Efficient Sonogashira and A3 coupling reactions catalyzed by biosynthesized magnetic Fe3O4@Ni nanoparticles from Euphorbia maculata extract

In this work, biosynthesized Fe₃O₄@Ni nanoparticles using Euphorbia maculata aqueous have been used as effective catalysts in the synthesis of 2,3-disubstituted benzo[b]furan derivatives using three component coupling of aldehydes, secondary amines and alkynes (A³ coupling reaction). Using novel nanoscale materials, the current green, practical and economical method leads to short reaction times and high yields. The biosynthesized catalyst was also successfully employed in the Sonogashira cross-coupling reactions of various aryl halides with phenylacetylene. The best performance was observed using just 20 mg of the catalyst and ethanol as a green solvent. The developed protocol provides easy workup, short reaction times and good to excellent product yields. Furthermore, since the composite is highly stable, an external permanent magnet can be easily used for separating the catalyst. Thus, the catalyst can be recycled several times without considerable loss of catalytic activity.     

Magnetically separable g‐C3N4 hybrid nanocomposite: Highly efficient and eco‐friendly recyclable catalyst for one‐pot synthesis of α‐aminonitriles

A magnetically separable graphitic carbon nitride nanocomposite (Fe₃O₄/g‐C₃N₄) as a catalyst for the three‐component condensation reactions of carbonyl compounds, amines and trimethylsilylcyanide was thoroughly investigated. The reaction of these three components was found to be efficient, economical and green and took place in the presence of a catalytic amount of the magnetically separable catalyst to yield the corresponding α‐aminonitriles in good to excellent yields. The prepared nanocomposite was characterized using scanning electron microscopy and energy‐dispersive X‐ray and Fourier transform infrared spectroscopies. The nanocomposite was also found to be reusable could be recovered easily and reused several times without distinct deterioration in its catalytic activity.     

Ethylene/Norbornene Copolymerization with iPr(Cp)(Flu)ZrCl2 Catalyst: Effect of MAO Cocatalyst and 3rd Monomer

The copolymerization of ethylene and norbornene (N) was carried out with iPr(Cp)(Flu)ZrCl₂ catalyst and modified methylaluminoxane (MMAO) cocatalyst. The catalytic activity was dependent on the structure of MMAO, i.e., MMAO-4 exhibited higher catalyst activity than MMAO-3A containing more i-butyl groups. The glass transition temperature (T_g) and the composition of the produced copolymer were not affected by MMAO type. With styrene derivatives as 3^rd monomer, T_g of copolymer increased while the catalytic activity decreased. With the addition of 3^rd monomer, not only the content of 3^rd monomer but also the content of N increased.     

Highly dispersed palladium nanoclusters incorporated in amino‐functionalized silica spheres for the selective hydrogenation of succinic acid to γ‐butyrolactone

Highly dispersed palladium nanoclusters incorporated on amino‐functionalized silica sphere surfaces (Pd/SiO₂‐NH₂) were fabricated by a simple one‐pot synthesis utilizing 3‐(2‐aminoethylamino)propyltrimethoxysilane (AAPTS) as coordinating agent. Uniform palladium nanoclusters with an average size of 1.1 nm can be obtained during the co‐condensation of tetraethyl orthosilicate and AAPTS owing to the strong interaction between palladium species and amino groups in AAPTS. The palladium particle size can be controlled by addition of AAPTS and plays a significant role in the catalytic performance. The Pd/SiO₂‐NH₂ catalyst exhibits high catalytic activity for succinic acid hydrogenation with 100% conversion and 94% selectivity towards γ‐butyrolactone using 1,4‐dioxane as solvent at 240°C and 60 bar for 4 h. Moreover, the Pd/SiO₂‐NH₂ catalyst is robust and readily reusable without loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Green synthesis of Fe3O4@SiO2‐Ag magnetic nanocatalyst using safflower extract and its application as recoverable catalyst for reduction of dye pollutants in water

This paper reports the green and in situ preparation of Fe₃O₄@SiO₂‐Ag magnetic nanocatalyst synthesized using safflower (Carthamus tinctorius L.) flower extract without the addition of any stabilizers or surfactants. The catalytic performance of the resulting nanocatalyst was examined for the reduction of 4‐nitrophenol (4‐NP), methylene blue (MB) and methyl orange (MO) in an environment‐friendly medium at room temperature. The main factors such as pH, temperature and amount of catalyst influencing the nanocatalyst performance were studied. The apparent rate constants for 4‐NP, MO and MB reduction were calculated, being 0.756 min^?1, 0.064 s^?1 and 0.09 s^?1, respectively. The catalyst was recovered using an external magnet and reused several times with negligible loss of catalytic activity. The as‐synthesized nanoparticles were characterized using powder X‐ray diffraction, transmission electron microscopy, UV–visible, Fourier transform infrared and inductively coupled plasma atomic emission spectroscopies, dynamic light scattering and vibrating sample magnetometry.     

NH2SO3H–SiO2 as a new water‐compatible,recyclable heterogeneous catalyst for the synthesis of novel (α,β‐unsaturated) β‐amino ketones via aza‐Michael reaction

NH₂SO₃H–SiO₂/water as a novel catalytic system was used for the synthesis of (α,β‐unsaturated) β‐amino ketones via aza‐Michael reaction at reflux conditions. The methodology was of general applicability and the catalyst exhibited activity up to five cycles. The catalyst was characterized for the first time using FT‐IR, X‐ray diffraction and scanning electron microscopic–energy dispersion analytical X‐ray. The stability of the catalyst was evaluated by differential scanning calorimetry and TGA/differential thermal analysis. High efficiency of the catalyst along with its recycling ability and the rather low loading demonstrated in reactions are the merits of the presented protocol. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation of 1-butyl-3-methylimidazolium dodecatungstophosphate and its catalytic performance for esterification of ethanol and acetic acid

1-Butyl-3-methylimidazolium dodecatungstophosphate catalyst ([bmim]₃PW₁₂O₄₀) with high water tolerance was prepared from 1-butyl-3-methylimidazolium bromide ([bmim]Br) and phosphotungstic acid (H₃PW₁₂O₄₀). The catalyst was characterized by means of Fourier transform infrared spectroscopy, thermogravimetry-differential scanning calorimetry, n-BuNH₂ potentiometric titration, elemental analysis and so on. Its catalytic activity for esterification of ethanol and acetic acid to ethyl acetate was measured. The results show that there were three crystal-water molecules in the [bmim]₃PW₁₂O₄₀ catalyst, and it preserved the primary Keggin structure and acid strength of H₃PW₁₂O₄₀. The acid amount of [bmim]₃PW₁₂O₄₀ catalyst was less than that of H₃PW₁₂O₄₀. The [bmim]₃PW₁₂O₄₀ catalyst exhibited higher catalytic activity and reusability in the esterification of ethanol and acetic acid to ethyl acetate. __________ Translated from Chinese Journal of Catalysis, 2008, 29(7) (in Chinese)     

Magnetically Recyclable Nano-Fe2O3-Catalyzed Chemoselective Synthesis and Antioxidant Activity of Diethyl (3-((5-Aryl-1H-1,2,4-triazol-3-yl)thio)propyl)phosphonates

An efficient, green, and chemoselective S-alkylation of 5-aryl-1H-1,2,4-triazole-3-thiones with diethyl (3-bromopropyl)phosphonate in water, catalyzed by nano-Fe₂O₃ under ligand- and base-free conditions, is reported. Clean reaction, less expensive catalyst, excellent yields, and easy workup are the advantages of the present method. The catalyst can be easily collected by a magnet and recycled without significant loss in catalytic activity. The newly synthesized compounds were screened for their antioxidant property by using 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging assay. The majority of the compounds exhibited good antioxidant activity.     

Manganese(III) Salen Complex Immobilized on Fe3O4 Magnetic Nanoparticles: The Efficient,Green and Reusable Nanocatalyst

A new Fe₃O₄ magnetic nanoparticles supported manganese salen complex was successfully prepared by attaching manganese acetates to a novel N,N′‐bis(salicylidine)ethylenediamine ligand functionalized Fe₃O₄. The as‐prepared catalyst was characterized by TGA, XRD, FTIR, VSM, and TEM. It was found to be an efficient catalyst for the synthesis of benzopyranopyrimidines in aqueous medium. High catalytic activity and ease of recovery from the reaction mixture using external magnet, and several reuse times without significant losses in performance are additional eco‐friendly attributes of this catalytic system.     

Synthesis of magnetically recyclable Fe3O4@[(EtO)3Si–L1H]/Pd(II) nanocatalyst and application in Suzuki and Heck coupling reactions

A Pd(II) Schiff base complex as an efficient and highly heterogeneous catalyst was developed by immobilization of a palladium complex on the surface of modified Fe₃O₄ magnetite nanoparticles. These surface‐modified nanoparticles were characterized using various techniques such as transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, vibrating sample magnetometry, elemental analysis and Fourier transform infrared spectroscopy. The palladium catalyst exhibited efficient catalytic activity in Suzuki and Heck coupling reactions. This method has notable advantages such as excellent chemoselectivity, mild reaction conditions, short reaction times and excellent yields. The yields of the products were in the range 85–100%. Also, the nanocatalyst can be easily recovered with a permanent magnet and reused at least five times without noticeable leaching or loss of its catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

Magnetic carbon nanotube as a highly stable support for the heterogenization of InCl3 and its application in the synthesis of isochromeno[4,3-c]pyrazole-5(1H)-one derivatives

In the present study, a novel magnetically retrievable catalytic system involving indium nanoparticles on magnetic carbon nanotube (Fe₃O₄-CNT-In) was synthesized and characterized using various techniques, such as Fourier transform-infrared, thermogravimetric analysis, energy-dispersive X-ray analysis, vibrating-sample magnetometry1, X-ray diffraction, field emission-scanning electron microscopy and inductively coupled plasma-optical emission spectrometry. The catalytic activity of the synthesized nanocatalyst was evaluated in green synthesis of isochromeno[4,3-c]pyrazole-5(1H)-one derivatives from the reaction of ninhydrin and arylhydrazones under solvent-free conditions. The catalyst was magnetically separated from the reaction mixture using an external magnet and recovered for five cycles without an appreciable decrease in its catalytic efficiency. Performing the reactions in environmentally friendly and affordable conditions, the low catalyst percentage, high yield of products, short reaction times, large substrate scope and easy work-up are the merits of this protocol. Furthermore, four of the synthesized isochromeno[4,3-c]pyrazole-5(1H)-one derivatives are also new.     

A novel hydrophobic copper complex supported on γ‐Fe2O3 as a magnetically heterogeneous catalyst for one‐pot three‐component synthesis of α‐aminophosphonates

A novel hydrophobic copper complex supported on γ‐Fe₂O₃ is synthesized and characterized by different methods such as FT‐IR, XRD, TEM, SEM, TGA, VSM, ICP and CHN analysis. It was used as a magnetically recyclable heterogeneous catalyst for the efficient synthesis of α‐aminophosphonates via a one‐pot three‐component reaction under solvent‐free conditions. The present catalytic system worked extremely well for the synthesis of α‐aminophosphonates even up to five subsequent trails without significant loss of its catalytic activity or copper leaching. The TEM image and FT‐IR spectrum of the catalyst after five times recovery showed that the structure of the catalyst was stable under the reaction conditions with no change being observed. The strong magnetic properties of the reused catalyst were revealed by complete and easy attraction using an external magnet and also by VSM curve. This work represents the first and unique example of a hydrophobic copper complex for catalysis in water generating reactions.     

MnO2@Fe3O4 Magnetic Nanoparticles as Efficient and Recyclable Heterogeneous Catalyst for Benzylic sp3 C−H Oxidation

Herein, we report a highly chemoselective and efficient heterogeneous MnO₂@Fe₃O₄ MNP catalyst for the oxidation of benzylic sp³ C?H group of ethers using TBHP as a green oxidant to afford ester derivatives in high yield under batch/continuous flow module. This catalyst was also effective for the benzylic sp³ C?H group of methylene derivatives to furnish the ketone in high yield which can be easily integrated into continuous flow condition for scale up. The catalyst is fully characterized by spectroscopic techniques and it was found that 0.424 % MnO₂@Fe₃O₄ catalyzes the reaction; the magnetic nanoparticles of this catalyst could be easily recovered from the reaction mixture. The recovered catalyst was recycled for twelve cycles without any loss of the catalytic activity. The advantages of MnO₂@Fe₃O₄ MNP are its catalytic activity, easy preparation, recovery, and recyclability, gram scale synthesis with a TOF of up to 14.93 h^?1 and low metal leaching during the reaction.     

Copper(II) Schiff Base Complex Immobilized on Superparamagnetic Fe3O4@SiO2 as a Magnetically Separable Nanocatalyst for Oxidation of Alkenes and Alcohols

A new heterogeneous catalyst containing a copper(II) Schiff base complex covalently immobilized on the surface of silica‐coated Fe₃O₄ nanoparticles (Fe₃O₄@SiO₂‐Schiff base‐Cu(II)) was synthesized. Characterization of this catalyst was performed using various techniques. The catalytic potential of the catalyst was investigated for the oxidation of various alkenes (styrene, α‐methylstyrene, cyclooctene, cyclohexene and norbornene) and alcohols (benzyl alcohol, 3‐methoxybenzyl alcohol, 3‐chlorobenzyl alcohol, benzhydrol and n ‐butanol) using tert ‐butyl hydroperoxide as oxidant. The catalytic investigations revealed that Fe₃O₄@SiO₂‐Schiff base‐Cu(II) was especially efficient for the oxidation of norbornene and benzyl alcohol. The results showed that norbornene epoxide and benzoic acid were obtained with 100 and 87% selectivity, respectively. Moreover, simple magnetic recovery from the reaction mixture and reuse for several times with no significant loss in catalytic activity were other advantages of this catalyst     

Immobilization of copper nanoparticles on WO3 with enhanced catalytic activity for the synthesis of 1,2,3-triazoles

In this study, a heterogeneous catalyst based on copper nanoparticles immobilized on metal oxide, WO₃, was fabricated using an impregnation method as an easy and straightforward nanoparticle synthesis strategy. The successful synthesis of the nanocatalyst was confirmed using various spectroscopic techniques such as X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, and transmission electron microscopy. The catalytic performance of the well-characterized material was evaluated through the azide–alkyne cycloaddition reaction (click reaction) in the aqueous medium. To optimize reaction conditions, different reaction parameters such as nanocatalyst amount, reaction time, temperature, and solvents were studied. Experimental results showed that as-prepared nanocatalyst (Cu/WO₃) could act as an effective and reusable heterogeneous catalyst in water for the synthesis of 1,2,3-triazoles in good-to-excellent yields. In addition, Cu/WO₃ has some advantages such as simple preparation procedure, easy separation, and recyclability for three runs with no remarkable loss of catalytic activity, which is essential from a catalytic application point of view.     

Environmentally friendly and highly efficient synthesis of benzoxazepine and malonamide derivatives using HPA/TPI‐Fe3O4 nanoparticles as recoverable catalyst in aqueous media

A magnetic inorganic–organic nanohybrid material (HPA/TPI‐Fe₃O₄ NPs) was produced as an efficient, highly recyclable and eco‐friendly catalyst for the one‐pot multi‐component synthesis of malonamide and 2,3,4,5‐tetrahydrobenzo[b ][1,4]oxazepine derivatives with high yields in short reaction times (25–35 min) in aqueous media at room temperature. The nanohybrid catalyst was prepared by the chemical anchoring of H₆P₂W₁₈O₆₂ onto the surface of modified Fe₃O₄ nanoparticles (NPs) with N ‐[3‐(triethoxysilyl)propyl]isonicotinamide (TPI) linker. The magnetic recoverable catalyst was easily recycled at least ten times without any loss of catalytic activity.     

Copolymerization of carbon dioxide and propylene oxide under inorganic oxide supported rare earth ternary catalyst

Recently, rare earth ternary coordination catalyst represented as Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ has been used for producing poly(propylene carbonate) (PPC, an alternating copolymer of carbon dioxide and propylene oxide) in industry scale, but its catalytic activity needs further improvement. One reason for the relatively low catalytic activity lied in that only 11.7% of active center was efficient due to possible embedding of active center in the heterogeneous catalyst. In this report, supporting strategy was developed, where Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ was supported on various inorganic oxides. Two supporting methods were carried out. One way was to mix Y(CCl₃OO)₃‐Glycerin with inorganic oxide first and then ZnEt₂ was dropped to form the supported catalyst, and the other was to make Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ at first and then mixing with inorganic oxides. The former showed decreasing catalytic activity compared with corresponding unsupported rare earth ternary catalyst, while an improvement of 16–36% in catalytic activity was realized in the latter. PPC with an average number molecular weight (M_n) of over 100 kg/mol and carbonate unit (CU) content of higher than 96% was prepared by both supported catalysts. The catalytic activity of the supported catalyst depended significantly on the supports, which increased in the following order: α‐Al₂O₃ < MgO < ZnO ≈ SiO₂ <γ‐Al₂O₃. γ‐Al₂O₃ was the best support for rare earth ternary catalyst, which showed a remarkable 36% increase in catalytic activity, corresponding to the utilization of 17% of active center. Although MgO supported catalyst gave only an 8% increase in catalytic activity, the M_n and CU content of PPC were raised to about 143 kg/mol and 99%, whereas the PPC from common rare earth ternary catalyst was about 108 kg/mol and 97%, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

The Novel Synthesis of Functionalized Indenopyrazolones Using Fe3O4 nanoparticles stabilized on MMT: An Efficient Magnetically Recoverable Heterogeneous Nanocomposite Catalyst

A practical and simple approach for the one‐pot multicomponent synthesis of indenopyrazolones is described via the condensation of ninhydrin (indan‐1,2,3‐trione), phenylhydrazine, and various aldehydes in the presence of MMT@Fe₃O₄ as an environmentally benign core/shell nanocomposite catalyst. The catalyst could be recycled using an external magnet easily and reused several times without remarkable loss of its catalytic activity. Furthermore, avoiding hazardous solvents, reusability of the catalyst, easy work‐up, short reaction times, room temperature, and mild reaction conditions are the advantages of this new eco‐friendly protocol.     

Design and characterization of Dendrimer of MNPs as a novel,heterogeneous and reusable nanomagnetic organometallic catalyst for one‐pot synthesis of hydroxyl naphthalene‐1,4‐dione derivatives under solvent‐free conditions

A novel super acidic magnetic nanoparticle as catalyst was successfully synthesized. The preparation of this dendrimer sulfonic acid functionalized γ‐Fe₂O₃ magnetic core‐shell silica nanoparticles as a new recoverable and heterogeneous nanocatalyst was described. The new catalyst was characterized using various techniques such as scanning electron microscopy (SEM), energy dispersive spectrum (EDS), and thermo gravimetric synthesis (TGA). Moreover, we have examined the catalytic activity of the catalyst for one‐pot, efficient and facile synthesis of 2‐hydroxy‐1,4‐naphthoquinone derivatives via a three‐component condensation reaction of 2‐hydroxynaphthalene‐1,4‐dione, aromatic aldehydes and aniline derivatives. High yields of products, short reaction times, waste‐free, mild, ambient and solvent‐free reaction conditions are advantages of this protocol. Also, the catalyst can be easily recovered by an external magnetic and reused several times without significant loss of its catalytic activity.     

Synthesis and characterization of a novel and green rod-like magnetic ZnS/CuFe2O4/agar organometallic hybrid catalyst for the synthesis of biologically-active 2-amino-tetrahydro-4H-chromene-3-carbonitrile derivatives

The magnetic biocompatible rod-like ZnS/CuFe₂O₄/agar organometallic hybrid catalyst was designed and prepared based on a natural macromolecule (agar) through a green and convenient method using inexpensive, nontoxic, and easily available substances. Then, the as-prepared catalyst was characterized by several techniques such as Fourier transform-infrared spectroscopy, energy-dispersive X-ray analysis, scanning electron microscopy image, transmission electron microscopy, vibrating sample magnetometry curve, X-ray diffraction pattern, and thermogravimetric analysis. Eventually, the catalytic application of the ZnS/CuFe₂O₄/agar nanobiocomposite was assessed in sequential Knoevenagel condensation–Michael addition reaction of dimedone, malononitrile, and different substituted aromatic aldehydes for the synthesis of 2-amino-tetrahydro-4H-chromene-3-carbonitrile derivatives. Some notable strengths of this environmentally benign catalyst include simplicity of catalyst preparation and separation, affording desired products with satisfactory yields (81%–97%) in very short reaction times (3–18 min), and with no need for complicated work-up processes. Experimental tests showed that the catalyst can be successfully reused after five sequential runs without significant reduction in its catalytic efficiency.