Preparation of Esters of Phosphoric Acid by the Reaction of Trivalent Phosphorus Compounds with Diethyl Azodicarboxylate in the Presence of Alcohols

Abstract Trivalent phosphorus compounds, phosphine or trialkylphosphites, have been oxidized by means of diethyl azodicarboxylate and either benzyl or allyl alcohol to give the corresponding phosphine oxide or trialkyl phosphates. The reaction was then extended to the phosphorylation of alcohols. When allyl diethyl phosphite was treated with diethyl azodicarboxylate in the presence of an alcohol at room temperature, a corresponding alkyl diethyl phosphate and diethyl N-allyl hydrazodicarboxylate were obtained in good yields. On the other hand, when phenol was treated with allyl diethyl phosphite and diethyl azodicarboxylate, diethyl phenyl phosphate, allyl phenyl ether and diethyl hydrazodicarboxylate were obtained. The mechanism of their formation will also be discussed.