Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Further Kinetic Studies of Solvolytic Reactions of Isobutyl Chloroformate in Solvents of High Ionizing Power Under Conductometric Conditions

  • Received : 2012.09.16
  • Accepted : 2012.12.05
  • Published : 2013.02.20
Download PDF
⟨ Previous Next ⟩

Abstract

Solvolyses of isobutyl chloroformate (4) in 43 binary solvent mixtures including highly aqueous media, water, $D_2O$, $CH_3OD$, 2,2,2-trifluoroethanol (TFE) as well as aqueous 1,1,1,3,3,3-hexafluoro-isopropanol (HFIP) solvents were performed at $45^{\circ}C$, in order to further investigate the recent results of D'Souza, M. $J^1$. et al.; solvolyses of 4 are found to be consistent with the proposed mechanism ($Ad_E$). The variety of solvent systems was extended to comprise highly ionizing power solvent media ($Y_{Cl}$ > 2.7 excepted for aqueous fluorinated solvents and pure TFE solvent) to investigate whether a mechanistic change occurs as solvent compositions are varied. However, in case of 18-solvent ranges having aqueous fluorinated solvent systems (TFE-$H_2O$ and HFIP-$H_2O$) and/or having $Y_{Cl}$ > 2.7 solvent systems, the solvent effect on reactivity for those of 4 are evaluated by the multiple regression analysis as competition with $S_N2$ - type mechanism. And in pure TFE and 97 w/w % HFIP solvents with high $Y_{Cl}$ and weak $N_T$, these solvolyses are understood as reactions which proceed through an ionization ($S_N1$) pathway.

Keywords

References

  1. D'Souza, M. J.; McAneny, M. J.; Kevill, D. N.; Kyong, J. B.; Choi, S. H. Beilstein J. Org. Chem. 2011, 7, 543. https://doi.org/10.3762/bjoc.7.62
  2. Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 53, 2700.
  3. Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845. https://doi.org/10.1021/jo00005a034
  4. Bentley, T. W.; Carter, G. E. J. Am Chem. 1982, 104, 5741. https://doi.org/10.1021/ja00385a031
  5. Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121. https://doi.org/10.1002/9780470171967.ch5
  6. Kevill, D. N.; D'Souza, M. J. J. Chem. Res(S) 1993, 174.
  7. Ryu, Z. H.; Ju, C.-K.; Sung, D. D.; Sung, N. C.; Bentley, T. W. Bull. Korean Chem. Soc. 2002, 23, 123. https://doi.org/10.5012/bkcs.2002.23.1.123
  8. Bentley, T. W.; Shim, C. S. J. Chem. Soc. Perkin Trans. 2 1993, 1659.
  9. Bentley, T. W.; Koo, I. S.; Norman, S. J. J. Org. Chem. 1991, 56, 1604. https://doi.org/10.1021/jo00004a048
  10. Bentley, T. W.; Harris, H. C. J. Chem. Soc. Perkin Trans. 2 1986, 619.
  11. Bentley, T. W.; Carter, G. E.; Harris, H. C. J. Chem. Soc. Perkin Trans. 2 1985, 983.
  12. Bentley, T. W.; Carter, G. E.; Harris, H. C. J. Chem. Soc., Chem. Commun. 1984, 387.
  13. Lee, I. J. Korean Chem. Soc. 1972, 16, 334.
  14. Kevill, D. N. The Chemistry of the Functional Groups: The Chemistry of Acyl Halides; Patai, S., Ed.; John Wiley & Sons:New York, NY, USA, 1972.
  15. Erben, M. F.; Della, E. W.; Vedova, C. O.; Boese, R.; Willner, H.; Oberhammer, H. J. Phys. Chem., A 2004, 108, 699. https://doi.org/10.1021/jp036966p
  16. Bentley, T. W. J. Org. Chem. 2008, 73, 6251. https://doi.org/10.1021/jo800841g
  17. Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667. https://doi.org/10.1021/ja00440a037
  18. Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; 1, 81.
  19. Ryu, Z. H.; Lee, Y. H.; Oh, Y. Bull. Korean Chem. Soc. 2005, 11, 1761.
  20. Kyong, J. B.; Kim, Y.-G.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2000, 21, 662.
  21. D'Souza, M. J.; Reed, D. N.; Erdman, K. J.; Kyong, J. B.; Kevill, D. N. Int. J. Mol. Sci. 2009, 10, 862. https://doi.org/10.3390/ijms10030862
  22. D'Souza, M. J.; Shuman, K. E.; Omondi, A. O.; Kevill, D. N. Eur. J. Chem. 2011, 2(2), 130. https://doi.org/10.5155/eurjchem.2.2.130-135.405
  23. D'Souza, M. J.; Carter, S. E.; Kevill, D. N. Int. J. Mol. Sci. 2011, 12, 1161. https://doi.org/10.3390/ijms12021161
  24. Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; 1, 81.
  25. Kevill, D. N.; D'Souza, M. J. J. Chem. Soc. Perkin Trans. 2 1997, 1721.
  26. Seong, M. H.; Kyong, J. B.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2008, 29, 1747. https://doi.org/10.5012/bkcs.2008.29.9.1747
  27. Park, K. H.; Lee, Y.; Lee, Y.-W.; Kyong, J. B.; Kevill, D. N. Bull. Korean Chem. Soc. 2012, 33, 3657. https://doi.org/10.5012/bkcs.2012.33.11.3657
  28. Ryu, Z. H.; Shin, S. H.; Lee, J. P.; Lim, G. T.; Bentley, T. W. J. Chem. Soc., Perkin Trans. 2 2002, 1283.
  29. Neal, W. C., Jr.; Dukes, M. D.; Harris, J. M.; Mount, J. J. Am. Chem. Soc. 1978, 8137.
  30. Kyong, J. B.; Won, H.; Kevill, D. N. Int. J. Mol. Sci. 2005, 6, 87. https://doi.org/10.3390/i6010087
  31. Bentley, T. W.; Llewellyn, G.; Ryu, Z. H. J. Org. Chem. 1998, 63, 4654. https://doi.org/10.1021/jo980109d
  32. Bentley, T. W.; Harris, H. C. J. Org. Chem. 1988, 53, 724. https://doi.org/10.1021/jo00239a004
  33. Oh, Y. H.; Jang, G. G.; Lim, G. T.; Ryu, Z. H. Bull. Korean Chem. Soc. 2002, 23, 1089. https://doi.org/10.5012/bkcs.2002.23.8.1089
  34. Ryu, Z. H.; Lim, G. T.; Bentley, T. W. Bull. Korean Chem. Soc. 2003, 24, 1293. https://doi.org/10.5012/bkcs.2003.24.9.1293
  35. Bentley, T. W.; Harris, H. C.; Ryu, Z. H.; Lim, G. T.; Sung, D. D.; Szajda, S. R. J. Org. Chem. 2005, 70, 8963. https://doi.org/10.1021/jo0514366
  36. Bentley, T. W.; Jones, R. O. J. Chem. Perkin Trans. 2 1993, 2351.
  37. Bentley, T. W.; Jones, R. O.; Koo, I. S. J. Chem. Soc. Perkin Trans. 2 1994, 753.
  38. Bentley, T. W.; Ebdon, D.; Llewellyn, G.; Abduljabor, M. H.; Miller, B.; Kevill, D. N. J. Chem. Soc. Dalton Trans. 1997, 3819.
  39. Koo, I. S. Yang, K.; Kang, K.; Lee, I.; Bentley, T. W. J. Chem. Soc., Perkin Trans. 2 1998, 1179.
  40. Mayr, H.; Minegishi, S. Angew. Chem. Int. Ed. 2002, 23, 4493.
  41. Ryu, Z. H.; Bentley, T. W. Bull. Korean Chem. Soc. 2008, 29, 2145. https://doi.org/10.5012/bkcs.2008.29.11.2145
  42. Gugggenheim, E. A. Philos. Mag. 2 1928, 538.
  43. Frost, A. A.; Pearson, R. G. Kinetics and Mechanism, 2nd ed.; Wiley: New York, 1961; p 49.

Cited by

  1. Mechanistic Analysis of 4-Methylthiobenzoyl Chloride in Solvolysis vol.37, pp.4, 2016, https://doi.org/10.1002/bkcs.10726
  2. Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds vol.15, pp.10, 2014, https://doi.org/10.3390/ijms151018310
  3. Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates vol.16, pp.12, 2015, https://doi.org/10.3390/ijms160510601
  4. LFER Studies Evaluating Solvent Effects on an α-Chloro-and two β,β,β-Trichloro-Ethyl Chloroformate Esters vol.2, pp.2, 2013, https://doi.org/10.13179/canchemtrans.2014.02.02.0093