- 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 0081-0083
(2021/06/23)
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- Direct synthesis of phosphorotrithioites and phosphorotrithioates from white phosphorus and thiols
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White phosphorus (P4) is still the major commercial P-atom source for the production of organophosphorus compounds. Conventionally, C-S-P bonds were constructed from environmentally questionable P(O)X directly or indirectly. From the green chemistry point of view, formation of C-S-P bonds from inorganic molecule P4 in an easy-to-operate and atom-economical way is essential because it will avoid the hazardous chlorination process. Only five methods for the formation of C-S-P bonds from P4 have been developed over the past 70 years. Here, the first general and high-yielding synthesis of P(SR)3 and P(O)(SR)3 involving P4 and thiols is presented. With the use of KOH or K2CO3 as a base and DMSO-toluene as a solvent, both arythiols and alkylthiols are tolerant in this transformation. The reaction is characterized by a complete conversion of white phosphorus. This operationally simple and environmentally sound reaction shows a broad scope of substrates and good functional group tolerance. Moreover, this method can be easily adapted to large-scale preparation.
- Cao, Yinwei,Huangfu, Xinlei,Lu, Guozhang,Tang, Guo,Wang, Yueqiao,Zhao, Yufen
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supporting information
p. 5303 - 5309
(2020/09/17)
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- Process for the production of S,S,S-tributylphosphorotrithioate
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S,S,S-tributylphosphorotrithioite is oxidized with a perborate or percarbonate at a pH of from about 6 to about 12 and at a temperature of from about 40° to about 65° C. Sodium perborate is a particularly preferred oxidizing agent. The product S,S,S-tributylphosphorotrithioate may be recovered by simple phase separation.
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- Pesticide compositions and method
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Toxicant, especially pesticide compositions, having lowered dermal toxicity are provided. The compositions include a lipophilic-pesticide, a nonionic surfactant and a dry inert diluent carrier. Methods for reducing the dermal toxicity of lipophilic toxicants, especially pesticides are provided, as well as methods for controlling insect pests using the disclosed compositions.
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