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
AbstractSubstituents 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.
|Journal series||Structural Chemistry, ISSN 1040-0400, (A 25 pkt)|
|Publication size in sheets||0.55|
|Keywords in English||Substituent effects Electronic structure Molecular modeling Substituent effect stabilization energy Charge of the substituent active region|
|Score|| = 25.0, 24-07-2018, ArticleFromJournal|
= 25.0, 24-07-2018, ArticleFromJournal
|Publication indicators||: 2017 = 0.525; : 2017 = 2.019 (2) - 2017=1.526 (5)|
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