Kaishuo Zhao , Zilin Fang , Shuai Peng , Xixuan Zhao , Yongguo Liu , Baoguo Sun , Hongyu Tian , Sen Liang
{"title":"Divergent decomposition pathways of DMSO mediated by solvents and additives","authors":"Kaishuo Zhao , Zilin Fang , Shuai Peng , Xixuan Zhao , Yongguo Liu , Baoguo Sun , Hongyu Tian , Sen Liang","doi":"10.1080/17415993.2023.2280671","DOIUrl":null,"url":null,"abstract":"<div><p>DMSO (dimethyl sulfoxide) plays an increasingly significant role in various synthetic processes by generating diverse active intermediates in situ, which actively participate in reactions. It is crucial to control the formation of these active intermediates to prevent their mutual interference during utilization. Our previous research identified methyl methanethiosulfonate (MMTS) as a major decomposition product of DMSO when catalyzed by small amounts of (COCl)<sub>2</sub> in CH<sub>3</sub>CN. In the current study, we investigated how different solvents and additives can mediate the formation of MMTS. Complete avoidance of MMTS formation was achieved in 1,4-dioxane, while only trace amounts were observed in toluene, MTHF, or CHCl<sub>3</sub>. Moreover, the decomposition pathway of DMSO in these solvents was effectively mediated through the addition of strong acids (HX, where X = TfO, ClO<sub>4</sub>, I, Br, or Cl) or in the presence of LiI, CH<sub>3</sub>I, or Br<sub>2</sub>. The effects of solvents and additives on the decomposition of DMSO were explored. The possible mechanisms for the decomposition of DMSO under different conditions were proposed and discussed.</p></div>","PeriodicalId":17081,"journal":{"name":"Journal of Sulfur Chemistry","volume":"45 3","pages":"Pages 315-329"},"PeriodicalIF":2.1000,"publicationDate":"2024-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Sulfur Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1741599323001058","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
DMSO (dimethyl sulfoxide) plays an increasingly significant role in various synthetic processes by generating diverse active intermediates in situ, which actively participate in reactions. It is crucial to control the formation of these active intermediates to prevent their mutual interference during utilization. Our previous research identified methyl methanethiosulfonate (MMTS) as a major decomposition product of DMSO when catalyzed by small amounts of (COCl)2 in CH3CN. In the current study, we investigated how different solvents and additives can mediate the formation of MMTS. Complete avoidance of MMTS formation was achieved in 1,4-dioxane, while only trace amounts were observed in toluene, MTHF, or CHCl3. Moreover, the decomposition pathway of DMSO in these solvents was effectively mediated through the addition of strong acids (HX, where X = TfO, ClO4, I, Br, or Cl) or in the presence of LiI, CH3I, or Br2. The effects of solvents and additives on the decomposition of DMSO were explored. The possible mechanisms for the decomposition of DMSO under different conditions were proposed and discussed.
期刊介绍:
The Journal of Sulfur Chemistry is an international journal for the dissemination of scientific results in the rapidly expanding realm of sulfur chemistry. The journal publishes high quality reviews, full papers and communications in the following areas: organic and inorganic chemistry, industrial chemistry, materials and polymer chemistry, biological chemistry and interdisciplinary studies directly related to sulfur science.
Papers outlining theoretical, physical, mechanistic or synthetic studies pertaining to sulfur chemistry are welcome. Hence the target audience is made up of academic and industrial chemists with peripheral or focused interests in sulfur chemistry. Manuscripts that truly define the aims of the journal include, but are not limited to, those that offer: a) innovative use of sulfur reagents; b) new synthetic approaches to sulfur-containing biomolecules, materials or organic and organometallic compounds; c) theoretical and physical studies that facilitate the understanding of sulfur structure, bonding or reactivity; d) catalytic, selective, synthetically useful or noteworthy transformations of sulfur containing molecules; e) industrial applications of sulfur chemistry; f) unique sulfur atom or molecule involvement in interfacial phenomena; g) descriptions of solid phase or combinatorial methods involving sulfur containing substrates. Submissions pertaining to related atoms such as selenium and tellurium are also welcome. Articles offering routine heterocycle formation through established reactions of sulfur containing substrates are outside the scope of the journal.