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Abstract:

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.

Registro:

Documento: Artículo
Título: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
Autor:De Kowalewski, D.G.; Contreras, R.H.; Díez, E.; Esteban, A.
Filiación:Departamento de Física, FCEyN, CONICET (C1428EHA), Buenos Aires, Argentina
Depto. de Quim. Fis. Aplicada, Facultad de Ciencias, C2, Univ. Autónoma de Madrid, E-28049 Madrid, Spain
Depto. de Quim. Física, Universidad de Alicante, Apartado 99, E-03080 Alicante, Spain
Palabras clave:Computational geometry; Concentration (process); Dielectric materials; Fermi level; Molecular physics; Nuclear magnetic resonance; Paramagnetic resonance; Probability density function; Solubility; Ultraviolet detectors; Gas phase; Liquid phase; Scalar coupling analysis; Tautomeric equilibrium; Organic solvents
Año:2004
Volumen:102
Número:23-24
Página de inicio:2607
Página de fin:2615
DOI: http://dx.doi.org/10.1080/00268970412331292902
Título revista:Molecular Physics
Título revista abreviado:Mol. Phys.
ISSN:00268976
CODEN:MOPHA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00268976_v102_n23-24_p2607_DeKowalewski

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Citas:

---------- APA ----------
De Kowalewski, D.G., Contreras, R.H., Díez, E. & Esteban, A. (2004) . 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. Molecular Physics, 102(23-24), 2607-2615.
http://dx.doi.org/10.1080/00268970412331292902
---------- CHICAGO ----------
De Kowalewski, D.G., Contreras, R.H., Díez, E., Esteban, 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" . Molecular Physics 102, no. 23-24 (2004) : 2607-2615.
http://dx.doi.org/10.1080/00268970412331292902
---------- MLA ----------
De Kowalewski, D.G., Contreras, R.H., Díez, E., Esteban, 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" . Molecular Physics, vol. 102, no. 23-24, 2004, pp. 2607-2615.
http://dx.doi.org/10.1080/00268970412331292902
---------- VANCOUVER ----------
De Kowalewski, D.G., Contreras, R.H., Díez, E., Esteban, 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. Mol. Phys. 2004;102(23-24):2607-2615.
http://dx.doi.org/10.1080/00268970412331292902