Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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MO Theoretical Studies on 1,5-Sigmatropic Hydrogen Shifts in Systems with Terminal Heteroatoms, O and S

말단 헤테로원자가 산소(O)와 황(S)인계의 1,5-수소원자 이동반응에 관한 MO 이론적 연구

  • 김호순 (인하대학교 이과대학 화학과) ;
  • 이익춘 (인하대학교 이과대학 화학과)
  • Published : 1986.04.20
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Abstract

MO studies have been carried out on 1,5-hydrogen shifts between tautomeric forms (6${\pi}$ system) of ${\beta}$-diketones, ${\beta}$-thioxoketones and ${\beta}$-dithioketones by determining transition state and analyzing structural stability effects on the activation barriers using MNDO method. The barrier was found to increase with the stability of the ground state having greater charge separation and with the increase (less stabilization) in the one electron energy ${\Delta}(2\sum\limits^{occ}{\varepsilon}i)^{\neq}$ in the activation process.

${\beta}$-diketones, ${\beta}$-thioxoketones and ${\beta}$-dithioketones류의 tautomeric forms (6${\pi}$ 전자계)의 1,5-H shift에 관해서 MNDO 방법으로 전이상태 구조를 결정하고, 활성화 에너지 장벽에 미치는 구조적 안정성을 분석하였다. 그 결과 1전자항 ${\Delta}( 2\sum\limits^{occ}{\varepsilon}_i)^{\neq}$ 이 증가할수록 활성화 장벽이 큼을 알았다. 또한 말단 헤테로원자의 하전분리가 클수록 바닥상태 분자의 안정성이 크며, 활성화 에너지 장벽$({\Delta}E^{\neq})$이 크다.

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