LePree J M, Connors K A
School of Pharmacy, University Wisconsin-Madison 53706, USA.
J Pharm Sci. 1996 Jun;85(6):560-6. doi: 10.1021/js960031l.
The phenomenological theory of solvent effects is extended to chemical reaction rates and is tested against experimental data on the decarboxylative dechlorination of N-chloroalanine and N-chloroleucine at 25 degrees C in binary aqueous-organic solvent mixtures. The organic cosolvents studied were methanol, ethanol, l-propanol, 2-propanol, ethylene glycol, propylene glycol, acetonitrile, and dioxane. Reaction rates increased in all cosolvent systems. The kinetic solvent effects could be quantitatively described by the theory, and the parameters of the theory (solvation exchange constants K1 and K2 and cavity surface area parameter delta g++) were found to possess magnitudes reasonable for the physical significance assigned to them. In particular, the delta g++ value is consistent with a recent measurement of the volume of activation delta V++ of the reaction.
溶剂效应的现象学理论被扩展到化学反应速率，并针对25℃下N-氯代丙氨酸和N-氯代亮氨酸在二元水-有机溶剂混合物中的脱羧脱氯实验数据进行了检验。所研究的有机共溶剂有甲醇、乙醇、1-丙醇、2-丙醇、乙二醇、丙二醇、乙腈和二氧六环。在所有共溶剂体系中反应速率均增加。动力学溶剂效应可用该理论进行定量描述，并且发现该理论的参数（溶剂化交换常数K1和K2以及空穴表面积参数δg++）对于赋予它们的物理意义而言具有合理的量级。特别是，δg++值与该反应活化体积δV++的最近测量结果一致。
