利用四氯乙烷胺化反应合成联氢化嘧啶衍生物的研究

利用均四氯乙及二氯甲烷的胺化反应,合成了联氢化嘧啶衍生物1～5,4a,8b-反-4,5,8a,9a-四氮杂全氢芴(6)和8b,8c-顺-3a,4a,7a,8a-四氮杂环戊并全氢芴(7)。化合物(6)和(7)的顺反异构体在酸催化下开环,异构生成较稳定的6b和7a。     

Hydrogen abstraction reactions of hydroxyl radicals with 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane and pentachloroethane studied by using semi-classical transition state theory

The hydrogen abstraction reactions by OH radicals from CHCl₂CHCl₂ (R1), CH₂ClCCl₃ (R2) and C₂HCl₅ (R3) are investigated theoretically by semi-classical transition state theory. Many high-level density functional, ab initio and combinatory electronic structure calculation methods are used to evaluate the energies and ro-vibrational properties of the stationary points for the title reactions. x_ij vibrational anharmonicity coefficients, needed for semi-classical transition state theory, are calculated at the KMLYP/cc-pVTZ level of theory. Thermal rate coefficients are computed over the temperature range from 200 to 2000 K and compared with available experimental data. The computed rate constants for the reactions R1, R2 and R3 are fitted to the equation k(T) = ATⁿexp?[ ? E(T + T₀)/(T² + T²₀)].