高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (1): 106.

• 研究论文 • 上一篇    下一篇

锗苯与亲二烯体的Diels-Alder反应的理论研究

王岩1, 曾小兰1, 方德彩2   

  1. 1. 信阳师范学院化学化工学院, 信阳 464000;
    2. 北京师范大学化学学院, 北京 100875
  • 收稿日期:2009-03-17 出版日期:2010-01-10 发布日期:2010-01-10
  • 通讯作者: 王岩, 男, 博士, 副教授, 主要从事计算化学研究. E-mail: wangyanxytc@163.com
  • 基金资助:

    国家自然科学基金(批准号: 20773016)和河南省基础与前沿技术研究计划项目(批准号: 092300410207)资助.

Theoretical Study on the Diels-Alder Reactions Between Germabenzenes and Dienophiles

WANG Yan1*, ZENG Xiao-Lan1, FANG De-Cai2   

  1. 1. College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, China;
    2. College of Chemistry, Beijing Normal University, Beijing 100875, China
  • Received:2009-03-17 Online:2010-01-10 Published:2010-01-10
  • Contact: WANG Yan. E-mail: wangyanxytc@163.com
  • Supported by:

    国家自然科学基金(批准号: 20773016)和河南省基础与前沿技术研究计划项目(批准号: 092300410207)资助.

摘要:

采用密度泛函理论方法在B3LYP/6-311G(d,p)水平上研究了锗苯与一些亲二烯体的Diels-Alder反应的微观机理和势能剖面, 考察了取代基和苯溶剂对反应势能剖面的影响, 探讨了杂Diels-Alder反应中区域选择性的起源. 计算结果表明, 所研究反应均以协同的方式进行. 亲二烯体分子碳原子上的苯基取代基对杂Diels-Alder反应中2个新键形成的非同步性和活化能垒的影响与最终产物中苯基和锗原子间的相对位置有关, 锗苯分子中锗原子上的CCl3取代基在热力学和动力学上均有利于反应的进行. 苯溶剂对所研究反应的势能剖面影响较小. 实验观察到的杂Diels-Alder反应的区域选择性由动力学因素所控制.

关键词: 锗苯; 亲二烯体; Diels-Alder反应; 反应机理; 密度泛函理论

Abstract:

Density functional theory(DFT) calculations, at the B3LYP/6-311G(d,p) level of theory, were performed to study the reaction mechanism and potential energy surface of the Diels-Alder reactions between germabenzenes and some dienophiles. The influences of substituents and benzene as a solvent on the potential energy surface of the hetero-Diels-Alder reactions were investigated and the origin of regioselectivity in the he-tero-Diels-Alder reactions was explored. Our calculation results show that all of studied reactions proceed in a concerted way. The influences of phenyl at C atom of dienophiles on the asynchronicity in the bond-formation process and activation barrier of reaction are closely related to the relative position of phenyl with respect to Ge atom in products. The CCl3 group at Ge atom of germabenzene molecule is in favor of process of the hetero-Diels-Alder reactions and solvent effect is not crucial for the potential energy surfaces of the studied reactions. The present calculations reproduce the regioselectivity observed experimentally in hetero-Diels-Alder reactions, which indicates that the kinetic factor controls the reaction proceeding.

Key words: Germabenzene; Dienophile; Diels-Alder reaction; Reaction mechanism; Density functional theory

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