从频哪酮制备1,3,5- 三取代-1H- 1,2,4 -三唑  

Synthesis of 1,3,5 Trisubstituted 1 H 1,2,4 trazoles from Pinakolone

作　　者：刘毅[1] 刘现军[1] 王全瑞[1] 

机构地区：[1]复旦大学化学系,上海200433

出　　处：《应用化学》1999年第5期73-75,共3页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金

摘　　要：Aza 2 azoniaallene cations 3(denoted also as azo carbenium ions) were generated in situ as reactive intermediates by chlorination of pinakolone hydrazones 1 with tert butyl hypochlorite and treatment of the resulted(1 choroalkyl)azo compounds 2 with a Lewis acid (SbCl 5). The allene like cations 3 were trapped by cycloaddition to the triple bond of nitriles giving 3 H 1,2,4 triazolium salts 4. The initially formed heterocycles 4 couldn′t be isolated but underwent smooth 1,2 tert butyl shift accompanied by elimination of isobutene to afford 1 H 1,2,4 triazolium salts 5, from which 1,3,5 trisubstituted 1 H 1,2,4 triazoles 6 have been obtained in moderate to high yields after basic work up. Heterocycles 6 are characterized by elemental analysis and IR, 1H NMR measurements.Aza 2 azoniaallene cations 3(denoted also as azo carbenium ions) were generated in situ as reactive intermediates by chlorination of pinakolone hydrazones 1 with tert butyl hypochlorite and treatment of the resulted(1 choroalkyl)azo compounds 2 with a Lewis acid (SbCl 5). The allene like cations 3 were trapped by cycloaddition to the triple bond of nitriles giving 3 H 1,2,4 triazolium salts 4. The initially formed heterocycles 4 couldn′t be isolated but underwent smooth 1,2 tert butyl shift accompanied by elimination of isobutene to afford 1 H 1,2,4 triazolium salts 5, from which 1,3,5 trisubstituted 1 H 1,2,4 triazoles 6 have been obtained in moderate to high yields after basic work up. Heterocycles 6 are characterized by elemental analysis and IR, 1H NMR measurements.

关 键 词：三取代 三唑 合成 频哪酮 非线性光学材料 

分 类 号：TN204[电子电信—物理电子学] O626.26[理学—有机化学]