Amines and Diazonium Salts

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ORGANIC CHEMISTRY- FUNCTIONAL GROUP- 3

AMINES
Amines are alkyl or aryl derivatives of ammonia. Amines are classified into primary, secondary
and tertiary amines. If one hydrogen atom of ammonia is replaced, a primary amine results.
The substitution of two or three hydrogen atoms leads to secondary and tertiary amines respectively.

H H R R
H N H R N H R N H R N R
o o o
Ammonia 1 Amine 2 Amine 3 Amine
The amines are called ‘simple’ when all the alkyl groups are same and ‘mixed’ when they are different.
Nomenclature
In common system, amines are named by adding the suffix ‘amine’ to the corresponding alkyl group.
In case of mixed amines, the names of alkyl groups are arranged in alphabetical order.
In IUPAC system, they are called aminoalkanes or alkanamines.

Formula Common name IUPAC name

CH3 – NH2 Methyl amine Methanamine


CH3 – CH2 – NH2 Ethyl amine Ethanamine
CH3 CH CH3 Iso-Propyl amine Propan-2-amine

NH2
CH3 – NH – CH3 Dimethyl amine N-methyl methanamine
CH3 – NH – C2H5 Ethyl methyl amine N-methyl ethanamine
CH3 N CH3 Tri-methyl amine N,N-Dimethyl methanamine

CH3
CH3 N CH2 CH3 Ethyl methyl propyl amine N-Ethyl-N-methyl propanamine

CH2 CH2 CH3


CH2 = CH – CH2 – NH2 Allylamine Prop-2-en-1-amine
H2N – (CH2)6 – NH2 Hexamethylenediamine Hexane-1,6-diamine

CH3 CH3
NH2 CH3 CH3
N
NH2

NH2
Aniline O - Toluidine P - Toluidine
(Benzenamine) (2-methyl benzenamine) N, N -Dimethylaniline
(4-methyl benzenamine) (N,N-dimethyl benzenamine)
NH2
Diphenylamine P - Anisidine
NH (N-phenyl benzenamine) (4-methoxy benzenamine)

O CH3

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Electronic structure
In amines, nitrogen has sp3 hybridisation. Three of the sp3 hybrid orbitals overlap
with other atoms to form 3 sigma bonds. These sigma bonds are directed to the corners of
N
a tetrahedron. The remaining hybrid orbital contains a lone pair of electron. Therefore
amines have pyramidal shapes. Bond angle is around 108o. R R 
R
Preparation
(1) From alkyl halides: [By Hofmann’s ammonolysis method]
Alkyl halides react with ethanolic solution of ammonia to form primary, secondary and tertiary
amines. If ammonia is used in excess primary amine is the major product.
R – X + NH3 → R – NH2 + HX
If alkyl halide is in excess, the primary amine formed further reacts with alkyl halides to form
2o and 3o amine and finally quaternary ammonium salt. The reaction is carried out in sealed tube at 373K.
R−X R−X R−X
R – NH2 ⎯⎯⎯→ R – NH – R ⎯⎯⎯→ R3N ⎯⎯⎯→ R4N+ X-
This reaction is a typical example of nucleophilic substitution reaction. The ammonium salt
can be converted to free amine by treatment with strong base.
R – NH3+ X- + NaOH → R – NH2 + H2O + Na+X-
The reactivity of various halides in this method is R – I > R – Br > R – Cl
(2) From nitro compounds by reduction.
Nitro compounds can be reduced to primary amines either by using H2/Pt, Ni or by using
Fe/HCl, or Sn/HCl or LiAlH4
H /N
R – NO2 ⎯⎯2 ⎯
⎯1
→ R – NH2 + 2H2O
Fe / HCl

This method is important for the preparation of aromatic primary amines as they cannot
be obtained easily from alkyl halides.
NO2 NH2

+ 3H2 ⎯⎯ ⎯⎯→
Sn / HCl
+ 2H2O

Here Fe/HCl is preferred because FeCl2 formed get hydrolysed to release HCl. Therefore only
small amount of HCl is needed.
(3) From Alkyl cyanides on reduction with H2/Ni, LiAlH4 or Na/C2H5 – OH give primary amines.
H / Ni
R – CN + 4H ⎯⎯2 ⎯
⎯→ R – CH2 – NH2
Na / C 2H5 OH

(4) By reduction of amides using Na/C2H5OH or LiAlH4. Here primary amides give primary amines.
Secondary and tertiary amides can give secondary or tertiary amines.

Li Al H
CH3 C NH2 ⎯⎯⎯
⎯4
→ CH3 CH2 NH2 + H2O
4[H]
o
1 Amine
O

LiAl H
CH3 C NH CH3 ⎯⎯ ⎯
⎯4
→ CH3 CH2 NH CH3 + H2O
o
2 Amine
O

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(4) From amides by Hoffmann bromamide degradation reaction
Acid amides on reaction with Br2 in the presence of alkalies at about 343 K give primary amines.

NH2 + Br2 + 4KOH ⎯⎯ ⎯⎯→ CH3


343 K
CH3 C NH2 + 2H2O + 2 KBr + K2CO3
O

Here the amine formed by this method has one carbon atom less than the parent compound.
(5) From Alcohols (Industrial method)
Low molecular weight aliphatic amines are manufactured by passing a mixture of an alcohol and
ammonia in the vapour phase over heated alumina catalyst. Here a mixture of 1o, 2o and 3o amines are formed.
Al O / 575 K
R – OH + NH3 ⎯⎯2⎯3 ⎯ ⎯
⎯→ R – NH2 + R2NH + R3N [ R = CH3 or C2H5 ]
(6) Manufacture of aniline
Aniline is manufactured by vapour phase reduction of nitrobenzene with hydrogen using copper
oxide or vanadium-platinum as catalyst.

NO2 NH2
H2 / CuO
⎯⎯⎯⎯→
or V −pt,680 K

(7) Gabriel Phthalimide synthesis


In this method, phthalimide is first converted into potassium phthalimide by reaction with KOH.
The potassium phthalimide on treatment with alkyl halide gives N-alkyl phthalimide. It is then hydrolysed
to get pure primary amine.
O O O
C C C COONa
R− X
NH ⎯⎯⎯→
KOH
N K+ ⎯⎯⎯→ N – R ⎯⎯ ⎯⎯→
NaOH

C C COONa + R – NH2
C
1o Amine
O O O
This method cannot be used for the preparation of aromatic amines. This is because aryl halides do not
undergo nucleophilic substitution with anion of phthalimide.
Physical Properties
Ethyl and methyl amines smell like ammonia, higher amines have fishy odours. They are
colorless when pure, but get coloured on keeping due to oxidation by air.
Boiling point Amines are polar compounds. All amines except the tertiary amines are capable of forming
inter-molecular hydrogen bonds. The inter-molecular hydrogen bond is more in primary than in secondary.
Tertiary amines do not have inter-molecular hydrogen bonding due to the absence of H on nitrogen.
The boiling points of isomeric amines is Primary > Secondary > Tertiary
As a result amines have higher boiling point than
H R H
non- polar compounds of comparable molecular masses.
However amines have lower boiling points than R N H N H N R
corresponding alcohols or carboxylic acids. This is
because the O – H bond is more polar than N – H bond. H H
Hence hydrogen bonds in alcohols and carboxylic acids
are stronger than the hydrogen bonds in amines. H N R

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Solubility Aliphatic amines of lower molecular mass are soluble in water. The solubility in water is due to
their ability to form hydrogen bonds with water molecules.
The higher amines are soluble in less polar solvents like ethers, alcohols and benzene. Aromatic
amines are insoluble in water but soluble in ether, alcohols and benzene.
Chemical Properties
1) Basic character
Due to the presence of a lone pair of electrons on nitrogen, amines are basic in nature.
Like ammonia amines are more basic than water and are protonated by water. The basic strength of
amines are compared in terms of the equilibrium constant Kb.

[ R − NH3+ ] [OH− ]
R – NH2 + H2O R – NH3+ + OH− Keq =
[ R − NH2 ] [H2O]

Since [H2O] is constant, it is convenient to incorporate it in to the equilibrium constant.


Then the constant obtained is called basicity constant. Each amine has a characteristic Kb.
The larger the value of Kb, the stronger is the base.

[ R − NH3+ ] [OH− ]
Kb =
[ R − NH2 ]

But the basic strength is more conveniently expressed in terms of their pKb values (pKb = –log Kb).
Smaller the value of pKb, more is the basic strength of amine. 
I. Alkyl amines are stronger bases than ammonia.
This is due to the electron releasing inductive effect of alkyl groups. Due to electron releasing
effect, the electron density on nitrogen increases and the lone pair of nitrogen is more available for sharing.
More over, electron releasing effect of alkyl group, stabilizes the alkyl ammonium ion formed.
R NH2 + H2O R N + H3 + OH –
II. Basic strength of 1o, 2o, and 3o amines
Among 1o, 2 o, and 3 o amine the electron releasing effect is maximum in tertiary amines. Thus the
basic strength is expected to increase from primary amine to tertiary amine. But the observed basicity is

(i) CH3 NH CH3 CH3 NH2 (CH3)3 N NH3


H2o
o
1o 3

(ii) CH3 CH2 NH CH2 CH3 (CH3 – CH2)3 N CH3 CH2 NH2 NH3
H2o 3 o

This anomalous behavior is due to (i) Steric effect and (ii) Hydration effect.
(i) Steric effect
Due to the crowding of alkyl groups on nitrogen atom, the attack of a proton on the amine is
hindered. Thus the basic strength is decreased. Crowding of alkyl groups increases form primary to
tertiary amines. Consequently basic strength should decrease in the order 1o > 2o > 3o.
(ii) Hydration effect (solvation effect)
The protonated amines can be hydrated by forming hydrogen bonds with water.
Hydration releases energy called hydration energy. Higher the hydration energy, more stable the
molecule. Hydration due to hydrogen bond is maximum in primary amine and least in tertiary amine.
Therefore basic strength should decrease from 1o > 2o > 3o.

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Thus in 3o amine, hydration is least and steric hindrance and + I effect are maximum.
In1o amines, steric effect and + I effect are minimum and hydration effect is maximum. The resultant of
all these effects make the secondary amines more basic than primary or tertiary amines.
But in gas phase and in non-polar solvents like chlorobenzene the solvent effect is
missing. Therefore the order of basic strength is
3o > 2o > 1o > Ammonia
III. Aromatic amines such as aniline are less basic than ammonia
This is because in aniline the lone pair of electrons on nitrogen undergoes delocalization with
the  electrons of benzene ring. Thus aniline is a hybrid of the following resonating structures.
Thus the availability of the lone pair of electrons on the nitrogen is decreased.
+ + +
NH2 N H2 N H2 N H2 NH2
(–)
Cl Cl
+ (–) +

(–)

Effect of substituents on basic character


The presence of electron releasing groups such as –OCH3, – CH3 – NH2 etc at the para position
increases the basic strength.
The presence of electron withdrawing groups such as – NO2 –CN, – X etc at the para position
decrease the basic strength.

NH2 NH2 NH2 NH2

CH3 Cl NO2

NH2 NH2 NH2 NH2


NO2
Nitro anilines
NO2
NO2
NH2 NH2
NH2 NH2
Toluedines CH3
CH3
CH3

NH2 NH2 NH2


NH2
NH2
Diamines
NH2
NH2

1) Salt formation
Due to the basic nature, amines readily dissolve in acids to form salts.

(CH3)2 NH + HCl → (CH3)2 NH2+ Cl−

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Salts of amines are ionic compounds. They are non-volatile solids. They are soluble in water but
insoluble in non-polar solvents. From these solutions the amine can be regenerated by treatment with
aqu.NaOH
2) Reaction with metal ions
Like ammonia, amines also form co-ordination compounds with metal ions like Ag+ and Cu2+.
For example, silver chloride dissolves in methyl amine solution.
Ag Cl + 2 CH3 – NH2 → [Ag (CH3 NH2)2]+ Cl–
Similarly copper sulphate solution forms a deep blue solution.

CuSO4 + 4 CH3 – NH2 → [Cu (CH3NH2 )4 ]2 + SO24−


Deep blue solution

3) Reaction with alkyl halides


Amines react with alkyl halides to form higher amines. In this reaction the amine acts as a nucleophile.
R− X R− X RX
R − NH2 ⎯⎯⎯→ R2 NH ⎯⎯
−HX
⎯→ R3 N
−HX
⎯⎯⎯→
−HX
R4 N + x −
o o Tetraalkyl ammonium halide
2 A min e 3 A min e

4) Reaction with acid chlorides and acid anhydrides (Acylation)


Primary and secondary amines react with acid chlorides and acid anhydrides to form substituted
amides. Tertiary amines do not undergo this reaction because they do not have H atom on the nitrogen.

C2H5 – NH2 + CH3 – COCl ⎯⎯ ⎯→


base
C2H5 – NH – CO – CH3 + HCl
Mechanism
H CH3
CH3

C2H5 NH H C Cl ⎯⎯ ⎯→ C2H5
base N+ C Cl C2H5 N C CH3 + HCl

H O− H O
H O
This reaction is carried out in presence of a strong base than ammonia which removes HCl so formed and
shifts the equilibrium to the right.
In this reaction the reactivity order is Acid chlorides > Anhydrides > Esters
5. Benzoylation
1o and 2 o amines react with benzoyl chloride (C6H5COCl) in the presence of a base like pyridine
(or NaOH) to form benzoyl derivative.

C6H5 – NH2 + C6H5 – COCl ⎯⎯ ⎯⎯⎯⎯ ⎯→ C6H5 – NH – CO – C6H5 + HCl


Pyridine or NaOH

Benzoylation of compounds containing active hydrogen such as alcohol, phenol or amines with
benzoyl chloride in the presence of a base in called Schotten-Baumann reaction
7. Reaction with aldeydes
Primary amines react with aldehydes to form Schiff’s bases.

R NH2 + O C R R N C R + H2O

H H
Schif’s base

C6H5 NH2 + O C C6H5 C6H5 N C C6H5 + H2O

H H

Schiff’s bases on reduction give secondary amines.

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8. Ring substitution of aromatic amines
The amine group in aromatic amines is an electron donating group. Hence it increases the
electron density at the ortho and para positions. Hence the electrophilic substitution takes place at the
ortho and para positions.
(a) Halogenation
Aniline readily reacts with excess bromine to give 2, 4, 6 - tri bromoaniline.

NH2 NH2
Br Br
+ 3 Br2 + 3 HBr

Br

To get a mono bromo compound, the amino group is acetylated before bromination.

NH2 NH CO CH3 NH CO CH3 NH2


Br2
+ CH3 C Cl H2O/H+ + CH3 COOH
O
Br Br

(b) Nitration
Direct treatment of aniline with HNO3 leads to the formation of complex tarry oxidation products.
More over in strongly acidic medium aniline get protonated to m-directing and deactivating +NH3 group.
Therefore nitration of aniline, unexpectedly gives 47% m-nitroaniline.

NH2 NH2 NH2 NH2


HNO
NO2
⎯⎯⎯
⎯3
→ + +
H2 SO 4
NO2
NO2
51 % 47 % 2%

Therefore, before nitration, aniline is first acetylated to protect the –NH2 group. Acetanilide on
treatment with HNO3 / H2SO4, gives ortho and para nitro acetanilide. This on hydrolysis give ortho and
para nitro aniline.
NH2 NH CO CH3

+ CH3 CO Cl ⎯⎯ ⎯→
base
+ HCl

NH CO CH3 NH CO CH3 NH CO CH3


HNO / H SO NO2
⎯⎯ ⎯3 ⎯2⎯⎯
4
→ +

NO2

NH CO CH3 NH CO CH3 NH2 NH2


NO2 +
H O/H
+ ⎯⎯2 ⎯⎯→ + NO2
− CH3 − COOH

NO2 NO2

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(c) Sulphonation
Aniline on treatment with con H2SO4 form the salt, anilinium hydrogen sulphate.
This on heating gives sulphanilic acid.
NH2 N+H3 HSO −4 NH2 N+H3
455 − 475 K
+ H2SO4 ⎯⎯ ⎯⎯⎯→

SO3 H SO3−

Sulphanilic acid is an important intermediate in the manufacture of dyes and drugs. Sulpha drugs
like sulphathiazole and sulphadiazine are made from sulphanilic acid.
Aniline does not give Friedel-Crafts reaction. This is because AlCl3, the catalyst used in this reaction
is a Lewis acid and it forms a salt with –NH2 group. Thus N of aniline acquires positive charge and hence
acts as a strong deactivating group.

9. Reaction with nitrous acid


(a) With primary amines
Aromatic primary amines react with HNO2 to give diazonium salts at low temperature. (273-278K).
NH2 N2+ Cl−
273 − 278 K
+ NaNO2 + 2 HCl ⎯⎯ ⎯ ⎯⎯→ + NaCl + 2 H2O

Aliphatic primary amines react with nitrous acid to form diazonium salts. However the aliphatic
diazonium salts are unstable and decompose to yield mixture of alcohols and alkenes, and N2 gas is evolved.
CH3 – CH2 – NH2 ⎯⎯ ⎯ 2⎯ ⎯ 
⎯→ C2 H5 N2+ Cl−
Na NO / HCl

Unstable
 H O
⎯⎯2⎯→ C2 H5 OH + CH2 = CH2 + N2 + H2O

Test for amines


(1) Carbylamine test [ Isocyanide Test]
When a primary amine is treated with chloroform and alkali, a carbylamine or isocyanide with a
characteristic foul smell is formed. This is a test for primary amines. 20 and 30 amines do not show this reaction.
R ─ NH2 + CHCl3 + 3 KOH → R − NC + 3KCl + 3H2O
Isocyanide

2) Hinsberg’s test [Reaction with benzene sulphonyl chloride]


Benzenesulphonyl chloride [C6H5SO2Cl] , also known as Hinsberg’s reagent reacts with
primary and secondary amines to form sulphonamides.
(1) Primary amine react with benzenesulphonyl chloride to form N-ethylbenzenesulphonamide.
It contain an acidic hydrogen on N and hence it is soluble in aqueous KOH .
(2) Secondary amine react with benzenesulphonyl chloride to form N,N-diethylbenzenesulphonamide
It does not contain any acidic hydrogen attached to N atom. Hence it is insoluble in KOH solution.
(3) A tertiary amine do not react with benzene sulphonyl chloride.
This test helps to distinguish between primary, secondary and tertiary amines.

SO2 Cl + C2H5 NH2 ⎯⎯ ⎯→ SO2 N H ⎯⎯ ⎯→


KOH
SO2 NK+
−HCl
NH2 NH2
C2H5 C2H5
Soluble

SO2 Cl + C2H5 N H ⎯⎯ ⎯→
−HCl
SO2 N C2H5 ⎯⎯⎯→
KOH
Insoluble

NH2 NH2
C2H5 C2H5

SO2 Cl + C2H5 N C2H5 No reaction

C2H5

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Uses of amines
1) Lower aliphatic amines are used as solvents.
2) Aromatic amines are used in the manufacture of dyes, indicators and drugs.
3) In laboratory, aromatic primary amines are converted into a variety of compounds via diazonium salts.
4) Aniline is used as antioxidant in the manufacture of rubber.
5) Amines are also used in petroleum refining and manufacture of detergents.
DIAZONIUM SALTS
Aromatic primary amines react with nitrous acid to form a class of compounds called diazonium salts.
They have the general formula Ar N2+ X–. Where X– ion may be anion such as Cl–, Br–, HSO4– etc.
The N2+ group is (+N  N) and is called diazonium group.
They are named by adding the word diazonium to the name of the aromatic compound followed
by the name of the anion.

N2+ Cl− N2+ HSO−4

Benzene diazonium chloride Benzene diazonium hydrogen sulphate

Stability: Primary aliphatic amines form alkyl diazonium salts which are highly unstable. But primary
aromatic amines form arene diazonium salts which are stable. The stability of arene diazonium salts
can be explained on the basis of resonance.
+ + + +
+
N N N =N N =N N =N N N

+ +

+
Method of preparation (Diazotisation)
The primary aromatic amines react with nitrous acid at low temperature (273 - 278K) to give
aromatic diazonium salts. This reaction is known as diazotisation. Nitrous acid is unstable and therefore
it is prepared in situ by the reaction of sodium nitrite and dilute HCl.
NH2 Na2Cl
273 − 278 K
+ NaNO2 + 2HCl ⎯⎯ ⎯ ⎯⎯→ + NaCl + 2H2O

Reactions of diazonium salts


Reactions of diazonium salts can be classified into two types.
(1) Replacement reactions and (2) Coupling reactions
(1) Replacement reactions
In replacement reactions, the nitrogen is lost as N2 gas and a different group is introduced in its place.
(i) Replacement by hydrogen: This is done by treatment with hypophosphorus acid
(phosphinic acid) or ethanol.
C6H5 – N2Cl + H3PO2 + H2O → C6 H6 + N2 + H3PO3 + HCl
C6H5 – N2Cl + C2 H5 – OH → C6 H6 + N2 + CH3 – CHO + HCl

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(ii) Replacement by– OH This involves warming of the diazonium salt with water.
N2Cl OH

+ H2O + N2 + HCl

(iii) Replacement by –Cl, –Br, or –CN (Sandmayer’s reaction)


The diazonium group is replaced by –Cl, –Br or –CN group respectively.
When an aqueous solution of benzene diazonium chloride is warmed with CuCl and HCl,
CuBr and HBr, or CuCN and KCN. This reaction is known as Sandmayer’s reaction.
Cl
CuCl/HCl
+ N2

N2+ Cl− Br
CuBr/HBr
+ N2

CN
CuCN/HCN
+ N2

Gatterman modified Sandmayer’s reaction by warming the diazonium salt solution with copper
powder in the presence of the corresponding halogen acid.
Cl
Cu/HCl
+ N2

N2+ Cl− Br
Cu/HBr
+ N2

CN
Cu/KCN
+ N2

This reaction is called Gattermann reaction.


(iv) Replacement by iodine

C6H5 – N2+ Cl− + KI → C6 H5 – I + N2 + KCl

(v) Replacement by fluorine [Balz Shiemann reaction]

N2+ Cl− N2+ BF4− F


HBF4
⎯⎯⎯→ ⎯⎯⎯→ heat + N2 + BF3
−HCl
Flurobenzene

(vi) Replacement by – NO2 group:

N2+ Cl− N2+ BF4− NO2


Na NO
+ HBF4 ⎯⎯⎯⎯
2
→ + N2 + NaBF4
Fluoroboric acid Cu, 

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(II) Coupling reactions
Diazonium salts react with electron rich aromatic compounds such as phenols and amines to form
azo compounds. Azo compounds are coloured and are used as dyes and indicators.
(i) Reaction with phenol
OH−
N2+ Cl− + H OH ⎯⎯⎯→ N N OH + Cl
273 − 278 K
P- hydroxy azobenzene
(ii) Reaction with aniline

+
N2+ Cl− + H NH2 ⎯⎯
⎯→
H
N N NH2 + HCl
273 − 278
P- Amino azobenzene
(iii) Methyl orange:
The acid-base indicator methyl orange is obtained by coupling of diazonium salt of sulphanilic
acid and N, N-dimethyl aniline.

NaO3S N2+ Cl− + H N(CH3)2 ⎯⎯ ⎯


⎯→ NaO3S
Na OH N N N(CH3)2

Methyl Orange

Importance of diazonium salts


1. Aryl fluorides and iodides cannot be prepared by direct halogenation. But they can be prepared
from diazonium salts.
2. The cyano compounds cannot be obtained by nucleophilic substitution of chlorobenzene.
But they can be easily obtained from diazonium salt.
3. Diazonium salts are also useful in for introduction of –F, – Cl, –Br, –I, –OH, –NO2 etc in benzene ring.

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