화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Applied Chemistry for Engineering, Vol.27, No.6, 659-663, December, 2016
DOI10.14478/ace.2016.1106  Export Citation
루테늄 지르코니아 불균일 촉매를 이용한 알켄 또는 알킨의 효과적인 산화절단반응
Efficient Oxidative Scission of Alkenes or Alkynes with Heterogeneous Ruthenium Zirconia Catalyst
모비나 이르샤드1, 최봉길1, †, 강온유1, 홍석복1, 황성연2, 허영민3, 4, 김정원1, †
  • 1강원대학교 에너지공학부
  • 2한국화학연구원
  • 3SKC 첨단기술중앙연구소
  • 4서강대학교
Mobina Irshad1, Bong Gill Choi1, †, Onyu Kang1, Seok Bok Hong1, Sung Yeon Hwang2, Young Min Heo3, 4, and Jung Won Kim1, †
  • 1Department Chemical Engineering, Kangwon National University, Samcheok 25913, Republic of Korea
  • 2Korea Research Institute of Chemical Technology, Ulsan 681-802, Republic of Korea
  • 3SKC Advanced Technology R&D Center, Suwon, Gyeonggi-do 440-301, Korea
  • 4Department of Chemical and Biomolecular Engineering, Sogang University, Seoul, Korea
E-mail:,
초록
알켄 또는 알킨의 산화 반응이 루테늄 지르코니아 불균일 촉매에 의해 매우 선택적이며 효율적으로 전환되었다. 절단반응을 통해, C-C 이중 결합은 알데히드 관능기로, 삼중 결합은 다이케톤 또는 카르복시산으로 전환되었는데, 다양한 기질들이 30 °C에서 PhI(OAc)2 산화제와 dichloromethane 및 물(각각 5 mL와 0.5 mL)의 혼합 용매 조건에서 반응이 수행되었다. 사용된 촉매 Ru(OH)x/ZrO2는 이 절단 반응에 대해 기존의 다른 루테늄 기반 불균일 또는 균일 촉매들보다 더 좋은 활성과 선택성을 보였다. 반응이 진행되는 동안, 제조된 촉매의 기계적인 물성은 안정적이었고, 금속의 침출은 전혀 보이지 않았다. 불포화된 탄화수소들의 산화적 절단에 대해, 합성된 촉매는 여러 번 재사용해도 그 촉매의 성능을 그대로 유지하였다.
The efficiency of a heterogeneous ruthenium zirconia catalyst (Ru(OH)x/ZrO2) was demonstrated to the selective oxidative transformation of alkenes or alkynes. The scissions of C-C double bonds to aldehydes and triple bonds to diketones or carboxylic acids were carried out with (diacetoxyiodo)benzene as an oxidant under dichloromethane (5 mL)/water (0.5 mL) solvent system at 30 °C for wide range of substrates. The Ru(OH)x/ZrO2 composite showed higher catalytic activity and selectivity than other ruthenium-based homogeneous or heterogeneous catalysts for the scission reaction. The catalyst exhibited a high mechanical stability, and no leaching of the metal was observed during the reaction. These features ensured the reusability of the catalyst for several times for the oxidative cleavage of unsaturated hydrocarbons.
Keywords:heterogeneous;ruthenium zirconia catalyst;alkenes or alkynes;scission;reusability
  1. Daw P, Petakamsetty R, Sarbajna A, Laha S, Ramapanicker R, Bera JK, J. Am. Chem. Soc., 136(40), 13987 (2014)
  2. Lee DG, Chen T, Comprehensive organic synthesis. In: Knochel P, Molander GA (eds.). Cleavage Reactions, 541-591, Elsevier, Oxford, UK (1991).
  3. Nishiyama Y, Nakagawa Y, Mizuno N, Angew. Chem.-Int. Edit., 40, 3639 (2001)
  4. Soares IV, Vieira EG, Filho NLD, Bastos AC, da Silva NC, Garcia EF, Lima LJA, Chem. Eng. J., 218, 405 (2013)
  5. Dong GB, Teo PL, Wickens ZK, Grubbs RH, Science, 333(6049), 1609 (2011)
  6. Namboodiri VV, Varma RS, Demessie ES, Pillai UR, Green Chem., 4, 170 (2002)
  7. Chen S, Liu Z, Shi E, Chen L, Wei W, Li H, Cheng Y, Wan X, Org. Lett., 13, 2274 (2011)
  8. Maurya MR, Kumar A, Pessoa JC, Coord. Chem. Rev., 255, 2315 (2011)
  9. Jiang WC, Gorden JD, Goldsmith CR, Inorg. Chem., 51(5), 2725 (2012)
  10. Shringarpure P, Patel A, J. Mol. Catal. A-Chem., 321(1-2), 22 (2010)
  11. Moghadam M, Mirkhani V, Angestaninejad S, Mohammadpoor-Baltork I, Javadi MM, Polyhedron, 29, 648 (2010)
  12. Vafaeezadeh M, Hashemi MM, Chem. Eng. J., 221, 254 (2013)
  13. Weiner B, Baeza A, Jerphagnon T, Feringa BL, J. Am. Chem. Soc., 131(27), 9473 (2009)
  14. Baskaran S, Das SJ, Chandrasekaran S, J. Org. Chem., 54, 5182 (1989)
  15. Travis BR, Narayan RS, Borhan B, J. Am. Chem. Soc., 124(15), 3824 (2002)
  16. Whitehead DC, Travis BR, Borhan B, Tetrahedron Lett., 47, 3797 (2006)
  17. Hiroshi O, Kazuhiro O, Shinji B, Synlett, 3201 (2007)
  18. Goulart MOF, Cioletti AG, de Souza Filho JD, de Simone CA, Castellano EE, Emery FS, de Moura KCG, M. Pintod MCFR, Pinto AV, Tetrahedron Lett., 44, 3581 (2003)
  19. Noh JH, Patala R, Meijboom R, Appl. Catal. A: Gen., 514, 253 (2016)
  20. Xing D, Guan B, Cai G, Fang Z, Yang L, Shi Z, Org. Lett., 8, 693 (2006)
  21. Kim YH, Hwang SK, Kim JW, Lee YS, Ind. Eng. Chem. Res., 53(31), 12548 (2014)
  22. Neisius NM, Plietke B, J. Org. Chem., 73, 3218 (2008)
  23. Hong ZY, Liu L, Sugiyama M, Fu Y, Wong CH, J. Am. Chem. Soc., 131(24), 8352 (2009)
  24. Gao A, Yang F, Li J, Wu Y, Tetrahedron, 68, 4950 (2012)
  25. Xu Y, Wan X, Tetrahedron Lett., 54, 642 (2013)