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化学学报 ›› 2009, Vol. 67 ›› Issue (20): 2343-2348. 上一篇    下一篇

研究论文

新型高能量密度化合物3,6-双（3,5-二硝基-1,2,4-三唑-1-）-1,2,4,5-四嗪-1,4-二氧化物的性能预估及合成路线设计

廉鹏*,a   来蔚鹏a   王伯周a   葛忠学a   朱维良b   薛永强c   

  1. (a西安近代化学研究所 西安 710065) (b中国科学院上海药物研究所药物发现与设计中心 上海 201203) (c太原理工大学应用化学系 太原 030024)
  • 投稿日期:2009-02-02 修回日期:2009-04-02 发布日期:2009-06-09
  • 通讯作者: 廉鹏
  • 基金资助:

    火炸药十一五预研基金(No. 40406020302)

Design of Synthetic Route and Prediction of Properties for a Novel High Energetic Density Compound 3,6-Bis(3,5-dinitro-1,2,4- triazol-1-yl)-1,2,4,5-tetrazine-1,4-dioxide

Lian, Peng*,a    Lai, Weipenga    Wang, Bozhoua    Ge, Zhongxuea    Zhu, Weiliangb    Xue, Yongqiangc   

  1. (a Xi'an Modern Chemistry Research Institute, Xi'an 710065) (b Drug Discovery and Design Center, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203) (c Applied Chemistry Department, Taiyuan University of Technology, Taiyuan 030024)
  • Received:2009-02-02 Revised:2009-04-02 Published:2009-06-09

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采用C＋＋自编译程序及组合原理, 设计并筛选出一种未见报道的新型富氮类高能量密度化合物——3,6-双(3,5-二硝基-1,2,4-三唑-1)-1,2,4,5-四嗪-1,4-二氧化物, 用B3LYP法, 在6-31G**基组水平上得到该化合物全优化构型; 在振动分析的基础上求得体系的振动频率、IR谱; 通过键级分析得到热解引发键的键离解能(BDE); 采用Monte-Carlo方法预估了密度; 设计等键等电子反应计算了生成焓; 运用Kamlet-Jacobs公式预测爆速、爆压和爆热; 运用Keshavarz等推导的预估撞击感度H50的公式预测了撞击感度性能; 并利用逆合成分析法设计其合成路线. 结果表明: 该化合物存在8个强吸收峰, 校正后的热解引发键的BDE为264 kJ•mol－1, 稳定性较优; 密度1.955 g•cm－3、生成焓901.72 kJ• mol－1、爆速9191.48 m•s－1、爆压39.32 GPa、爆热6705.15 J•g－1; 撞击感度H50为55.85 cm, 低于黑索金(RDX)和奥克托今(HMX); 以上性能均达到了高能量密度化合物的标准, 且该化合物设计合成路线步骤较少、原料易得, 有望得到广泛应用.

关键词: 3,6-双(3,5-二硝基-1,2,4-三唑-1)-1,2,4,5-四嗪-1,4-二氧化物, 密度泛函理论, 等键反应, 爆轰性能, 撞击感度, 逆合成分析

A novel high energetic density compound — 3,6-bis(3,5-dinitro-1,2,4-triazole-1-yl)-1,2,4,5- tetrazine-1,4-dioxide was designed by our C++ program implementing the combinatorial principle. The stable geometry of the compound was optimized at B3LYP/6-31G++ theoretical level. Its vibrational frequencies and IR spectra were obtained on the basis of vibrational analysis. The bond dissociation energy (BDE) of thermolysis initiation bond was calculated theoretically by bond order analysis. The density and enthalpy of formation of the compound were calculated theoretically by Monte-Carlo method and the isodesmic reaction scheme, respectively. Its velocity detonation, detonation pressure and detonation heat were also predicted by the formula of Kamlet-Jacobs. The impact sensitivity was predicted by the formula of Keshavarz and co-worker. The reaction route was designed by retrosynthesis analysis method. The results show that: there are 8 strong peaks in the IR spectra of the molecule. BDE value of the thermolysis initiation bond was 264 kJ·mol-1, and the stability of the molecule was excellent. The density, enthalpy of formation, detonation velocity, detonation pressure and detonation heat are 1.955 g·cm-3, 901.72 kJ·mol-1, 9191.48 m·s-1，39.32 GPa and 6705.15 J·g-1, respectively. Predicted H50 value is 55.85cm, and is lower than these of RDX and HMX. The compound is a potential energetic compound of desirable explosive properties. The characteristics of reaction route designed are little steps and easily-found raw material.

Key words: 3,6-bis(3,5-dinitro-1,2,4-triazol-1-yl)-1,2,4,5-tetrazine-1,4-dioxide, density functional theory, isodesmic reaction, detonation property, impact sensitivity, retrosynthesis analysis