598-02-7Relevant articles and documents
Rhodium-catalyzed phosphorylation reaction of water-soluble disulfides using hypodiphosphoric acid tetraalkyl esters in water
Arisawa, Mieko,Fukumoto, Kohei,Yamaguchi, Masahiko
, p. 13820 - 13823 (2020)
RhCl3 catalyzed the exchange reaction of disulfides and hypodiphosphoric acid tetraalkyl esters in water under homogeneous conditions, which indicated the hypodiphosphoric acid tetraalkyl esters to be novel and efficient phosphorylation reagent
Diethyl Isopropyl and Isopropenyl Phosphate via Differently Generated Ketyl Radicals of Acetone Reacting with Diethyl Phosphoric Acid
Schole, Juergen,Schole, Christine,Eikemeyer, Juergen,Krebs, Hans Christoph
, p. 1125 - 1128 (1994)
Photochemically excited acetone reacts in 1,2-dimethoxy ethane with diethyl phosphoric acid to diethyl isopropyl phosphate.The same product is formed by reduction of acetone with magnesium amalgam in benzene in the presence of the same phosphoric acid derivative.Thermal decomposition of tetramethyldioxetane in benzene in the presence of diethyl phosphoric acid appears to yield primarily diethyl isopropenyl phosphate.
Synthesis and structure of complexes of phosphorus pentachloride with 4-dimethylaminopyridine and n-methylimidazole
Pipko, Sergey E.,Bezgubenko, Ludmila V.,Sinitsa, Anatoliy D.,Rusanov, Eduard B.,Kapustin, Evgeniy G.,Povolotskii, Mark I.,Shvadchak, Volodymyr V.
, p. 171 - 177 (2008)
Complexes of phosphorus pentachloride with 4-dimethylaminopyridine and N-methylimidazole were synthesized. The molecular structure of the phosphorus pentachloride complex with N-methylimidazole was determined by single-crystal X-ray diffraction. In the cationic part of the complex, the phosphorus atom possesses four P - Cl bonds within the range 2.109-2.148 A and two cis-P-N bonds (1.811 and 1.832 A) with N-methylimidazole and exhibits slightly distorted octahedral coordination with angles at phosphorus atom in the range 87.57°-91.50°. The relative stability of the cis and trans conformations of the complex was studied by DFT calculations. The chemical properties and reactivity of the compounds obtained are determined; their utility as condensing agents in the synthesis of amides from acids and amines was shown.
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Mukaiyama,Fujisawa
, p. 812 (1961)
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Broad-Spectrum Liquid- and Gas-Phase Decontamination of Chemical Warfare Agents by One-Dimensional Heteropolyniobates
Guo, Weiwei,Lv, Hongjin,Sullivan, Kevin P.,Gordon, Wesley O.,Balboa, Alex,Wagner, George W.,Musaev, Djamaladdin G.,Bacsa, John,Hill, Craig L.
, p. 7403 - 7407 (2016)
A wide range of chemical warfare agents and their simulants are catalytically decontaminated by a new one-dimensional polymeric polyniobate (P-PONb), K12[Ti2O2][GeNb12O40]?19 H2O (KGeNb) under mild conditions and in the dark. Uniquely, KGeNb facilitates hydrolysis of nerve agents Sarin (GB) and Soman (GD) (and their less reactive simulants, dimethyl methylphosphonate (DMMP)) as well as mustard (HD) in both liquid and gas phases at ambient temperature and in the absence of neutralizing bases or illumination. Three lines of evidence establish that KGeNb removes DMMP, and thus likely GB/GD, by general base catalysis: a) the k(H2O)/k(D2O) solvent isotope effect is 1.4; b) the rate law (hydrolysis at the same pH depends on the amount of P-PONb present); and c) hydroxide is far less active against the above simulants at the same pH than the P-PONbs themselves, a critical control experiment.
Does phosphoryl protonation occurs in aqueous phosphoesters solutions
Azema,Ladame,Lapeyre,Zwick,Lakhdar-Ghazal
, p. 287 - 292 (2005)
Ionisation of trimethylphosphate (TMP), dimethylphosphate (DMP) and diethylphosphate (DEP) is investigated by acidic titration in water by Raman (R), Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies. The vibrational frequencies of the PO2- ionic form and the neutral form were found in accord with the literature. While increasing further H+ concentration, the PO band disappears in the benefit of new ones. These results, together with deuteration experiments indicate the presence of a new ionic form positively charged with general formula R1R2R3P(OH)+ or R 1R2P(OH)+2. The pK of this phosphonium entities is lying in the range -2, -4. These results were confirmed by 31P NMR titration. The occurrence of such a phosphonium ion in aqueous solutions might be of crucial importance for biochemical reactions and interactions, owing to the large spread of phosphoryl group in biomolecules and keeping in mind that intracellular compartments are more likely concentrated media with little free water than real aqueous solutions. Furthermore, pK's can be shifted by physical-chemical parameters like dielectric constant and electric field. This may involve at least fractional positive charge apparition that might be important in biochemical regulation by charge-charge and charge-dipole interactions. This finding will gain to be further explored on more complex molecules like phospholipids, nucleic acids and proteins.
Kinetic and isotope effect studies on the intermediacy of ethyl metathiophosphate in ethanolysis of O-ethyl N-1-adamantyl phosphoramidothioate
Jankowski, Stefan,Quin, Louis D.,Paneth, Piotr,O'Leary, Marion H.
, p. 23 - 27 (1997)
The fragmentation of O-ethyl N-l-adamantylphosphoramidothioate (1a) and its oxygen counterpart 1b was examined in ethanol at 65-100°C. The solvent hydrogen effect kEtOH/kEtOD and kinetic nitrogen effect k14/k15 were determined at 80°C. The rates and parameters of activation of ethanolysis of 1a and 1b are slightly different. The solvent effect kEtOH/kEtOD was found to be equal to 0.84 ± 0.05 for 1a and 0.83 ± 0.04 for 1b. The nitrogen effect k14/k15 was found to be sensitive to replacement of sulfur by oxygen, and equal to 1.0083 ± 0.0004 for 1a and 1.0065 ± 0.0006 for 1b. The data indicate that proton transfer from the OH group to the amine moiety precedes the P-N bond breakage. The kinetic nitrogen isotope effect for the amine elimination recalculated for the pre-equilibrium step is equal to 1.0232 for 1a and 1.0215 for 1b. These results are consistent with the intermediacy of ethyl metathiophosphate in the solvolysis of 1a.
MIL-101(Cr) with incorporated polypyridine zinc complexes for efficient degradation of a nerve agent simulant: spatial isolation of active sites promoting catalysis
Zhang, Kai,Cao, Xingyun,Zhang, Zhiyan,Cheng, Yong,Zhou, Ying-Hua
supporting information, p. 1995 - 2000 (2021/02/26)
Development of an efficient catalyst for degradation of organophosphorus toxicants is highly desirable. Herein, an MIL-101(Cr)LZn catalyst was fabricated by incorporating polypyridine zinc complexes into a MOF to achieve the spatial isolation of active si
Organic-inorganic hybrid thorium polyacid salt and preparation method and application thereof
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Paragraph 0027, 0028, (2020/07/21)
The invention discloses an organic-inorganic hybrid thorium polyacid salt of which the chemical formula is {Th (DMSO) 6 (H2O) [SiW12O40]}. 2H2O, wherein DMSO is dimethyl sulfoxide, the molecular formula of thorium polyacid salt is C12H42O49S6SiThW12, the molecular weight of thorium polyacid salt is 3629, the thorium polyacid salt is a monoclinic system, the space group is P21/c, and the cell parameters of thorium polyacid salt are as follows: alpha = 90 degrees, beta = 99.4970 (10) degrees, gamma = 90 degrees and Z = 4. The thorium polyacid salt synthesized by the method has the characteristics of simplicity in synthesis, convenience in operation, high catalyst yield, mild reaction conditions, quickness in degradation, high degradation rate and the like and can be recycled without secondary pollution.
