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Question

Reaction for the preparation of 10 amine is:

A
Hinsberg reaction
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B
Hoffman mustard oil reaction
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C
Hoffman bromamide reaction
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D
Liberman nitroso reaction
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Solution

The correct option is C Hoffman bromamide reaction
  1. Hinsberg reaction is a test which involves the reaction of amines with benzene sulphonyl chloride and is used to distinguish between primary, secondary and tertiary amines on the basis of sulphonamide formation. Primary amines on reaction with benzene sulphonyl chloride form sulphonamide which is soluble in aqueous NaOH, while secondary amines form sulphonamides insoluble in aqueous NaOH. On the other hand, tertiary amines do not form sulphonamides at all.
  2. Hoffmann Mustard oil test is used to detect primary, secondary and tertiary amines. In this reaction amines are reacted with a mixture of alcoholic CS2 and excess of HgCl2. Primary amines react with this mixture to form isothiocyanates having a pungent smell like that of mustard oil. Secondary amines react with CS2 to form dithiocarbamic acids, but they do not react with HgCl2. While tertiary amines do not react with either of them.
  3. Hoffmann bromamide reaction is used for the preparation of primary amines. Primary amides are reacted with bromine (Br2) in a solution of NaOH and forms primary amine with one carbon less than the reacting amide. Only amides having unsubstituted N (primary amides, C||ONH2) undergo Hoffmann bromamide reaction. RC||ONH2 undergo deprotonation in the presence of a base and the anion reacts with bromine to form bromoamide, which again undergoes deprotonation to form bromoamide anion. This anion rearranges to form a bond between the alkyl group and the N-atom with the elimination of bromide ion leading to the formation of isocyanate (RN=C=O). Isocyanate undergoes hydrolysis and decarboxylation to form primary amine (RNH2). Secondary and tertiary amides do not give this reaction.
  4. Liberman nitroso reaction is a test used for the detection of secondary amines. Secondary amines react with nitrous acid to form N-nitroso amine.

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