Solvent Effects on Solvolysis Reactivity of t-Butyl and p-Methoxybenzyl Substrate Systems Having a Sulfonate Leaving Anion

Abstract

Solvent effects on solvolytic reactivity were analyzed for t-butylbis(trimethylsilyl)methanesulfonate and related substrates in terms of a modified Grunwald-Winstein equation, log k = m₀Y + Δ, where m₀ was intrinsic sensitivity determined as a slope for non-aqueous solvents and Δ was a hydrophobic factor determined as a difference in the rate constant in pure water in log unit between the observed value and the one predicted from the correlation line for organic solvents. The substrate was characterized by an m₀ value of 0.75, significantly smaller than that for the chloride, and a distinct effect of solvent nucleophilicity.