Cycloreversion of 1-(1-Naphthyl)-5-phenylbicyclo[3.2.0]hept-6-ene to 1-(1-Naphthyl)-4-phenyl-1,3-cycloheptadiene by Triplet Sensitization and Direct Irradiation

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Author(s)

    • ARIMURA Junichi
    • Department of Material Science, Faculty of Engineering, Miyazaki University
    • YASUDA Masahide
    • Department of Material Science, Faculty of Engineering, Miyazaki University
    • SHIMA Kensuke
    • Department of Material Science, Faculty of Engineering, Miyazaki University
    • TAKAMUKU Setsuo
    • The Institute of Scientific and Industrial Research, Osaka University

Abstract

The cycloreversion of 1-(1-naphthyl)-5-phenylbicyclo[3.2.0]hept-6-ene (<b>1b</b>) to 1-(1-naphthyl)-4-phenyl-1,3-cycloheptadiene (<b>2b</b>) upon benzophenone (BP) sensitization and direct irradiation has been investigated. The triplet sensitization of <b>1b</b> in benzene gave <b>2b</b> quantitatively up to a stationary state where the quantum yield was 0.96. The triplet state of <b>2b</b> (<i>λ</i><sub>max</sub> = 455 nm, <i>τ</i> = 4.6 μs) was formed by the pulse radiolysis of <b>1b</b> in benzene. It has been found that cycloreversion proceeds by an adiabatic mechanism via a triplet state. The quantum yield for the formation of <b>2b</b> by the irradiation of <b>1b</b> at 313 nm was determined to be 0.17 in hexane. The fluorescence spectra of <b>1b</b> and <b>2b</b> indicated that diabatic cycloreversion occurred via a singlet state. The singlet and triplet energies of <b>1b</b>, as well as those of <b>2b</b>, were estimated to be 88, 60, 72, and 39 kcal mol<sup>−1</sup>, respectively. The effect of a substitution of the naphthalene chromophore on bicyclo[3.2.0]hept-6-ene was estimated.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 69(5), 1313-1317, 1996-05-15

    The Chemical Society of Japan

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Codes

  • NII Article ID (NAID)
    10008903072
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • Data Source
    CJP  J-STAGE 
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