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Worked Examples · Example 8.4

Q.An organic compound (A) with molecular formula C8H8OC_8H_8O forms an orange-red precipitate with 2,4-DNP reagent and gives yellow precipitate on heating with iodine in the presence of sodium hydroxide. It neither reduces Tollens' or Fehlings' reagent, nor does it decolourise bromine water or Baeyer's reagent. On drastic oxidation with chromic acid, it gives a carboxylic acid (B) having molecular formula C7H6O2C_7H_6O_2. Identify the compounds (A) and (B) and explain the reactions involved.

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The clues point to an aromatic methyl ketone with no C=C double bond and no aldehyde group. Compound (A) is acetophenone (C6H5COCH3C_6H_5COCH_3) and (B) is benzoic acid (C6H5COOHC_6H_5COOH).

Reading the clues

  • Molecular formula C8H8OC_8H_8O -> degree of unsaturation =2(8)+2−82=5= \dfrac{2(8)+2-8}{2} = 5 (a benzene ring = 4, plus one C=OC=O).
  • Orange-red precipitate with 2,4-DNP -> a carbonyl group (>C=O>C=O) is present.
  • Yellow precipitate with I2I_2/NaOH (iodoform test) -> a CH3CO−CH_3CO- (methyl ketone) group is present.
  • Does not reduce Tollens or Fehling reagent -> it is not an aldehyde (so the carbonyl is a ketone).
  • Does not decolourise bromine water or Baeyer reagent -> no C=CC=C or C≡CC\equiv C; the only unsaturation besides the ring is the carbonyl.
  • Drastic oxidation with chromic acid -> C7H6O2C_7H_6O_2 (benzoic acid) -> the benzene ring survives and the side chain is cut down to −COOH-COOH.

Identifying (A) …

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