BAZI 4- (FENİLDİAZENİL)BENZEN-1,3-DİOL TÜREVLERİNİN SENTEZİ, KARAKTERİZASYONU, TAUTOMER VE ASİTLİK SABİTLERİNİN SPEKTROSKOPİK YÖNTEM İLE HESAPLANMASI

Yıl 2016, Cilt: 4 Sayı: 1, 11 - 28, 19.03.2016

Halil Berber , Nilüfer Aksu Ateş Müjgan Yaman Özkütük

https://doi.org/10.20290/btdb.01190

Öz

Bu çalışmada, benzen-1,3-triol ve bazı sübstitüe amino benzen ile monoazo boyar maddeleri sentezlendi. Kimyasal yapıları spektroskopik teknikler ile aydınlatıldı. 4-(fenildiazenil)benzen-1,3-diol türevi bileşiklerinin tautomerik özellikleri saf polar ve apolar çözücülerde (dimetil sülfoksit, etanol, kloroform, benzen ve siklohekzan) asidik ve bazik ortamlarda 25±1 °C, 35±1 °C ve 45±1 °C UV-Vis. Spektrometresinde ölçüldü. Sentezlenen bileşiklerin azo-hidrazon tautomerleri hesaplandı. Bütün azo boyar madde bileşiklerinde azo tautomer formunun baskın olduğu belirlendi. Aynı bileşiklerin asitlik sabitleri 25 °C (0,1 °C) UV-Vis. Spektroskopik teknik ile belirlendi.

Anahtar Kelimeler

Azo boyarmadde, Azo-hidrazon tautomerizmi, İyonlaşma sabitleri, Asitlik sabitleri

SYNTHESIS, CHARACTERIZATION AND SPECTROSCOPIC STUDIES ON TAUTOMERISM AND ACIDITY CONSTANTS OF CERTAIN 4- (PHENYLDIAZENYL) BENZENE-1,3-DIOL DERIVATIVES

Öz

In this study, monoazo dyes were synthesized through the diazotization of several substituted aminobenzenes and couplings with benzene-1,3-diols. The chemical structures of these compounds were characterized using spectroscopic techniques. The tautomeric properties of the 4-(phenyldiazenyl)benzene-1,3-diol derivative compounds were examined using UV-Vis. spectrophotometry in pure polar or apolar media (dimethyl sulfoxide, ethanol, chloroform, benzene and cyclohexane) under acidic and basic conditions at 25 ± 1 °C, 35 ± 1 °C and 45 ± 1 °C. The percentage of the azo-hydrazone tautomers was calculated for all of the compounds. The UV-Vis. analysis reveals that the azo form is dominant in the presence of azo-hydrazone tautomerism for all azo dyes. Concurrently, the acidity constants for these derivatives were determined using a UV-Vis. spectroscopic technique at 25 °C (± 0.1 °C).

Anahtar Kelimeler

Azo dyes, Azo-hydrazone tautomerism, Ionization constants, Acidity constants

Kaynakça

• Silva, C. G., Wang, W. & Faria, J. L. Photocatalytic and Photochemical Degradation of Mono-, Di- and Tri-azo Dyes in Aqueous Solution Under UV Irradiation. Journal of Photochemistry and Photobiology A: Chemistry, 181, 314-324, 2006.
• Isak, S. J., Eyring, E. M., Spikes, J. D. & Meekins, P. A. Direct Blue Dye Solutions: Photo Properties. Journal of Photochemistry and Photobiology A: Chemistry, 134, 77-85, 2000.
• Joshi, H., Kamounah, F. S., Gooijer, C., van der Zwan, G. & Antonov, L. Excited State Intramolecular Proton Transfer in Some Tautomeric Azo Dyes and Schiff Bases Containing an Intramolecular Hydrogen Bond. Journal of Photochemistry and Photobiology A: Chemistry. 152, 183-191, 2002.
• Bauer, C., Jacques, P. & Kalt, A. Photooxidation of an Azo Dye Induced by Visible Light Incident on the Surface of Tio2. Journal of Photochemistry and Photobiology A: Chemistry. 140, 87-92, 2001.
• Wang, J. & Ha, C. A Colorimetric and Fluorescent Turn-On Chemosensor for Zn2+ Based on an Azobenzene-Containing Compound. Tetrahedron, 65, 6959–6964, 2009.
• Wang, Y., Han, P., Xu, H., Wang, Z., Zhang, X. & Kabanov, A. V. Photocontrolled Self-Assembly and Disassembly of Block Ionomer Complex Vesicles: A Facile Approach Toward Supramolecular Polymer Nanocontainers. Langmuir, 26, 709-715, 2010.
• Lee, H. Y., Song, X., Park, H., Baik M. & Lee D. Torsionally Responsive C3-Symmetric Azo Dyes: Azo−Hydrazone Tautomerism, Conformational Switching, and Application for Chemical Sensing. Journal of the American Chemical Society, 132, 12133–12144, 2010.
• Inoue, Y., Kuad, P., Okumura, Y., Takashima, Y., Yamaguchi, H. & Harada, A. Thermal and Photochemical Switching of Conformation of Poly(ethylene glycol)-Substituted Cyclodextrin with an Azobenzene Group at the Chain End. Journal of the American Chemical Society, 129, 6396–6397, 2007. [9] Yager, K. G. & Barrett, J. C. Novel Photo-Switching Using Azobenzene Functional Materials. Journal of Photochemistry and Photobiology A: Chemistry, 182, 250–261, 2006.
• Ding, L. & Russell, T. P. A Photoactive Polymer with Azobenzene Chromophore in The Side Chains. Macromolecules, 40, 2267–2270, 2007.
• Gao, J., He, Y., Xu, H., Song, B., Zhang, X., Wang, Z. & Wang, X. Azobenzene-Containing Supramolecular Polymer Films for Laser-Induced Surface Relief Gratings. Chemistry of Materials, 19, 14–17, 2007.
• Shinkai, S., Nakaji, T., Nishida,Y., Ogawa, T. & Manabe, O. Photoresponsive Crown Ethers. 1. Cis-Trans Isomerism of Azobenzene as A Tool to Enforce Conformational Changes of Crown Ethers and Polymers. Journal of the American Chemical Society, 102, 5860-5865, 1980.
• Kelemen, J. Azo-Hydrazone Tautomerism in Azo Dyes. I. A Comparative Study of 1-Phenylazo- 2-Naphthol and 1-Phenylazo-2-Naphthylamine Derivatives by Electronic Spectroscopy. Dyes and Pigments 2, 73-91, 1981.
• Klotz, I. M., Fiess, H. A., Chen Ho, J. Y. & Mellody, M. The Position of the Proton in Substituted Azobenzene Molecules. Journal of the American Chemical Society, 76, 5136-5140, 1954.
• Richard, L., Reeves, R., Kaiser, S. Selective Solvation of Hydrophobic Ions in Structured Solvents. Azo-Hydrazone Tautomerism of Azo Dyes in Aqueous Organic Solvents. The Journal of Organic Chemistry, 35, 3670-3675, 1970.
• Sawicki, E. Physical Properties of the Aminoazobenzene Dyes. IV. The Position of Proton Addition. The Journal of Organic Chemistry, 22, 365-367,1957.
• Bouchoux, G., Defaye, D., McMahon, T., Likholyot, A., Mo, O. & Yañez, M. Structural and Energetic Aspects of the Protonation of Phenol, Catechol, Resorcinol, And Hydroquinone. Chemistry- A European Journal, 8, 2900–2909, 2002.
• Blanco, S. E., Almandoz, M. C. & Ferretti, F. H. Determination of the Overlapping pKa Values of Resorcinol Using UV-Visible Spectroscopy and DFT Methods. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 61, 93–102, 2005.
• Wang, W., Gong, S., Chen, Y. & Meng, I. The Effects of Intramolecular Hydrogen Bonding on the Reaction of Phenols with Epoxide in The Presence of Nano Calcium Carbonate. Supramolecular Chemistry, 18, 311–315, 2006.
• Klaes, M,, Agena, C., Köhler, M., Inoue, M., Wada, T., Inoue, Y. & Mattay, J. First Synthesis, Isolation and Characterization of Enantiomerically Pure and Inherently Chiral Resorc[4]Arenes by Lewis Acid Cyclization of A Resorcinol Monoalkyl Ether. European Journal of Organic Chemistry, 8, 1404–1409, 2003.
• Wang, X. S., Shi, D. Q.; Tu, S. T. & Yao, C. S. A Convenient Synthesis of 5-Oxo-5,6,7,8 Tetrahydro-4H-Benzo-[B]-Pyran Derivatives Catalyzed by KF-alumina. Synthetic Communications, 33, 119–126, 2003.
• Seferoğlu, Z., Ertan, N., Hökelek, T. & Şahin, E. The Synthesis. Spectroscopic Properties and Crystal Structure of Novel. Bis-Hetarylazo Disperse Dyes. Dyes and Pigments, 77, 614-625, 2008.
• Ghasemi, J., Ahmadi, S., Kubista, M. & Forootan, A. Determination of Acidity Constants of 4-(2- Pyridylazo)resorcinol in Binary Acetonitrile + Water Mixtures. Journal of Chemical Engineering. Data, 48, 1178–1182, 2003.
• Fabian, W. M. F., Antonov, L., Nedeltcheva, D., Kamounah, F. S. & Taylor, P. J. Tautomerism in Hydroxynaphthaldehyde Anils and Azo Analogues: A Combined Experimental and Computational Study. The Journal of Physical Chemistry A, 108, 7603–7612, 2004.
• Ghasemi, J., Lotfi, S., Safaeian, M., Niazi, A., Ardakani M. M. & Mohammad N. Spectrophotometric Determination of Acidity Constants of Alizarine Red S in Mixed Aqueous−Organic Solvents. Journal of Chemical Engineering Data, 51, 1530–1535, 2006.
• Matazo, D. R. C., Ando, R. A.; Borin, A. C. & Santos, P. S. Azo-Hydrazone Tautomerism in Protonated Aminoazobenzenes: Resonance Ramanspectroscopy and Quantum-Chemical Calculations. The Journal of Physical Chemistry A, 112, 4437–4443, 2008.
• Zollinger, H. Color Chemistry: Synthesis, Properties and Applications of Organic Dyes and Pigments. (3rd ed. pp. 165-241) Germany:VCH: Weinheim, 2001.
• Peters, A. T. & Freeman, H. S. Colour Chemistry: The Design and Synthesis of Organic Dyes and Pigments. (pp. 90-103). London and New York: Elsevier Applied Science, 1991.
• Gilli, G. & Gilli, P. The Nature of the Hydrogen Bond: Outline of A Comprehensive Hydrogen Bond Theory. Oxford: Oxford University Press, 2009.
• Rogers, M. T., Campbell, T. W. & Maatman. R. W. The Ionization Constants of Some p-Substituted p'-Dimethylaminoazobenzenes. Journal of the American Chemical Society. 73, 5122-5124, 1951.
• Berber, H., Öğretir, C., Sev Lekesiz, E. C. & Ermis, E. Spectroscopic Determination of Acidity Constants of Some Monoazo Resorcinol Derivatives. Journal of Chemical Engineering. Data 53, 1049–1055, 2008.
• Vogel, A. I. Vogel's Textbook of Quantitative Chemical Analysis (Revised by J. Mendham, 6th ed. pp. 920 – 945) Harlow, England: Prentice Hall, 2000.
• Türkoğlu, G.; Berber, H.; Dal, H. & Öğretir, C. Synthesis, Characterization, Tautomerism and Theoretical Study of Some New Schiff Base Derivatives. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 79, 1573–1583, 2011.
• Unver, H., Yildiz, M., Ocak, N. & Durlu, T. N. Spectroscopic Studies and Crystal Structure of 3-[(2- morpholinoethylimino)methyl]benzene-1,2-diol. Journal of Chemical Crystallography. 38, 103–108, 2008. [34] Hayvalı, Z., Hayvalı, M., Kılıç, Z., Hökelek, T. & Weber, E. New Benzo-15crown5 Ethers Featuring Salicylic Schiff Base Substitutions–Synthesis, Complexes and Structural Study. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 45, 285–294, 2003.
• Albert, A. & Serjant, E. P. The Determination of Ionization Constants (3rd Edition London, U.K.: Chapman and Hall Ltd, 1984.
• Sıdır, İ., Gülseven Sıdır, Y. & Berber. H. Acidity Constant Determination of Novel Drug Precursor Benzothiazolon Derivatives Including Acyl and Piperazine Moieties Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 111, 211–216, 2013.
• Özkütük, M., Öğretir, C., Arslan, T., Kandemirli, F. & Köksoy, B. Acid Dissociation Constants of Some Novel Isatin Thiosemicarbazone Derivatives. Journal of Chemical Engineering Data, 55, 2714–2718, 2010. [38] Öğretir, C., Dal, H., Berber, H. & Taktak, F.F. Spectroscopic Determination of Acid Dissociation Constants of Some Pyridyl Shiff Bases. Journal of Chemical Engineering Data, 51, 46–50, 2006.
• Perrin, D. D. & Dempsey, B. Book Review: Buffers for pH and Metal Ion Control. Angewandte Chemie International Edition in English, 14, 190, 1975.
• Bowden, K. Acidity Functions for Strongly Basic Solutions. Chemical Reviews. 66, 119–131, 1966. [41] Johnson, C. D. & Stratton, B. Concerning the Hammett Acidity Function Method for Determination of pKa Values. The Journal of Organic Chemistry. 51, 4100–4106,1986.
• Johnson, C. D. & Stratton, B. A Comparison of the Hammett Acidity Function Method for Determination of pKa Values with the Bunnett-Olsen and Excess Acidity Function Methods. The Journal of Organic Chemistry, 52, 4798–4800, 1987.
• Gilli, P., Bertolasi, V., Pretto, L., Lycˇka, A. & Gilli, G. The Nature of Solid-State N–H…O/O– H…N Tautomeric Competition in Resonant Systems. Intramolecular Proton Transfer in Low-Barrier Hydrogen Bonds Formed by The O=C–C=N–NH
• System. A Variable-Temperature X-Ray Crystallographic and DFT Computational Study. Journal of the American Chemical Society, 124, 13554–13567, 2002.
• HO–C=C–N=N Ketohydrazone–Azoenol [44] Gilli, P., Bertolasi, V., Pretto, L., Antonov, L. & Gilli, G. Variable Temperature X-Ray Crystallographic and DFT Computational Study of The N–H…O/O–H…N Tautomeric Comeptition in 1- (Arylazo)-2-Naphthols. Outline of A Transition State Hydrogen Bond Theory. Journal of the American Chemical Society, 127, 4943–4953, 2005.
• Mahmudov, K. T., Maharramov, A. M., Aliyeva, R. A., Chyragov, F. M., Askerov, R. K., Hasanov, P. Q., Kopylovich, M. N. & Pombeiro, A. J. L. Tautomeric Equilibria of Para-Bromophenyl Substituted Arylhydrazones of β-diketones. Journal of Molecular Structure, 1006, 576–579, 2011.