Kinetics and mechanism of the anilinolysis of diethyl thiophosphinic chloride in acetonitrile

Bulletin of the Korean Chemical Society

Volumn 32, Issue 7, 2011, Pages 2306-2310

  Hoque, Md Ehtesham Ul ^a   Lee, Hai Whang ^a  

^a Inha University   (South Korea)

Author keywords

Anilinolysis; Deuterium kinetic isotope effect; Diethyl thiophosphinic chloride; Phosphoryl transfer reaction

Indexed keywords

ANILINOLYSIS; DEUTERIUM KINETIC ISOTOPE EFFECT; DIETHYL THIOPHOSPHINIC CHLORIDE; GRADUAL TRANSITION; KINETICS AND MECHANISM; NUCLEOPHILIC SUBSTITUTION REACTIONS; PHOSPHORYL TRANSFER REACTION; REACTION MECHANISM; SUBSTITUTED ANILINES;

ACETONITRILE; ANILINE; CARRIER MOBILITY; CHLORINE COMPOUNDS; DEUTERIUM; SUBSTITUTION REACTIONS;

KINETICS;

EID: 79960493121     PISSN: 02532964     EISSN: 12295949     Source Type: Journal    
DOI: 10.5012/bkcs.2011.32.7.2306     Document Type: Article

References (70)

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.
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.
4. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936.
5. Dey, N. K.; Han, I. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 2003.
6. Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944.
7. Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2008, 21, 544.
8. Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 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.
10. Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2009, 30, 975.
11. Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919.
12. Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403.
13. Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717.
14. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997.
15. Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12.
16. Lee, H. W.; Guha, A. K.; Kim, C. K.; Lee, I. J. Org. Chem. 2002, 67, 2215.
17. Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 1135.
18. 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.
19. Adhikary, K. K.; Lumbiny, B. J.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 851.
20. Lumbiny, B. J.; Adhikary, K. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 1769.
21. Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2010, 23, 1022.
22. Dey, N. K.; Adhikary, K. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 3856.
23. Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 709.
24. Hoque, M. E. U.; Dey, S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1138.
25. Guha, A. K.; Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1375.
26. Guha, A. K.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2011, 24, 474.
27. Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1625.
28. 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.
29. Han, I. S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 889.
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.
34. Perrin and coworkers reported that the basicities of β-deuterated analogs of benzylamine, N,N-dimethylaniline and methylamine increase roughly by 0.02 pKa units per deuterium, and that these effects are additive;
35. Perrin, C. I.; Engler, R. E. J. Phys. Chem. 1991, 95, 8431.
36. Perrin, C. I.; Ohta, B. K.; Kuperman, J. J. Am. Chem. Soc. 2003, 125, 15008.
37. Perrin, C. I.; Ohta, B. K.; Kuperman, J.; Liberman, J.; Erdelyi, M. J. Am. Chem. Soc. 2005, 127, 9641.
38. Charton, M. Prog. Phys. Org. Chem. 1987, 16, 287.
39. Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
40. Taft, R. W. Steric Effect in Organic Chemistry; Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
41. Hengge, A. C.; Onyido, I. Curr. Org. Chem. 2005, 9, 61.
42. Omakor, J. E.; Onyido, I.; van Loon, G. W.; Buncel, E. J. Chem. Soc., Perkin Trans. 2 2001, 324.
43. Gregersen, B. A.; Lopez, X.; York, D. M. J. Am. Chem. Soc. 2003, 125, 7178.
44. Hondal, R. J.; Bruzik, K. S.; Zhao, Z.; Tsai, M. D. J. Am. Chem. Soc. 1997, 119, 5477.
45. Onyido, I.; Swierczek, K.; Purcell, J.; Hengge, A. C. J. Am. Chem. Soc. 2005, 127, 7703.
46. Holtz, K. M.; Catrina, I. E.; Hengge, A. C.; Kantrowitz, E. R. Biochemistry 2000, 39, 9451.
47. Liu, Y.; Gregersen, B. A.; Hengge, A. C.; York, D. M. Biochemistry 2006, 45, 10043.
48. Zhang, L.; Xie, D.; Xu, D.; Guo, H. J. Phys. Chem. A 2005, 109, 11295.
49. Dunn, E. J.; Buncel, E. Can. J. Chem. 1989, 67, 1440.
50. Dunn, E. J.; Moir, R. Y.; Buncel, E.; Purdon, J. G.; Bannard, R. A. B. Can. J. Chem. 1990, 68, 1837.
51. Buncel, E.; Albright, K. G.; Onyido, I. Org. Biomol. Chem. 2004, 2, 601.
52. Onyido, I.; Albright, K.; Buncel, E. Org. Biomol. Chem. 2005, 3, 1468.
53. Williams, A.; Naylor, R. A. J. Chem. Soc. B 1971, 1967.
54. Douglas, K. T.; Williams, A. J. Chem. Soc., Perkin Trans 2 1976, 515.
55. Until now, the anilinolysis of O-aryl methyl phosphonochloridothioates is the only one yielding nonlinear biphasic free energy correlations among all of the studied P=O and P=S systems.
56. D = 0.367 for the reaction of O-4-cyanophenyl methyl phosphonochloridothioates with 4-chloroaniline in MeCN at 55.0 °C is the smallest value, i.e., unprecedented greatest secondary inverse.
57. Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
58. Lee, I. Chem. Soc. Rev. 1995, 24, 223.
59. Marlier, J. F. Acc. Chem. Res. 2001, 34, 283.
60. Westaway, K. C. Adv. Phys. Org. Chem. 2006, 41, 217.
61. Villano, S. M.; Kato, S.; Bierbaum, V. M. J. Am. Chem. Soc. 2006, 128, 736.
62. Gronert, S.; Fajin, A. E.; Wong, L. J. Am. Chem. Soc. 2007, 129, 5330.
63. Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526.
64. Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631.
65. Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826.
66. D = 1.42-1.82) of 4O, there is no doubt that the anilinolyses of both substrates predominantly proceed through frontside nucleophilic attack.
67. This lab has cumulated data of DKIEs for the anilinolyses and benzylaminolyses of various kinds of substrates in MeCN and DMSO.
68. D = 1.0-1.3 with the strongly basic anilines and kH/ kD = 0.37-0.57 with the weakly basic anilines), and the present work simultaneously yielded both primary normal and secondary inverse DKIEs. All the other studied P=O and P=S substrates yielded either primary normal or secondary inverse DKIEs.
69. The reactions of O-aryl methyl phosphonochloridothioates with the weakly basic anilines proceed through a stepwise mechanism with a rate-limiting bond breaking.
70. Birdsall, D. J.; Slawin, A. M. Z.; Woollins, J. D. Polyhedron 2001, 20, 125.