Electron transfer reactions between pentafluorobenzoyl peroxide and dimethoxybenzenes

Abstract

Pentafluorobenzoyl peroxide (FBP) reacted rapidly with dimethoxybenzenes in F 113 (CCl 2FCClF 2) with kinetics of first order in each component. High yields of ring-substituted esters of m -dimethoxybenzene ( m -DMB) and p -dimethoxybenzene ( p -DMB) were obtained, whereas for 2,5-di- t -butyl-1,4-dimethoxybenzene (DBDMB), the t -Bu group was simultaneously eliminated. For 2,5-dimethyl-1,4-dimethoxybenzene (DMDMB), the benzylic hydrogen was substituted. Rate and product studies both indicate a rate-determining electron transfer step leading to radical ion pairs which collapse to products.