Example 9.4

Example . S Cl + H S + H Cl N,N-Diethylbenzenesulphonamide . Carbylamine reaction Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium hydroxide form isocyanides or carbylamines which are foul smelling substances. Secondary and tertiary amines do not show this reaction. This reaction is known as carbylamine reaction or isocyanide test and is used as a test for primary amines. . Reaction with nitrous acid Three classes of amines react differently with nitrous acid which is prepared in situ from a mineral acid and sodium nitrite. (a) Primary aliphatic amines react with nitrous acid to form aliphatic diazonium salts which being unstable, liberate nitrogen gas quantitatively and alcohols. Quantitative evolution of nitrogen is used in estimation of amino acids and proteins. (b) Aromatic amines react with nitrous acid at low temperatures ( - K) to form diazonium salts, a very important class of compounds used for synthesis of a variety of aromatic compounds discussed in Section . . Secondary and tertiary amines react with nitrous acid in a different manner. . Reaction with arylsulphonyl chloride Benzenesulphonyl chloride (C H SO Cl), which is also known as Hinsberg’s reagent, reacts with primary and secondary amines to form sulphonamides. (a) The reaction of benzenesulphonyl chloride with primary amine yields N-ethylbenzenesulphonyl amide. The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of strong electron withdrawing sulphonyl group. Hence, it is soluble in alkali. (b) In the reaction with secondary amine, N,N-diethyl- benzenesulphonamide is formed. Since N, N-diethylbenzene sulphonamide does not contain any hydrogen atom attached to nitrogen atom, it is not acidic and hence insoluble in alkali. (c) Tertiary amines do not react with benzenesulphonyl chloride. This property of amines reacting with benzenesulphonyl chloride in a different manner is used for the distinction of primary, secondary and tertiary amines and also for the separation of a mixture of amines. However, these days benzenesulphonyl chloride is replaced by p -toluenesulphonyl chloride. . Electrophilic substitution You have read earlier that aniline is a resonance hybrid of five structures. Where do you find