Stryzhak O. Phosphorylation of 1,3-azoles by phosphorus (V) chlorides

The thesis is devoted to the synthesis of imidazole and thiazole series phosphonic and phosphinic acids and their derivates by direct phosphorylation of corresponding azoles with phosphorus (V) chlorides. Synthesized compounds were used for obtaining composite materials based on aminosilica, these materials are perspective sorbents for UO22+ ions extraction from neutral and weak acid solution media in terms of practical usage. It was found that 1-aryl and 1-hetarylimidazoles and benzoimidazoles react with phosphonic acid chorides yielding corresponding derivates of imidazol-2-yl phosphinic acids, similar to simple 1-alkylimidazoles. In the typical procedure, 1-substiuted imidazole (1 eq.) was dissolved in pyridine with stirring, triethylamine (1.3 eq.) was added followed by dropwise addition of phosphonic acid chloride (1.1 eq.). Reaction progress can be easily monitored by 31P-NMR spectra of reaction mixture. After completion (usually during 24h at room temperature) the mixture was hydrolysed with aqueous sodium/potassium carbonate (for free phosphinic acid or its salt isolation) or excess of corresponding amine was added dropwise (for phosphinamide synthesis).