Topological electron density properties at critical points along aromatic rings as reactivity and regioselectivity descriptors in electrophilic substitutions

Author(s)

Da Silva, Natieli Alves ^[1] ; Bruns, Roy Edward ^[2] ; Haiduke, Roberto Luiz Andrade ^[1]

Affiliation

^[1] Univ Sao Paulo, Inst Quim Sao Carlos, Dept Quim & Fis Mol, Av Trabalhador Sao Carlense, 400 CP 780, BR-13560970 Sao Carlos - Brazil

^[2] Univ Estadual Campinas, Inst Quim, Campinas - Brazil

• Document type: Journal article
• Source: JOURNAL OF PHYSICAL ORGANIC CHEMISTRY; v. 34, n. 10 OCT 2021.
• Web of Science Citations: 0

Abstract

In order to evaluate the substituent effect on the reactivity and regioselectivity of aromatic rings with respect to electrophilic substitution reactions, we considered several benzene derivatives containing activating (-NH2, -NHCH3, -N(CH3)(2), -OH, -OCH3, and -CHCH2) and deactivating (-F, -Cl, -Br, -COH, -COCH3, -COOCH3, -COOH, -COCl, -CN, and -NO2) groups. In this sense, we propose alternative theoretical descriptors of reactivity and regioselectivity, which are based only on electron density properties of initial substrates. The descriptors investigated here were obtained from the quantum theory of atoms in molecules (electron density curvatures at the ring critical point {[}RCP] and at the critical points of carbon nuclei along with kinetic and potential energy densities at the RCP) and from the interacting quantum atom formalism (intra-atomic energy values of carbon atoms). The topological parameters at the RCPs and at carbon nuclei within the aromatic moiety were particularly successful in this task, being able to provide quantitative predictions of reactivity as compared with traditional resonance parameters used to that same end. (AU)

• FAPESP's process: 10/18743-1 - Employment of multipoles from the quantum theory of atoms in molecules and kinetic studies in systems found in the interstellar medium
• Grantee: Roberto Luiz Andrade Haiduke
• Support Opportunities: Regular Research Grants
• FAPESP's process: 14/23714-1 - Electronic structure relativistic calculations for evaluation of new prolapse-free basis sets
• Grantee: Roberto Luiz Andrade Haiduke
• Support Opportunities: Regular Research Grants