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JEE Main levelSingle correct optionDifficulty 2 of 3g2198

2,6-Dimethylbenzoic acid (pKa 3.25) is a considerably stronger acid than 4-methylbenzoic acid (pKa 4.37) in water. The best explanation is that

  1. Athe two ortho methyl groups twist out of the plane of the ring, which removes resonance stabilisation of the undissociated acid (steric inhibition of resonance)
  2. Bthe effect of the ortho methyl groups stabilises the carboxylate ion
  3. Chyperconjugation from the ortho methyl groups withdraws electrons from
  4. Dthe ortho methyl groups form an intramolecular hydrogen bond with

Answer: A

Methyl groups donate electrons, which on its own would weaken the acid, as in the para isomer. In the 2,6-isomer, steric crowding turns the carboxyl group out of the ring plane, so the ring can no longer stabilise the neutral acid by conjugation. The acid ionises more readily, and the ortho effect makes the acid stronger.
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