Reactions of Aroyl Peroxides. IV. Benzolyl Peroxide with some halides and oxyhalides of Phosphorus and Sulphur

Abstract

When benzoyl peroxide was heated with phosphorus trichloride (1 and 2 mol) in benzene, or chlorobenzene solution, carbon dioxide, benzoyl chloride, and phenyl phosphonyl chloride were the major products. Diphenyl phosphonyl chloride was also formed in small yield, p-Chlorobenzoyl peroxide reacted with phosphorus trichloride, in benzene solution, yielding carbon dioxide, p-chlorobenzoyl chloride, p-chlorophenyl phosphonyl chloride, and p-chlorobenzoic anhydride. The reaction of benzoyl peroxide with phosphorus trichloride alone yielded benzoyl chloride only. Phosphorus oxychloride, on the other hand, does not enter into the reaction. Thionyl chloride, in benzene, gave a complex mixture consisting of carbon dioxide, chlorobenzene, benzoyl chloride, phenyl benzoate, benzene sulphonyl chloride, diphenyl, and benzoic anhydride. Sulphuryl chloride in benzene yielded a mixture of carbon dioxide, chlorobenzene, benzoic acid, phenyl benzoate, and diphenyl. The mechanisms of these various reactions are discussed.