• Ä°zzet Åžener Pamukkale University, Faculty of Science-Arts,Department of Chemistry, 20017,Denizli, Turkey
  • GÃœlÅžah Aydin Gedik University, Higher Vocational School of Gedik, Chemical Programme, 34913, Ä°stanbul, Turkey.


Objective: The aim of the work was to designed and synthesized novel heterocyclic tetrakisazo dyes.

Methods: 2,2'[(4,4'-dihydrazonebiphenyl)]-bis(3-iminobuthyronitrile) (1) were synthesized by diazotization of benzidine using hydrochloric acid in water. Compounds (1) reacted with hydrazine hydrate to afford the corresponding 4,4'-bis [3-methyl-5-amino-1-H-pyrazol-4-ylazo]biphenyl (2). Seven novel hetaryltetrakisazobenzidine Derivatives 3(a-g) were achieved by diazotization of 4,4'-bis [3-methyl-5-amino-1-H-pyrazol-4-ylazo]biphenyl and coupling with various coupling components.

Results: The obtained hetaryltetrakisazo dyes 3(a-g) were characterized based on FT-IR, 1H-NMR, and mass spectroscopic techniques as well as elemental analysis. The solvatochromic behavior of these dyes in various solvents was examined. Acid-base effects on the visible absorption maxima of the dyes were also reported.

Conclusion: Synthesis and characterization of seven of these nine novel compounds synthesized, which are hetaryltetrakisazo dyes 3(a-g).


Keywords: Diazotization, Solvatochromism, Pyrazole, Diazo-coupling reaction, Tetrakisazo dyes.


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Author Biography

Ä°zzet Åžener, Pamukkale University, Faculty of Science-Arts,Department of Chemistry, 20017,Denizli, Turkey


1. Pielesz A. The process of the reduction of azo dyes used in dyeing textiles on the basis of infrared spectroscopy analysis. J Mol Struct 1999;511–512:337-44.
2. Yazdanbakhsh MR, Abbasnia M, Sheykhan M, Ma’mani L. Synthesis, characterization and application of new azo dyes derived from uracil for polyester fibre dyeing. J Mol Struct 2010;297:266-73.
3. Junnarkar N, Murty DS, Bhatt NS, Madamwar D. World Journal of Microbiology and Biotechnology. World J Microb Biotech 2006;22(2):163-8.
4. Oranusi NA, Ogugbue CJ. Effect of pH and nutrient starvation on biodegradation of azo dyes by pseudomonas sp. J Appl Sci Environ Manage 2005;9(1):39-43.
5. Peters AT, Chisowa E. Colour-constitution relationships in 2-acylamino-4-N,N-diethylaminobenzene disperse dyes. Dyes and Pigments 1993;22(4):223-38.
6. Hartmann H, Schulze M, Guenter R. Nucleophilic substitution in arylazo phenols-a simple route for preparing chloro-substituted azobenzenes. Dyes Pigments 1991;15(4):255-62.
7. Hallas G, Choi JH. Synthesis and properties of novel aziridinyl azo dyes from 2-aminothiophenes-Part 2:Application of some disperse dyes to polyester fibres. Dyes Pigments 1999;40:119-29.
8. Weaver MA, Shuttleworth L. Heterocyclic diazo components. Dyes Pigments 1982;3(2-3):81-121.
9. Jaiswal N, Jaiswal R, Barthwal J, Kishor K. Synthesis and biological-activity of some new 10-[(3,5-diaryl-2-pyrazolin-1-yl)acethyl]phenothiazines. Indian J Chem 1981;20B:252-6.
10. Küçükgüzel SG, Rollas S, Erdeniz H, Kiraz M, Ekinci AC, Vidin A. Synthesis, charaacterization and pharmocological properties of some 4-arylhydrazono-2-pyrazoline-5-one derivatives obtained from heterocyclic amines. J Medicinal Chem 2000;35:761-71.
11. Ertan N. Synthesis of some hetarylazopyrazolone dyes and solvent effects on their absorption spectra. Dyes Pigments 1999;44:41-8.
12. Khalil AK, Hassan MA, Mohamed MM, El-Sayed AM. Metal salt-catalyzed diazocoupling of 3-substituted-1H-pyrazol-2-in-5-ones in aqueous medium. Dyes Pigments 2005;66:241-5.
13. Emandi A, Serban I, Bandula R. Synthesis of some new solvatochromic 1(4)-substituted Pyrazol-5-one Azo derivatives. Dyes Pigments 1999;41:63-77.
14. Tsai PC, Wang IJ. Synthesis and solvatochromic properties of some disazo dyes derived from pyrazolo[1,5-a]pyrimidine derivatives. Dyes Pigments 2005;64, 259-64.
15. Ho YW. Synthesis of some new azo pyrazolo[1,5-a]pyrimidine-thieno[2,3-b]pyridine derivatives and their application as disperse dyes. Dyes Pigments 2005;64:223-30.
16. Karcı F, Demirçalı A. Synthesis of disazo pyrazolo[1,5-a]pyrimidines Dyes Pigments 2007;74:288-97.
17. Rockville, MD. US National Institute for Occupational Safety, Health (NIOSH), Special Occupational Hazard Review for Benzidine-based Dyes, National Institute for Occupational Safety and Health, 1980 (publication no. 80-109).
18. Powell R, Murray M, Chen C, Lee A. Survey of the Manufacture, Import and Uses for Benzidine, Related Substances and Related Dyes and Pigments. EPA Report 560/13-79-005, Environmental Protection Agency, Washington, DC;1979.
19. Woo T, Arcos JC, Lai DY, Handbook of Carcinogen Testing (New Jersey: Noyes Publications; 1985).
20. Shahin MM, Bugaut A, Kalopissis G. Structure-activity relationship within a series of m-diaminobenzene derivatives. Mut Res 1980;78(1):25-31.
21. Shahin MM, Rouers A, Bugaut A, Kalopissis G. Structure-activity relationships within a series of 2,4-diaminoalkoxybenzene compounds. Mut Res 1980;79(4):289-306.
22. Hunger K, Froelich H, Hertel H, Habig KC. Manuf. of 3,3'-dialkoxybenzidines DE 3511544;1986.
23. Hunger K, Froelich H, Hertel H, Habig KC. Benzidine derivatives DE 3511545:1986.
24. Sokolowska J, Hinks D, Freeman HS. Synthesis and evaluation of organic pigments. 3. Studies based on nonmutagenic twisted benzidines. Dyes Pigments 2001;48(1):15-27.
25. Freeman HS, Hinks D, Sokolowska-Gajda J. Twisted benzidines, their preparation, pigments derived from them, and preparation of the pigments. US 5965717;1999.
26. Hinks D, Freeman HS, Nakpathom M, Sokolowska J. Synthesis and evaluation of organic pigments and intermediates. 1. Nonmutagenic benzidine analogs. Dyes Pigments 2000;44(3):199-207.
27. Bauer W, Hunger K. Water-soluble disazo dyes. DE 3534634:1987.
28. Wang J, Freeman HS, Claxton LD. Synthesis and mutagenic properties of 4,4-diamino-p-terphenyl and 4,4-diamino-pquaterphenyl. Coloration Technology 2007;123:34–8.
29. Robert MC, Bruce DH. Potential alternatives for 3,3ï‚¢-dichlorobenzidine as tetrazo components for diarylide yellow and orange pigments, Part 1:p-Phenylenediamine and its derivatives. Dyes Pigments 2009;80:245-53.
30. Karcı F, Şener İ, Deligöz H. Azocalixarenes. 1:Synthesis, Characterization and Investigation of The Absorption Spectra of Substituted Azocalix[4]arenas. Dyes Pigments 2003;59(1):53-61.
31. Karcı F, Şener İ, Deligöz H. Azocalixarenes. 2:Synthesis, Characterization and Investigation of The Absorption Spectra of Azocalix[6]arenes Containing Chromogenic Groups. Dyes Pigments 2004;62(2):131-40.
32. Şener İ, Karcı F, Kılıç E, Deligöz H. Azocalixarenes. 3:Synthesis and Investigation of The Absorption Spectra of Hetarylazo Disperse Dyes Derived From Calix[4]arenes. Dyes Pigments 2004;62(2):141-8.
33. Şener İ, Karcı F, Kılıç E, Deligöz H. Azocalixarenes. 4:Synthesis, Characterization and Investigation of The Absorption Spectra of Hetarylazo-substituted Calix[6]arenes Containing Heterocyclic Groups. Dyes Pigments 2004;62(2):149-57.
34. Tilki T, Şener İ, Karcı F, Gülce A, Deligöz H. Approach to the Synthesis of Chemically Modified Bisazocalix[4]arenes and their Extraction Properties. Tetrahedron 2005;61(40):9624-29.
35. Şener İ, Karcı F, Ertan N, Kılıç E. Synthesis and investigations of the absorption spectra of hetarylazo disperse dyes derived from 2,4-quinolinediol. Dyes Pigments 2006;70(2):143-8.
36. Åžener Ä°, Kadifeli F. Synthesis and absorption spectra of some novel hetaryldisazocalix[4]arene derivatives. Coloration Technology 2011;127(6):404-10.
37. Åžener Ä°, Åžener N, EriÅŸkin S. Synthesis and absorption spectra of some novel hetaryltetrakisazocalix[4]arene derivatives. Dyes Pigments 2013;96:256-63.
38. Elnagdi MH, Fahmy SM, Elmoghayar MRH, Elias MAM. Pyrimidine derivatives and related compounds. I. Synthesis of some 2,3-disubstituted-4,5,6-tetrahydropyrazole[1,5-a]pyrimidine derivatives. Zeitschrift für naturforschung, Teil B: Anorganische Chemie, Organische Chemie 1975;30B(9-10):778-83.
39. Elnagdi MH, Sallam MMM, Fahmy HM, Ä°brahim SAM, Elias MAM. Reactions with the arylhydrazones of-cyanoketones: The structure of 2-arylhydrazone-3-ketimino-nitriles. Helv Chim Acta 1976;59(2):551-7.
40. Elnagdi MH, Elmoghaya MRH, Fleita DH, Hafez EAA, Fahmy SM. Pyrimidine derivatives and related compounds. 4. A route for synthesis of pyrazolo[3,4-e]-as-triazines, pyrazolo[3,4-d] pyrimidines, and pyrazolo[1,5-c]-as-triazines. J Organic Chem 1976;41(24):3781-4.
41. Ghozlan SAS, Abdelhamid IA, Abdelshaft GH, Elnagdi MH. Studies with functionally substituted enamines: synthesis of new amino-pyrimidines and-1,2,4-triazines. J Chem Res 2004;12:789-93.
42. Karcı F. Synthesis of disazo dyes derived from heterocyclic components. Coloration Technology 2005;121:275-80.
43. Zvilichovsky G, Davıd M. The reactıon of phenylmalononitrile wıth hydrazine-synthesis and properties of 3,5-diamino-4-phenylpyrazole, 2-amino-3-phenylpyrazolo[1,5-a]pyrimidine, and related-compounds. J Chem Soc Perkin Trans I 1983;1:11-6.
44. Kandeel ZE, Abdelrazek FM, Eldin NEMS, Elnagdi MH. Activated nitriles in heterocyclic synthesis-novel synthesis of benzo[g]imidazo [1,2-c]pyrimidines and benzo[g]imidazo [1,2-a]pyridine derivatives. J Chem Soc Perkin Trans I 1985;1499-501.
45. Sing SP, Kumar D. Reınvestgation of the reoported synthesis of naphtho[2’,1’-4,5]thiazolo[2,3-c][1,2,4]triazepines. Heterocycles 1990;31:855-60.
46. C Reichart, T Welton. Solvent and Solvent Effect in Organic Chemistry. Fourth Edition.(Willey-VCH Verlag & Co. KgaA):Weinheim;2011.
47. Jain KJ, Kanaiya PH, Bhojak N. Synthesis, spectral characterization of azo dyes derived from calix[4]resorcinarene and their application in dyeing of fibers. Fibers Polymers 2008;9(6):720-6.
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How to Cite
Åžener Ä°zzet, and G. Aydin. “SYNTHESIS, CHARACTERIZATION AND ABSORPTION PROPERTIES OF SOME NOVEL HETEROCYCLIC TETRAKISAZO DYES”. International Journal of Pharmacy and Pharmaceutical Sciences, Vol. 6, no. 9, 1, pp. 540-5,
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