Theoretical Studies on the reaction control and the molecular design for the ground and excited states of electrocyclic reactions

电环反应基态和激发态的反应控制和分子设计的理论研究

• 批准号: 11650852
• 负责人: SAKAI Shogo
• 金额: $ 2.18万
• 依托单位: Osaka Sangyo University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650852/
• 关键词: electro-cyclic reaction; Cope rearrangements; 1,3-Dipolar; CiLC-IRC; IMiC MO; ab initio MO; ぺり環状反応; IMiC MO; ab innitio MO; o-Xylylene; ab initio MO; 芳香族性; 視覚化プログラム; Diels-Alder反応; Conical Intersection; ヘキサトリエン; ブタジェン

Four projects as peri-cyclic reactions were investigated by theoretical methods.(1) The substitution effects of phenyl group for the Cope rearrangements of 1,5-hexadiene. From our calculation results, the Cope rearrangement is classified into two types: concerted reaction through the transition state with aromaticity and bi-radical path with intermediate.(2) The CiLC- IRC analysis for the reaction mechanisms of cyclic reactions of two ethylene. The two reaction mechanisms, supra and antara, for cyclic reaction of two ethylene were analyzed by the CiLC-IRC method. The both reaction mechanisms occur through the sudden polarized states, and are in the control of overlap between both orbitals.(3) The CiLC-IRC analysis for the reaction mechanisms of 1,3-Dipolar reactions. The reaction mechanisms of 1,3-Dipolar reaction were investigated by ab initio MO methods. The activation energies are govern with the dissociation energies of bi-radical type for double bond part.(4) The development of the molecular orbital methods including solvent effects for the molecular dynamics. New molecular orbital method (IMiC MO) for molecular dynamics were presented.

通过理论方法研究了四个项目作为周期反应。（1）苯基对1,5-己二烯的COPE重排的替代作用。从我们的计算结果中，应对重排被分为两种类型：通过过渡状态通过中间体进行芳香性和双激进路径的协同反应。通过CILC-IRC方法分析了两个乙烯环反应的两种反应机制，即上文和安塔拉。两种反应机制都通过突然的极化状态出现，并控制了两个轨道之间的重叠。（3）1,3-二元反应的反应机理的CILC-IRC分析。通过Ab Itible MO方法研究了1,3-肺电反应的反应机理。激活能以双键部分的双激进类型的分离能进行控制。（4）分子轨道方法的发展，包括分子动力学的溶剂效应。提出了用于分子动力学的新分子轨道方法（IMIC MO）。

项目成果

S.Sakai: "Theoretical Analysis of Concerted and Stepwise Mechanisms of Diels-Alder Reaction Between Butadiene and Ethylene"J.Phys.Chem.A. (印刷中).

S.Sakai：“丁二烯和乙烯之间 Diels-Alder 反应的协同和逐步机理的理论分析”J.Phys.Chem.A（出版中）。

S.Morita, S.Sakai: "IMiCMO : A New Integrated Ab Initio Multi-Center Molecular Orbital Method for Molecular Dynamics Calculations in Solvent Cluster Systems"J.Comp.Chem.. 22. 1107-1112 (2001)

S.Morita, S.Sakai：“IMiCMO：一种新的集成从头算多中心分子轨道方法，用于溶剂簇系统中的分子动力学计算”J.Comp.Chem.. 22. 1107-1112 (2001)

S. Sakai: "Theoretical Analysis of the Cope Rearrangement of 1,5-Hexadiene and Phenyl Derivatives"J. Mol. Strct. (THEOCHEM). (in press).

S. Sakai：“1,5-己二烯和苯基衍生物的Cope重排的理论分析”J。

S. Sakai: "Theoretical Analysis of Cyclic Reaction Mechanisms of Two Ethylenes"Int. J. Quantum Chem.. (in press).

S. Sakai：“两种乙烯的循环反应机理的理论分析”Int。

S.Sakai and S.Takane: "Theoretical Studies on the Electrocyclic Reaction Mechanisms of Hexatriene to Cyclohexadiene"J.Phys.Chem.A. 103. 2878-2882 (1999)

S.Sakai和S.Takane：“己三烯到环己二烯的电循环反应机理的理论研究”J.Phys.Chem.A.