DOI QR코드

DOI QR Code

Aminolysis of 4-Nitrobenzenesulfenyl Chloride

  • Lee, Jong-Pal (Department of Chemistry, Dong-A University) ;
  • Lee, Sung-Sik (Department of Chemical Engneering, Dong-A University) ;
  • Koo, In-Sun (Department of Chemistry Education and Research Institute of Natural Science, Gyeongsang National University)
  • Received : 2010.12.03
  • Accepted : 2011.01.08
  • Published : 2011.03.20

Abstract

The reactions of 4-nitrobenzenesulfenyl chloride with substituted benzylamines proceed through three pathways, the uncatalyzed ($k_2$) and catalyzed ($k_3$) paths including solvolysis ($k_o$) by the solvent. The large value of primary normal kinetic isotope effects imply that the proton transfer occurs concurrently from benzylamine to Cl atom of the substrate. The ${\beta}_x$ and ${\rho}_x$ values for the catalyzed path, $k_3$, are greater than those for the uncatalyzed path, indicating that greater degree of bond formation in the catalyzed TS compared to the uncatalyzed TS.

Keywords

References

  1. Kice, J. L. Adv. Phys. Org. Chem. 1980, 17, 115.
  2. Okuyama, T. The Chemistry of Sulphenic Acids and TheirDerivatives; Wiley: Chichester, 1990; Chapter 18.
  3. Okuyama, T.; Nagase, S. J. Chem Soc., Perkin Trans. 2 1994, 1011.
  4. Lee, J. P.; Kim, W. R.; Okuyama, T. Bull. Korean Chem. Soc. 2009,30, 493. https://doi.org/10.5012/bkcs.2009.30.2.493
  5. Lee, J. P.; Lee, H. W.; Okuyama, T.; Koo, I. S. Bull. Korean Chem.Soc. 2009, 30, 1893. https://doi.org/10.5012/bkcs.2009.30.8.1893
  6. Castro, E. A.; Pizzaro, M. I.; Santos, J. G. J. Org. Chem. 1996,61, 5982. https://doi.org/10.1021/jo960781f
  7. Castro, E. A.; Ibanez, F.; Santos, J. G.; Ureta, C. J.Org. Chem. 1993, 58, 4908. https://doi.org/10.1021/jo00070a028
  8. Castro, E. A.; Cubillos, M.; Santos, J. G. J. Org. Chem. 1996, 61, 3501. https://doi.org/10.1021/jo951726u
  9. Castro, E. A.; Araneda, C. A. J. Org. Chem. 1997, 62, 126. https://doi.org/10.1021/jo961275t
  10. Williams, A. Chem. Soc. Rev. 1994, 23, 93. https://doi.org/10.1039/cs9942300093
  11. Koh, H. J.; Kim, T. H.; Lee, B. S.; Lee, I. J. Chem. Res.(S) 1996,482
  12. Koh, H. J.; Kim, T. H.; Lee, B. S.; Lee, I. J. Chem. Res.(M) 1996, 2714.
  13. Menger, F. M.; Smith, J. J. J. Am. Chem. Soc. 1972, 94, 384. https://doi.org/10.1021/ja00757a013
  14. Ciuffarin, E.; Guaraldi, G. J. Am. Chem. Soc. 1969, 91, 1745. https://doi.org/10.1021/ja01035a024
  15. Neuvonen, H. J. Chem. Soc. Perkin Trans. 2 1995, 951.
  16. Hong, S. W.; Koh, H. J.; Lee, I. J. Phy. Org. Chem. 1999, 12, 425. https://doi.org/10.1002/(SICI)1099-1395(199906)12:6<425::AID-POC147>3.0.CO;2-3