1,4-Diaza-1,3-butadiene류의 Diels-Alder반응에 미치는 치환기 효과에 대한 DFT연구

DFT Studies for the Substituent Effect on the Diels-Alder Reaction of 1,4-Diaza-1,3-butadiene

  • 이갑용 (대구가톨릭대학교 자연대학 화학과)
  • Lee, Gab-Yong (Department of Chemistry, Catholic University of Taegu)
  • 발행 : 20010600

초록

1.4-Diaza-1,3-butadiene(1,4-DAB)과 acrolein 과의 Diels-Alder 반응의 반응성을 조사하기 위해 1,4-DAB의 말단 두 질소에 전자를 끌거나 주는 기들을 치환시킨 여러 치환 1,4-DAB들에 대해 DFT계산을 수행하였다. 최적화된 구조들에 대해 계산된 FMO(Frontier Mole cular Orbital) 에너지로서 상대적인 반응성을 설명할 수 있었다. 즉, 전자를 주는 기가 치환될 경우에는 normal electron demand 반응이 유리하며, 전자를 끄는 기가 치환될 경우에는 inverse electron demand 반응 메카니즘으로 진행됨을 알 수 있었다.

DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4-DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular Orbital) energies for the optimized 1,4-disubstituted-1,4-DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively.

키워드

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