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  

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

作　　者：白鹤翔[1] 孟青青[1] 王全瑞[1] 陶凤岗[1] 

机构地区：[1]复旦大学化学系,上海200433

出　　处：《高等学校化学学报》2006年第5期867-870,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20372015)资助

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A lC l3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.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 ni- triles 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 tficyclic 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-di- hydro- [ 1,2,4 ] triazolo [ 1,5-a ] quinolinium picrates （ 12a--12c ） were prepared from 2,3-dihydro-1 -indanone in moderate yields.

关 键 词：1 3-偶极环加成 扩环 [1 2 4]-三唑并[1 苯并氮杂[艹卓] 1 2 4-三唑并[1 5-a]喹啉 

分 类 号：O626[理学—有机化学]