Cinnamic Acid Derivatives III, The Kinetics and Mechanism of the Nucleophilic Addition of Thioglycolic Acid to Benzalacetophenone Derivatives

신남산 유도체III, Benzalacetophenone 유도체에 대한 Thioglycolic acid의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구

The Kinetics of the addition of benzalacetophenone derivatives was investigated by ultraviolet spectrophotometery in 5% dioxane $H_2O$ at $50^{\circ}C$. A rate equation was obtained in wide range of pH. The substituent effects on benzalacetophenone derivatives were studied, and addition were facilitated by electron attracting groups. The final product was benzalacetophenone-${\beta}$-thioglycolic acid synthesized by the addition of thioglycolic acid to benzalacetophenone. On the base of the rate equation, substituent effect, general base effect and final product, the plausible addition mechanism was proposed: Below pH 9.0, only neutral thioglycolic acid molecule was added to the carbon-carbon double bond, and in the range of pH $9.0{\sim}11.0$, neutral thioglycolic acid molecule and thioglycolic acid anion competitively attacted the double bond. By contrast, above pH 11.0, the reaction was dependent upon only the addition of thioglycolic acid anion.