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JEE Advanced 2017 Paper 2 · Chemistry · Alcohols, Phenols, Ethers and Haloalkanes · medium

Correct statement(s) about nucleophilic substitution is(are)

One or more options correct

Correct statement(s) about nucleophilic substitution is(are)
  1. A. (S)(S)-2-bromobutane reacts with NaI\mathrm{NaI} in acetone to give (R)(R)-2-iodobutane
  2. B. (R)(R)-3-bromo-3-methylhexane on hydrolysis in aqueous acetone gives an optically active alcohol with complete inversion
  3. C. tert-Butyl bromide with sodium ethoxide in ethanol gives mainly tert-butyl ethyl ether
  4. D. 1-Bromo-2,2-dimethylpropane undergoes SN2\mathrm{S_N2} faster than bromoethane
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Answer: A

Option A is correct: NaI\mathrm{NaI} in acetone is a strong nucleophile in a polar aprotic solvent, so the secondary bromide reacts by SN2\mathrm{S_N2} with inversion; because I keeps the same CIP priority order as Br (I > ethyl > methyl > H), inversion converts (S)(S) into (R)(R). Option B is wrong: a tertiary halide in a polar protic solvent ionises (SN1\mathrm{S_N1}) to a planar carbocation, giving a racemic alcohol, not complete inversion. Option C is wrong: a tertiary bromide treated with a strong base such as ethoxide undergoes E2 elimination (back-side SN2\mathrm{S_N2} attack at the tertiary carbon is blocked), giving 2-methylpropene as the main product. Option D is wrong: the neopentyl substrate has a quaternary carbon next to the reaction centre, so back-side attack is severely hindered and it reacts far more slowly than bromoethane.
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