Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Kinetics Studies on the Mechanism of Hydrolysis of S-Phenyl-S-vinyl-N-p-tosylsulfilimine Derivatives

  • Published : 2003.03.20
Download PDF
⟨ Previous Next ⟩

Abstract

Hydrolysis reactions of S-phenyl-S-vinyl-N-p-tosylsulfilimine (VSI) and its derivatives at various pH have been investigated kinetically. The hydrolysis reactions produced phenylvinylsulfoxide and p-toluene sulfonamide as the products. The reactions are first order and Hammett ρ values for pH 1.0, 6.0, and 11.0 are 0.82, 0.45, and 0.57, respectively. This reaction is not catalyzed by general base. The plot of k vs pH shows that there are three different regions of the rate constants $(k_t)$ in the profile.; At pH < 2 and pH > 10, the rate constants are directly proportional to the concentrations of hydronium and hydroxide ion catalyzed reactions, respectively. The rate constant remains nearly the same at 2 < pH < 10. On the bases of these results, the plausible hydrolysis mechanism and a rate equation have been proposed: At pH < 2.0, the reaction proceeds via the addition of water molecule to sulfur after protonation at the nitrogen atom of the sulfilimine, whereas at pH > 10.0, the reaction proceeds by the addition of hydroxide ion to sulfur directly. In the range of pH 2.0-10.0, the addition of water to sulfur of sulfilimine appears to be the rate controlling step.

Keywords

References

  1. Jencks, W. P. Catalysis in Chemistry and Enzymology; McGrew-Hill Co: New York, 1969; p 463.
  2. Patai, S.; Rapport, Z. The Chemistry of Alkene; Interscience: New York, 1964; p 469.
  3. Sandrfy, S. The Chemistry of Carbon-Nitrogen Double Bond; New York, 1970; p 1.
  4. Bernasconi, C. F.; Schuck, D. F. J. Org. Chem. 1992, 57, 2365. https://doi.org/10.1021/jo00034a032
  5. Bernasconi, C. F.; Renfrow, R. A. J. Org. Chem. 1994, 59, 5404. https://doi.org/10.1021/jo00097a051
  6. Bernasconi, C. F.; Leyes, A. E.; Eventova, I.; Rapport, Z. J. Am. Chem. Soc. 1995, 117, 1703. https://doi.org/10.1021/ja00111a006
  7. Bernasconi, C. F.; Leyes, A. E.; Rapport, Z. J. Org. Chem. 1999, 64, 2897. https://doi.org/10.1021/jo990044u
  8. Nicolet, B. H.; Willard, J. Science 1921, 53, 217. https://doi.org/10.1126/science.53.1366.217
  9. Mann, F. G.; Pope, W. J. J. Chem. Soc. 1922, 121, 1052. https://doi.org/10.1039/ct9222101052
  10. Doerhoefer, G. German Offen. 1976, 2, 107, 520.
  11. Heubner, C. F. U. S. Pat. 1970, 3, 291, 794.
  12. Tsujihara, K.; Furukuwa, N. Bull. Chem. Soc. Jap. 1969, 42, 2631. https://doi.org/10.1246/bcsj.42.2631
  13. Ross, W. C. J. Biochem. Pharmacol. 1959, 2, 215. https://doi.org/10.1016/0006-2952(59)90071-1
  14. Kim, T. R.; Pyun, S. Y.; Go, D. H. J. Natural Sciences 1991, 32, 21.
  15. Kim, T. R.; Pyun, S. Y.; Lee, C. R. J. Natural Sciences 1991, 32, 27.
  16. Kim, T. R.; Pyun, S. Y.; Lee, S. Y. J. Korean Chem. Soc. 1992, 36, 318.
  17. Kwon, H. S.; Kim, K. K.; Kim, T. R.; Pyun, S. Y.; Hwang, D. S. Bull. Natural Sci. 1995, 9, 33.
  18. Kim, T. R.; Pyun, S. Y.; Han, M. S. J. Korean Chem. Soc. 1996, 40, 663.
  19. Verheijen, J. H. Synthesis 1975, 451.
  20. Ishida, S. Agr. Bio. Chem. 1966, 30, 800. https://doi.org/10.1271/bbb1961.30.800
  21. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry; Plenum Press Co: New York & London, 1984; p 189.

Cited by

  1. Kinetic studies on the addition of phenol to S-phenyl-S-vinyl-N-p-tosylsulfilimine derivatives vol.49, pp.5, 2008, https://doi.org/10.1134/S0023158408050054
  2. 이금속성 형태 몰리브덴 촉매를 이용한 질소화합물의 반응속도 연구 vol.22, pp.4, 2003, https://doi.org/10.12925/jkocs.2005.22.4.7
  3. Systematic identification of engineered methionines and oxaziridines for efficient, stable, and site-specific antibody bioconjugation vol.117, pp.11, 2003, https://doi.org/10.1073/pnas.1920561117