Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Hydrolysis of 1-Halo-3-Phenyl-1,2-Propadienes

1-Halo-3-Phenyl-1,2-Propadiene들의 가수분해에 대한 반응속도론적 연구

  • Lee, Kang Ryul (Department of Chemistry, the Catholic Universitry of Korea) ;
  • Yoo, Hil Ra (Department of Chemistry, the Catholic Universitry of Korea) ;
  • Jung, In Chan (Department of Chemistry, Hanseo University) ;
  • Huh, Tae Sung (Department of Chemistry, the Catholic Universitry of Korea)
  • Published : 19970700
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Abstract

Extended Huckel Molecular Orbital (EHMO) calculations of haloallene (1-halo-3-phenyl-1,2-propadiene) derivatives have been performed. From the MO calculation data and kinetic experimental results, the mechanism for the hydrolysis of haloallenes is proposed.; Below pH 8.0, the hydrolysis proceeds through a solvent assisted $S_N1$ mechanism involving the formation of carbonium ion Ⅱ as intermediate. However above pH 9.5, the hydrolysis proceeds through an $S_N2'$ mechanism via transition state Ⅲ.

haloallene 유도체(1-halo-3-phenyl-1,2-propadiene)에 대해 EHMO계산을 하여, 에너지적으로 안정한 haloallene 분자의 구조를 결정하였다. MO 계산 데이터와 속도론적인 실험 결과로부터 haloallene의 가수분해반응 메카니즘을 제안하였다. pH 8.0 이하에서는 중간체로 carbonium ion Ⅱ이 생성되는 용매도움 $S_N1$ 메카니즘에 의해 진행된다. 그러나 pH 9.5 이상에서는 전위상태 Ⅲ를 거치는 $S_N2'$ 메카니즘에 의해 진행된다.

Keywords

References

  1. J. Parkt. Chem. v.35 Michael, A.
  2. The Chemistry of Alkene Patai, S.
  3. Structure and Mechanism in Organic Chemistry Ingold,C. K.
  4. J. Am. Chem. Soc. v.73 Heunion, G. F.;Maloney, D. E.
  5. J. Org. Chem. v.30 Jacobs, T. L.;Fenton, D. E.
  6. J. Chem. Soc.(C) Greaves, P. M.;Kall, M.;Landor, P. D.;Landor, S. R.
  7. J. Chem. Soc. (C) Landor, S. R.;Patel, A. N.;Whiter, P. F.;Greaves, P. M.
  8. J. Chem. Phys. v.39 Hoffmann, R.
  9. J. Chem. Phys. v.40 Hoffmann, R.
  10. J. Chem. Phys. v.41 Burns, G.
  11. J. Am. Chem. Soc. v.78 Fainberg, A. H.;Winstein, S.
  12. Acta. Chem. Scanc. v.19 Kivinen, A.