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One-pot synthesis of ferrocenyl-pyrimidones using a recyclable molibdosilicic H4SiMo12O40 heteropolyacid

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Abstract

A series of ferrocene-containing dihydropyrimidines (DHPs) were prepared by the one-pot Biginelli reaction of formylferrocene, 1,3-dicarbonyl component and urea/thiourea. The reaction was catalyzed by a commercial Keggin heteropolyacid (H4SiMo12O40) as a safe, clean and recyclable catalyst. Three different synthetic protocols were examined in order to improve the yields of the reaction and to elucidate its mechanism. Intermediates of the competitive Knoevenagel reaction were also isolated. The methodology is operationally simple and provides access to highly substituted dihydropyrimidines containing ferrocene in very good yields. The catalyst can be used and recycled without appreciable loss of the catalytic activity.

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Notes

  1. 8: 1H NMR (CDCl3): 7.48 (1H, s, =CH), 4.46 (2H, m, 2′ and 5′), 4.42 (m, 3′ and 4′), 4.26 (2H, q, J = 7.1 Hz, CH2), 4.21 (5H, s, C5H5), 2.41 (3H, s, COCH3), 1.33 (3H, t, J = 7.1 Hz, CH3); 13C NMR (CDCl3): 203.6 (CO), 164.7 (OCO), 142.1 (=CH), 129.0 (=C), 75.6 (1′-C), 71.9 (2′ and 5′-C), 70.7 (3′ and 4′-C), 69.9 (C5H5), 61.1 (CH2), 31.2 (COCH3), 14.2 (CH3); 9: 1H NMR (CDCl3): 7.46 (1H, s, = CH), 4.51 (2H, m, 2′ and 5′), 4.48 (m, 3′ and 4′), 4.37 (2H, q, J = 7.1 Hz, CH2), 4.21 (5H, s, C5H5), 2.34 (3H, s, COCH3), 1.38 (3H, t, J = 7.1 Hz, CH3); 13C NMR (CDCl3): 193.8 (CO), 168.5 (OCO), 143.2 (=CH), 130.1 (=C), 75.3 (1′-C), 72.3 (2′ and 5′-C), 70.7 (3′ and 4′-C), 70.0 (C5H5), 61.4 (CH2), 26.5 (COCH3), 14.1 (CH3).

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Acknowledgments

We thank Universidad Nacional de La Plata, CONICET and ANPCyT for financial support. GR is member of CONICET. J.L.J. acknowledges the Deutscher Akademischer Austauschdienst, Germany (DAAD), for a scholarship.

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Authors and Affiliations

  1. Unidad Laseisic-Plapimu (UNLP-CIC), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115 (1900), La Plata, Argentina

    Jorge L. Jios

  2. Lehrstuhl für Anorganische Chemie I—Bioanorganische Chemie, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, Universitatstrasse 150, D-44801, Bochum, Germany

    Nils Metzler-Nolte

  3. Centro de Investigación y Desarrollo en Ciencias Aplicadas “Dr. Jorge J. Ronco” (CINDECA-CCT-CONICET), Universidad Nacional de La Plata, Calle 47 No. 257, B1900AJK, La Plata, Argentina

    Patricia G. Vázquez & Gustavo P. Romanelli

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  1. Jorge L. Jios
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  2. Nils Metzler-Nolte
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  3. Patricia G. Vázquez
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  4. Gustavo P. Romanelli
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Correspondence to Jorge L. Jios.

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Jios, J.L., Metzler-Nolte, N., Vázquez, P.G. et al. One-pot synthesis of ferrocenyl-pyrimidones using a recyclable molibdosilicic H4SiMo12O40 heteropolyacid. Res Chem Intermed 42, 977–986 (2016). https://doi.org/10.1007/s11164-015-2067-5

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  • DOI: https://doi.org/10.1007/s11164-015-2067-5

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