Browse > Article
http://dx.doi.org/10.5012/bkcs.2011.32.5.1625

Kinetics and Mechanism of the Benzylaminolysis of O,O-Diphenyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide  

Adhikary, Keshab Kumar (Department of Chemistry, Inha University)
Lee, Hai-Whang (Department of Chemistry, Inha University)
Publication Information
Abstract
Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.
Keywords
Phosphoryl transfer reaction; Benzylaminolysis; Deuterium kinetic isotope effect; Nonlinear biphasic free energy correlation;
Citations & Related Records
Times Cited By KSCI : 15  (Citation Analysis)
Times Cited By Web Of Science : 15  (Related Records In Web of Science)
연도 인용수 순위
1 Oh, H. K.; Kim, S. K.; Cho, I. H.; Lee, H. W.; Lee, I. J. Chem., Soc., Perkin Trans. 2 2000, 2306.
2 Oh, H. K.; Yang, J. H.; Cho, I. H.; Lee, H. W.; Lee, I. Int. J. Chem. Kinet. 2000, 32, 485.   DOI   ScienceOn
3 Koh, H. J.; Lee, H. W.; Lee, I. J. Chem., Soc., Perkin Trans. 2 1994, 125.
4 Lee, I.; Kim, H. Y.; Kang, H. K.; Lee, H. W. J. Org. Chem. 1988, 53, 2678.   DOI
5 Lee, I.; Choi, Y. H.; Lee, H. W. J. Chem. Soc., Perkin Trans 2 1988, 1537.
6 Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526.   DOI   ScienceOn
7 Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631.   DOI
8 Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826.   DOI
9 Melander, L., Jr.; Saunders, W. H. Reaction Rates of Isotopic Molecules; Wiley-Interscience: New York, 1980.
10 Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
11 Oh, H. K. Bull. Korean Chem. Soc. 2011, 32, 137.   DOI   ScienceOn
12 Oh, H. K.; Park, J. E.; Sung, D. D.; Lee, I. J. Org. Chem. 2004, 69, 9285.   DOI   ScienceOn
13 Oh, H. K.; Park, J. E.; Sung, D. D.; Lee, I. J. Org. Chem. 2004, 69, 3150.   DOI   ScienceOn
14 Oh, H. K.; Lee, J. Y.; Lee, H. W.; Lee, I. New J. Chem. 2002, 26, 473.   DOI   ScienceOn
15 Oh, H. K.; Park, C. Y.; Lee, J. M.; Lee, I. Bull. Korean Chem. Soc. 2001, 22, 383.
16 Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717.   DOI   ScienceOn
17 Koh, H. J.; Shin, C. H.; Lee, H. W.; Lee, I. J. Chem., Soc., Perkin Trans. 2 1998, 1329.
18 Koh, H. J.; Lee, J. W.; Lee, H. W.; Lee, I. New J. Chem. 1997, 21, 447.
19 Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403.   DOI   ScienceOn
20 Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12.   DOI   ScienceOn
21 Lee, H. W.; Guha, A. K.; Kim, C. K.; Lee, I. J. Org. Chem. 2002, 67, 2215.   DOI   ScienceOn
22 Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 1135.   DOI   ScienceOn
23 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.   DOI   ScienceOn
24 Adhikary, K. K.; Lumbiny, B. J.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 851.   DOI   ScienceOn
25 Lumbiny, B. J.; Adhikary, K. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 1769.   DOI   ScienceOn
26 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2010, 23, 1022.   DOI   ScienceOn
27 Dey, N. K.; Adhikary, K. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 3856.   DOI   ScienceOn
28 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2009, 22, 425.   DOI   ScienceOn
29 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2008, 21, 544.   DOI   ScienceOn
30 Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065.   DOI   ScienceOn
31 Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2009, 30, 975.   DOI   ScienceOn
32 Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919.   DOI   ScienceOn
33 Oh, H. K.; Lee, J. Y.; Lee, I. Bull. Korean Chem. Soc. 1998, 19, 1198.
34 Oh, H. K.; Lee, Y. H.; Lee, I. Int. J. Chem. Kinet. 2000, 32, 131.   DOI   ScienceOn
35 Oh, H. K.; Kim, S. K.; Lee, I. Bull. Korean Chem. Soc. 1999, 20, 1017.
36 Oh, H. K.; Woo, S. Y.; Shin, C. H.; Lee, I. Int. J. Chem. Kinet. 1998, 30, 849.   DOI   ScienceOn
37 Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780.   DOI   ScienceOn
38 Oh, H. K.; Kim, S. K.; Lee, H. W.; Lee, I. J. Chem., Soc., Perkin Trans. 2 2001, 1753.
39 Oh, H. K.; Lee, J. Y.; Yun, J. H.; Park, Y. S.; Lee, I. Int. J. Chem. Kinet. 1998, 30, 419.   DOI   ScienceOn
40 Oh, H. K.; Yang, J. H.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 1999, 20, 1418.
41 Han, I. S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 889.   DOI   ScienceOn
42 Oh, H. K.; Kim, S. K.; Lee, H. W.; Lee, I. New J. Chem. 2001, 25, 313.   DOI
43 Guha, A. K.; Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1375.   DOI   ScienceOn
44 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.   DOI   ScienceOn
45 Coetzee, J. F.; Padmanabhan, G. R. J. Am. Chem. Soc. 1965, 87, 5005.   DOI
46 Kolthoff, I. M.; Chantooni, Jr., M. K.; Bhowmik, S. J. Am. Chem. Soc. 1968, 90, 23.   DOI
47 Bordwell, F. G. Acc. Chem. Res. 1988, 21, 556.
48 Crampton, M. R.; Robotham, I. A. J. Chem. Res. (S) 1997, 22.
49 Cook, A. G.; Mason, G. W. J. Inorg. Nucl. Chem. 1966, 28, 2579.   DOI   ScienceOn
50 Spillane, W. J.; Hogan, G.; McHugh, F. A.; Burke, P. O. J. Chem. Soc., Perkin Trans. 2 1998, 13.
51 Lee, I. Chem. Soc. Rev. 1990, 19, 317.   DOI
52 Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
53 Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529.   DOI   ScienceOn
54 Oh, H. K.; Yang, J. H.; Lee, H. W.; Lee, I. New J. Chem. 2000, 24, 213.   DOI
55 Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
56 Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 709.   DOI   ScienceOn
57 Guha, A. K.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. DOI 10.1002/ poc.1788.   DOI   ScienceOn
58 Hoque, M. E. U.; Dey, S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1138.   DOI   ScienceOn
59 Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632.   DOI   ScienceOn
60 Hoque, M. E. U.; Dey, S.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Org. Chem. 2007, 72, 5493.   DOI   ScienceOn
61 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936.   DOI   ScienceOn
62 Dey, N. K.; Han, I. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 2003.   DOI   ScienceOn
63 Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944.   DOI   ScienceOn