Acta Chimica Sinica ›› 2006, Vol. 64 ›› Issue (4): 306-312. Previous Articles     Next Articles

Original Articles

NO2气相硝化金刚烷的计算研究

许晓娟1,2,肖鹤鸣*,1,贡雪东1,居学海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:2005-05-08 修回日期:2005-10-24 出版日期:2006-02-28 发布日期:2006-02-28
  • 通讯作者: 肖鹤鸣

Computational Studies on the Nitration of Adamantane with NO2

XU Xiao-Juan1,2, XIAO He-Ming*,1, GONG Xue-Dong1, JU Xue-Hai1   

  1. (1 Chemistry Department of Nanjing University of Science and Technology, Nanjing 210094)
    (2 Yancheng Normal College, Yancheng 224002)
  • Received:2005-05-08 Revised:2005-10-24 Online:2006-02-28 Published:2006-02-28
  • Contact: XIAO He-Ming

The density functional theory (DFT) and semi-empirical MO-PM3 methods were employed to study the reaction mechanism of the nitration of adamantane with NO2. The calculated results showed that the H atom in adamantane can not be directly substituted with NO2. By comparing the potential barriers Ea of the three possible reaction mechanisms at the B3LYP/6-311++G(3df,2pd)//B3LYP/6-31G* level, it was found that the process of N to attack H competed with that of O to attack H during the crucial step, and 1-nitroadamantane was considered to be the main product. In addition, the changes of molecular geometry, atomic natural charge and IR spectra of the reaction system during the crucial step of O to attack H showed that the rupture of C—H bond and the formation of O—H bond were concerted stepwise. Obvious changes of atomic natural charge happened to atoms C(1), H(11), O(28), O(29) and N(27). The bond lengths and bond angles related to these atoms were also varied greatly. The dipole moment changes predicted that polar solvent could decrease reaction potential barrier Ea to facilitate the reaction.

Key words: adamantane, density functional theory, nitration mechanism, potential barrier