- Cu-catalyzed oxidative phosphorylation of alkanols with white phosphorus and H2O2
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Oxidative phosphorylation of alkanols with white phosphorus in the presence of catalytic amounts of CuCl2 has been effected. The reaction proceeds in the aqueous H2O2-HCl system exothermically to form dialkylphosphites and trialkylphosphates in a total yield of up to 35%. Conditions for selective synthesis of dialkylphosphites in moderate yield have been found.
- Trofimov, Boris,Timokhin, Boris,Gusarova, Nina,Kazantseva, Marina,Golubin, Alexander
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- Catalytic method of synthesis of phosphorus acids esters from zinc phosphide and alcohol
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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.
- Polimbetova,Ibraimova,Borangazieva
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- Phosphadioxirane Intermediates in the Reaction of Singlet Oxygen with Phosphites and Phosphines
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Intermediates in the singlet oxygen reaction of phosphites and phosphines have been studied by trapping and tracer experiments.Trapping study with diphenyl sulfoxide revealed that the added substrate and phosphite are competing toward the same intermediate.The relative reactivity of (BuO)3P/Ph2S/Ph2SO = 300:4:1 and the negative ρ-value of -0.63 for diphenyl sulfoxides are not consistent with 1,3-dipolar phosphine peroxides, but suggest electrophilic O-transfers by cyclic phosphadioxiranes.Intermediacy of phosphadioxiranes was supported by an 18O-tracer study on the formation of rearranged diphenylphosphinate from 1O2 and triphenylphosphine.Theoretical calculations also supported the dioxirane intermediate by predicting no existence of 1,3-dipolar peroxide.
- Tsuji, Shoei,Kondo, Masaaki,Ishiguro, Katsuya,Sawaki, Yasuhiko
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- Oxidizing alkoxylation of phosphine in alcoholic solutions of iodine
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Oxidizing alkoxylation of PH3 to trialkyl phosphates was performed in pyridine-alcoholic solutions of iodine. The optimal conditions of the reaction were found.
- Polimbetova,Borangazieva
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- Utilization of Oxidizing Character of TeCl4 in the Reaction with Trialkyl Phosphite. A Novel Redox Phosphorylation
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Oxidation-reduction reaction of a trialkyl phosphite with TeCl4 in the presence of an alcohol and tert-amine proceeded smoothly to afford the corresponding phosphorylation product in good yield.
- Watanabe, Yutaka,Yamamoto, Takashi,Iwasaki, Taroh,Ozaki, Shoichiro
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- ELECTROCHEMICALLY INDUCED PROCESSES IN THE FORMATION OF PHOSPHORUS ACID DERIVATIVES. 1. SYNTHESIS OF TRIALKYL PHOSPHATES FROM WHITE PHOSPHORUS
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An electrochemical method, based on the joint action of nucleophilic and electrophilic reagents on P4, is proposed in order to utilize white phosphorus in the formation of the esters of phosphorus acids.The action of alkoxide ions on white phosphorus in an alcohol medium in the presence of iodine generated at the anode leads to the formation of phosphate esters.A scheme in which the intermediate products are dialkyl and trialkyl phosphites and the side product is dialkyl alkylphosphonate is proposed for the process.Key words: Phosphate esters, white phosphorus, electrosynthesis.
- Romakhin, A. S.,Budnikova, Yu. G.,Zaripov, I. M.,Kargin, Yu. M.,Nikitin, E. V.,et al.
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- Oxidation of phosphine with quinone and quinoid redox polymers in alcohol solutions of copper
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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.
- Polimbetova,Mukhitdinova,Ergozhin,Borangazieva,Khakimbolatova, K. Kh.,Tasmagambet,Dauletkulova,Ibraimova, Zh. U.
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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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- 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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- Hydrophosphonylation of Alkynes with Trialkyl Phosphites Catalyzed by Nickel
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The use of simple and inexpensive NiCl2?6 H2O as a catalyst precursor for C?P bond formation in the presence of commercially available trialkyl phosphites (P(OR)3, R=Et, iPr, Bu, SiMe3) along with several alkynes is presented. Control experiments showed the in situ formation of (RO)2P(O)H as the species that undergo the addition into the C≡C bond at the alkynes to yield the product of P?H addition. The hydrophosphonylation of diphenylacetylene with P(OEt)3, P(OiPr)3, and P(OSiMe3)3 proceeds in high yields (>92 %) without the need of a specific solvent or ligand. This method is useful for the preparation of organophosphonates for both phenylacetylene as a terminal alkyne model and internal alkynes in yields that range from good to modest.
- Islas, Rosa E.,García, Juventino J.
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p. 4125 - 4131
(2017/10/09)
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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 0033; 0034
(2017/01/02)
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- Trends in small angle neutron scattering of actinide-trialkyl phosphate complexes: A molecular insight into third phase formation
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The "third phase" formation phenomenon in solvent extraction is due to the aggregation of extracted species and formation of reverse micelles. As Small Angle Neutron Scattering (SANS) is a powerful tool to probe colloidal particles, it is considered as an important technique to study the aggregation behaviour of actinide complexes in solvent extraction systems. The actinide specific trialkyl phosphate (TalP) based extractants, namely, tri-n-butyl phosphate (TBP), tri-iso-butyl phosphate (TiBP), tri-sec-butyl phosphate (TsBP) and tri-sec-amyl phosphate (TsAP) have been examined for the first time using the SANS technique to investigate third phase formation phenomena with some of the actinides. SANS was employed to get insight into third phase formation in the extraction of Th(iv) and U(vi) from 1 M HNO3 by 1.1 M solutions of TalP in deuterated dodecane (n-C12D26, 98 atom% D). Deuterated diluent was used in order to provide contrast during the neutron scattering measurements. Potential energy and the stickiness parameter of reverse micelles formed in the above solvent systems have been quantified as a function of organic metal loading. The data are fitted using Baxter's sticky-sphere model. The stickiness parameter, (τ-1) a measure of the attractive interaction between the micelles, as well as the attractive potential energy (U0) was quantified. A clear correlation has been established between the stickiness parameter and the tendency for third phase formation with TalP systems. As U(vi) does not form a third phase with these extractants at 1 M HNO3, comparative studies were carried out with U(vi)-TalP complexes. These studies established lower stickiness and attraction between the micelles with the U(vi) system. The correlation between SANS parameters and third phase formation tendency was extended to a temperature dependence study and these studies established higher third phase limits when the temperature was enhanced, corroborating well with our experimental results. Our studies also revealed the "prediction of third phase formation" before its occurrence for a range of actinide-extractant systems.
- Chandrasekar, Aditi,Suresh,Sivaraman,Aswal
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p. 92905 - 92916
(2016/10/11)
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- Oxidative alkoxylation of phosphine in alcohol solutions of copper halides
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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.
- Polimbetova,Borangazieva,Ibraimova, Zh. U.,Bugubaeva,Keynbay
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p. 1539 - 1544
(2016/08/26)
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- Function of substituents in coordination behaviour, thermolysis and ligand crossover reactions of phosphine oxides
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Some selected aminophosphine oxides (AmPOs) of the type OP(NMe2)3, OPPh(NMe2)2, OP(NC2H4O)3, OPPh(NC2H4O)2 and their corresponding La(III) and Th(IV) complexes are synthesized and analyzed by FT-IR, 1H-NMR, 31P{1H}-NMR, elemental analysis and TGA data. The coordination behavior of AmPOs was compared with some of the known ligands that include trioctylphosphine oxide (TOPO), tributylphosphate (TBP) and diethylphosphite (DEP). Thermogravimetric analysis of these complexes showed a distinct decomposition trend either by a single step or multi-step elimination of ligand species, which are strongly dependent on the electronic and steric behaviour of substituents on the P=O group and the nature of the metal. Phosphine oxide based La(III) and Th(IV) complexes undergo three unique intermolecular ligand exchange reactions at room temperature: relative competition among phosphine oxides to form a strong complex by exchanging the weaker ligand and complete ligand transfer from La(III) to Th(IV) metal centers. Ligand crossover is well controlled by priority rules and the trend is TOPO > TBP > DEP > AmPO > Ph3PO. This tendency closely agrees with the stability constants of metal complexes. On comparison, Th(IV) complexes showed slightly higher stability than La(III) analogues.
- Pavankumar,Goud, E. Veerashekhar,Selvakumar,Kumar, S. K. Ashok,Sivaramakrishna, Akella,Vijayakrishna, Kari,Rao, C. V. S. Brahmananda,Sabharwal,Jha, Prakash C.
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p. 4727 - 4736
(2015/03/03)
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- Obtaining of trialkylphosphates in anodic dissolution of copper phosphide
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Due to obtain trialkylphosphate is suggested to use anodic solution of copper phosphide in alcohol solutions. At this, it can use copper phosphide, obtained at the processing of wastes of phosphorus production. Moreover, it is presented ways of obtaining of tri-n-butylphosphate and tri-izo-butylphosphate.
- Aueshov,Satayev,Tukibayeva
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p. 1553 - 1556
(2015/04/22)
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- A flash photolysis and theoretical study of the reaction of arylnitroso oxides with phosphorus(III) compounds
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The kinetic features of the reaction of aromatic nitroso oxides (ArNOO) with tri-n-butyl phosphite and substituted phosphines were studied by flash photolysis. It was shown that the trans-isomers of nitroso oxides enter into the reaction. The mechanism of the reaction was studied by theoretical methods, and the inertness of the cis-form of ArNOO was explained.
- Khursan,Kovaleva,Chainikova,Talipov,Safiullin
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experimental part
p. 284 - 289
(2011/11/12)
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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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- Rapid and high yield oxidation of phosphine, phosphite and phosphinite compounds to phosphine oxides, phosphates and phosphinates using hypofluorous acid-acetonitrile complex
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The hypofluorous acid acetonitrile complex was used as a mild, rapid, and effective agent to oxidize a wide variety of phosphines, phosphites and phosphinites to the corresponding phosphine oxide, phosphate and phosphinate compounds.
- Peng, Weimin,Shreeve, Jean'Ne M.
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p. 1054 - 1056
(2007/10/03)
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- Oxidative alkoxylation of zinc phosphide in a butanolic solution of iron(III) chloride
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Zinc phosphide in a butanolic solution of FeCl3 was oxidized by oxygen at 60 to 90°C into dibutyl phosphite (BuO)2HPO. The kinetics and mechanism of the oxidative alkoxylation of Zn3P 2 in the presence of FeCls
- Ibraimova,Polimbetova,Aleshkova,Borangazieva
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p. 1265 - 1269
(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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- Irreversibility of single electron transfer occurring from trivalent phosphorus compounds to iron(III) complexes in the presence of ethanol
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Various types of trivalent phosphorus compounds (1; Ph(3-n)P(OR)n) underwent single electron transfer (SET) to unsubstituted (2H) and 5-chloro-substituted tris(1, 10-phenanthroline)iron(III) complexes (2Cl) in the presence of ethanol in acetonitrile, resulting in the reduction of 2 to the corresponding iron(II) complexes. The rate constants (kp) for the overall SET process were determined spectrophotometrically to show that within each series of 1 with an identical alkoxy group OR, log kp correlates linearly with the difference in the half-wave potentials (ΔE1/2) between 1 and 2. The slope of each correlation line gave an α-value for each series of 1. The α-values were significantly smaller than unity, indicating that the SET step is irreversible, even though this step is endothermic. The trivalent phosphorus radical cation 1.+ generated in the SET step undergoes a rapid ionic reaction with ethanol, which is certainly the origin of the irreversibility. Upon examining the α-values more closely, it was found that the transition state of the SET step becomes earlier with increasing bulkiness of the substituent OR. It is concluded that 1 and 2 form a tight encounter complex to undergo SET from the former to the latter.
- Yasui, Shinro,Itoh, Kenji,Tsujimoto, Munekazu,Ohno, Atsuyoshi
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p. 1311 - 1318
(2007/10/03)
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- Dehydration of LnCl3·6H2O (Ln=Tb, Nd, Dy) in the reaction with i-Bu3Al, Et3Al, Et2AlCl, EtAlCl2 and formation of the complexes LnCl3·3(BuO)3PO
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The dehydration of toluene insoluble salts TbCl3·6H2O (1), DyCl3·6H2O (2) and NdCl3·6H2O (3) in their reaction with organoaluminum compounds (RnAlX3-n): i-Bu3Al, Et3Al, Et2AlCl, EtAlCl2 and the influence of (BuO)3PO (TBP) on the process were studied. In the reaction of RnAlX3-n with the water of crystallization of salts 1-3, aluminoxanes and the following gases are formed: i-BuH for i-Bu3Al, EtH for Et3Al, EtH and HCl for Et2AlCl and EtAlCl2 as a result of the attack on the Al-C or Al-Cl bond independent of the presence of TBP. In the absence of TBP the salts 1-3 are dehydrated by RnAlX3-n to give insoluble products LnCl3·0.5H2O·0.5(R2Al) 2O, where R is alkyl for i-Bu3Al and Et3Al, or R is alkyl and Cl for Et2AlCl. The reaction of RnAlX3-n with 1-3 in the mixture of toluene-TBP at the ratio TBP/Ln≥12:1 results in the complete removal of water from LnCl3·6H2O and leads to the formation of homogeneous solutions, containing aluminoxanes and LnCl3·3TBP complexes. Homogeneous solutions, obtained after interaction in the system NdCl3·6H2O+TBP+PhMe+R3Al were then activated with either i-Bu3Al or (i-Bu2Al)2O and used as catalysts for polymerization of butadiene. All the catalysts were highly active for polymerization of butadiene, and produced a low-molecular polybutadiene.
- Bulgakov, Ramil G.,Kuleshov, Sergei P.,Zuzlov, Aleksei N.,Mullagaleev, Ildar R.,Khalilov, Leonard M.,Dzhemilev, Usein M.
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- Quenching of a photosensitized dye through single-electron transfer from trivalent phosphorus compounds
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Various types of trivalent phosphorus compounds 1 undergo single-electron transfer (SET) to the photoexcited state of rhodamine 6G (Rho+(*)) in aqueous acetonitrile to quench the fluorescence from Rho+(*). The rate constants k(p) for the overall SET process were determined by the Stern-Volmer method. The rate is nearly constant at a diffusion-controlled limit in the region of E( 1/2 )(1) +), whereas log k(p) depends linearly on E( 1/2 )(1) in the region of E( 1/2 )(1) > 1.3 V, the slope of the correlation line being -αF/RT with α = 0.2. The potential at which the change in dependence of log k(p) on E( 1/2 )(1) occurs (1.3 V) is in accordance with the value of E( 1/2 )(Rho+(*)) (1.22 V) that has been obtained experimentally. Thus, the SET step is exothermic when E( 1/2 )(1) 1.3 V. The α-value (0.2) obtained in the endothermic region shows that the SET step from 1 to Rho+(*)is irreversible in this region. Trivalent phosphorus radical cation 1(·+) generated in the SET step undergoes an ionic reaction with water in the solvent rapidly enough to make the SET step irreversible. In contrast, the SET from amines 2 and alkoxybenzenes 3 to Rho+(*) is reversible when the SET step is endothermic, meaning that the radical cations 2(·+) and 3(·+) generated in the SET step undergo rapid 'back SET' in the ground state to regenerate 2 and 3.
- Yasui, Shinro,Tsujimoto, Munekazu,Itoh, Kenji,Ohno, Atsuyoshi
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p. 4715 - 4720
(2007/10/03)
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- Some properties of cyclic phosphoramidites and their phosphites: Phosphitylation, ester exchange, and hydrolysis
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Phosphorylation of diols using sterically bulky cyclic phosphoramidites was performed in a good selectivity. Their phosphite derivatives underwent tetrazole-catalyzed hydrolysis and transesterification. The reaction was shown to proceed via a phosphorane intermediate by NMR analysis.
- Watanabe, Yutaka,Maehara, Shin-Ich
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p. 799 - 810
(2007/10/03)
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- Chlorine free synthesis of organophosphorus compounds based on the functionalization of white phosphorus (P4)
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Oxidative alkoxylations of P4 in toluene-alcohol solutions are studied. These reactions need oxygen, a catalyst (PdCl2, RuOHCl3, RuCl3) and a co-oxidant (CuCl2, NaNO2, FeCl3, 1,4-benzoquinone, NaBrO3). Trialkylphosphates (RO)3P(O) and dialkylphosphites (RO)2P(O)H are the major products of the reaction. Kinetic experiments concerning the rate of absorption of O2 during these reactions are also reported.
- Abdreimova, Rumiya R.,Akbayeva, Dina N.,Polimbetova, Gulshara S.,Caminade, Anne-Marie,Majoral, Jean-Pierre
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p. 239 - 254
(2007/10/03)
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- Transesterification process
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PCT No. PCT/GB95/01883 Sec. 371 Date Jul. 21, 1997 Sec. 102(e) Date Jul. 21, 1997 PCT Filed Aug. 9, 1995 PCT Pub. No. WO96/05208 PCT Pub. Date Feb. 22, 1996A process for the preparation of a phosphate ester is disclosed. A triaryl phosphate is reacted with an alcohol in the presence of a catalytic quantity of a base to produce the phosphate ester product. The base has a base strength of less than 11, and is preferably potassium fluoride or potassium carbonate. Trialkyl phosphates, dialkyl monoaryl phosphates, monoalkyl diaryl phosphates, and mixtures of these compounds can be produced by this process.
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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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- Reaction of pyrimidyl esters of some phosphorus acids with isomeric butyl alcohols
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A series of pyrimidyl esters of some phosphorus acids was prepared with the purpose of investigation of their reaction with isomeric butyl alcohols. According to31P NMR data, the obtained phosphates all are capable of phosphorylating isomeric butyl alcohols. The reactions with diphenyl (4-oxo-3,4-dihydro-2-pyrimidyl) phosphate and diphenyl (2-pyrimidyl) phosphate occur in quantitative yield under mild conditions, and the reactions with diphenyl (4,6-dimethyl-2-pyrimidyl) phosphate and dibutyl (4,6-dimethyl-2-pyrimidyl) phosphate require severe conditions to occur. In the latter two cases, certain reaction selectivity was observed, depending on the nature of the solvent and some other factors. Pyrimidyl esters of sulfur-containing phosphorus acids do not react with isomeric butyl alcohols under the studied conditions.
- Semenov,Akamsin,Enikeev,Reznik
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p. 1386 - 1388
(2007/10/03)
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- Process for preparing organic pentavalent phosphorus compounds
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A process for preparing an organic pentavalent phosphorus compound comprising oxidizing an organic trivalent phosphorus compound with an aqueous hydrogen peroxide solution in the presence of an inorganic or organic base at a temperature of 0° C. to 50° C. to obtain the corresponding organic pentavalent phosphorus compound.
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- Reaction of trivalent phosphorus compounds with an Fe(III) complex in the presence of alcohol. Single electron transfer accompanied by a P-O bond formation
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Reactions of various types of trivalent phosphorus compounds with iron(III) complex in the presence of ethanol have been examined kinetically, showing that the single electron transfer from the former compounds to the latter is followed by rapid reaction of the resulting trivalent phosphorus radical cations with ethanol.
- Yasui, Shinro,Itoh, Kenji,Tsujimoto, Munekazu,Ohno, Atsuyoshi
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p. 1019 - 1020
(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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- 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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- Electrosynthesis of aliphatic esters of phosphorus acids from white phosphorus in alcohol solutions, involving radical cations of phenothiazine and triarylamine
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Aliphatic esters of phosphorus acids can be prepared from white phosphorus by electrolysis of emulsified white phosphorus in alcohol solutions of phenothiazine or triarylamine.
- Budnikova, Yu. G.,Kargin, Yu. M.
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p. 504 - 507
(2007/10/03)
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- Direct Transformation of Trialkyl Phosphates into Organolithium Compounds by a DTBB-Catalysed Lithiation
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The reaction of different alkylic or phenylic phosphates 1 with an excess of lithium powder and a catalytic amount of DTBB (5 mol percent) in the presence of an electrophile -Barbier-type reaction conditions- in THF at -30 deg C leads to the formation of the expected products 2, resulting from the reaction of the in situ generated organolithium compound with the corresponding electrophile.
- Guijarro, David,Mancheno, Balbino,Yus, Miguel
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p. 8551 - 8558
(2007/10/02)
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- KINETIC RELATIONS IN THE SYNTHESIS OF DIALKYL CHLOROPHOSPHATES
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Kinetics of the reaction between butyl dichlorophosphate and butanol has been studied in a wide range of reactant molar ratios and temperatures in ampuls with complete conservation of hydrogen chloride and in a batch reactor with periodic purging of hydrogen chloride from the reaction mixture.In the first case consumption of dibutyl chlorophosphate is markedly accelerated, and its yield is considerably decreased.Removal of hydrogen chloride from the reaction zone is important.This was confirmed by study of the influence of various solvents on the process in question: the maximum yield of product is attained when the process is carried out in pyridine.
- Savel'yanov, V. P.,Klochkov, A. N.
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p. 1769 - 1771
(2007/10/03)
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- FACTORS DETERMINING THE REACTIVITY OF PHOSPHOROUS TRIESTERS IN REACTIONS WITH CUMENE HYDROPEROXIDE
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The kinetics of reduction of cumene hydroperoxide with a wide range of aliphatic and aromatic phosphorous triesters in benzene were studied by the polarographic method.Factors determining the reactivity of the phosphites in this reaction were investigated by the method of correlation analysis.
- Cherkasova, O. A.,Galkin, V. I.,Sayakhov, R. D.,Mukmeneva, N. A.,Cherkasov, R. A.
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p. 862 - 865
(2007/10/02)
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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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- PROMOTING ACTION OF POCl3 IN o-PHOSPHORIC ACID ESTERIFICATION BY n-BUTANOL
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The opportunity of tri-n-butylphosphate (TBP) synthesis via esterification of o-phosphoric acid with n-butanol, under special conditions, was investigated.The reagents were contacted without solvent in an autoclave, in the presence of small amounts of phosphorus oxichloride (ca. 6E-4 mole per gram of reaction mixture), under argon pressure, during 3 hours.A strong dependence is observed between all operating parameters i.e. temperature, pressure, phosphorus oxichloride content and the reagents mole.The results obtained show clearly the promoting action of phosphorus oxichloride.It was also depicted that TBP synthesis is the main reaction in such conditions.An additive optimization study allowed to confirm the previous observations.Compared to the classical TBP synthesis ways, the present procedure appears as being a very interesting low cost alternative if one takes into account that the use of phosphorus oxichloride as reagent is avoided.
- Attou, Mouloud,Zaoui, Brahim,Azzouz, Abdelkrim
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p. 673 - 678
(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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- 1H-Tetrazole Catalysed Reactions of Trialkyl Phosphites: Observation of a Five-membered Cyclic Hydrophosphorane Intermediate during the Transesterification
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1H-Tetrazole-catalysed transesterification of a trialkyl phosphite with an alcohol and a (31)P NMR experiment in the case of 4,4,5,5-tetramethyl-2-(3-phenylpropoxy)-1,3,2-dioxaphospholane showed the existence of the corresponding cyclic five-coordinate hydrophosphorane as an intermediate.
- Watanabe, Yutaka,Maehara, Shin-ichi,Ozaki, Shoichiro
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p. 1879 - 1880
(2007/10/02)
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- CHLORINATION OF PHOSPHINE IN ALCOHOLS
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Trialkyl phosphates are rapidly and selectively formed when dilute gaseous PH-Ar and Cl2-Ar mixtures are passed into alcohols (ROH, R=Bu, i-Bu, Am, i-Am, Oct) at 50-70 deg C.Analogous results are obtained in the presence of pyridine at 8-25 deg C.The reaction was studied by gas chromatography, 31P NMR spectroscopy, and potentiometry.The reaction was shown to pass successively through the stages of the chlorination of phosphine to PCl5, the alcoholysis of phosphorus pentachloride to phosphoryl chloride, and finally by the esterification of phsophoryl chloride to trialkyl and dialkyl phosphates.Pyridine, excess af alcohol, and high temperature accelerate the stage of the esterification of phosphoryl chloride to the trialkyl phosphate.
- Dorfman, Ya. A.,Polimbetova, G. S.,Aibasov, E. Zh.,Borangazieva, A. K.,Kokpanbaeva, A. O.,Faizova, F. Kh.
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p. 1860 - 1864
(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 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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- SYNTHESIS OF TRIALKYL PHOSPHATES FROM RED PHOSPHORUS
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The oxidation of red phosphorus by oxygen in an alcohol solution of a heterovalent copper (II, I) complex leads to the formation of trialkyl phosphates and alkyl chlorides at high rates with high selectivity.Quantitative yields of trialkyl phosphates are observed in neutral alcohol media in the absence of water at up to 323 deg K and an oxygen pressure of up to 2.5*10-6 Pa.The reaction rate increases in solutions of alcohols in the following order: iso-AmOH BuOH PrOH EtOH MeOH.
- Dorfman, Ya. A.,Aleshkova, M. M.,Karinskaya, A. S.,Borangazieva, A. K.,Kebekbaeva, M. M.
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p. 999 - 1008
(2007/10/02)
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