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Question of 108

Q.Explain following:

(a) Carbylamine reaction
(b) Hoffman bromide reaction. OR What happens when: (write equations only)
(i) Ethyl amine react with Nitrous acid.
(ii) Aniline reacts with bromine water in aqueous medium.
(iii) Aniline reacts with sodium Nitrite and hydrochloric acid at 278 K.
Madhya Pradesh MpbseMP Board Higher Secondary 2020Subjective· 3mImportance★★★★★
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The carbylamine reaction identifies primary amines by their foul-smelling isocyanide product; the Hofmann bromamide degradation converts an amide into a primary amine with loss of one carbon.

  1. Carbylamine reaction: When a primary amine is heated with chloroform (CHCl3_3) and alcoholic potassium hydroxide (KOH), it forms an offensive-smelling isocyanide (carbylamine): R−NH2+CHCl3+3KOH→ΔR−NC+3KCl+3H2OR-NH_2 + CHCl_3 + 3KOH \xrightarrow{\Delta} R-NC + 3KCl + 3H_2O This reaction is given only by primary amines (aliphatic and aromatic), so it distinguishes primary amines from secondary and tertiary amines.
  2. Hofmann bromamide degradation reaction: An amide reacts with bromine in the presence of aqueous/ethanolic NaOH to give a primary amine with one carbon atom less than the starting amide: R−CONH2+Br2+4NaOH→R−NH2+2NaBr+Na2CO3+2H2OR-CONH_2 + Br_2 + 4NaOH \rightarrow R-NH_2 + 2NaBr + Na_2CO_3 + 2H_2O This proceeds via an isocyanate intermediate and a 1,2-shift of the R group from carbon to nitrogen, and is useful for stepping down a homologous series. OR
    1. Ethylamine + Nitrous acid: C2H5NH2+HNO2→C2H5OH+N2↑+H2OC_2H_5NH_2 + HNO_2 \rightarrow C_2H_5OH + N_2\uparrow + H_2O (Primary aliphatic amines react with HNO2_2, generated from NaNO2_2 + dilute acid, to liberate N2_2 gas quantitatively and form the corresponding alcohol.)
    2. Aniline + bromine water: C6H5NH2+3Br2(aq)→2,4,6-tribromoaniline↓+3HBrC_6H_5NH_2 + 3Br_2(\text{aq}) \rightarrow 2,4,6\text{-tribromoaniline}\downarrow + 3HBr …

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