Comparison of theoretical and experimental investigation of protonation process of some thiones in acid media

Mirjana S. Jankulovska; Vesna Dimova; Ilinka Spirevska; Milena Jankulovska

doi:10.5937/zasmat2101009J

Authors

Mirjana S. Jankulovska Ss.Cyril and Methodius University, Faculty of Agricultural Sciences and Food, Skopje, North Macedonia Author
Vesna Dimova Ss.Cyril and Methodius University, Faculty of Technology and Metallurgy, Skopje, North Macedonia Author
Ilinka Spirevska Ss.Cyril and Methodius University, Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Skopje, North Macedonia Author
Milena Jankulovska University St. Kliment Ohridski, Faculty of Veterinary Medicine, Skopje, North Macedonia Author

DOI:

https://doi.org/10.5937/zasmat2101009J

Keywords:

1,2,4-triazoline-3-thiones, protonation, dissociation constants, proton affinity, UVspectrophotometry, PM3 semiempirical method

Abstract

PM3 semiempirical method was used for quantum chemical investigation in order to investigate the electronic properties and to determine the protonation centre in 1,2,4-triazoline-3-thione molecule. Confirmation of protonation center in acid media of investigated compounds was made using the values of atomic charges, as well as, proton affinity values. The results from semiempirical calculations indicated that the protonation center in the thione molecule was the sulphur atom. The behavior of thiones was investigated in mineral acid media using UV spectroscopy. The influence of the strength of the acid and its anion on the protonation process was discussed using three different mineral acids (perchloric, hydrochloric and phosphoric acid) for protonation. The protonation process in perchloric and hydrochloric acid took place in one step, while in phosphoric acid was not finished even when its concentration was to the highest degree. The dissociation constants of protonated forms (pKBH + ) and the solvation parameter m* values were calculated in accordance with "excess acidity" function method (Cox and Yates) using the absorbance data from the experimental and reconstructed spectra (Characteristic Vector Analysis (CVA)). The determined pKBH + values in hydrochloric acid had more negative value than those obtained in perchloric acid media. The pKBH + values were in agreement with the literature data for this class of compounds.

References

Albert, A., Serjeant, E.P. (1971) The Determination of Ionization constants: A laboratory manual. London - New York: Chapman and Hal, 2 d edition

Arman-Zubić, L., Perišić-Janjić, N., Lazarević, M. (2000) A study of the behavior of some substituted l,2,4-triazoline-3-thiones in different media.Journal of the Serbian Chemical Society, vol. 65, br. 9, str. 619-630

https://doi.org/10.2298/JSC0009619A

Brown, H.C., Schleyer, P.W.R. (1977) The Non-Classical Ion Problem. New York: Plenum Press

Cetin, A., Geçibesler, I.H. (2015) Evaluation as antioxidant agents of 1,2,4-triazole derivatives: Effects of essential functional groups.Journal of Applied Pharmaceutical Science, 5(06): 120-126

https://doi.org/10.7324/JAPS.2015.50620

Chaudharya, N., Dubeyb, R., Panwarc, H. (2014) Designing, synthesis and pharmacology of some novel 4-{4-(4-bromobenzyliden)amino}piperidin-1-yl)-5-aryl-3-thiol-4H-1,2,4-triazole.Der Pharma Chemica, 6: 115-119

Cox, R.A. (1987) Organic reactions in sulfuric acid: The excess acidity method.Journal of American Chemical Society, 20: 27-31

https://doi.org/10.1021/ar00133a004

Cox, R.A., Yates, K. (1978) Excess acidities: A generalized method for the determination of basicities in aqueous acid mixtures.Journal of the American Chemical Society, 100: 3861-3867

https://doi.org/10.1021/ja00480a033

Cox, R.A. (2000) Advances in physical organic chemistry. Toronto, Ontario, Canada: Department of Chemistry of Toronto

Cox, R.A., Yates, K. (1983) Acidity functions: An update.Canadian Journal of Chemistry, 61: 2225-2243

https://doi.org/10.1139/v83-388

Cox, R.A., Yates, K. (1981) Medium effects in protonation equilibrium studies: Accurate acidity constants using the excess acidity method.Canadian Journal of Chemistry, 59: 1560-1573

https://doi.org/10.1139/v81-230

Davis, T., Geissman, T.A. (1954) Basic Dissociation Constants of Some Substituted Flavones.Journal of the American Chemical Society, 76: 3507-3511

https://doi.org/10.1021/ja01642a045

Dimova, V., Perisic-Janjic, N. (2007) Determination and QSAR study of the dissociation constants of some 4,5-disubsituted-2,4-dihydro-3h-1,2,4-triazoline-3-thiones.Organic Chemistry: An Indian Journal, 3(2): 51-59

Edward, T.E., Wong, S.C. (1977) Ionization of carbonyl compounds in sulfuric acid: Correction for medium effects by characteristic vector analysis.Journal of the American Chemical Society, 99: 4229-4232

https://doi.org/10.1021/ja00455a003

https://doi.org/10.1021/ja00467a603

Eicher, T., Hauptmann, S. (2003) The Chemistry of Heterocycles: Structure, Reactions, Synthesis and Application. Weinheim: Wiley-VCH Verlag, 2 nd ed

Ekiert, R.J., Krzek, J., Talik, P. (2010) Chromatographic and electrophoretic techniques used in the analysis of triazole antifungal agents: A review.Talanta, 82(4): 1090-1100

https://doi.org/10.1016/j.talanta.2010.06.056

Garcia, B., Casado, R.M., Castillo, J., Ibeas, S., Domingo, I., Leal, J.M. (1993) Acidity constants of benzamide and someOrtho-substituted derivatives.Journal of Physical Organic Chemistry, 6: 101-106

https://doi.org/10.1002/poc.610060206

Ikizler, A.A., Abbasoğlu, R., Saltek, N., Şerifova, M. (1997) A Quantum -Chemical Ivestigation on 5,5'-BI(1H-1,2,4-triazole).Turkish Journal of Chemistry, 21: 353-362

Jankulovska, M., Spirevska, I., Ragenovic, K.C. (2006) Behaviour of some newly synthesized substituted 1,2,4-triazoline-3-thiones in sulfuric acid media.Bulletin of the Chemists and Technologists of Macedonia, 25(1): 29-37

Jankulovska, M., Spirevska, I., Šoptrajanova, L. (2006) Determination of the dissociation constants of some newly synthesized derivatives of 1,2,4-triazoline-3-thione in sodium hydroxide media.Bulletin of the Chemists and Technologists of Macedonia, 25(2): 99-106

Karakuü, S., Çoruh, U., Barlas-Durgun, B., Vázquez-López, E.M., Özbaü-Turan, S., Akbuùa, J., Rollas, S. (2010) Synthesis and cytotoxic activity of some 1,2,4-triazoline-3-thione and 2,5-disubstituted-1,3,4-thiadiazole derivatives.Marmara Pharmaceutical Journal, 14: 84-90

https://doi.org/10.12991/201014454

Katritzky, R., Rees, C.W. (1984) Comprehensive Heterocyclic Chemistry-Five-membered Rings with Three or more Heteroatoms, each with their Fused Carbocyclic Derivatives. London: Pergamon Press LTD

https://doi.org/10.1016/B978-008096519-2.00070-9

Lauria, A., Delisi, R., Mingoia, F., Terenzi, A., Martorana, A., Barone, G., Almerico, A.M. (2014) 1,2,3-Triazole in Heterocyclic Compounds, Endowed with Biological Activity, through 1,3-Dipolar Cycloadditions.European Journal of Organic Chemistry, 16: 3289-3306

https://doi.org/10.1002/ejoc.201301695

Öğretir, C., Öztürk, İ.İ., Tay, N.F. (2007) Quantum chemical studies on tautomerism, isomerism and deprotonation of some 5(6)-substituted benzimidazole-2-thiones.Arkivoc, XIV: 75-99

https://doi.org/10.3998/ark.5550190.0008.e09

Perisic-Janić, N., Podunavac-Kuzmanović, S., Vlaović, D. (1994) Electronic spectra and ionization constants of newly synthesized derivatives 1-benzyl-2-amino 5,6dimethyl-benzimidazoles.Journal of Serbian Chemical Society, 59(10): 743-748

Pospieszny, T., Małecka, I., Paryzek, Z. (2012) Synthesis and spectroscopic studies of new bile acid derivatives linked by a 1,2,3-triazole ring.Tetrahedron Letters, 53: 301-305

https://doi.org/10.1016/j.tetlet.2011.11.027

Pospieszny, T., Koenig, H., Kowalczyk, I., Brycki, B. (2014) Synthesis, Spectroscopic and Theoretical Studies of New Quasi-Podands from Bile Acid Derivatives Linked by 1,2,3-Triazole Rings.Molecules, 19: 2557-2570

https://doi.org/10.3390/molecules19022557

Ragenovic, K.C., Dimova, V., Kakurinov, V., Gabor, D.M. (2003) Synthesis of 1-Nonanoyl/octadecanoyl 1-4-substituted Thiosemicarbazides and substituted 1,2,4-Triazoles as biological active compounds.Journal of Hetrocyclic Chemistry, 40: 905-908

https://doi.org/10.1002/jhet.5570400525

Ragenović, K.C., Dimova, V., Kakurinov, V., Gabor, D.M., Buzarovska, A. (2001) Synthesis and antibacterial and antifungal activity of 4-substituted-5-aryl-1,2,4-triazole.Moleculs, 6: 815-824

https://doi.org/10.3390/61000815

Sahu, J.K., Ganguly, S., Kaushik, A. (2014) Synthesis and antimicrobial activity of some novel fused heterocyclic 1,2,4-triazolo [3,4-b][1,3,4] thiadiazine derivatives.Journal of Advanced Pharmaceutical Technology and Research, 5: 90-95

https://doi.org/10.4103/2231-4040.133434

Sharba, A.H.K., Al-Bayati, R.H., Rezki, N., Aouad, M.R. (2005) Synthesis of thiadiazoles and 1,2,4-triazoles derived from cyclopropane dicarboxylic acid.Molecules, 10: 1153-1160

https://doi.org/10.3390/10091161

https://doi.org/10.3390/10091153

Simonds, J.L. (1963) Application of Characteristic Vector Analysis to Photographic and Optical Response Data.Journal of the Optical Society of America, 53: 968-974

https://doi.org/10.1364/JOSA.53.000968

Stewart, J.J.P. (1989) Optimization of parameters for semiempirical methods I. Method.J. Comput. Chem, 10: 209-216

https://doi.org/10.1002/jcc.540100208

Stepanchikova, A.V., Lagunin, A.A., Filimonov, D.A., Poroikov, V.V. (2003) Prediction of biological activity spectra for substances: Evaluation on the diverse sets of drug-like structures.Current Medicinal Chemistry, 10: 225-233

https://doi.org/10.2174/0929867033368510

Tang, R., Jin, L., Mou, C., Yin, J., Bai, S., Hu, D., Wu, J., Yang, S., Song, B. (2013) Synthesis, antifungal and antibacterial activity for novel amide derivatives containing a triazole moiety.Chemistry Central Journal, 7(30): 1-7

https://doi.org/10.1186/1752-153X-7-30

Temple, C., Montgomery, J.A. (2008) The Chemistry of Heterocyclic Compounds, Triazoles 1, 2, 4. in: Chemistry of Heterocyclic Compounds: A Series of Monographs, Hoboken, NJ, USA: John Wiley & Sons, Inc

Thakur, A. (2005) QSAR study on benzenesulfonamide ionization constant : Physicochemical approach using surface tension.Arkivoc, XIV: 49-53

https://doi.org/10.3998/ark.5550190.0006.e06