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Bulletin of the Korean Chemical Society v.26 no.7, 2005년, pp.1017 - 1024   피인용횟수: 1

Base-Promoted, Ketene-Forming Elimination Reactions. Mechanistic Borderline between E2 and E1cb Mechanisms

Pyun, Sang-Yong    (Department of Chemistry, Pukyong National University   ); Cho, Bong-Rae    (Department of Chemistry, Korea University  );
  • 초록

    Elimination reactions of $XC_6H_4CH_2CO_2C_6H_3-2-Y-4-NO_2$ have been studied under various conditions. When X was moderately electron-withdrawing, Y = H, and base-solvent was $R_2$ NH-MeCN, the reaction proceeded by the E2 mechanism via an E1cb-like transition state. Concave downward curve was noted in the Hammett plots. When X = 4- $NO_2$ , Y = Cl, $CF_3,\;NO_2$ , and the base-solvent was ${R_2NH/R_2NH_2}^+$ in 70 mol % MeCN(aq), the reaction proceeded by the E2 mechanism. The mechanism changed to a competing E2 and E1cb when X = 4- $NO_2$ and Y = H, MeO, and to the E1cb when X = 2,4-( $NO_2)_2$ , and Y = $NO_2$ . From these results, a plausible pathway of the change of the mechanism from E2 to the E1cb extreme is proposed.


  • 주제어

    Elimination reactions .   Mechanistic borderline .   E2 and E1cb mechanisms.  

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  • 이 논문을 인용한 문헌 (1)

    1. 2014. "" Bulletin of the Korean Chemical Society, 35(7): 2143~2147     

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