fluoresce. The sodium salt is known in commerce

Safrosin, or Lutecienne.

as

Eosin Scarlet,

142

CHEMISTRY OF ORGANIC DYESTUFFS.

It produces a beautiful bluish-red shade on wool, and may be used in conjunction with yellow dyestuffs, giving fine scarlet Its application in wool-dyeing has fallen off considerably tones.

since the introduction of the red azo-dyes.

Tetrabromdichlorfluoresce'in.

C 20 H 6 Cl2 Br5

5.

Tetrabromtetraclilorftuoresce'in. C 2 oH 4 Cl4 Br4 O6

.

These bodies are prepared in a similar manner to the cosines, by bromination of the di- and tetra-chlorfluorescei'n. The soluble
alkali-salts of these acids are brought into commerce as the various brands of Phloxin. Their ethyl ethers, which, like those of eosin, are soluble in

dilute

alcohol, are known commercially as derivatives of di- and tetra-chlorfluorescein

Cyanosin.

Iodine

form the principal

constituents of the dyestuff known as Rose Bengal. The fluorescei'n derivatives containing chlorine are
in shade

much

bluer

than the corresponding derivatives of ordinary fluorescei'n. Their principal application is in silk-dyeing. Rose Bengal prepared from tetrachlorphthalic acid is the bluest of these dyestuffis, while Phloxin from dichlorphthalic acid is the yellowest. Here again the shade may be varied at will by introduction of

more or

less iodine or

bromine.

Rhodamine

[75].

The phthaleins of metamidophenol and its derivatives have been introduced into commerce under the above name. These dyestuffs are characterised by the brilliancy of the shades which they
are capable of producing, in fact excelling in beauty
dyestuffs.
all

other red

Commercial rhodamine consists principally of the phthale'in of The condensation of metamidophenol diethylmetamidophenol.
with phthalic anhydride only takes place in of strong sulphuric acid. presence Rhodamines may also be prepared by action of dimethyl- or
(and
its derivatives)

diethylamine on the chloride formed on treating fluorescem with

phosphorus oxychloride.

TRIPHENYLMETHANE DYESTUFFS.

143

The

constitution
to

of
of

the

simplest

analogous formula
:

that

fluorescem,

rhodamine is probably and is expressed by the

H NC H
2
6

H NC H
2
6

o<

C 6 H4 >c<r \co.

X X

acid properties.

Unlike the ordinary phthalems, rhodamine possesses basic and It forms soluble salts,, from which the base is not separated by alkalies. The solutions are turned yellow by an excess of mineral acid. The shade of rhodamine is a magnificent red, and exhibits on

silk a hitherto unrivalled fluorescence.

recently the condensation-product of succinic acid and dimethylmetamidophenol has been prepared on a large scale and
sold as

More

fUiodamine

S.

It is especially

adapted for cotton-dyeing.

Pyronines [76]. The Pyronines are a series of red basic dyestuffs of comparatively recent introduction. They are derivatives of dipheny 1m ethane, and resemble the rhodamines in shade. A typical pyronine may be
Dimethylmetamidophenol is condensed prepared as follows with formaldehyde, and the resulting dioxytetramethyldiamido:

diphenylmethane is treated with strong sulphuric acid, whereby one molecule of water is split off, and a leuco-base, tetramethyldiamidodiphenylmethane-oxide,
tion
:

is

formed, according to the equa-

CH,/ C' H
From

= H 0+CH2<
2

*<N(CH 3

C6 H 3-N(CH 3) 2 > C 6 H 3-N(CH 3 ) 2

) 2

this the dyestuff (Pyronine

G)

is

obtained by oxidation.

It has the

formula

C 6 H 3 -N(CH 3

CH<

>Q C 6 H N(CH
3
I

8 ) a Cl.

Pyronine B is the corresponding ethyl derivative. The pyronines yield brilliant bluish-red shades on cotton mordanted with tannic acid.

144

CHEMISTRY OF ORGANIC DYESTUFFS.

Gallem and
Gallem.

Ccerule'in [65].

product of the interaction of phthalic is a phthalem anhydride analogous to fluoresce'in, which, however, undergoes further oxidation by the The air, two hydroxyl groups being converted to quinone groups. thus formed possesses the formula gallem
first

The

anhydride and pyrogallol

It differs from fluorescei'n in containing two quinone oxygen atoms in combination with two benzene rings. Gallem is generally prepared by heating phthalic anhydride

with gallic acid to 200. The latter is converted into pyrogallol at this temperature, carbonic acid being split off.

In the pure state gallem forms brilliant green crystals or a brownish-red powder, easily soluble in alcohol with a dark red
colour,

and
salts

difficultly soluble in ether.

with the alkalies, lime, and baryta are soluble in water with a red colour, which is turned blue by an excess of alkali. On reduction, it is converted to hydrogallem and, finally, to gallin. It forms greyish-violet lakes with alumina and chromic oxide. It produces a fine violet on wool mordanted with
bichromate.

The

In printing it is applied with acetate of aluminium or chromium and steamed, whereby acetic acid is liberated, and the aluminium
or

chromium lake of gallem

Coerule'in

is

fixed

[65],
its
is

C 20 H 8 O 6

is

on the fibre. formed by heating gallein with

slightly in glacial acetic acid with a green colour, and easily in concentrated sulphuric acid with an olive-green colour. It forms a blue

weight of concentrated sulphuric acid to 200. by water, and in this state forms a bluish-black powder, which takes a metallic lustre on rubbing. It is almost insoluble in water, alcohol, and soluble ether,

twenty times

The dyestuff

precipitated

solution with hot aniline.

TRIPHENYLMETHANE DYESTUFFS.
It crystallises

145

from hot concentrated sulphuric acid in warty Reducing-agents convert it to reddish-brown coerulin, C 20 H 12 O 6 On warming with acetic anhydride, a triacetylcoerulein, C 2 oH 9 O 6 (C 2 H 3 O) 3 is formed. Coerulein forms colourless soluble compounds with bisulphites; these compounds being easily
crystals.
.

decomposed by boiling or by action of

alkalies
is

or acids.

In

dyeing and printing the bisulphite compound

generally used.

For printing, the coerulein bisulphite compound (Coerulein S) is mixed with aluminium or chromium acetate, printed, and steamed. This decomposes the acetate and the bisulphite compound simultaneously, and coerulein becomes fixed as aluminium or chromium Wool is previously mordanted with bichromate and tartar. lake. The shades produced are dark green, not very bright, but useful on account of their great fastness.
with zinc powder, coerulein gives phenylanthracene, and, according to Buchka, is a derivative of phenyloxandistilling

On

thranol

OH
I

CO
The constitution of
formula
:

coerulein

is

expressed by the following

CO
CTT 6^4
/

OH
\n Tjr_ /^n
^C.H,
r\

[66].

O-

.0

Glycere'ins [67].

Reichl gives this

name to

a series of coloured products obtained

by action of phenols on glycerin in presence of concentrated sulphuric acid. The quantity of dyestuff formed is, however, so small that one can scarcely formulate any reaction in form
of an equation.

Similar bodies to these from glycerin are also obtained from

many

organic acids, alcohols, and sugars.

146

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER

VI.

QUINONEBIIDE DYESTUFFS.
THE dyestuffs comprised under this Lead are derivatives of the hitherto unknown imido-compounds of the quinones, and include, amongst others, the Indarnines and Indophenols. By replacing the oxygen atoms of quiiione by the divalent as the group NH, the following compounds are obtained, according substitution takes place once or twice.

and

NH
Various These compounds are unknown in the free state. the simplest of which derivatives are, however, known, amongst may be mentioned quinonechlorimide and quinonedichlordiimide.

Quinonechlorimide.

Quinonedichlordiiraide.

QUINONEIMIDE DYESTUFFS.

1-17

above-mentioned indamines and indophenols must be regarded as more complex derivatives of the quinoneimides. These dyestuffs are formed by oxidation of a paradiamine in
presence of a monamine or a phenol, or by action of quinonedichlordiimide on the latter.

The

In the oxidation process,, as, for example, that of paraphenylenediamine with aniline, the former is probably converted into which, on further oxidation 6 H 4 =NH, quinonediimide attacks the benzene chain of the aniline, and enters in the para

HN=C

position to the amido- group. constitution [1]

:

The indamiiie produced has the

This
facts
:

constitutional

formula
the

On

reduction

deduced from the following compound takes up two atoms of

is
:

hydrogen, forming paradiamidodiphenylamine

HN
2

C 6 H4

NH

C 6 H4

NH

2.

As the indamine may be reproduced on oxidation, this body must be regarded as the leuco-base of the dyestuff. That the nitrogen atom effecting the linkage in the indamine is tertiary is seen from the fact that a paradiamine substituted in both
amido-groups,
as, for

example, diethylparapheiiylenediamine,

C2 H 5
is

HN

C6 H4

NH

C2 H5

That the nitrogen atom incapable of forming an indamine. the linkage in the indamines occupies the para position to effecting the amido-group is easily proved, as paradiamines do not react with
para substituted monamines, or at least only in a different manner. Para-diamines substituted in one amido-group react like primary
amines, and the

many

monamine may also be secondary or tertiary. In such cases the formation of an ammonium-chloride group

L2

148

CHEMISTRY OF ORGANIC DYESTUFFS.

Cl

(N(CH
has to be assumed.

8) 2)

The behaviour of

certain tertiary

indamines shows that their

production is attended by an intermediate formation ofaquinoneimide. If, on the one hand, paraphenylenediamine is oxidised with diaiethylaniline, and, on the other, unsymmetrical dimethyl2 ] with aniline, indamines paraphenylenediamine [(CH 3 ) 2 NC 6 4 are formed in both cases, but are not identical with each other, but isomeric, as by further action of aniline they yield two

H NH

different dimethylsaffranines.

This

behaviour
:

is

easily

explained

under

the
first

assumptions

HN

C 6 H4

Paraphenylenediamine

yields

following the body

NH;

while
3) 2

from

The NH, chlormethylate, C1(CH t produced. further action of these compounds on the respective monamines must necessarily produce different indamines, the constitution of
is

C6H

dimethylphenylenediaraine

the

which

is

expressed by the following formula

II

Cl
I

]S

(CET 3 )

Nil,

It is not

by oxidation of dimethylparaphenylenediamine
the chlormethylate of methylquinoneimide
:

improbable that the red dyestuff obtained by Wurstcr is none other than

C1(CH 3 ) 2

=N=C H NH.
6

This compound yields dimethylphenylenediamme on reduction, and reacts with monamines and phenols to produce indamines and indophenols.
related to the analogues of oxyamidodiphenylamine in the same manner as the indamines are todiamido-

The indophenols

are

diphenylamine.

QUIXONEIMIDE DYESTUFFS.

149

The formation of dyestuffs by oxidation of paradiamines with monamines was first discovered by R. Nietzki [48] in 1879, who
later
[1]

determined the constitution of the iridammes.

Witt,

in 1879, discovered the reaction between nitrosodimethylaniline

later that certain dyestuffs containing blue and Lauth's violet) also belong to this sulphur (methylene
class of colouring- matters.

and amines and phenols. Bernthsen [36] showed

1.

IND AMINES.
[l].j

Indamine (PHENYLENE BLUE)

HN
2

C 6 H4 ^

This compound is formed by oxidation of p-diamidodiphenylamine, or of a mixture of equal molecules of paraphenylenediamine and aniline. It is the simplest member of the indamine series,

and its salts are greenish blue and are mostly soluble in water. Acids turn the solutions green, and rapid decomposition, with formation of quinone, sets in. The iodide separates in long brilliant green crystals from a mixture of the hydrochloride and potassium iodide. Indamine, on reduction, yields paradiamidodiphenylamine. On heating with a solution of an aniline-salt,
phenosaffranine
is

formed.

Tetrametliylindamine

[1, 2, 3],

(BINDSCHEDLER'S GREEN.)

(CH 3

)2

C6 H 4

This compound

is

obtained by oxidation of equal molecules of

The

dimethylparaphenylenediamine and dimethylaniline [1, 2, 3]. solutions of the salts have a fine green colour, which is turned

150
blue by alkalies.

CHEMISTRY OF ORGANIC DYESTUFFS.

If the action of the latter
is

protracted, dimethyl-

amine

is evolved,,

and probably an indophenol

(CH 3

) 2

NC H
6

4Vx

is

formed.

This indamine
is

is

in

general

more

stable than the

acids,

former one, but

decomposed on warming with

quinone

and dimethylaniline being formed.

It yields tetramethyldiamidodiphenylamine [1] on reduction. Iodide, C 16 20 3 I [1], is formed on addition of potassium

H N

iodide to a solution of the hydrochloride or zinc double salt, and It is pretty soluble in pure separates in long green needles. but insoluble in a solution of potassium iodide. water,

Zinc double salt [2, 3], (C 16 20 3 Cl) 2 ,ZnCl 2 needles, which are easily soluble in water.

H N
2

forms coppery

Mercury double
Platinum double

salt,

(C 16

H N Cl)
20
3

salt,

C 16 H 20N 3 C) 2 ,PtCl 4

,HgCl 2
.

Toluylene Blue
Cl
I

[1, 4].

(CH 3

)2

=NC H
6

HNCH >NH
Toluylene blue

may

be obtained by

mixing

solutions

of

equivalent quantities of nitrosodimethylaniline hydrochloride and metatoluylenediamine, and also by oxidation of the latter base
It is an amido-indamine with dimethylparaphenylenediamine. characterised by a greater degree of stability than the previous

ones.

The monoacid

salts

are

blue,

and the diacid

salts

are

colourless.

The hydrochloride, C 15 possess a coppery lustre.

H N4 ,HC1,
12

forms soluble needles which

On reduction, toluylene blue gives triamidotolylphenylamine. On heating, toluylene red [4] (see Azine Dyestuffs) is formed.
The red dyestuff obtained by Wurster by oxidation of dimethylparaphenylenediamine is probably closely related to the indamines [5]. According to Wurster and Sendtner, this compound

QUIXONEIMIDE DYESTUFFS.

151
.

It possesses the corresponds to a base of the formula C 8 10 2 remarkable property of reacting with amines and phenols to prothis

H N

duce ind amines and indophenols respectively. It is possible that compound is a methylate of methylquinone-diimide of the
constitution

Cl
3

CH
C 10 H 14N2 on
,

\^jp
/

_ TT _
4

TV/TTT

Tetramethylparaphenylenediamine
oxidation.

gives

blue

dyestuff,

2.

INDOPHENOLS

[7, 8, 12].

This series of dyestuffs, which were first prepared by Witt and Koechlin, by simultaneous oxidation of paradiamines or paraamidophenols with phenols, exhibit, both as regards constitution

and general behaviour, a close relationship to the indamines. Like the latter, they are decomposed by acids with formation of a quinone. In general they possess a weak basic nature, but, unlike the indamines, form colourless salts, and have mostly a blue
or violet colour in the free state.

On
amine.

reduction they yield analogues of paraniido-oxydiphenyl-

Indophenols

may

be obtained by oxidation of paradiamines with

phenols, or by action of nitrosodimethylaniline or quinonechlorimide on the latter class of compounds.

According to the above remarks the constitution of the simplest indophenol (from paraphenylenediamine and phenol) should be
expressed by the formula,

HN=C H4=N
6

C 6 H4

OH

but the properties of the compounds of this class agree better with the formula

0=C H =N
6

H 4 NH

2.

as

For example, the indophenols do not possess acid properties, might be expected if an hydroxyl group were present; on the

contrary, they are

weak

bases.

The leuco-compounds, however, possess decided phenolic properties. They are soluble in alkalies, but oxidise extremely

152

CHEMISTRY OF ORGANIC DYESTUFFS.

being formed, which, being In presence of acid the leuco-

readily in the air, iiidophenols insoluble in alkalies, separate out.

indophenols are stable in the

air.

of these dyestuffs in dyeing and printing is based on the above properties of the leuco-compouuds. The

The application

The goods are impregprocess is similar to indigo vat-dyeing. nated with an alkaline solution of the leuco-compound, the colour
being developed by oxidation in the air, or by passing through a bath of potassium bichromate. Indophenol may also be produced directly on the fibre, a mixture of the diamine and phenol being
applied, and the dyestuff developed by passing through bichromate or bleaching-powder solution. Only the indophenols from dimethylparaphenylenediamine and

a-naphthol
application.

and phenol have been found capable of technical

The former
crystallises

compound
with

is

of

an

indigo-blue

colour,

and

from benzene in
of

colourless solution

brilliant green needles. It forms a acids ; an excess decomposes it with

formation

a-naphthaquinone and dimethylparaphenylenediamine [12]. The dyestuff from phenol is greenish blue. The manufacture of the indophenols is effected by oxidation of an alkaline solution of the reacting compounds with sodium hypoAn interesting chlorite, or with air in presence of copper oxide.

method of obtaining indophenol is by the action of dibrom-anaphthol on dimethylparaphenylenediamine. The indophenols are very fast to soap and light their great sensitiveness towards acids and certain difficulties encountered in their application, however, render them unable to compete with Indophenol, however, appears to be of use when combined indigo. with indigo, i.e. when a vat of the mixed dyestuffs is used. It is claimed that this mixed vat is more economical than the simple indigo vat, while the fastness and beauty of the shades are not affected.
;

trichlorindophenol,

HN-CH
by action of
It

has been obtained by Schmitt and Andresen [10]

trichlorquinonechlorimide on dimethylaniline.

forms beautiful

green needles.
Dyestuffs may also be produced by action of quinonechlorimide and of nitrosophenol on phenols in alkaline solution. They are,

QUINONEIMIDE DYESTUFFS.

153

however, very unstable, and probably contain an bydroxyl group in place of the amido-group in the previously described indoThe simplest of these compounds would possess the phenols.

formula

HOC H
6

3.

INDAMINES AND INDOPHENOLS CONTAINING SULPHUR.

(THIAZINES.) This class comprises a series of dyestuffs corresponding to the indamines and indophenols, but which contain one atom of sulphur
in their molecule.

This sulphur atom effects a linkage between two benzene rings, and the indamines of this series stand in the same relationship to thiodiphenylamine,

as the

common indamines do

to diphenylamine.

The sulphur atom

enters the two benzene chains in the ortho position to the imido-

group, and accordingly thiodiphenylamine may be regarded as containing three rings each containing six members. This is exemplified by the following formula [36]
:

H ^C HC^
HC
I

H
S

C
c
II

c
II

CH

CH

H
The amido and hydroxyl
like those of

derivatives of thiodiphenylamine are,

There

is

diphenylamine, leuco-compounds. an erroneous impression that the group

S

154

CHEMISTRY OF ORGANIC DYESTUFFS.

acts as chromophor, and that tliiodiphenylamine is the chromogen of this class of dyestuffs. From Bernthsen's constitutional fortheir

mulae, however, these bodies belong to the Indamine group, and chromophor must be the paraquinonediimide group

This

is

evident from

the

fact

that

the amido derivatives

of

thiodiphenylamine are not dyestuffs, but leueo-compounds. The presence of the sulphur atom serves to give greater stability
to the molecule, and these bodies are stable to acids.

In general, the whole character of the series modified.

is

considerably

The simplest

indarnine,

/CeH,

corresponds to Lauth's Violet

<

C 6 H 3-NH2 >S

In this series also the nitrogenous groups are generally in the para position to each other. The sulphuretted indamines may be produced by introduction of amido groups into thiodiphenylamine, and oxidation of the resulting leuco-com pounds. They are generally prepared, however, by
a peculiar reaction discovered by Lauth [14]. If a paradiamine is oxidised in presence of sulphuretted hydrogen in acid solution,

one atom of nitrogen splits off as ammonia, and two molecules of the diamine combine, one atom of sulphur entering into both rests The resulting body is an indamine containing simultaneously. These compounds are also formed on oxidation of thio sulphur.

QUIXONEIMIDE DYESTUFFS.

155

derivatives of paradiamines. Small quantities are further obtained by oxidation of amidodiphenyl amines in presence of sulphuretted

hydrogen. These dyestuffs are far more stable than the indamines and indophenols, and, unlike these, do not give quinone when treated

For this reason they are capable of practical applicaone of them,, methylene blue, discovered by Caro, being used tion, on a very large scale. The dyestuffs of this class have a violet or
with acid.
blue shade.

LautKs

Violet (Thionine) [14, 36].

/C 6 H 3

N=H
>s

in presence of sulphuretted hydrogen,

formed by oxidation of paraphenylenediamine hydrochloride by fusing paraphenylenediamine with sulphur and oxidising the resulting compound, and finally by oxidation of paradiamidothiodiphenylamine. The base, C 12 H 9 N 3 S, forms a black crystalline powder or needles
is

with a greenish
violet solution,

It dissolves in alcohol, forming a reddishreflex. and in ether, forming an orange solution. Hydrochloride, C 12 H 9 N 3 S,HC1, forms beetle-green needles, so-

luble in water with a violet colour.

Hydriodide, C 12 9 N 3 S,HI, is sparingly soluble in water [36]. Lauth/s Violet gives a green solution with concentrated sulphuric acid, and on dilution the colour changes through blue to violet.

On

reduction it yields paradiamidothiodiphenylamine [36] Isothionine is an isomerie dyestuff formed by oxidation of a

.

diamidothiodiphenylamine of

unknown

constitution [36]

Methylene Slue [13, 15, 16, 36, 53].

>S
who obtained

This dyestuff was discovered by Caro,

it

by oxida-

156

CHEMISTRY OF ORGANIC DYESTUFFS.

tion of dimethylparaphenylenediamine in presence of sulphuretted

hydrogen.

The dimethylparaphenylenediamine used in this and other processes is prepared by reduction of nitrosodimethylaniline, obtained by action of nitrous acid on dimethylaniline.
Carols process was formerly used on an industrial scale.
siderable

con-

improvement was effected by oxidising equivalent quantities of dimethylparaphenylenediamine and dimethylaniline in presence of thiosulphuric acid. The most recent processes have
for
their

starting-point

dimethylparaphenylenediamine-thiosul-

phonicacid:

C 6 H 3-S S0 3 H
.

x N(CH

)v[l]
[3J

This compound is obtained by oxidation of dimethylparaphenylenediamine in presence of sodium hyposulphite, or by action of hyposulphurous acid (thiosulphuric acid, H 2 S 2 O 3 ) on the red oxi-

Two processes dation product of dimethylparaphenylenediamine. be employed for the manufacture of methylene blue from this may
compound. (1) The thiosulphonic acid is oxidised with dimethylaniline, whereby an insoluble compound
:

N(GH,) 9
S

H N(CH
4

S0 3
3) 3

tetramethylindamine-thiosulphonate, is formed. On boiling with zinc-chloride solution, it yields sulphuric acid and leucomethylene blue, which is converted into the dyestuff on oxidation. (2) On
reduction, the thiosulphonic acid yields dimethylparaphenylene-

diamine mercaptan

C 6 H 3 -SH
or,

N(CH

3 [1]

[3]
[4]

on treating with

On

acids, the corresponding disulphide (C 8 n 2 S) 2 oxidation with dimethylauiline, both these compounds give the
.
:

H N

same soluble green indamine

,.-!
I

tetramethylindamine sulphide, which

is

transformed

to leuco-

QUINONKIMIDE DYESTUFFS.
methylene blue and methylene blue on standing or on warming Small quantities of methylene blue are formed by

the solution.

oxidation of tetramethyldiamidodiphenylamine in presence of sulphuretted hydrogen, and by treating tetramethyliiidamine with

sulphuretted hydrogen. Another method used in the manufacture of the so-called ethylene blue consists in treating nitrosodimethylaniline in sulphuric

with zinc sulphide. Leuco-methylene and yields the dyes tuff on oxidation. blue produced, It is certain that methylene blue is the tetramethyl derivative of Lauth's violet, although it cannot be obtained by direct methylacid solution (sp. gr. 1*4)
is

ation of the latter.

Its constitution is

analogous to that of tetra-

methylindamine. Like this, it contains a pentavalent nitrogen atom, which is in combination with two methyl groups and an hydroxyl or acid radical. The hydrochloride has the constitution expressed at the head of the section. The properties of the base of methylene blue are those of an ammonium base, and this agrees with the above conception of its constitution. The base is not easily separated from its salts. 'It is best obtained by decomposition of the hydrochloride with silver oxide, and has probably
the formula blue colour.

C 16 H 18 N 3 SOH.

It

dissolves

easily in water with a

Hydrochloride,

C 16 H 18 N3 SCL, forms

small

lustrous

leaflets,

H 18 3 SC1) + ZnCl 3 + H 3 O (commercial methylene blue), forms coppery needles, easily soluble in water,
sparingly soluble in zinc chloride solution. Hydriodide, C 16 18 3 SI, forms lustrous brown needles, sparingly soluble in water.

easily soluble in water. Zinc double salt, 2(C 16

H N

Concentrated sulphuric acid dissolves methylene blue with a green colour. Reducing agents convert it to its leuco-derivative,

tetramethyldiamidothiodiphenylamine

NH X

/C 6 H3-N=(CH 3

C 6 H 3 -N=(CH 3
leaflets,

>S

This base forms colourless

which oxidise in the

air to

methylene blue. On treating with methyl iodide, the dimethyliodide of pentamethyldiamidothiodiphenylamine

158

CHEMISTRY OF ORGANIC DYESTUFFS.

CH -N
3

is

formed.

/C 6 H -N(CH S X > C 6 H 3 -N(CH 3

:!

3)

As

this

compound

is

also

compound
stuffs is

of Lauth's violet,

formed by metliylation of the leucothe relationship between the two dye-

demonstrated.

ammonium bases, methylene blue does not dye wool but is readily fixed on silk and tannined cotton. It has easily, also a slight affinity for un mordanted vegetable fibres.
Like most
It dyes a greenish principally used in cotton-dyeing. shade of blue, which shows a dull tone similar to that of indigo.

Methylene

blue

is

It is very fast to light, and tlie shades may be readily modified by other basic dyestufts, such as methyl violet or malachite-green. An analogous dyestuff to methylene blue is obtained from mono-

ethylparaphenylenediamine [Oehler, 20], and another from meth-

oxydimethylparaphenylenediamine [Miilhauser, 21].

ImidotModiphenylimide [36].

^C H
Q

>S ^C H =NH
6 3

This body contains one amido group less than Lauth's and is formed by oxidation of monamidothiodiphenylamine.

violet,

The base forms small reddish -brown needles, soluble in alcohol and ether with the same colour. forms a brown preciHydrochloride, C 1 oH 8 N 2 S,HCl + liH 2 O,
pitate insoluble in ether.
It dissolves in

water with blue-violet

colour, and gives a green solution with concentrated sulphuric acid. The zinc-chloride double salt, (C 12 8 2 S 5 HCl) 2 ZriCl 2 , forms

HN

long brownish-violet needles. The compounds hitherto described correspond to the indamines ; the following ones must be regarded as sulphuretted indophenols,
as

oxygen partly takes the place of the nitrogenous groups of the

former.

atom in adding to the stability of also very apparent in these bodies, as they exhibit a far greater resistance to the action of chemical agents than the
The
influence of the sulphur
is

the molecule

corresponding simple indophenols.

QUINONEIM1DE DYESTUFFS.

159

Thionoline (Thioxindophenol) [36].

N
This compound

/ C H NH
6 3
]

>S

may be

obtained by oxidation of paramidophenol

in presence of sulphuretted hydrogen, or by treating Lauth's violet with an alkali. In the latter case the imido-group is eliminated
as

ammonia.

The base forms yellowish-brown

leaflets,

with a green reflex

the hydrochloride crystallises in fine black needles, forming a reddish-violet solution with water.

The dimethyl

derivative of thionoline

formed by boiling methylene blue with sulphone of methylene blue, C 16 H 17 produced [36].

(Methylene Violet) is methylene azure, the 3 SO 2 , being simultaneously

alkali,

The base of dimethyl thionoline, C U H 13 SN 3 O, forms long

and
its

needles, alcoholic solution shows a reddish-brown fluorescence.

The hydrochloride crystallises in brilliant green needles which dissolve in concentrated sulphuric acid with a green colour, and
dyes silk
violet.

Oxythiodiphenylimide [36],

produced by oxidation of oxythiodiphenylamine (from oxyIt forms reddish-brown needles diphenylamine and sulphur). which dissolve sparingly in ether, acetone, &c., with an orange-red
is

colour.

Thionol (Dioocytlnodiphenylimide) [36],

'

Nx
is

>

formed, along with thionoline. by boiling Lauth's violet with

160

CHEMISTRY OF ORGANIC DYESTUFFS.

and also by treating thiodiphenylIt is amine with sulphuric acid containing 75 per cent. SO 3 insoluble in water and crystallises from hydrochloric acid in It possesses simultaneneedles, which contain hydrochloric acid. weak basic and strong acid properties. ously The acid solutions are reddish violet, the alkaline solutions
alkali or dilute sulphuric acid,
.

violet in colour.

The barium

salt,

C l3 H 7 NSO.,BaO, forms

brilliant

green

leaflets

soluble in water.

Metlnjlene

Red

[19, 36, 53].

This compound is a bye-product in the preparation of methylene Its formation is greatest in presence of blue by the old process.
a large amount of sulphuretted hydrogen. Its constitution is expressed by the formula

/N(CH
C 6 H 3 -N

3) 2

C1

\ >S \s/
This
is

deduced from the following properties.

On
3

reduction

it

yields dimethylparaphenylenediamine-mercaptanC 6

H NH
X SH

/N(CH
2

3 ) 2 [4]

[1] [2]

and
acid,

is

decolorised

by
3) 3
,

alkalies, the

corresponding thiosulphonic

C6 H

/N(CH

X S-SO 3 H

NH

being formed amongst other compounds.

is easily soluble in water, The hydriodide is extracted from the solution by phenol. more sparingly soluble and crystallises from water in thick prisms. On reduction, and subsequent oxidation with dimethylaniline,

The hydrochloride, C 8 H 9 N 2 S 2 ,HC1,

is

and

methylene blue

is

formed.

QUINONEIMIDE DYESTUFFS.

161

Methylene Green.
This compound
nitrous acid.
is

obtained by treating methylene blue with

appears, from blue. In its behaviour towards

It dyes textile fibres a fine dark green colour, its properties, to be a nitro-derivative of
fibres it

and

methylene

resembles

j;he latter.

4.

OXYINDAMINES AND OXYINDOPHENOLS.

(OXAZINES.)

This denomination includes a series of compounds analogous to the thioindamines and containing an oxygen atom in place of the

sulphur atom of the latter. These compounds are formed by the action of iiitrosodimethylaniline or of quinonedichlorimide on certain phenols or phenolcarbonic acids in a hot alcoholic or acetic acid solution, or by
oxidation of these phenols with paradiamines at a
perature.

medium tem-

The dyestuffs from /3-naphthol and from gallic acid are best known. The former was discovered almost simultaneously by Witt and Meldola.

Naphthol Blue [29,

51].

C 18 H 15 N2 O.C1
This dyestuff
is

C1.N(CH 3 2 = C 6 H 3^
)

N
C 10 H 6
.

by heating nitrosodimethylaniline hydrochloride part of the nitrosodimethylaniline becomes reduced to dimethylparaphenylenediamine during the reaction.
with. /3-naphthol in alcoholic solution.

best prepared

The base is soluble in benzene with a red colour. The hydrochloride, C 18 H U N2 O,HC1, and the zinc chloride double salt form bronzy needles, which form blue-violet solutions
with water.
salt, (C 18 H 14 N 2 O,HCl) 2 PtCl4 The compound dyes on cotton prepared with tannic acid, and produces a somewhat dull violet-blue shade similar to indigo. The dyestuff is known commercially as Fast Blue, Naphthol Blue, and

Platinum double

162
Meldola's Blue.

CHEMISTRY OF ORGANIC DYESTUFFS.

The dyestuff

exerts an extremely irritating action

nostrils.

on the mucous membrane of the

/3-naphthol reacts with chlorquinonediimide, producing a red It does not form a dyestuff of the composition C 16 10 2 O [51]

H N

diazo-compound, and therefore probably contains no free amidogroup. Its constitution is probably expressed by the formula

NH
fluorescence, the salts dissolve in concentrated sulphuric acid with a green colour, which on dilution turns through blue to red.

The base has a yellow colour without

Under similar conditions a-naphthol yields a dyestuff which dissolves in dilute hydrochloric acid with a red colour, and produces a greyish-violet shade in dyeing.
Resorcin reacts with nitrosodimethylaniline, producing a fluorescent violet dyestuff [29] Sulphonic acids of this
.

series

may

also

be obtained from

sulphonic acids of the phenols.

Muscarine.

C 18 H 15N 2

2 C1.

This dyestuff is an hydroxyl derivative of naphthol blue, and is obtained by interaction of nitrosodimethylaniline hydrochloride

and a dioxynaphthalene, M.P. 186. sented by the formula

:

Its

constitution

is

repre-

C1N(CH 3 2 C 6 H
)

^\ C

10

OH.

The base is yellowish brown, and is obtained by precipitating the violet solution of one of the salts with an alkali. It forms a
bluish-green solution with concentrated sulphuric acid, and on dilution the colour changes through blue to violet, a violet precipitate being

formed finally.
tannic acid.

It dyes a dull blue

shade on cotton

mordanted with

QUINONEIMIDE DYESTUFFS.

163

Nile Blue.
(C 18

H N 0) S0
16 3
2

4.

chloride

This dyestuff is prepared by heating a-naphthylamine hydrowith nitrosodimethylmetamidophenol hydrochloride in

acetic-acid solution to

100.

Nile blue

is

soluble in water and

alcohol with

Alkalies produce a brownish presoluble in ether with a brown fluorescence. cipitate, Sulphuric acid dissolves it with a yellow colour, which on dilution changes

a blue colour.

On adding hydrochloric acid to an through green to blue. solution of Nile blue, the sparingly soluble hydrochloride aqueous
is

precipitated.

The hydrochloride has the

Cl
.

constitution expressed

by the formula

NCH = CH<
on cotton prepared

CHNH.
10

Nile blue
tartar emetic,

dyes

with

tannic

acid

and

producing a greenish-blue shade of great beauty and similar to methylene blue, but clearer. purity,

Gallocyanine [32, 51].

This dyestuff has attained considerable importance, especially in calico-printing, and is obtained by acting with nitrosodimethylaniline hydrochloride on gallic acid in a hot alcoholic or
acetic acid solution.

green needles.
Gallocyanine
acid.

The compound crystallises out in brilliant The mother-liquors always contain dimethyl-

paraphenylenediamine.
is sparingly soluble in hot water, alcohol, and It possesses The solutions have a violet colour. simultaneously acid and basic properties, and is precipitated from

acetic

the reddish- violet alkaline solution by acids. Gallocyanine dissolves with difficulty in hydrochloric acid,

forming a reddish- violet solution.

acid
It
is

Its solution in strbng sulphuric

blue.

forms an almost colourless crystalline compound with sodium

of gallocyanine
is

bisulphate.

The composition

expressed by the formula

6 ;

C 15 H 12N2

MS

164
and
its

CHEMISTRY OF ORGANIC DYESTUFFS.

formation
is

explained by the following equation

G

3C 8 H 10N 2
aniline.

+ 2C H
7

2C 15 H 12N 2
Gallocyaniue.

+ C H 12N 2 + H
8

O.

-Nitrosodimetliyl-

Gallic
acid.

Dimetliyl-

Water.

paraphenyldianiine.

Gallocyanine is easily soluble in hot aniline, and, on cooling, an This anilide is formed anilide crystallises in long green needles. by action of two molecules of aniline, according to the equation

C 15 H 12 N 2
This

+ 2C H
6

NH = C H N O
3

27

24

+H

O.

compound may be regarded

as

an aniline addition-product
[51].

of the anilide
5

The anilide possesses well-marked basic properties. The methyl-ether of gallic acid reacts with nitrosodimethylaniline,
producing a methyl-ether of gallocyanine,
)
.

compound
Prune

is

a dyestuff, and

differs

C 15 H n N2 O 5 (CH 3 This commerce as Prune [51] from gallocyanine inasmuch as the former is a
is

known

in

base forming stable soluble

salts,

while in gallocyanine the acid

also

properties are predominant. Nitrosodimethylaniline reacts

with the amide

of gallic

acid (" gallaminic acid "), and forms a blue dyestuff, which is met with in commerce in form of its bisulphite compound under the

name Gallamine
Gallocyanine formulae
:

Blue.
is

constituted according to one of the following

HOOC

HOOC

OH
N(CH 3 )
5

the fact that the methyl-ether of gallocyanine yields a diacetyl derivative, the second formula appears the more probable. The pentatomic nitrogen present is probably saturated by the

From

QUINONEIMIDE DYESTUFFS.

165

carboxyl group in gallocyanine, or by an hydroxyl group in Prune, as the base contains no ammonium hydroxyl group. These three dyestuffs are capable of dyeing on mordants, and

produce violet lakes with iron, aluminium, and especially with chromium oxides. On account of the fastness of the shades produced, these dyestuffs are largely used in calico-printing and in In printing, a mixture with sodium bisulphite and wool-dyeing. chromium acetate is used, the insoluble chromium-lake being produced by steaming. Wool may be dyed without any mordant, but faster shades are obtained by chroming the wool first. Prune having more pronounced basic properties may be dyed on cotton prepared with tannic acid and tartar emetic. Prune comes into the market as a powder Gallocyanine and
;

Gallamine Blue generally as pastes.

5.

DICHROl'NES.

Liebermann's Phenol Dyestuffs [30].

As it has been demonstrated that certain of these dyestuffs are derivatives of phenoxazine, they are best described here. On treating phenols in concentrated sulphuric acid solution at

40-50

are formed.

C. with nitrous acid, peculiar violet or blue compounds They are of distinctly acid character, and are repre-

Their cipitated from alkaline solutions on addition of acids. alkaline solutions exhibit a remarkable fluorescence, and for this
reason this class of compounds is also known as Dichroi'nes. The dyestuff from phenol has the composition, C 18 15 3

H NO

It

forms a brown powder, insoluble in water, soluble in alkalies with The thymol dyestuff has the formula C 3 oH3 6 2 O 4, a blue colour.

and the orcin dyestuff C 2 iH 18

NO
2

6.

Both have a

violet colour.

Eesofujin (Weselsktfs Diazoresorufiri).

C 12 H 7 NO 3

[31, 33, 34, 54.]

This compound is formed by action of nitro- or nitrosoresorcin or nitrobenzene on resorcin in presence of concentrated sulphuric It may also be obtained from resazurin (see below) acid at 1 70.

by various methods.

Resazurin yields resorufin on heating alone

166

CHEMISTRY OF ORGANIC DYESTUFFS.

or with concentrated sulphuric acid to 110, by reduction with

sodium bisulphite, or with zinc powder or iron, and subsequent oxidation in the air. Resorufin is also formed in the preparation of resazurin. The following synthetic methods give a clear idea of its constitution. On dissolving an equal number of molecules of nitrosoresorcin and resorcin in concentrated sulphuric acid a dyestuff is formed, which, on heating the mixture to 100, goes
over into resorufin.

may

The intermediate product of the reaction be regarded as an indophenol of resorcin formed according
scheme
:

to the

O=

OH

HO

=N

QUINONEIMIDE DYESTUFFS.

167

concentrated hydrochloric acid. It dissolves readily in alkalies, and the solution exhibits a beautiful cinnabar-red fluorescence.
Resorufin ethyl-ether,
silver
salt

C 12 H 6 NO 3 (C 2 H 5 ), is formed by
It

heating the

with ethyl iodide and alcohol.

:

forms orange-red

needles,

M.P. 225.

Hydroresorufin (Dioxyphenoxazm)

o\
This
acid
is

tHOH.

a leuco-compound formed
It

solution.

forms long silky needles,

by reduction of resorufin in M.P. 216. In

alkaline solution

it oxidises rapidly to resorufin. Tetrabromresorufin is obtained by action of bromine on an Na alkaline solution of resorufin. Its sodium salt, C 13 2 Br4 3

NO

commercial Resorcin Blue or Fluorescent Blue. It dyes wool and silk in an acid bath, and produces bluish- violet shades, remarkable for their beautiful red fluorescence.

+ 2H 2 O, forms the

Eesazurin (WeselsJcy's Diazoresorcin]

[31, 33, 34.]

C 12 H 7 N0 4
This

formed by action of nitrous acid on an It forms lustrous green prisms, which are insoluble in water and ether, sparingly soluble in The alkaline solutions alcohol, and easily soluble in alkalies. are violet, and have a brown fluorescence.

compound

is

ethereal solution of resorcin.

The

constitution of resazurin

is

not known with certainty.

It

contains one oxygen atom more than resorufin, and the two are evidently closely related from the ease with which resazurin may

be transformed into resorufin.

dioxyphenazoxin on reduction. expressed by the formula

:

The two also yield the same It is probable that resazurin is

168

CHEMISTRY OF ORGANIC DYESTUFFS.

Acetyl resazurin,

C 12 H 6 NO 4 (C 2 H 3 O), forms

long red needles,

M.P. 222.
Resazurin ethyl ether,

C 12 H 6 NO4 (C 2 H 5 ), forms

dark red needles,

M.P. 215.

Orcirufin.

[33,34, 55.]
.

C 14 H UN0 3
This compound
is

formed by action of nitrous acid on an

ethereal orcin solution, and is identical with the dyestuff obtained by Liebermann by action of nitrous acid on orcin in presence of

sulphuric acid. Orcirufin yields a monoacetyl derivative, M.P. 204. This body is closely related to resoResorufamin, C l2 8 2 O 2

HN

rufin, one oxygen atom of the latter being replaced by an amidoIt is obtained by heating quinonedichlorimide with group.

resorcin in alcoholic solution.

Resorufamin is only obtained in small quantity. It is a base forming salts which are easily soluble, and the solutions exhibit practically the same fluorescence as the alkaline solution of resorufin.

is

Orcirufamin, C 13 H 10 2 O 2 , is obtained in a similar manner, but formed in larger quantity. It closely resembles the above. Lacmoid. This colouring-matter, which probably belongs to the above series, was obtained by heating resorcin with sodium It forms blue salts with alkalies, nitrite [46, Traube and Hock]. and their solutions are turned red by acids. For this reason it has been proposed as an indicator in titration.

AZINE DYESTUFFS.

169

CHAPTER

VII.

AZINE DYESTUFFS.
THIS chapter comprises the saffranines and their allies, amongst which are the eurhodines, toluylene red, the so-called neutral dyes, Basle blue, and probably Magdala red and Mauveine. Most of these dyestuffs have been long known, but we owe most

knowledge of their constitution to the researches of Witt on the eurhodines. Witt observed that a compound of this class [37], obtained by action of a-naphthylamine on orthoamidoazotoluene, gives, on removal of the amido- group, tolunaphthazine (naphthylene-toluylenequinoxaline). All these dyestuffs The are derivatives of an azine (quinoxaline of Hinsberg).
simplest body of the azine group
is

of our

phenazine (azophenylene of

Clans and Rasenack)

The group

'

N
I

which replaces two ortho-hydrogen atoms

in

each benzene ring,

is the chromophor of the whole series. The azine group, with the four adjacent carbon atoms, forms a new ring, containing six atoms, so that phenazine may be regarded

as containing three rings, like* anthracene.

N
.

Phenazine.

170

CHEMISTRY OF ORGANIC DYESTUFFS.

azines are
in

The

some

respects analogous to the quinone-

anilides.

in the reaction between a paraquinone and a diamine, one amido-group enters into the reaction with one quinone only group, the action of an orthodiamine and an orthoquinone is just double, both oxygen atoms being eliminated in form of water with the hydrogen of the amido-group, the nitrogen of the
latter entering in the place of the oxygen. The reaction will be easily understood

While

from the following

graphic equation

o
11

RH N
11

+ H

0.

The simplest

bodies, their salts being

azines are not dyestuffs, they are slightly coloured generally yellow, and possessing weak basic properties,

decomposed by water.
intensifies tlie basic character

The introduction of amido-groups

of the azine, and increases the dyeing properties. Hydroxyl groups produce colouring-matters of a slightly acid nature, which have, however, only little tinctorial power. Monamidoazines (Eurhodines) are only weak dyestuffs, the dyeing-power being fully developed by introduction of two or

more amido-groups. The azines are closely

related to

the indamines; the latter

being derivatives of paraquinonediimide, while the former correspond to the orthoquinonediimides, only in this case the condensation so

The

in the ortho series takes place. relationship between the two classes of compounds

common

is

shown

by the fact that the indamines may be easily converted into azines, and that monamines, with a free para position capable of
yielding indamines on positions are occupied.
is

oxidation, give azines when the para The conversion of indamines into azines in

especially

instructive

the case of amidoindamines

for

AZINE DYESTUFFS.
example, Toluylene blue.
this

171

On

heating an

compound

for

some time, Toluylene

red,

formed with elimination of hydrogen. liberated as such, but converts a portion of the toluylene blue to
its

aqueous solution of an amidoazine, is The hydrogen is not

The

leuco-base [4] reaction will

.
:

be readily

understood from the following

equation

(CII 3 ) 2

N
Toluylene blue.
Toluylene red.

The amido-group adjacent to the nitrogen atom linking the benzene chains in the indamine, loses its hydrogen atoms, and becomes linked to the second benzene chain, while the imidogroup is simultaneously reduced to an amido-group. If an oxidising agent is present, the conversion of toluylene
blue into leuco-base does not take place.
yield azines in presence of a In this case saffranines are formed. amine. These primary bodies contain probably a phenylazonium group, viz., an azine group containing a pentatomic nitrogen atom, w hich is linked with chlorine and a benzene ring.
r

The simpler indamines only

Although the basic character of the azines

is

increased by the

introduction of amido-groups, the azine group plays the principal If acetyl groups are introduced part in the formation of salts.
into the amido-groups the basic properties of the

compound

are

decreased, but not entirely destroyed. further confirmation of this is seen in the behaviour of the

polyacid salts and of the corresponding diazo-compounds. Diamidoazines generally form three series of salts, of which the

monoacid are red, the diacid blue, and the triacid green. The two latter compounds are decomposed by water, the first one is
stable.

If a diazo-group is introduced into a diamidoazine the compound forms stable diacid salts, which have likewise a blue colour. With a second diazo-group a stable green salt may be obtained.

172

CHEMISTRY OF ORGANIC DYESTUFFS.

as

As diazo-groups can only be formed from amido-groups, and

the conversion into diazo-compound increases the

stable salt-

forming capacity once for each diazo-group,

it is a necessary conclusion that the acid radical present in the red stable salt cannot be connected with the amido-groups.

dye monoacid, and not of the polyacid salts, thus showing that the azine group effects the combination with
fibres the colour of the

Another point in

this connection is that the amidoazines

the

fibre.

nitrogen atoms appear capable of with acids, at least this is probable from the various combining colour-reactions which these bodies give with strong acids.

In the

mon amidoazines both

The azine dyestuffs mostly possess a well-marked fluorescence ; this appears in some cases in the alcoholic solutions of the salts,
and in others in the ethereal solution of the base.

1.

EURHODINES

[37, 38].

(AMIDOAZINES.)
This class of bodies was discovered by Witt. They are formed by action of orthoamidoazo-compounds on monamines (ortho-

amidoazotoluene on a-naphthylamine), by action of orthoquinones on triamines with two adjacent amido-groups, and by action of nitrosodimethylaniline or of quinonedichlordiimide on certain monamines, in which the para position is occupied [50, 52]
.

The eurhodines
is

are in general

weak

green.

usually yellow, the monoacid Both are readily decomposed by water. The monoacid salts dye silk red, but on washing a change to the yellow colour of the base takes place. Most eurhodines give a red solution with

basic dyestuffs. The base salts red, and the diacid salts

concentrated sulphuric acid, the colour changing through black and green into red again on dilution. The ethereal solutions of
the bases exhibit a yellowish-green fluorescence.

Eurhodine,

C 17 H 13 N 3

[37].

(Amidotolunaphthazine.)

This compound is obtained by heating orthoamidoazotoluene with a-naphthylamine hydrochloride. The base forms golden-

AZINE DYESTUFFS.

173

yellow needles sparingly soluble in alcohol and ether, easily in The aniline and phenol. It sublimes without decomposition.

Concentrated sulethereal solution shows a green fluorescence. acid dissolves it with a red colour, which changes through phuric black and green into red on dilution. It reacts with nitrous acid

producing a diazo-compound, which is decomposed on boiling with alcohol, eurhodol ethyl ether, C 17 n 2 O C 2 H 5 , being formed. The hydrochloride, C 17 13 3 ,HC1, forms deep red, bronzy

H N

H N

needles.

Witt accords the following constitution to

this eurhodine [28]

Eurhodine,

H N-C H
2

[50].

(Amidophe?maphthazine. )
Is

formed by action of quinonedichlordiimide on /3-naphthylamine according to the following equation

:

N
H
tion.

>C 10 H 6 + 2HC1.

The base has a yellow colour, and fluoresces in ethereal soluThe salts are red, without fluorescence, and are decomposed

174

CHEMISTRY OF ORGANIC DYESTUFFS.

by water.

The compound forms a brown

:

solution with concen-

It yields naphthophenazine on boiling with trated sulphuric acid. nitrous acid and alcohol

Dimethy lamidop liennaph thazin e, (CH 8 ) 2NC 6 H 3

is

<^

\C

10

6.

prepared by action of nitrosodimethylaniline on /3-naphthyl-

aniline [52].

The base is yellow, dissolves in concentrated sulphuric acid with a violet colour, and forms blue unstable salts [52].

Amidoplienophenanthrazine.

This eurhodine

is

unsymmetrical triamidobenzene. or a brown crystalline powder.

formed by action of phenanthrenequinone on The base forms yellow flocks

and of a carmine-red colour.

The salts are sparingly soluble, The reactions are similar to those

of the preceding compounds [38]. Eurhodines are also formed by the action of triamidobenzene

on j-naphthoquinone, glyoxal, benzil, isatine, and leuconic A dimethyl eurhodine (dimethylamidophenotoluazine),

[39],
is

acid.

formed on boiling diazotised toluylene red with

alcohol.

AZINE DYESTUFFS.

175

2.

EURHODOLS.

(OXYAZINES.) These bodies are formed by melting the azinesulphonic acids with caustic potash [40] and by heating the eurhodines with concentrated hydrochloric acid to 180 [38]. They resemble the eurhodines in colour and fluorescence, and in
their reactions with concentrated

sulphuric acid,

but

differ in

possessing both phenolic and basic properties.

Oxynaphthoto luazine,

C 17 H 12N 3 0.
This eurhodol
is

obtained by heating the corresponding eurho-

dine, C 17 13 3 , with hydrochloric acid or dilute sulphuric acid. It dissolves in concentrated sulphuric acid with a red colour, and is

H N

precipitated from this solution in yellow flocks

on addition of

water [38].

Eurhodol,

C 24 H 14N 2 O.
(

Oxyphenanthrenenaphthazine.)

This

compound

is

formed by melting phenanthrene-naphthazine-

sulphonic acid (from phenanthrenequinone and a/3-naphthylenediaminesulphonic acid) with caustic potash. It dissolves in concentrated

sulphuric
into

acid with

blue

colour,

which suddenly
a

changes

bright red on dilution.

Its sulphonic acid is

yellow dyestuff.
different concentrations

by the eurhodols with acids of can only be explained on the assumption that mono- and diacid salts exist, in which, according to circumstances, one or both nitrogen atoms of the azine group exert basic
colour-reactions exhibited
functions.

The

3.

TOLUYLENE RED.

(CH 3 2NC 6 H 3 <f ^>C 6 H 2

)

/
NH

N/

[4] .

Toluylene Red is a diamidoazine, the simplest of which, diamido-

176
phenazine,
is

CHEMISTRY OF ORGANIC DYESTUFFS.

obtained by oxidation of triamidophenylamine with

manganese

dioxide.

NH -C H <
2 6 3

NH

NH/

\C H 4 NH +
6
.

\N/

C 6 H 3 -NH 2

Toluylene red is a dimethyl derivative of a homologue of diamidophenazine, and is prepared by oxidation of dimethylparaphenylenediamine with metatoluylenediamine at the boil, and is
also formed by heating toluylene blue (amidoindamine) [4] (see introduction to the Azine Dyestuffs) The base forms orange-red which contain four molecules of water. The water may crystals,
.

be expelled at 150, leaving the anhydrous compound, which is of a blood-red colour [4J. The alcoholic and ethereal solutions
fluoresce strongly.

The monoacid hydrochloride is a fine red dyes tuff, which is turned blue by hydrochloric acid, and green by concentrated The zinc-chloride double salt forms crystals with sulphuric acid.
a metallic lustre [4] . Toluylene red comes into commerce as Neutral Red, and being a basic dyestuff is fixed on cotton by means of tannic acid.

Toluylene red contains one free amido-group and yields a diazocompound, which gives a dimethyl eurhodine on boiling with
of paraphenylene-diamine and metatoluylenediamine, a non-methylated toluylene blue is formed which yields This latter forms a corresponding toluylene red on heating. a tetrazo-compound which yields methylphenazine (benzenetolazine)
:

alcohol [39]. By oxidation

N
C 6 H 4 <;
|

>C H CH
6 3

[39],

on boiling with

alcohol.

violet dyestuff,

formula

C U H 14 N4

is

Toluylene Violet, to which Witt ascribes the formed by treating toluylene blue with an
.

similar dyestuff, known excess of metatoluylenediamine [4] as Neutral Violet, is the product of the oxidation commercially of dimethylparaphenylenediamine with metaphenylenediamiue.

AZINE DYESTUFFS.

177

4.

SAFFRANINES

[1, 2, 3, 4].

dyestuffs coming under this classification contain four Unlike the previous azine dyestuffs, they contain nitrogen atoms. at least three hydrocarbon chains. Although their behaviour shows them to be phenazine derivatives,, they differ in many respects from those previously described. Especially noticeable is their strong basic character, which in many respects resembles that of the quaternary ammonium bases, and the characteristic
bitter taste of the latter

The

compounds

is

nines.

Another point of difference from the

also present in the saffrarest of the azine

dyestuffs is that the free base has the acid salts.

same colour

as the

mono-

basic properties of the saffranines are doubtfunctions of the azine group, although two amido-groups are The hydrogen atoms of the latter may be replaced also present.
less

The well-marked

and from the fact that the diacetyl mono-acid bases, it is evident that the strongly basic properties of the azine group remain unaffected. The saffranines form three series of salts. The mono-acid salts are, like the base, red and very stable ; the diacid salts are blue, and the triacid green. The two latter series are decomposed by water and in fact the green salts can only exist in presence of

by alcohol or acid

radicals

derivatives are

still

concentrated sulphuric or hydrochloric acids. Both amido-groups may be diazotised [1], The primary diazo-compound forms blue

which are formed in slightly acid solutions, and to the blue diacid saffranine salts. The green tetrazocorrespond
diacid salts,

compounds have not been analysed, but probably correspond to The salts of these diazo-compounds are not the triacid salts.
decomposed by water.

The
latter

saffranines are products of the following reactions

By

heating primary monamines with indamines, whereby part of the

undergo reduction [1, 3, 4] ; by oxidation of paradiamidodiphenylamine and its analogues with primary bases [1] ; and by oxidation of paradiamines with two molecules of the latter [3, 4] In the oxidation of paradiamines with monamines two different monamines may be used, of which one only need be primary. For the diamine and one monamine the same conditions must be observed as for the production of an indamine, *. e. that the diamine must only be substituted in one amido-group, and the monamine must possess a free para position. As an indamine is
.

I-'Q /O

CHEMISTRY OF ORGANIC DYESTUFFS.

always formed as an intermediate product, all three processes may be said to depend on the same reaction i. e. an indamine is formed either from diamidodiphenylamine or from the diamine and one

molecule of monamine. The monamine used in the second stage of the process must not be substituted in the amido-group, but
the para position need not be free. As, however, certain monamines are not capable of reacting in this sense, as, for example, ortho substituted monamines such as mesidine and adjacent

metaxylidine do not form saffranine with indamines [41], it may be conjectured that the monamine not only becomes connected through its nitrogen atom, but also through an ortho position in the ring, This assumption receives further confirmation from the fact that the formula of the simplest saffranine cannot be sym-

Two different metrical, as the amido-groups react differently. each substituted in one amido-group, may be dialkyl saffranines,
prepared, each yielding a diazo-compound, and
therefore each

containing one free amido-group. Numerous formulae have been proposed to express the constitution of the simplest saffranine in accordance with the above facts;
that of Witt, however, alone fulfils the necessary conditions. According to Witt the formation of saffranine from the simplest

indamine and aniline proceeds as shown in the following schematic

equation
:

NH

NH,

HC1

+4H
Aniline
hydroehloride.

11

NH
NH,
Indamine.

Phenosaflranine hydrochloride.

According to this assumption the aniline becomes connected with the nitrogen atom of the diphenylamine through its benzene

AZINE DYESTUFFS.
ring,

179

and a derivative of triphenylamiiie is formed, the indamine link being dissolved. The nitrogen atom of the aniline simulenters one benzene chain of the indamine, in the ortho taneously
position to the diphenylamine nitrogen atom, and the nitrogen atoms become linked and form the azine ring. This saffranine

formula

may

be shortly written thus

/ N\ H N-C H <|>C H
2 6
3

4,

and corresponds completely with the properties of the compound, Here the amido-groups have different values, and this explains the isomerism of the alkyl-substitution products. The pentatomic nitrogen atom, simultaneously linked with chlorine and benzene,
offers distinct
salts.

reason for the stability of the monoacid* saffranine

Further evidence is afforded by the fact that the saffranine base contains one molecule of water, and that other phenylazonium

compounds have been prepared synthetically. Witt obtained such a compound by action of phenanthrenequinone on orthoamidophenyl-/3-naphthylamine,

HN
2

C 10 H 6

NH
it
:

C6 H5

and

ascribes the following formula to

C 10 H 6 < >C 14 H 8

N N
[

OH

Csl15

The dyestuffs obtained by action of nitrosodimethylaniline or oE quinonedichlorimide on phenyl-/3-naphthylamine are also probably members of this class of compounds [50, 52] The monoacid salts of the saffranine series are generally red ; the introduction of alcohol radicals into the amido-groups makes the
.

violet, while the introduction of methoxyl and ethoxyl groups into the benzene ring tends to produce yellower shades. The saffranines are dyed on cotton mordanted with tannic acid, and produce the shade of their monoacid salts. Unmordanted

shade more

cotton

is

The

diacid

capable of fixing small amounts of saffranine. salts are produced by concentrated hydrochloric

N2

180

CHEMISTRY OF ORGANIC DYESTUFFS.

;

acid and are blue

the green triacid salts are obtained with con-

Both are only capable of existence in centrated sulphuric acid. presence of excess of acid, and are decomposed by water with
formation of a monoacid
salt.

The bases may be obtained by

decomposition of the sulphates with barium hydrate; they are of the same colour as the monoacid salts, and are easily soluble in
water.

They form carbonates with carbonic

acid.

saffranines yield leuco-compounds on reduction, which are pretty stable in acid solution, but are almost immediately oxidised to the original dyestuff in presence of alkalies. If the reduction

The

saffranine

be effected with acid stannous-chloride solution, one molecule of is found to require one molecule of stannous chloride,
for the conits

showing that two atoms of hydrogen are required

version of saffranine into
leuco-base.

Phenosaffranine, by continued boiling with zinc powder and hydrochloric acid, may be converted into a very stable colourless base, C 18 19 3 0.

H N

Besides the reactions already mentioned, saffranines are also formed by action of amines on amidoazo- compounds [45], by oxidation of the latter, and by oxidation of the mauveines [28]
.

The formation from amidoazo -com pounds comes under one

general methods, as
it

of the

doubtless depends on the splitting up of the

by the which depends on the oxidation of one molecule of a process paradiamine with two molecules of a monamine. The bases necessary are obtained by reduction of amidoazo-compounds. Orthotoluidine (" Echappes/' the recovered oil from Magentamanufacture, consisting of orthotoluidine and aniline, may be used) is submitted to the action of sodium nitrite and hydrochloric acid, whereby a mixture of amidoazotoluene and orthotoluidine is obtained or, if Echappes are used, a mixture of amidoazotoluene, amidoazotoluenebenzene, amidoazobenzene, aniline, and orthoThe mixture is then reduced with zinc or toluidine is produced. iron and hydrochloric acid, the result in the simplest case being the production of a mixture of one molecule paratoluylenediamine and two molecules of orthotoluidine, while the principal products from the mixture of bases are toluylenediamine and paraphenylenediamine with orthotoluidine and aniline. In any case the mixture is treated in dilute neutral solution with potassium bichromate and
;

azo-compound into a paradiamine and a monamine. The manufacture of the saffranines is always effected

boiled,

or

the oxidation

may

be

effected

by manganese oxide

AZINE DYESTUFFS.

181

(Weldon mud)

an indamine which yields a

the moriamine.

in presence of an organic acid. The first product is saffraiiine on further oxidation with

Violet dyestuffs are formed along with the and these, being less basic, may be separated by soda and saflranine, chalk, and the saffranine remaining in solution is salted out. The tolusaffranines are the only ones of importance, and their chief use is in cotton-dyeing. In conjunction with yellow dyestuffs

similar to

The

aurarnine, turmeric) they produce shades Turkey red, but of course inferior as regards fastness. saffranines are also used in silk-dyeing and produce beautiful
(chryso'idine,

rose shades.

Phenosaffranine [22,

1, 2, 3].

C 18 H 14 N4

This compound was first obtained by Witt by the oxidation of one molecule of paraphenylenediamine with two molecules of It may also be obtained by oxidation of equal aniline [4]. molecules of aniline and paradiamidodiphenylaimne [1]. The free base may be obtained by decomposing the sulphate On with an exactly equivalent quantity of barium hydrate.
evaporating the resulting solution in vacua, the base suddenly crystallises out in green leaflets, and is then found to have lost its
easy solubility in water. The composition of the base dried at 100

corresponds to the

formula

At 150

it

loses about \ molecule of water.

is

Saffranine base

not very stable

it

loses

ammonia on
its

boiling

with water.

The

alcoholic

solutions of
is

the base

and

salts

fluoresce

strongly, while this property

entirely absent in aqueous solutions.

The hydrochloride, C 18 14 4 ,HC1, crystallises from dilute hydrochloric acid in brilliant green leaflets, and from water in long It is preIts solution has a fine red colour. steel-blue needles.
cipitated in water,

H N
by

from

its

solutions

salt

and by strong hydrochloric

nitric acid [1, 2].

acid.

Nitrate,

C 18 H 14 N4 HNO 3 forms
,

green crystals sparingly soluble

and almost insoluble in dilute

The
golden

sulphate,

C 1S H UN4 H 2 SO 4

forms steel-blue needles.

Platinum double

salt [1], (C 18

H N 4 HC1)
14

PtCl 4 , forms lustrous

leaflets, insoluble in

water.

182

CHEMISTRY OF ORGANIC DYESTUFFS.

Diacetyl-hydrochloride [1], (C 18 12 4 ) (C 2 3 O) 2 HC1, is obtained by the action of acetic anhydride and sodium acetate on phenosaffranine hydrochloride. It forms lustrous brown leaflets,
dissolves in alcoholic potash with a violet colour. It is on boiling with dilute sulphuric acid, acetic acid and decomposed

H N

and

phenosafFranine being produced.

Diazo-compounds
The
diazochloride,

[1].

C 18 H 12 N8 HC1

is

formed by action of nitrous acid on the (blue) acid solution of

phenosaffranine hydrochloride. blue like the diacid saffranine

The
salts,

'

solution of the

compound

is

but unlike these does not

salt

change colour on dilution.

blue needles.

Its

platinum double
) 2,

forms broad

The gold

salt,

C 1 8H 13N5 Cl2 (AuCl 3

forms greenish-grey needles.

two molecules of nitrogen are evolved. On boiling the diazo-compound with alcohol the base C 18 H 13 N 3 is formed (see below)
boiling with water
.

On

tetrazo-compound of safFranine may be obtained in solution by treating the green solution of phenosaffranine in concentrated sulphuric acid with nitrous acid [1], The colour of the solution is not changed on dilution. On boiling with alcohol a violet base,
forming yellow
is

salts, is

produced.

The

chloride of this

compound

probably phenazinephenyl-chloride,

H
Ci

4,

the mother substance of the saiFranines It is interesting to [43]. note that the colour-reactions of this compound with acids are
it

exactly the same as those of the acetylated s affrani nes, from which appears that the acetylation has the same effect as the removal

of the amido-groups [43]. The easily obtained from the base C 18

H N
13

compound
3,

in question is more the intermediate product

in this case being a yellow diazo-compound.

AZINE DYESTUFFS.

183

a-Dimethylphenosaffran ine [2 ]

C 18 H 12 N4 (CH 3
is

) 2,

formed by oxidation of one molecule of dimethylparaphenylenediamine with two molecules of aniline.

is

The hydro chloride, C 20 H 18 N4 _,HC1, known commercially as Fuchsia. The nitrate, C 20 H 18 N 4 ,HNO 3 forms
,

a magenta-red dyestuff

Platinum double

salt,

(C 20

H N4 HCl)
18

lustrous green needles.

2

PtCl 4

(3-DimetJ^lphenosqff'ranine [41, 43].

This compound, isomeric with the above, is obtained by oxidation of one molecule of paraphenylenediamine with one molecule of dimethylaniline and one molecule of aniline. Its nitrate forms

brown

leaflets.

For

the crystallographic comparison of the

nitrates see [43].

Tetramethylphenosaffranine [2 ]

formed by oxidation of one molecule of dimethylparaphenylenediamine, one molecule of dimethylaniiiue,

This dyestuff
is

with one molecule of aniline.

Hydrochloride,

Nitrate, , brownish-violet thick crystals.

C 22 H 22N 4 ,HC1. C 22 H 22N 4 ,HNO 3 is

a fluorescent

dyestuff forming

Diethylsaffranines [1].

C 18 H 12 N4 (C 2 H 5

2.

a. From one molecule of dietbylparaphenylenediamine and two molecules of aniline, and From equal molecules of paraphenylenediamine, diethyl/3.

aniline,

and

aniline.
brilliant green

of both modifications form which are violet-red dyestufPs. needles,

The hydrochlorides

The /3-hydrochloride

is

much more
,

soluble in water than the

a-compound. Platinum salt, (C 22 H 23 N4 Cl) 2 PtCl 4

184
Acetyl

CHEMISTRY OF ORGANIC DYESTUFFS.

derivatives
[1].

monoacetyl sodium acetate.

derivatives

Both diethylsaffranines yield basic on heating with acetic anhydride and

possess the formula
3
3

The hydrochlorides
2

a H N Cl,C H 0,
23

with a violet colour.

and form lustrous brown needles, soluble in water and alcohol The alcoholic solutions do not fluoresce.

DiazO'Compoimds.

When treated with nitrous acid the diethylsaffranines yield diazo-compounds, analogous to the primary diazo-compounds of The solutions have a greenish-blue colour. pheiiosaffranine. The chloride corresponds to the formula
C 22 H 20N 3 HC1-N=NC1.
Platinum salt, C 22 21 5 Cl 2 PtC] 4 forms almost black needles with a coppery lustre. The fact that both modifications of dimethyl- and diethylsaffranine yield diazo-compounds, gives a certain proof of the
,

H N

presence of two amido-groups in saffraniue. Two isomeric monoethylsaffranines may be

obtained in

an

analogous manner.

The

constitution of the a-

and /3-compounds

is

probably ex-

pressed by the formulae

(CH 3 ) 2 N-C 6 H 3 V;C 6 H 4

7 X
Cl

C 6 H 4NH 2

a-Dimethylsafframne.

/Nx H,N-C,H/ 7 X

Wi
)

Cl

X C 6 H 4N(CH 3

j3-Dimetliylsafframne.

(Compare Indamines.)

AZINE DYESTUFFS.

185

Tetraethylphenosaffranin e [1 ]

C 18 H 10N 4 (C 2 H 5 ) 4
is

obtained by oxidation of equal molecules of diethylparaphenyIt forms a zinc chloride lenediamine, diethylaniline, and aniline. double salt which forms beautiful crystals with a golden-yellow
lustre.

fluorescence on
It
is

It is a bluish-violet dyestuff and exhibits a magnificent silk, but is speedily altered on exposure to light.

known

in

commerce
salt,

as Amethyst-Violet.

(C 26 30 4 ,HCl) 2 PtCl 4 does not react with either nitrous acid or Tetraethylsaffranine

Platinum double

H N

acetic anhydride.
dyestuifs, the constitution of which has not been definitely ascertained, but which from their method of preparation belong to the saffrauine series, are Eubramine and Girofle.

Two

Rubramine

is

prepared by acting on orthotoluidine with nitrosoIt

dimethylaniline in hydrochloric acid solution.

comes into
fine red-

greenish-brown powder, and produces a violet shade on cotton mordanted with tannic acid.
as
Girofle,
sia), is

commerce

It

is

probably a homologue of a-dimethylsaffranine (Fuchobtained by acting onxylidine with nitrosodimethylaniline. used for shading alizarine violet and reds.

Tolusaffranine [24].

C 21 H 20N4
Hydrochloride,
soluble in water and alcohol.

C 21 H 20 N 4) HC1, forms
salt,

fine

reddish-brown needles

Platinum double

(C 21

H N HCl)
20

PtCl 4 forms a yellowish,

red crystalline powder.

The

nitrate,.

C 21 H 20 N4 ,HNO 3 forms reddish-brown

,

needles

sparingly soluble in cold water.

Pier ate,

C 21 H 20N 4 C 6 H 2 (NO 2

) 3,

OH, forms

reddish-brown needles

insoluble in water and alcohol.

Besides the ortho-compound, formed by oxidation of one molecule of paratoluylenediamine, there exists a second one which is formed from equal molecules of toluylenediamine, aniline, and

orthotoluidine, and
solubility.

is distinguished from the former by its Both come into commerce as hydrochlorides.

lesser

The

186
latter, if

CHEMISTRY OF ORGANIC DYESTUFFS.

prepared as usual from a mixture of aniline and toluiThese dine, generally contains a lower homologue, C 20 18 4 differ but little in shade, and produce on silk, wool, and dyestuffs

H N

cotton prepared with tannic acid, tones about halfway between magenta and ponceau. Dyestuffs which are to be regarded

oxymethyl- and oxyethyl-derivatives of phenosaffraiiine are produced by oxidation of paraphenylenediamine with two molecules of orthoanisidine or two molecules of orthoamidophenetol.
as

The orthoanisidine compound has probably the composition

C 18 H 12 (OCH 3

4.

Similar bodies are formed if the orthoanisidine is partly replaced by paranisidine or another primary monamine. These dyestuffs are especially characterized by their pure yellow shade. When dyed on silk they fluoresce strongly, the shades obtained resembling those produced by some of the cosines. Owing to their high price, however, they have not been used on a large scale.

The compound C 18 13 3 [43, 49] has already been mentioned as the product obtained on boiling the primary diazo-compound Its salts have a magenta-red of phenosaffranine with alcohol.
colour and do not fluoresce in alcoholic solution.

H N

Concentrated

sulphuric acid dissolves them with a yellowish-green colour, and on dilution the colour changes through green to red ; the blue

phase does not occur.

Nitrate, needles.

C 18 H 13 N 3,HNO 3
salt

forms

brown,

difficultly

soluble

Zinc chloride double

Acetyl derivative,

forms lustrous brown needles.

is

C 18 H 12 N 3 C 3 H 3 O,

a violet

compound forming

yellow monoacid salts. The compounds obtained by Witt [52], and by Nietzki and Otto [50, 51], by action of nitrosodimethylaniline and of quinonedichlorimide on phenyl-/3-naphthylamine in all probability belong
to this series.

By

action of quinonedichlorimide on phenyl-/3-naphthylamine, a

violet base is

produced forming magenta-red salts. dissolves in concentrated sulphuric acid with a violet colour which on dilution changes through dirty green into red. The composition of the salts may be expressed by the C 22 H 15 3 R. general formula

The compound

AZINE DYESTUFFS.
Nitrate,

187

C oH 15 N 3; HNO3, forms

fine needles or thicker lustrous

green crystals.

The constitution of the compound

formula [50]
:

is

probably expressed by the

-NIL

The product of the interaction

phenyl-/3-naphthylamine
is

of nitrosodimethylaniline and a bluish-violet dyestuff, probably a

:

dimethyl derivative of the former [5.2] Neutral Blue. Nitrosodimethylaniline reacts with paratoluyl-/3-naphthylamine also, and produces a bluish-violet dyestuff of the composition

C 25 H 22N 3 C1.
From the salts, a red base may be separated, which dissolves in alcohol with an orange-yellow fluorescence. The compound dissolves in concentrated sulphuric acid with a red-violet colour, which on dilution changes through green and
blue to violet.

The

nitrate

is

very sparingly soluble [52]

Saffranol.

C 18 H 12N3 (OH) 2

This compound is formed by continued boiling of phenosaffranine with baryta water, or alcoholic potash solution. It may be regarded as phenosaffraniue in which both amido-groups are

The compound agrees with this assumption replaced by hydroxyl. inasmuch as it possesses simultaneously acid and weak basic
properties. Saffranol

forms brass-coloured

leaflets,

almost

insoluble

in

indifferent solvents, but easily in

ammonia and

alkalies with a

188

CHEMISTRY OF ORGANIC DYESTUFFS.

deep carmine-red colour. It is separated from these solutions by acids, and produces the sparingly soluble salts if an excess be
present.
It

forms

red

diacetyl-compound,

which

yields

yellow,

sparingly soluble salts with acids [49].

Indazine

[53],

C
Cl^

(CH 3 C 34 H 30 N 6 C1 2 =

-N-C H
6 6

(^\ -N
|

(CH 3

-N-C H (
3

produced by action of nitrosodimethylaniline hydrochloride on diphenylmetaphenylenediamine. It dyes fine blue shades on cotton prepared with tannic acid.
is

Sasle Blue [54].

C 32 H 29 N4 C1=(CH 3 ) 2NC 6 H 3

/N
; / 10 XN ;C
|

H N-C H CH
5
6

Clc'6 H 4 CH 3
is obtained by the action of nitrosodimethylaniline on the ditolylnaphthylenediamine obtained by heating chlorhydrate a-dioxynaphthalene (M.P. 180) with paratoluidine and paratoluidine hydrochloride. The dyestuff forms a brownish crystalline soluble in water with a bluish-violet colour. It dissolves powder, in concentrated sulphuric acid with a greenish-blue colour, which on dilution changes through green to violet, a bluish-violet Basle blue is a basic dyestuff and is precipitate being formed. best dyed on cotton prepared with tannic acid and tartar emetic.

This dyestuif

AZINE DYESTUFFS.

189

Azine Green [55]

is

analogous to the above in constitution, and results from the action of nitrosodimethylaniline hydrochloride on the diphenyl-

naphthylenediamine obtained from dioxynaphthylene, M.P. 216. It is a basic dyestuff, producing dark green shades which are
pretty fast.
5.

MAGDALA
;

RED.

This dyestuff has been long known, and was investigated almost twenty years ago by Hofmann [27] but from the recent researches
appears that the earlier formula, C 30 21 3 , is incorrect, and that its composition is analogous to that of the
of Julius [44]
it

H N

saffranines, its

red

may

formula being C 30 H 20 4 Accordingly Magdala be regarded as a saffranine of the naphthalene series.

.

Indeed the great

this assumption.

strong fluorescence of

stability of the dyestuff, its properties, and the its salts are strong arguments in favour of

obtained by heating a-amidoazonaphthalene with a-naphthylamine hydrochloride in glacial acetic acid solution. The yield is extremely small. better yield is claimed in a more

Magdala red

is

recent modification of the above process, in which a mixture of the hydrochlorides of a-naphthylamine and paranaphthylenedia-

mine is heated with amidoazonaphthalene to 130-140 till the melt has a pure red colour. Analogous dyestuffs may also be obtained from mixtures of naphthylenediamine hydrochloride and amidoazobenzene, or with naphthylenediamiiieaniline and amidoazobenze [56] Magdala red hydrochloride forms lustrous green needles,
.

sparingly soluble in water, more easily in alcohol. decomposed by ammonia or caustic soda [27].

The salt is not The sulphate

forms large green needles [45].

The

picrate

and platinum double

magnificent yellow

salt are sparingly soluble in alcohol. The alcoholic solutions of the salts exhibit a

fluorescence, which surpasses that of any of the saffranines. The salts dissolve in concentrated sulphuric acid with a bluish-black
colour.

Magdala red

still

finds

a slight application in special cases in

silk-dyeing, but owing to its enormous price has been almost entirely superseded by rhodamine.

190

CHEMISTRY OF ORGANIC DYESTUFFS.

6.

MAUVEINE C H N4
27 24
.

[28].

Mauveine was the first aniline dyestuff prepared on a large scale (Perkin, 1856) , and is certainly closely related to the saffranine Like these,, it has strong basic properties, and gives dyestuffs.
similar reactions with sulphuric acid.
saffranine,

C 20 H 18 N4

Finally, a saffranine (para-

[28])

is

formed by oxidation of mauveine in

characteristic of alcoholic

acetic acid solution.

The fluorescence

however, absent with mauveine. Free mauveine forms a black crystalline powder, insoluble in It is a strong water, soluble in alcohol with bluish-violet colour.
saffranine solution
is,

base, taking

up carbonic acid from the

its salts.

air,

and capable of ex-

pelling
It

ammonia from

forms three

series of salts

with acids, and these are exactly

analogous to those of the saffranines. The triacid salts are green, and only obtainable with concentrated sulphuric acid. The
diacids are blue, and, like the former, are decomposed by water. The monoacid salts are crystalline, have a reddish-violet colour, and are stable. The mauveine salts do not produce their characteristic reddishviolet colour when dyed on wool, but the shade is the bluer one

of the free base.

Hydro chloride,

C 27 H 24N4 ,HC1,

forms

small

lustrous

green

prisms, sparingly soluble in water, easily in alcohol. Acetate, C 27 24 4 ,C 2 4 O 2 , forms lustrous green prisms. Is decomposed Carbonate, green prisms with a metallic lustre.

H N

on boiling or drying. Platinum double salt, (C 27 H 24

N ,HCl)
4

PtCl 4 , forms large golden

crystals, sparingly soluble in alcohol. C 27 H24N4 (HCl) 2 PtCl4, dark blue precipitate.

C 27 H 24N4 ,AuCl 3

crystalline powder.
,

Ethyl derivative, C 27 H 23 (C 2 H 5 )N4 is formed by action of ethyliodide on mauveine in alcoholic solution. Hydrochloride, C 29 H 28 4 ,HC1, forms a reddish-brown crystalline

powder, sparingly soluble in water, easily in alcohol, forming a purple solution.

Iodide,

(CsoHagN^HClJaPtCLt, golden-green precipitate. C 29 28 4,HI,I 2, golden-green crystals.

H N

AZINE DYESTUFFS.

191

Pseudomauveine, C 24 20 4 is obtained by oxidation of pure aniline, and is very similar to mauveine.

,

H N

A dyestuff probably identical with pseudomauveine has been obtained synthetically by Fischer and Hepp, by action of paranitrosodiphenylamine on aniline hydrochloride [51]. Hydrochloride, C 24 20 4 ,HC1, green crystals. Platinum double salt, (C 24 20 4 ,HCl) 2 PtCl 4

H N

H N

The mauveine
quantities,

by

dyestuffs are formed,, although only in small oxidation of primary monamines in neutral solution

with potassium bichromate, cupric chloride, lead peroxide, and It has not been determined with certainty other oxidising agents.

what monamines are capable of yielding dyestuffs of this class but it is probable that the mauveine C 27 H 24 N4 is formed from three molecules of toluidine (ortho and para?) and one molecule of
;

aniline, according to the equation

3C

H N + C H N = C H N + 10H.
9 6
7

27

24

It is not certain if the violet coloration obtained with bleachingpowder and aniline solution is due to the formation of mauveine,

although this

is is

historical interest. It was by Perkin by oxidation of (impure ?) allyltoluidine with potassium bichromate. It is still manufactured in small quantities, and used in printing English postage-stamps and for At present mauveine salts tinting silk for production of white. in commerce under the designation Rosolane. are met with

Mauveine

generally stated. now of little but

obtained

first

synthetical process for production of a series of saffranine related to mauveine is the subject of a recent dyestuffs closely It consists in the oxidation of one molecule of parapatent. midodiphenylamine, or one of its homologues, with two molecules
of aniline, orthotoluidine, or xylidine [58] . The dyestuffs have a violet colour, and in

general closely
saffranine,

C 21 H 19N4 (C 6 H 5 ).

resemble the mauveines. Mauveine may be regarded

as

phenylated

Certainly the violet dyestuffs obtained by action of aniline on saffranine are totally different from mauveine, The fact that and apparently belong to the Induline series. mauveine cannot be obtained in this manner is, however, no

argument against the assumption that it is a phenylsaffranine, as all these dyestuffs undergo a complete change in constitution on
boiling with aniline.

192

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER

VIII.

ANILINE BLACK.
MOST oxidising agents acting in acid solution produce a peculiar This body is characterised by its dyestuff with aniline salts. dark colour, and its sparingly solubility in most solvents. Its
formation has been observed
agents
:

by the
;

action

of

the following

Manganese
;

dioxide [1]

ferric salts [3]

ferricyanides [3] ; alone [6], or chlorates in presence of certain metallic salts [7], amongst which vanadium, cerium, and copper compounds are

lead peroxide, chromic acid [2]; permanganates [5] ; chloric acid

the most effective.

In

all

cases these oxidising agents withdraw

hydrogen from the

aniline molecule.

The formation

of aniline black
salts
is

from

chlorates

and the above-

especially of interest, inasmuch as small quantities of the latter suffice for the oxidation of very Vanadium has the most relatively large quantities of aniline.

mentioned metallic

powerful action in this respect. According to Witz [8], one part of vanadium, aided by the necessary amount of a chlorate, is sufficient to convert 270,000 parts of an aniline salt into aniline
black.

After vanadium, cerium and copper are the most

effective,

iron having considerably less action. It is evident from this that the metallic

compounds

act only

From the fact that only those metals which as oxygen-carriers. form several oxygen or chlorine compounds are capable of producing the desired action,
it is

probable that the higher metallic

oxides effect the ^xidation of the aniline, and that these oxides are continuously regenerated by the chlorate present.'
If cupric chloride
chlorate,
it is is applied with an insufficient quantity of possible to detect the formation of cuprous chloride

ANILINE BLACK.
in the mixture.
tions
it

193

For the production of aniline black from solu-

The formation of necessary that the latter be acid. black from chlorate and copper salts may, however,, take place in
is

presence of excess of aniline,, is the case in black-printing.

if

the mixture be allowed to dry, as

The formation of

aniline black

from chloric acid and aniline

likewise only takes place on drying. Chlorate of aniline is pretty stable in solution, but if the crystallised salt be dried, it is converted into aniline black, which generally retains the crystalline

form of the chlorate [33]. Finally, aniline black is formed at the positive pole on the electrolysis of salts of aniline [10, 16]. The substance formed in all these reactions exhibits practically the same properties. It consists principally of a compound of

weak but

distinctly basic character.

The base

in the free state

has a dark violet, almost black, colour, while its salts are dark The latter are unstable and partly decomposed by water. green. It is, however, difficult to remove the whole of the acid by washing.

The base is almost insoluble in most solvents. It dissolves with difficulty in aniline with a violet colour, which on long standing changes to brown [11]. It dissolves somewhat more easily in phenol, with a bluish-green
colour.
solution,

With concentrated
from which water

sulphuric

acid

it

forms a

violet

With fuming sulphuric according to the temperature and duration of the reaction. The sulphonic acids are green in the free state, and form easily These latter have a violet-black soluble salts- with the alkalies.
colour.

precipitates the dark green sulphate. acid it yields sulphonic acids differing

The
to

obtain

instability of the salts of aniline black renders it difficult them with a constant amount of acid. The hydro-

chloride loses hydrochloric acid

definite

on drying, and does not form

compound with platinum chloride. With acetic anhydride, aniline black yields an acetyl derivative, which possesses little colour, and which is insoluble in concentrated sulphuric acid [34]. Methyl and ethyl iodides

appear to produce substitutionbut differ only slightly from the original compound derivatives, On treating with potassium bichromate, aniline black [34]. a violet-black compound, which contains chromic acid and gives

CHEMISTRY OF ORGANIC DYESTUFFS.

appears to be the chromate of the black base It is not turned green by acids. [34].

(Chrome-black)

Energetic oxidising agents, for example chromic acid in a strongly acid solution, convert aniline black into quinoue [34],

Reducing

agents

form

an

insoluble

leuco-compound,

which

oxidises slowly in presence of acids, and rapidly in presence of alkalies, aniline black being reproduced. If the reduction be more energetic, for example, with tin and

hydrochloric acid, or hydriodic acid and phosphorus,

is

the black

completely

split

up, paraphenylenediamine, paracliamidodiphe-

nylamine
formed.

[34], and small quantities of diphenylamine being If the black is submitted to dry distillation, aniline,

paraphenylenediamine, diamidodiphenylamine, and diphenylparaphenylenediamine are produced [33] By continued action of aniline on aniline black, products One of these has been resembling the indulines are formed.
.

isolated,

and

is

a blue dyestuff of the formula,

C 36 H 29 N5 or C 36 H 31 N5

[18].

This substance resembles the indulines, the base having a red colour in alcoholic or ethereal solution, while the salts are blue. It probably bears the same relationship to aniline black as the higher indulines discovered by Witt and Thomas do to the indu.

line

C 18 H 16N 3

(See page 202.)

The numerous analyses made of aniline black show that it is formed from aniline by simple abstraction of hydrogen. The
values

obtained approximate nearly to the simple expression, Naturally the molecule corresponds to a multiple of this formula, but the instability of the salts has hitherto rendered

C 6 H 5N.

it

impossible to determine the molecular formula accurately. The following formulae have been proposed by investigators in
:

this direction

1."

C 12 H 10N2
C 24 C 30

2.''C 18 H 15
3.
20

4.

N H N H N
25

3.

4.
5.

1 was proposed by Kayser [12], No. 3 by Goppelsroeder and Nos. 2 and 4 are due to Nietzki. [15], Formula No. 4 was based, principally on the formation of the above-named blue dyestuff, which was regarded as phenylated

No.

ANILINE BLACK.
aniline black,

195

C 30 H 25 N5

C6 H5
aniline,

has shown that from the induline

Since then, however, Witt [27] C 18 15 3 dyestuffs may be pro-

H N

duced by the action of

which contain

five

nitrogen atoms

in the molecule, so that this

argument for the formula

C 30 H 2 5N5

becomes

useless.

aniline black into its

Determinations of the amount of hydrogen required to convert ieuco-compounds point nearly to two atoms

of hydrogen for the formula C 18 correct molecular formula [9]

.

H N
15

This appears to be the

renders

black gives throughout it possible that the formula

fact that the analysis of the lower values for the hydrogen, slightly

The

C 18 H 13 N 3 may

be accurate.

Some

conclusions as to the constitution of aniline black are

obtained from its decomposition on oxidation and reduction. The production of quinone in the former, and of paraphenylamine, &c., in the latter, render it apparent that the nitrogen atom of one benzene residue enters the chain of another benzene residue in the

para position to the nitrogen atom. Goppelsroeder's formula [15] in which the benzene chains are represented as linked in a circle
of imido-groups, corresponds to this view to a certain extent. This entirely symmetrical formula, however, does not account for the
tinctorial character of the

compound

in a satisfactory

manner

and from the formation of a stable leuco- compound it may be deduced that in all probability at least two nitrogen atoms of the molecule are linked together. Liechti and Suida [33] regard the black from aniline chlorate
as a chlorinated product. This is improbable, as on treating with concentrated sulphuric acid, hydrochloric acid is evolved, and a sulphate almost free from chlorine is produced.

The adoption

the formation of a

of similar processes with orthotoluidine results in compound probably homologous with aniline

black, of the formula

C 7 H 7N

[34].

This compound resembles aniline black in all its properties. The salts are dark green and the free base is bluish black. The latter differs from aniline-black base by the fact that it dissolves
in chloroform with a bluish-violet colour [34]
.

Paratoluidine does not form an analogous compound on oxidation. Besides the compound described in detail, aniline black generally

contains

others.

One

of these

is

the product of a less

energetic oxidation, and is distinguished from the former compound by the brighter green colour of its salts and a brighter violet

o 2

196

CHEMISTRY OF ORGANIC DYESTUFFS.

colour of the free base.

It also possesses a considerably higher It dissolves in of solubility in alcohol, acetic acid, &c. degree concentrated sulphuric acid with a red-violet colour. This sub-

probably the principal constituent of the dyestuff sold as Emeraldine, and is probably identical with the formerly
stance
is

product

formed by diphenylamine [17].

oxidation

of

paraphenylenediamine with
is

An

interesting reaction in which emeraldine

formed was

observed by Caro [16]. If aqueous solution of free aniline is oxidised with potassium permanganate, and filtered from the separated manganese dioxide, the nitrate is a yellowish liquid, This from which ether takes up a yellow amorphous compound.
latter is converted into a green salt of emeraldine by mere contact with acids. substance possessing the properties of emeraldine

is

formed simultaneously with quinone by oxidation of paramido-

diphenylamine. A larger yield is obtained if this base is oxidised with an equivalent of aniline, and in this case quinone is not formed [17]. On further oxidation emeraldine yields a darker
coloured compound, but it is doubtful if this is aniline black. The formation of emeraldine from paraphenylenediamine and diphenylamine leads to the supposition that it is a phenylated iiidamine of the formula
:

C 6 H 5N

C 6 H4 /

On

line black yields green with acids.

further oxidation, especially with chlorinating agents, ania darker product which is no longer turned

On boiling the acetate or the hydrochloride of aniline black with aniline, a mixture of dyestuffs is formed, one of which, a base of the composition C 36 H 29 5 , has already been mentioned. The free base dissolves in ether with magenta-red colour; its salts with

acids

are

insoluble in

water,

soluble

in

alcohol

with a blue

colour [18].

C 36 H 29 N5 ,HC1

crystallises

from alcohol
a
violet

in small needles

which

have a coppery lustre. (C 36 H 29 5 ,HCl) 2 PtCl 4

forms

precipitate

sparingly

soluble in alcohol.

C 3 6H 29N5 ,HI is similar to C 36 H 29 N5 ,C 6 H 2 (N0 2 3 OH,

)

the hydrochloride. sparingly soluble precipitate.

ANILINE BLACK.

197

TECHNICAL ANILINE BLACK.

Aniline black in substance is scarcely ever prepared in the colour manufactory, but is always produced directly on the fibre. It has an extended application in calico-printing and cotton-

For anilineinnumerable recipes have been published and printing patents taken, all depending on one or other of the methods of formation mentioned in the introduction to this chapter. The oxidising agent most generally employed is potassium (or
dyeing-, but as yet is of little service in wool-dyeing.

black

As soluble sodium) chlorate in presence of copper salts [7]. are liable to attack the iron portions of the copper compounds On printing, printing-machine, copper sulphide [19] is used. this is partly converted into copper sulphate, which then enters
into the reaction.

For example, a mixture of aniline hydrochloride, potassium and copper sulphide, thickened with starch, is printed. The printed goods are then aged in a moist room, at a temperature of about 30, and the oxidation of the sulphide to sulphate and of
chlorate,

the aniline to black takes place.

Vanadium compounds (vanadic

acid and

vanadium

chloride)

have been proposed as substitutes for copper sulphide, but without much practical success. Potassium ferrocyanide and ferricyanide are also used to a certain extent. A mixture of these salts with
is printed, and the goods aged. that the ferricyanide oxidises the aniline, and is continually regenerated from the ferrocyanide formed by the Thus these salts play the part of oxygen chloric acid present.

aniline salt

and potassium chlorate

action
is

The probable

manner to the copper and vanadium comIn the opinion of technologists, the black produced by pounds. this process differs somewhat in its properties from that obtained with copper, but this may be ascribed to the presence of prussian
carriers in a similar

blue in the former.

potassium chlorate, chlorate has recently been employed in black-printing. In printing it is absolutely necessary that the formation of black should not take place in the liquid mixture, as in this case it would soon become useless. Oxidants, like chromic acid, manga-

In place of the aniline hydrochloride and a mixture of aniline sulphate and barium

198

CHEMISTRY OF ORGANIC DYESTUFFS.

nese dioxide, &c., which act directly on the aniline, cannot be

employed

in printing.

In cotton-dyeing, however, the case is just the opposite, as the black formation should be as rapid as possible. For this purpose the formation of black is often effected by the
action between manganese dioxide and aniline salts. The goods are treated with manganese chloride, and then passed through an alkaline bath whereby manganous oxide is precipitated

subsequent oxidation by air or by a bath of chloride of lime serves to convert this into peroxide, a bottom of

on the

fibre.

On passing into the so-called manganese-bronze being obtained. an acid solution of aniline, aniline black is precipitated on the
fibre in a firmly

adherent condition.
is

An the oxidant generally employed. acid is mixed with a aniline solution containing free sulphuric On heating, the black soluble bichromate,, and the goods entered.
However, chromic acid
is

formed

on the fibre. In all cases the aniline-black salt converted into the free base by a weak alkaline bath (soda, soap, or chalk) It is merely a matter of conjecture at present if the black
precipitated
is
.

produced on the
the free state.

fibre is identical

with the products examined in

The conditions employed in black-printing differ considerably from those when the compound is prepared in substance; for example, the formation of black from aniline salts, chlorates, and
metallic salts only takes place in presence of a considerable excess of acid. In printing, on the other hand, an excess is avoided,
as

besides would

would tend to injure the fibre during the ageing process, and form the black in the liquid printing-mixture. For this reason an excess of aniline is generally used, and in
it

addition a part of the aniline hydrochloride the tartrate.

may

be replaced by

this first takes place

fibre.

Such a mixture does not form black even on long standing; when the mass has somewhat dried on the
In general the oxidation appears to go further than when

working in solution.
salts

The black prepared in substance is converted into dark green by acids, and this property is often a serious drawback to
This " greening/' as
it

the black on fibres.

is called, is

produced

ANILINE BLACK.

199

on the goods by acid vapours, for example, by the sulphurous acid produced by the combustion of coal-gas in work-rooms. This greening may be avoided 01% at any rate, reduced to a minimum, by energetic oxidation. The compounds produced in this manner are certainly different from the one described, and
are probably its higher oxidation or chlorination products. Sometimes the goods are submitted to a subsequent treatment

This may consist in passing through a bath to prevent greening. of bichromate (formation of aniline-black chromate) or of dilute

bleaching-powder. Aniline black dyed on fibres

is

is

stable against soap, is only slightly attacked

one of the fastest colours. It is by light and air, and

treatment with chlorine.

More

capable of withstanding a slight chlorine turns it reddish brown.

200

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER

IX.

INDULINES AND NIGROSINES.

THE
dyestuffs included in this classification comprise a series of colouring-matters produced by action of azo-, nitro-, and nitroso-

compounds on aromatic amines. They comprise a great shades, from red through blue to almost black. The indulines are formed in a great number of

variety of
reactions.

Nearly all azo-, azoxy-, and amidoazo- compounds, if heated with salts of aniline or other aromatic amines, produce indulines, and the dyestuffs formed on oxidation of aromatic amines under
It is certain conditions belong in all probability to this class. difficult to say with certainty to what extent the products of

different reactions are identical with

one another.

secondary aud tertiary aromatic amines also react with aniline and its analogues, producing indulines ; and to the study of this reaction and that of the amidoazobenzene process we owe our present knowledge of the compoResearches in this direction sition and structure of the indulines. have been made by Caro and Dale [21], Martius and Griess [22], Hofmann and Geyger [23], and Fischer and Hepp [35].

The

nitroso-derivatives

of

The lower members of the induline

the higher ones in alcohol.

series are soluble in water,

The nigrosines comprise that section of these dyestuffs produced by action of nitro-compounds on aniline hydrochloride in presence of ferrous chloride. The method employed technically for production of indulines consists in heating aniline hydrochloride with amidoazobenzene. If the reaction be carried out at a low temperature, and especially if the mixture contains an excess of aniline hydrochloride, soluble indulines are produced in larger quantity,

INDULINES AND NIGROSINES.

201

while with a protracted reaction insoluble indulines, generally of bluer shade, are formed.
Induline

C 18 H 13N 3

is

melt for 10 minutes at 140.

formed by heating an amidoazobenzene Another induline, C 24 H 18 N 4 , is also

is

formed

(see below),

and

separated by the less solubility of

its

acetate in water.

The base, C 18 H 13 N 3 forms needles with a green metallic lustre, the salts are easily soluble in water and dye reddishM.P. 135
, ;

violet shades.

The indulines
constitution
:

are derivatives of phenazine; the simplest has the

6
II

"

X N^ X
^N
C6 H5

=C H N
18

13

3.

NH
From

formed by introduction of and by introduction of the rest of anilido-groups, by phenylation,

this the higher indulines are

This latter reaction always takes place in a normal induline melt, the paraphenylenediamine being formed from decomposition of amidoazobenzene.

paraphenylenediamine.

Induline C 24 18 4 [36] is produced by operating in a manner similar to above, the temperature of the melt being about 150. The melt is extracted with a solution of acetate of soda under
pressure,

H N

whereby the induline, C 24 18 4 , goes into solution, and the free base precipitated by an alkali. The base forms lustrous leaflets soluble in alcohol with magenta-red colour. The hydrochloride forms bronzy crystals soluble in warm water bluish- violet colour. It dyes bluish-violet shades.

H N

with a

Azophenine,

C 30 H 24N 4

is

a constant product of the induline melt

and plays an important part, especially in the production of higher indulines. It is formed also by the action of various nitrosocompounds on aniline and aniline hydrochloride, the best result
being obtained by paranitrosodiphenylamine.
synthetically
It may be produced This by action of aniline on dianilidoquinone. synthesis and the production of dianilidoquinone on heating azophenine with sulphuric acid explains its constitution, which is

that of a dianilidoquinonedianil

202

CHEMISTRY OF ORGANIC DYESTUFFS.

N.C
1

an,

6 H, ATM C 6 H 5 NH Nil C 6 H 5
. .

'

N.C H
6

in alcohol

Azophenine forms red leaflets, M.P. 240, which are insoluble and ether, but soluble in aniline, benzene, and toluene

On heating the melt containing azophenine, other [27, 28]. indulines are formed, amongst which the following, investigated
by Witt and Thomas, may be mentioned
:

Induline B, C 18 15 3 Azodiphenyl blue. The hydrochloride Induline 3 B, C 3 oH 23 5

,

H N

is

sparingly soluble

in alcohol.

Induline 6 B,
iriduline series.

C 36 H 27 N5
Its

This

is

the best characterised of the

crystals

hydrochloride forms well-defined

Its sulphonic acid dyes
is

which are insoluble in alcohol.

pure blue shade.
This induline

wool a

probably a phenazine produced action of aniline on azophenine according to the equation [37] by
:

-NC H
~
6

-NC H
6

C6 H 5N C 6 H5

According to Wichelhaus and v. Dechend induline B is also formed by action of nitrobenzene on aniline hydrochloride, a reaction also observed by Staedeler. An interesting method of obtaining this body is by heating the aniline salt of phenylamidobenzeneIn this case sulphanilic acid sulphonic acid (Tropaolin OO).
splits off. Azodiphenyl blue is also obtained by action of azoxybenzene on aniline hydrochloride [24] According to Wichelhaus and v. Dechend a new colour-base
.

Triphenylenediamine,

C 18 H 12 N 2

is

formed on heating the hydro.

chloride of azodiphenyl blue to 230 [24] On a large scale the indulines are prepared by heating a mixture of amidoazobenzene, aniline hydrochloride, and free aniline to the

boiling-point of the latter.

Reddish-violet compounds are

blue.

first

formed which gradually change to

The

first

products of the reaction are simple soluble indulines

and azophenine, and from these the higher products are formed by
pheiiylation.

la

all

probability commercial induline contains a

INDULINES AND NJGROSINES.

mixture of
dyestuflfs.

203

Paraphenylenediamine and diplienylamine

by heating amidoazobenzene hydrochloride with neutral aniline hydrochloride to 100 with a little water [29] This induline may be fixed on
.

are formed as bye-products in the induline melt. According to Caro a soluble induline is formed

tannined cotton.
apparently different soluble induline is described by Istel as formed on heating 2| parts aniline hydrochloride,, 1 part of being amidoazobenzene chloride, and 6 parts of water to 70 80 C. for

An

twenty-four hours.

The new

dyestuff gives a blue solution with

It dyes on water, and exhibits a reddish-brown fluorescence. tannined cotton, and may be also fixed on unmordanted cotton from a bath containing common salt or acetate of soda. The shades on tannined cotton are very fast to light [38] Indulines have also been prepared technically by heating azobenzene with aniline hydrochloride [25]
. .

Recently a number of patents for the production of soluble indulines have been published. These are based for the greater

number on

diamine,, for the aniline in the usual induline melts.

the substitution of a diamine, generally paraphenyleneshort

of these processes can be given here. The most important of these consists in heating amidoazobenzene hydrochloride with paraphenylenediamine to 180 for three or four

summary only

hours.

similar

product

is

obtained

with amidoazotoluene.

The

dyestuffs obtained by this process have found technical application, and are known in commerce as Paraphenylene Blues

[39, 40].

not so fast to
diamine.

Metaphenylenediamine may also be used, but the products are Triamidoazobenzenes (Bismark brown) and light. soluble indulines on heating with paraphenyleneChrysoidine give
Soluble indulines are also obtained
:

(1)

By

heating spirit-

soluble indulines,, azophenine_, quinone, chloranil, azobenzene, azotoluene, or oxyazobenzene with paradiamines (Poirrier) (2)
.

By heating diamidoazoxybenzene with aniline and aniline hydrochloride. (3) By heating nitro-derivatives of the amines with
aniline &c. in presence of ferrous chloride. (4) By heating the azo-derivatives of naphthylenediamine [1, 5] with paraphenylene-

diamine and benzoic acid.

204

CHEMISTRY OF ORGANIC DYESTUFFS.

are prepared by heating a mixture of nitrobenzene, and iron filings to 180-220. The

The nigrosines

aniline, hydrochloric acid,

colour of the mixture changes through reddish violet to deep blue. They are also prepared by heating a mixture of crude nitrophenol (mixture of ortho and para) with aniline hydrochloride

and iron filings. The nigrosines possess a more greyish shade than the indulines, but it is not known with certainty if the
series of similar products to colouring-matters are different. the nigrosines and indulines are formed by oxidation of pure

aniline with arsenic acid, but the exact relationship of these dyeG. Wolf [31] has published a stuffs one to another is unknown.
series of formulae for these bodies, which cannot, however, be looked upon as trustworthy, as the necessary analytical data are not given.

The

violet dyestuffs of

magenta residues

differ

from the indu-

lines in so far that they give a brown solution with sulphuric acid, while all the latter give a blue.

Sulphonic acids of the indulines and nigrosines are also known. The sodium salts of the sulphonic acids of various indulines come into commerce under the names of Fast Blues, Blackley Blue,
Indigo substitute, &c. The difference of the various marks depends on the shade of the induline sulphonated and the number of sulphogroups introduced.

The indulines are mostly insoluble

bases and
salts,

in water both in

form of

but are soluble in alcohol.

The

solutions of the

bases are red to reddish violet, the salts are bluish violet, blue, or bluish grey. They are soluble in concentrated sulphuric acid with a pure blue colour, the sulpho-acids have the same colour as the
salts of the original induline, and the salts of the sulpho-acids have the same colour as the free bases.

The indulines are destroyed on oxidation, quinone being formed

reducing agents produce easily oxidisable leuco-compounds. The nigrosines have similar properties.

Spirit-soluble indulines and nigrosines are employed as hydroand are principally used for colouring varnishes. Spiritsoluble indulines are applied in printing by a peculiar process.
chlorides,

They

are printed in combination with tannin and the acetic ethers of glycerine (monoacetine, diacetine) ; on steaming, these ethers are decomposed, and the liberated glycerine effects the combination

TNDULINES AND N1GROSINES.

205

of the induline with the tannin and the tannin lake with the fibre

(Acetine blue).

Another process for printing consists in the application of a

mixture of induline and levulinic acid along with tannic acid, the colour being fixed by steaming [41]. The soluble (sulphonated) indulines are dyed on cotton mordanted with tannin and tartar emetic, a considerable amount of

alum being added to the dye-bath. Wool may be dyed directly from an acid bath,, the induline generally being used in combination with other acid colours.

Silk

is

dyed in a bath containing

boiled -off liquor, the shades being brightened by addition of sul-

phuric acid. Soluble indulines of the unsulphonated class are basic dyestuffs, and are principally used in cotton-dyeing on a mordant of tannic
acid and tartar emetic.

Ilosindulines [42. 43, 44].

These dyestuffs are indulines of the naphthalene and benzenenaphthalene

aniline,
series.
if heated with produce a deep-red dyestuff, and an analogous compound is obtained by heating naphthoquinone and certain of its derivatives with aniline and aniline hydrochloride. The latter dyestuff

Nitrosoethyl and nitrosophenylnaphthylamine,

yields sulphonic acids which dye animal fibres brilliant bluish or brownish-red shades. The sodium salt of one of these acids is known as Azocarmine. The rosinduline from nitrosophenyl and

naphthylamine and aniline has the composition C 38 H 19 3 It forms red monoacid and green diacid salts, the latter are decomposed by water. Hydrochloride, (C 2 8H 18 3 HC1) 2 -flH 2 O, reddish-brown soluble in water and alcohol. Sulphate, C 28 H 19 3 H 2 SO 4 -|prisms H 2 O. The constitution of the base may be expressed by the
.

formula

CH,

206

CHEMISTRY OF ORGANIC DYESTUFFS.

Fluorindines.

These comprise a series of weak dyestuffs discovered by Caro and Witt, the type of which is obtained by heating azophenine with concentrated sulphuric acid or with zinc powder. The formation of this compound, which contains two azine rings, may be
represented by the following equation
:

C 6 H 5 NH\ n

/NC H
6

Fluorindines are also produced by heating orthodiamines and by heating a mixture of diamidoplienazine and orthophenylene-

diamine [45]

The

fluorindines are blue or violet

compounds.

In sulphuric

acid or alcoholic solution they exhibit a magnificent brick-red fluorescence which is very characteristic.

QUINOLINE AND ACRIDINE DYESTUFFS.

207

CHAPTER

X.

QUINOLINE AND ACRIDINE DYESTUITS.

QUINOLINE and Acridine and their homologues belong chromogens. The chromogen character is but slight, and
to the
is

only inconsiderably developed by introduction of amido-groups. The simple amido bases form yellow salts,, which are,, however, not
dyestuffs.

These are formed, however, by introduction of an amidated benzene residue. This is the case with flavaniline and chrysaniline, which are derivatives of phenylquinoline and phenylacridine respectively-

XH.

C G H 4NH 2

N
Flavaniline.
6

H NII
4

Chrysaniline.

class of dyestuffs is known in which quinoline does not The fact that these bodies to be the real chromogen. appear cannot be obtained from pure quinoline, but only in presence of

Another

its

homologues, gives reason for the assumption that they are analogous to the phenylmethane dyestuffs, and that a methane carbon atom links together several quinoline rings. These dyestuffs include the cyanines, quinoline red, and probably quinoline yellow
(?).

208

CHEMISTRY OF ORGANIC DYESTUFFS.

Cyanine

[2, 3, 4, 5].

On

one molecule of each of the bases and the alcohol radical used twice. It is also formed by treating a mixture of the alkyl iodide compounds of quinoline and lepidine with alkali [4] One molecule of hydriodic acid is split off and
.

line) [4] with an alkyl iodide in stuff is formed, which contains

heating a mixture of quinoline and lepidine (rnethylquinopresence of an alkali, a blue dye-

the iodide of cyanine formed.

The cyanines are strongly basic compounds ; the iodine can only be removed from the iodides by silver oxide. The monoacid salts are crystalline and of a beautiful blue colour. With weak acids, often even with carbonic acid, they are
[2, 5]. shades, which are, however, too sensitive to light and acids to be of practical value. Dimethylcyanine [4]. The iodide C 2 iH 19 2 I is formed from the

converted into the colourless di-acid salts

The cyanines dye blue

methyl

iodides of quinoline

and

lepidine.

It

forms lustrous

green needles, carbonic acid.

M.P. 291. Its blue solution is decolorised by The ethyl iodides of the above bases form the correis

sponding cyanine iodide C^R^Ngl. An isomeric cyanine is formed if quinaldine

lepidine [4].

used in place of

Isoamylcyanine, discovered by Greville Williams [5] and exlater by Hofmann [2], is best known. According to Hofmann it is formed from pure lepidine and possesses the composition C 3 oH39N 2 I. In all these iodides the iodine may be replaced by

amined

other acid radicals.

It is possible that the cyanines are constituted similarly to the phenylmethane dyestuffs., the methyl group of the lepidine fur-

The cyanines belong to the nishing the methane carbon atom. earliest artificial dyestuffs, the first representative having been
discovered by Greville Williams in 1856.

Qiimoline
is

Red

obtained by action of benzo-trichloride on coal-tar quinoline in

presence of zinc chloride [1, 6]. According to Hofmann's researches there are two different dyestuffs of this class, one of

QUINOLINE AND ACRIDINE DYESTUFFS.

209

which

is

derived from quinoline and quinaldine and the other from

derivative
is

quinaldine and isoquinoline.

The isoquinoline
yield
is

easier to prepare

and a

far better

obtained.

The quinoline red

C 26 H 18N 2 It C 26 H 18N 2 HC1.

.

is

from isoquinoline has the composition a base and forms a hydrochloride of the formula

larger prisms.

It crystallises in thin quadratic leaflets or in It is sparingly soluble in cold water, easily in hot,

and is separated again by an excess of hydrochloric acid. The platinum double salt has the formula (C 26 H 19 N 2 C1) 2 PtCl 4 On heating quinoline red with ammonium sulphide, benzyl mercaptan is split off, and a compound of the composition C 19 H 14 N 2
.

is

formed.

dry distillation it yields a base of the composition C 17 15 N. Quinoline red may be regarded as analogous in constitution to the tripheiiy 1m ethane dyestuffs, the methane carbon atom of the
benzotrichloride entering into two quinoline residues. It gives a magnificent eosine-red shade on silk, and exhibits a
fluorescence which surpasses that of every other dyestuff. shades are, however, extremely sensitive to light.

On

The

T Quinoline Yellow (QUDS OPHTHALON) [1, 6].

C 18 H n N0 2
Is
coal-tar

formed by action of phthalic anhydride on quinaldine or on

quinoline containing

quinaldine in presence of zinc Quinoline yellow crystallises from alcohol in fine yellow It is insoluble in water and ether, pretty needles, M.P. 235. easily soluble in hot alcohol and glacial acetic acid, and easily in strong sulphuric acid. It has no basic properties and dyes wool
chloride.

fuming sulphuric

sulphonic acid, obtained by treating with dyes wool and silk pure yellow like picric Basic dyestuffs may be obtained by heating with ammonia acid. under pressure. Probably these are formed by substitution of

and

silk

yellow.

Its

acid,

oxygen by nitrogenous groups. The homologues of quinaldine yield

similar dyestuffs with

phthalic anhydride [7]. similar dyestuff, pyrophthalon, of the composition C 14 9 is obtained from coal-tar picoline and phthalic anhydride [7] .

H NO

2,

210
In
all

CHEMISTRY OF ORGANIC DYESTUFFS.

these reactions, phtlialic anhydride

may

be replaced by

the anhydrides of the chlorinated phthalic acids.

to its high price quinoline yellow has only found a limited It gives very fast shades, and would be valuable in application.

Owing

the cost of production were less. It is applied solely as The shades acid and is dyed like the acid dyestuffs. sulphonic produced are pure yellow, free from any tinge of red.

dyeing

if

Fara^midophenyl-y-lepidine (Flavaniline)

[8, 9, 10].

C 16 H 14N 2

This dyestuff is prepared by heating acetanilide with zinc chloride to 250-270. The melt is extracted with hydrochloric
acid,

and the

of soda.

The

flavaniline precipitated yield is very small.

is

by addition

of salt and acetate

Flavaniline
It

a strong base

it

forms long colourless needles,

sparingly soluble in water, easily in alcohol and benzene,

M.P. 97.

may be distilled without decomposition. The monoacid salts of flavaniline dye wool and silk pretty pure yellow shades. Hydro chloride, C 16 14 2 ,HC1, forms yellowish-red prisms with

H N

a bluish-red reflex.

It is easily soluble in water.

is a white salt obtained , Dihydrochloride, by concentrated hydrochloric acid to the aqueous solution of adding the former. It is decomposed by water or on heating.

C 16 H 14N 2 ,(HC1) 2

C 16 H 14N 2 2HCl,PtCl4 forms

Ethyl flavaniline
Iodide,
is

a yellow crystalline precipitate. obtained by action of ethyl iodide on an

alcoholic solution of the base.

C 16 13 2 (C 2 5 )HI, forms long ruby-red needles. Flavaniline contains an amido-group, and forms a diazo-comis

H N

pound which
water.

converted into flavenol,

exhibits

C 16 H 13 NO, on
basic

boiling with
properties.

This

compound

weak

and acid

It forms colourless leaflets,

which may be sublimed with partial decomposition, M.P. 128. It forms colourless salts with acids. On distilling with zinc powder it yields a new base flavoline, C 16 H 13 3 This latter compound forms colourless lustrous crystals, M.P. 65. It yields monoacid salts. The behaviour of flavolinc on oxidation shows it to belong to

the quinoline series. By oxidation with permanganate first lepidine carbonic acid,

it

yields

QUINOLIXE AND AC1UDINE DYESTUFFS.

211

COOH
on further oxidation picoline trioarbonic
acid,
,

C 5 HN(COOH) 3

and finally pyridine tetracarboiiic These facts show that flavoline

acid,
is

C 5 NH(COOH) 4

a methylpheiiylquinoline

CPI,

-C H
6

Flavenol

is

derivative of this

therefore an hydroxyl- and flavaniline an amiilocompound. The constitution of flavaniline is

:

expressed by the formula

An interesting synthesis of flavaniline was effected by O. Fischer. It consists in the condensation of equal molecules of
ortho- and para-amidoacetophenone, according to the equation
:

+H.O
XII,

21.2

CHEMISTRY OF ORGANIC DYESTUFFS.

zinc chloride

Probably the formation of flavaniline from acetanilicle and is due to a molecular change of the acetanilide to the isomeric amidoacetophenones, which then form flavaniline.

Berlerine.

C 20 H 17 N0 4
Berberine
is

an alkaloid occurring in

many

longs to the quinoline dyestuffs.

ledge reaches,
nature, and
is it
is

So

far as

plants, and beour present know-

the only

member

of this series occurring in

also the only natural dyestuff with basic properties of being fixed on fibres like basic aniline dyes. capable Berberine has been found in many plants. The largest quan-

tities are

found in Calumba roots (Cocculw palmatus) [19], and in

[20].

the roots of Berberis vulgaris, Linn.

The

latter is

the

only one of importance in dyeing. Pure berberine forms yellow needles, sparingly soluble in It loses water of crystallisation at 100 alcohol and in water.

and melts

at

120.

It is a

monoacid base forming soluble

nitrate

crystal-

line salts with acids.

The

C 20 H 17 NO 4 ,HNO 3

is

especially

noteworthy for the ease with which it forms large crystals; it is Berberine is capable of forming insoluble in excess of nitric acid. The dry hydrochloride is turned red lakes with metallic oxides. by chlorine. On melting with potash it yields quinoline and two
one of which, C 8 8 O 4 , appears to be homologous with On oxidation with nitric acid, proto-catechuic acid [16]. berberine gives pyridine tricarbonic acid [17, 18]. Reducing agents convert berberine to colourless hydro-berberine,
acids,

C 20 H 21 N04

[16].

In dyeing, berberine is used in form of a decoction of the On animal fibres it is dyed from a neutral bath, berberis roots. and On cotton it is fixed with tannic acid. It is almost exclusively
used for dyeing leather.

Chrysanilines.

C 19 H 15 N 3 and C 20 H 17N

3.

The chrysanilines are formed in small quantities as bye-products in the manufacture of magenta, both by the arsenic acid and the

QUINOLINE AND ACRIDINE DYESTUFFS.

nitrobenzene processes.

213

They are separated from the first magenta mother-liquors by partial precipitation with soda, and are finally

The chrysaniliiie from pretty strong nitric acid. examined by Hofmann [11] has without doubt the formula C 2 oH 17 3 ; bnt recent researches by Fischer and Koerner [12] render it probable that crude chrysaniline contains two homoAt least the analytical logous bases, C 19 H 15 N 3 and C 20 H 17 3
crystallised

by Hofmann cannot be brought in unison with the formula C19H 15 Na set up by the latter chemists. The chrysaniline C 2 oH 17 N3 [11], when precipitated from its
results obtained
salts

by

alkali,

forms a light yellow powder similar to precipitated

lead chromate.

It is almost insoluble in water, dissolves easily in The two latter solutions exhibit a alcohol, benzene, and ether.

beautiful yellow-green fluorescence.

The base may be

distilled

with partial decomposition. Chrysaniline forms two series of salts with acids, both of which are yellow to orange in colour. With the exception of the picrate and the hydriodide, the salts
are soluble in water, but sparingly soluble in an excess of acid. On dilution, the diacid salts are split up into monoacid sale and

water.

forms orange-yellow needles, sparingly Nitrate, C 2oH 17 8 3, From the solution, nitric soluble in cold water, easily in hot. acid precipitates the diacid nitrate, C 20 17 3 ,2HNO 3 , in orange-

N ,HNO

H N

yellow

Chrysaniline is capable of withthe action of pretty strong nitric acid. standing If impure chrysaniline is dissolved in strong nitric acid, the
clusters

of

needles.

nitrate crystallises out on standing, and this property the purification of the dyestuff.

is

utilised in

The hydrochlorides, C 20 H 17 N 3 ,HC1 and C 20 H 17 N 3 ,2HC1, more easily soluble than the corresponding nitrates.

are

2 O, forms red needles Picrate, C 20 17 3 2(C 6 2 (NO 2 ) 3 OH) insoluble in water and sparingly soluble in alcohol.

H N

+H

Trimethylchrysaniline,

C 20 H 14 (CH 3

The

dihydriodide,

formed by heating chrysaniline, methyl iodide, and methyl alcohol to 100 for five hours. It forms orangered needles, soluble in hot water. On adding ammonia to the hot solution, the mono-hydriodide separates in yellow needles. The base may be obtained from these iodides by action of silver It forms easily soluble salts with most acids. oxide. C 20 H 14 (CH 3 ) 3 N 3 (HCl) 2 ,PtCl4 forms yellow felted needles.
)

C 20 H U (CH 3

(HI) 2

is

214

CHEMISTRY OF ORGANIC DYESTUFFS.

The corresponding ethyl derivatives may be obtained in an analogous manner by the action of ethyl iodide. Amyl derivatives have also been prepared [11].

Chrysaniline C 19 H 15 N 3 [12] was obtained by Fischer and Koerner from commercial chrysamline. The base crystallises from benzene in clusters of golden-yellow needles, containing one molecule of benzene, which is expelled on drying. It melts at upwards of 200,, and distils \vith partial decomposition. Chrysophenol C 19 H 13 N 2 O [12] is formed by heating the above compound with concentrated hydrochloric acid to 180. It forms small orange needles, forming salts with acids, and also It dissolves in soda, reacting like a weak acid towards alkalies. a light yellow solution from which acids precipitate it as forming

an orange precipitate. On heating with acetic anhydride, chrysamline yields a diacetyl compound [13], C 1 j>H 3N 3 (C 2 H 3 O) 2 , which still possesses basic properties, forming monoacid salts with acids. C 19 H 13 s (C 2 H O) 2 HCl forms long yellow needles, easily soluble in water [13].
1

tH

The corresponding

nitrate

is

acid, two chrysaniline, atoms are converted into diazo-groups. On boiling the nitrogen resulting diazo-compound with alcohol, phenylacridine is formed

By

treating

C 19 H 15 N3

sparingly soluble. with nitrous

,

N
C6 H4
|

H4

C6H5
It follows therefore that chrysaniline is a diamidophenylacri-

dine [12].

An interesting synthesis of chrysaniline was effected by Fischer and Koerner [12]. Orthonitrobenzaldehyde condenses with aniline to form orthonitroparadiamido-triphenylmethane, which on reduction yields
orthodiparatriamido-triphenylmethane
:

QUINOLINE AND ACRIDIXE DYESTUFFS.

215

NH
This

compound
in

and carbon atoms take up ortho positions in both benzene-nuclei, chrysaniline

has the following: constitution
:

As

yields chrysaniline on oxidation. the formation of acridine the nitrogen

-XH,

period chrysaniline was the only basic and for this reason was largely used in cottonyellow dyestuff, Wool and silk are dyed directly, cotton requires a tannin dying. mordant. The shade produced is an orange-yellow, noteworthy

For a

considerable

for its fastness to light.

216

CHEMISTRY OF ORGANIC DYESTUFFS.

chrysaniline, which is used as nitrate or hydrounder the name of Phosphine, has but a limited application in silk and cotton-dyeing. The reason for this is that there is no good method for production of phosphine, and as its preparation from magentaresidues is somewhat complicated, its price is relatively high.
chloride,,

At present

Acridine Yellow [22].

This dyestuff the constitution
is
:

a hydrochloride of diamidodimethylacridine of

preparation formaldehyde is condensed with metatoluylenediamine, and the resulting body treated with acid, ammonia It dyes silk splits off, and the resulting leuco-base is oxidised.
its

For

yellow with green fluorescence.

Acridine Orange.
Acridine orange diamidoacridine
:

is

according to

its

formation a tetramethyl-

CH
(CH 3
)2

NC H <
6 3

>C 6 H N(CH 3
J5

) 2,

and is obtained by heating of tetramethyltetramidodiphenylmethane with acids and subequerit oxidation of the resulting leucoacridine. Acridine orange is a basic dyestuff producing reddishorange shades on cotton.

Benzqflavine.

A diamidophenyldimethylacridine isomeric with chrysaniline been brought into commerce under the above name.

QUINOLINE AND ACRID1XE DYESTUFFS.

217

According to a patent of C. Oehler,

following manner
[21]
:

it

is

obtained in the

Metaphenylenediamine, or metatoluylenediamine, is condensed with benzaldehyde, forming tetramidotriphenylmethane or its The latter base on heating with acid loses one homologues. molecule of ammonia, yielding diamido-hydrophenylacridine, the leuco-base of benzoflavine_, which is formed on oxidation
:

NII 2

Tetramidotiiphenylme thane.

Diamidoliydrophenylacridine.

Benzoflavme.

easily soluble in hot water,

Benzoflavine comes into commerce as a yellow powder. and the solution solidifies to a

It is

cooling.

From

jelly

on

the solution concentrated hydrochloric acid pre-

218

CHEMISTRY OF ORGANIC DYESTUFFS.

The free cipitates the sparingly soluble orange hydrochloride. base precipitated by an alkali forms a light yellow powder, which dissolves in ether with a beautiful green fluorescence, similar to
that of chrysaniiine. The dyestuff dissolves in concentrated sulphuric acid with a
light yellow colour,

which becomes orange on dilution. silk, and on cotton mordanted with tannic acid resemble those with auramine. They may be

The shades produced on wool,

distinguished by their behaviour towards concentrated hydrochloric acid, benzoflavine becoming orange, while auramine is
destroyed.

The

stability of benzoflavine
it

towards acids
be so

is

a decided
light
as

advantage, but auramine.

does not

appear

to

fast to

INDIGO DYESTUFFS.

219

CHAPTER

XI.

INDIGO DYESTUFFS.

THE

colouring-matters of the indigo group,, of which the most important is indigo blue,, are derivatives of indol. This compound is closely related to pyrrol, both as regards constitution and properties.

The

relationship existing between indol

and pyrrol
:

is

analogous to that of benzene to naphthalene,, or of pyridine to quinoline, and is best shown by the following formulae

CH
||

^v

CII
"

/CH NH 7

C6H4 \

CH
NH-"
Indol.

Pyrrol.

positions in the benzene ring,, a closed chain containing five

The nitrogen and carbon atoms of the side ring occupy ortho and form with the third carbon atom members [1, 2] Indol, like pyrrol, possesses slight basic properties, and also
.

colours a strip of
less leaflets,

fir,

moistened with

acid, red.

It

forms colour-

boils at

yields a With acetic anhydride

M.P. 52, which have a peculiar, unpleasant smell. It 245 w ith partial decomposition. With nitrous acid it nitroso-derivative. Of the salts, only the picrate is stable.
r

it

forms acetylindol.

obtained by reduction of indigo blue. It is aho in the pancreatic digestion of albuminoids [2], and by produced melting the latter with potash.
first

Indol was

It may be obtained synthetically by heating orthonitrocinnamic acid with potash and iron filings, and by passing diethylorthotoluidiue through a red-hot tube.

formed by melting carbostyril with caustic potash by heating orthoamidostyrol with sodium ethylate [9], by passing
Indol
is

also

[7],

by

distillation of nitropropeiiylbenzoic acid with lime [8],

220

CHEMISTRY OF ORGANIC DYESTUFFS.

tetrahydroquinoline through a red-hot tube [10], and by treating orthonitrophenylacetaldehyde with zinc powder and ammonia [11]
.

general synthetic method for production of that of Emil Fischer.

alkyl-indols

is

Ketones react with phenylhydrazine to produce hydrazones

o.
The hydrazones, on heating with zinc chloride, split off one molecule of ammonia, with production of a substituted indol
:

dols

Substituted hydrazines yield the corresponding substituted infor example, from diphenylhydrazine and acetone ; diphenylis

indol

formed

DERIVATIVES OP INDOL.
IndoxyL

/CH.
This hydroxy-indol occurs in the urine of herbivorous animals Indol is converted into indoxylindoxylsulphuric acid.

as

indoxyl
acid.

From this compound sulphuric acid in the animal organism. is formed by warming with concentrated hydrochloric
It

may

also be obtained
:

by heating indoxylic
[13].

acid, accord-

ing to the equation

C 9 H 7 NO 3 = C 8 H 7NO + CO 2
Indoxyl
dation
it

is

an

oil

not volatile in a current of steam.

On. oxi-

by heating indoxyl with potassium pyrosulphate [1^]. It exists only in the form of These are colourless and yield indigo blue on heating its salts.
or on oxidation.

gives indigo blue. Indoxylsulphuric acid may be obtained

INDIGO DYESTUFFS.

221

Indoxylic Acid,

C 6 H/
The

/C(OH) X

,C

COOH.

ethyl ether of this acid is formed by reduction of orthonitrophenylpropiolic acid ethyl ether with ammonium sulphide [13]. The free acid is obtained by saponification of the ether with an
alkali.

water.

forms a crystalline precipitate, sparingly soluble in up into indoxyl and carbonic acid on heating. convert it to indigo blue, while on heating with Oxidising agents
It
It splits

concentrated sulphuric acid indigo sulphonic acid

is

formed.

O.xindol [14, 24],

This compound is an inner anhydride of orthoarnidophenyl acetic and is isomeric with indoxyl. It is formed by reduction of isatin with sodium amalgam [14], and of acetylorthoamidophenylacid,

glycollic acid needles, M. P.

with hydriodic acid [15].

It

forms colourless

properties.

exhibits simultaneously basic and acid It reacts with nitrous acid, producing isatinoxime

120, and

Itioxindol,

is

the
It

the inner anhydride of orthoamidophenylgly collie acid. It is first product of the reduction of isatin with zinc powder [14].

forms colourless prisms, M.P. 180. On heating strongly, is formed. It oxidises in aqueous solution, forming first Reducing agents convert it to oxindol. isatyde, and then isatin.
aniline

Dioxindole
perties.

is a dibasic acid, but also possesses Its acetyl derivative is decomposed

slight basic pro-

by baryta water,
It yields a nitroso-

acetylamidophenylglycollic acid being formed.

derivative with nitrous acid.

222

CHEMISTRY OF ORGANIC DYESTUFFS.

Isatin.

>N'
This compound
oxylic acid
:

is

the inner anhydride of orthoamidophenylgly-

/CO COOH
6

4-x^

Isatin is formed by oxidation of indigo with nitric acid or It may also be obtained by oxidation of chromic acid [16]. and of carbostyril [18], and by boiling orthoarnido-oxindol, Further nitrophenylpropiolic acid with caustic-potash solution. methods of formation are given under the synthesis of indigo-

blue.
It is sparingly soluble Isatin forms orange prisms, M.P. 200. It possesses the properties in water, easily in alcohol and ether. of a weak monobasic acid, but also reacts like the aldehydes and

ketones

for example,

it

combines with bisulphites of the

alkalies,

and with phenylhydrazine

By oxidation with and on melting with caustic potash, aniline is formed. By oxidation with chromic acid in acetic-acid solution anthranilcarbonic
acid (Kolbe's Isatoic Acid) [21]
is

arid its sul phonic acids [65]. dilute nitric acid it yields nitrosalicylic acid,

produced

C 6 H4 X

/CO

N COOH
isatin to isatin chloride
:

Phosphorus pentachloride converts

C6 H4

C^
with

/CC1.
with

Isatin forms a blue condensation-product (indophenine)

thiophene.

On
4

reduction
is

C 16 Hi 2 N 2

[16]

formed.

ammonium sulphide, isatide With zinc powder in acetic-acid

solution, isatin yields hydroisatin; by more energetic reducingChlorine and bromine oxy- and dioxy-indol are formed.

agents react with

isatin,

forming chlorine and

bromine derivatives
isatiii

respectively.

Acetic anhydride produces an acetyl

[15],

INDIGO DYESTUFFS.

223

Isatin cliloride yields probably a derivative of pseudo-isatin. blue on reduction, indigo-purpurin being sometimes formed indigo as a bye-product [22]. Isatin forms ethers with the alcohol radicals.

Isatin combines C 17 H 12 N3 O 4 methyl mine, forming an oxime, C 8 H 6 N 3 O 2 [25], which

isatide,
.

The methyl ether of

isatin yields a condensation-product,

is

with hydroxylaidentical with

the

nitroso-oxindol discovered by Bayer and Knop [14, 24] (pseudo-isatin, see constitution of the Indigo group). Isatin is capable of yielding condensation-products with hydro.

In the formation of these bodies one oxygen atom replaced by two monovalent hydrocarbon rests. From their behaviour these bodies appear to be derivatives of the toluene derivative has accordingly the formula pseudo-isatin
carbons [58] of the isatin
is
;
:

(C;H 7 ) 3

Similar condensation-products may be obtained with tertiary bases and phenols. They yield dyestuffs on oxidation, which proto the triphenylmethane series [58] bably belong
.

The compound formed from

formula
:

isatin

and thiophene has the

C 12 H 7 NOS
Indolin, see 62, 63.

[58].

Isatic Acid.
-

/CO

COOH.

(Orthoamidophenylglyoxylic acid, orthoamidobenzoylformic acid.) The salts of this acid are formed on heating isatin with a stron^
solution of caustic alkali.

The free acid may be obtained by decomposition of the lead salt with sulphuretted hydrogen [26], or synthetically by reduction of orthonitrophenylglyoxylic acid with
ferrous sulphate and caustic soda. The acid is unstable, its aqueous solution decomposes on boiling, isatin and water being formed.
Acetylisatic acid is formed by treating acetylisatin with a cold solution of a caustic alkali [15],

224

CHEMISTRY OF ORGANIC DYESTUFFS.

Isatogenic Ether [13, 27].

C 6 H4 ^
This body
acid,
is

/CO C.COO.CoH

/\ ^N O

and

is

phuric acid.

isomeric with the ether of orthonitrophenylpropiolic formed on treating the latter with concentrated sulIt forms yellow needles, M.P. 115.

Diisatogen [27],

c6H4 ^
formed on treating trated sulphuric acid.
is

^CO C C CO X /\ |\ ;:c H ^ O O

4,

dinitrodiphenyldiacetylene with concenIt forms red needles, soluble only in It is easily chloroform, nitrobenzene, and strong sulphuric acid. converted by reducing agents to indigo blue.

Indoxanthic Ether [28].

PR/
This

CO C(OH)C0 2 C 2 H

5.

compound
it
;

ferric chloride.
lies

convert

obtained by oxidation of indoxylic ether with forms straw-yellow needles, M.P. 107. Alkato anthranilic acid. It forms a nitrosamine with
is

It

nitrous acid

on reduction indoxylic ether

is

reproduced.

Indigo-Blue.

C6H4

CO

C=C CO

C6 H4

NH
Indigo blue
is

NH

the most important, in fact the only important

derivative of indol from a technical point of view.

INDIGO DYESTUFFS.

225

Indigo occurs as a glucoside, indican, in various plants (Indigofera tinctoria, Indigofera anilj Polygonum tinctorium, and Isatis According to Schunck [29] , indican from Isatis tinctinctoria)
.

toria has the composition to the equation

:

C 26 H 31 NO 17 and decomposes
,

according

2C 26 H 31 N0 17 + 4H 2

= C H 10N
16

+C H O
6

10

6.

Indigo-blue.

Indiglucine.

It is, however, uncertain if the same indican occurs in all plants. In the industrial preparation of indigo, an aqueous extract of the The indigo blue produced is plants is submitted to fermentation.

probably reduced by the sugar, soluble indigo white being formed. On subsequent oxidation in the air, indigo blue separates mixed

manner

The crude product obtained in this with various impurities. is the valued dyestnff known as indigo. The amount of

pure colouring-matter (indigotin) contained in indigo varies, being generally between 20 and 90 per cent. Besides this, it contains various substances indigo red, indigo brown, indigo yellow, and indiglutin, of most of which but little is known.
:

Indigotin occurs sometimes in urine. Indigotin is best obtained from indigo by conversion of the latter into the soluble reduced compound, and subsequent oxidation

by

air [30]

(indigo vat)

Another method consists in ex-

tracting the indigo with aniline or chloroform and allowing the indigotin to crystallise from the solvent. According to the method of preparation, indigotin forms lustrous coppery needles

On heating it does not melt, but sublimes with partial decomposition in form of coppery needles. Indigo vapour has a purple-red colour. It disIndigotin is insoluble in most of the usual solvents.
or a dark blue powder.

chloroform, nitrobenzene, phenol, paraffin, petroleum, naphthalene, and in certain fatty oils. The solutions have not all the same colour ; for example, the aniline and chloroaniline,

solves

in

form solutions have a deep indigo-blue

colour, while the solution in paraffin has the purple-red colour of indigo vapour, a behaviour somewhat similar to that of iodine.

corresponds to the formula determination of its vapour-density, the molecule contains twice this and is therefore C 16 10 2 O 2

The composition of indigotin

C 8 H 5 NO, but from

H N

Indigotin dissolves unchanged in concentrated sulphuric acid

226

CHEMISTRY OF ORGANIC DYESTCJFFS.

On heating, sulphonic acids are formed, the colour of the solution changing to blue.
with a green colour.

By destructive distillation, indigotin yields aniline ; on melting with caustic potash, aniline, anthranilic acid, and salicylic acid are
formed [16].
Chlorine Oxidising agents convert indigotin to isatin [16]. produces chlorine derivatives of isatin first, and then chlorinated

Bromine acts in a similar manner. phenols and chloranil [16] Indigotin dissolves in hot concentrated caustic potash solution with an orange-yellow colour, indigo white and isatic acid being
.

probably formed. On reduction in alkaline solution indigo blue takes up two atoms of hydrogen, forming indigo white, which possesses phenoloid properties and dissolves in the alkaline liquid. In the air, indigo white solution oxidises immediately, insoluble This property is extensively employed in indigo blue separating.

dyeing with indigo, and also serves for the isolation of pure indigo from the commercial product. The reducing-agents more commonly employed are ferrous salts,
arsenious acid, stannous oxide, hyposulphurous acid, zinc powder,

and grape-sugar.

Dilenzoylindigo [32],

C 16 H 8N 2
is

(C 7

0) 2 ,

formed on heating indigotin with benzoyl chloride. Halogen derivatives [33] of indigotin have been prepared from the corresponding derivatives of isatin and of orthonitrobenzaldehyde [37]. Dinitro- and
diamido-indigotin have been prepared from " Synthesis of Indigo Blue," (Compare the
.

dinitro-isatin [33]
p. 231.),

Indigo

White,

is formed by reduction of indigotin, and contains two atoms of hydrogen more than the latter. In distinction from indigotin, which possesses neither basic nor acid properties, it exhibits the

INDIGO DYESTUFFS.
character of a

227

weak acid like the phenols. It dissolves in alkalies, and may be precipitated from the solutions by an acid. Carbonic

acid separates it as a silky greyish- white mass. Indigo white can be dried and preserved in an atmosphere of carbonic acid or only
It oxidises rapidly to indigotin on exposure to the the properties of indigo white, it is apparent that the carbonyl oxygen atoms of the indigotin are converted into

hydrogen.
air.

From

hydroxyl groups.

From

the

derivatives of indigo blue

(sulphonic

acids, &c.),

substitution-derivatives of indigo white are obtained

on reduction.

Indigo Slue Sulphonic Acids.

MonosulpJionic Acid [34], C 16 H 9 N 2 2 S0 3 H,
(Sulphopurpuric Acid.}

obtained by heating indigo with concentrated sulIt forms purple-red flocks which dissolve in pure acid. phuric water with a blue colour, but are insoluble in dilute sulphuric
This acid
is

acid.

The

salts are sparingly soluble in water, insoluble in saline

solutions.

Disulphonic Acid [34],

C 16 H 8N2
is

(S0 3 H) 2

formed by further action of sulphuric acid on indigotin.

It

forms an amorphous powder, soluble in water. The salts are also solutions by easily soluble, and may be separated from aqueous

The sodium salt comes into commerce as a paste, It is as Indigo Extract, Indigo carmine, &c. applied like the acid dyestuffs, and has a somewhat extensive Indigo-disulphonic acid may also be application in wool-dyeing.
addition of
is

salt.

and

known

obtained synthetically, the method will be found under Synthesis

of Indigotin.

Q2

228

CHEMISTRY OF ORGANIC DYESTUFFS.

APPLICATION OF INDIGO IN DYEING.

The
tinctorial properties of indigo are
:

due to the presence of

the chromophorous group

CO

which forms a closed chain with the benzene ring. As it contains no salt-forming groups it is not a real dyestuff, and owing to its This may be produced by insolubility has no affinity for the fibre. introduction of sulpho- groups, and the indigo then assumes the The principal application of indigo character of an acid dyestuff. The however, on its conversion into soluble indigo. depends, based on this property is termed vat-dyeing, and has been process

Most of the reducing-agents in use since the earliest periods. acting in alkaline solution have been applied, but in practice the
Ferrous sulphate, stannous chloride, following are important grape-sugar, arsenious acid, zinc powder, and sodium hydro:

sulphite.

The reducing- agent employed is generally added along with lime or soda to a finely divided indigo suspended in water. The ferrous sulphate and stannous chloride are hereby converted to the corresponding hydrates. The indigo blue is slowly converted
to indigo white, which dissolves in the alkaline liquid. vat is used for dyeing both wool and cotton.

The indigo-

Wool
is

appears to have a certain attraction for indigo white and capable of withdrawing it from solution, while cotton is only

In all cases the conversion of impregnated with the liquid. white to indigo blue on the fibre is effected by atmospheric indigo oxidation. Only in recent years has indigo been applicable for direct printing. Previously calico was dyed in an indigo-vat, and
then the necessary effects produced by printing on discharges. Of late years, however, the following methods have been employed on direct printing. Cotton fabrics impregnated with grape-sugar solutions are
printed with a mixture of finely divided indigo and strong caustic soda suitably thickened. On steaming the indigo white produced

INDIGO DYESTUFFS.
thoroughly penetrates the
effects are obtained.
fibre,

229
fast

and on oxidation

indigo

The

difficulties in

this direction

have also been to a certain

extent vanquished by the introduction of artificial indigo. thickened mixture of orthonitrophenylpropiolic acid and grapesugar, or better an alkaline xanthate with an alkali is printed,

and the indigo blue developed by steaming and drying. However, orthonitrophenylpropiolic acid does not appear to have

made

serious competition with natural indigo in this direction,

and interesting as the synthesis is from a scientific standpoint, it has not yet been applied practically to any great extent. Indigo carmine is almost exclusively used in wool-dyeing, and is applied in an alum bath at the boil. The shades obtained are finer than those from the vat, but are not so fast. They are principally used in production of mixed
shades.

Indigodicarbonic Acid [36],

C 16 H 8 N2
This acid
is

(COOH) 2

formed by treating nitroterephthalaldehydic

acid,

COOH
NO,

with acetone and soda solution, and by action of alkali and grapeIt sugar on the carbonic acid of orthonitrophenylpropiolic acid.

forms a blue precipitate, insoluble in chloroform. with alkalies is green, and is precipitated by acids.

The

solution

Indo'ine [13],

Indo'ine

is

formed by reduction of orthonitrophenylpropiolic

It closely

acid with ferrous sulphate in sulphuric acid solution.

resembles indigo, but

:

be distinguished by the following It dissolves in cold concentrated sulphuric acid with a reactions blue colour (indigo gives a green solution), and is only converted

may

It is also easily soluble in into a sulphonic acid with difficulty. aniline and in aqueous sulphurous acid, forming blue solutions.

230

CHEMISTRY OF ORGANIC DYESTUFFS.

Indigopurpurin.

C 16 H 10N 2 O 2

This compound is isomeric with indigotin, and is formed as a bye-product in the preparation of the latter from isatin chloride

[22,38].
It
is

fine red needles.

similar to indigotin, but is more readily sublimed, forming On It dissolves in alcohol with a red colour.

it

dissolving in concentrated sulphuric acid and diluting with water, gives a red solution.

Indirulin [13, 60].

C6 H 4

CO C=C C (OH) =N.

NH
Indirubin
indigotin.
is

^C H
6

It

may

the indogenide of isatin, and is isomeric with be obtained by mixing aqueous solutions of

indoxyl and isatin in presence of a little caustic soda. Indirubin forms a reddish-brown powder. It dissolves in alcohol with a violet colour, and in concentrated sulphuric acid

with a greyish-black colour.

The latter solution becomes violet on heating, a sulphonic acid being formed. With reducing-agents gives a vat, and on further reduction indileucin, C 16 H 12 2 O, is

produced. From the present state of our knowledge, it is not certain mdigopurpurin and indirubin are identical or different.

if

Indigo

Red

[61].

This compound, which occurs in crude indigo, is also an isomer of indigotin. The exact relationship existing between this body

and the two previous ones is not certain. According to Baeyer, it differs from mdigopurpurin. Schunck obtained a compound from indican which he named Indirubin, and which he regards as identical with indigo purpurin [61].

INDIGO DYESTUFFS.

231

dyeing.

Indigo red forms a vat and a sulphonic acid, both capable of The shades produced in the vat are noteworthy for their extreme fastness to light.

SYNTHESIS OF INDIGO BLUE.

In the years 1865 and 1866 Baeyer and Knop [14] converted and indigotin through dioxindol and oxindol into indol ; three years later Baeyer and Emmerling [5] prepared indol
synthetically by melting- a mixture of nitrocinnamic acid, caustic The nitrocinnamic acid employed was a potash, and iron filings.

mixture of the ortho and para compounds, and only later was
discovered that the ortho acid
is

it

alone capable of yielding indol. In 1870 the same chemists observed the formation of indigo

blue by treating isatin with a mixture of phosphorus trichloride

and acetyl chloride. In the same year Emmerling and Engler [39] obtained small quantities of indigo by heating nitroacetophenone with zinc powder and soda-lime, but subsequently were unsuccessful in producing the necessary conditions for the formation of the
dyestuffs.

The

first

certain

method

for

producing

artificial

indigo

is

due to
.

Nencki, who obtained it by oxidation of indol with ozone [40] The same chemist had already obtained indol by the pancreatic
fermentation of albumen

In 1877 Baeyer and Caro [2, 40]. obtained indol by passing the vapour of certain aromatic amines, especially of diethylorthotoluidine, through a red-hot tube.

In 1878 the constitution of oxindol was discovered by Baeyer It was found to be the inner anhydride [17] and by Suida [15]. of orthoamidophenylacetic acid, and was obtained synthetically from the latter. In the same year [17] Baeyer prepared isatin from oxindol. The nitroso-compound of oxindol yields the amido-compound on reduction, and this is converted into isatin by oxidation or by
nitrous acid.

As isatin had already been converted into indigo, the formation of the former from orthoamidophenylacetic acid effects a At the same time Baeyer [17] complete synthesis of indigo.
improved the process whereby
isatin

was converted into indigo.

232
Isatin
is first

CHEMISTRY OF ORGANIC DYESTUFFS.

submitted to the action of phosphorus
tri-

or penta-

and the resulting isatin chloride yields indigotin on reduction. In this case indigopurpurin is formed as a byechloride,

product. Claisen and Shadwell discovered a

production of isatin in 1879.

By

new synthetical method for action of silver cyanide on

orthonitrobenzoyl chloride, orthonitrobenzoyl cyanide is produced, and this is converted into orthonitrophenylglyoxylic acid by On saponification and subsequent treatment with an alkali.

reduction of this acid in alkaline solution, a salt of isatic acid

(orthoamidophenylglyoxylic acid) may be separated by an acid.

is

produced, from which isatin

These researches effect another complete synthesis of indigotin. In 1880 Baeyer prepared indigo synthetically from cinnamic
acid
I.

by various processes

[19, 41] Orthonitrocinnamic acid,

= CH COOH
C 6H4

[1]
[2]

N0

unites with bromine to form orthonitrodibromhydrocinnamic acid,

C 6 H4<

CHBr-CHBr-COOH

II] [2]

N0

On treating this compound with HBr split off and an unsaturated acid
acid,

alkalies,

two molecules of

orthonitrophenylpropiolic

C=C-COOH
N0
is
2

[1] [2]

This acid yields isatin on boiling with an alkali, and on reduction in an alkaline solution (alkaline grape-sugar indigo

formed.

solution, or an alkaline xanthate)

II.

By

treating

Orthonitrocinnamic

acid

with
acid

chlorine in
is

alkaline

solution, orthonitrophenylchlorlactic according to the equation

:

formed

INDIGO DYESTUFFS.

233

C 6 H/

CH = CH-COOH

N0 2

+HC10 = C 6 H 4x

CHOH-CHC1
|

COOH.

N0

This acid gives orthonitrophenyloxyacrylic acid on treating with

an

alkali,

O
C 6 H 4<

CH-CHCOOH
NO
2

On
pound
III.

heating in phenol, or glacial acetic-acid solution, this comyields indigo. yields

Orthonitrophenylpropiolic acid acetylene on boiling with water [42]

:

orthonitrophenyl-

C 6 H 4<

C^CH
2

N0

On

oxidation of the copper

compound

of the latter with potasis

sium ferricyanide, dinitrodiphenyldiacetylene

produced

C=C C=C
C^H^x

NO

NO

/C 6 H 4
2

On treatment with fuming sulphuric acid this body undergoes a molecular change, an isomer, diisatogen, being formed. The latter gives indigo on reduction [42]
.

IV. In 1882 orthonitrobenzaldehyde was used as a startingpoint for the artificial production of indigotin [2]. On dissolving orthonitrobenzaldehyde in acetone and adding an excess of dilute caustic-soda solution, indigo blue separates on
standing.

pyruvic acid.

The acetone may be replaced by acetaldehyde or This reaction was studied in detail by Baeyer [44],

The

the formation of

C 10 H nNO 4

interaction of acetone and orthonitrobenzaldehyde results in an intermediate product of the composition

(probably the methyl ketone of orthonitrophenyl-1

234
acid).

CHEMISTRY OF ORGANIC DYESTUFFS.

This compound decomposes under the influence of alkalies according to the equation
:

2C 10 H n N0 4 + 2H 2

=C H N
16

10

+ 2C H 4O + 4H
2

O,

indigotin and acetic acid being formed.

With acetaldehyde, orthpnitrobenzaldehyde forms the aldehyde of orthonitrophenyl-lactic acid

:

CHOH-CH.COH,
which
[45]
.

splits

up with

alkalies,

forming indigotin and formic acid

in the case of pyruvic acid
:

The intermediate product

is

orthonitrocinnamyl-formic acid [44]

CH= CH

CO

COOH.

This body is best obtained by action of ga'seous hydrochloric acid on a mixture of the reacting compounds. Orthonitrocinnamylformic acid is split up by alkalies into indigotin and oxalic acid.

A patent

of Meister, Lucius,

similar reaction.

ketone

C 6 H5

CH = CHCO CH
is is

& Briining [46] depends on a Claisen's benzylidene-acetone (cinnamylmethyl3)

[47] , obtained

of benzaldehyde and acetone,

paranitro derivatives by action of alkalies.

nitrated.

A mixture of ortho

by condensation and

formed, and the former yields indigotin

Ortho-nitrometa-tolualdehyde [48] gives a homologue of indigoblue, and chlorine derivatives may be obtained from chlor-orthonitroaldehydes [37]
.

Another method has

its

starting-point in

ortho-amidoacetophenone. This compound is converted into its The reacetyl derivative and treated with bromine in the cold.

bromine derivative, when dissolved in concentrated sulhydrobromic acid, a crystalline compound being formed, which, under the influence of air in presence of alkalies,
sulting

phuric acid, loses

yields indigotin.

Indigotin may also be obtained from ortho-amidophenylacetylene by an analogous process.

Gevekoht [50] obtained indigotin by action of ammonium

sulis

phide on ortho-nitroacetophenone, in which the methyl group brominated.

INDIGO DYESTUFFS.

235

From the researches of Baeyer [51] and Bloem it is shown that on brominating acetylortho-amidoacetophenone, the bromine atom enters in the methyl group. If the benzene chain is substituted brominated indigos are formed ; but if only the benzene chain contains bromine^ indigo cannot be produced. Tn these reactions as an intermediate product in the indoxyl appears to be formed
reaction.

[52] prepared substituted indigo blues from the corresponding substituted isatins. This process depends on the fact that the final products of the action of dichloracetic acid on
P.

Meyer

amines in which the para position is occupied are substituted The first product of the action of dichloracetic acid on paratoluidine is a paratolylimide derivative of paramethyli satin, C 16 H 16 2 O, which decomposes on boiling with acids into paratoluidine and methylisatin, C 9 H 7 NO 2 Perhaps the simplest methods for the synthetic production of indigo are those which have their starting-point in certain aniline
isatins.

derivatives of acetic acid.

Flimm discovered that bromacetanilide,

2 Br, gives a trace of indigo on heating with caustic potash (B. B. 1890, p. 57). Heumann's process gives a somewhat better result, but still the yield (about 15 per cent.) is not sufficiently great for technical application. In this method phenyl-

C 6 H 5 NH

CO

CH

glycocine, formed by action of monochloracetic acid on aniline, is heated with caustic potash with exclusion of air to about 260. The orange-yellow melt obtained is dissolved in water, and on ex-

The course of the reaction is not posure to air indigo separates. exactly understood, but in all probability the first stage consists in the formation of pseudoindoxyl
:

IH

C 6 H4

NH CH CO|OH
.

In alkaline solution pseudoindoxyl oxidises immediately, producing indigo

:

CO

236

CHEMISTRY OF ORGANIC DYESTUFFS.

somewhat better

result is obtained
is

orthocarbonic acid, which

acid on anthranilic acid.

by using phenylglycocineprepared by action of monochloracetic This compound is fused with caustic

potash, the reaction taking place at a considerably lower temperature than when phenylglycocine is employed.
If phenylglycocine is mixed with sand and introduced into a large quantity of sulphuric acid containing a considerable amount

of sulphuric anhydride, taking care to avoid an increase in temperature, a reaction immediately takes place, sulphurous acid being

This is due to evolved, while the solution takes a blue colour. the formation of indigo-disulphonic acid, which may easily be isolated by dilution and addition of salt. The yield by this process
is

satisfactory,

amounting to about 60 per

cent, of the phenyl-

glycocine used.

CONSTITUTION OF THE INDIGO GROUP.

his synthesis of indol from orthonitrocinnamic ascribed to it the constitutional formula Baeyer
:

From

acid

H 4C 6 /

CH \

CH,

which is now generally accepted. Kekule had already (1869) [53] published an opinion that isatin is an inner anhydride of orthoamidophenylglyoxylic acid, and accordingly suggested the structural formula
:

C 6 H 4<(

/CO

NET

">CO.

Claisen and Shadwell proved that isatic acid is orthoamidophenylglyoxylic acid, and that isatin is its inner anhydride by a direct synthesis [26]. However, various properties of isatin

noted by Baeyer speak for the presence of an hydroxyl group according to the formula
:

INDIGO DYESTUFFS.

237

Oxindol is, from its synthetic production, an inner anhydride of orthoamidophenylacetic acid, and has the formula
:

:CO.

is,

The formation of oxindol and dioxindol by reduction however, more in favour of the following constitution
:

of isatin
for these

compounds

f^ TJ

( (~\

CTT / 6"4\

/\JITL

(UrlJL'Uxl
.^

C*f\ TJ

r^ZT
,

^-N^

/ ^6^-4^
tl

Ujl 2

r^l(~\~LX\

TJ

U(Url)

^^ ^N^
Oxindol.
its

Dioxindol.

The

constitution of indoxyl
:

may be deduced by

formation

from indoxylic acid

i'\~>

C 6 H 4^

r\ r\(C\\3\ =v>--^ r\c\ TJ \ \Jr\-) L/L/gJcl

^NH^
in combination with the carbon

The hydroxyl group must be

atom in the adjacent position to the benzene ring. The constitution of indoxyl is accordingly represented by the formula

C 6 H4
From
acid,

X C(OH)

CH

NH
appears probable that isatin, indoxylic

certain reactions

it

and indoxyl are capable of existing in two isomeric forms. One of these exists only in the form of derivatives (for example, ' Baeyer terms these labile or pseudo forms/'' and gives ethers)
'
.

the following formulas to them

fi

.CO-COH
Isatin.

C 6 H 4^

/CO CO

/
CO

Tseudoisatin.

C 6 H 4C(OH)=CH

C 6 H4

CH

Indoxyl,

Pseudoindoxyl.

238

CHEMISTRY OF ORGANIC DYESTUFFS.

C6 H4

C (OH) ^C

COOH

C6H4

CO

CH COOH

Indoxylic acid.

Pseudoindoxylic acid.

These pseudo-modifications are stable when certain of their In the case of pseudoisatin a hydrogen atoms are replaced. monovalent group suffices ; while in pseudoindoxyl both hydrogen atoms of the carbon atom in the side-ring must be replaced. In
this

manner the following compounds may be obtained

C6 H 4

CO

CO
5

C 6 H4

CO

C=CHC H
6

NC H
2

Ethylpseudoisatin.

Benzylidenepseudoindoxyl.

The

divalent rest of pseudoindoxyl,

C 6 H4

w
CO
C =C

C=

is

must be contained

especially interesting, as researches on this subject show that it in indigotin. Baeyer designates this rest as

the indogene group, and those derivatives in which the indogene group replaces an atom of oxygen are termed indogenides. The

above benzylidenepseudoindoxyl must therefore be regarded as the indogenide of benzaldehyde, as it is formed by heating indoxylic acid with benzaldehyde, carbonic acid and water splitting off.
Indigotin may be regarded as a combination of two indogene groups, as expressed by the constitutional formula
:

C 6 H4

CO

CO

C 6 H4

Indigotin.

This constitution

is

also that of

an indogenide of pseudoisatiu

.CO c 6 H 4<; X
and indigotin
is

CO

NH
by replacement of an oxygen

therefore formed

INDIGO DYESTUFFS.

239
Similarly, indi--

atom of pseudoisatin by the indogene group.

rubin
is

the indogenide of isatin

C 6 H4

CO

C=C C(OH)=:N

Indirubin
reaction
it

is formed by action of isatin on iudoxyl, in which must be accepted that the latter undergoes a molecular

change into pseudoindoxyl.

Baeyer arrives

By

at these conclusions from the following facts the action of nitrous acid on indoxyl a nitrosamine of the
:

latter is

formed

CTT -"

N(NO)

On reduction it is converted through By action of nitrous acid on ethylindoxylic

indoxyl to indigotin. acid [56] an isomeric

compound, possessing the properties of an isonitroso compound, is formed. It yields isatin on reduction and subsequent oxidation. It is probable that in the formation of this body from ethylindoxylic acid
:

a molecular change takes place, as two monovalent groups are split off from two different carbon atoms, and the isonitroso group is always divalent and connected with one carbon atom.

The formation of

isatin

from

this
:

body shows

it

to be pseud-

isatoxime or isonitrosopseudoindoxyl

CO C=NOH.

This constitution receives further support from the behaviour on ethylation, whereby a mono-ethyl ether is produced. This ether also yields isatin, and therefore cannot contain the ethyl group
in direct combination with a carbon atom, nor yet in the imide It is stable to hydrochloric acid, which would not be the group. case were the ethyl group connected with hydroxyl.

240
.

CHEMISTRY OF ORGANIC DYESTUFFS.

constitution of the
:

The

compound

is

therefore expressed by the

formula

C 6 H4 \X

X CO ^
NH

C=NO(C H
2

5)

It is pseudoisatinethyl-a-oxime.
di ethyl ether is

On

further ethylation the

formed

CO

C=NOC H
2

On

reduction and subsequent oxidation, ethylpseudoisatin

:

is

formed

CO

CO

It differs

from the isomeric ethylisatin by being

it

difficult to

saponify.

Alkalies convert

to ethylisatic acid

CO
C 6 H 4<T
With hydroxylamine
X

COOH
2 5

NHC H

ethylpseudoisatin gives the /3-oxime

,C(NOH)

CO

It

combines with indoxyl to form the indogenide

C6H4

CO

C=C CO NC H
2

diethyl ether of pseudoisatin-a-oxime yields diethyl blue if treated with mild reducing-agents, precisely in the indigo same manner that pseudoisatoxime gives indigo blue under similar
conditions.

The

As in this reaction the ethylated isonitroso group is split off, while the ethyl group attached to the imide-nitrogen atom remains intact, it follows that if the above constitution of ethyl pseudo-

INDIGO DYESTUFFS.
isatin

241

ethyl a-oxime is correct, diethyl-indigotin must possess the constitution expressed by the formula
:

C6 H4

CO

C=C_ CO
2

C 6 H4
5

C2 H5 C 6 H4

NC H

and consequently indigotin the analogous one

CO

C=C CO

C6H4

Baeyer summarises the conclusions leading to

follows
1. 2.
:

this

formula as

Indigotin contains an imi do-group.

Its formation from diphenyl-diacetylene shows carbon atoms are placed in the following manner
:

that

the

C6 H 5

C 6 H5

3. Indigotin is formed only from those compounds in which the carbon atom adjacent to the benzene ring is connected with an

atom of oxygen. 4. The formation and properties of indigotin show a close relationship to indirubin and to the indogenide of ethylpseudoThe latter is formed by the coupling of the a-carbon isatin. atom of pseudoindoxyl with the /3-carbon atom of pseudoisatin.

242

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER

XII.

EUXANTHIC ACID AND GALLOFLAYINE.

THESE yellow dyestuffs, though of totally different origin, show some relationship in chemical properties, and possibly owe their tinctorial value to the same chromophor. In euxanthic acid this is a carbonyl group, which forms a ring with one oxygen atom and
two benzene nuclei. Euxanthic acid contains as chromogen the
ketone-oxide
:

rest of diphenylene-

somewhat similar in constitution

to anthraquinone,
4

/C CO X 6
It has not

H \ CO

C 6 H/

been determined with certainty that galloflavine

contains the same group.

Euxanthic Acid.
CieHisOn.

The magnesium salt is the essential constituent of the dyestuff known in commerce as Purree or Indian Yellow. This product is
obtained from the urine of cows, fed on mango-leaves. The goldyellow urine is heated, and the yellow deposit formed into a ball.
is purified by removing the outer portions and thoroughly washing the remainder. The recent researches of v. Kostanecki [8] demonstrate that the origin is from urine, as they proved that the urine of animals whose food contained euxanthone separated euxanthic acid. It is probable

This

EUXANTHIC ACID AND GALLOFLAVINE.

243

that the euxanthone contained in certain plants combines with glucuronic acid in the animal organism, euxanthic acid thus being formed. To prepare euxanthic acid, purree is exhausted with water,
treated with dilute hydrochloric acid, and the residue extracted with ammonium carbonate. The resulting ammonium salt is decomposed with hydrochloric acid, and the euxanthic acid crystallised

from alcohol

(2).

It forms lustrous straw-yellow needles, sparingly soluble in cold water, more easily in hot water, and readily in alcohol, but in-

soluble in ether.

On heating to 130 one molecule of water splits off, an anhydride, C 19 H 16 O 10 [6], being formed. This was formerly regarded as
anhydrous euxanthic acid, the crystallised acid having the formula C ]9 H 16 O 10 + H 2 0. Euxanthic acid is monobasic; its salts with the alkalies are easily soluble, those with magnesium and lead sparingly The alkali salts are precipitated by an excess of alkali. soluble. On heating with water or dilute sulphuric acid to 140, euxanthic acid splits up into euxanthone [1], C 13 H 8 O 4 and glucuronic acid,
,

C 6 H 10
or

[6].

Euxanthone is

also formed by heating euxanthic acid to 160 180, with concentrated sulphuric acid 38] by warming Chlorine and bromine act on euxanthic acid, producing di-sub.
|

stitution products [2]

Nitric acid produces nitro-euxanthic acid

finally styphnic

in the cold

acid

is

on warming, trinitro-euxanthone, and formed [1].

;

Euxanthone.

C 13 H 8
decomposition.

4.

This compound forms pale yellow needles which sublime without

easily in boiling alcohol.
It is insoluble in water, sparingly soluble in ether, It is formed as described above from
is

euxanthic acid, and

also a

constituent of purree, the lower

It is soluble in aqueous solutions qualities containing most. Its of the alkalies, but possesses no further acid properties.

alcoholic solution

On heating with is precipitated by lead acetate. zinc powder, benzene, phenol, and methylenediphenylene-oxide, The last-named compound (C 6 4 ) 2 2 [9], are formed.

CH

H O

yields diphenyleneketone- oxide

on oxidation,
6

/C OX

H 4\ CO
R2

C 6 H/

244

CHEMISTRY OF ORGANIC DYESTUFFS.

is formed ou boiling euxanthone with acetic M.P. 185. Dichloreuxanthone and dibromenxanthone anhydride, maybe produced by decomposition of the corresponding derivatives

Diacetyleuxanthone

of euxanthic acid [2] Trinitroeuxantlione forms yellow needles, and

.

is

a monobasic acid

[2].

The constitution of euxanthone is explained by the following reOn melting with potash it searches of Baeyer and Graebe [21] yields euxanthonic acid (tetraoxybenzophenone),
.

OH

OH OH

-CO

OH

which on further heating splits up into resorcin and hydroquinone. Euxanthone is the inner anhydride of euxanthonic acid,

co-

and

is

therefore 2.6 dioxydiphenyleneketone-oxide.

its

This

is

con-

synthesis, on heating hydroquinone carbonic acid with /3-resorcylic acid in presence of acetic anhydride. Euxanthic acid is apparently an ether of euxanthone (or euxan-

firmed by

thonic acid) with glucuronic acid.

C 6 H 10 O 7
Euxanthone.
Glucuronic
acid.

=C H O
19 18

Euxanthic
acid.

acid

Euxanthone, although yellow, is not a dyestuff, while euxanthic is capable of dyeing on metallic mordants. Its principal application is as an artists' pigment under the name

of Indian Yellow.

EUXANTHIC ACID AND GALLOFLAVINE.

245

SYNTHETICAL OXYKETONE DYESTUFFS [22].

method

for the production of

hydroxyl derivatives of benzo-

phenone and its homologu.es has been patented by the Badische Anilin- und Sodafabrik.

The process consists in heating fatty or aromatic acids with a phenol or oxycarbonic acid containing at least two hydroxyl groups in the ortho position to each other with a dehydrating agent.

The

reaction

may

be best explained by the following example.

Trioxybenzophenone.
part of pyrogallol and one part of benzoic acid are heated 145, and three parts of zinc chloride gradually stirred into the mixture, and the above temperature maintained for three hours.
to

One

The melt

is

extracted with boiling water, and on cooling the dye-

M.P. 137-138. It dyes shades on cotton mordanted with alumina the golden-yellow presence of lime-salts renders the tone more orange. Another
stuff is deposited in yellow needles,
;

process for production of trioxybenzophenone, due to the same firm, consists in heating pyrogallol with benzotrichloride in It is known in comaqueous, alcoholic, or acetic acid solution.

merce as Alizarin Yellow A.

Gallacetoplienone.
This compound is a trioxyacetophenone { (OH) 3 C 6 2 COCH 3 ^ obtained by heating pyrogallol with acetic acid and zinc chloride It may be used for printing with chromium acetate, and to 150.
gives

brown shades

[23]

It is

named

Alizarin Yellow

Gr.

Ellagic Acid.

This compound
flavine,

is

although

its

related to the above dyestuffs and to galloconstitution has not been determined with cer-

tainty.

Ellagic acid

may be obtained by action of various oxidising

agents on

acids, and by heating gallic ether with gallic soda solution. It also occurs naturally in bezoar stones. Ellagic acid gives greenish-yellow shades when printing with chromium acetate.

and tannic

246

CHEMISTRY OF ORGANIC DYESTUFFS.

Gallqflavine.
This dyestuff is formed by oxidation of a gallic acid solution, containing about two molecules of an alkali, by atmospheric oxygen
It is best prepared by dissolving gallic acid in alcoholic [12]. potash solution, and passing a current of air through the solution. A potassium salt of the dyestuff, which is sparingly soluble in

alcohol, separates [11].

Galloflavine forms greenish-yellow leaflets, sparingly soluble in ether and alcohol, more easily in acetic acid, and best in aniline. It is soluble in alkalies, and is reprecipitated on the addition of acids. The composition of galloflaviue is probably represented, by the

formula C 13 H 6 O 9 It forms dibasic

.

salts

those with the alkalies are easily soluble

it

in water.

If heated with acetic anhydride,

yields
[11].

compound, C 13 H 2
Galloflavine
it

a colourless acetyl

(C

i!

H3O) 4 /M.P. 230

is used along with metallic mordants. On alumina a greenish-yellow shade, on tin oxide a pure produces yellow, and on chromium oxide an olive-green. It has been used to a slight extent in wool-dyeing ; on chromed wool it gives results

similar to fustic.

CANARINE.

247

CHAPTER
CANAEINE.

XIII.

[13, 14, 15.]

ON treating potassium sulphocyanide with potassium chlorate, in presence of hydrochloric acid, canarine is formed (Prokoroff and
Miller) [13].

Liebig [16], and named pseudo- or persulpho-cyanogen, C 3 N 3 HS 3 although the identity of the two is denied by Miller.
soluble in alkalies

This compound

is

probably identical with that discovered

by:
,

Canarine forms a yellow powder, insoluble in neutral solvents, and in borax solution.
application of canarine depends

The

on

its

property of dyeing

cotton yellow from an alkaline solution.

The shades vary from

light yellow to orange-yellow, according to the concentration of the solution. They are very fast both to soap and light. In comparison with other artificial dyestuffs, canarine only possesses weak
tinctorial properties.

Canarine dyed on cotton is capable of acting as a mordant for In this respect it resembles Cachou de Laval and basic dyestuffs. the benzidine series of direct colours.

248

CHEMISTRY OF ORGANIC DYESTUFFS.

CHAPTER
MUREXIDE.
MUREXIDE
picric acid
is

XIV.

[17, 18, 19, 20.]

the acid

ammonium
It is

salt of

purpuric acid, which does

Its

not exist in the free

it is

state.

of historical interest, as besides

application dates

the oldest artificial dyestuff used technically. from the year 1853.

Murexide

is

obtained by action of

ammonia on the mixture

of alloxan and alloxantin, obtained by evaporating a solution of uric acid in strong nitric acid.

formed further by heating alloxantin in ammonia gas, and boiling uramil with mercuric oxide.
It
is

It

forms four-sided prisms, with a green lustre, appearing red

.

by transmitted light.

C 8 H 4N 5 O 6NH4

The composition
.

By

the potassium salt

of murexide is expressed by the formula double decomposition with potassium nitrate, The salts with (C 8 4 6 O 6 K) is obtained.

HN

calcium, barium, tin,

and mercury are sparingly soluble red or

violet precipitates. Murexide dissolves in

is

water with a fine purple-red colour, which to blue-violet on addition of excess of alkali. Mineral changed acids set free purpuric acid, which immediately decomposes into
uramil and alloxan, the solution being decolorised. Murexide may be dyed on tin, lead, or mercury mordants, the last producing the best results. It is at present out of use.

DYESTUFFS OF

UNKNOWN

CONSTITUTION.

249

CHAPTER XV.
DYESTUFFS OF UNKNOWN CONSTITUTION.
THE following chapter comprises those dyestuffs which cannot be It has already placed under the foregoing chemical classifications. been mentioned that many of the dyestuffs treated of under the
previous groups are of unknown constitution ; but, being products of chemical synthesis, certain relationships to the various classes are easily deduced.

The number of colouring-matters included in the present chapter unfortunately very large most of them are natural products obtained from plant and animal sources. As these natural dyestuffs are very numerous, only those are described which are of interest from a technical or scientific point of view.
is
;

Although the artificial dyestuffs have to a great extent replaced the natural ones, certain of the latter still retain great importance in dyeing, being in fact indispensable, as no synthetical products have been able to do their work.
is

The great importance of a large number of the natural dyestuffs based on the property which they possess of forming firmly-

adherent lakes with metallic oxides.

adjective dyestuffs. Some of them, for

They

are,

like

alizarin,

example Hsematoxylin, Hsemate'in, Brasilin, and Brasilei'n, are possibly quinones ; others appear to be related to Euxanthone. Some of these compounds are glucosides, which may be split up by action of dilute acids, forming a sugar, and a compound which
is

the real colouring-matter. Some natural dyestuffs (Curcumin,Bixin,Carthamin) are capable, like the tetrazo dyestuffs, of dyeing on unmordanted cotton.

250

CHEMISTRY OF ORGANIC DYESTUFFS.

Hcematoxylin
Ci 6

[1, 2, 3, 13].
6.

H HO

Haematoxylin

is

contained in logwood or campeachy, the

wood

of Haematoxylon campechianum. Although scarcely a dyestuff, hsematoxylin is the only important constituent of logwood, as on

oxidation

it

yields

haematem

[2]

compound

of strong tinctorial

properties.

Heematoxylin is prepared by extracting freshly rasped logwood with aqueous ether, evaporating, and mixing the residue with water [3] The crystals which separate are recrystallised from
.

water, preferably with addition of oxidation.

ammonium

bisulphite to prevent

Hasmatoxylin crystallises with 3 H 2 O in colourless tetragonal It dissolves prisms [4], or with 1 H 2 O in rhombic crystals. in cold water, and is dissolved with facility by hot water, sparingly It has a sweet taste. It melts in its water of alcohol, and ether.

somewhat over 100. Its solution turns a ray of towards the right [3] polarised light It dissolves in alkalies with a purple colour ; the colour rapidly changes, with formation of ha3matem, to blue-violet, afterwards
crystallisation
.

becoming brown. Chromic acid, ferric chloride, and vanadic acid form higher oxidation products, which give black lakes with
metallic oxides.
it

On

melting with potash, or on dry

.

distillation,

yields pyrogallol and resorcin [99] Formic acid has also been observed amongst the products formed in the potash melt [99] Bromine acts on hsernatoxylin in acetic acid solution, forming a dibromo derivative. Acetic anhydride yields a pentacetyl derivative, C 16 H 9 O 6 (C 2 H 3 O) 5 M.P. 165-166, which on treating with bromine combines with four atoms, and by cautious bromi.

nation a

monobromo derivative may be produced [6, 13, 99]. Nitrous and nitric acid convert hsematoxylin to hsematem j the final product of oxidation with nitric acid is oxalic acid.

Hcematem

[2, 3, 7].
.

Ci6H 12 O 6

Hsematem is produced by careful oxidation of hsematoxylin with nitric acid [5], or by action of atmospheric oxygen on an

DYESTUFFS OF
alkaline

UNKNOWN CONSTITUTION.
3].
It is best obtained

251

solution

of this body [2,

air.

by

exposing an ethereal hsematoxylin solution mixed with a few drops

of nitric acid to the
It

forms dark green masses with a metallic lustre or lustrous silvery leaflets, which form a red powder on rubbing [5, 100]. It is sparingly soluble in hot water, alcohol, and ether, forming
yellowish-brown
violet.

solutions.

Its

alkaline

solutions
,

are

bluish

soluble

The ammonia compound, C 16 H 12 O 6 ,2NH 3 and evolves ammonia on heating [3j. On

is

sparingly

treating with

aqueous sulphurous acid, hsematein is dissolved without reduction, and forms easily soluble colourless addition compounds, which are

More stable compounds are obtained decomposed on boiling. from haemate'm and bisulphites.
Hsemate'in forms peculiar addition products with hydrochloric, hydrobromic, and sulphuric acids, which are decomposed by water
at a

high temperature [8]

In dyeing and printing, hsematoxylin and hsematem are used in form of logwood extract or decoction. Haematoxylin produces a greyish-violet shade on alumina mordants, probably due to formation of hsematem by oxidation. Copper salts produce a dark blue, iron salts and chromic acid a deep black. In practice, several of these mordants may be applied simultaneously; for example, logwood may be printed on an alumina mordant and afterwards passed through a bath of potassium bichromate or copper sulphate. The lakes with iron and chromium are derived from higher oxidation products which have as yet been little examined. Logwood is largely used in cotton, wool, and silk dyeing. For wool, it serves especially for producing black on iron and chromium mordants. The wool is generally mordanted in a bath of bichromate and sulphuric acid and dyed in a logwood bath. Cotton is dyed black by alternate passages through logwood and bichromate baths. For production of a deep black without a
violet tone, the addition of fustic or a similar yellow dyestuft'
is

mixture used in dyeing and printing, under the necessary. name of indigo substitute, is composed of logwood extract and

chromium

acetate.

252

CHEMISTRY OF ORGANIC DYESTUFFS. Brazilin [1,

Ci 6
9, 10].
5.

14

Brazilin occurs in the

wood of various

species of

especially in C&salpinia brasiliensis, essential constituent of the dye woods

and with

brazilei'n

C&salpinia, forms the

known

as Brazil-wood, Peach-

wood, and Sapan-wood.

Brazilin often separates

wood in form of crystalline crusts

from the commercial extract of the dye[9] and these are the best material
,

for a pure preparation of the compound. These crystals contain brazilin mixed with its calcium compound, and on boiling with

very dilute alcohol, with a little hydrochloric acid and zinc powder, a solution is obtained from which brazilin crystallises on
cooling. Brazilin crystallises from water, according to the concentration of the solution, in clear amber rhombic crystals containing 1 2 O,

or in colourless needles [10] with 1J It dissolves pretty 2 O. Alkalies give a carmine-red easily in water, alcohol, and ether. solution, which is decolorised by zinc powder, the colour returning

quickly on exposure to air. quantities of resorcin [9]

.

On

dry distillation
is

it

gives

large

By

action of nitric acid styphnic acid

formed; potassium
.

chlorate and hydrochloric acid produce isotrichlorglyceric acid [12] On adding lead acetate to an aqueous solution of brazilin, the
lead

compound
2

separates in fine colourless

needles,

C 16 H 12 PbO 5
,

O, which rapidly turn red. On reduction with hydroiodic acid and phosphorus, brazilin yields brazinol, C 16 H 14O 4 and finally C 16 H 26 O 3 , both amorphous bodies [15]. On distillation with zinc
powder, brazinol gives a hydrocarbon C J6 14 or C 16 16 [15]. Tetracetyl brazilin, C 16 10 O 5 (C 2 3 O) 4 [11], and triacetyl brazilin are formed by treating brazilin with acetic anhydride [14] Dibrom- and dichlorbrazilin are formed by cautious bromination

+H

brazilin [11, 13]. applied technically in form of extract or decoction It can be fixed only by use of mordants, and is of brazil-wood.

and chlorination of
Brazilin
is

On alumina mordants it used both in cotton and wool dyeing. shades resembling alizarin, but inferior both in beauty produces Wool and fastness. The tin lake has a brighter colour. mordanted with potassium bichromate is dyed a fine brown
shade.

DYESTUFFS OF

UNKNOWN

CONSTITUTION.

253

Brazile'in [11, 12, 7].

C 16 H
Brazilei'n bears the

12

5.

same relationship to brazilin that hsemate'm does to hsematoxylin. It is formed by oxidation of an alkaline solution of brazilin in the air and by the action of alcoholic iodine solution [11] or of nitrous acid on the same compound. Brazilei'n forms grey silvery leaflets, which dissolve sparingly
in water, easily in alkalies with a purple colour.
it

Like hsematein, forms unstable combinations with hydrochloric, hydrobromic, It resembles brazilin from a tinctorial and sulphuric acids [8] of view, but has greater dyeing power. point
.

Morin
Morin
tinctoria
(

[1, 16, 15].

Ci2H 1 oO6=C 12 H 8 O5 + H 2 O.
is

the colouring-matter of fustic, the

.

wood of Morus

Macluria tinctoria (Nettel) It is best prepared boiling the wood with water and decomposing the lime comby
Jacq.) or

pound with hydrochloric

acid [17]. Morin crystallises from alcohol in long yellow needles. It is insoluble in water and carbon It disulphide, sparingly soluble in ether, and easily in alcohol.

dissolves in alkalies with a dark yellow colour. On dry distillation morin yields resorcin and paramorin. On treatment with sodium amalgam or by melting with caustic

potash it yields phloroglucol, oxalic acid latter case [18]

.

being also formed in the

morin the formula C 15 H 10 O 7 + 2H 2 O [16]. monobasic acid, the salts of the alkali metals are easily soluble, those with lime, aluminium, lead, and zinc almost

Lowe

ascribes to

It acts as a

insoluble [18].

Tribrommorin, bromine [18].

Paramorin, C 12

C 12 H 7 Br3 O 6

is

formed on treating morin with

distillation of

HO
8

4,

formed by dry

morin, forms

yellow woolly crystals easily soluble in water, and which volatilise

unchanged [19].
Isomorin [18] is formed by incomplete reduction of morin with sodium amalgam. It forms purple-red prisms, and yields morin on treatment with alkali or on heating. A compound known as maclurin or morintannic acid, C 13 H 10 O 6 , is also contained
in fustic, but
is

not a dyestuff.

254

CHEMISTRY OF ORGANIC DYESTUFFS.

Morin is used largely in wool and cotton dyeing as decoction or extract of fustic. Its principal application is in shading blacks, browns, &c. Wool is generally mordanted with potassium bichroThe morin is fixed as a very stable mate and sulphuric acid. chromium lake, which has a dull yellow colour. Young fustic, the wood of Rhus cotinus, is totally different from Koch isolated the colouring-matter [20J, termed it old fustic. This has been corfisetin, and gave it the formula C 15 H 10 O 6 rected by recent researches of Schmid [94]. According to this
.

with acetic acid.

sugar and
fisetin,

up into the glucoside, fustin, C 46 H 42 O 21 and a tannic acid on warming The glucoside splits up with dilute acids into
,

chemist, the colouring-matter of young fustic occurs as a glucoside in combination with tannic acid. This tannin compound splits

C 2 3H 10 O 3 (OH) 6 On boiling with acetic anhydride, hexacetyl fisetin, C 23 H 10 O 9 (C 2 H 3 O) 6 M.P. 200, is produced. Hexamethyl fisetin, C 23 H 10 O 9 (CH 3 6 is formed by action of
.

methyl

iodide,

M.P. 152 and 153.

is

principal use of fisetin modifying cochineal scarlets.

The

in wool-dyeing, especially for

Quercitrin [1, 21, 22, 24].

C36H 38 O 20 + 3H 2 O.
the colouring-matter of the dye wood known as Quercitrin quercitron bark, obtained from Quercus tinctoria. The bark is boiled Quercitrin may be obtained as follows
is
:

with strong alcohol and the extract precipitated with lead acetate

The filtrate is freed from lead by sulphuretted and evaporated. The residue is crystallised from water hydrogen, It forms light yellow lustrous needles, which contain one [25] molecule H 2 O after drying at 100, and can be obtained anIt melts at 168 [22] hydrous only by long heating at 130 [21]
and
acetic acid.
. .

dissolves sparingly in hot water, easily in alcohol. Its solution a green coloration with ferric chloride. Ammoniacal silver gives

solution

is

reduced easily; Fehling's copper solution only after

is

long boiling. Quercitrin

a diabasic acid

the alkali salts are easily soluble,

those with lead and alumina sparingly so. soluble in dilute sulphuric acid.

The former

is

easily

DYESTUFFS OF
Quercitrin
isodulcite
is

UNKNOWN

CONSTITUTION.
dilute acids
it

255
yields

a glucoside

on boiling with

[24], C 6 ]4 6 , and quercin, C 24 occurs also in hops, horse-chestnuts, tea, and

H O

H On
16

Quercitrin other plants.

many

Tetrabromquercitrin is obtained by bromination in acetic acid solution and forms light yellow crystals [25]
.

Quercitin [24, 26, 27],

is

formed from quercitrin

as above, according to the equation

C 3 6H 38

2()

4 3H 3

= 2C H O + C 24 H O n
6

14

16

[24]

It also occurs naturally in many plants. It forms fine lemon-yellow needles, sparingly soluble in water, but readily in alcohol. It melts above 250, and sublimes with
partial decomposition.
ferric chloride,

Its solution gives a green coloration with

which turns red on heating; lead acetate gives an Silver nitrate is reduced in the cold, and orange precipitate. Nitric acid oxidises it to oxalic Fehling's solution on warming.
acid.

On

fusion with caustic potash, quercitin

is split

querciglucin,

C H O
6 6

up, yielding
acid,

(Phloroglucin

?)

and

quercitic

C 15 H 10 0,

[28].

At a higher temperature protocatechuic acid is formed. On reduction of quercitin the final product is phloroglucin [28] Amide by action of ammonia at 150. Is a brown, amorphous
.
:

compound.
needles.

Dibromquercitin
:

light

yellow needles.

Diacetyl:

dibromquercitin

yellow

needles.

Tetrabromquercitin
needles,

white

M.P. 218.
:

Diacetyltetrabromquercitin
[25].

white

M.P.

226-228

Quercitin and quercitrin give beautiful yellow shades on cotton mordanted with alumina. With tin mordants a more orange shade On a large scale these bodies have an extensive appliis produced. cation, and are used in form of a decoction of the bark or as flavin. In dyeing with the extract, it is probable that the quercitrin splits up, and that the shades obtained are due to the formation of quercitin lakes. Flavin consists in some cases of nearly pure quercitrin and in

256

CHEMISTRY OF ORGANIC DYESTUFFS.

Quercitron and flavin serve principally for others of quercitin. use with cochineal in dyeing scarlet. They are also used in calicoprinting on iron, aluminium, and chromium mordants. Rutin, the glucoside contained in Chinese yellow berries and in the leaves of Rut a graveolens, is closely allied to quercitrin. On
boiling with dilute acids
it

splits

up into quercitin and a sugar

[29,30,31].

Xanthorhamnin, Ehamnetin [32, 33, 34].

fruit of

These colouring- matters are contained in Persian berries, the Rhamnus infectoria and oleoides.
(or

Xanthorhamnin
sition

Rhamnegin)

is

a glucoside of the compo-

be obtained by extracting the berries Resinous matters separate and are filtered off, and with alcohol. xanthorhamnin crystallises out afterwards. It may be purified by
.

C 48 H 66 O 29

It

may

the crystals obtained contain recrystallisation from alcohol [34]; two molecules of alcohol, which are expelled at 120. It is very in alcohol, and insoluble in ether easily soluble in water, less easily and chloroform. Its It reduces silver nitrate and Fehling's copper solution. solution gives a dark brown coloration with ferric chloride, and On hydroa yellow precipitate with lead acetate and ammonia. it gives rhamnetin and isodulcite ; the same lysis with dilute acids change may be effected by simply heating to 150.

On acetylation with acetic anhydride (Schiitzenberger 33), twelve acetyl groups enter into xanthorhamnin.

Rhamnetin,

C 12 H 10
is

[34],

formed along with isodulcite, C 6 H 14 O 6 , by hydrolysis of xanthorhamnin. It forms a lemon-yellow powder sparingly soluble in It is easily soluble water, alcohol, ether, and indifferent solvents. It reduces in phenol, from which it crystallises in yellow needles. ammoniacal silver solution and Fehling's copper solution.
Its

aqueous solution gives yellow or brownish-yellow precipitates

DYESTUFFS OF

UNKNOWN

CONSTITUTION.

257

On fusion with with lead, alumina, barium, and lime-salts. or reduction with sodium amalgam, rhamnetin yields potash,
phloroglucin and protocatechuic acid. Dimethylrhamnetin is formed by heating rhamnetin with potassium-methylsulphate, and methyl alcohol to 120, M.P. 157 [34].

Herzig has recently found that the highest products obtained

by methylation of rhamnetin and quercitin are identical, and has further obtained quercitin by removal of a methyl group from
rhamnetin with hydriodic acid. From these results he regards rhamnetin as a dimethylquercitin. Diacetylrhamnetin, M.P. 185 [34]. Dipropionylrhamnetin, M.P. 162 [34],
Dibenzoylrhamnetin, M.P. 210^212. These three compounds are obtained by action of the respective

anhydrides on rhamnetin [34] Dibromrhamnetin, obtained by bromination of rhamnetin in acetic acid solution, forms yellow needles soluble in hot benzene,
.

alcohol,

and

acetic acid [34]

formed by bromination of diacetylDiacetyldibromrhamnetin M.P. 212 [34]. rhamnetin, Xanthorhamnin is not a dyestuff, and it must therefore be accepted that rhamnetin is formed in the dyeing operations. Rhamnetin in form of Persian-berry extract is of considerable importance in calico-printing ; no artificial dyestuff has been found
is

to replace

with advantage. It is generally fixed as tin or tinThe both of which have a fine yellow colour. chromium lake has a browner tone and is also used in printing. The alumina lake also sometimes used in dyeing has lemon shade ; its principal application (mixed with chalk) is as an artists' colour.
it

alumina

lake,

yields

Persian berries also contain rhamnin or /3-rharnnegin, which on hydrolysis [39]. The composition of these fi- rhamnetin
is

bodies

unknown.

Luteolin

[1, 36, 37, 38].

.

C 12 H 8 O 5
is

the colouring-matter of weld, the leaves and skin of Luteolin Luteolin crystallises from alcohol in small yellow luteola. Reseda

258

CHEMISTRY OF ORGANIC DYESTTJFFS.

needles which contain 1J molecules of water of crystallisation, which are expelled at 150 [38]. It melts at 320 [36] and may

be sublimed with partial decomposition. It soluble in water and ether; alcohol dissolves
facility.

is

it

very sparingly with tolerable

It dissolves readily in alkalies with a yellow colour,

and gives

yellow lakes with lead and alumina salts. Ferric chloride produces a green coloration, changing to with excess of the reagent.
.

brown

On fusion with potash, luteolin yields phloroglucin and photocatcchuic acid [37] Luteolin is obtained by extracting weld with dilute alcohol,
evaporating the extract, and recrystallising the compound which
separates.

An aqueous decoction of weld is used in dyeing. On alumina mordants it produces a beautiful fast yellow. Its principal application is in silk-dyeing, for which weld is a valuable material. Silk is previously mordanted with alum.

Bixin [48, 49, 50, 51],

Bixin is the principal colouring-matter contained in annatto. This dyeware consists chiefly of the pulp of the fruit of Bixa orellana which has been allowed to ferment.

Bixin

is

carbonate.

prepared by boiling annatto with alcohol and sodium On adding soda solution to the extract, the sodium
of bixin separates; this is purified by recrystallising from and the bixin liberated by hydrochloric acid [51].
leaflets,

compound

dilute alcohol,

Bixin forms dark red metallic

M.P. 176.

It

is

almost

insoluble in water, sparingly soluble in cold alcohol, benzene, soluble in hot alcohol and glacial acetic acid, arid ether, readily
in chloroform.

Bixin
It

is

a dibasic acid.

It reduces

Fehling's

solution in the cold.

sulphuric acid, water. Sodium

forms a blue solution with concentrated whHch gives a dirty green precipitate on addition of

C 28 H 40 O 5 [51]. On oxidation with nitric acid, bixin acid. On distillation with zinc powder, it yields meta-ethyl toluene, and a hydrocarbon C 14 H 14 ? [51].
,

amalgam converts

it

to a colourless

compound,

yields oxalic

metaxylene,

DYESTUFFS OF

UNKNOWN
salts:

CONSTITUTION.

259
forming

Bixin gives two sodium

NaC 28 H 33 O + H 2 O,
5 5,

coppery-red crystals, Annatto contains a second colouring-matter known as Orellin, the composition of which is unknown. It dyes a yellow shade on alumina mordants, and is probably an oxidation product of bixin.
It is used
is

and

Na 2 C 28 H 32 O

a red powder [51].

Bixin dyes both animal and vegetable fibres without a mordant. both in silk and cotton dyeing in form of annatto. It

either fixed directly on cotton, or in form of its tin lake, the result being a fine orange-yellow shade. Annatto has a large application in colouring butter and cheese.

Chrysin [52

Chrysin occurs in the buds of the poplar (Populus balsamifera and monilifera) It forms light yellow needles, M.P. 275, insoluble
.

in water, sparingly soluble in benzene, ligroin, and cold alcohol, It dissolves easily in glacial acetic acid, aniline, and hot alcohol.
in alkalies with a yellow colour. Its alcoholic solution is coloured violet by ferric chloride, and gives a yellow precipitate with dirty

Chrysin is decomposed on boiling with concentrated potash solution, forming acetophenone, acetic acid, benzoic acid, and phloroglucin. On heating with methyl iodide it yields
lead acetate.

a monomethylether (tectochrysin) , C 15 9 O 3 which also 3, occurs in poplar-buds. It forms thick sulphur-yellow crystals, M.P. 164. It is insoluble in alkalies, sparingly soluble in
alcohol,

OCH

and

easily in benzene.

Nitrochrysin,
chrysin.

C 15 H 9NO 2 O4

is

formed by action of

nitric acid

on

Dibromchrysin,
Diiodochrysin,

C 15 H 8 Br2 O 4 C 15 H 8 I 2 O 4
.

Curcumin

[53, 54, 55, 56].

4 ?

C 14 H 14

This slightly acid colouring-matter is contained in turmeric, the underground stem of Curcuma longa and C. viridiflora.

s2

260

CHEMISTRY OF ORGANIC DYESTUFFS.

Curcumin is prepared by steaming turmeric, or extracting with carbon bisulphide to remove oily matters, and extracting the residue with ether. The crude product is purified by recrystallisation from ether or benzene. It forms orange-yellow prisms, M.P. 178 [56] It is very sparingly soluble in hot water, more
.

It easily in benzene, and readily in alcohol, ether, and fatty oils. dissolves in alkalies with a brown colour, and also gives a brown coloration with boric acid, changing to blue on addition of dilute
alkali [53].

(Reaction for boric acid.)

lakes with lead calcium and

barium

salts.

It gives insoluble brown It dissolves in concen-

trated sulphuric acid with a cherry-red colour. Nitric acid oxidises curcumin to oxalic acid

chromic acid

produces terephthalic acid [54]. Curcumin is extensively used in dyeing, although not fast to Its principal application is in modifying red shades on light.
cotton, for

mordant.
water.

example saffranine. Curcumin dyes cotton without The powdered root is generally used suspended in The cotton is boiled in a mixture, and the curcumin

becomes fixed as it dissolves. An alcoholic extract is sometimes Turmeric is also used, and is mixed with water to an emulsion. used for colouring butter, wax, and fatty oils.

Carotin [57, 58, 59],

Ci 8

24

O.

Carotin
carota).

is

It

forms rhombic

the colouring-matter contained in the carrot (Daucus crystals, M.P. 168, reddish brown in

It is easily transmitted light, and gold green by reflected light. soluble in carbon disulphide, sparingly in alcohol and ether.
It gives a violet solution

with strong sulphuric acid, and

is

coloured

blue by sulphurous acid.

Arnaud
is

carbon, but this assumption properties of the compound.

[96] regards carotin as a hydroextremely improbable from the

Archil and Litmus.

Various kinds of lichens, for example Lecanora tinctoria and
Roccella tinctoria, possess the property of giving violet or blue dyestuffs when submitted to the joint action of ammonia and air.

DYESTUFFS OF UNKNOWN CONSTITUTION.

261

These lichens contain a number of peculiar acids (lecanoric acid,

erythric acid, roccellic acid, &c.), the final products being orcin,
.

which are

split
,

up by

alkalies,

C4 H 10 O4
Orcin

C 6 H 3 CH 3 (OH) 2 and

erythrite,

is

the only

compound important

for the production of

lichen colours; with air and ammonia it yields orcei'n, C 7 7 3 ?, which is the principal dyestuff contained in archil [60, 61, 62, 63] . Orcei'n gives sparingly soluble lakes with calcium and the

H NO

heavy metals, but does not appear to be a real adjective dyestuff. Commercial archil is prepared by moistening the weeds with ammonia and exposing the mixture to the air. Formerly putrid urine was used in place of the ammonia. The product obtained " may be worked up into extract, "Archil liquor; or dried and

powdered, or

form as " Archil paste." These products all contain orcei'n in form of its ammonia salt. The dyeware known as Cudbear is similar to powdered archil. Besides orcei'n, archil is said to contain two other colouringmatters of unknown composition, azoerythrin and erythroleic
is

sold in the crude

acid [60].

Archil

is

principally
It

calico-printing. alkaline baths.

employed in wool and silk dyeing, less in may be dyed on wool from acid, neutral, or
addition of alum, stannous chloride, oxalic
is

An

acid, or tartaric acid is made to the dyebath. The calcium lake is used in printing, and

dissolved in acetic

acid

and fixed by steaming

obtained with archil

or cochineal.

The shades (" French purple"). are purple, and may be modified with indigo

but

Archil has been displaced to a certain extent by azo dyestuffs, This, is due still has considerable importance in wool-dyeing. to the various conditions under which archil may be employed,

and

it

can therefore be used to modify the shades of nearly

all

other dyestuffs.

Litmus.
If the lichens used for the manufacture of archil are submitted to a longer treatment with ammonia, potash and lime being also a dyestuff which is red to litmus added, the orcin is converted similar product may be in the free state, and yields blue salts.

262

CHEMISTRY OF ORGANIC DYESTU1TS.

of

obtained direct from orcin by continued digestion with a mixture ammonia and soda solution [64] Litmus comes into commerce in small tablets mixed with chalk
.

or gypsum,

the
best

commercial

product containing only a small

quantity of dyestuff.

Litmus
is

also

an indicator in volumetric analysis, but used to inconsiderable extent for colouring wine and for
is

known

as

blueing in laundries.

According to Kane

(60), litmus contains four colouring-matters

first Erythrolein, Azolitmin, Erythrolitmin, and Spaniolitmin the two being the most important. It is improbable, however, that these compounds are chemical individuals. According to Wartha (61), some kinds of litmus contain indigo.

Carthamin [62],

C W H 17

(?).

Safflower, the petals of Carthamus tmctorius, &c., contains, besides a yellow dyestuff, a red one, carthamine, which was of considerable importance before the introduction of the artificial
dyestuffs.

To prepare carthamin, safflower is washed with water to remove the yellow dyestuff, and is then extracted with dilute soda solution, and filtered. Cotton yarn is immersed in the alkaline solution,
and the liquid acidulated with citric acid. The cotton takes up carthamin, which is removed with soda solution, and preObtained in this manner carthamin cipitated with citric acid. forms a lustrous green powder, sparingly soluble in water and ether,
the
It dissolves in alkalies with yellowish-green readily in alcohol. On fusion with potash it gives oxalic acid and para-oxycolour.

Carthamin dyes animal fibres and unmordanted It produces a beautiful pink cotton from a slightly acid bath. colour on silk.
benzoic acid.

Cartharain enters commerce in

flower extract.

For dyeing, the extract

citric

a nearly pure state as safis dissolved in soda and the

dyebath acidified with

extract the soda solution

or other acid.
safflower,

from

In place of this which has been extracted

talc, chalk,

with water,
or starch.

may be
is

Carthamin

directly employed. also used as rouge in

admixture with

It is also

employed

as

an

artists' colour.

DYESTUFFS OF

UNKNOWN

CONSTITUTION.

263

The yellow colouring-matter of safflower, which according to Malin has the composition C 2 4H 30 O 15 [63], is of no importance in
dyeing.

Santalin [64, 65, 66].

Sandal-wood or Sanders- wood (from Pterocarpus santalinus)
contains
acid properties. Santalin, C 15 14 O 5 , is obtained by precipitating an alcoholic extract of sandal-wood with lead acetate, and decomposing the lead lake

resinous

red

dyestuff of slightly

with dilute sulphuric acid.

is

It crystallises

from alcohol in red

It prisms, M.P. 104. sparingly soluble in water, dissolves in alcohol and ether with a blood-red colour, and in alkalies with a violet colour. It gives violet insoluble lakes with calcium, barium,

and the heavy metals. Franchimont [67], who could obtain santalin only in an amorOn heating with phous state, ascribes to it the formula C 17 H 16 O 6 acid to 200, he obtained methyl chloride and an hydrochloric amorphous body (C 8 H 19 O 5 ?), which gives a violet-black solution
.

with alkalies. used in wool-dyeing and is employed which is directly added to the dyebath. rasped sanders-wood, produces a good reddish-brown shade on chromed wool, which
Santalin
is

largely

as
It
is,

however, not very

fast to light.
is

An

alcoholic extract of sanders-wood

also used for colouring

tinctures, varnishes,

and

also for staining wood.

Alkannin [70],
Alkanet, the root cf Anchusa iinctoria, contains the above red It is of slightly acid character, and has not been obtained dyestuff.
It is insoluble in water, dissolves easily in in a crystalline state. It alcohol, ether, ligroin, and fatty oils, forming red solutions. dissolves in alkalies with a blue colour, and is reprecipitated by acids It is proIt gives an insoluble lake with baryta. in red flakes.

bably a derivative of methylanthracene, C 15 12 as hydrocarbon on distillation with zinc powder [93]

,
.

it

yields this

diacetyl compound, C 15 12 (C 2 3 O)2O 4 , is formed action of acetic anhydride and sodium acetate [70].

The

by the

264
Alkannin
colour.

CHEMISTRY OF ORGANIC DYESTUFFS.

dissolves in concentrated sulphuric acid with a blue it to oxalic acid and succinic acid.
(in

Nitric acid oxidises

Alkannin
colouring

form of an extract of alkanet

root)

is

used for

oils,

pomades,, tinctures., &c.

Crocin and Crocetin.

Saffron, the stigmata of Crocus sativus, contains according to

Quadrat [71] and Weiss [72] a yellow glucoside, polychroite, C 48 H 68 O 18 [73]. According to these chemists it may be split up into crocin, C 16 H 18 O 6 , sugar, and an ethereal oil. R. Kayser [74] terms poly chroit " crocin," and crocin "crocetic," and ascribes to the former the formula C 44 H 70 O 28 and to the latter C 34 H 46 O 9 According to him, crocin splits up into crocetin and
,
.

saffron sugar, C 6 12 6 , while the ethereal oil is a product of the decomposition of picrocrocin. L. Meyer [73] and "Rochleder obtained crocin from the pods of Gardenia grandiflora, but it is not certain whether their product is

identical with the above.

They obtained

a glucoside,
.

C 58 H 86 O 31

which splits up into sugar and crocetin, C34H 36 O 4 As these bodies were only obtained in an amorphous state, these formulae appear
to be doubtful.

Lo-Kao (CHINESE GKEEN).

The above is a commercial green dyestuff prepared from the bark of various species of Ehamnus (Rhamnus utilis,Rh. chlorophlorus] It consists chiefly of the alumina and lime lakes of the glucoside.
.

This latter is termed loka'in by Cloez and Guignet [75], and lokaonic acid by Kayser [76]. According to Cloez and Guignet a compound has the formula

C 28 H 34 O 17 and is decomposed by acids, yielding glucose and C 9 H 8 O 5 [75] Kayser, on the other hand, gives to lokai'n (lokaonic acid) the formula C 42 H 48 O 27 and to lokaetin (lokanic The sugar produced in the formation acid) the formula C 36 H 36 O 21
,

lokaetin,

is not glucose, but an inactive modification which terms Lokaose. Lokam forms a deep bluish-black mass Kayser which takes a metallic lustre on rubbing. It is insoluble in water,

of the latter

alcohol, ether, chloroform,

with a blue colour, which

is

and benzene, but soluble in alkalies changed to red by reducing agents.

DYESTUFFS OF

UNKNOWN

CONSTITUTION.

265

The ammonium
salts are

salt
;

forms lustrous bronzy crystals.

The other

those of the heavy metals are insoluble. Lokaetin (lokanic acid) forms a violet-black powder only soluble in alkalies, with a violet colour.

amorphous

According to Kayser it reacts with sulphuretted hydrogen, forming a crystalline compound containing sulphur. Concentrated sulphuric acid produces a brown amorphous compound, which is stated to be C 7 H 6 O 4 by Cloez and Guignet, and
Kayser. for the compounds described above must be reas doubtful, as the nature of the substances affords little garded guarantee for their purity, and the analysis gives little idea of the

C 36 H 26 O 16 by

The formulae

true size of the molecules.

Lo-kao
silk.

It

used, especially by the Chinese, for dyeing wool and may be fixed on cotton from an alkaline bath, but is also
is

frequently used in a reduced state as a vat, stannous chloride or

ammonium
produced
is

sulphide being used as reducing agents. a fine bluish green, very fast to light.

The shade

Cochineal.

The important dyeware known as cochineal consists of the dried female of an insect, the Coccus cacti coccinellifera, which lives on

The colouring principle of cochineal is carminic acid, of the formula C 17 H 16 O 10 [77]. glucoside Carminic acid is prepared by precipitating an aqueous decoction
certain species of cactus.

of cochineal with lead acetate, and decomposing the lead lake with a quantity of sulphuric acid insufficient for the whole. The
solution of carminic acid thus obtained

a low temperature,
alcohol.

and the residue

evaporated to dryness at crystallised from absolute

is

Obtained in this manner, carminic acid forms a purple-brown mass which gives a scarlet powder on trituration. It is with difficulty soluble in ether, easily in water and alcohol.
It is a

weak

alkalies are easily soluble,

dibasic acid, forming violet salts ; those with the with the earths and heavy metals they

are insoluble.
salts are

The sodium

salt

may

be crystallised; the other

amorphous. On boiling with dilute acids, carminic acid is split up into carmine-red, C n H 12 O 7 , and a sugar, C 6 H 10 O 5 . In general, car-

266

CHEMISTRY OF ORGANIC DYESTUFFS.

minic acid gives the same decomposition products as carmine-red. If an ammoniacal solution is allowed to stand, a nitrogenous
is formed, possessing totally different dyeing properties. a large scale this product is prepared for dyeing by maceration of ground cochineal with ammonia, and is used under the name of

compound

On

ammoniacal cochineal. In dyeing, this product gives much bluer shades, and modifying cochineal scarlets.

is

used for

Carmine-red.

C n H 12 O 7
Carmine-red
is

a cochineal decoction with lead acetate.

prepared from the lake obtained by precipitating This lead lake is dis-

solved in dilute sulphuric acid, freed from lead by sulphuretted hydrogen, and boiled with very dilute sulphuric acid for some

Barium carbonate is added till a violet coloration ensues, and then filtered rapidly and precipitated with lead acetate. The lead lake is decomposed and the nitrate evaporated to dryness in
hours.

vacuo.

Carmine-red
reflected light.

is

It is insoluble in ether,

a dark red substance, which appears green by but soluble in water and

alcohol with a red colour.

less

Keducing agents convert it to a colourcompound. On fusion with potash carminic acid yields coccinin [80] and on heating with water to 200 ruficarmine is formed [82]
,
.

By

boiling carminic acid with nitric acid, trinitrococcussic acid

,

(trinitrocresotinic acid)

OH

is

formed [78]

compounds,

two brominated a-bromcarmine, C 10 H 4 Br4 O 3 [81], forms colourless On boiling with needles, M.P. 248, which are soluble in alkalies. strong potash solution it yields oxybromcarmine, which behaves like an oxyacid of the formula

Bromine

reacts with carminic acid, producing

DYESTUFFS OF

UNKNOWN

CONSTITUTION.

267

On
yields

oxidation with potassium permanganate, oxybromcarmine an acid of the formula C 9 6 Br2 O 4 , probably dibromoxy-

tolylformic acid,

C 7 H 5 OBr 2 COCOOH.

Dibrommethoxylmethyl-

phthalic anhydride,

CH
is

C 6 Br2 -CO X

^OCR, Q

also

formed [81].
3i

/3-bromcarmine, C l} Ji 5 Br O 4f forms yellow needles, M.P. 232, and gives red dibasic salts with the alkalies. On oxidation with potassium permanganate it yields dibrom-

oxymethylbenzoyldicarbonic acid,

,COOH
and the above dibrommethoxymethylphthalic anhydride [81]. Ruficoccin, C 16 H 10 O 6 is formed along with a compound of the
,

composition
to

C 32 HooO 13 by
[82~f.
is

heating carmine-red with sulphuric acid

130-140
Ruficoccin

a brick -red powder, sparingly soluble in water and

It dissolves in alkalies with a ether, easily soluble in alcohol. brown colour. On distillation with zinc powder a hydrocarbon,

C 16 H 12

is

formed [82].

Ruficarmine [82J forms a carmine-red powder insoluble in water, but easily soluble in alcohol.

Carmine-red
carminic acid.
Coccinin,

is

a dibasic acid, and forms salts similar to those of

[80] , is formed on melting carminic acid or with potash. It forms yellow leaflets, insoluble in carmine-red The alkaline solution water, but soluble in alcohol and alkalies.

C 14 H 12 O 5

becomes oxidised on exposure to the air, the colour changing through green to red. A solution of coccinin in concentrated sulphuric acid gives a blue coloration on addition of manganese
dioxide.

Carmine.

This

is

which

is

used by

artists

a commercial product made from cochineal, and for colouring confectionery, and also

as rouge. Carmine forms porous red masses, which are easily rubbed to fine powder. It is insoluble in water and alcohol, but

dissolves completely in

ammonia

if

free

from adulteration with

kaolin, starch, &c.

268

CHEMISTRY OF ORGANIC DYESTUFF8.

for this preparation is unknown ; are in vogue, according to which the essential recipes consists in precipitating an aqueous decoction of cochineal with

The exact method employed

various

According to the researches of Liebermann [83] carmine contains about 3 per cent, of alumina and about the same quantity of lime, and also about 20 per cent, of albuminoid matters. As the lime and alumina dissolve in ammonia and cannot be
alum.

by the ordinary reagents, it is probable that a lake of carmine-red is present, in which the albuminoids peculiar play a part.
detected therein

The colour of carmine, and

solution, differ

especially that of its ammoniacal from that of carmine-red. considerably The above ammoniacal solutions were formerly used as red ink.

Cochineal is employed in dyeing for production of scarlet shades. Before the introduction of the red azo-dyestuffs cochineal was the only material which could be used for scarlets, but recently, owing
to competition with the artificial dyestufPs, its use has greatly diminished. Neither carminic acid nor carmine-red can be fixed

without mordant. The finest scarlet tones are obtained with the tin lake of carminic acid, or probably of the carmine-red formed

by

its

decomposition.

scarlet, the mordanting and dyeing operations are generally carried out in. one bath, the material being boiled with ground cochineal and stannous chloride, an addition of tartar

In dyeing wool

Yellower shades are obtained or oxalic acid being generally made. by addition of weld, flavine, or fustic.
violet colour, and the iron a blackish- grey. to the latter, it is important to have water mordants, &c., perfectly free from iron in dyeing cochineal scarlet.

The alumina lake has

Owing

tin mordants. seldom used in cotton-dyeing. Cochineal lakes are Cochineal often used in printing, being mixed with albumen and fixed by
is

Ammoniacal cochineal produces bluer shades on

colour known as Florentine lake is prepared a decoction of cochineal with alum and soda or "by precipitating It contains the alumina lake of carminic acid, mixed with chalk.

steaming.

The

artists'

excess of alumina and chalk.

DYESTUFFS OF UNKNOWN CONSTITUTION.

269

Lac-dye.
also a product of a species of Coccus, the Coccus Lac-dye These insects live on the branches of Ficus lacca or C. ficus.
is

religiosa and Ficus indica. tree and envelopes the insects. the resin, and sold as stick-lac.

resinous matter exudes from the

The twigs

On

are cut off along with treating stick-lac with water,

the colouring-matter dissolves, and the residue, melted and squeezed through calico, forms commercial shellac. The exact method by

which commercial lac-dye

alum.

is

consists in precipitation of

prepared is kept secret, but it probably an alkaline decoction of stick-lac with

The colouring-matter contained in lac-dye was long considered to be identical with that of cochineal, but, as shown by the researches of R. E. Schmidt [95], it is a new body, laccainic acid, C 16 12 O 8 Lac-dye is used in dyeing in a similar manner to cochineal, the

The principal difference being that it requires a very acid bath. shades produced are not so clear as those of cochineal, but surpass the latter in fastness both to light and alkalies.
Kermes, another insect (Coccus ilicis, C. baphia), contains analogous colouring-matters, and was formerly used in dyeing, but has now gone out of use.
Other
insects, for

example Coccus polonicus, C.fragaria, contain

red dyestuffs.

Colouring-matter of Tynan Purple [84, 85].

Certain molluscs (Purpura lapillus, P. hamastoma, and various species of Murex), when crushed and exposed to sunlight, develop a purple dyestuff which was highly prized by the ancients.

According to Schunck [84] the dyestuff, punicine, is insoluble in water, alcohol, and ether, slightly soluble in benzene and glacial acetic acid, and easily soluble in aniline and concentrated sulIt sublimes with partial decomposition in phuric acid [85]. which have a metallic lustre. leaflets, Witt regards this dyestuff as indigo mixed with a red dyestuff
fast to light. On ancient purple cloth this red has been bleached in course of time, and only the blue-indigo ground remains. Compare Witt [98]
less
.

270

CHEMISTRY OF ORGANIC DYESTUFFS.

Catechu.

The commercial products known as Catechu and Cutch are prepared by evaporation of aqueous extracts of the wood of Acacia Gambier is a similar catechu and allied species,, common in India.
its exact composition has not been investigated. Catechu serves technically both as a colouring-matter and as a tannin, and is largely employed in cotton-dyeing and in tanning. The principal constituents of catechu are catechin and catechu-

preparation

tannic acid.

On treating catechu with cold water, catechu-tannic Catechin. acid dissolves,, and the catechin contained in the residues may be Catechin separates obtained by extraction with boiling- water.
lising

from the solution on cooling, and may be purified by recrystalfrom boiling-water. It forms minute white needles, M.P. 217, which are sparingly soluble in cold water, readily in alcohol and in boiling-water. Catechin yields pyrocatechin and phloroIt glucin on heating with dilute sulphuric acid under pressure.
does not precipitate solutions of gelatine, tartar-emetic, or alkaloids, thus differing from the tannins.

There
catechin.

is

some uncertainty as to the exact composition of Liebermann and Tauchert give the formula

C 21 H 20
as

+ 5H

most probable, and they have also analysed a diacetyl compound, M.P. 128-130, which supports this formula [105]. Etti ascribes to catechin the formula C 38 H 36 O 16 , and uses this ia
the following series of anhydrides described by him [106] By the action of heat, or of dilute acids, catechin gives rise to a
.

series

and the dianhydride C 38 H 32 O U and the trianhydride C 38 H 30 O 13 , and have a resemblance to the true tannins. precipitate gelatine,
,

C 38 H34Oi 5

The first of these, catechu-tannic acid, of anhydrides. is a natural constituent of catechu. This compound,
,

Further heating gives

rise to the

, catechuretin, compound insoluble in water. Catechin reacts with two molecules of diazobenzene chloride, producing a catechinazobenzene.

C 38 H 28 O 12

production of a fourth anhydride,

with potassium bichromate, catechin yields a reddish- brown compound, the chromium or copper japonic acid,
oxidation

On

DYESTUFFS OF
lake of which

UNKNOWN

CONSTITUTION.

271

is probably formed in the ordinary methods o with catechu. dyeing This body, also known as catechin-red, Catechu-tannic Acid. is obtained by extracting catechu with cold water, or by heating

catechin with water to 110.

It precipitates gelatine but not and gives a green coloration with ferric acetate. tartar-emetic, It yields a reddish-brown compound on oxidation with potassium bichromate, probably identical with the japonic acid formed on oxidation of catechin. It gives yelCatechu is principally used in cotton-dyeing. lowish shades on goods mordanted with aluminium or tin salts ;

but

its

main

application

is

for the production of

brown

shades,

which are very fast. The goods are steeped in a solution of catechu and passed through a bath of potassium bichromate, to which copper sulphate is sometimes added. The brown may also be developed by airing or ageing. In calico-printing, catechu may be fixed by one of the methods used for aniline black. A mixture of catechu, potassium chlorate, and sal-ammoniac is printed, and the colour developed by steaming.

Cachou de Laval [97]. The above dyestuff, also known as Fast Grey,

is

a commercial

product prepared by melting various organic substances (sawdust, bran, &c.) with sodium sulphide. These products, discovered by Croissant and Bretonniere, contain
peculiar weak acid dyestuffs, which contain sulphur. Cachou de Laval dyes unmordanted cotton from an alkaline bath, producing brownish shades, which are capable of modification by

passage through baths of various metallic salts (copper and iron, chromium salts). In spite of its very unpleasant smell, it has an
extensive application in cotton-dyeing. The shades are very fast to soap. Like canarin and the direct

dyeing tetrazo-colours, Cachou de Laval is capable of fixing basic thus be topped at will. dyestuffs, and the shades can By fusing sodium acetate with sulphur, E. Kopp obtained a substance closely resembling Cachou de Laval in its properties.

REFERENCES.
The
1.

references are divided into the following sections

2.

3.
4.
5.

INTRODUCTION. NlTRO-COMPOUNDS. AZO-COMPOUNDS.

6. 7.

8.

9.

OXYQUINONES AND QuiNONEOXIMES. KETONEIMIDES AND HYDRAZIDES. TBIPHENYLMETHANE DYESTUFFS. QuiNONEIMIDE AND AziNE DYESTUFFS. ANILINE BLACK, INDULINES AND NIGROSINES. QuiNOLINE AND ACRIDINE DYESTUFFS.
INDIGO DYESTUFFS.

10.
11.
12.

EUXANTHIC ACID, GALLOFLAVINE, CANARINE, AND MUREXIDE. DYESTUFFS OF UNKNOWN CONSTITUTION.

ABBREVIATIONS.
Ber.

Berichte der deutschen chemischen Gesellschaft zu Berlin.

Annal.
Journ.

Annalen d. Chemie und Pharmazie (now Liebig's Annalen). Chem. = Journal fur practische Chemie. Jahresb. = Jahresbericht iiber die Fortschritte d. Chemie (Giessen Kicker,
f.

pr.

publisher).
Friedl.

Dr. P. Friedlander

'
:

Fortschritte der Theerfarbenfabrication,' 1877:

1887 and 1887-1890 (Berlin

1891).

Julius Springer, publisher,

1888 and

INTRODUCTION.
Annal. xxxi. pp. 65 [1] Runge, Poggendorffs
Journal
f.

& 512

Reichenbach, Schweiger's

Ch.

Ixviii. p. 1.

[8]

xcviii. p. 297. [2] Natanson, Annal. Hofmann, Jahresb. 1858, p. 351.

[4]

Renard

freres

et

Franc, Brev. d'invent. of

8th April, 1859, and five

additional patents. Brev. d'invent. of 29th October, 1859. [5] Gerber-Keller, Medlock, Brit, patent of 18th January, 1860 ; Nicholson, Brit, patent of [6] 26th January, I860.

274

CHEMISTRY OF ORGANIC DYESTUFFS.

26th May, 1860.

[7] Girard et de Laire, Brev. d'invent. of [8] Brev. d'invent. of 10th

December, 1861. [9] Kolbe and Schmitt, Annal. cxix. p. 169.

;

[10] Nicholson, Monit. scientif. vii. p. 5 Brev. d'invent. of 10th July, 1862. [11] Monnet et Dury, Brev. d'invent. of 30th May, 18U2.

[12] Wanklyn, Brit, patent, November 1862. [13] A. W. Hofrnann, Compt. rend. liv. p. 428, Ivi. pp. 945 & 1033, Jahresb. 1862, p. 428 Zeitsch. f. Ch. 1863, p. 393. p. 1131 Usebe, Brev. d'invent. of 28th October, 1862. [14]
; ;

Ivii.

[15] Lightfoot, Brit, patent, 17th January, 1863; Brev. d'invent. 28th January,

1863.
[16] Martius and Griess, Zeitsch.
f.

Ch.

ix. p.

132.

[17] Caro and Griess, Zeitsch. f. Ch. x. p. 278. [18] Caro and Wanklyn, Journ. f. pr. Ch. c. p. 49.
[19] Keisser, Brev. d'invent. 18th April, 1866.

[20] Girard,

de

Laire,

and Chappotot, Brev.

d'invent.

21st

March, 18C6,

16th March, 1867.

Hofmann and Girard, Ber. ii. p. 447. [22] Rosenstiehl, Bull, de 1. Soc. industr. de Mulhouse, 1869. [23] Ber. ii. p. 14.
[21]
[24]

Hofmann and Geyger,

Ber. v. p. 526.

Hofmann, Ber. vi. p. 352. [26] E. and O. Fischer, Ann. cxciv. p. 274. [27] Germ, patent of 15th December, 1877, No. 1886.
[25]
[28] Ber. ix.
p.

1035.

[29] E. and 0. Fischer, Ann. ccvi. p. 130. [80] Doebner, Ber. xi. p. 1236.
[31]

Germ, patent, No. 11857, of 19th March, 1880

No. 1177.

Brit,

patent,

1880,

Witt and Koechlin, Germ, patents, No. 15915 and No. 1958 Brit, patents, 1881, No. 1373 and No. 5249. [33] Caro and Kern, Amer. patents, 25th December, 1883, 22nd April, 8th July, and 2nd December, 1884.
[32]
j

NITRO-COMPOUNDS.
[1] Laurent, Annal. xliii. p. 219. [2] Schmitt and Glutz, Ber. ii. p. 52.
[3]

Schunck, Ann. xxxix.

viii. p.

p. 6, Ixv. p. 234.

[4] Piccard, Ber.

[5] Martius

685.

and Wichelhaus, Ber. ii. p. 207. f. Ch. 1868, p. 80. [7] Darmstadter and Wichelhaus, Annal. clii. p. 299. [8] Germ, patent, No. 10785, of 28th December, 1879; Friedl.
[6] Martius, Zeitschr. [9] Lauterbach, Ber. xiv. p. 2028.

i.

p. 327.

REFERENCES.
[10]
[11]

275

Merz and Weith, Ber.

xv. p. 2714.

Gnehm,

Ber.

ix. p.

1245.

[12] Hlasiwetz, Annal. ex. p. 289.

[18] Schering,

Germ, patent, No. 15117 and No. 15889.

AZO-COMPOUNDS.
[1]

Liebermann, Ber. xvi.

p.

2858.

[2] Zinke, Ber. xviii. p. 3132. [3] Zinke and Bindewald, Ber. xvii. p. 3026.

[4] Spiegel, Ber. xviii. p. 1479. [5] Griess and Martins, Zeitschr.

f.

Ch. 1866,

p. 132.

[6] Kekute, Zeitschr. f. Ch. 1866, p. 688. [7] Janowsky, Ber. xix. p. 2157.

Germ, patent. [9] Griess, Ber. xv. p. 2183.

[8] Graessler,

4186

Friedl.

i.

p. 439.

[10] Griess, Ber. x. p. 528.

[11] Witt, Chemikerzeit. 1880, No. 26. [12] Witt, Ber. xii. p. 259.
[13] Nietzki, Ber. x. pp. 662, 1155. [14] Noelting and Witt, Ber. xii. p. 77. [15] Nietzki, Ber. xiii. p. 472.
[16] Noelting and Forel, Ber. xviii. p. 2681. [17] Hofmann, Ber. x. p. 213.

[18] Witt, Ber. x.

p.

656.

[19] Mixter, Ainer. Chem. Journ. v. p. 282. [20] Nietzki, Ber. xvii. p. 345.
[21]

Lippmann and

Fleissner, Ber. xv. p. 2136, xvi. p. 1415.

[22] Noelting, Ber. xviii. p. 1143. [23] Annal. Ixxv. p. 74.

[24] Annal. cxxxv. p. 164. [25] Caro and Griess, Zeitschr. [26] Buckney, Ber. xi. p. 1453.
[27]

f.

Ch. 1867,

p.

278.

A.

W.

Hofmann, Ber.

x. p. 28.

[28] Griess, Annal. cxxxvii. p. 60. [29] Weselsky and Benedikt, Ber. xii. p. 228. [30] Perkin and Church, Annal. cxxix. p. 108. [31] Griess, Annal. cliv. p. 211. [32] KekulS and Hidegh, Ber. iii. p. 234. [33] Kimmich, Ber. viii. p. 1026.
[34]

Wallach and Kiepenheuer, Ber.

viii. p.

xiv. p. 2617.

[35] Baeyer and Jaeger, Ber. [36] Griess, Ber. xi. p. 2192.

148,

[38] Jaeger,

[37] Witt, Ber. v. p. 2196. er. viii, p. 1499.

T2

276

CHEMISTRY OF ORGANIC DYESTUFFS.

[39] Liebermann and Kostanecki, Ber. xviii. pp. 130 [40] Wallach and Schutze, Ber. xv. p. 3020. [41] Mazzara, Gaz. chim.
[42] Noel ting and
It. ix. p.

&

882.

424.

Kohn, Ber.

xvii. p. 351.

[43] Nietzki, Ber. xvii. pp. 344 [44] Griess, Ber. xvii. p. 608.

&

1350.

[45] Meister, Lucius, and Briining,

Germ, patent, No. 3229, of 24th April,

p. 377.

1878

Brit, patent, 1878,

No. 1715, Friedl.

[46] Wallach, Ber. xv. p. 2825. [47] Germ, patent, No. 5411, of 12th March, 1878; Brit, patent, 1878, No. 786; Friedl. p. 358.

[48] Brit, patent, 1881, No. 2030 [49] Griess, Ber. xiv. p. 2032.

Friedl. p. 373.

[50] Griess, Ber. x. p. 527. [51] Brit, patent, 1880, No. 4091. [52] Stebbins, Ber. xiii. p. 716.

[53] Frankland, Journ. of Ch. Soc. xxxvii. p. 747. [54] Brit, patent, 1881, No. 1767 ; FriedL i. p. 324.

[55] Germ, patent, No. 22707, of 9th September, 1882 [56] Griess, Ber. ix. p. 627.
[57] Griess, Ber. xvi. p. 2028.

Friedl. p. 539.

[58] Germ, patent, No. 22714, of 8th November, 1882; Friedl. [59] Caro and Schraube, Ber. x. p. 2230. [60] Nietzki, Ber. xiii. p. 1838. [61] Brit, patent, 1881, Nos. 1225, 2030 ; Friedl. p. 364. [62] Journ. of the Chem. Soc., November 1883, March 1884. [63] Witt, Brit, patent, 1883, No. 2237; Friedl. i. p. 391.

i.

p.

453.

[64] Germ, patent, No. 28753, of 27th February, 1884; Friedl. i. p. 470. [65] Paul, Germ, patent, No. 28820, of 13th December, 1883 Friedl. p. 447. [66] Brit, patents, 1884, Nos. 9162, 9606; Friedl. i. p. 465.
;

. [67] Brit, patent, 1883, No. 5767 ; Friedl. i. p. 552. [68] Oassella, Brit, patent, 1885, No. 9214 ; Friedl. i. p. 451. [69] Farbenfabr. Bayer and Co., Brit, patent, 1885, No. p. 473.

3803; Friedl.
i.

i.

[70] Farbenfabr. Bayer, Brit, patent, 1885, No. 14424 [71] Schultz, Ber. xvii. p. 463.

Friedl.

pp. 488-491.
p. 531.

[72] Roussin and Poirrier, Brit, patent, 1878, No. 4490 Friedl. [73] Meister, Lucius, and Briining, Brit, patent, 1878, No. 1715. [74] Griess, Ber. xiii. p. 1956.
;

i.

[75] Glaus and Oehler, Ber. xv. p. 312. [76] Baeyer and Duisberg, Bsr. xx. p. 1426. [77] Weinberg, Ber. xx. pp. 2906 & 3353.

[78] Germ, patent, No. 38735, of 29th January, 1886 [79] Bender and Schultz, Ber. xix. p. 3237.

Friedl.

i.

p. 510.

[80] A. G. Green, Journ. of

Chem. Ind. 1888,

p.

108; Ber.

xxii. p.

968; Dahl

REFERENCES.

277

and Co., Germ, patent, No. 47012, of 8th June, 1888; Pfitzinger, Gattermann, and Jakobsen, Ber. xxii. pp. 330, 422, 580, 1063 (Erica) Engl. patent, 1888, No. 17333 K. Anschiitz and G. Sehultz, Ber. xxii.
:

p.

583.

[81] Engl. patent, 1888, No. 6319.

OXYQU1NONES AND QUINONEOXIMES.

[1] Rochleder, Annal. Ixxx. p. 324.
[2] Schunck, Annal. Ixvi. p.
[3]

176 Jahresb. 1855, p. 666. Graebe and Liebermann, Ann. Suppl. vii. p. 300 Ber.
;

ii.

pp. 14, 332, 505,

iii.

p.

359.
vii. p.

[4]

Baeyer and Caro, Ber.

'

972.
'

[5] Schunck, Jahresb. 1874, p. 446. [6] Schutzenberger, Farbstoffe [7] Baeyer, Ber. ix. p. 1232.
(Berlin, 1870),
ii.

p. 114.

[8] Diehl, Ber. xi. p. 187. [9] Perkin, Jahresb. 1874, p. 485. [10] Stenhouse, Anual. cxxx. p. 343.

[11] Perger, Journal

f.

pr.

Ch.

xviii. p. 184.

[12] Graebe and Liebermann, Annal. clx. p. 144. [13] Wiedemann, Ber. ix. p. 856.

[14] Brit, patent, No. 1936, of 25th June, 1869. [15] Perkin, Brit, patent, No. 1948, of 26th June, 1869.
[16] Meister, Lucius, and Briining, Jahresb. 1873, p. 1122. [17] Perkin, Ber. ix. p. 281.

[18] Rosenstiehl, Bullet, de la Soc. chirn. xxvi. [19] Schunck and Homer, Ber. xii. p. 584. [20] Strecker, Annal. Ixxv. p. 20.

p. 63.

[21] De Lalande, Jahresb. 1874, p. 486. [22] Vogel, Ber. ix. p. 1641. [23] Lepel, Ber. ix. p. 1845 x. p. 159.
;

[24] Auerbach, Jahresb. 1874, p. 488. [25] Perkin, Jahresb. 1873, p. 450.
[26] Schunck and Homer, Ber. [27] Caro, Ber. ix. p. 682. [28]
ix. p.

679, x. p. 1823,

xiii. p.

42,

Prudhomme,

Bullet, de la Soc. indust. de Mulhouse, xxviii. p. 62.

cci. p.

[29] Graebe, Annal.

333.

[80] Journ. of the

Soc. xxxv. p. 800. [31] Brit, patent, 1881, No. 3603 ; Friedl. i. p. 168. [32] Fitz, Ber. viii. p. 631. [83] Kostanecki, Ber. xx. p. 3133.

Chem.

[34] Fuchs, Ber.

viii.

pp.

625

&

1026.
p.

[35] Liebermann and Kostanecki, Ber. xviii. [36] Jakobsen and Julius, Ber. xx. p. 2588.
[37] Kostanecki, Ber. xx. p. 3143.

2138.

278

CHEMISTRY OF ORGANIC DYESTUFFS.

[38] Hoffmann, Ber. xviii. p. 46. [39] Brit, patent, 1884, No. 2269 Friedl. i. p. 335. [38 a] Graebe, Ber. xxiii. p. 3739 Rob. E. Schmidt, Journ.
;

f.

pract.
;

Ch.

xliii.

p.

237 Gattermann, Journ. f. pract. Ch. 1890, NosT 8725, 12715, 17712, 18729.
;

xliii. p.

246

Engl. patent,

[39 ] Engl. patent, 1884, No. 2269. [40] R. E. Schmidt and Gattermann, Journ. patent, 1888, Nos. 14353, 15121.
[41] Seuberlich, Ber. x. p. 38. [42] R. E. Schmidt, Journ. f. pract. Ch.

f.

pract. Ch. xliv. p.

103

Engl.

xliii. p.

232.

KETONEIMIDES AND HYDRAZIDES.

[I] Brit, patents, 1884, Nos.
Friedl.

Caro and Kern, Arner. patents, 5512, 5741 December 25th, 1883, April 22nd, July 8th, December 2nd, 1884;
;

i.

p. 99.

[2] Michler, Ber. ix. p. 716. [3] Brit, patent, 1886, No. 120022 Fehrmann, Ber. xx. p. 2844.
;

Friedl. p. 94; Ber. xix., Ref. p. 889.

[4]

[5] Graebe, Moniteur scientif. 1887, p. 600. [6] Ziegler and Locher, Ber. xx. p. 834. [7] Graebe, Ber. xx. p. 3260.

[8] Engl. patent, 1885, No. 9858.

TRIPHENYLMETHANE DYESTUFFS.
[1] Brit, patents, 1884, Nos. 5512,

5741

ber 25th, 1883, April 22nd, July 8th,

p. 99.

Caro and Kern, Amer. patents, DecemDecember 2nd, 1884 Friedl. i.

;

[2] Bottinger, Ber. xii. p. 975. [8] E. & 0. Fischer, Ber. xi. p. 950, xii. pp. 796 [4] O. Doebner, Ber. xi. p. 1236. [5] O. Fischer, Annal. ccvi. p. 130. [6] Brit, patent, 1878, No. 728 Friedl. p. 40. [7] 0. Fischer, Ber. xiv. p. 2521. [8] 0. Fischer and T. Ziegler, Ber. xiii. p. 672.
;

&

2348.

[9] Brit, patent, 1878, No. 4406; Friedl. p. 117. [10] Brit, patent, 1879, No. 2509.

[II] Germ, patent, No. 4988, June 8th, 1878. [12] E. & O. Fischer, Annal. cxciv. p. 274.

[13] Dale and Schorlemmer, Ber. x. p. 1016. [14] Germ, patent, No. 16750, February 8th, 1881
[15] Ph.

Friedl.

i.

p. 57.
;

Greiff, patent, No. 15120, January 26th, 1881 [16] Rosenstiehl, Annal. de Chim. & Phys. (5) viii. p. 192. [17] Germ, patent, No. 16710, February 24th, 1881.

Germ,

Friedl.

i.

p. 49.

[18] Brit, patent, 1881, No. 1212; Friedl. [19] A. W. Hofmann, Ber. vi. p. 352.

i.

p. 54.

REFERENCES.
[20] Greiff, Brit, patents, 1879, Nos. 2515, 4828. [21] Brunner and Brandenburg, Ber. x. p. 1845, xi. p. 697. [22] O. Fischer and Koerner, Ber. xvii. p. 98.
[23] Fischer and Germaner, Ber. xvi. p. 706. [24] E. Fischer, Ber. xii. p. 798. [25] 0. Fischer and Koerner, Ber. xvi. p. 2904. [26] A.

279

W. Hofmann,

Ber. xviii. p. 767.

Ivi.

[27] Lange, Ber. xviii. p. 1918. [28] Hofmann, Compt. rend. liv. p. 428, Jahresb. 1862, p. 347. [29] Victor Meyer, Ber.
xiii. p.

pp. 1033

&

945,

Ivii.

p.

1131

2343.
;

[30] Brit, patents, 1877, No. 3731

1879, No. 2828. [31] Caro and Graebe, Annal. clxxix. p. 203. [32] Hofmann and Girard, Ber. ii. p. 447.
[33]

Hofmann, Ber.

vi. p.

263.

[34] Beckerhinn, Jahresb. 1870, p. 768.

Matieres color.,' Paris, 1867, i. p. 506. [36] Girard, de Laire, and Chappotot, Zeitschr. f. Ch. 1867, p. 236. [37] Girard and de Laire, Jahresb. 1862, p. 696.
[35] Schiitzenberger, [38]
[39]

'

Hofmann, Jahresb. 1863, p. 417. Hofmann, N. Handworterbuch d. Ch.

i.

p.

626.

[40] Bulk, Ber. v. p. 417. [41] E. Kopp, Kiinstl. Farbstoffe, pp. 319 & 320. [42] Usebe, Journ. f pr. Ch. xcii. p. 337 ; Lauth, Bullet, de la Soc. Chim. 1861, French patent, June 26th, 1861. p. 78
.

[43]

Hofmann, Ber.

iii.

p.

761.

[44] Kolbe and Schmitt, Annal. cxix. p. 169. [45] Nencki and Schmitt, Journ. f. pr. Ch. (2)

xxiii. p. 549.

[46] Graebe and Caro, Ber. xi. p. 1350. [47] Liebermann and Schwarzer, Ber. ix. p. 800.
[48] Dale and Schorlemmer, Annal. clxvi. p. 281, cxcvi. p. 77. [49] Zulkowsky, Annal. cxciv. p. 119, ccii. p. 194 ; Ber. x. p. 1201. [50] Caro and Wanklyn, Journ. f. pr. Ch. c. p. 49.

[51] Runge, Poggendorffs Annal. xxxi. pp. 65 [52] Persoz fils, Pelouze, Traite* de Chirnie. [53] Guinon,

&

612.

Mamas, and Bonnet, Brev.

f.

d'invent. 1862.

[54] Reichenbach, Schweiger's Journ. [55] Liebermann, Ber. ix. p. 334. [56]

Ch.

Ixviii. p. 1.

Hofmann, Ber.

xi. p.

1455,

xii.

[57] Poebner, Ber. xii. p. 1462, [58] Baeyer, Ber. iv. p. 662.

xiii. p.

pp. 1371 610.

&

2216.

[59] Claus and Andreae, Ber. x. p. 1305. [60] Gukassianz, Ber. xi. p. 1179.

[61] Rosicki, Ber.

xiii. p.

208.
68.

[62] Baeyer, Annal.

ccii. p.

280

CHEMISTRY OF ORGANIC DYESTUFFS.

1.

[63] Baeyer, Annal. clxxxiii. p. [64] Hofmann, Ber. viii. p. 62.

[65] Baeyer, Ber.

iv. pp. 457, 663. [66] Buchka, Annal. ccix. p. 261. [67] Reichl, Dingl. Polyt. Journ. ccxxxv. p. 232.

[68] A. Kern, Germ, patent. [69] Girard and de Laire, Jahresb. 1867, p. 963. [70] L. Gattermann and Wichmann, Ber. xxii. p. 227.
[71] [72]

W.

v. Miller

and Plochl, Ber. xxiv.

p.

1700.

M. Nathanson and P.

Miiller, Ber. xxii. p. 1888.

[73] Engl. patent, 1889, No. 3333. [74] Heumann and Rey, Ber. xxii. p. 3001.
[75]

M.

Ceresole, Engl. patents, 1887, No.

15374, 1888, No.

9600, 1889,

No. 2635.
[76] Engl. patent, 1889, No. 13217.

QUINONEIMIDE AND AZINE DYESTUFFS.

[1] Nietzki, Ber. xvi. p. 464. [2] Bindschedler, Ber. xvi. p. 865.
[3] Bindschedler, Ber. xiii. p. 207. [4] Witt, Ber. xii. p. 931.

Wurster and Sendtner, Ber. xii. p. 1803 Wurster, Ber. xii. p. 2072. Wurster and Schobig, Ber. xii. p. 1809. [7] Koechlin and Witt, Brit, patents, 1881, Nos. 1373, 5249 Friedl. i. p. 283. [8] Witt, Journ. of Chem. Ind. 1882. [9] Cassella, Germ, addit. patent, No. 15915 Friedl. p. 285. [10] Schmitt and Andressen, Journ. f. pract. Ch. (2) xxiv. p. 435.
[5]
;

[6]

[11] Hirsch, Ber. xiii. p. 1909. [12] Mohlau, Ber. xvi. p. 2845. [13] Bernthsen, Ber. xvii. p. 611. [14] Lauth, Ber. ix. p. 1035.

[15] Engl. patent, No. 3751. [16] Bernthsen, Ber. xvi. pp. 2903 [17] Mohlau, Ber. xvi. p. 2728. [18] Nietzki, Ber. xvii. p. 223.
[19] Koch, Ber.
xii. p.

&

1025.

592.

[20] Engl. patent, 1880, No. 2906.

[21] Mulhauser, Germ, patent, No. 23291, 3rd January, 1883. [22] 0. N. Witt, Ber. xii. p. 939. [23] 0. N. Witt, Journ. Soc. Chem. Ind. 1882.

[24]

Hofmann & Geyger,

Ber. v. p. 526.

ii. p. 374. [27] A. W. Hofmann, Ber. Perkin, Jahresb. 1859-1863; and Proc. of the Royal Soc. XXXY. p. 717. [28] Ber. xii. p. 2065. [29] Meldola,

xviii. p. 1119. [25] Witt, Ber. Private communication. [26]

REFERENCES.
[30] Liebermann, Ber. vii. pp. 247 & 1098. [31] Weselsky, Annal. clxii. p. 273.
[33]

281

H. Koechiin, Engl. patent, 1881, No. 4899 Friedl. i. p. 269. Weselsky and Benedikt, Wiener Monatshefte, i. p. 886 Ber. [34] Brunner and Kramer, Ber. xvii. p. 1817. [35] Bindschedler and Busch, Eng. patent 1881, No. 939. [86] Bernthsen, Annal. ccxxx. pp. 73 & 211.
[82]
;
;

xiv. p. 530.

[37] Witt, Ber. xviii. p. 1119. [38] Witt, Ber. xix. p. 411. F39] Bernthsen, Ber. xix. p. 2604
[40] Witt, Ber. xix. p. 2791. [41] Nietzki, Ber. xix. pp. 3017 [42] Witt, Ber. xix. p. 3121.

Annal. ccxxxvi.
3136.

p. 332.

&

[43] Nietzki, Ber. xix. p. 3017. [44] Julius, Ber. xix. p. 1365. [45] Witt, Ber. x. p. 873.
[46] Wiener Monatsh., July 1884. [47] Eng. patent, 1886, No. 43 Friedl. [48] R. Nietzki, Ber. x. p. 1157.
;

i.

p.

254.

[49] Nietzki and Otto, Ber. xxi. p. 1590. [50] Nietzki and Otto, Ber. xxi. p. 1598. [51] Nietzki and Otto, Ber. xxi. p. 1736. [52] Witt, Ber. xxi. p. 719. [53] Eng. patent, 1888, No. 5852.

[54] Eng. patent, 1886, No. 14283. [55] Eng. patent, 1890, No. 3098.

[54 a] R. Nietzki, A. Dietze, &Mackler, Ber. xxii. [55 a] Nietzki and Mackler, Ber. xxiii. p. 720.
[56] Germ, patent, 1886, No. 40868. [57] O. Fischer and E. Hepp, Ber. xxi. p. 2620.

p.

3030.

[58] Germ, patent, 1888, No. 49853.

ANILINE BLACK, INDULINES AND NIGROSINES.

[1]

Lauth, Bullet,

d.

1.

Soc. chim. Dec. 1864.

[2] Castelhaz, Deutsche Industriez. 1874. [3] Persoz, Deutsche Industriez. 1868. [4] E.
[5]

Kopp, Moniteur scientif. 1861, Rich Meyer, Ber. ix. p. 141.

f.

p. 79.

[6] Fritzsche, Journ.

pract.

Chem.

xxviii. p. 202.

[7] Lightfoot, Jahresb. 1872, p. 1076. [8]

[9] Nietzki,

Witz, Jahresber. 1877, p. 1239. Unpublished observations.

[10] Coquillon,

Compt. rend. Ixxxi.

p.

404.

[11] Nietzki, Ber. ix. p. 616.

[12] B. Kayser, Verh. d. Kgl.

Gewerbemuseums

z.

Niirnberg, 1877.

282
[13] Witt,

CHEMISTRY OF ORGANIC DYESTUFFS.

and Thomas, Ber. xvi. p. 1102. Lowe, Clifft, Eng. patent, June llth, 1860.

[14] Calvert,

[15] Goppelsroeder, Jahresber. 1876, p. 702. [16] Caro, Private communication.

[17] Nietzki, Ber. xvii. p. 223. [18] Nietzki, Ber. ix. p. 1168. [19] Lauth, Bull. d. 1. Soc. chim. Dec. 1864.
[20] Cordelot, Monit. scientif. vi. p. 569.

[21] Caro and Dale, Dingl. Journ. clix. p. 46-5. [22] Martius and Griess, Zeitschr. f, Chem. 1866, p. 136. [23] Hof inann and Geyger, Ber. v. p. 472. [24] v.

Dechend and Wichelhaus, Ber.

viii. p.

1609.

[25] Stadeler, Dingl. Journ. clxxvii. p. 395. [26] Witt, Ber. xvii. p. 74.

[27] [28] [29]

Witt and Thomas, Chem. Soc. Journ. 1883, p. 112. Kimmich, Ber. viii. p. 1028. Caro, Neues Haudworterb. d. Chem., Art. Indulin.
French patent, No. 77854. Chem. News, xl. p. 4.
p. 546.
z.

[30] Coupier,

[31] Justus Wolff, [33] Liechti

[32] Kruis, Jahresb. 1874, p. 1217.

and Suida, Wagner's Jahresber. 1884,

Verb.
d.

[34] Nietzki, Ber. xi. p. 1094;

Vereins

Bef.

d.

Gewerbefleisses

Berlin, 1877.
[35] Fischer

[36] Meister, Lucius, p. 195. [37] 0. Fischer

and Hepp, Annal. cclvi. p. 263, cclxii. p. 237, cclxvi. p. 249. and Briining, Eugl. patent, 1888, No. 16325 Friedl.
;

ii.

and E. Hepp, Ber.

xxi. p.

2617

Ber. xxiii. p. 838.

[38] Chemikerzeitung, 1891. [39]

Dahl and

Co., Germ, patent No. 36899, March llth, 1886, Nos. 39763, 45803, 43008; Farbwerke, Meister, Lucius, and Briining, Germ, patent, No. 50819.

[40] Oehler,

[41] Meister, Lucius, [42] [43]

Germ, patent, No. 533357. and Bruning, Germ, patent, No. 34515. O. Fischer and Hepp, Ber. xxi. p. 2621. C. Schraube, Eng. patent, No. 15259, October 23rd, 1888, and No. 6875 of
1890.

[44] Annal. cclvi. p. 240. [45] 0. Fischer and E. ftepp, Ber. xxiii. pp. 2789-2793.

QUINOLINE AND ACRIDINE DYESTUFFS.

[1] [2] [3] [4] [6]

Jacobsen and Reimer, Ber. xvi.

p.

1082.

Hofmann, Jahresb. 1862, p. 351. Nadler and Merz, Jahresb. 1867, p. 512. Hoogewerff and van Dorp, Ber. xvii. Kef. Williams, Chem. News, ii. p. 219.

p. 48.

REFERENCES.
[6] Jacobsen,

283
;

Germ, patents 23962, December 16th, 1882

i.

23188,

November

4th, 1882; Friedl.

[7] [8]

p. 161.

Jacobsen and Reimer, Ber. xvi. Fischer and Rudolf, Ber. xv.
p. 68.

p. 2604.
p.

1500; Fischer and Besthorn, Ber. xvi.

[9]

[10] Fischer

Fischer and Timber, Ber. xvii. p. 2925. and Bedall, Ber. xv. p. 684.

[11]

Hofmann, Jahresber. 1862,

and Koerner, Ber.

[12] Fischer

p. 346: Ber. xvii. p. 203.

ii.

p.

379.

[13] Anschiitz, Ber. xvii. p. 434. [14] Renouf, Ber. xvi. p. 1304.

Hofmann, Ber. xx. p. 5. [15] A. [16] Hlasiwetz and Gilm, Annal. Supl. [17] Weidel, Ber. xii. p. 410.
[18] Fiirth,

W.

ii.

p.

191.

Wiener Monatshefte,

ii.

p.

416.

[19] Boedecker, Annal. xxiv. p. 228. [20] Biichner, Annal. Ixix. p. 40. [21] Oehler, [22]

Eng. pat. 1888, No. 9614. Leonhardt and Co., Eng. patent, No. 17971, 1889 1890, No. 8243.

and English patent,

INDIGO DYESTUFFS.
Baeyer, Annal. Suppl. vii. p. 56 Baeyer, Ber. xv. Nencki, Ber. vii. p. 1593, viii. p. 336. [3] Engler and Janeke, Ber. ix. p. 1411. [4] Nencki, Journ. f. pract. Chem. [2] xvii. p. 98.
[1]
;

p.

785.

[2]

[5] [6] [7]

Baeyer and Emmerling, Ber. ii. p. 680. Baeyer and Caro, Ber. x. pp. 692 & 1262. Morgan, Jahresb. 1877, p. 788.

[8] Widmann, Ber. xv. p. 2547. [9] Lipp, Ber. xvii. p. 1072.

[10]

Hofmann and Konigs,

Ber. xvi. p. 738.

[11] Forrer, Ber. xvii. p. 984. [12]

Baumann and Tiemann,

Bayer and Knop, Annal.

Ber.

xii. p.

1192,

xiii. p.

415.

[13] Bayer, Ber. xiv. p. 1741. [14]

cxi. p. 29.

[15] Suida, Ber. xi. p. 584. [16] Erdmann, Journ. f. pract. [17] Baeyer, Ber. xi. p. 1228. [18] Friedlander [20] Friedlander

Chem.

xxiv. p. 11

Laurent, ibid. xxv. p. 434.

and Ostermaier, Ber. xiv.

p.

1921.

[19] Baeyer, Ber. xiii. p. 2259.

and Wleiigel, Ber.

xvi. p. 2227.
f.

[21] E. v. Meyer, Ber. xviii. Ref. p. 274; Journ.

pr.

Ch.

(2) xxx. p. 467.

[22] Baeyer, Ber. xii. p. 456. [23]

Baeyer and Oekonomides, Ber. xv.

p.

2093.

284

CHEMISTRY OF ORGANIC DYESTUFFS.

[24] Baeyer and Comstock, Ber. xvi. p. 1704. [25] Gabriel, Ber. xvi. p. 518.

[26] Claisen

and Sliadwell, Ber. xii. p. 350. 746. [27] Baeyer, Ber. xv. pp. 50

&

[28] Baeyer, Ber. xv. p. 775. [29] Schunck, Phil. Magazine (4) x. p. 73, xv. pp. 29, 117, 183; 1855, p. 660, 1858, p. 465. [30] Fritsche, Annal. xliv. p. 290. [31] Sommaruga, Annal. cxcv. p. 305. [32] Schwarz, Jahresb. 1863, p. 557. [33] Baeyer, Ber. xii. p. 1315. [34]
[35] [36]

Jahresb.

[37]

Crum, Berzelius Jahresb. iv. p. 189 Berzelius, Berz. Jahresb. iv. Dumas, Annal. xlviii. p. 257. Loew, Ber. xviii. p. 950. Germ, patent, No. 32238 of March 28th, 1884; Friedl. i. p. 145.
;

p. 190.

[38]

[89] Engler

Baeyer and Emmerling, Ber. iii. p. 514. and Emmerling, Ber. iii. p. 885. A. Baeyer, Eng. patent, 1880, No. 1177, and Germ, patent, No. 11857, March 19th, 1880; Friedl. i. p. 127.
i.

[40] Nencki, Ber. viii. p. 727, vii. p. 1593, ix. p. 299. [41]

[43]

[42] Glaser, Annal. cxliii. p. 325, cxlvii. p. 78, cliv. p. 137. Germ, patent, No. 19266, December 23rd, 1881 ; Friedl.

p.

136

Eng.

patent 1882, No. 1266 ; Friedl. i. p. 140. [44] Baeyer and Drewsen, Ber. xv. p. 2856. [45] Baeyer and Drewsen, Ber. xvi. p. 2205.
[46]

Eng. patent, 1882, No. 1453 ; Friedl. i. p. 141. [47] Claisen, Ber. xiv. pp. 350, 2460, 2468.

[48] Meister, Lucius, p. 142.

and Briining, Eng. patent, 1882, No. 3216; Friedl.

i.

[49] Germ, patent, No. 21592, 12th August, 1882 ; Friedl. i. p. 138. [50] Gevekoht, Annal. ccxxi. p. 330 ; Germ, patent, No. 23785, 13th January, 1883; Friedl. i. p. 139.
[51]

Baeyer and Bloem, Ber.

xvii. p. 963.
;

[62] P. Meyer, Ber. xvi. p. 2261, Germ, patent, No. 25136, 2nd March, 1883

No. 27979, 22nd December, 1883; Friedl.

[53] Kekule-, Ber. ii. p. 748. [54] Baeyer, Ber. xvi. p. 769. [55] Baeyer, Ber. xvi. p. 2188. [56] Baeyer, Ber. xv. p. 782. [57] Compt. rend. xii. p. 539.

i.

pp. 148

&

149.

[58] Baeyer

and Lazarus, Ber.

xiii. p.

xviii. p.

2637.

[69] Baeyer, Ber.

2254.

[60] Forrer, Ber. xvii. p. 976. [61] Schunck, Mem. of Manchester Phil. Soc. (2) xiv. pp.
p.

185-237

Ber. xii.

1220.

[62] Liubawin, Journ. d. russ.

Chem. Ges.

xiii. p.

659.

586. [63] Schiitzenberger, Jahresb. 1877, p. 611 ; Giraud's Jahresb. 1880, p. [64] E. Fischer, Ber. xix. p. 1563, xvii. p. 559.

REFERENCES.

285

EUXANTHIC
[1] [2] [3]

ACID, GALLOFLAVINE, CANARINE,

AND MUREXIDE.
Stenhouse, Annal.
li.

p.

423.
p. 190.

Erdmann, Journ.
Baeyer, Annal.

f.

pr.

Ch. xxxiii.

civ. p. 257.
p. 1675.

[4]
[5]

Graebe and Ebrard, Ber. xv. Schmidt, Annal. xciii. p. 88.

[6] Spiegel, Ber. xv. p. 1964. [7]

[8] v.

Graebe, Ber. xix. p. 2607. Kostanecki, Ber. xix. p. 2918.

[9]

Wichelhaus and Salzmann, Ber.

x. p.

1397.

[10] Graebe, Ber. xix. p. 2607. [11]

[12]

Bonn and Graebe,

Ber. xx.p. 2327.

;

[13] [14]
[15]

Germ, patent, No. 37934, 20th April, 1886 Friedl. i. p. 567. Prochoroff and Miller, Dingl. Journ. ccliii. p. 130. Markownikoff, Journ. d. russ. Chem. Ges. 1884, p. 380.
Lindow,
ibid. 1884, p. 271.

[16] Liebig, Poggend. Annal. xv. p. 546. [17] Prout, Annal. d. [18] Liebig

Chim. & Phys. xi. p. 48. and Wohler, Annal. xxvi. p. 319.

[19] Fritsche, Annal. xxxii. p. 316.

[20] Beilstein, Annal. cvii. p. 176. [21] Graebe, Annal. ccliv. p. 265.

Bohn, Engl. patent, No. 8373, 20th May, 1889 Engl. patent, No. 9427, 28th June, 1859 Graebe and Eichengriin, Ber. xxiv. p. 967. [23] Nencki and Siebert, Journ. f. pr. Ch. xxiii. pp. 147 & 538; Badische Aniline and Sodafabrik., Engl. patent, 1889, No. 9429.
[22] R.
;
;

DYESTUFFS OF UNKNOWN CONSTITUTION.

[1] Chevreul,

Annal. d. Chim. Chimie a la teinture, ii.

332.

et
;

Phys.

(2) Ixxxii. pp.

53-126

Le9ons de
157.

Journ. de Chimie Medicale,

vi. p.

[2] [3]

Erdmann, Annal.

xliv. p. 292.
p.

Hesse, Annal. cix.

[4] [5] [6] [7]

.

[8] [9]

Rammelsberg, Jahresb. 1857, p. 490. Reim, Ber. iv. p. 329. Buchka, Ber. xvii. p. 683. Halberstadt and Reis, Ber. xiv. p. 611. Hummel and Perkin, Ber. xv. p. 2344.
E. Kopp, Ber.
vi. p.
f.

447.

Journ. [10] Bolley,

[11]

j>r.

Ch.

cliii.

p. 351.

Liebermann and Burg, Ber.

ix. p.

1885.

Annal. clxxviii. p. 100. [12] Benedict,

286

CHEMISTRY OF ORGANIC DYESTUFFS.

[13] Dralle, Ber. xyii. p. 372. [14] [15] [16]

[17] [18] Hlasiwetz

Buchka and Erck, Ber. xviii. p. 1138. Wiedemann, Ber. xvii. p. 194. Loewe, Fresenius Zeitscbr. xiv. p. 119 Wagner, Journ. f. pr. Oh. li. p. 482.
and Pfaundler, Annal.
viii.

cxxvii. p. 353.

[19] Benedict, Ber.

[20]

p.

606.

Koch, Ber.

v. p. 285.

[21] Hlasiwetz, Annal. cxii. p. 109. [22]

Zwenger and Dronke, Annal. Suppl.

i.

p.

267.

[23] Bolley, Annal. xxxvii. p. 101. [24] Rigaud, Annal. xc. p. 283.
[25]

Liebermann and Hamburger, Ber.

xii. p.

1179.

[26] Rochleder, Jahresb. 1859, p. 523. [27] Bolley, Anual. cxv. p. 54.

[28] Hlasiwetz p. 500.

and Pfaundler, Jahresb. 1864,

p.

560

Stein, Jahresb.

1862,

[29] Stein, Journ. f. pr. Ch. Iviii. p. 309. [30] Borntrager, Annal. Ixxxii. p. 197. [31] Hlasiwetz, Annal. xcvi. p. 123.

Kane, Berz. Jahresb. xxiv. p. 505 ; Gelatly, Jahresb. 1858, p. 473. [33] Schiitzenberger, Jahresb. 1868, p. 774. [34] Liebermann and Hormann, Annal. cxcvi. p. 307.
[32]
[35] Smorawsky, Ber. xii. p. 1595. Journ. f. pr. Ch. Ixx. p. 428. [36] Moldenhauer, Annal. c. p. 180 Rochleder, Zeitschr. f. Chem. 1866, p. 602. [37]
;

[38] Schutzenberger

and Paraf, Jahresb. 1861,

p. 18.

p.

707; Bullet, de la Soc.

Chimique, 1861,

[39] Schutzenberger andBerteche, Bullet, d. Mulhouse, xxxv. p. 1868, p. 776.

[40] Stenhouse, Annal. [41]
li.

455

Jahresb.

p. 423.

Erdmann, Journ.

f.

pr.

Ch.

xxxiii. p. 190.

[42] Baeyer, Annal. civ. p. 257. [43] Graebe and Ebrard, Ber. xv. p. 1675. Schmidt, Annal. xciv. p. 88. [44]

W.

[45] Spiegel, Ber. xv. p. 1964. [46]

Wichelhaus and Salzmann, Ber.

x. p. 1397.

[47] Graebe, Ber. xix. p. 2607. [48] Piccard, Journ. f. pr. Ch. 1861, p. 709. [49] Mylius, Journ. f. pr. Ch. 1864, p. 546. r50] Stein, Jahresb. 1867, p. 731. [51] Etti, Ber. xi. p. 864. [52] Piccard, Ber. vi. p. 884. [53] Daube, Ber. [54]
iii.

p. 609.
iii.

Iwanow-Gajewsky, Ber.

p.

624,

REFERENCES.
[55] Kachler, Ber.
iii.

287

p. 713.
p.

[56] Jackson, Ber. xiv.

485.
xii. p.

[57]

Wackenroder, Berg. Jahresb.

Ixii. p.

277.

[58] Zeise, Annal. [59]

202.

Husemann, Annal.

cxvii. p. 200.

[60] Kane, Annal. xxxix. p. 25. [61] Robiquet, Annal. xv. p. 292.
[62]

Dumas, Anual.
Wartha, Ber.

xxvii. p. 147.
vii. p.

[63] Liebermann, Ber.

[81 a]

ix. p.

247, 217.

viii. p.

1649.

[62 a] Schlieper, Annal. Iviii. p. 362. [63 a] Malin, Annal. cxxxvi. p. 117.
[64] Luynes, Jahresb. 1864, p. 551. [65] [66]

Leo Meyer, Jahresb. 1847,

p.

784.
p. 22(3.

Hafely, Annal. Ixxiv. [67] Franchimont, Ber. xii. p. 14.

Iviii. p.

Weyermann and

[68] Pelletier, Annal.

27.
Ixii. p.

[69]

Bolleyand Wydler, Annal. [70] Carnelutti and Nasini, Ber.

141.

xiii. p.

1514.

[71] Quadrat, Jahresb. 1851, p. 532. [72] Weiss, Zeitschr. f. Chemie, 1865, p. 552. [73] L.

Meyer and Kochleder, Journ.

f.

pr.

Oh. xxiv. p.
1068.

1.

[74] K. Kayser, Ber. xvii. p. 2228. [75] Cloez

and Guignet, Jahresb. 1872, 410

p.

[76] Kayser, Ber. xviii. p. 3417.

[77] Schaller, Jahresb. 1864, p.

[78]

Zeitschr.

f.

Chem. 1865,

p. 140.

Warren De La Eue, Annal.

Ixiv. p. 1.

[79] Schiitzenberger, Jahresb. 1858. [80] Hlasiwetz and Grabowsky, Annal. cxli. p. 329. [81] [82]

Will and Leymann, Ber. xviii. p. 3180. Liebermann and van Dorp, Annal. clxiii.

p. 105.

[83] Liebermann, Ber. xviii. p. 1975. [84] Lacaze Duthiers, Wagner's Jahresb. 1860, [85] Schunck, Ber. xii. p. 1359.

p.

448.

[86] Perrins, Annal., Suppl.

ii.

p.

191.

[87] Fleitmann, Annal.

lix. p.

60.
ii.

[88] Hlasiwetz u. v. Gilm, Annal., Suppl. [89] Weidel, Ber. xii. p. 410.
[90] Fiirth, Wiener Monatshefte, ii. p. 416. [91] Boedecker, Annal. xxiv. p. 228. [92] Biichner, Annal. Ixix. p. 40. [92] R. Meyer, Ber. xii. p. 1393. [93] [94] J.

p.

191.

Liebermann and Roemer, Ber. xx. Schmid, Ber. xix. p. 1734. [95] R. E. Schmidt, Ber. xx. p. 1285.

p.

2428.

288

CHEMISTRY OF ORGANIC DYESTUFFS.

cii. p.

[96] Arnaud, Compt. rendus, [97] Witt, Ber. vii. pp. 1530 [98] Bizio, Ber. vi. p. 142.

1119.

&

1746.

[99] G. Schultz, Annal. ccii. [100] C. Schall and Dralle, Ber. xxiii. p. 1433.

[105] Liebermann and Tauchert, Ber.

xcvi. p.

337

clxxxvi. p.
p.

see also Neubauer, Annal. xiii. p. 694 Kraut and Delden, Annal. cxxviii. p. 285 Etti, Annal. 327 Schiitzenberger and Rack, Bullet, d. 1. Soc. Chim. iv.
; ; ; ;

Hlasiwetz, Annal. cxxxiv. p. 118.

ii.

[106] Etti,

Wiener Monatshefte,

p. 547.

APPENDIX,

NITRO-COMPOUNDS.
P. 25.

Naphthol Yellow

S.

The G-naphtholtrisulphonic acid used

in the manufacture of
:

naphthol yellow S has the constitutional formula

OH
S0 3 H
S0 9 H

S0 3 H

The

free acid of naphthol yellow

:

is

constituted according to

the formula

OH
S0 3 H

AZO-DYES.
P. 56.

Chromotropes.

These colouring-matters are prepared by action of diazo-comThe commercial pounds on the chromotrope acid (see p. 295).

290

CHEMISTRY OF ORGANIC DYESTUFFS.

brands are 2 R, 2 B, 6 B, 8 B, and 10 B. They dye wool from an acid bath ; the shades vary from a bright scarlet with 2 R to a reddish violet with 10 B, but are not fast to soap. More valuable results are obtained when the chromotropes are applied in conjunction with a mordant. Darker and faster shades are obtained

by boiling the goods dyed with these dyestuffs with salts of copper, aluminium, and iron, and various shades of black are produced by action of potassium bichromate. It has been found advantageous to use the mordant after dyeing, the operation taking place in the same bath. Chromotrope 8 B gives the best and fastest shade of black. The property of combining with metallic mordants possessed by these dyestuffs is due to the presence of two hydroxylgroups in the peri position. Chromotropes 2 R, 2 B, and 6 B give a red solution with concentrated sulphuric acid, 8 B and 10 B give
a blue solution.

Amidonaphtholsulphonic Acids.
Several of these acids are
is

of importance.

It is prepared

known, but only one, the 7 or G acid, by action of caustic soda on

/3-naphthylaminedisulphonic acid Gr (from /3-naphtholdisulphonic acid and ammonia) at about 260. It may be diazotised, and
reacts with diazo-compounds to produce azo-colours, which may be diazotised and combined on the fibre with other amines and

phenols. (See below, under Tetrazo-colours.) The reaction between tetrazo-compounds and y-amidonaphtholsulphonic acid may be effected in either alkaline or slightly acid
solution,
is

and the products

differ

according to which condition

observed.

The exact reason

for this behaviour has not been

explained.

For example, in the preparation of diamine blacks R and B, and diamine blue-black E, the combination of the tetrazoacid
is

compound with ry-amidonaphtholsulphonic

alkaline solution, while in the cases of Red a slightly acid solution is used.

effected

in

Diamine Violet and Fast

P. 60.

The following Azo-dyes contain the groups necessary

In fact theoretically for the formation of mordant-dyeing colours. fast shades when applied in conjunction with a chromium they yield
mordant.
to the
It

may be remarked that Diamond Black

(p.

66) belongs

same category.

APPENDIX.

291

Dyestuff.

292
It is
acid.

CHEMISTRY OF ORGANIC DYESTUFFS.

known as naphthalidinesulphonic
It is used,

of azo-colours.

acid or simply as Laurent's but not to any great extent, in the manufacture The more easily soluble sodium salt obtained above

yields a-naphthylaminesulphonic acid It has the constitution

:

S
2

(peri -acid)

on reduction.

S0

NH

It

has hitherto not been

made use
is

of in the preparation

of

azo-dyes.

The preparation

of these acids

described in British Patents

Nos. 15775 and 15782, 1885. The Laurent acid is also formed by action of fuming sulphuric acid on a-naphthylamine hydrochloride or on acet-a-naphthalide.
a-Naphthylaminedisulphonic Acids.
Certain of these acids are used in the manufacture of black mixture of acids is formed by sulphonation of

azo-colours.

fuming sulphuric acid, and these are separated by treating the calcium salts of the mixture with alcohol. The calcium salt soluble in alcohol of 96 / yields acid No. I., the residue contains acids II. and III., of which II. is soluble in alcohol
naphthionic
acid with

Acid I. yields azo-colours of no value, and No. III. is of 85 %. Germ. Pat. 41957, Sept. 4, of greater importance than No. II.
1886.
ft-Naphthylaminedisulphonic Acids.

These acids are prepared by heating the corresponding /3-naphR-amidotholdisulphonic acids with ammonia. Thus K acid yields The G-amido-acid acid and G-(7)-acid yields G-(y)-amido-acid. is also obtained by sulphonation of /3-naphthylamine at 100-140
with fuming sulphuric acid.
a-Naphtholdisulphonic Acids.

is

a-naphthylaminesulphonic acid S (suprh] Schollkopf acid. converted into sulphonated, and the resulting disulphonic acid
I.

APPENDIX,

293

naphtholdisulphonic acid by the diazo-reaction. acid has the constitution

The Schollkopf

SO,H

OH

SO8H
(Brit. P.

1885, 15775-15782).

It is

used in the manufacture of

azo-dyes.
II. a-naphtliol-e-disulplionic

acid (Andresen acid).

The mixture

of disulphonic acids obtained by sulphonatioii of naphthalene is nitrated and reduced. The sodium salts of the amidodisulphonic
acids obtained are treated with water.
salt yields the

The more easily soluble Andresen acid by the diazo-reaction, the sparingly

soluble one corresponds to the Schollkopf acid. The Andresen acid has the constitution

SO.H

OH
S0 3 H

Nevile-Winther

It yields azo-dyes of a pure bluish shade, and is, next to the acid, the most important derivative of a-naphthol.

A peculiar property possessed by a-naphtholsulphonic acids which contain hydroxyl- and sulpho-groups in the peri (1*8) position, is that they yield anhydrides by elimination of water, and
these anhydrides (called sultones) are frequently obtained in place of the acids, on decomposing the diazo-compounds with boiling
water.

Thus

the

naphtholsulphonic

acid

corresponding

to

a-naphthylaminesulphonic acid S yields naphtho-sultone,

SO

294

CHEMISTRY OF ORGANIC DYESTUFFS.

acid gives naphthosultone-sulphonic acid,

The Schollkopf

S0 2

san
while an isomer
is obtained from the Andre sen acid. (Literature G. Schultz, Ber. xx. p. 3162 H. Erdmann, Annalen, ccxlvii. Bernsthen, Ber. xxii. p. 3327 ; Armstrong & Wynne, p. 344 Proc. Chem. Soc. 1890, p. 125. Brit. Patents, 1885, 15775:

15782; 1888,4625, 5910.)

Dioxynaphthalenesulphonic Acids.
Several of these acids are used in the manufacture of azo-colours.

Dioxynaphthalenemonosulphonic acid S is prepared by melting a-naphtholdisulphonic acid (Schollkopf) with caustic soda, and has accordingly the constitutional formula
I.
:

OH

S0 3 H

Azo-fuchsine B.

Diazotoluene and dioxynaphthalenesulphonic Acid S.

Azo-fuchsine G.

Diazobenzenesulphonic acid and dioxynaphthalenesulphonic Acid S.

and

dyestuflfs dissolve in water with a bluish-red colour, in concentrated sulphuric acid with a violet colour. Azofuchsine B comes into commerce as a brownish-black powder,

These two

azo-fuchsine

as a reddish-brown powder.

APPENDIX.

295

They produce magenta shades on wool and are recommended as magenta on account of their fastness to light and the clearness of the shades obtained. They may also be used for printing woollens prepared with alum and stannic chloride.
substitutes for acid

German

Pat. 54116, Oct. 25, 1889.

Dioxynaphthalenedisulphonic Acid (Chromotrope Acid).

sulphonated with fuming sulphuric acid at from according to the strength of acid employed. The trisulphonic acid obtained has the constitution

Naphthalene

is

80-180

SO,H

SO,H

S0 3 H

It is nitrated

to the diazo-reaction

and reduced, and the resulting amido-acid submitted whereby a-naphtholtrisulphonic acid or its

sultone
acid

This yields a dioxynaphthalenedisulphonic Acid) on fusion with caustic soda. (Chromotrope The chromotrope acid is constituted according to the formula
is

formed.

OH

S0 3 H

SOJJ

Dyes from Benzidine and Analogous Bases. In the Table on p. 72 several derivatives of ethoxybenzidine are enumerated, and the reactions whereby this base is obtained are described here. Diazobenzene chloride reacts with j9-phenolsulphonic acid, producing benzene -azo-paraphenolsulphonic acid, the azo-chain taking up an ortho-position with regard to the hydroxylgroup.

296

CHEMISTRY OF ORGANIC DYESTUFFS.

is

Accordingly the compound formula

:

constituted

according to the

C 6 H 5 -N=N

C 6 H/

OH U
SO 3 H

On heating with ethyl chloride or bromide and alcohol in On reduction presence of alcoholic potash, an ether is formed. with stannous chloride or zinc-powder and caustic soda, the ether
undergoes an intramolecular change, a sulphonic acid of ethoxybenzidine, of the constitution
4
:

NH
is

1 1

C6H4

C 6 H 2rS0 3 H

/OC

H
2

3 6

NH

formed.

This

is

heated with water under pressure to 170, and

off,

sulphuric acid splits

forming ethoxybenzidine sulphate.

OC2 H 5

Ethoxybenzidine

is

used in the manufacture of a number of the

so-called diamine colours.

Toluylenediaminesulphonic acid of the constitution

NIL

S0 3 H

may

be diazotised. The^ tetrazo-compound reacts with amines and phenols; the toluylene browns are combinations with two

molecules of a metadiamine.
the Table on p. 74, cotton-yellow and salmon-red are described as obtained from diamidodiphenylene. They are derivatives of diamidodiphenylurea, but are prepared

In

erroneously

indirectly.

APPENDIX.

297

Cotton-yellow is obtained by action of phosgene on two molecules of amidobenzene-azo- salicylic acid, and has the formula
:

CO[NH-C H4 -N=N-C H OH COOH]

6 6 3
.
.

2.

prepared in an analogous manner from amidobenzene-azonaphthionic acid, and has the formula

Salmon-red

is

CO[NH-C H -N=N-C H NH S0
6

10

H] 2

Mimosa

is

prepared by action of ammonia on the diazo-compound

of primuline.

Mikado Colours. The yellow-orange and brown dyestuffs known under this designation are prepared by action of alkalies on paranitrotoluenesulphonic acid in presence of oxidizable substances, such as arsenic us acid, glycerine, phenols, tannic acids, &c. Brit.
Pat. 1888, 2664. They are probably
less impure azoxystilbenedisulcotton directly from a salt bath and dye

more or

phonic

acids.

They

give moderately fast shades.

The following Table comprises some of the most important

direct dyes of recent introduction.

Dyestuff.

298

CHEMISTRY OF ORGANIC DYESTUFFS.

obtained from tetrazo-diphenyl with 1 mol. of salicylic acid and 1 mol. of resorcin.
tised

Diamine Blue 6 G. /3-naphthylaminedisulphonic acid diazoand combined with 1'2 amidonaphthol ether. The product is diazotised and combined with /3-naphthol. Benzo-grey. Tetrazodiphenyl is combined with equal molecules of salicylic acid and a-naphthylamine, the product diazotised and combined with a-naphtholsulphonic acid (Nevile and Winther) Is prepared similarly to the above ; dioxynaphthaBenzo-olive. lenesulphonic acid S being substituted for the last-named com.

ponent.
Benzo-indigo-blue.

The combination of benzidine with

diazotised

1 mol.

a-naphthylamine

is

and combined with two molecules

of dioxynaphthalenesulphonic acid S.

OXYQUINONES AND QUINONE OXIMES.

P. 91. Alizarin-blue

has the composition expressed by the

formula

C 17 H 9NO4 + 2NaHSO 3
(H. Brunck and Graebe, Ber. 1882, vol. xv.
p. 1783.)

TRIPHENYLMETHANE DYESTUFFS.
P. 110. Cyanine 60961.)
It is a greenish-blue dyestuff, tolerably fast to soap and light, and recommended as a substitute for indigo-extract. P. 112. New Magenta. This product is prepared commercially by the synthetic process outlined on p. 112.

is

prepared by oxidation of the sulphonic

acids of meta-oxytetralkyldiamidotriphenylcarbinol.

(Germ. Pat.

= CH 2 , is heated with a Anhydroformaldehyde-aniline, C 6 H 6 mixture of orthotoluidine and its hydrochloride to 100. Aniline

splits off,

and diamido-ditolylmethane

APPENDIX.

299

NH
is

formed.

On

further heating with ortho-toluidine, hydrochloric

and an oxidising agent, a third molecule of ortho-toluidine enters into reaction, the " new magenta " being produced. It is
acid,

accordingly a salt of triamidotritolyl-carbinol,

OH
New magenta
is

more

easily soluble

than ordinary magenta, and

dyes a somewhat bluer shade.

P. 128. Diphenylamine blue.

This compound has long been con-

sidered as triphenylpararosaniline identical with that obtained by Hausdorfer (Ber. xxiii. p. 1961) phenylation of pararos aniline.

has compared diphenylamine blue with triphenylpararosaniline, and demonstrated their identity.
P. 130.

New

Green.

Is

condensation product

of

analagous to Victoria-blue, beiug the dimethylamidobenzophenone with a-

phenylnaphthylamine (Germ. Pat. 41756). The commercial product is a paste. It is principally intended for calico-printing, and gives yellowish-green shades.
the sodium salt of tetranitrophenolnitration of phenolphthalein in sulphuric phthalem, prepared by It dyes wool or acetic acid solution (Eng. P. 3441, 1889).
P. 138.

Aurotine

is

chromium mordant, proshades fairly fast to light and washing. ducing orange-yellow On heating dichlorfluorescem with sodium P. 142. Cyclamine.
either

from

an acid bath or on a

sulphide in aqueous solution, a thiodichlorfluorescem is formed. This is converted into a tetraiodthiodichlorfluorescem by action

of iodine, and the sodium salt appears in commerce as cyclamine. It dyes bluish-red shades resembling those obtained with In general the thio-derivatives dye bluer shades than phloxine.
the corresponding fluoresceins. P. 143. Violamine (Fast acid violet],

.B

.These

dyestuffs are

300

CHEMISTRY OF ORGANIC DYESTUFFS.

obtained by action of ortho- and para-toluidine respectively on fluorescein-chloride. (Germ. Pats. 49057, 53300, 1889.) The Violamines are used for wool and silk, and give shades
fast to alkalies

and

light.

QUINONEIMIDE DYESTUFFS.
P. 158. Thionine blue

0.

This dyestuff
is

is

closely allied to
:

methylene blue, and

its

constitution
6
3

expressed by the formula

3) 2

^C

H -N(CH
S

C 6 H 3 = N^C 2 H 5 X C1
It is prepared

CH

by oxidation of dimethylparaphenylenediamine-

thiosulphonic acid (see Methylene Blue) with ethyl-methylaniline, and boiling the resulting insoluble green compound with zincchloride solution. leuco-compound is formed, and is converted

into

dyestuff by oxidation.

The commercial product forms a

is

reddish-brown powder. This body Toluidine Blue.

also

an analogue of methylene

blue, the dimethylparaphenylenediamine-thiosulphonic acid being The hydrochloride has the constioxidised with ortho-toluidine.

tution expressed by the formula

C 6 H 3 -N(CH 3 C6 H 2 ^
The commercial product

CH
.

NH

HC1

is the sulphate and forms a dark green soluble in water forming a bluish-violet solution. powder, easily In dyeing, toluidine blue gives redder shades than methylene

blue.

series,

Methylene Blue N. This dyestuff is a recent member of the and is obtained from ethyl -ortho-toluidine in the same manner as methylene blue from dimethyl-aniline.

APPENDIX.
It dyes redder shades

301

Its constitution is expressed

than methylene blue. by the formula

CH
C6H2

NH

C2 H 5

C 2 H5
a

Cl
Thiocarmine.

This

compound

is

sulphonic acid

of

the

methylene-blue series, and is obtained from ethylbenzylanilinemonosulphonic acid. Thiocarmine is an acid dyestuff and produces very pure greenish shades of blue on wool, which are, however, not very fast to light.

(English Patents, 4596 and 19065, 1890.)

The oxyindamines and oxyindophenols (Fast Blue, P. 161. Gallocyanines, &c.) are characterised by the ease with which they react with amines of the fatty and aromatic series, and certain
compounds resulting
commerce.
resulting

from

such

reactions

have

appeared in

This name has been given to the compounds from the action of ammonia and amines in presence of an oxidising agent on Fast Blue E/. (A description of Fast Blue K or Naphthol Blue occurs on p. 161.)

Cyanamines.

blue
of

Ammonia-cyanamine has a greener shade than the original fast the dimethylamine-cyanamine is more valuable on account ;
its

pure greenish-blue shade. been demonstrated that the green shades of fast blue contain one of these cyanamines the formation of which results
It has
;

from the interaction of fast blue B, with the dimethylparaphenylenediamine formed during the reaction. (Schlarb. Chem. Zeit. 1891, pp. 1281 and 1318; Witt. Ber. 1890, xxiii. p. 2247.)
P. 165. Delphine Blue and Gallic Indigo are sulphonic acids of compounds obtained by heating gallocyanine with aniline and analo-

gous bases.

The

constitution of these bodies has not been deter-

they are not simple anilides of gallocyanine, as a carboxylgroup splits off during the reaction. These dyestuffs are employed in calico-printing, giving pure
;

mined

302

CHEMISTRY OF ORGANIC DYESTUFFS.

blue shades when applied with chromium acetate. (Germ. Pat. 55942, Sept. 27, 1889; 50999, July 23, 1889.) Wool Greys. These dyestuffs are obtained by action of aniline

and analogous bases on the condensation-products of nitrosodimethyl- and diethyl- aniline on Schaeffer's /3-naphtholsulphonic
acid.

AZINE DYESTUFFS.
Fast Black.
obtained

The commercial product bearing

action

this

name

is

by

of

nitroso-dimethylaniline

on meta-oxyboth of the

diphenylamine.

and is fixed oxyindamines on cotton prepared with sumac and acetate of iron. Malta Grey and Nigrisine are bodies of unknown constitution
prepared

It contains the groups characteristic and the azines. It is a basic dyestuff,

by heating nitrosodimethylaniline hydrochloride in or alcoholic solution. aqueous Methylene Grey is a similar solution obtained by oxidation of
dimethylparaphenylene diamine. (German Patent, 49446, Feb.
2, 1889.)

INDULINES AND NIGROSINES.

The simplest Induline o the naphthalene series, rosinduline par excellence, is formed by heating benzene-azo-a-naphthylamine
with aniline in alcoholic solution under pressure. base forms reddish-brown crystals, M.P. tution is expressed by the formula
:

Rosinduline
Its consti-

198-199.

Accordingly the compound described on

duline.

p.

205

is

a phenyl-rosin-

APPENDIX.

303

On

heating with hydrochloric acid, rosinduline yields

ammonia
:

and rosindulone, a compound having the constitutional formula

Some

of the sulphonic

acids

of rosindulone

are

now

pre-

pared commercially, and come into commerce as Eosindulines. Rosinduline 2 B dyes wool bluish red from an acid bath. Rosindulines 2 G and G produce orange-red and scarlet shades respectively, and when dyed on silk exhibit a fine yellow
fluorescence.

heating benzene-azo-a-dinaphthylamine with and isonaphthylrosindulines are formed. thyl

On

aniline,

naph-

Isonaphthylrosinduline has the constitution expressed by the

formula

N.C

An

anilide of isonaphthylrosinduline having the formula

CHN
is

CH

5,

formed along with phenylrosinduline when benzene-azo-a-naphis

heated with aniline. is probably a salt of a sulphonic acid of amidoof similar isonaphthylrosinduline, and naphthyl violet is a dyestuff

thylamine

Naphthyl blue

character.

show

are principally intended for silk, a red fluorescence.

They

on which they
v.

(O. Fischer and E. Hepp, Annal.

Perger, Mittheil. Techn.

cclxii. pp.

237-264; H.

Gewerbemuseums, 1891, pp. 202-253.)

304

CHEMISTRY OF ORGANIC DYESTUFFS.

INDIGO.
process in the preparation of indigo from the plant consists in macerating the plants in water and subjecting the liquor to This "ammonia the action of air in presence of ammonia.

"

process
purity.

is

said to give larger yields

and a product of greater

Diacetylindigo.

heating indigo blue with acetic anhydride, sodium acetate, On oxidation zinc powder, a diacetylindigo white is obtained. and with nitrous acid in presence of acetic acid, diacetylindigo blue is

On

formed.

This compound forms small glittering red crystals, soluble

Its constitution is ex:

in benzene with a beautiful red colour. pressed by the formula

/CO\
6

4X

A NX

C2

P/

C \ r
isr 1N

A* 11 \C H
2

TT
*
3

Indigo disulphonic Acid.

The mechanism of the

for preparing this

reactions involved in the synthetic process

compound has been explained by Heymann Ber. 1891, p. 3066). The yellow solution resulting from the (Berl. action of the sulphuric anhydride on phenyl-glycine contains the

On dilution of this sulphonic acid of indoxyl-sulphuric ester. oxidation is effected by the sulphuric anhydride. solution,

QUINOLINE AND ACRID INE DYESTUFFS.

Berberine.

Extensive researches on the constitution of berberine have been

made by W. H. Perkin, Jun. (Chem.

Berberine
is allied

Soc. Journal, 1890, p. 991). to papaverine, hydrastine, and narcotine ; it is a derivative of isoquinoline, and has probably the constitution

expressed by the formula

APPENDIX.

305

GIL O
.

CH

306
protocatechuic

CHEMISTRY OF ORGANIC DYESTUFFS.

acid,

while

yields phloroglucin and protocatechuic

quercitin under similar conditions acid, these results being in

is

accordance with the idea that quercitin

a hydroxyfisetin.

Orce'in.

(Zulkowski

&

Peters, Monats.

f.

Chem. 1890,

p. 227.)

study of the process by which orcei'n is formed from lichens, action of ammonia and air, shows that three colouring-matters by are formed, viz., orcein, a yellow crystalline compound, and an

amorphous body resembling litmus. Pure crystallised orcein is insoluble in water, ether, and benzene soluble in alcohol, acetone, and acetic acid. Pure orcein possesses two hundred times the tinctorial power of orchil extract. nearly The composition of orcein is expressed by the formula
;

C28 H 24 N2 O 7

an(i its formation

may be

expressed by the equation

4 C 7 H 8 O 2 + 2NH 3 + 60 = C 28 H 24N2 O 7 + 7H 3 O.
The yellow compound has the formula C 21 H 19N0 5 , and ably formed according to the equation
is

prob-

It

was found that the formation of orcein from orcin

in

is

much

more rapid

presence of hydrogen peroxide ; other oxidising did not give favourable results. agents No compound of the orcein class can be obtained from resorcin

by action of hydrogen peroxide and ammonia. From a mixture of resorcin and orcin a mixed orcein, " Reso-orcein," C 20 H 20 N 2 O 7,
is

formed.

ALPHABETICAL INDEX.

Anthrapurpurin, 88.

ACID dyes,

14.

Acridine dyes tuffs, 207. orange, 216.

yellow, 216. Aldehyde green, 128. Alizarin, 82. Alkyl-, 83. black, 81. blue, 91. blue OR, 90. blue S, 298. Bordeaux, 89. brown, 89. Ohloro-, 83. cyanine, 89.
,

Anthraquinoline, 91. Anthraquinone, 84.

Dichloro-, 84. disulphonic acids, 84.

dyes, 81.

monosulphonic

acid, 84.

Archil, 260.

brown, 65. Auramine, 98.

Aurantia, 26. Aurin, 132. Aurin-tricarbonic acid, 134. Aurotine, 299.

Auxochromic groups,
Azarin S, 75. Azine dyes, 169.

13.

dyeing, 86. green S, 92.

indigo blue S, 92.

Nitro-, 87. orange, 87. red S, 83.

Azine-green, 189. Azoaniline, 41. Azobenzeneazoparacresol, 66.

Azobenzenedimethylamidobenzoic
uU*

acid,

sulphonic acid, 83. synthesis, 83.

yellow, 61, 245.

Alkannin, 263.

Azobenzene-a-naphthol, 53. monosulphonic acid, 54. Azobenzene-jft-naphthol, 54. disulphonic acids, 55.

Amaranth,
,

56.

Amidoazobenzene, 35.
Acetyl-, 37.

monosulphonic acids, 54. Azobenzene salicylic acid, 61.

acid

/3-naphtholdisulphonic
55.

Azo-black, 291. Azo-blue, 71, 73. Azo-carmine, 205.

disulphonic acid, 36.

monosulphonic acid, 36. Amidoazonaphthalene, 43.

Amidoazotoluenebenzene, 39. Amidoazotoluenes, 39. Amidoazoxylenes, 40. Amidonaphtholsulphonic acids, 290. Amidooxyazobenzene, 46. Annatto, 258. Anthracene yellow, 92. Anthracite black, 291.
Anthraflavic acid, 89.

Azo-cornpounds, 28. Azodibenzenephenylenediamine, 65. Azodibenzenetoluylenediamine, 66. Azo - d - diamidobenzoic acid-y-benzene-

Azofuchsine, 294.

Anthragallol, 89.

sulphonic acid, 60.

application, 34.
63.

Azo-des

from amidoazo-compounds, from benzidine, 68.

manufacture, 34. on fibre, 77.

Azonaphthalene /3-naphthol, 57.

disulphonic acids, 58.

308
Azonaphthalene inonosulphonic
resorcin, 46.
salicylic acid, 61.

INDEX.
acid, 57.

Azoorseilline, 72.

Azophenine, 201. Azophenols, 45. Azorubine, 58.

Azoviolet, 74. Azyline, 42.

Blue, Diphenylamine, 128, 299. Fast, 161. Gallamine, 164. Meldola, 162. Methylene, 155, 300. Naphthol, 161. Naphtyl, 303. Night, 127. , Nile, 163.
, .
,

B.
Basic dyes, 14. Basle blue, 188.

Paraphenylene, 203. Phenylene, 149.

Eesorcin, 167. Toluidine, 300. Toluylene, 150. Victoria, 130. Water, 127.

Benzaurine, 135. Benzeneamidoazouaphthalene, 43. Benzenedisazobenzene /3-naphthol, 64.

disulphcnic acid, 64. raonosulphonic acid, 64. Benzenetetrazobeuzenephenol, 63. Benzhydrol, 97. Benzidine blue, 72.

Bordeaux, 56, 57.

- B, 58.

Benzoazurines, 73, 74. Benzo-black, 74. Benzo-blue-black & E, 74. Benzo-brown B, 74. Benzoflavine, 216. Benzo-grey, 298.

extra, 72. Brazilein, 253. Brazilin, 252. Brilliant azurine 5 black, 66.

Gr,

74.

Congo, 72. purpurin, 73.

Archil, 65.

Brown,
,

Benzoindigo-blue, 298.
Benzo-olive, 298.

Benzo, 74. Bismark, 42.

Cloth, 291. Congo, 297. Diaruine, 297. Toluylene, 296.

Benzo-orange, 72. Benzopurpurines, 72, 73. Berberine, 212, 304. Bismark brown, 42.
Bixin, 258. Black, Alizarin, 81. Aniline, 192.
, ,

C.

dyeing, 197. Anthracite, 291. Azo, 66, 295. Benzo-, 74.

Cachou de Laval, 271.

Canarine, 247. Carmine-red, 266.

Benzo-blue, 74.
Brilliant, 66.

Carminic

acid, 265.

Carminnaphthe, 58.
Carotin, 260. Carthamin, 262. Catechin, 271. Catechu, 270. tannic acid, 271. Chinese green, 264.

Diamine, E, 72, 290. B, 73, 290. Blue E, 73, 290.

,

Diamond, 66.
Fast, 302. Jet, E, 66.

Naphthol, 291. Naphthylamine, D, 66.

Chrome

violet, 134.

New, 291.
,
,

Wool,

Victoria, 291. 65.

Chromogens, 3. Chromophors, 3. Chromotropes, 289. Chrysamine G, 71, 72.

E, 72.
Chrysanilines, 124, 212. Chrysin, 259. Chrysoidine, 40.

Blue, Alkali, 127. Aniline, 126.

,

Azo, 71, 73.

Basle, 188.
72.

Benzidine, - black B, 295.

,

Chrysophenine, 74.
Cbrysotoluidine, 124. Citronine, 39.
Classification, 21.

Cotton, 127. Delphine, 300. Diamine, 73, 298.

Cloth brown, 291.

INDEX.
Cloth orange, 291.
Coccinines, 56, 57, 267. Cochineal, 265. Colour, 1. Ccerulein, 144.

309

Congo
,

red, 68, 72. Brilliant, G, 72. Corinth, 72.

Erythrosin, 141. Ethoxybenzidine, 296. Eupittonic acid, 133. Eurhodines, 172. Eurhodoles, 175. Euxanthic acid, 243. Euxanthone, 243.

violet, 72.

Crocetin, 264. Crocin, 264.

F.
20.

Crude products,

Cumeneazoresorcin, 45.

Fisetin, 254, 305. Flavaniline, 210.

Curcumin, 259. Cyanamines, 300.

Cyanine, 203. B, 298. Cyanosine, 142. CycJamine, 299.

Flavin, 254.

Flavopurpurin, 88.
Fluorescein, 139.
, ,

Tetrabrom-, 139. Tetrabromodichlor-, 142. Tetrabromotetrachlor-, 142.

Tetraiodo-, 141.

D.
Dehydrothiotoluidine, 75.

Fluorescent blue, 167. Fluorindine, 206. Fuchsine, 118.

'

Fustic, 253.
,

Delphine blue, 300. Deltapurpurin, 72, 73. Developers, 76. Diaruidoazobenzene, 40.
Diamidoazotoluenes, 42.
yellow, 291. Dichroines, 165. Diisatogen, 224.

Young, 254.

Fustine, 305.

G.
Gallacetophenone, 245.

Diamond

Gallamine blue, 165.

Gallein, 144. Gallic indigo, 300. Gallocyanine, 163.

Dimethylamidoazobenzene, 37. sulphonic acid, 37. Dinaethylamidobenzeueazobenzoic

'

acid

59.

Galloflavine, 246. Gambine, 95.

Girofle, 185.

Dimethylamidobenzoic
acid, 60.

acid-azobenzoic

Dinitrocresol, 24.

Dinitronaphthol, 25. sulphonic acid, 25, 289.

Dinitrosoresorcin, 93. Dioxindol, 221.

Glycereins, 145. Green, Acid, 110. , Aldehyde, 128.

, ,

Azine, 189. Azo, 116. Benzaldehyde, 107.

Bindschedler's, 149. Brilliant, 109. Chinese, 264. Ethyl, 109. Fast, 94.

Dioxyazobenzenes, 44, 45. sulphonic acid, 45. Dioxy naphthalene sulphonic acids, 294.

Dioxynaphthoquinone, 81. Dioxy tartaric acid, 101. Diphenylamine blue, 128, 299.
Diphenylrosaniline, 126.

Disazo dyestuffs, 62.

Dyeing

(theories), 3.

Ellagic acid, 245. Eosin, 139. ether, 140. scarlet, 141. Erica, 76.

Helvetia, 109. Iodine, 122. Light, 110. 107. , Malachite, , Methyl, 116. Methylene, 161. , Naphthol, 95. New. 299. , New solid 3 B, 109. , Victoria 3 B, 109. , 110. , Quinoline, Solid, 109. , , Victoria, 109.
, ,

310
Grey, Fast, 271. , Methylene, 302.
,

INDEX.
K.
Ketone-imides, 96.

Wool, 302.

H.
Hsematein, 250. Hsematoxylin, 260. Helianthine, 38.
Heliotrope, 74. Hexaethylpararosaniline, 116. Hexamethoxylaurin, 133.

Laccaic acid, 269. Lac-dye, 269.

Lacmoid, 168.
Lakes, 15.

Lanuguinic acid, 5. Leuco-compounds, 2.

Litmus, 261.

Hexamethoxylpararosaniline, 134. Hexametkylpararosaniline, 115. Hexamethyl-rosaniline, 122. Hexanitrodiphenylamine, 26. History, 17. Hydrazides, 96.

Logwood, 250.
Lokaetin, 265. Lokain, 264. Lo-Kao, 264.
Lutecienne, 141. Luteolin, 257.

I.

M.
Maclurine, 253.

Imidothiodiphenylimide, 158.
Indarnines, 146, 149. Indazine M, 188. Indian yellow, 242. Indiglucine, 225. Indigo, 219.
,

Magenta, 118.
Acid, 121. New, 298. residues, 124. S, 121. Mauvaniline, 124. Mauveine, 190. Mikado colours, 297. Mimosa, 297.
, 1

process, 304. application, 228. blue, 224. carmine, 227. , Ohloro-, 226. Diacetyl, 304.
, ,

ammonia

Dibenzoyl, 226. dicarbonic acid, 229. extract, 227. purpurin, 230. red, 230. rubin, 230. substitute, 251.

Monophenylrosaniline, 125. Mordant-dyeing, 15, 80. Morin, 253. Murexide, 248. Muscarine, 162.

sulphonic acids, 227, 304.

,

synthesis, 231.

Naphthaquinoneoximes, 94. Naphthazarin, 81.

Naphthol-azo-dyes, 46. Naphthol black B, 2B, 6B, 291.

white, 226. Indigotin, 225. Indoine, 229. Indol, 219. Indophenine, 222. Indophenols, 151.

a Naphtholmonosulphonic and Winther, 49.

,

acid,

Nevile

Schaefler, 49.
acid, Schollkopf,

a Naphtholdisulphonic
50,292.

Indoxanthic ether, 224.

Indoxyl, 220. Indoxylic acid, 221. Induliues, 200, 302. , application, 204. , soluble, 203. Isatic acid, 223. Isatin, 222. Isatogenic ether, 224.

e, 275. trisulphonic acid, 289.

(3

3 Naphthol

Naphtholazobenzoic acid, 59. disulphonic acid Q-, 52.

d,

53.

E, 53.

monosulphonic acid crocein, 51.

F, 52.
Schaeffer, 52.

Isopurpuric acid, 27. Isopurpurin, 88.

Naphthol yellow, 25, 289.

INDEX.
a Naphtho-Sultone, 293. a Naphthylamine disulphonic acids, 292. monosulphonic acids, 69, 291.

311

312
Kesorufamine, 168.
Kesorufin, 165. Ehamnetin, 256, 305.

INDEX
Tetraethylrosaniline, 123.

Tetramethyldiamidobenzophenone, 96.
chloride, 97.

Ehodamine, 142.
S, 143. Eoccelline, 57. Eosamine, 135. Eosaniline, 118. Acetyl, 123.
,

Tetramethyldiamidotriphenylcarbinol,
106.
,

Chlor-, 109. Nitro-, 108.

- aldehyde compounds, base, 120.

benzoyl, 123. DiphenyJ, 126. dyes, 105. Hexamethyl, 122. Monophenyl, 125. Pentamethyl, 122. sulphonic acids, 121. Tetrabroin-, 121. , Tetraethyl, 122. Tetramethyl, 122.
,
,

123.

sulphonic acid, 109. Tetramethylpararosaniline, 114. Tetramethylrosaniline, 122.

Tetranitrodiphenol, 26. Tetranitronaphthol, 26. Tetrazo-dyes, 62. Thiazines, 153. Thiocarmine, 301.

Thiodiphenylamine, 153.
Thioflavine, 76, 77. Thionine, 155, 300. Thionol, 159. Thionoline, 159.

tribenzyl-methyliodide, 123. Triethyl, 123. Trirnethyl, 122. Triphenyl, 126. Eosazurines, 73. Eose Bengal, 142. Eosindulines, 205, 303. Eosolic acid, 133. dyes, 132. Euberythric acid, 82. Eubramine, 185. Euficoccin, 267. Eutin, 256.
,

Thiotoluidine, 75. Toluidine blue, 300.

Toluylenediaminesulphonic acid, 296. Toluylene orange, 297. Triamidoazobenzene, 42.

Triamidotriphenylcarbinol, 111, 118. Tribenzylrosaniline-methyliodide, 123.
Triethylrosaniline, 123. Trimethylrosaniline, 122. Trinitroeuxanthone, 244. Trinitrophenol, 24. Trioxyacetophenone, 245.

Trioxy-anthraquinone, 87. Trioxybenzophenone, 245. Tripheny 1m ethane dyes, 102.

Triphenylrosaniline, 126. sulphonic acids, 126, 127. Tropaolin II & OO, 38.

S.

Saifranine, 177.

Pheno-, 178, 181. Tolu-, 185. Saffranol, 187. Saffron substitute, 24. Saffrosine, 141. Santalin, 263. Scarlet, Biebrich, 64. Brilliant, 59.
,
,

Y&0,44. OOONo. 1,
Turkey
red, 86.

54.

Turmeric, 260. Tyrian purple, 269.

V.

Brilliant Crocein

Crocein, 3 B & Crystal, 58. Diamine, 297. 2 G, 55. , Silk-, 59.

, ,
,

65. 7 B, 65.

M,

Valuation of dyestuffs, 15. Yesuvine, 42.

Yictoria-black, 291. blue, 130. green, 109. yellow, 24. Violamine, 299. Violaniline, 124. Yiolet, Acid, 114.
,

Styrogallol, 92.

Sulphonazurine, 73. Sun Gold, 26. Yellow, 75.

T.

Amethyst, 185.
Azo-, 74.

Chrome-, 135. Congo, 72.

Crystal-, 115. Diamine, N, 72.

Tannin

lakes, 16.

Tartrazine, 100.

INDEX.
Violet, Hessian, 74. Hofmann's, 123.
, ,

313

Yellow, Alizarin, 61.

, ,

A & G,

245.

Lauth's, 155. Methyl-, 112. Neutral-, 176. Toluylene-, 176.

Brilliant-, 26, 74. Carbazol, 74.

paste, 72. Cotton-, 74, 297. Diamine, N, 73.

Congo

X.

Fast-, 36.

Xanthorhamnin, 256.
Y.
Yellow, Acid, 36. Acridine-, 216.
,

Hessian, 74. Indian, 39.

Marti us, 25.

Metanil, 38.

Naphthol,

8, 25, 289.

Quinoline, 209.
Salicyl-, 26.

Sun, 75.

FEINTED BY TAYLOR AND FRANCIS, RED LION COURT, FLEET STREET.

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