Browse > Article
http://dx.doi.org/10.5012/bkcs.2002.23.10.1459

Kinetic Studies on the Nucleophilic Addition Reactons of Vinylic β-Diketones  

Oh, Hyuck-Keun
Lee, Jae-Myon
Publication Information
Bulletin of the Korean Chemical Society / v.23, no.10, 2002 , pp. 1459-1462 More about this Journal
Abstract
The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.
Keywords
Nucleophilic addition reaction; Single-step process; Cross-interaction constant; Kinetic isotope;
Citations & Related Records

Times Cited By Web Of Science : 3  (Related Records In Web of Science)
Times Cited By SCOPUS : 3
연도 인용수 순위
1 Lee, I. Chem. Soc. Rev. 1990, 19, 317.   DOI
2 Page, M.; Williams, A. Organic and Bio-organic Mechanisms, Longman: London, 1977; p 250.
3 Bernasconi, C. F.; Fornarini, S. J. Am. Chem. Soc. 1980, 102, 5329.   DOI
4 Lee, I.; Lee, H. W. Coll. Czech. Chem. Commun. 1999, 64, 1529.   DOI   ScienceOn
5 Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301.   DOI
6 Horning, E. C.; Fish, M. S.; Walker, G. N. Organic Synthesis; Wiley: New York, 1983; Collect. Vol. 4, p 408.
7 Lee, I. Chem. Soc. Rev. 1995, 24, 223.   DOI
8 Oh, H. K.; Yang, J. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 5391.   DOI   ScienceOn
9 Oh, H. K.; Yang, J. H.; Sung, D. D.; Lee, I. J. Chem. Soc., Perkin Trans. 2 2000, 101.
10 Oh, H. K.; Yang, J. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 2188.   DOI   ScienceOn
11 Bernasconi, C. F. Tetrahedron 1989, 45, 4017.   DOI   ScienceOn
12 Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
13 Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.   DOI
14 Bernasconi, C. F.; Leonarduzzi, G. D. J. Am. Chem. Soc. 1982, 104, 5133.   DOI
15 Hansch, C.; Hoekman, D.; Gao, H. Chem. Rev. 1996, 96, 1045.   DOI   ScienceOn
16 Oh, H. K.; Kim, T. S.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 2002, 282.
17 Bernasconi, C. F.; Ketner, R. J. J. Org. Chem. 1998, 63, 6266.   DOI   ScienceOn
18 Lee, I. Chem. Soc. Rev. 1990, 19, 317.   DOI
19 Isaacs, N. S. Physical Organic Chemistry, 2nd ed.; Longman: Harlow, 1995; p 186.
20 Wiberg, K. B. Physical Organic Chemistry; Wiley: New York, 1964; p 378.
21 Lee, I. Prog. Phys. Org. Chem. 1992, 27, 57.
22 Oh, H. K.; Lee, J. Y.; Lee, I. Bull. Korean Chem. Soc. 1998, 19, 1198.
23 Bernasconi, C. F.; Murray, C. J. J. Am. Chem. Soc. 1986, 108, 5251.   DOI
24 Bernasconi, C. Kanavarioti, A. J. Am. Chem. Soc. 1986, 108, 7744.   DOI   ScienceOn