Unexpected stoichiometry in the cleavage of bis(4-nitrophenyl) phosphate and 4-nitrophenyl phosphorochloridate by alkaline hydrogen peroxide

Reaction of alkaline hydrogen peroxide with bis(4-nitrophenyl) phosphate io n proceeds with simultaneous liberation of ca 2 equiv. of 4-nitrophenol per mole of substrate, and no evidence for build-up of an intermediate. Reacti on of HO2- with the more activated 4-nitrophenyl phosphorochloridate gives 4-nitrophenol in up to 40% yield with simple first-order kinetics and no in dication of a long-lived intermediate. A fast intramolecular nucleophilic d isplacement of 4-nitrophenolate ion by peroxide in the initially formed I-n itrophenyl peroxophosphate is proposed to explain this behavior. Copyright (C) 2000 John Wiley & Sons, Ltd.