- Single-stage synthesis of alkyl-H-phosphinic acids from elemental phosphorus and alkyl bromides
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Elemental phosphorus (red or white) reacts with alkyl bromides at 60–62 °C in the phase-transfer catalytic system KOH/H2O/PhMe/Et3BnNCl to afford alkyl-H-phosphinic acids in up to 47% yield.
- Gusarova, Nina K.,Sutyrina, Anastasiya O.,Kuimov, Vladimir A.,Malysheva, Svetlana F.,Belogorlova, Natalia A.,Volkov, Pavel A.,Trofimov, Boris A.
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p. 328 - 330
(2019/06/13)
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- Photolytic C-O Bond Cleavage with Quantum Dots
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Quantum dots are used as photoredox catalysts to drive bond cleavage in lignin model substrates. Cadmium selenide quantum dots selectively cleave C-O bonds with yields comparable to the best transition-metal-based molecular photocatalysts, thereby emulating depolymerization of the β-O-4 linkages that account for 45-60% of all linkers in native lignin. Compared to their molecular catalyst counterparts, the quantum dots demonstrate higher turnover frequencies, higher surface tunability for solvent versatility, and lower catalyst loading under mild, ambient temperature reaction conditions. The robust nature and solvent versatility of these quantum dot photoredox catalysts enable a direct, single-vessel route to convert benzylic alcohols (a majority of species in native and processed lignin) into high-value guaiacols and acetophenones without any prerequisite filtration, purification, or solvent change.
- Enright, Michael J.,Gilbert-Bass, Kito,Sarsito, Harrison,Cossairt, Brandi M.
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p. 2677 - 2682
(2019/04/25)
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- A trioctylphosphine phosphine oxide compound and its preparation method
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The invention aims to provide a trioctylphosphine oxide compound and a preparation method thereof, which is high in yield, low in cost and moderate in reaction conditions. In order to fulfill the aim of the invention, the technical scheme of the invention is that the preparation method for the trioctylphosphine oxide compound comprises the following steps of: preparing trioctylphosphine oxide from sodium hypophosphite by performing octene addition, trichlorosilane reduction, bromoalkane addition and hydrolysis in turn; or preparing the trioctylphosphine oxide from the sodium hypophosphite by performing the octene addition, the trichlorosilane reduction, the hydrolysis and the octene addition again in turn; or preparing the trioctylphosphine oxide from the sodium hypophosphite by performing the octene addition, the trichlorosilane reduction and alcoholysis in turn. According to the synthesis method provided by the invention, the selected raw materials are easy to obtain; the addition reaction is performed on the sodium hypophosphite and octene, so that the reaction conditions are moderate and are easy to control; the operation safety is enhanced; the reaction yield is high and can reach over 90 percent; the trioctylphosphine oxide is convenient to purify; and the product purity is high.
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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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- Synthesis, purification, and characterization of phosphine oxides and their hydrogen peroxide adducts
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Reactions of the tertiary phosphines R3P (R = Me, Bu, Oct, Cy, Ph) with 35% aqueous H2O2 gives the corresponding oxides as the H2O2 adducts R3PO·(H 2O2)x (x = 0.5-1.0). Air oxidation leads to a mixture of products due to the insertion of oxygen into one or more P-C bonds. 31P NMR spectroscopy in solution and in the solid state, as well as IR spectroscopy reveal distinct features of the phosphine oxides as compared to their H2O2 adducts. The single crystal X-ray analyses of Bu3PO and [Cy3PO·(H2O2)] 2 show a PO stacking motif for the phosphine oxide and a cyclic structure, in which the six oxygen atoms exhibit a chair conformation for the dimeric H2O2 adduct. Different methods for the decomposition of the bound H2O2 and the removal of the ensuing strongly adsorbed H2O are evaluated. Treating R 3PO·(H2O2)x with molecular sieves destroys the bound H2O2 safely under mild conditions (room temperature, toluene) within one hour and quantitatively removes the adsorbed H2O from the hygroscopic phosphine oxides within four hours. At 60°C the entire decomposition/drying process is complete within one hour.
- Hilliard, Casie R.,Bhuvanesh, Nattamai,Gladysz, John A.,Bluemel, Janet
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experimental part
p. 1742 - 1754
(2012/03/22)
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- Facile purification of C60O-containing [60]fullerene using trialkylphosphines at room temperature
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A novel method using trialkylphosphines is reported for the facile purification of [60]fullerene containing C60O. When tri-n-butylphosphine and tri-n-octylphosphine were added to unrefined C 60 (ca. 97% purity) in 1,2,4-trimethylbenzene, C60O was readily reduced to give high-purity C60 (>99% purity). The best results were obtained for a high concentration (>1.0 wt %) of unrefined fullerene treated with tri-n-octylphosphine at room temperature. This method is simple and fast in comparison with conventional alumina chromatography, and thus, it is well-suited to industrial-scale separation.
- Hashiguchi, Masahiko,Nagata, Koichi,Tanaka, Katsutomo,Matsuo, Yutaka
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experimental part
p. 643 - 646
(2012/08/07)
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- Effect of the structure of functionalized phosphoryl carriers on the membrane transport of proton-donor substrates
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A series of phosphoryl compounds functionalized in the side chain were synthesized, and their membrane-transport properties with respect to proton-donor substrates of various acidity were studied. It was found that the efficiency of phase transport of the strong monobasic perchloric acid correlates with the basicity of the phosphoryl carriers in a series of carriers containing oxygen-containing functional groups. The transport flow sharply increases in going to phosphorylated amines, whereas phosphoramidates in their efficiency are closer to phosphonates than to amines. The efficiency of transport of dibasic acids (oxalic and tartaric) is low, since the hydroxy and carboxy groups not bound to the carrier make ionic associates highly hydrophilic. Fine details of the structure-transport acitivity relationship in the series of phosphorus compounds were discussed. Three-dimensional correlation analysis was used to compare the structure of the carriers with their characteristics: basicity of amine centers, atomic charges of oxygen and nitrogen, and hardness and hydrophobicity parameters. Nauka/Interperiodica 2006.
- Cherkasov,Garifzyanov,Krasnova,Cherkasov,Talan
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p. 1537 - 1544
(2008/02/05)
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- Preparation of organohalosilanes
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In an industrial process for preparing organohalosilanes by reacting metallic silicon particles with an organohalide in the presence of a copper catalyst, a contact mass composed of the metallic silicon and the catalyst further contains an effective amount of a phosphine chalcogenide compound. The invention drastically increases the silane formation rate and the utilization of silicon without lowering the selectivity of useful silane.
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- Peroxo-containing metal complexes having amine oxide, phosphine oxide, arsine oxide, pyridine N-oxide or pyridine ligands as epoxidation catalysts
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PCT No. PCT/EP96/03888 Sec. 371 Date Mar. 11, 1998 Sec. 102(e) Date Mar. 11, 1998 PCT Filed Sep. 4, 1996 PCT Pub. No. WO97/10054 PCT Pub. Date Mar. 20, 1997Olefins can be epoxidized using catalysts I where M is a metal of the 4th to 7th transition group of the Periodic Table of the Elements, L1 is an amine oxide, phosphine oxide, arsine oxide, pyridine N-oxide or pyridine ligand of the formula II, III, VII or VIII, L2 is a customary auxiliary ligand or a further ligand L1 or a free coordination site, X is oxo oxygen or an imido ligand, m is 1 or 2, and n is 1, 2 or 3.
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- Preparation of epoxides from olefins using bis(triorganosilyl) peroxides in the presence of activators based on metallic acid derivatives
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PCT No. PCT/EP97/00982 Sec. 371 Date Sep. 2, 1998 Sec. 102(e) Date Sep. 2, 1998 PCT Filed Feb. 28, 1997 PCT Pub. No. WO97/32867 PCT Pub. Date Sep. 12, 1997Epoxides are prepared from olefins using bis(triorganosilyl) peroxides in the presence of activators based on metalic acid derivatives of the formula where M is a metal of transition groups IV to VII, in particular molybdenum, tungsten or rhenium L is an uncharged ligand selected from the group consisting of amine oxides, phosphine oxides, arsine oxides, phosphoric triamides, formamides and pyridine N-oxides X is an inorganic ligand x is from 1 to 5 y is 0, 1 or 2, Z is 1 or 2 and n is 1 or 2.
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- Qualitative Assessment of the Catalytic Effect of Tertiary Phosphines
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The catalytic effect of trialkylphosphine oxides on reaction of diphenylphosphininc hydrazide with phenyl isocyanate in benzene at 25 deg C was evaluated. The catalytic effect was found to be linearly related to the electron-donor factor E, the sum of the Taft constants ?* and the constants ?P of the substituents in the phosphorus atom.
- Yanchuk, N. I.
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- Process for preparing organophosphines
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Olefins can be induced to react with phosphines at ambient temperature and pressure to produce organophosphines by free-radical addition. Suitable olefins include C1 to C4 alpha-olefins, cyclic olefins, polycycloalkenyl species, allyl alcohol and esters of vinyl phosphonic acid.
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- SUPERBASE-INDUCED GENERATION OF PHOSPHIDE AND PHOSPHINITE IONS AS APPLIED IN ORGANIC SYNTHESIS
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A series of new direct reactions of red phosphorus (or white) with organyl halides, alkenes and acetylenes have been developed.Reactions occur in superbasic systems, such as alkali metal hydroxide-dipolar aprotic complexing solvent (DMSO, HMPA) or under phase-transfer conditions to afford earlier inaccessible triorganylphosphines and -phosphine oxides including unsaturated ones in good yield.
- Trofimov, B. A.,Gusarova, N. K.,Malysheva, S. F.,Rakhmatulina, T. N.,Voronkov, M. G.,et al.
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p. 271 - 274
(2007/10/02)
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- ALKYLATION IN SITU OF ARYLPHOSPHINES FORMED DURING THERMOLYSIS OF HYDROPHOSPHORYL COMPOUNDS
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In the course of the thermolysis (ca. 200 deg C) of diorganophosphonous and phenylphosphonous acids in the presence of alkyl halides, polyalkylation products are obtained - dialkyldiphenyl- and trialkylphenylphosphonium salts and dialkylphenylphosphine oxides.Combined with alkaline splitting of the phosphonium salts, it is possible to synthesize dialkylphenyl- and trioctylphosphine oxides from available hydrophosphoryl compounds using these reactions.
- Chauzov, V. A.,Kostina, L. P.
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p. 2026 - 2031
(2007/10/02)
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- Oxidation of Heterocyclic Nitrogen Ylids to Nitro Heterocycles. Comparison of Dimethyldioxirane with Peracids
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Oxidation of 3-amino-4-(4-chlorophenyl)furazan (1) and its phosphine imine derivative, 3-(4-chlorophenyl)-4-trioctylphosphiniminofurazan (3), with dimethyldioxirane (DMD) gave 3-(4-chlorophenyl)-4-nitrofurazan (4) as the exclusive product.However, the sulfilimine derivative, 3-(4-chlorophenyl)-4-dimethylsulfiliminofurazan (2), was converted by DMD to the sulfoximine, 3-(4-chlorophenyl)-4-dimethylsulfoximinofurazan (6).These results contrast dramatically with the oxidations of these compounds with peracids.
- Coburn, Michael D.
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p. 1883 - 1884
(2007/10/02)
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- Process for preparing organic chlorophosphanes
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Organic chlorophosphanes of the formula III STR1 in which R1 is chlorine or an aliphatic radical, preferably only chlorine, and R2 is an aromatic, heterocyclic or aliphatic radical, are prepared by reacting organic phosphorus oxychlorides of the formula I STR2 in which R1 is chlorine or an aliphatic radical, preferably only chlorine, R2 is an aromatic or heterocyclic radical in the event that R1 is chlorine and an aromatic, heterocyclic or aliphatic radical in the event that R1 is an aliphatic radical, with a trialkylphosphane of the formula II in which R3 is an aliphatic radical, at temperatures between about 20° and about 170° C. Said organic chlorophosphanes III are mainly intermediates in various fields, such as pharmaceuticals, plant protection, dyestuffs and polymers.
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- SYNTHESE ET STRUCTURE D'OXYDES ET DIOXYDES DE PHOSPHINES TERTIAIRES
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Tertiary phosphine oxides have been prepared in excellent yield from primary alkyl halides and dihalides or aromatic halides and activated sodium phosphinates obtained by reaction of dialkyl phosphine oxides with complex bases (NaNH2/tBuONa).We have studied by 13C NMR the structure of these compounds.We have reported more particularly the influence of carbon atoms number between the two phosphorus in the case of dioxides and the influence of some parameters such as the temperature and the solvent on the NMR spectra.
- Platzer, Nicole,Dardoise, Francois,Bergeret, Wilfrid,Gautier, Jean Claude,Raynal, Serge
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p. 275 - 284
(2007/10/02)
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- Oxidation of Heterocyclic Nitrogen Ylids to Nitro Heterocycles. Comparison of a Sulfilimine and a Phosphine Imine
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Oxidation of 3-amino-4-(4-chlorophenyl)furazan (1) with peroxytrifluoroacetic acid (ptfa) gave azoxy(4-chlorophenylfurazan) (6) as the major product along with a small amount of 3-(4-chlorophenyl)-4-nitrofurazan (5).The dimethylsulfilimine 2 derived from 1 gave near quantitative yields of 5 when subjected to oxidation with either pfta or m-chloroperoxybenzoic acid (mcpba).In contrast, both the trioctylphosphine imine 3 and the triphenylphosphine imine 4 derived from 1 were oxidized by mcpba to give 6 as the exclusive product.
- Coburn, Michael D.
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p. 421 - 423
(2007/10/02)
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- Process for the synthesis of tertiary phosphine oxides, and new tertiary phosphine oxides
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The invention relates to the synthesis of tertiary phosphine oxides and also to certain tertiary phosphine oxides. According to the invention, an organic phase containing a halogenomethyl derivative, a secondary phosphine oxide and a phase transfer catalyst in an organic medium is reacted with an aqueous phase containing an inorganic base. The halogenomethyl derivative can be a micromolecule or a macromolecule. The tertiary phosphine oxides are substances which are useful, in particular, in fireproofing, in hydrometallurgy and in the field of plant health.
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- Process for the preparation of phosphine oxides and sulphides
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A process for the preparation of phosphine oxides or sulphides of the formula: EQU1 in which R is a linear or branched aliphatic radical containing 5-12 carbon atoms, aralkyl radical selected from the group consisting of lower alkyl of 2-3 carbon atoms substituted by a phenyl group or R is cyclohexyl and X is an oxygen or sulphur atom comprising reacting a halo-compound of the formula R--Hal, in which Hal is chlorine, bromine or iodine, with magnesium to form a Grignard derivative of the formula RMgHal, the reaction being carried out initially in a very small amount of diethyl ether and then in a solvent mixture containing a preponderant amount of an aliphatic or aromatic hydrocarbon, which is liquid at room temperature or triethylamine, adding phosphorus oxychloride or phosphorus sulphochloride to the reaction mixture containing the Grignard derivative, and isolating the phosphine oxide or phosphine sulphide formed by removing the solvent by steam stripping or steam distillation. These compounds are valuable for use in the selective extraction of rare metals.
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