高等学校化学学报 ›› 2006, Vol. 27 ›› Issue (5): 867.

• 研究论文 • 上一篇    下一篇

新型三环系稠杂环[1,2,4]-三唑并[1,5-a][1]-苯并氮杂及[1,2,4]-三唑并[1,5-a]-喹啉的合成

白鹤翔, 孟青青, 王全瑞, 陶凤岗   

  1. 复旦大学化学系, 上海 200433
  • 收稿日期:2005-05-08 出版日期:2006-05-10 发布日期:2006-05-10
  • 通讯作者: 王全瑞(1963年出生),男,博士,教授,博士生导师,主要从事有机合成研究. E-mail: qrwang@fudan.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 20372015)资助.

Syntheses of Novel Tricyclic Fused Heterocycles:[1,2,4]Triazolo[1,5a][1] benzazepine and [1,2,4]
Triazolo[1,5a]quinoline Derivatives

BAI He-Xiang, MENG Qing-Qing, WANG Quan-Rui*, TAO Feng-Gang   

  1. Department of Chemistry, Fudan University, Shanghai 200433, China
  • Received:2005-05-08 Online:2006-05-10 Published:2006-05-10
  • Contact: WANG Quan-Rui, E-mail: qrwang@fudan.edu.cn

摘要:

α-四氢萘酮的乙氧羰基腙(1)经LTA氧化, 得到α-偶氮-α-乙酰氧基化合物2. 在AlCl3作用下, 化合物2脱去乙酰氧基产生重氮正离子中间体3, 再经与腈的1,3-偶极环加成、 [1,2]-迁移扩环、 碱性水解和与苦味酸作用, 得到新型[1,2,4]-三唑并[1,5a][1]苯并氮杂苦味酸盐6a~6c. 以2,3-二氢-1-茚酮为底物, 采用相同的合成路线, 合成了1,2,4-三唑并[1,5-a]-二氢喹啉苦味酸盐12a~12c.

关键词: 1,3-偶极环加成; 扩环;  [1,2,4]-三唑并[1,5-a][1]苯并氮杂; 1,2,4-三唑并[1,5-a]喹啉

Abstract:

Oxidation of αtetralone ethoxycarbonylhydrazone(1) with lead tetraacetate afforded the bicyclic geminal ethyl azoester 2. On addition of equimolecular aluminum trichloride, the azocarbenium salt 3 was generated in situ as a reactive intermediate, which could be trapped by the cycloadditions to the triple bonds of nitriles giving 3H1,2,4-triazolium salts. These initially cycloadducts couldn′t be isolated but underwent smooth 1,2-aryl-shift with concurrent ring enlargement and insertion of a nitrogen atom to the carbon skeleton to provide the tricyclic salts 4a—4c, from which the literature unprecedentate [1,2,4]triazolo[1,5-a][1]benzazepinium picrates 6a—6c were obtained in 23%~56% yields upon hydrolytic removal of the Nethoxycarbonyl group and subsequent treatment of the resulted heterocycles 5 with picric acid. Analogously, the novel 4,5dihydro-[1,2,4]triazolo[1,5-a]quinolinium picrates(12a—12c) were prepared from 2,3dihydro-1-indanone in moderate yields.

Key words: 1,3-Dipolar cycloaddition; Ring enlargement; [1,2,4]Triazolo[1,5a][1]benzazepine; [1,2,4]Triazolo[1,5-a]quinoline

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