Toward the Physical Interpretation of Inductive and Resonance Substituent Effects and Reexamination Based on Quantum Chemical Modeling

Halina Szatylowicz; Anna Jezuita; Tomasz Siodła; Konstantin S Varaksin; Mateusz A Domanski; Krzysztof Ejsmont; Tadeusz M Krygowski

doi:10.1021/acsomega.7b01043

Toward the Physical Interpretation of Inductive and Resonance Substituent Effects and Reexamination Based on Quantum Chemical Modeling

ACS Omega. 2017 Oct 26;2(10):7163-7171. doi: 10.1021/acsomega.7b01043. eCollection 2017 Oct 31.

Authors

Halina Szatylowicz¹, Anna Jezuita², Tomasz Siodła³, Konstantin S Varaksin⁴, Mateusz A Domanski¹, Krzysztof Ejsmont², Tadeusz M Krygowski⁵

Affiliations

¹ Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland.
² Faculty of Chemistry, Opole University, Oleska 48, 45-052 Opole, Poland.
³ Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań, Poland.
⁴ Department Organic Chemistry, Omsk F.M. Dostoevsky State University, Mira 55A, 644077 Omsk, Russia.
⁵ Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland.

Abstract

An application of a charge of the substituent active region concept to 1-Y,4-X-disubstituted derivatives of bicyclo[2.2.2]octane (BCO) [where Y = NO₂, COOH, OH, and NH₂ and X = NMe₂, NH₂, OH, OMe, Me, H, F, Cl, CF₃, CN, CHO, COMe, CONH₂, COOH, NO₂, and NO] provides a quantitative information on the inductive component of the substituent effect (SE). It is shown that the effect is highly additive but dependent on the kind of substituents. An application of the SE stabilization energy characteristics to 1,4-disubstituted derivatives of BCO and benzene allows the definition of inductive and resonance contributions to the overall SE. Good agreements with empirical approaches are found. All calculations have been carried out by means of the B3LYP/6-311++G(d,p) method.