Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Nucleophilic Displacement at Sulfur Center (X). Solvolysis of Phenylmethanesulfonyl Chloride

黃의 親核性 置換反應(제10보). 鹽化페닐메탄술포닐의 加溶媒分解反應

  • Ikchoon Lee (Department of Chemistry, Inha University) ;
  • Wang Ki Kim (Department of Science Education, Chonnam National University)
  • 이익춘 (仁荷大學校 理科大學 化學科) ;
  • 김왕기 (全南大學校 師範大學 化學敎育科)
  • Published : 1978.06.30
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Abstract

The kinetics of phenylmethanesulfonyl chloride in methanol-water, ethanol-water, acetone-water and acetonitrile-water has been investigated. The rate was faster in protic solvents than in aprotic solvents while susceptibility of rate to the ionizing power, i. e., m of the Winstein plot and solvation number of the transition state were much smaller in protic solvents. This was considered in the light of initial state stabilization by hydrogen-bonding solvation of the protic solvents. It was concluded that the reaction proceeds by an $S_N2$ mechanism in which bond-formation precedes bond-breaking at the transition state in all solvent systems.

메탄올-물, 에탄올-물, 아세톤-물 및 아세토니트릴-물의 二成分 混合溶媒에서 鹽化페닐메탄술포닐의 加溶媒分解反應을 速度論的으로硏究하였다. 反應速度는 反陽性子溶媒에서 보다 陽性子溶媒에서 더 빨랐으며, 이온化能力에 對한 反應速度의 感度 즉 Winstein 圖示의 m와 轉移狀態의 溶媒和數는 陽性子溶媒에서 훨씬 작았다. 이것은 陽性子溶媒의 水素結合溶媒和에 依한 初期狀態의 安定化로서 생각할 수 있다. 反應은 모든 溶媒系에 있어서 轉移狀態의 結合形成이 結合破壤을 앞지르는$S_N2$ 메카니즘으로 일어난다 할 수 있다.

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