连三嗪化合物的合成及反应机理  

Synthesis and Reaction Mechanism of 1,2,3-Triazine Compound

作　　者：李亚南[1] 常海波[1] 王伯周[1] 王友兵[1] 杨威[1] 廉鹏[1] 李辉[1] 张志忠[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《含能材料》2013年第1期19-24,共6页Chinese Journal of Energetic Materials

基　　金：国防科研产品创新计划项目(No.2371000415);国防科研基础计划项目(No.B09201100051)资助

摘　　要：以2-氰基-4-硝基苯胺、3-氨基-4-氰基吡唑为原料,分别经肟化、重氮化等反应合成了两种连三嗪化合物——6-硝基苯并[3,4-e]-1,2,3-三嗪-4(1H)-肟和吡唑并[3,4-e]-1,2,3-三嗪-4(1H)-肟;利用红外光谱、核磁共振(HMNR、CMNR)、元素分析、质谱等鉴定了化合物的结构;考察不同因素对肟化反应的影响,确定了2-偕氨肟基-4-硝基苯胺的最适宜合成条件:2-氰基-4-硝基苯胺/盐酸羟胺的料比为11.20,反应温度为80℃,pH值为10,反应时间为2 h,收率为95.6%;3-氨基-4-偕氨肟基吡唑的最适宜合成条件:3-氨基-4-氰基吡唑/盐酸羟胺的料比为11.25,反应温度为80℃,pH值为10,反应时间为2 h,收率为79.3%;初步探讨了反应机理,分析了重氮化、消除反应发生在不同分子结构中不同位置氨基上的原因。Two novel 1 ,2,3 -riazi ne compounds-6-n itrobenzene [3,4-e ] -1 , 2,3 -triazi ne-4 （ 1 H ） -oxi me and pyrazole 13,4-e 1-1 , 2,3 - triazine-4（1 H）-oxime were prepared using 2-cyano-4-nitroaniline and 3-amino-4-cyanopyrazole as starting materials via the reactions of oxime and diazotization. The structures of intermediates and target compounds were characterized by means of IR,^1H NMR, ^13C NMR,elementa（ analysis and MS. The influences of different factors on the yield of oxime were studied. The suitable synthetical condition of 2-amino oxime-4-nitroaniline were confirmed that the material ratio of 2-cyano-4-nitroaniline and hydrochloric hydrox- yLaminewasl ： 1.20,80 ℃,pH=10,reaction time2 h and the yield was 95.6%. The suitable synthetical conditions of 3-amino-4- amino oximepyrazole were that the material ratio of 3-amino-4-cyanopyrazole and hydrochloric hydroxylamine was 1 ： 1.25,80 ℃, pH =10,reaction time2 h and the yield was 79.3%. The reaction mechanism was studied ,and the reasons why it occured that the different amino in the reactions of diazotization and elimination were analyzed.

关 键 词：有机化学 连三嗪化合物 合成 表征 反应机理 

分 类 号：TQ560.1[化学工程—炸药化工]