Synthesis and Absorption Properties of Trisubstituted Hetarylazo Indole Dyes

Abstract

In this study, as a result of azo coupling of diazonium salts prepared with various aromatic amines with 2-(4-methylphenyl)-1H-indole and 2-(4-chlorophenyl)-1H-indole compounds, a series of new hetarylazo indole dyes were synthesized. N-substituted indole derivatives were synthesized by alkylation of the prepared dyes with the isopropyl alcohol from the N-position by Mitsunobu reaction. The chemical structures of the synthesized compounds were determined by NMR, FT-IR, UV-vis, mass spectrometry and elemental analysis. In order to determine the photophysical properties of the dyes obtained, visible region absorption spectra were examined in solvents of different polarity. In addition, the behavior of acid and base addition on absorption maxima were examined in detail.

Keywords

• Indole derivatives,Azo compounds,Mitsunobu alkylation,Solvent effect

Trisübstitüe Hetarilazo İndol Boyalarının Sentezi ve Absorpsiyon Özelliklerinin İncelenmesi

Abstract

Bu çalışmada, çeşitli aromatik aminler ile hazırlanan diazonyum tuzlarının, 2-(4-metilfenil)-1H-indol ve 2-(4-klorfenil)-1H-indol bileşikleri ile azo kenetlenmesi sonucu, bir dizi yeni hetarilazo indol boyası sentezlendi. Hazırlanan boyarmaddelerin, Mitsunobu reaksiyonu ile N-pozisyonundan izopropil alkol ile alkillenmesi sonucu N-sübstitue indol türevlerinin sentezi gerçekleştirildi. Sentezlenen bileşiklerin kimyasal yapıları, NMR, FT-IR, UV-vis, kütle spektrometresi ve elementel analiz ile aydınlatıldı. Elde edilen boyarmaddelerin fotofiziksel özelliklerini belirlemek için, farklı polariteye sahip çözücüler içerisinde görünür bölge absorpsiyon spektrumları incelendi. Ek olarak, asit ve baz ilavesinin absorpsiyon maksimumları üzerine etkileri ayrıntılı olarak incelendi.

Keywords

• İndol türevleri,Azo bileşikleri,Mitsunobu alkilasyonu,Çözücü etkisi

References

1. [1] G.H. Mock and H. Freeman, “Dye application, manufacture of dye intermediates and dyes,” In Kent and Riegel’s, Handbook of industrial chemistry and biotecnology, 11th ed. Springer, 2007, 449-590.
2. [2] U. Meyer, “Biodegradation of systemic organic colorants,” In microbial degradation of xenobiotics and recalcitrant compounds. FEMS Symp. Vol. 12, T. Lesinger, A.M. Cook, R.M. Hutter, J. Neesch, Eds. New York: Academic Press, 1981, 371.
3. [3] N. Puvaneswari, J. Muthukrishnan and P. Gunasekkaran, “Toxicity assessment and microbial degradation of azo dyes,” Ind. J. Exp. Biol., 44, 618-626, 2006.
4. [4] A.D. Towns, “Developments in azo disperse dyes derived from heterocyclic diazo components,” Dyes Pigments, 42, 3-28, 1999.
5. [5] J.B. Dickey, E.B. Towne, M.S. Bloom, W.H. Moore, H.M. Hill, H. Heynemann, D.G. Hedberg, D.C. Sievers and M.V. Otis, “Azo dyes from substituted 2-Aminothiazoles,” J. Org. Chem., 24, 187-196, 1959.
6. [6] B. Sui, W. Zhao, G. Ma, T. Okamura, J. Fan, Y-Z. Li, S-H. Tang, W-Y. Sun and N. Ueyama, “Novel Pb(II) coordination frameworks: synthesis, crystal structures and unusual third-order nonlinear optical properties,” J. Mater. Chem., 14, 1631-1639, 2004.
7. [7] E.C. Taylor, Series Ed.; “The chemistry of heterocyclic compounds,” J.E. Saxton, Ed.; New York: Wiley-Interscience; 1983, 25, Part 4 and Suppl.
8. [8] (a) J.A. Joule, “In science of synthesis: methods of molecular transformations,” E.J. Thomas, Ed.; Stuttgart, New York: Gerorg Thieme Verlag; 2000, 10, 361-652. (b) G.W. Gribble, “Recent developments in indole ring synthesis-methodology and applications,” J. Chem. Soc., Perkin Trans. I, 1045-1075, 2000.

9. [9] Y. Higashio and T. Shoji, “Heterocyclic compounds such as pyrrole, pyridines, pyrrolidine, piperidine, indole, imidazol and pyrazines,” Appl. Catal. A, 260, 251-259, 2004.
10. [10] H. Pauly and K. Gundermann, “Über jodbindende Systeme in den EiweiS-Spaltkorpern,” Chem. Ber., 41, 3999-4012, 1908.
11. [11] Z. Seferoğlu and N. Ertan, “Synthesis of some novel Bis(Hetaryl)azo disperse dyes and investigation of their absorption spectra,” Heteroatom Chemistry, 18(6), 622-630, 2007.
12. [12] Z. Seferoğlu and N. Ertan, “Synthesis and spectral properties of new hetarylazo indole dyes,” Rus. J. Org. Chem., 43(7), 1035-1041, 2007.
13. [13] Z. Seferoğlu, N. Ertan, E. Yılmaz and G. Uraz, “Synthesis, spectral characterisation and antimicrobial activity of new disazo dyes derived from heterocyclic coupling components,” Color. Tech., 124, 27-35, 2008.
14. [14] Z. Seferoğlu and N. Ertan, “Hetarylazoindoles 1. Synthesis, characterization and spectroscopic properties of new hetarylazoindole dyes,” Phosp. Sulf. and Sil., 183, 1236-1251, 2008.
15. [15] Z. Seferoğlu, N. Tokay, T. Hökelek and E. Şahin, “Synthesis and crystal structures of two hetarylazo indole disperse dyes,” Struct. Chem., 19, 559-564, 2008.
16. [16] N. Tokay, Z. Seferoğlu, C. Öğretir and N. Ertan, “Quantum chemical studies on the structures of some heterocyclic azo disperse dyes,” Arkivoc, 15, 9-20, 2008.
17. [17] Z. Seferoğlu, N. Ertan, T. Hökelek and E. Şahin, “The synthesis, spectroscopic properties and crystal structure of novel, bis-hetarylazo disperse dyes,” Dyes Pigments, 77, 614-625, 2008.
18. [18] Z. Seferoğlu, N. Ertan, G. Kickelbick and T. Hökelek, “Single crystal X-ray structure analysis for two thiazolylazo indole dyes,” Dyes Pigments, 82, 20-25, 2009.
19. [19] Z. Seferoğlu, F.B. Kaynak, N. Ertan and S. Özbey, “Hetarylazoindoles 2. Spectroscopic and structural investigation of new benzothiazolylazo indole dyes,” J. Mol. Struct., 1047, 22-30, 2013.
20. [20] Ç. Karabacak and Ö. Dilek, “Synthesis, solvatochromic properties and theoretical calculation of some novel disazo indole dyes,” J. Mol. Liq., 199, 227-236, 2014.
21. [21] (a) O. Mitsunobu, M. Yamada and T. Mukaiyama, “Preparation of esters of phosphoric acid by the reaction of trivalent phosphorus compounds with diethyl azodicarboxylate in the presence of alcohols,” Bull. Chem. Soc. Jpn., 40, 935-939, 1967. (b) O. Mitsunobu and M. Eguchi, “Preparation of carboxylic esters and phosphoric esters by the activation of alcohols,” Chem. Soc. Jpn., 44, 3427-3430, 1971.
22. [22] D.L. Hughes, “Progress in the Mitsunobu reaction. A review,” Org. Prep. Pro. Inter., 28, 127-164, 1996.
23. [23] (a) D.L. Hughes, R.A. Reamer, J.J. Bergan and E.J.J. Grabowski, “A mechanistic study of the Mitsunobu esterification reaction,” J. Am. Chem. Soc., 110, 6487-6491, 1988. (b) M. Varasi, K.A.M. Walker and M.L. Maddox, “A revised mechanism for the Mitsunobu reaction,” J. Org. Chem., 52, 4235-4238, 1987. (c) D. Crich, H. Dyker and R.J. Harris, “Some observations on the mechanism of the Mitsunobu reaction,” J. Org. Chem., 54, 257-259, 1989. (d) A.P. Cooper and S.A. Evans Jr., “Mechanistic implications of 1,3,2λ5-Dioxaphospholanes in the Mitsunobu reaction,” J. Org. Chem., 54, 2485-2488, 1989.
24. [24] K.C. Kumara Swamy, N.N. Bhuvan Kumar, E. Balaraman and K.V.P. Pavan Kumar, “Mitsunobu and related reactions: Advances and applications,” Chem. Rev. 109, 2551-2651, 2009.
25. [25] A. Dhakshinamoorthy and K. Pitchumani, “Facile caly-induced Fischer indole synthesis: A new approach to synthesis of 1,2,3,4,-tetrahydrocarbazole and indoles,” App. Cat. A: Genaral, 292, 305-311, 2005.
26. [26] S. Daly, K. Hayden, I. Malik, N. Porch, H. Tang, S. Rogelj, L.V. Frolova, K. Lepthien, A. Kornienko and I.V. Magedov, “Unprecedented C-2 arylation of indole with diazonium salts: Syntheses of 2,3-disubstituted indoles and their antimicrobial activity,” Bioorg. Med. Chem. Lett., 21(16), 4720-4723, 2011.