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

我们提出了一个轨道相位保护的原则，它包括在一个基本反应中反应器的分子轨道相位应该在那些具有最小变形的产品中得到遵守。由于轨道相位的保护在这个原则上是一个非常重要的概念，我们已经尝试将其格式化为这个概念。首先，我们认为从A到B的基本反应，轨道相位的保护显示为eq。（一）; N=<PSI^B| Q（Q）|PSI^A> （1）这里， N是A和B的波函数之间的相关关系的保护因子，而Q是A到B反应的适当运算符。N_<ij>对重叠积分之间的正确回应|PSI_j ^B&gt;和Q| PSI_i ^A&gt;.对轨道阶段的保护已被估计为|N_N_<ij>|^2，因为N_的信号<ij>并不重要，第二，总保护因子被定义为PHI_<ij>... kl=| N_N_<ij>|第二个..。|N_N_<kl>|^2 （2）对总保护因子的基本反应对应关系图，对总保护因子价值最高的对应关系图，在此，我们应用原则来分析烯烃的顺式异构化和电循环反应，利用简单的Huckel MO计算。获得的演示结果表明，该方法是适用的，并且与实验事实兼容。在另一方手中，转子子被合成和分析了，并与MO计算。

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.