Oxidative Alkoxylation of Hypophosphite in Coordination Sphere of Iron(III)

The kinetics of oxidation of sodium hypophosphite with oxygen in Fe(III) alcoholic solutions is studied. At 50-90°C, hypophosphite was found to be oxidized to dialkyl phosphite (RO)₂HPO, di-, and trialkyl phosphates (RO)₂(OH)PO, (RO)₃PO. The redox potentiometry, IR, UV, EPR, Mössbauer, and ³¹P NMR spectroscopies, X-ray powder diffraction analysis, and gas-liquid chromatography were used to determine the key stages of the process: the Fe(III) reduction with hypophosphite with the formation of the phosphorus ethers and the reoxidation of Fe(II) with oxygen. The molar ratio of the products depends on the composition of the Fe(III) coordination sphere.     

Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR ³¹Р-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.     

Oxidative Alkoxylation of Red Phosphorus in the Presence of the FeCl<Subscript>3</Subscript>-I<Subscript>2</Subscript> Catalytic System

A new effective catalytic system FeCl₃-I₂ was found, that allows the direct oxidative alkoxylation of red phosphorus to trialkyl phosphates to be performed with high rate and selectivity at 60–80°C. Kinetics of the process were studied, and a separate redox mechanism of the process and a scheme of formation of phosphorus esters were offered. Kinetic and activation parameters of the reaction are calculated.