5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑)及其含能离子盐的合成与表征

Synthesis and Characterization of 5,5'-(2-(Trifluoromethyl)-1H-imidazole-4,5-diyl) bis(1H-tetrazole) and Its Energetic Ionic Salts

以二氨基马来腈为原料,经过与三氟乙酸酐缩合、环化,与叠氮化纳再次缩合,合成得到了新型含能化合物5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑),收率61.3%;基于该化合物的酸性,设计合成了2种含能离子盐5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑)的羟胺盐和胍盐。利用红外光谱、核磁共振和元素分析对中间体及产物结构进行了表征。探讨了生成5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑)过程中影响四唑环化反应的关键因素,确定的最佳反应条件为:反应介质为水,n(2-三氟甲基-4,5-二氰基咪唑)∶n(Na N3)=1∶2.4,反应温度98℃,反应时间4 h。收率最高达86.3%。通过DSC-TG研究了5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑)的热分解性能,热分解曲线表明化合物直到223.65℃才开始分解,整个分解过程经历了两个主要的放热分解阶段和热失重阶段,最大放热峰温度为285.78℃,说明该化合物结构比较稳定。

Using diaminomaleonitrile as starting material, a novel energetic compound 5,5＇-（2-（trifluoromethyl）-1 H-imidazole-4. 5-diyl） bis（1 H-tetrazole） was synthesized by condensation cyclization reaction with trifluoroacetic anhydride and the second condensation cyclization reaction with NaN3 in the yield of 61.3% ; based on acidity of the compound, two energetic ionic salts of hydroxylamine and guanidine of 5,5 ＇-（ 2-（ trifluoromethyl ） -1 H-imidazole-4,5 -diyl ） bis （ 1 H-tetrazole ） were designed and synthesized. The structures of products and intermediates were characterized by IR, NMR and elemental analysis. Key factors affecting the cyclization reaction for tetrazole in the formation process of 5,5 ＇-（ 2-（ trifluoromethyl ） -1 H-imidazole-4,5-diyl ） bis （ 1 H-tetrazole） were discussed, the optimum reaction conditions were determined as： H2O as reaction medium, n（2-（trifluoromethyl）- 1 H-imidazole-4,5-dicarbonitrile） ： n（NaN3）= 1 ： 2.4, reaction temperature 98 ℃, reaction time 4 h, yield up to 86.3%. The thermal decomposition of 5,5 ＇-（ 2-（ trifluoromethyl ） -1 H-imidazole-4,5-diyl ） bis （ 1 H-tetrazole ） was studied by DSC-TG which shown the compound decomposition starts at 223.65 ℃, and the whole decomposition process undergos two main exothermic decomposition stages and weight loss stages, the maximum exothermic peak temperature is 285.78 ℃, the structure of the compound is relatively stable.