Free Radical Chemistry of White Phosphorus: γ-Irradiation of P4 in Bromoform

Abstract

CHBr2PBr2 and (CHBr2)2PBr are formed in high yields and in preparatively useful amounts when solutions of white phosphorus in bromoform are exposed to γ-radiation. In the first stages of irradiation, a red phosphorus containing many groups from the solvent is the only reaction product. About 1000 molecules of P4 are consumed per 100 eV of energy absorbed. In the later stages of irradiation, free radicals from the solvent attack this red phosphorus and lead to the formation of bromophosphines in high yield. Chain reactions are formulated for the formation of both the red phosphorus and the bromophosphines.