By kinetics, volumetry, gas chromatography, elemental analysis, IR, NMR spectroscopy the oxidative alkoxylation of yellow phosphorus to phosphorus esters in alcohol solutions of copper and iron salts was studied using oxygen as an oxidant. The effect of temperature, oxygen partial pressure, nature and concentration of reagents was investigated on the phosphorus conversion. The novelty and relevance of research is associated with the development of “chlorine-free” direct syntheses of esters of phosphorus acids from phosphorus and alcohols. It was established that copper halides are characterized by the highest catalytic activity at a 5–10 optimal ratio of CuX 2 /P 4 and a temperature of 60°C. The partial pressure of oxygen does not significantly affect the yield of phosphorus acid esters. Enlarged laboratory tests of the catalytic synthesis of tributyl phosphate from yellow phosphorus and butanol were carried out under optimal conditions, in which the amount of phosphorus added to the reaction was increased 20–40 times as compared with experimental studies.

Полифторалкилдихлорфосфаты легко реагируют с пропаргиловым спиртом в достаточно мягких условиях (22-62°С, 3 ч, пиридин-толуол), образуя неизвестные ранее бис(2-пропинил)полифторалкилфосфаты с выходом 36-41%, тройная связь в которых способна участвовать в реакции азид-алкинового циклоприсоединения.

Polyfluoroalkyl dichlorophosphates react easily with propargyl alcohol under mild conditions (22–62°С, 3 h, pyridine-toluene) to form previously unknown bis(2-propynyl) polyfluoroalkyl phosphates with a yield of 36–41%, a triple bond in which is capable of participating in the azide-alkyne cycloaddition reaction.

Polyfluoroalkanols readily reacted with 2-chloro-1,3,2-dioxaphospholanes and 2-chloro-1,3,2-dioxaphosphinanes in hexane in the presence of triethylamine (–10 to 25°C, 5 h) to give 2-polyfluoroalkoxy-1,3,2- dioxaphospholanes and 2-polyfluoroalkoxy-1,3,2-dioxaphosphinanes in 48–72% yield. The products were found to exist as mixtures of cis and trans isomers with the trans isomer predominating for the phospholanes and cis isomer predominating for the phosphinanes according to the 1H, 13C, 19F, and 31P NMR data.

Polyfluoroalkyl dichlorophosphates easily react with 1,2- or 1,3-alkanediols in a system pyridine–diethyl ether and afford 2-polyfluoroalkoxy-1,3,2-dioxaphospholane oxides or 2-polyfluoroalkoxy-1,3,2-dioxaphosphorinane oxides. In similar conditions the reaction of methyl dichlorophosphate with 1,2- and 1,3-alkanediols proceeds less effectively.