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JEE Main 2016 · Chemistry · Carbonyl Compounds, Carboxylic Acids and Amines · hard

Propanoic acid is treated successively with (i) Br2 / red P, then H2O; (ii) excess NH3; (iii) NaNO2 / dilute HCl at 273 K. The final organic product…

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Propanoic acid is treated successively with (i) Br2\mathrm{Br_2} / red P\mathrm{P}, then H2O\mathrm{H_2O}; (ii) excess NH3\mathrm{NH_3}; (iii) NaNO2\mathrm{NaNO_2} / dilute HCl\mathrm{HCl} at 273 K273\ \mathrm{K}. The final organic product, as actually obtained, is
  1. A. 2-hydroxypropanoic acid, a single optically active enantiomer
  2. B. 2-hydroxypropanoic acid, a racemic (optically inactive) mixture
  3. C. 3-hydroxypropanoic acid, optically inactive
  4. D. propenoic acid, optically inactive
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Answer: (B) 2-hydroxypropanoic acid, a racemic (optically inactive) mixture

(i) Hell-Volhard-Zelinsky bromination replaces an α\alpha-hydrogen: CH3CHBrCOOH\mathrm{CH_3CHBrCOOH}. (ii) Nucleophilic substitution by excess NH3\mathrm{NH_3} gives 2-aminopropanoic acid (alanine). (iii) The primary amino group on the aliphatic α\alpha-carbon reacts with nitrous acid to give a diazonium salt that is displaced by water, forming 2-hydroxypropanoic (lactic) acid with loss of N2\mathrm{N_2}. The α\alpha-carbon is a stereocentre, but the HVZ step is not stereoselective and the later steps do not create a single enantiomer from an achiral precursor, so the product is racemic and optically inactive.
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