Beruflich Dokumente
Kultur Dokumente
Ms.Sayyed Mohsina
CONTENTS
➢ A: REACTIONS OF –NH2 GROUP
1. 1.Salt Formation
2. Acylation
3. Sulphonylation
4. Alkylation and Arylation
5. Reaction with Nitrous acid
6. Oxidation
7. Reaction with Aldehyde
8. Carbylamine Reaction
9. Reaction with Carbon Disulphide
10. Reaction with Grignard Reagent
➢ B: REACTIONS INVOLVING THE BENZENE RING
1. Bromination
2. Nitration
3. Sulphonation
4. Hofmann-Martius Rearrangement
A: REACTIONS OF –NH2 GROUP
1.Salt Formation
As aromatic amines are weaker bases than ammonia or aliphatic amines, they form
well-defined crystalline salts on reaction with strong mineral acids as HCl or H2SO4.
2.Acylation
The primary and secondary aromatic amines react with aryl chlorides or anhydrides,
the hydrogen atom attached to N-atom is replaced by acyl group (Acylation).
3.Sulphonylation
The arylation of aniline can be carried more readily by heating together, under
pressure, aniline and anilinium chloride at about 140°C
5. Reaction with Nitrous acid
Aromatic amines react with nitrous acid (NaNO2 + HCl) and the nature of the
reaction depends on whether the amine is primary, secondary or tertiary.
Aromatic amines are readily oxidised. They undergo slow aerial oxidation on storage
and become dark in colour. Thus freshly distilled aniline is colourless but soon turns
yellow and then dark red on exposure to the air.Vigorous oxidation of primary
aromatic amines with pot. dichromate and sulphuric acid results in the formation of
quinones.
7.Reaction with Aldehydes
Primary aromatic amines react with aldehydes, giving condensation products. Thus
when aniline reacts with an aldehyde on warming to give Schiff's bases. These
products are most stable when the aldehyde is an aromatic one e.g., benzaldehyde.
The Schiff's base obtained from aromatic amines and aromatic aldehydes are
crystalline solids, often useful for the identification of either the amine or the
aldehyde.
8.Carbylamine Reaction
Primary aromatic amines react with chloroform and ethanolic potash, to form
Carbylamines (isocyanides or isonitriles). These have very disagreeable odour. The
reaction is used as a test for the detection of amides and for chloroform.
9. Reaction with Carbon Disulphide
Aniline does not react with carbon disulphide at room temperature. When aniline
and carbon disulphide are heated together, thiocarbanilide (diphenylthiourea) and
H2S are obtained.
(10) Reaction with Grignard Reagents
Primary and secondary aromatic amines react with Grignard reagents to form
hydrocarbons.
B:Reactions Involving Benzene Ring
1. Bromination