- Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus
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Industrially important triaryl phosphites, traditionally prepared from PCl3, have been synthesized by a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen- and transition metal-free way to these compounds. Subsequent oxidation of triaryl phosphites produces triaryl phosphates and triaryl thiophosphates. Phosphorotrithioates are also prepared efficiently from aromatic thiols and aliphatic thiols.
- Zhang, Yue,Cai, Ziman,Chi, Yangyang,Zeng, Xiangzhe,Chen, Shuanghui,Liu, Yan,Tang, Guo,Zhao, Yufen
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supporting information
p. 5158 - 5163
(2021/07/20)
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- Method for preparing phosphate ester derivatives from white phosphorus
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A method for preparing phosphate ester derivatives from white phosphorus relates to the field of chemical engineering, and comprises the following steps: adding alkali, a catalyst, a white phosphorus solution, ROH or RSH (R represents alkyl or aromatic group) into a reaction container in an inert atmosphere, and heating and stirring the mixture in a mixed solvent of toluene and DMSO (dimethyl sulfoxide) to react for a certain time, so as to obtain three-coordinated phosphate ester derivatives; and 2) continuing to add H2O2, air or sulfur powder until the oxidation is completed, thereby obtaining the tetra-coordinated phosphate ester derivative. According to the method, chlorine, phosphorus trichloride and halogen are not needed, phosphite ester is directly prepared from elementary white phosphorus in an efficient, green and environment-friendly manner, and phosphate and thiophosphate can be directly prepared after oxidation. High pollution and high corrosivity of a traditional method are avoided in the whole process; meanwhile, white phosphorus is completely converted in the whole process, white phosphorus residues are avoided, and the post-reaction treatment process is safe.
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Paragraph 0062-0064
(2021/06/23)
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- Aerobic Oxidation of Phosphite Esters to Phosphate Esters by Using an Ionic-Liquid-Supported Organotelluride Reusable Catalyst
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We describe the synthesis of an ionic-liquid (IL)-supported organotelluride catalyst and its application as a recyclable catalyst for the aerobic oxidation of phosphite esters to phosphate esters. This method shows high conversion rates, allows the ready isolation and purification of the resulting products, and exhibits good reusability of the catalyst.
- Mihoya, Aya,Shibuya, Yuga,Ito, Akane,Toyoda, Anna,Oba, Makoto,Koguchi, Shinichi
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supporting information
p. 2043 - 2045
(2020/11/10)
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- Catalytic synthesis of triaryl phosphates from white phosphorus
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Triaryl phosphates were synthesized from white phosphorus and phenols under aerobic conditions and in the presence of iron catalysts and iodine. Full conversion to phosphates was achieved without the use of chlorine, and the reactions do not produce acid waste. Triphenyl phosphate, tritolyl phosphate and tris(2,4-di-tert-butyl)phenyl phosphate were synthesized by this method with high selectivities. Various iron(III) diketonates were used to catalyze the conversion. Mechanistic studies showed that the reaction proceeds by formation of PI3, then O=PI(OPh)2 before the final formation of the phosphate. The nucleophilic substitution of O=PI(OPh)2 with phenol to form O=P(OPh)3 was found to be the rate-limiting step.
- Armstrong, Kenneth M.,Kilian, Petr
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experimental part
p. 2138 - 2147
(2011/06/28)
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- Nickel-catalyzed amination of aryl phosphates through cleaving aryl C-O bonds
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The amination of triaryl phosphates was achieved using a Ni(II)-(σ-Aryl) complex/NHC catalyst system in dioxane at 110 °C in the presence of NaH as base. Electron-neutral, -rich, and -deficient triaryl phosphates were coupled with a wider range of amine partners including cyclic and acyclic secondary amines, aliphatic primary amines, and anilines in good to excellent yields.
- Huang, Jin-Hua,Yang, Lian-Ming
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supporting information; experimental part
p. 3750 - 3753
(2011/09/14)
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- Absolute viscosity and density of trisubstituted phosphoric esters
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This paper presents measurements on the absolute viscosity (η) and density (ρ) of trisubstituted phosphoric esters which are useful in understanding their flow mechanism necessary for accessing their role as plasticizers. The effect of chain length and branching has been examined on the η and ρ trends. From η data, by using the Vogel-Tammann-Fulchur (VTF) equation, the VTF temperature (To) has been obtained which also represents the ideal glass transition temperature. To is related to the flexibility of the molecules. It is observed that To initially decreases with molecular weight, reaches a minimum, and increases thereafter. The initial decrease in To has been attributed to the enhanced flexibility of the phosphate esters. Reversal of flexibility with relative molar mass beyond 400 is due to the gentle collision of the arms of the trisubstituted phosphoric esters. This has been further corroborated from the molar mass exponent as exhibited in the η-molar mass plot. The isomeric effect on η has also been investigated in tricresyl phosphates, hitherto for the first time. The ortho isomer has highest η among the isomers. The para isomer was found to have lowest To and hence highest flexibility compared to the ortho and meta isomers.
- Kannan,Kishore
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p. 649 - 655
(2007/10/03)
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- Polymer supported reagents: An efficiant and simple method for the synthesis of triaryl phosphates
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The reaction of phosphoryl chloride with insoluble polymer-supported phenoxide ion reagents in benzene at room temperature, produced triaryl phosphates in excellent yields. The isolation of pure products by simple filtration and evaporation is an important feature of this method.
- Sagar,Thorat,Salunkhe
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p. 2029 - 2033
(2007/10/02)
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- ELECTROCHEMICALLY INDUCED PROCESSES OF FORMATION OF PHOSPHORUS ACID DERIVATIVES. 4. SYNTHESIS OF TRIALKYL PHOSPHATES FROM WHITE PHOSPHORUS
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The products of electrolysis in dipolar aprotic solvents on the background of tetraethylammonium iodide in the presence of white phosphorus are trialkyl phosphite (the primary product after splitting of all the P - P bonds in the phosphoric oligomers) and triaryl phosphate.It was found that the formation of triaryl phosphate from white phosphorus proceeds by way of electrochemical reduction of pentaaroxyphosphorane - an intermediate product of the reaction of triaryl phosphite with iodine and phenol.A strong dependence of the yields and distribution of the products on the composition of the electrolyte has been observed. Keywords: white phosphorus, electrosynthesis, triaryl phosphate.
- Budnikova, Yu. G.,Kargin, Yu. M.,Zaripov, I. M.,Romakhin, A. S.,Ignat'ev, Yu. A.,et al.
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p. 1585 - 1588
(2007/10/02)
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