Simple and Efficient Synthesis of Explosive Cocrystals containing 3,5-Dimethylpyrazol-1-yl-substituted-1,2,4,5-tetrazines.
Simple and Efficient Synthesis of Explosive Cocrystals containing 3,5-Dimethylpyrazol-1-yl-substituted-1,2,4,5-tetrazines.
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DOI：
10.1002/chem.201704394
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发表时间：
2017-11
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影响因子：
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通讯作者：
C. Snyder;D. Chavez;Gregory H. Imler;E. Byrd;Philip W Leonard;D. Parrish
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文献类型：
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作者：
C. Snyder;D. Chavez;Gregory H. Imler;E. Byrd;Philip W Leonard;D. Parrish
3，4-二硝基吡唑、5-硝基四唑或4-硝基-1，2，3-三唑与3，5-二甲基吡唑基（dmp）取代的1，2，4，5-四嗪反应，回流1分钟后冷却至室温，产率为89- 92%。dmp基团与高能杂环的N-H之间的氢键是稳定新共晶的主要相互作用。每个共晶以不同的晶格结构堆积，并且具有片状和人字形晶体堆积取向的共晶比具有互锁结构的共晶不太敏感。静电势图有助于解释为什么dmp取代的四嗪容易形成共晶，而更多的缺电子吡唑基四嗪不。计算的新的共晶的能量性能接近2，4，6-三硝基甲苯（TNT），重要的是，这些材料将有助于新的共晶含能材料的合理设计。
The reaction of 3,4-dinitropyrazole, 5-nitrotetrazole, or 4-nitro-1,2,3-triazole with 1,2,4,5-tetrazines substituted with 3,5-dimethylpyrazolyl (dmp) groups results in energetic cocrystals after 1 minute of reflux and cooling to room temperature in yields of 89-92 %. Hydrogen-bonding between the dmp group to the N-H of the energetic heterocycles are the predominant interaction that stabilizes the new cocrystals. Each cocrystal packs in a different lattice structure and the cocrystals with sheet-like and herring-bone crystal packing orientations are less sensitive than the cocrystal with the interlocked structure. Electrostatic potential mapping helps rationalize why dmp-substituted tetrazines readily form cocrystals, whereas more electron-deficient pyrazolyl tetrazines do not. The calculated energetic performance of the new cocrystals approaches that of 2,4,6-trinitrotoluene (TNT) and importantly, these materials will aid in the rational design of new cocrystalline energetic materials.