AMINES

Nitrogen Containing Compounds

Amines:-

H
RN

RN
H

RN
H

(1 - amine) (primary amine) (2 - amine) (Secondary amine)

(3- amine) (Tertiary amine)

Methods of preparation
(1)
Hoffmann ammonolysis method

R
RI R N H
RI R N R
RI RNR I
RI + NH3 RNH2

Not a good method of prepare primary amines

(2)

Gabriel phthalimide reaction

O

KOH
NH

O
C

C2H5 X

:N: K+

C
NR

O
O

H2O

COH
+RNH2
COH
O
Very good method to generate primary amines
(3)

Reduction of nitrocompounds

O
RN

(4)

Sn/HCl - - - - - - -
Zn/HCl
O H or
2 /Ni
LiA/H4

Reduction of cyanides

H/Ni
2

RCN

Na / EtOH
(5)

Reduction of amides

O
R

LiA /H

4
NH2

(6)

Reduction of oximes
H2 /Ni
R CH = NOH

LiA /H4

(7)

Hoffmann Bromamide Reaction

O
R

Br /KOH

2
NH2

(8)

RMgX + ClNH2

(9)

H
O
R N
H
C+ H

O
Hinsberg Test:-

S Cl (Hinsberg Reagant)
O
O
NaOH - - - - - - SCl + RNH2 - - - - - - - -

1.

O
Primary amines forms sulphonamide; which is soluble in NaOH.

O
NaOH
(Insoluble)
SCl + RNH - - - - - - - -
R
O

2.

(Teitiary amines do not react)

Chemical Properties of amines
1.
Basic Nature
Na - - - - - - - 2.
R NH
2

3.

4.
1.

CHCl3
R NH2
- - - - - - - - (foulsmell) [Carbyl amine reaction]
KOH

Libermanns Nitroso Test

HONO - - - - - - - R NH
2

2.

HONO - - - - - - - - [yellow oily liquids insoluble in H O]

RNH
2

R
3.

HONO - - - - - - - RNR

5.

Hoffmann Mustard oil Reaction

..
R NH2 + CS2 + HgCl2 - - - - - - - -

H
HgCl

2
- - - - - - - R N:+ S = C = S - - - - - - - -

H
6.

Reactions with Carbonyl Compounds

R NH2

R NR

imines - - - - - - - enamines
--------

H
RNR

No. Reaction - - - - - - - -