Bulletin of the Korean Chemical Society

  • 제31권2호
  • /
  • Pages.303-308
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  • 2010
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of 4-Nitrophenyl X-Substituted Benzoates with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Seo, Jin-A (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Kim, Song-I (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Hong, Yeon-Ju (Amorepacific Corporation R&D Center) ;
  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
  • 발행 : 2010.02.20
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초록

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl benzoate (5a), 4-nitrophenyl 4-methoxybenzoate (5b), and 4-nitrophenyl 4-hydroxybenzoate (5c) with alkali metal ethoxides, $EtO^-M^+$ ($M^+=Li^+$, $Na^+$ and $K^+$) in anhydrous ethanol (EtOH) at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [$EtO^-M^+$] exhibit upward curvatures in all cases, indicating that $M^+$ ions catalyze the reactions and ionpaired $EtO^-M^+$ species are more reactive than dissociated $EtO^-$. Second-order rate constants for reactions with dissociated $EtO^-$ and ion-paired $EtO^-M^+$ (i.e., $k_{EtO^-}$ and $k_{EtO^-M^+}$, respectively) have been calculated from ion-pair treatment for the reactions of 5a and 5b. However, such ion-pair treatment has failed to determine $k_{EtO^-}$ and $k_{EtO^-M^+}$ values for the reactions of 5c. It has been concluded that reactions of 5a and 5b are catalyzed by one metal ion, which increases electrophilicity of the reaction center through coordination on the carbonyl oxygen. In contrast, reactions of 5c have been suggested to involve two metal ions, i.e., the one coordinated on the carbonyl oxygen increases the electrophilicity of the reaction center while the other one associated on the phenoxy oxygen decreases the charge repulsion between the anionic reagents (i.e., $EtO^-$ and deprotonated 5c). It has been found that the rate equation derived from the mechanism involving two metal ions fits nicely to the kinetic results obtained for the reactions of 5c.

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참고문헌

  1. Brown, R. S.; Neverov, A. A. Adv. Phys. Org. Chem. 2007, 42, 271-331. https://doi.org/10.1016/S0065-3160(07)42006-8
  2. Brown, R. S.; Neverov, A. A.; Tsang J. S. W.; Gibson, G. T. T.; Montoya-Pelaez, P. J. Can. J. Chem. 2004, 82, 1791-1805. https://doi.org/10.1139/v04-167
  3. Williams, N. H.; Takasaki, B.; Wall, M.; Chin, J. Acc. Chem. Res. 1999, 32, 485-493. https://doi.org/10.1021/ar9500877
  4. Pregel, M. J.; Dunn, E. J.; Nagelkerke, R.; Thatcher, G. R. J.; Buncel, E. Chem. Soc. Rev. 1995, 24, 449-455. https://doi.org/10.1039/cs9952400449
  5. Fife, T. H.; Chauffe, L. Bioorg. Chem. 2000, 28, 357-373. https://doi.org/10.1006/bioo.2000.1176
  6. Fife, T. H.; Bembi, R. J. Am. Chem. Soc. 1993, 115, 11358-11363. https://doi.org/10.1021/ja00077a039
  7. Fife, T. H.; Pujari, M. P. J. Am. Chem. Soc. 1990, 112, 5551-5557. https://doi.org/10.1021/ja00170a020
  8. Kim, H. M.; Jang, B.; Cheon, Y. E.; Suh, M. P.; Suh, J. J. Biol. Inorg. Chem. 2009, 14, 151-157. https://doi.org/10.1007/s00775-008-0434-z
  9. Jang, B.; Suh, J. Bull. Korean Chem. Soc. 2008, 29, 202-204. https://doi.org/10.5012/bkcs.2008.29.1.202
  10. Jang, S. W.; Suh, J. Org. Lett. 2008, 10, 481-484. https://doi.org/10.1021/ol702860h
  11. Kim, M. G.; Kim, M. S.; Lee, S. D.; Suh, J. J. Biol. Inorg. Chem. 2006, 11, 867-875. https://doi.org/10.1007/s00775-006-0139-0
  12. Suh, J.; Son, S. J.; Suh, M. P. Inorg. Chem. 1998, 37, 4872-4877. https://doi.org/10.1021/ic980205x
  13. Suh, J.; Kim, N.; Cho, H. S. Bioorg. Med. Chem. Lett. 1994, 4, 1889-1892. https://doi.org/10.1016/S0960-894X(01)80391-7
  14. Edwards, D. R.; Liu, C. T.; Garrett, G. E.; Neverov, A. A.; Brown, R. S. J. Am. Chem. Soc. 2009, 131, 13738-13748. https://doi.org/10.1021/ja904659e
  15. Liu, C. T.; Melnychuk, S. A.; Liu, C.; Neverov, A. A.; Brown, R. S. Can. J. Chem. 2009, 87, 640-649. https://doi.org/10.1139/V09-026
  16. Tsang, W. Y.; Edwards, D. R; Melnychuk, S. A.; Liu, C. T.; Liu, C.; Neverov, A. A.; Willams, N. H.; Brown, R. S. J. Am. Chem. Soc. 2009, 131, 4159-4166. https://doi.org/10.1021/ja900525t
  17. Edwards, D. R.; Neverov, A. A.; Brown, R. S. J. Am. Chem. Soc. 2009, 131, 368-377. https://doi.org/10.1021/ja807984f
  18. Liu, C. T.; Neverov, A. A.; Brown, R. S. J. Am. Chem. Soc. 2008, 1301, 16711-16720.
  19. Gibson, G. T. T.; Mohamed, M. F.; Neverov, A. A.; Brown, R. S. Inorg. Chem. 2006, 45, 7895-7902.
  20. Gibson, G. T. T.; Neverov, A. A.; Teng, A. C.-T.; Brown, R. S. Can. J. Chem. 2005, 83, 1268-1276. https://doi.org/10.1139/v05-065
  21. Dunn, E. J.; Buncel, E. Can. J. Chem. 1989, 67, 1440-1448. https://doi.org/10.1139/v89-220
  22. Buncel, E.; Dunn, E. J.; Bannard, R. B.; Purdon J. G. Chem. Commun. 1984, 162-163.
  23. Buncel, E.; Albright, K. G.; Onyido, I. Org. Biomol. Chem. 2005, 3, 1468-1475. https://doi.org/10.1039/b501537e
  24. Buncel, E.; Albright, K. G.; Onyido, I. Org. Biomol. Chem. 2004, 2, 601-610. https://doi.org/10.1039/b314886f
  25. Nagelkerke, R.; Thatcher, G. R. J.; Buncel, E. Org. Biomol. Chem. 2003, 1, 163-167. https://doi.org/10.1039/b208408b
  26. Buncel, E.; Nagelkerke, R.; Thatcher, G. R. J. Can. J. Chem. 2003, 81, 53-63. https://doi.org/10.1139/v02-202
  27. Pregel, M. J.; Dunn, E. J.; Buncel, E. J. Am. Chem. Soc. 1991, 113, 3545-3550. https://doi.org/10.1021/ja00009a049
  28. Pregel, M. J.; Buncel, E. J. Org. Chem. 1991, 56, 5583-5588. https://doi.org/10.1021/jo00019a022
  29. Pregel, M. J.; Dunn, E. J.; Buncel, E. Can. J. Chem. 1990, 68, 1846-1858. https://doi.org/10.1139/v90-287
  30. Buncel, E.; Pregel, M. J. J. Chem. Soc., Chem. Commun. 1989, 1566-1567.
  31. Um, I. H.; Shin, Y. H.; Lee, S. E.; Yang, K.; Buncel, E. J. Org. Chem. 2008, 73, 923-930. https://doi.org/10.1021/jo702138h
  32. Um, I. H.; Jeon, S. E.; Baek, M. H.; Park, H. R. Chem. Commun. 2003, 3016-3017.
  33. Um, I. H.; Lee, S. E.; Hong, Y. J.; Park, J. E. Bull. Korean Chem. Soc. 2008, 29, 117-121. https://doi.org/10.5012/bkcs.2008.29.1.117
  34. Um, I. H.; Hong, Y. J.; Lee, Y. J. Bull. Korean Chem. Soc. 1998, 19, 147-150.
  35. Um, I. H.; Nahm, J. H.; Lee, Y. J.; Kwon, D. S. Bull. Korean Chem. Soc. 1996, 17, 840-845.
  36. Pechanec, V.; Kocian, O.; Zavada, J. Collect. Czech. Chem. Commun. 1982, 47, 3405-3411. https://doi.org/10.1135/cccc19823405
  37. Barthel, J.; Justice, J.-C.; Wachter, R. Z. Phys. Chem. 1973, 84, 100-113. https://doi.org/10.1524/zpch.1973.84.1-4.100
  38. Um, I. H.; Hong, Y. J.; Kwon, D. S. Tetrahedron 1997, 53, 5073-5082. https://doi.org/10.1016/S0040-4020(97)00227-5
  39. Um, I. H.; Lee, J. Y.; Ko, S. H.; Bae, S. K. J. Org. Chem. 2006, 71, 5800-5803. https://doi.org/10.1021/jo0606958
  40. Um, I. H.; Lee, J. Y.; Fujio, M.; Tsuno, Y. Org. Biomol. Chem. 2006, 4, 2979-2985. https://doi.org/10.1039/b607194e
  41. Um, I. H.; Jeon, S. E.; Seok, J. A. Chem. Eur. J. 2006, 12, 1237-1243. https://doi.org/10.1002/chem.200500647
  42. Um, I. H.; Kim, K. H.; Park, H. R.; Fujio, M.; Tsuno, Y. J. Org. Chem. 2004, 69, 3937-3942. https://doi.org/10.1021/jo049694a
  43. Um, I. H.; Han, H. J.; Ahn, J. A.; Kang, S.; Buncel, E. J. Org. Chem. 2002, 67, 8475-8480. https://doi.org/10.1021/jo026339g
  44. Um, I. H.; Min, J. S.; Ahn, J. A.; Hahn, H. J. J. Org. Chem. 2000, 65, 5659-5663. https://doi.org/10.1021/jo000482x
  45. Um, I. H.; Kim, E. H.; Lee, J. Y. J. Org. Chem. 2009, 74, 1212-1217. https://doi.org/10.1021/jo802446y
  46. Um, I. H.; Hwang, S. J.; Yoon, S.; Jeon, S. E.; Bae, S. K. J. Org. Chem. 2008, 73, 7671-7677. https://doi.org/10.1021/jo801539w
  47. Um, I. H.; Lee, J. Y.; Kim, H. T.; Bae, S. K. J. Org. Chem. 2004, 69, 2436-2441. https://doi.org/10.1021/jo035854r
  48. Um, I. H.; Chun, S. M.; Chae, O. M.; Fujio, M.; Tsuno, Y. J. Org. Chem. 2004, 69, 3166-3172. https://doi.org/10.1021/jo049812u
  49. Um, I. H.; Hong, J. Y.; Kim, J. J.; Chae, O. M.; Bae, S. K. J. Org. Chem. 2003, 68, 5180-5185. https://doi.org/10.1021/jo034190i
  50. Cevasco, G.; Vigo, D.; Thea, S. Org. Lett. 1999, 1, 1165-1167. https://doi.org/10.1021/ol990796a
  51. Cevasco, G.; Guanti, G.; Hopkins, A. R.; Thea, S.; Williams, A. J. Org. Chem. 1985, 50, 479-484. https://doi.org/10.1021/jo00204a011
  52. Thea, S.; Cevasco, G.; Guanti, G.; Kashefi-Naini, N.; Williams, A. J. Org. Chem. 1985, 50, 1867-1872. https://doi.org/10.1021/jo00211a016

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