Artículo
Abstract:
A multiple-linear-regression analysis (MLRA) has been carried out using the Kamlet-Abboud-Taft (KAT) solvatochromic parameters in order to elucidate and quantify the solvent effects on the 17O chemical shifts of N-methylformamide (NMF), N,N-dimethylformamide (DMF), N-methylacetamide (NMA), and N,N-dimethylacetamide (DMA). The chemical shifts of the four molecules show the same dependence (in ppm) on the solvent polarity-polarizability, i.e., -22π*. The influence of the solvent hydrogen-bond-donor (HBD) acidities is slightly larger for the acetamides NMA and DMA, i.e., -48α, than for the formamides NMF and DMF, i.e., -42α. The influence of the solvent hydrogen-bond-acceptor (HBA) basicities is negligible for the nonprotic molecules DMF and DMA but significant for the protic molecules NMF and NMA, i.e., -9β. The effect of substituting the N-H hydrogen by a methyl group amounts to -5.9 ppm in NMF and 5.4 ppm in NMA. The effect of substituting the O=C-H hydrogen amounts to 5.5 ppm in NMF and 16.8 ppm in DMF. The model of specific hydration sites of amides by I. P. Gerothanassis and C. Vakka [J. Org. Chem. 59, 2341 (1994)] is settled in a more quantitative basis and the model by M. I. Burgar, T. E. St. Amour, and D. Fiat [J. Phys. Chem. 85, 502 (1981)] is critically evaluated. 17O hydration shifts have been calculated for formamide (FOR) by the ab initio LORG method at the 6-31G* level. For a formamide surrounded by the four in-plane molecules of water in the first hydration shell, the calculated 17O shift change due to the four hydrogen bonds, -83.2 ppm, is smaller than the empirical hydration shift, -100 ppm. The 17O shift change from each out-of-plane water molecule hydrogen-bonded to the amide oxygen is -18.0 ppm. These LORG results support the conclusion that no more than four water molecules are hydrogen-bonded to the amide oxygen in formamide. © 1997 Academic Press.
Registro:
| Documento: | Artículo |
| Título: | Solvent Effects on Oxygen-17 Chemical Shifts in Amides. Quantitative Linear Solvation Shift Relationships |
| Autor: | Díez, E.; Fabián, J.S.; Gerothanassis, I.P.; Esteban, A.L.; Abboud, J.M.; Contreras, R.H.; De Kowalewski, D.G. |
| Filiación: | Depto. de Quim. Fis. Aplicada, Facultad de Ciencias C2, Univ. Autónoma de Madrid, E-28049, Madrid, Spain Sect. of Organ. Chem. and Biochem., Department of Chemistry, University of Ioannina, Ioannina GR-45110, Greece Depto. de Quim. Física, Facultad de Ciencias, Universidad de Alicante, E-03080 Alicante, Spain Inst. de Quim. Fis. Rocasolano, CSIC, C/Serrano 119, E-28006, Madrid, Spain Departamento de Física, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires (1428), Argentina |
| Año: | 1997 |
| Volumen: | 124 |
| Número: | 1 |
| Página de inicio: | 8 |
| Página de fin: | 19 |
| DOI: | http://dx.doi.org/10.1006/jmre.1996.7481 |
| Título revista: | Journal of Magnetic Resonance |
| Título revista abreviado: | J. Magn. Reson. |
| ISSN: | 10907807 |
| CODEN: | JMARF |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10907807_v124_n1_p8_Diez |
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Citas:
---------- APA ----------
Díez, E., Fabián, J.S., Gerothanassis, I.P., Esteban, A.L., Abboud, J.M., Contreras, R.H. & De Kowalewski, D.G. (1997) . Solvent Effects on Oxygen-17 Chemical Shifts in Amides. Quantitative Linear Solvation Shift Relationships. Journal of Magnetic Resonance, 124(1), 8-19.http://dx.doi.org/10.1006/jmre.1996.7481
---------- CHICAGO ----------
Díez, E., Fabián, J.S., Gerothanassis, I.P., Esteban, A.L., Abboud, J.M., Contreras, R.H., et al. "Solvent Effects on Oxygen-17 Chemical Shifts in Amides. Quantitative Linear Solvation Shift Relationships" . Journal of Magnetic Resonance 124, no. 1 (1997) : 8-19.http://dx.doi.org/10.1006/jmre.1996.7481
---------- MLA ----------
Díez, E., Fabián, J.S., Gerothanassis, I.P., Esteban, A.L., Abboud, J.M., Contreras, R.H., et al. "Solvent Effects on Oxygen-17 Chemical Shifts in Amides. Quantitative Linear Solvation Shift Relationships" . Journal of Magnetic Resonance, vol. 124, no. 1, 1997, pp. 8-19.http://dx.doi.org/10.1006/jmre.1996.7481
---------- VANCOUVER ----------
Díez, E., Fabián, J.S., Gerothanassis, I.P., Esteban, A.L., Abboud, J.M., Contreras, R.H., et al. Solvent Effects on Oxygen-17 Chemical Shifts in Amides. Quantitative Linear Solvation Shift Relationships. J. Magn. Reson. 1997;124(1):8-19.http://dx.doi.org/10.1006/jmre.1996.7481
