Bulletin of the Korean Chemical Society

  • 제33권6호
  • /
  • Pages.1879-1884
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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 Anilinolysis of Dipropyl Chlorophosphate in Acetonitrile

  • 투고 : 2012.02.15
  • 심사 : 2012.03.02
  • 발행 : 2012.06.20
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초록

The kinetic studies on the reactions of dipropyl chlorophosphate (3O) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.09-1.01) with the strongly basic anilines while secondary inverse ($k_H/k_D$ = 0.74-0.82) with the weakly basic anilines. The steric effects of the two ligands on the rates are extensively discussed for the anilinolyses of the ($R_1O$)($R_2O$)P(=O or S)Cl-type chlorophosphates and chlorothiophosphates. A concerted mechanism is proposed with a frontside nucleophilic attack involving a hydrogen-bonded four-center-type transition state for the strongly basic anilines and with a backside attack transition state for the weakly basic anilines on the basis of the DKIEs, primary normal and secondary inverse with the strongly and weakly basic anilines, respectively.

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참고문헌

  1. Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
  2. Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632. https://doi.org/10.1002/kin.10081
  3. 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
  4. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936. https://doi.org/10.5012/bkcs.2007.28.6.936
  5. 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
  6. 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
  7. 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
  8. Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065. https://doi.org/10.5012/bkcs.2008.29.10.2065
  9. 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
  10. 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
  11. 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
  12. Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403. https://doi.org/10.5012/bkcs.2010.31.5.1403
  13. Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717. https://doi.org/10.1039/c0ob00517g
  14. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1939. https://doi.org/10.5012/bkcs.2011.32.6.1939
  15. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997. https://doi.org/10.5012/bkcs.2011.32.6.1997
  16. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2306. https://doi.org/10.5012/bkcs.2011.32.7.2306
  17. 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
  18. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3245. https://doi.org/10.5012/bkcs.2011.32.9.3245
  19. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3355. https://doi.org/10.5012/bkcs.2011.32.9.3355
  20. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3783. https://doi.org/10.5012/bkcs.2011.32.10.3783
  21. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3880. https://doi.org/10.5012/bkcs.2011.32.11.3880
  22. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4185. https://doi.org/10.5012/bkcs.2011.32.12.4185
  23. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4361. https://doi.org/10.5012/bkcs.2011.32.12.4361
  24. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4403. https://doi.org/10.5012/bkcs.2011.32.12.4403
  25. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 663. https://doi.org/10.5012/bkcs.2012.33.2.663
  26. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 843. https://doi.org/10.5012/bkcs.2012.33.3.843
  27. Taft, R. W. Steric Effect in Organic Chemistry; Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
  28. Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
  29. Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
  30. Ritchie, C. D. In Solute-Solvent Interactions; Coetzee, J. F., Ritchie, C. D., Eds.; Marcel Dekker: New York, 1969; Chapter 4.
  31. Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 54.
  32. Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099
  33. Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780. https://doi.org/10.1021/jo970413r
  34. Perrin, C. I.; Engler, R. E. J. Phys. Chem. 1991, 95, 8431. https://doi.org/10.1021/j100175a004
  35. Perrin, C. I.; Ohta, B. K.; Kuperman, J. J. Am. Chem. Soc. 2003, 125, 15008. https://doi.org/10.1021/ja038343v
  36. Perrin, C. I.; Ohta, B. K.; Kuperman, J.; Liberman, J.; Erdelyi, M. J. Am. Chem. Soc. 2005, 127, 9641. https://doi.org/10.1021/ja0511927
  37. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165. https://doi.org/10.1021/cr00002a004
  38. Streitwieser, A., Jr.; Heathcock, C. H.; Kosower, E. M. Introduction to Organic Chemistry, 4th ed.; Macmillan: New York, 1992; p 735.
  39. Crumpler, T. B.; Yoh, J. H. Chemical Computations and Errors; John Wiley: New York, 1940; p 178.
  40. Lee, I. Chem. Soc. Rev. 1990, 19, 317. https://doi.org/10.1039/cs9901900317
  41. Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
  42. Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529. https://doi.org/10.1135/cccc19991529
  43. Hengge, A. C.; Onyido, I. Curr. Org. Chem. 2005, 9, 61. https://doi.org/10.2174/1385272053369349
  44. Omakor, J. E.; Onyido, I.; vanLoon, G. W.; Buncel, E. J. Chem. Soc., Perkin Trans. 2 2001, 324.
  45. Gregersen, B. A.; Lopez, X.; York, D. M. J. Am. Chem. Soc. 2003, 125, 7178. https://doi.org/10.1021/ja035167h
  46. Hondal, R. J.; Bruzik, K. S.; Zhao, Z.; Tsai, M. D. J. Am. Chem. Soc. 1997, 119, 5477. https://doi.org/10.1021/ja964217y
  47. Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
  48. Lee, I. Chem. Soc. Rev. 1995, 24, 223. https://doi.org/10.1039/cs9952400223
  49. Marlier, J. F. Acc. Chem. Res. 2001, 34, 283. https://doi.org/10.1021/ar000054d
  50. Westaway, K. C. Adv. Phys. Org. Chem. 2006, 41, 217. https://doi.org/10.1016/S0065-3160(06)41004-2
  51. Villano, S. M.; Kato, S.; Bierbaum, V. M. J. Am. Chem. Soc. 2006, 128, 736. https://doi.org/10.1021/ja057491d
  52. Gronert, S.; Fajin, A. E.; Wong, L. J. Am. Chem. Soc. 2007, 129, 5330. https://doi.org/10.1021/ja070093l
  53. Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526. https://doi.org/10.1021/ja00085a037
  54. Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631. https://doi.org/10.1021/jo00178a010
  55. Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826. https://doi.org/10.1021/ja00003a015

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