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ISSN : 1225-0112(Print)
ISSN : 2288-4505(Online)
Applied Chemistry for Engineering Vol.26 No.3 pp.372-376
DOI :

Article : A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using Cr(VI)-6-Methylquinoline

Young Cho Park

Abstract

6-MQCC (Cr(VI)-6-methylquinoline) complex was synthesized by the reaction of 6-methylquinoline with chromium(VI) trioxide in 6 M HCl. The structure was characterized using IR (Infrared Spectroscopy) and ICP (Inductively Coupled Plasma) analysis. The oxidation of benzyl alcohol using 6-MQCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in descending order of DMF > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as sulfuric acid (H2SO4 solution), 6-MQCC oxidized benzyl alcohol (H) and its derivatives (p-OCH3, m-CH3, m-OCH3, m-Cl, m-NO2) were effectively oxidized. Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (ρ) was -0.69 (308 K). The observed experimental data was used to rationalize the fact that the hydride ion transfer occurred at the rate-determining step.

Cr(VI)-6-Methylquinoline을 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구

박영조,김영식

초록

6M HCl 용매 하에서 6-메틸퀴놀린과 chromium(VI) trioxide의 반응을 통하여 6-MQCC(크롬(VI)-6-메틸퀴놀린) 착물을 합 성하였다. 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 6-MQCC을 이용하여 벤질 알코올의 산화반응을 측정한 결과, 용매의 유전상수 값이 증가함에 따라 반응수율이 증가했다. 그 순서는 DMF > 아세톤 > 클로로포름 > 시클로헥센이었다. 산(H2SO4) 촉매를 이용한 DMF 용매 하에서, 6-MQCC은 벤질 알코올 (H)과 그의 유도체들(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 -0.69 (308 K)이었다. 본 실험에 서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어났다.

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