Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Correlation of the Rates of Solvolysis of Isopropyl Fluoroformate Using the Extended Grunwald-Winstein Equation

  • Lee, So-Hee (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Rhu, Chan-Joo (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) ;
  • Dennis N. Kevill (Department of Chemistry and Biochemistry, Northern Illinois University)
  • Published : 2007.04.20
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Abstract

The specific rates of solvolysis of isopropyl fluoroformate are well correlated using the extended Grunwald-Winstein equation, with a sensitivity (l ) to changes in solvent nucleophilicity (NT) and a sensitivity (m) to changes in solvent ionizing power (YCl). The sensitivities (l = 1.59 ± 0.16 and m = 0.80 ± 0.06) toward changes in solvent nucleophilicity and solvent ionizing power, and the kF/kCl values are very similar to those for solvolyses of n-octyl fluoroformate, suggesting that the addition step of an addition-elimination mechanism is rate-determining. For methanolysis, a solvent deuterium isotope effect of 2.53 is compatible with the incorporation of general-base catalysis into the substitution process. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.

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References

  1. Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700 https://doi.org/10.1021/ja01150a078
  2. Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; Vol. 1, pp 81-115
  3. Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845 https://doi.org/10.1021/jo00005a034
  4. Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667 https://doi.org/10.1021/ja00440a037
  5. Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121 https://doi.org/10.1002/9780470171967.ch5
  6. Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741 https://doi.org/10.1021/ja00385a031
  7. Kevill, D. N.; D'Souza, M. J. J. Chem. Res., Synop. 1993, 174
  8. Lomas, J. S.; D'Souza, M. J.; Kevill, D. N. J. Am. Chem. Soc. 1995, 117, 5891 https://doi.org/10.1021/ja00126a045
  9. Kyong, J. B.; Park, B. C.; Kim, C. B.; Kevill, D. N. J. Org. Chem. 2000, 65, 8051 https://doi.org/10.1021/jo005630y
  10. Kevill, D. N.; D'Souza, M. J. J. Phys. Org. Chem. 2002, 15, 881 https://doi.org/10.1002/poc.569
  11. Kyong, J. B.; Kim, Y. G.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2000, 21, 662
  12. Kevill, D. N.; Kyong, J. B.; Weitl, F. L. J. Org. Chem. 1990, 55, 4304 https://doi.org/10.1021/jo00301a019
  13. Kevill, D. N.; Weitl, F. L. Tetrahedron Lett. 1971, 707
  14. Kevill, D. N.; Kyong, J. B. J. Org. Chem. 1992, 57, 258 https://doi.org/10.1021/jo00027a046
  15. Kevill, D. N.; D'Souza, M. J. J. Chem. Soc., Perkin Trans. 2 2002, 240
  16. Kyong, J. B.; Ryu, S. H.; Kevill, D. N. Int. J. Mol. Sci. 2006, 7, 187
  17. Kevill, D. N. In The Chemistry of the Functional Groups: The Chemistry of Acyl Halides; Patai, S., Ed.; Wiley: New York, 1972;Chapter 12
  18. Kevill, D. N.; D'Souza, M. J. J. Org. Chem. 1998, 63, 2120 https://doi.org/10.1021/jo9714270
  19. Kevill, D. N.; D'Souza, M. J. J. Chem. Soc., Perkin Trans. 2 1997, 1721
  20. Kevill, D. N.; Miller, B. J. Org. Chem. 2002, 67, 7399 https://doi.org/10.1021/jo020467n
  21. Kevill, D. N.; D'Souza, M. J. J. Org. Chem. 2004, 69, 7044 https://doi.org/10.1021/jo0492259
  22. Kevill, D. N.; Kim, J. C.; Kyong, J. B. J. Chem. Res., Synop. 1999, 150
  23. Swain, C. G.; Scott, C. B. J. Am. Chem. Soc. 1953, 75, 246 https://doi.org/10.1021/ja01097a520
  24. Song, B. D.; Jencks, W. P. J. Am. Chem. Soc. 1989, 111, 8470 https://doi.org/10.1021/ja00204a021
  25. Glew, D. N.; Moelwyn-Hughes, E. A. Proc. R. Soc. London Ser. A 1952, 211, 254
  26. Fells, I.; Moelwyn-Hughes, E. A. J. Chem. Soc. 1959, 398
  27. Bathgate, R. H.; Moelwyn-Hughes, E. A. J. Am. Chem. Soc. 1959, 2642
  28. Robertson, R. E. Prog. Phys. Org. Chem. 1967, 4, 213 https://doi.org/10.1002/9780470171837.ch5
  29. Bunton, C. A. Nucleophilic Substitution at a Saturated Carbon Atom; Elsevier: Amsterdam, The Netherlands, 1963; pp 160-162
  30. Wiberg, K. B.; Hadad, C. M.; Rablen, P. R.; Cioslowski, J. J. Am. Chem. Soc. 1992, 114, 8644 https://doi.org/10.1021/ja00048a044
  31. Wiberg, K. B.; Rablen, P. R. J. Org. Chem. 1998, 63, 3722 https://doi.org/10.1021/jo980463b
  32. Kivinen, A. In The Chemistry of Acyl Halides; Patai, S., Ed.; Interscience: New York, 1972; pp 198-200
  33. Queen, A. Can. J. Chem. 1967, 45, 1619 https://doi.org/10.1139/v67-264
  34. Yew, K. H.; Koh, H. J.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1995, 2263
  35. Koo, I. S.; Yang, K.; Kang, K.; Lee, I. Bull. Korean Chem. Soc. 1988, 19, 968
  36. Ryu, Z. H.; Shin, S. H.; Lee, J. P.; Lim, G. T.; Bentley, T. W. J. Chem. Soc., Perkin Trans. 2 2002, 1283
  37. Oh, Y. H.; Jang, G. G.; Lim, G. T.; Ryu, Z. H. Bull. Korean Chem. Soc. 2002, 23, 1083
  38. Orlov, S. I.; Chimishkyan, A. L.; Grabarnik, M. S. J. Org. Chem. USSR (Engl. Tranl.) 1983, 19, 1981
  39. Lorca, A. A.; Malfroot, T.; Senet, J. P. United States Patent Application Pub. 2003, 0120103A1, Jun. 26
  40. Cuomo, J.; Olofson, R. A. J. Org. Chem. 1979, 44, 1016 https://doi.org/10.1021/jo01320a034
  41. Queen, A.; Nour, T. A. J. Chem. Soc., Perkin Trans. 2 1976, 935

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