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JEE Advanced 2019 Paper 2 · Chemistry · Carbonyl Compounds, Carboxylic Acids and Amines · medium

Benzaldehyde and an excess of formaldehyde are treated with concentrated aqueous NaOH (crossed Cannizzaro reaction).

One or more options correct

Benzaldehyde and an excess of formaldehyde are treated with concentrated aqueous NaOH (crossed Cannizzaro reaction). The correct statement(s) is(are)
  1. A. C6H5CH2OH\mathrm{C_6H_5CH_2OH} is obtained as the reduction product
  2. B. Sodium formate is obtained as the oxidation product
  3. C. Sodium benzoate is the major carboxylate formed because the aromatic aldehyde is the better hydride donor
  4. D. If CD2O\mathrm{CD_2O} is used instead of HCHO\mathrm{HCHO}, the alcohol obtained is C6H5CHDOH\mathrm{C_6H_5CHDOH}
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Answer: A, B, D

Neither aldehyde has an α\alpha-hydrogen, so hydroxide adds to a carbonyl to give a hydrate anion that transfers hydride to a second aldehyde molecule. Formaldehyde is far more electrophilic and is hydrated much more easily, so its hydrate anion is the hydride donor and it is oxidised to formate, while benzaldehyde, the hydride acceptor, is reduced to benzyl alcohol; (A) and (B) are correct and (C) is wrong because the donor is formaldehyde, not benzaldehyde. With CD2O\mathrm{CD_2O} the transferred species is a deuteride, which ends on the carbonyl carbon of benzaldehyde: C6H5CHO+D−→C6H5CHD-O−\mathrm{C_6H_5CHO + D^-\to C_6H_5CHD\text{-}O^-}, giving C6H5CHDOH\mathrm{C_6H_5CHDOH} (racemic, with the formate being DCOO−\mathrm{DCOO^-}); (D) is correct.
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