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JEE Main 2025 · Chemistry · Alcohols, Phenols, Ethers and Haloalkanes · medium

Ethyl tert-butyl ether is treated with one equivalent of cold, concentrated HI. The products are

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Ethyl tert-butyl ether is treated with one equivalent of cold, concentrated HI\mathrm{HI}. The products are
  1. A. (CH3)3C−OH\mathrm{(CH_3)_3C{-}OH} and C2H5I\mathrm{C_2H_5I}
  2. B. (CH3)3C−I\mathrm{(CH_3)_3C{-}I} and C2H5OH\mathrm{C_2H_5OH}
  3. C. (CH3)2C=CH2\mathrm{(CH_3)_2C{=}CH_2} and C2H5I\mathrm{C_2H_5I}
  4. D. (CH3)3C−I\mathrm{(CH_3)_3C{-}I} and C2H5I\mathrm{C_2H_5I}
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Answer: (B) (CH3)3C−I\mathrm{(CH_3)_3C{-}I} and C2H5OH\mathrm{C_2H_5OH}

The ether oxygen is protonated first. With a tertiary alkyl group the C-O bond breaks through an SN1S_N1 path because the tertiary cation (CH3)3C+\mathrm{(CH_3)_3C^+} is stable; iodide then attacks it, giving (CH3)3CI\mathrm{(CH_3)_3CI} and ethanol. With one equivalent of HI\mathrm{HI} in the cold the ethanol is not converted further. Cleavage by SN2S_N2 at the ethyl carbon (giving C2H5I\mathrm{C_2H_5I}) occurs only when both groups are primary or methyl.
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