1-取代的4-硝基咪唑含能衍生物的合成、表征及热分解性能

Synthesis,Characterization and Decomposition of 1-Substitued 4-Nitroimidazole Energetic Derivatives

以4-硝基咪唑为原料,通过与2-氨基-3,5-二硝基-6-氯吡啶、2,6-二氯-3-硝基吡啶缩合,合成出未见文献报道的化合物6-（4-硝基-咪唑-1-基）-2-氨基-3,5-二硝基吡啶（1#）及6-氯-3-硝基-2-（4-硝基-咪唑-1-基）-吡啶（3#）,收率分别为65%、52%;并采用此种方法优化了3-硝基-2-（4-硝基-咪唑-1-基）-吡啶（2#）的合成,收率为85%。进一步尝试了化合物3#的叠氮化反应,得到5-叠氮基-6-硝基四唑基[1,5-a]吡啶（4#）。采用核磁共振、质谱、红外光谱、元素分析等方法对相关化合物的结构进行了表征。利用TG和DSC分析法研究了化合物1#的热行为,结果表明：化合物1#的初始分解温度为221.83℃,分解放热总量为302.65 k J/mol,热失重温度范围为209.17~398.67℃,累计热失重71.84%。

By using 4-nitroimidazole as a raw material in condensation with 2-amino-3,5-dinitro-6-chloropyridine and2,6-chloro-3-nitro-pyridine,6-（ 4-nitro-imidazol-1-yl）-2-amino-3,5-dinitro-pyridine（ 1#） and 6-chloro-3-nitro-2-（ 4-nitro-imidazol-1-yl）-pyridine（ 3#） were synthesized with yields of 65% and 52% respectively. The synthesis of 3-nitro-2-（ 4-nitro-imidazol-1-yl）-pyridine（ 2#） was optimized by this method with a yield of 85%. Further azidation of compound 3#was carried on to give 5-azido-6-nitrotetrazolo [1,5-a]pyridine（ 4#）. The structures of these compounds were characterized by1 H NMR,13 C NMR,MS and elemental analysis. Thermal behavior of compound 1#was studied by TG and DSC. Results show that the initial decomposition temperature of compound 1#was 221. 83℃,the total decomposition heat 302. 65 k J /mol,while its mass loss of 71. 84% takes place at the temperature of 209. 17 ~ 398. 67 ℃.