Synthesis of Phosphorus-Containing Podands―Analogs of Diglycolamide Based on Diphenyl- and Dibutylphosphorylmethanol under Phase Transfer Catalysis Conditions

Abstract

A convenient method for preparation of phosphorus-containing podands R₂P(O)CH₂OCH₂X, where X = C(O)NBu₂; P(O)R′₂, R = R′ = Ph, Bu, R = Ph, R′ = Bu via OH-alkylation of phosphorylmethanols under the phase transfer conditions in the presence of Cs₂CO₃ was developed. Carbamoyl-substituted dimethyl ethers were synthesized via transformation of phosphorylmethanols to phosphorylmethoxyacetic acids, followed by amidation. Symmetrical bisphosphoryl substituted dimethyl ethers were obtained by reaction of phosphorylmethanols with tosyl chloride in the presence of Cs₂CO₃. The synthesis of unsymmetrical substituted ether in the presence of Cs₂CO₃ was complicated by transesterification of phosphorylmethyl tosylate resulting in the formation of symmetrical dimethyl ethers as byproducts.