Inorganic Chemistry Research

Synthesis, DFT calculations and catalytic activity in the Biginelli reaction of two hydrazone Cu(II) complexes

Document Type : Research Paper

Authors

Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran

10.22036/icr.2022.336558.1127

Abstract

In this work, two Cu(II) complexes containing 5-amino-1-R-1H-benzimidazol-4-yl)(4-chloro)phenylmethanone hydrazones ligands were synthesized and their spectral characterization, DFT calculations, and catalytic activity were reported. New heterocyclic hydrazone ligands were prepared by the reaction of o-amino-ketones with hydrazine hydrate in high yield. Structural assignments of new compounds were based on their microanalytical and spectral data and formula [Cu(L)2(H2O)2](SO4) was suggested for complexes. Moreover, to gain a further insight into the geometry of synthesized complexes, the DFT calculations were carried out at the B3LYP/6-311+G(d,p) level of theory. The catalytic activity of Cu(II) complexes as heterogeneous catalysts were also investigated in the synthesis of biologically active compound 3,4-dihydropyrimidin-2(1H)-one C5 ester, via classical Biginelli reaction followed by trans-esterification reaction. The results confirmed that the current method formed the products at the lower reaction time and high yields, which might as a result of the enhanced reactivity of the reactants on the surface sites of Cu(II) complexes.

Graphical Abstract

Synthesis, DFT calculations and catalytic activity in the Biginelli reaction of two hydrazone Cu(II) complexes

Keywords

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    1. González-Hernández, R. Aparicio, M. Garayoa, M. Montero, M. Sevilla, C. Pérez-Melero, Med. Chem. Comm. 2019, 10, 1589-1598.
    2. Thipparapu, R. Ajumeera, V. Venkatesan, In Silico Pharmacol. 2017, 5, 1-9.
    3. Chioua, E. Buzzi, I. Moraleda, I. Iriepa, M. Maj, A. Wnorowski, C. Giovannini, A. Tramarin, F. Portali, L. Ismaili, P. López-Alvarado, M. Bolognesi, K. Jóźwiak, J. Menéndez, J. Marco-Contelles, M. Bartolini, Eur. J. Med. Chem. 2018, 155, 839-846.
    4. Majellaro, W. Jespers, A. Crespo, M. Núñez, S. Novio, J. Azuaje, R Prieto-Díaz, C. Gioé, B. Alispahic, J. Brea, M. Loza, M. Freire-Garabal, C. Garcia-Santiago, C. Rodríguez-García, X. García-Mera, O. Caamaño, C. Fernandez-Masaguer, J. Sardina, A. Stefanachi, A. El Maatougui, A. Mallo-Abreu, J. Åqvist, H. Gutiérrez-de-Terán, E. Sotelo, J. Med. Chem. 2020, 64, 458-480.
    5. Ehsani-Nasab, A. Ezabadi, Comb. Chem. High Throughput Screen. 2020, 23, 157-67.
    6. Shen, M. Xu, D. Yin, S. Xie, C. Zhou, F. Li, Catal. Commun. 2016, 77, 18-21.
    7. Phukan, M. Kalita, R. Borah, Green Chem. Lett. Rev. 2016, 3, 329-34.
    8. Bebout, A. DeLanoy, D. Ehmann, M. Kastner, D. Parrish, R. Butcher, Inorg. Chem. 1998, 37, 2952-2959.
    9. Sheykhan, A. Yahyazadeh, Z. Rahemizadeh, RSC Advances 2016, 6, 34553-34563.
    10. Kumar Kundu, V. Chhabra, N. Malviya, R. Ganguly, G. Mishra, S. Mukhopadhyay, Microporous Mesoporous Mater. 2018, 271, 100-117.
    11. Ziegler, K. Lakshmi, T. Tilley, Organometallics 2017, 36, 2116-2125.
    12. Li, K. Zhou, Z. Wen, S. Cao, X. Shen, M. Lei, L. Gong, J. Am. Chem. Soc. 2018, 140, 15850-15858.
    13. Popov, A. Morozov, I. Shcherbakov, Y. Tupolova, V. Lukov, V. Kogan, Usp. Khim., 2009, 78, 697-702.
    14. Alexeev, B. Kharisov, T. García, A. Garnovskii, Coord. Chem. Rev. 2010, 254, 794-798.
    15. Lobana, R. Sharma, G. Bawa, S. Khanna, Coord. Chem. Rev. 2009, 253, 977-1055.
    16. M. Stadler, J. Harrowfild, Inorg. Chim. Acta, 2009, 362, 4298-4314.
    17. Kogan, V. Lukov, I. Shcherbakov, Koord. Khim., 2010, 36, 401-429.
    18. Starikov, V. Kogan, V. Lukov, V. Minkin, R. Minyaev, 2009, 35, 625.
    19. A. Kogan, S. I. Levchenkov, L. D. Popov, I. N. Shcherbakov, Ross. Khim. Zh., 2009, 53, 86.
    20. Uraev, I. Vasilchenko, V. Ikorskii, T. Shestakova, A. Burlov, K. Lyssenko, V. Vlasenko, T. Kuz’menko, L. Divaeva, I. Pirog, G. Borodkin, I. Uflyand, M. Antipin, V. Ovcharenko, A. Garnovskii, V. Minkin, Mendeleev Commun., 2005, 15, 133-135.
    21. Burlov, V. Ikorskii, S. Nikolaevskii, Y. Koshchienko, V. Vlasenko, Y. Zubavichus, A. Uraev, I. Vasil’chenko, D. Garnovskii, G. Borodkin, A. Garnovskii, Curr. Org. Synth. 2008, 14, 40-60.
    22. Ghaemi, M. Pordel, Chem. Heterocycl. Compd. 2016, 52, 52-57.
    23. Rastegarnia, M. Pordel, S. Allameh, Arab. J. Chem. 2020, 13, 3903-3909.
    24. Rahimizadeh, M. Pordel, M. Bakavoli, S. Rezaeian, H. Eshghi, Can. J. Chem. 2009, 87, 724-728.
    25. C. Vosburgh, G. R. Cooper, J. Am. Chem. Soc. 1941, 63, 437-442.
    26. Alikhani, M. Pordel, S. A. Beyramabadi, Indian J. Heterocycl. Chem. 2019, 29, 311-318.
    27. Nagarajaiah, A. Mukhopadhyay, J. N. Moorthy, Catal. Commun. 2016, 8, 179-182.
    28. R., Kalita, P. Phukan, Catal. Commun. 2007, 8, 179-182.
    29. Patil, S. D. Jadhav, S. Y. Mane, Int. J. Org. Chem. 2011, 1, 125.
    30. V. Chopda, P. N. Dave, ChemistrySelect 2020, 5, 5552-5572.
    31. S. Diarjani, F. Rajabi, A. Yahyazadeh, A. R. Puente-Santiago, R. Luque Materials. 2018, 11, 2458
    32. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian 03, Revision A.1, Gaussian In, PA, 2003.
    33. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1998, 37, 785.
    34. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270-283.
    35. R. Cammi, J. Tomasi, J. Comput. Chem. 1995, 16, 1449-1458.
Inorganic Chemistry Research
Volume 6, Issue 1
Spring and Summer; Special Issue: In Memory of Prof. Mehdi Rashidi
2022
Pages 69-75
  • Receive Date: 08 April 2022
  • Revise Date: 11 May 2022
  • Accept Date: 15 May 2022
  • First Publish Date: 27 May 2022