3位氨基或硝基取代5-硝基-1,2,4三唑衍生物的合成与表征

以3-氨基-5-硝基-1,2,4三唑(ANTA)、3,5-二硝基-1,2,4三唑的铵盐(ADNT)及2,4,6-三硝基氯苯为原料,设计、合成了1-苦基-3-氨基-5-硝基-1,2,4三唑,4-苦基-3,5-二硝基-1,2,4三唑2种未见文献报道的硝基三唑衍生物,其熔点分别为251～252℃,156～157℃,同时改进了2,4,6-三(3-氨基-5-硝基-1,2,4三唑)-1,3,5-均三嗪合成方法,并采用红外光谱、核磁共振光谱、元素分析等对目标化合物进行了结构表征。探讨了3-氨基-5-硝基-1,2,4三唑与2,4,6-三硝基氯苯缩合反应机理,并研究了反应介质、催化剂等关键因素对缩合反应的影响。确定适宜的反应条件为:DMF作为介质,温度70℃,时间8h。

Synthesis and Characterization of 3-Amino( nitro)-5-nitro- 1,2,4-triazole derivatives

Two new heat-resistant explosives of 1-picryl-3-amino-5-nitro-1,2,4-triazole(TNTA-TNB) and 4-picryl-3,5-dinitro-1,2,4-triazole(DNT-TNB) were synthesized via condensation of 3-amino-5-nitro-1,2,4-triazole(ANTA)(or ammonium 3,5-dinitro-1,2,4-triazole(ADNT)) with 2,4,6-trinitrochlorobenzene. The condensation mechanism was explored and discussed. The effects of some key reaction conditions,such as media,temperature,time and catalysts,on condensation were investigated. The explosive synthesis was carried out at 70 ℃,8 h in DMF and NaF as catalyst. IR,NMR and elemental analysis confirmed the synthesized compound structures. In addition,we imroved the synthetic process of 2,4,6-tris(3-amino-5-nitro-1,2,4-triazole-1-yl)-1,3,5-triazine by means of direct reaction of ANTA with 2,4,6-trichloro-1,3,5-triazine omitting the preparation of ANTA-Na and without using phase transfer catalyst,lowering the production cost,simplifing the procedure,and improving the reaction safety.