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
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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.
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