Bulletin of the Korean Chemical Society

  • 제34권9호
  • /
  • Pages.2697-2701
  • /
  • 2013
  • /
  • 0253-2964(pISSN)
  • /
  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지
DOI QR코드

DOI QR Code

Correlation of the Rates of Solvolysis of Electron-Rich Benzoyl Chloride Using the Extended Grunwald-Wistein Equation

  • Oh, Hyunjung (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Choi, Hojune (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Park, Jong Keun (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Yang, Kiyull (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Koo, In Sun (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University)
  • 투고 : 2013.06.04
  • 심사 : 2013.06.19
  • 발행 : 2013.09.20
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

The solvolysis rate constants of piperonyloyl chloride (1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale, $Y_{Cl}$ solvent ionizing scale, and I aromatic ring parameter with sensitivity values of $0.30{\pm}0.05$, $0.71{\pm}0.02$, and $0.60{\pm}0.04$ for l, m, and h, respectively. The solvent kinetic isotope effect values (SKIE, $k_{MeOH}/k_{MeOD}$ and $k_{50%MeOD-50%D2O}$) of 1.16 and 1.12 were also in accord with the values for the $S_N1$ mechanism and/or the dissociative $S_N2$ mechanism. The product selectivity values (S) for solvolysis of 1 in alcohol/water mixtures were in the range of 0.5 to 1.9, which is also consistent with the proposed unimolecular ionization mechanism.

키워드

참고문헌

  1. Kyong, J. B.; Yoo, J. S.; Kevill, D. N. J. Org. Chem. 2003, 68, 3425. https://doi.org/10.1021/jo0207426
  2. Choi, H. J.; Koh, H. J.; Yang, K.; Koo, I. S. Bull. Korean Chem. Soc. 2012, 33, 3293. https://doi.org/10.5012/bkcs.2012.33.10.3293
  3. Kim, C. H.; Han, I. S.; Sohn, C. K.; Yu, Y. H.; Su, Z.; Kim, C. K. Bull. Korean Chem. Soc. 2012, 33, 1955. https://doi.org/10.5012/bkcs.2012.33.6.1955
  4. Kim, C. H.; Han, I. S.; Sohn, C. K.; Yu, Y. H.; Su, Z.; Kim, C. K. J. Phys. Chem. A 2011, 115, 1364. https://doi.org/10.1021/jp104484g
  5. Faurholt, C.; Gjaldbaek, J. C. Dansk. Tids. Farm. 1945, 19, 255.
  6. Faurholt, C.; Gjaldbaek, J. C. Chem. Abstr. 1946, 40, 513.
  7. Kevill, D. N.; Kyong, J. B.; Weitl, F. L. J. Org. Chem. 1990, 55, 4304. https://doi.org/10.1021/jo00301a019
  8. Baer, S.; Brinkman, E. A.; Brauman, J. I. J. Am. Chem. Soc. 1991, 113, 805. https://doi.org/10.1021/ja00003a012
  9. Williams, A. Chem. Soc. Rev. 1994, 23, 93. https://doi.org/10.1039/cs9942300093
  10. Blake, J. F.; Jorgensen, W. L. J. Am. Chem. Soc. 1987, 109, 3856. https://doi.org/10.1021/ja00247a007
  11. Kevill. D. N. The Chemistry of Acyl Halide; Patai, S. Ed.; Interscience: New York, 1973; Ch. 12.
  12. Queen, A. Can. J. Chem. 1967, 45, 1619. https://doi.org/10.1139/v67-264
  13. Castro, E. A.; Ibanez, F.; Salas, M.; Santos, J. G. J. Org. Chem. 1991, 56, 4819. https://doi.org/10.1021/jo00016a002
  14. Chrystiuk, E.; Williams, A. J. Am. Chem. Soc. 1987, 109, 3040. https://doi.org/10.1021/ja00244a028
  15. Castro, E. A.; Salas, M.; Santos, J. G. J. Org. Chem. 1994, 59, 30. https://doi.org/10.1021/jo00080a008
  16. Grunwald, E.; Winstein, S. J. Am. Chem. Soc. 1948, 70, 846. https://doi.org/10.1021/ja01182a117
  17. Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121. https://doi.org/10.1002/9780470171967.ch5
  18. Kevill, D. N.; D'Souza, M. J. J. Chem. Res. Synop. 1993, 174.
  19. Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741. https://doi.org/10.1021/ja00385a031
  20. Koo, I. S.; Bentley, T. W.; Kang, D. H.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1991, 296.
  21. Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700. https://doi.org/10.1021/ja01150a078
  22. Fainberg, A. H.; Winstein, S. J. Am. Chem. Soc. 1956, 78, 2770. https://doi.org/10.1021/ja01593a033
  23. Fainberg, A. H.; Winstein, S. J. Am. Chem. Soc. 1957, 79, 1597. https://doi.org/10.1021/ja01564a021
  24. Bunton, C. A.; Mhala, M. M.; Moffatt, J. R. J. Org. Chem. 1984, 49, 3639. https://doi.org/10.1021/jo00193a037
  25. da Roza, D. A.; Andrews, L. J.; Keefer, R. M. J. Am. Chem. Soc. 1973, 95, 7003. https://doi.org/10.1021/ja00802a022
  26. Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996, Vol. 1, pp 81-115.
  27. Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7658. https://doi.org/10.1021/ja00440a036
  28. Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667. https://doi.org/10.1021/ja00440a037
  29. Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845. https://doi.org/10.1021/jo00005a034
  30. Kevill, D. N.; Ismail, N. H. J.; D'Souza, M. J. J. Org. Chem. Soc. 1994, 59, 6303. https://doi.org/10.1021/jo00100a036
  31. Kevil, D. N.; D'Souza, M. J. J. Chem. Soc. Perkin Trans. 2 1995, 973.
  32. Kevill, D. N.; D'Souza, M. J. J. Chem. Soc. Perkin Trans. 2 1997, 257.
  33. Kevil, D. N.; Bond, M. W.; D'Souza, M. J. J. Org. Chem. Soc. 1997, 62, 7869. https://doi.org/10.1021/jo970657b
  34. Bentley, T. W.; Ebdon, D. N. J. Phys. Org. Chem. 2001, 14, 759. https://doi.org/10.1002/poc.425
  35. Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 1998, 63, 9834. https://doi.org/10.1021/jo9814905
  36. Crumpler, T. B.; Yoh, J. H. Chemical Computations and Error; Wiley: New York, 1940; p 178.
  37. Bentley, T. W.; Koo, I. S.; Norman, S. J. J. Org. Chem. 1991, 56, 1604. https://doi.org/10.1021/jo00004a048
  38. Koo, I. S.; An, S. K.; Yang, K.; Lee, I.; Bentley, T. W. J. Phys. Org. Chem. 2002, 15, 758. https://doi.org/10.1002/poc.550
  39. Choi, H. J.; Ali, D.; Lee, J. P.; Yang, K.; Park, J. K.; Koo, I. S. Bull. Korean Chem. Soc. 2011, 32, 3941. https://doi.org/10.5012/bkcs.2011.32.11.3941
  40. Bentley, T. W.; Koo, I. S. J. Chem. Soc., Perkin Trans. 2 1989, 1385.
  41. Kyong, J. B.; Park, B. C.; Kim, C. B.; Kevil, D. N. J. Org. Chem. 2000, 65, 8051. https://doi.org/10.1021/jo005630y
  42. Bentley, T. W.; Carter, G. E.; Harris, H. C. J. Chem. Soc., Chem. Commun. 1984, 388.
  43. Bentley, T. W.; Carter, G. E.; Harris, H. C. J. Chem. Soc., Perkin Trans. 2 1985, 983.
  44. Bentley, T. W.; Harris, H. C. J. Chem. Soc., Perkin Trans. 2 1986, 619.
  45. Bentley, T. W.; Harris, H. C.; Koo, I. S. J. Chem. Soc., Perkin Trans. 2 1988, 783.
  46. Swain, C. G.; Mosely, R. B.; Bown, D. E. J. Am. Chem. Soc. 1955, 77, 3731. https://doi.org/10.1021/ja01619a018
  47. Kevill, D. N.; D'Souza, M. J. J. Phys. Org. Chem. 2002, 15, 881. https://doi.org/10.1002/poc.569
  48. Lee, I.; Koo, I. S.; Sohn, S. C.; Lee, H. H. Bull. Korean Chem. Soc. 1982, 3, 92.
  49. Bentley, T. W.; Harris, H. C. J. Org. Chem. 1988, 53, 724. https://doi.org/10.1021/jo00239a004
  50. Bentley, T. W.; Koo, I. S. J. Chem. Soc., Perkin Trans. 2 1989, 1385
  51. Kyong, J. B.; Kim, Y. G.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2000, 21, 662.
  52. D'Souza, M. J.; Reed, D. N.; Erdman, K. J.; Kevill, D. N. Int. J. Mol. Sci. 2009, 10, 862. https://doi.org/10.3390/ijms10030862
  53. Kevill, D. N.; Park, B.-C.; Park, K.-H.; D'Souza, M. J.; Yaakoud, L.; Mlynarski, S. L.; Kyong, J. B. Org. Biomol. Chem. 2006, 4, 1580. https://doi.org/10.1039/b518129a
  54. Koo, I. S.; Yang, K.; An, S. K.; Lee, C.-K.; Lee, I. Bull. Korean Chem. Soc. 2000, 21, 1011.
  55. Kevill, D. N.; Ryu, Z. H.; Niedermeyer, M. A. Koyoshi, F.; D'Souza, M. J. J. Phys. Org. Chem. 2007, 20, 431. https://doi.org/10.1002/poc.1168
  56. Kevill, D. N.; Carver, J. S. Org. Biomol. Chem. 2004, 2, 2040. https://doi.org/10.1039/b402093f
  57. Kevill, D. N.; Kim, J. C.; Kyong, J. B. J. Chem. Res. Synop. 1999, 2, 150.
  58. Bentley, T. W.; Dau-Schmidt, J. P.; Llewellyn, G.; Mayr, H. J. Org. Chem. 1992, 57, 2387. https://doi.org/10.1021/jo00034a035
  59. Liu, K. T.; Sheu, H. C. J. Org. Chem. 1991, 56, 3021. https://doi.org/10.1021/jo00009a018
  60. Oh, H. K.; Kown, Y. B.; Koh, H. J.; Lee, I. New J. Chem. 1996, 20, 579.
  61. Bentley, T. W.; Llewllyn, G. Ryu, Z. H. J. Org. Chem. 1998, 63, 4654. https://doi.org/10.1021/jo980109d
  62. Kevill, D. N.; D'Souza, M. J. J. Org. Chem. 1998, 63, 2120. https://doi.org/10.1021/jo9714270
  63. Bentley, T. W.; Ryu, Z. H. J. Chem. Soc. Perkin Trans. 2 1994, 761.
  64. Shiner, V. J., Jr.; Dowd, W.; Fisher, R. D.; Hartshorn, S. R.; Kessick, M. A.; Milakofsky, L.; Rapp, M. W. J. Am. Shem. Soc. 1969, 91, 4838. https://doi.org/10.1021/ja01045a043
  65. Harris, J. M.; Clark, D. C.; Becker, A.; Fagan, J. F. J. Am. Chem. Soc. 1974, 96, 4478. https://doi.org/10.1021/ja00821a021
  66. Harris, J. M.; Becker, A.; Fagan, J. F.; Walden, F. A. J. Am. Chem. Soc. 1974, 96, 4484. https://doi.org/10.1021/ja00821a022
  67. Karton, Y.; Pross, A. J. Chem. Soc. Perkin Trans. 2 1977, 1860.
  68. McLennan, D. J.; Martin, P. L. J. Chem. Soc. Perkin Trans. 2 1982, 1099.
  69. Ritche, C. D. J. Am. Chem. Soc. 1971, 93, 7324. https://doi.org/10.1021/ja00755a039
  70. Exner, O. J. Chem. Soc. Perkin Trans. 2 1993, 973.
  71. Koh, H. J.; Kang, S. J. Bull. Korean Chem. Soc. 2011, 32, 3799. https://doi.org/10.5012/bkcs.2011.32.10.3799
  72. Koh, H. J.; Kang, S. J. Bull. Korean Chem. Soc. 2012, 33, 1.
  73. Bentley, T. W.; Koo, I. S. J. Chem. Soc., Chem. Commun. 1988, 41.
  74. Bentley, T. W.; Harris, H. C. J. Org. Chem. 1988, 53, 724. https://doi.org/10.1021/jo00239a004
  75. Bentley, T. W.; Jones, R. O. J. Chem. Soc., Perkin Trans 2 1993, 2351.
  76. Bentley, T. W.; Jones, R. O.; Koo, I. S. J. Chem. Soc., Perkin Trans 2 1994, 753.

피인용 문헌

  1. Studies of Solvolyses of Biphenyl-4-carbonyl Chloride by Extended Grunwald-Winstein Equation vol.60, pp.1, 2016, https://doi.org/10.5012/jkcs.2016.60.1.16