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.

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 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.

Hypophosphites are widely used as reducers in the metal protection coating, as reagents in the synthesis of various organophosphorus compounds, in analytical chemistry, and in many other fields. NaH2PO2 difficultly reacts with many oxidizers without catalysts despite of the significant reduction potential. The kinetics and the mechanism of hypophosphite oxidation in aqueous acid solution of the metal and nonmetal salts are studied in detail. The reactivity of hypophosphite in the organic solvents was not almost studied. In this work the basic possibility of synthesis dialkylphosphites from cheap, accessible and harmless NaH2PO2 and alcohols is shown. Sodium hypophosphite is oxidized by oxygen in alcoholic solutions of FeCl3 at 50-80 °С to dialkylphosphites. Kinetic and mechanism of the reaction are investigated by methods of volumetry, redox-potentiometry, GC, IR-, UV-, EPR-, Mössbauer- and NMR 31Р-spectroscopy and X-ray powder diffraction analysis, optimum conditions are found, kinetic and activation parameters of the reaction are calculated. It is shown, that the process follows redox-mechanism and consists of two key stages: reduction of Fe (III) by hypophosphite with formation of dialkylphosphite and reoxidation of Fe (II) by oxygen. The coordination mechanism of reduction reaction of Fe (III) by hypophosphite is proposed. According to this mechanism the dialkylphosphite forms through innersphere redox-decomposition of intermediate alcoxyhypophosphite complex of Fe (III). The coordination mechanism of the process is confirmed by low values of Е≠ and negative activation entropies ∆S≠. The availability in an inner sphere of Fe (III) bromide, low-molecular alcohols, water, characterized by high acidity, increases the reaction rate of oxidative alcoxylation of hypophosphite and promotes the further transformation of dialkylphosphite to di- and trialkylphosphate.

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.

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.

This article presents the synthesis of phosphoric acid esters from phosphoric hydrogen РН3 and aliphatic alcohols. The process is based on the oxidation of phosphine by quinones and redox polymers on the basis of mono- and disubstituted quinoid derivatives of monoethanolamine vinyl ether. Molecular iodine is used as a catalyst. Two-, three-, four- and multicomp onent systems are studied in order to determine optimal conditions of the oxidation of phosphine quinones and repoxpolymers on their basis. The rate and selectivity of reaction were monitored by the absorption of РН3. As alcohols used aliphatic alcohols: BuOH, PrOH, EtOH, MeOH. Organophosphorus compounds were analyzed by a chromatographic method. It was established that alcohol solutions of individual components of reactionary system (quinones, redox ionites or iodine) are characterized by a low activity in relation to phosphine. Organophosphorus compounds are formed in insignificant quantities. In the mixed alcohol solution of benzoquinone takes place PH3 oxidation forming trialkylphosphates. Conversion of phosphine constitutes 80-100%. Increasing the concentration of reagents of catalytic system has a positive effect on the process as a whole. Similar patterns were obtained when redox monomers and polymers on the base of quinones in the presence of iodine were used as oxidants. Esters of phosphoric acid – dialkylphosphites and esters of phosphorous acid – trialkylphosphates were identified as organophosphorus compounds. By selecting a redox agent in a zone of the catalysis it is possible to direct process in the desirable direction. The most activity in the oxidation of phosphine by iodine-alcohol solutions of quinoid monomers and polymers, is exhibited by 2-[N-(2-vinyloxy) ethyl]amino-NQ and polymer on their basis. Results of our experiments and literature data on oxidation-reduction processes with participation of iodine and quinones in organic solutions allowed to propose the separate oxidation-reduction mechanism of formation of organophosphorus compounds. In investigated multicomponent systems, the synergetic effect is manifested which is reached at the expense of distribution of oxidation-reduction functions among iodine, quinones and its derivatives. In this report, for the first time, it is established reactionary ability of quinones and redox ionites on their basis in an oxidizing alkoxylation of phosphine to valuable esters of acids of phosphorus. Reaction can be used for purification of exhaust and technological gases from phosphine and its utilization.

The oxidative alkoxylation of zinc phosphide to tributyl phosphate occurred at a high rate and with high selectivity in a solution of FeCl 3 -I 2 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.

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.

Zinc phosphide in a butanolic solution of FeCl3 was oxidized by oxygen at 60 to 90degreesC into dibutyl phosphite (BuO)(2)HPO. The kinetics and mechanism of the oxidative alkoxylation of Zn3P2 in the presence of FeCl3 were studied by volumetric analysis, redox potentiometry, IR, UV, and P-31 NMR spectroscopy, and gas chromatography. It was found that the process follows a separate redox mechanism and consists of two key steps, namely, the oxidation of zinc phosphide with Fe(III) into (BuO)(2)HPO and the reoxidation of Fe(II) with oxygen. The coordination mechanism of the oxidation of Zn3P2 with alkoxy complexes of Fe(III) was proposed.

The various esters of the phosphoric and phosphorous acids have been obtained directly from white phosphorus and aliphatic (or aromatic) alcohols under aerobic atmosphere in the presence of the CuX2 or FeX3 (X = Cl, NO3, C3H7CO2) salts. Irrespective of the variable nature of the used alcohols and catalysts, trialkyl(aryl) phosphates and dialkyl phosphites are a major products, whereas trialkyl(aryl) phosphites and dialkyl phosphates are a minor products of the phosphorylation process. Thanks to the presence of catalysts, the possible side reaction route of the radical chain oxidation of white phosphorus by oxygen to phosphorus oxides has been precluded. A comparison between the catalytic properties of CuX2 and FeX3 has been done. Although both of them have been found an efficient catalysts for the syntheses, the Cu(II) salts are active at 50-65 °C, whereas the Fe(III) based catalytic systems become competitive in terms of catalytic efficiency when reaction is carried out at 70-90 °C. Aromatic alcohols are characterised by less reactivity in this catalytic reaction as compared with an aliphatic ones. The same coordinative redox mechanism of the oxidative P-O coupling of P4 to ROH in the presence of both Cu(II) and Fe(III) catalysts has been proposed. Relevant steps of the catalytic cycle including the complexation of both white phosphorus and alcohol molecules to metal ion, the reduction of catalyst by white phosphorus, and the oxidation of reduced form of catalyst by oxygen have been also considered.

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

It was experimentally shown that dioxane solutions of 1,4-benzoquinone and HgCl2 at 50-80 degrees C rapidly absorb even trace amounts of PH3 from PH3-Ar gas mixtures with the formation of tetrakis(hydroxyphenoxy)phosphonium chloride [(HOC6H4O)(4)PCl]. In water-dioxane solutions of P-C6H4O2 and HgCl2, (HOC6H4O)(4)PCl and bis(hydroxyphenoxyl) phosphite [(HOC6H4O)(2)HPO] art: formed. In aqueous solutions of P-C6H4O2 and HgCl2, only (HOC6H4O)(2)HPO is formed. In the absence of HgCl2, dioxane solutions of p-C6H4O2 at 50-80 degrees C practically do not absorb PH3, whereas water-dioxane solutions of P-C6H4O2 absorb PH3 very slowly with the formation of phosphonic acid and hydroquinone. The kinetics and mechanism of the process as well as the intermediate compounds involved were studied by P-31 NMR spectroscopy, gas-liquid chromatography, redox potentiometry, and chemical modeling. Optimal conditions for the oxidative hydroxyphenoxylation of phosphine by 1,4-benzoquinone in the presence of Hg(II) chloride, a new reaction, were found.