高等学校化学学报

高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (9): 1506.

• 研究论文 • 上一篇    下一篇

应用AM1方法研究3-芳胺甲烯基-6-烷基-5,6-二氢-二氢吡喃-2,4'-二酮的催化氢化反应机理

方亚寅1,2, 沈荣欣2, 孙宏伟2, 袁满雪2, 刘洁2,3, 李正名2,3, 赖城明2,3   

  1. 1. 徐州师范大学化学系, 徐州 221009;
    2. 南开大学化学学院, 天津 300071;
    3. 南开大学元素有机化学国家重点实验室, 天津 300071
  • 收稿日期:2000-08-19 出版日期:2001-09-24 发布日期:2001-09-24
  • 通讯作者: 赖城明(1934年出生),男,博士,教授,博士生导师,主要从事分子模拟及结构化学研究.
  • 基金资助:

    国家自然科学重点基金(批准号:29832050)资助

AM1 Study on the Mechanism of Catalytic Hydrogenation of 3-Anilinomethy lidene-6-alkyl-5,6-2H-dihydropyran-2,4-diones

FANG Ya-Yin1,2, SHEN Rong-Xin2, SUN Hong-Wei2, YUAN Man-Xue2, LIU Jie-LI Zheng-Ming2,3, LAI Cheng-Ming2,3   

  1. 1. Department of Chemistry, Xuzhou Normal University, Xuzhou 221009, China;
    2. College of Chemistry, Nankai University, Tianjin 300071, China;
    3. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianj in 300071, China
  • Received:2000-08-19 Online:2001-09-24 Published:2001-09-24

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摘要： 以3-(对甲基)苯胺甲烯基-6-甲基-5,6-二氢-二氢吡喃-2,4'-二酮为例,用半经验量子化学方法和UHF/6-311G水平上的从头算研究了3-芳胺甲烯基-6-烷基-5,6-二氢-二氢吡喃-2,4'-二酮类农药化合物催化氢化的反应机理.通过对反应物、中间物和产物的生成热、净电荷、键序以及前线轨道能量的计算和分析认为标题化合物的催化氢化反应不仅发生了碳碳双键的加成反应,还同时发生了碳氮键的催化氢解反应.

关键词: AM1, 催化氢化, 反应机理, 二氢吡喃-2, 4'-二酮

Abstract: 3-(p-Methyl) anilinomethylidene 6-methyl 5,6-Hdihydropyran-2,4-dione was selected as model reactant to study the mechanism of catalytic hydrogenation of 3-anilinomethylidene 6-alkyl-5,6-2Hdihydropyran-2,4-diones by means of the AM1 and UHF/6-311Gmethods. The molecular informations such as heats of formation, net charges, bond orders, the values of frontier orbital energies, composition, their proportion and bonding contribution were acquired and analyzed. Thus the possible reactive sites were put forward and the reaction mechanism was postulated via two steps. The postulated intermediates and products of the two steps were also computed by AM1 method. Their heats of formation and energies of HOMO/LOMO/LUMOindicate that the mechanism of catalytic hydrogenation of 3-anilinomethylidene 6-alkyl-5,6-2Hdihydropyran-2,4-diones is not only a hydrogenolytic addition on CCbond but also a hydrogenolytic cleavage of the C-Nbond of anilinomethylidene.

Key words: AM1, Catalytic hydrogenation, Reaction mechanism, Dihydropyran-2,4-dione

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