Determination of 1H and 13C Nuclear Magnetic Resonance Chemical Shift Values of Glyoxime Molecule with Experimental and Theoretical Methods

Abstract

In this study, the conformational analysis was performed by the semi-empirical PM3 method to determine the molecular structure of the glyoxime molecule. Each of conformer  is optimized using the Density Functionals Theory (DFT) with DFT / B3LYP / 6-311G ++ (d, p) method basis set combination. As a result of the optimization, the most stable structure was determined according to the energy order. The chemical shift values ​​of ¹H and ¹³C, which are Nuclear Magnetic Resonance (NMR) parameters of this stable structure, were calculated in liquid phase and gas phase using DFT method and six different basis sets. Furthermore, the effect of intermolecular hydrogen bonding on ¹H chemical shift values ​​was investigated by dimer molecular modeling at the level of B3LYP / 6-31G ++ (d, p) in the DFT method. The ¹H and ¹³C chemical shift values ​​of the glyoxime molecule were determined experimentally. Structural analyzes of the glyoxime molecule were made by comparing the calculated NMR parameters with the experimental NMR parameters.

Keywords

• Glyoxime,Nuclear Magnetic Resonance,Density Functional Theory,Hydrogen Bonding

Glioksim Molekülünün 1H ve 13C NMR Kimyasal Kayma Değerlerinin Deneysel ve Teorik Metotlar ile Belirlenmesi

Abstract

Bu çalışmada glioksim molekülünün moleküler yapısını belirlemek için konformasyon analizi yarı deneysel PM3 metodu ile yapılmıştır. Elde edilen konformasyonlar Yoğunluk Fonksiyonelleri Metodu (DFT) kullanılarak DFT/B3LYP/6-311G++(d,p) metot baz seti kombinasyonu ile optimize edilmiştir. Optimizasyon sonucunda enerji durumuna göre en kararlı yapı bulunmuştur. Bu kararlı yapıya ait Nükleer Manyetik Rezonans (NMR) parametreleri olan 1H ve 13C kimyasal kayma değerleri, DFT metodu ve 6 farklı baz seti kullanılarak sıvı fazda ve gaz fazında hesaplanmıştır. Ayrıca moleküller arası hidrojen bağının, 1H kimyasal kayma değerlerine etkisi DFT metodunda B3LYP/ 6-31G++(d,p) seviyesinde dimer moleküler modellemesi yapılarak incelenmiştir. Aynı zamanda glioksim molekülünün 1H ve 13C kimyasal kayma değerleri deneysel olarak da tespit edilmiştir. Hesaplanan NMR parametreleri ile deneysel NMR parametreleri karşılaştırılarak glioksim molekülünün yapı analizleri yapılmıştır.

Keywords

• Glioksim,Nükleer manyetik rezonans,Yoğunluk fonksiyonelleri teorisi,Hidrojen bağı

References

1. Kaupp, M., Bühl, M., Malkin, V. G., Calculation of NMR and EPR parameters, Wiley-Vch, Weinheim, 2004.
2. Wu, A., Zhang, Y., Xu X., Yan, Y., Systematic Studies on the Computation of Nuclear Magnetic Resonance Shielding Constants and Chemical Shifts: The Density Functional Models, Journal of Computational Chemistry, 28 (15), 2431-2442, 2007.
3. Hehre, W. J., Radom, L., Schleyer, Pvon R., Pople, J. A., Ab Initio Molecular Orbital Theory, John Wiley & Sons, New York, 1986.
4. Foresman, J. B., Frisch, A., Exploring Chemistry with Electronic Structure Methods, Gaussian, Pittsburgh, 1996.
5. Frisch, M. J., Frisch, A., Foresman, J. B., Gaussian 94 Users Reference, Gaussian, Pittsburgh, 1995.
6. Ruud, K., Helgaker, T., Kobayashi, R., Jorgensen, P., Bak, K. L., Jensen, H. J. A., Multiconfigurational self-consistent field calculations of nuclear shieldings using London atomic orbitals, Journal of Chemical Physics, 100 (11), 8178-8185, 1994.
7. Chesnut, D.B., Ab Initio Calculations of NMR Chemical Shielding, Annual, Reports on NMR Spectroscopy,29, 71-122, 1994.
8. de Dios, A.C., Ab initio calculations of the NMR chemical shift, Progress in Nuclear Magnetic Resonance Spectroscopy, 29 (3-4), 229-278, 1996

9. Barszczewicz, A., Jaszu´nski, M., Jackowski, K., Ab initio calculations of the oxygen atom NMR shielding in the carbonyl group, Chemical Physical Letters, 203 (4), 404-408, 1993.
10. Cheeseman, J.R., Trucks, G.W., Keith, T.A., Frisch, M.J., A comparison of models for calculating nuclear magnetic resonance shielding tensors, Journal of Chemical Physics, 104 (14), 5497-5509, 1996.
11. Kupka, T., Koaski, M., Pasterna, G., Ruud, K., Towards more reliable prediction of formaldehyde multinuclear NMR parameters and harmonic vibrations in the gas phase and solution, Journal of Molecular Structure ( THEOCHEM), 467 (1), 63-78, 1999.
12. DeHaven-Hudkins, D.L., Komer, K.M., Peterson, J.A., Mavunkel, B.J., Rzeszotarski, W.J., Opioid agonist properties of two oxime derivatives of naltrexone, NPC 831 and NPC 836, Pharmacology Biochemistry and Behavior, 44 (1), 45-50, 1993.
13. DeHaven-Hudkins, D.L., Brostrom, P.A., Allen, J.T., Lesko, L.J., Ferkany, J.W., Kaplita, P.V., Mavunkel, B.J., Rzeszotarski, W.J., Steranka, L.R., Pharmacologic Profile of NPC 168 (naltrexone phenyl oxime), A Novel Compound With Activity At Opioid Receptors, Pharmacology Biochemistry and Behavior, 37 (3), 497-504, 1990.
14. Schenone, S., Bruno, O., Ranise, A., Bondavalli, F., D'Amico, M., Parrillo, C., Lampa, E., Rossi, F., N-Substituted 0-(3-amino-2- hydroxypropyl) Oximes of 1,3,3-trimethyl-5-endo-(1-piperidinyl or 4- morpholinyl)-2-oxabicyclo(2,2,2)-octan-6-ones With Platelet Antiaggregating and Local Anesthetic Activities, Farmaco, 47 (10), 1249-1262, 1992.
15. Ranise, A., Bondavalli, F., Bruno, O, Schenone, P,, Faillace, G., Coluccino, A., Filippelli, W., Di Sarno, A., Marmo, E., Omega-dialkylaminoalkyl Ethers of 3-EXO-dialkylamino-(z)-camphoroximes With Anitarrhythmic and Local Anesthetic Activities, Farmaco, 45 (2), 187-202, 1990.
16. Gasc, J.C., d'Ambrieres, S.G., Lutz, A., Chantot, J F., New Ether Oxime Derivates of Erythromycin A. A Structure-Activity Relationship Study, The Journal of Antibiotics (Tokyo), 44 (3), 313-330, 1991.
17. Cooper, C.S., Klock, P.L., Chu, D. T. W., Hardy, D. J., Swanson, R. N., Plattner, J. J., Preparation and in vitro and in vivo evaluation of quinolones with selective activity against Gram-positive organisms, Journal of Medicinal Chemistry, 35 (8), 1392-1398, 1992.
18. Tsukamoto, Y., Sato, K., Mio, S., Sugai, S., Yanai, T., Kitano, N., Muramatsu, S., Nakada, Y., Ide, J., Synthesis of 5-keto-5-oxime Derivates of Milbemycins and Their Activities Against Microfilariae, Agricultural and Biological Chemistry, 55 (10), 2615-2621, 1991.
19. Bowman, D.D., Darigrand, R.A., Frongillo, M.K., Barr, S.C., Flanders, J.A., Carbone, L.G., Treatment of experimentally induced trichinosis in dogs and cats, American Journal of Veterinary Research, 54 (8), 1303-1305, 1993.
20. Abdalla, S., Khalili, F., Effects of Dichloroglyoxime on Isolated Guinea-Pig Smooth Muscle and Atrium, Drug and Chemical Toxicology, 15 (2), 145-159, 1992.
21. Bodor, N., Elkoussi, A., Improved Delivery Through Biological Membranes.LVI.Pharmocological Evaluation of Alprenoxime-A New Potential Aniglaucoma Agent, Pharmaceutical Research, 8 (11), 1389-1395, 1991.
22. Ballantyne, B., Ophtalmic Effects of Oximes: A Review, Veterinary and Human Toxicology, 33 (2), 151-154, 1991.
23. Olofson, R., Michelman, J., Furuzan, Journal of Organic Chemistry, 30, 1854-1859, 1965.
24. Spartan 08 Programme, Wavefunction Inc., Irvine, CA 92612, USA, 2008.
25. Lee, C., Yang, W., Par,r R.G., Development of the Colle–Salvetti correlation- energy formula into a functional of the electron density, Physical Review B 37 (2), 785–789, 1988
26. Gaussian 03 Programme, Revision E.01, Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, Jr., J.A., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., Cross, J.B., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador,P., Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Ortiz, J.V., Cui, Q., Baboul, A.G., Clifford, S., Cioslowski, J., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T., Al- Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Gonzalez, C., Pople, J.A., 2003. Gaussian, Inc., Pittsburgh PA.
27. Taşdemir H.U., Calculation of NMR Parameters of Some Molecules Using HF, Post HF and DFT Methods Selçuk University, Master Thesis, Konya, 2010.
28. Jeffrey, G.A., Ruble, J.R., Pople, J.A., Neutron Diffraction at 9 K and ab initio Molecular Orbital Studies of the Molecular Structure of Glyoxime, Acta Crystallography, B38: 1975-1980, 1982.
29. Hori, S., Yamauchi, K., Kuroki, S., Ando, I., Proton NMR Chemical Shift Behavior of Hydrogen-Bonded Amide Proton of Glycine-Containing Peptides and Polypeptides as Studied by ab initio MO Calculation, International Journal of Molecular Sciences, 3 (8), 907-913, 2002.
30. Malek, K., Vala, M., Kozlowski, H., Proniewicz, L. M., Experimental and theoretical NMR study of selected oxocarboxylic acid oximes, Magnetic Resonance in Chemistry, 42 (1), 23-29, 2004.