Mechanism of the reaction between trialkyl phosphates and dialkyl phosphorochloridates: nucleophilic sites in phosphorus(V) esters

Abstract

Reaction between the phosphate 2-methoxy-5,5-dimethyl-1,3,2-dioxaphosphorinan-2-one (Ia), labelled with ¹⁸O in the phosphoryl group, and the phosphorochloridate 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinan-2-one (II), to give the labelled pyrophosphate 2,2′-oxybis-(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-one)(III) shows that the reaction proceeds through nucleophilic attack on the chloridate by both the methoxy and the phosphoryl oxygen atoms of the phosphate. The former route is probably rather more important than the latter.