A New Construction of Organic Reaction Theory Based on the Consideration of the MO Phases

基于MO相考虑的有机反应理论新构建

基本信息

批准号：
03804034
负责人：
NOHIRA Hiroyuki
金额：
$ 1.28万
依托单位：
Saitama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

We have proposed a principle of orbital-phase conservation which comprises that in an elementary reaction the phases of molecular orbitals of the reactant should be conserved in those of the product with minimum deformation. As the conservation of orbital-phase is very important concept in this principle, we have attempted to formulate this concept.First, we consider an elementary reaction from A to B, the conservation of orbital-phase are shown as eq.(1). N=<PSI^B|Q|PSI^A> (1)Here, N is a conservation factor which exhibits the correlation between the wave functions of A and those of B, Q is an appropriate operator for the reaction from A to B. N_<ij> corresponds to the overlap integral between |PSI_j^B> and Q|PSI_i^A>. The conservation of orbital-phase is estimated by |N_<ij>|^2, because a sign of N_<ij> is not significant.Second, the total conservation factor is defined as PHI_<ij>・・・kl=|N_<ij>|^2・・・|N_<kl>|^2 (2)A correlation diagram for an elementary reaction corresponds to a total conservation factor, the most appropriate one corresponds to the largest value of the total conservation factor.Here, we apply the principle to analyze the cis-trans isomerization of olefins and the electrocyclic reactions employing the simple Huckel MO calculations. The result obtained demonstrates that the method is applicable and virtually compatible with the experimental facts.On the other hand, the toropones having pi-electrons were synthesized and analyzed with MO calculations.

我们提出了一个轨道循环保守的原理，该原理包括在基本反应中，反应物的分子轨道的相应在产物的分子轨道相位以最小变形为单位。由于轨道相的保护是该原理非常重要的概念，因此我们试图形成这一概念。首先，我们考虑从A到B的基本反应，因此轨道相的保守性显示为等式（1）。 n = <psi^b | q | psi^a>（1）在这里，n是一个保护因素，它表现出A与B，Q的波函数之间的相关性，是A到B到B的反应的合适算子B。n_<ij>对应于| psi_j^b>和q | psi_i_i^a>之间的重叠积分。 The conservation of orbital-phase is estimated by |N_<ij>|^2, because a sign of N_<ij> is not significant.Second, the total conservation factor is defined as PHI_<ij>・・kl=|N_<ij>|^2・・|N_<kl>|^2 (2)A correlation diagram for an elementary reaction corresponds to a total conservation factor, the most appropriate one corresponds to the在这里，我们采用原理来分析烯烃的顺式转移异构化和采用简单的Huckel MO计算的电循环反应。获得的结果表明，该方法适用于实验事实。另一方面，与MO计算合成并分析了具有PI-ELECTRON的Toropones。