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.

Key words

esterification - green chemistry - ionic liquids - phosphates - phosphorylation

Publication History

Received: 03 March 2022

Accepted after revision: 30 March 2022

Accepted Manuscript online:
30 March 2022

Article published online:
03 May 2022

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