Pyrolysis of 1-Methycycloalkyl (Substituted phenyl) Sulfoxide

DOI Web Site Web Site 16 References
  • YOSHIMURA Toshiaki
    Department of Industrial Chemistry, Faculty of Engineerin g, Toyama University;
  • SEKIOKA Tadayasu
    Department of Industrial Chemistry, Faculty of Engineerin g, Toyama University;
  • TSUKURIMICHI Eiichi
    Department of Industrial Chemistry, Faculty of Engineerin g, Toyama University;
  • SIMASAKI Choichiro
    Department of Industrial Chemistry, Faculty of Engineerin g, Toyama University;
  • HASEGAWA Kiyoshi
    Department of Industrial Chemistry, Faculty of Engineerin g, Toyama University;

Bibliographic Information

Other Title
  • 1一メチルシクロアルキル=(置換フェニル)=スルホキシドの熱分解反応
  • 1-メチルシクロアルキル=(置換フェニル)=スルホキシドの熱分解反応
  • 1 メチルシクロアルキル チカン フェニル スルホキシド ノ ネツ ブンカイ

Search this article

Abstract

The effect for the pyrolysis of the ring size of cycl oalkyl group in 1-methylcycloalkyl (substituted phenyl) sulfoxide was investigated using three kinds of the substrates having cyclopentyl, cyclohexyl and cycloheptyl groups.<BR>Taking the rate constant for the cyclo hexyl sulfoxide as a reference substrate (k=1.86 X 10-4s-1 in dioxane at 100.0 °C), the reaction rates of the other two substrates were abou t seven times for the 5-membered and thirty six times for the 7-membered, respectively, larger than that of the 6-membered. The mixtures of methylenecycloalkane (exo-olefin)and 1-mehylcycloalkene (endo-olefin) as pyrolytic products were obtained from the substrates. The ratio of olefin isomers, (exo/endo), of the 6-membered substrate was much larger than the others, respective ratio of 5-, 6- and 7-membered ones being 0.04: 4.38: 0.15. The distinguished results for the pyrolysis manner of the 6-membered substrate compared with the others were considered to be due to bring on the steric strain in six-membered ring to get the endo-olefin isomer.<BR>Activation paramet e rs for the cyclohexyl sulfoxides were estimated as Ea=ca.121 kJmol-'and 4, 54-= 1.7 JK-1mol-1. Substituent effect on phenyl group in the reference substrate correlated well with Hammett a constants with p value of ca. +0.9 (γ =0.984). The solvent effect on the pyrolysis was not observed as in the pyrolysis of other sulfoxides and sulfilimines. The kinetic isotope effect for p-hydrogen in cyclohexyl group of the referen ce substrate was relatively large (4, 14=4.6). On the basis of these results, it was suggested that the pyrolysis of 1-methycycloalkyl phenyl sulfoxide proceeds via E 1 like mechanism in a transition state.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1992 (8), 817-823, 1992-08-10

    The Chemical Society of Japan

References(16)*help

See more

Keywords

Details 詳細情報について

Report a problem

Back to top