Bulletin of the Korean Chemical Society

  • 제33권7호
  • /
  • Pages.2260-2264
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  • 2012
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Kinetics and Mechanism of the Pyridinolysis of Dimethyl Isothiocyanophosphate in Acetonitrile

  • 투고 : 2012.02.15
  • 심사 : 2012.04.04
  • 발행 : 2012.07.20
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초록

The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of dimethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for substituent X variations in the nucleophiles exhibit two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with a rate-limiting expulsion of the isothiocyanate leaving group from the intermediate. The relatively large ${\beta}x$ values imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb. The steric effects of the two ligands play an important role to determine the pyridinolysis rates of isothiocyanophosphates.

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참고문헌

  1. Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2012, 33, 1042. https://doi.org/10.5012/bkcs.2012.33.3.1042
  2. Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 1135. https://doi.org/10.5012/bkcs.2003.24.8.1135
  3. Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2010, 23, 1022. https://doi.org/10.1002/poc.1709
  4. Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12. https://doi.org/10.1021/jo990671j
  5. Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
  6. Dey, N. K.; Han, I. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 2003. https://doi.org/10.5012/bkcs.2007.28.11.2003
  7. Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944. https://doi.org/10.1039/b713167d
  8. Han, I. S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 889. https://doi.org/10.5012/bkcs.2011.32.3.889
  9. Fischer, A.; Galloway, W. J.; Vaughan, J. J. Chem. Soc. 1964, 3591. https://doi.org/10.1039/jr9640003591
  10. Dean, J. A. Handbook of Organic Chemistry; McGraw-Hill: New York, 1987; Chapter 8.
  11. Lee, I.; Kim, C. K.; Han, I. S.; Lee, H. W.; Kim, W. K.; Kim, Y. B. J. Phys. Chem. B 1999, 103, 7302. https://doi.org/10.1021/jp991115w
  12. Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 45. https://doi.org/10.1002/9780470171837.ch2
  13. Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099.
  14. Ritchie, C. D. Solute Solvent Interactions; Marcel- Dekker: New York, 1969; p 228.
  15. Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 1998, 63, 9834. https://doi.org/10.1021/jo9814905
  16. Taft, R. W. Steric Effect in Organic Chemistry; Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
  17. Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
  18. Lee, I. Chem. Soc. Rev. 1990, 19, 317. https://doi.org/10.1039/cs9901900317
  19. Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
  20. Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529.
  21. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 1055. https://doi.org/10.5012/bkcs.2012.33.3.1055
  22. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3505. https://doi.org/10.5012/bkcs.2011.32.9.3505
  23. Gresser, M. J.; Jencks, W. P. J. Am. Chem. Soc. 1977, 99, 6963, 6970. https://doi.org/10.1021/ja00463a032
  24. Castro, E. A.; Ibanez, F.; Salas, M.; Santos, J. G.; Sepulveda, P. J. Org. Chem. 1993, 58, 459. https://doi.org/10.1021/jo00054a033
  25. Castro, E. A.; Leandro, L.; Millan, P.; Santos, J. G. J. Org. Chem. 1999, 64, 1953. https://doi.org/10.1021/jo982063u
  26. Castro, E. A.; Cubillos, M.; Santos, J. G. J. Org. Chem. 2001, 66, 6000. https://doi.org/10.1021/jo0100695
  27. Guha, A. K.; Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1375. https://doi.org/10.5012/bkcs.2011.32.4.1375
  28. Bernat, J.; Kristian, P.; Guspanova, J.; Imrich, J.; Busova, T. Collect. Czech. Chem. Commun. 1977, 62, 1491.

피인용 문헌

  1. Anilinolysis of Dimethyl Isothiocyanophosphate in Acetonitrile vol.33, pp.8, 2012, https://doi.org/10.5012/bkcs.2012.33.8.2769