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化学学报
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化学学报 ›› 2006, Vol. 64 ›› Issue (12): 1228-1236. 上一篇    下一篇

研究论文

3-羟基哒嗪及其CH3, NO2和Cl取代衍生物质子转移过程的理论研究

周子彦1,3，谢玉忠1，苏忠民2，赵继阳1，金正哲1， 吴学*,1,3   

  1. (1延边大学理学院化学系 延吉 133002)
    (2东北师范大学化学学院 功能材料化学研究所 长春 130024)
    (3延边大学长白山天然资源和功能分子教育部重点实验室 延吉 133002)
  • 投稿日期:2005-10-02 修回日期:2006-02-20 发布日期:2006-06-28
  • 通讯作者: 吴学

Theoretical Investigation of Proton-Transfer Reactions of 3-Hydropyridazine and Its Derivatives Bearing Methyl, Nitro or Chloro Groups

ZHOU Zi-Yan1,3, XIE Yu-Zhong1, SU Zhong-Min2, ZHAO Ji-Yang1, JIN Zheng-Zhe1, WU Xue*,1,3   

  1. (1 Department of Chemistry, College of Science, Yanbian University, Yanji 133002)
    (2 Department of Chemistry, Institute of Functional Material Chemistry, Northeast Normal University, Changchun 130024)
    (3 Key Laboratory of Natural Resources of the Changbai Mountain and Functional Molecules, Ministry of Education, Yanbian University, Yanji 133002)
  • Received:2005-10-02 Revised:2006-02-20 Published:2006-06-28
  • Contact: WU Xue

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用密度泛函理论(DFT) B3LYP方法, 在6-311＋G*基组下, 对3-羟基哒嗪及其CH3, NO2和Cl取代衍生物分子醇式和酮式结构互变异构化反应进行了研究, 优化化合物的几何构型, 寻找反应的过渡态, 通过振动分析和内禀反应坐标(IRC)分析加以证实, 计算了反应的活化能. 结果表明, 3(2H)-哒嗪酮及其带取代基的衍生物不论是单体, 还是相对应的二聚体, 比其相对应的异构体能量低, 表明在通常情况下是以3(2H)-哒嗪酮及其衍生物形式稳定存在的, 这与前人通过实验数据对3-羟基哒嗪互变异构体的比率进行预测的结果是一致的. 根据计算结果讨论了异构化反应的机理.

关键词: 3-羟基哒嗪, 密度泛函理论, 互变异构, 过渡态, 质子转移

Density functional theory B3LYP method at the 6-311＋G* basis set was used to investigate the mechanism of tautomerism between enol form and keto form of 3-hydropyridazine as well as its methyl, nitro or chloro derivatives, with the geometric structures of reactants, transition states and products optimized completely. In addition, the transition states have been explored and proved by vibration analysis and intrinsic reaction coordination analysis, and meanwhile, the total energies and reaction activation energies have been calculated. The results showed that the most stable isomers are compounds with the structure of 2-hydropyridazin-3-one or its derivatives compared with the other corresponding isomers, which was in good agreement with the previous reports that predicted the ratio of isomers by experimental data. The mechanism of the isomerization was discussed on the basis of the theoretical values.

Key words: 3-hydropyridazine, density functional theory, tautomerism, transition state, prototropy