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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 28, Number 4
JKCSEZ 28(4)
August 20, 1984 

 
Title
Kinetics and Mechanism of Hydrolysis of Benzenesulfonylimido Phosgene

Benzenesulfonylimido Phosgene 의 가수분해 반응메카니즘과 반응속도론적 연구
Author
Nack-Do Sung, Sun-Ho Han, Ki-Sung Kwon, Tae-Rin Kim

성낙도, 한선호, 권기성, 김태린
Keywords
Abstract
1 : 4 dioxane-물의 혼합용매중에서 benzenesulfonylimido phosgene의 가수분해 반응속도 상수를 자외선 분광법으로 측정하여 넓은 pH범위에서 잘 맞는 반응속도식을 구하였다. Grunwald-Winstein식에 적용하여 pH 4.0에서 m=0.4의 값을 얻었으며 열역학적 활성화 파라미터 값은 pH 4.0에서 ΔH≠ = 15kcal mol-1과 ΔS≠ = 21e.u. pH 10.0에서는 ΔH≠ = 8kcal mol-1, ΔS≠ = -39e.u이었다. 이와 같은 결과로부터 잘 알려져 있지 않은 benzenesulfonylimido phosgene의 친핵성 첨가-제거 반응메카니즘을 정량적으로 잘 설명할 수 있었다.

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℃ 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 ΔH≠ = 15kcal mol-1, ΔS≠ = 21e.u. at pH 4.0 and ΔH≠ = 8kcal mol-1, ΔS≠ = -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.

Page
259 - 264
Full Text
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