Synthesis of 1-(2H-tetrazol-5-yl)-5-nitraminotetrazole and its derivatives from 5-aminotetrazole and cyanogen azide: a promising strategy towards the development of C-N linked bistetrazolate energetic materials
Synthesis of 1-(2H-tetrazol-5-yl)-5-nitraminotetrazole and its derivatives from 5-aminotetrazole and cyanogen azide: a promising strategy towards the development of C-N linked bistetrazolate energetic materials
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由5-氨基四唑和叠氮化氰合成1-(2H-四唑-5-基)-5-硝氨基四唑及其衍生物：开发C-N连接的双四唑含能材料的一个有前途的策略
DOI：
10.1039/c7ta05905a
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发表时间：
2017
影响因子：
11.9
通讯作者：
Zhang Qinghua
中科院分区：
文献类型：
--
作者：
Wang Binshen;Qi Xiujuan;Zhang Wenquan;Wang Kangcai;Li Wei;Zhang Qinghua
以易得的5-氨基四唑为原料，成功制备了一系列C-N连接的双四唑酸硝基化合物，即1-（2h -四唑-5-酰基）-5-硝胺四唑(2)及其含能盐（3-8）。所有新发现的含能化合物均通过IR、NMR和元素分析进行了表征，其中6个（1,3 - 7）通过单晶x射线衍射进一步鉴定。含氮量为59.3%(3)~ 74.8%(7)，远高于常用烈性炸药RDX （N: 37.8%）、HMX （N: 37.8%）和CL-20 （N: 38.3%）。利用Gaussian 09程序包进行理论计算表明，化合物1 - 8具有较高的正生成热，其中铵盐4 （3.60 kJ g−1）、氨基硝基胍5 （3.11 kJ g−1）和二肼盐7 （3.25 kJ g−1）的生成热约为RDX （0.39 kJ g−1）和HMX （0.39 kJ g−1）的8倍，CL-20 （0.83 kJ g−1）的4倍。高氮含量和高生成热使这些含能化合物具有突出的爆轰性能。值得注意的是，化合物7的计算爆轰速度为9822 m s - 1，优于CL-20 (9730 m s - 1)，而化合物7 （is = 8 J, FS = 192 N）的冲击和摩擦灵敏度与HMX （is = 7 J, FS = 112 N）相当。化合物7具有良好的爆轰性能和中等的灵敏度，是一种很有前途的高性能能材料。
A series of C–N linked bistetrazolate nitramino compounds, i.e., 1-(2H-tetrazol-5-yl)-5-nitraminotetrazole (2) and its energetic salts (3–8), were successfully prepared from readily available 5-aminotetrazole. All new energetic compounds were fully characterized by IR and NMR spectra and elemental analysis, and six of them (1, 3–7) were further determined by single-crystal X-ray diffraction analysis. The nitrogen contents of these energetic bistetrazolate compounds, ranging from 59.3% (3) to 74.8% (7), are much higher than those of the commonly used high explosives such as RDX (N: 37.8%), HMX (N: 37.8%) and CL-20 (N: 38.3%). And theoretical calculations by using the Gaussian 09 program package demonstrate that compounds 1–8 have high positive heats of formation, of which the heats of formation of ammonium salt 4 (3.60 kJ g−1), aminonitroguanidinium 5 (3.11 kJ g−1) and dihydrazinium salt 7 (3.25 kJ g−1) are approximately eight times higher than those of RDX (0.39 kJ g−1) and HMX (0.39 kJ g−1), and four times higher than that of CL-20 (0.83 kJ g−1). The high nitrogen contents and high heats of formation have endowed these energetic compounds with prominent detonation performance. It is noteworthy that compound 7 exhibits an excellent calculated detonation velocity of 9822 m s−1 superior to that of CL-20 (9730 m s−1), while the impact and friction sensitivities of 7 (IS = 8 J, FS = 192 N) are comparable to those of HMX (IS = 7 J, FS = 112 N). The good detonation properties with moderate sensitivities demonstrate that compound 7 is a promising candidate for application as a high-performance energetic material.