Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Pyridinolysis of Diisopropyl Chlorothiophosphate in Acetonitrile

  • Received : 2012.04.25
  • Accepted : 2012.07.02
  • Published : 2012.10.20
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Abstract

The nucleophilic substitution reactions of diisopropyl chlorothiophosphate (5) with X-pyridines have been kinetically studied in MeCN at $35.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for the substituent X variations in the nucleophiles show biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 5 exhibits great negative deviation from the Taft plot. A concerted $S_N2$ mechanism is proposed involving a change of the attacking direction of the X-pyridines from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines.

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References

  1. 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
  2. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 325. https://doi.org/10.5012/bkcs.2012.33.1.325
  3. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 1085. https://doi.org/10.5012/bkcs.2012.33.3.1085
  4. Adhikary, K. K.; Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3947. https://doi.org/10.5012/bkcs.2011.32.11.3947
  5. Hoque, M. E. U.; Dey, S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1138. https://doi.org/10.5012/bkcs.2011.32.4.1138
  6. Taft, R. W. Steric Effect in Organic Chemistry; Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
  7. Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
  8. Fischer, A.; Galloway, W. J.; Vaughan, J. J. Chem. Soc. 1964, 3591. https://doi.org/10.1039/jr9640003591
  9. Dean, J. A. Handbook of Organic Chemistry; McGraw- Hill: New York, 1987; Chapter 8.
  10. Castro, E. A.; Freudenberg, M. J. Org. Chem. 1980, 45, 906. https://doi.org/10.1021/jo01293a027
  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. Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
  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.
  20. Hoque, M. E. U.; Dey, S.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Org. Chem. 2007, 72, 5493. https://doi.org/10.1021/jo0700934
  21. 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
  22. Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2008, 21, 544. https://doi.org/10.1002/poc.1314
  23. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4403. https://doi.org/10.5012/bkcs.2011.32.12.4403
  24. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 843. https://doi.org/10.5012/bkcs.2012.33.3.843
  25. Hoque, M. E. U.; Lee, H. W. unpublished data.
  26. Williams, A. Free Energy Relationships in Organic and Bioorganic Chemistry; RSC: Cambridge, UK, 2003; Chapter 7.
  27. Ruff, A.; Csizmadia, I. G. Organic Reactions Equilibria, Kinetics and Mechanism; Elsevier: Amsterdam, Netherlands, 1994; Chapter 7.
  28. 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
  29. Oh, H. K.; Park, J. E.; Lee, H. W. Bull. Korean Chem. Soc. 2004, 25, 1041. https://doi.org/10.5012/bkcs.2004.25.7.1041
  30. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 8995. https://doi.org/10.1021/jo0264269
  31. Castro, E. A.; Angel, M.; Campodonico, P.; Santos, J. G. J. Org. Chem. 2002, 67, 8911. https://doi.org/10.1021/jo026390k
  32. Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 4494. https://doi.org/10.1021/jo0255532
  33. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 3874. https://doi.org/10.1021/jo025637a
  34. Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 3129.
  35. Castro, E. A.; Pavez, P.; Arellano, D.; Santos, J. G. J. Org. Chem. 2001, 66, 6571. https://doi.org/10.1021/jo0101252
  36. Spillane, W. J.; McGrath, P.; Brack, C.; O'Byrne, A. B. J. Org. Chem. 2001, 66, 6313. https://doi.org/10.1021/jo015691b
  37. Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 4706. https://doi.org/10.1021/jo000411y
  38. Humeres, E.; Debacher, N. A.; Sierra, M. M. D.; Franco J. D.; Shutz, A. J. Org. Chem. 1998, 63, 1598. https://doi.org/10.1021/jo971869b
  39. Baynham, A. S.; Hibbert, F.; Malana, M. A. J. Chem. Soc., Perkin Trans 2 1993, 1711.
  40. 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
  41. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2109. https://doi.org/10.5012/bkcs.2011.32.6.2109
  42. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2339. https://doi.org/10.5012/bkcs.2011.32.7.2339
  43. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2805. https://doi.org/10.5012/bkcs.2011.32.8.2805
  44. Adhikary, K. K.; Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3743. https://doi.org/10.5012/bkcs.2011.32.10.3743
  45. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4387. https://doi.org/10.5012/bkcs.2011.32.12.4387
  46. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 309. https://doi.org/10.5012/bkcs.2012.33.1.309

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