单取代苯环定位效应定量分析和图形可视化解释
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摘要
目前对于苯环上亲电取代反应定位规律的解释基本上都停留在基于实验的定性层面。本文以5个典型的单取代苯分子(苯胺、甲苯、氯苯、硝基苯和苯甲醛)为代表,采用多种量子化学方法(静电势、原子电荷、前线分子轨道理论、福井函数及双描述符等),对它们的亲电取代反应位点进行了研究。通过定量的数据和直观的图形,揭示苯分子亲电取代反应定位规律的本质,弥补了教材与教学中存在的不足,研究结果可以为大学《有机化学》教材的编写和课程教学提供有用的参考。
Currently,the interpretation of the location effect of electrophilic substitution reaction on benzene ring is mainly based on the qualitative explanation of the experiment. In this paper, we chose five typical mono-substituted benzene molecules(including aniline, toluene, chlorobenzene, nitrobenzene, benzaldehyde) as the representative,and carried out a study on the electrophilic substitution reaction sites of those molecules by quantum chemical methods(including electrostatic potential, atomic charges, frontier molecular orbital theory, Fukui function and dual descriptor,etc.). Through quantitative data and visual graphics, this paper reveals the nature of the orientation of benzene molecular electrophilic substitution reaction, and makes up for the shortcomings in teaching and teaching materials.The results of this study can provide useful reference for the compilation of the organic chemistry textbook and teaching of the organic chemistry course.
Currently,the interpretation of the location effect of electrophilic substitution reaction on benzene ring is mainly based on the qualitative explanation of the experiment. In this paper, we chose five typical mono-substituted benzene molecules(including aniline, toluene, chlorobenzene, nitrobenzene, benzaldehyde) as the representative,and carried out a study on the electrophilic substitution reaction sites of those molecules by quantum chemical methods(including electrostatic potential, atomic charges, frontier molecular orbital theory, Fukui function and dual descriptor,etc.). Through quantitative data and visual graphics, this paper reveals the nature of the orientation of benzene molecular electrophilic substitution reaction, and makes up for the shortcomings in teaching and teaching materials.The results of this study can provide useful reference for the compilation of the organic chemistry textbook and teaching of the organic chemistry course.
引文
[1]李景宁.有机化学.第5版.北京:高等教育出版社, 2014:176–183.
[2]王兴明,康明.基础有机化学.北京:科学出版社, 2015:144–147.
[3]乐厂高,仝小兰,盛寿日.有机化学.上海:华东理工大学出版社, 2012:102–106.
[4]周乐.有机化学.北京:科学出版社, 2009:240–246.
[5]彭凤鼐,毛璞,卢奎.有机化学.北京:化学工业出版社, 2008:132–137.
[6]谷文祥.有机化学.北京:科学出版社, 2007:112–117.
[7]Bruice, P. Y. Organic Chemistry, 4th ed.; Prentice Hall:New Jersey, USA, 2004; pp 629–638.
[8]Carey, F. A.; Giuliano, R. M. Organic Chemistry, 8th ed.; McGraw-Hill:New York, USA, 2011; pp 499–506.
[9]赵银芝,陈海群,霍发力.安徽农业科学, 2008, 36(1), 24.
[10]付蓉,卢天,陈飞武.物理化学学报, 2014, 30(4), 628.
[11]曹静思,陈飞武.有机化学, 2016, 36(10), 2463.
[12]Murray, J. S.; Politzer, P. Electrostatic Potentials:Chemical Applications//Encyclopedia of Computational Chemistry; Schleyer, P. v. R., Ed.; JohnWiley&Sons:West Sussex, USA, 1998; pp 912–920.
[13]Politzer, P.; Murray, J. S. Molecular Electrostatic Potentials and Chemical Reactivity//Reviews in Computational Chemistry; Lipkowitz, K. B.,Boyd, D. B., Eds.; John Wiley&Sons:New York, USA, 1991; pp 273–312.
[14]Mottishaw, J. D.; Erck, A. R.; Kramer, J. H. J. Chem.Educ. 2015, 92, 1846.
[15]卢天,陈飞武.物理化学学报, 2012, 28(1), 1.
[16]Fukui, K. Theory of Orientation and Stereoselection//Orientation and Stereoselection; Springer:Berlin, Germany, 1970; pp 1–85.
[17]卢天,陈飞武.化学学报, 2011, 69(20), 2393.
[18]Morell, C.; Grand, A.; Toro-Labbé, A. J. Phys. Chem. A 2005, 109(1), 205.
[19]James, B. F.; Eleen, F. Exploring Chemistry with Electronic Structure Method, 2nd ed.; Gaussian, Inc.:Pittsburgh, USA, 2002; pp 6–66.
[2]王兴明,康明.基础有机化学.北京:科学出版社, 2015:144–147.
[3]乐厂高,仝小兰,盛寿日.有机化学.上海:华东理工大学出版社, 2012:102–106.
[4]周乐.有机化学.北京:科学出版社, 2009:240–246.
[5]彭凤鼐,毛璞,卢奎.有机化学.北京:化学工业出版社, 2008:132–137.
[6]谷文祥.有机化学.北京:科学出版社, 2007:112–117.
[7]Bruice, P. Y. Organic Chemistry, 4th ed.; Prentice Hall:New Jersey, USA, 2004; pp 629–638.
[8]Carey, F. A.; Giuliano, R. M. Organic Chemistry, 8th ed.; McGraw-Hill:New York, USA, 2011; pp 499–506.
[9]赵银芝,陈海群,霍发力.安徽农业科学, 2008, 36(1), 24.
[10]付蓉,卢天,陈飞武.物理化学学报, 2014, 30(4), 628.
[11]曹静思,陈飞武.有机化学, 2016, 36(10), 2463.
[12]Murray, J. S.; Politzer, P. Electrostatic Potentials:Chemical Applications//Encyclopedia of Computational Chemistry; Schleyer, P. v. R., Ed.; JohnWiley&Sons:West Sussex, USA, 1998; pp 912–920.
[13]Politzer, P.; Murray, J. S. Molecular Electrostatic Potentials and Chemical Reactivity//Reviews in Computational Chemistry; Lipkowitz, K. B.,Boyd, D. B., Eds.; John Wiley&Sons:New York, USA, 1991; pp 273–312.
[14]Mottishaw, J. D.; Erck, A. R.; Kramer, J. H. J. Chem.Educ. 2015, 92, 1846.
[15]卢天,陈飞武.物理化学学报, 2012, 28(1), 1.
[16]Fukui, K. Theory of Orientation and Stereoselection//Orientation and Stereoselection; Springer:Berlin, Germany, 1970; pp 1–85.
[17]卢天,陈飞武.化学学报, 2011, 69(20), 2393.
[18]Morell, C.; Grand, A.; Toro-Labbé, A. J. Phys. Chem. A 2005, 109(1), 205.
[19]James, B. F.; Eleen, F. Exploring Chemistry with Electronic Structure Method, 2nd ed.; Gaussian, Inc.:Pittsburgh, USA, 2002; pp 6–66.
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