Kinetic Studies on the Nucleophilic Addition of Cysteine and Thioglycolic Acid to ${\beta},\;{\beta}$-Dichlorostyrene Derivatives

${\beta},\;{\beta}$-Dichlorostyrene 유도체의 Cysteine 및 Thioglycolic Acid에 대한 친핵성 첨가반응의 반응속도론적 연구

  • Tae-Rin Kim (Department of Chemistry, Korea University) ;
  • Jong-Yol Ryu (Department of Chemistry, Korea University) ;
  • Duk-Chan Ha (Department of Chemistry, Korea University)
  • 김태린 (고려대학교 이과대학 화학과) ;
  • 류정열 (고려대학교 이과대학 화학과) ;
  • 하덕찬 (고려대학교 이과대학 화학과)
  • Published : 1988.06.20


The rate constants for the nucleophilic addition reactions of thioglycolic acid and cysteine to ${\beta},\;{\beta}$-dichlorostyrene derivatives(p-H, p-Cl, $p-CH_3,\;and\;p-OCH_3$) were photochemically determined at various pH and a rate equation which can be applied over a wide pH range was obtained. On the bases of rate equation, general base catalysis and substituent effect, the plausible addition reaction mechanism was proposed: Above pH 9.0, the reaction was initiated by the addition of sulfide anion, and in the range of pH 7.0 to 9.0, the neutral molecules and it's anions attacked to the double bond, competitively. However, below pH 7.0, only the neutral molecules of thioglycolic acid or cysteine added to the carbon-carbon double bond.



  1. J. Am. Chem. Soc. v.95 T. R. Kim;T. I. Crowell
  2. Fast Reaction E. T. Caldin
  3. J. Org. Chem. v.43 H. O. Krabbenhoft
  4. Modern Synthetic Reaction H. O. House
  5. Tetraheron v.32 H. Esterbauer;A. Ertl;N. Scholtz
  6. Zertschrift fur Naturforc H. Esterbauer;H. Zollner;N. Scholtz
  7. J. Meienhofer, Notur v.233 R. A. Alarcon
  8. pharm. v.22 H. Zollner;Bichem
  9. 大韓化學會誌 v.12 金泰麟;崔永翔
  10. 大韓化學會誌 v.12 金泰麟;朴玉鉉
  11. 大韓化學會誌 v.12 金泰麟;朴玉鉉
  12. 大韓化學會誌 v.16 金泰麟;권동숙
  13. J. Chem. Soc. Z. Rapport;S. Geitter
  14. J. Am. Chem. Soc. v.78 W. E. Truce
  15. J. Am. Chem. Soc. v.102 C. F. Bernasconi;G. D. Leonarduzzi
  16. J. Am. Chem. Soc. v.104 C. F. Bernasconi;G. D. Leonarduzzi
  17. J. Org. Chem. v.51 C. F. Bernasconi;M. W. Stronach
  18. J. Am. Chem. Soc. v.108 C. F. Bernasconi;C. J. Murray.
  19. J. Am. Chem. Soc. v.108 C. F. Bernasconi;A Kanavarioti
  20. J. Am. Chem. Soc. v.84 A. S. Speziable
  21. J. Chem. Soc. v.B V. Ogata;I. Klshi
  22. J. Chem. Soc. H. Shemher;Z. Rapport;S. Patai
  23. J. Am. Chem. Soc. v.106 C. F. Bernascone;K. A. Moward;A. Kanavariot
  24. Physical Organic Chemistry J. Hine
  25. can. J. chem. v.47 J. A. Markisz;J. D. Getller
  26. 大韓化學會誌 v.17 金泰麟;許泰聖