Yeni Di-{2-[(3-alkil)-4,5-dihidro-1H-1,2,4-triazol-5-on-4-il)-azometin]-6-metoksi}-fenil Tereftalat Bileşiklerinin Sentezi ve Potansiyometrik Titrasyonları

Bu çalışmada, 3-alkil(aril)-4-amino-4,5-dihidro-1H-1,2,4-triazol-5-on (3) bileşiklerinin trietiamin varlığında o-vanillinin tereftaloil klorür ile reaksiyonundan elde edilen di-(2-formil-6-metoksifenil) tereftalat (3) ile reaksiyonundan yedi yeni di-{2-[(3-alkil)-4,5-dihidro-1H-1,2,4-triazol-5-on-4-il)-azometin]-6-metoksi}-fenil tereftalat (4) bileşikleri sentez edilmiştir. Sentezlenen yeni bileşikler elementel analiz ve spektroskopik yöntemlerle karakterize edilmiştir. Ayrıca, asitlik üzerine çözücü and molekül yapısının etkisini incelemek için, sentezlenen 4 tipi yeni bileşiklerin aseton, 2-propanol, tert-butanol ve N,N-dimetilformamid (DMF) susuz çözücüleri içerisinde tetrabutilamonyum hidroksit (TBAH) ile potansiyometrik titrasyon incelemeleri yapılmıştır. Her bileşik için kullanılan susuz çözücülerdeki yarı nötralizasyon potansiyel (HNP) değerleri ve karşın olan pKa değerleri tayin edilmiştir.

Anahtar Kelimeler:

Sentez, Schiff bazı, pKa, Potansiyometrik titrasyon, 124-Triazol-5-on

Synthesis and Potentiometric Titrations of Novel Di-{2-[(3-alkyl/aryl-4,5-dihydro-1H-1,2,4-triazol-5-one-4-yl)-azomethine]-6-methoxy}-phenyl Terephtalates

In this study, 3-alkyl(aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) reacted with di-(2-formyl-6-methoxyphenyl) terephtalate (3), which was synthesized by the reaction of o-vanillin with terephthaloyl chloride by using triethylamine, to afford the corresponding seven novel di-{2-[(3-alkyl/aryl-4,5-dihydro-1H-1,2,4-triazol-5-one-4-yl)-azomethine]-6-methoxy}-phenyl terephtalates (4). The structures of new synthesized compounds were characterized by mains of elemental analysis and spectroscopic methods. In addition, to investigate the effects of solvents and molecular structure upon acidity, the prepared compounds 4 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents, including acetone, 2-propanol, tert-butyl alcohol and N, N-dimethylformamide (DMF). The half-neutralization potential (HNP) values and the corresponding pKa values were determined.

Keywords:

124-Triazol-5-one, Syntheses, Schiff base, pKa, Potentiometric titration,

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Aktaş-Yokuş, Ö., Yüksek, H., Gürsoy-Kol, Ö., Alpay-Karaoğlu, S. (2015). Synthesis and biological evaluation of new 1,2,4-triazol derivatives with their potentiometric titrations. Med. Chem. Res., 24: 2813–2824.
Bahçeci, Ş., Ocak, Z., Yıldırım, N., Yüksek, H., 2021. Solvent and molecular structure effects on acidity strength in non-aqueous medium. Turk J Anal Chem., 3(1): 27-32.
Çiftçi, E., Beytur, M., Calapoğlu, M., Gürsoy Kol, Ö., Alkan, M., Toğay, V.A., Manap, S., Yüksek, H. (2018). Synthesis, characterization, antioxidant and antimicrobial activities and DNA damage of some novel 2-[3-alkyl (aryl)-4,5-dihydro-1H-1,2,4-triazol-5-one-4-yl]-phenoxyacetic acids in Human Lymphocytes. Res. J. Pharm. Biol. Chem. Sci., 9(5): 1760-1771.
Demirbaş, A., Kula, I., Erdoğan, Y., Aslan, A., Yaylı, N., Karslıoğlu, S. (1998). Non-aqeous medium titration of some acidic compounds. Energy Education Science and Technology, 1: 13–16.
Demirbas, N., Ugurluoglu, R., Demirbas, A. (2002). Synthesis of 3-alkyl(Aryl)-4-alkylidenamino-4,5-dihydro-1H-1,2,4-triazol-5-ones and 3-alkyl-4-alkylamino-4,5-dihydro-1H-1,2,4-triazol-5-ones as antitumor agents. Bioorg. Med. Chem., 10(12): 3717-3723.
Frey, P.A., Kokesh, F.C., Westheimer, F.H. (1971). A reporter group at active site of acetoacetate decarboxylase. I. Ionization constant of the nitrophenol. Journal of the American Chemical Society, 93: 7266-7269.
Gündüz, T., Gündüz, N., Kılıç, E., Kenar, A. Çetinel, G. (1986). Part II. Basicity order of Aliphatic Amines in Nitrobenzene Solvent. Analyst, 111: 1099-1101.
Gündüz, T., Gündüz, N., Kılıç, E. Gürkan, P. (1987). Part VI. Effects of Substituents on Basicity or Acidity of N-Salicylidene-2-Hydroxyaniline. Analyst, 112: 1057-1061.
Gündüz, T. (2001). İnstrümental Analiz. Ankara Üniversitesi Fen Fakültesi Yayınları, s.936-940, Ankara-Türkiye.
Gürsoy-Kol, O., Yuksek, H., Islamoglu, F. (2012). In vitro antioxidant and acidic properties of novel 4-(5-methyl-2-thienylmethyleneamino)-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives. Synthesis and characterization. Revista de Chimie -Bucharest, 63(11): 1103-1111.
Gürsoy-Kol, O., Yuksek, H., Islamoglu, F. (2013). Synthesis and in vitro antioxidant activities of novel 4-(3-methyl-2-thienylmethyleneamino)-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives with their acidic properties. Journal of the Chemical Society of Pakistan, 35(4): 1179–1190.
Gürsoy-Kol, Ö., Ocak, Z., Yüksek, H. (2016). Bazı 3-alkil(aril)-4-(3-asetoksibenzilidenamino)-4,5-dihidro-1H-1,2,4-triazol-5-on bileşiklerinin susuz ortam titrasyonları. Süleyman Demirel Üniversitesi Fen Bilimleri Enstitüsü Dergisi, 20(3): 518-523.
Gürsoy-Kol, Ö., Manap, S., Ozdemir, G., Beytur, M., Agdaş, E., Azap, F., Yuca, S., Alkan, M., Yüksek, H. (2020). Synthesis, antioxidant and antimicrobial activities of novel 4-(2-cinnamoyloxybenzylidenamino)-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives. Heterocyclic letters, 10(4): 575-587.
Güven, A., Yekeler, H. Özkan, R. (2000). Prediction of the acidities of organic bases in aqueous solution using AM1 COSMO solvent model. Journal Of Molecular Structure (Theochem), 499: 13-19.
Holla, B.S., Veerendra, B., Shivananda, M.K., Poojary, B. (2003). Synthesis characterization and anticancer activity studies on some Mannich bases derived from 1,2,4-triazoles. European Journal of Medicinal Chemistry. 38(7-8): 759-767.
İkizler, A.A., Ün, R. (1979). Reactions of ester ethoxycarbonylhydrazones with some amine type compounds. Chim Acta Turc. 7: 269-290.
Ikizler, A., Yüksek, H. (1993). Acetylation of 4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones. Org. Prep. Proc. Int., 25(1): 99-105.
King, E.J. (1965). Acid Base Equilibria, First Edition, Pergamon Press Inc. Oxford.
Manap, S., Gürsoy-Kol, Ö., Alkan, M., Yüksek, H. (2020). Synthesis, in vitro antioxidant and antimicrobial activities of some novel 3-substitued-4-(3-methoxy-4-isobutyryloxybenzylidene-amino)-4,5-dihydro- 1H-1,2,4-triazol-5-one derivatives. Indian J. of Chem. Sect. B, 59B (02): 271-282.
Padmavathi, V., Thriveni, P., Sudhakar, R.G., Deepti, D. (2008). Synthesis and antimicrobial activity of novel sulfone-linked bis heterocycles. European Journal of Medicinal Chemistry, 43(5): 917-924.
Putun, A.E., Bereket, G., Keskin, E. (1995). Potentiometric titrations of some 2-substituted 5-nitrobenzimidazole derivatives in nonaqueous solvent. Journal of Chemical & Engineering Data, 40: 221–224.
Salgin-Goksen, U., Gokhan-Kelekci, N., Goktas, O., Köysal, Y., Kılıç, A., Işık, Ş., Aktay, G., Özalp, M. (2007). 1-Acylthiosemicarbazides, 1,2,4-triazole-5(4H)-thiones, 1,3,4-thiadiazoles and hydrazones containing 5-methyl-2-benzoxazolinones: synthesis, analgesic-anti-inflammatory and antimicrobial activities. Bioorganic & Medicinal Chemistry, 15(17): 5738-5751.
Shaker, R.M., Mahmoud, A.F., Abdel-Latif, F.F. (2005). Synthesis and biological activities of novel 1,4-bridged bis-1,2,4-triazoles, bis-1,3,4-thiadiazoles and bis-1,3,4-oxadiazoles. Phosphorus, Sulfur, and Silicon and the Related Elements, 180(2): 397-406.
Sztanke, K., Tuzimski, T., Rzymowska. J., Pasternak, K., Kandefer-Szerszen, M. (2008). Synthesis, determination of the lipophilicity, anticancer and antimicrobial properties of some fused 1,2,4-triazole derivatives. European Journal of Medicinal Chemistry, 43(2): 404-419.
Yüksek, H., Demirbaş, A., İkizler, A., Johansson, C.B., Çelik, C., İkizler, A.A. (1997). Synthesis and antibacterial activities of some 4,5-dihydro-1H-1,2,4-triazol-5-ones. Arzneim.-Forsch./Drug Res., 47: 405-409.
Yüksek, H., Gürsoy-Kol, Ö. (2008). Preparation, characterization, and potentiometric titrations of some new di-[3-(3-alkyl/aryl-4,5-isophthalate/terephthalate derivatives. Turkish Journal of Chemistry, 32: 773-784.
Yüksek, H., Akyıldırım, O., Yola, M.L., Gürsoy-Kol, Ö., Çelebier, M., Kart, D. (2013). Synthesis, in vitro antimicrobial and antioxidant activities of some new 4,5-dihydro-1H-1,2,4-triazol-5-one derivatives. Archiv Der Pharmazie, 346(6): 470-480.
Yüksek, H., Koca, E., Gürsoy-Kol, Ö., Akyıldırım, O., Çelebier, M. (2015). 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: 359-366.