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Eliminations from (E)-2,4-Dinitrobenzaldehyde O-Aryloximes Promoted by R3N/R3NH+ in 70 mol% MeCN(aq). Effects of Leaving Group and Base-Solvent on the Nitrile-Forming Transition-State
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  • Eliminations from (E)-2,4-Dinitrobenzaldehyde O-Aryloximes Promoted by R3N/R3NH+ in 70 mol% MeCN(aq). Effects of Leaving Group and Base-Solvent on the Nitrile-Forming Transition-State
  • Eliminations from (E)-2,4-Dinitrobenzaldehyde O-Aryloximes Promoted by R3N/R3NH+ in 70 mol% MeCN(aq). Effects of Leaving Group and Base-Solvent on the Nitrile-Forming Transition-State
저자명
Cho. Bong Rae,Pyun. Sang Yong
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2013년|34권 4호|pp.1030-1034 (5 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

Elimination reactions of $(E)-2,4-(NO_2)_2C_6H_2CH=NOC_6H_3-2-X-4-NO_2$ (1a-e) promoted by $R_3N/R_3NH^+$ in 70 mol % MeCN(aq) have been studied kinetically. The reactions are second-order and exhibit Br$ddot{o}$nsted ${eta}$ = 0.80-0.84 and ${mid}{eta}_{lg}{mid}$ = 0.39-0.42, respectively. For all leaving groups and bases employed in this study, the ${eta}$ and ${mid}{eta}_{lg}{mid}$ values remained almost the same. The results can be described by a negligible $p_{xy}$ interaction coefficient, $p_{xy}={partial}{eta}/pK_{lg}={partial}{eta}_{lg}/pK_{BH}{approx}0$, which describes the interaction between the base catalyst and the leaving group. The negligible pxy interaction coefficient is consistent with the $(E1cb)_{irr}$ mechanism. Change of the base-solvent system from $R_3N$/MeCN to $R_3N/R_3NH^+$-70 mol % MeCN(aq) changed the reaction mechanism from E2 to $(E1cb)_{irr}$. Noteworthy was the relative insensitivity of the transition state structure to the reaction mechanism change.