Role of peroxophosphate intermediates in reactions of tris(4-nitrophenyl) phosphate and phenyl phosphoro-chloridate with alkaline hydrogen peroxide

Abstract

Reaction of alkaline hydrogen peroxide with tris(4-nitrophenyl) phosphate generates ca 1.5 equiv. of 4-nitrophenol per mole of substrate with no evidence of build-up of an intermediate, and reaction of bis(4-nitrophenyl) phosphate anion is too slow to give a product. The initially formed bis(4-nitrophenyl) peroxophosphate is assumed to decompose to the phosphate ester by reaction with H2O2 or to eliminate 4-nitrophenoxide ion with the formation of a transient cyclic peroxophosphate. Reaction of phenyl phosphorochloridate anion with HO2− does not give phenoxide ion by this intramolecular reaction. Semi-empirical and ab initio simulations indicate that elimination of aryloxide ion from an aryl peroxophosphate should generate a cyclic rather than an open-chain peroxophosphate. Copyright © 2001 John Wiley & Sons, Ltd.