- Sulfonyl-Promoted Michaelis-Arbuzov-Type Reaction: An Approach to S/Se-P Bonds
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By facilitating the chemical conversion of thiols to thiosulfonates, phosphoramidite/phosphite bearing sp3-hybridized carbon serves as an ideal coupling material to forge new connections at room temperature. In this work, a functional group-induced, additive-free, novel, S-P bond-forming approach is presented. This protocol exhibits good functional group tolerance with wide applications that include phosphorylation of cysteine derivatives, development of a one-pot approach to mixed unsymmetrical thiophosphonates, and extension of the concept to different Se-P bonds. Meticulously, our reaction also generated a S-P bond against cyclic 1,2-dithiane-1-dioxide in a byproduct-free manner. These Michaelis-Arbuzov-type reactions are easy to conduct, work efficiently in a reduced reaction time, and are applicable to gram-scale preparation as well.
- Rather, Suhail A.,Bhat, Mohammad Yaqoob,Hussain, Feroze,Ahmed, Qazi Naveed
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p. 13644 - 13663
(2021/10/01)
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- Photoinduced Decarboxylative Phosphorothiolation of N-Hydroxyphthalimide Esters
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A visible-light-induced protocol for the synthesis of phosphorothioates is developed by employing the Ir-catalyzed decarboxylative phosphorothiolation of N-hydroxyphthalimide esters. This novel synthesis method utilizes carboxylic acids as raw material, which is stable, cheap, and commercially available. Scope studies show that this reaction has good compatibility of functional groups. Notably, both the synthesis of steric hindrance phosphorothioates and the later modification of some bioactive compounds are successfully achieved.
- Guo, Yu,Luo, Ying,Mu, Shiqiang,Xu, Jian,Song, Qiuling
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p. 6729 - 6734
(2021/09/11)
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- Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies
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Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.
- Xue, Jing-Wen,Zeng, Miao,Zhang, Sicheng,Chen, Zhuqi,Yin, Guochuan
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p. 4179 - 4190
(2019/04/30)
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- Benign synthesis of thiophosphates, thiophosphinates and selenophosphates in neat condition using N-chalcogenoimides as the source of electrophilic sulfur/selenium
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A neat reaction protocol has been developed for synthesis of thiophosphate, thiophosphinate and selenophosphate compounds. N-chalcogenoimides have been used for chalcogenylation of P(O)H moieties of various H-phosphonates under solvent, catalyst and base free condition at room temperature in aerial atmosphere. Both S-aryl and S-alkyl phosphorothioate compounds were prepared by this method in good yields. Selenophosphates were also synthesized using N-(phenylseleno)phthalimide under solvent free condition.
- Mondal,Saha, Amit
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- Synthetic method for benzyl thiophosphate
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The invention provides a synthetic method for benzyl thiophosphate. The method comprises the step of carrying out a stirring reaction for 6-24 hours on benzyl alcohol which is cheap and easily available, wide in source and stable and low in toxicity as an alkylation reagent and sulfur powder and phosphite ester to prepare a benzyl thiophosphate compound in one step at 70-100 DEG C without a catalyst. The method is simple in reaction condition, the raw materials are easily available, excessive alkali is not used, a solvent is not needed, and the method is easy to operate with only one reaction.The method can be also used for amplifying and gram-grade preparation of products conveniently, and has certain research and industrial application prospects.
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Paragraph 0024-0028
(2019/02/06)
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- Synthesis of Thiophosphates by Coupling of Phosphates with Bunte Salts under Mild Conditions
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A simple, green, and efficient method has been developed for the preparation of thiophosphates with sodium S-benzyl thiosulfates. The method uses an NaBr-catalyzed coupling reaction of Bunte salts with phosphonates in the presence of an acid and hydrogen peroxide (30%), and the desired products were obtained in good yields.
- Min, Cong,Zhang, Rongxing,Liu, Qian,Lin, Sen,Yan, Zhaohua
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supporting information
p. 2027 - 2030
(2018/09/14)
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- Cs2CO3-Catalyzed Aerobic Oxidative Cross-Dehydrogenative Coupling of Thiols with Phosphonates and Arenes
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An efficient Cs2CO3-catalyzed oxidative coupling of thiols with phosphonates and arenes that uses molecular oxygen as the oxidant is described. These reactions provide not only a novel alkali metal salt catalyzed aerobic oxidation, but also an efficient approach to thiophosphates and sulfenylarenes, which are ubiquitously found in pharmaceuticals and pesticides. The reaction proceeds under simple and mild reaction conditions, tolerates a wide range of functional groups, and is applicable to the late-stage synthesis and modification of bioactive molecules.
- Song, Song,Zhang, Yiqun,Yeerlan, Adeli,Zhu, Bencong,Liu, Jianzhong,Jiao, Ning
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supporting information
p. 2487 - 2491
(2017/02/23)
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- A thiophosphate synthetic method of compound and the method in a plurality of pharmaceutical application in the synthesis of (by machine translation)
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The invention discloses a having the general formula (III) of the thiophosphate synthetic method of compound, the purpose is to provide a novel, condition is simple, easy to industrial production of the thiophosphate synthetic method of compound. The method is to have the general formula (I) of the organophosphorus oxygen apperception compound having the general formula (II) with a mercaptan or phenyl-sulfhydryl apperception compound mixed, under the effects of catalyst, obtained by the reaction of the formula (III) of the thiophosphate compound. The method of the invention, can be cheap efficient synthesis of thiophosphate compounds, in actual production will have extensive application prospect. (by machine translation)
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Paragraph 0235; 0236; 0237; 0238
(2017/07/20)
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- Method of preparing kitazin
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The invention discloses a method for preparing iprobenfos. The method comprises the following steps: (1) by taking phosphorus trichloride and isopropanol as esterification raw materials, performing deacidification reaction, thereby preparing O,O-diisopropyl phosphite; (2) removing residual 2-chloropropane; (3) reacting O,O-diisopropyl phosphite with sulfur and sodium hydroxide at low temperature in the presence of a solvent, thereby generating O,O-diisopropyl sulfo-sodium phosphate; (4) removing the solvent and filtering; (5) reacting O,O-diisopropyl sulfo-sodium phosphate with benzyl chloride, filtering, and separating the liquid, thereby preparing iprobenfos crude raw oil; (6) washing with water, crystallizing, filtering, and removing the solvent, thereby preparing a iprobenfos active compound. According to the method, as the sodium hydroxide is adopted to prepare salt at low temperature, the decomposition of O,O-diisopropyl phosphite is reduced, the impurities are reduced, no ammonia nitrogen wastewater is generated, and as 2-chloropropane of O,O-diisopropyl phosphite is removed, the generation of a byproduct thiophosphoric acid triisopropyl ester is reduced, and the quality of iprobenfos is improved.
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Paragraph 0082-0084
(2017/06/29)
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- Rearrangement of lithiated S-alkyl O,O-dialkyl thiophosphates: Scope and stereochemistry of the thiophosphate-mercaptophosphonate rearrangement
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S-Alkyl O,O-dialkyl thiophosphates are prepared by alkylation of the triethylammonium salt of O,O-diisopropyl thiophosphoric acid. S-Benzyl thiophosphate was metallated at temperatures of ≥-45 °C by trityllithium and LiTMP (lithium 2,2,6,6-tetramethylpiperidide) and S-alkyl thiophosphates only by LiTMP to give dipole-stabilised carbanions which rearrange to α-mercaptophosphonates in yields of up to 45%. Metallation occurs with a high primary kinetic isotope effect (kH/kD up to ≈50). When the lithium (R)-N-isopropyl-1-phenylethylamide was used to induce the isomerisation of S-pentyl thiophosphate an α-mercaptophosphonate with an ee of 22% was isolated. (R)-S-[1-D1]hexyl O,O-diisopropyl thiophosphate was rearranged to a dextrorotary α-mercapto-[1-D 1]hexylphosphonate, whose (R)-configuration was determined by chemical correlation. The thiophosphate-mercaptophosphonate rearrangement proceeds with retention of configuration. The Royal Society of Chemistry 2011.
- Philippitsch, Violeta,Hammerschmidt, Friedrich
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experimental part
p. 5220 - 5227
(2011/08/10)
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- Composition for controlling harmful bio-organisms and method for controlling harmful bio-organisms using the same
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A composition for controlling harmful bio-organisms comprising (a) at least one imidazole compound represented by formula (I): wherein R represents a lower alkyl group or a lower alkoxy group; and n represents an integer of 1 to 5, as an active ingredient, and (b) at least one inorganic phosphorus compound and/or at least one fungicide for Phycomycetes as an active ingredient or (c) a spreader as an activity-enhancing ingredient, and a method for controlling harmful bio-organisms comprising applying the composition for controlling harmful bio-organisms onto harmful bio-organisms.
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- Method for preparing high purity indane bisphenols
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A process for preparing high purity indane bisphenols in high yield is disclosed. The method comprises heating a bisphenol in the presence of Montmorillonite K10 clay, which catalyzes the synthesis reaction more rapidly and effectively than other clays previously disclosed. The high purity (≥97%) of the synthesized indane bisphenol is obtained by two successive selective recrystallizations, the first from an organic solvent, and the second from an acetic acid solution. The high purity indane bisphenols produced may be made substantially pure (>99%) by employing a purification process which includes at least one selective recrystallization from a 45%-80% by volume aqueous acetic acid solution. Alternatively, substantially pure indane bisphenol may be obtained by recrystallization from a solution of 89-93% by volume toluene and 7-11% by volume n-propanol, or by a combination of recrystallizations from toluene/n-propanol and from aqueous acetic acid. Substantially pure indane bisphenols, such as 5-hydroxy-3-(4-hydroxyphenyl)-1,1,3-trimethylindane, are suitable for conversion to high molecular weight polymers.
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- Insect pesticidal composition
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An insect pesticidal composition comprises O,O-di-C2-3 alkyl S-benzyl- or S-halobenzyl-phosphorothiolate and a pyrethroid compound having the formula STR1 wherein X represents hydrogen atom or ethynyl group as active ingredients.
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- Insecticidal and/or acaricidal composition exhibiting low toxicity to mammals and fish
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The present invention relates to insecticidal compositions of low toxicity to fishes and mammals characterized by containing m-(p-bromophenoxy)-α-cyanobenzyl trans- or trans-rich-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate of the formula (I), STR1 and a carbamic ester of the formula (III), STR2 wherein R is a group of the formula, STR3 in which X is a C1 -C4 alkyl or C1 -C4 alkoxyl group and n is 1 or 2, in a ratio of 1 to 1-100 (part by weight) of the former to the latter, and insecticides obtained by mixing said compositions with a carrier or a diluent and if necessary an additive. The term "trans-rich" shows the ratio of trans/cis is not less than 75/25.
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- Process for the preparation of O,O-dialkyl-S-benzyl thiophosphates
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O,O-Dialkyl-S-benzyl thiophosphates are obtained by reacting a diester of phosphorous acid such as dimethyl phosphite or diethyl phosphite, in an organic solvent such as toluene or xylene which is sparingly soluble or insoluble in water, with sulfur and an alkali or alkaline earth metal hydroxide or oxide such as NaOH or Ca(OH)2, extracting the reaction product with water and then reacting the extract with a benzyl halide. In this manner, O,O-dialkyl-S-benzyl thiophosphates useful as agricultural and horticultural bactericidal and insecticidal agents are industrially advantageously obtained in a high purity and in a high yield.
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