- METHOD FOR PRODUCING PHOSPHOESTER COMPOUND
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PROBLEM TO BE SOLVED: To provide a method whereby, a phosphate compound selected from the group consisting of orthophosphoric acid, phosphonic acid, phosphinic acid, and anhydrides of them is used as raw material and, by one stage reaction, a corresponding phosphoester compound is produced. SOLUTION: To an aqueous solution of a phosphate compound, added is an organic silane or siloxane compound having an alkoxy group or an aryloxy group, and the mixture is subjected to a heating reaction, thereby producing a corresponding phosphoester compound without requiring a catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0023; 0026-0028
(2021/09/27)
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- Kinetics and adsorption calculations: insights into the MgO-catalyzed detoxification of simulants of organophosphorus biocides
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We report the targeted decomposition of the organophosphate methyl paraoxon by means of its transesterification with 1-propanol catalyzed by magnesium oxide. Catalyst characterization by energy dispersive X-ray fluorescence (EDXRF), nitrogen adsorption/desorption measurements (BET and BJH methods), and temperature programmed desorption of CO2(CO2-TPD) showed that the employed MgO presents properties favorable for the methyl paraoxon adsorption and transesterification to occur. A thorough kinetic investigation showed that rate enhancements up to 3 × 106-fold can be achieved in comparison with the spontaneous propanolysis of the substrate, and that the material can be used in additional cycles without loss of catalytic activity, with the catalyst recovery achieved through a simple washing procedure. Energies for adsorption of 1-propanol and methyl paraoxon onto a MgO model surface were obtained by density functional theory calculations, which showed that the latter displays a stronger affinity for the catalyst surface, and that the reaction should proceed with methyl paraoxon and 1-propanol molecules juxtapositioned at adjacent Mg2+sites, with nucleophilic and electrophilic centersca.2.4 ? away from each other. Additionally, MgO also promoted rate enhancements up to 5 × 104-fold in the propanolysis of a further range of representative phosphate triesters, and in most of the cases the final transesterified products are trialkyl phosphates structurally related to a family of flame-retardants. The results thus provide insights into the development of novel systems for the targeted conversion of organophosphorus compounds into value-added products by employing simple, highly efficient, and low-cost metal oxide catalysts.
- Almerindo, Gizelle I.,Buratto, Suelen C.,Caramori, Giovanni F.,Fiedler, Haidi D.,Medeiros, Michelle,Micke, Gustavo A.,Nicolazi, Lucas M.,Nome, Faruk,Parreira, Renato L. T.,Sangaletti, Patrícia,Schneider, Felipe S. S.,Wanderlind, Eduardo H.
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p. 19011 - 19021
(2020/10/02)
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- Method for synthesis of n-propyl phosphoric acid
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The invention provides a preparation method for n-propyl phosphate. The preparation method comprises the following steps: (1) reacting tri-n-propyl phosphite with bromopropane under the catalysis of potassium iodide to obtain n-propyl di-n-propyl phosphate, wherein the reaction temperature is 50-70 DEG C; (2) reacting n-propyl di-n-propyl phosphate with trimethylsilyl chloride at the circumfluence temperature in an aprotic solvent under the catalysis of potassium bromide or potassium iodide to obtain n-propyl phosphate. The preparation method is easy to get the adopted raw materials, low in toxicity, less in by-products, easy to purify, low in cost and suitable for industrialized production. The reaction route of the preparation method is as follows: (as is shown in the Specification).
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Paragraph 0029; 0030; 0031
(2016/11/21)
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- Method of synthesizing alkyl phosphate
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The invention relates to a method of synthesizing alkyl phosphate. The method includes: in the process of synthesizing alkyl phosphate, using inert substance to mix with reactant alcohol; dropwise adding phosphorus oxychloride at low temperature, allowing reaction at normal temperature for a period of time, and rising temperature for reaction; using alkali for neutralizing, washing with water, and distilling to remove low-boiling-point solvent and reactant; depressurizing and distilling to obtain high-purity alkyl phosphate. Due to existence of the third inert substance, reaction is enabled to be milder, and high yield is realized; a lot of generated hydrogen chloride is removed in a gaseous mode, so that alkali consumption is reduced and production cost is lowered.
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Paragraph 0046; 0047
(2017/01/02)
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- Electrocatalytic eco-efficient functionalization of white phosphorus
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The novel eco-efficient methods to transform white phosphorus into the esters of phosphoric, phosphorous and phosphonic acids, tertiary phosphines and other organophosphorus compounds under conditions of electrochemical catalysis were elaborated. The mechanism of these processes was investigated using the method of cyclic voltammetry and preparative electrolysis.
- Budnikova, Yulia H.,Yakhvarov, Dmitry G.,Sinyashin, Oleg G.
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p. 2416 - 2425
(2007/10/03)
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- Synthesis of mixed alkylphosphites and alkylphosphates
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Some mixed phosphites having two different alkyl chain were obtained as forerunners for mixed phosphates Mixed dialkyl phosphates were obtained in good yields (40-80%) by phase transfer catalysis in liquid-liquid sistem, starting from different dialkyl phosphites and aliphatic alcohols. The reaction conditions were optimized in order to obtain good yields in phosphites and phosphates respectively. Compounds were analyzed by IR, P31-NMR.
- Ilia, Gheorghe,Popa, Adriana,Iliescu, Smaranda,Bora, Alina,Dehelean, Gheorghe,Pascariu, Aurelia
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p. 1513 - 1519
(2007/10/03)
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- Oxidative alkoxylation of zinc phosphide in alcoholic solutions of copper(II) chloride
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Oxidative alkoxylation of Zn3P2 with the formation of valuable phosphoric and phosphorous acid esters occurred at a high rate and with a high selectivity in alcoholic solutions of CuCl2 under the action of oxygen at 30-60°C. Depending on the nature of the alcohol, two products were formed, namely, trialkyl phosphates (RO)3PO and dialkyl phosphites (RO)2HPO. Water favored the formation of dialkyl phosphates (RO)2(HO)PO. The kinetics and mechanism of the new catalytic reaction were studied, and the optimal conditions for conducting this reaction were found. The reaction proceeded in a topochemical mode by a separate redox mechanism.
- Dorfman,Ibraimova,Polimbetova
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- Absolute viscosity and density of trisubstituted phosphoric esters
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This paper presents measurements on the absolute viscosity (η) and density (ρ) of trisubstituted phosphoric esters which are useful in understanding their flow mechanism necessary for accessing their role as plasticizers. The effect of chain length and branching has been examined on the η and ρ trends. From η data, by using the Vogel-Tammann-Fulchur (VTF) equation, the VTF temperature (To) has been obtained which also represents the ideal glass transition temperature. To is related to the flexibility of the molecules. It is observed that To initially decreases with molecular weight, reaches a minimum, and increases thereafter. The initial decrease in To has been attributed to the enhanced flexibility of the phosphate esters. Reversal of flexibility with relative molar mass beyond 400 is due to the gentle collision of the arms of the trisubstituted phosphoric esters. This has been further corroborated from the molar mass exponent as exhibited in the η-molar mass plot. The isomeric effect on η has also been investigated in tricresyl phosphates, hitherto for the first time. The ortho isomer has highest η among the isomers. The para isomer was found to have lowest To and hence highest flexibility compared to the ortho and meta isomers.
- Kannan,Kishore
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p. 649 - 655
(2007/10/03)
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- Synthesis of Trialkyl Phosphates from White Phosphorus
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A new method was proposed for preparing trialkyl phosphates directly from white phosphorus by its electrolysis in a mixture of acetonitrile, alcohol, and water with tetraethylammonium iodide as supporting electrolyte. To increase the amount of the product synthesized in the unit volume of the electrolyte solution and the productivity of the process, phosphorus and water are added to the electrolyte in portions, which allows synthesis of up to 1 mol of trialkyl phosphate in 1 1 of the electrolyte solution.
- Romakhin,Nikitin
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p. 1023 - 1026
(2007/10/03)
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- Electrochemical Oxidation of Metal Dialkyl Phosphites and Their Reaction with Halogens
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Electrochemical oxidation of sodium dialkyl phosphites with alkyl radicals of normal structure leads to formation of tetraalkyl pyrophosphites as the main products, while electrochemical oxidation of litium dialkyl phosphites and sodium salts with branched alkyl radicals yields tetraalkyl hypophosphates. The reaction of metal dialkyl phosphites with halogens leads to analogous results.
- Romakhin,Zagumennov,Nikitin
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p. 1022 - 1026
(2007/10/03)
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- Oxidative P-O and P-C Coupling of Butanol with Phosphine in the Presence of Oxidizers and Platinum(IV) and Platinum(II)
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A butanol solution of Na2PtCl6 at 60-80°C in the presence of p-benzoquinone or NaBrO3 is found to rapidly consume even traces of PH3 until complete reduction of benzoquinone to hydroquinone or NaBrO3 to NaBr, respectively. The nature of products depends on the valence state of platinum and the nature of the oxidizer. Without an oxidizer, platinum(IV) is reduced to platinum(II) with formation of tributyl phosphate, the product of P-O coupling of PH3 with BuOH, while platinum(II) is reduced to platinum(0) with formation of butylbis(α-hydroxybutyl)phosphine oxide Bu(α-PrCHOH)2PO, the product of P-C coupling of PH3 with BuOH. In the presence of benzoquinone, which oxidizes Pt(0) to Pt(II), a P-C bond is formed, while in the presence of sodium bromate, which regenerates Pt(II) to Pt(IV), P-O coupling of PH3 with BuOH occurs. The products and principal steps of this new reaction were studied by the methods kinetics, red-ox potentiometry, chemical modeling, inhibition of free-radical reactions, 31P NMR, IR and X-ray photoelectron spectroscopy, X-ray spectral microanalysis, and gas-liquid chromatography. We showed that the P-C coupling of PH3 with BuOH is promoted by platinum(II) complex, while P-O coupling is promoted by platinum(IV) complex. In the key steps the Pt(II) butoxyphosphide complex PtCl3(OBu)(PH2)- arises from reaction of the Pt(II) phosphide complex with platinum(IV). The red-ox decomposition of intermediate complexes leads to formation of phosphinite (BuO)2PH2 and Pt(II), or (α-hydroxybutyl)phosphine and Pt(0). The catalytic cycles are completed by fast steps of oxidative butoxylation of (BuO)PH2 to (BuO)3PO or by α-hydroxybutylation of (PrCHOH)PH2 to Bu(PrCHOH)2PO, and oxidation of Pt(II) to Pt(IV) with bromate or Pt(0) to Pt(II) with benzoquinone, respectively.
- Dorfman,Polimbetova,Aibasov
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p. 231 - 247
(2007/10/03)
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- Synthesis of dialkyl phosphites and trialkyl phosphates by oxidation of sodium hypophosphite by copper(II) chloride
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Sodium hypophosphite oxidazies in alcoholic solution of CuCl2 at 50-80 deg C to give dialkyl phosphite and trialkyl phosphate.The yield of trialkyl phosphate increases with decreasing molecular weight of the alcohol and reaches ca. 100percent for MeOH and EtOH.The optimal conditions were found, and the mechanism of oxidation of NaPH2O2 to (RO)2PHO and (RO)3PO by copper(II) chloride was studied.The reaction proceeds via the formation of alkyl hypophosphite and copper(II) complexes with alkyl hypophosphite and dialkyl phosphite, which undergo inner-sphere two-electron redox decomposition with the liberation of dialkyl phosphite and trialkyl phosphate, respectively.
- Dorfman, Ya. A.,Aleshkova. M. M.
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p. 515 - 520
(2007/10/03)
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- OXIDATIVE ALKOXYLATION OF TETRAPHOSPHORUS
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A new quick and selective reaction of the oxidative alkoxylation of tetraphosphorus to trialkyl phosphates in the presence of CuCl2 is examined.Quantitative data are given on the effect of all the components and products of the reaction on the yield of trialkyl phosphates and on the key stages of the process: the reduction of CuCl2 by tetraphosphorus and the oxidation of CuCl by oxygen.The mechanism of the reaction is discussed.
- Dorfman, Ya. A.,Abdreimova, R. R.
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p. 206 - 214
(2007/10/02)
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- ELECTROCHEMICALLY INDUCED PROCESSES OF FORMATION OF PHOSPHORIC ACID DERIVATIVES. 3. ELECTROSYNTHESIS FROM WHITE PHOSPHORUS IN ALCOHOL-WATER SOLUTIONS
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It has been established that the process of splitting of the P-P bonds of the white phosphorus molecules is initiated by cathode-generated nucleophiles (HO-, RO-), while functionalization of the P-H bond formed in phosphoric oligomers occurs under the action only of alcohol.The primary product after splitting of all the P-P bonds in phosphoric oligomers is dialkylphosphite (in alcohol-water media), or trialkylphosphite (in absolute alcohol), in the course of electrolysis being transformed into trialkylphosphate.Formation of esters of pyrophosphoric acid with reduced protogenic character of the medium was examined.It is proposed that under these conditions nucleophilic reagents of the type (>P)c-O- form and participate in splitting of the P-P bonds. Keywords: phosphoric acid derivatives, white phosphorus, electrosynthesis, alcohol-water solution.
- Budnikova, Yu. G.,Kargin, Yu. M.,Zaripov, I. M.,Romakhin, A. S.,Ignat'ev, Yu. A.,et al.
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p. 1580 - 1584
(2007/10/02)
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- OXIDATIVE PHOSPHORYLATION OF ALCOHOLS BY ZINC PHOSPHIDE IN PRESENCE OF Cu(II) CHLORIDE
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Zinc phosphide in the absence of O2 is shown to decompose in alcoholic (EtOH, PrOH, and BuOH) solutions of CuCl2 to form corresponding trialkyl phosphates and cuprous chloride.Presence of O2 in these solutions results in the oxidative phosphorylation of alcohols by zinc phosphide to form corresponding trialkyl phosphates.The oxidative alcoholysis of zinc phosphide in the alcoholic solution of CuCl2 runs topochemically via the stages of partial hydrolysis of Zn3P2 to from zinc hydrogen phosphides, subsequent reduction of alcoholic complexes of cupric chloride by zinc hydrogen phosphide to cuprous complexes, and final oxidation of Cu(I) to Cu(II) by oxygen.
- Dorfman, Ya. A.,Petrova, T. V.,Sagandykova, R. R.,Doroshkevich, D. M.
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p. 1667 - 1681
(2007/10/02)
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- OXIDATIVE SYNTHESIS OF ALKYL PHOSPHATES FROM PHOSPHINE AND ALCOHOLS
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Neutral alkyl phosphates are prepared at a high rate and selectivity by direct oxidation of phosphine by oxygen in alcohol solutions of Cu(II, I) chlorides or acetates and in mixed solutions of Cu(I, II) with Hg(II), and of Cu(II, I) with Pd(II) chlorides.The process consists of two key stages: reduction of Cu(II) to Cu(I) chlorides or Cu(II) to Cu(0) acetates by phosphine with the formation of trialkyl phosphates and dialkyl ethers, accelerated by Cu(I) ions and mixtures of Cu(I) with Hg(II) and of Cu(I) with Pd(II) ions; regeneration of the Cu(I) or Cu(0) formed in the first stage by oxygen.Redox decomposition of binuclear heterovalent phosphine-alcohol complexes of Cu(II, I) is the limiting stage of substitute oxidative alkoxylation of the phosphine.In the mixed systems, Cu(II, I) complexes include Hg(II) or Pd(II) phospides instead of PH3.It was shown by CNDO and MOP that phosphine is converted into a strong electron acceptor forming strong bonds with coordinated compounds as a result of coordination.
- Dorfman, Ya. A.,Levina, L. V.,Aibasov, E. Zh.,Tungatarov, S. A.,Polimbetova, G. S.
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p. 1840 - 1853
(2007/10/02)
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- Chromogenic compounds and method for preparation thereof
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Chromogenic compounds for use in pressure sensitive recording sheets represented by the formula: SPC1 Are disclosed, wherein R1 and R2 are independently, hydrogen substituted or unsubstituted lower alkyl, aliphatic acyl, phenyl substituted aliphatic acyl, benzoyl, aralky, phenyl (the benzene nuclei of those substituents may be further substituted by chlorine, bromine, lower alkyl, lower alkoxy or nitro), allyl, allyl substituted by lower alkyl or phenyl, propargyl, or propargyl substituted by lower alkyl or a phenyl; R3 and R4 are independently lower alkyl, benzyl and phenyl (the benzene nuclei or those substiutents may be further substituted by chlorine, bromine, lower alkyl or lower alkoxy), either R1 or R2 being other than hydrogen when R3 and R4 are both ethyl groups.
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