Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Photochemistry of Some 1,1'-Dicycloalkenyls. The Mechanism of Sensitized Photocyclization

1,1'-디시클로알케닐 화합물에 대한 광화학적 연구

  • Sang Chul Shim (Department of Chemical Science, The Korea Advanced Institute of Science) ;
  • Frederick P. Targos (Undergraduate Research, Participant at PIB)
  • 심상철 (한국과학원 화학 및 화학공학과) ;
  • Published : 1976.06.30
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Abstract

The photocyclization of 1,1'-dicycloalkenyls (1,1'-dicyclohexenyl, 1,1'-dicyclopentenyl, 1,1'-dicycloheptenyl and 1,1'-dicyclooctenyl) is studied. Irradiation at liquid nitrogen temperature does not show trans double bond band in IR spectra. Even though naphthalene and pyrene fluorescence are quenched very efficiently by 1, 1'-dicycloalkenyls, no or trace amount of cyclobutenes are accompanied. When acetophenone or benzophenone is used, cyclobutene is obtained only from 1,1'-dicyclohexenyls, 1,1'-dicycloheptenyl giving some adducts. Naphthalene and pyrene sensitizes adduct formation but not cyclization. From above observations, it is concluded that photocyclization occurs from the planar s-cis triplet state rather than twisted triplet, singlet excited state or vibrationally excited ground state in sensitized photocyclization of 1,1'-dicycloalkenyls.

1,1'-디시클로알케닐의 광고리화 반응을 형광 퀘ㄴ칭, 증감제등을 써서 연구하였다. 증감제를 쓰는 경우 이 디엔의 광고리화 반응은 비틀린 삼중상태나 평면구조의 트란스 삼중상태보다 높은 에너지 준위에 있는 평면구조의 s-시스 삼중상태에서 일어남을 알았다.

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