Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of Hydrolysis of Benzenesulfonylimido Phosgene

Benzenesulfonylimido Phosgene 의 加水分解 反鷹메카니즘과 反鷹速度論的 硏究

  • Sung, Nack-Do (Department of Agricultural Chemistry, Chungnam National University) ;
  • Han, Sun-Ho (Department of Chemistry, Chungnam National University) ;
  • Kwon, Ki-Sung (Department of Chemistry, Chungnam National University) ;
  • Kim, Tae-Rin (Department of Chemistry, Korea University)
  • 성낙도 (忠南大學校 農科大學 農化學科) ;
  • 한선호 (忠南大學校 理科大學 化學科) ;
  • 권기성 (忠南大學校 理科大學 化學科) ;
  • 김태린 (高麗大學校 理科大學 化學科)
  • Published : 1984.08.20
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Abstract

The rate constants for the hydrolysis of benzenesulfonylimido phosgene at various pH were determined by ultraviolet spectrophotometry in 1 : 4 dioxane-water mixed solvents at 25$^{\circ}$C and a rate equation which can be applied over a wide pH range was obtained. Based on the Grunwald-Winstein equation, m = 0.4 was obtained. The thermodynamic activation parameters for the hydrolysis were ${\Delta}H^{\neq}$ = 15kcal mol$^{-1}$, ${\Delta}S^{\neq}$ = 21e.u. at pH 4.0 and $ {\Delta}H^{\neq}$ = 8kcal. mol$^{-1}$, ${\Delta}S^{\neq}$ = -39e.u. at pH 11.0, respectively. It was concluded that the hydrolysis of benzenesulfonylimido phosgene in 1 : 4 dioxane-water mixed solvents proceed via nucleophilic addition-elimination.

1 : 4 dioxane-물의 혼합용매중에서 benzenesulfonylimido phosgene의 가수분해 반응속도 상수를 자외선 분광법으로 측정하여 넓은 pH범위에서 잘 맞는 반응속도식을 구하였다. Grunwald-Winstein식에 적용하여 pH4.0에서 m=0.4의 값을 얻었으며 열역학적 활성화 파라미터 값은 pH4.0에서 ${\Delta}H^{\neq}$ = 15kcal/mol과 $ {\Delta}S^{\neq}$ =-21e.u 그리고 pH10.0에서는 $ {\Delta}H^{\neq}$ = 8kcal/mol, ${\Delta}S^{\neq}$ = -39e.u.이었다. 이와 같은 결과로부터 잘 알려져 있지않은 benzenesulfonylimido phosgene의 친핵성 첨가-제거 반응메카니즘을 정량적으로 잘 설명할 수 있었다.

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