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JEE Main 2021 · Chemistry · Alcohols, Phenols, Ethers and Haloalkanes · easy

Which combination is the best practical synthesis of ethyl tert-butyl ether, (CH3)3C-O-C2H5, in good yield?

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Which combination is the best practical synthesis of ethyl tert-butyl ether, (CH3)3C−O−C2H5(\mathrm{CH_3})_3\mathrm{C-O-C_2H_5}, in good yield?
  1. A. C2H5ONa+(CH3)3CBr\mathrm{C_2H_5ONa}+(\mathrm{CH_3})_3\mathrm{CBr}
  2. B. (CH3)3CONa+C2H5Br(\mathrm{CH_3})_3\mathrm{CONa}+\mathrm{C_2H_5Br}
  3. C. C2H5OH+(CH3)3COH\mathrm{C_2H_5OH}+(\mathrm{CH_3})_3\mathrm{COH} with conc. H2SO4\mathrm{H_2SO_4} at 413 K413\ \mathrm{K}
  4. D. (CH3)3CONa+(CH3)3CBr(\mathrm{CH_3})_3\mathrm{CONa}+(\mathrm{CH_3})_3\mathrm{CBr}
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Answer: (B) (CH3)3CONa+C2H5Br(\mathrm{CH_3})_3\mathrm{CONa}+\mathrm{C_2H_5Br}

Williamson synthesis proceeds by SN2\mathrm{S_N2}, which needs an unhindered (primary) alkyl halide. With C2H5ONa\mathrm{C_2H_5ONa} and tert-butyl bromide, the alkoxide acts as a strong base and the tertiary halide undergoes E2 elimination to give 2-methylpropene. Using tert-butoxide with the primary halide ethyl bromide gives substitution. Dehydration of a mixture of alcohols gives a mixture of three ethers (Et2O\mathrm{Et_2O}, tt-Bu2O\mathrm{Bu_2O} and the unsymmetrical ether), and tertiary alcohol mostly dehydrates to alkene.
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