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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 21, Number 3
JKCSEZ 21(3)
June 20, 1977 

HMO Correlation Diagrams for a few Competing 1,2-and 1,4-Cycloaddition Reactions

경쟁 1,2-와 1,4-고리화 첨가반응의 상관도
Byung Kak Park

경쟁 1,2-와 1,4-고리화첨가반응에 대한 frontier 분자궤도와 전전자에너지의 상관도를 작도하고 이 상관도에 의해서 반응기구를 설명할 수 있었다. 고찰해서 유도된 중요 결론은 다음과 같다. 1) HO와 LU사이에 교차가 일어나지 않았다. 그러므로 반응은 열반응이다. 2) diradical을 경유하는 이단계기구가 일단계기구 보다 에너지장벽으로 미루어 보아 유리하다. 3) [2+2]와 [2+4] 고리화첨가물의 생성물분포를 예측할 수 있다.

HMO correlation diagrams for some competing 1,2-and 1,4-cycloaddition reactions have been made to elucidate the reaction mechanism. The main conclusions obtained from this study are as follows. 1) The crossing between the highest occupied molecular orbital and the lowest unoccupied molecular orbital was not observed, which indicates that the reaction proceeds thermally, in agreement with the experimental results. 2) From the consideration of the energy barrier in the process of the energy transformation going from reactants to product, the two-step mechanism via a diradical intermediate is preferred over the concerted one. 3) The existance of diradical intermediates can account for the observed product distributions.

155 - 160
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