Chemistry Answer the following in brief.

(1) Aniline into p-nitroaniline

(2) Aniline into sulphanilic acid.

This reaction is useful for the distinction of primary, secondary and tertiary amines.

(i) Primary amine (like ethyl amine) is treated with Hinsberg’s reagent (benzene sulphonyl chloride) forms N-alkyl benzene sulphonamide which dissolve in aqueous KOH solution to form a clear solution of potassium salt and upon acidification gives insoluble N-alkyl benzene sulphonamide.

(ii) Secondary amine like diethyl amine is treated with benzene sulphonyl chloride forms N,N-diethyl benzene which sulphonyl amide remains insoluble in aqueous KOH and does not dissolve in acid.

(iii) Tertiary amine like triethyl amine does not react with benzene sulphonyl chloride and remains insoluble in KOH, however it dissolves in dil. HCl to give a clear solution due to formation of ammonium salt.

a. Ethanamine from acetonitrile :

b. Ethanamine from nitroethane :

c. Ethanamine from Propionamide :

(a)
(b)

(1) Methanamine into ethanamine

(2) Aniline into p-bromo aniline

Aliphatic or aromatic primary amines on heating with chloroform and alcoholic potassium hydroxide solution form carbyl amines or isocyanides with extremely unpleasant smell. This reaction is a test for primary amines.

Secondary and tertiary amines do not give this test.

Phthalimide is reacted with alcoholic KOH to form potassium phthalimide. Further potassium phthalimide is treated with an ethyl iodide. The product N-ethylphthalimide is hydrolysed with aq NaOH to form ethyl amine. This reaction is known Gabriel phthalimide synthesis.

Aryl amines react with nitrous acid in cold condition (273 – 278 K) forms arene diazonium salts. The conversion of primary aromatic amine into diazonium salts is called diazotisation.

Diazotisation of aniline :

Arene diazonium salt on treatment with mild reducing agents like phosphinic acid (hypophosphoric acid) or ethanol, arene is obtained.

The reaction of amines with acetyl chloride is called acetylation of amines.

(1) Acetyl chloride on reaction with ethylamine forms monoacetyl derivative, N-ethylacetamide (or N-acetyl ethylamine).


(2) Diethyl amine on reaction with acetyl chloride forms N-acetyl dimethylamine.


(3) Triethyl amine, being a tertiary amine does not have H atom attached to nitrogen of amine, hence it does not react with acetyl chloride.

Alkyl cyanides (nitriles) on reduction by sodium and ethyl alcohol form corresponding primary amines. This reaction is called Mendius reduction.

For example; propionitrile on reduction by sodium and ethanol gives n-propyl amine (Propan-1-amine).

Methyl cyanide or acetonitrile on reduction by sodium and ethanol gives ethanaminc.

Amines : The alkyl or aryl derivatives of ammonia in which one, two or all the three hydrogen atoms attached to nitrogen are replaced by same or different alkyl or aryl groups are called amines. OR Amines are nitrogen-containing organic compounds having basic character.