Oxidation of secondary alcohols with t-butyl hypochlorite in the presence of pyridine

Abstract

When treated with t-butyl hypochlorite and pyridine in methylene dichloride, secondary alcohols give the corresponding ketones in very high yield. The relative reactivities of a number of p-substituted 1-phenylethanols containing electron-donating and -withdrawing substituents were investigated. Oxidation of cis- and trans-4-t-butylcyclohexanol, as well as some other cycloalkanols, proceeds with the same relative rate. On the basis of this and other data a cyclic transition state and loss of α-hydrogen of the starting alcohol as hydride ion are proposed as characteristics of the reaction mechanism.