78-50-2Relevant articles and documents
Single-stage synthesis of alkyl-H-phosphinic acids from elemental phosphorus and alkyl bromides
Gusarova, Nina K.,Sutyrina, Anastasiya O.,Kuimov, Vladimir A.,Malysheva, Svetlana F.,Belogorlova, Natalia A.,Volkov, Pavel A.,Trofimov, Boris A.
, p. 328 - 330 (2019/06/13)
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.
Photolytic C-O Bond Cleavage with Quantum Dots
Enright, Michael J.,Gilbert-Bass, Kito,Sarsito, Harrison,Cossairt, Brandi M.
, p. 2677 - 2682 (2019/04/25)
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.
A trioctylphosphine phosphine oxide compound and its preparation method
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Paragraph 0058; 0059, (2018/01/13)
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.
Function of substituents in coordination behaviour, thermolysis and ligand crossover reactions of phosphine oxides
Pavankumar,Goud, E. Veerashekhar,Selvakumar,Kumar, S. K. Ashok,Sivaramakrishna, Akella,Vijayakrishna, Kari,Rao, C. V. S. Brahmananda,Sabharwal,Jha, Prakash C.
, p. 4727 - 4736 (2015/03/03)
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.
Synthesis, purification, and characterization of phosphine oxides and their hydrogen peroxide adducts
Hilliard, Casie R.,Bhuvanesh, Nattamai,Gladysz, John A.,Bluemel, Janet
experimental part, p. 1742 - 1754 (2012/03/22)
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.
Facile purification of C60O-containing [60]fullerene using trialkylphosphines at room temperature
Hashiguchi, Masahiko,Nagata, Koichi,Tanaka, Katsutomo,Matsuo, Yutaka
experimental part, p. 643 - 646 (2012/08/07)
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.
Effect of the structure of functionalized phosphoryl carriers on the membrane transport of proton-donor substrates
Cherkasov,Garifzyanov,Krasnova,Cherkasov,Talan
, p. 1537 - 1544 (2008/02/05)
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.
Preparation of organohalosilanes
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, (2008/06/13)
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.
Peroxo-containing metal complexes having amine oxide, phosphine oxide, arsine oxide, pyridine N-oxide or pyridine ligands as epoxidation catalysts
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, (2008/06/13)
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.
Preparation of epoxides from olefins using bis(triorganosilyl) peroxides in the presence of activators based on metallic acid derivatives
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, (2008/06/13)
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.
