Question:hard

An organic compound \(A\) with molecular formula \(C_3H_5N\) on reaction with \(C_6H_5MgBr\) followed by hydrolysis gives compound \(B\). Compound \(B\) forms orange-red precipitate with 2,4-DNP reagent and does not give iodoform test. It neither reduces Tollens' or Fehling's reagent nor decolourises bromine water. On drastic oxidation with chromic acid it gives carboxylic acid \(C\) having molecular formula \(C_7H_6O_2\). Identify \(A\), \(B\), and \(C\). Write the reactions.

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Nitrile plus Grignard reagent followed by hydrolysis gives ketone.
Updated On: Jun 29, 2026
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Solution and Explanation

Step 1: Identify compound A with molecular formula $C_3H_5N$.
Degrees of unsaturation for $C_3H_5N$ = $(2 \times 3 + 2 + 1 - 5)/2 = 4/2 = 2$. Two degrees of unsaturation corresponds to a triple bond ($C \equiv N$, i.e., a nitrile group). Compound A with $C_3H_5N$ and 2 DoU is propionitrile (ethyl cyanide): $CH_3CH_2CN$.
Step 2: Determine compound B from $A + C_6H_5MgBr$, then hydrolysis.
A nitrile reacts with a Grignard reagent followed by hydrolysis to give a ketone: \[ CH_3CH_2CN + C_6H_5MgBr \xrightarrow{1.\;\text{react}\;2.\;H_3O^+} CH_3CH_2-CO-C_6H_5 \] Compound B is propiophenone (phenyl ethyl ketone, 1-phenylpropan-1-one): $C_6H_5COCH_2CH_3$.
Step 3: Confirm compound B using all given chemical tests.
(i) Orange-red precipitate with 2,4-DNP: confirms a carbonyl group ($C=O$). B has a ketone $C=O$. (ii) No iodoform test: iodoform ($CHI_3$) forms only with $CH_3CO-$ or $-CHOH-CH_3$ groups. $C_6H_5CO-CH_2CH_3$ has $-CH_2-$ next to $C=O$, not $-CH_3$. No iodoform. (iii) No Tollens'/Fehling's test: aldehydes reduce these; ketones do not. B is confirmed as a ketone. (iv) No Br2 water decolourisation: no C=C bond in the aliphatic chain. All tests are consistent with propiophenone.
Step 4: Identify compound C from $B + NH_2OH$.
Ketones react with hydroxylamine ($NH_2OH$) in acid catalyst by nucleophilic addition-elimination to form oximes: \[ C_6H_5COCH_2CH_3 + NH_2OH \rightarrow C_6H_5C(=NOH)CH_2CH_3 + H_2O \] Compound C is the oxime of propiophenone: $C_6H_5C(=NOH)CH_2CH_3$.
Step 5: Summarise the structural identifications.
A = $CH_3CH_2CN$ (propionitrile). B = $C_6H_5COCH_2CH_3$ (propiophenone). C = $C_6H_5C(=NOH)CH_2CH_3$ (oxime of propiophenone).
Step 6: State the final boxed answer.
\[ \boxed{A = CH_3CH_2CN;\; B = C_6H_5COCH_2CH_3;\; C = C_6H_5C(=NOH)CH_2CH_3} \]
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