Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Metal-Ion Catalysis in Alkaline Ethanolysis of 2-Pyridyl Thionobenzoate: Effects of Modification of Electrophilic Center from C=O to C=S

  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Song, Yoon-Ju (Department of Chemistry and Plant Resources Research Institute, Duksung Women's University) ;
  • Kim, Min-Young (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Lee, Jae-In (Department of Chemistry and Plant Resources Research Institute, Duksung Women's University)
  • Received : 2013.02.21
  • Accepted : 2013.02.27
  • Published : 2013.05.20
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Abstract

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

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References

  1. Martin, D. W.; Mayes, P. A.; Rodwell, V. W.; Granner, D. K. Harper's Review of Biochemistry, 20th ed.; Lange Medical Publications: Los Altos, 1985; p 630.
  2. Dugas, H. Bioorganic Chemistry, 2nd ed.; Springer-Verlag: New York, 1989; p 284.
  3. Mohamed, M. F.; Sanchez-Lombardo, I.; Neverov, A. A.; Brown, R. S. Org. Biomol. Chem. 2012, 10, 631-639. https://doi.org/10.1039/c1ob06482g
  4. Barrera, I. F.; Maxwell, C. I.; Neverov, A. A.; Brown, R. S. J. Org. Chem. 2012, 77, 4156-4160. https://doi.org/10.1021/jo300329x
  5. Raycroft, M. A. R.; Liu, C. T.; Brown, R. S. Inorg. Chem. 2012, 51, 3846-3854. https://doi.org/10.1021/ic300059e
  6. Brown, R. S. Prog. Inorg. Chem. 2012, 57, 55-117.
  7. Dhar, B. B.; Edwards, D. R.; Brown, R. S. Inorg. Chem. 2011, 50, 3071-3077. https://doi.org/10.1021/ic200007v
  8. Edwards, D. R.; Neverov, A. A.; Brown, R. S. Inorg. Chem. 2011, 50, 1786-1797. https://doi.org/10.1021/ic102220m
  9. Brown, R. S.; Lu, Z. L.; Liu, C. T.; Tsang, W. Y.; Edwards, D. R.; Neverov, A. A. J. Phys. Org. Chem. 2010, 23, 1-15.
  10. Mohamed, M. F.; Neverov, A. A.; Brown, R. S. Inorg. Chem. 2009, 48, 11425-11433. https://doi.org/10.1021/ic9015965
  11. Brown, R. S.; Neverov, A. A. Adv. Phys. Org. Chem. 2007, 42, 271-331. https://doi.org/10.1016/S0065-3160(07)42006-8
  12. Feng, G.; Tanifum, E. A.; Adams, H.; Hengge, A. C. J. Am. Chem. Soc. 2009, 131, 12771-12779. https://doi.org/10.1021/ja904134n
  13. Humphry, T.; Iyer, S.; Iranzo, O.; Morrow, J. R.; Richard, J. P.; Paneth, P.; Hengge, A. C. J. Am. Chem. Soc. 2008, 130, 17858-17866. https://doi.org/10.1021/ja8059864
  14. Zalatan, J. G.; Catrina, I.; Mitchell, R.; Grzyska, P. K.; O'Brien, P. J.; Herschlag, D.; Hengge, A. C. J. Am. Chem. Soc. 2007, 129, 9789-9798. https://doi.org/10.1021/ja072196+
  15. Davies, A. G. J. Chem. Res. 2008, 361-375.
  16. Davies, A. G. J. Chem. Soc., Perkin Trans. 1 2000, 1997-2010.
  17. Fife, T. H.; Chauffe, L. Bioorg. Chem. 2000, 28, 357-373. https://doi.org/10.1006/bioo.2000.1176
  18. Fife, T. H.; Bembi, R. J. Am. Chem. Soc. 1993, 115, 11358-11363. https://doi.org/10.1021/ja00077a039
  19. Fife, T. H.; Pujari, M. P. J. Am. Chem. Soc. 1990, 112, 5551-5557. https://doi.org/10.1021/ja00170a020
  20. Chei, W. S.; Ju, H.; Suh, J. Bioorg. Med. Chem. Lett. 2012, 22, 1533-1537. https://doi.org/10.1016/j.bmcl.2012.01.008
  21. Chei, W. S.; Ju, H.; Suh, J. J. Biol. Inorg. Chem. 2011, 16, 511-519. https://doi.org/10.1007/s00775-010-0750-y
  22. 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
  23. Chei, W. S.; Suh, J. Prog. Inorg. Chem. 2007, 55, 79-142. https://doi.org/10.1002/9780470144428.ch2
  24. Jeung, C. S.; Song, J. B.; Kim, Y. H.; Suh, J. Bioorg. Med. Chem. Lett. 2001, 11, 3061-3064. https://doi.org/10.1016/S0960-894X(01)00615-1
  25. Suh, J.; Son, S. J.; Suh, M. P. Inorg. Chem. 1998, 37, 4872-4877. https://doi.org/10.1021/ic980205x
  26. 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
  27. Suh, J. Acc. Chem. Res. 1992, 25, 273-279. https://doi.org/10.1021/ar00019a001
  28. Lee, J. H.; Park, J.; Lah, M. S.; Chin, J.; Hong, J. I. Org. Lett. 2007, 9, 3729-3731. https://doi.org/10.1021/ol071306e
  29. Livieri, M.; Manicin, F.; Saielli, G.; Chin, J.; Tonellato, U. Chem. Eur. J. 2007, 13, 2246-2256. https://doi.org/10.1002/chem.200600672
  30. Livieri, M.; Mancin, F.; Tonellato, U.; Chin, J. Chem. Commun. 2004, 2862-2863.
  31. Williams, N. H.; Takasaki, B.; Wall, M.; Chin, J. Acc. Chem. Res. 1999, 32, 485-493. https://doi.org/10.1021/ar9500877
  32. Buncel, E.; Dunn, E. J.; Bannard, R. B.; Purdon J. G. J. Chem. Soc. Chem. Commun. 1984, 162-163.
  33. Dunn, E. J.; Buncel, E. Can. J. Chem. 1989, 67, 1440-1448. https://doi.org/10.1139/v89-220
  34. 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
  35. Koo, I. S.; Ali, D.; Yang, K.; Park, Y.; Esbata, A.; van Loon, G. W.; Buncel, E. Can. J. Chem. 2009, 87, 433-439. https://doi.org/10.1139/v08-178
  36. Buncel, E.; Albright, K. G.; Onyido, I. Org. Biomol. Chem. 2005, 3, 1468-1475. https://doi.org/10.1039/b501537e
  37. Buncel, E.; Albright, K. G.; Onyido, I. Org. Biomol. Chem. 2004, 2, 601-610. https://doi.org/10.1039/b314886f
  38. Nagelkerke, R.; Thatcher, G. R. J.; Buncel, E. Org. Biomol. Chem. 2003, 1, 163-167. https://doi.org/10.1039/b208408b
  39. Buncel, E.; Nagelkerke, R.; Thatcher, G. R. J. Can. J. Chem. 2003, 81, 53-63. https://doi.org/10.1139/v02-202
  40. Cacciapaglia, R.; Mandolini, L. Chem. Soc. Rev. 1993, 22, 221-231. https://doi.org/10.1039/cs9932200221
  41. Cacciapaglia, R.; Mandolini, L.; Tomei, A. J. Chem. Soc., Perkin Trans. 2 1994, 367-372.
  42. Cacciapaglia, R.; Van Doorn, A. R.; Mandolini, L.; Reinhoudt, D. N.; Verboom, W. J. Am. Chem. Soc. 1992, 114, 2611-2617. https://doi.org/10.1021/ja00033a038
  43. Cacciapaglia, R.; Mandolini, L.; Reinhoudt, D. N.; Verboom, W. J. Phys. Org. Chem. 1992, 5, 663-669. https://doi.org/10.1002/poc.610051008
  44. Cacciapaglia, R.; Mandolini, L. J. Org. Chem. 1988, 53, 2579-2582. https://doi.org/10.1021/jo00246a033
  45. Um, I. H.; Shin, Y. H.; Park, J. E.; Kang, J. S.; Buncel, E. Chem. Eur. J. 2012, 18, 961-968. https://doi.org/10.1002/chem.201102404
  46. Um, I. H.; Shin, Y. H.; Lee, S. E.; Yang, K. Y.; Buncel, E. J. Org. Chem. 2008, 73, 923-930. https://doi.org/10.1021/jo702138h
  47. Um, I. H.; Jeon, S. E.; Baek, M. H.; Park, H. R. Chem. Commun. 2003, 3016-3017.
  48. Um, I. H.; Kang, J. S.; Shin, Y. H.; Buncel, E. J. Org. Chem. 2013, 78, 490-497. https://doi.org/10.1021/jo302373y
  49. Um, I. H.; Seo, J. Y.; Kang, J. S.; An, J. S. Bull. Chem. Soc. Jpn. 2012, 85, 1007-1013. https://doi.org/10.1246/bcsj.20120104
  50. Um, I. H.; Kim, C. W.; Kang, J. S.; Lee, J. I. Bull. Korean Chem. Soc. 2012, 33, 519-523. https://doi.org/10.5012/bkcs.2012.33.2.519
  51. Lee, J. I.; Kang, J. S.; Kim, S. I.; Um, I. H. Bull. Korean Chem. Soc. 2010, 31, 2929-2933. https://doi.org/10.5012/bkcs.2010.31.10.2929
  52. Lee, J. I.; Kang, J. S.; Im, L. R.; Um, I. H. Bull. Korean Chem. Soc. 2010, 31, 3543-3548. https://doi.org/10.5012/bkcs.2010.31.12.3543
  53. An, J. S.; Namkoong, G.; Kang, J. S.; Um, I. H. Bull. Korean Chem. Soc. 2011, 32, 2423-2427. https://doi.org/10.5012/bkcs.2011.32.7.2423
  54. Pechanec, V.; Kocian, O.; Zavada, J. Collect. Czech. Chem. Commun. 1982, 47, 3405-3411. https://doi.org/10.1135/cccc19823405
  55. Barthel, J.; Justice, J.-C.; Wachter, R. Z. Phys. Chem. 1973, 84, 100-113.
  56. Pearson, R. G.; Songstad, J. J. Am. Chem. Soc. 1967, 89, 1827-1836. https://doi.org/10.1021/ja00984a014
  57. Pregel, M. J.; Dunn, E. J.; Buncel, E. Can. J. Chem. 1990, 68, 1846-1858. https://doi.org/10.1139/v90-287
  58. Kay, R. L.; Evans, D. F. J. Phys. Chem. 1966, 70, 2325-2335. https://doi.org/10.1021/j100879a040
  59. Eisenman, G. Biophys. J. 1962, 2, 259-323. https://doi.org/10.1016/S0006-3495(62)86959-8

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