PEROXIDE TRANSFER-REACTION

A new method for synthesis of dialkyl peroxides is described which is based on the novel peroxide transfer reaction between germanium or tin peroxides and alkyl trifluoromethanesulfonates (triflates). Yields are generally superior to those obtainable by alkylation of hydrogen peroxide with alkyl methanesulfonates (mesylates) in the presence of base, especially for secondary alkyl peroxides. Mixed dialkyl peroxides are obtained from the reaction of tri-n-butyltin peralkoxide with alkyl triflates. Bis(tri-n-butyltin) peroxide reacts with alkyl triflates to afford symmetrical dialkyl peroxides, and with alkyl bistriflates to afford five- to eight-membered cyclic peroxides. The strained bicyclic peroxide nucleus of prostaglandin endoperoxides, 2,3-dioxabicyclo[2.2.1]heptane, is obtained in 22% yield from the bistriflate of m-1,3-cyclopentanediol. © 1979, American Chemical Society. All rights reserved.