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Kinetics and Mechanism of the Pyridinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile

  • Received : 2011.11.08
  • Accepted : 2011.11.21
  • Published : 2012.01.20

Abstract

The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1c) with X-pyridines are investigated kinetically in acetonitrile at $-25.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 1c with a cyclic five-membered ring is $2.70{\times}10^5$ times faster than its acyclic counterpart (1a: phenyl ethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}$ = +26 eu) compared to negative value of 1a (${\Delta}S^{\neq}$= -24 eu) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=20.5kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=12.7kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater selectivity parameters (${\rho}_X$ = -1.99 and ${\beta}_X$ = 0.41) with the strongly basic pyridines compared to those (${\rho}_X$ = -0.42 and ${\beta}_X$ = 0.07) with the weakly basic pyridines.

Keywords

Phosphoryl transfer reaction;Pyridinolysis;1,2-Phenylene phosphorochloridate;Biphasic concave upward free energy correlation

References

  1. Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12. https://doi.org/10.1021/jo990671j
  2. Lee, H. W.; Guha, A. K.; Kim, C. K.; Lee, I. J. Org. Chem. 2002, 67, 2215. https://doi.org/10.1021/jo0162742
  3. 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
  4. Hoque, M. E. U.; Dey, N. K.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 1797. https://doi.org/10.5012/bkcs.2007.28.10.1797
  5. Adhikary, K. K.; Lumbiny, B. J.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 851. https://doi.org/10.5012/bkcs.2008.29.4.851
  6. Lumbiny, B. J.; Adhikary, K. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 1769. https://doi.org/10.5012/bkcs.2008.29.9.1769
  7. 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
  8. Dey, N. K.; Adhikary, K. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 3856. https://doi.org/10.5012/bkcs.2010.31.12.3856
  9. Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 709. https://doi.org/10.5012/bkcs.2011.32.2.709
  10. 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
  11. 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
  12. Guha, A. K.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2011, 24, 474. https://doi.org/10.1002/poc.1788
  13. Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1945. https://doi.org/10.5012/bkcs.2011.32.6.1945
  14. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2109. https://doi.org/10.5012/bkcs.2011.32.6.2109
  15. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2339. https://doi.org/10.5012/bkcs.2011.32.7.2339
  16. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2805. https://doi.org/10.5012/bkcs.2011.32.8.2805
  17. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3505. https://doi.org/10.5012/bkcs.2011.32.9.3505
  18. 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
  19. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4347. https://doi.org/10.5012/bkcs.2011.32.12.4347
  20. Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
  21. Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632. https://doi.org/10.1002/kin.10081
  22. 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
  23. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936. https://doi.org/10.5012/bkcs.2007.28.6.936
  24. 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
  25. 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
  26. 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
  27. Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065. https://doi.org/10.5012/bkcs.2008.29.10.2065
  28. Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2009, 22, 425. https://doi.org/10.1002/poc.1478
  29. Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2009, 30, 975. https://doi.org/10.5012/bkcs.2009.30.4.975
  30. Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919. https://doi.org/10.1039/b903148k
  31. Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403. https://doi.org/10.5012/bkcs.2010.31.5.1403
  32. Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717. https://doi.org/10.1039/c0ob00517g
  33. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1939. https://doi.org/10.5012/bkcs.2011.32.6.1939
  34. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997. https://doi.org/10.5012/bkcs.2011.32.6.1997
  35. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2306. https://doi.org/10.5012/bkcs.2011.32.7.2306
  36. Adhikary, K. K.; Lumbiny, B. J.; Dey, S.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2628. https://doi.org/10.5012/bkcs.2011.32.8.2628
  37. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3245. https://doi.org/10.5012/bkcs.2011.32.9.3245
  38. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3355. https://doi.org/10.5012/bkcs.2011.32.9.3355
  39. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3783. https://doi.org/10.5012/bkcs.2011.32.10.3783
  40. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4185. https://doi.org/10.5012/bkcs.2011.32.12.4185
  41. Fischer, A.; Galloway, W. J.; Vaughan, J. J. Chem. Soc. 1964, 3591. https://doi.org/10.1039/jr9640003591
  42. Dean, J. A. Handbook of Organic Chemistry; McGraw-Hill: New York, 1987; Chapter 8.
  43. 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
  44. Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 45. https://doi.org/10.1002/9780470171837.ch2
  45. Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
  46. Coetzee, J. F.; Padmanabhan, G. R. J. Am. Chem. Soc. 1965, 87, 5006.
  47. Brown, H. C.; McDaniel, D. H.; Hafliger, O. Determination of Organic Structures by Physical Methods; Braude, E. A., Nachode, F. C., Eds.; Academic Press Inc.: New York, N. Y. 1955.
  48. Streitwieser, A., Jr.; Heathcock, C. H.; Kosower, E. M. Introduction to Organic Chemistry, 4th ed.; Macmillan: New York, 1992; p 735.
  49. Dewar, M. J. S. The Molecular Orbital Theory of Organic Chemistry; McGraw-Hill: New York, 1969; p 358.
  50. Westheimer, F. H. Acc. Chem. Res. 1968, 1, 70. https://doi.org/10.1021/ar50003a002
  51. Gorenstein, D. G. Chem. Rev. 1987, 87, 1047. https://doi.org/10.1021/cr00081a009
  52. Yang, J. C.; Gorenstein, D. G. Tetrahedron 1987, 43, 479. https://doi.org/10.1016/S0040-4020(01)89980-4
  53. Winstein, S.; Fainberg, A. H. J. Am. Chem. Soc. 1956, 78, 2770. https://doi.org/10.1021/ja01593a033
  54. Winstein, S.; Fainberg, A. H. J. Am. Chem. Soc. 1957, 79, 5937. https://doi.org/10.1021/ja01579a027
  55. Ingold, C. K. Structure and Mechanism in Organic Chemistry; 2nd ed. Cornell University Press: Ithaca/N.Y. and London, 1969; p 457.
  56. Gillard, R. D.; McKenzie, E. D.; Ross, M. D. J. Inorg. Nucl. Chem. 1966, 28, 1429. https://doi.org/10.1016/0022-1902(66)80175-6

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