Substituent cross-interaction effects on the electronic character of the C=N bridging group in substituted benzylidene anilines - Models for molecular cores of mesogenic compounds. A 13C NMR study and comparison with theoretical results

Helmi Neuvonen, Kari Neuvonen, Ferenc Fülöp

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Abstract

13C NMR chemical shifts δc(C=N) were measured in CDCl 3 for a wide set of mesogenic molecule model compounds, viz. the substituted benzylidene anilines P-X-C6H4CH=NC 6H4-p-Y (X = NO2, CN, CF3, F, Cl, H, Me, MeO, or NMe2; Y = NO2, CN, F, Cl, H, Me, MeO, or NMe2). The substituent dependence of δc(C=N) was used as a tool to study electronic substituent effects on the azomethine unit. The benzylidene substituents X have a reverse effect on δc(C=N): electron-withdrawing substituents cause shielding, while electron-donating ones behave oppositely, the inductive effects clearly predominating over the resonance effects. In contrast, the aniline substituents Y exert normal effects: electron-withdrawing substituents cause deshielding, while electron-donating ones cause shielding of the C=N carbon, the strengths of the inductive and resonance effects being closely similar. Additionally, the presence of a specific cross-interaction between X and Y could be verified. The electronic effects of the neighboring aromatic ring substituents systematically modify the sensitivity of the C=N group to the electronic effects of the benzylidene or aniline ring substituents. Electron-withdrawing substituents on the aniline ring decrease the sensitivity of δc(C=N) to the substitution on the benzylidine ring, while electron-donating substituents have the opposite effect. In contrast, electron-withdrawing substituents on the benzylidene ring increase the sensitivity of δc(C=N) to the substituent on the aniline ring, while electron-donating substituents act in the opposite way. These results can be rationalized in terms of the substituent-sensitive balance of the electron delocalization (mesomeric effects). The present NMR characteristics are discussed as regards the computational literature data. Valuable information has been obtained on the effects of the substituents on the molecular core of the mesogenic model compounds.

Original languageEnglish
Pages (from-to)3141-3148
Number of pages8
JournalJournal of Organic Chemistry
Volume71
Issue number8
DOIs
Publication statusPublished - Apr 14 2006

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ASJC Scopus subject areas

  • Organic Chemistry

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