Theoretical Study on the Correlation of the Experimental Nucleophilic and Electrophilic Reaction Rates of Aromatic Compounds with the Prediction Results of Theoretical Methods

doi:10.6023/cjoc201602026

Chin. J. Org. Chem. ›› 2016, Vol. 36 ›› Issue (10): 2463-2471.DOI: 10.6023/cjoc201602026 Previous Articles Next Articles

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芳香化合物亲核、亲电反应活性的理论预测和实验反应速率的相关性研究

曹静思, 陈飞武

北京科技大学化学与生物工程学院化学与化学工程系北京 100083

收稿日期:2016-02-26 修回日期:2016-05-12 发布日期:2016-06-01
通讯作者: 陈飞武,E-mail:chenfeiwu@ustb.edu.cn E-mail:chenfeiwu@ustb.edu.cn
基金资助:
国家自然科学基金（Nos.21173020，21473008）资助项目.

Theoretical Study on the Correlation of the Experimental Nucleophilic and Electrophilic Reaction Rates of Aromatic Compounds with the Prediction Results of Theoretical Methods

Cao Jingsi, Chen Feiwu

Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083

Received:2016-02-26 Revised:2016-05-12 Published:2016-06-01
Supported by:
Project supported by the National Natural Science Foundation of China (Nos.21173020, 21473008).

Natural population analysis (NPA) charge, Hirshfeld charge, electrostatic potential, average local ionization energy, orbital composition of lowest unoccupied molecular orbital (LUMO), condensed Fukui function and condensed dual descriptor were exploited to predict the reaction active sites of nucleophilic and electrophilic reactions of aromatic compounds. It was found that the predicted reaction sites of these methods were all in consistent with the experimental results. It was also found that the correlations of the prediction results of theoretical methods reflecting local hardness such as Hirshfeld charges and electrostatic potential with the experimental reaction rate were excellent no matter the reactions of aromatic compounds are nucleophilic or electrophilic. However, the prediction results of theoretical methods reflecting local softness such as the condensed Fukui function and the condensed dual descriptor were in poor correlation with the experimental reaction rates as unexpected.

Key words: reaction rate, atom charge, electrostatic potential, average local ionization energy, orbital composition

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Cao Jingsi, Chen Feiwu. Theoretical Study on the Correlation of the Experimental Nucleophilic and Electrophilic Reaction Rates of Aromatic Compounds with the Prediction Results of Theoretical Methods[J]. Chin. J. Org. Chem., 2016, 36(10): 2463-2471.

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芳香化合物亲核、亲电反应活性的理论预测和实验反应速率的相关性研究

Theoretical Study on the Correlation of the Experimental Nucleophilic and Electrophilic Reaction Rates of Aromatic Compounds with the Prediction Results of Theoretical Methods

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