Chromium (III) Nitrate Nonahydrate: An Environmentally Benign and Efficient Heterogeneous Catalyst for Facile One-Pot Biginelli Synthesis of 3,4-Dihydropyrimidin-2-(1H)-One/Thione Derivatives Under Solvent-Free Conditions
The use of chromium(III) nitrate nonahydrate (Cr(NO3)3·9H2O) as an efficient, mild and economical catalyst for the one-pot three-component Biginelli synthesis of 3,4-dihydropyrimidin-2-(1H)-one/thione derivatives in the reaction between β-keto esters (methyl or ethyl acetoacetate), aromatic aldehydes (benzaldehye derivatives) and urea or thiourea under thermal and solvent-free conditions with good yields and short reaction times is reported. The most benefits of this synthetic method include the use of an efficient, eco-friendly, inexpensive and non-toxic catalyst, as well as the solvent-free conditions. All products were characterized by 1H NMR spectroscopy and melting point determination.
1. Strecker, A. Ueber die künstliche Bildung der Milchsäure und einen neuen, dem Glycocoll homologen Körper. Leibigs. Ann. Chem. 1850, 7, 27-45.
2. Mohamadpour, F.; Maghsoodlou, M. T.; Heydari, R.; Lashkari, M. Saccharin: a green, economical and efficient catalyst for the one-pot, multicomponent synthesis of 3,4-dihydropyrimidin-2-(1H)-one derivatives and 1H-pyrazolo [1,2-b]phthalazine-5,10-dione derivatives and substituted dihydro-2-oxypyrrole. J. Iran. Chem. Soc. 2016, 13, 1549-1560.
3. Mohamadpour, F.; Maghsoodlou, M. T.; Heydari, R.; Lashkari, M. Nano Zno: As an efficient and environmentally benign nature catalyst assisted one- pot four-component synthesis of polysubstituted dihydro-2-oxypyrroles. J. Chem. Pharm. Res. 2015, 7, 941-944.
4. Mohamadpour, F.; Maghsoodlou, M. T.; Heydari, R.; Lashkari, M. Oxalic acid dihydrate catalyzed synthesis of 3,4-dihydropyrimidin-2- (1H)-one derivatives under thermal and solvent-free conditions. Iran. J. Catal. 2016, 6, 127-131.
5. Mohamadpour, F.; Maghsoodlou, M. T.; Heydari, R.; Lashkari, M. Tartaric acid: A naturally green and efficient di-functional Brønsted acid catalyst for the one-pot four-component synthesis of polysubstituted dihydropyrrol-2-ones at ambient temperature. Iran. J. Sci. Technol. Trans. Sci. 2016, DOI: 10.1007/s40995-016-0049-0.
6. Biginelli, P. Aldehyde-urea derivatives of aceto- and oxaloacetic acids. Gazz. Chim. Ital. 1893, 23, 360-413.
7. Prakash, O.; Kumar, R.; Parkash, V. Synthesis and antifungal activity of some new 3-hydroxy-2-(1-phenyl-3-aryl-4-pyrazolyl) chromones. Eur. J. Med. Chem. 2008, 43, 435-440.
8. Sujatha, K.; Shanmugam, P.; Perumal, P. T.; Muralidharan, D.; Rajendran, M. Synthesis and cardiac effects of 3,4-dihydropyrimidin-2(1H)-one-5 carboxylates. Bioorg. Med. Chem. Lett. 2006, 16, 4893-4897.
9. Wisen S.; Androsavich, J.; Evans, C. G.; Chang, L.; Gestwi cki, J. E. Chemical modulators of heat shock protein 70 (Hsp70) by sequential, microwave-accelerated reactions on solid phase. Bioorg. Med. Chem. Lett. 2008, 18, 60-65.
10. Heys, L.; Moore, C. G.; Murphy, P. The guanidine metabolites of Ptilocaulis spiculifer and related compounds; isolation and synthesis. Chem. Soc. Rev. 2000, 29, 57-67.
11. Ashok, M.; Holla, B. S.; Kumara, N. S. Convenient one pot synthesis of some novel derivatives of thiazolo[2,3-b]dihydropyrimidinone possessing 4-methylthiophenyl moiety and evaluation of their antibacterial and antifungal activities. Eur. J. Med. Chem. 2007, 42, 380-385.
12. Hurst, E. W.; Hull, R. Two new synthetic substances active against viruses of the psittacosis-lymphogranuloma-trachoma group. J. Med. Pharm. Chem. 1961, 3, 215-219.
13. Magerramow, A. M.; Kurbanova, M. M.; Abdinbekova, R. T.; Rzaeva, I. A.; Farzaliev, V. M.; Allokhverdiev, M. A. Synthesis and antioxidative properties of some 3, 4-dihydropyrimidin-2(1H)ones(-thiones). Russ. J. Appl. Chem. 2006, 79, 787-790.
14. Bahekar, S. S.; Shinde, D. B. Synthesis and anti-inflammatory activity of some [4,6-(4-substituted aryl)-2-thioxo-1,2,3,4-tetrahydro-pyrimidin-5-yl]-acetic acid derivatives. Bioorg. Med. Chem. Lett. 2004, 14, 1733-1736.
15. Chitra, S.; Pandiarajan, K. Calcium fluoride: an efficient and reusable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones and their corresponding 2(1H)thione: an improved high yielding protocol for the Biginelli reaction. Tetrahedron Lett. 2009, 50, 2222-2224.
16. Liu, J. N.; Li, J.; Zhang, L.; Song, L. P.; Zhang, M.; Cao, W. J.; Zhu, S. Z.; Deng, H. G.; Shao, M. Facile one-pot three-component reaction to synthesize trifluoromethylated cyclopenta[b]pyran derivatives and their further transformation. Tetrahedron Lett. 2012, 53, 2469-2472.
17. Kumar, A.; Maurya, R. A. An efficient bakers’ yeast catalyzed synthesis of 3, 4-dihydropyrimidin-2-(1H)-ones. Tetrahedron Lett. 2007, 48, 4569-4571.
18. Lai, J.; Sharma, M.; Gupta, S.; Parashar, P.; Sahu, P.; Agarwal, D. D. Hydrotalcite: A novel and reusable solid catalyst for one-pot synthesis of 3, 4-dihydropyrimidinones and mechanistic study under solvent free conditions. J. Mol. Catal. A. Chem. 2012, 352, 31-37.
19. Litvic, M.; Vecani, I.; Ladisic, Z. M.; Lovric, M.; Voncovic, V.; Filipan- Litvic, M. First application of hexaaquaaluminium(III) tetrafluoroborate as a mild, recyclable, non-hygroscopic acid catalyst in organic synthesis: a simple and efficient protocol for the multi gram scale synthesis of 3,4- dihydropyrimidinones by Biginelli reaction. Tetrahedron. 2010, 66, 3463-3471.
20. Ahmad, B.; Khan, R. A.; Habibullah, A.; Keshai, M. An improved synthesis of biginelli-type compounds via phase-transfer catalysis. TetrahydronLett. 2009, 50, 2889-2892.
21. Kamal, A.; Krishnaji, T.; Azhar, M. A.Copper (II) tetrafluoroborate as a mild and efficient catalyst for the one-pot synthesis of 3, 4- dihydropyrimidin-2(1H)-ones under solvent-free conditions. Catal. Commun. 2007, 8, 1929-1993.
22. Zhang, Y.; Wang, B.; Zhang, X.; Huang, J.; Liu, C. An Efficient Synthesis of 3,4-Dihydropyrimidin-2(1H)-Ones and Thiones Catalyzed by a Novel Brønsted Acidic Ionic Liquid under Solvent-Free Conditions. Molecules. 2015, 20, 3811-3820.
23. Attri, P.; Bhatia, R.; Gaur, J.; Arora, B.; Gupta, A.; Kumar, N.; C hoi, E. H. Triethylammonium acetate ionic liquid assisted one-pot synthesis of dihydropyrimidinones and evaluation of their antioxidant and antibacterial activities. Arab. J. Chem. 2014, DOI: 10.1016/j.arabjc.2014.05.007.
24. Aswin, K.; Mansoor, S. S.; Logaiya, K.; Sudhan, P. N.; Ahmed, R. N. Facile synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones and-thiones and indeno [1, 2-d] pyrimidines catalyzed by p-dodecylbenzenesulfonic acid. J. Taibah Univ. Sci. 2014, 8, 236-247.