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http://dx.doi.org/10.5762/KAIS.2012.13.1.462

Kinetics and Mechanism of the Oxidation of Substituted Benzyl Alcohols by Cr(VI)-4,4'-Bipyridine Complex  

Kim, Young-Sik (Department of Chemical Engineering, Kangwon National University)
Park, Young-Cho (Department of Chemical Engineering, Kangwon National University)
Publication Information
Journal of the Korea Academia-Industrial cooperation Society / v.13, no.1, 2012 , pp. 462-469 More about this Journal
Abstract
Cr(VI)-4,4'-bipyridine complex(4,4'-bipyridinium dichromate) was synthesized by the reaction of 4,4'-bipyridine with chromium trioxide in H2O, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene, H, m-Br, m-$NO_2$) smoothly in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.63(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;
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