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http://dx.doi.org/10.5012/jkcs.2017.61.1.25

Application of the Extended Grunwald-Winstein Equation to the Solvolyses of 4-(Chlorosulfonyl)biphenyl  

Kang, Suk Jin (Department of Science Education, Jeonju National University of Education)
Koh, Han Joong (Department of Science Education, Jeonju National University of Education)
Publication Information
Journal of the Korean Chemical Society / v.61, no.1, 2017 , pp. 25-28 More about this Journal
Abstract
Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl ($C_6H_5C_6H_4SO_2Cl$, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative $S_N2$ mechanism. These l and m values for the solvolyses of 1 can be considered to support a $S_N2$ pathway with some ionization reaction. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.
Keywords
4-(Chlorosulfonyl)biphenyl; Extended Grunwald-Winstein equation; $S_N2$ pathway; Kinetic solvent isotope effect;
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1 (a) Grunwald, E.; Winstein, S. J. Am. Chem. Soc. 1948, 70, 846.   DOI
2 (b) Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700.   DOI
3 (a) Fainberg, A. H.; Winstein, S. J. Am. Chem. Soc. 1957, 79, 1579.   DOI
4 (b) Fainberg, A. H.; Winstein, S. J. Am. Chem. Soc. 1957, 79, 1602.   DOI
5 (a) Kevill, D. N.; Lin, G. M. L. J. Am. Chem. Soc. 1979, 101, 3916.   DOI
6 (b) Kevill, D. N.; Anderson, S. W. J. Am. Chem. Soc. 1986, 108, 1579.   DOI
7 (a) Kevill, D. N. In Advances in Quantitative Structure-Property Relationships, Vol. 4; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; pp. 81-115.
8 (b) Kevill, N. D.; D'Souza, M. J. Collect. Czech. Chem. Commun. 1999, 64, 1790.   DOI
9 Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121.
10 (a) Swain, C. G.; Langsdorf, W. P. J. Am. Chem. Soc. 1951, 73, 2813.   DOI
11 (b) Jenkins, F. E.; Hambly, A. N. Austral. J. Chem. 1961, 14, 205.   DOI
12 (a) Jr. Hall, H. K. J. Am. Chem. Soc. 1956, 78, 1450.   DOI
13 (b) Jr. Hall, H. K.; Lucck, C. H. J. Org. Chem. 1963, 28, 2818.   DOI
14 (c) Ko, E. C. F.; Robertson, R. E. J. Am. Chem. Soc. 1972, 94, 573.   DOI
15 (a) Rogne, O. J. Chem. Soc, B. 1969, 663.
16 (b) Lee, B. C.; Lee, I. J. Korean Chem. Soc. 1980, 24, 342.
17 (a) Kim, S. R.; Choi, H. J.; Park, J. K.; Koo, I. S.; Koh, H. J. Bull. Korean Chem. Soc. 2014, 35, 51.   DOI
18 (b) Ingold, C. K. Structure and Mechanism in Organic Chemistry, 2d ed.; Cornell University Press: Ithaca, N. Y., 1969; pp. 427-457.
19 (a) Lee, S. H.; Rhu, C. J.; Kyong, J. B.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2007, 28, 657.   DOI
20 (b) Koh, H. J.; Kang, S. J.; Kevill, D. N. Bull. Korean Chem. Soc. 2009, 30, 383.   DOI
21 (c) Seong, M. H.; Choi, S. H.; Lee, Y. W.; Kyong, J. B.; Kim, D. K. Bull. Korean Chem. Soc. 2009, 30, 3408.
22 (d) Seong, M. H.; Kyong, J. B.; Lee, Y. H.; Kevill, D. N. Int. J. Mol. Sci. 2009, 10, 929.   DOI
23 (a) Lee, Y. W.; Seong, M. H.; Kyong, J. B.; Kevill, D. N. Bull. Korean Chem. Soc. 2010, 31, 3366.   DOI
24 (b) Kyong, J. B.; Park, B. C.; Kim, C. B.; Kevill, D. N. J. Org. Chem. 2000, 65, 8051.   DOI
25 (c) Koh, H. J.; Kang, S. J. Bull. Korean Chem. Soc. 2011, 32, 1897.   DOI
26 (a) Kevill, D. N.; Kamil, W. A. J. Org. Chem. 1982, 47, 3785.   DOI
27 (b) Kaspi, J.; Rappoport, Z. J. J. Am. Chem. Soc. 1980, 102, 3829.   DOI
28 Koh, H. J.; Kang, S. J.; Kim, C. J. J. Bull. Korean Chem. Soc. 2009, 30, 378.   DOI
29 Kyong, J. B.; Park, B. C.; Kim, C. B.; Kevill, D. N. J. Org. Chem. 2000, 65, 8051.   DOI
30 D'Souza, M. J.; Reed, D. N.; Erdman, K. J.; Kyong, J. B.; Kevill, D. N. Int. J. Mol. Sci. 2009, 10, 862.   DOI
31 Koh, H. J.; Kang, S. J. Bull. Korean Chem. Soc. 2011, 32, 3799.   DOI