Electron-Transfer Reactions between Perfluoroacyl Peroxides and Methoxybenzenes

Article abstract of DOI:10.1021/jo00173a025

(C3F7COO)2 and (C7F15COO)2 react rapidly with p-methoxytoluene and several p-dimethoxybenzenes in CCl2FCClF2 at 0 deg C.With p-dimethoxybenzene kinetics are first order in each component.High yields of ring-substituted products are obtained except for 2,5-dimethyl-1,4-dimethoxybenzene, 5, which gives the substituted benzyl perfluoroacyl ester.Rates and products are consistent with a rate-determining electron transfer, followed by product-forming reactions between the resulting radical cation-radical anion pairs.This is further supported by the formation of a perfluoroalkyl-substituted product from p-methoxytoluene and CIDNP emission from one system, indicating the presence of transient radical intermediates, although no free radicals were detected by scavenging experiments.