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1992 Fiscal Year Final Research Report Summary

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

Research Project

Project/Area Number 03804034
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionSaitama University

Principal Investigator

NOHIRA Hiroyuki  Saitama Univ., Faculty of Engineering, Professor, 工学部, 教授 (50008819)

Co-Investigator(Kenkyū-buntansha) MIYASHITA Akira  Saitama Univ., Faculty of Engineering, Assistant Professor, 工学部, 助教授 (90132729)
MACHIGUCHI Takahisha  Saitama Univ., College of Liberal Arts and Science, Professor, 教養部, 教授 (00008864)
Project Period (FY) 1991 – 1992
KeywordsOrbital-Phase conservation / Woodward-Hoffmann rule / cis-trans isomerization / Electrocyclic Reaction / Correlation diagram / Frontier Orbital / Tropone / Spiropyran
Research Abstract

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.

  • Research Products

    (8 results)

All Other

All Publications (8 results)

  • [Publications] T.MACHIGUCHI: "A Simple Synthesis of Pure 2-Aminotroponimine, the NItrogen Analogue of Tropone" Chemistry Letter. 1821-1822 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.HIGASHI: "Magnetic Circular Dichroism and Electronic Apectra of Tropotione" Helvetica Chimica Acta. 75. 1880-1884 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.YAMABE: "Frontier Orbitals along Intrinsic Reaction Coordinates of Sulfur-aontaining [4+2] and [8+2] Cycloadditions" Journal of Organic Chemistry. 58. IN PRESS (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.MACHIGUCHI: "Novel Cage Molecules From the Reaction of 8,8-Dicyanoheptafulvene with Cycloheptadienide Anion: Structure and Mechanism" Joernal of the American Chemical Sciety. 115. 1004-1012 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Machiguchi, et al.: "A Simple Synthesis of Pure 2-Aminotroponimine, the Nitrogen Analogue of Tropone" Chemistry Letter. 1821 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Higashi, et al.,: "Magnetic Circular Dichromism and Electronic Spectra of Tropotione" Helvetica Chimica Acta. 75. 1880 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Yamabe, et al.: "Frontier Orbitals along Intrinsic Reaction Coordinates of Sulfur-containing [4+2] and [8+2] Cycloadditions" Journal of Organic Chemistry,.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Machiguchi, et al.: "Novel Cage Molecules from the Reaction of 8,8-Dicyanoheptafulvene with Cycloheptadienide Anion: Structure and Mechanism" Journal of American Chemical Society. 115. 1004 (1993)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1994-03-24  

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