Abstract
This work shows the modification of barbituric acid (BA) chemical shifts by dimethylsulphoxide (DMSO) molecules. The discussed changes are caused by creation of the H-bonded associates formed by barbituric acid with DMSO in solution. Free molecule of barbituric acid, the cluster of BA with two DMSO molecules and two different clusters of BA with four DMSO units are taken into consideration. The chemical shifts of these systems have been calculated and the obtained results have been compared with experimental data. Theoretical calculations predict a significant downfield shift for imino protons of barbituric acid involved in intermolecular-N-H...DMSO hydrogen bonds. The influence of the solvent molecules on other nuclei chemical shifts, especially protons of barbituric acid methylene group, is also reported.
The calculations have involved Hartree-Fock and several Density Functional Theory methods. All methods correctly describe experimental 1H and 13C NMR spectra of barbituric acid. The best consistence between experiment and theory is observed for the BLYP functional. Four approximations of magnetic properties calculations embedded in the Gaussian’98 package have been tested. The results of the performed calculations indicate that from a practical point of view the GIAO method should be preferred.
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References
F.W. Wehrli and T. Wirthlin: Interpretation of Carbon-13 NMR Spectra, Heyden & Son Limited, London, Philadelphia, Rheine, 1978.
T. Helgaker, M. Jaszunski and K. Ruud: “Ab Initio Methods for the Calculation of NMR Shielding and Indirect Spin-Spin Coupling Constants”, Chem. Rev., Vol. 99, (1999), pp. 293–352.
J.W. Emsley, J. Feeney and L.H. Sutcliffe: High Resolution Nuclear Magnetic Resonance Spectroscopy, Pergamon Press, Oxford, 1965.
J. Pople, W.G. Schneider and H.J. Bernstein: High-Resolution Nuclear Magnetic Resonance, Wiley, New York, Toronto, London, 1959.
J.C. Davis and K.S. Pitzer: “Nuclear Magnetic Resonance Studies of Hydrogen Bonding. I. Carboxylic Acids”, J. Phys. Chem., Vol. 64, (1960), pp. 886–892.
A.J. Barnes, L. LeGall and L. Lauransan: “Vibrational Spectra of Barbituric Acid Derivatives in Low-temperature Matrices: Part 2. Barbituric Acid and 1,3-dimethyl Barbituric Acid”, J. Mol. Struct., Vol. 56, (1979), pp. 15–27.
M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery, 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, P. Salvador, J.J. Dannenberg, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz, J.G. Baboul, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, L. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, A. Al-Laham, C.Y. Peng, A. Nanayakkara, 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 Rev. A10, Gaussian Inc., Pittsburgh PA, 2001.
J.C. Slater: The Self-Consistent Field for Molecules and Solids in Quantum Theory of Molecules and Solids, Vol. 4, McGraw-Hill, New York, 1974.
S.J. Vosko, L. Wilk and M. Nussair: “Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis”, Canadian J. Phys., Vol. 58, (1980), pp. 1200–1211.
A.D. Becke: “Density-functional Exchange-energy Approximation with Correct Asymptotic Behavior”, Phys. Rev. A, Vol. 38, (1988), pp. 3098–3100.
C. Lee, W. Yang and R.G. Parr: “Development of the Colle-Salvetti Correlationenergy Formula Into a Functional of the Electron Density”, Phys. Rev. B, Vol. 37, (1998), pp. 785–789.
A.D. Becke: “Density-functional Thermochemistry. III. The Role of Exact Exchange”, J. Chem. Phys., Vol. 98, (1993), pp. 5648–5652.
E. Frisch and M.J. Frish: Gaussian’98 User’s Manual Second Edition, Gaussian Inc., Pittsburgh USA, 1994–1999.
T.A. Keith and R.F.W. Bader: “Calculation of Magnetic Response Properties Using a Continuous Set of Gauge Transformations”, Chem. Phys. Lett., Vol. 210, (1993), pp. 223–231.
T.A. Keith and R.F.W. Bader: “Calculation of Magnetic Response Properties Using Atoms in Molecules”, Chem. Phys. Lett., Vol. 194, (1992), pp. 1–8.
K. Wolinski, J.F. Hilton and P. Pulay: “Efficient Implementation of the Gaugeindependent Atomic Orbital Method for NMR Chemical Shift Calculations”, J. Am. Chem. Soc., Vol. 112, (1990), pp. 8251–8260.
G. Schaftenaar and J.M. Noordik: “Molden: A pre-and post-Processing Program for Molecular and Electronic Structures”, J. Computer-Aided Mol. Design, Vol. 14, (2000), pp. 123–134.
F. Zuccarello, G. Buemi, C. Gandolfo and A. Contino: “Barbituric and Thiobarbituric Acids: a Conformational and Spectroscopic Study”, Spectrochim Acta A, Vol. 59, (2003), pp. 139–151.
G. Zuchowski and K. Zborowski, in preparation.
R.M. Aminova, G.A. Schamov and A.V. Aganov: “Calculation of the Structure and Nuclear Magnetic Shielding Constants of Some H-bonded Carbon Acid Complexes”, J. Mol. Struct. (Theochem), Vol. 498, (2000), pp. 233–246.
A. Kaczor and L.M. Proniewicz: “NMR Spectra of Salicylohydroxamic Acid in DMSO-d6 Solution: a DFT Study”, J. Mol. Struct. (Theochem), Vol. 640, (2003), pp. 133–141.
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Żuchowski, G., Zborowski, K. The influence of solvent molecules on NMR spectrum of barbituric acid in the DMSO solution. cent.eur.j.chem. 4, 523–532 (2006). https://doi.org/10.2478/s11532-006-0019-z
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DOI: https://doi.org/10.2478/s11532-006-0019-z