Solvent and moleculer structure effects on acidity strength in non-aqueous medium

Year 2021, , 27 - 32, 29.06.2021

Şule Bahçeci Zafer Ocak , Nuri Yıldırım , Haydar Yüksek

https://doi.org/10.51435/turkjac.939857

Cited By: 2

Abstract

The acidic properties of ten 3-alkyl(aryl)-4-[3-hydroxy-4-methoxy benzylidenamino]-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives were investigated. In this study, isopropyl alcohol and tert‐butanol were used as an amphiprotic solvent. Aceton and N,N‐ dimethylformamide (DMF) were preferred as a dipolar aprotic solvent. Compounds were titrated with tetrabuthylamonnium hydroxide (TBAH) in isopropyl alcohol and titrimetric analyses were used potentiometric method determining the end-points, half-neutralization method determining acidity. Typical S-shaped titration graphs excepted were determined. The acidity strengths of 4,5-dihydro-1H-1,2,4-triazol-5-one derivatives in amphiprotic and dipolar aprotic solvents were calculated using tables and graphs. The pKa values obtained in the solvents were found to be differentiated. The effects of solvent, molecular structure, autoprotolysis constant dielectric constant, and leveling‐differentiation effects of the solvents upon acidity strength of the compounds were discussed.

Keywords

triazole, amphiprotic, pKa, potentiometry

Supporting Institution

Scientific Research Projects Coordination Unit of Karadeniz Technical University.

Project Number

2008.116.006.1

References

• [1] D.A. Skoog, D.M. West, F.J. Holler, S.R. Crouch, Potansiyometri, Analitik Kimya Temel İlkeler, E. Kılıç, H. Yılmaz, 2007, Ankara, Bilim Yayıncılık.
• [2] J. Reijenga, A. Hoof, A. Loon, B. Teunissen, Development of methods for the determination of pKa values, Analytical Chemistry Insights, 8, 2013, 53–71.
• [3] S. Zafar, S. Akhtar, T. Tariq, N. Mushtag, A. Akram, A. Ahmed, M. Arif, S. Naeem, S. Anwar, Determination of pKa values of new phenacyl-piperidine derivatives by potentiometric titration method in aqueous medium at room temperature (25±0.5oC), Pakistan Journal of Pharmaceutical Sciences, 27(4), 2014, 925-929.
• [4] S. Sharif Manesh, M. Masrournia, Carbon nitride nanoparticles modifed carbon paste electrodes as potentiometric sensors for determination of nickel(II) and chromium(III) ions in tap water samples, Journal of the Iranian Chemical Society, 18, 2021,1219–1229.
• [5] Ö. Işıldak, O. Özbek, Application of potentiometric sensors in real samples, Krit Rev Anal Chem, 2020, 1-14. DOI: 10.1080/10408347.2019.1711013.
• [6] K. Braininaa, N. Stozhko, M. Bukharinova, E, Khamzina, M. Vidrevich, Potentiometric method of plant microsuspensions antioxidant activity determination, Food Chemistry 278, 2019, 653-658.
• [7] Kh.Z. Brainina, E.L. Gerasimova, D.P. Varzakova, S.L. Balezin, I.G. Portnov, V.A. Makutina, E.V. Tyrchaninov, Potentiometric method for evaluating the oxidant/ antioxidant activity of seminal and follicular fluids and clinical significance of this parameter for human reproductive function, The Open Chemical and Biomedical Methods Journal, 5, 2012, 1-7.
• [8] Kh.Z. Brainina, A.V. Ivanova, E.N. Sharafutdinova, E.L. Lozovskaya, E.I. Shkarina, Potentiometry as a method of antioxidant activity investigation, Talanta, 71, 2007, 13–18.
• [9] K.D. Bhesaniya, S. Baluja, Potentiometric determination of dissociation constant and thermodynamic parameters of dissociation process of some newly synthesized pyrimidine derivatives in MeOH/DMF– water medium at different temperatures, Journal of Molecular Liquids, 190, 2014, 190–195.
• [10] Z. Farkas, M. Posa, V. Tepavcevic, Determination of pKa values of oxocholanoic acids by potentiometric titration, J Surfact Deterg, 17, 2014, 609‐614.
• [11] V.R. Almeida, B. Szpoganicza, S. Bonnevilleb, Potentiometric titration and out-of-equilibrium pH response of the biotite‑water system, Journal of the Brazilian Chemical Society, 26(9), 2015, 1848-1860.
• [12] A.S. Katea, K.C. Basavaraju, A simple potentiometric titration method for estimation of maleic anhydride in high molecular weight styrene-maleic anhydride copolymer, Polymer Testing, 65, 2018, 369–373.
• [13] M. Lakubowska, B. Bas, E. Niewiara, W. Reczynski, W.W. Kubiak, Potentiometric titration of industrial samples—end‐point detection by means of wavelets, AIP Conference Proceedings, 1148, 2009, 613‐616.
• [14] T. Lisa, D. Chansyanah, S. Marina, K. Nina, S. Andrian, Using potentiometric acid-base titration to determine pKa from Mangosteen Pericarps Extract, Periódico Tchê Química, 16, 2019, 768-773.
• [15] Ş. Bahçeci, N. Yıldırım, Ö. Gürsoy-Kol, S. Manap, M. Beytur, H. Yuksek, Synthesis, characterization and antioxidant properties of new 3-alkyl(aryl)-4-(3-hydroxy-4-methoxy-benzylidenamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones, Rasayan J Chem, 9, 2016, 494-501.
• [16] E. Kılıc¸ O. Atakol, E. Canel, Z. Alibeşeoğlu, T. Gunduz, F. Köseoğlu, Potentiometric investigation of the effects of several substituents on the basicity of benzilidene-o-hydroxyaniline, Turk J Chem, 22, 1998, 387-391.
• [17] H. Yüksek, E. Koca, Ö. Gürsoy-Kol, O, Akyıldırım, M. Çelebier, Synthesis, in vitro antioxidant activity, and physicochemical properties of novel 4,5-dihydro-1H-1,2,4-triazol-5-one derivatives, Journal of Molecular Liquids, 206, 2015, 359-366.
• [18] M. Kurtoğlu, N. Birbiçer, Ü. Kimyonsen, S. Serin, Determination of pKa values of some azo dyes in acetonitrile with perchloric acid, dyes and pigments, 41, 1999, 143‐147.
• [19] N. Gündüz, T. Gündüz, M. Havyalı,Titrations in non‐aqueous media: Potentiometric investigation of symmetrical and unsymetrical tetra‐aryl porphyrins with 4‐ nitrophenyl and 4‐aminophenyl substituents in nitrobenzene solvent, Talanta, 48, 1999, 71‐79.
• [20] Z. Ocak, Amfiprotik ve dipolar aprotik çözücülerde 3-(4-Aril) propiyonik asit türevlerinin asitlik kuvvetleri, Igdır Üniversitesi Fen Bilimleri Enstitüsü Dergisi, 10(3), 2020, 1876-1885. Doi: 10.21597/jist.675630.
• [21] O. Hakli, K. Ertekin, M.S. Ozer, S. Aycan, Determination of pKa values of clinically important perfluorochemicals in nonaqueous media, Journal of Analytical Chemistry, 63( 11), 2008, 1051–1056.
• [22] R.H. Loeppert, L.W. Zelazny, B.G. Volk, Titration of pH-dependent sites of Kaolinite in water and selected nonaqueous solvents, Clays and Clay Minerals, 27 (1), 1979, 57-62.
• [23] H. Yüksek, M. Küçük, M. Alkan, Ş. Bahçeci, S. Kolaylı, Z. Ocak, U. Ocak, E. Şahinbaş, M. Ocak, Synthesis and antioxidant activities of some new 4-(4-hydroxy-benzylidenamino)-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives with their acidic properties, Asian Journal of Chemistry, 18(1), 2006, 539-550.
• [24] A. Arslantaş, H. Yüksek, Ö. Gürsoy Kol, Z. Ocak , Z. Tomruk, M. Calapoğlu, Study of antioxidant properties and DNA interaction of some novel 4,5-dihydro-1H-1,2,4-triazol-5-one derivates, Asian Journal of Chemistry, 24(8), 2012, 3327‐3334.