Preparations and Reactions of 2‐Cyanoindole Derivatives
Preparations and Reactions of 2‐Cyanoindole Derivatives
复制标题
2-氰基吲哚衍生物的制备和反应
DOI：
10.1002/jccs.199300092
复制
发表时间：
1993
期刊：
影响因子：
--
通讯作者：
Jim
中科院分区：
文献类型：
--
作者：
Chih;Jim
2-氰基-1-苯磺酰基吲哚 (1a) 和 2-氰基-1-甲基吲哚 (1b) 通过化学和电解方法以适度的产率制备。苯硫醇钠、丁基锂和二甲基铜酸锂等亲核试剂攻击1a的磺酰基，而攻击1b的氰基。 1a和1b与2,4,6-三甲基苯甲腈氧化物在氰基处发生1,3-偶极环加成。 1b与N-溴代琥珀酰亚胺、Vilsmeir试剂和乙酰氯的亲电反应以适度或高产率提供相应的3-溴-、3-甲酰基-和3-乙酰基吲哚衍生物，尽管比1-甲基吲哚的反应慢。将乙炔二甲酸二甲酯光化学加成到1b上，然后裂解环丁烯中间体，得到(2-氰基-1-甲基苯并氮杂卓)-3,4-二甲酸二甲酯。
2-Cyano-1-phenylsulfonylindole (1a) and 2-cyano-1-methylindole (1b) were prepared by chemical and electrolytic methods in modest yields. Nucleophiles such as sodium benzenethiolate, butyllithium and lithium dimethylcuprate attacked the sulfonyl group of 1a, whereas they attacked the cyano group of 1b. 1,3-Dipolar cycloadditions of 1a and 1b with 2,4,6-trimethylbenzonitrile oxide occurred at the cyano groups. Electrophilic reactions of 1b with N-bromosuccinimide, Vilsmeir reagent and acetyl chloride afforded the corresponding 3-bromo-, 3-formyl- and 3-acetylindole derivatives in modest or high yields, albeit less rapidly than the reactions of 1-methylindole. Photochemical addition of dimethyl acetylenedicarboxylate to 1b was followed by cleavage of the cyclobutene intermediate to give dimethyl (2-cyano-1-methylbenzazepine)-3,4-dicarboxylate.