ABSTRACT
Saponin, as a green and available phytochemical, was immobilized on the surface of magnetite nanoparticles then doped with Cu ions (Fe3O4@Sap/Cu(ii)) and used as an efficient nanocatalyst for the synthesis of quinazoline and acridine derivatives, due to their high application and importance in various fields of science. Different spectroscopic and microscopic techniques were used for the catalyst characterization such as FT-IR, XRD, FE-SEM, EDX, TEM, TGA, VSM, BET, DLS, CV, and XPS analyses. All characterization data were correlated with each other so that the structure of the catalyst was accurately characterized. The reactions were performed in the presence of a low amount of Fe3O4@Sap/Cu(ii) (0.42 mol%) as a green catalyst in water over a short period of time. The results show well the effective role of saponin in solving the problem of mass transfer in aqueous medium, which is the challenge of many organic reactions in aqueous medium and in the presence of heterogeneous medium. High catalytic activity was found for the catalyst and high to excellent efficiency was obtained for all quinazoline (68-94% yield) and acridine (66-97% yield) derivatives in short reaction times (less than 1 hour) under mild reaction conditions in the absence of any hazardous or expensive materials. There is not any noticeable by-product found whether for acridine or quinazoline derivatives, which reflects the high selectivity. Two reasonable mechanisms were proposed for the reactions based on observations from control experiments as well as literature reports. The catalyst could be easily recovered magnetically for at least six consecutive runs with insignificant reactivity loss.
ABSTRACT
A novel magnetically recyclable bimetallic catalyst was prepared by anchoring imidazolium moiety and PEG chains on Fe3O4 NPs and named as Fe3O4@PEG/Cu-Co. It was found to be a powerful catalyst for the Sonogashira, Suzuki, and C-N cross-coupling reactions in water as a green solvent without the need for any external base. Fe3O4@PEG/Cu-Co was well characterized with FT-IR, FE-SEM, TEM, VSM, EDX, ICP, UV-visible, CV, and XPS analyses. Optimum ranges of parameters such as time, temperature, and amount of catalyst were investigated by Design-Expert 10.0.7 software for C-C Suzuki, Sonogashira, and C-N cross-coupling reactions to find the optimum conditions. The catalyst was compatible with a variety of aryl halides and N-arenes and gave favorable coupling products with good to high yields for all of them. Hot filtration and Hg poisoning tests involving the nanocatalyst revealed the stability, low metal leaching, and heterogeneous nature of the catalyst. Reaction mechanisms were proposed by study of the UV-visible spectra in situ as well as hydroquinone tests during the progress of reactions. In situ XPS analysis was also used to study the reaction mechanism. To prove the synergistic performance of Co and Cu in the catalyst, its various homologues were synthesized and applied to a model reaction separately, and then their catalytic activities were investigated. Finally, the catalyst could be recovered from the reaction mixture simply, and reused for several cycles with a minimum loss in catalytic activity and performance.
