New 1,3,4-thiadiazole compounds: synthesis, spectroscopic characterisation and theoretical analyses based on DFT calculations

Abstract

In this study, four novel 1,3,4-thiadiazole compounds, derived from α-methyl cinnamic acid, were synthesised. The structural elucidation was carried out using UV-Vis, FT-IR, 1H-NMR and 13C-NMR spectroscopy. In addition, the chemical and electronic properties of the compounds as well as UV-Vis, IR and NMR analyses were theoretically performed using the density functional theory (DFT). Based on the frontier molecular orbital (FMO) energies of the compounds, which were obtained from different methods and basis sets, some chemical reactivity parameters and their relationship with the methods were analysed. Theoretical calculations were compared with the experimental results. The electronegative substituents Cl and NO2 reduced the HOMO–LUMO energy gap (ΔE), and the ones caused a bathochromic shift in the UV absorption wavelength. The Pearson correlation coefficients between the experimental and theoretical IR and 13C NMR results were approximately R = 0.99. It was seen that, the chemical shift of hydrogen bound to an electronegative nitrogen atom was affected by intarmolecular hydrogen bond interactions.

Keywords

• 1 3 4-thiadiazoles
• α-methyl cinnamic acid
• computational chemistry
• density functional theory

Yeni 1,3,4-tiadiazol bileşikleri: sentez, spektroskopik karakterizasyon ve DFT hesaplamalarına dayanan teorik analizler

Abstract

Bu çalışmada, α-metil sinnamik asitten türetilen dört yeni 1,3,4-tiadiazol bileşiği sentezlendi. Bileşiklerin yapısal özellikleri UV-Vis, FT-IR, 1H-NMR ve 13C-NMR spektroskopisi kullanılarak incelendi. Buna ek olarak, bileşiklerin kimyasal ve elektronik özelliklerinin yanı sıra UV-Vis, IR ve NMR analizleri teorik olarak yoğunluk fonksiyonel teorisi (DFT) kullanılarak gerçekleştirildi. Farklı yöntemler ve baz setleri kullanılarak elde edilen, bileşiklerin sınır moleküler orbital (FMO) enerjilerine dayanılarak, bazı kimyasal reaksiyon parametreleri ve bunların kullanılan yöntemlerle ilişkisi analiz edildi. Teorik hesaplamalar deney sonuçları ile karşılaştırıldı. Elektronegatif Cl ve NO2 sübstitüentlerinin HOMO-LUMO enerji aralığını (ΔE) düşürdüğü ve UV-absorbsiyon dalga boyunda bir batokromik kaymaya neden olduğu gözlendi. Deneysel ve teorik IR ve 13C NMR sonuçları arasındaki Pearson korelasyon katsayıları yaklaşık olarak R = 0.99 olarak hesaplandı. Elektronegatif azot atomuna bağlı hidrojenin kimyasal kaymasının, molekül içi hidrojen bağı etkileşimlerinden etkilendiği gözlendi.

Keywords

• 1 3 4-tiadiazol
• α-metil sinnamik asit
• hesaplamalı kimya
• yoğunluk fonksiyonel teorisi

References

1. Şener, N. and Gür, M., Novel 1,3,4-thiadiazole compounds derived from 4-phenylbutyric acid: Synthesis, characterization and DFT studies, Journal of Balıkesir University Institute of Science and Technology, DOI: 10.25092/baunfbed.343149
2. Gür, M. and Şener, N., Synthesis and Characterizatıon Of Some New 1,3,4-Thiadiazole Compounds Derived From α-Methyl Cinnamic Acid and Their Energetics and Spectral Analyses Based on Density Functional Theory Calculations, Anadolu University Journal of Science and Technology, A-Applied Sciences and Engineering, DOI: 10.18038/aubtda.310899
3. Jaiswal, S. and Sigh, S., A novel POCl3 catalysed expeditious synthesis and antimicrobial activities of 5-subtituted-2-arylbenzalamino-1,3,4-thiadiazole, International Journal of Engineering Research and General Science, 2, 6, (2014).
4. Ahmed, M., Jahan, J. and Banco S., A simple spectrophotometric methods for the determination of copper in industrial, environmental, biological and soil, samples using 2, 5-dimercapto 1, 3, 4-thiadiazole, Journal of Analytical Science and Technology, 18, 805-810, (2002).
5. Aliabadi, A., Eghbalian, E. and Kiani, A., Synthesis and evaluation of the cytotoxicity of a series of 1,3,4-thiadiazole based compounds as anticancer agents, Iranian Journal of Basic Medical Sciences, 16, 1133-1138, (2013).
6. Young, G. and Eyre, W., III. -Oxidation of benzalthiosemicarbazone, Journal of the Chemical Society, 79: 54-60, (1901).
7. Freund, M. and Meinecke, C., Uber derivate des thiobiazolins, Chemische Berichte, 29, 2511-2517, (1896).
8. Praphulla, C.G., Constitution of the so-called dithio-urazole of martin freund. ii. New methods of synthesis, isomerism and poly-derivatives, Journal of the American Chemical Society, 44 (7), 1510-1517, (1922).

9. Hamama, W.S., Gouda, M.A., Abd-El-Wahab, M.H. and Zoorob, H.H., Recent advances in the chemistry and synthetic uses of amino-1,3,4-thiadiazoles, Journal of Heterocyclic Chemistry, 51: 1558–1581, (2014).
10. Kuz'Mich, N.N., Lalaev, B.Y., Yakovlev, I.P., Semakova, T.L. and Zakhs, V.E., Thiobenzohydrazides and dithiocarbazates in the synthesis of new 1,3,4-thiadiazine and 1,3,4-thiadiazole derivatives, Russian Journal of General Chemistry, 79: 7: 1583–1584, (2009).
11. Young, R.W. and Wood, K.H., The cyclization of 3-acyldithiocarbazate esters, Journal of the American Chemical Society, 77 (2), 400-403, (1955).
12. Ainsworth, C., The condensation of aryl carboxylic acid hydrazides with orthoesters, Journal of the American Chemical Society, 77 (5): 1148-1150, (1955).
13. Gray, C.J. and Parker, R.C., The Synthesıs of an α-Azaornithine Derivative and its Reaction with Ttrypsin, Tetrahedron, 31, 2940-2943, (1975).
14. Guha, P.J., Ring closure of hydrazodithio- and -Monothio-Dicarbonamides with acetic anhydride, Journal of the American Chemical Society, 45, 1036, (1923).
15. Xuan, L., Song, Z., Yi-Ming, J., Guang-Zhao, L., Liang, J., Xiao, L., Qiu-Lei, X. and You-Xuan, Z., Syntheses, crystal structure and photophysical property of iridium complexes with 1,3,4-oxadiazole and 1,3,4-thiadiazole derivatives as ancillary ligands, Journal of Organometallic Chemistry, 785, 11-18, (2015).
16. Ruangchai, T., Siriporn, J. and Visit, V., Computational calculations of substitution pattern effects on the optical properties of benzobis (thiadiazole) derivatives as near-infrared-emitting organic compounds, Computational and Theoretical Chemistry, 1098, 31–40, (2016).
17. Tarek, A.M., Ahmed, E.H., Ibrahim, A.S., Ahmed, M.A. and Wajdi M.Z., Conformational stability, spectral analysis (infrared, Raman and NMR) and DFT calculations of 2-Amino-5-(ethylthio)-1,3,4-thiadiazole, Journal of Molecular Structure, 1130, 434-441, (2017).
18. Gür, M., Muğlu, H., Çavus M.S.¸ Güder, A., Sayıner, H.S. and Kandemirli, F., Synthesis, characterization, quantum chemical calculations and evaluation of antioxidant properties of 1,3,4-thiadiazole derivatives including 2- and 3-methoxy cinnamic acids, Journal of Molecular Structure, 1134, 40-50, (2017).
19. Gür, M., Şener, N., Muğlu, H., Çavus¸ M.S., Özkan, O.E., Kandemirli, F. and Şener, İ., New 1,3,4-thiadiazole compounds including pyrazine moiety: Synthesis, structural properties and antimicrobial features, Journal of Molecular Structure, 1139, 111-118, (2017).
20. Er, M., Isildak, G., Tahtaci, H. and Karakurt, T., Novel 2-amino-1,3,4-thiadiazoles and their acyl derivatives: Synthesis, structural characterization, molecular docking studies and comparison of experimental and computational results, Journal of Molecular Structure, 1110, 102-113, (2016).
21. Hohenberg, P. and Kohn, W., Inhomogeneous electron gas, Physical Review Letters, 136, B864–B871, (1964). Kohn, W. and Sham, L., Self-consistent equations including exchange and correlation effects, Physical Review Letters, 140, A1133–A1138, (1965).
22. Gaussian 09, Revision B.01, Frisch M. J.; Trucks G. W.; Schlegel H. B.; Scuseria G. E.; Robb M. A.; Cheeseman J. R.; Scalmani G.; Barone V.; Mennucci B.; Petersson G. A.; Nakatsuji H.; Caricato M.; Li X.; Hratchian H. P.; Izmaylov A. F.; Bloino J.; Zheng G.; Sonnenberg J. L.; Hada M.; Ehara M.; Toyota K.; Fukuda R.; Hasegawa J.; Ishida M.; Nakajima T.; Honda Y.; Kitao O.; Nakai H.; Vreven T.; Montgomery J. A.; Jr.; Peralta J. E.; Ogliaro F.; Bearpark M.; Heyd J. J.; Brothers E.; Kudin K. N.; Staroverov V. N.; Keith T.; Kobayashi R.; Normand J.; Raghavachari K.; Rendell A.; Burant J. C.; Iyengar S. S.; Tomasi J.; Cossi M.; Rega N.; Millam J. M.; Klene M.; Knox J. E.; Cross J. B.; Bakken V.; Adamo C.; Jaramillo J.; Gomperts R.; Stratmann R. E.; Yazyev O.; Austin A. J.; Cammi R.; Pomelli C.; Ochterski J. W.; Martin R. L.; Morokuma K.; Zakrzewski V. G.; Voth G. A.; Salvador P.; Dannenberg J. J.; Dapprich S.; Daniels A. D.; Farkas O.; Foresman J. B.; Ortiz J. V.; Cioslowski J.; Fox D. J., Gaussian, Inc., Wallingford CT, (2010).