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Q.The reaction of amines with mineral acids to form ammonium salts shows that these are basic in nature. Aliphatic amines are stronger bases than ammonia whereas aromatic amines are weaker bases than ammonia. Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and esters by nucleophilic substitution reaction. The main problem encountered during electrophilic substitution reactions of aromatic amines is that of their high reactivity. Substitution tends to occur at ortho-and para-positions. Hinsberg reagent is used for the identification and distinction between primary, secondary and tertiary amines. Aryldiazonium salts, usually obtained from arylamines, undergo replacement of the diazonium group with a variety of nucleophiles to provide advantageous methods for producing aryl halides, cyanides, phenols and arenes. Answer the following questions :

(a)
(i) Why CH3−NH2CH_3-NH_2 is a stronger base than (CH3)3N(CH_3)_3N in aqueous solution ?
(ii) Write structural formulae of the compound A and B : CH3CONH2→NaOBrA→BaseC6H5COClBCH_3CONH_2 \xrightarrow{NaOBr} A \xrightarrow[\text{Base}]{C_6H_5COCl} B
(b) A compound ‘X’ with molecular formula C3H9NC_3H_9N reacts with Hinsberg reagent to give a product insoluble in alkali. Identify ‘X’.
(OR)
(b) How can you convert aniline to benzonitrile ?
(c) Why is −NH2-NH_2 group of aniline acetylated before carrying out nitration ?
CBSECBSE Class XII Board 2026Subjective· 4mImportance★★★★★
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Part (a): CH3NH2>(CH3)3NCH_3NH_2>(CH_3)_3N in water (better solvation of the conjugate acid); CH3CONH2→NaOBrCH3NH2→C6H5COClC6H5CONHCH3CH_3CONH_2\xrightarrow{NaOBr}CH_3NH_2\xrightarrow{C_6H_5COCl}C_6H_5CONHCH_3; the C3H9NC_3H_9N amine giving an alkali-insoluble Hinsberg product is CH3NHCH2CH3CH_3NHCH_2CH_3. Part (b): aniline → benzonitrile by diazotisation + Sandmeyer (CuCN); −NH2-NH_2 is acetylated before nitration to moderate reactivity and prevent oxidation.

Part (a)

(i) Why CH3NH2CH_3NH_2 is a stronger base than (CH3)3N(CH_3)_3N in water

In water the base's strength depends on how well its conjugate acid is stabilised by hydrogen bonding to solvent. CH3N+H3CH_3\overset{+}{N}H_3 has three N–H bonds and is heavily solvated; (CH3)3N+H(CH_3)_3\overset{+}{N}H has only one N–H, and the three bulky methyl groups block water molecules. This poor solvation outweighs the greater inductive donation of three methyls, so CH3NH2CH_3NH_2 is the stronger base (aqueous order: (CH3)2NH>CH3NH2>(CH3)3N>NH3(CH_3)_2NH>CH_3NH_2>(CH_3)_3N>NH_3).

(ii) Structures of A and B

CH3CONH2→NaOBrCH3NH2⏟A (Hofmann bromamide; one C lost)CH_3CONH_2\xrightarrow{NaOBr}\underbrace{CH_3NH_2}_{\mathbf{A}}\ (\text{Hofmann bromamide; one C lost})

CH3NH2→baseC6H5COClC6H5CONHCH3⏟B (N-methylbenzamide, Schotten–Baumann benzoylation).CH_3NH_2\xrightarrow[\text{base}]{C_6H_5COCl}\underbrace{C_6H_5CONHCH_3}_{\mathbf{B}}\ (\textit{N}\text{-methylbenzamide, Schotten–Baumann benzoylation}).

(b) Identifying X (C3H9NC_3H_9N)

A Hinsberg product insoluble in alkali means a secondary amine (its sulphonamide has no acidic N–H). Among the isomers of C3H9NC_3H_9N — propan-1-amine, propan-2-amine (both 1°), NN-methylethanamine (2°) and trimethylamine (3°) — only the secondary amine fits: …

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