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Three-component synthesis of pyrano[2,3-d]pyrimidinone derivatives catalyzed by Ni2+ supported on hydroxyapatite-core-shell-γ-Fe2O3 in aqueous media
Sobhan Rezayati1,*, Zahra Abbasi2, Eshagh RezaeeNezhad3, Rahimeh Hajinasiri1, Abdolhadi Farrokhnia2
1Chemistry Department, Qaemshahr Branch, Islamic Azad University, PO BOX 163, Qaemshahr, Iran
Chemistry Department, College of Science Shahid Chamran University, Ahvaz, Iran2
3Department of Chemistry, Payame Noor University, Tehran, P.O. Box 19395-4697, Iran
Table of contents
Materials and methods / 2Preparation of γ-Fe2O3@HAp-Ni2+NPs / 2
General Procedure for the synthesis of pyrano[2,3-d]pyrimidinone derivatives 4(a-p) / 3
FT-IR spectra of A: γ-Fe2O3@HAp-Ni2+ NPs, B: γ-Fe2O3@Hap, C: HAp (c). / 4
The XRD pattern of the γ-Fe2O3@HAp-Ni2+NPs. / 5
The TEM ofγ-Fe2O3@HAp-Ni2+ NPs. / 6
The SEM micrographs of γ-Fe2O3@HAp-Ni2+ NPs. / 7
Magnetization curve of γ-Fe2O3@HAp-Ni2+ NPs. / 8
Materials and methods
All chemicals were purchased from Merck or Fluka chemical companies. All the products are knowncompounds and were characterized by comparing the 1H-NMR and 13C-NMR spectroscopic data and their melting point the literature values.The uncorrected melting points of all compounds were measured in an open capillary in a paraffin bath. 1H and 13C NMR spectra were recorded using a Bruker instrument (1H at 400 MHz and 13C at 100 MHz) in DMSO-d6 solvent with tetramethylsilane (TMS) as the internal standard. IRspectra were recorded on a Frontier FT-IR (PerkinElmer) spectrometer using a KBr disk.Thin-layerchromatography (TLC) was performed with silica gel 60 F254 plates, and UVlight was used for visualization.The phasespresent in the magnetic materials were analyzed using apowder XRD, Philips (Holland), model X0Pert with X´ Pert withCuKα1 radiation (λ = 1.5401 Å), and the X-ray generatorwas operated at 40 kV and 30 mA. Diffraction patternswere collected from 2h = 20º–80º.
Preparation of γ-Fe2O3@HAp-Ni2+NPs
In this study, γ-Fe2O3@HAp-Ni2+ NPs was prepared in two steps. The Iron Oxide Magnetic Particles (IOMP) were synthesized by chemical coprecipitation technique of ferric and ferrous chlorides in aqueous solution. IOMP/HAP was prepared by the impregnation method according to known procedures with some modications [22]. Then Hydroxyapatite-Encapsulated γ-Fe2O3 (0.6 g) was introduced into 100 ml of distilled water containing 6.4 mmol of NiCl2.4H2O. The mixture was stirred (500 rpm) for 48 h, filtered, and washed several times with ethanol. The recovered solid was dried at 50 ºC overnight (Scheme 2). The mean size and the surface morphology of the γ-Fe2O3@HAp-Ni2+NPs were characterized by TEM, SEM, VSM, XRD and FTIR techniques [23-24].
General Procedure for the synthesis of pyrano[2,3-d]pyrimidinone derivatives4(a-p)
Substituted aromatic aldehydes 1 (1 mmol), malononitrile 2 (1 mmol), barbituric acid 3 (1 mmol) and γ-Fe2O3@HAp-Ni2+NPs (10 mg) in EtOH (10mL) was stirred at room temperaturefor appropriate time (see Table 4). After completion of the reaction, which was monitored by TLC (ethyl acetate and n-hexane 7:3), The filtrate mixture was recrystallized to provide pure crystals of pyrano[2,3-d]pyrimidinone derivatives with excellent yields (85–95%).The products were known compounds and were characterized based on IR and NMR spectroscopic data. Their melting points (m.p.) were compared with reported values.
Figure 1.FT-IR spectra of A: γ-Fe2O3@HAp; B: γ-Fe2O3@Hap-Ni2+
Figure 2.The XRD pattern of the γ-Fe2O3@HAp-Ni2+NPs.
Figure 3. The TEM ofγ-Fe2O3@HAp-Ni2+ NPs.
Figure 4. The SEM micrographs of γ-Fe2O3@HAp-Ni2+NPs.
Figure 5. Magnetization curve of γ-Fe2O3@HAp-Ni2+ NPs.