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以自制的3,5-二甲基-4-氨基吡唑为原料,经重氮化、环化、硝化、氧化、脱羧硝化以及N-胺化等反应合成了1,4-二氨基-3,6-二硝基吡唑[4,3-c]并吡唑(LLM-119),采用红外光谱、核磁共振、质谱及元素分析等手段表征了中间体及目标物的结构;对4-重氮基-3,5-二甲基吡唑内盐的后处理方法进行了改进,采用冷冻结晶法代替萃取法,避免大量使用有机试剂,简化操作过程,收率由77.0%提高到86.1%;初步探讨了N-胺化反应的机理,从理论上分析了收率偏低的原因;利用DSC,TG等热分析手段研究了LLM-119的热性能,其热分解峰温为232.05℃,表明LLM-119具有较好的热稳定性;首次采用B3LYP方法,在6-31G(d,p)基组水平上对LLM-119的结构进行了全参数优化,获得其稳定的几何构型和键级;在振动分析的基础上求得体系的振动频率、IR谱及不同温度下的热力学性质,并得到了温度对热力学性能影响的关系式;用Monte-Carlo方法从理论上计算LLM-119的密度为1.85 g/cm3,与实验值接近,运用Kamlet公式预测爆速为8733.94 m/s.
In this paper, 1,4-diamino-3-methyl-4-aminopyrazole was synthesized by the reaction of self-made 3,5-dimethyl-4-aminopyrazole with diazotization, cyclization, nitration, oxidation, , 6-dinitropyrazolo [4,3-c] pyrazole (LLM-119). The structures of intermediates and target compounds were characterized by IR, 1HNMR, MS and elemental analysis. The method of aftertreatment of diazo-3,5-dimethylpyrazole inner salt is improved. The method of freezing crystallization instead of extraction is adopted to avoid the extensive use of organic reagents and to simplify the operation. The yield is increased from 77.0% to 86.1% The mechanism of N-amination reaction was preliminarily discussed, and the reason of low yield was theoretically analyzed. The thermal properties of LLM-119 were studied by means of thermal analysis such as DSC and TG. The peak temperature of thermal decomposition was 232.05 ℃, LLM-119 has good thermal stability. For the first time, using the B3LYP method, the structure of LLM-119 has been optimized on 6-31G (d, p) basis set to obtain the stable geometry and The vibrational frequency, IR spectrum and the thermodynamic properties at different temperatures were obtained based on the vibration analysis. The relationship between the temperature and the thermodynamic properties was obtained. Mon According to the te-Carlo method, the density of LLM-119 is calculated to be 1.85 g / cm3, which is close to the experimental value. The detonation velocity predicted by Kamlet formula is 8733.94 m / s.