본문 바로가기
HOME> 논문 > 논문 검색상세

논문 상세정보

European journal of organic chemistry v.2017 no.6, 2017년, pp.1052 - 1062   SCI SCIE
본 등재정보는 저널의 등재정보를 참고하여 보여주는 베타서비스로 정확한 논문의 등재여부는 등재기관에 확인하시기 바랍니다.

Expanding the Hammett Correlations for the Vinylheptafulvene Ring‐Closure Reaction

Kilde, Martin Drøhse (Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark ) ; Hansen, Mia Harring (Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark ) ; Broman, Søren Lindbæk (Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark ) ; Mikkelsen, Kurt V. (Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark ) ; Nielsen, Mogens Brøndsted (Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark ) ;
  • 초록  

    A selection of 2,3‐diarylated photochromic dihydroazulenes (DHAs) was prepared by following two different protocols. The first protocol relies on the synthesis of a 3‐bromo‐substituted dihydroazulene, which is subjected to a Suzuki cross‐coupling reaction in the final step. In the second protocol, the two aryl substituents are introduced early in the synthesis. The DHAs are photoactive and undergo light‐induced ring‐opening reactions to form vinylheptafulvene (VHF) isomers. These VHFs are quickly converted back to DHAs at room temperature in thermal ring‐closure reactions. The kinetics of these reactions was studied at –20 °C for two series for which the substituent at the C‐2 position (DHA numbering) was kept constant, and a linear free‐energy relationship (Hammett correlation) was revealed in both cases. The relationships show that an electron‐donating substituent at C‐3 (the exocyclic VHF carbon atom) enhances the ring‐closure reaction, in contrast to its influence when placed at C‐2. In a computational study (density functional theory), three different methods were benchmarked against the experimental results. Overall, this work shows for the first time how the VHF to DHA switch is influenced by donor–acceptor substitution at the exocyclic heptafulvene carbon atom.


  • 주제어

    Cyclization .   Donor–acceptor systems .   Fused‐ring systems .   Kinetics .   Photochromism.  

 활용도 분석

  • 상세보기

    amChart 영역
  • 원문보기

    amChart 영역

원문보기

무료다운로드
  • 원문이 없습니다.
유료다운로드

유료 다운로드의 경우 해당 사이트의 정책에 따라 신규 회원가입, 로그인, 유료 구매 등이 필요할 수 있습니다. 해당 사이트에서 발생하는 귀하의 모든 정보활동은 NDSL의 서비스 정책과 무관합니다.

원문복사신청을 하시면, 일부 해외 인쇄학술지의 경우 외국학술지지원센터(FRIC)에서
무료 원문복사 서비스를 제공합니다.

NDSL에서는 해당 원문을 복사서비스하고 있습니다. 위의 원문복사신청 또는 장바구니 담기를 통하여 원문복사서비스 이용이 가능합니다.

이 논문과 함께 출판된 논문 + 더보기