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http://dx.doi.org/10.5012/bkcs.2010.31.03.689

Kinetics and Mechanism of Nucleophilic Displacement Reactions of Y-Substituted Phenyl Benzoates with Cyanide Ion  

Kim, Song-I (Department of Chemistry and Nano Science, Ewha Womans University)
Kim, Eun-Hee (Department of Chemistry and Nano Science, Ewha Womans University)
Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
Publication Information
Bulletin of the Korean Chemical Society / v.31, no.3, 2010 , pp. 689-693 More about this Journal
Abstract
Second-order rate constants ($k_{CN^-}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-r) with $CN^-$ ion in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot is linear with ${\beta}_{1g}$ = -0.49, a typical ${\beta}_{1g}$ value for reactions reported to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^{\circ}$ and ${\sigma}^-$ constants exhibit many scattered points. In contrast, the Yukawa-Tsuno plot for the same reaction exhibits excellent linearity with ${\rho}_Y$ = 1.37 and r = 0.34, indicating that a negative charge develops partially on the oxygen atom of the leaving aryloxide in the rate-determining step (RDS). Although two different mechanisms are plausible (i.e., a concerted mechanism and a stepwise pathway in which expulsion of the leaving group occurs at the RDS), the reaction has been concluded to proceed through a concerted mechanism on the basis of the magnitude of ${\beta}_{1g}$ and ${\rho}_Y$ values.
Keywords
Aryl benzoates; Br${\o}$nsted-type plot; Hammett plot; Rate-determining step; Yukawa-Tsuno plot;
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1 Almerindo, G. I.; Pliego, J. R. Chem. Phys. Lett. 2006, 423, 459- 462.   DOI   ScienceOn
2 Fang, Y.; MacMillar, S.; Eriksson, J.; Kolodziejska-Huben, M.; Dybala-Defratyka, A.; Paneth, P.; Matsson, O.; Westaway, K. C. J. Org. Chem. 2006, 71, 4742-4747.   DOI   ScienceOn
3 Park, G.; Kim, S. C.; Kang, H. Y. Bull. Korean Chem. Soc. 2005, 26, 1339-1343.   DOI   ScienceOn
4 Almerindo, G. I.; Pliego, J. R., Jr. Org. Lett. 2005, 7, 1821-1823.   DOI   ScienceOn
5 Matsson, O.; Persson, J.; Axelsson, B. S.; Laangstroem, B.; Fang, Y.; Westaway, K. C. J. Am. Chem. Soc. 1996, 118, 6350-6354.   DOI   ScienceOn
6 Richard, J. P.; Jencks, W. P. J. Am. Chem. Soc. 1984, 106, 1383-1396.   DOI
7 Ritchie, C. D.; VanVerth, J. E.; Virtanen, P. O. I. J. Am. Chem. Soc. 1982, 104, 3491-3497.   DOI
8 Um, I. H.; Lee, J. Y.; Kim, H. T.; Bae, S. K. J. Org. Chem. 2004, 69, 2436-2441.   DOI   ScienceOn
9 Um, I. H.; Kim, E. H.; Lee, J. Y. J. Org. Chem. 2009, 74, 1212-1217   DOI   ScienceOn
10 Um, I. H.; Lee, J. Y.; Fujio, M.; Tsuno, Y. Org. Biomol. Chem. 2006, 4, 2979-2985.   DOI   ScienceOn
11 Um, I. H.; Kim, E. H.; Han, H. J. Bull. Korean Chem. Soc. 2008, 29, 580-584.   DOI   ScienceOn
12 Um, I. H.; Han, J. Y.; Buncel, E. Chem. Eur. J. 2009, 15, 1011-1017.   DOI   ScienceOn
13 Um, I. H.; Han, J. Y.; Hwang, S. J. Chem. Eur. J. 2008, 14, 7324-7330.   DOI   ScienceOn
14 Um, I. H.; Park, J. E.; Shin, Y. H. Org. Biomol. Chem. 2007, 5, 3539-3543.   DOI   ScienceOn
15 Um, I. H.; Lee, J. Y.; Bae, S. Y.; Buncel, E. Can. J. Chem. 2005, 83, 1365-1371.   DOI   ScienceOn
16 Middleton, W. J.; Howard, E. G.; Sharkey, W. H. J. Org. Chem. 1965, 30, 1375-1384.   DOI
17 Pedersen, B. S.; Scheibye, S.; Nilsson, N. H.; Lawesson, S. O. Bull. Soc. Chim. Belg. 1978, 87, 223-228.
18 Um, I. H.; Kim, E. Y.; Park, H. R.; Jeon, S. E. J. Org. Chem. 2006, 71, 2302-2306.   DOI   ScienceOn
19 Um, I. H.; Lee, S. E.; Kwon, H. J. J. Org. Chem. 2002, 67, 8999-9005.   DOI   ScienceOn
20 Um, I. H.; Han, H. J.; Baek, M. H.; Bae, S. Y. J. Org. Chem. 2004, 69, 6365-6370.   DOI   ScienceOn
21 Jones, R. A. Y. Physical and mechanistic organic chemistry; 2nd ed.; Cambridge University Press: London, 1984; pp 135-137.
22 Um, I. H.; Yoon, S.; Park, H. R.; Han, H. J. Org. Biomol. Chem. 2008, 6, 1618-1624.   DOI   ScienceOn
23 Um, I. H.; Hwang, S. J.; Yoon, S.; Jeon, S. E.; Bae, S. K. J. Org. Chem. 2008, 73, 7671-7677.   DOI   ScienceOn
24 Ho, T. L. In Hard and soft acid and bases; Pearson, R. G. Ed.; Academic Press: New York, 1977.
25 Gresser, M. J.; Jencks, W. P. J. Am. Chem. Soc. 1977, 99, 6963- 6970.   DOI
26 Um, I. H.; Seo, J. A.; Lee, H. M. Bull. Korean Chem. Soc. 2008, 29, 1915-1919.   DOI   ScienceOn
27 Um, I. H.; Akhtar, K. Bull. Korean Chem. Soc. 2008, 29, 772-776.   DOI   ScienceOn
28 Bourne, N.; Chrystiuk, E.; Davis, A. M.; Williams, A. J. Am. Chem. Soc. 1988, 110, 1890-1895.   DOI
29 Um, I. H.; Seo, J. A.; Chun, S. M. Bull. Korean Chem. Soc. 2008, 29, 1459-1463.   DOI   ScienceOn
30 Harris, J. F.; Stacey, F. W. J. Am. Chem. Soc. 1963, 85, 749-754.   DOI
31 Douglas, K. T.; Williams, A. J. Chem. Soc., Perkin Trans. 2 1976, 515-521.
32 Younker, J. M.; Hengge, A. C. J. Org. Chem. 2004, 69, 9043-9048.   DOI   ScienceOn
33 Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2001, 66, 3129-3132.   DOI   ScienceOn
34 Castro, E. A.; Angel, M.; Arellano, D.; Santos, J. G. J. Org. Chem. 2001, 66, 6571-6575.   DOI   ScienceOn
35 Castro, E. A.; Angel, M.; Pavez, P.; Santos, J. G. J. Chem. Soc., Perkin Trans. 2 2001, 12, 2351-2354.
36 Tsuno, Y.; Fujio, M. Chem. Soc. Rev. 1996, 25, 129-139.   DOI
37 Um, I. H.; Han, J. Y.; Hwang, S. J. Chem. Eur. J. 2008, 14, 7324- 7330   DOI   ScienceOn
38 Um, I. H.; Hwang, S. J.; Baek, M. H.; Park, E. J. J. Org. Chem. 2006, 71, 9191-9197.   DOI   ScienceOn
39 Yukawa, Y.; Tsuno, Y. Bull. Chem. Soc. Jpn. 1959, 32, 965-970.   DOI
40 Tsuno, Y.; Fujio, M. Adv. Phys. Org. Chem. 1999, 32, 267-385.   DOI
41 Nakata, K.; Fujio, M.; Nishimoto, K.; Tsuno, Y. J. Phys. Org. Chem. 2003, 16, 323-335.   DOI   ScienceOn
42 Fujio, M.; Rappoport, Z.; Uddin, H. J.; Kim, H. J.; Tsuno, Y. Bull. Chem. Soc. Jpn. 2003, 76, 163-169.   DOI   ScienceOn
43 Fujio, M.; Uchida, M.; Okada, A.; Alam, M. A.; Fujiyama, R.; Siehl, H. U.; Tsuno, Y. Bull. Chem. Soc. Jpn. 2005, 78, 1834-1842.   DOI   ScienceOn
44 Fujio, M.; Umezaki, Y.; Alam, M. A.; Kikukawa, K.; Fujiyama, R.; Tsuno, Y. Bull. Chem. Soc. Jpn. 2006, 79, 1091-1099.   DOI   ScienceOn
45 Andres, G. O.; Granados, A. M.; Rossi, R. H. J. Org. Chem. 2001, 66, 7653-7657.   DOI   ScienceOn
46 Um, I. H.; Shin, Y. H.; Han, J. Y.; Mishima, M. J. Org. Chem. 2006, 71, 7715-7720.   DOI   ScienceOn
47 Um, I. H.; Han, J. Y.; Shin, Y. H. J. Org. Chem. 2009, 74, 3073-3078.   DOI   ScienceOn
48 Um, I. H.; Park, J. E.; Shin, Y. H. Org. Biomol. Chem. 2007, 5, 3539-3543.   DOI   ScienceOn
49 Oh, H. K.; Jin, Y. C.; Sung, D. D.; Lee, I. Org. Biomol. Chem. 2005, 3, 1240-1244.   DOI   ScienceOn
50 Stefanidis, D.; Cho, S.; Dhe-Paganon, S.; Jencks, W. P. J. Am. Chem. Soc. 1993, 115, 1650-1656.   DOI   ScienceOn
51 Lee, I.; Sung, D. D. Curr. Org. Chem. 2004, 8, 557-567.   DOI   ScienceOn
52 Wubbels, G. G.; Brown, T. R.; Babcock, T. A.; Johnson, K. M. J. Org. Chem. 2008, 73, 1925-1934.   DOI   ScienceOn
53 Tumanov, V. V.; Tishkov, A. A.; Mayr, H. Angew. Chem., Int. Ed. 2007, 46, 3563-3566.   DOI   ScienceOn
54 Jencks, W. P. Chem. Rev. 1985, 85, 511-527.   DOI
55 Page, M. I.; Williams, A. Organic and Bio-organic Mechanisms; Longman: Harlow, U. K., 1997; Chapter 7.
56 Castro, E. A. Chem. Rev. 1999, 99, 3505-3524.   DOI   ScienceOn
57 Menger, F. M.; Smith, J. H. J. J. Am. Chem. Soc. 1972, 94, 3824-3829.   DOI
58 Williams, A. Acc. Chem. Res. 1989, 22, 387-392.   DOI
59 Ba-Saif, S.; Luthra, A. K.; Williams, A. J. Am. Chem. Soc. 1987, 109, 6362- 6368.   DOI
60 Minegishi, S.; Mayr, H. J. Am. Chem. Soc. 2003, 125, 286-295.   DOI   ScienceOn
61 Westaway, K. C.; Fang, Y. R.; Persson, J.; Matsson, O. J. Am. Chem. Soc. 1998, 120, 3340-3344.   DOI   ScienceOn
62 Buncel, E.; Um, I. H.; Hoz, S. J. Am. Chem. Soc. 1989, 111, 971-975.   DOI
63 Castro, E. A.; Angel, M.; Arellano, D.; Santos, J. G. J. Org. Chem. 2001, 66, 6571-6575.   DOI   ScienceOn
64 Hess, R. A.; Hengge, A. C.; Cleland, W. W. J. Am. Chem. Soc. 1997, 119, 6980-6983.   DOI   ScienceOn
65 Guthrie, J. P. J. Am. Chem. Soc. 1996, 118, 12878-12885.   DOI   ScienceOn
66 Pregel, M.; Dunn, E. J.; Buncel, E. J. Am. Chem. Soc. 1991, 113, 3545-3550.   DOI
67 Um, I. H.; Han, H. J.; Ahn, J. A.; Kang, S.; Buncel, E. J. Org. Chem. 2002, 67, 8475-8480.   DOI   ScienceOn