Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Selective Oxidation of Amines to Imines or Nitriles by Manganese Dioxide in Air

공기 중에서 망간 다이옥사이드에 의한 아민에서 이민 또는 나이트릴로의 선택적 산화 반응

  • Kim, Yo Han (School of Chemical and Biological Engineering, Seoul National University) ;
  • Hwang, Seung Kyu (Department of Chemical Engineering, Kangwon National University) ;
  • Lee, Yoon Sik (School of Chemical and Biological Engineering, Seoul National University) ;
  • Kim, Jung Won (Department of Chemical Engineering, Kangwon National University)
  • 김요한 (서울대학교 화학생물공학부) ;
  • 황승규 (강원대학교 화학공학과) ;
  • 이윤식 (서울대학교 화학생물공학부) ;
  • 김정원 (강원대학교 화학공학과)
  • Received : 2014.02.24
  • Accepted : 2014.02.26
  • Published : 2014.04.10
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Abstract

A simple heterogeneous system has been developed by using base treated manganese dioxide (B-$MnO_2$) for the aerobic oxidation of amines under mild reaction conditions of 1 atm of air and $50^{\circ}C$ in hexane. This system was highly efficient to oxidize various kinds of primary or secondary amines including aliphatic, aromatic, and hetero-atomic ones under the applied reaction conditions. Amines were oxidized to nitriles or diimines by the self-condensation or oxidative dehydrogenation through imine intermediate. The B-$MnO_2$ was reused for at least 5 times without any loss of its catalytic performance and showed its cost effectiveness, easy workup, and easy separation of the products for achieving the protocol of green chemistry.

염기 처리에 의한 간단한 방법으로 합성된 $MnO_2$ (B-$MnO_2$)는 불균일 촉매시스템으로 호기성 조건에서 효과적인 아민 산화반응을 보여주었다. 이 B-$MnO_2$ 촉매는 다양한 종류의 방향족, 이원자 화합물, 비활성 지방족 등의 아민의 전환에 높은 활성과 선택성을 보여주었다. 이러한 산화반응은 온화한 온도($50^{\circ}C$)와 대기압의 공기 조건하에서 아민을 중간체인 이민으로 전환하고 자가 축합(self-condensation) 또는 산화적 탈수소화(oxidative dehydrogenation)을 통해 다이이민(diimine) 또는 나이트릴(nitrile)을 생성하였다. 사용된 촉매는 여과로 쉽게 분리할 수 있었고 5번 이상의 재사용 실험에서도 일정이상의 높은 수율을 보여주었다. 따라서 B-$MnO_2$는 아민 산화반응을 통해 이민과 나이트릴을 얻음에 있어 경제적으로나 환경친환적으로 효과적인 면을 보여 줌으로써, 그린화학(green chemistry)의 목적에 적합하다.

Keywords

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