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JEE Advanced 2016 Paper 2 · Chemistry · Carbonyl Compounds, Carboxylic Acids and Amines · medium

Aldehydes, on heating with concentrated aqueous NaOH, undergo(es) the Cannizzaro reaction (self-redox to give an alcohol and a carboxylate)?

One or more options correct

Which of the following aldehydes, on heating with concentrated aqueous NaOH\mathrm{NaOH}, undergo(es) the Cannizzaro reaction (self-redox to give an alcohol and a carboxylate)?
  1. A. Benzaldehyde
  2. B. 2,2-Dimethylpropanal
  3. C. Phenylacetaldehyde
  4. D. Furan-2-carbaldehyde (furfural)
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Answer: A, B, D

The Cannizzaro reaction needs an aldehyde with no α\alpha-hydrogen. Hydroxide adds to the C=O to give a tetrahedral alkoxide, which transfers a hydride to a second molecule of aldehyde; the acid ends up as its salt and the other molecule as the alcohol. Benzaldehyde has its carbonyl attached to an aromatic carbon without hydrogens, so it gives benzyl alcohol and benzoate (A correct). Pivaldehyde has a quaternary α\alpha-carbon (B correct). Furfural has the CHO group on an sp2 ring carbon, so no α\alpha-H exists and it gives furfuryl alcohol and furoate (D correct). Phenylacetaldehyde, C6H5CH2CHO\mathrm{C_6H_5CH_2CHO}, has acidic α\alpha-hydrogens; with base it forms an enolate and undergoes aldol condensation instead (C wrong).
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