Abstract
The influence of aqueous OH − concentration in the solvent medium dioxan-water 40:60 upon the oxidation rates of diphenylphosphine oxide by peroxybenzoic acid (PBA) and p-nitroperoxy-benzoic acid has been studied. In alkaline media, the substituent effects have been investigated by determining the rates of oxidation by PBA for a series of unsymmetrically substituted diarylphosphine oxides (X·C 6H 4)PhPHO [with X = p-OMe, p-Me, H, p-Cl] and for two symmetrically substituted terms (Y·C 6H 4) 2PHO [with Y = p-Me, p-Cl]. On the basis of the kinetic results, a mechanism involving nucleophilic attack by peroxyacid anions RCO 3 − on the phosphorus substrate is proposed for the reactions in alkaline media.
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