P-Chloride-Free Synthesis of Phosphoric Esters: Microwave-Assisted Esterification of Alkyl- and Dialkyl Phosphoric Ester-Acids Obtained from Phosphorus Pentoxide

Abstract It is a reasonable endeavour to replace P-chloride starting materials (e.g., POCl3) with greener and cheaper reagents. Our purpose was to start from phosphorus pentoxide, i.e. to utilize its reaction with alcohols in the preparation of (HO)2P(O)(OR) and HOP(O)(OR)2, and to convert the mixtures of the corresponding monoester and diester, so obtained, into the target trialkyl esters. Separate experiments showed that the monobutylphosphate undergo microwave (MW)-assisted esterification with butanol in the presence of [bmim][BF4] catalyst at 200 °C to afford dibutylphosphate in a selective manner (ca. 95%) that, in turn, may be converted into tributylphosphate by alkylation under MW irradiation. In this way, the mixtures of (HO)2P(O)(OR) and HOP(O)(OR)2 obtained by the practical reaction of phosphorus pentoxide and alcohol (ROH) could also be converted in two additional steps into the corresponding trialkyl esters. The three-step synthesis of trialkylphosphates starting from phosphorus pentoxide was also transformed in a one-pot (step 1: preparation of the monoester diester mixture, step 2: diesterification) and telescoping (step 3: triesterification) variation, avoiding the isolation and purification of the intermediates, and affording the triesters­ in 86–93% yields. The three- and two-step P-chloride-free methods developed are ‘green’ and of more general value.