Monoazo Dyes: Coupling Reactions between Indanone Compounds and Heterocyclic Aminothiophene-Containing Spiro Group

Abstract

In this study, firstly, 2-amino-spiro[benzo]thiophene derivatives were prepared using the Gewald method. Subsequently, monoazo dyes were synthesized using conventional diazotization method, with 2-indanone or 1,3-indandione compounds as preferred coupling components. The chemical structures of the monoazo dyes have been characterized using several spectroscopic methods (FT-IR, 1H-NMR, 13C-APT NMR). The tautomeric forms of the dyes were discussed, and it was concluded that the hydrazo form is the dominant tautomer.

Keywords

• 2-Aminothiophene
• Spiro[benzo]thiophene
• Azo dyes
• Heterocyclic components

References

1. Christie RM. Colour Chemistry. 2nd ed. Cambridge: The Royal Society of Chemistry; 2015. Chapter 3, Azo Dyes and Pigments; p. 72-98.
2. Mishra VR, Ghanovatkar CN, Sekar N. UV protective heterocyclic disperse azo dyes: Spectral properties, dyeing, potent antibacterial activity on dyed fabric and comparative computational study. Spectrochim Acta A: Mol Biomol Spectrosc. 2019;223:117353. doi:10.1016/j.saa.2019.117353
3. Mohammadi A, Khalili B, Tahavar M. Novel push-pull heterocyclic azo disperse dyes containing piperazine moiety: Synthesis, spectral properties, antioxidant activity and dyeing performance on polyester fibers. Spectrochim Acta A: Mol Biomol Spectrosc. 2015;150:799-805. doi:10.1016/j.saa.2015.06.024
4. Manjunatha B, Bodke YD, Nagaraja O, Lohith TN, Nagaraju G, Sridhar MA. Coumarin-Benzothiazole based azo dyes: Synthesis, characterization, computational, photophysical and biological studies. J Mol Struct. 2021;1246:131170. doi: 10.1016/j.molstruc.2021.131170
5. Sujamol MS, Athira CJ, Sindhu Y, Mohanan K. Synthesis, spectroscopic characterization, dyeing performance and corrosion inhibition study of transition metal complexes of a novel azo derivative formed from 2-aminothiophene. Chem Data Coll. 2021;31:100634. doi: 10.1016/j.cdc.2020.100634
6. Karcı F, Bakan E. New disazo pyrazole disperse dyes: synthesis, spectroscopic studies and tautomeric structures. J Mol Liq. 2015;206:309-315. doi: 10.1016/j.molliq.2015.02.032
7. Khedr AM, El-Ghamry H, Kassem MA, Saad FA, El-Guesmi N. Novel series of nanosized mono- and homobi-nuclear metal complexes of sulfathiazole azo dye ligand: Synthesis, characterization, DNA-binding affinity and anticancer activity. Inorg Chem Commun. 2019;108:107496. doi:10.1016/j.inoche.2019.107496
8. Mughal EU, Raja QA, Alzahrani AYA, Naeem N, Sadiq A, Bozkurt E. Pyrimidine-based azo dyes: Synthesis, photophysical investigations, solvatochromism explorations and anti-bacteral activity. Dyes Pigm. 2023;220:111762. doi:10.1016/j.dyepig.2023.111762

9. Yıldırım F, Demirçalı A, Karcı F, Bayrakdar A, Taşlı PT, Kart, HH. New coumarin-based disperse disazo dyes: synthesis, spectroscopic properties and theoretical calculations. J Mol Liq. 2016;223:557-565. doi:10.1016/j.molliq.2016.08.008
10. Karabacak Ç, Dilek Ö. Synthesis, solvatochromic properties and theoretical calculation of some novel disazo indole deys. J Mol Liq. 2014;199:227-236. doi:10.1016/j.molliq.2014.09.019
11. Harisha S, Keshavayya J, Kumara Swamsy BE, Viswanath CC. Synthesis, characterization and electrochemical studies of azo dyes derived from barbituric acid. Dyes Pigm. 2017 Jan;136:742-753. doi:10.1016/j.dyepig.2016.09.004
12. Erten G, Karcı F, Demirçalı A, Söyleyici S. 1H-pyrazole-azomethine based novel diazo derivative chemosensor for the detection of Ni2+. J Mol Struct. 2020 Apr 15;1206:127713. doi:10.1016/j.molstruc.2020.127713
13. Derkowksa-Zielinska B, Skowronski L, Biitseva A, Grabowski A, Naparty MK, Smokal V, Kysil A, Krupka O. Optical characterization of heterocyclic azo dyes containing polymers thin films. Appl Surf Sci. 2017;421(B):361-366. doi: 10.1016/j.apsusc.2016.12.080
14. Ayare NN, Sharma S, Sonigara KK, Prasad J, Soni SS, Sekar N. Synthesis and computational study of coumarin thiophene-based-π-A azo bridge colorants for DSSC and NLOphoric application. J Photochem Photobiol A. 2020;394:112466. doi: 10.1016/j.jphotochem.2020.112466
15. Karabulut YK, Gürkan YY. Investigation of some azo dyes by QSAR method and acute toxicity test with Daphnia Magna. J Ins Sci Tech. 2023;13(2):1110-1119. doi:10.21597/jist.1214772
16. Karcı F, Karcı F. Synthesis and tautomeric structures of some novel thiophene-based bis-heterocyclic monoazo dyes. J Mol Struct. 2012;1024:117-122. doi: 10.1016/j.molstruc.2012.05.021
17. Singh MV, Tiwari AK, Sharma YK, Chauhan MS, Sethi M, Guo Z. Synthetic procedures, properties, and applications of thiophene-based azo scaffolds. ES Food Agrofor. 2023;12:887. doi: 10.30919/esfaf887
18. Abdou MM. Thiophene-based azo dyes and their applications in dyes chemistry. Am.J. Chem. 2013;3(5):126-135. doi:10.5923/j.chemistry.20130305.02
19. Nassar HS. New azo disperse dyes with thiophene moiety for dyeing polyester fibers. Int. J. Text. Sci. 2015;4(5):102-112. doi: 10.5923/j.textile.20150405.02
20. Sharma SJ, Khan ZN, Zambare AA, Bagal MS, Barshi AS, Rindle SM, Sekar N. Synthesis, spectroscopic, DFT, TD-DFT, and dyeing studies of 2-amino-3-cyano thiophene-based azo dyes on wool and nylon. Dyes Pigm. 2024;228:112209. doi: 10.1016/j.dyepig.2024.112209
21. Mezgebe K, Mulugeta E. Synthesis and pharmacological activities of azo dye derivatives incorporating heterocyclic scaffolds: a rewiev. RSC Adv. 2022;12(40):25932-25946. doi: 10.1039%2Fd2ra04934a
22. Gouda MA, Eldien HF, Girges MM, Berghot MA. Synthesis and antitumor evaluation of thiophene based azo dyes incorporating pyrazolone moiety. J. Saudi Chem. Soc. 2016;20(2):151-157. doi:10.1016/j.jscs.2012.06.004
23. Al-Azmi A, John E. Synthesis of 4-arylazo-2-(N-pyrazolylcarboxamido)thiophene disperse dyes for dyeing of polyester and their antibacterial evaluation. Text. Res. J. 2020;90(23-24):1-11. doi: 10.1177/0040517520931476
24. Ayare NN, Sharma S, Sonigara KK, Prasad J, Soni SS, Sekar N. Synthesis and computational study of coumarin thiophene-based D-π-A azo bridge colorants for DSSC and NLOphoric application. J. Photochem. Photobiol. A Chem. 2020;394:112466. doi: 10.1016/j.jphotochem.2020.112466
25. Sharma SJ, Sekar N. Exploration of 4-substituted thiophene-based azo dyes for dye-senditized solar cells and non-linear optical materials: synthesis and an in silico approach. Phys. Chem. Chem. Phys. 2024; Advance article. doi: 10.1039/D4CP00918E
26. El-Haddad MN, Fouda AS, Mostafa HA. Corrosion inhibition of carbon steel by new thiophene azo dye derivatives in acidic solution. J. Materi. Eng. Perform. 2013; 22:2277-2287. doi: 10.1007/s11665-013-0508-0
27. Gadow HS, Fawzy A, Khairy M, Sanad MMS, Toghan A. Experimental and theoretical approaches to the inhibition of carbon steel corrosion by thiophene derivative in 1 M HCl. Int. J. Electrochem. Sci. 2023;18(7):100174. doi: 10.1016/j.ijoes.2023.100174
28. Peet NP, Sunder S, Barbuch RJ, Vinogradoff AP. Mechanistic observations in the Gewald syntheses of 2-aminothiophenes. J Heterocycl Chem. 1986;23(1):129–134. doi: 10.1002/jhet.5570230126
29. Gewald K. Methods for the synthesis of 2-aminothiophenes and their reactions (review). Chem Hetrocycl Compd. 1976;12:1077-1090. doi: 10.1007/BF00945583
30. Gewald K, Schinke E, Bottcher H. Heterocyclen aus CH-aciden Nitrilen, VIII. 2-Amino-thiophene aus methylenaktiven Nitrilen, Carbonylverbindungen und Schwefel. Chem Ber. 1966;99(1): 94-100. doi: 10.1002/cber.19660990116
31. Buldurun K, Turan N, Savci A, Alan Y, Colak N. Synthesis, characterization, X-ray diffraction analysis of a tridentate Schiff base ligand and its complexes with Co (II), Fe (II), Pd (II) and Ru (II): Bioactivity studies. Iran J Chem Chem. Eng. 2022;41(8):2635-2649. doi: 10.30492/ijcce.2021.531629.4775
32. Çolak N, Gündüzalp AB, Mamaş S, Akkaya D, Kaya K. Synthesis, spectroscopic studies and electrochemical properties of Schiff bases derived from 5-chloro-2-hydroxybenzaldehyde with methyl 2-amino-6-methyl-4, 5, 6, 7-tetrahydrobenzo [b] thiophene-3-carboxylate. Bulg Chem Commun. 2016;48(Special C):20-26.
33. Çolak N, Altıner S, Şahin ZS, Gündüzalp AB. Synthesis, Spectroscopic and Computational Studies of (E)-2-(2,3-dihydroxy)-benzylidene)amino)-6-methyl-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile. Gazi University Journal of Science. 2017;30(3):245 – 254.
34. Maradiya HR. Synthesis of azobenzo[b]thiophene derivatives and their dyeing performance on polyester fibre. Turk J Chem. 2001;25(4):441-450.