Olga C. Dennehy, Denis Lynch, U. B. Rao Khandavilli, Simon E. Lawrence, Stuart G. Collins, Anita R. Maguire and Humphrey A. Moynihan
{"title":"优化流动合成Z-α-硫-β-氯丙烯酰胺过程中杂质e异构体的形成E/Z在间歇和流动中的光异构化,以及两种异构体的固态表征","authors":"Olga C. Dennehy, Denis Lynch, U. B. Rao Khandavilli, Simon E. Lawrence, Stuart G. Collins, Anita R. Maguire and Humphrey A. Moynihan","doi":"10.1039/D5RE00137D","DOIUrl":null,"url":null,"abstract":"<p >\r\n <em>N</em>-(4-Methylphenyl)-<em>Z</em>-3-chloro-2-(phenylthio)propenamide (<strong><em>Z</em>-3</strong>), which is valuable as a reactive substrate for a range of synthetic transformations, can be obtained by a three-step process involving both batch and flow methodologies. Compound <strong><em>Z</em>-3</strong> was isolated as a crystalline material of high purity, however, the <em>E</em>-isomer, <strong><em>E</em>-3</strong>, was found to form in solid samples of <strong><em>Z</em>-3</strong> material during storage. Increased ratios of <strong><em>E</em>-3</strong> and pure isolated samples were obtained by photoisomerization in batch and flow modes, with the flow process being optimal in terms of process time. Crystal structure analysis of both the <em>Z</em> and <em>E</em> isomers highlighted key differences in molecular conformations and supramolecular interactions with greater deviation from planarity evident in <strong><em>E</em>-3</strong> relative to <strong><em>Z</em>-3</strong>. Analysis of samples of <strong><em>Z</em>-3</strong> by PXRD and DSC after recrystallization from a variety of solvents gave data consistent with the determined crystal structure of <strong><em>Z</em>-3</strong>.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 1878-1886"},"PeriodicalIF":3.1000,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d5re00137d?page=search","citationCount":"0","resultStr":"{\"title\":\"Formation of the E-isomer as an impurity in the optimized flow synthesis of a Z-α-thio-β-chloroacrylamide; E/Z photoisomerization in batch and flow, and solid state characterization of both isomers†\",\"authors\":\"Olga C. Dennehy, Denis Lynch, U. B. Rao Khandavilli, Simon E. Lawrence, Stuart G. Collins, Anita R. Maguire and Humphrey A. Moynihan\",\"doi\":\"10.1039/D5RE00137D\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >\\r\\n <em>N</em>-(4-Methylphenyl)-<em>Z</em>-3-chloro-2-(phenylthio)propenamide (<strong><em>Z</em>-3</strong>), which is valuable as a reactive substrate for a range of synthetic transformations, can be obtained by a three-step process involving both batch and flow methodologies. Compound <strong><em>Z</em>-3</strong> was isolated as a crystalline material of high purity, however, the <em>E</em>-isomer, <strong><em>E</em>-3</strong>, was found to form in solid samples of <strong><em>Z</em>-3</strong> material during storage. Increased ratios of <strong><em>E</em>-3</strong> and pure isolated samples were obtained by photoisomerization in batch and flow modes, with the flow process being optimal in terms of process time. Crystal structure analysis of both the <em>Z</em> and <em>E</em> isomers highlighted key differences in molecular conformations and supramolecular interactions with greater deviation from planarity evident in <strong><em>E</em>-3</strong> relative to <strong><em>Z</em>-3</strong>. Analysis of samples of <strong><em>Z</em>-3</strong> by PXRD and DSC after recrystallization from a variety of solvents gave data consistent with the determined crystal structure of <strong><em>Z</em>-3</strong>.</p>\",\"PeriodicalId\":101,\"journal\":{\"name\":\"Reaction Chemistry & Engineering\",\"volume\":\" 8\",\"pages\":\" 1878-1886\"},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2025-05-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2025/re/d5re00137d?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Reaction Chemistry & Engineering\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/re/d5re00137d\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reaction Chemistry & Engineering","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/re/d5re00137d","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Formation of the E-isomer as an impurity in the optimized flow synthesis of a Z-α-thio-β-chloroacrylamide; E/Z photoisomerization in batch and flow, and solid state characterization of both isomers†
N-(4-Methylphenyl)-Z-3-chloro-2-(phenylthio)propenamide (Z-3), which is valuable as a reactive substrate for a range of synthetic transformations, can be obtained by a three-step process involving both batch and flow methodologies. Compound Z-3 was isolated as a crystalline material of high purity, however, the E-isomer, E-3, was found to form in solid samples of Z-3 material during storage. Increased ratios of E-3 and pure isolated samples were obtained by photoisomerization in batch and flow modes, with the flow process being optimal in terms of process time. Crystal structure analysis of both the Z and E isomers highlighted key differences in molecular conformations and supramolecular interactions with greater deviation from planarity evident in E-3 relative to Z-3. Analysis of samples of Z-3 by PXRD and DSC after recrystallization from a variety of solvents gave data consistent with the determined crystal structure of Z-3.
期刊介绍:
Reaction Chemistry & Engineering is a new journal reporting cutting edge research into all aspects of making molecules for the benefit of fundamental research, applied processes and wider society.
From fundamental, molecular-level chemistry to large scale chemical production, Reaction Chemistry & Engineering brings together communities of chemists and chemical engineers working to ensure the crucial role of reaction chemistry in today’s world.