KINETICS AND MECHANISM OF THE OXIDATIVE ALKOXYLATION OF TETRAPHOSPHORUS IN THE PRESENCE OF COPPER(II) SULFATES AND CARBOXYLATES

A new reaction of oxidative alkoxylation of tetraphosphorus in the presence of copper(II) sulfates and carboxylates is investigated by P-31 NMR and IR spectroscopy, gas chromatography, potentiometry, and volumetry. The major products of the reactions involving primary, secondary, and tertiary alcohols are trialkyl phosphates and trialkyl phosphites; dialkyl phosphites; and monoalkyl phosphites, respectively. The reaction proceeds via two key stages: (1) the reduction of Cu(II) to Cu(0) by tetraphosphorus giving alkyl phosphates and phosphites and (2) the oxidation of Cu(0) by oxygen. The manner in which the concentrations of Cu(II), tetraphosphorus, oxygen, alcohol, and water; pH; and temperature affect the rates and directions of the key stages is examined.