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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 32, Number 3
JKCSEZ 32(3)
June 20, 1988 

Kinetic Studies on the Nucleophilic Addition of Cysteine and Thioglycolic Acid to β,β-Dichlorostyrene Derivatives

β,β-Dichlorostyrene 유도체의 Cysteine 및 Thioglycolic Acid에 대한 친핵성 첨가반응의 반응속도론적 연구
Tae-Rin Kim, Jong-Yol Ryu, Duk-Chan Ha

김태린, 유정렬, 하덕찬
β,β-Dichlorostyrene 유도체(p-H, p-Cl, p-CH3, 및 p-OCH3)에 대한 thioglycolic acid 및 cysteine의 친핵성 첨가반응속도를 자외선 분광분석법으로 측정하여 pH에 따르는 반응속도상수의 변화, 일반염기(general base) 및 치환기 효과등으로 부터 넓은 pH범위에서 실험치와 잘 일치하는 반응속도식을 구하였고, 실험사실에 잘 맞는 반응 메카니즘을 제안하였다. 즉 pH 9.0 이상에서의 반응속도는 sulfide anion이 pH 9.0∼7.0에서는 thioglycolic acid 및 cysteine의 중성분자와 그의 anion들이 경쟁적으로 첨가되며 pH 7.0 이하에서는 thioglycolic acid 및 cysteine의 중성분자만이 첨가됨을 알았다.

The rate constants for the nucleophilic addition reactions of thioglycolic acid and cysteine to β, β-dichlorostyrene derivatives(p-H, p-Cl, p-CH3, and p-OCH3) were photochemically determined at various pH and a rate equation which can be applied over a wide pH range was obtained. On the bases of rate equation, general base catalysis and substituent effect, the plausible addition reaction mechanism was proposed: Above pH 9.0, the reaction was initiated by the addition of sulfide anion, and in the range of pH 7.0 to 9.0, the neutral molecules and it's anions attacked to the double bond, competitively. However, below pH 7.0, only the neutral molecules of thioglycolic acid or cysteine added to the carbon-carbon double bond.

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