Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Pyridinolyses of 2,4-Dinitrophenyl Phenyl Carbonate and 2,4-Dinitrophenyl Benzoate: Effect of Nonleaving Group on Reactivity and Mechanism

  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Son, Min-Ji (Department of Chemistry, Duksung Women's University) ;
  • Kim, Song-I (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Akhtar, Kalsoom (Department of Chemistry and Nano Science, Ewha Womans University)
  • Received : 2010.04.13
  • Accepted : 2010.05.07
  • Published : 2010.07.20
Download PDF
⟨ Previous Next ⟩

Abstract

Second-order rate constants $(k_N)$ have been measured for reactions of 2,4-dinitrophenyl phenyl carbonate (2) with a series of pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ and compared with the $k_N$ values reported for the corresponding reactions of 2,4-dinitrophenyl benzoate (1) to investigate the effect of nonleaving group on reactivity and mechanism. The reactions of 2 result in larger $k_N$ values than those of 1. The Br${\o}$nsted-type plot for the reactions of 2 exhibits a downward curvature (i.e., ${\beta}2$ = 0.84 and ${\beta}1$ = 0.16), which is typical for reactions reported to proceed through a stepwise mechanism with a change in rate-determining step. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a{^{\circ}}$, has been found to be 8.5 and 9.5 for the reactions of 2 and 1, respectively. Dissection of $k_N$ into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1}$ ratio) has revealed that the reactions of 2 result in larger k1 values than those of 1, indicating that PhO behaves as a stronger electron-withdrawing group than Ph. However, the $k_2/k_{-1}$ ratio has been found to be independent of the electronic nature of Ph and PhO.

Keywords

References

  1. Menger, F. M.; Smith, J. H. J. Am. Chem. Soc. 1972, 94, 3824-3829. https://doi.org/10.1021/ja00766a027
  2. Jencks, W. P. Chem. Rev. 1985, 85, 511-527. https://doi.org/10.1021/cr00070a001
  3. Castro, E. A. Chem. Rev. 1999, 99, 3505-3524. https://doi.org/10.1021/cr990001d
  4. Page, M. I.; Williams, A. Organic and Bio-organic Mechanisms; Longman: Singapore, 1997; Chapter 7.
  5. Maude, A. B.; Williams, A. J. Chem. Soc., Perkin Trans. 1997, 2, 179-183.
  6. Castro, E. A. Pure Appl. Chem. 2009, 81, 685-696. https://doi.org/10.1351/PAC-CON-08-08-11
  7. Castro, E. A.; Gazitua, M.; Rios, P.; Tobar, P.; Santos, J. G. J. Phys. Org. Chem. 2009, 22, 443-448. https://doi.org/10.1002/poc.1488
  8. Castro, E. A.; Acuna, M.; Soto, C.; Trujillo, C.; Vasquez, B.; Santos, J. G. J. Phys. Org. Chem. 2008, 21, 816-822. https://doi.org/10.1002/poc.1399
  9. Castro, E. A.; Aliaga, M.; Santos, J. G. J. Phys. Org. Chem. 2008, 21, 271-278. https://doi.org/10.1002/poc.1312
  10. Castro, E. A.; Echevarria, G. R.; Opazo, A.; Robert, P.; Santos, J. G. J. Phys. Org. Chem. 2006, 19, 129-135. https://doi.org/10.1002/poc.1007
  11. Sung, D. D.; Jang, H. M.; Jang, D. I.; Lee, I. J. Phys. Org. Chem. 2008, 21, 1014-1019. https://doi.org/10.1002/poc.1418
  12. Oh, H. K.; Lee, J. M.; Lee, H. W.; Lee, I. Int. J. Chem. Kinet. 2004, 36, 434-440. https://doi.org/10.1002/kin.20000
  13. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 8995-8998. https://doi.org/10.1021/jo0264269
  14. Han, J. K.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 4706-4711. https://doi.org/10.1021/jo000411y
  15. Um, I. H.; Park, Y. M.; Fujio, M.; Mishima, M.; Tsuno, Y. J. Org. Chem. 2007, 72, 4816-4821. https://doi.org/10.1021/jo0705061
  16. Um, I. H.; Kim, E. Y.; Park, H. R. Jeon, S. E. J. Org. Chem. 2006, 71, 2302-2306. https://doi.org/10.1021/jo052417z
  17. Um, I. H.; Lee, J. Y.; Whang Lee, H.; Nagano, Y.; Fujio, M.; Tsuno, Y. J. Org. Chem. 2005, 70, 4980-4987. https://doi.org/10.1021/jo050172k
  18. Um, I. H.; Lee, E. J.; Seok, J. A.; Kim, K. H. J. Org. Chem. 2005, 70, 7530-7536. https://doi.org/10.1021/jo050624t
  19. Um, I. H.; Kim, S. I.; Baek, H. W. Bull. Korean Chem. Soc. 2009, 30, 2909-2912. https://doi.org/10.5012/bkcs.2009.30.12.2909
  20. Um, I. H.; Akhtar, K. Bull. Korean Chem. Soc. 2008, 29, 772-776. https://doi.org/10.5012/bkcs.2008.29.4.772
  21. Um, I. H.; Min, S. W.; Chun, S. M. Bull. Korean Chem. Soc. 2008, 29, 1359-1363. https://doi.org/10.5012/bkcs.2008.29.7.1359
  22. Um, I. H.; Seo, J. A.; Lee, H. M. Bull. Korean Chem. Soc. 2008, 29, 1915-1919. https://doi.org/10.5012/bkcs.2008.29.10.1915
  23. Um, I. H.; Baek, M. H.; Bae, S. Y. J. Org. Chem. 2004, 69, 6365-6370. https://doi.org/10.1021/jo0492160
  24. Um, I. H.; Baek, M. H.; Han, H. J. Bull. Korean Chem. Soc. 2003, 24, 1245-1250. https://doi.org/10.5012/bkcs.2003.24.9.1245
  25. Gresser, M. J.; Jencks, W. P. J. Am. Chem. Soc. 1977, 99, 6970-6980. https://doi.org/10.1021/ja00463a033
  26. Castro, E. A.; Valdivia, J. L. J. Org. Chem. 1986, 51, 1668-1672. https://doi.org/10.1021/jo00360a007
  27. Castro, E. A.; Santander, C. L. J. Org. Chem. 1985, 50, 3595-3600. https://doi.org/10.1021/jo00219a029
  28. Castro, E. A.; Steinfort, G. B. J. Chem. Soc., Perkin Trans. 1983, 2, 453-457.
  29. Castro, E. A.; Aguayo, R.; Bessolo, J.; Santos, J. G. J. Org. Chem. 2005, 70, 7788-7791. https://doi.org/10.1021/jo051052f
  30. Castro, E. A.; Aguayo, R.; Bessolo, J.; Santos, J. G. J. Org. Chem. 2005, 70, 3530-3536. https://doi.org/10.1021/jo050119w
  31. Castro, E. A.; Vivanco, M.; Aguayo, R.; Santos, J. G. J. Org. Chem. 2004, 69, 5399-5404. https://doi.org/10.1021/jo049260f
  32. Castro, E. A.; Aguayo, R.; Santos, J. G. J. Org. Chem. 2003, 68, 8157-8161. https://doi.org/10.1021/jo0348120
  33. Oh, H. K.; Kim, S. K.; Lee, H. W.; Lee, I. New J. Chem. 2001, 25, 313-317. https://doi.org/10.1039/b006974o
  34. Oh, H. K.; Kim, S. K.; Cho, I. H.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2000, 2, 2306-2310.
  35. Lim, W. M.; Kim, W. K.; Jung, H. J.; Lee, I. Bull. Korean Chem. Soc. 1995, 16, 252-256.
  36. Um, I. H.; Hong, J. Y.; Seok, J. A. J. Org. Chem. 2005, 70, 1438-1444. https://doi.org/10.1021/jo048227q
  37. 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
  38. Um, I. H.; Hong, J. Y.; Kim, J. J.; Chae, O. M.; Bea, S. K. J. Org. Chem. 2003, 68, 5180-5185. https://doi.org/10.1021/jo034190i
  39. 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
  40. 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
  41. Um, I. H.; Hwang, S. J.; Baek, M. H.; Park, E. J. J. Org. Chem. 2006, 71, 9191-9197. https://doi.org/10.1021/jo061682x
  42. Um, I. H.; Lee, J. Y.; Ko, S. H.; Bea, S. K. J. Org. Chem. 2006, 71, 5800-5803. https://doi.org/10.1021/jo0606958
  43. Isaacs, N. S. Physical Organic Chemistry; Longman: England, 1995; p 153.
  44. Lowry, T. H; Richardson, K. S. Mechanism and Theory in Organic Chemistry; Harper Collins: New York, 1987; p 153.
  45. Um, I. H.; Park, H. R.; Kim, E. Y. Bull. Korean Chem. Soc. 2003, 24, 1251-1255. https://doi.org/10.5012/bkcs.2003.24.9.1251
  46. Castro, E.; Moodie, R. B. I. Chem. Soc., Chem. Commun. 1973, 828-829.
  47. Carroll, F. A. Perspectives on Structure and Mechanism in Organic Chemistry; Brooks/Cole: New York, 1998.
  48. Jencks, W. P. Catalysis in Chemistry and Enzymology; McGraw-Hill: New York, 1969.

Cited by

  1. A Kinetic Study on Nucleophilic Substitution Reactions of Phenyl Y-Substituted-Phenyl Carbonates with Z-Substituted-Phenoxides: Effect of Modification of Nonleaving Group from Benzoyl to Phenyloxycarbonyl on Reactivity and Reaction Mechanism vol.33, pp.10, 2012, https://doi.org/10.5012/bkcs.2012.33.10.3253
  2. -(4-nitropheny) S-(4-nitrophenyl) thio and dithiocarbonate vol.27, pp.4, 2013, https://doi.org/10.1002/poc.3231
  3. Pyridinolysis of 2,4-Dinitrophenyl Phenyl Thionocarbonate: Effect of Changing Electrophilic Center from C=O to C=S on Reactivity and Mechanism vol.32, pp.4, 2010, https://doi.org/10.5012/bkcs.2011.32.4.1165
  4. Concerted aminolysis of diaryl carbonates: Kinetic sensitivity on the basicity of the nucleophile, nonleaving group, and nucleofuge vol.44, pp.9, 2010, https://doi.org/10.1002/kin.20700