The specific rates of solvolysis of methyl perchlorate in a wide variety of organic and aqueousorganic solvents have been measured and correlated by the extended Grunwald-Winstein equation.Each of the NT and NoTs scales of solvent nucleophilicity have been combined with each of the Yocl0, and YoTs scales of solvent ionizing power. The analysis shows the superiority of the Yoclo, scale for correlating perchlorate esters and indicates a sensitivity to changes in solvent nucleophilicity about equal to that found previously for the S-methyldibenzothiophenium ion or methyl p-toluenesulphonate and a sensitivity to changes in solvent ionizing power slightly less than that for methyl p-toluenesulphonate; these sensitivities are consistent with a conventional SN2 mechanism for the solvolyses. A claim for nucleophilic attack by the solvent at the chlorine of a secondary perchlorate ester is discussed and an alternative, involving attack at carbon, is proposed.
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