Isoniazid-functionalized Fe3O4 Magnetic Nanoparticles as a Green and Efficient Catalyst for the Synthesis of 3, 4-dihydropyrimidin-2(1H)-ones and their Sulfur Derivatives

Farzaneh       Moradi; Masumeh       Abdoli-Senejani; Majid       Ramezani

doi:10.2174/1570179416666191118110316

Abstract

Background: A wide variety of dihydropyrimidins (DHPMs) exhibit pharmacological and biological activities. Herein, an efficient one-pot synthesis of some 3, 4-dihydropyrimidin-2(1H)-one derivatives is reported using Fe3O4 @SiO2–Pr-INH.

Objective: Recently, several catalysts have been used to improve the Biginellis-reaction. However, some of these catalysts have imperfections. Herein, a convenient method for the synthesis of 3, 4-dihydropyrimidin- 2(1H)-ones and their sulfur derivatives using Fe3O4 @SiO2–Pr-INH is reported.

Materials and Methods: Firstly, the catalyst was synthesized through a simple four-step method. The Fe3O4 MNPs were synthesized using the chemical co-precipitation method, coated with a layer of silica using TEOS, and then functionalized with CPTMS. Subsequently, a nucleophilic substitution of Cl by isoniazid resulted in the formation of the magnetic Fe3O4@SiO2–Pr-INH. After the preparation and characterization of Fe3O4@SiO2–Pr-INH, its catalytic activity was studied in the synthesis of 3, 4-dihydropyrimidin-2(1H)-one derivatives. Following the optimization of the reaction conditions, several 3, 4-dihydropyrimidin-2(1H)-one derivatives were synthesized by the reaction of ethyl acetoacetate or acetylacetone, thiourea or urea and aromatic aldehydes at 80 °C under solvent-free conditions.

Results: Isoniazid-functionalized Fe3O4 magnetic nanoparticles (Fe3O4@SiO2–Pr-INH) were prepared using Fe3O4 with silica layer and their surface was modified with isoniazid. They were characterized successfully by infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy and were used for the synthesis of some 3, 4-dihydropyrimidin-2(1H)-one derivatives as catalysts. Aromatic aldehydes with electron-donating or electron-withdrawing groups afforded 3, 4- dihydropyrimidin-2(1H)-ones and their sulfur derivatives in good to excellent yields in short reaction times.

Conclusion: Isoniazid-functionalized Fe3O4 magnetic nanoparticles (Fe3O4@SiO2–Pr-INH) were used as an efficient catalyst for Biginelli-type synthesis of 3, 4-dihydropyrimidin-2(1H)-ones and 3, 4-dihydropyrimidin- 2(1H)-thiones in good to excellent yields and short reaction times. It is noteworthy that this method has several advantages such as simple experimental procedures, the absence of solvent, environmentally benign process, stability and reusability of the catalyst.

Keywords: Magnetic nanoparticles, solvent free, dihydropyrimidine, nanocatalyst, one-pot synthesis, green chemistry, Fe3O4.

« Previous Next »

Graphical Abstract

[1] 
Sandhu, J.S. Past, present and future of the Biginelli reaction: A critical perspective. J. Org. Chem.,  2012, 1, 66-133.
[2] 
Biginelli, P.; Gazz, P. Synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones. Gazz. Chim. Ital.,  1893, 23, 360-372.
[3] 
Safaei-Ghomi, J.; Tavazo, M.; Mahdavinia, G.H. Ultrasound promoted onepot
synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones/thiones using dendrimerattached
phosphotungstic acid nanoparticles immobilized on nanosilic. Ultrason. Sonochem.,,  2018, 40, 230-237.Availble at. 
[http://dx.doi.org/10.1016/j.ultsonch.2017.07.015.] 
[4] 
Starcevich, J.T.; Laughlin, T.J.; Mohan, R.S. Iron (III) tosylate catalyzed
synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones/thiones via the Biginelli
reaction. Tetrahedron Lett.,,  2013, 54, 983-985.Availble at. 
[http://dx.doi.org/10.1016/j.tetlet.2012.12.032.] 
[5] 
Lima, C.G.; Silva, S.; Goncalves, R.H.; Leite, E.R.; Schwab, R.S.; Correa, A.G.; Paixao, M.W. Highly efficient and magnetically recoverable niobium nanocatalyst for the multicomponent Biginelli reaction. Chem. Cat. Chem.,,  2014, 6, 3455-3463.Availble at. 
[http://dx.doi.org/10.1002/cctc.201402689.] 
[6] 
Quan, Z-J.; Da, Y-X.; Zhang, Z.X-C. Wang, PS–PEG–SO3H as an efficient catalyst for 3, 4-dihydropyrimidones via Biginelli reaction. Catal. Commun.,  2009, 10, 1146-1148.Available at. 
[http://dx.doi.org/10.1016/j.catcom.2008.12.017] 
[7] 
Salehi, H.; Guo, Q.X. A facile and efficient one pot synthesis of dihydropyrimidinones catalyzed by magnesium bromide under solvent free conditions. Synth. Commun.,,  2004, 34, 171-179.Availble at. 
[http://dx.doi.org/10.1081/SCC-120027250.] 
[8] 
Varala, R.; Alam, M.M.; Adapa, S.R. Bismuth triflate catalyzed one-pot synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones: An improved protocol for the Biginelli reaction. Synlett, 2003.
[9] 
Shirini, F.; Ali Zolfigol, M.; Mollarazi, E. ZrOCl2·8H2O as an efficient
reagent for the solvent free synthesis of 3, 4-dihydropyrimidin-2-(1h)-ones. Synth. Commun.,,  2006, 36, 2307-2310.Availble at. 
[http://dx.doi.org/10.1080/00397910600639828.] 
[10] 
Abdoli, M.; Hasani, M.; Momeni Isfahani, T. One-Pot synthesis of 3, 4-dihydropyrimidin-2(1H)-ones catalyzed by barium chloride. J. Chem. Pharm. Res.,  2016, 8, 214-217.
[11] 
Nassr-Esfahani, M.; Hoseini, S.J.; Mohammadi, F.  Fe3O4 Nanoparticles as an
efficient and magnetically recoverable catalyst for the synthesis of 3,4-
dihydropyrimidin-2(1H)-ones under solvent-free conditions. Chin. J. Catal.,,  2011, 32, 1484-1489.Availble at. 
[http://dx.doi.org/10.1016/S1872-2067(10)60263-X.] 
[12] 
Lyon, J.L.; Fleming, D.A.; Stone, M.B.; Schiffer, P.; Williams, M.E. Synthesis of Fe oxide core/Au shell nanoparticles by iterative hydroxylamine
seeding. Nano Lett.,,  2004, 4, 719-723.Availble at. 
[http://dx.doi.org/10.1021/nl035253f.] 
[13] 
Yang, P.; Quan, Z.; Hou, Z.; Li, C. kang, X.; Cheng, Z.; Lin, J. A magnetic,
luminescent and mesoporous core-shell structured composite material as
drug carrier. Biomaterials,,  2009, 30, 4786-4795.Availble at. 
[http://dx.doi.org/10.1016/j.biomaterials.2009.05.038.] 
[14] 
Zhang, M.; Wu, Y.; Feng, X.; He, X.; Chen, L.; Zhang, Y. Fabrication of mesoporous silica-coated CNTs and application in size-selective protein separation. J. Mater. Chem.,,  2010, (20), 5835-5842.Availble at. 
[http://dx.doi.org/10.1039/b925137e.] 
[15] 
Liu, S.; Chen, H.; Lu, X.; Deng, C.; Zhang, X.; Yang, P. Facile synthesis of
copper (II) immobilized on magnetic mesoporous silica microspheres for
selective enrichment of peptides for mass spectrometry analysis. Angew.Chem. Int. Ed.,,  2010, 49, 7557-7561.Availble at. 
[http://dx.doi.org/10.1002/anie.201003602.] 
[16] 
Won, Y-H.; Aboagye, D.; Jang, H.S.; Jitianu, A.; Stanciu, L.A. Core/shell
nanoparticles as hybrid platforms for the fabrication of a hydrogen peroxide
biosensor. J. Mater. Chem.,,  2010, 20, 5030-5034.Available at. 
[http://dx.doi.org/10.1039/c0jm00182a.] 
[17] 
Xuan, S.; Wang, Y-X.J.; Leung, K.C-F.; Shu, K. Synthesis of Fe3O4@
polyaniline core/shell microspheres with well-defined blackberry-like
morphology. J. Phys. Chem. C.,,  2008, 112, 18804-18809.Availble at. 
[http://dx.doi.org/10.1021/jp807124z.] 
[18] 
Deng, Y.; Qi, D.; Deng, C.; Zhang, X.; Zhao, D. Superparamagnetic highmagnetization
microspheres with an Fe3O4@ SiO2 core and perpendicularly
aligned mesoporous SiO2 shell for removal of microcystins. J. Am. Chem.Soc.,,  2008, 130, 28-29.Availble at. 
[http://dx.doi.org/10.1021/ja0777584.] 
[19] 
McCarthy, S.A.; Davies, G-L.; Gun’ko, Y.K. Preparation of multifunctional
nanoparticles and their assemblies. Nat. Protoc.,,  2012, 7, 1677.Availble at. 
[http://dx.doi.org/10.1038/nprot.2012.082.] 
[20] 
Qin, H.; Wang, C.; Dong, Q.; Zhang, L.; Zhang, X.; Ma, Z.; Han, Q. Preparation and characterization of magnetic Fe3O4–chitosan nanoparticles
loaded with isoniazid J. Magn. Magn. Mater.,  2015, 38, 1120-1126.Availble at. 
[http://dx.doi.org/10.1016/j.jmmm.2014.12.076.] 
[21] 
Zhao, C.; Liu, X.; Zhang, X.; Yan, H.; Qian, Z.; Li, X.; Ma, Z.; Han, Q.; Pei, C. A facile one-step method for preparation of Fe3O4/CS/INH nanoparticles
as a targeted drug delivery for tuberculosis. Mater. Sci. Eng. C.,,  2017, 77, 1182-1188.Availble at. 
[http://dx.doi.org/10.1016/j.msec.2017.03.137.] 
[22] 
Sedlák, M.; Bhosale, D.S.; Beneš, L.; Palarčík, J.; Kalendová, A.; Královec, K.; Imramovský, A. ynthesis and characterization of a pH-sensitive
conjugate of isoniazid with Fe3O4@ SiO2 magnetic nanoparticles. Bioorg.
Med. Chem. Lett.,,  2013, 23, 4692-4695.Availble at. 
[http://dx.doi.org/10.1016/j.bmcl.2013.05.103.] 
[23] 
Mehdinia, A.; Kayyal, T.B.; Jabbari, A.; Aziz-Zanjani, M.O.; Ziaei, E. Magnetic molecularly imprinted nanoparticles based on grafting
polymerization for selective detection of 4-nitrophenol in aqueous samples. J. Chromatogr. A,,  2013, 1283, 82-88.Availble at. 
[http://dx.doi.org/10.1016/j.chroma.2013.01.093.] 
[24] 
Sadeghzadeh, S.M.; Nasseri, M.A. Methylene dipyridine nanoparticles stabilized on Fe3O4 as catalysts for efficient, green, and one-pot synthesis of pyrazolophthalazinyl spirooxindoles. Catal. Today.,,  2013, 217, 80-85.Availble at. 
[http://dx.doi.org/10.1016/j.cattod.2013.07.018.] 
[25] 
Chen, L.; Li, B.; Liu, D. Schiff base complex coated Fe 3 O 4 nanoparticles:
A highly recyclable nanocatalyst for selective oxidation of alkyl aromatics. Catal. Lett.,,,  2014, 144(6), 1053-1061.Availble at. 
[http://dx.doi.org/10.1007/s10562-014-1244-2] 
[26] 
Chen, L.; Li, B.; Liu, D. Schiff base complex coated Fe3O4 nanoparticles: A highly recycl able nanocatalyst for selective oxidation of alkyl aromatics. Catal. Lett.,,  2014, 144, 1053-1061.Availble at. 
[http://dx.doi.org/10.1007/s10562-014-1244-2.] 
[27] 
Abbasi, F.; Azizi, N.; Abdoli-Senejani, M. Highly efficient synthesis of
dicoumarols and xanthene derivatives in presence of Brønsted–Lewis acidic
ionic liquids catalyst. J. Iran. Chem. Soc.,,  2017, 14, 2097-2103.Availble at. 
[http://dx.doi.org/10.1007/s13738-017-1146-5.] 
[28] 
Siadatifard, S.H.; Abdoli-Senejani, M.; Bodaghifard, M.A. An efficient
method for synthesis of bis (indolyl) methane and di-bis (indolyl) methane
derivatives in environmentally benign conditions using TBAHS. Cogent.
Chem.,,  2016, 2, 1188435.Availble at. 
[http://dx.doi.org/10.1080/23312009.2016.1188435.] 
[29] 
Keshavarz, M.; Abdoli-Senejani, M.; Hojati, S.F.; Askari, S. Fe3O4
magnetic nanoparticles coated with a copolymer: A novel reusable catalyst
for one-pot three-component synthesis of 2-amino-4H-chromene, React.
Kinet. Mech. Cat.,,  2018, 124, 757-766.Availble at. 
[http://dx.doi.org/10.1007/s11144-018-1361-9.] 
[30] 
Heidarizadeh, F.; Rezaee Nezhad, E.; Sajjadifar, S. Novel acidic ionic liquid as a catalyst and solvent for green synthesis of dihydropyrimidine derivatives. Sci. Iran.,  2013, 20, 561-565.
[31] 
Kuraitheerthakumaran, A.; Pazhamalai, S.; Gopalakrishnan, M. Microwaveassisted
multicomponent reaction for the synthesis of 3,4-dihydropyrimidin-
2(1H)-ones and their corresponding 2(1H)-thiones using lanthanum oxide as
a catalyst under solvent-free conditions. Arab. J. Chem.,,  2016, 9, S461-S465.Availble at. 
[http://dx.doi.org/10.1016/j.arabjc.2011.06.005.] 
[32] 
Dekamin, M.G.; Mehdipoor, F. Yaghoubi, Amene. 1,3,5-Tris(2-
hydroxyethyl)isocyanurate functionalized graphene oxide: A novel and
efficient nanocatalyst for the one-pot synthesis of 3,4-dihydropyrimidin-
2(1H)-ones. New J. Chem.,,  2017, 41, 6893-6901.Availble at. 
[http://dx.doi.org/10.1039/C7NJ00632B.] 
[33] 
Nasr-Esfahani, M.; Abdizadeh, T. Vanadatesulfuric Acid: A novel,
recyclable, and heterogeneous catalyst for the one-pot synthesis of
dihydropyrimidinones and dihydropyrimidinthiones under solvent-free
conditions. Phosphorus Sulfur,,  2013, 188, 596-608.Availble at. 
[http://dx.doi.org/10.1080/10426507.2012.694001.] 
[34] 
Yarapathi, R.V.; Kurva, S.; Tammishetti, S. Synthesis of 3,4-
dihydropyrimidin-2(1H)ones using reusable poly(4-vinylpyridinecodivinylbenzene)–
Cu(II)complex. Catal. Commun.,,  2004, 5, 511-513.Availble at. 
[http://dx.doi.org/10.1016/j.catcom.2004.06.007.] 
[35] 
Patel, H.A.; Sawant, A.M.; Rao, V.J.; Patel, A.L.; Bedekar, A.V. Polyaniline
supported FeCl3: An effective heterogeneous catalyst for Biginelli reaction. Catal. Lett.,,  2017, 147, 2306-2312.Availble at. 
[http://dx.doi.org/10.1007/s10562-017-2139-9] 
[36] 
Dilmaghani, K.A.; Zeynizadeh, B.; Amirpoor, M. Ultrasound-mediated
synthesis of 3,4-dihydropyrimidin-2-(1H)-Ones (or thiones) with
NaHSO4·H2O. Phosphorus Sulfur,,  2013, 188, 1634-1642.Availble at. 
[http://dx.doi.org/10.1080/10426507.2013.777725.] 
[37] 
Bahekar, S.P.; Sarode, P.B.; Wadekar, M.P.; Chandak, H.S. Simple and
efficient synthesis of 3, 4-dihydropyrimidin-2 (1H)-thiones utilizing Lproline
nitrate as a proficient, recyclable and eco-friendly catalyst. J. Saudi
Chem. Soc.,,  2017, 21, 415-419.Availble at. 
[http://dx.doi.org/10.1016/j.jscs.2015.09.004.] 
[38] 
Khatri, C.K.; Potadar, S.M.; Chaturbhuj, G.U. A reactant promoted solvent
free synthesis of 3,4-dihydropyrimidin-2(1H)-thione analogues using
ammonium thiocyanate. Tetrahedron Lett.,,  2017, 58, 1778-1780.Availble at. 
[http://dx.doi.org/10.1016/j.tetlet.2017.03.070.] 
[39] 
Dilmaghani, K.A.; Zeynizadeh, B.; Paraajsam, H. The efficient synthesis of
3,4-dihydropyrimidin-2-(1H)-ones and their sulfur derivatives with H2SO4
immobilized on activated charcoal. Phosphorus Sulfur,,  2012, 187, 544-553.Availble at. 
[http://dx.doi.org/10.1080/10426507.2011.631644.] 
[40] 
Raj, M.K.; Rao, H.S.P.; Manjunatha, S.G.; Sridharan, R.; Nambiar, S.; Keshwan, J.; Rappai, J.; Bhagat, S.; Shwetha, B.S.; Hegde, D.; Santhosh, U. A mechanistic investigation of Biginelli reaction under base catalysis. Tetrahedron Lett.,,  2011, 52, 3605-3609.Availble at. 
[http://dx.doi.org/10.1016/j.tetlet.2011.05.011.] 
[41] 
Lu, J.; Bai, Y.; Wang, Z.; Yang, B.; Ma, H. One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones using lanthanum chloride as a catalyst. Tetrahedron Lett.,  2000, 41, 9075-9078.Available at . 
[http://dx.doi.org/10.1016/S0040-4039(00)01645-2.] 
[42] 
Kumar, K.A.; Kasthuraiah, M.; Reddy, C.S.; Reddy, C.D. Mn(OAc)3·2H2Omediated
three-component, one-pot, condensation reaction: An efficient
synthesis of 4-aryl-substituted 3,4-dihydropyrimidin-2-ones. Tetrahedron
Lett.,,  2001, 42, 7873-7875.Availble at. 
[http://dx.doi.org/10.1016/S0040-4039(01)01603-3.] 
[43] 
Paraskar, A.; Dewkar, G.; Sudalai, A. Cu (OTf) 2: a reusable catalyst for
high-yield synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones. Tetrahedron
Lett.,,  2003, 44, 3305-3308.Availble at. 
[http://dx.doi.org/10.1016/S0040-4039(03)00619-1.] 
[44] 
Tamaddon, F.; Razmi, Z.; Jafari, A.A. Synthesis of 3, 4-dihydropyrimidin-2
(1H)-ones and 1, 4-dihydropyridines using ammonium carbonate in water. Tetrahedron Lett.,,  2010, 51, 1187-1189.Availble at. 
[http://dx.doi.org/10.1016/j.tetlet.2009.12.098.] 
[45] 
Chari, M.A.; Syamasundar, K. Silicagel supported sodium hydrogensulfate
as a heterogenous catalyst for high yield synthesis of 3, 4-dihydropyrimidin-
2 (1H)-ones. J. Mol. Catal. Chem.,,  2004, 221, 137-139.Availble at. 
[http://dx.doi.org/10.1016/j.molcata.2004.06.019.] 
[46] 
Heravi, M.M.; Bakhtiari, K.; Bamoharram, F.F. 12-Molybdophosphoric acid:
A recyclable catalyst for the synthesis of Biginelli-type 3, 4-
dihydropyrimidine-2 (1H)-ones. Catal. Commun.,,  2006, 7, 373-376.Availble at. 
[http://dx.doi.org/10.1016/j.catcom.2005.12.007.] 
[47] 
Mondal, J.; Sen, T.A. Bhaumik, Fe3O4@ mesoporous SBA-15: a robust and magnetically recoverable catalyst for one-pot synthesis of 3, 4-dihydropyrimidin-2 (1 H)-ones via the Biginelli reaction. Dalton Trans.,  2012, 416, 173-6181.
[48] 
Zhu, Y.; Pan, Y.; Huang, S. Trimethylsilyl Chloride: A facile and efficient
reagent for one-pot synthesis of 3, 4-dihydropyrimidin-2 (1 H)-ones. Synth.
Commun.,,  2004, 34, 3167-3174.Availble at. 
[http://dx.doi.org/10.1081/SCC-200028607.] 
[49] 
Starcevich, J.T.; Laughlin, T.J.; Mohan, R.S. Iron (III) tosylate catalyzed synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones/thiones via the Biginelli reaction. Tetrahedron Lett.,  2013, 54, 983-985.Availble at. 
[http://dx.doi.org/10.1016/j.tetlet.2012.12.032.] 

Rights & Permissions Print Cite

Article Metrics

10

Journal Information

For Authors

For Editors

For Reviewers

Explore Articles

Open Access

Open Access Articles

For Visitors

DOI https://dx.doi.org/10.2174/1570179416666191118110316	Print ISSN 1570-1794
Publisher Name Bentham Science Publisher	Online ISSN 1875-6271

Current Organic Synthesis

Isoniazid-functionalized Fe3O4 Magnetic Nanoparticles as a Green and Efficient Catalyst for the Synthesis of 3, 4-dihydropyrimidin-2(1H)-ones and their Sulfur Derivatives

Abstract Play Pause

Graphical Abstract

Related Journals

Related Books

Abstract