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JEE Advanced 2022 Paper 1 · Chemistry · Alcohols, Phenols, Ethers and Haloalkanes · medium

(s) about substituted benzenes.

One or more options correct

Choose the correct statement(s) about substituted benzenes.
  1. A. pp-Cresol is a stronger acid than phenol because the methyl group stabilises the phenoxide ion by inductive donation
  2. B. Benzenediazonium chloride couples with phenol in mildly alkaline medium (pH about 99–1010) to give pp-hydroxyazobenzene
  3. C. Direct nitration of aniline with a HNO3/H2SO4\mathrm{HNO_3/H_2SO_4} mixture gives exclusively pp-nitroaniline, as −NH2-\mathrm{NH_2} is an ortho/para-directing group
  4. D. Phenol on heating with CHCl3\mathrm{CHCl_3} and aqueous NaOH gives mainly salicylaldehyde through an electrophilic dichlorocarbene intermediate
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Answer: B, D

A is incorrect: an electron-donating methyl group destabilises the phenoxide ion, so pp-cresol (pKa≈10.3pK_a\approx10.3) is weaker than phenol (pKa≈10.0pK_a\approx10.0). B is correct: in mildly alkaline medium the phenoxide ion, a strongly activated nucleophile, attacks the diazonium ion at the para position (azo coupling). In strongly acidic medium phenol is not ionised and coupling fails, and in strongly basic medium the diazonium ion converts to diazotate. C is incorrect: in the strongly acidic nitrating mixture aniline is protonated to the anilinium ion, a meta director, so a large fraction of the mm-isomer forms along with oxidation products; hence the product is not exclusively para. D is correct: Reimer–Tiemann reaction: CHCl3+OH−→:CCl2\mathrm{CHCl_3+OH^-\to{:}CCl_2}, attack by the phenoxide ortho carbon, then hydrolysis to the o-hydroxybenzaldehyde. Hence B and D.
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