Theoretical Study on Molecular Structure and Electronic Properties of New 1,3-Diaza-adamantan-6-ones Derivatives

https://doi.org/10.22146/ijc.44403

Haithem Abdulhasan(1), Ahmed Al-Yasari(2*), Rahman Alasadi(3)

(1) University of Kerbala, P.O. Box 1125, Kerbala, Iraq
(2) University of Kerbala, P.O. Box 1125, Kerbala, Iraq
(3) University of Kerbala, P.O. Box 1125, Kerbala, Iraq
(*) Corresponding Author

Abstract


In this study, the structural geometry and vibrational frequencies (IR) of 1,3-Diaza-adamantane-6-ones derivatives including Adamantane (A), 1,3-Diaza-adamantan (D), 1,3-Diaza-adamantan-6-one (DO), 5-Benzyl-1,3-diaza-adamantan-6-one (BD), 5-(4-Hydroxybenzyl)-1,3-diaza-adamantan-6-one (HBD), 5-(4-Methoxybenzyl)-1,3-diaza-adamantan-6-one (MBD), and 5-(4-Hydroxy-3-methoxybenzyl)-1,3-diaza-adamantan-6-one (HMBD) were theoretically studied. In addition, molecular orbital energies, including the highest occupied molecular orbitals (HOMOs), and lowest unoccupied molecular orbitals (LUMOs), and electronic properties of the titled molecules were theoretically studied using the computational method. Optimized molecular structures were obtained by DFT method with the hybrid B3LYP functional at a relatively small basis set of 6-31G. The calculated vibrational wavenumbers were obtained using the same level of the theory mentioned above. The contributions to the molecular orbitals of adamantane and substituted-phenyl groups in the title compounds were determined. Moving from A to HMBD, a decrease in the value of LUMO and total energy are noticed, while an increase in the value of HOMO is noted. These findings are supported by the decreasing in the EHOMO-LUMO gap values. Furthermore, a decrease in the value of ionization potential (IP) is obtained, while an increase in the electronegativity (EA) is observed.


Keywords


Adamantane; 1,3-Diaza-adamantan; DFT/B3LYP

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References

[1] Štimac, A., Šekutor, M., Mlinarić-Majerski, K., Frkanec, L., and Frkanec, R., 2017, Adamantane in drug delivery systems and surface recognition, Molecules, 22 (2), 297.

[2] Savel’eva, S.A., Leonova, M.V., Baimuratov, M.R., and Klimochkin, Y.N., 2018, Synthesis and transformations of aryl-substituted alkenes of the adamantane series, Russ. J. Org. Chem., 54 (7), 996–1002.

[3] Ivleva, E.A., Tkachenko, I.M., and Klimochkin, Y.N., 2017, Synthesis of adamantane functional derivatives basing on N-[(adamantan-1-yl)alkyl]acetamides, Russ. J. Org. Chem., 52 (11), 1558–1564.

[4] Suslov, E., Zarubaev, V.V., Slita, A.V., Ponomarev, K., Korchagina, D., Ayine-Tora, D.M., Reynisson, J., Volcho, K., and Salakhutdinov, N., 2017, Anti-influenza activity of diazaadamantanes combined with monoterpene moieties, Bioorg. Med. Chem. Lett., 27 (19), 4531–4535.

[5] Hickmott, P.W., Wood, S., and Murray-Rust, P., 1985, Introduction of pharmacophoric groups into polycyclic systems. Part 3. Amine derivatives of adamantane and diaza-adamantane, J. Chem. Soc., Perkin Trans. 1, 0, 2033–2038.

[6] Vrynchanu, N.A., Sergienko, O.V., and Maksimov Yu, N., 2009, Research of some sides of antifungal activity mechanism act of new adamantane derivative, Морфологія, 3 (2), 24–27.

[7] Schwertfeger, H., Fokin, A.A., and Schreiner, P.R., 2008, Diamonds are a chemist's best friend: Diamondoid chemistry beyond adamantane, Angew. Chem. Int. Ed., 47 (6), 1022–1036.

[8] Gunawan, M.A., Hierso, J.C., Poinsot, D., Fokin, A.A., Fokina, N.A., Tkachenko, B.A., and Schreiner, P.R., 2014, Diamondoids: Functionalization and subsequent applications of perfectly defined molecular cage hydrocarbons, New J. Chem., 38 (1), 28–41.

[9] Karthik, G., Sundaravadivelu, M., Rajkumar, P., and Manikandan, M., 2014, Diaza-adamantane derivatives as corrosion inhibitor for copper in nitric acid medium, Res. Chem. Intermed., 41 (10), 7593–7615.

[10] Arutyunyan, G.L., Paronikyan, R.V., Saakyan, G.S., Arutyunyan, A.D., and Gevorkyan, K.A., 2008, Synthesis and reactions of polyhedral compounds. 29. Synthesis and antibacterial activity of 1,3-diazaadamantane derivatives, Pharm. Chem. J., 42 (1), 18–22.

[11] Arutyunyan, G.L., Dzhagatspanyan, I.A., Nazaryan, I.M., Akopyan, A.G., and Arutyunyan, A.D., 2007, Synthesis and conversions of polyhedral compounds: 28. Synthesis and psychotropic activity of some 1,3-diazaadamantane derivatives, Pharm. Chem. J., 41 (11), 591–593.

[12] Sharabi-Ronen, Y., Levinger, S., Lellouche, M.B., and Albeck, A., 2014, Anti-neoplastic activity of 1,3-diaza-2-functionalized-adamantan-6-one compounds against melanoma cells, Med. Chem., 10 (1), 27–37.

[13] Kuznetsov, A.I., Alasadi, R.T., Senan, I.M., and Serova, T.M., 2014, Synthesis of fragrant 1,3-diazaadamantan-6-ones, Russ. Chem. Bull., 63 (9), 2195–2197.

[14] Gordon, M.S., and Schmidt, M.W., 2005, “Advances in electronic structure theory: GAMESS a decade later” in Theory and Applications of Computational Chemistry: The first forty years, Eds., Dykstra, C., Frenking, G., Kim, K., and Scuseria, G., 1st Ed., Elsevier Science, Amsterdam, 1167–1189.

[15] Becke, A.D., 1993, A new mixing of Hartree–Fock and local density‐functional theories, J. Chem. Phys, 98 (2), 1372.

[16] Fernández, M.J., Gálvez, E., Lorente, A., Camuñas, J.A., Sanz, J., and Fonseca, I., 1990, Synthesis, structural and conformational study of 6‐hydroxy (or acyloxy) derivatives of the 1,3‐dimethyl‐1,3‐diazoniatricyclo[3.3.1.13–7]decane system, J. Heterocycl. Chem., 27 (5), 1355–1359.

[17] Hanwell, M.D., Curtis, D.E., Lonie, D.C., Vandermeersch, T., Zurek, E., and Hutchison, G.R., 2012, Avogadro: An advanced semantic chemical editor, visualization, and analysis platform, 2012, J. Cheminform., 4 (1), 17.

[18] Jiménez-Cruz, F., Ríos-Olivares, H., and Gutiérrez, J.L.G., 2005, “Molecular structure in 1-azaadamantanes and 1,3-diazaadamantanes” in Structural Analysis of Cyclic Systems, Eds., Iriepa, I., Research Signpost, Trivandum, India, 101–125.

[19] Parr, R.G., Donnelly, R.A., Levy, M., and Palke, W.E., 1978, Electronegativity: The density functional viewpoint, J. Chem. Phys., 68 (8), 3801.

[20] Figueredo, S., Páez, M., and Torresbc, F., 2019, The electrophilic descriptor, Comput. Theor. Chem., 1157, 34–39.



DOI: https://doi.org/10.22146/ijc.44403

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