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Studies of Solvolyses of Di-n-butyl Phosphorochloridate by Extended Grunwald-Winstein Equation
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 Title & Authors
Studies of Solvolyses of Di-n-butyl Phosphorochloridate by Extended Grunwald-Winstein Equation
Kang, Min Sung; Kim, Cheul Ju; Kang, Suk Jin; Koh, Han Joong;
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 Abstract
The solvolysis rate constants of di-n-butyl phosphorochloridate ((CH3CH2CH2CH2O)2POCI, 1) in 28 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivities values of 1.40 and 0.42 for l and m, respectively. These l and m values can be considered to support an SN2 reaction pathway. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH (8.0 to 15.9 kcal·mol−1 ) values and large negative ΔS (−25.8 to −53.1 cal·mol−1 ·K−1 ) values, the Kivinen’s n values (0.9~1.7), and the solvent kinetic isotope effect (1.62).
 Keywords
Di-n-butyl phosphorochloridate;Extended Grunwald-Winstein equation; mechanism;Kivinen’s equation;
 Language
Korean
 Cited by
 References
1.
(a) Hudson, R. F.; Loveday, G. W. J. Chem. Soc. 1966, 766. crossref(new window)

2.
(b) Hyne, J. B.; Will, R. J. Am. Chem. Soc. 1959, 81, 2371. crossref(new window)

3.
(c) Kevill, D. N.; D’Souza, M. J. J. Chem. Soc., Perkin Trans. 2. 1997, 1721.

4.
(a) Skoog, M. T.; Jencks, W. P. J. Am. Chem. Soc. 1984, 106, 7597. crossref(new window)

5.
(b) Bourne, N. J.; Chrystiuk, E.; Davis, A. M.; Williams, A. J. Am. Chem. Soc. 1988, 110, 1890. crossref(new window)

6.
(c) Thatcher, G. R.; Luger, R. K. Adv. Phys. Org. Chem. 1989, 25, 99.

7.
(d) Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans 2 1999, 765.

8.
Koh, H. J.; Kang, S. J.; Kevill, D. N. Phosphorus, Sulfur,and Silicon 2010, 185, 1404. crossref(new window)

9.
Guggenheim, E. A. Phil. Mag. 1926, 2, 538. crossref(new window)

10.
Koh, H. J.; Kang, S. J.; Kevill, D. N. Bull. Korean Chem. Soc. 2008, 29, 1927. crossref(new window)

11.
Chen, L. J.; Burka, L. T. Tetrahedron Lett. 1989, 39, 5351.

12.
Glasstone, G.; Laidler, K. J.; Eyring, H. The Theory of Rate Processes; McGraw-Hill: New York, 1941; 418.

13.
(a) Bentley, T. W.; Schleyer, P. V. R. J. Am. Chem. Soc. 1976, 98, 7658. crossref(new window)

14.
(b) Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121. crossref(new window)

15.
Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M. ed.; JAI Press: Greenwich, CT, 1996, 1, 81.

16.
Dean, J. A. Handbook of Organic Chemistry; McGraw-Hill: New York, 1987; Table 4~10.

17.
Grunwald, E.; Winstein, S. J. Am. Chem. Soc. 1948, 70, 846. crossref(new window)

18.
Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741. crossref(new window)

19.
Koh, H. J.; Kang, S. J. Bull Korean Chem. Soc. 2009, 30, 2437. crossref(new window)

20.
Moon, D. H.; Seong, M. H.; Kyong, J. B.; Lee, Y.; Lee, Y. W. Bull Korean Chem. Soc. 2011, 32, 2413. crossref(new window)

21.
Koh, H. J.; Kang, S. J. Bull Korean Chem. Soc. 2011, 32, 3799. crossref(new window)

22.
Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700. crossref(new window)

23.
Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845. crossref(new window)

24.
(a) Koo, I. S.; Bentley, T. W.; Kang, D. H.; Lee, I. J. Chem. Soc., Perkin Trans. 2. 1991, 296.

25.
(b) Kevill, D. N.; D’Souza, M. J. J. Chem. Res. Synop. 1993, 174.

26.
(c) Kyong, J. B.; Yoo, J. S.; Kevill, D. N. J. Org. Chem. 2003, 68, 3425. crossref(new window)

27.
Kyong, J. B.; Park, B. C.; Kim, C. B.; Kevill, D. N. J. Org. Chem. 2000, 65, 8051. crossref(new window)

28.
Kevill, D. N.; Park, K. H.; Koh, H. J. J. Phys. Org. Chem. 2010, 23, 1.

29.
Yew, K. H.; Koh, H. J.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1995, 2263.

30.
Kevill, D. N.; Ryu, J. H.; Neidermeyer, M. A.; Koyoshi, F.; D’Souza, M. J. J. Phys. Org. Chem. 2007, 20, 431. crossref(new window)

31.
Kevill, D. N.; Koyoshi, F.; D’Souza, M. J. Int. J. Mol. Sci. 2007, 8, 346. crossref(new window)

32.
Koh, H. J.; Kang, S. J. Bull. Korean Chem. Soc. 2014, 35, 2285. crossref(new window)

33.
D’Souza, M. J.; Yaakoubd, L.; Mlynarski, S. L.; Kevill, D. N. Int. J. Mol. Sci. 2008, 9, 914. crossref(new window)

34.
Koh, H. J.; Kang, S. J. Bull. Korean Chem. Soc. 2012, 33, 4117. crossref(new window)

35.
(a) Frost, A.; Pearson, R. G. Kinetics and Mechanism; 2nd ed., Wiley: New York, 1961; Chap. 7.

36.
(b) Lee, I.; Koh, H. J.; Park, Y. S.; Lee, H. W. J. Chem. Soc. Perkin Trans 2 1993, 1575.

37.
(a) Kivinen, A. Acta Chem. Scand. 1965, 19, 845. crossref(new window)

38.
(b) Tommila, F. Acta Chem. Scand. 1955, 9, 975. crossref(new window)

39.
Zhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826. crossref(new window)