Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Kinetics and Mechanism of the Anilinolysis of Dicyclohexyl Phosphinic Chloride in Acetonitrile

  • Received : 2011.04.08
  • Accepted : 2011.04.26
  • Published : 2011.06.20
Download PDF
⟨ Previous Next ⟩

Abstract

The nucleophilic substitution reactions of dicyclohexyl phosphinic chloride [3; $cHex_2$P(=O)Cl] with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 60.0 $^{\circ}C$. The anilinolysis rate is too slow to be rationalized by the stereoelectronic effects. The rate is contrary to expectations for the electronic influence of the two ligands and exhibits exceptionally great negative deviation from the Taft's eq. The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines invariably change from primary normal ($k_H/k_D$ > 1; max $k_H/k_D$ = 1.10 with X = 4-MeO) with the strongly basic anilines (X = 4-MeO, 4-Me, 3-Me) to secondary inverse ($k_H/k_D$ < 1; min $k_H/k_D$ = 0.673 with X = 3-Cl) with the weakly basic anilines (X = H, 4-F, 4-Cl, 3-Cl). A concerted $S_N2$ mechanism is proposed on the basis of both secondary inverse and primary normal DKIEs. The obtained DKIEs imply that the fraction of a frontside attack increases as the aniline becomes more basic. A hydrogen-bonded, four-center-type transition state is suggested for a frontside attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a backside attack.

Keywords

References

  1. Hudson, R. F. Structure and Mechanism in Organophosphorus Chemistry; Academic Press: London, 1965; Chapter 3.
  2. Thatcher, G. R. J.; Kluger, R. Adv. Phys. Org. Chem. 1989, 25, 99. https://doi.org/10.1016/S0065-3160(08)60019-2
  3. Williams, A. Concerted Organic and Bio-Organic Mechanisms; CRC Press: Boca Raton, 2000; Chapter 7-8.
  4. Um, I. H.; Hong, J. Y.; Buncel, E. Chem. Commun. 2001, 27.
  5. Um, I. H.; Jeon, S. E.; Baek, M. H.; Park, H. R. Chem. Commun. 2003, 3016.
  6. Kirby, A. J.; Lima, M. F.; da Silva, D.; Nome, F. J. Am. Chem. Soc. 2004, 126, 1350. https://doi.org/10.1021/ja038428w
  7. Hengge, A. C. Adv. Phys. Org. Chem. 2005, 40, 49. https://doi.org/10.1016/S0065-3160(05)40002-7
  8. Kumara Swamy, K. C.; Satish Kumar, N. Acc. Chem. Res. 2006, 39, 324. https://doi.org/10.1021/ar050188x
  9. Um, I. H.; Shin, Y. H.; Han, J. Y.; Mishima, M. J. Org. Chem. 2006, 71, 7715. https://doi.org/10.1021/jo061308x
  10. Um, I. H.; Akhtar, K.; Shin, Y. H.; Han, J. Y. J. Org. Chem. 2007, 72, 3823. https://doi.org/10.1021/jo070171n
  11. Um, I. H.; Park, J. E.; Shin, Y. H. Org. Biomol. Chem. 2007, 5, 3539. https://doi.org/10.1039/b712427a
  12. Um, I. H.; Shin, Y. H.; Lee, S. E.; Yang, K.; Buncel, E. J. Org. Chem. 2008, 73, 923. https://doi.org/10.1021/jo702138h
  13. Kirby, A. J.; Souza, B. S.; Medeiros, M.; Priebe, J. P.; Manfredi, A. M.; Nome, F. Chem. Commun. 2008, 4428.
  14. Um, I. H.; Han, J. Y.; Hwang, S. J. Chem. Eur. J. 2008, 14, 7324. https://doi.org/10.1002/chem.200800553
  15. Um, I. H.; Han, J. Y.; Shin, Y. H. J. Org. Chem. 2009, 74, 3073. https://doi.org/10.1021/jo900219t
  16. Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
  17. Lee, I. Chem. Soc. Rev. 1995, 24, 223. https://doi.org/10.1039/cs9952400223
  18. Marlier, J. F. Acc. Chem. Res. 2001, 34, 283. https://doi.org/10.1021/ar000054d
  19. Westaway, K. C. Adv. Phys. Org. Chem. 2006, 41, 217. https://doi.org/10.1016/S0065-3160(06)41004-2
  20. Villano, S. M.; Kato, S.; Bierbaum, V. M. J. Am. Chem. Soc. 2006, 128, 736. https://doi.org/10.1021/ja057491d
  21. Gronert, S.; Fajin, A. E.; Wong, L. J. Am. Chem. Soc. 2007, 129, 5330. https://doi.org/10.1021/ja070093l
  22. Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526. https://doi.org/10.1021/ja00085a037
  23. Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631. https://doi.org/10.1021/jo00178a010
  24. Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826. https://doi.org/10.1021/ja00003a015
  25. Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
  26. Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632. https://doi.org/10.1002/kin.10081
  27. 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
  28. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936. https://doi.org/10.5012/bkcs.2007.28.6.936
  29. 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
  30. 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
  31. 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
  32. Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065. https://doi.org/10.5012/bkcs.2008.29.10.2065
  33. 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
  34. 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
  35. 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
  36. Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403. https://doi.org/10.5012/bkcs.2010.31.5.1403
  37. Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717. https://doi.org/10.1039/c0ob00517g
  38. Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12. https://doi.org/10.1021/jo990671j
  39. Lee, H. W.; Guha, A. K.; Kim, C. K.; Lee, I. J. Org. Chem. 2002, 67, 2215. https://doi.org/10.1021/jo0162742
  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.; 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
  42. 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
  43. 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
  44. 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
  45. 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
  46. 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
  47. Guha, A. K.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2011, 24, 474. https://doi.org/10.1002/poc.1788
  48. 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
  49. 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
  50. Taft, R. W. Steric Effect in Organic Chemistry, ed.; Newman, M. S.; Wiley: New York, 1956; Chapter 3.
  51. Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
  52. Ritchie, C. D. In Solute-Solvent Interactions, Coetzee, J. F., Ritchie, C. D., Eds.; Marcel Dekker: New York, 1969; Chapter 4.
  53. Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 54.
  54. Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099.
  55. 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
  56. Perrin, C. I.; Engler, R. E. J. Phys. Chem. 1991, 95, 8431. https://doi.org/10.1021/j100175a004
  57. Perrin, C. I.; Ohta, B. K.; Kuperman, J. J. Am. Chem. Soc. 2003, 125, 15008. https://doi.org/10.1021/ja038343v
  58. 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
  59. Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
  60. Charton, M. Prog. Phys. Org. Chem. 1987, 16, 287. https://doi.org/10.1002/9780470171950.ch6
  61. Dunn, E. J.; Buncel, E. Can. J. Chem. 1989, 67, 1440. https://doi.org/10.1139/v89-220
  62. Dunn, E. J.; Moir, R. Y.; Buncel, E.; Purdon, J. G.; Bannard, R. A. B. Can. J. Chem. 1990, 68, 1837. https://doi.org/10.1139/v90-286
  63. Buncel, E.; Albright, K. G.; Onyido, I. Org. Biomol. Chem. 2004, 2, 601. https://doi.org/10.1039/b314886f
  64. Onyido, I.; Albright, K.; Buncel, E. Org. Biomol. Chem. 2005, 3, 1468. https://doi.org/10.1039/b501537e
  65. Williams, A.; Naylor, R. A. J. Chem. Soc. B 1971, 1967. https://doi.org/10.1039/j29710001967
  66. Douglas K. T.; Williams, A. J. Chem. Soc., Perkin Trans 2 1976, 515.
  67. Lee, H. W.; Lee, J. W.; Koh, H. J.; Lee, I. Bull. Korean Chem. Soc. 1998, 19, 642
  68. Koh, H. J.; Kim, O. S.; Lee, H. W.; Lee, I. J. Phys. Org. Chem. 1997, 10, 725 https://doi.org/10.1002/(SICI)1099-1395(199710)10:10<725::AID-POC943>3.0.CO;2-X
  69. Chang, S.; Koh, H. J.; Lee, B. S.; Lee, I. J. Org. Chem. 1995, 60, 7760 https://doi.org/10.1021/jo00129a016
  70. Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper and Row: New York, 1987; p 239
  71. Melander, L.; Saunders, W. H., Jr. Reaction Rates of Isotopic Molecules; Wiley: New York, 1981; Chapter 6.
  72. Menger, F. M.; Smith, J. H. J. Am. Chem. Soc. 1972, 94, 3824. https://doi.org/10.1021/ja00766a027
  73. Buncel, E.; Albright, K.; Onyido, I. Org. Biomol. Chem. 2004, 2, 601. https://doi.org/10.1039/b314886f
  74. Onyido, I.; Albright, K.; Buncel, E. Org. Biomol. Chem. 2005, 3, 1468. https://doi.org/10.1039/b501537e

Cited by

  1. Kinetics and Mechanism of the Anilinolysis of Diisopropyl Thiophosphinic Chloride in Acetonitrile vol.32, pp.11, 2011, https://doi.org/10.5012/bkcs.2011.32.11.3880
  2. Pyridinolysis of Dicyclohexyl Phosphinic Chloride in Acetonitrile vol.32, pp.6, 2011, https://doi.org/10.5012/bkcs.2011.32.6.2109
  3. Kinetics and Mechanism of the Pyridinolysis of Diethyl Thiophosphinic Chloride in Acetonitrile vol.32, pp.8, 2011, https://doi.org/10.5012/bkcs.2011.32.8.2805
  4. Pyridinolysis of Diisopropyl Chlorophosphate in Acetonitrile vol.32, pp.9, 2011, https://doi.org/10.5012/bkcs.2011.32.9.3505
  5. Kinetics and Mechanism of the Pyridinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile vol.33, pp.1, 2012, https://doi.org/10.5012/bkcs.2012.33.1.270
  6. 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
  7. Pyridinolysis of Dipropyl Chlorothiophosphate in Acetonitrile vol.33, pp.1, 2012, https://doi.org/10.5012/bkcs.2012.33.1.325
  8. Kinetics and Mechanism of the Anilinolysis of Dibutyl Chlorophosphate in Acetonitrile vol.33, pp.2, 2012, https://doi.org/10.5012/bkcs.2012.33.2.663
  9. Concerted Pathway to the Mechanism of the Anilinolysis of Bis(N,N-diethylamino)phosphinic Chloride in Acetonitrile vol.70, pp.1, 2017, https://doi.org/10.1071/CH16202
  10. Kinetics and Mechanism of the Pyridinolysis of Aryl Ethyl Chlorothiophosphates in Acetonitrile vol.32, pp.11, 2011, https://doi.org/10.5012/bkcs.2011.32.11.3947
  11. Kinetics and Mechanism of the Pyridinolysis of Bis(2,6-dimethylphenyl) Chlorophosphate in Acetonitrile vol.32, pp.12, 2011, https://doi.org/10.5012/bkcs.2011.32.12.4179
  12. Kinetics and Mechanism of the Anilinolysis of Ethylene Phosphorochloridate in Acetonitrile vol.32, pp.12, 2011, https://doi.org/10.5012/bkcs.2011.32.12.4185
  13. Kinetics and Mechanism of the Benzylaminolysis of O,O-Dimethyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide vol.32, pp.12, 2011, https://doi.org/10.5012/bkcs.2011.32.12.4304
  14. Kinetics and Mechanism of the Anilinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile vol.32, pp.12, 2011, https://doi.org/10.5012/bkcs.2011.32.12.4361
  15. Kinetics and Mechanism of the Pyridinolysis of Diisopropyl Thiophosphinic Chloride in Acetonitrile vol.32, pp.12, 2011, https://doi.org/10.5012/bkcs.2011.32.12.4387
  16. Kinetics and Mechanism of the Anilinolysis of Dipropyl Chlorothiophosphate in Acetonitrile vol.32, pp.12, 2011, https://doi.org/10.5012/bkcs.2011.32.12.4403
  17. Kinetics and Mechanism of the Anilinolysis of Diethyl Thiophosphinic Chloride in Acetonitrile vol.32, pp.7, 2011, https://doi.org/10.5012/bkcs.2011.32.7.2306
  18. Kinetics and Mechanism of the Anilinolysis of Diisopropyl Chlorophosphate in Acetonitrile vol.32, pp.9, 2011, https://doi.org/10.5012/bkcs.2011.32.9.3245
  19. Kinetics and Mechanism of the Anilinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile vol.32, pp.9, 2011, https://doi.org/10.5012/bkcs.2011.32.9.3355
  20. Kinetics and Mechanism of the Benzylaminolysis of O,O-Diethyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide vol.32, pp.10, 2011, https://doi.org/10.5012/bkcs.2011.32.10.3587
  21. Pyridinolysis of Dibutyl Chlorophosphate in Acetonitrile vol.33, pp.3, 2011, https://doi.org/10.5012/bkcs.2012.33.3.1055
  22. Kinetics and Mechanism of the Anilinolysis of Dibutyl Chlorothiophosphate in Acetonitrile vol.33, pp.3, 2011, https://doi.org/10.5012/bkcs.2012.33.3.843
  23. Kinetics and Mechanism of the Anilinolysis of Dipropyl Chlorophosphate in Acetonitrile vol.33, pp.6, 2012, https://doi.org/10.5012/bkcs.2012.33.6.1879