- A New, Efficient Synthesis of Thioloesters
-
The reaction between phosphorothioic and thiocarboxylic acids and O-alkyl-N,N-dicyclohexylisoureas has been found to give the corresponding phosphorothiolates and thiolocarboxylates in high yields (65-95percent), providing a new method for the thiophosphorylation and thiocarboxylation of alcohols.
- Nowicki, Tomasz,Markowska, Anna,Kielbasinski, Piotr,Mikolajczyk, Marian
-
-
Read Online
- Reactions of Disulfides with Silyl Phosphites to Generate Thiophosphates Under Neat Conditions
-
An efficient procedure for the synthesis of thiophosphates is described. Without using any metallic catalyst or base, the direct sulfur–phosphorus coupling reaction of disulfides and dialkyl trimethylsilyl phosphite (DTSP) was carried out under solvent-fr
- Zhan, Zhen,Yang, Zhongzhen,Ma, Dena,Zhang, Hao,Shi, Yuesen,Wang, Qiantao,Deng, Yong,Hai, Li,Wu, Yong
-
-
Read Online
- A convenient method for the synthesis of phosphorothioates and their anticholinesterase activites
-
A simple, efficient, and general method has been developed for the synthesis of phosphorothioates through a one-pot reaction of alkyl halides with the mixture of diethyl phosphite in the presence of NH4OAc/S/CaO under solvent-free conditions. T
- Kaboudin, Babak,Emadi, Saeed,Norouzi, Hamid
-
-
Read Online
- Easy access to phosphonothioates.
-
A new and particularly mild method for the formation of phosphorus-sulfur bonds has been achieved through base-catalyzed addition of thiocyanate to the corresponding H-phosphine oxide, phosphinate, or phosphonate. This reaction procedure offers many advantages: the use as starting material of a stable and not oxygen-sensitive phosphorus(v) species, particularly mild and nonaqueous reaction conditions and workup (a pivotal point for these sensitive phosphonothioates), and, through optimized access to thiocyanates, a wider scope of substrates. This method has been applied to achieve the synthesis of substrate analogues for the study of antibody-catalyzed hydrolysis of acetylcholinesterase inhibitor PhX (11).
- Renard, Pierre-Yves,Schwebel, Herve,Vayron, Philippe,Josien, Ludovic,Valleix, Alain,Mioskowski, Charles
-
-
Read Online
- Photoinduced Decarboxylative Phosphorothiolation of N-Hydroxyphthalimide Esters
-
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
-
p. 6729 - 6734
(2021/09/11)
-
- Sulfonyl-Promoted Michaelis-Arbuzov-Type Reaction: An Approach to S/Se-P Bonds
-
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
-
p. 13644 - 13663
(2021/10/01)
-
- Electrochemically driven synthesis of phosphorothioates from trialkyl phosphites and aryl thiols
-
A facile and elegant protocol for synthesis of phosphorothioates from trialkyl phosphites and aryl thiols via indirect electrochemical oxidation mediated by KI has been successfully developed. KI as a redox mediator, enabled the reaction of trialkyl phosp
- Guo, Xiaqun,Li, Meichao,Liu, Xin,Shen, Zhenlu,Shi, Shuxian,Wu, Zengzhi,Zhao, Lingmin
-
-
- Trichloroisocyanuric acid-promoted thiolation of phosphites by thiols
-
A simple and convenient method for the synthesis of thiophosphates by coupling of phosphites with thiols under mild conditions has been developed. The reactions were promoted by trichloroisocyanuric acid (TCCA) and were carried out at room temperature in
- Chen, Yingying,Li, Meichao,Gong, Zhangshui,Shen, Zhenlu
-
-
- Synthetic method of thiophosphate compound
-
The invention discloses a synthetic method of a phosphorothioate compound. The preparation method comprises the following steps: with thiol as a reaction substrate and trichloroisocyanuric acid (TCCA)as an accelerant, reacting the reaction substrate and the accelerant in an organic solvent at normal temperature and normal pressure for 10-20 minutes, then adding phosphite triester, continuing reacting for 10-20 minutes, and after the reaction is finished, carrying out separation treatment to obtain the phosphorothioate compound. According to the synthesis method disclosed by the invention, thereaction is carried out at normal temperature and normal pressure without special requirements; reaction time is short; and reaction substrate universality is good.
- -
-
Paragraph 0063-0064
(2020/05/30)
-
- A Robust Methodology for the Synthesis of Phosphorothioates, Phosphinothioates and Phosphonothioates
-
A robust methodology for the synthesis of phosphorothioates, phosphinothioates and phosphonothioates, including those bearing low molecular weight S-alkyl side-chains, is presented. Application of the “caesium effect” in conjunction with the disulfide 3,3’-dithiobis(propionitrile), which acts as a shelf-stable sulfur source, avoids recourse to malodorous alkanethiols and toxic P?Cl precursors. A diverse range of sulfur-containing organophosphorus targets, including phosphorus-based heterocycles, may be prepared in consistently high yields. This chemistry also provides ready access to the corresponding DBU salts which are potential substrates for Pd-catalysed coupling reactions. (Figure presented.).
- Jones, David J.,O'Leary, Eileen M.,O'Sullivan, Timothy P.
-
supporting information
(2020/03/27)
-
- High-efficiency green preparation method of thio-organic phosphonic acid derivative
-
The invention discloses a high-efficiency green preparation method of a thio-organic phosphonic acid derivative. The thio-organic phosphonic acid derivative is directly prepared by reaction of a P (O)-H compound, sulfur powder and alcohol, the reaction temperature is 80-120 DEG C, and the reaction time is 12-48 hours. According to the method, alcohol and sulfur powder which are stable, easy to obtain, low in price and relatively green can be directly used as raw materials, the P (O)-H compound can be directly used without any activation treatment, and the P (O)-H compound, sulfur powder and alcohol can directly react under the one-pot condition to efficiently prepare the thio-organic phosphonic acid derivative without any transition metal or non-metal catalyst and an additive. The method has the advantages of low requirements on reaction conditions, simplicity and feasibility in operation, no need of inert gas protection, water as a byproduct and small green pollution, and has high academic value and potential wide application prospect due to the wide application of the thio-organic phosphonic acid derivative in the fields of pesticides, medicines, materials and the like.
- -
-
Paragraph 0066-0069
(2020/09/23)
-
- Benign synthesis of thiophosphates, thiophosphinates and selenophosphates in neat condition using N-chalcogenoimides as the source of electrophilic sulfur/selenium
-
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
-
supporting information
(2019/08/08)
-
- Synthetic method for benzyl thiophosphate
-
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.
- -
-
Paragraph 0016-0023; 0030-0037
(2019/02/06)
-
- Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies
-
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
-
p. 4179 - 4190
(2019/04/30)
-
- Synthesis of Thiophosphates by Coupling of Phosphates with Bunte Salts under Mild Conditions
-
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
-
supporting information
p. 2027 - 2030
(2018/09/14)
-
- Practical Reagents and Methods for Nucleophilic and Electrophilic Phosphorothiolations
-
New late-stage phosphorothiolation methods are disclosed that allow the efficient transfer of SP(O)(OR)2 groups to diversely functionalized substrates using nucleophilic and electrophilic reagents. The nucleophilic reagent, tetramethylammonium O,O-dimethyl phosphorothioate, was synthesized in near-quantitative yield from Me3SiP(O)(OMe)2, elemental sulfur and Me4NF. Its umpolung with N-bromophthalimide provided the electrophilic reagent, O,O-dimethyl-S-(N-phthalimido)phosphorothioate. Complementary methods based on these reagents enable the phosphorothiolation of diversely functionalized alkyl halides, arenediazonium salts, arylboronic acids and electron-rich arenes in good yields under mild conditions. (Figure presented.).
- Kovács, Szabolcs,Bayarmagnai, Bilguun,Aillerie, Alexandre,Goo?en, Lukas J.
-
supporting information
p. 1913 - 1918
(2018/03/30)
-
- Base-controlled Fe(Pc)-catalyzed aerobic oxidation of thiols for the synthesis of S-S and S-P(O) bonds
-
Fe(Pc)-Catalyzed aerobic oxidation of thiols for the synthesis of disulfides has been developed under mild reaction conditions. In addition, an aerobic oxidative cross-dehydrogenative coupling (CDC) reaction of thiols with P(O)-H compounds (H-phosphonates and H-phosphine oxide) for the formation of S-P(O) bonds has been demonstrated under the Fe(Pc) catalysis system with a base additive. Control experiments revealed that the use of a base (DIPA) in this system controls the synthetic pathways in which thiophosphates are formed.
- Huang, Hai,Ash, Jeffrey,Kang, Jun Yong
-
p. 4236 - 4242
(2018/06/21)
-
- Cs2CO3-Catalyzed Aerobic Oxidative Cross-Dehydrogenative Coupling of Thiols with Phosphonates and Arenes
-
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
-
supporting information
p. 2487 - 2491
(2017/02/23)
-
- A thiophosphate synthetic method of compound and the method in a plurality of pharmaceutical application in the synthesis of (by machine translation)
-
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)
- -
-
Paragraph 0151; 0152; 0153; 0154
(2017/07/20)
-
- Camphorquinone: A new and efficient oxidant for the preparation of 2-thio-substituted benzothiazoles from alcohols by oxidation-reduction condensation
-
A convenient one-pot procedure for the preparation of various 2-thio-substituted benzothiazoles from alcohols and benzothiazole-2-thiol utilizing camphorquinone-mediated oxidation-reduction condensation is disclosed. The condensation between benzothiazole-2-thiol and alkyl diphenylphosphinites, generated in situ from alcohols and chlorodiphenylphosphine, proceeded smoothly in the presence of camphorquinone to furnish the corresponding benzothiazoles in good to moderate yields.
- Pluempanupat, Wanchai,Temyarasilp, Parinthorn,Widhalm, Michael,Chavasiri, Warinthorn
-
p. 418 - 430
(2014/06/10)
-
- New benzotriazole-based reagents for the phosphonylation of various N-, O-, and S-nucleophiles
-
Benzotriazole surrogates showing higher stabilities than the corresponding chlorophosphates, allow phosphonylation of a variety of N-, O-, and S-nucleophiles in good yields.
- Panmand, Deepak S.,Tiwari, Anand D.,Panda, Siva S.,Monbaliu, Jean-Christophe M.,Beagle, Lucas K.,Asiri, Abdullah M.,Stevens, Christian V.,Steel, Peter J.,Hall, C. Dennis,Katritzky, Alan R.
-
supporting information
p. 5898 - 5901
(2015/01/08)
-
- Copper(I)-induced sulfenylation of H-phosphonates, H-phosphonites and phosphine oxides with aryl/alkylsulfonylhydrazides as a thiol surrogate
-
Aerobic dehydrogenative sulfenylation of H-phosphonites, and phosphine oxides with aryl/alkylsulfonyl hydrazides catalyzed by a sub-stoichiometric amount of copper iodide has been accomplished. This protocol is compatible with functional groups, and results in various thiophosphate derivatives in good to high yields.
- Kumaraswamy, Gullapalli,Raju, Ragam
-
p. 2591 - 2598
(2014/09/29)
-
- Copper(I) iodide catalyzed synthesis of thiophosphates by coupling of H -phosphonates with benzenethiols
-
A simple, efficient, and new method has been developed for the preparation of thiophosphates from benzenethiols. The method involves copper(I) iodide catalyzed coupling of thiols with H-phosphonates in the presence of triethylamine. The reaction proceeds effectively to afford the corresponding thiophosphates in moderate to good yields via an aerobic dehydrogenative coupling of H-phosphonates with benzenethiols. This method is easy, rapid, and good-yielding for the synthesis of thiophosphates from benzenethiols. Georg Thieme Verlag Stuttgart. New York.
- Kaboudin, Babak,Abedi, Yaghoub,Kato, Jun-Ya,Yokomatsu, Tsutomu
-
p. 2323 - 2327
(2013/09/02)
-
- Ga(OTf)3-catalyzed direct substitution of alcohols with sulfur nucleophiles
-
It is reported that Ga(OTf)3 catalyzes the direct displacement of alcohols with sulfur nucleophiles. The products are versatile intermediates that can be utilized in carbon - carbon, carbon - sulfur bond formation or used in modified Julia olef
- Han, Xinping,Wu, Jimmy
-
supporting information; experimental part
p. 5780 - 5782
(2011/03/18)
-
- A simple and new method for the synthesis of thiophosphates
-
A simple, efficient, and general method has been developed for the synthesis of thiophosphates through a one-pot reaction of alkyl halides with the mixture of diethyl phosphite in the presence of ammonium acetate/sulfur and acidic alumina under solvent-fr
- Kaboudin, Babak
-
p. 8713 - 8714
(2007/10/03)
-
- The thionophosphate-thiolophosphate photoisomerization proceeds predominantly through a non-chain radical pathway. Synthetically viable benzylation of tetrahydrofuran, propan-2-ol and olefins
-
The photoirradiation of thionophosphates, ROP(S)(OEt)2, derived from benzyl and vinylogously benzyl alcohols in CH3CN, with a Hanovia medium-pressure mercury lamp in a quartz vessel leads to the formation of the corresponding thiolophosphates, RSP(O)(OEt)2, through a non-chain radical pathway. This behavior of thionophosphates is unlike that of the related phosphates, which react through ionic dissociation-recombination processes. When the irradiation is conducted in solvents such as PriOH, THF and toluene, benzylation of these solvents takes place in synthetically respectable yields. Irradiation of thionophosphates in CH3CN leads to a convenient allylic benzylation of olefins.
- Yadav, Veejendra K.,Balamurugan, Rengarajan,Parvez, Masood,Yamdagni, Raghav
-
p. 323 - 332
(2007/10/03)
-
- Process for the preparation of O,O-dialkyl-S-benzyl thiophosphates
-
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.
- -
-
-
- Triazolylthiophosphoric acid esters
-
Triazolylthiophosphonic esters corresponding to the formula SPC1 Wherein R1 represents a phenyl radical which is substituted by one or more fluorine, bromine and/or iodine atoms, by lower alkyl, lower alkoxy, lower alkylthio, lower trihalogenoalkyl, lower alkyl-SO, lower alkyl-SO2 or O2 N groups, which may be the same or different, or by at least one chlorine and at least one fluorine, bromine or iodine atom, one lower alkyl, lower alkoxy, lower alkylthio, lower trihalogenoalkyl, lower alkyl-SO, lower alkyl-SO2 or O2 N group, or represents an unsubstituted or halogenated and/or alkoxylated phenyl-lower alkyl radical or diphenylmethyl, and one of the symbols R2 and R3 represents hydrogen or a lower alkyl radical and the other represents the radical EQU1 wherein R4 represents a lower alkyl radical or the phenyl radical and R5 represents a lower alkyl radical their manufacture and their use in pest control.
- -
-
-
- Condensation products
-
Formamidine compounds of the formula EQU1 or WHEREIN R1 represents a substituted or unsubstituted phenyl radical, R2 represents hydroogen, alkyl, alkenyl or alkinyl and R3 represents acyl their manufacture and their use in pest control.
- -
-
-
