THEORETICAL STUDIES OF 1H, 13C AND 15N NMR SPECTRA FOR MODEL STRUCTURES OF N-METHYLMORPHOLINIUM AND N-METHYLPIPERIDINIUM BETAINES*
Wieczorek Daria 1, Dega-Szafran Zofia 2, Szafran Mirosław 2, Szymusiak Henryk 1, Zieliński Ryszard 1, Głembalska Renata 2
1 Department of Technology and Environmental Protection, Poznan University of Economics,
Aleja Niepodleglości 10, 60-967 Poznan, Poland
e-mail: ktos@novci1.ae.poznan.pl
2Faculty of Chemistry, Adam Mickiewicz University
Grunwaldzka 6, 60-780 Poznan, Poland
e-mail: degasz@amu.edu.pl
Received:
Rec. 7 November 2003
DOI: 10.12921/cmst.2003.09.01.147-161
OAI: oai:lib.psnc.pl:547
Abstract:
Screening constants for model structures of linear and twisted conformers of N-(ω-carboxyalkyl)-N-methylmorpholinium inner salts (MMBn) and N-(ω-carboxyalkyl)-N-methylpiperidinium inner salts (MPBn) with the alkyl spacer (n) containing 1-5 methylene groups calculated by the GIAO/B3LYP/6-31+G(d, p) are reported and analyzed. Linear correlations between the experimental 1H and 13C chemical shifts and computed absolute shielding constants have been obtained. These results suggest that in solution twisted conformers dominate. The linear correlations between the calculated 15N absolute shielding constants for MMBn and MPBn suggest that the two kinds of betaines have similar structures.
References:
[1] J. Vaara, Theory and calculations of NMR and EPR parameters. CSC Report on Scientific
Computing 1999-2000. S. Kotila and J. Haataja, eds. CSC – Scientific Computing Ltd., Finland,
118-121 (2001).
[2] D. A. Forsyth and A. B. Sebag, Computed 13C NMR chemical shifts via empirically scaled GIAO shieldings and molecular mechanics geometries. Conformation and configurationfrom 13C shifts, J. Am. Chem. Soc. 119, 9483-9494 (1997).
[3] A. B. Sebag, D. A. Forsyth, and M. A. Plante, Conformation and configuration of tertiary amines via GIAO-derived (13)C NMR chemical shifts and a multiple independent variable regression analysis, J. Org. Chem. 66, 7967-7973 (2001).
[4] J. Casanovas, A. M. Namba, S. León, G.L.B. Aquino, G.V. J. da Silva and C. Alemán, Calculated
and experimental NMR chemical shifts of p-menthane-3,9-diols. A combination of molecular
dynamics and quantum mechanics to determine the structure and the solvent effects, J. Org. Chem. 66, 3775-3782 (2001).
[5] M. Barfield and P. Fagerness, Density functional theory/GIAO studies of the 13C, 15N and 1HNMR chemical shifts in aminopirymidines and aminobenzenes: relationships to electron densities and amine group orientations, J. Am. Chem. Soc. 119, 8699-8711 (1997).
[6] X. Domingo, in E. G. Lomax, ed, Amphoteric Surfactants, p. 75 (Marcel Dekker, New York, 1996).
[7] G. Schaack, Experimental results on phase transitions in betaine compounds, Ferroelectrics 104, 147-158 (1990).
[8] Z. Dega-Szafran, I. Gąszczyk, D. Maciejewska, M. Szafran, E. Tykarska and I. Wawer, 13C CP MAS NMR, FTIR, X-ray diffraction and PM3 studies of some N-(ω-carboxyalkyl)morpholine
hydrohalides. J. Mol. Struct. 560, 261-273 (2001).
[9] P. Barczyński, Z. Dega-Szafran, E. Dulewicz, M. Petryna, and M. Szafran, Aqueous basicity and proton affinity of zwitterionic ω-(N-methylpiperidine)-alkanocarboxylates and ω-(N-piperidine)-alkanocarboxylic acids, Polish J. Chem. 74, 1149-1161 (2000).
[10] A. D. Becke, Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys. 98, 5648-5655 (1993).
[11] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman,
V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam,
A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi,
B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui,
K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski,
J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts,
R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M.
Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M.
Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian 98, Revision A.6. Gaussian, Inc., Pittsburgh PA, 1998.
[12] Z. Dega-Szafran, E. Dulewicz, and M. Szafran, 1H and 13C NMR spectra of betaines,
>N+(CHz)nCOO , and their hydrogen halides. Additivity rulesfor carbon-13 chemical shifts. Magn. Reson. Chem. 38, 43-50 (2000).
[13] M. Szafran and Z. Dega-Szafran, Conformational preferences of isostructural N-methylpiperidine betaine and (1-methylcyclohexyl)acetic acid studies byPM3 andB3LYP calculations. The effect of electrostatic interactions on the rotation barrier. J. Mol. Struct. 598, 251-260 (2001).
[14] E. L. Eliel, S. H. Wilen, and L. M. Mander, Stereochemistry of Organic Compounds, Wiley, New York, 1994 (and references therein).
[15] Z. Dega-Szafran, A. Katrusiak, and M. Szafran, Molecular structure of bis(pyridiniumvalerate) hydrogen perchlorate studied by X-ray diffraction, FTIR spectroscopy, PM3 and SAM1 calculations, J. Mol. Struct. 555, 203-212 (2000).
[16] Z. Dega-Szafran, Z. Kosturkiewicz, E. Dulewicz, and M. Szafran, Conformational analysis of
N-methylpiperidine betaine studied by X-ray diffraction, FTIR spectroscopy and ab initio
calculations, J. Mol. Struct. 478, 49-55 (1999).
[17] M. Szafran, Z. Dega-Szafran, E. Dulewicz, Z. Kosturkiewicz, M. Nowakowska, W. Orwat, and M. Ratajczak-Sitarz, Conformational analysis of 5-piperidinevaleric acid, 5-(N-methylpiperidine)-valerate and their hydrogen halides by MO calculations, X-ray diffraction and FTIR spectroscopy. J. Mol. Struct. 484, 125-138 (1999).
[18] Z. Dega-Szafran, M. Szafran, A. Antkowiak, M. Grundwald-Wyspianska, E. Nowak, M. Gdaniec, and Z. Kosturkiewicz, Structure of and hydrogen bonding in a 3:2 inclusion compound ofN-methylmorpholine betaine hydrochloride with acetonitrile, J. Mol. Struct. 605, 325-330 (2002).
[19] W. Kutzelnigg, U. Fleischer and M. Schindler, in P. Diehl, E. Fluck, H. Gunther, R. Kosfeld, and J. Seelig, eds, NMR Basic Principles and Progress, vol. 23, p. 165 (Springer-Verlag, Berlin, 1991).
Screening constants for model structures of linear and twisted conformers of N-(ω-carboxyalkyl)-N-methylmorpholinium inner salts (MMBn) and N-(ω-carboxyalkyl)-N-methylpiperidinium inner salts (MPBn) with the alkyl spacer (n) containing 1-5 methylene groups calculated by the GIAO/B3LYP/6-31+G(d, p) are reported and analyzed. Linear correlations between the experimental 1H and 13C chemical shifts and computed absolute shielding constants have been obtained. These results suggest that in solution twisted conformers dominate. The linear correlations between the calculated 15N absolute shielding constants for MMBn and MPBn suggest that the two kinds of betaines have similar structures.
[1] J. Vaara, Theory and calculations of NMR and EPR parameters. CSC Report on Scientific
Computing 1999-2000. S. Kotila and J. Haataja, eds. CSC – Scientific Computing Ltd., Finland,
118-121 (2001).
[2] D. A. Forsyth and A. B. Sebag, Computed 13C NMR chemical shifts via empirically scaled GIAO shieldings and molecular mechanics geometries. Conformation and configurationfrom 13C shifts, J. Am. Chem. Soc. 119, 9483-9494 (1997).
[3] A. B. Sebag, D. A. Forsyth, and M. A. Plante, Conformation and configuration of tertiary amines via GIAO-derived (13)C NMR chemical shifts and a multiple independent variable regression analysis, J. Org. Chem. 66, 7967-7973 (2001).
[4] J. Casanovas, A. M. Namba, S. León, G.L.B. Aquino, G.V. J. da Silva and C. Alemán, Calculated
and experimental NMR chemical shifts of p-menthane-3,9-diols. A combination of molecular
dynamics and quantum mechanics to determine the structure and the solvent effects, J. Org. Chem. 66, 3775-3782 (2001).
[5] M. Barfield and P. Fagerness, Density functional theory/GIAO studies of the 13C, 15N and 1HNMR chemical shifts in aminopirymidines and aminobenzenes: relationships to electron densities and amine group orientations, J. Am. Chem. Soc. 119, 8699-8711 (1997).
[6] X. Domingo, in E. G. Lomax, ed, Amphoteric Surfactants, p. 75 (Marcel Dekker, New York, 1996).
[7] G. Schaack, Experimental results on phase transitions in betaine compounds, Ferroelectrics 104, 147-158 (1990).
[8] Z. Dega-Szafran, I. Gąszczyk, D. Maciejewska, M. Szafran, E. Tykarska and I. Wawer, 13C CP MAS NMR, FTIR, X-ray diffraction and PM3 studies of some N-(ω-carboxyalkyl)morpholine
hydrohalides. J. Mol. Struct. 560, 261-273 (2001).
[9] P. Barczyński, Z. Dega-Szafran, E. Dulewicz, M. Petryna, and M. Szafran, Aqueous basicity and proton affinity of zwitterionic ω-(N-methylpiperidine)-alkanocarboxylates and ω-(N-piperidine)-alkanocarboxylic acids, Polish J. Chem. 74, 1149-1161 (2000).
[10] A. D. Becke, Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys. 98, 5648-5655 (1993).
[11] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman,
V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam,
A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi,
B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui,
K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski,
J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts,
R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M.
Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M.
Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian 98, Revision A.6. Gaussian, Inc., Pittsburgh PA, 1998.
[12] Z. Dega-Szafran, E. Dulewicz, and M. Szafran, 1H and 13C NMR spectra of betaines,
>N+(CHz)nCOO , and their hydrogen halides. Additivity rulesfor carbon-13 chemical shifts. Magn. Reson. Chem. 38, 43-50 (2000).
[13] M. Szafran and Z. Dega-Szafran, Conformational preferences of isostructural N-methylpiperidine betaine and (1-methylcyclohexyl)acetic acid studies byPM3 andB3LYP calculations. The effect of electrostatic interactions on the rotation barrier. J. Mol. Struct. 598, 251-260 (2001).
[14] E. L. Eliel, S. H. Wilen, and L. M. Mander, Stereochemistry of Organic Compounds, Wiley, New York, 1994 (and references therein).
[15] Z. Dega-Szafran, A. Katrusiak, and M. Szafran, Molecular structure of bis(pyridiniumvalerate) hydrogen perchlorate studied by X-ray diffraction, FTIR spectroscopy, PM3 and SAM1 calculations, J. Mol. Struct. 555, 203-212 (2000).
[16] Z. Dega-Szafran, Z. Kosturkiewicz, E. Dulewicz, and M. Szafran, Conformational analysis of
N-methylpiperidine betaine studied by X-ray diffraction, FTIR spectroscopy and ab initio
calculations, J. Mol. Struct. 478, 49-55 (1999).
[17] M. Szafran, Z. Dega-Szafran, E. Dulewicz, Z. Kosturkiewicz, M. Nowakowska, W. Orwat, and M. Ratajczak-Sitarz, Conformational analysis of 5-piperidinevaleric acid, 5-(N-methylpiperidine)-valerate and their hydrogen halides by MO calculations, X-ray diffraction and FTIR spectroscopy. J. Mol. Struct. 484, 125-138 (1999).
[18] Z. Dega-Szafran, M. Szafran, A. Antkowiak, M. Grundwald-Wyspianska, E. Nowak, M. Gdaniec, and Z. Kosturkiewicz, Structure of and hydrogen bonding in a 3:2 inclusion compound ofN-methylmorpholine betaine hydrochloride with acetonitrile, J. Mol. Struct. 605, 325-330 (2002).
[19] W. Kutzelnigg, U. Fleischer and M. Schindler, in P. Diehl, E. Fluck, H. Gunther, R. Kosfeld, and J. Seelig, eds, NMR Basic Principles and Progress, vol. 23, p. 165 (Springer-Verlag, Berlin, 1991).
