Correlation of the rates of solvolysis of phenyl chloroformate

Abstract

The specific rates of solvolysis of phenyl chloroformate in 21 solvents can be very well correlated using the extended Grunwald–Winstein equation, with incorporation of the NT solvent nucleophilicity scale and the YCl solvent ionizing scale, with sensitivities towards changes in the scale having values of 1.68 ± 0.10 and 0.57 ± 0.06, respectively. This is a solvolysis which, on the basis of several other types of evidence, is believed to follow an addition–elimination pathway with addition being rate-determining (or possibly an enforced concerted variant), and these sensitivities can be considered to be representative values for chloroformate esters following such a pathway.