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Kinetic Study on the Oxidation Reaction of Substituted Benzyl Alcohols by Cr(VI)-Heterocyclic Complex (2,2'-Bipyridinium Dichromate)  

Kim, Young Sik (Department of Chemical Engineering, Kangwon National University)
Park, Young Cho (Department of Chemical Engineering, Kangwon National University)
Publication Information
Applied Chemistry for Engineering / v.23, no.2, 2012 , pp. 241-246 More about this Journal
Abstract
Cr(VI)-heterocyclic complex (2,2'-bipyridinium dichromate) was synthesized by the reaction between of 2,2'-bipyridine and chromium trioxide in $H_2O$, and characterized by IR and ICP. The oxidation of benzyl alcohol using 2,2'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexene < chloroform < acetone < N,N-dimethylformamide. In the presence of DMF solvent with acidic catalyst such as $H_2SO_4$ solution, 2,2'-bipyridinium dichromate oxidized the benzyl alcohol and its derivatives (p-$p-OCH_3$, $m-CH_3$, H, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant was -0.66 (303 K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.
Keywords
substituted benzyl alcohol; Hammett reaction constant $({\rho})$; hydride ion transfer; rate-determining step;
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