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JEE Advanced 2020 Paper 1 · Chemistry · Alcohols, Phenols, Ethers and Haloalkanes · hard

(CH3)3C-CH2Br (neopentyl bromide) is heated in ethanol and, in a separate experiment, treated with NaOEt in ethanol and with NaI in acetone.

One or more options correct

(CH3)3C−CH2Br\mathrm{(CH_3)_3C{-}CH_2Br} (neopentyl bromide) is heated in ethanol and, in a separate experiment, treated with NaOEt\mathrm{NaOEt} in ethanol and with NaI\mathrm{NaI} in acetone. Which of the following statement(s) is/are correct?
  1. A. With NaOEt\mathrm{NaOEt} in ethanol it gives mainly 22-methylbut-22-ene by an E2 pathway
  2. B. On heating in ethanol alone, the principal substitution product is 22-ethoxy-22-methylbutane, formed through a 1,21,2-methyl shift
  3. C. With NaI\mathrm{NaI} in acetone it undergoes SN2\mathrm{S_N2} exchange faster than nn-propyl bromide does
  4. D. The primary carbocation formed on ionisation rearranges by a 1,21,2-hydride shift to a tertiary carbocation
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Answer: B

Neopentyl bromide has a quaternary carbon next to the CH2Br\mathrm{CH_2Br} group, which governs everything. (A) is wrong: E2 needs a β\beta-hydrogen, but the β\beta-carbon is quaternary and bears none, and the SN2\mathrm{S_N2} route is also blocked, so with ethoxide the reaction is extremely slow and cannot give 2-methylbut-2-ene by E2. (B) is right: under solvolysis the leaving of bromide is accompanied by migration of a methyl group (a 1,21,2-methyl shift) which converts the primary centre into the tertiary (CH3)2C+CH2CH3\mathrm{(CH_3)_2C^+CH_2CH_3} cation; ethanol then traps it to give 2-ethoxy-2-methylbutane. (C) is wrong because the back-side approach is shielded by the three methyl groups on the neighbouring carbon, and neopentyl bromide reacts about 10510^5 times slower than nn-propyl bromide in SN2\mathrm{S_N2}. (D) is wrong because the adjacent carbon carries no hydrogen, so no hydride shift is possible; only a methyl shift can occur.
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