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

N. Chkanikov
{"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}
引用次数: 0

摘要

以半缩乙基三氟乙醛2和丙二腈为原料,在碱的存在下原位生成了吡咯衍生物与2-(2,2,2-三氟乙基)丙二腈1的c2 -烷基化反应。通过这种三组分反应,得到了4,5,6,7-四氢吲哚和吡咯4a, b, c的衍生物。与之竞争的反应是吡咯环与半缩醛2的c2 -氧烷基化反应。结果表明,将反应温度降低至-30∞C,副反应完全被抑制。三氟丙酮酸3乙酯在丙二腈存在下与吡咯衍生物反应时,主要反应是吡咯环的c2 -氧烷基化,而不是烯烃10在原位形成的c2 -烷基化。以吡咯衍生物和烯烃10为原料,高收率地得到了腈6 9。化合物的结构通过1H、13C、19F核磁共振谱、质谱和高分辨率质谱证实。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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.
求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
自引率
0.00%
发文量
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信