Mechanism of Alcohol to Ester Rearrangement in Phosphorus Compounds

Abstract

The kinetics of the base-catalyzed rearrangement of dialkyl 2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl-phosphonate, (RO) 2 P(O)C(OH)(CF 3 ) 2 to 1,1,1,3,3,3-hexafluoroisopropyldialkyl phosphate, (RO) 2 P(O)OCH(CF 3 ) 2 , where R = methyl, ethyl, n-butyl, have been studied. Energies of activation and entropies of activation have been obtained and the base strength of the catalyst has been varied. A mechanism is proposed to account for the results.