Acta Chimica Sinica ›› 2011, Vol. 69 ›› Issue (03): 269-276. Previous Articles     Next Articles

Full Papers

苯的硝基和叠氮基衍生物的理论研究

杜洪臣1,许晓娟2,刘彦1,刘卉1,王芳1,张建英1,贡雪东*,1   

  1. (1南京理工大学化学系 南京 210094)
    (2盐城师范学院化学系 盐城 224002)
  • 收稿日期:2010-07-14 修回日期:2010-08-29 出版日期:2011-02-14 发布日期:2010-09-30
  • 通讯作者: 贡雪东 E-mail:gongxd325@163.com
  • 基金资助:

    江苏省高校自然科学基础研究项目

Theoretical Studies on the Nitro and Azido Derivatives of Benzene

Du Hongchen1 Xu Xiaojuan2 Liu Yan1 Liu Hui1 Wang Fang1 Zhang Jianying1 Gong Xuedong*,1   

  1. (1 Department of Chemistry, Nanjing University of Science and Technology, Nanjing 210094)
    (2 Department of Chemistry, Yancheng Teachers University, Yancheng 224002)
  • Received:2010-07-14 Revised:2010-08-29 Online:2011-02-14 Published:2010-09-30
  • Contact: Xue-Dong GONG E-mail:gongxd325@163.com

The geometries of the nitro and azido substituted derivatives of benzene were optimized at the B3LYP/6-31G* level of density functional theory, the detonation velocity and pressure were calculated with the Kamlet-Jacobs method and eleven candidates satisfying the energetic requirements for high energy density compound (HEDC) were found. The bond dissociation energies (BDE) of the possible trigger bonds were computed for these candidates and the activation energy (Ea) of the pyrolysis process following “furoxan mechanism” were also evaluated for the candidates with the adjacent nitro and azido groups. The calculated results show that Ea is much lower than BDE, implying that when there are adjacent azido and nitro groups in molecule, the stability of compounds will be greatly decreased and the pyrolysis happens in “furoxan mechanism”. Otherwise, the pyrolysis will be initiated from the rupture of C-NO2 or C-N3 bond. The calculated BDE are essentially larger than 200 kJ/mol and all Ea are larger than 100 kJ/mol, therefore, the eleven candidates basically satisfy the energetic and stability requirements as HEDC.

Key words: benzene, azido, nitro, density functional theory, detonation property, pyrolysis mechanism