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

Autor: Szatylowicz H; Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland., Jezuita A; Faculty of Chemistry, Opole University, Oleska 48, 45-052 Opole, Poland., Siodła T; Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań, Poland., Varaksin KS; Department Organic Chemistry, Omsk F.M. Dostoevsky State University, Mira 55A, 644077 Omsk, Russia., Domanski MA; Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland., Ejsmont K; Faculty of Chemistry, Opole University, Oleska 48, 45-052 Opole, Poland., Krygowski TM; Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland.
Jazyk: angličtina
Zdroj: ACS omega [ACS Omega] 2017 Oct 26; Vol. 2 (10), pp. 7163-7171. Date of Electronic Publication: 2017 Oct 26 (Print Publication: 2017).
DOI: 10.1021/acsomega.7b01043
Abstrakt: 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 = NO 2 , COOH, OH, and NH 2 and X = NMe 2 , NH 2 , OH, OMe, Me, H, F, Cl, CF 3 , CN, CHO, COMe, CONH 2 , COOH, NO 2 , 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.
Competing Interests: The authors declare no competing financial interest.
Databáze: MEDLINE
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