R2NH/R2NH2 +-20 mol% DMSO(aq)의 조건에서 2,4-dinitrophenyl 5-substituted-2- furoates의 아실 이동반응에 대한 반응속도론적 연구. 반응 메커니즘에 미치는 비이탈기와 이탈기의 효과
A Kinetic Study on the Nucleophilic Substitution Reaction of 2,4-dinitrophenyl 5-substituted-2-furoates Under R2NH/R2NH2 + in 20 mol% DMSO(aq). Effects of Nonleaving Group and Leaving Group on the Reaction Mechanism
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본 연구에서는 2,4-dinitrophenyl-5-substituted-2-furoates (1a-d)와 R2NH/R2NH2 +-20 mol%DMSO(aq)의 아실 이동 반응을반응속도론적으로 연구하였다. 이 반응은 이차반응이고, pKa 0 = 9.5, β1 = 0.23-0.35 및 β2 = 0.88-0.99의 결과와 함께 아래 방향으로 굽은 Brönsted plots이 관측되었다. k1값은 5-furyl 치환기의 전자끄는 능력이 증가하고 친핵체의 친핵성도가 커질수록 증가하였다. 반면, k2/k-1 값 비율은 5-furyl 치환기에 관계없이 거의 일정하였다. 실험결과로 부터 반응은 속도결정단계가 변하는 단계반응 메커니즘으로 진행됨을 제안하였다.
Abstract
Acyl transfer reactions of 2,4-dinitrophenyl-5-substituted-2-furoates (1a-d) promoted by R2NH/R2NH2 + in 20 mol% DMSO(aq) have been studied kinetically. The reactions are second-order and exhibit downward curves of the Brönsted plots with pKa 0 = 9.5, β1 = 0.23-0.35 and β2 = 0.88 ̶ 0.99. The k1 values increased with a stronger nucleophile and as the electron- withdrawing ability of the 5-furyl substituent increases. In contrast, the k2/k-1 values were nearly idential regardless of the 5-furyl substituents. From these results, a stepwise mechanism with a change in the rate-determining step(RDS) is proposed.
참고문헌 (57)
- Kirsh, J. F., , J. Org. Chem, 33, pp.127~ (1968)
- Kirsh, J. F, , J. Am. Chem. Soc, 91, pp.1841~ (1969)
- Chaw, Z. S., , J. Chem. Soc. B, 1818 (1971)
- Gresser, M. J, , J. Am. Chem. Soc, 96, pp.7018~ (1974)
- Gresser, M. J, , Chem. Soc. Rev, 10, pp.345~ (1981)
- Gresser, M. J., , Chem. Rev, 85, pp.511~ (1985)
- Castro, E. A., , J. Chem. Soc., Perkin Trans, 2, pp.453~ (1983)
- Castro, E. A., , J. Org. Chem, 50, pp.3595~ (1985)
- Castro, E. A., , J. Org. Chem, 51, pp.1668~ (1986)
- Castro, E. A, , Chem. Rev, 99, pp.3505~ (1999)
- Castro, E. A., , J. Org. Chem, 67, pp.8911~ (2002)
- Castro, E. A., , J. Org. Chem, 68, pp.8157~ (2003)
- Campodonico, P. R., , J. Org. Chem, 70, pp.1754~ (2005)
- Campodonico, P. R., , Chem. Phy. Lett, 498, pp.221~ (2010)
- Nummert, V., , J. Collect. Czech. Chem. Commun, 71, pp.107~ (2006)
- Um, I. H., , Bull. Korean Chem. Soc, 12, pp.406~ (1991)
- Kwon, D. S, , Bull. Korean Chem. Soc, 15, pp.860~ (1994)
- Um, I. H, , Tetrahedron Lett, 38, pp.6903~ (1995)
- Um, I. H, , J. Org. Chem, 69, pp.3937~ (2004)
- Um, I. H., , Chem. Eur. J, 12, pp.1237~ (2006)
- Um, I. H., , J. Org. Chem, 71, pp.5800~ (2006)
- Page, M. I., "Organic and Bio-organic Mechanisms" (1977), Longman
- Gresser, M. J, , J. Am. Chem. Soc, 99, pp.6970~ (1977)
- Cook, R. D, , Can. J. Chem, 64, pp.213~ (1986)
- Williams, A., , Acc. Chem. Res, 22, pp.387~ (1989)
- Oh, H. K., , J. Org. Chem, 69, pp.9285~ (2004)
- Castro, E. A, , J. Phys. Org. Chem, 22, pp.1003~ (2009)
- Deacon, T., , J. Am. Chem. Soc, 100, pp.2525~ (1978)
- D'Rozario, P., , J. Am. Chem. Soc, 106, pp.5027~ (1984)
- Ba-Saif, S., , J. Am. Chem. Soc, 109, pp.6362~ (1987)
- Bourne, N., , J. Am. Chem. Soc, 110, pp.1890~ (1988)
- Stefanidis, D., , J. Am. Chem. Soc, 115, pp.1650~ (1993)
- Hengge, A. C, , J. Am. Chem. Soc, 116, pp.5045~ (1994)
- Hengge, A. C., , J. Am. Chem. Soc, 116, pp.11256~ (1994)
- Hess, R. A., , J. Am. Chem. Soc, 119, pp.6980~ (1997)
- Campbell, B, , J. Am. Chem. Soc, 99, pp.5375~ (1977)
- Buncel, E., , J. Am. Chem. Soc, 110, pp.1275~ (1988)
- Buncel, E., , J. Am. Chem. Soc, 111, pp.971~ (1989)
- Pyun Sang Yong, "Reactions of 4-Nitrophenyl 5-substituted Furan-2-carboxylates with R2NH", R2NH2 + in 20 mol% DMSO(aq): Effect of Aryl Group on the Acyl-Transfer Reaction, 2021, pp.42(7), 994~1000[DOI]
- 변상용, "Reactions of 2,4-Dinitrophenyl 5-substituted-2-thiophenecarboxylates with R2NH", R2NH2+ in 20?Mol % DMSO(aq). Effects of 5-Thienyl Substituent and Leaving Group on the Reaction Mechanism, 2019, pp.40(10), 983~990[DOI]
- Um, I. H., , J. Org. Chem, 72, pp.3823~ (2007)
- Jencks, W. P., , J. Am. Chem. Soc, 90, pp.2622~ (1968)
- Gresser, M. J., , J. Am. Chem. Soc, 99, pp.6963~ (1977)
- Castro, E. A, , J. Org. Chem, 54, pp.2153~ (1989)
- Castro, E. A, , J. Org. Chem, 55, pp.1676~ (1990)
- Castro, E. A, , J. Chem. Soc., Perkin Trans, 2, pp.1919~ (1991)
- Castro, E. A, , J. Org. Chem, 58, pp.4908~ (1993)
- Chapman, N. B., "Advanced in Linear Free Energy Relationships" (1972), Plenum
- Bernardi, F., , J. Mol. Struct, 163 (1988)
- Cho, B. R., , J. Org. Chem, 63, pp.8304~ (1998)
- Lee, C. K., , J. Heterocyclic Chem, 39, pp.1207~ (2002)
- Barka, R. H, , J. Am. Chem. Soc, 88, pp.3744~ (1966)
- Fersht, A, "Enzyme Structure and Mechanism" (1985), W.H. Freeman and Company
- Castro, E. A., , J. Org. Chem, 69, pp.2411~ (2004)
- Castro, E. A., , J. Org. Chem, 65, pp.9047~ (2000)
- Castro, E. A., , J. Org. Chem, 62, pp.6568~ (1997)
- Albert, A, "A Physical Methods in Heterocyclic Chemistry vol. 1", pp.44~ (1963), Academic Press