Abstract
The reaction of ${\beta}$-picoline with substituted benzoyl chlorides has been studied by means of conductometry under various pressures in acetonitrile. From the values of pseudo-first order and second order rate constants, the activation parameters (${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$, ${\Delta}H{\neq}$, ${\Delta}S{\neq}$ and ${\Delta}G{\neq}$) and the pressure dependence of Hammett ${\rho}$ value were studied. The activation volume, the activation compressibility coefficient and the activation entropy were all negative. By increasing pressure the rate constant and Hammett ${\rho}$ value were increased, and the reaction mechanism was proceed in bond formation favored.
10$^{\circ}C$와 20$^{\circ}C$에서 ${\beta}$-피콜린과 치환된 벤조일클로라이드류의 반응을 압력변화에 따라 아세토니트릴용매내에서 전기전도도법으로 연구하였다. 유사 1차속도상수와 2차속도상수로부터 여러 가지 활성화파라미터들(${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$, ${\Delta}H{\neq}$, ${\Delta}S{\neq}$ and ${\Delta}G{\neq}$)을 구하고, Hammett ${\rho}$값의 압력의존성을 설명하였다. ${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$ 및 ${\Delta}S{\neq}$ 는 모두 음의 값을 나타내었고, 압력증가에 따라 속도상수와 Hammett ${\rho}$값은 증가하며, 결합형성이 더욱 촉진된 반응메카니즘으로 진행됨을 알 수 있었다.