Bulletin of the Korean Chemical Society

  • 제32권6호
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  • Pages.1945-1950
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  • 2011
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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 Methyl Phenyl Phosphinic Chloride in Acetonitrile

  • 투고 : 2011.04.08
  • 심사 : 2011.04.26
  • 발행 : 2011.06.20
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초록

The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.

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참고문헌

  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. Guha, A. K.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2011, 24, 474. https://doi.org/10.1002/poc.1788
  11. 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
  12. 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
  13. Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
  14. Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632. https://doi.org/10.1002/kin.10081
  15. 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
  16. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936. https://doi.org/10.5012/bkcs.2007.28.6.936
  17. 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
  18. 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
  19. 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
  20. Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065. https://doi.org/10.5012/bkcs.2008.29.10.2065
  21. 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
  22. 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
  23. 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
  24. Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403. https://doi.org/10.5012/bkcs.2010.31.5.1403
  25. Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717. https://doi.org/10.1039/c0ob00517g
  26. Lee, I.; Kim, C. K.; Li, H. G.; Sohn, C. K.; Kim, C. K.; Lee, H. W.; Lee, B. S. J. Am. Chem. Soc. 2000, 122, 11162. https://doi.org/10.1021/ja001814i
  27. 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
  28. Fischer, A.; Galloway, W. J.; Vaughan, J. J. Chem. Soc. 1964, 3591. https://doi.org/10.1039/jr9640003591
  29. Dean, J. A. Handbook of Organic Chemistry; McGraw- Hill: New York, 1987; Chapter 8.
  30. 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
  31. Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 45. https://doi.org/10.1002/9780470171837.ch2
  32. Charton, M. Prog. Phys. Org. Chem. 1987, 16, 287. https://doi.org/10.1002/9780470171950.ch6
  33. Taft, R. W. Steric Effect in Organic Chemistry, Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
  34. Coetzee, J. F.; Padmanabhan, G. R. J. Am. Chem. Soc. 1965, 87, 5005. https://doi.org/10.1021/ja00950a006
  35. Streitwieser, A., Jr.; Heathcock, C. H.; Kosower, E. M. Introduction to Organic Chemistry, 4th ed.; Macmillan Publishing Co.: New York, 1992; p 735.
  36. Lee, I. Chem. Soc. Rev. 1990, 19, 317. https://doi.org/10.1039/cs9901900317
  37. Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
  38. Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529. https://doi.org/10.1135/cccc19991529
  39. Williams, A. Free Energy Relationships in Organic and Bioorganic Chemistry; RSC: Cambridge, UK, 2003; Chapter 7.
  40. Ruff, A.; Csizmadia, I. G. Organic Reactions Equilibria, Kinetics and Mechanism; Elsevier: Amsterdam, Netherlands, 1994; Chapter 7.
  41. 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
  42. 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
  43. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 8995. https://doi.org/10.1021/jo0264269
  44. Castro, E. A.; Angel, M.; Campodonico, P.; Santos, J. G. J. Org. Chem. 2002, 67, 8911. https://doi.org/10.1021/jo026390k
  45. Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 4494. https://doi.org/10.1021/jo0255532
  46. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 3874. https://doi.org/10.1021/jo025637a
  47. Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 3129.
  48. Castro, E. A.; Pavez, P.; Arellano, D.; Santos, J. G. J. Org. Chem. 2001, 66, 6571. https://doi.org/10.1021/jo0101252
  49. Spillane, W. J.; McGrath, P.; Brack, C.; O'Byrne, A. B. J. Org. Chem. 2001, 66, 6313. https://doi.org/10.1021/jo015691b
  50. Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 4706. https://doi.org/10.1021/jo000411y
  51. 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
  52. Baynham, A. S.; Hibbert, F.; Malana, M. A. J. Chem. Soc., Perkin Trans 2 1993, 1711.
  53. Jencks, W. P.; Brant, S. R.; Gandler, J. R.; Fendrich, G.; Nakamura, C. J. Am. Chem. Soc. 1982, 104, 7045. https://doi.org/10.1021/ja00389a027
  54. Onyido, I.; Swierczek, K.; Purcell, J.; Hengge, A. C. J. Am. Chem. Soc. 2005, 127, 7703. https://doi.org/10.1021/jo00129a016
  55. Lee, I.; Lee, W. H.; Lee, H. W.; Bentley, T. W. J. Chem. Soc., Perkin Trans 2 1993, 141. https://doi.org/10.1021/cr00070a001
  56. Chang, S.; Koh, H. J.; Lee, B. S.; Lee, I. J. Org. Chem. 1995, 60, 7760. https://doi.org/10.1021/jo00129a016
  57. Jencks, W. P. Chem. Rev. 1985, 85, 511. https://doi.org/10.1021/cr00070a001
  58. Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301. https://doi.org/10.1021/ar00140a006
  59. Bernasconi, C. F. Adv. Phys. Org. Chem. 1992, 27, 119.
  60. Gilliom, R. D. Introduction to Physical Organic Chemistry; Addison-Wesley; Philippines, 1970; pp 167-169.

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