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

Author(s): Farzaneh Moradi, Masumeh Abdoli-Senejani*, Majid Ramezani.

Journal Name: Current Organic Synthesis

Volume 17 , Issue 1 , 2020

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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.

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VOLUME: 17
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Year: 2020
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DOI: 10.2174/1570179416666191118110316
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