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.     

Oxidation of white phosphorus by peroxides in water

A mixture of hypophosphorous, phosphorous, and phosphoric acids is formed during the anaerobic oxidation of white phosphorus by peroxides [ROOН; R = Н, 3-ClC₆H₄CO, (СН₃)₃С] in water. The rate of reactions grows considerably upon adding nonpolar organic solvents. The activity series of peroxides and solvents are determined experimentally. NMR spectroscopy shows that the main product of the reaction is phosphorous acid, regardless of the nature of the peroxide and solvent. A radical mechanism of oxidation of white phosphorus by peroxides in water is proposed. It is initiated by the homolysis of peroxide with the formation of НO^? radicals that are responsible for the homolytic opening of phosphoric tetrahedrons. Further oxidation and stages of the hydrolysis of intermediate phosphorus-containing compounds yield products of the reaction.     

Oxidation of phosphine with quinone and quinoid redox polymers in alcohol solutions of copper

New quinoid redox polymers were obtained by chemical modification of commercial weakly basic anion exchangers with quinone and its derivatives. The redox properties of quinone and quinoid redoxites with respect to phosphine were studied in alcohol solutions of copper complexes.     

The kinetics of oxidative alcoholysis of zinc phosphide in the presence of oxygen and the FeCl<Subscript>3</Subscript>-I<Subscript>2</Subscript> mixed catalyst in solution in butanol

The oxidative alkoxylation of zinc phosphide to tributyl phosphate occurred at a high rate and with high selectivity in a solution of FeCl₃-I₂ in butanol at 50–70°C. The kinetic characteristics and optimum conditions of the process were determined. The experimental and literature data were used to identify key stages of the formation of tributyl phosphate in the presence of the mixed catalytic system.     

Oxidative hydroxylation of phosphine in aqueous alcohol solutions of p-benzoquinone

The oxidation of phosphine in aqueous alcohol solution of benzoquinone in the presence of iodide ions is studied. Kinetic measurements, redox potentiometry, and gas chromatography are used to determine the kinetic regularities of the oxidative hydroxylation of phosphine, and a single-stage redox mechanism is proposed for this reaction. It is found that the iodine resulting from the oxidation of I^? ions by quinone is the reagent responsible for the formation of phosphorus-containing products.     

Catalytic method of synthesis of phosphorus acids esters from zinc phosphide and alcohol

Ecologically safe effective catalytic method for preparing phosphorous and phosphoric acid esters by oxidation of zinc phosphide with oxygen in the solution of copper(II) halides in butanol at 50–70°C is developed. It is found that in the presence of Cu(II) chloride a mixture of dibutyl hydrogen phosphite and tributyl phosphate is formed, while at the catalysis with Cu(II) bromide tributyl phosphate is mainly obtained. Promoting action of hydrogen chloride on the reaction rate and yield of organophosphorus compounds is established. Optimal reaction conditions are found and redox mechanism of catalytic process is assumed.     

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.     

Oxidizing Alkoxylation of Phosphine in Alcoholic Solutions of Iodine

Oxidizing alkoxylation of PH₃ to trialkyl phosphates was performed in pyridine-alcoholic solutions of iodine. The optimal conditions of the reaction were found.     

Catalytic Synthesis of Phosphorus-Containing Extractant: Tributyl Phosphate

Russian Journal of Applied Chemistry - By kinetics, volumetry, gas chromatography, elemental analysis, IR, NMR spectroscopy the oxidative alkoxylation of yellow phosphorus to phosphorus esters in...     

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.