812-00-0Relevant articles and documents
Loci of ceric cation mediated hydrolyses of dimethyl phosphate and methyl methylphosphonate
Moss, Robert A.,Morales-Rojas, Hugo
, p. 1791 - 1793 (1999)
(formula presented) Dimethyl phosphate and methyl methylphosphonate are cleaved by Ce(IV)-mediated hydrolysis with 91% and 88% P-O scission, respectively, and rate accelerations of ≥ 1010 relative to pH 7 P-O hydrolysis.
METHOD FOR PRODUCING PHOSPHOESTER COMPOUND
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Paragraph 0023; 0026-0028, (2021/09/27)
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
Isomer of linker for NU-1000 yields a newshe-type, catalytic, and hierarchically porous, Zr-based metal-organic framework
Lu, Zhiyong,Wang, Rui,Liao, Yijun,Farha, Omar K.,Bi, Wentuan,Sheridan, Thomas R.,Zhang, Kun,Duan, Jiaxin,Liu, Jian,Hupp, Joseph T.
, p. 3571 - 3574 (2021/04/14)
The well-known MOF (metal-organic framework) linker tetrakis(p-benzoate)pyrene (TBAPy4?) lacks steric hindrance between its benzoates. Changing the 1,3,6,8-siting of benzoates in TBAPy4?to 4,5,9,10-siting introduces substantial steric hindrance and, in turn, enables the synthesis of a new hierarchically porous,she-type MOF Zr6(μ3-O)4(μ3-OH)4(C6H5COO)3(COO)3(TBAPy-2)3/2(NU-601), where TBAPy-24?is the 4,5,9,10 isomer of TBAPy4?.NU-601shows high catalytic activity for degradative hydrolysis of a simulant for G-type fluoro-phosphorus nerve agents.
An Unusual Two-Step Hydrolysis of Nerve Agents by a Nanozyme
Khulbe, Kritika,Roy, Punarbasu,Radhakrishnan, Anusree,Mugesh, Govindasamy
, p. 4840 - 4845 (2018/09/27)
Organophosphate-based nerve agents irreversibly inhibit acetylcholinesterase enzyme, leading to respiratory failure, paralysis and death. Several organophosphorus hydrolases are capable of degrading nerve agents including pesticides and insecticides. Development of stable artificial enzymes capable of hydrolysing nerve agents is important for the degradation of environmentally toxic organophosphates. Herein, we describe a Zr-incorporated CeO2 nanocatalyst that can be used for an efficient capture and hydrolysis of nerve agents such as methyl paraoxon to less toxic monoesters. This unusual sequential degradation pathway involves a covalently linked nanocatalyst-phosphodiester intermediate.
A Light-Releasable Potentially Prebiotic Nucleotide Activating Agent
Mariani, Angelica,Russell, David A.,Javelle, Thomas,Sutherland, John D.
supporting information, p. 8657 - 8661 (2018/07/15)
Investigations into the chemical origin of life have recently benefitted from a holistic approach in which possible atmospheric, organic, and inorganic systems chemistries are taken into consideration. In this way, we now report that a selective phosphate activating agent, namely methyl isocyanide, could plausibly have been produced from simple prebiotic feedstocks. We show that methyl isocyanide drives the conversion of nucleoside monophosphates to phosphorimidazolides under potentially prebiotic conditions and in excellent yields for the first time. Importantly, this chemistry allows for repeated reactivation cycles, a property long sought in nonenzymatic oligomerization studies. Further, as the isocyanide is released upon irradiation, the possibility of spatially and temporally controlled activation chemistry is thus raised.
Intriguing structural chemistry of neutral and anionic layered monoalkylphosphates: Single-source precursors for high-yield ceramic phosphates
Bhat, Gulzar A.,Kalita, Alok Ch.,Murugavel, Ramaswamy
, p. 5390 - 5401 (2017/09/26)
Building up on an available synthetic methodology, phosphate monoesters ROPO3H2 have been synthesized in good yields. The synthetic procedure employed features acetic anhydride mediated activation of phosphoric acid in the presence of alcohols, leading to the formation of phosphate monoesters. The products have been isolated as their cyclohexyl amine salts, [CyNH3]2[(MeO)PO3]·3H2O (1) and [CyNH3][(RO)PO3H] (Cy = cyclohexyl; R = Et (2), iPr (3), or tBu (4)). Neutralization of 1-4 by readily available inexpensive ion exchange resin Amberlite produces monoalkylphosphates (RO)P(O)(OH)2 (R = Me (5), Et (6), iPr (7), or tBu (8)). Thermally labile 1-4 and 7 have been structurally characterized by single crystal X-ray diffraction studies. Due to their intrinsic thermal instability due to β-H elimination, these compounds can be used as ligands for the preparation of single-source precursors for ceramic phosphates by reacting them with suitable metals ions. It is also possible to isolate co-crystals of the anionic and neutral forms of these phosphates as it has been demonstrated in the isolation and structural characterization of [(iPrO)PO3H2]·{[CyNH3][(iPrO)PO3H]} (9). To demonstrate the utility of these monoalkylphosphates in the low-temperature synthesis of metal phosphate bioceramics, isopropyl phosphate 7 has been employed to prepare calcium phosphate [{Ca((iPrO)PO3)(OH2)}·H2O]n (10), which undergoes neat thermal decomposition in two stages to lose water and propene to yield β-Ca2P2O7 at low temperatures (280 °C).
Method for preparing monoalkyl hypophosphite
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Paragraph 0035; 0036; 0037, (2017/09/18)
The invention relates to a method for preparing monoalkyl hypophosphite. The method comprises the steps of oxidizing monoalkyl hydrogen phosphide halate solution by virtue of hydrogen peroxide, wherein the molar ratio of the monoalkyl hydrogen phosphide halate solution to hydrogen peroxide is 1 to 2 or 1 to 2.1, and the reaction temperature is between (-50)-(20) DEG C. The molecular formula of monoalkyl hypophosphite is RP(H)OOH, wherein R is C1-C10 straight-chain, branched-chain alkyl groups. The method for preparing monoalkyl hypophosphite has the beneficial effects that the reaction yield is more than 80%, and water and halogen hydride can be easily evaporated at a reduced pressure after the reaction is finished and can be recycled by virtue of a sodium hydroxide solution and are not the main content of the invention, so that the method described by the invention is safe, environment-friendly and economic.
Reactions of phosphate and phosphorothiolate diesters with nucleophiles: Comparison of transition state structures
Ye, Jing-Dong,Barth, Christofer D.,Anjaneyulu, Potluri S. R.,Tuschl, Thomas,Piccirilli, Joseph A.
, p. 2491 - 2497 (2008/02/14)
A series of methyl aryl phosphorothiolate esters (SP) were synthesized and their reactions with pyridine derivatives were compared to those for methyl aryl phosphate esters (OP). Results show that SP esters react with pyridine nucleophiles via a concerted SN2(P) mechanism. Bronsted analysis suggests that reactions of both SP and OP esters proceed via transition states with dissociative character. The overall similarity of the transition state structures supports the use of phosphorothiolates as substrate analogues to probe mechanisms of enzyme-catalyzed phosphoryl transfer reactions. This journal is The Royal Society of Chemistry.
Regioselective phosphorylation of carbohydrates and various alcohols by bacterial acid phosphatases; probing the substrate specificity of the enzyme from Shigella flexneri
Van Herk, Teunie,Hartog, Aloysius F.,Van Der Burg, Alida M.,Wever, Ron
, p. 1155 - 1162 (2007/10/03)
Bacterial non-specific acid phosphatases normally catalyze the dephosphorylation of a variety of substrates. As shown previously the enzymes from Shigella flexneri and Salmonella enterica are also able to catalyze the phosphorylation of inosine to inosine monophosphate and D-glucose to D-glucose 6-phosphate (D-G6P) using cheap pyrophosphate as the phosphate donor. After optimization high yields (95%) are achieved in the latter reaction and we show here that it is possible to use these enzymes in a preparative manner. This prompted us to investigate by using 31P NMR and HPLC also the phosphorylation of a broad range of carbohydrates and alcohols. Many cyclic carbohydrates are phosphorylated in a regioselective manner. Non-cyclic carbohydrates are phosphorylated as well. Phosphorylation of linear alcohols, cyclic and aromatic alcohols is also possible. In all cases the acid phosphatase from Shigella prefers a primary alcohol function above a secondary one. We conclude that these enzymes are an attractive alternative to existing chemical and enzymatic methods in the phosphorylation of a broad range of compounds.
Amino acid N-carboxyanhydrides: Activated peptide monomers behaving as phosphate-activating agents in aqueous solution
Biron, Jean-Philippe,Pascal, Robert
, p. 9198 - 9199 (2007/10/03)
The hydrolysis of valine N-carboxyanhydride (NCA) in aqueous phosphate buffers was shown to proceed through nucleophilic catalysis via an aminoacyl phosphate intermediate that displays phosphorylating capabilities through a potentially prebiotic process that simulates modern biochemical metabolic pathways. Copyright
