A Computational Study on Some Pyridine-Substituted-Bis-1,2,4-Triazole Derivatives and Investigation of Their Catalytic Activities

Year 2020, Volume: 6 Issue: 2, 200 - 207, 31.12.2020

Ragip Adiguzel , Ebru Aktan , Enes Evren Ahmet Çetin

https://doi.org/10.29132/ijpas.789914

Cited By: 3

Abstract

In this work were specified catalytic activity of pyridine-substituted-bis-1,2,4-triazole (PBTT) derivative ligands 5,5′-(pyridine-2,5-diyl)bis(4-ethyl-4H-1,2,4-triazole-3-thiol) (L1) and 5,5′-(pyridine-2,5-diyl)bis(4-phenyl-4H-1,2,4-triazole-3-thiol) (L2) in biaryl synthesis in situ-reaction condition. Catalytic activities are determined in terms of conversion percentages to derivatives of biaryl of aryl bromides by GC-MS. The highest catalytic effect for L1 ligand was measured as 61% with 4-bromobenzaldehyde. Apart from catalytic activity studies, some structural properties of related ligands were discussed by computational methods. As a result, the ground state geometries, frontier molecular orbitals (FMOs) and also the maps of molecular electrostatic potential (MEP) of L1 and L2 ligands were obtained using DFT/B3LYP/6-31+G(d) calculations. Additionally, the global reactivity descriptors were reached using the FMOs calculations.

Keywords

Catalytic activity,, density-functional theory,, in situ-reaction condition,, pyridine-substituted-bis-1,2,4-triazole derivatives

Supporting Institution

Scientific Research Projects Coordination Unit

Project Number

MFTUB015-01

Bazı Piridin-Sübstitüe-Bis-1,2,4-Triazol Türevleri Üzerine Hesaplamalı Bir Çalışma ve Katalitik Aktivitelerinin İncelenmesi

Abstract

Bu çalışmada piridin-sübstitüe-bis-1,2,4-triazol türevi (PBTT) ligandlarının (L1: 5,5′-(piridin-2,5-diil)bis(4-etil-4H-1,2,4-triazol-3-tiyol) ve L2: 5,5′-(piridin-2,5-diil)bis(4-fenil-4H-1,2,4-triazol-3-tiyol)) biaril sentezinde in situ-reaksiyon koşullarında katalitik aktiviteleri belirlendi. Katalitik aktiviteler, GC-MS ile aril bromürlerin biaril türevlerine dönüşüm yüzdeleri cinsinden belirlendi. L1 ligandı için en yüksek katalitik etki 4-bromobenzaldehit ile %61 olarak ölçüldü. Katalitik aktivite çalışmalarının yanı sıra, ilgili ligandların bazı yapısal özellikleri hesaplama yöntemleriyle tartışıldı. Sonuç olarak, DFT/B3LYP/6-31+G(d) hesaplamaları kullanılarak L1 ve L2 ligandlarının temel durum geometrileri, sınır moleküler orbitalleri (FMOs) ve ayrıca moleküler elektrostatik potansiyel (MEP) haritaları elde edildi. Ek olarak, global reaktivite tanımlayıcıları FMOs hesaplamaları kullanılarak elde edildi.

Keywords

Katalitik aktivite, Yoğunluk fonksiyonal teorisi, In situ-reaksiyon koşulları, Piridin-sübstitüe-bis-1,2,4-triazol türevleri

Project Number

MFTUB015-01

References

• Ahirwar, J., Ahirwar, D., Lanjhiyana, S., Jha, A.K., 2017. Synthesis and characterization of 1,2,4-triazole- pyridine hybrids as potential antimicrobial, agents. International Journal of Pharmaceutical and Clinical Research, 9(12):702-709.
• Bulut, N., Kocyigit, U.M, Gecibesler, I.H., Dastan, T., Karci, H., Taslimi, P., Dastan, S.D., Gulcin I., Cetin, A., 2018. Synthesis of some novel pyridine compounds containing bis-1,2,4-triazole/ thiosemicarbazide moiety and investigation of their antioxidant properties, carbonic anhydrase, and acetyl cholinesterase enzymes inhibition profiles. Journal of Biochemical and Molecular Toxicology, 32(1), Article Number: e22006.
• Cansız, A., Çetin, A., Kutulay, P., Koparir, M., 2009. Synthesis of tautomeric forms of 5-(2-hydroxyphenyl)-4-substituted-3H-1,2,4-triazole-3-thione. Asian Journal of Chemistry, 21(1):617-626.
• Çetin, A., Dayan, O., 2009. Transfer hydrogenation of acetophenone catalyzed by in situ generated 2,6-bis(5-thioxo-4,5-dihydro-1,2,4-triazole-3-yl)pyridine -ruthenium(II) complexes. Chinese Journal of Chemistry, 27,1-10.
• Coyanis, E.M.; Vedova, D.C.O.; Haas, A.; Winter, M., 2002. Preparation, characterization and thiol–thione tautomeric studies of 2-thiono-4-methyl-5-(2,2,2-trifluoro-1-trifluoromethylethyl)-1,3-thiazoline. Journal of Fluorine Chemistry, 117:185-192.
• Dege, N., Andac, O., Cansız, A., Çetin, A., Şekerci, M., Dinçer, M., 2004. 5-(Furan-2-yl)-4-(p-tolyl)-2, 4-dihydro-1, 2,4-triazole-3-thione. Acta Crystallographica Section E: Structure Reports Online 60(8):o1405-o1407.
• Dege, N., Özdemir, N., Çetin, A., Cansız, A., Şekerci, M., Dinçer, M., 2005. 4-Ethyl-5-(2-hydroxyphenyl)-2H-1,2,4-triazole-3(4H)-thione. Acta Crystallographica Section E: Structure Reports Online 61(1):o17-o19.
• Frisch, M.J., et al., 2010. Gaussian 09, Revision C.01, Gaussian, Inc., Wallingford CT.
• Grabowski S.J., Leszczynski, J., 2006. Unrevealing the nature of hydrogen bonds: p-electron delocalization shapes H-bond features, S. J. Grabowski (Ed.): Hydrogen Bonding, New Insights. Kluwer Academic Publishers, New York, p. 491-495.
• Gündüzalp, A.B., Parlakgümüş, G., Uzun, D., Özdemir Özmen, Ü., Ozbek, N., Sarı, M., Tunç, T., 2016. Carbonic anhydrase inhibitors: Synthesis, characterization and inhibition activities of furan sulfonylhydrazones against carbonic anhydrase I (hCA I). Journal of Molecular Structure, 1105:332-340.
• İnce, S., 2016. Synthesis of new secondary amine benzoylthiourea ligand derivatives: Investigation of catalytic activity in Pd catalyzed Suzuki cross coupling reactions, MSc. Thesis, Science Institute of Mersin University, Mersin, Turkey.
• Muneer, C.P., Shalina, B.T., Shafi, P. M., 2014. Synthesis characterization and antioxidant study of a few 3-substituted1,2,4-triazole-5-thiones and their derivatives. International Journal of Chemical Science, 12(1):129-135.
• Muthal, N., Ahirwar Jyoti, J., Ahriwar, D., Masih Pankaj, P., Mahmdapure T., Sivakumar, T., 2010. Synthesis, antimicrobial and anti-inflammatory activity of some 5-substituted-3-pyridine-1,2,4-triazoles. International Journal of PharmTech Research. 2(4):2450-2455.
• Özdemir, İ., Gök, Y., Gurbuz N., Çetinkaya, B., 2007. Benzimidazolylidene carbene ligated palladium catalysis of the Heck reaction in aqueous media. Turkish Journal of Chemistry, 31(4):397-402.
• Özdemir Özmen, Ü., Aktan, E., İlbiz, F., Gündüzalp, A.B., Ozbek, N., Sarı, M., Çelik, Ö., Saydam, S., 2014. Characterization, antibacterial, anticarbonic anhydrase II isoenzyme, anticancer, electrochemical and computational studies of sulfonic acid hydrazide derivative and its Cu(II) complex. Inorganica Chimica Acta, 423:94-203.
• Özdemir Özmen , Ü., Özbek, N., Genç, Z.K., İlbiz F., Gündüzalp, A.B., 2017. New bioactive silver(I) complexes: Synthesis, characterization, anticancer, antibacterial and anticarbonic anhydrase II activities. Journal of Molecular Structure, 1138:5-63.
• Tomasi, J., Mennucci, B., Cammi, R., 2005. Quantum mechanical continuum solvation models. Chemical Reviews, 105(8):2999- 3094.
• Turek, J., Panov, I., Semler, M., Štěpnička, P., Proft, F.D., Z. Padělková Z., Růžička, A., 2014. Palladium(II) complexes of 1,2,4-triazole-based N‑heterocyclic carbenes: synthesis, structure, and catalytic activity. Organometallics, 33(12):3108-3118.
• Yiğit, B., Yiğit, M., Özdemir, İ., Çetinkaya, E., 2010. The synthesis of some benzimidazolium salts and use as carbene precursors in the Heck and Suzuki reactions. Heterocycles, 81:943-953.