Reaction of thiolo and selenolo esters of phosphorus acids with halogens. Part 2. Interaction of S-methyl t-butyl(phenyl)- and di-t-butyl-phosphinothiolates with elemental bromine and iodine

Abstract

The reaction of S-methyl t-butyl(phenyl)- and di-t-butyl-phosphinothiolates with bromine and iodine involves the transient formation of the same type of halosulphonium salts, Bu^tRP(O)S⁺(X)MeX^– and phosphonium salts, Bu^tRP⁺(SMe)OP(O)Bu^tRX^–(R = Ph, Bu^t; X = Br, I) as described¹for the reaction of S-methyl t-butyl(phenyl)phosphinothiolate with chlorine and sulphuryl chloride. The considerable stability at room temperature of intermediates containing two phosphorus atoms, and their predominant decomposition with preservation of the P–O–P bridge in the reaction product, has been demonstrated. The stereochemistry of this transformation has been established by stereochemical correlations.