Studies on the Reactivities of Radical Anions of Norbornadiene and Quadricyclane Derivatives by Pulse Radiolysis

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  • NISHINO Hideo
    The Institute of Scientific and Industrial Research, Osaka University
  • SHIDA Tadamasa
    Department of Chemistry, Faculty of Science, Kyoto University
  • TAKAMIJKU Setsuo
    The Institute of Scientific and Industrial Research, Osaka University

Bibliographic Information

Other Title
  • パルスラジオリシスによるノルボルナジエン-クアドリシクラン誘導体のラジカルアニオンの化学反応性
  • パルス ラジオリシス ニ ヨル ノルボルナジエン クアドリシクラン ユウドウタ

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Description

Chemical reactivities of radical anions of dimethylbicyclo[2.2.1]hepta-2, 5-diene-2, 3-dicarboxylate(NE) and dimetyltetracyclo[3.2.0.02.04, 6]heptane-1, 5-dicarboxylate(QE) have been investigated by pulse radiolysis of hexamethylphosphorictriamide(HMPA) solutions and 77 K r irradiation of 2-methyltetrahydrofuran(MTHF) solutions. Solvated electrons were captured by QE in HMPA with a rate constant of 1.3 x 10 dmol-i-i at room temperature. The resultant radical anion of QE, which could not be detected, isomerized to NE radical anion very rapidly, even at 77 K.<BR>On the other hand, the NE radical anion which was formed from NE and solvated electron with a diffusion-controlled rate, did not isomerize to QE radical anion but reacted with a neutral NE molecule with a rate constant of 1.2 x 107 dm3ol-1-'. The dimer anion thus formed shows a strong UV absorption band at wavelengths shorter than 330 nm and was estimated to be a a-bonded dimer. For the r radiolysis of HMPA solution of NE, it has been observed that G(E) depends on the concentration of NE and reached 142 at 0.04 molm-3 of NE, suggesting a chain reaction to form polymeric products.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1984 (11), 1842-1848, 1984-11-10

    The Chemical Society of Japan

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