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크롬(VI)-헤테로고리 착물(2,4'-비피리디늄 클로로크로메이트)에 의한 치환 벤질 알코올류의 산화반응에서 속도론과 메카니즘

Kinetics and Mechanism of the Oxidation of Substituted Benzyl Alcohols by Cr(VI)-Heterocyclic Complex (2,4'-Bipyridinium Chlorochromate)

  • 박영조 (강원대학교 화학공학과) ;
  • 김영식 (강원대학교 화학공학과)
  • Park, Young Cho (Department of Chemical Engineering, Kangwon National University) ;
  • Kim, Young Sik (Department of Chemical Engineering, Kangwon National University)
  • 투고 : 2014.09.16
  • 심사 : 2014.10.13
  • 발행 : 2014.12.10

초록

크롬(VI)-헤테로고리 착물(2,4'-비피리디늄 클로로크로메이트)을 합성하여, 적외선 분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였고, 여러 가지 용매 하에서, 2,4'-비피리디늄 클로로크로메이트를 이용하여 벤질알코올의 산화반응을 측정한 결과, 유전상수값의 증가에 따라 반응도 증가했다는 것을 보였다. 그 순서는 : N,N-디메 틸포름아미드(DMF) > 아세톤 > 클로로포름 > 시클로헥센산 촉매(HCl)를 이용한 DMF 용매 하에서, 2,4'-비피리디늄 클로로 크로메이트은 벤질 알코올(H)과 그의 유도체들(p-$CH_3$, m-Br, m-$NO_2$)을 효과적으로 산화시켰다. 전자받개 그룹들은 반응 속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰고, Hammett 반응상수(${\rho}$) 값은 -0.67 (303 K)이었다. 속도결정단계에서 크로메이트 에스테르의 형성과정을 거친 후, 양성자 전이가 일어났다.

키워드

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

참고문헌

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