Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Nucleophilic Substitution Reactions of α-Bromoacetanilides with Benzylamines

  • Published : 2008.01.20
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Abstract

Kinetic studies of the reactions of a-bromoacetanilides [YC6H4NHC(=O)CH2Br] with substituted benzylamines (XC6H4CH2NH2) have been carried out in dimethyl sulfoxide at 35.0 oC. The Hammett plots for substituent (Y) variations in the substrate (log kN vs. sY) are biphasic concave upwards/downwards with breaks at Y = 4-Cl (sY = 0.23). The Hammett coefficients rY and the cross-interaction constant rXY (= +0.16) are positive for sY 0.23, while the rY values are positive/negative [rY > 0 for X = (4-MeO and 4-Me) and rY < 0 for X = (H, 4-Cl and 3-Cl)] and the rXY (= -1.51) value is negative for sY ³ 0.23. Based on these and other results, the benzylaminolyses of a-bromoacetanilides are proposed to proceed through rate-limiting expulsion of the bromide leaving group from a zwitterionic tetrahedral intermediate, T, with a bridged transition state for s Y 0.23, while the reaction proceeds through concerted mechanism with an enolate-like TS in which the nucleophile attacks the a-carbon for s Y ³ 0.23.

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References

  1. Baker, J. W. Trans. Faraday Soc. 1951, 37, 643
  2. Bunton, C. A. Nucleophilic Substitution at a Saturated Carbon Atom; Elsevier: New York, 1963; p 5
  3. Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700 https://doi.org/10.1021/ja01150a078
  4. Dewar, M. J. S. The Electronic Theory of Organic Chemistry; Oxford University Press: Oxford, 1949; p 73
  5. McLennan, D. J.; Pross, A. J. Chem. Soc. Perkin Trans. 2 1984, 981
  6. Streitwieser, A. Jr. Solvolytic Displacement Reactions; McGraw- Hill: New York, 1962
  7. Lee, I.; Sung, D. D. Curr. Org. Chem. 2004, 8, 557 https://doi.org/10.2174/1385272043370753
  8. Yousaf, T. I.; Lewis, E. S. J. Am. Chem. Soc. 1987, 109, 6137 https://doi.org/10.1021/ja00254a038
  9. Forster, W.; Laird, R. M. J. Chem. Soc. Perkin Trans. 2 1982, 135
  10. Lee, I.; Shim, C. S.; Chung, S. Y.; Lee, H. W. J. Chem. Soc. Perkin Trans. 2 1988, 975
  11. Lee, I.; Kim, I. C. Bull. Korean Chem. Soc. 1988, 9, 133
  12. Lee, I.; Shim, C. S.; Lee, H. W. J. Phys. Org. Chem. 1989, 2, 484 https://doi.org/10.1002/poc.610020607
  13. Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 4706 https://doi.org/10.1021/jo000411y
  14. Lee, K. S.; Adhikary, K. K.; Lee, H. W.; Lee, B. S.; Lee, I. Org. Biomol. Chem. 2003, 1, 1989 https://doi.org/10.1039/b300477e
  15. Lee, I.; Lee, H. W.; Yu, Y. K. Bull. Korean Chem. Soc. 2003, 24, 993 https://doi.org/10.5012/bkcs.2003.24.7.993
  16. Dey, S.; Adhikary, K. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2005, 26, 776 https://doi.org/10.5012/bkcs.2005.26.5.776
  17. Lee, I. Chem. Soc. Rev. 1990, 19, 317 https://doi.org/10.1039/cs9901900317
  18. Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57
  19. Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529 https://doi.org/10.1135/cccc19991529
  20. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165 https://doi.org/10.1021/cr00002a004
  21. Blackwell, L. F.; Fischer, A.; Miller, J.; Topsom, R. D.; Vaughan, J. J. Chem. Soc. 1964, 3588 https://doi.org/10.1039/jr9640003588
  22. Parker, A. J. Recent Advance in Physical Organic Chemistry; Gold, V. Ed.; Academic Press: New York, 1967; pp 216-217
  23. Oh, H. K.; Yang, J. H.; Lee, I. Bull. Korean Chem. Soc. 1999, 20, 1418
  24. Oh, H. K.; Yang, J. H.; Cho, I. H.; Lee, H. W.; Lee, I. Int. J. Chem. Kinet. 2000, 32, 485 https://doi.org/10.1002/1097-4601(2000)32:8<485::AID-KIN6>3.0.CO;2-X
  25. Lee, I.; Koh, H. J. New J. Chem. 1996, 20, 131
  26. Oh, H. K.; Kim, S. K.; Lee, I. Bull. Korean Chem. Soc. 1999, 20, 1017 https://doi.org/10.1007/BF02706930
  27. Koh, H. J.; Lee, J. W.; Lee, H. W.; Lee, I. New J. Chem. 1997, 21, 447
  28. Oh, H. K.; Lee, J. Y.; Lee, I. Bull. Korean Chem. Soc. 1998, 19, 1198
  29. Oh, H. K.; Woo, S. Y.; Shin, C. H.; Lee, I. Int. J. Chem. Kinet. 1998, 30, 849 https://doi.org/10.1002/(SICI)1097-4601(1998)30:11<849::AID-KIN7>3.0.CO;2-V
  30. Oh, H. K.; Kim, S. K.; Lee, H. W.; Lee, I. New J. Chem. 2001, 25, 313 https://doi.org/10.1039/b006974o
  31. Oh, H. K.; Kim, S. K.; Cho, I. H.; Lee, H. W.; Lee, I. J. Chem. Soc. Perkin Trans. 2 2000, 2306
  32. Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780 https://doi.org/10.1021/jo970413r
  33. Oh, H. K.; Kim, S. K.; Lee, H. W.; Lee, I. J. Chem. Soc. Perkin Trans. 2 2001, 1753
  34. Oh, H. K.; Shin, C. H.; Lee, I. J. Chem. Soc. Perkin Trans. 2 1995, 1169
  35. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 3874 https://doi.org/10.1021/jo025637a
  36. Koh, H. J.; Han, K. L.; Lee, I. J. Org. Chem. 1999, 64, 4783 https://doi.org/10.1021/jo990115p
  37. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 8995 https://doi.org/10.1021/jo0264269
  38. Lee, I. Bull. Korean Chem. Soc. 1994, 15, 985
  39. Yew, K. H.; Koh, H. J.; Lee, H. W.; Lee, I. J. Chem. Soc. Perkin Trans. 2 1995, 2263
  40. Gresser, M. J.; Jencks, W. P. J. Am. Chem. Soc. 1977, 99, 6970 https://doi.org/10.1021/ja00463a033
  41. Castro, E. A.; Steinfort, G. B. J. Chem. Soc. Perkin Trans. 2 1983, 453
  42. Song, B. D.; Jencks, W. P. J. Am. Chem. Soc. 1989, 111, 8479 https://doi.org/10.1021/ja00204a022
  43. Oh, H. K.; Lee, J. M.; Lee, H. W.; Lee, I. Int. J. Chem. Kinet. 2004, 36, 434 https://doi.org/10.1002/kin.20000
  44. Oh, H. K.; Shin, C. H.; Lee, I. Bull. Korean Chem. Soc. 1995, 16, 657
  45. Lee, I.; Lee, W. H.; Lee, H. W.; Bentley, T. W. J. Chem. Soc. Perkin Trans. 2 1993, 141
  46. Shpan'ko, I. V. Mendeleev Commun. 1991, 119

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