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

化学反应尤其是有机化学反应中存在着诸多竞争反应, 如何通过量子化学计算确定竞争反应尤其是动力学控制产物(Kinetically-controlled product, KP)和热力学控制产物(Thermodynamically-controlled product, TP)不一致反应的主产物及其产率, 是分析反应产物组成、 占比及获得高产率目标产物的关键, 但也仍是困扰研究人员的难题. 本文定义KP和TP产率相等的时间点为临界时间（t _c）, 反应时间t与t _c的比值为临界时间比ζ, 基于数值解法分析得到了 t _c 和产率比 r _y=c(KP)/c(TP)的公式, 分别为 t _c=pK _(KP)/k _(TP)和 r _y={r _k, ζ<0.3/r _k; 1/(2^ζ−1), 5/r _k<ζ<log₂(r _K/5+1); 1/r _K, ζ>log₂(5r _K)}. 运用上述公式研究了呋喃与马来酰亚胺的Diels-Alder 反应, 研究发现, 50 ℃以下主产物为endo型产物, 65 ℃以上为exo型产物, 与实验中25和90 ℃时分别得到endo和exo型产物相符合, 验证了所得公式确定竞争反应主产物的准确性. 此外, 对核苷氯化反应的研究结果表明, APT电荷和静电势仅适用于预测氯化反应中动力学控制反应的主产物, 但无法预测包含热力学控制的反应.

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 (t _c) 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 t _c. Based on numerical solution and further analysis, formulas oft _c and ratio of yields r _y=c(KP)/c(TP) were obtained as follows: t _c=pK _(KP)/k _(TP) and r _y={r _k, ζ<0.3/r _k; 1/(2^ζ−1), 5/r _k<ζ<log₂(r _K/5+1); 1/r _K, ζ>log₂(5r _K)}. 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

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基金资助

国家自然科学基金(22276004)

国家自然科学基金(21777006)

北京市自然科学基金(8212021)

北京市自然科学基金(8172013)