{"title":"氟羰基化合物、吡咯衍生物和丙二腈三组分反应中的c2 -烷基化与c2 -氧烷基化的竞争","authors":"N. Chkanikov","doi":"10.17677/fn20714807.2022.01.02","DOIUrl":null,"url":null,"abstract":"The C2-alkylation of pyrrole derivatives with 2-(2,2,2-trifluoroethylidene) malononitrile 1, formed in situ from ethyl hemiacetal trifluoroacetaldehyde 2 and malononitrile in the presence of a base, has been carried out. As a result of this three-component reaction, nitriles were obtained derivatives of 4,5,6,7-tetrahydroindole and pyrrole 4a, b, c. A competing reaction is C2-oxyalkylation of the pyrrole ring with hemiacetal 2. It has been shown that the side reaction can be completely suppressed by lowering the reaction temperature to -30∞C. When the ethyl ester of trifluoropyruvic acid 3 reacts with pyrrole derivatives in the presence of malononitrile, the main reaction is the C2-oxyalkylation of the pyrrole ring, rather than its C2-alkylation formed in situ by alkene 10. Nitriles 6 9 were obtained in high yields from pyrrole derivatives and alkene 10. The structure of the compounds was confirmed by 1H, 13C, 19F NMR spectroscopy, mass spectrometry and high-resolution mass spectrometry.","PeriodicalId":12217,"journal":{"name":"Fluorine Notes","volume":"39 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2022-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"C2-Alkylation in a three-component reaction of fluorocarbonyl compounds, pyrrole derivatives and malononitrile in competition with C2-oxyalkylation\",\"authors\":\"N. Chkanikov\",\"doi\":\"10.17677/fn20714807.2022.01.02\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The C2-alkylation of pyrrole derivatives with 2-(2,2,2-trifluoroethylidene) malononitrile 1, formed in situ from ethyl hemiacetal trifluoroacetaldehyde 2 and malononitrile in the presence of a base, has been carried out. As a result of this three-component reaction, nitriles were obtained derivatives of 4,5,6,7-tetrahydroindole and pyrrole 4a, b, c. A competing reaction is C2-oxyalkylation of the pyrrole ring with hemiacetal 2. It has been shown that the side reaction can be completely suppressed by lowering the reaction temperature to -30∞C. When the ethyl ester of trifluoropyruvic acid 3 reacts with pyrrole derivatives in the presence of malononitrile, the main reaction is the C2-oxyalkylation of the pyrrole ring, rather than its C2-alkylation formed in situ by alkene 10. Nitriles 6 9 were obtained in high yields from pyrrole derivatives and alkene 10. The structure of the compounds was confirmed by 1H, 13C, 19F NMR spectroscopy, mass spectrometry and high-resolution mass spectrometry.\",\"PeriodicalId\":12217,\"journal\":{\"name\":\"Fluorine Notes\",\"volume\":\"39 1\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2022-02-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Fluorine Notes\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.17677/fn20714807.2022.01.02\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Fluorine Notes","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.17677/fn20714807.2022.01.02","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
C2-Alkylation in a three-component reaction of fluorocarbonyl compounds, pyrrole derivatives and malononitrile in competition with C2-oxyalkylation
The C2-alkylation of pyrrole derivatives with 2-(2,2,2-trifluoroethylidene) malononitrile 1, formed in situ from ethyl hemiacetal trifluoroacetaldehyde 2 and malononitrile in the presence of a base, has been carried out. As a result of this three-component reaction, nitriles were obtained derivatives of 4,5,6,7-tetrahydroindole and pyrrole 4a, b, c. A competing reaction is C2-oxyalkylation of the pyrrole ring with hemiacetal 2. It has been shown that the side reaction can be completely suppressed by lowering the reaction temperature to -30∞C. When the ethyl ester of trifluoropyruvic acid 3 reacts with pyrrole derivatives in the presence of malononitrile, the main reaction is the C2-oxyalkylation of the pyrrole ring, rather than its C2-alkylation formed in situ by alkene 10. Nitriles 6 9 were obtained in high yields from pyrrole derivatives and alkene 10. The structure of the compounds was confirmed by 1H, 13C, 19F NMR spectroscopy, mass spectrometry and high-resolution mass spectrometry.