Studies on phosphorylation. Part XXX. Phosphorylation via carbonium, phosphonium, and sulphonium intermediates

Abstract

Dichlorodiphenylmethane in polar solvents converts monoesters of phosphoric acid at room temperature into P¹P²-diesters of pyrophosphoric acid, and when an excess of the dihalogeno-compound is present the mixture will phosphorylate alcohols. The active phosphorylating agent producing pyrophosphate is believed to be a carbonium compound of the P–X–Y⁺ type. Other phosphorylating agents of an analogous type are mixtures of phenyl dihydrogen phosphate with (a) triphenylphosphine dihalides, (b) mixtures of triphenylphosphine with polyhalogenomethanes, and (c) diphenyl sulphide dihalides, the active intermediates in (a) and (b) being phosphonium and in (c) sulphonium compounds. The Witting reagent dichloromethylenetriphenylphosphorane will also convert phenyl dihydrogen phosphate into the corresponding pyrophosphate.