Abstract：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.
许晓娟,肖鹤鸣,贡雪东,居学海. NO2气相硝化金刚烷的计算研究[J]. 化学学报, 2006, 64(4): 306-312.
XU Xiao-Juan1,2, XIAO He-Ming*,1, GONG Xue-Dong, JU Xue-Hai. Computational Studies on the Nitration of Adamantane with NO2. Acta Chimica Sinica, 2006, 64(4): 306-312.