- METHOD FOR PRODUCING PHOSPHOESTER COMPOUND
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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
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Paragraph 0023; 0026-0028
(2021/09/27)
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- Intriguing structural chemistry of neutral and anionic layered monoalkylphosphates: Single-source precursors for high-yield ceramic phosphates
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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).
- Bhat, Gulzar A.,Kalita, Alok Ch.,Murugavel, Ramaswamy
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p. 5390 - 5401
(2017/09/26)
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- Regioselective phosphorylation of carbohydrates and various alcohols by bacterial acid phosphatases; probing the substrate specificity of the enzyme from Shigella flexneri
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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.
- Van Herk, Teunie,Hartog, Aloysius F.,Van Der Burg, Alida M.,Wever, Ron
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p. 1155 - 1162
(2007/10/03)
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- Synthesis of Trialkyl Phosphates from White Phosphorus
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A new method was proposed for preparing trialkyl phosphates directly from white phosphorus by its electrolysis in a mixture of acetonitrile, alcohol, and water with tetraethylammonium iodide as supporting electrolyte. To increase the amount of the product synthesized in the unit volume of the electrolyte solution and the productivity of the process, phosphorus and water are added to the electrolyte in portions, which allows synthesis of up to 1 mol of trialkyl phosphate in 1 1 of the electrolyte solution.
- Romakhin,Nikitin
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p. 1023 - 1026
(2007/10/03)
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- Poly-perfluoroalkyl-substituted alcohols and acids, and derivatives thereof
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Di-, tri- and poly-perfluoroalkyl-substituted alcohols and acids and derivatives thereof are described which are prepared from perfluoroalkyl iodides and di-, tri- or polyallyl alcohols or acids. These compounds contain two or more perfluoroalkyl-iodoalkyl or perfluoroalkyl-alkenyl groups and one or two alcohol or acid groups or derivatized alcohol or acid functions. They can be reacted with isocyanates, epoxy compounds, anhydrides, acids or acid derivatives to prepare a great variety of oil- and water-repellent compositions which are useful for oil- and water-repellent treatment of textiles, glass, paper, leather and other substrates.
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- ALKYLATING PROPERTIES OF ACID ORGANIC PHOSPHATES
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Under the action of phenols and alcohols, acid alkyl phosphates undergo transesterification, which is accompanied by dealkylation of the latter and alkylation of the alcohols (phenols) at the hydroxy groups and aromatic rings.Isopropyl phosphates are stronger alkylating agents than methyl phosphates.Diphenyl methyl and phenyl dimethyl phosphates yield products of methylation of their own aromatic rings only upon prolonged pyrolysis.In all cases organic polyphosphates are formed.
- Munik, S. N.,Eliseenkov, V. N.,Ivanov, B. E.
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p. 378 - 382
(2007/10/03)
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- Photochemistry of phosphate esters: α-keto phosphates as a photoprotecting group for caged phosphate
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Irradiation of two families of α-keto phosphates yielded rearrangement products and deprotected phosphates as the major products. For both sets of reactants, the triplet excited state of the ketone reacted with quantum efficiencies that ranged from 0.10 to 0.38. Desyl phosphates yielded 2-phenylbenzo[6]furan independent of the nature of the solvent whereas phosphate esters of α-hydroxy-p-methoxyacetophenone rearranged to esters of p-methoxyphenylacetic acid. In all cases, the phosphate group with the remaining ligands intact was released in nearly quantitative yield. The desyl group was further developed as a cage ligand for cAMP. Upon photolysis, the desyl caged ester of cAMP (13) quantitatively released the nucleotide with a quantum efficiency of 0.33 ± 0.01 and a unimolecular rate constant of 7.1 × 108s-1. Additional synthetic, product, and mechanistic studies are reported for the two series of α-keto phosphates.
- Givens, Richard S.,Athey, Phillip S.,Matuszewski, Bogdan,Kueper III, L. William,Xue, Jie-You,Fister, Thomas
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p. 6001 - 6012
(2007/10/02)
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- CONVENIENT SYNTHETIC ROUTE TO MONO- OR DIAKLYL PHOSPHATE FROM INORGANIC PHOSPHORUS ACIDS
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Mono- or dialkyl phosphate was synthesized in a favorable yield by oxidation of phosphonic or phosphinic acid in alcohol with oxygen at the presence of a catalytic amount of copper(II)chloride.The reaction may proceed via the formation of corresponding phosphorochloridate or phosphorochloridite.
- Okamoto, Yoshiki,Kusano, Tetuya,Takamuku, Setsuo
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p. 195 - 200
(2007/10/02)
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- Phosphorylation with Pyrophosphoric Acid
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Dihydrogenphosphates of primary and secondary aliphatic alcohols as well as phenol were prepared by a very simple procedure with pyrophosphoric acid. t-Butyl and benzyl dihydrogenphosphates could be obtained by a slight modification of the reaction conditions.For the purpose of phosphorylation pyrophosphoric acid was more reactive than orthophosphoric acid.
- Yamaguchi, Hachiro,Ogura, Fumio,Otsubo, Tetsuo,Ikeura, Yasuhiro
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p. 1891 - 1892
(2007/10/02)
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