Browse > Article

Kinetics of the Oxidation of Substituted Benzyl Alcohols with 4-(Dimethylamino)pyridinium Dichromate  

Choi, Sun do (Department of Chemical Engineering, Samchok National University)
Park, Young Cho (Department of Chemical Engineering, Samchok National University)
Publication Information
Applied Chemistry for Engineering / v.16, no.1, 2005 , pp. 153-157 More about this Journal
Abstract
4-(Dimethylamino)pyridinium dichromate was synthesized by the reaction of 4-(dimethylamino)pyridine with chromium(VI)trioxide in $H_2O$, and characterized by IR, EA and ICP. The oxidation of benzyl alcohol using 4-(dimethylamino)pyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexen < chloroform < acetone < N,N-dimethylformamide. In the presence of hydrochloric acid(HCl), 4-(dimethylamino)pyridinium dichromate oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) smoothly in N,N-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron-withdrawing groups retarded the reaction. The Hammett reaction constant($\rho$) was -0.70 at 303K. The observed experimental data have been rationalized as follows: the proton transfer occurs after the prior formation of a chromate ester in the rate-determining step.
Keywords
substituted benzyl alcohol; Hammett reaction constant($\rho$); proton transfer; chromate ester; rate-determining step;
Citations & Related Records
연도 인용수 순위
  • Reference
1 M. K. Mahanti and J. Nongkynrih, Bull. Chem., Soc. Jpn., 67, 2320 (1994)   DOI   ScienceOn
2 H. H. Yaou and Y. C. Chuh, Bull. Chem. Soc. Jpn., 64, 3059 (1991)   DOI
3 Y. C. Kim, J. W. Lim, and S. Y. Choi, J. Korean Chem. Soc., 42, 150 (1998)
4 J. F. Kuo, Y. H. Huang, and C. Y. Chen, Bull. Chem. Soc. Japan, 64, 3059 (1991)
5 K. K. Banerji and S. Jain, Bull. Chem. Soc. Japan, 61, 1767 (1988)   DOI
6 M. R. Pressprich, R, D. Willett, and H. B. Davis, Inorg. Chem., 27, 260 (1988)   DOI
7 K. K. Banerji, Indian J. Chem., 17A, 300 (1979)
8 M. K. Mahanti and D. Dey, J. Org. Chem., 55, 5848 (1990)   DOI
9 G. D. Yadav, J. Phys. Chem., 101, 36 (1997).   DOI   ScienceOn
10 M. K. Mahanti, B. Kuotsu, and E. Tiewsoh, J. Org. Chem., 61, 8875 (1996)   DOI   ScienceOn
11 H. B. Davis, R. M. Sheets, and W. W. Pandler, Heterocycles, 22, 2029 (1984)   DOI
12 M. K. Mahanti and J. Nongkynrih, J. Org. Chem., 58, 4925 (1993)   DOI   ScienceOn
13 M. H. Cho, J. H. Kim, and H. B. Park, J. Korean Chem. Soc., 33, 366 (1989)