화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of the Korean Industrial and Engineering Chemistry, Vol.13, No.3, 291-296, May, 2002
Export Citation
4,4'-Bipyridinium Chlorochromate를 이용한 치환 벤질알코올류의 산화반응 속도
Kinetics of the Oxidation of Substituted Benzyl Alcohols with 4,4'-Bipyridinium Chlorochromate
최선도†, 박영조
  • 삼척대학교 화학공학과, 강원 245-711
Sun Do Choi†, and Young Cho Park
  • Department of Chemical Engineering, Samchok National University, Kwangwon 245-711, Korea
E-mail:
초록
4,4'-bipyridinium chlorochromate(4,4'-BPCC)를 합성하여 IR, EA 및 ICP로 구조를 확인하였다. 4,4'-BPCC를 이용하여 벤질알코올의 산화반응을 측정한 결과, 유전상수 값이 큰 용매 순서인 시클로헥센 < 클로로포름 < 아세톤 < 아세토니트릴 용매에서 높은 산화반응성을 보였다. 4,4'-BPCC를 이용하여 치환 벤질알코올류의 산화반응속도를 측정한 결과 Hammett 반응상수 ρ값은 -0.69이였다. 이상과 같은 고찰로부터 4,4'-BPCC를 이용한 알코올의 산화반응 과정의 메카니즘은 RC(+)HOH 중간체가 형성되는 단계가 반응속도 결정단계인 두 단계 반응 메카니즘으로 진행됨을 알 수 있었다.
4,4'-bipyridinium chlorochromate(4,4'-BPCC) was synthesized by the reaction of 4,4'-bipyridine with chromium(VI) trioxide in 6 M hydrochloric acid. 4,4'-BPCC structure was verified by IR, EA, and ICP. The oxidation of benzyl alcohol using 4,4'-BPCC in various solvents showed that the reactivity increased with the increase of the dielectric constant's order: cyclohexen < chloroform < acetone < acetonitrile. In the presence of acid, 4,4'-BPCC oxidized the substituted benzyl alcohols in N,N-dimethylformamide. The Hammett reaction constant ρ was -0.69 at 303 K. The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.
Keywords:4,4'-bipyridinium chlorochromate;dielectric constant;substituted benzyl alcohol;Hammett reaction constant ρ;hydride ion transfer
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