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

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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.