高等学校化学学报2026，Vol.47Issue(7)：146-156,11.DOI:10.7503/cjcu20250357
基于量子化学计算的动力学控制与热力学控制竞争反应主产物及其产率的确定
Determination of Main Products and Their Yields in Competitive Reactions Governed by Kinetics and Thermodynamics Using Quantum Chemical Computation
摘要
Abstract
There are many competitive reactions in chemical reactions,especially in organic chemical reactions.However,how to determine the main products and their yields in the competitive reactions whose kinetically-controlled product(KP)and thermodynamically-controlled product(TP)are inconsistent is of significance to analyze the compositions and proportions of products and to obtain high-yield target product and is also a problem puzzled the researchers.In this study,a critical time(tc)was defined as the time when the yield of KP is equal to that of TP and critical time ratio ζ was defined as the ratio of reaction time t to tc.Based on numerical solution and further analysis,formulas of tc and ratio of yields ry=c(KP)/c(TP)were obtained as follows:tc=pK(KP)/k(TP)and ry={rk,ζ<0.3/rk;1/(2ζ-1),5/rk<ζ<log2(rK/5+1);1/rK,ζ>log2(5rK)}.Based upon above formulas,the main products of Diels-Alder reaction between furan and maleimide were investigated.The results indicated that the main product is endo-product and exo-product when temperature is below 50℃and above 65℃,respectively,which is in good agreement with experimental results that endo-product and exo-product were obtained at 25 and 90℃,respectively.This verified the accuracy of the obtained formula in determining the main product in the competitive reaction.Moreover,studies on chlorination of nucleosides showed that the APT charge and electrostatic potential parameters are only applicable for kinetically-controlled reaction to predict main products,but not for thermodynamically-controlled reaction.关键词
竞争反应/主产物/产率/动力学控制产物/热力学控制产物/量子化学计算Key words
Competitive reaction/Main product/Yield/Kinetically-controlled product/Thermodynamically-controlled product/Quantum chemical computation分类
化学化工引用本文复制引用
莫泳航,刘永东,钟儒刚..基于量子化学计算的动力学控制与热力学控制竞争反应主产物及其产率的确定[J].高等学校化学学报,2026,47(7):146-156,11.基金项目
国家自然科学基金(批准号:22276004,21777006)和北京市自然科学基金(批准号:8212021,8172013)资助. Supported by the National Natural Science Foundation of China(Nos.22276004,21777006)and the Natural Science Foundation of Beijing,China(Nos.8212021,8172013). （批准号:22276004,21777006）
