Kinetics and mechanism of the benzylaminolysis of O,O-diethyl S-aryl phosphorothioates in dimethyl sulfoxide

Bulletin of the Korean Chemical Society

Volumn 32, Issue 10, 2011, Pages 3587-3591

  Adhikary, Keshab Kumar ^a   Lee, Hai Whang ^a  

^a Inha University   (South Korea)

Author keywords

Benzylaminolysis; Concave downward free energy correlation; Crossinteraction constant; O; O Diethyl Z S aryl phosphorothioate; Phosphoryl transfer reaction

Indexed keywords

BENZYLAMINOLYSIS; CONCAVE DOWNWARD FREE ENERGY CORRELATION; CROSSINTERACTION CONSTANT; PHOSPHOROTHIOATES; PHOSPHORYL TRANSFER;

KINETICS; NUCLEOPHILES; REACTION INTERMEDIATES;

DIMETHYL SULFOXIDE;

EID: 80055017414     PISSN: 02532964     EISSN: 12295949     Source Type: Journal    
DOI: 10.5012/bkcs.2011.32.10.3587     Document Type: Article

References (62)

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. I; 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, 111.
14. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1939.
15. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997.
16. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2306.
17. Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12.
18. Lee, H. W.; Guha, A. K.; Kim, C. K.; Lee, I. J. Org. Chem. 2002, 67, 2215.
19. Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 1135.
20. 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.
21. Adhikary, K. K.; Lumbiny, B. I; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 851.
22. Lumbiny, B. I; Adhikary, K. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 1769.
23. Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2010, 23, 1022.
24. Dey, N. K.; Adhikary, K. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 3856.
25. Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 709.
26. Hoque, M. E. U.; Dey, S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1138.
27. Guha, A. K.; Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1375.
28. Guha, A. K.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2011, 24, 474.
29. Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1945.
30. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2109.
31. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2339.
32. Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1625.
33. 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.
34. Han, I. S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 889.
35. Cook, A. G; Mason, G W. J. Inorg. Nucl. Chem. 1966, 28, 2579.
36. Spillane, W. I; Hogan, G; McHugh, F. A.; Burke, R O. J. Chem. Soc, Perkin Trans. 2 1998, 13.
37. The k2(1) of 1.18 × 10-4 M-1 s-1 at 55.0 °C was calculated by extrapolation in the Arrhenius plot (r = 0.999) with empirical kinetic data: k2 = 2.71 (75.0 °C), 3.87 (85.0 °C), and 5.67 × 10-4 M-1 s-1 (95.0 °C). Enthalpy of activation, ΔH = 8.7 ± 0.3 kcal mol1, and entropy of activation, ΔS = -50 ± 1 cal mol1 K1, were obtained.
38. The basicity of benzylamine [pKa = 10.16 (DMSO), 16.76 (MeCN), 9.34 (H2O)] is much greater (ΔpKa = 4-7) than those of pyridine [pKa = 3.45 (DMSO), 12.33 (MeCN), 5.17 (H2O)] and aniline [pKa = 3.82 (DMSO), 10.56 (MeCN), 4.58 (H2O)]. The pKa values of amines in three solvents (DMSO, MeCN, and water) are collected from
39. Coetzee, J. R; Padmanabhan, G. R. J. Am. Chem. Soc. 1965, 87, 5005.
40. Kolthoff, I. M.; Chantooni, M. K., Jr.; Bhowmik, S. J. Am. Chem. Soc. 1968, 90, 23.
41. Bordwell, R G. Acc. Chem. Res. 1988, 21, 556.
42. Crampton, M. R.; Robotham, I. A. J. Chem. Res. (S) 1997, 22. 9. Aer (dielectric constant) = 46. 45 (DMSO)-35. 94 (MeCN) = 10. 51.
43. Lee, I. Chem. Soc. Rev. 1990, 19, 317.
44. Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
45. Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529.
46. As seen in Fig. 3, the twelve values [(four of Z-substituted leaving groups) x (three of X-substituted nucleophiles) for both the strongly and weakly basic nucleophiles] are used to determine the pxz values, respectively. Although the multiple correlation coefficients do not show satisfactory results, the trends of pxz values are manifest. In general, more than 20 points are employed to calculate the CIC in order to minimize the experimental error.
47. Williams, A. Free Energy Relationships in Organic and Bio-organic Chemistry; RSC: Cambridge, UK, 2003; Chapter 7.
48. Ruff, A.; Csizmadia, I. G Organic Reactions Equilibria, Kinetics and Mechanism; Elsevier: Amsterdam, Netherlands, 1994; Chapter
49. Oh, H. K.; Lee, J. M.; Lee, H. W; Lee, I. Int. J. Chem. Kinet. 2004, 36, 434.
50. Oh, H. K.; Park, J. E.; Lee, H. W. Bull. Korean Chem. Soc. 2004, 25, 1041.
51. Oh, H. K.; Ku, M. FL; Lee, H. W; Lee, I. J. Org. Chem. 2002, 67, 8995.
52. Castro, E. A.; Angel, M.; Campodonico, P.; Santos, J. G. J. Org. Chem. 2002, 67, 8911.
53. Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 4494.
54. Oh, H. K.; Ku, M. FL; Lee, H. W; Lee, I. J. Org. Chem. 2002, 67, 3874.
55. Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 3129.
56. Castro, E. A.; Pavez, P.; Arellano, D.; Santos, J. G. J. Org. Chem. 2001, 66, 6571.
57. Spillane, W. J.; McGrath, P.; Brack, C; O'Byrne, A. B. J. Org. Chem. 2001, 66, 6313.
58. Koh, H. J.; Han, K. L.; Lee, H. W; Lee, I. J. Org. Chem. 2000, 65, 4706.
59. Humeres, E.; Debacher, N. A.; Sierra, M. M. D.; Franco J. D.; Shutz, A. J. Org. Chem. 1998, 63, 1598.
60. Baynham, A. S.; Hibbert, R; Malana, M. A. J. Chem. Soc, Perkin Trans 2 1993, 1711.
61. Primary normal deuterium kinetic isotope effects (DKIEs: fc/fe > 1) involving deuterated benzylamines [XC6H4CH2ND2] are essential to substantiate a hydrogen bonded, four-center-type TSf The values of in/fo =1. 11 with X = 4-C1 and Z = H, and in/fo = 1. 28 with X = 4-C1 and Z = 4-C1 are obtained.
62. Secondary inverse DKE of k/ku = 0. 71 is obtained with X = Z = 4-MeO.