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AMINES
 QUIZRR 75

AMIN
INEES

1. Am in e s

Amines are organic compounds and functional groups that contain a basic nitrogen atom with
a lone pair. Amines are derivatives of ammonia, wherein one or more hydrogen atoms have
replaced a substituent such as an alkyl or aryl group. Important amines include amino acids,
biogenic amines, trimethylamine and aniline.

1.1 Al
Aliip ha
hatt ic Amin es

As displayed in the images below, primary amines arise when one of three hydrogen atoms in
ammonia is replaced by an organic substituent. Secondary amines have two organic substituent
bound to N together with one H. In tertiary amines all three hydrogen atoms are replaced by
organic substituents.

(a) Primary amines

CH3 CH2 NH2 CH3 · CH · NH2

1-ethanamine |
CH3
1-methyl-1-ethanamine

(b) Secondary amines

CH3 CH2 NHCH 3 NHCH3

N-methyl ethanamine
N-methyl cyclohexanamine
(C) Tertiary amines

CH2 CH2 CH2 · N · CH2 CH3 (CH3)3 N

|
CH3 N-N-dimethyl methanamine
N-ethyl-N-methyl-1-1propanamine

1.2 Ar
Arom
om
omaatic amine
An aromatic amine is an amine with an aromatic substituent ă that is ăNH2, ăNHă or nitrogen
group(s) attached to an aromatic hydrocarbon, whose structure usually contains one or more
benzene rings. Aniline is an example.

NH2 NHCH(CH3 )2

Benzenamine (Aniline) N-isopropyl benzenamine

AMINES
 76 QUIZRR
1.3 Phy sic al prope rt ie s

1.3. 1 General prope

perr ties

1. Hydrogen bonding significantly influences the properties of primary and secondary amines
as well as the protonated derivatives of all amines. Thus the boiling point of amines is higher
than those of the corresponding phosphines, but generally lower than those of the
corresponding alcohols. Alcohols, or alkanols, resemble amines but feature an OH group in
place of NR2. Since oxygen is more electronegative than nitrogen, RO-H is typically more
acidic than the related R2N-H compound.
2. Methyl, dimethyl, trimethyl and ethylamine are gases under standard conditions, whereas
diethylamine and triethylamine are liquids. Most other common alkyl amines are liquids;
high-molecular-weight amine are solids.
3. Most aliphatic amines display some solubility in water, reflecting their ability to form hydrogen
bonds. Solubility decreases with the increase in the number of carbon atoms, especially
when the carbon atom number is greater than 6.
4. The aromatic amines, such as aniline, have their lone pair electrons conjugated into the
benzene ring, thus their tendency to engage in hydrogen bonding is diminished. Otherwise
they display the following properties :
Ć Their boiling points are usually still high due to their larger size.
Ć Diminished solubility in water, although they retain their solubility in suitable organic
solvents only.
Ć They are toxic and are easily absorbed through the skin : thus hazardous.

R1 R1

R3 N N R3

R2 R2

1.3. 2 Chi
hirr ality

Tertiary amines of the type NHRR´ and NRR´R´´ are chiral : the nitrogen atom bears four distinct
substituents counting the lone pair. The interconversion of the stereoisomers has been compared
to the inversion of an open umbrella into a strong wind. Quaternary ammonium salts with four
distinct groups on the nitrogen are capable of exhibiting optical activity.

1.3. 3 P
Prrope
perr ties a
ass b
baases

Like ammonia, amines act as bases but are reasonably weak. The basicity of amines depends
on :

AMINES
 QUIZRR 77

1. The electronic properties of the substituents (alkyl groups enhance the basicity, aryl
groups diminish it).
2. Steric hindrance offered by the groups on nitrogen.
3. The degree of solvation of the protonated amine.
The nitrogen atom features a lone electron pair that can bind H+ to form an ammonium ion
R3NH+ . The water solubility of simple amines is largely due to hydrogen bonding between
protons on the water molecules and these lone electrons pairs.
1. Inductive effects of alkyl group : + I effect of alkyl groups raises the energy of the lone pair
of electrons, thus elevating the basicity. Thus the basicity of an amine may be expected to
increase with the number of alkyl groups on the amine. However, there is no strict trend
in this regard, as basicity is also governed by other factors. The increase in Kb from
methylamine to dimethylamine may be attributed to + I effect; however, there is a decrease
from dimethylamine to trimethyl amine due to the predominance of steric hindrance offered
by the three methyl groups to the approaching Lewis acid.
2. Mesomeric effect of aromatic systems : ă M effect of aromatic ring delocalises the lone pair
of electrons on nitrogen into the ring, resulting in decreased basicity. Substituents on the
aromatic ring, and their positions relative to the amine group may also considerably alter
basicity.
3. The degree of solvation of protonated amines : The degree of solvation of the protonated
amine depends on the approachability of solvent molecules. If the molecule is sterically
hindered (as in the case of trimethylamine), the protonated form is not well-solvated, thereby
reducing basicity. This also explains the oroder of basicity of the methyl amines.
The major determinant of basic strength in alkyl-substituted anilines remain mesomeric stabilisation
of the aniline molecule with respect to the cation; born out by the irregular effect of introducing
Me groups into the o-, m- and p-positions in aniline.
A group with a more powerful (electron-withdrawing) inductive effect, e.g. NO2 is found to have
rather more influence. Electron withdrawal is intensified when the nitro group is in the o- or p-
position, for the interaction of the unshared pair of the amino nitrogen with the delocalised 
orbital system of the benzene nucleus is then enhanced. The neutral molecule is thus stabilised
even further respect to the cation, resulting in further weakening as a base. Thus the nitro-
amines are found to have related pKa values.

+
NH2 NH2

PhNh2 NO2 C6 H4 NH2

4.62 o ă 0.28
m ă 2.45
p ă 0.95
N N
ă + ă +
O O O Oă

AMINES
 78 QUIZRR
The extra base-weakening effect, when the substituent is in the o-position, is due in part to the
short distance over which its inductive effect is operating, and also to direct interaction, both steric
and by hydrogen bonding with the NH2 group. o-Nitroaniline is such a weak base that its salts
are largely hydrolysed in aqueous solution, while 2, 4-dinitroaniline is insoluble in aqueous acids,
and 2, 4, 6-trinitroaniline resembles an amide; it readily undergoes hydrolysis to picric acid (2, 4,
6-trinitrophenol).
With substituents such as OH and OMe that have unshared electron pairs, an electron-donating,
i.e. base-strengthening, mesomeric effect can be exerted from the o- and p-, but not from the m-
position, with the result that the p-substituted aniline is a stronger base than the corresponding
m-compound. The m-compound is a weaker base than aniline itself, due to the electron-withdrawing
inductive effect exerted by the oxygen atom in each case. As so often, the effect of the o-
substituent remains somewhat anomalous, due to the interaction with the NH2 group by both
steric and polar effects.

NH2 NH2

OMe OMe
+

Exa mpl
plee 1

Compare the basicities of

PhNH 2 Ph2NH
NH2

I II III
Solution :
III > I > II
In structure III, lone pair electron of Nitrogen does not participate in resonance.

Ex
Exaa mpl
plee 2

Arrange the following compound according to their basic strength (with suitable
explanation) : C6 H5NH2 , C6 H5NHMe, C6 H5 NMe2, o-MeC6H4NH2
Solution : C 6H5 NH2 C6 H 5NHMe C6H 5NMe2 o-MeC 6H4NH2
pKa = 4.62 pK a = 4.84 pKa = 5.15 pK a = 4.38

AMINES
 QUIZRR 79

The major determinant of basic strength in alkyl substituted anilines remains mesomeric stabilization
of aniline molecule (A) w.r.t. to the cation (B). Where (A) and (B) are
+ +
NH 2 H NH2

(A) (B)

1.4. P
Prr epa
parr ation of Am
Amiines

1.4. 1 Alkylation of Am
Ammmon
oniia

+
R ă X + 2NH 3  R ă NH2 + N H4 X

Ć Ammonia reacts as a nucleophile with alkyl halides to give primary amines in a nucleophilic
substitution reaction.
Ć Yields are often poor as the product, a primary amine, RNH 2, is itself a nucleophile and can
react with more alkyl halide.
Ć The result are mixtures containing primary amines, secondary amines, tertiary amines and
quaternary ammonium salts.

R´CH2X R´CH2 X R´CH2 X + ă

RNH2 RNH(CH2 R´) RN(CH2 R´)2 RN(CH2R´)3X
primary secondary tertiary quaternary

Ć As aryl halides do not undergo simple nucleophilic substitution, they cannot be prepared
using this method.

1.4. 2 Alkylation of Az
Aziide ion and R edu
ducction

A much better method for preparing a primary amine from alkyl halide first to convert the alkyl
halide to an alkyl azide (RN3) by a nucleophilic substitution reaction with sodium azide (NaN 3).
2ă
+ + ă
N N N N N N
Azide ion

ă + ă ă + ă ă
N N N + R·X N N N·R + X
Alkyl azide

The alkyl azide is then reduced to a primary amine with Na/C 2H5OH or LiAlH4.
+ ă Na/C 2H 5OH
R·N N N R · NH 2 + N 2
or LiAlH4

AMINES
 80 QUIZRR
1.4 .3 G abri el P htha
hall imide Sy nt
nthhe sis

Another method used for the preparation of primary aliphatic amines only is the Gabriel
Phthalimide synthesis. Phthalimide (pKa = 9) is quite acidic in nature. It can be converted to
potassium phthalimide by its reaction with KOH. The phthalimide anion is a strong nucleophile.
It reacts with alkyl halide, preferably methyl halide and primary alkyl halide only, by an SN2
mechanism to give Năalkylphthalimide. The secondary and tertiary alkyl halides are not employed
because they undergo elimination reactions also. The Năalkyl phthalimide is hydrolysed with
dilute HCl or KOH solution to give primary aliphatic amine.

O O O
COOK
KOH ă + RăX 2KOH
N·H N K N·R + RNH2
(1Ĉ only)
ăKX
COOK

O O O
Năalkyl phthalimide

Năalkylphthalimide can also be converted to primary amine and phthalazineă1, 4ădione by

treating it with hydrazine.

O
O O

C · NH · NH 2
NH
N · R + NH2 · NH2 + R · NH2
NH
C · NHR
O O
O
Phthalazineă1, 4 ă dione

This method is not suitable for preparing aromatic primary amines as aryl halides are not good
substrates for nucleophilic substitution.

1.4. 4 Reduction of Nitro Com

ompo
po
pouund
ndss

Aliphatic primary amines can be synthesised by reducing nitroalkanes with metal and acid or
with H2 in presence of nickel as a catalyst.
Ni
R · NO 2  3H 2 
 R · NH 2  2H 2O

Sn/HCl
+ Base
R · NO 2   R · N H 3  R · NH 2

For example :

2 H / Ni
O2 N · CH2 CH2 · OH  H2 N · CH2 CH2 · OH
2-nitro ethanol 2-amino ethanol

AMINES
 QUIZRR 81

Primary aromatic amines are also prepared by the reduction of corresponding nitro compounds.

+
NO 2 NH3 NH2

Sn/HCl Base

Other reducing agents such as LiAlH4 and H2 /Pt also reduce nitrobenzene to aniline.

Reduc
ucttion in n eutral me di
diuum

1. With Fe and steam, a nitro group gets reduced to nitroso group.

Fe/steam
C6 H5 · NO2 
 C6 H5 · NO

2. Zn/NH 4Cl H 2O or Zn/CaCl 2/H 2O reduces nitro group to hydroxylamine.

Zn/NH Cl/H O
C6 H5 · NO2 
4 2  C H · NHOH
6 5
50-50C

Re duc
uctt ion in a lkal ine me
medi
di
diuum

Nitro benzene when reduced with Zn/NaOH/C2 H5OH gives hydroazobenzene.

Zn/NaOH/C H OH
2C 6H 5 · NO 2 
2 5 
 C 6H 5 · NH · NH · C 6H 5

By means of aqueous ethanolic NH4HS, aqueous Na2S or SnCl 2 in HCl, nitro groups in a
polynitro compound can be reduced one at a time. For example, m-dinitrobenzene can be reduced
to m-nitroaniline.
NO2 NH 2

+ 3NH4 HS + 3NH 3 + 3S + 2H 2O
NO 2 NO 2
It is not always possible to predict that which nitro group will be reduced first. For instance, 2,
4ădinitrotoluene when treated with NH4HS, the 4ănitro group is reduced whereas treatment with
SnCl2 /HCl results in the reduction of 2ănitro group.
CH3 CH3 CH3

NO2 NO2 NH2

NH 4HS SnCl2/HCl

NH2 NO2 NO2

2,4ădinitrotoluene

AMINES
 82 QUIZRR
1.4. 5 R edu
ducction of ni
nittr iles, isoni
nitt riles & oximes

H2 (g)
R·C N R · CH 2
Pt
NH2

Nitriles are reduced to amines using hydrogen in the presence of a nickel catalyst, although acidic
or alkaline conditions should be avoided to avoid hydrolysis of -CN group. LiAlH 4 is more commonly
employed for the reduction of nitriles on the laboratory scale. Both aliphatic & aromatic amines
can be synthesised by reduction.


C6 H6 · N  C 
H2 / Ni
C6 H5 · NH · CH3
LiAlH4

(2Ĉ amine)

H 3C H3C
Na/C3 H5 OH
C N · OH or LiAlH4
CH · NH2 + H2O

C 2H 3 H5C2
(oxime) (1Ĉ amine)

1.4. 6 Reductive Amination of Carbony

nyll Compou
ounnds

Aldehydes and ketones are converted to amines through catalytic or chemical reduction in the
presence of ammonia or amine. Primary, secondary and tertiary amines can be prepared this
method.

R
NH3
R´ · CH · NH2 (1Ĉ amine)
[H]

R
R
R´´NH2
C=O R´ · CH · NH · R´´ (2Ĉ amine)
[H]
R´

R
R´´
R´NHR´´´
R´ · CH · N (3Ĉ amine)
[H]
R´´´

(R´ may be hydrogen or an alkyl group)

AMINES
 QUIZRR 83

The above process appears to proceed through the following mechanism.

R
R R
ăH2O
C=O + H2N · R´´ R´ · C · NH · R´´ C = N · R´´
(1Ĉ amine)
R R (imine)
OH
unstable 2[H]

R´ · CH · NH · R´´
1.4. 7 Reduc
uctt ion o
off Am
Amii des (2Ĉ amine)

O R

LialH4 + C H C NH2

R NH2
H
Reactions usually in Et2O or THF followed by H 3 O + work-ups.

Ć Amides RCONR´2 , can be reduced to the amine, RCH2 NR´2 by conversion of the C = O to
-CH2 ă
Ć Amides can be reduced by LiAlH4 but not by the less reactive NaBH4.
Ć Typical reagents : LiAlH4/ether solvent, followed by aqueous work-up.
Ć Note that this reaction is different to that of other C = O compounds which reduce to
alcohols.
Ć The nature of the amine obtained depends on the substituents present on the original
amide.

LiAlH 4
CH3 CH2 · N · C · CH3 CH3 CH2 · N · C H2 · CH 3

CH3 CH3 (3Ĉ amine)

LiAlH 4
NH · C · CH 3 NH · CH2 · CH3

(2Ĉ amine)

AMINES
 84 QUIZRR
1.4. 8 Ho
Hoffmann rearrangement

Hofmann rearrangement is the organic reaction of a primary amide to a primary amine with one
fewer carbon atom.

O O
Br2 H2 O
R C R·NH2
NaOH ăCO 2
R NH2 N

The reaction of bromine with sodium hydroxide forms sodium hypobromite in situ, which transforms
the primary amide into an intermediate isocyanate. The intermediate isocyanate is hydrolyzed to
a primary amine giving off carbon dioxide.

The reaction is also sometimes called the Hofmann degradation, and should not be confused with
the Hofmann elimination.

Mechanism :

O O O
Br 2 NaOH
NaOH
R NH 2 R NHBr R N·Br

H
ă
N N OH
ă Br H 2O ăCO2
R C R R·NH 2
O O

Ex
Exaa mpl
plee 3 O

NH2
Br 2
Identify the product : H2 C Product
NaOH
C6H5
Solution :

O
NH2
NH2
Br2
H3 C H3C
NaOH
C 6H5
C6H5

This is a example of Hofmann bromide reaction.

AMINES
 QUIZRR 85

Exa mpl
plee 4

A compound X (C7H7 Br) reacts with KCN to give Y (C 8H 7N). Reduction of Y with LiAlH4
yields Z (C8 H11 N). Z gives carbylamine reaction, reacts with HinsbergÊs reagent in the presence
of aq. KOH to give a clear solution. With NaNO 2 and HCl at 0ĈC (Z) gives a neutral compound
which gives red colour. What are X, Y and Z ?
Solution :

KCN LiAlH4
C7 H7 Br   C8 H7 N  C8 H11 N
-KBr
X  Y  Z 
CH2Br CH2CN CH2 CH2 NH2

KCN LiAlH 4
ăKBr

(X) (Y) (Z)

Ex
Exaa mpl
plee 5

Convert Benzene to benzylamine.

Solution :
Friedel-crafts alkylation, can easily obtain Toluene from benzene. The sequence of reaction is thus

CH 3
CH3 Cl Cl 2 NH3
Cl NH2
AlCl 3 (Anhyd.) hv

Ex
Exaa mpl
plee 6

One mole of each of bromo derivative (A) and NH 3 react to give one mole of an organic
compound (B). (B) reacts with CH3 I to give (C). Both (B) and (C) react with HNO2 to give
compounds (D) and (E), respectively. (D) on oxidation and subsequent decarboxylation
gives 2-methoxy-2-methyl propane. Give structures of (A) to (E) with proper reasoning.
Solution : H3CO H3 CO H3CO
Br NH 2 NH
A B C
CH3
CH3 CH3 CH3
CH3 CH 3 CH3

NO
H 3CO
OH H 3CO
D N
E
CH3 CH3
CH3 CH 3
CH3
AMINES
86 QUIZRR
REACTION
ONSS OF AM
AMIINES

1. 5.1 Hofmann Eli minati on

1. excess CH 3I
H · C · C · NH2 C C + N(CH3) 3 + H2O
2. Ag 2O / H 2O

Ć Like alcohols, amines can undergo elimination reactions.

Ć Quaternary ammonium salts undergo an E2 elimination when heated with silver oxide
Ag2O, in water.
Ć Amines can readily be converted into quaternary ammonium iodides by treating them with
excess methyl iodide.
Ć Ag 2O/H2O reacts giving the quaternary ammonium hydroxide, silver iodide precipitates.

excess Ag 2O
+ AgI
CH3I H 2O ă
NH2 (CH 3) 3NI ă (CH 3) 3NOH

Ć When heated the hydroxide induces a base promoted 1, 2- or -elimination giving an amine
and alkene.
Ć The addition is opposite to that predicted by SaytzeffÊs rule in that it leads to the less highly
substituted alkene.
Ć The less highly substituted alkene is sometimes referred to as the Hofmann product.

+ + N(CH3)3

major minor
heat
ă
(CH3)3 NOH
+
Ć The outcome is dictated by steric effects of the large leaving group and the alkyl chain.

Ć NH 2 and NR2 are very poor leaving groups (both anionic), but NR3 is much better (neutral).

Mechani
nissm of the Hof
ofmmann Elimination

The initial steps are an example of the alkylation of H

an amine by methyl iodide. The mechanism of the
elimination step is shown. CH 3 CH 2 · C · C · H
H2
When heated, the hydroxide removes the more (CH3 )3 N
+
accessible proton, the  bond of the alkene C = C
forms and the leaving group, a neutral amine departs. HO

CH3 CH2 CH = CH2 + H2O + N(CH3)3

AMINES
 QUIZRR 87

1.5 .2 Nucleophilic acyl sub

ubss titut ion

Acyl chlorides and acid anhydrides react with primary and secondary amines in cold to form
amides in the Schotten-Baumann reaction. Tertiary amines cannot be acylated due to the absence
of a replaceable hydrogen atom. With the much less active benzoyl chloride, acylation can still be
performed by the use of excess aqueous alkali to facilitate the reaction.

O O

R 1 · CH 2 + R2 · C R2 · C + H·X

NH 2 X NH · R1

O O O

R1 · CH2 + R2 · C R2 · C + R2 · C

NH 2 O NH · R 1 X

R2 · C
O

Because amines are basic, they neutralize carboxylic acid to form the corresponding ammonium
carboxylate salts. Upon heating to 200ĈC, the primary and secondary amine salts dehydrate to
form the corresponding amides.

R1 O R1 R1 O
+ heat
H · N: + R3 · C · OH H · N · H + R3 · COOă N · C · R 3 + H 2O
dehydration

R2 R2 R2
amine carboxylic substituted-ammonium amide water
acid carboxylate salt

1.5. 3 Ni
Nitt ros
osaation of A
Ammine
ness
+

HNO 2 + R · NH 2 R·N N + 2 H 2O
1Ĉ amine diazoniumion

R R
HNO 2 + NH 2 N·N O + H2O

R R
2Ĉ amine Nănitrosoamine

AMINES
88 QUIZRR
Ć Typical reagents : sodium nitrite and aq. HCl or H2 SO 4 (this mixture yields nitrous acid,
HNO2)
Ć The most useful reactions are probably those of primary aryl amines, Ar-NH 2, which give

aryl diazonium salts, Ar- N +2 which can then be used to prepare substituted benzenes.

Ć The actual nitrosation reagent is the nitrosyl cation, NO+ which is formed in situ :

H
+ + ăH 2O
H H
O·N O H·O·N O H·O·N O N O
+
+
Nitrite anion Nitrous acid Nitrosylcation

Ć The nature of the product depends on the nature of the initial amine
Ć Primary alkyl or aryl amines yield diazonium salts (hence the diazotisation reaction).

H H
+ + +
+ ăH +H
R · N: + :N O: R · N·N O: ăH2O
R·N N:

H
Primary Nitrosyl Diazonium
alkyl amine cation cation

Ć Alkyl diazonium salts are very unstable and yield carbocation-derived products by loss of the
very good leaving group, N2.

+
R·N N: R+ + :N N:

Alkyl Carbocation Nitrogen

diazoniumion

Ć Secondary alkyl or aryl amines yield N-nitrosoamines :

+
+ + ăH
R2 N + N O R2N · N O R2N · N O

H H
Secondary Nitrosyl NăNitrosoamine
alkylamine cation

Ć Tertiary alkyl amines do not react in a useful fashion.

AMINES
 QUIZRR 89

Ć Tertiary aryl amines undergo nitrosation of the ring (an electrophilic aromatic substitution
reaction).

CH3 CH2 CH2 CH3 CH3CH2 CH2 CH3

N N

+
N=O

N
O

Di a zoni u m C om po un d

N N

{phenyldiazonium compound}

Aromatic diazonium chlorides, sulphates, nitrates etc. are reasonably stable in aqueous solution
at room temperature or below but cannot be readily isolated without decomposition. The -orbital
system of benzene ring stabilizes the diazonium cation by resonance.

N N N N N N

N N N N

The diazonium salts are very important synthetic reagents, being the starting point in the preparation
of various aromatic compounds. Their reactions may be divided into two groups, those which

involve the liberation of N 2 gas and the displacement of the diazo group N+2 by another univalent
group and those in which the two N-atoms are retained (coupling reactions).

AMINES
90 QUIZRR
1.5. 4 R
Reeplacement Re
Reaac tion
onss :

H 2O,   C H · OH + N  H+
 6 5 2

H 3PO 2O/ H 2O   C H  N + H PO  H +
 6 6 2 3 3

CuCl/ HCl, 
 C6 H5 Cl + N2  H + 
 Sandmeyer
CuBr/HCl,    reaction
  C6 H5 Br + N2  H 

KI, 
 C6 H5 · I + N2  K +


+ 4   C H N + BF  
HBF ,
 
 C6 H5 F  N2  BF3  Baltz Scheimann reaction
C6 H5 · N  N 6 5 2 4

Cu/KCN
  C6H 5 · CN + N 2  K +


NaNO2/ Cu
  C6 H5 · NO2  N2  Na+


C6H6/NaOH
  C6 H5 · C6 H5 + N2  H2 O


1.5. 5 Azo coupl

pliing

An azo coupling is an organic reaction between a diazonium compound and an aniline, phenol
or other aromatic compound which produces an azo compound. In this reaction the diazonium
salts is an electrophile and the activated arene is a nucleophile in an electrophilic aromatic
substitution. In most cases, including the example below, the diazodium compound is also aromatic.

OH
N N OH N
N
H
ăHCl

N N OH

(coupling)

AMINES
 QUIZRR 91

Azo couplings are important in the production of dyes and pH indicators such as methyl red.
Coupling with benzene substrates occurs preferentially in the para position to the hydroxyl group.
But if this position is blocked, then the coupling occurs at the ortho position.

OH

OH
C 6H 5 · N N + ă
OH
C6H5 · N N

CH3

CH3

Example : 1 and 2 naphthols in alkaline soln. couple with diazonium salt in the 4 and 1-position
respectively.

N N · C 6H 5 OH

OH
2 ă naphthol +
ă 1 ă naphthol
ă C 6H 5 N 2Cl
+OH +OHă

N N · C6H5

Note : With aromatic amines, there is the possibility of attack on either nitrogen or carbon. In
the case of primary amines, the attack of diazonium ion mainly takes place at the nitrogen
forming diazo-amino compound (A).
H
+ +
C6H5 · N N + H 2N C6 H5 · N N ·N

H
+
ăH

C 6H 5 · N N · NH

In secondary amines two products will be formed.

NH · CH3 PhN N · N · CH3 NH · CH 3

+
C6H6N 2 + +

N N · C6 H5
AMINES
92 QUIZRR
1.5. 6 Oxidat
atiion React ions

Both the primary and secondary amines undergo oxidation. The oxidation products obtained
depend on the oxidising agent used and on the nature of alkyl group.

Primary amines :
(i) With KMnO4 :

O  H 2O
   R · CH = NH 
R · CH2 · NH2   R · CHO + NH3
Aldimine

 O
H2 O  R C = O + NH
   R C = NH 
R 2CH · NH 2  2 2 3
Ketimine

(ii) With CaroÊs acid (H2 SO5)/H 2O2/Peroxy carboxylic acid :

OH
 O  O  O |
 
   
  

R · CH2 · NH2 R · CH2 · NHOH R · CH = N · OH R · C = N · OH
N-alkyl
H2O Aldoxime Hydroxamic
hydroxylamine acid

 O  O
   R CH · NHOH 
R 2CH · NH 2     R C  N · OH
2  H2 O 2
Ketoxime

Secondary amines :
(i) With KMnO4 :

R R
[O]
2R2NH N·N
ăH 2O
R R
Tetraalkyl hydrazine

(ii) With CaroÊs acid (H2 SO5)/H 2O2/Peroxy carboxylic acid :

R
[O]
R 2NH N · OH
R
N,Nădialkyl hydroxylamine

AMINES
 QUIZRR 93

Tertiary amines

  O  
 
(i) With H2O2/Peroxy carboxylic acid  R 3N  R 3 N · O 
 

 
Tertiary amines are oxidised to amine oxide, R N · O (a dipolar ion or Zwitterion).
3

1.5. 7 Reactions of Quaternary Ammo

moni
ni
niuum Salts

(1) Formation of 4Ĉ Ammonium Hydroxides

2R4N+Xă + Ag2 O + H2O  2R 4N + OHă + 2AgX

very strong
bases like NaOH

(2) Hofmann Elimination of Quaternary Ammonium Hydroxides

When a quaternary ammonium hydroxide is heated strongly it decomposes to yield water,
a tertiary amine and alkene.

[CH3 )3 NCH(CH 3)CH 2CH3 ] + OH ă  (CH3 )3N + H2C = CHCH 2CH 3 + H 2O
s-Butyltrimethylammonium hydroxide 1-Butene

This E 2 elimination gives the less substituted alkene (Hofmann product) rather than the
more substituted alkene (Saytzeff product).

Ex
Exaa mpl
plee 7

Identify the end product (C).

CH3

CH 3I moist 
  
 A 
  B 
C
excess Ag 2 O
N

H
Solution :
CH3 CH3 CH3 CH3 CH 3
H
2CH3 I Ag 2O/H 2O  CH3I

+ + ă +
N N Iă N OH N N Iă

H3C CH3 H3 C CH 3 H3C CH3 H3 C CH3

H H 3C

AMINES
 94 QUIZRR
CH3 CH3
H
Ag2O/H2O 
+
N
H3C CH3
H 3C

1.5. 8 R
Riing Re
Reaaction
onss of Ar
Arom
om
omaatic A
Ammine
ness

NH2 , ă NHR and ă NR 2 strongly activate the benzene ring towards electrophilic substitution.
(1) Halogenation
For monohalogenation, ă NH 2 is first acetylated, because

CH3 · C · N ·
|| |
O H

is only moderately activating

NH2 NH 2 NHCOCH3 NHCOCH3 NH2

Br Br
Br 2 Ac2O Br 2 H 2O
ă
H2 O OH

Br Acetanilide Br Br

(2) Sulfonation
+
NH3 +HSO 4
ă
NH2 NHSO3 H NH3

H2SO4 180Ĉ C 180Ĉ C

H2O 3 hours
ă
Anilinium Sulfamic SO3
Sulfate acid Sulfanilic acid
a dipolar ion
(3) Nitration
O O

NH 2 NH · C · CH3 NH · C · CH3 NH 2
ă
(CH3CO) 2O HNO 3.H 2SO 4 OH
heat
Aniline Acetanilide NO2 NO 2
p-Nitroacetanilide p-Nitroaniline

To prevent oxidation by HNO3 and meta substitution of C 6H 5NH3+ , amines are first
acetylated.

AMINES
 QUIZRR 95

1.5. 9. Rearr ang

ngee me
ment
nt React ion
onss

A remarkable property of monoă, diă, and trialkyl anilinium chlorides (or bromides) is their ability
to undergo rearrangement on strong heating, an alkyl group migrating from the Năatom and
entering preferentially the păposition. If this position is occupied, then the alkyl group migrates
to the oăposition. For example, when trimethyl anilinium chloride is heated under pressure, the
following rearrangement takes place.

+
ă
(1) N(CH 3) 3Cl N(CH 3) 2.HCl NH(CH3).HCl NH 2.HCl

CH3 H3 C CH3
300Ĉ C  

CH3 CH3 CH3

This reaction is known as the HofmannăMartius rearrangement.

(2) Rearrangements of this kind have been observed to take place with aniline derivatives of
the type C6 H5 ă NH ă Z where Z is R, X, NH 2, OH, NO or NO2 . For example,

R · N · NO NHR NHR

+ HCl + NOCl + HCl

NO

This reaction is called FischerăHepp rearrangement.

NH2 · NH2.HCl NH2 .HCl

250ĈC

NH 2

(3) Benzidine Rearrangement

Hydroazobenzene, C6H5NH ă NHC6H 5 undergoes rearrangement when heated in the presence
of acid to yield benzidine (4, 4´ădiamino diphenyl).

AMINES
96 QUIZRR
NH · NH
NH2
+
H
NH2 NH2 + NH2

4,4'ădiaminodiphenyl 2,4'ădiaminodiphenyl

This is known as benzidine rearrangement. The p, p´ăisomer is the major product (70%) and the
rest is o, p´ and o, o´ăisomer. The reaction probably follows the given mechanism.

+ +
NH · NH NH2 NH2 NH 2 NH2

HH
+
ă2H

+ + (o,o'ăisomer)
2H
+ +
+ +
NH2 NH2
NH 2 · NH 2

+
ă2H
NH2 NH 2

H H (p, p'ăisomer)

+
+
NH2 NH2
+ +
H ă2H
NH 2 NH2
H

(o, p'ăisomer)

1.5. 10 R
Ree action with D
Diiethyl Oxalate

1Ĉ, 2Ĉ and 3Ĉ amines can be distinguished by their reaction with diethyl oxalate. Primary (1Ĉ)
amines react with diethyl oxalate forming N, Năoxamide, which is a solid.

COOC2 H5 HăNHăR CONHR

+ + 2C2 H5 OH
COOC2 H5 HăNHăR CONHR
N, N´ădialkyl
oxamide (solid)

AMINES
 QUIZRR 97

Secondary (2Ĉ ) amines react with diethyl oxalate forming oxamic ester, which is a liquid.

COOC2 H5 CONHR2
+ HNR2 + C2 H5 OH
COOC2 H5 COOC2H5
oxamic ester
(liquid)

Tertiary (3Ĉ) amines do not react with diethyl oxalate.

Test fo
forr Am
Amii ne
ness

(1) Hinsberg Test : This reaction is used for the separation of amines from a mixture. The
mixture containing primary, secondary and tertiary amines is treated with an aromatic
sulphonyl chloride.

O
1Ĉ amine (RNH 2)
p ă CH 3 ă C 6 H 4 ă S ă NHR

O
O NaOH O
+
P ă CH3 ă C6 H6 ă S ă Cl p ă CH3 ă C6 H4 ă S ă N ă R K
2Ĉ a
min
O e (R O
2N H)
O

3Ĉ amine (R3 N) p ă CH3 ă C6 H4 ă S ă NR2

O
KOH

No reaction No reaction

(2) Carbylamine Reaction : This is a chemical test for the detection of primary amines. Both
aliphatic and aromatic primary amines when heated with chloroform and ethanolic KOH
form isocyanide, also called carbylamine, a foul smelling compound.

R ă NH2 + CHCl3 + 3KOH RăN C + 3KCL + H2O

or or
Ar ă NH 2 Ar ă N C

AMINES
 98 QUIZRR
Mechanism :
OH
CHCl3 ă : CCl 2
ăCl
ăH 2O
H Cl
.. + ă
R · NH2 + : CCl2 R·N·C

H Cl

ă HCl

+ ă
ăHCl H Cl
R·N C
+
ă
R·N C

Exa mpl
plee 8

How will you bring about the following conversion ? Aniline  Benzylamine
Solution :
ă
NH2 N2Cl

CH 3
CH 3Cl Cl 2 Cl NH NH 2
NaNO2 + HCl H3 PO4 2
0ă5Ĉ C  AlCl 3(Anhyd) h

Ex
Exaa mpl
plee 9

Convert :
Cl Cl

Br
NH 2

Cl Cl

Solution :
Cl Cl Cl Cl Cl
COOH Br
NH2 OH
HNO2 [O]  Br2 /Fe
ăCO2

Cl Cl Cl Cl Cl

AMINES
 QUIZRR 99

Exa mpl
plee 10

CH3 OH
NH
+
H 3C CH3
H
O + CH3 NH2
O

O
Predict the mechanism of above conversion.
Solution :
CH 3 CH3

ă
O O ă
+ CH3NH ă H + + CH3 NH
H +

O O
+
H
CH3
NH

H 3C OH

Ex
Exaa mpl
plee 11

Bring out the following conversion.

O

NH 2

Solution :
O
CH3
H
O ă
NH2 1)NaNO2/HCl O 3/zn/H 2O OH
O

CH3

AMINES
100 QUIZRR
Exa mpl
plee 12
Amphetamine is a liquid that is nearly insoluble in water, but quite soluble in aqueous
acid. It can be resolved into enantiomers and liberates nitrogen spontaneously when reacted
with nitrous acid. When amphetamine is quarternised with CH 3I, heated with Ag 2O and
heated, 3ăphenylă1ăpropene is the major product. Deduce the structure of amphetamine.
Solution : +
H2 N (H3C)3N
CH3 CH3

H H

CH3I

Amphetamine Quaternary salt

( chiral carbon)
Ag2O
+
HNO2/H
ă N2 H

HO CH2
CH3

H + (CH3)3N

3 - Phenyl propene

1 - Phenyl 2 - propanol

Ex
Exaa mpl
plee 13

NaNO 2 /HCl
C5 H13 N 
  
 N2
 Y  other products . (X) is optically active. Identify the
 X 3 alcohol

structure of (X) and (Y). Explain the formation of (Y) from (X). Will (Y) also be optically
active ? Justify your answer. Draw the structure of important intermediates, if any.
Solution :

CH 3 CH 3 CH 3 CH 3 CH3 CH3 CH3

+ ă
CH3·CH·CH·NH2 .
(Optically active)
NaNO 2/HCl
CH 3·CH·CH·N N
·N2
CH3·CH·CH
+
·H
CH3 ·C·CH2 CH3
+
3Ĉ carbocation
(X) 2Ĉ carbocation
+
ă H2 O/·H
ăH
CH 3 CH3 CH 3 CH 3
+
NaNO2 ·N2
CH3CH2·CH·CH2NH2 CH3CH2·CH·CH2·N N CH3 ·CH2 ·CH ·CH2 CH3·C·CH2CH3
HCl +
1Ĉ carbocation
OH (Y)
Optically inactive

AMINES
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