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NEET CHEMISTRYMedium

An organic compound (C3H9NC_3H_9N) (A), when treated with nitrous acid, gave an alcohol, and N2N_2 gas was evolved. (A) on warming with CHCl3CHCl_3 and caustic potash gave (C) which on reduction gave isopropylmethylamine. The structure of (A) is:

A

CH3CH2CH2NH2CH_3CH_2CH_2-NH_2

B

CH3CH2NHCH3CH_3CH_2-NH-CH_3

C

(CH3)3N(CH_3)_3N

D

(CH3)2CHNH2(CH_3)_2CH-NH_2

Step-by-Step Solution

Let us deduce the structure of compound A step-by-step:

  1. Reaction with Nitrous Acid (HNO2HNO_2): Compound A (C3H9NC_3H_9N) reacts with HNO2HNO_2 to yield an alcohol and N2N_2 gas. This is a characteristic reaction of primary aliphatic amines. Secondary and tertiary amines do not release nitrogen gas with HNO2HNO_2.
  2. Carbylamine Reaction: Compound A warms with CHCl3CHCl_3 and caustic potash (KOH) to give compound C. This is the Carbylamine test, which is exclusively given by primary amines to form foul-smelling isocyanides (carbylamines). Thus, C is an alkyl isocyanide (RNCR-NC).
  3. Reduction of C: Isocyanide C (RNCR-NC) on reduction gives isopropylmethylamine, which is a secondary amine with the structure (CH3)2CHNHCH3(CH_3)_2CH-NH-CH_3. Reduction of an isocyanide always yields a secondary amine with one methyl group: RNC+4[H]RNHCH3R-NC + 4[H] \rightarrow R-NH-CH_3. Comparing RNHCH3R-NH-CH_3 with the product (CH3)2CHNHCH3(CH_3)_2CH-NH-CH_3, we can identify the alkyl group 'RR' as the isopropyl group (CH3)2CH(CH_3)_2CH-.
  4. Conclusion: Since the alkyl group is isopropyl, the original primary amine 'A' must be isopropylamine, (CH3)2CHNH2(CH_3)_2CH-NH_2.
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