Browse > Article
http://dx.doi.org/10.5012/bkcs.2013.34.9.2697

Correlation of the Rates of Solvolysis of Electron-Rich Benzoyl Chloride Using the Extended Grunwald-Wistein Equation  

Oh, Hyunjung (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University)
Choi, Hojune (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University)
Park, Jong Keun (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University)
Yang, Kiyull (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University)
Koo, In Sun (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University)
Publication Information
Bulletin of the Korean Chemical Society / v.34, no.9, 2013 , pp. 2697-2701 More about this Journal
Abstract
The solvolysis rate constants of piperonyloyl chloride (1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale, $Y_{Cl}$ solvent ionizing scale, and I aromatic ring parameter with sensitivity values of $0.30{\pm}0.05$, $0.71{\pm}0.02$, and $0.60{\pm}0.04$ for l, m, and h, respectively. The solvent kinetic isotope effect values (SKIE, $k_{MeOH}/k_{MeOD}$ and $k_{50%MeOD-50%D2O}$) of 1.16 and 1.12 were also in accord with the values for the $S_N1$ mechanism and/or the dissociative $S_N2$ mechanism. The product selectivity values (S) for solvolysis of 1 in alcohol/water mixtures were in the range of 0.5 to 1.9, which is also consistent with the proposed unimolecular ionization mechanism.
Keywords
Piperonyloyl chloride; Extended Grunwald-Winstein equation; $S_N1$ mechanism; Solvent kinetic isotope effect; Product selectivity;
Citations & Related Records
Times Cited By KSCI : 4  (Citation Analysis)
연도 인용수 순위
1 Shiner, V. J., Jr.; Dowd, W.; Fisher, R. D.; Hartshorn, S. R.; Kessick, M. A.; Milakofsky, L.; Rapp, M. W. J. Am. Shem. Soc. 1969, 91, 4838.   DOI
2 Harris, J. M.; Clark, D. C.; Becker, A.; Fagan, J. F. J. Am. Chem. Soc. 1974, 96, 4478.   DOI
3 Harris, J. M.; Becker, A.; Fagan, J. F.; Walden, F. A. J. Am. Chem. Soc. 1974, 96, 4484.   DOI
4 Karton, Y.; Pross, A. J. Chem. Soc. Perkin Trans. 2 1977, 1860.
5 McLennan, D. J.; Martin, P. L. J. Chem. Soc. Perkin Trans. 2 1982, 1099.
6 Ritche, C. D. J. Am. Chem. Soc. 1971, 93, 7324.   DOI
7 Exner, O. J. Chem. Soc. Perkin Trans. 2 1993, 973.
8 Koh, H. J.; Kang, S. J. Bull. Korean Chem. Soc. 2011, 32, 3799.   DOI   ScienceOn
9 Koh, H. J.; Kang, S. J. Bull. Korean Chem. Soc. 2012, 33, 1.
10 Bentley, T. W.; Koo, I. S. J. Chem. Soc., Chem. Commun. 1988, 41.
11 Bentley, T. W.; Harris, H. C. J. Org. Chem. 1988, 53, 724.   DOI
12 Bentley, T. W.; Jones, R. O. J. Chem. Soc., Perkin Trans 2 1993, 2351.
13 Bentley, T. W.; Jones, R. O.; Koo, I. S. J. Chem. Soc., Perkin Trans 2 1994, 753.
14 Swain, C. G.; Mosely, R. B.; Bown, D. E. J. Am. Chem. Soc. 1955, 77, 3731.   DOI
15 Kevill, D. N.; D'Souza, M. J. J. Phys. Org. Chem. 2002, 15, 881.   DOI   ScienceOn
16 Lee, I.; Koo, I. S.; Sohn, S. C.; Lee, H. H. Bull. Korean Chem. Soc. 1982, 3, 92.
17 Bentley, T. W.; Harris, H. C. J. Org. Chem. 1988, 53, 724.   DOI
18 D'Souza, M. J.; Reed, D. N.; Erdman, K. J.; Kevill, D. N. Int. J. Mol. Sci. 2009, 10, 862.   DOI   ScienceOn
19 Bentley, T. W.; Koo, I. S. J. Chem. Soc., Perkin Trans. 2 1989, 1385
20 Kyong, J. B.; Kim, Y. G.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2000, 21, 662.
21 Kevill, D. N.; Park, B.-C.; Park, K.-H.; D'Souza, M. J.; Yaakoud, L.; Mlynarski, S. L.; Kyong, J. B. Org. Biomol. Chem. 2006, 4, 1580.   DOI   ScienceOn
22 Koo, I. S.; Yang, K.; An, S. K.; Lee, C.-K.; Lee, I. Bull. Korean Chem. Soc. 2000, 21, 1011.
23 Kevill, D. N.; Ryu, Z. H.; Niedermeyer, M. A. Koyoshi, F.; D'Souza, M. J. J. Phys. Org. Chem. 2007, 20, 431.   DOI   ScienceOn
24 Kevill, D. N.; Carver, J. S. Org. Biomol. Chem. 2004, 2, 2040.   DOI   ScienceOn
25 Kevill, D. N.; Kim, J. C.; Kyong, J. B. J. Chem. Res. Synop. 1999, 2, 150.
26 Bentley, T. W.; Dau-Schmidt, J. P.; Llewellyn, G.; Mayr, H. J. Org. Chem. 1992, 57, 2387.   DOI
27 Liu, K. T.; Sheu, H. C. J. Org. Chem. 1991, 56, 3021.   DOI
28 Oh, H. K.; Kown, Y. B.; Koh, H. J.; Lee, I. New J. Chem. 1996, 20, 579.
29 Bentley, T. W.; Llewllyn, G. Ryu, Z. H. J. Org. Chem. 1998, 63, 4654.   DOI   ScienceOn
30 Kevill, D. N.; D'Souza, M. J. J. Org. Chem. 1998, 63, 2120.   DOI   ScienceOn
31 Bentley, T. W.; Ryu, Z. H. J. Chem. Soc. Perkin Trans. 2 1994, 761.
32 Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7658.   DOI
33 Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667.   DOI
34 Kevill, D. N.; D'Souza, M. J. J. Chem. Soc. Perkin Trans. 2 1997, 257.
35 Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845.   DOI
36 Kevill, D. N.; Ismail, N. H. J.; D'Souza, M. J. J. Org. Chem. Soc. 1994, 59, 6303.   DOI   ScienceOn
37 Kevil, D. N.; D'Souza, M. J. J. Chem. Soc. Perkin Trans. 2 1995, 973.
38 Kevil, D. N.; Bond, M. W.; D'Souza, M. J. J. Org. Chem. Soc. 1997, 62, 7869.   DOI   ScienceOn
39 Bentley, T. W.; Ebdon, D. N. J. Phys. Org. Chem. 2001, 14, 759.   DOI   ScienceOn
40 Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 1998, 63, 9834.   DOI   ScienceOn
41 Crumpler, T. B.; Yoh, J. H. Chemical Computations and Error; Wiley: New York, 1940; p 178.
42 Bentley, T. W.; Koo, I. S.; Norman, S. J. J. Org. Chem. 1991, 56, 1604.   DOI
43 Koo, I. S.; An, S. K.; Yang, K.; Lee, I.; Bentley, T. W. J. Phys. Org. Chem. 2002, 15, 758.   DOI   ScienceOn
44 Choi, H. J.; Ali, D.; Lee, J. P.; Yang, K.; Park, J. K.; Koo, I. S. Bull. Korean Chem. Soc. 2011, 32, 3941.   DOI   ScienceOn
45 Bentley, T. W.; Koo, I. S. J. Chem. Soc., Perkin Trans. 2 1989, 1385.
46 Kyong, J. B.; Park, B. C.; Kim, C. B.; Kevil, D. N. J. Org. Chem. 2000, 65, 8051.   DOI   ScienceOn
47 Bentley, T. W.; Carter, G. E.; Harris, H. C. J. Chem. Soc., Chem. Commun. 1984, 388.
48 Bentley, T. W.; Carter, G. E.; Harris, H. C. J. Chem. Soc., Perkin Trans. 2 1985, 983.
49 Bentley, T. W.; Harris, H. C. J. Chem. Soc., Perkin Trans. 2 1986, 619.
50 Bentley, T. W.; Harris, H. C.; Koo, I. S. J. Chem. Soc., Perkin Trans. 2 1988, 783.
51 Baer, S.; Brinkman, E. A.; Brauman, J. I. J. Am. Chem. Soc. 1991, 113, 805.   DOI
52 Williams, A. Chem. Soc. Rev. 1994, 23, 93.   DOI   ScienceOn
53 Blake, J. F.; Jorgensen, W. L. J. Am. Chem. Soc. 1987, 109, 3856.   DOI
54 Kevill. D. N. The Chemistry of Acyl Halide; Patai, S. Ed.; Interscience: New York, 1973; Ch. 12.
55 Queen, A. Can. J. Chem. 1967, 45, 1619.   DOI
56 Castro, E. A.; Ibanez, F.; Salas, M.; Santos, J. G. J. Org. Chem. 1991, 56, 4819.   DOI   ScienceOn
57 Chrystiuk, E.; Williams, A. J. Am. Chem. Soc. 1987, 109, 3040.   DOI
58 Castro, E. A.; Salas, M.; Santos, J. G. J. Org. Chem. 1994, 59, 30.   DOI   ScienceOn
59 Grunwald, E.; Winstein, S. J. Am. Chem. Soc. 1948, 70, 846.   DOI
60 Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121.   DOI
61 Kevill, D. N.; D'Souza, M. J. J. Chem. Res. Synop. 1993, 174.
62 Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741.   DOI
63 Koo, I. S.; Bentley, T. W.; Kang, D. H.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1991, 296.
64 Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700.   DOI
65 Fainberg, A. H.; Winstein, S. J. Am. Chem. Soc. 1956, 78, 2770.   DOI
66 Fainberg, A. H.; Winstein, S. J. Am. Chem. Soc. 1957, 79, 1597.   DOI
67 Kyong, J. B.; Yoo, J. S.; Kevill, D. N. J. Org. Chem. 2003, 68, 3425.   DOI   ScienceOn
68 Bunton, C. A.; Mhala, M. M.; Moffatt, J. R. J. Org. Chem. 1984, 49, 3639.   DOI
69 da Roza, D. A.; Andrews, L. J.; Keefer, R. M. J. Am. Chem. Soc. 1973, 95, 7003.   DOI
70 Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996, Vol. 1, pp 81-115.
71 Faurholt, C.; Gjaldbaek, J. C. Dansk. Tids. Farm. 1945, 19, 255.
72 Choi, H. J.; Koh, H. J.; Yang, K.; Koo, I. S. Bull. Korean Chem. Soc. 2012, 33, 3293.   DOI   ScienceOn
73 Kim, C. H.; Han, I. S.; Sohn, C. K.; Yu, Y. H.; Su, Z.; Kim, C. K. Bull. Korean Chem. Soc. 2012, 33, 1955.   DOI   ScienceOn
74 Kim, C. H.; Han, I. S.; Sohn, C. K.; Yu, Y. H.; Su, Z.; Kim, C. K. J. Phys. Chem. A 2011, 115, 1364.   DOI   ScienceOn
75 Faurholt, C.; Gjaldbaek, J. C. Chem. Abstr. 1946, 40, 513.
76 Kevill, D. N.; Kyong, J. B.; Weitl, F. L. J. Org. Chem. 1990, 55, 4304.   DOI