AMINES
SYMBOL OF EXCELLENCE
PREPARATION OF AMINES: CHEMICAL RXN OF AMINES:
Reduction of nitro compounds Basic character of amines
r
Catalyst : (i) H2 /P d + ethanol
i
(ii) Sn + HCl
S
Alkylation
(iii) Fe + HCl
j i
Ammonolysis of alkyl halides Acylation
D
Carbylamine reaction
Reduction of nitriles
A Reaction with nitrous acid
(a) Primary aliphatic amines
Reduction of amides
(b) Aromatic amines
Gabriel phthalimide synthesis Reaction with arylsulphonyl chloride
Aromatic primary amines cannot be prepared by this method because aryl halides
do not undergo nucleophilic substitution Benzenesulphonyl chloride (C H SO Cl), which is also known as
with the anionformed by phthalimide 6 5 2
Hinsberg’s reagent, reacts with primary and secondary amines to
form sulphonamides.
. Electrophilic substitution
(a) Bromination:
Ho mann bromamide degradation reaction
The amine so formed contains one carbon less than that present in the amide.
R − CONH2 + Br2 + 4NaOH → R − NH2 + Na 2CO3 + 2Na Br + 2H2O
(b) Nitration:
(c) Sulphonation:
ff
PREPARATION OF DIAZONIUM Salts:
The conversion of primary aromatic amines into diazonium salts is known as diazotisation.
C6H5NH2 + NaNO2 + 2HCl ⎯273-278K⎯⎯⎯⎯→ C6H5 N2 Cl+ NaCl + 2H2O
CHEMICAL RXN OF DIAZONIUM Salts:
i S i r
D j
A
[A] Reactions involving displacement of nitrogen
1. Replacement by halide or cyanide ion:
(a) Sandmeyer reaction (b) Gatterman reaction.
2. Replacement by iodide ion: 3. Replacement by uoride ion:
4. Replacement by H: 5. Replacement by hydroxyl group
6. Replacement by –NO2 group:
[B] Reactions involving retention of diazo group
coupling reactions
The azo products obtained have an extended conjugate system having both the aromatic rings joined
through the –N=N– bond. These compounds are often coloured and are used as dyes.
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