Solvent and structural effects in tautomeric 2(6)-hydroxy-4-methyl-6(2)-oxo-1-(substituted phenyl)-1,2(1,6)-dihydropyridine-3-carbonitriles: UV, NMR and quantum chemical study
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AuthorsAjaj, Ismail A.
Milčić, Miloš K.
Article (Published version)
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The state of the tautomeric equilibria of 2(6)-hydroxy-4-methyl-6(2)-oxo-1-(substituted phenyl)-1,2(1,6)-dihydropyridine-3-carbonitriles, 2-PY/6-PY, was evaluated using experimental and theoretical methodology. The experimental data were interpreted with the aid of time-dependent density functional (TD-DFT) method. Electron charge density was obtained by the use of Quantum Theory of Atoms in Molecules, i.e. Bader's analysis. Linear solvation energy relationships (LSER) rationalized solvent influence on tautomeric equilibrium. Linear free energy relationships (LFERs) were applied to the substituent-induced NMR chemical shifts (SCS) using SSP (single substituent parameter) and DSP (dual substituent parameter) model. Theoretical calculations and obtained correlations gave insight into the influence of molecular conformation on the transmission of substituent electronic effects, as well as on different solvent solute interactions, and the state of tautomeric equilibrium.
Keywords:Tautomerism / Solvent effects / Substituent effects / DFT / Derivative spectroscopy
Source:Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, 2015, 150, 575-585
- Pergamon-Elsevier Science Ltd, Oxford
- Study of the Synthesis, Structure and Activity of Natural and Synthetic Organic Compounds (RS-172013)
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3421