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DOI: 10.1039/A803859G (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 1865-1868

Correlation of the rates of solvolysis of (arylmethyl)methylphenylsulfonium ions[hair space]†

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Dennis N. Kevill and Norsaadah HJ Ismail

Abstract

The specific rates of solvolysis of the benzylmethylphenylsulfonium ion (prepared as the trifluoromethanesulfonate salt) and five benzylic ring-substituted derivatives can be satisfactorily correlated using NT solvent nucleophilicity values. Addition of a secondary term, governed by the aromatic ring parameter (I[hair space]), shows the sensitivities towards changes in this parameter to fall and those towards changes in NT to rise with increasing electron-withdrawing ability of the substituent. The Hammett ρ values with electron-withdrawing substituents (based on σ+ values) vary from –0.9 in 95% acetone to –1.8 in 97% 2,2,2-trifluoroethanol. These Grunwald–Winstein and Hammett analyses are compared to those previously reported, with essentially the same solvents and substituents, for solvolyses of arylmethyl p-toluenesulfonates.

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