Acta Phys. -Chim. Sin. ›› 2014, Vol. 30 ›› Issue (4): 628-639.doi: 10.3866/PKU.WHXB201401211

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Comparing Methods for Predicting the Reactive Site of Electrophilic Substitution

FU Rong, LU Tian, CHEN Fei-Wu   

  1. Department of Chemistry and Chemical Engineering, School of Chemical and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China
  • Received:2013-11-18 Revised:2014-01-20 Published:2014-03-31
  • Contact: CHEN Fei-Wu E-mail:chenfeiwu@ustb.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21173020).

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