Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Fluoroformate and a Consideration of Leaving Group Effects

  • Seong, Mi-Hye (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Kyong, Jin-Burm (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Kim, Dong-Kook (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Kevill, Dennis N. (Department of Chemistry and Biochemistry, Northern Illinois University)
  • Published : 2008.09.30
Download PDF
⟨ Previous Next ⟩

Abstract

Reactions of n-propyl fluoroformate in a variety of pure and binary solvents have been studied at 40.0 {^{\circ}C}. The extended (two-term) Grunwald-Winstein equation has been applied to the specific rates of solvolysis of npropyl fluoroformate. The sensitivities (l = 1.80 ${\pm}$ 0.17 and m = 0.96 ${\pm}$ 0.10) to changes in solvent nucleophilicity and solvent ionizing power and the $k_F/k_{Cl}$ values are similar to those for solvolyses of n-octyl fluoroformate over the full range of solvents, suggesting that the addition step of an addition-elimination mechanism is ratedetermining. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.

Keywords

References

  1. Kyong, J. B.; Won, H.; Kevill, D. N. Int. J. Mol. Sci. 2005, 6, 87 https://doi.org/10.3390/i6010087
  2. Kevill, D. N.; Kyong, J. B.; Weitl, F. L. J. Org. Chem. 1990, 55, 4304 https://doi.org/10.1021/jo00301a019
  3. Kevill, D. N.; Kyong, J. B. J. Org. Chem. 1992, 57, 258 https://doi.org/10.1021/jo00027a046
  4. Queen, A.; Nour, T. A. J. Chem. Soc., Perkin Trans. 2 1976, 935
  5. Hudson, R. F.; Green, M. J. Chem. Soc. 1962, 1055 https://doi.org/10.1039/jr9620001055
  6. Orlov, S. I.; Chimishkyan, A. L.; Grabarnik, M. S. J. Org. Chem. USSR (Engl. Transl.) 1983, 19, 1981
  7. Kevill, D. N.; D'Souza, M. J. J. Chem. Soc., Perkin Trans. 2 2002, 240
  8. Kyong, J. B.; Ryu, S. H.; Kevill, D. N. Int. J. Mol. Sci. 2006, 7, 186 https://doi.org/10.3390/i7070186
  9. Grunwald, E.; Winstein, S. J. Am. Chem. Soc. 1948, 70, 846 https://doi.org/10.1021/ja01182a117
  10. Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700 https://doi.org/10.1021/ja01150a078
  11. Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; Vol 1, pp 81-115
  12. Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845 https://doi.org/10.1021/jo00005a034
  13. Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667 https://doi.org/10.1021/ja00440a037
  14. Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121 https://doi.org/10.1002/9780470171967.ch5
  15. Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741 https://doi.org/10.1021/ja00385a031
  16. Kevill, D. N.; D'Souza, M. J. J. Chem. Res., Synop. 1993, 174
  17. Lomas, J. S.; D'Souza, M. J.; Kevill, D. N. J. Am. Chem. Soc. 1995, 117, 5891 https://doi.org/10.1021/ja00126a045
  18. Kyong, J. B.; Park, B.-C.; Kim, C.-B.; Kevill, D. N. J. Org. Chem. 2000, 65, 8051 https://doi.org/10.1021/jo005630y
  19. Lorca, A. A.; Malfroot, T.; Senet, J. P. United States Patent Application Pub 2003, 0120103A1, Jun. 26
  20. Cuomo, J.; Olofson, R. A. J. Org. Chem. 1979, 44, 1016 https://doi.org/10.1021/jo01315a004
  21. Kyong, J. B.; Rhu, C. J.; Kim, Y. G.; Kevill, D. N. J. Phys. Org. Chem. 2007, 20, 525 https://doi.org/10.1002/poc.1194
  22. Kevill, D. N.; Kim, J. C.; Kyong, J. B. J. Chem. Res., Synop. 1999, 150
  23. Kevill, D. N.; D'Souza, M. J. J. Org. Chem. 1998, 63, 2120 https://doi.org/10.1021/jo9714270
  24. Kevill, D. N.; D'Souza, M. J. J. Chem. Soc., Perkin Trans. 2 1997, 1721
  25. Kevill, D. N.; Miller, B. J. Org. Chem. 2002, 67, 7399 https://doi.org/10.1021/jo020467n
  26. Swain, C. G.; Scott, C. B. J. Am. Chem. Soc. 1953, 75, 246 https://doi.org/10.1021/ja01097a520
  27. Song, B. D.; Jencks, W. P. J. Am. Chem. Soc. 1989, 111, 8470 https://doi.org/10.1021/ja00204a021
  28. Wiberg, K. B.; Hadad, C. M.; Rablen, P. R.; Cioslowski, J. J. Am. Chem. Soc. 1992, 114, 8644 https://doi.org/10.1021/ja00048a044
  29. Wiberg, K. B.; Rablen, P. R. J. Org. Chem. 1998, 63, 3722 https://doi.org/10.1021/jo980463b
  30. Kevill, D. N.; D'Souza, M. J. J. Org. Chem. 2004, 69, 7044 https://doi.org/10.1021/jo0492259
  31. Lee, S. H.; Rhu, C. J.; Kyong, J. B.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2007, 28, 657 https://doi.org/10.5012/bkcs.2007.28.4.657
  32. Yew, K. H.; Koh, H. J.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1995, 2263
  33. Koo, I. S.; Yang, K.; Kang, K.; Lee, I. Bull. Korean Chem. Soc. 1998, 19, 968
  34. Kyong, J. B.; Kim, Y. G.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2000, 21, 662

Cited by

  1. Grunwald-Winstein Analysis - Isopropyl Chloroformate Solvolysis Revisited vol.10, pp.3, 2009, https://doi.org/10.3390/ijms10030862
  2. Corrrelation of the Specific Rates of Solvolysis of Ethyl Fluoroformate Using the Extended Grunwald-Winstein Equation vol.10, pp.3, 2009, https://doi.org/10.3390/ijms10030929
  3. Correlation of the Rates of Solvolysis of i-Butyl Fluoroformate and a Consideration of Leaving-Group Effects vol.12, pp.12, 2011, https://doi.org/10.3390/ijms12117806
  4. Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters vol.14, pp.4, 2013, https://doi.org/10.3390/ijms14047286
  5. Correlation of the Rates of Solvolysis of Methyl Fluoroformate Using the Extended Grunwald-Winstein Equation vol.30, pp.10, 2008, https://doi.org/10.5012/bkcs.2009.30.10.2408
  6. Rate and Product Studies with 2-Methyl-2-Chloroadamantane under Solvolytic Conditions vol.31, pp.5, 2008, https://doi.org/10.5012/bkcs.2010.31.5.1209
  7. Rate and Product Studies of 1-Adamantylmethyl Haloformates Under Solvolytic Conditions vol.33, pp.11, 2008, https://doi.org/10.5012/bkcs.2012.33.11.3657
  8. Further Kinetic Studies of Solvolytic Reactions of Isobutyl Chloroformate in Solvents of High Ionizing Power Under Conductometric Conditions vol.34, pp.2, 2008, https://doi.org/10.5012/bkcs.2013.34.2.615