Abstract
The specific rates of solvolysis have been determined for chloromethyl ethyl ether (3) and chloromethyl octyl ether (4) at −10.0 °C and for chloromethyl methyl sulfide (5) at 25.0 °C in a variety of pure and binary solvents. These values were used for a correlation analysis treatment using the extended Grunwald–Winstein equation incorporating literature values for solvent nucleophilicity ( NT) and solvent ionising power ( YCl). Appreciable values were found for the sensitivities towards changes in both NT and YCl values. Using a literature specific rate of hydrolysis at 25.0 °C for fluoromethyl methyl ether (2), the required value for chloromethyl methyl ether (1) was obtained from use of NT and YCl values and the sensitivities for 3 to changes in their values, to adjust an experimental specific rate value for 1 in 100% ethanol to the corresponding value in 100% water. In this way, an estimated kCl/ kF of 1.2 × 105 was obtained, essentially identical to values for the solvolyses of tert-butyl halides. A unimolecular mechanism for the solvolyses, with appreciable nucleophilic solvation of the developing carbocation, is proposed. Electronic supplementary information provides, for several solvents, specific rates of solvolysis for 3, 4, and 5 at additional temperatures and the calculated activation parameters.
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