Title
Synthesis, structure and properties of 2(6)-hidroxy-6(2)-oxo-N(1), 4-disubtituted-1,2(1,6)-dihydropyridine-3-carbonitriles and their azo derivates
Creator
Ajaj, Ismail A., 1979-
Copyright date
2015
Object Links
Select license
Autorstvo-Nekomercijalno-Bez prerade 3.0 Srbija (CC BY-NC-ND 3.0)
License description
Dozvoljavate samo preuzimanje i distribuciju dela, ako/dok se pravilno naznačava ime autora, bez ikakvih promena dela i bez prava komercijalnog korišćenja dela. Ova licenca je najstroža CC licenca. Osnovni opis Licence: http://creativecommons.org/licenses/by-nc-nd/3.0/rs/deed.sr_LATN. Sadržaj ugovora u celini: http://creativecommons.org/licenses/by-nc-nd/3.0/rs/legalcode.sr-Latn
Language
English
Cobiss-ID
Theses Type
Doktorska disertacija
description
Datum odbrane: 17.06.2015.
Other responsibilities
mentor
Marinković, Aleksandar, 1970-
član komisije
Ušćumlić, Gordana, 1951-
član komisije
Mijin, Dušan, 1962-
član komisije
Milčić, Miloš, 1973-
University
Univerzitet u Beogradu
Faculty
Tehnološko-metalurški fakultet
Alternative title
Sinteza, struktura i svojstva 2(6)-hidroksi-6(2)-okso-N(1), 4-disuptituisanih-1,2(1,6)-dihidropiridina-3-karbonitrila i njihovih azo derivata edoktorska disertacija
Publisher
[I. Ajaj]
Format
242, VI listova
description
Organic chemistry / Organska hemija
Abstract (en)
In this work, a simple and convenient synthesis of tautomeric (6 or 2)-hydroxy-4-methyl-(2 or 6)-oxo-1-(substituted phenyl)-(1,2 or 1,6)-dihydro- pyridine-3-carbonitriles from ethyl acetoacetate and 2-cyano-N-(substituted phenyl)-ethanamides using microwave assisted chemistry is presented. The structure of the obtained product was confirmed by the use of FTIR, NMR, UV and MS techniques. Presence of tautomeric forms, 6-hydroxy-4-methyl-2-oxo-1-(substituted phenyl)-1,2-dihydropyridine-3-carbonitriles and 2-hydroxy-4-methyl -6-oxo-1-(substituted phenyl)-1,6-dihydropyridine-3-carbonitriles, and state of equilibrium in DMSO-d6 of the obtained product was studied by 1H and 13C NMR spectroscopy, as well as B3LYP/6-311++G(d,p) and GIAO/WP04/aug-cc-pVDZ theoretical calculations.
Tautomeric equilibria of title compounds were quantitatively analyzed by UV/Vis spectroscopy and theoretical approaches. Kamlet-Taft and Catalán correlation analysis were done. The LFER correlation results showed significant influence of the solvent effects on the transmission mode of substituent effects. In order to calculate optimal geometries of investigated compounds, a conformation with minimum energies were determined using semi-empirical PM6 method, as well as B3LYP (DFT) hybride method with 6-311G(d,p) basis set.
The state of the tautomeric equilibria of 6(2)-hydroxy-4-methyl-2(6)-oxo-1-(substituted phenyl)-1,2(1,6)-dihydropyridine-3-carbonitriles were evaluated from UV/Vis and NMR spectral data. Quantum chemical calculations of geometries and electronic energies were
performed by density functional theory (B3LYP). 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) was applied to the substituent-induced NMR chemical shifts (SCS) with σ using SSP (single substituent parameter), inductive (σI) and resonance (σR) parameters using DSP (dual substituent parameter), as well as the Yukawa–Tsuno model. Theoretical calculations and obtained correlations gave insight into the influence molecular conformation on the transmission of substituent effects, as well as on different solvent‒solute interactions on state of tautomeris equilibria.
Abstract (sr)
Sinteza proizvoda tautomerne smeše 2(6)-hidroksi-4-metil-6(2)-okso-1-(supstituisanih fenil)-1,2(1,6)-dihidropiridina-3-karbonitrila (serija 1), izvršena je polazeći iz etil-acetoacetata i 2-cijano-N-(supstituisanih fenil)-etanamida primenom konvencionalne i mikrotalasne metode...
Authors Key words
Heterocycles, Microwave assisted synthesis, Tautomerism, Solvent effects, Substituent effects, UV/Vis spectroscopy, NMR spectroscopy,DFT
Authors Key words
heterociklična jedinjenja, mikrotalasna sinteza, tautomerija, efekat rastvrača, efekat supstituenata, UV/Vis spektroskopija, NMR spektroskopija, teorija funkcionalne gustine - DFT
Classification
547.7(043.3)
Type
Tekst
Abstract (en)
In this work, a simple and convenient synthesis of tautomeric (6 or 2)-hydroxy-4-methyl-(2 or 6)-oxo-1-(substituted phenyl)-(1,2 or 1,6)-dihydro- pyridine-3-carbonitriles from ethyl acetoacetate and 2-cyano-N-(substituted phenyl)-ethanamides using microwave assisted chemistry is presented. The structure of the obtained product was confirmed by the use of FTIR, NMR, UV and MS techniques. Presence of tautomeric forms, 6-hydroxy-4-methyl-2-oxo-1-(substituted phenyl)-1,2-dihydropyridine-3-carbonitriles and 2-hydroxy-4-methyl -6-oxo-1-(substituted phenyl)-1,6-dihydropyridine-3-carbonitriles, and state of equilibrium in DMSO-d6 of the obtained product was studied by 1H and 13C NMR spectroscopy, as well as B3LYP/6-311++G(d,p) and GIAO/WP04/aug-cc-pVDZ theoretical calculations.
Tautomeric equilibria of title compounds were quantitatively analyzed by UV/Vis spectroscopy and theoretical approaches. Kamlet-Taft and Catalán correlation analysis were done. The LFER correlation results showed significant influence of the solvent effects on the transmission mode of substituent effects. In order to calculate optimal geometries of investigated compounds, a conformation with minimum energies were determined using semi-empirical PM6 method, as well as B3LYP (DFT) hybride method with 6-311G(d,p) basis set.
The state of the tautomeric equilibria of 6(2)-hydroxy-4-methyl-2(6)-oxo-1-(substituted phenyl)-1,2(1,6)-dihydropyridine-3-carbonitriles were evaluated from UV/Vis and NMR spectral data. Quantum chemical calculations of geometries and electronic energies were
performed by density functional theory (B3LYP). 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) was applied to the substituent-induced NMR chemical shifts (SCS) with σ using SSP (single substituent parameter), inductive (σI) and resonance (σR) parameters using DSP (dual substituent parameter), as well as the Yukawa–Tsuno model. Theoretical calculations and obtained correlations gave insight into the influence molecular conformation on the transmission of substituent effects, as well as on different solvent‒solute interactions on state of tautomeris equilibria.
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