Oxidation of White Phosphorus by Peroxides in Aqueous and Alcoholic Solutions: Mechanistic Aspects and Catalytic Studies

The oxidation of white phosphorus by hydrogen peroxide or different organic peroxides (such as tert-butyl hydroperoxide, dibenzoylperoxide, 3-chloroperoxybenzoic acid) has been studied in both aqueous and alcoholic solutions under anaerobic conditions. Depending on the reaction conditions, P(I) (hypophosphorous acid), P(III) [phosphorous acid, mono- and dialkyl (or diaryl) hydrogen phosphonates] and P(V) [phosphoric acid or trialkyl (or triaryl) phosphates] derivatives are produced. The catalytic oxidative P-O coupling of P-4 to water, aliphatic alcohols and phenol under mild reaction conditions is accomplished by using copper(I), copper(II) and vanadium(IV) complexes. Catalytic conversion of white phosphorus with complete efficiency and high selectivity for monoalkyl hydrogen phosphonates (>95%) maybe achieved using 3-ClC6H4C(O)OOH as oxidant under optimized conditions. An identical radical mechanism is suggested to account for both the stoichiometric and the catalytic oxidative hydroxydation, alkoxydation and phenoxydation of white phosphorus promoted by peroxides in both aqueous biphasic conditions and organic solutions.