Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Hydrolysis Mechanism of Phenyl-N-benzoylchlorothioformimidate Derivatives

Phenyl-N-benzoylchlorothioformimidate 誘導體의 加水分解 反應메카니즘

  • Ki-Sung Kwon (Department of Chemistry, Chungnam National University) ;
  • Chon-Suk Kim (Department of Chemistry, Chungnam National University) ;
  • Yong-Gu Lee (Department of Chemistry, Chungnam National University) ;
  • Nack-Do Sung (Department of Agricultural Chemistry, Chungnam National University)
  • 권기성 (충남대학교 이과대학 화학과) ;
  • 김천석 (충남대학교 자연과학대학 화학과) ;
  • 이용구 (충남대학교 자연과학대학 화학과) ;
  • 성낙도 (충남대학교 농과대학 농화학과)
  • Published : 1992.08.20
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Abstract

The rate constants of hydrolysis of phenyl-N-benzoylchlorothioformimidates were determined by UV spectrophotometry in 30% (v/v) aqueous dioxane at $25^{\circ}C$. On the basis of rate equation, general base catalysis, solvent effect, substituent effect, thermodynamic parameters, frontier orbital interaction and hydrolysis product analysis, it may be concluded that the hydrolysis of phenyl-N-benzoylchlorothioformimidates proceeds through $S_N1$ mechanism via azocarbocation intermidiate below pH 10.0, while above pH 10.00 the hydrolysis proceeds through nucleophilic addition-elimination ($Ad_{N-E}$) mechanism. In the range of pH from 10.0 to 11.0 these two reaction occur competitively.

$25^{\circ}C$의 30%(v/v) dioxane-물의 혼합용매 속에서 pH 변화에 따른 X와 Y-치환된 phenyl-N-benzo-ylchlorothioformimidates(S)들의 가수분해 반응 속도상수를 측정하여 반응 속도식을 유도하고, 경계 궤도함수 상호작용, 용매 효과, 일반 염기 촉매효과, 열 역학적 활성화 파라미터, 및 가수분해반응 생성물 분석 등의 결과로부터 pH 10.0 이하의 낮은 pH 에서는 azocarbocation 중간체를 지나는 $S_N1$형 반응, pH 11.0이상의 높은 pH에서는 사면체 중간체를 지나는 친핵성 첨가-제거 ($Ad_{N-E}$)반응 그리고 pH 10.0과 11.0 사이에서는 이들 두가지 유형의 궤도 조절 반응이 서로 경쟁적으로 일어남을 제안하였다.

Keywords

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