2510-86-3Relevant academic research and scientific papers
Transesterification vs hydrolysis: The reactivity of metal-bound hydroxo moiety in [TPANi(II)(μ-OH)2Ni(II)TPA](ClO4)2 (TPA = tris(2-pyridylmethyl)amine)
Ito, Masami,Kawano, Hiroyuki,Takeuchi, Takashi,Takita, Yu-Saku
, p. 372 - 373 (2000)
In the reaction of triphenyl phosphate with ethanol in the presence of complex 1, the transesterification to give diethyl phenyl phosphate was observed, in which system direct nucleophilic attack of ligated hydroxo moiety in 1 toward triphenyl phosphate a
Monitoring the phosphorylation of phenol with diethyl chlorophosphate in aqueous medium in the presence of sodium hydroxide by in situ fourier transform infrared spectroscopy
Keglevich, Gyoergy,Puskas, Reka Eszter,Gruen, Alajos,Csontos, Istvan
, p. 832 - 837 (2010)
In situ Fourier transform IR spectroscopy has been found to be an appropriate tool for monitoring the title reaction resulting in the formation of diethyl phenylphosphate.
Electrochemical Activation of Diverse Conventional Photoredox Catalysts Induces Potent Photoreductant Activity**
Chernowsky, Colleen P.,Chmiel, Alyah F.,Wickens, Zachary K.
supporting information, p. 21418 - 21425 (2021/08/25)
Herein, we disclose that electrochemical stimulation induces new photocatalytic activity from a range of structurally diverse conventional photocatalysts. These studies uncover a new electron-primed photoredox catalyst capable of promoting the reductive cleavage of strong C(sp2)?N and C(sp2)?O bonds. We illustrate several examples of the synthetic utility of these deeply reducing but otherwise safe and mild catalytic conditions. Finally, we employ electrochemical current measurements to perform a reaction progress kinetic analysis. This technique reveals that the improved activity of this new system is a consequence of an enhanced catalyst stability profile.
Identification of organophosphorus simulants for the development of next-generation detection technologies
Ellaby, Rebecca J.,Clark, Ewan R.,Allen, Nyasha,Taylor, Faith R.,Ng, Kendrick K. L.,Dimitrovski, Milan,Chu, Dominique F.,Mulvihill, Daniel P.,Hiscock, Jennifer R.
, p. 2008 - 2014 (2021/03/16)
Organophosphorus (OP) chemical warfare agents (CWAs) represent an ongoing threat but the understandable widespread prohibition of their use places limitations on the development of technologies to counter the effects of any OP CWA release. Herein, we describe new, accessible methods for the identification of appropriate molecular simulants to mimic the hydrogen bond accepting capacity of the PO moiety, common to every member of this class of CWAs. Using the predictive methodologies developed herein, we have identified OP CWA hydrogen bond acceptor simulants for soman and sarin. It is hoped that the effective use of these physical property specific simulants will aid future countermeasure developments.
Electrochemical phosphorylation of arenols and anilines leading to organophosphates and phosphoramidates
Xu, Pan,Zhong, Zijian,Zhou, Aihua
supporting information, p. 5342 - 5347 (2021/06/30)
A practical phosphorylation for generating organophosphates and phosphoramidatesviaelectrochemical dehydrogenative cross-coupling of P(O)H compounds with arenols and anilines is disclosed. This method involves using inorganic iodide salts as both redox catalysts and electrolytes in an undivided cell without the addition of oxidants or bases. A preliminary mechanistic study suggests that radicals are not involved in this process. This method is green and eco-friendly and has good functional group tolerance, high yields and broad substrate scope, with the potential for practical synthesis.
Diselenide-Mediated Catalytic Functionalization of Hydrophosphoryl Compounds
Handoko,Benslimane, Zacharia,Arora, Paramjit S.
supporting information, p. 5811 - 5816 (2020/07/27)
We report a diaryldiselenide catalyst for cross-dehydrogenative nucleophilic functionalization of hydrophosphoryl compounds. The proposed organocatalytic cycle closely resembles the mechanism of the Atherton-Todd reaction, with the catalyst serving as a recyclable analogue of the halogenating agent employed in the named reaction. Phosphorus and selenium NMR studies reveal the existence of a P-Se bond intermediate, and structural analyses indicate a stereospecific reaction.
Transition State Analysis of the Reaction Catalyzed by the Phosphotriesterase from Sphingobium sp. TCM1
Bigley, Andrew N.,Xiang, Dao Feng,Narindoshvili, Tamari,Burgert, Charlie W.,Hengge, Alvan C.,Raushel, Frank M.
, p. 1246 - 1259 (2019/03/07)
Organophosphorus flame retardants are stable toxic compounds used in nearly all durable plastic products and are considered major emerging pollutants. The phosphotriesterase from Sphingobium sp. TCM1 (Sb-PTE) is one of the few enzymes known to be able to hydrolyze organophosphorus flame retardants such as triphenyl phosphate and tris(2-chloroethyl) phosphate. The effectiveness of Sb-PTE for the hydrolysis of these organophosphates appears to arise from its ability to hydrolyze unactivated alkyl and phenolic esters from the central phosphorus core. How Sb-PTE is able to catalyze the hydrolysis of the unactivated substituents is not known. To interrogate the catalytic hydrolysis mechanism of Sb-PTE, the pH dependence of the reaction and the effects of changing the solvent viscosity were determined. These experiments were complemented by measurement of the primary and secondary 18-oxygen isotope effects on substrate hydrolysis and a determination of the effects of changing the pKa of the leaving group on the magnitude of the rate constants for hydrolysis. Collectively, the results indicated that a single group must be ionized for nucleophilic attack and that a separate general acid is not involved in protonation of the leaving group. The Br?nsted analysis and the heavy atom kinetic isotope effects are consistent with an early associative transition state with subsequent proton transfers not being rate limiting. A novel binding mode of the substrate to the binuclear metal center and a catalytic mechanism are proposed to explain the unusual ability of Sb-PTE to hydrolyze unactivated esters from a wide range of organophosphate substrates.
LiI/TBHP Mediated Oxidative Cross-Coupling of P(O)–H Compounds with Phenols and Various Nucleophiles: Direct Access to the Synthesis of Organophosphates
Anitha, Thippani,Ashalu, Kashamalla Chinna,Sandeep, Mummadi,Mohd, Aabid,Wencel-Delord, Joanna,Colobert, Francoise,Reddy, Kallu Rajender
, p. 7463 - 7474 (2019/12/03)
An efficient and mild method for the direct phosphorylation of phenols, alcohols, and amines with P(O)–H has been reported by LiI/TBHP mediated oxidative cross-coupling reaction. Moreover, this protocol extended to β-keto esters for the synthesis of enol phosphates using H-phosphonates. Notably, this developed method applied for the synthesis of organopesticides such as paraoxon, cyanophos, and methyl parathion. The key features of this protocol are mild conditions, short reaction time, good functional group tolerance, and broad substrate scope.
METAL-FREE DIRECT ARYLATION OF DIALKYL PHOSPHONATES FOR THE SYNTHESIS OF MIXED ALKYL ARYL PHOSPHONATES
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Paragraph 00385-00386; 00425; 00427; 00440, (2019/02/15)
Provided herein are phosphates, thiophosphates, phosphonates, and phosphinates, methods of making same, and methods of using these compounds and methods for the generation of pharmaceutically relevant phosphate, phosphonate, and phosphinate analogs. This
Enantioselective and Regioselective Hydroetherification of Alkynes by Gold-Catalyzed Desymmetrization of Prochiral Phenols with P-Stereogenic Centers
Zheng, Yin,Guo, Linna,Zi, Weiwei
supporting information, p. 7039 - 7043 (2018/11/24)
The gold(I)-catalyzed enantioselective hydroetherification of alkynes was achieved via desymmetrization of prochiral bisphenols bearing P-stereogenic centers. (S)-DTBM-Segphos(AuCl)2/AgNTf2 proved to be a highly efficient catalyst system for this transformation, affording P-chiral cyclic phosphine oxides in good yields with high enantioselectivities (with up to 99% ee). The same catalyst system allowed for the enantioselective desymmetrization of dialkynes. Synthetic transformations of the cyclization products afforded other P-chiral molecules with high enantiospecificity.
