{"title":"过氧单硫酸盐氧化二甲亚砜的机理及动力学研究","authors":"Xingyu Shao, Wei Feng, Wenqian Wu, Zichao Guo*, Liping Chen and Wanghua Chen, ","doi":"10.1021/acs.oprd.5c00115","DOIUrl":null,"url":null,"abstract":"<p >Dimethyl sulfone (DMSO<sub>2</sub>) plays a crucial role in human health, particularly in collagen synthesis, owing to its significant biochemical functions. Although traditional oxidation methods are effective, they present significant environmental and operational challenges that hinder their widespread application. This study systematically investigated the reaction kinetics and mechanistic pathway of dimethyl sulfoxide (DMSO) oxidation catalyzed by peroxymonosulfate (PMS) under low-temperature (0–20 °C) and nonactivated catalytic conditions. A comprehensive oxidation kinetic model was developed, and all kinetic parameters were meticulously determined. Density functional theory (DFT) calculations confirmed that the nucleophilic attack by the O–O bond in PMS on the sulfur atom of DMSO facilitates the oxidation process. Experimental and DFT-derived activation energies for the oxidation reaction were measured at 64.33 and 65.54 kJ/mol, respectively. These findings elucidate the potential mechanism of PMS-mediated oxidation of DMSO and offer a reliable reference for the safe production of DMSO<sub>2</sub>.</p>","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"29 7","pages":"1766–1774"},"PeriodicalIF":3.5000,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Insights into the Oxidation Mechanism and Kinetics of Dimethyl Sulfoxide by Peroxymonosulfate\",\"authors\":\"Xingyu Shao, Wei Feng, Wenqian Wu, Zichao Guo*, Liping Chen and Wanghua Chen, \",\"doi\":\"10.1021/acs.oprd.5c00115\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Dimethyl sulfone (DMSO<sub>2</sub>) plays a crucial role in human health, particularly in collagen synthesis, owing to its significant biochemical functions. Although traditional oxidation methods are effective, they present significant environmental and operational challenges that hinder their widespread application. This study systematically investigated the reaction kinetics and mechanistic pathway of dimethyl sulfoxide (DMSO) oxidation catalyzed by peroxymonosulfate (PMS) under low-temperature (0–20 °C) and nonactivated catalytic conditions. A comprehensive oxidation kinetic model was developed, and all kinetic parameters were meticulously determined. Density functional theory (DFT) calculations confirmed that the nucleophilic attack by the O–O bond in PMS on the sulfur atom of DMSO facilitates the oxidation process. Experimental and DFT-derived activation energies for the oxidation reaction were measured at 64.33 and 65.54 kJ/mol, respectively. These findings elucidate the potential mechanism of PMS-mediated oxidation of DMSO and offer a reliable reference for the safe production of DMSO<sub>2</sub>.</p>\",\"PeriodicalId\":55,\"journal\":{\"name\":\"Organic Process Research & Development\",\"volume\":\"29 7\",\"pages\":\"1766–1774\"},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2025-06-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Process Research & Development\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.oprd.5c00115\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Process Research & Development","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.oprd.5c00115","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Insights into the Oxidation Mechanism and Kinetics of Dimethyl Sulfoxide by Peroxymonosulfate
Dimethyl sulfone (DMSO2) plays a crucial role in human health, particularly in collagen synthesis, owing to its significant biochemical functions. Although traditional oxidation methods are effective, they present significant environmental and operational challenges that hinder their widespread application. This study systematically investigated the reaction kinetics and mechanistic pathway of dimethyl sulfoxide (DMSO) oxidation catalyzed by peroxymonosulfate (PMS) under low-temperature (0–20 °C) and nonactivated catalytic conditions. A comprehensive oxidation kinetic model was developed, and all kinetic parameters were meticulously determined. Density functional theory (DFT) calculations confirmed that the nucleophilic attack by the O–O bond in PMS on the sulfur atom of DMSO facilitates the oxidation process. Experimental and DFT-derived activation energies for the oxidation reaction were measured at 64.33 and 65.54 kJ/mol, respectively. These findings elucidate the potential mechanism of PMS-mediated oxidation of DMSO and offer a reliable reference for the safe production of DMSO2.
期刊介绍：
The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools，process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.
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