(C10H8N2H)2Cr2O7를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구

박영조; 김영식; 김수종; Young Cho Park; Young Sik Kim; Soo Jong Kim

Applied Chemistry for Engineering, Vol.28, No.5, 597-600, October, 2017

DOI10.14478/ace.2017.1063 Export Citation

(C10H8N2H)2Cr2O7를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구

A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using (C10H8N2H)2Cr2O7

박영조, 김영식^†, 김수종¹

강원대학교 교양학부
¹한라대학교 신소재화학공학과

Young Cho Park, Young Sik Kim^†, and Soo Jong Kim¹

The School of General Studies, Kangwon National University, 346 Joongang-ro, Samcheok, Gangwon-do 25913, Karea, Korea
¹Department of Advanced Materials & Chemical Engineering, Halla University, 28 Halladaegil, Wonju, Gangwon-do 26404, Karea, Korea

E-mail:

초록

4,4’-비피리딘과 크롬(VI) 산화물을 반응시켜 (C10H8N2H)2Cr2O7을 합성하였다. 적외선분광광도법(FT-IR)과 원소분석으로 구조를 확인하였다. 여러 가지 용매 하에서 (C10H8N2H)2Cr2O7을 이용하여 벤질알코올의 산화반응을 측정한 결과, 용매의 유전상수 값이 증가함에 따라 반응수율이 증가했다. 그 순서는 DMF (N,N’-디메틸포름아미드) > 아세톤 > 클로 로포름 > 시클로헥센이었다. H2SO4 촉매를 이용한 DMF 용매 하에서, (C10-H8N2H)2Cr2O7은 벤질알코올(H)과 그의 유도 체들(p-OCH3, m-CH3, m-OCH3, m-Cl, m-NO2)을 효과적으로 산화시켰다. 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰고, Hammett 반응상수(ρ) 값은 -0.70 (308 K)이었다. 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어났다.

(C10H8N2H)2Cr2O7 was synthesized by reacting 4,4’-bipyridine and chromium (VI) trioxide. The structure of the product was characterized with FT-IR (infrared spectroscopy) and elemental analysis. The oxidation of benzyl alcohol using (C10H8N2H)2Cr2O7 in various solvents showed that the reactivity increased with the increase of the solvent dielectric constant, in the order of DMF (N,N’-dimethylformamide) > acetone > chloroform > cyclohexane. In the presence of DMF, an acidic catalyst such as H2SO4 (C10H8N2H)2Cr2O7 oxidized benzyl alcohol (H) and its derivatives (p-OCH3, m-CH3, m-OCH3, m-Cl, m-NO2). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (ρ) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

Keywords:substituted benzyl alcohol;Hammett reaction constant (ρ);hydride ion transfer

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