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Synthesis and Application of Transition Metal Spinels (Cu, Ni, Co, Pd and Fe) as a Catalyst in Organic Reactions

Daneshfar, Maryam | 2022

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  1. Type of Document: Ph.D. Dissertation
  2. Language: Farsi
  3. Document No: 55186 (03)
  4. University: Sharif University of Technolog
  5. Department: Chemistry
  6. Advisor(s): Matloubi Moghaddam, Firouz
  7. Abstract:
  8. In the first section, due to the important role of nanocatalysts in different fields of chemistry, magnetic metal ferrite nanoparticles were synthesized. Ferrite nanoparticles were synthesized using co-precipitation method and were characterized. Then, these nanoparticles were applied as catalyst system for one-pot β-ketophosphonates and thiophosphate synthesis.This is a green and efficient route for S-P and C-P bond construction using copper ferrite nanoparticles as catalyst. The application of a highly active recyclable heterogeneous nanocopper ferrite catalyst for the oxyphosphorylation reaction of various alkenes was conducted under ligand-free conditions, in acetonitrile as solvent at 85 0C.Synthesis of thiophosphate via the reaction aryl sulfonyl chlorides with H-phosphonates was also conducted. This is an extremely efficient and green method for thiophosphate synthesis under base- and solvent-free conditions and thiophosphates were obtained in good to excellent yields under the optimized reaction conditions in a short time. The nano copper ferrite was used as a heterogenous efficient, inexpensive, magnetically separable and recyclable catalyst which can be used for several cycles. In this study, TD-DFT B3LYP/6-31G(d) calculations are in good accord with the experimental results. The aim of this work is to investigate the best method and basis set for thiophosphate compounds; therefore, predictions for these compounds can be performed in theoretical studies. In the second section, a comprehensive study was carried out for the first time on the acidity of eleven different leaves. After functionalization of the leaves with -SO3H groups, the most acidic one was magnetized using nickel ferrite nanoparticles. This novel, inexpensive, green and biodegradable catalyst showed high activity in the synthesis of pyrazoline and 2-amino nicotinonitriles. Some compounds are new and have never been synthesized before and confirmed by FT IR, 1H NMR and 13C NMR analysis. All of these compounds possess multiple biological activities. The heterogeneous magnetic catalyst (NiFe2O4 - Alnus-SO3H) was characterized by various physicochemical techniques such as FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermal gravimetric analysis/differential thermogravimetry (TGA/DTG), and VSM techniques which showed high sulfur content 0.92 (mmol g-1) and high acidic strength. The main advantages of this method are high yields, short reaction time, easy work-up, green solvent, heterogeneity of the catalyst and simple purification of compounds. It is important to mention that there is no report on the preparation of heterogeneous acid catalyst from waste leaves for the synthesis pyrazoline and 2-amino nicotinonitriles derivatives.In the third section, the green and nano catalyst CoFe2O4@Cell/Fe (III) MTF (Metformin) was simply prepared through the reaction of ferric metformin with nanomaterial CoFe2O4@cellulose as a magnetic biopolymer surface. This novel heterogeneous organometallic catalyst was characterized by X-ray diffraction, field emission scanning electron microscopy, FT-IR spectroscopy, thermal gravimetric analysis, and energy dispersive analysis of X-rays, and inductively coupled plasma-mass spectrometry. This green sulfasalazine drug complex supported on CoFe2O4 cellulose was applied as an efficient and recyclable catalyst for the synthesis of functionalized 4H-pyrans derivatives. All of the reactions were carried out successfully at 60 ̊C in EtOH as a green solvent in a short reaction time. The used catalyst was easily separated by an external magnet and reused for 6 runs without noticeable loss of its catalytic activity. Antimicrobial activity of the products showed excellent activity against all the bacterial and fungal strains compared with Ampicillin and Amphotericin B as standard drugs.
  9. Keywords:
  10. Multicomponent Reaction ; Ferrite ; Beta-Ketophosphonate ; Thiophosphate ; Heterogeneous Catalysis ; Ferrite ; Nanomagnetic Catalyst ; Co-Precipitation ; Organic Reactions

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