One or more options correct
(neopentyl bromide) is heated in ethanol and, in a separate experiment, treated with in ethanol and with in acetone. Which of the following statement(s) is/are correct?
- A. With in ethanol it gives mainly -methylbut--ene by an E2 pathway
- B. On heating in ethanol alone, the principal substitution product is -ethoxy--methylbutane, formed through a -methyl shift
- C. With in acetone it undergoes exchange faster than -propyl bromide does
- D. The primary carbocation formed on ionisation rearranges by a -hydride shift to a tertiary carbocation
Show answer and solution
Answer: B
Neopentyl bromide has a quaternary carbon next to the group, which governs everything. (A) is wrong: E2 needs a -hydrogen, but the -carbon is quaternary and bears none, and the 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 -methyl shift) which converts the primary centre into the tertiary 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 times slower than -propyl bromide in . (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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