Methods of

preparation of
aromatic amines
Prepared by
Ms.M.Sayyed
 CONTENTS
I • Method of Preparation of Monoamines
1. REDUCTION OF NITRO COMPOUNDS

2. AMMONOLYSIS OF ARYL HALIDES

3.AMMONOLYSIS OF PHENOLS

4.DEGRADATION OF AMIDES

(HOFMANN REARRANGEMENT)

5.REDUCTION OF AZO COMPOUNDS

II • Method of Preparation of Seconary And Tertiary Amines

1. ALKYLATION OF 1° AND 2° AROMATIC AMINES

2.REDUCTION OF ANILIDES

3.REDUCTIVE AMINATION
1. REDUCTION OF NITRO COMPOUNDS

Monoamines are prepared by the reduction of corresponding nitro

compounds. This reduction may bee carried with metal and mineral acid
e.g tin, zinc or iron, and HCl or H2SO4.
2. AMMONOLYSIS OF ARYL HALIDES

Aryl halides react with ammonia in the presence of a catalyst (copper

salts) at high temperature and under high pressure to form the
corresponding amino compounds.
3.AMMONOLYSIS OF PHENOLS

Phenols react with ammonia in the presence of zinc chloride

at about 300 oC to form the corresponding amines.
4.DEGRADATION OF AMIDES
(HOFMANN REARRANGEMENT)

Primary aromatic amine can be obtained by the degradation of aryl

amides with bromine or chlorine in alkaline solution.
5.REDUCTION OF AZO COMPOUNDS

The reduction of azo compounds by the way of hydrazo compounds

yields primary aromatic amines.
6.ACTION OF HYDROXYLAMINE WITH HYDROCARBONS

Aromatic hydrocarbons react directly with hydroxylamine in the

presence of a catalyst (FeCl2, AlCl3) to give monoamines.
1. ALKYLATION OF 1° AND 2° AROMATIC AMINES

Primary and secondary aromatic amines on reaction with alkyl halide,

give secondary and tertiary aromatic amines.
2.REDUCTION OF ANILIDES

When anilides are reduced with LiAlH4, secondary and tertiary

aromatic amines are formed.
3.REDUCTIVE AMINATION

Aldehydes and ketones react with primary or secondary aromatic

amines in the presence of a reducing agent to form secondary or tertiary
aromatic amines.