| Summary: | The microwave (MW)-assisted direct esterification of certain P-acids is a green method. Quantum chemical calculations revealed that the activation enthalpy (Δ<i>H</i><sup>#</sup>) for the exothermic monoalkylphosphate → dialkylphosphate transformation was on the average 156.6 kJ mol<sup>−1</sup>, while Δ<i>H</i><sup>#</sup> for the dialkylphosphate → trialkylphosphate conversion was somewhat higher, 171.2 kJ mol<sup>−1</sup>, and the energetics of the elemental steps of this esterification was less favorable. The direct monoesterification may be performed on MW irradiation in the presence of a suitable ionic liquid additive. However, the second step, with the less favorable energetics as a whole, could not be promoted by MWs. Hence, dialkylphosphates had to be converted to triesters by another method that was alkylation. In this way, it was also possible to synthesize triesters with different alkyl groups. Eventually a green, P-chloride free MW-promoted two-step method was elaborated for the synthesis of phosphate triesters.
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