Chlorine-free synthesis of phosphinic derivatives by change in the P-function

Abstract

Abstract To replace the traditional synthesis of phosphinic amides and phosphinates involving the reaction of phosphinic chlorides with amines and alcohols, respectively, a new chlorine-free approach was aimed at utilizing aminolysis of the phosphinate and alcoholysis of the phosphinic amide. Under microwave conditions, in the presence of [bmim][PF6] catalyst, alkyl diphenylphosphinates were converted to the corresponding phosphinic amides by reaction with primary amines. The reversed transformations involving the alcoholysis of the diphenylphosphinic amides under similar but somewhat more forcing conditions led to phosphinates. The reactivity of the starting phosphinic derivatives, as well as that of the primary amines and alcohols, was evaluated. The work-up included the removal of the excess of the nucleophiles (amine or alcohol) in vacuum followed by flash chromatography. The regenerated nucleophiles could be recycled and reused.