Effective fabrication of poly(anilin-formaldehyde)-supported hybrid nanomaterial and catalytic synthesis of dihydropyridines

Nanochem Res 4(2): 101-111, Summer and Autumn 2019 RESEARCH PAPER Effective fabrication of poly(anilin-formaldehyde)-supported hybrid nanomaterial and catalytic synthesis of dihydropyridines Mohammad Ali Bodaghifard 1,2*, Zahra Faraki1, Sajad Asadbegi1 1 Department of Chemistry, Faculty of Science, Arak University, Iran 2 Institute of Nanosciences and Nanotechnology, Arak University, Arak, Iran A B ST R AC T ARTICLE INFO Article History: Received 08 July 2019 Accepted 21 September 2019 Published 15 October 2019 Keywords: Surface modification Magnetic nanoparticle Multi-component reactions 1,4-dihydropyridine In this study, Fe3O4@SiO2-PAF-SO3H nanocomposite was successfully fabricated by immobilization of sulfonic acid groups on the surface of poly(anilin-formaldehyde)-supported on magnetic Fe3O4@SiO2 nanoparticles through layer-by-layer assembly. The Fe3O4@SiO2-PAF-SO3H composite nanostructure was fully characterized using various techniques including Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction patterns (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and vibrating sample magnetometry (VSM). The one-pot synthesis of mono and bis 1,4-dihydropyridine derivatives, as pharmaceutically interesting compounds, were achieved in high yields via three-component and pseudo-five-component condensation of an aromatic aldehyde, ammonium acetate and ethyl acetoacetate in the presence of Fe3O4@ SiO2-PAF-SO3H as a novel retrievable hybrid nanocatalyst under solventfree conditions. This protocol has advantages in terms of short reaction time, solvent-free condition, high yield and purity, easy work-up and ecofriendly process as well as recyclability of the nanocatalyst (at least 6 times) with no decrease in catalytic activity. How to cite this article Bodaghifard MA, Faraki Z, Asadbegi S. Effective fabrication of poly(anilin-formaldehyde)-supported hybrid nanomaterial and catalytic synthesis of dihydropyridines. Nanochem Res, 2019; 4(2):101-111. DOI: 10.22036/ncr.2019.02.001 INTRODUCTION Magnetic nanoparticles (MNPs) attract great attention of worldwide scientist and researchers because of their ripsnorting distinguished properties such as high surface area, low cost, low toxicity, high stability, simple separation, easy synthesis and functionalization [1-3]. Due to the unique and valuable properties of MNPs, several applications and potential activities have been reported for MNPs in the field of electronic, biology, pharmacology, drug delivery and catalysis area [3-5]. The heterogenization of homogeneous acidic and basic groups in catalytic reactions (such as covalently bound acidic or basic catalysts) allows * Corresponding Author Email: for the facile separation and reuse of catalysts. The inorganic-supported catalysts especially hybrid magnetic nanomaterials, inorganic-polymer hybrid nanocomposites have been widely used in recent years that could be applied in diverse applications such as drug delivery system, catalysis and biological diagnostics [3, 6-8]. In multicomponent reactions (MCRs), several available compounds (three or more starting materials) react simultaneously in one container to result a desired product. MCRs produce complex and diverse combinations of products and follow many principles of green chemistry, such as solvent-free or aqueous condition, atom economy, energy saving with short reaction times, waste diminish, high yields and selectivity [9-12]. The This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. M. A. Bodaghifard et al. / Catalytic synthesis of dihydropyridines Scheme 1. Synthesis of 1,4-dihydropyridine derivatives using novel Fe3O4@SiO2-PAF-SO3H as a catalyst. Scheme 1. Synthesis of 1,4-dihydropyridine derivatives using novel Fe3O4@SiO2-PAF-SO3H as a 1,4-dihydropyridine derivatives are known as an thermal gravimetric (DTG) data for Fe3O4@SiO2catalyst. important group of heterocyclic compounds having PAF-SO3H MNPs were recorded on a Mettler a special place in organic chemistry due to their TA4000 System under an atmosphere of N2 at a extensive pharmaceutical activities [13,14]. These heating rate of 10 °C min-1. The magnetization and compounds have many therapeutic treatments as hysteresis loop were measured at room temperature sedative, anti-hypertensive [15,16], anticonvulsant using a Vibrating Sample Magnetometer (Model [17], calcium channel blockers [18-21] and anti7300 VSM system, Lake Shore Cryotronic, Inc., clot treatment [22,23]. Many reported synthetic Westerville, OH, USA). The scanning electron methods for 1,4-dihydropyridine suffer from microscope measurement was carried out using a limitations such as low efficiency, long reaction Hitachi S-4700 field emission-scanning electron time, the use of toxic solvents, the use of expensive microscope (FE-SEM). The transmission electron catalysts, difficult reaction conditions and boring microscopy (TEM) measurements were performed purification procedures. To overcome some of these on a Philips CM10 analyzer operating at 150 kV. obstacles, we have synthesized a novel magnetic hybrid nanocatalyst, namely Fe3O4@SiO2-PAFSynthesis of Fe3O4@SiO2-PAF-SO3H hybrid nanoSO3H, and investigated its role as an efficient catalyst material for synthesize of 1,4-dihydropyridine derivatives Fe3O4 nanoparticles were prepared by chemical via the one-pot three-component and pseudo five co-precipitation method described in the literature component condensation of an aromatic aldehyde, [24]. The synthesized Fe3O4 MNPs were used for ammonium acetate and ethyl acetate under solventcoating with a silica shell according to the Stober free condition (Scheme 1). method [25]. Aminopropyl-modified silica-coated MNPs were prepared according to a reported EXPERIMENTAL SECTION procedure [26] .In a typical procedure, 1.0 g of Materials and methods Fe3O4@SiO2 MNPs was dispersed in 40 mL of dry The chemicals were purchased from reputable toluene using an ultrasonic bath for 30 minutes to chemical companies (Merck, Aldrich, and Fluka) produce a uniform suspension. Then, 0.6 mL of or were synthesized and purified in the laboratory. 3-aminopropyltriethoxysilane (APTES) was added The FT-IR spectra were recorded using a Galaxyusing a syringe. The reaction mixture was refluxed series FT-IR 5030 spectrophotometer in the region under N2 atmosphere at 110 °C for 12 h. Finally, 4000–400 cm-1 using pressed KBr Discs. The 1H the aminopropyl-functionalized solid (Fe3O4@ and 13C-NMR spectra were recorded on a Brucker SiO2–PrNH2 MNPs) was washed with toluene for Avance spectrometer operating at 300 MHz for 1H several times, separated using a magnet, and dried and 75 MHz for 13C-NMR in DMSO-d6 with TMS under vacuum. To synthesize Fe3O4@SiO2-PAFas an internal standard. Powder X-ray diffraction NH2, a mixture of 1 g o (...truncated)