- 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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- α-Radiolysis of the tributyl phosphate–hydrocarbon diluent–nitric acid system
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α-Radiolysis of tributyl phosphate in Sintin n-paraffin diluent in equilibrium with HNO3 solutions at single “internal” irradiation from the extracted 238Pu was studied. The radiation-chemical yields (molecules/100 eV) of butyl hydrogen phosphates (BHP), carboxylic acids, carbonyl compounds, and nitro compounds upon irradiation of 20% TBP in the treated Sintin in equilibrium with 3 M HNO3 were 0.4 (at dibutyl hydrogen phosphate to monobutyl dihydrogen phosphate ratio HDBP: H2MBP = 4.3), 1.4, 0.2–0.3, and 0.2–0.3, respectively. The degradation and oxidation processes occur more deeply than under γ-irradiation. A simple volumetric method for determining carboxylic acids in the extract was developed. In the course of irradiation, the Pu(IV) oxidation state in the extract does not change, and its retention is due to the interaction with BHP at the ratio BHP: Pu = 2 in stripping with 0.02 M HNO3 and BHP: Pu = 4 in stripping with Fe(II). The retention can be eliminated by the displacing action of Np(IV).
- Zilberman, B. Ya.,Chistyakov
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- Convenient preparation of long-chain dialkyl phosphates: Synthesis of dialkyl phosphates
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Reaction of phosphorus oxychloride with a primary alcohol (1.8 equiv) and triethylamine (1.8 equiv) in toluene, followed by filtration and treatment with steam, gives dialkyl phosphates in good yield and essentially free from trialkyl phosphate contamination. Georg Thieme Verlag Stuttgart · New York.
- Aitken, R. Alan,Collett, Chris J.,Mesher, Shaun T. E.
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- Oxidative cleavage of o-hydroxyphenyl phosphate by iodobenzene diacetate
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The protecting o-hydroxyphenyl group in the synthesis of mono- or dialkyl phosphates (6 or 8) could be removed by oxidative cleavage of mono- or dialkyl o-hydroxyphenyl phosphates (3 or 7) using iodobenzene diacetate.
- Wu, Pei-Lin,Chen, Jhy-Hong,Huang, Ded-Shih
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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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- Phosphorylated Glycoconjugates Based on Isosteviol, d-Arabinofuranose, and d-Ribofuranose
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First phosphorylated glycoconjugates were synthesized in three stages on the basis of isosteviol, d-arabinofuranose, and d-ribofuranose. In the first stage, isosteviol reacted with methyl 5-O-(p-tosyl)-2,3-di-O-benzoyl-d-ribofuranoside and methyl 5-O-(p-tosyl)-2,3-di-O-benzoyl-d-arabinofuranoside to give glycoconjugates in which the diterpenoid fragment is linked through ester bond to the carbohydrate C5 atom. In the second stage, the anomeric methoxy group in the furanoside fragment was replaced by bromine, and the resulting 2,3-di-O-benzoyl-d-ribofuranosyl and 2,3-di-O-benzoyl-d-arabinofuranosyl bromides were treated with dibutyl phosphate to afford the target phosphorylated derivatives.
- Sharipova,Belenok,Strobykina, I. Yu.,Kataev
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p. 508 - 513
(2019/06/05)
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- Novel photolabile protecting group for phosphate compounds
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A novel photolabile protecting group, thiochromone S,S-dioxide, containing the diazomethyl group for protection of phosphate derivatives is described. Deprotection of the successfully protected phosphate derivatives proceeded smoothly under photoirradiation using an ultrahigh-pressure mercury lamp to recover the corresponding phosphates quantitatively, and the photoproduct derived from the thiochromone derivative showed high fluorescence intensity. Georg Thieme Verlag Stuttgart · New York.
- Zhang, Youlai,Tanimoto, Hiroki,Nishiyama, Yasuhiro,Morimoto, Tsumoru,Kakiuchi, Kiyomi
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scheme or table
p. 367 - 370
(2012/03/11)
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- Reactivity of an electrophilic hypervalent iodine trifluoromethylation reagent with hydrogen phosphates - A mechanistic study
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The electrophilic trifluoromethylation of hydrogen phosphates with the reagent trifluoromethyl-1,3-dihydro-3,3-dimethyl-1,2-benziodoxole (1) was studied by means of initial rates determined for pseudo first order setups and subsequent Taft analysis of the calculated relative rates. A positive polar sensitivity factor, indicative of a negative charge forming during the rate-determining step, was found for the whole data set.
- Santschi, Nico,Geissbühler, Patrik,Togni, Antonio
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- Selective P-P and P-O-P bond formations through copper-catalyzed aerobic oxidative dehydrogenative couplings of H-phosphonates
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(Chemical Equation Presented) Different copper complexes selectively catalyze the aerobic oxidative coupling of H-phosphonates to afford either hypophosphates and pyrophosphates in high yields with high selectivity (see scheme; tmeda = N, N, N', N'-tetramethylethylenediamine).
- Zhou, Yongbo,Yin, Shuangfeng,Gao, Yuxing,Zhao, Yufen,Goto, Midori,Han, Li-Biao
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body text
p. 6852 - 6855
(2010/12/19)
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- Determination of phosphoric acid mono- and diesters in municipal wastewater by solid-phase extraction and ion-pair liquid chromatography-tandem mass spectrometry
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The first analytical method for the determination of 13 phosphoric acid mono- and diesters from aqueous samples is presented. The method consists of solid-phase extraction (SPE) and ion-pair liquid chromatographic separation with tri-n-butylamine coupled to electrospray ionization tandem mass spectrometry in the negative ion mode. Due to a lack of pure standards, only 3 of the 13 esters could be quantified. SPE recoveries ranged from 71 to 112% for di-n-butyl phosphate, diphenyl phosphate, and di-(2-ethylhexyl) phosphate (DEHP) with limits of quantification from 7 to 14 ng/L for 100-mL samples. At analyte concentrations ≥1 μg/L, aqueous samples can be analyzed by direct injection without extraction. In municipal wastewater, six diesters and one monoester were unambiguously identified by comparison with synthesized reference material. DEHP showed highest concentrations of 60 and 5 μg/L in raw and treated wastewater, respectively. The detection of monoethylhexyl phosphate was confirmed by LC-Q-TOF-MS analysis, and it was found at a concentration level comparable to DEHP. Laboratory degradation tests show that phosphoric acid diesters can be formed as intermediates in the microbial degradation of trialkyl phosphates that are being used as flame retardants and plasticizers.
- Quintana, Jose Benito,Rodil, Rosario,Reemtsma, Thorsten
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p. 1644 - 1650
(2008/02/05)
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- Synthesis of mono-and dialkylphosphates by the reactions of hydroxycompounds with the phosphorus pentaoxide under microwave irradiation
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The reactions of phosphorus pentoxide with two alcohols and one phenol were performed in different conditions under microwave irradiation. The products (alkylphosphates and dialkylphosphates) were identical to those formed by classic heating and were obtained with better yields. The speed of the reaction was increased by a factor from 100 to 4000.
- Elias, Abdelhamid,Didi, M. Amine,Villemin, Didier,Semaoune,Ouattas
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p. 2599 - 2607
(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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- 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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- An alternative route to the preparation of (3' → 5') methylene acetal linked di- and trinucleosides
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Reaction of deoxynucleoside 3'-O-(methylthiomethyl) acetals 1 with N-iodosuccinimide (NlS) and dibutyl phosphate furnished the corresponding 3'-O-(dibutoxyphosphoryloxy)methyl acetals 6. Condensation of the latter with appropriately protected deoxynucleoside acceptors 3, in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf), afforded in most cases the (3' → 5') methylene acetal linked d(B(1Λ) B2) dimers 4. In addition, TMSOTf-promoted coupling of donor 6 (B1 = C(Bz)) with 3'-O-(methylthiomethyl)thymidine (8) yielded dimer 9. Reaction of 9 with NIS and dibutyl phosphate gave dimer 10, which was applied successfully in the TMSOTf-assisted fusion with acceptors 3 (B2 = C(Bz) and A(Bz)), to afford the corresponding trimers d(C(Λ)T(Λ)C) 11 and d(C(Λ)T(Λ)A) 12.
- Quaedflieg,Timmers,Van Der Marel,Kuyl-Yeheskiely,Van Boom
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p. 627 - 633
(2007/10/02)
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- CONVENIENT SYNTHETIC ROUTE TO MONO- OR DIAKLYL PHOSPHATE FROM INORGANIC PHOSPHORUS ACIDS
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Mono- or dialkyl phosphate was synthesized in a favorable yield by oxidation of phosphonic or phosphinic acid in alcohol with oxygen at the presence of a catalytic amount of copper(II)chloride.The reaction may proceed via the formation of corresponding phosphorochloridate or phosphorochloridite.
- Okamoto, Yoshiki,Kusano, Tetuya,Takamuku, Setsuo
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p. 195 - 200
(2007/10/02)
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