- Synthesis of Symmetrical and Unsymmetrical Thiosulfonates from Disulfides through Electrochemically Induced Disulfide Bond Metathesis and Site-Selective Oxidation
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The anodic generation of symmetrical and unsymmetrical thiosulfonates is presented. First, the oxidation of disulfides yielding symmetrical thiosulfonates was realized. The direct synthesis is performed using a simple quasi-divided cell design, whereby using a supporting electrolyte is unnecessary. Its principle was then expanded to the conversion of unsymmetrical disulfides that were generated in situ through metathesis of two symmetrical disulfides. This enables a direct access to unsymmetrical thiosulfonates without any pre-functionalization or elaborate synthesis of the starting materials for the first time. The reaction scope was investigated by converting differently functionalized aliphatic and aromatic disulfides in moderate to very good yields. Furthermore, a sensitivity assessment for an improved reproducibility and a robustness screen to determine the compatibility of the reaction against functional groups were performed.
- Strehl, Julia,Hilt, Gerhard
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supporting information
(2021/10/14)
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- Metal-Free Radical Annulation of Oxygen-Containing 1,7-Enynes: Configuration-Selective Synthesis of (E)-3-((Arylsulfonyl)methyl)-4-Substituted Arylidenechromene Derivatives
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A novel strategy for the synthesis of (E)-3-((arylsulfonyl)methyl)-4-substituted benzylidenechromene derivatives via a metal-free radical annulation reaction of oxygen-containing 1,7-enynes with thiosulfonates has been developed. The reaction shows broad substrate scope, wide functional group tolerance, and moderate to excellent yields. Moreover, thiosulfonates were well driven to achieve the bifunctionalization reaction of oxo-1,7-enynes which derived from aliphatic alkynes. In addition, the (E)-configuration of the products was highly controlled by the structure of 1,7-enyne.
- Bian, Mouwang,Dai, Lei,Mao, Kaimin,Rong, Liangce,Wang, Chang,Yu, Qiuyu,Zhang, Jinghang
-
supporting information
p. 218 - 224
(2021/01/13)
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- Direct conversion of sulfinamides to thiosulfonates without the use of additional redox agents under metal-free conditions
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Direct conversion of sulfinamides to thiosulfonates is described. Without the use of additional redox agents, the reaction proceeds smoothly in the presence of TFA under metal-free conditions. This protocol possesses many advantages such as odourless and stable starting materials, broad substrate scope, selective synthesis, and mild reaction conditions. This journal is
- Ji, Yuan-Zhao,Li, Hui-Jing,Wang, Jun-Hu,Wu, Yan-Chao,Zhang, Chi
-
p. 9291 - 9298
(2021/11/13)
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- Synthesis of symmetrical / unsymmetrical thiosulfonates through the disproportionate coupling reaction of sulfonyl hydrazide mediated by phosphomolybdic acid
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Phosphomolybdic acid (H3PMo12O40) is reported as a green low-cost catalyst for the synthesis of symmetrical / unsymmetrical thiosulfonates via the disproportionate coupling reaction of sulfonyl hydrazide. The attributes of this reported catalytic system include low catalyst loadings (1 mol%), efficient turnover, and high yields (up to 94%). Additionally, this reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via sulfinyl radical disproportionation.
- Lv, Mengting,Liu, Yufeng,Li, Ke,Yang, Guoping
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supporting information
(2021/01/21)
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- Dual Roles of Rongalite: Reductive Coupling Reaction to Construct Thiosulfonates Using Sulfonyl Hydrazides
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A tunable and practical transformation of structurally diverse sulfonyl hydrazides into thiosulfonates in the presence of Rongalite (NaHSO 2·CH 2O) was developed. Transition-metal-free conditions, operational simplicity, and readily available reagents are the striking features of this protocol. It is the first example for the synthesis of thiosulfonates using sulfonyl hydrazides with the assistance of reductant. Additionally, the mechanistic studies revealed that this transformation probably undergoes via a reducing-coupling pathway.
- Zhang, Guofu,Fan, Qiankun,Zhao, Yiyong,Wang, Huimin,Ding, Chengrong
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supporting information
p. 81 - 85
(2020/11/03)
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- H4SiW12O40-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides: An efficient synthesis of 3,4-disubstituted 1H-pyrazoles
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A simple and efficient method for the synthesis of pyrazoles through a silicotungstic acid (H4SiW12O40)-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides has been developed. Various epoxides/aldehydes were smoothly reacted with sulfonyl hydrazides to furnish regioselectivity 3,4-disubstituted 1H-pyrazoles. The application of such an earth-abundant, readily accessible, and nontoxic catalyst provides a green approach for the construction of 3,4-disubstituted 1H-pyrazoles. A plausible reaction mechanism has been proposed on the basis of control experiments, GC-MS and DFT calculations.
- Cheng, Mengyuan,Cheng, Yuanyuan,Gao, Xiaofei,Li, Ke,Lin, Xiaoling,Liu, Yufeng,Xie, Xuanjie,Yang, Guoping
-
supporting information
(2021/09/06)
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- CuCl2-promoted decomposition of sulfonyl hydrazides for the synthesis of thiosulfonates
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Sulfonyl hydrazides recently received much attention as reagents for the introduction of sulfur-containing functional groups into organic compounds, because both sulfonyl and sulfenyl sources could be generated by the oxidation and decomposition of the sulfonyl hydrazides, respectively. However, the transformations of sulfonyl hydrazides into thiosulfonates, which could be produced by the reaction between sulfonyl and sulfenyl sources, have been less investigated. In this manuscript, we describe CuCl2-promoted selective synthesis of thiosulfonates from sulfonyl hydrazides. A variety of thiosulfonates were produced in moderate to good yields. The mechanism involving radical intermediates such as sulfonyl radical and thiyl radical was proposed on the basis of the previously reported references and mechanistic investigations. In addition, quantum chemical simulations revealed that Cu-promoted decomposition of sulfonyl hydrazides is thermodynamically viable in the developed conditions.
- Kim, Junsu,Park, Sanggil,Kim, Hyungjun,Kim, Jinho
-
supporting information
(2020/07/02)
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- S-(4-Methoxyphenyl)-4-methoxybenzenesulfonothioate as a Promising Lead Compound for the Development of a Renal Carcinoma Agent
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Organosulfur compounds show cytotoxic potential towards many tumor cell lines. Disulfides and thiosulfonates act through apoptotic processes, inducing proteins associated with apoptosis, endoplasmic reticulum stress, and the unfolded protein response. Three p-substituted symmetric diaryl disulfides and three diaryl thiosulfonates were synthesized and analyzed for inhibition of tubulin polymerization and for human cancer cell cytotoxic activity against seven tumor cell lines and a non-tumor cell line. S-(4-methoxyphenyl)-4-methoxybenzenesulfonothioate (6) exhibited inhibition of tubulin polymerization and showed the best antiproliferative potential, especially against the 786-0 cell line, being six times more selective as compared with the non-tumor cell line. In addition, compound 6 was able to activate caspase-3 after 24 and 48 h treatments of the 786-0 cell line and induced cell-cycle arrest in the G2/M stage at the highest concentration evaluated at 24 and 48 h. Compound 6 was able to cause complete inhibition of proliferation, inducing the death of 786-0 cells, by increasing the number of cells at G2/M and greater activation of caspase-3.
- Nantes, Camilla I.,Pereira, Ingrid D.,Bai, Ruoli,Hamel, Ernest,Burnett, James C.,de Oliveira, Rodrigo J.,de F. C. Matos, Maria,Beatriz, Adilson,Yonekawa, Murilo K. A.,Perdomo, Renata T.,de Lima, Dênis P.,Bogo, Danielle,dos A. dos Santos, Edson
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p. 449 - 458
(2020/01/25)
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- Electrochemical synthesis of sulfinic esters from alcohols and thiophenols
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Electrochemical oxidative couplings between S[sbnd]H and O[sbnd]H bonds are achieved herein directly from readily-available alcohols and thiophenols, affording a series of diverse sulfinic esters. This strategy can take advantage of 6 equivalents of alcohol, relative to thiophenol, to achieve moderate to good yields, without the assistance of any metallic catalysts, bases, and additional oxidants.
- He, Yang,Zhang, Jinli,Xu, Liang,Wei, Yu
-
supporting information
(2020/01/31)
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- Preparation method of thiosulfonate compounds in aqueous phase
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The invention relates to a preparation method of thiosulfonate compounds in an aqueous phase. The preparation method comprises adding sulfonyl hydrazide, an accelerant, an oxidant and solvent water into a Schlenk reaction bottle, stirring to allow to react under certain temperature and air atmosphere, and carrying out free radical coupling reaction to obtain the thiosulfonate compounds.
- -
-
Paragraph 0054-0056
(2019/06/27)
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- Electrochemical oxidations of thioethers: Modulation of oxidation potential using a hydrogen bonding network
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A highly efficient chemo-selective electrochemical oxidation of thioethers to sulfoxides and sulfones was developed. The hydrogen bonding network generated from hexafluoro-2-propanol (HFIP) and acetic acid (AcOH) plays an important role in the modulation of oxidation potential. The hydrogen bonding network complexes strongly with the sulfoxide, making it less prone to further oxidation. Therefore, thioethers can be selectively electrochemically oxidized to sulfoxides and over-oxidization could be minimized. Moreover, this modulation of oxidization via hydrogen bonding was supported by density functional theory (DFT) calculations and cyclic voltammetry experiments.
- Liu, Shiwen,Chen, Bocheng,Yang, Yi,Yang, Yuhao,Chen, Qianjin,Zeng, Xiaojun,Xu, Bo
-
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- Visible-light mediated sulfonylation of thiols via insertion of sulfur dioxide
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A simple and efficient visible-light mediated synthesis of thiosulfonates via a radical-radical coupling of sulfenyl radicals and arylsulfonyl radicals was developed. The reaction of thiols, aryldiazonium tetrafluoroborates and DABSO proceeded at room temperature using 5 mol% eosin Y. The reaction displayed wide functional group tolerance and delivered the unsymmetrical thiosulfonates in good to excellent yields.
- Nair, Akshay M.,Kumar, Shreemoyee,Halder, Indranil,Volla, Chandra M. R.
-
supporting information
p. 5897 - 5901
(2019/06/24)
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- Disulfide-Catalyzed Iodination of Electron-Rich Aromatic Compounds
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Herein, a disulfide-catalyzed electrophilic iodination of aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) has been developed. The disulfide activates DIH as a Lewis base to promote the iodination reaction in acetonitrile under mild conditions. This system is applicable to a wide range of electron-rich aromatic compounds, including acetanilide, anisole, imidazole, and pyrazole derivatives.
- Iida, Keisuke,Ishida, Shunsuke,Watanabe, Takamichi,Arai, Takayoshi
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- Disulfide-Catalyzed Iodination of Electron-Rich Aromatic Compounds
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Herein, a disulfide-catalyzed electrophilic iodination of aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) has been developed. The disulfide activates DIH as a Lewis base to promote the iodination reaction in acetonitrile under mild conditions. This system is applicable to a wide range of electron-rich aromatic compounds, including acetanilide, anisole, imidazole, and pyrazole derivatives.
- Iida, Keisuke,Ishida, Shunsuke,Watanabe, Takamichi,Arai, Takayoshi
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p. 7411 - 7417
(2019/06/18)
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- Disproportionate Coupling Reaction of Sodium Sulfinates Mediated by BF3·OEt2: An Approach to Symmetrical/Unsymmetrical Thiosulfonates
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The BF3·OEt2-mediated disproportionate coupling reaction of sodium sulfinates was found for the first time. In this reaction, various S-S(O)2 bonds can be formed, efficiently giving thiosulfonates in moderate to excellent yields. As a convenient protocol for the synthesis of symmetrical and unsymmetrical thiosulfonates, its reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via a sulfinyl radical disproportionation. What is more, this transformation can also be applied practically as a gram-scale reaction and to the two-step synthesis of sulfone and sulfonamide in one pot in situ using thiosulfonate as an intermediate.
- Cao, Liang,Luo, Shi-He,Jiang, Kai,Hao, Zhi-Feng,Wang, Bo-Wen,Pang, Chu-Ming,Wang, Zhao-Yang
-
supporting information
p. 4754 - 4758
(2018/08/24)
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- Synthetic method for preparing thiosulfonates on basis of sulfinic acid sodium salt disproportionated reaction
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The invention relates to a synthetic method for preparing thiosulfonates on the basis of a sulfinic acid sodium salt disproportionated reaction. The preparation method comprises the steps that sulfinic acid sodium salts serve as the raw materials, boron trifluoride diethyl etherate serves as accelerant, dichloromethane serves as solvent, and by means of a disproportionation coupled reaction, a thiosulfinate compound with good biological activity is synthesized; two different sulfinic acid sodium salts serve as the raw materials, and by means of a crossed disproportionation coupled reaction method, an asymmetric thiosulfinate compound can be synthesized. By means of a one-pot method and a two-step method, and by means of a thiosulfonates intermediate prepared on site, a sulfones compound and a sulfonamides compound can be synthesized by directly starting from sulfinic acid sodium salts. Accordingly, a synthetic route for preparing thiosulfonates on the basis of the sulfinic acid sodiumsalt disproportionated reaction is provided for the first time, operation is easy, raw materials are easy to obtain, the condition is mild, no metal catalyst is needed, no additional oxidant or reductant is needed, and the prepared thiosulfonates can have the good biological activity, and can also serve as the intermediate of the reaction to be applied to organic synthesis.
- -
-
Paragraph 0026; 0027; 0029
(2018/10/19)
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- Transition-Metal-Free Synthesis of Thiosulfonates through Radical Coupling Reaction
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An efficient and practical transition-metal-free radical coupling reaction of sulfonyl hydrazides mediated by NIS/K 2 S 2 O 8 has been developed to afford a variety of biological activity thiosulfonates in moderate to excellent yields. Compared to a known approach for the synthesis of thiosulfonates from sulfonyl hydrazides, this strategy features high yields, mild reaction conditions, and broad substrate scope. The mechanistic studies revealed that the procedure undergoes via a radical cross-coupling process for the construction of S-S bonds.
- Zhou, Guodong,Xu, Xu-Dong,Chen, Gan-Ping,Wei, Wen-Ting,Guo, Zhiyong
-
supporting information
p. 2076 - 2080
(2018/09/18)
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- Selective oxidation method of disulfide
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The invention relates to a selective oxidation method of disulfide, and discloses a novel synthesis method of a single sulfone compound shown as a formula (I). According to the invention, disulfide shown in a formula (II) is taken as a raw material, under existence of tert-butyl hydroperoxide, an oxidation reaction is carried out in a solvent, after the reaction is completed, and through post-treatment, the single sulfone compound shown as the formula (I) is obtained. Compared with the prior art, an oxidizing agent tert-butyl hydroperoxide which is friendly to environment is employed, usage ofa metal catalyst is avoided, the reaction condition is mild, selectivity is high, the operation is simple, the applicability is wide, and the reaction yield is high.
- -
-
Paragraph 0032; 0033; 0034
(2018/09/26)
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- Visible light induced decomposition of sulfonyl hydrazides using Pd/ZrO2nanocomposite photocatalyst
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A new approach to synthesis of thiosulfonates has been developed under mild conditions without any oxidants and promoting reagents through a Pd/ZrO2nanocomposite photocatalyst catalyzed decomposition of sulfonyl hydrazides. This protocol gave the products in moderate yields, comparable to the best results reported so far. Finally, a plausible reaction mechanism was proposed.
- Li, Xiaoji,Zhou, Chao,Diao, Pinhui,Ge, Yanqin,Guo, Cheng
-
supporting information
p. 1296 - 1300
(2017/03/10)
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- Copper-Catalyzed Aerobic Formation of Unstable Sulfinyl Radicals for the Synthesis of Sulfinates and Thiosulfonates
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Copper-catalyzed aerobic coupling of thiols and alcohols affords sulfinates and thiosulfonates. These products are assumed to form via sulfinyl radicals which are not commonly found in oxidative coupling reactions of thiols. A reaction mechanism involving sulfinyl radicals is proposed, and mass and electron paramagnetic resonance (EPR) experimental results are provided.
- Shyam, Pranab K.,Kim, Yu Kwon,Lee, Chan,Jang, Hye-Young
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supporting information
p. 56 - 61
(2016/01/25)
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- Oxidation of disulfides to thiolsulfinates with hydrogen peroxide and a cyclic seleninate ester catalyst peroxide and a cyclic seleninate ester catalyst
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Cyclic seleninate esters function as mimetics of the antioxidant selenoenzyme glutathione peroxidase. They catalyze the reduction of harmful peroxides with thiols, which are converted to disulfides in the process. The possibility that the seleninate esters could also catalyze the further oxidation of disulfides to thiolsulfinates and other overoxidation products under these conditions was investigated. This has ramifications in potential medicinal applications of seleninate esters because of the possibility of catalyzing the unwanted oxidation of disulfide-containing spectator peptides and proteins. A variety of aryl and alkyl disulfides underwent facile oxidation with hydrogen peroxide in the presence of catalytic benzo-1,2-oxaselenolane Se-oxide affording the corresponding thiolsulfinates as the principal products. Unsymmetrical disulfides typically afforded mixtures of regioisomers. Lipoic acid and N,N′-dibenzoylcystine dimethyl ester were oxidized readily under similar conditions. Although isolated yields of the product thiolsulfinates were generally modest, these experiments demonstrate that the method nevertheless has preparative value because of its mild conditions. The results also confirm the possibility that cyclic seleninate esters could catalyze the further undesired oxidation of disulfides in vivo.
- McNeil, Nicole M. R.,McDonnell, Ciara,Hambrook, Miranda,Back, Thomas G.
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p. 10748 - 10762
(2015/08/11)
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- Facile synthesis of symmetric thiosulfonates by oxidation of disulfide with oxone/MX (MX = KBr, KCl, NaBr and NaCl)
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Abstract A new method is described for the oxidation of aliphatic- and aromatic disulfides containing electron-donating and electron-withdrawing groups to their corresponding thiosulfonates using oxone in combination with the MX (MX = KBr, KCl, NaBr and NaCl). No obvious electronic effects influence the yields of thiosulfonates. Avoiding the usage of toxic and unstable reagents, mild reaction conditions, short reaction times and cost-effectiveness are advantages of this methodology when likened to known methods for thiosulfonates syntheses.
- Natarajan, Palani
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p. 4131 - 4134
(2015/08/03)
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- A mild and facile synthesis of aryl and alkenyl sulfides via copper-catalyzed deborylthiolation of organoborons with thiosulfonates
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An efficient deborylthiolation of aryl- and alkenylborons with thiosulfonates has been achieved under mild conditions using a copper catalyst. All steps of the experimental process were free from unpleasant odors. The mild reaction conditions as well as ready availability of boron compounds and thiosulfonates enabled easy access to an array of sulfides, including those bearing sensitive functional groups.
- Yoshida, Suguru,Sugimura, Yasuyuki,Hazama, Yuki,Nishiyama, Yoshitake,Yano, Takahisa,Shimizu, Shigeomi,Hosoya, Takamitsu
-
supporting information
p. 16613 - 16616
(2015/11/25)
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- Nitromethane as a cyanating reagent for the synthesis of thiocyanates
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Nitromethane has been developed to be an effective cyanating reagent for the synthesis of thiocyanates. In the presence of iodine and base, a wide range of disulfides were reacted with nitromethane smoothly to give diverse thiocyanates in moderate to good yields.
- Wang, Zuo-Hui,Ji, Xiao-Ming,Hu, Mao-Lin,Tang, Ri-Yuan
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p. 5067 - 5070
(2015/08/06)
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- Oxidation of disulfides with electrophilic halogenating reagents: Concise methods for preparation of thiosulfonates and sulfonyl halides
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The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. Conversely, the reaction of disulfides with 6.5 equiv of Selectfluor or thiosulfonates with 4.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluorides in high yields. Accufluor and FP-T300 are also effective in preparing sulfonyl fluorides from disulfides under the similar reaction conditions. Sulfonyl chlorides or sulfonyl bromides were effectively obtained from the reaction of disulfides with 6 equiv of either N-chlorosuccinimide or N-bromosuccinimide in acetonitrile/water (10:1) at room temperature. Some other electrophilic chlorinating or brominating reagents are also able to be used instead of N-chlorosuccinimide or N-bromosuccinimide for the syntheses of sulfonyl halides from disulfides. These reactions of disulfides with electrophilic halogenating reagents are convenient methods to prepare thiosulfonates and sulfonyl halides.
- Kirihara, Masayuki,Naito, Sayuri,Nishimura, Yuki,Ishizuka, Yuki,Iwai, Toshiaki,Takeuchi, Haruka,Ogata, Tomomi,Hanai, Honoka,Kinoshita, Yukari,Kishida, Mari,Yamazaki, Kento,Noguchi, Takuya,Yamashoji, Shiro
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p. 2464 - 2471
(2014/04/03)
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- Silver-mediated decarboxylative C-S cross-coupling of aliphatic carboxylic acids under mild conditions
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A silver-mediated decarboxylative C-S cross-coupling reaction of aliphatic carboxylic acid is described. This reaction occurs smoothly under mild conditions and shows good tolerance of functional groups. It provides an alternative approach for the synthesis of alkyl aryl sulfides.
- Wang, Peng-Fei,Wang, Xiao-Qing,Dai, Jian-Jun,Feng, Yi-Si,Xu, Hua-Jian
-
supporting information
p. 4586 - 4589
(2015/01/08)
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- Synthesis of S-Aryl arenethiosulfonates from N,N-Di(arenesulfonyl) hydrazines: Reduction of sulfonyl chlorides with an organic reagent
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N,N-Di(arenesulfonyl)-N′,N′-dimethyl-hydrazines, readily prepared from arenesulfonyl chlorides and N,N-dimethylhydrazine, were heated at 120°C in chlorobenzene to give S-aryl arenethiosulfonates, ArSSO 2Ar, in good yields.
- Iwata, Satoshi,Senoo, Masato,Hata, Takeshi,Urabe, Hirokazu
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p. 336 - 344
(2013/08/23)
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- Synthesis of sulfonyl chlorides and thiosulfonates from H2O 2-TiCl4
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A new method is described for the oxidative chlorination of thiols to sulfonyl chlorides using titanium tetrachloride in combination with the oxidant hydrogen peroxide. Direct conversion of thiols into their corresponding thiosulfonates is also reported. Good to excellent yields, short reaction times, high efficiencies, cost-effectiveness, and, facile isolation of the desired products make the present methodology a practical alternative.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Khaledian, Donya
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experimental part
p. 354 - 358
(2012/01/19)
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- Oxidation of disulfides with Selectfluor: Concise syntheses of thiosulfonates and sulfonyl fluorides
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The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. On the other hand, the reaction of disulfides with 6.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluoride in high yields.
- Kirihara, Masayuki,Naito, Sayuri,Ishizuka, Yuki,Hanai, Honoka,Noguchi, Takuya
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experimental part
p. 3086 - 3089
(2011/06/26)
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- Zinc dichromate trihydrate (ZnCrmiddot;3H) as an efficient reagent for the one-pot synthesis of thiosulfonates from thiols
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ZnCrH is a readily available and efficient reagent for the one-pot synthesis of a variety of thiosulfonates by chemoselective oxidation of thiols. Georg Thieme Verlag Stuttgart New York.
- Sobhani, Sara,Aryanejad, Sima,Maleki, Mahdi Faal
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experimental part
p. 319 - 322
(2011/03/22)
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- TCCA-promoted solvent-free chemoselective synthesis of thiosulfonates on grinding
-
Trichloroisocyanuric acid (TCCA) is an inexpensive and efficient reagent for solvent-free chemoselective synthesis of thiosulfonates by grinding, providing a metal-free new methodology for the oxidation of disulfides. The important features of this method are that it is reasonably fast, very clean, high yielding, has a simple workup and is environmentally benign.
- Xu, Yali,Peng, Yong,Sun, Junhui,Chen, Jiuxi,Ding, Jinchang,Wu, Huayue
-
experimental part
p. 358 - 360
(2010/10/21)
-
- Unexpected differences in the α-halogenation and related reactivity of sulfones with perhaloalkanes in KOH-t-BuOH
-
Most alkyl phenyl sulfones are readily α-chlorinated with CCl4 and α-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily α-chlorinated with CCl4, it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting α-anion formation. This effect is reversed by the electron-withdrawing influence of two α-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily α-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the α-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the α-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-α-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that α,α-dihalogenation is attained while much substrate is still present and the mono-α-halogenated product is not detected. The ease of reductive debromination of α-bromo sulfones with Cl3C- was correlated with the stability of the formed α-anions, explaining the success with α-bromobenzylic sulfones but failure with α-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the α-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes.
- Meyers, Cal Y.,Chan-Yu-King, Roch,Hua, Duy H.,Kolb, Vera M.,Matthews, Walter S.,Parady, Thomas E.,Horii, Toyokazu,Sandrock, Paul B.,Hou, Yuqing,Xie, Songwen
-
p. 500 - 511
(2007/10/03)
-
- Reactions of bis(p-methoxyphenyl)trisulfane and its oxides with dimethyldioxirane and (trifluoromethyl)methyldioxirane
-
The reactions of dimethyldioxirane and (trifluoromethyl)methyldioxirane with bis(p-methoxyphenyl)-trisulfane, its 1-oxide, its 2-oxide, and its 1,1-dioxide derivatives have been investigated. The reactions were followed by careful monitoring of the methox
- Clennan, Edward L.,Stensaas, Kristina L.
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p. 7911 - 7917
(2007/10/03)
-
- Chemistry of Organo Halogenic Molecules. 140. Role of the Reagent Structure on the Transformations of Hydroxy Substituted Organic Molecules with the N-Fluoro Class of Fluorinating Reagents
-
Hydroxy-substituted organic molecules were used as target molecules in investigations of the role of the reagent structure on the reactivity of three types of N-F class fluorinating reagents: 1-chloromethyl-4-fluoro-1,4-diazoniabicyclooctane bis(tetrafluoroborate) F-TEDA (1a), N-fluorobis(phenylsulfonyl)amine NSF (1b), and N-Fluoropyridinium heptafluorodiborate-pyridine (1/1) NFP (1c).Methanol is stable, but hydroquinone is very quickly transformed in acetonitrile to quinone with F-TEDA at room temperature: on the other hand, NSF is less reactive, while oxidation with NFP is achieved only at an elevated temperature; a structure variation of the hydroquinone derivatives did not influence oxidation.Fluorination was achieved with monohydroxy-substituted aromatic compounds; a similar trend concerning the reactivity of N-F reagent (1) was also observed in reactions with 1- and 2-naphthol, while 9-phenanthrol gave 10,10-difluoro-9-(10H)-phenanthrenone with F-TEDA in acetonitrile and 9,10-phenanthrenequinone with NSF.Dealkylation was observed in a reaction with 4-methoxyphenol; although the thio analogue gave bis(4-methoxyphenyl) disulfide, the reactivity was changed and NSF was more reactive than F-TEDA and NFP.
- Zupan, Marko,Iskra, Jernej,Stavber, Stojan
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p. 1655 - 1660
(2007/10/02)
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- CO-OXIDATIONS OF SQUALENE WITH DISULFIDES AND THIOSULFINATES
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Comparison of the activities of alkyl and aryl disulfides in inhibiting the autoxidation of squalene show the greater efficiency of the alkyl derivatives.The effect of electron donating substituents in aryl derivatives, promoting efficiency in the order CH3O > CH3 > H, is reversed in the thiosulfinates when added directly, although they are considered to be inhibitors formed in situ from the disulfides.The anomaly is discussed in terms of rates of oxidation and stabilities of the oxidation products and leads to the concept of thiosulfinate/disulfide mixture as a more efficient antioxidant.Key words: Antioxidants; disulfides; thiosulfinates; sulfinyl group; stability.
- Cole, Edward R.
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p. 147 - 160
(2007/10/02)
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- Thermal Decomposition of some Allyl Methoxyarenesulphinates
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The thermal decomposition of some allyl methoxyarenesulphinates in boiling acetic acid has been studied.The principal products are the diaryl sulphides together with small amounts of the aryl arenethiosulphonates, diaryl sulphoxides, diaryl sulphones, aromatic hydrocarbons, and in one case, some of the allyl aryl sulphone.
- Bell, Kevin H.
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p. 1957 - 1960
(2007/10/02)
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- PREPARATION AND SPECTRAL PROPERTIES OF SYMMETRICAL S-ARYL ARENESULFONOTHIOATES (THIOSULFONATES)
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Arenesulfinyl chlorides (4-XC6H4S(O)Cl; X = H, CH3, F, Cl, Br) react with activated zerovalent zinc in benzene at 6 to 8 deg C to give symmetrical S-aryl arenesulfonothioates (thiosulfonates) in good to excellent yields. 2- and 3-substituted arenesulfinyl chlorides (X=Cl, CH3) give a mixture of products (disulfide, thiosulfinate, and/or thiosulfonate). 2,4,6-Triisopropylbenzenesulfinyl chloride reacts with zinc in 1,2-dimethoxyethane to give S-(2,4,6-triisopropylphenyl) 2,4,6-triisopropylbenzenesulfinothioate and bis(2,4,6-triisopropylphenyl) disulfide.Possible mechanisms for the reaction, the 1H and 13C NMR spectra and the chemical ionization and electron impact mass spectra of the thiosulfonates are discussed.The para carbon substituent chemical shifts (Cp-SCS) for the thiosulfonates and for symmetrical diaryl disulfides have been subjected to several dual substituent parameter (DSP) correlations. Key Words: S-aryl-arenesulfonothioates (thiosulfonates); arenesulfinyl chlorides; 1H and 13C NMR; mass spectrometry; substituent shift parameters.
- Freeman, Fillmore,Bartosik, Lisa G.,Bui, Nghe Van,Keindl, Monica C.,Nelson, Eric L.
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p. 375 - 386
(2007/10/02)
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- Reactions of Arenesulfonyl Chlorides with Olefins Catalyzed by a Ruthenium(II) Complex
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Arenesulfonyl chlorides react with vinylarenes in the presence of dichlorotris(triphenylphosphine)ruthenium(II) catalyst and 1 molar equiv of a tertiary amine to form α,β-unsaturated sulfones 2.Only the E isomers of the sulfones are formed.In reactions of arenesulfonyl chlorides containing an electron-withdrawing Cl or NO2 substituent with α-methylstyrenes, 2-aryl-3-(arylsulfonyl)propenes (5) are also formed.Mechanisms for these reactions are proposed.
- Kamigata, Nobumasa,Sawada, Hideo,Kobayashi, Michio
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p. 3793 - 3796
(2007/10/02)
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- Sulphur Nitrides in Organic Chemistry. Part 8. Reaction of Tetrasulphur Tetranitride with Grignard Reagents and Organolithium Compounds
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The reaction of tetrasulphur tetranitride (N4S4) (1) with Grignard reagents (2a-h) and organolithium compounds (10a-h) was investigated.It was found that the reaction of (1) with (2) gave the corresponding disulphides (4a-h) in good yields together with 1,5-diaryl-1,3,5,2,4-trithiadiazapenta-2,3-dienes (3a-c), bisarylamino sulphides (5a and b), ammonium thiosulphates (6a-e), and thiosulphonates (7a-d).Reaction of (1) with (10a-f), generated from benzyl sulphides, afforded diaryl disulphides (4a, b, and e) in moderate yields accompanied by trans-stilbenes (11a and b) and 1,2-bisphenylthio-1,2-diarylethanes (12a and b).Reaction of (1) with diphenyl(phenylthio)methyl-lithium (10g), gave diphenyl disulphide (4a), the tetraphenylethylene (11c), and benzophenone (13a), while reaction of sulphur with (10g) afforded 1,2-epithio-1,1,2,2-tetraphenylethane (15) in 52percent yield besides (4a), (11c), and (13c).Reaction of (1) with 9-phenylthiofluoren-9-yl-lithium (10h) gave (4a), bifluorenylidene (11d), 1,1'-bisphenylthiobifluorenyl (12c), fluorenone (13b), fluorenylideneaminosulphenamide (14).
- Mataka, Shuntaro,Takahashi, Kazufumi,Yamamoto, Hajime,Tashiro, Masashi
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p. 2417 - 2421
(2007/10/02)
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- Asymmetric Induction in the Additions of Anions of Allylic Sulfoxides to Benzaldehyde
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Addition reactions of anions of aryl allyl sulfoxides to benzaldehyde proceed readily in moderate yields and afford mixtures of products resulting from α- and γ-attack on the allyl anion.The γ-products all possess the (E)-configuration around the double bond, and asymmetric induction occurs in the addition to the extent that the major/minor diastereomer ratio exceeds 2:1, generally.Electronic factors are believed to be responsible for this "remote" asymmetric induction.Mixtures of all four possible diastereomers are observed in the products from α-attack and evidence is presented which suggests that the ratios of these products are as a result of epimerization of two of the chiral centres by sigmatropic rearrangement.
- Antonjuk, David J.,Ridley, Damon D.,Smal, Mary A.
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p. 2635 - 2651
(2007/10/02)
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- SULFENYL CHLORIDES, XIII; A NEW PROCEDURE FOR THE SYNTHESIS OF SULFONIC ACID THIOL ESTERS FROM THIOLS
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Chlorination of thiols in alkali carbonate media yielded symmetrically substituted alkyl- and arylsulfonic acid thiol esters (thiosulfonates).The procedure is simple, intermediates need not be isolated.
- Pintye, J.,Stajer, G.
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p. 155 - 157
(2007/10/02)
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