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Kinetics and Mechanism of the Oxidation of Alcohols by C9H7NHCrO3Cl

C9H7NHCrO3Cl에 의한 알코올류의 산화반응에서 속도론과 메카니즘

  • Park, Young-Cho (The School of General Studies, Kangwon National University) ;
  • Kim, Young-Sik (The School of General Studies, Kangwon National University) ;
  • Kim, Soo-Jong (Department of Advanced Materials & Chemical Engineering, Halla University)
  • 박영조 (강원대학교 교양학부) ;
  • 김영식 (강원대학교 교양학부) ;
  • 김수종 (한라대학교 신소재화학공학과)
  • Received : 2018.06.28
  • Accepted : 2018.08.03
  • Published : 2018.08.31

Abstract

$C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.

Keywords

benzyl alcohol;Hammett reaction constant (${\rho}$);hydride ion transfer;rate-determining step;substituted

Acknowledgement

Supported by : 강원대학교

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