Simultaneous Generation of t-BuO· and t-BuOO· from the Decomposition of 2,2-Bis(t-butyldioxy)propane. A New Synthetic Method for Introducing a t-BuOO Group into Organic Molecules

Abstract

Abstract A free-radical synthetic method for introducing a t-BuOO group into various organic substrates has been developed using 2,2-bis(t-butyldioxy)propane (1a) which can efficiently give two oxygen-centered radicals, t-BuO· and t-BuOO·, by thermolysis. The thermal reaction of 1a with cumene afforded the desired dialkyl peroxide, t-butyl 1-methyl-1-phenylethyl peroxide, in good yield (53% based on 1a reacted) together with an appreciable amount of a dimer, 2,3-dimethyl-2,3-diphenylbutane, as a by-product. The addition of t-BuOOH increased the yield of the dialkyl peroxide to as high as 82%, by suppressing the dimer formation ( < 10%). Also, reaction with isobutyronitrile and isopropyl methyl ketone gave good yields of dialkyl peroxides. The present method makes it possible to prepare unsymmetrical dialkyl peroxides containing functional groups, if the substrates are good hydrogen donors.