Facile and selective polynitrations at the 4-pyrazolyl dual backbone: straightforward access to a series of high-density energetic materials
Facile and selective polynitrations at the 4-pyrazolyl dual backbone: straightforward access to a series of high-density energetic materials
复制标题
DOI：
10.1039/c8nj05266b
复制
发表时间：
2019-01-21
影响因子：
3.3
通讯作者：
Stierstorfer, Joerg
中科院分区：
文献类型：
--
作者：
Domasevitch, Kostiantyn V.;Gospodinov, Ivan;Stierstorfer, Joerg
仍然需要硝基官能化的含能材料来满足新的安全性、性能和化学可及性要求。4，4-联吡唑骨架成功地解决了含氮杂环化合物的多次C-硝化问题。通过4的高选择性直接硝化，以优异的产率获得了一系列逐渐官能化的3-硝基-4，4’-联吡唑（2）、3，3’-二硝基-4，4’-联吡唑（3）、3，5’-二硝基-4，4’-联吡唑（4）、3，3’，5-三硝基-4，4’-联吡唑（5）和3，3’，5，5’-四硝基-4，4’-联吡唑（6），4-联吡唑（1）。所有合成的多硝基衍生物3-6都表现出高于290 ℃的高分解温度。在4，4 '-联吡唑骨架中引入三个（5）和四个硝基（6）产生具有优异密度和爆炸性能的不敏感且热稳定的高能炸药。化合物2-6的无水结构通过低温XRD得到。此外，化合物5和6的性能进行了研究与小规模的冲击反应性测试。
Nitro-functionalized energetic materials are still needed to meet new safety, performance and chemical accessibility demands. The problem of multiple C-nitrations on N-containing heterocycles was resolved successfully for the 4,4-bipyrazole scaffold. A progression of gradually functionalized 3-nitro-4,4'-bipyrazole (2), 3,3'-dinitro-4,4'-bipyrazole (3), 3,5'-dinitro-4,4'-bipyrazole (4), 3,3',5-trinitro-4,4'-bipyrazole (5) and 3,3',5,5'-tetranitro-4,4'-bipyrazole (6) was obtained in excellent yields by highly selective direct nitrations of 4,4-bipyrazole (1). All synthesized polynitro derivatives 3-6 exhibit high decomposition temperatures of above 290 degrees C. The introduction of three (5) and four nitro groups (6) into the 4,4'-bipyrazole scaffold yields insensitive and thermally stable high explosives with excellent densities and detonation properties. The anhydrous structures of compounds 2-6 were obtained by low-temperature XRD. In addition, the performance of compounds 5 and 6 was investigated with a small scale shock reactivity test.