新型2-氧代-1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂类稠杂环的合成  

Synthesis of Novel 2-Oxo-1,2,4-[triazolo][3,2-d] [1,5]benzoxazepine Derivatives

作　　者：李诤[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》2004年第10期1840-1844,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 0 3 72 0 15 );江苏省有机合成重点实验室开放课题 (批准号 :KJS0 10 16)资助

摘　　要：将取代色满酮 ( 1 )与芳肼反应生成的腙与 HNCO发生 [3 +2 ]环加成反应 ,加成产物 ( 2 )经氧化得到偕偶氮异氰酸酯 ( 3 ) .化合物 3在 HBF4 的催化下发生环化 -重排反应 ,得到新颖的三环系 2 -氧代 -1 ,2 ,4-三唑并[3 ,2 -d][1 ,5 ]苯并氧氮杂化合物 5 a～ 5Many [1,2,4]triazolobenzoheteroazepine derivatives show interesting biological activities. In this paper, the geminal arylazo isocyanato compounds 3 were prepared from chroman-4-ones in three steps, i.e. condensation with arylhydrazine, cycloaddition of the resulting hydrazone with HNCO, and oxidative ring cleavage by KMnO 4. Compounds 3 were allowed to react with HBF 4, producing the respective 3-spiro substituted 1-aryl-4,5-dihydro-5-oxo-3H-1,2,4-triazolium salts 4. The concurrent rearrangement of compound 4 with insertion of the nitrogen atom into the carbon skeleton provided, after the basic work-up, 2-oxo-[1,2,4]triazolo[3,2-d][1,5]benzoxazepines 5a—5h. An unambigous structutal proof was obtained from the X-ray diffraction analysis for compound 5h.

关 键 词：2-氧代-1 2 4-三唑并[3 2-d][1 5]苯并氧氮杂Zhuo类稠杂环 合成 环化反应 重排反应 偕偶氮异氰酸酯 

分 类 号：O626[理学—有机化学]