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DOI: 10.1039/A605340H (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 257-264

Application of the aromatic ring parameter (I[thin space (1/6-em)]) to solvolyses of β-arylalkyl toluene-p-sulfonates

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Dennis N. Kevill and Malcolm J. D’Souza

Abstract

The specific rates of solvolysis of a variety of β-arylalkyl toluene-p-sulfonates, where the solvolyses proceed with anchimeric assistance (a kΔ pathway), are shown to be very well correlated by a Grunwald–Winstein treatment involving YOTs and I (the aromatic ring parameter), previously successfully applied to kc solvolyses of substrates with aryl groups at the α-carbon. A recently proposed alternative treatment, using YOTs in conjunction with YΔ [a scale derived from 2-methyl-2-(p-methyoxyphenyl)propyl toluene-p-sulfonate solvolyses], is shown to be equivalent to use of YOTs plus I; the sensitivity coefficients from the two treatments can be readily interconverted. Three methods (similarity models of type YBnX, use of YX plus I and use of YX plus YΔX have now been proposed for treatment of dispersion in Grunwald–Winstein plots due to the presence in the substrate of conjugated π electrons. The relative efficiencies of these three methods are discussed.

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