The chlorination of quinquevalent phosphorus esters

Abstract

Oxygen-18 labelling experiments have shown that in the reaction of a representative phosphinate, phosphonate, and phosphate with chlorinating agents, reaction proceeds via an initial attack by the phosphoryl-oxygen atom. In the reaction with phosphorus pentachloride and oxalyl chloride there is evidence for the importance of symmetrical intermediates.

The high reactivity of a cyclic phosphorus ester towards phosphorus pentachloride is interpreted in terms of the initial formation of a trigonal-bipyramidal intermediate.