Bhanwar K. Malviya, Gabriele Laudadio, C. Oliver Kappe, David Cantillo
{"title":"准分裂电池法实现氨基苯酚衍生物的可扩展无催化剂电化学氯化反应","authors":"Bhanwar K. Malviya, Gabriele Laudadio, C. Oliver Kappe, David Cantillo","doi":"10.1039/d4gc03569k","DOIUrl":null,"url":null,"abstract":"Chlorinated 4-aminophenol derivatives are widespread in pharmaceutical ingredients. An electrochemical procedure for the synthesis of these compounds <em>via</em> mono- and dichlorination of the corresponding electron-rich precursors using dichloromethane (DCM) both as the solvent and the chlorine source has been developed. The method is based on the degradation of DCM at the cathode, which releases chloride ions that can be used to generate active chlorine at the anode. Key to the success of this protocol is the utilization of a “quasi-divided” cell with a cathode surface area much smaller than the anode, ensuring that only the solvent and not the molecules in solution are degraded by cathodic reduction. The electrochemical protocol has been demonstrated for a wide range of substrates (25 examples) in moderate to excellent isolated yield (up to 94%). Importantly, the procedure has been translated to a parallel plate flow electrolysis cell. To achieve this goal, a bespoke cell design featuring a PTFE mesh that partially covers the cathode surface has been developed, which provides adequate anode to cathode surface area ratio for quasi-divided cell operation. This is the first example of quasi-divided cell operation in a parallel plate flow electrochemical reactor.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3000,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Scalable catalyst free electrochemical chlorination of aminophenol derivatives enabled by a quasi-divided cell approach\",\"authors\":\"Bhanwar K. Malviya, Gabriele Laudadio, C. Oliver Kappe, David Cantillo\",\"doi\":\"10.1039/d4gc03569k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Chlorinated 4-aminophenol derivatives are widespread in pharmaceutical ingredients. An electrochemical procedure for the synthesis of these compounds <em>via</em> mono- and dichlorination of the corresponding electron-rich precursors using dichloromethane (DCM) both as the solvent and the chlorine source has been developed. The method is based on the degradation of DCM at the cathode, which releases chloride ions that can be used to generate active chlorine at the anode. Key to the success of this protocol is the utilization of a “quasi-divided” cell with a cathode surface area much smaller than the anode, ensuring that only the solvent and not the molecules in solution are degraded by cathodic reduction. The electrochemical protocol has been demonstrated for a wide range of substrates (25 examples) in moderate to excellent isolated yield (up to 94%). Importantly, the procedure has been translated to a parallel plate flow electrolysis cell. To achieve this goal, a bespoke cell design featuring a PTFE mesh that partially covers the cathode surface has been developed, which provides adequate anode to cathode surface area ratio for quasi-divided cell operation. This is the first example of quasi-divided cell operation in a parallel plate flow electrochemical reactor.\",\"PeriodicalId\":78,\"journal\":{\"name\":\"Green Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.3000,\"publicationDate\":\"2024-09-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Green Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4gc03569k\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Green Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4gc03569k","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Scalable catalyst free electrochemical chlorination of aminophenol derivatives enabled by a quasi-divided cell approach
Chlorinated 4-aminophenol derivatives are widespread in pharmaceutical ingredients. An electrochemical procedure for the synthesis of these compounds via mono- and dichlorination of the corresponding electron-rich precursors using dichloromethane (DCM) both as the solvent and the chlorine source has been developed. The method is based on the degradation of DCM at the cathode, which releases chloride ions that can be used to generate active chlorine at the anode. Key to the success of this protocol is the utilization of a “quasi-divided” cell with a cathode surface area much smaller than the anode, ensuring that only the solvent and not the molecules in solution are degraded by cathodic reduction. The electrochemical protocol has been demonstrated for a wide range of substrates (25 examples) in moderate to excellent isolated yield (up to 94%). Importantly, the procedure has been translated to a parallel plate flow electrolysis cell. To achieve this goal, a bespoke cell design featuring a PTFE mesh that partially covers the cathode surface has been developed, which provides adequate anode to cathode surface area ratio for quasi-divided cell operation. This is the first example of quasi-divided cell operation in a parallel plate flow electrochemical reactor.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.