How far the substituent effects in disubstituted cyclohexa-1,3-diene derivatives differ from those in bicyclo[2.2.2]octane and benzene?

Halina Szatyłowicz , Anna Jezuita , Tomasz Siodla , Konstantin S. Varaksin , Krzysztof Ejsmont , Mozhgan Shahamirian , Tadeusz Marek Krygowski


Substituents effects in cyclic diene derivatives are studied using quantum chemical modeling and compared to the corresponding effects in aromatic (benzene) and fully saturated (bicyclo[2.2.2]octane) compounds. In particular, electronic properties of the fixed group Y in a series of 3- and 4-X-substituted cyclohexa-1,3-diene-Y derivatives (where Y = NO2, COOH, COO− OH, O−, NH2, and X = NMe2, NH2, OH, OMe, Me, H, F, Cl, CF3, CN, CHO, COMe, CONH2, COOH, NO2, NO) are examined using the B3LYP/6-311++G(d,p) method. For this purpose, quantum chemistry models of the substituent effect: cSAR (charge of the substituent active region) and SESE (substituent effect stabilization energy) as well as traditional Hammett’s substituent constants (σ) and their inductive (F) and resonance (R) components are used. π-electron delocalization of the transmitting moiety (butadiene fragment of the CHD) is described by the HOMA index. This comparative study reveals interplay between inductive and resonance contributions to the substituent effect.
Author Halina Szatyłowicz (FC / DPC)
Halina Szatyłowicz,,
- Department Of Physical Chemistry
, Anna Jezuita
Anna Jezuita,,
, Tomasz Siodla
Tomasz Siodla,,
, Konstantin S. Varaksin
Konstantin S. Varaksin,,
, Krzysztof Ejsmont
Krzysztof Ejsmont,,
, Mozhgan Shahamirian
Mozhgan Shahamirian,,
, Tadeusz Marek Krygowski
Tadeusz Marek Krygowski,,
Journal seriesStructural Chemistry, ISSN 1040-0400, (A 25 pkt)
Issue year2018
Publication size in sheets0.55
Keywords in EnglishSubstituent effects Electronic structure Molecular modeling Substituent effect stabilization energy Charge of the substituent active region
ASJC Classification1606 Physical and Theoretical Chemistry; 3104 Condensed Matter Physics
Languageen angielski
Szatylowicz2018_Article_HowFarTheSubstituentEffectsInD.pdf 1.57 MB
Score (nominal)25
ScoreMinisterial score = 25.0, 24-07-2018, ArticleFromJournal
Ministerial score (2013-2016) = 25.0, 24-07-2018, ArticleFromJournal
Publication indicators Scopus SNIP (Source Normalised Impact per Paper): 2017 = 0.525; WoS Impact Factor: 2017 = 2.019 (2) - 2017=1.526 (5)
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