Ch 9.
Amines
Named Reactions
Ammonolysis
Sandmeyer Reaction
Gattermann Reaction
Gabriel phthalimide synthesis
Hoffmann bromamide degradation reaction
Carbylamine reaction
Hinsberg’s Test
Coupling Reactions
1. Ammonolysis
An alkyl or benzyl halide on reaction with an ethanolic solution of
ammonia undergoes nucleophilic substitution reaction in which the halogen
atom is replaced by an amino (–NH2) group. This process of cleavage of the C–
X bond by ammonia molecule is known as ammonolysis. The reaction is carried
out in a sealed tube at 373 K. The primary amine thus obtained behaves as a
nucleophile and can further react with alkyl halide to form secondary and
tertiary amines, and finally quaternary ammonium salt.
2. Sandmeyer Reaction:
The Sandmeyer reaction is a chemical reaction which is used to
synthesize aryl halides from aryl diazonium salts. This reaction is a
method for substitution of an aromatic amino group by preparing
diazonium salt, that is followed by its displacement and copper salts often
catalyze it.
The Br, Cl and CN– nucleophiles can be easily present in the benzene
ring of benzene diazonium salt in the presence of Copper ion.
3. Gattermann Reaction:
Bromine and Chlorine can be substituted in the benzene ring by preparing
the benzene diazonium salt solution with similar halogen acid present
with copper powder. This is the Gattermann Reaction.
4. Gabriel phthalimide synthesis:
Phthalimide prepared with ethanolic potassium hydroxide produces
potassium salt of phthalimide when heated with alkyl halide followed by
alkaline hydrolysis forms the corresponding primary amine.
5. Hoffmann bromamide degradation reaction:
An amide with bromine in an aqueous solution of sodium hydroxide
produces primary amines. Migration of an alkyl or aryl group takes place
from carbonyl carbon of the amide to the nitrogen atom. The amine so
produced include one carbon less than that present in the amide.
5.
5. Carbylamine reaction:
Aliphatic and aromatic primary amines when heated with chloroform and
ethanolic potassium hydroxide produces isocyanides or carbyl amines
which are foul smelling substances.
6. Hinsberg’s Test:
Benzenesulfonyl chloride (C6H5SO2Cl) reacts with primary and
secondary amines to produce sulphonamides.
a. The reaction of benzene-sulfonyl chloride with primary amine
yields N-ethyl benzene-sulfonyl amide. The hydrogen attached to
the nitrogen in sulphonamide is strongly acidic due to the presence
of strong electron withdrawing sulfonyl group. Hence, it is soluble
in
alkali.
b. In the reaction with a secondary amine, N, N-diethyl-
benzenesulfonamide is formed. Since N, N- diethyl benzene
sulphonamide does not contain any hydrogen atom attached to a
nitrogen atom, it is not acidic and hence insoluble in alkali.
c. Tertiary amines do not react with benzene-sulfonyl chloride.
7. Coupling Reactions:
Benzene diazonium chloride gets reacted with phenol in which the phenol
molecule at its para position is mixed with the diazonium salt to give p-
hydroxyazobenzene.