GB767615A - Manufacture of peroxidic compounds - Google Patents

Abstract

Saturated peroxides of the general formula <FORM:0767615/IV(b)/1> are prepared from the corresponding unsaturated peroxides of the general formula <FORM:0767615/IV(b)/2> R representing an alkyl or aralkyl group linked to the peroxy-group by means of a tertiary carbon atom and R1 and R2 a hydrogen atom or alkyl group, by hydrogenation in the presence of a hydrogenation catalyst at a temperature below the decomposition temperature of the peroxide. The hydrogenation may be effected in the presence of an inert organic solvent such as cyclohexane and under atmospheric or slightly raised pressures. Temperatures from below to above room temperature may be employed. The saturated peroxides may be recovered from the reaction products by distillation or chromatography. The peroxides may be used as catalysts in oxidations, telomerizations or the polymerization of olefinic compounds. In examples: (1) allyl (tertiary-butyl) peroxide is converted into propyl (tertiary-butyl) peroxide using PdO2 as catalyst; (2) sec.-octenyl (tertiary-butyl) peroxide is converted into sec.-octyl (tertiary-butyl) peroxide using Adam's catalyst. Sec.-decenyl (tertiary-butyl) peroxide and unsaturated peroxides wherein R1 and R2 may represent hydrogen or methyl, ethyl, propyl, butyl or amyl and R tertiary-amyl or a -cumyl are other specified starting materials. Platinum oxide and Raney's catalyst are alternative catalysts. Unsaturated peroxides of the above general formula are prepared by reacting together appropriate allyl bromides and alkali metal salts of tertiary hydroperoxides.