Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Carbonylative Cyclization of Unsaturated Carboxylic Acids by Palladium Complexes with Phosphines [III] Palladium (0, II)-Phosphine Complexes Catalyzed Cabonylation of Unsaturated Carboxylic Acids and It's Theoretical Studies

포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화 고리반응 (제 3 보). 팔라듐 (0, II)-포스핀계 착물에 의한 불포화카르복실산의 카르보닐화 반응 및 그의 이론적 연구

  • Myung-Ki Doh (Department of Chemistry, Yeungnam University) ;
  • Bong-Gon Kim (Department of Chemistry Education, Gyeongsang National University) ;
  • Maeng-Jun Jung (Department of Chemistry, Yeungnam University) ;
  • Young-Dae Song (Department of Chemistry, Yeungnam University) ;
  • Park Byung-Kak (Department of Chemistry, Yeungnam University)
  • 도명기 (영남대학교 이과대학 화학과) ;
  • 김봉곤 (경상대학교 사범대학 화학교육과) ;
  • 정맹준 (영남대학교 이과대학 화학과) ;
  • 송영대 (영남대학교 이공대학 화학과) ;
  • 박병각 (영남대학교 이과대학 화학과)
  • Published : 1993.10.20
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Abstract

Reaction mechanism of palladium(0, II)-phosphines complexes catalyzed cyclocarbonylation for unsaturated carboxylic acid such as crotonic acid, methacrylic acid and 3-butenoic acid has been investigated by product analysis, molecular mechanics and extended Huckel molecular orbital method. Reaction of 3-butenoic acid with palladium(0, II)-phosphines catalyst gives palladium containing cycloester through intermediate palladium-olefin ${\pi}$ -complex in the catalytic carbonylation. Palladium(0, II)-phosphines complexes catalyze the cyclocarbonylation of 3-butenoic acid to give 3-methylsuccinic anhydride and glutaric anhydride. But ${\pi}$ -complexes with palladium(0, II)-phosphines and unsaturated carboxylic acids such as crotonic acid and methacrylic acid are not effective the catalytic cyclocarbonylation.

팔라듐(0, II)-포스핀계 착물을 촉매로 하여 crotonic acid, methacrylic acid 및 3-butenoic acid 같은 불포화가크복실산의 카르보닐화 고리반응에서 생성가능한 물질의 구조를 확인하고, 그 반응메카니즘을 MM2 와 EHMO 계산에 의해서 추정하였다. 이 반응은 ${\pi}$ -착물을 거쳐 금속 함유 고리화합물을 만든 다음 산화성 첨가반응과 환원성 제거반응이 일어나 진행된다. ${\pi}$ -착물을 안정화시키는 crotonic acid, methacrylic acid 등은 카르보닐화 고리반응이 진행되지 않고, 3-butenoic acid는 무수카르복실산 유도체로서 glutaric anhydride와 3-methylsuccinic anhydride 및 이중결합이 자리옮김된 crotonic acid가 얻어졌다.

Keywords

References

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