Nikita V. Teplyashin, Alexander S. Bobkov, Nadezhda M. Vitkovskaya, Viktor V. Manuilov, Igor A. Ushakov, Nikolai A. Korchevin, Igor B. Rozentsveig
{"title":"KOH/水合肼介质中2-氯丙-2-烯基异硫脲盐的二甲基-1,4-二硫胺：实验和量子化学研究","authors":"Nikita V. Teplyashin, Alexander S. Bobkov, Nadezhda M. Vitkovskaya, Viktor V. Manuilov, Igor A. Ushakov, Nikolai A. Korchevin, Igor B. Rozentsveig","doi":"10.1002/jhet.70025","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>We report on the synthesis of 2,6-dimethyl-1,4-dithiine from 2-chloroprop-2-enylisothiouronium salt in the KOH/N<sub>2</sub>H<sub>4</sub>·H<sub>2</sub>O medium. The yield of the target product amounted to 33% at 50°C, under the addition of a tenfold excess of potassium hydroxide. The structure of the product was characterized by <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy. The proposed mechanism of the formation of 2,6-dimethyl-1,4-dithiine and possible side reactions were explored by means of quantum chemistry methods. The complete reaction profile of the formation has been constructed and analyzed, and kinetics modeling of all the stages has been carried out. Our major finding is identifying the key reaction intermediate—methylidenethiirane—formed following the alkaline hydrolysis of the isothiouronium salt, which is responsible for the 1,2-migration of the sulfur atom.</p>\n </div>","PeriodicalId":194,"journal":{"name":"Journal of Heterocyclic Chemistry","volume":"62 9","pages":"739-751"},"PeriodicalIF":2.0000,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Dimethyl-1,4-Dithiines From 2-Chloroprop-2-Enylisothiouronium Salt in KOH/Hydrazine Hydrate Medium: Experiment and Quantum Chemical Study\",\"authors\":\"Nikita V. Teplyashin, Alexander S. Bobkov, Nadezhda M. Vitkovskaya, Viktor V. Manuilov, Igor A. Ushakov, Nikolai A. Korchevin, Igor B. Rozentsveig\",\"doi\":\"10.1002/jhet.70025\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div>\\n \\n <p>We report on the synthesis of 2,6-dimethyl-1,4-dithiine from 2-chloroprop-2-enylisothiouronium salt in the KOH/N<sub>2</sub>H<sub>4</sub>·H<sub>2</sub>O medium. The yield of the target product amounted to 33% at 50°C, under the addition of a tenfold excess of potassium hydroxide. The structure of the product was characterized by <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy. The proposed mechanism of the formation of 2,6-dimethyl-1,4-dithiine and possible side reactions were explored by means of quantum chemistry methods. The complete reaction profile of the formation has been constructed and analyzed, and kinetics modeling of all the stages has been carried out. Our major finding is identifying the key reaction intermediate—methylidenethiirane—formed following the alkaline hydrolysis of the isothiouronium salt, which is responsible for the 1,2-migration of the sulfur atom.</p>\\n </div>\",\"PeriodicalId\":194,\"journal\":{\"name\":\"Journal of Heterocyclic Chemistry\",\"volume\":\"62 9\",\"pages\":\"739-751\"},\"PeriodicalIF\":2.0000,\"publicationDate\":\"2025-07-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Heterocyclic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/jhet.70025\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Heterocyclic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/jhet.70025","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Dimethyl-1,4-Dithiines From 2-Chloroprop-2-Enylisothiouronium Salt in KOH/Hydrazine Hydrate Medium: Experiment and Quantum Chemical Study
We report on the synthesis of 2,6-dimethyl-1,4-dithiine from 2-chloroprop-2-enylisothiouronium salt in the KOH/N2H4·H2O medium. The yield of the target product amounted to 33% at 50°C, under the addition of a tenfold excess of potassium hydroxide. The structure of the product was characterized by 1H and 13C NMR spectroscopy. The proposed mechanism of the formation of 2,6-dimethyl-1,4-dithiine and possible side reactions were explored by means of quantum chemistry methods. The complete reaction profile of the formation has been constructed and analyzed, and kinetics modeling of all the stages has been carried out. Our major finding is identifying the key reaction intermediate—methylidenethiirane—formed following the alkaline hydrolysis of the isothiouronium salt, which is responsible for the 1,2-migration of the sulfur atom.
期刊介绍：
The Journal of Heterocyclic Chemistry is interested in publishing research on all aspects of heterocyclic chemistry, especially development and application of efficient synthetic methodologies and strategies for the synthesis of various heterocyclic compounds. In addition, Journal of Heterocyclic Chemistry promotes research in other areas that contribute to heterocyclic synthesis/application, such as synthesis design, reaction techniques, flow chemistry and continuous processing, multiphase catalysis, green chemistry, catalyst immobilization and recycling.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
