Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Kinetics and Mechanism of the Pyridinolysis of Bis(2,6-dimethylphenyl) Chlorophosphate in Acetonitrile

  • Received : 2011.09.09
  • Accepted : 2011.09.26
  • Published : 2011.12.20
Download PDF
⟨ Previous Next ⟩

Abstract

The nucleophilic substitution reactions of bis(2,6-dimethylphenyl) chlorophosphate (5), containing the four ortho-methyl substituents, with X-pyridines are investigated kinetically in MeCN at $65.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a breakpoint at a X = 3-Cl. Unusual positive ${\rho}_X$ (= +5.40) and negative ${\beta}_X$ (= -0.83) values are obtained with the weakly basic pyridines. The pyridinolysis rate of 5 is hundreds times slower compared to that of bis(phenyl) chlorophosphate because of the steric hindrance of the four ortho-methyl substituents in the two phenyl rings. Ion-pair mechanism is proposed and positive ${\rho}_X$ and negative ${\beta}_X$ values are substantiated by an imbalance of the transition state.

Keywords

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. Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
  19. Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632. https://doi.org/10.1002/kin.10081
  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.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936. https://doi.org/10.5012/bkcs.2007.28.6.936
  22. 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
  23. 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
  24. 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
  25. Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065. https://doi.org/10.5012/bkcs.2008.29.10.2065
  26. 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
  27. 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
  28. 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
  29. Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403. https://doi.org/10.5012/bkcs.2010.31.5.1403
  30. Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717. https://doi.org/10.1039/c0ob00517g
  31. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1939. https://doi.org/10.5012/bkcs.2011.32.6.1939
  32. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997. https://doi.org/10.5012/bkcs.2011.32.6.1997
  33. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2306. https://doi.org/10.5012/bkcs.2011.32.7.2306
  34. 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
  35. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3245. https://doi.org/10.5012/bkcs.2011.32.9.3245
  36. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3355. https://doi.org/10.5012/bkcs.2011.32.9.3355
  37. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3783. https://doi.org/10.5012/bkcs.2011.32.10.3783
  38. Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1625. https://doi.org/10.5012/bkcs.2011.32.5.1625
  39. 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
  40. 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
  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. Lee, I. Chem. Soc. Rev. 1990, 19, 317. https://doi.org/10.1039/cs9901900317
  47. Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
  48. Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529. https://doi.org/10.1135/cccc19991529
  49. House, H. O.; Hrabie, J. A.; VanDerveer, D. J. Org. Chem. 1986, 51, 921 https://doi.org/10.1021/jo00356a031
  50. Lunazzi, L.; Mancinelli, M.; Mazzanti, A. J. Org. Chem. 2007, 72, 5391 https://doi.org/10.1021/jo070679q
  51. Bender, M. L.; Chen, M. C. J. Am. Chem. Soc. 1963, 85, 30. https://doi.org/10.1021/ja00884a006
  52. Bentley, T. W.; Harris, H. C.; Koo, I. S. J. Chem. Soc., Perkin Trans. 2 1988, 783.
  53. Shorter, J. Correlation Analysis of Organic Reactivity; Research Studies Press: New York, 1982; p 112.
  54. Park, K.-H.; Kevill, D. N. J. Phys. Org. Chem. 2011, DOI 10.1002/poc.1851.
  55. Park, K.-H.; Kevill, D. N. J. Phys. Org. Chem. 2011, DOI 10.1002/poc.1906.
  56. Williams, A. Free Energy Relationships in Organic and Bioorganic Chemistry; RSC: Cambridge, UK, 2003; Chapter 7.
  57. Ruff, A.; Csizmadia, I. G. Organic Reactions Equilibria, Kinetics and Mechanism; Elsevier: Amsterdam, Netherlands, 1994; Chapter 7.
  58. 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
  59. 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
  60. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 8995. https://doi.org/10.1021/jo0264269
  61. Castro, E. A.; Angel, M.; Campodonico, P.; Santos, J. G. J. Org. Chem. 2002, 67, 8911. https://doi.org/10.1021/jo026390k
  62. Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 4494. https://doi.org/10.1021/jo0255532
  63. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 3874. https://doi.org/10.1021/jo025637a
  64. Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 3129.
  65. Castro, E. A.; Pavez, P.; Arellano, D.; Santos, J. G. J. Org. Chem. 2001, 66, 6571. https://doi.org/10.1021/jo0101252
  66. Spillane, W. J.; McGrath, P.; Brack, C.; O'Byrne, A. B. J. Org. Chem. 2001, 66, 6313. https://doi.org/10.1021/jo015691b
  67. Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 4706. https://doi.org/10.1021/jo000411y
  68. 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
  69. Baynham, A. S.; Hibbert, F.; Malana, M. A. J. Chem. Soc., Perkin Trans 2 1993, 1711.
  70. 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
  71. Onyido, I.; Swierczek, K.; Purcell, J.; Hengge, A. C. J. Am. Chem. Soc. 2005, 127, 7703. https://doi.org/10.1021/ja0501565
  72. Lee, I.; Lee, W. H.; Lee, H. W.; Bentley, T. W. J. Chem. Soc., Perkin Trans. 2 1993, 141.
  73. Chang, S.; Koh, H. J.; Lee, B. S.; Lee, I. J. Org. Chem. 1995, 60, 7760. https://doi.org/10.1021/jo00129a016
  74. Jencks, W. P. Chem. Rev. 1985, 85, 511. https://doi.org/10.1021/cr00070a001
  75. Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301. https://doi.org/10.1021/ar00140a006
  76. Bernasconi, C. F. Adv. Phys. Org. Chem. 1992, 27, 119.

Cited by

  1. Pyridinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile vol.33, pp.1, 2012, https://doi.org/10.5012/bkcs.2012.33.1.309
  2. Kinetics and Mechanism of the Pyridinolysis of (2R,4R,5S)-(+)-2-Chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-Sulfide in Acetonitrile vol.33, pp.3, 2012, https://doi.org/10.5012/bkcs.2012.33.3.1047
  3. Pyridinolysis of Dibutyl Chlorophosphate in Acetonitrile vol.33, pp.3, 2011, https://doi.org/10.5012/bkcs.2012.33.3.1055