亲电取代反应中活性位点预测方法的比较

doi:10.3866/PKU.WHXB201401211

Abstract

Abstract:

Predicting the reactivity of electrophilic substitution at different sites is of theoretical and practical significance, and many prediction methods based on the electronic structure of reactants have been proposed. We compared the reliability of 14 prediction methods, using 14 monosubstituted and 8 disubstituted benzenes as test sets. Methods reflecting local electronic softness, such as the Fukui function and average local ionization energy, are well-suited to monosubstituted benzenes with ortho-para directing groups and disubstituted benzenes. However, these methods often fail for systems containing a single meta directing group. Methods reflecting electrostatic effects perform worse overall than those reflecting local softness, but are better suited to systems containing a single meta directing group. Dual descriptor is the most overall robust method, and can be regarded as a universal prediction method.

Key words: Electrophilic substitution, Molecular surface, Fukui function, Dual descriptor, Electrostatic potential, Atomic charge, Orbital composition

MSC2000:

O641

FU Rong, LU Tian, CHEN Fei-Wu. Comparing Methods for Predicting the Reactive Site of Electrophilic Substitution[J].Acta Phys. -Chim. Sin., 2014, 30(4): 628-639.

References

(1) Koleva, G.; Galabov, B.; Kong, J.; Schaefer, H. F.; Schleyer, P. v. R. J. Am. Chem. Soc. 2011, 133, 19094. doi: 10.1021/ja201866h
(2) Kong, J.; Galabov, B.; Koleva, G.; Zou, J.-J.; Schaefer, H. F.; Schleyer, P. v. R.Angew. Chem. Int. Edit. 2011, 50, 6809. doi: 10.1002/anie.201101852
(3) Esteves, P. M.; de M. Carneiro, J. W.; Cardoso, S. P.; Barbosa, A. G. H.; Laali,K . K.; Rasul, G.; Prakash, G. K. S.; Olah, G. A. J. Am. Chem. Soc. 2003, 125, 4836. doi: 10.1021/ja021307w
(4) Hadzic, M.; Braïda, B.; Volatron, F. Org. Lett. 2011, 13, 1960. doi: 10.1021/ol200327s
(5) Xing, Q.; Xu, R.; Zhou, Z.; Pei, W. Basic Organic Chemistry, 2nd ed.;H igher Education Press: Beijing, 1993. [邢其毅, 徐瑞秋, 周政, 裴基础. 基础有机化学, 第二版; 北京: 高等教育出版社, 1993]
(6) Marx, D.; Hutter, J. Ab Initio Molecular Dynamics-Basic Theory and Advanced Methods; Cambridge University Press: Cambridge, 2009.
(7) Jensen, F. Introduction to Computational Chemistry, 2nd ed.; John Wiley &S ons: West Sussex, 2007; pp 487-492.
(8) Parr, R. G.; Yang, W. J. Am. Chem. Soc. 1984, 106, 4049. doi: 10.1021/ja00326a036
(9) Morell, C.; Grand, A.; Toro-Labbé, A. J. Phys. Chem. A 2004, 109, 205.
(10) Murray, J. S.; Politzer, P. Electrostatic Potentials: Chemical Applications. InEncyclopedia of Computational Chemistry; Schleyer, P. v. R. Ed.; John Wiley & Sons:W est Sussex, 1998; Vol. 2, pp 912-920.
(11) Lu, T.; Chen, F. W.Acta Phys. -Chim. Sin. 2012, 28, 1. [卢天, 陈飞武.物理化学学报, 2012, 28, 1.] doi: 10.3866/PKU.WHXB2012281
(12) Politzer, P.; Murray, J.; Bulat, F. J. Mol. Model. 2010, 16, 1731. doi: 10.1007/s00894-010-0709-5
(13) Murray, J. S.; Politzer, P. WIREs: Comp. Mol. Sci. 2011, 1, 153. doi: 10.1002/wcms.19
(14) Politzer, P.; Murray, J. S. Molecular Electrostatic Potentials and ChemicalR eactivity. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B.E ds.; John Wiley & Sons: New York, 1991; Vol. 2, pp 273-312.
(15) Politzer, P.; Murray, J. S. The Electrostatic Potential as a Guide to Molecular Interactive Behavior. In Chemical Reactivity Theory: A Density Functional View;Chattaraj, P. K. Ed.; CRC Press: Boca Raton, 2009.
(16) Geerlings, P.; Langenaeker, W.; Proft, F. D.; Baeten, A. Molecular Electrostatic Potentials vs DFT Descriptors of Reactivity. In Molecular Electrostatic Potentials: Concepts and Applications; Murray, J. S., Sen, K. Eds.; Elsevier Science B.V: Amsterdam, 1996.
(17) Politzer, P.; Murray, J. S.; Concha, M. C. Int. J. Quantum Chem. 2002, 88,19.
(18) Politzer, P.; Laurence, P. R.; Jayasuriya, K. Environ. Health Perspect. 1985,61, 191. doi: 10.1289/ehp.8561191
(19) Sjoberg, P.; Politzer, P. J. Phys. Chem. 1990, 94, 3959. doi: 10.1021/j100373a017
(20) Bader, R. F. W.; Carroll, M. T.; Cheeseman, J. R.; Chang, C. J. Am. Chem. Soc. 1987, 109, 7968. doi: 10.1021/ja00260a006
(21) Lu, T.; Chen, F. W. J. Mol. Graph. Model. 2012, 38, 314. doi: 10.1016/j.jmgm.2012.07.004
(22) Murray, J. S.; Peralta-Inga, Z.; Politzer, P.; Ekanayake, K.; LeBreton, P. Int. J. Quantum Chem. 2001, 83, 245.
(23) Sjoberg, P.; Murray, J. S.; Brinck, T.; Politzer, P. Can. J. Chem. 1990, 68,1 440. doi: 10.1139/v90-001
(24) Politzer, P.; Murray, J. S. The Average Local Ionization Energy: Concepts and Applications. In Theoretical Aspects of Chemical Reactivity; Toro-Labbé, A. Ed.;Elsevier: Amsterdam, 2007; pp 119-137.
(25) Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833. doi: 10.1063/1.1740588
(26) Breneman, C. M.; Wiberg, K. B. J. Comput. Chem. 1990, 11, 361.
(27) Weinhold, F. Natural Bond Orbital Methods. In Encyclopedia of Computational Chemistry; Schleyer, P. v. R. Ed.; John Wiley & Sons: West Sussex,1998; Vol.2, pp 1792-1811.
(28) Hirshfeld, F. L. Theor. Chem. Acc. 1977, 44, 129.
(29) Lu, T.; Chen, F. W. J. Theor. Comp. Chem. 2012, 11, 163. doi: 10.1142/S0219633612500113
(30) Bader, F. W. Atoms in Molecules: A Quantum Theory; Oxford University Press: New York, 1994.
(31) Fukui, K. Theory of Orientation and Stereoselection. In Orientation and Stereoselection; Springer: Berlin, 1970; Vol. 15/1, pp 1-85.
(32) Lu, T.; Chen, F. W. Acta Chim. Sin. 2011, 69, 2393. [卢天, 陈飞武. 化学学报, 2011, 69, 2393.]
(33) Liu, S. B. Acta Phys. -Chim. Sin. 2009, 25, 590. [刘述斌. 物理化学学报,2009, 25, 590.] doi: 10.3866/PKU.WHXB20090332
(34) Mohamed Imran, P. K.; Subramani, K. Acta Phys. -Chim. Sin. 2009, 25, 2357.[ Mohamed Imran, P. K.; Subramani, K. 物理化学学报, 2009, 25, 2357.] doi: 10.3866/PKU.WHXB20091131
(35) Yang, W.; Mortier, W. J. J. Am. Chem. Soc. 1986, 108, 5708. doi: 10.1021/ja00279a008
(36) Jin, J. L.; Li, H. B.; Lu, T.; Duan, Y. A.; Geng, Y.; Wu, Y.; Su, Z. M. J. Mol. Model. 2013, 19, 3437. doi: 10.1007/s00894-013-1845-5
(37) Manzetti, S.; Lu, T. J. Phys. Org. Chem. 2013, 26, 473. doi: 10.1002/poc.v26.6
(38) Oláh, J.; Van Alsenoy, C.; Sannigrahi, A. B. J. Phys. Chem. A 2002, 106,3 885.
(39) Pearson, R. G. J. Am. Chem. Soc. 1963, 85, 3533. doi: 10.1021/ja00905a001
(40) Yang, W.; Parr, R. G. Proc. Natl. Acad. Sci. U. S. A. 1985, 82, 6723. doi: 10.1073/pnas.82.20.6723
(41) Roy, R. K.; Krishnamurti, S.; Geerlings, P.; Pal, S. J. Phys. Chem. A 1998,102, 3746. doi: 10.1021/jp973450v
(42) Domingo, L. R.; Perez, P.; Saez, J. A. RSC Adv. 2013, 3, 1486. doi: 10.1039/c2ra22886f
(43) Fuster, F.; Sevin, A.; Silvi, B. J. Phys. Chem. A 2000, 104, 852. doi: 10.1021/jp992783k
(44) Lu, T.; Chen, F. W. Acta Phys. -Chim. Sin. 2011, 27, 2786. [卢天, 陈飞武 . 物理化学学报, 2011, 27, 2786.] doi: 10.3866/PKU.WHXB20112786
(45) MacDougall, P. J.; Henze, C. E. Theor. Chem. Acc. 2001, 105, 345. doi: 10.1007/s002140000225
(46) Bader, R. F. W.; Chang, C. J. Phys. Chem. 1989, 93, 2946. doi: 10.1021/j100345a020
(47) Koleva, G.; Galabov, B.; Wu, J. I.; Schaefer III, H. F.; Schleyer, P. v. R. J. Am. Chem. Soc. 2009, 131, 14722.
(48) Zhou, Z.; Parr, R. G. J. Am. Chem. Soc. 1990, 112, 5720. doi: 10.1021/ja00171a007
(49) Ehresmann, B.; Martin, B.; Horn, A. C.; Clark, T. J. Mol. Model. 2003, 9,342.
(50) Bruice, P. Y. Organic Chemistry, 4th ed.; Prentice Hall: New Jersey, 2004.
(51) McMurry, J. Organic Chemistry, 7th ed.; Thomson Higher Education:B elmont, 2008.
(52) Morrison, R. T.; Boyd, R. N. Organic Chemistry, 6th ed.; Prentice Hall, Inc.:New Jersey, 1992.
(53) Wang, J.T; Hu, Q.M; Zhang, B. Z.; Wang, Y.M. Organic Chemistry, 2nd ed.; NanKai University Press: Tianjin, 1993. [王积涛, 胡青眉, 张宝申, 王永梅. 有机化学,第二版; 天津: 南开大学出版社, 1993]
(54) Geerlings, P.; Langenaeker, W.; Proft, F. D.; Baeten, A. Molecular Electrostatic Potentials vs. DFT Descriptors of Reactivity. In Molecular Electrostatic Potentials: Concepts and Applications; Murray, J. S., Sen, K. Eds.; Elsevier Science:A msterdam, 1996; pp 587-617.
(55) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 03, RevisionB .02; Gaussian Inc.: Wallingford, CT, 2003.
(56) Becke, A. D. J. Chem. Phys. 1993, 98, 1372. doi: 10.1063/1.464304
(57) Hariharan, P. C.; Pople, J. A. Theor. Chem. Acc. 1973, 28, 213.
(58) Frisch, M. J.; Pople, J. A.; Binkley, J. S. J. Chem. Phys. 1984, 80, 3265. doi: 10.1063/1.447079
(59) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257. doi: 10.1063/1.1677527
(60) Multiwfn http://Multiwfn.codeplex.com (accessed Oct 10, 2013).
(61) Lu, T.; Chen, F. W. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.v33.5

[1]	Yongzhong OUYANG,Shugui HUA,Jinlian DENG. Rapid Assessment of Atoms-in-Molecules Charges for Polypeptides by the Electronegativity Equalization Method [J]. Acta Phys. -Chim. Sin., 2019, 35(1): 58-68.
[2]	Marco FRANCO-PÉREZ,José L. GÁZQUEZ,W. AYERS Paul,Alberto VELA. Thermodynamic Dual Descriptor [J]. Acta Phys. -Chim. Sin., 2018, 34(6): 683-391.
[3]	Carlos CÁRDENAS,Macarena MUÑOZ,Julia CONTRERAS,Paul W. AYERS,Tatiana GÓMEZ,Patricio FUENTEALBA. Understanding Chemical Reactivity in Extended Systems: Exploring Models of Chemical Softness in Carbon Nanotubes [J]. Acta Phys. -Chim. Sin., 2018, 34(6): 631-638.
[4]	Chaoxian YAN,Fan YANG,Ruizhi WU,Dagang ZHOU,Xing YANG,Panpan ZHOU. Application of Natural Orbital Fukui Functions and Bonding Reactivity Descriptor in Understanding Bond Formation Mechanisms Underlying [2+4] and [4+2] Cycloadditions of o-Thioquinones with 1, 3-Dienes [J]. Acta Phys. -Chim. Sin., 2018, 34(5): 497-502.
[5]	Zunwei ZHU,Qiaofeng YANG,Zhenzhen XU,Dongxia ZHAO,Hongjun FAN,Zhongzhi YANG. Fukui Function and Local Softness Related to the Regioselectivity of Electrophilic Addition Reactions [J]. Acta Phys. -Chim. Sin., 2018, 34(5): 519-527.
[6]	Robert C MORRISON. Fukui Functions for the Temporary Anion Resonance States of Be^-, Mg^-, and Ca^- [J]. Acta Phys. -Chim. Sin., 2018, 34(3): 263-269.
[7]	Helena W. QI,Maria KARELINA,Heather J KULIK. Quantifying Electronic Effects in QM and QM/MM Biomolecular Modeling with the Fukui Function [J]. Acta Phys. -Chim. Sin., 2018, 34(1): 81-91.
[8]	LIU Fen, ZOU Jian-Wei, HU Gui-Xiang, JIANG Yong-Jun. Quantitative Structure-Property Relationship Studies on the Adsorption of Aromatic Contaminants by Carbon Nanotubes [J]. Acta Phys. -Chim. Sin., 2014, 30(9): 1616-1624.
[9]	WU Xuan-Jun, ZHAO Peng, FANG Ji-Min, WANG Jie, LIU Bao-Shun, CAI Wei-Quan. Simulation on the Hydrogen Storage Properties of New Doping Porous Aromatic Frameworks [J]. Acta Phys. -Chim. Sin., 2014, 30(11): 2043-2054.
[10]	LIU Liang-Hong, ZHANG Peng-Fei, HUANG Ying. Molecular Acidity of Singly and Doubly Substituted Phenols: Predictions from Density Functional Reactivity Theory and Hammett Constants [J]. Acta Phys. -Chim. Sin., 2013, 29(03): 508-515.
[11]	HE Jing, XU Zhi-Guang, ZENG Yun-Xiu, XU Xuan, YU Lan, WANG Qi, LIU Hai-Yang. Effect of Substituents on Mn―O Bond in Oxo-Manganese(V) Corrole Complexes [J]. Acta Phys. -Chim. Sin., 2012, 28(07): 1658-1664.
[12]	LU Tian, CHEN Fei-Wu. Comparison of Computational Methods for Atomic Charges [J]. Acta Phys. -Chim. Sin., 2012, 28(01): 1-18.
[13]	LI Ya-Na, Lü Yang, ZHOU Li-Chuan, CHEN Li, LI Shen-Min. Atomic Partial Charges for Periodic Systems from First -Principles Calculations [J]. Acta Phys. -Chim. Sin., 2010, 26(10): 2793-2800.
[14]	MOHAMED IMRAN P. K., SUBRAMANI K.. Structure-Property Analysis of L-Ornithine and Its Substituted Analogues [J]. Acta Phys. -Chim. Sin., 2009, 25(11): 2357-2365.
[15]	YANG Xiang-Yan, ZHANG Yi-Heng, DING Lan, WANG Han-Qing. Cytotoxic Activity of a Natural ProductWangzaozin A [J]. Acta Phys. -Chim. Sin., 2009, 25(09): 1749-1755.

Comparing Methods for Predicting the Reactive Site of Electrophilic Substitution

PDF (PC)

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Metrics

Comments

Recommended 10