NMR J(C,C) scalar coupling analysis of the effects of substituents on the keto-enol tautomeric equilibrium in 2-OH-n-X-pyridines. An experimental and DFT study

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In order to study the effect of substituents on the preferential keto/enol forms of six mono-substituted 2-OH-pyridines, the energies corresponding to their DFT-optimized structures for both tautomeric forms were compared. To obtain an idea of how solvent dielectric effects affect such a tautomeric...

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Detalles Bibliográficos
Autor principal: De Kowalewski, D.G
Otros Autores: Contreras, Rubén Horacio, Díez, E., Esteban, A.
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: 2004
Acceso en línea:Registro en Scopus
DOI
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Registro en la Biblioteca Digital
Aporte de:Registro referencial: Solicitar el recurso aquí
Biblioteca Central Dr. Luis F. Leloir (FCEN) de Universidad de Buenos Aires
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024 7 |2 scopus  |a 2-s2.0-10944250507 
030 |a MOPHA 
040 |a Scopus  |b spa  |c AR-BaUEN  |d AR-BaUEN 
100 1 |a De Kowalewski, D.G. 
245 1 0 |a NMR J(C,C) scalar coupling analysis of the effects of substituents on the keto-enol tautomeric equilibrium in 2-OH-n-X-pyridines. An experimental and DFT study 
260 |c 2004 
270 1 0 |m Contreras, R.H.; Departamento de Física, FCEyN, CONICET (C1428EHA), Buenos Aires, Argentina; email: contrera@df.uba.ar 
504 |a Katritzky, A.R., Lagowski, J.N., (1963) Adv. Heterocycl. Chem., 1, p. 311 
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504 |a Zaccari, D., Barone, V., Peralta, J.E., Contreras, R.H., Taurián, O.E., Díez, E., Esteban, A., (2003) Int. J. Molec. Sci., 4, p. 93 
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506 |2 openaire  |e Política editorial 
520 3 |a In order to study the effect of substituents on the preferential keto/enol forms of six mono-substituted 2-OH-pyridines, the energies corresponding to their DFT-optimized structures for both tautomeric forms were compared. To obtain an idea of how solvent dielectric effects affect such a tautomeric equilibrium, geometry optimizations were performed considering both an isolated molecule and an infinitely diluted dimethylsulfoxide solution (ε = 46.7). It was found that, for all these compounds, the dielectric solvent effect tends to increase the presence of the keto form. NMR 1J( 13C,13C) and 3J(13C,13C) isotropic couplings were measured for the same mono-substituted 2-OH-pyridines as well as for the corresponding mono-substituted pyridines. These isotropic coupling constants were also calculated within the DFT framework, where all four isotropic contributions, Fermi contact, spin dipolar, paramagnetic spin-orbit and diamagnetic spin-orbit, were taken into account. For the mono-substituted-2-OH-pyridines studied in this work, coupling constants were calculated using both the optimized keto and enol forms. The possible use of these couplings as probes to detect the keto and enol forms is discussed.  |l eng 
536 |a Detalles de la financiación: Dirección General de Enseñanza Superior e Investigación Científica, BQ-2000-0221-C02, BQU2000-0211-CO2 
536 |a Detalles de la financiación: The Argentine authors gratefully acknowledge financial support from CONICET and UBACyT. Financial support from Dirección General de Enseñanza Superior e Investigación Científica (ED: grant BQU2000-0211-CO2; ALE: BQ-2000-0221-C02) is gratefully acknowledged. 
593 |a Departamento de Física, FCEyN, CONICET (C1428EHA), Buenos Aires, Argentina 
593 |a Depto. de Quim. Fis. Aplicada, Facultad de Ciencias, C2, Univ. Autónoma de Madrid, E-28049 Madrid, Spain 
593 |a Depto. de Quim. Física, Universidad de Alicante, Apartado 99, E-03080 Alicante, Spain 
690 1 0 |a COMPUTATIONAL GEOMETRY 
690 1 0 |a CONCENTRATION (PROCESS) 
690 1 0 |a DIELECTRIC MATERIALS 
690 1 0 |a FERMI LEVEL 
690 1 0 |a MOLECULAR PHYSICS 
690 1 0 |a NUCLEAR MAGNETIC RESONANCE 
690 1 0 |a PARAMAGNETIC RESONANCE 
690 1 0 |a PROBABILITY DENSITY FUNCTION 
690 1 0 |a SOLUBILITY 
690 1 0 |a ULTRAVIOLET DETECTORS 
690 1 0 |a GAS PHASE 
690 1 0 |a LIQUID PHASE 
690 1 0 |a SCALAR COUPLING ANALYSIS 
690 1 0 |a TAUTOMERIC EQUILIBRIUM 
690 1 0 |a ORGANIC SOLVENTS 
700 1 |a Contreras, Rubén Horacio 
700 1 |a Díez, E. 
700 1 |a Esteban, A. 
773 0 |d 2004  |g v. 102  |h pp. 2607-2615  |k n. 23-24  |p Mol. Phys.  |x 00268976  |w (AR-BaUEN)CENRE-420  |t Molecular Physics 
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856 4 0 |u https://doi.org/10.1080/00268970412331292902  |x doi  |y DOI 
856 4 0 |u https://hdl.handle.net/20.500.12110/paper_00268976_v102_n23-24_p2607_DeKowalewski  |x handle  |y Handle 
856 4 0 |u https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00268976_v102_n23-24_p2607_DeKowalewski  |x registro  |y Registro en la Biblioteca Digital 
961 |a paper_00268976_v102_n23-24_p2607_DeKowalewski  |b paper  |c PE 
962 |a info:eu-repo/semantics/article  |a info:ar-repo/semantics/artículo  |b info:eu-repo/semantics/publishedVersion 

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