Abstract:
The 13C NMR spectra of a series of alkyl formates which show the coexistence of s-cis and s-trans rotamers at room temperature were measured at 125 MHz. 13C chemical shifts and 1J(CH) couplings are compared for both types of rotamers. Their differences are rationalized in terms of different intramolecular interactions. The 17O NMR spectra of these compounds could be observed only for the most abundant rotamer, which in all cases was identified as the s-cis rotamer. In the three members of this series with the shortest alkyl chains, a 2J(17O,1H) coupling constant of ca. 40 Hz was observed. In ethyl formate, 13C magnetic shielding constants were calculated using the LORG approach with ab initio optimized geometries in both types of rotamers for the carbon atom β to the dicoordinated oxygen atom. A comparison between the calculated and experimental values yields support for the rationalizations quoted above. © 1998 John Wiley & Sons, Ltd.
Registro:
Documento: |
Artículo
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Título: | Conformational effects on 13C NMR parameters in alkyl formates |
Autor: | De Kowalewski, D.G.; Kowalewski, V.J.; Contreras, R.H.; Diez, E.; Esteban, A.L. |
Filiación: | Departamento de Física, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón I, 1428 Buenos Aires, Argentina Facultad de Ciencias C2-103, Univ. Autónoma de Madrid, 28049 Madrid, Spain Depto. de Quim. Física, Universidad de Alicante, 03080 Alicante, Spain
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Palabras clave: | 13C NMR; 17O NMR; Ab initio LORG study; Alkyl formates; Conformational effects; NMR |
Año: | 1998
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Volumen: | 36
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Número: | 5
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Página de inicio: | 336
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Página de fin: | 342
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DOI: |
http://dx.doi.org/10.1002/(SICI)1097-458X(199805)36:5<336::AID-OMR273<3.0.CO;2-C |
Título revista: | Magnetic Resonance in Chemistry
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Título revista abreviado: | Magn. Reson. Chem.
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ISSN: | 07491581
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CODEN: | MRCHE
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v36_n5_p336_DeKowalewski |
Referencias:
- Bond, D., Schleyer, P.V.R., (1990) J. Org. Chem., 55, p. 1003
- Contreras, R.H., Biekofsky, R.R., De Kowalewski, D.G., Orendt, A.M., Facelli, J.C., (1993) J. Phys. Chem., 97, p. 91
- Esteban, A.L., Galache, M.P., Diez, E., Biekofsky, R.R., Contreras, R.H., (1994) Magn. Reson. Chem., 32, p. 199
- Biekofsky, R.R., Pomilio, A.B., Aristegui, R.A., Contreras, R.H., (1995) J. Mol. Struct., 344, p. 143
- Peralta, J.E., Ruiz De Azúa, M.C., Contreras, R.H., Int. J. Quantum Chem., , in press
- Knittel, J.J., Makriyannis, A., (1981) J. Med. Chem., 24, p. 906
- Roth, B., Aig, E., Rauckman, B.S., Strelitz, J.Z., Phillips, A.P., Ferone, R., Bushby, S.R.M., Sigel, C.W., (1981) J. Med. Chem., 24, p. 933
- Roth, B., Rauckman, B.S., Ferone, R., Baccanari, D.P., Champness, J.N., Hyde, R.M., (1987) J. Med. Chem., 30, p. 348
- Blom, C.E., Gunthard, H.H., (1981) Chem. Phys. Lett., 84, p. 267
- Grindley, T.B., (1982) Tetrahedron Lett., 23, p. 1757
- Ferraro, M.B., De Kowalewski, D.G., Contreras, R.H., Ortiz, F.S., (1987) Chem. Phys., 118, p. 325
- Hansen, A.E., Bouman, T.D., (1985) J. Chem. Phys., 82, p. 5035
- Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.E., Koseki, S., Montgomery, J.A., (1993) J. Comput. Chem., 14, p. 1347
- Bouman, T.D., Hansen, A.E., (1991) RPAC Molecular Properties Package, Version 9.0, , Souther Illinois University, Edwardsville, IL
- Hansen, P.E., (1981) Prog. Nucl. Magn. Reson. Spectrosc., 14, p. 175
- Koole, N.J., De Bie, M.J.A., Hansen, P.E., (1984) Org. Magn. Reson., 22, p. 146
- Biekofsky, R.R., Pomilio, A.B., Contreras, R.H., (1990) J. Mol. Struct. THEOCHEM, 210, p. 211
- Perlin, A.S., Casu, B., (1969) Tetrahedron Lett., p. 292
- Wolfe, S., Pinto, B.M., Varma, V., Leung, R.Y.N., (1990) Can. J. Chem., 68, p. 1051
- Dorman, D.E., Bauer, D., Roberts, J.D., (1975) J. Org. Chem., 40, p. 3729
- Couperus, P.A., Clague, A.D.H., Van Dongen, J.P.C.M., (1978) Org. Magn. Reson., 11, p. 590
- Levy, G.C., Nelson, G.L., (1972) Carbon-13 Nuclear Magnetic Resonance for Organic Chemists, , Wiley, New York
- Grant, D.M., Cheney, B.V., (1967) J. Am. Chem. Soc., 89, p. 5315
- Cheney, B.V., Grant, D.M., (1967) J. Am. Chem. Soc., 89, p. 5319
- Li, S., Chesnut, D.B., (1985) Magn. Reson. Chem., 23, p. 625
- Li, S., Chesnut, D.B., (1986) Magn. Reson. Chem., 24, p. 93
- McFarlane, W., (1970) Chem. Commun., p. 418
- Jiao, D., Barfield, M., Hruby, H.J., (1993) Magn. Reson. Chem., 31, p. 75
- Riveros, J.M., Wilson E.B., Jr., (1969) J. Chem. Phys., 46, p. 4605
- Boykin, D.W., (1990) 17O NMR Spectroscopy in Organic Chemistry, , CRC Press, Boca Raton, FL
- Facelli, J.C., Orendt, A.M., Contreras, R.H., Tufró, M.F., De Kowalewski, D.G., (1992) J. Phys. Chem., 96, p. 7895
- Contreras, R.H., Biekofsky, R.R., Esteban, A.L., Diez, E., San Fabian, J., (1996) Magn. Reson. Chem., 34, p. 447
- Kalabin, G.A., Kushnarev, D.F., Valeyev, R.B., Trofimov, B.A., Fedotov, M.A., (1982) Org. Magn. Reson., 18, p. 1
- Delseth, C., Kintzinger, J.P., (1978) Helv. Chim. Acta, 61, p. 1327
- Chandrasekaran, S., (1990) 17O NMR Spectroscopy in Organic Chemistry, p. 141. , edited by D. W. Boykin, Chapt. 7, CRC Press, Boca Raton, FL
- Boykin, D.W., Baumstark, A.L., (1989) Tetrahedron, 45, p. 3613
- Boykin, D.W., Dewprashad, B., Eisenbraun, E.J., (1990) J. Org. Chem., 55, p. 425
- Gribble, W., Keavy, D.J., Olson, E.R., Rae, I.D., Staffa, A., Herr, T.E., Ferraro, M.B., Contreras, R.H., (1991) Magn. Reson. Chem., 29, p. 422
- Facelli, J.C., Contreras, R.H., Tufró, M.F., (1993) J. Mol. Struct. THEOCHEM, 281, p. 61
- Canet, C., Goulon-Ginet, C., Marshal, J.P., (1976) J. Magn. Reson., 22, p. 539
- (1977) J. Magn. Reson., 25, p. 397
- Hansen, P.E., (1989) The Chemistry of Double-bonded Functional Groups, p. 81. , edited by S. Patai, Wiley, Chichester
- De Kowalewski, D.G., Kowalewski, V.J., Botek, E., Contreras, R.H., Facelli, J.C., (1997) Magn. Reson. Chem., 35, p. 351
- Contreras, R.H., Natiello, M.A., Scuseria, G.E., (1985) Magn. Reson. Rev., 9, p. 239
Citas:
---------- APA ----------
De Kowalewski, D.G., Kowalewski, V.J., Contreras, R.H., Diez, E. & Esteban, A.L.
(1998)
. Conformational effects on 13C NMR parameters in alkyl formates. Magnetic Resonance in Chemistry, 36(5), 336-342.
http://dx.doi.org/10.1002/(SICI)1097-458X(199805)36:5<336::AID-OMR273<3.0.CO;2-C---------- CHICAGO ----------
De Kowalewski, D.G., Kowalewski, V.J., Contreras, R.H., Diez, E., Esteban, A.L.
"Conformational effects on 13C NMR parameters in alkyl formates"
. Magnetic Resonance in Chemistry 36, no. 5
(1998) : 336-342.
http://dx.doi.org/10.1002/(SICI)1097-458X(199805)36:5<336::AID-OMR273<3.0.CO;2-C---------- MLA ----------
De Kowalewski, D.G., Kowalewski, V.J., Contreras, R.H., Diez, E., Esteban, A.L.
"Conformational effects on 13C NMR parameters in alkyl formates"
. Magnetic Resonance in Chemistry, vol. 36, no. 5, 1998, pp. 336-342.
http://dx.doi.org/10.1002/(SICI)1097-458X(199805)36:5<336::AID-OMR273<3.0.CO;2-C---------- VANCOUVER ----------
De Kowalewski, D.G., Kowalewski, V.J., Contreras, R.H., Diez, E., Esteban, A.L. Conformational effects on 13C NMR parameters in alkyl formates. Magn. Reson. Chem. 1998;36(5):336-342.
http://dx.doi.org/10.1002/(SICI)1097-458X(199805)36:5<336::AID-OMR273<3.0.CO;2-C