INDUCED DECOMPOSITION OF PER ESTERS AND MIXED PEROXIDES IN PRESENCE OF ALCOHOLS AND ETHERS

Rates and products observed in the fast decomposition of t-butyl peracetate and perbenzoate in alcohol and ether solvents confirm an induced chain similar to that recognized with benzoyl peroxide. High yields of t-butyl alcohol and only traces of Co2 implicate the -butoxy radical as the chain carrier, and it is suggested that both steric and polar effects may determine the point of attack by radicals on the peroxide bond. Induced chains are much longer with cyclic than noncyclic ethers. The latter give α-alkoxyalkyl radicals which undergo extensive β scission interfering with the induced chain. With cyclic ethers, β scission is apparently reversible since the fragments cannot separate. © 1968, American Chemical Society. All rights reserved.