Jump to main content
Jump to site search

Issue 17, 2016
Previous Article Next Article

Towards physical interpretation of substituent effects: the case of meta- and para-substituted anilines

Author affiliations

Abstract

Quantum chemical modeling was used to investigate the electron-donating properties of the amino group in a series of meta- and para-X-substituted anilines (X = NMe2, NH2, OH, OMe, CH3, H, F, Cl, CF3, CN, CHO, COMe, CONH2, COOH, NO2, and NO). Different methods (HF, B3LYP, and M06-2X) and basis sets (6-31+G(d,p), 6-311++G(d,p), and aug-cc-pVDZ) were applied and compared with the MP2 approach. The B3LYP/6-311++G(d,p) method was chosen as the most appropriate one. The substituent properties were described by σ, cSAR(X) and SESE descriptors; the amino group was characterized by structural (dCN, dNH and ΣNH2) and electronic [δ(N) and cSAR(NH2)] parameters; whereas the transmitting moiety was characterized by aromaticity indices HOMA and NICS, as well as by QTAIM characteristics at the ring critical point. All the used parameters were found to be mutually interrelated with much better correlations for the para-derivatives than the meta-derivatives. It was numerically confirmed that sensitivity of the amino group to the substituent effect was greater by over three times when the substituent was located in the para-position. In the case of the meta-derivatives, variability of characteristics for both the reaction center and the substituent was small. The reverse substituent effect was clearly shown by comparison of the cSAR(X) characteristics for monosubstituted benzenes, and meta- and para-substituted anilines.

Graphical abstract: Towards physical interpretation of substituent effects: the case of meta- and para-substituted anilines

Back to tab navigation

Supplementary files

Publication details

The article was received on 03 Nov 2015, accepted on 09 Dec 2015 and first published on 09 Dec 2015


Article type: Paper
DOI: 10.1039/C5CP06702B
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2016,18, 11711-11721
  •   Request permissions

    Towards physical interpretation of substituent effects: the case of meta- and para-substituted anilines

    H. Szatylowicz, T. Siodla, O. A. Stasyuk and T. M. Krygowski, Phys. Chem. Chem. Phys., 2016, 18, 11711
    DOI: 10.1039/C5CP06702B

Search articles by author

Spotlight

Advertisements