1-(1-乙基-1H-5-吲哚基)-2-苯基-1,2-二酮缩合成1,2,4-三嗪类化合物反应
Condensation of 1-(1-Ethyl-1H-indol-5-yl)-2-phenylethane- 1,2-dione to 1,2,4-Triazines
Received date: 2015-09-08
Revised date: 2015-10-06
Online published: 2015-10-13
报道了一种1-(1-乙基-1H-5-吲哚基)-2-苯基-1,2-二酮与氨基胍碳酸氢盐缩合生成互为同分异构体的两种1,2,4-三嗪的反应, 并通过运用目标定向合成和核磁的方法, 研究了1,2-二酮苯环上不同取代基对反应产品比例的影响. 反应总收率为40%～81%, 且当不对称1,2-二酮苯环上无取代基时, 其生成的同分异构体6-(1-乙基-1H-5-吲哚基)-5-苯基- 3-氨基-1,2,4-三嗪(2a)和5-(1-乙基-1H-5-吲哚基)-6-苯基-3-氨基-1,2,4-三嗪(4a)比例为40:60; 当苯环上取代基为吸电子基时, 6-(1-乙基-1H-5-吲哚基)-5-(4-硝基苯基)-3-氨基-1,2,4-三嗪(2b)和5-(1-乙基-1H-5-吲哚基)-6-(4-硝基苯基)-3-氨基-1,2,4-三嗪(4b)比例为63:37; 当苯环上取代基为供电子基时, 绝大部分生成2系列构型结构.
刘剑功 , 黎晓龙 , 程旭 , 郝文梅 , 海俐 , 吴勇 . 1-(1-乙基-1H-5-吲哚基)-2-苯基-1,2-二酮缩合成1,2,4-三嗪类化合物反应[J]. 有机化学, 2016 , 36(2) : 370 -376 . DOI: 10.6023/cjoc201509010
This paper reports the selective condensation of aminoguanidine with 1-(1-ethyl-1H-indol-5-yl)-2-phenylethane- 1,2-dione to afford 1,2,4-triazines. The constituents and relative proportion of these condensation products are identified by the methods of target-oriented synthesis and nuclear magnetic resonance. And the influences on the relative proportion by different substituents are described. When the phenyl is substituted with the electron-withdrawing group, the ratio of the isomers 6-(1-ethyl-1H-indol-5-yl)-5-phenyl-1,2,4-triazin-3-amine/5-(1-ethyl-1H-indol-5-yl)-6-phenyl-1,2,4-triazin-3-amine [n(2a):n(4a)] is 40:60; when without the substituent, the ratio of the isomers 6-(1-ethyl-1H-indol-5-yl)-5-(4-nitrophenyl)- 1,2,4-triazin-3-amine/5-(1-ethyl-1H-indol-5-yl)-6-(4-nitrophenyl)-1,2,4-triazin-3-amine [n(2b):n(4b)] is 63:37; when substituted with the electron-donating group, the type of the major products was 2.
Key words： condensation; unsymmetrical 1,2-diketone; isomer; 1,2,4-triazine
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