Journal of the Korea Academia-Industrial cooperation Society (한국산학기술학회논문지)

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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

  • Kim, Young-Sik (Department of Chemical Engineering, Kangwon National University) ;
  • Park, Young-Cho (Department of Chemical Engineering, Kangwon National University)
  • 김영식 (강원대학교 화학공학과) ;
  • 박영조 (강원대학교 화학공학과)
  • Received : 2011.09.14
  • Accepted : 2011.12.13
  • Published : 2011.12.31
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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.

$H_2O$ 용매 하에서 6-methylquinoline 과 chromium trioxide의 반응을 통하여 6-methylquinolinium dichromate [$(C_{10}H_9NH)_2Cr_2O_7$]를 합성하여, 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 6-methylquinolinium dichromate를 이용하여 벤질 알코올의 산화반응을 측정한 결과 유전상수(${\varepsilon}$) 값이 큰 용매 순서인 시클로헥센 < 클로로포름 < 아세톤 < N,N-디메틸포름아미드 용매 하에서 높은 산화반응성을 보였다. 산촉매($H_2SO_4$)를 이용한 DMF 용매 하에서 6-methylquinolinium dichromat는 벤질 알코올과 그의 유도체들(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$)을 효과적으로 산화시켰다. 그리고 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰다. 또한 Hammett 반응상수(${\rho}$) 값은 -0.67(303K) 이였다. 그러므로 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어나는 메카니즘임을 알 수 있었다.

Keywords

References

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