5-Merkapto-2-(3-metil-tiyofen-2-il-metilidenamino)-1,3,4-tiyadiazol Bileşiğinin Sentezi, Karakterizasyonu ve DFT Hesaplamaları

Year 2019, , 411 - 418, 25.08.2019

Murat Beytur , Onur Akyıldırım , Özlem Aktaş Yokuş

https://doi.org/10.19113/sdufenbed.500767

Abstract

5-Merkapto-2-(3–metil–tiyofen-2–il-metiliden-amino)-1,3,4-tiyadiazol bileşiği
sentezlenmiş ve IR, 1H-NMR ve 13C-NMR spektroskopik
yöntemleri ile karakterize edilmiştir. Sentezlenen bileşiğin geometrik
optimizasyonu Gaussian G09W yazılımı kullanılarak DFT/B3LYP yöntemi ve
6-311G+(d,p) temel seti yapılmıştır. Elde edilen optimize yapıdan molekülün
geometrik yapıları, titreşim dalga sayıları, 1H ve 13C
nükleer manyetik rezonans kimyasal kayma değerlerinin kuantum kimyasal
hesaplamaları elde edilmiştir. Bu değerler ile deneysel spektroskopik değerler
karşılaştırılmıştır. Teorik değerlerin deneysel değerleri desteklediği
gözlemlenmiştir. İlaveten, ilgili bileşiğin, çizgisel olmayan optik
özellikleri; tek nokta enerji hesabında polar hesapları yapılarak
polarizebilite ve hiperpolarizebilite değerleri hesaplanmıştır. Son olarak,
Mulliken atomik yükleri, HOMO-LUMO enerjileri, dipol momentleri, toplam
enerjileri, iyonlaşma potansiyeli, elektron ilgisi, moleküler yumuşaklık,
moleküler sertlik ve elektronegatifliği aynı metotlar ve aynı set kullanılarak
hesaplanmıştır.

Keywords

B3LYP, GIAO, Tiyadiazol, Polarizebilite, Hiperpolarizebilite, 6-311G+(d.p)

Synthesis, Characterization and DFT Calculations of 5-Mercapto-2-(3-methylthiophene-2-yl-methylidenamino)-1,3,4-thiadiazole

Abstract

5-Mercapto-2-(3-methyl-thiophene-2-yl-methylidenamino)-1,3,4-thiadiazole
compound was synthesized, and it was characterized by IR, ¹H-NMR
and ¹³C-NMR spectroscopic methods. Geometrical optimization of the
synthesized compound was carried out by DFT/B3LYP method and 6-311G+(d,p)basic
sets by using Gaussian GO9W computer software. From the optimized structure,
the geometric structures of the molecule, vibration wave numbers, quantum
chemical calculations of ¹H and ¹³C nuclear magnetic
resonance chemical shift values were obtained. These values were compared with
experimental spectroscopic values. It was observed that theoretical values
support the experimental values. Additionally, polarizability and hyperpolarizability
values of non-linear optical characteristic of the related compounds were
calculated using polar calculations in single point energy account. Finally,
Mulliken atomic charges, HOMO-LUMO energies, dipol moments, total energies,
ionization potential, electron information, molecular softness, molecular stiffness
and electronegative characteristics were calculated by using the same methods
and same sets.

Keywords

B3LYP, GIAO, Thiadiazole, Polarizability, Hyperpolarizability, 6-311G+(d.p)

References

• [1] Gür, M., Muglu, H., Çavus, M. S., Güder, A., Sayıner, H. S., Kandemirli, F. 2017. Synthesis, Characterization, Quantum Chemical Calculations and Evaluation of Antioxidant Properties of 1,3,4-Thiadiazole Derivatives İncluding 2- and 3-Methoxy Cinnamic Acids. Journal of Molecular Structure. 1134, 40-50.
• [2] Gür, M., Şener, N., Muglu, H., Çavus, M. S., Ozkan, O. E., Kandemirli, F., Şener, İ. 2017. New 1,3,4-Thiadiazole Compounds İncluding Pyrazine Moiety: Synthesis, Structural Properties and Antimicrobial Features, Journal of Molecular Structure. 1139, 111-118.
• [3] Yang, S. J., Lee, S. H., Kwak, H. J., Gong Y. D. 2013. Regioselective Synthesis of 2-Amino-Substituted 1,3,4-Oxadiazole and 1,3,4-Thiadiazole Derivatives via Reagent-Based Cyclization of Thiosemicarbazide Intermediate, The Journal of Organic Chemistry. 78 (2), 438-444.
• [4] Farghaly, T. A., Abdallah, M. A., Masaret, G. S., Muhammad Z. A. 2015. New and Efficient Approach for Synthesis of Novel Bioactive [1,3,4] Thiadiazoles İncorporated with 1,3-Thiazole Moiety, European Journal of Medicinal Chemistry. 97, 320-333.
• [5] Gür, M., Şener, N., Kaştas, Ç. A., Ozkan, O. E., Muğlu, H., Elmaswaria, M. A. M. 2017. Synthesis and Characterization of Some New Heteroaromatic Compounds Having Chirality Adjacent to a 1,3,4-Thiadiazole Moiety and Their Antimicrobial ActivitiesJournal of Heterocyclic Chemistry. 54 (6), 3578-3590.
• [6] Aliabadi, A., Eghbalian, E., Kiani, A. 2013. 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.
• [7] Mohammadi-Farania, A., Heidarian, N., Aliabadi, A. N. 2014. N-(5-Mercapto-1,3,4-Thiadiazol-2-yl)-2-Phenylacetamide Derivatives: Synthesis and in-vitro Cytotoxicity Evaluation as Potential Anticancer Agents, Iranian Journal of Pharmaceutical Research. 13 (2), 487-492.
• [8] Kaur, H., Kumar, S., Vishwakarma, P., Sharma, M., Saxena, K. K., Kumar, A. 2010. Synthesis and Antipsychotic and Anticonvulsant Activity Of Some New Substituted oxa/thiadiazolylazetidinonyl/thiazolidinonyl carbazoles, European Journal of Medicinal Chemistry. 45, 2777-2783.
• [9] Bhatia, R., Sharma, A., Kaundal, A. A. 2014, Review on 1, 3, 4-Thiadiazole Derivatives, Indian Journal of Pharmaceutical Sciences. 4 (3), 165-172.
• [10] Gupta, J. K., Yadav, R. K., Dudhe, R., Sharma, P. K. 2010. Recent Advancements in the Synthesis and Pharmacological Evaluation of Substituted 1,3,4-Thiadiazole Derivatives, International Journal of PharmTech Research. 2, 1493-1507.
• [11] Yar, M. S., Akhter, M. W. 2009. Synthesis and Anticonvulsant Activity of Substituted Oxadiazole and Thiadiazole Derivatives, Acta Poloniae Pharmaceutica. Drug Research. 66 (4), 393-397.
• [12] Hafez, H. N., Hegab, M. I., Ahmed-Farag, I. S., El-Gazzar, A. B. A. 2008. A Facile Regioselective Synthesis of Novel Spiro-Thioxanthene and Spiro-Xanthene-90,2-[1,3,4] Thiadiazole Derivatives as Potential Analgesic and Anti-İnflammatory Agents, Bioorganic & Medicinal Chemistry. 18, 4538-4543.
• [13] Poorrajab, F., Ardestani, S. K., Emani, S., Behrouzi-Fardmoghadam, M., Shafiee, A., Foroumadi, A. 2009. Nitroimidazolyl-1,3,4-thiadiazole-Based Antileishmanial Agents: Synthesis and in vitro Biological Evaluation, European Journal of Medicinal Chemistry. 44, 1758-1762.
• [14] Balaji, K., Bhatt, P., Mallika, D., Jha, A. 2015. Design, Synthesis and Antimicrobial Evaluation of Some Mannich Base Derivative of 2(2-Substituted)-5-aminothiadiazoles, International Journal of Pharmacy and Pharmaceutical Sciences. 7 (11), 145-149.
• [15] Gomha, S. M., Kheder, N. A., Abdelhamid, A. O., Mabkhot, Y.N. 2016. One Pot Single Step Synthesis and Biological Evaluation of Some Novel Bis(1,3,4-Thiadiazole) Derivatives as Potential Cytotoxic Agents, Molecules. 21, 1532.
• [16] Pattan, S. R., Kekare, P., Dighe, N. S., Nirmal, S. A., Musmade, D. S., Parjane, S. K., Daithankar, A. V. 2009. Synthesis and Biological Evaluation of Some 1,3,4-Thiadiazoles, Journal of Chemical and Pharmaceutical Research. 1 (1), 191-198.
• [17] Asif, K. A., Himaja, M., Sunil, M. V., Jagadeesh, K. P., Sikarwar, M. S. 2011. One-Pot Synthesis and Antitubercular Activity of 2-Amino-5-Aryl-5H-Thiazolo [4,3-B]-1,3,4-Thiadiazoles, International Research Journal of Pharmacy. 2 (1), 153-158.
• [18] Balaji, K., Bhatt, P., Mallika, D., Jha, A. 2015. Design, Synthesis and Antimicrobial Evaluation of Some Mannich Base Derivative of 2(2-Substituted)-5-aminothiadiazoles, International Journal of Pharmacy and Pharmaceutical Sciences. 7 (11), 145-149.
• [19] Zhao, H. C., Shi, Y. P., Liu, Y. M., Li, C. W., Xuan, L. N. Wang, P., Zhang, K., Chen B. Q. 2013. Synthesis and antitumor-evaluation of 1,3-selenazole-containing 1,3,4-thiadiazole derivatives, Bioorganic & Medicinal Chemistry Letters. 23, 6577-6579.
• [20] 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., Vreven, T.Jr., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, N., Staroverov, V. N., 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. J., Ochterski, W., Martin, L. R., 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., and Fox, D. J., 2009. Gaussian Inc. (Wallingford, CT).
• [21] Keith, T., Millam, J. 2009. GaussView, Version 5, R Dennington, Semichem Inc, Shawnee Mission, KS.
• [22] Becke, A. D. 1993. Density-functional thermochemistry. III. The role of exact Exchange, The Journal of Chemical Physics. 98, 5648.
• [23] Lee, C., Yang, W., Parr, R. G. 1988. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Physical Review B .37, 785.
• [24] Jamroz, M. H. 2004. Vibrational Energy Distribution Analysis VEDA4 (Warsaw).
• [25] Jamroz, M. H., Dobrowolski, J. C. 2001. Potential energy distribution (PED) analysis of DFT calculated IR spectra of the most stable Li, Na, and Cu(I) diformate molecules, Journal of Molecular Structure. 475, 565-566.
• [26] London, F. 1937. The quantic theory of inter-atomic currents in aromatic combinations, Journal de Physique et Le Radium. 8. 397-409.
• [27] McWeeny, R. 1962. Perturbation Theory for Fock-Dirac Density Matrix, Physical Review. 126. 1028.
• [28] Wolinski, K., Hilton, J. F. Pulay, P. 1990. Efficient Implementation of the Gauge-Independent Atomic Orbital Method for NMR Chemical Shift Calculations, Journal of the American Chemical Society. 112. 8251-8260.
• [29] Cheeseman, J. R., Trucks, G. W., Keith, T. A., Frisch, M. J. 1996. A Comparison of Models for Calculating Nuclear Magnetic Resonance Shielding Tensors, The Journal of Chemical Physics. 104. 5497-5509.
• [30] Avcı, D., Başoglu, A., Atalay, Y. 2009. Theoretical analysis of vibrational spectra and scaling-factor of 2-aryl-1,3,4-oxadiazole derivatives, International Journal of Quantum Chemistry. 109, 328-341.
• [31] Dege, N., Şenyüz, N., Batı, H., Günay, N., Avcı, D., Tamer, Ö., Atalay, Y. 2014. The synthesis, characterization and theoretical study on nicotinic acid [1-(2,3-dihydroxyphenyl) methylidene]hydrazide, Spectrochimica Acta Part A. 120, 323-331.
• [32] Tamer, Ö., Avcı, D., Atalay, Y. 2014. Calculations of electronic structure and nonlinear optical parameters of 4-methoxybenzaldehyde-N-methyl-4-stilbazolium tosylate, Journal of Applied Spectroscopy. 80, 971-982.
• [33] Tao, Y., Han, L., Han, Y., Liu, Z. 2015. Experimental and theoretical studies on the vibrational spectra of trans-3-phenylacryloyl chloride, Spectrochimica Acta Part A. 137, 892-898.
• [34] Koşar, B., Albayrak, C. 2011. Spectroscopic investigations and quantum chemical computational study of (E)-4-methoxy-2-[(p-tolylimino)methyl]phenol, Spectrochimica Acta Part A. 78, 160-167.
• [35] Pearson, R. G., 1986. Absolute electronegativity and hardness correlated with molecular orbital theory, in: Proceeding of the National Academy of Sciences, 83, 8440-8441.
• [36] Jamróz, M. H. 2004. Vibrational energy distribution analysis: VEDA 4 program, Warsaw.
• [37] Demir, S., Dincer, M., Cukurovali, A., Yilmaz, I. 2016. Synthesis, characterization, and theoretical studies on N’-furan-2ylmethylene-N-[4-(3-methyl-3-phenylcyclobutyl)-thiazol-2-yl]-chloro-acetic acid hydrazide, Molecular Crystals and Liquid Crystals. 629 (1), 44-60.
• [38] Foresman, J. B., Frisch, E., 1993. Exploring Chemistry with Electronic Structure Methods, Gaussian Inc, Pittsburgh, PA, USA.
• [39] Pihlaja, K., Kleinpeter, E. 1994. Carbon-13 NMR Chemical Shifts in Structural and Sterochemical Analysis, VCH Publishers, Deerfield, Beach.
• [40] Kalinowski, H. O., Berger, S., Braun, S. 1988. Carbon-13 NMR Spectroscopy, John Wiley & Sons, Chichester.
• [41] Avcı, D., Cömert, H., Atalay, Y. 2008. Ab initio Hartree-Fock calculations on linear and second-order nonlinear optical properties of new acridinebenzothiazolylamine chromophores, Journal of Molecular Modeling. 14, 161-169.
• [42] Turhan Irak Z, Gümüş S, 2017. Heterotricyclic compounds via click reaction: A computational study. Noble International Journal of Scientific Research, 1(7), 80-89.
• [43] Mulliken RS, 1955. Electronic population analysis on LCAO–MO molecular wave functions. Journal of Chemical Physics, 23: 1833–1840.
• [44] Reed, A. E., Weinstock, R. B., Weinhold, F. 1985. Natural population analysis. The Journal of Chemical Physics, 735.
• [45] Reed, A. E., Weinhold, F. 1985. Natural localized molecular orbitals. The Journal of Chemical Physics, 1736.
• [46] Reed, A. E., Curtiss, L. A., Weinhold, F. 1988. Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chemical Reviews. 899.
• [47] Scrocco, E., Tomasi, J. 1979. Electronic molecular structure, reactivity and intermolecular forces: an heuristic interpretation by means of electrostatic molecular potentials, Advances in Quantum Chemistry. 11, 115-193.