Bulletin of the Korean Chemical Society

  • 제33권3호
  • /
  • Pages.881-884
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  • 2012
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Very Efficient Nucleophilic Aromatic Fluorination Reaction in Molten Salts: A Mechanistic Study

  • Jang, Sung-Woo (Department of Applied Chemistry, Kyunghee University) ;
  • Park, Sung-Woo (Department of Applied Chemistry, Kyunghee University) ;
  • Lee, Byoung-Se (Department of Chemistry, Sogang University) ;
  • Chi, Dae-Yoon (Department of Chemistry, Sogang University) ;
  • Song, Choong-Eui (Department of Chemistry and Department of Energy Science, Sungkyunkwan University) ;
  • Lee, Sung-Yul (Department of Applied Chemistry, Kyunghee University)
  • 투고 : 2011.11.10
  • 심사 : 2012.01.04
  • 발행 : 2012.03.20
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초록

We report a quantum chemical study of an extremely efficient nucleophilic aromatic fluorination in molten salts. We describe that the mechanism involves solvent anion interacting with the ion pair nucleophile $M^+F^-$(M = Na, K, Rb, Cs) to accelerate the reaction. We show that our proposed mechanism may well explain the excellent efficiency of molten salts for SNAr reactions, the relative efficacy of the metal cations, and also the observed large difference in rate constants in two molten salts $(n-C_4H_9)_4N^+\;CX_3SO_3^-$, (X=H, F) with slightly different sidechain ($-CH_3$ vs. $-CF_3$).

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