Reactivity of Some Tertiary Chlorides with Methoxy and Olefinic Neighboring Group

Abstract

Solvolysis rates of tertiary chlorides 1-6 and their hexadeuterated analogs 1-dg-6-đe were measured in ethanol (q> = 80%) and 2,2,2- trifluoroethanol (w = 97%). The (5-deuterium KIE calculated showed that chloride 1 solvolyzes with n-participation of the methoxy group in the rate determining step, while chloride 2 solvolyzes mainly by way of a kc process. Based on the reduced P-deuterium isotope effect, it was also concluded that in the solvolysis of chloride 5 7t-electrons take part in the rate-determining step