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http://dx.doi.org/10.14478/ace.2014.1108

Kinetics and Mechanism of the Oxidation of Substituted Benzyl Alcohols by Cr(VI)-Heterocyclic Complex (2,4'-Bipyridinium Chlorochromate)  

Park, Young Cho (Department of Chemical Engineering, Kangwon National University)
Kim, Young Sik (Department of Chemical Engineering, Kangwon National University)
Publication Information
Applied Chemistry for Engineering / v.25, no.6, 2014 , pp. 648-653 More about this Journal
Abstract
Cr(VI)-heterocyclic complex (2,4'-bipyridinium chlorochromate) was synthesized by the reaction between heterocyclic compound(2,4'-bipyridine) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium chlorochromate in various solvents showed that the reactivity increased with the increase of the dielectric constant (${\varepsilon}$), in the order : N,N-dimet-hylformamide (DMF) > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as hydrochloric acid (HCl solution), 2,4'-bipyridinium chlorochromate oxidized benzyl alcohol (H) and its derivatives (p-$CH_3$, m-Br, m-$NO_2$). Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.67 (303 K). The observed experimental data have been rationalize the proton transfer occurred followed the formation of a chromate ester in the rate-determining step.
Keywords
chromate ester; hydride ion transfer; Hammett reaction constant(${\rho}$); rate-determining step; substituted benzyl alcohol;
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Times Cited By KSCI : 3  (Citation Analysis)
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