ZOOM INTERNATIONAL SCHOOL

( Senior Secondary : Affiliated to CBSE, Delhi )

Study MaterialsAugust
Study Materials July 2020-21
2022-23

XII
Class : ……………. Chemistry
Subject : ………………………..

AMINES
All amines and R3H (3o) have one unshared pair of electrons on nitrogen
atom due to which they behave as lewis bases.

N
H R
H
(1) Preparation of Amines –
(i) Reduction of Nitro Compounds – Nitro Compounds are reduced by Paning hydrogen gas
in the presence of Ni, Pdor Pt or by metal in HCl.
2
NO
NH2
H 2 / Pd

E th a n o l

Sn / H Cl

(ii) Ammonolysis of alkylhalides – Alkyl or benzyl halides reacts with NH3 and given amine.
amines)
R–X
1 amine
(iii) Reduction of Nitrites – Nitriles ( on Reduction with LiAIH4 or Catalytic
hydrogenation produce primary amines.

(iv) Reduction of amides – Amides on reaction with LiAIH4 gives amines.

(v) Gabriel Phthalimide Synthesis –

Phthalimide

This method is used to prepare 1o-amine.

(vi) Hoffmann Broamide Degradation – It is a method to prepare 1o amine.
Reaction of amide with bramine in aqueous solution of NaOH.

1
 1o-amine.
(2) Basic Character of amines:
(i) In aqueous solution the basicity of methyl amines follow the order
(CH3)2 NH > CH3 NH2 > (CH3)3 N (2o > 1o > 3o)
(ii) For all higher amines the order is
R2NH > R3N > RNH2 (2o > 3o > 1o)
(iii) In gas phase the order of basicity is 3o > 2o > 1o
(iv) Aryl amines are less basic than aliphatic amines.
(3) Chemical reaction of amines:
(i) Acylation – Aliphatic and aromatic 1o and 2o amines react with acid chloride, anhydride
and ester to give acyl product.
O
||
C2H5 – N – H + CH3 – C – Cl C2H5 – N – C – CH3
| | ||
H H O

..
C6H5 – N – H + CH3 – C – O – C – CH3 NHCOCH3
| || || |
H O O

Acetanilide
(ii) Carbylamine reaction – Aliphatic and aromatic primary amines on heating with CHCl3 and
thanolic KOH gives isocyanides.

isocyanide
(iii) Reaction with nitrous acid – Primary amines react with nitrous acid to give alcoho.

unstable
(iv) Hinsberg’s reaction (with arylsulphonic choride) – Benzene sulphonyl chloride
(H6H5SO2Cl) reacts with 1o & 2o amines to form sulphonamides.
O O
|| ||
S Cl + H N C 2H 5 S N C 2H 5
|| | || |
O H O H
O O
|| ||
S Cl + H N C 2H 5 S N C 2H 5
|| | || |
O C 2H 5 O C 2H 5

(v) Bromination – Aniline reacts with Br2/water to give 2, 4, 6 – tribromoaniline.

NH2 NH2
| Br | Br
+ 3 B r2
|
Br 2, 4, 6 – Triomoaniline.
2
  Formation of p-bromoaniline.
O
||
NH2 H N C CH3 H N CHCH3
| | |
( C H 3 C O ) 2O B r 2 / C H 3C O O H
P y rid in e
OH

NH2
|

Br
(vi) Nitration – Reagent HNO3, H2SO4
NH2 NH2 NH2 NH2
| | | |
H N O 3, H 2S O 4 NO2
+ +
NO2
NO2
(vii) Sulphonation
+ +
NH2 N H 3 H SO 4 NH2 NH3
| | | |
H 2S O 4 (4 5 3 - 4 7 3 ) K

S O 3H So3
Z w itte r io n

DIAZONIUM SALTS
Diazonium salts have the general formula , where R stands for aryl group and X stands for
etc.
(1) Preparation of Benzenediazonium chloride – It is prepared by the reaction of aniline with
nitrous acid at (273 – 278) K. This conversion of aromatic amines into diazonium salt is called
diazotisation.

(2) Chemical reaction:

(i) Replacement by halide or cyanide ion (sand meyer reaction)
ions can be interoduced in benzene ring in presence Cu(I) ion.

and can also be introduced in benzene ring by using

+
N 2C l Cl

Cu / HCl
(Gatterman reaction)
(ii) Replacement by ion:

3
 +
N 2C l I

KI + KCl + N2

(iii) Replacement by ion:

+
N 2C l +
N 2B F 4 F

+ BH F4

Diazonium Fluroborate
(iv) Replacement by Hydeogen (H):
+
N 2C l

H 2O
+ H 3P O 2 + N 2 + H 3P O 3 + H C l

benzene

+
N 2C l

+ C H 3C H 2O H + C H 3C H O + N 2
+ HCl

(v) Replacement by hydroxyl group –

te m p e r a tu r e - 2 8 3 K
+
N 2C l OH

283 K
+ H 2O + N2 + HCl

(vi) Replacement by – NO2 group – When diazonium thuoroborate is heated with aqueous
NaNO2 solution in Presence of Cu, the diazonium group replaced by – NO2 group.
+ +
N 2C l N 2B F 4 NO2

N aN O 2
+ HBF4
C u,
(vii) Coupling reactions – The azo products obtained have an extended conjugated system
having both aramatic rings joined through – N = N – bond.
+ OH
N NCl + H OH N = N OH

+ C l + H 2O

P -h y d ro x y a z o b e n z e n e
(o ra n g e d y e )
+
+ H
N NCl + H NH2 N = N NH2

P - a m in o a z o b e n z e n e

+ C l + H 2O
Q. Convert 4-nitrotoluene 2-bromobenzoic acid?

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