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Kinetics of the Oxidation of Substituted Benzyl Alcohols using 6-Methylquinolinium Dichromate

6-Methylquinolinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응 속도

  • Received : 2011.09.14
  • Accepted : 2011.12.13
  • Published : 2011.12.31

Abstract

6-Methylquinolinium dichromate[$(C_{10}H_9NH)_2Cr_2O_7$] was synthesized by the reaction of 6-methylquinoline with chromium trioxide in $H_2O$, and characterized by IR, ICP. The oxidation of benzyl alcohol using 6-methylquinolinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene < chloroform < acetone < N,N- dimethylformamide. In the presence of hydrochloric acid($H_2SO_4$ solution), 6-methylquinolinium dichromate oxidized benzyl alcohol and its derivatives(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$) smoothly in DMF. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.67(303K). 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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