Reaction of ortho-Phenylenedioxytrihalophosphoranes with Epichlorohydrin

Abstract

Dynamic 31P NMR spectroscopy was applied to investigate the reactions of o-phenylenedioxytrihalophosphoranes and bis(o-phenylenedioxy)halophosphoranes with epichlorohydrin as a function of the reagent ratio. α-Opening of the epoxide ring predominantly occurs. With excess epichlorohydrin the reaction with o-phenylenedioxytrichlorophosphorane results in formation of pentaalkoxyphosphorane, while in the reaction with o-phenylenedioxytechintribromophosphorane a mixture of phosphate and pentaalkoxyphosphorane is formed.