16601-40-4Relevant academic research and scientific papers
Synthesis of Symmetrical and Unsymmetrical Thiosulfonates from Disulfides through Electrochemically Induced Disulfide Bond Metathesis and Site-Selective Oxidation
Strehl, Julia,Hilt, Gerhard
supporting information, (2021/10/14)
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.
Direct conversion of sulfinamides to thiosulfonates without the use of additional redox agents under metal-free conditions
Ji, Yuan-Zhao,Li, Hui-Jing,Wang, Jun-Hu,Wu, Yan-Chao,Zhang, Chi
, p. 9291 - 9298 (2021/11/13)
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
Preparation method of sulfuryl thioester
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Paragraph 0034-0037, (2021/11/10)
The invention provides a preparation method of sulfuryl thioester, which uses mercaptan as a starting material. The hydrogen peroxide is an oxidizing agent, an alkali metal halide or an alkaline earth metal halide is used as an additive to prepare the sulfuryl thioester. The product obtained by the method is high in purity and low in production cost, avoids introducing a metal oxidant, can be used for industrial production, and has a good application prospect.
CuCl2-promoted decomposition of sulfonyl hydrazides for the synthesis of thiosulfonates
Kim, Junsu,Park, Sanggil,Kim, Hyungjun,Kim, Jinho
, (2020/07/02)
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.
Selective Oxidation of Sulfides in Flow Chemistry
Silva, Filipa,Baker, Alastair,Stansall, James,Michalska, Weronika,Yusubov, Mehkman S.,Graz, Michael,Saunders, Robert,Evans, Gareth J. S.,Wirth, Thomas
, p. 2134 - 2137 (2018/05/31)
A packed-bed reactor with oxone has been employed for selective oxidations of sulfur compounds. Various sulfides containing different functional groups are efficiently oxidized to the corresponding sulfoxides without formation of sulfones or other side products.
A mild and facile synthesis of aryl and alkenyl sulfides via copper-catalyzed deborylthiolation of organoborons with thiosulfonates
Yoshida, Suguru,Sugimura, Yasuyuki,Hazama, Yuki,Nishiyama, Yoshitake,Yano, Takahisa,Shimizu, Shigeomi,Hosoya, Takamitsu
supporting information, p. 16613 - 16616 (2015/11/25)
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.
Oxidation of disulfides with electrophilic halogenating reagents: Concise methods for preparation of 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
, p. 2464 - 2471 (2014/04/03)
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.
Synthesis of sulfonyl chlorides and thiosulfonates from H2O 2-TiCl4
Bahrami, Kiumars,Khodaei, Mohammad M.,Khaledian, Donya
experimental part, p. 354 - 358 (2012/01/19)
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.
Oxidation of disulfides with Selectfluor: Concise syntheses of thiosulfonates and sulfonyl fluorides
Kirihara, Masayuki,Naito, Sayuri,Ishizuka, Yuki,Hanai, Honoka,Noguchi, Takuya
experimental part, p. 3086 - 3089 (2011/06/26)
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.
A kinetic study of S-nitrosothiol decomposition
Grossi, Loris,Montevecchi, Pier Carlo
, p. 380 - 387 (2007/10/03)
Under anaerobic conditions S-nitrosothiols 1a-e undergo thermal decomposition by homolytic cleavage of the S-N bond; the reaction leads to nitric oxide and sulfanyl radicals formed in a reversible manner. The rate constants, k1, have been determined at different temperatures from kinetic measurements performed in refluxing alkane solvents. The tertiary nitrosothiols 1c (k1(69°C) = 13 × 10-3 min-1) and 1d (k1(69°C) 91 × 10-3 min-1) decomposed faster than the primary nitrosothiols 1a (k1(69°C) = 3.0 × 10-3 min-1) and 1b (k1(69°C) = 6.5 × 10-3 min-1). The activation energies (E#= 20.5 - 22.8 Kcal mol-1) have been calculated from the Arrhenius equation. Under aerobic conditions the decay of S-nitrosothiols 1a-e takes place by an autocatalytic chain-decomposition process catalyzed by N2O3. The latter is formed by reaction of dioxygen with endogenous and/or exogenous nitric oxide. The autocatalytic decomposition is strongly inhibited by removing the endogenous nitric oxide or by the presence of antioxidants, such as pcresol, β-styrene, and BHT The rate of the chain reaction is independent of the RSNO concentration and decreases with increasing bulkiness of the alkyl group; this shows that steric effects are crucial in the propagation step.
