Design, Synthesis, and Characterization of a Novel

Article Cite This: Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

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Design, Synthesis, and Characterization of a Novel Magnetically Recoverable Copper Nanocatalyst Containing Organoselenium Ligand and Its Application in the A3 Coupling Reaction Yalda Rangraz, Firouzeh Nemati,* and Ali Elhampour Department of Chemistry, Semnan University, Semnan, Iran 35131-19111

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ABSTRACT: In the present work, a novel heterogeneous catalytic system involving copper(I) complex of moisture- and air-stable organoselenium ligand supported on Fe3O4 nanoparticles modified by SiO2/aminopropyltrieethoxysilane was designed, synthesized, and characterized using various physicochemical methods inclusive Fourier transform infrared spectroscopy, X-ray diffraction, vibrating sample magnetometry, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, atomic absorption spectroscopy, inductively coupled plasma optical emission spectroscopy, and thermogravimetry. The catalytic activity of the synthesized magnetic nanocatalyst which was named Fe3O4@SiO2-Se-T/CuI was evaluated in A3 coupling reactions for the preparation of propargylamine compounds using diverse aldehydes, secondary amines, and terminal alkynes. The benign reaction condition, variety of substrate scope, good yield, low reaction time, high stability, utilization of organoselenium compound as an air- and moisture-insensitive ligand and its immobilization on solid support, and, more importantly, effortless recovery and recyclability of the catalyst up to five consecutive cycles without remarkable loss in its activity are some of the interesting features of this protocol that makes it more beneficial from both industrial and environmental points of view.

1. INTRODUCTION In the past few decades, organic compounds containing selenium have attracted remarkable concern because of numerous uses in the synthesis of organic and natural products,1,2 pharmacological properties,3,4 biochemistry,5 catalytic activity,6,7 and synthesis of conducting and semiconducting materials.8 Also, a series of unique features of these compounds such as the potency of strong electron donating of selenium, stability against moisture and air, and solubility in diverse solvents have led to the preparation of diverse metal complexes of organoselenium ligands.9−13 The promising catalytic activity of these complexes has been displayed in different organic chemical transformations including carbon− carbon coupling reactions,14 direct boronation of allyl alcohols,15 oxidation of alcohols,16 transfer hydrogenation of ketones,17 and coupling of allyl alcohols and aldehydes.18 The catalytic role of these metal complexes, which are especially thermally stable and resistant to aerial oxidation, makes them not only rivals but special alternatives to their respective sulfur and phosphorus analogues.10 All of the aforementioned selenium-containing complexes are homogeneous catalysts, and there exist only a few reports in the literature on which solid supports are used for the immobilization of metal complexes of selenium-containing ligands as heterogeneous catalytic systems.19−23 Although common catalysts with homogeneous nature possess many advantages, such as excellent activity, efficient selectivity, high © XXXX American Chemical Society

product yields, and high turnover number, various problems including tedious and time-consuming separation processes and remaining impurities inclusive the ligand or metal in the structure of final products, the lack of catalyst reusability, and the loss of valuable metals cause some limitations to the wide use of these catalysts in industrial applications.24−26 On the other hand, despite having outstanding characteristics such as reusability and much less leaching, the activity and selectivity of heterogeneous catalysts are decreased compared with those of homogeneous ones.27 The combination of heterogeneous catalytic systems and nanotechnology can overcome the abovementioned drawbacks. This interesting strategy can be achieved through the anchoring of the complexes, stable ligands, and other homogeneous catalysts on the surface of different nanosupports.28,29 Among the different classes of nanosupports, magnetic nanoparticles (MNPs) have generated a lot of interest because of low toxicity, excellent chemical and thermal stability, easy synthesis and capability of being modified with reactive functional groups, high surface area to volume ratio, and convenient separation from media by applying a simple magnetic bar and recycling.30−33 Received: July 14, 2019 Revised: August 24, 2019 Accepted: August 26, 2019

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DOI: 10.1021/acs.iecr.9b03843 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

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Industrial & Engineering Chemistry Research Scheme 1. Synthetic Procedure of Fe3O4@SiO2-Se-T/CuI

Propargylamines are useful and valuable synthetic intermediates for the preparation of a broad spectrum of nitrogencontaining biologically active molecules and natural products including fungicides, herbicides, peptide isosteres, β-lactams, indolizines, oxazoles, pyrroles, pyrrolidines, and quinolines.34,35 In addition, some propargylamine derivatives have even been utilized as crucial precursors in the synthesis of antiParkinson’s, anti-Alzheimer’s, and antidepressant medicines.36,37 Traditional synthetic methodologies for the production of propargylamines involve the reaction of amines with less commercially available propargyl halides, propargyl phosphates, or propargyl triflates38,39 or the stoichiometric reaction of Grignard reagents or lithium acetylides with imines or their derivatives under inert reaction conditions.40−42 An alternative atom-economical and effective method to access high-value propargylamine derivatives is the A3 coupling reaction (threecomponent coupling of aldehydes, amines, and alkynes). Various salts and complexes of transition metals, such as nickel,43 iridium,44 silver,45 gold,46 iron,47 copper,48 zinc,49 mercury,50 indium,51 zirconium,52 and rhenium,53 have been reported as homogeneous or heterogeneous catalysts for C−H bond activations of terminal alkynes, and among them, copper

has received considerable attention because of its ease of handling, versatility, low toxicity, and low cost.54 Although all these reported catalytic systems are efficient for A3 coupling reactions, most of them suffer from disadvantages including harsh reaction conditions, low yields, high costs, recovery and recycling of the catalyst, and long reaction times. Therefore, development of novel catalytic systems for one-pot synthesis of propargylamines is an interesting research area for synthetic chemists. In continuation of our previous works on the expansion of new heterogeneous materials as catalysts based on organoselenium compounds and their application in different organic transformations,23,55,56 in the present study, we describe a novel organoselenium−copper(I) complex supported on Fe3O4 nanoparticles (Fe3O4@SiO2-Se-T/CuI) as a robust magnetically recoverable nanocatalyst (Scheme 1). We hoped to carry out the A3 coupling reaction using the selenium and nitrogen donor atoms containing ligand in the nanocatalyst construction (which provides a combination of hard and soft donor sites capable to chelate) that can forcefully immobilize the copper species. The catalytic activity of (Fe3O4@SiO2-Se-T/CuI) was next examined in the A3 coupling reaction of various aldehydes, B


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Industrial & Engineering Chemistry Research

the dispersed suspension and the reaction mixture was stirred at room temperature for 10 h. Afterward, the mixture was filtered magnetically and the obtained solid, Fe3O4@SiO2-CCl, was washed with hot THF (5 × 5 mL) and dried in an oven at 60 °C.58 2.2.3. Synthesis of Fe3O4@SiO2-SeCN. To a mixture of Fe3O4@SiO2-CCl (0.1 g) in degassed THF (6 mL) in an ice bath was added a solution of potassium selenocyanate (1.7 mmol, 0.244 g) in 10 mL of THF drop by drop over 10 min. Then, the reaction temperature was slowly increased to 50 °C and stirring was continued for 48 h. After that cooling to ambient temperature was done, and the Fe3O4@SiO2-SeCN nanoparticles were magnetically separated and washed several times with THF and then dried in an oven at 60 °C.59 2.2.4. Synthesis of 2,4,6-Triazido-1,3,5-triazine. A solution of sodium azide (5 g) in deionized water (20 mL) was added to a solution of cyanuric chloride (3.1 g, 1 mmol) in acetone (10 mL) and stirred at room temperature for 10 min at 50 °C. Then, the resulting white solid product was collected by filtration and washed with water and acetone and dried in air.60 2.2.5. Synthesis of Fe3O4@SiO2-Se-T. Fe3O4@SiO2-SeCN magnetic nanoparticles (0.5 g) and 2,4,6-triazido-1,3,5-triazine (1 g) were mixed with CuI (17 mg, 0.09 mmol) in a DMF/ THF solvent mixture of ratio 1:1 (10 mL, 1:1), and stirred for 24 h at 50 °C. After that, the afforded material (Fe3O4@SiO2Se-T) was collected using a permanent magnet, rinsed with diethyl ether, water, and acetone, respectively, and finally dried in an oven for 12 h.61 2.2.6. Procedure for Synthesis of Fe3O4@SiO2-Se-T/CuI. For complexation of Fe3O4@SiO2-Se-T heterogeneous ligand with CuI, first, CuI (0.03 g) dissolved in DMF (10 mL) was stirred for 30 min at 50 °C. Then, 1.0 g of Fe3O4@SiO2-Se-T dispersed in 5 mL of DMF was added to the resulting solution and the reaction mixture was stirred for 24 h. Finally, the resulting nanoparticles, Fe3O4@SiO2-Se-T-CuI, were separated by a magnet and washed several times with DMF and dried in an oven at 70 °C. 2.2.7. Catalytic Activity in the Synthesis of Propargylamines Using Fe3O4@SiO2-Se-T-CuI. Nano-Fe3O4@SiO2-SeT/CuI catalyst (20 mg) was added to a mixture of benzaldehyde derivatives (1.0 mmol), secondary amine (1.2 mmol), and phenylacetylene (1.5 mmol), and heated at 100 °C under solvent-free condition. The reaction progress was screened using thin layer chromatography (TLC). Upon the completion of the reaction, the mixture was cooled to ambient temperature and diluted with 10 mL of hot ethanol. Subsequently, the nanocatalyst was magnetically filtered by applying an external magnetic field, washed several times with ethanol, and dried in an oven at 80 °C to be ready for utilizing in other cycles without additional purification. After isolation of catalyst, the filter was concentrated and the resulting residue was purified by flash chromatography on silica gel eluting with an n-hexane and ethyl acetate mixture, to afford the desired purity.

amines, and phenylacetylenes, and the corresponding propargylamines were obtained in good to high yields. Our surveys in the literature show that this is the first report wherein an organoselenium−copper complex has been immobilized on the solid support and effectively exploited as a heterogeneous catalytic system for the preparation of a broad range of propargylamines.

2. EXPERIMENTAL SECTION 2.1. Chemicals and Instrumentation. Iron chloride salts [(FeCl3·6H2O) and (FeCl2·4H2O)], tetraethyl orthosilicate (TEOS), 25% ammonium hydroxide solution, 3-aminopropyltriethoxysilane (APTS), triethylamine, potassium selenocyanate, sodium azide (NaN3), cyanuric chloride, and different aldehydes, amines, and phenylacetylenes were obtained from Merck and Sigma-Aldrich and applied as received. All the solvents were acquired from laboratory reagent grade. Fourier transform infrared (FT-IR) spectroscopy was performed on pressed KBr pallets using a Shimadzu 8400s spectrometer in the range 400−4000 cm−1 with a resolution of 1 cm−1 under atmospheric conditions. The crystalline structures of the nanocatalyst and pure Fe3O4 were evaluated by powder Xray diffraction (XRD) analysis by employing a Philips instrument equipped with Cu Kα radiation source with a wavelength of 1.54 Å. The thermal stability of the catalyst was investigated with a thermal gravimetric analyzer (LINSEIS model STS PT 16,000) from room temperature to 800 °C at a heating rate of 10 °C min−1 under air flow. The field emission scanning electron microscopic (FE-SEM) image was collected on an FE-SEM microscope (model Tescanvega II XMU). For performing this technique, a low amount of material was placed on a carbon tape and next covered with a thin layer of gold by applying a sputter coater. Elemental compositions of nanocatalyst were determined with energy dispersive X-ray spectroscopic (EDX) analysis equipped with the SEM instrument. Magnetic susceptibility measurements performed using a vibrating sample magnetometer (VSM), model Lakeshore 7407, at ambient temperature. X-ray photoelectron spectroscopy (XPS) was investigated using a PHI Quantera II XPS scanning microprobe. The copper determination was performed using flame atomic absorption spectroscopy (FAAS) on a Shimadzu model AA-680 atomic absorption spectrometer by applying an acetylene flame. The amount of copper in the catalyst was also estimated by inductively coupled plasma (ICP) optical emission spectrometry (OES) on a VARIAN VISTA-PRO. Inductively coupled plasma optical emission spectroscopy (ICP-OES) was also employed to analyze the copper content in the obtained catalyst. The progress of the A3 coupling reaction and the purity determinations of the products were screened using thin layer chromatography (TLC) on commercial aluminum-backed plates coated with silica gel 60 F254, by UV light. 2.2. Procedure for the Synthesis of Core/Shell Catalyst. 2.2.1. Synthesis of Fe3O4@SiO2-NH2. First, magnetic nanoparticles Fe3O4, Fe3O4@SiO2, and Fe3O4@SiO2-NH2 were prepared based on our previously reported procedures.55,57 2.2.2. Synthesis of Fe3O4@SiO2-CCl. The prepared Fe3O4@ SiO2-NH2 (0.2 g) was dispersed in 10 mL of THF using ultrasonication for 20 min. Then, cyanuric chloride (0.185 g, 1 mmol) and triethylamine (0.14 mL, 1 mmol) were added to

3. RESULTS AND DISCUSSION 3.1. Preparation of Nano-Fe3O4@SiO2-Se-T/CuI. The schematically synthetic pathway used for the preparation of nano-Fe3O4@SiO2-Se-T/CuI is outlined in Scheme 1. In the first step, the silica-coated Fe3O4 nanoparticles (Fe3O4@SiO2) were synthesized based on our previously described procedure and chosen as a magnetic nanosupport. Afterward, the surface of magnetic nanoparticles was modified with 3-aminopropylC


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stretching vibration of the triazine ring strongly confirm the grafting of the cyanuric chloride (CC) on the surface of the magnetic nanoparticles. Also, the stretching vibration of unreacted C−Cl bonds is completely obscured by the symmetric stretching vibration of the Si−O−Si bond in SiO2 (Figure 1a). After the functionalization of Fe3O4@SiO2-CCl with potassium selenocyanate, new absorption band appeared at 2071 cm−1 which is related to stretching vibrations of the cyanide group of the selenocyanate moiety (Figure 1b). The cyanide peak disappeared after the formation of the 1Htetrazole linker during the “(2 + 3) cycloaddition” reaction. The absence of a cyanide peak and the emergence of the new absorption band at 2100 cm−1 corresponding to the N3 stretching vibration in the FT-IR spectrum of Fe3O4@SiO2Se-T/CuI demonstrate that the selenocyanate group successfully reacted with 2,4,6-triazido-1,3,5-triazine via the “(2 + 3) cycloaddition” reaction (Figure 1c). 3.2.2. X-ray Diffraction Analysis. To investigate the crystalline structure and chemical composition of the synthesized materials, XRD analysis of Fe3O4 (Figure 2a)

triethoxysilane to provide an amine group for further functionalization. Then, cyanuric chloride (CC) was anchored covalently onto the surface of the amine-functionalized magnetic nanoparticles while the temperature reaction was under control to avoid further substitution of chlorine atoms of CC to produce Fe3O4@ SiO2-CCl. Subsequently, two other chlorine atoms of CC were replaced with 2 equiv of potassium selenocyanate through the formation of C−Se bonds between the selenium atoms and the triazine ring. In the next step, 2,4,6-triazido-1,3,5-triazine was prepared by stirring of sodium azide in water with a solution of cyanuric chloride in acetone at 50 °C and then reacted with Fe3O4@ SiO2-SeCN nanoparticles via the “(2 + 3) cycloaddition” reaction in the presence of copper iodide to form the tetrazole ring to obtain Fe3O4@SiO2-Se-T. Ultimately, the resulting functionalized MNPs having chelating groups (selenium and nitrogen) on their surface were easily metalated with copper(I) iodide in DMF to provide the desired Cu complex which grafted onto the Fe3O4@SiO2-Se-T nanoparticles. The synthesized magnetic nanocatalyst was characterized using several various microscopic and spectroscopic techniques, including FT-IR spectroscopy, XRD, thermogravimetry (TG), FE-SEM, EDX, VSM, XPS, AAS, and ICP-OES. 3.2. Catalyst Characterization. 3.2.1. Functional Group Analysis. To characterize different functional groups present in structures of the Fe3O4@SiO2-CCl, Fe3O4@SiO2-SeCN, andFe3O4@SiO2-Se-T/CuI nanoparticles, Fourier transform infrared spectroscopy was conducted. As shown in Figure 1a,

Figure 2. X-ray diffraction patterns of (a) Fe3O4 and (b) Fe3O4@ SiO2-Se-T/CuI.

and Fe3O4@SiO2-Se-T/CuI (Figure 2b) was carried out. The high angle XRD patterns of both compounds indicate six distinguished Bragg’s diffraction peaks at the 2θ values of 30.86° (220), 36.26° (311), 43.15° (400), 53.81° (422), 57.19° (511), and 63.1° (440), which are imputed to the cubic inverse spinel structure of magnetite nanoparticles (JCPDS File No. 85-1436). The above results clearly show that the crystalline construction of the nanoparticles has no change after the surface modification with the copper complex. Besides the peaks of iron oxide, the emergence of a broad peak located at 2θ = 18−28° in the X-ray diffraction pattern of Fe3O4@SiO2-Se-T/CuI corresponds to the presence of amorphous SiO2 shell around the Fe3O4 nanoparticles. No characteristic peaks for copper species are observed in the XRD pattern of Fe3O4@SiO2-Se-T/CuI. According to the literature, this observation can be ascribed to the dispersion of copper iodide in the matrix that cannot lead to the formation of a regular crystal lattice.62,63 Stabilization of the copper species was confirmed by AAS and EDX. Also, according to the Scherrer equation (d = Kλ/(β cos θ)), the average crystalline size of the Fe3O4 cores for 2θ = 36.26° is calculated to be 13 nm. 3.2.3. TG Determination. To examine the thermal manner, as well as the percentage of organic moiety groups immobilized

Figure 1. FT-IR spectra of (a) Fe3O4@SiO2-CCl, (b) Fe3O4@SiO2SeCN, and (c) Fe3O4@SiO2-Se-T/CuI.

the characteristic absorption band at 574 cm−1 is attributed to the stretching vibration of the Fe−O bond in the crystalline lattice of Fe3O4. The stabilization of silane polymer on magnetic nanoparticle surface is certified by observation of the high-intensity band for asymmetric stretching vibration of Si− O−Si which appeared at 1070 cm−1. The weak absorption band at 2927 cm−1 is assigned to the stretching vibration frequency of the C−H in the alkyl chain. Additionally, the prominent peak at 1404 cm−1 can be ascribed to the C−N stretching vibrations. The observed absorption bands appearing at 3400 and 3141 cm−1 correspond to the stretching modes of OH and NH, respectively. Thus, the above results display that 3-aminopropyltriethoxysilane (APTS) is successfully immobilized onto the surface of the Fe3O4@SiO2 MNPs. Moreover, the emergence of two characteristic absorption bands at 1664 and 1579 cm−1 corresponding to the CN D


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Fe3O4@SiO2-Se-T/CuI are presented in Figure 5. The presence of iron, oxygen, silicon, carbon, nitrogen, and chlorine atoms in the EDX spectrum of Fe3O4@SiO2-CCl obviously confirms a silane shell was covered around the magnetic core Fe3O4 as well as the successive surface functionalization (the incorporation of the amine group), and the immobilization of cyanuric chloride (triazine ring) on the surface of the Fe3O4@SiO2 nanoparticles (Figure 5a). The presence of selenium element in the EDX spectrum of Fe3O4@ SiO2-SeCN is enough evidence for immobilization of the selenocyanate on Fe3O4@SiO2-CCl nanoparticles. Besides these elements, the observation of copper and iodine peaks authenticates the successful complexation of CuI with ligand as well as the structure of the final nanocatalyst. (Figure 5b). Also, the absence of chlorine atom in the EDX spectrum of Fe3O4@SiO2-Se-T-Se/CuI shows that all three chlorine atoms of cyanuric chloride are completely replaced with amine groups of APTS and as well as selenocyanate. The amount of copper obtained from EDX technique is 3.97 (wt %). 3.2.6. Magnetization Study. The magnetic behaviors of Fe3O4 and Fe3O4@SiO2-Se-T-Se/CuI nanoparticles were examined using vibrating sample magnetometer (VSM) analysis at ambient temperature. As can be shown in Figure 6, the values of the saturation magnetization are 66.27 and 23.15 emu/g for Fe3O4 (Figure 6a) and Fe3O4@SiO2-Se-T/ CuI (Figure 6b) nanoparticles, respectively. This decrease in the saturation magnetization value of Fe3O4@SiO2-Se-T/CuI in comparison with Fe3O4 MNPs is more evidence for functionalization of MNPs with nonmagnetic organic components. Regardless of this decrease in the saturation magnetization value, the nanocatalyst still can be completely isolated from the reaction mixture with an external magnet. 3.2.7. XPS Analysis. X-ray photoelectron spectroscopy (XPS) was carried out to identify the chemical oxidation state of selenium in the fresh and used Fe3O4@SiO2-Se-T/CuI catalyst (Figure 7). The high resolution scans of the Se 3d region (of both samples) reveal a peak at the binding energy of 55.78 eV that can be indexed to the selenium(II) oxidation state. After the catalytic reaction, the chemical state selenium remained unchanged, further exemplifying the robust stability of Fe3O4@SiO2-Se-T/CuI.64,65 3.2.8. Atomic Absorption Spectroscopic Analysis. Atomic absorption spectroscopy (AAS) analysis was performed for the estimation of copper amount in Fe3O4@SiO2-Se-T/CuI. To this purpose, a low amount of prepared catalyst (0.01 g) was dissolved in a mixture of HCl and HNO3 (3:1) and stirred at 70 °C for 1 h. The resulting filtrate was next analyzed by applying AAS. It was found that the amount of copper(I) ion was 3.74 (wt %), which is in good agreement with the result of EDX analysis. 3.2.9. ICP-OES Analysis. Also, ICP-OES analysis was exploited for measuring the content of copper in the synthesized nanocatalyst structure. The loading of copper was found to be 3.45 wt %, which is in good agreement with the results of EDX and AAS analyses. To investigate the nature of the catalysis and the leaching of copper, ICP-OES analysis of the reused catalyst was performed. According to the obtained results, no significant decrease was observed in the Cu content. The Cu content in the fresh catalyst and the recycled catalyst was 3.45 and 3.22 wt %, respectively, which indicated the copper leaching of this catalyst is very low, demonstrating the heterogeneous nature of

on the surface of synthesized nanoparticles, thermogravimetric analysis (TGA) was done under an air atmosphere with a ramping rate of 10 °C/min over the temperature range 30− 800 °C (Figure 3).

Figure 3. TGA plot of Fe3O4@SiO2-Se-T/CuI.

The corresponding thermogram demonstrates mass loss in two steps. As usual, the first weight loss (8%) at low temperatures (30−150 °C) is assigned to the removal of physically adsorbed solvents and hydrogen-bonded water molecules present at the surface of the nanoparticles. The second weight reduction (about 18%) in the temperature range starting from 150 to 600 °C is attributed to the decomposition of the organic layers supported on the surface of the sample. Therefore, on the basis of TGA results, the good grafting of organoselenium−copper(I) complex onto the surface of magnetic nanoparticles and the thermal stability of the nanocatalyst are verified. 3.2.4. FE-SEM Analysis. Field emission scanning electron microscopy (FE-SEM) analysis was applied for the investigation of morphology, surface structure, and size of the synthesized magnetite nanocatalyst (Figure 4). The FE-SEM

Figure 4. SEM image of Fe3O4@SiO2-Se-T/CuI.

micrograph of Fe3O4@SiO2-Se-T/CuI illustrates the relatively homogeneous and uniform distribution and spherical morphology of modified magnetic nanoparticles with a mean particle size of about 18−25 nm. 3.2.5. Energy Dispersive X-ray Spectroscopic Analysis. Energy dispersive X-ray spectra of Fe3O4@SiO2-CCl and E


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Figure 5. EDX spectra of (a) Fe3O4@SiO2-CCl and (b) Fe3O4@SiO2-Se-T/CuI.

of propargylamines, the model reaction was carried out in the absence of catalyst and no product was achieved after a prolonged reaction time (Table S1, entry 1). Additionally, to explore the effect of catalyst amount, the model reaction was performed with the various dosages of the synthesized catalyst. The best result was achieved with 20 mg of catalyst (Table S1, entry 3), as increasing the amount of catalyst from 20 to 30 mg did not increase the product yield and rate of reaction (Table S1, entry 4) and 10 mg of catalyst gave relatively lower conversion (Table S1, entry 2). Moreover, to investigate the role of the ligand in the activity of Fe3O4@SiO2-Se-T/CuI, the model reaction was tested in the presence of CuI as the homogeneous catalyst (Table S1,

the prepared catalyst. These results are also along with the recyclability test. 3.3. Evaluation of Catalytic Property of Fe3O4@SiO2Se-T/CuI through the A3 Coupling Reaction. After the successful preparation and fabrication of Fe3O4@SiO2-Se-T/ CuI, its catalytic applicability was explored in the threecomponent A3 reaction of aldehydes, amines, and alkynes. To obtain the optimum reaction profile, the coupling of benzaldehyde, morpholine, and phenylacetylene was selected as the plan reaction and the effect of disparate parameters such as the quantity of catalyst, solvent, and temperature were surveyed for model reaction. Outcomes are presented in Table S1. Initially, to demonstrate the role of catalyst in the synthesis F


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entry 5). The lower activity of CuI shows the synergy of the ligand and metal on the activity of the catalyst. The obtained results clearly demonstrate that Fe3O4@SiO2Se-T/CuI is a critical catalyst for this coupling reaction. Then, to scrutinize the influence of solvent, the test reaction was performed in variant solvents including toluene, THF, EtOH, and H2O and also in solvent-free condition. Among the different cases studied, solvent-free condition was recognized as the most favorable system (Table S1, entry 3). Subsequently, the effect of temperature on the reaction progress was surveyed. As can be seen in Table S1, the most suitable temperature for the A3 reaction in the presence of Fe3O4@SiO2-Se-T/CuI NPs was 100 °C (Table S1, entry 3). By decreasing the reaction temperature to 80 °C, a significant reduction in the product yield was seen (Table S1, entry 10), and increasing the temperature to 120 °C was not effective on the yield of the product (Table S1, entry 11). Also, a trace amount of coupling product was observed at room temperature (25 °C). Thus, entry 3 of Table S1 was chosen as optimal conditions for the reaction of benzaldehyde, morpholine, and phenylacetylene using Fe3O4@SiO2-Se-T/CuI catalyst. 3.4. Scope and Generality of Reaction. The scope of the A3 coupling reaction, on the basis of these undertaking results, was extended for a series of aromatic aldehydes, secondary amines, and terminal alkynes to confirm the generality of the developed protocol. As can be clearly seen in Table S2, both aromatic aldehydes and phenylacetylenes containing electron-withdrawing and electron-releasing functional groups on the benzene ring generated the desired propargylamines in good to excellent yields and electrondonating substitutions in the ortho position of benzaldehyde (entries 6 and 7) did not exert any influence on the product yield. Interestingly, a heterocyclic aldehyde such as 2-thiophene carbaldehyde and sterically demanding substrates such as 1naphthaldehyde well participated in this transformation, providing the desired compounds in good yields. Additionally, various amines including morpholine and piperidine reacted with aldehydes and alkynes effectively and obtained the corresponding propargylamines in high yield. 3.5. Possible Mechanism Route for the Synthesis of Propargylamines Using Fe3O4@SiO2-Se-T/CuI as a Catalyst. According to the reaction mechanisms proposed in the literature,66−68 the probable mechanism in the presence of Fe3O4@SiO2-Se-T/CuI was outlined in Scheme 2. As seen in Scheme 2, in the first step, the terminal alkyne is inserted in the

Figure 6. VSM curves for (a) nano-Fe3O4 and (b) Fe3O4@SiO2-SeT/CuI at room temperature

Figure 7. High resolution XPS spectra of Se in Fe3O4@SiO2-Se-T/ CuI before (a) and after (b) reaction.

Scheme 2. Plausible Reaction Mechanism for the A3 Coupling Reaction Using the Designed Catalyst

G


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recovery by a permanent magnet and reasonable reusability (entries 2−11). 3.7. Recycling of Fe3O4@SiO2-Se-T/CuI. In addition to environmental aspects, the easy workup and recycling of the supported catalysts are two essential issues from economic and industrial standpoints. Thus, the recoverability and recyclability of the present catalyst were explored in the test A3 coupling reaction under the optimized conditions. In order to do so, after the end of the reaction in each run (followed by TLC), the catalyst was easily recovered from the reaction mixture by applying an external magnetic field and washed several times with acetone and ethanol to eliminate any remaining product and dried at 60 °C in an oven. Then, the recovered nanocatalyst was used again in further runs under the same reaction conditions. As shown in Figure 8, the

immobilized copper species on the surface of Fe3O4@SiO2-SeT to create the Cu acetylide as an intermediate (I) with the activation of the terminal carbon−hydrogen bond of phenylacetylene. In the second step, the condensation reaction between aldehyde and amine generates in situ the corresponding iminium ion (II). In the final step, the intermediate of copper acetylide attacks the iminium ion in situ, to afford the desired product (III), the catalytic cycle is completed by regenerating the active copper species, and the catalyst becomes ready to insert another molecule of alkyne in the next catalytic cycle. In this process, water is only a theoretical byproduct generated from the hydrogen of the terminal alkyne and a hydroxyl group. 3.6. Comparison between the Catalytic Performance of Fe3O4@SiO2-Se-T/CuI in A3 Coupling Reaction and Previously Reported Catalytic Systems. In the next study, to elucidate the worthiness and efficiency of the present protocol in the synthesis of different propargylamine derivatives, the performance of Fe3O4@SiO2-Se-T/CuI for the model synthesis of propargylamine was compared with that of some of previously reported Cu-containing catalysts in the literature (Table 1). Even though all of the listed catalytic Table 1. Comparison of Catalytic Performance of Fe3O4@ SiO2-Se-T/CuI with Other Cu-Containing Catalysts Reported in the Literature in the A3 Coupling Reaction entry 1 2 3

catalyst Fe3O4/GO-CuOa,35 (20 mg) Cu@PMO-ILb,69 (0.15 mol %) Cu/G3c,70 (0.5 mol %)

7

Cu@MOF-5-Cd,71 (20 mg) Cu(OH)X·Fe3O472 (0.1 mol %) [Cu(N2S2)]Cl-Ye,73 (680 mg) CuNPs/TiO274 (20 mg)

8 9

Cu2(PiP)2f,75 (0.4 mol %) Cu-MCM-4176 (40 mg)

4 5 6

10 11 12

Cu-HAPg,77 (100 mg) Si(CH2)3SO3CuCl78 (50 mg) present work (20 mg)

reaction conditions

time (h)

yield (%)

EtOH, 78 °C

24

87

CHCl3, 60 °C

24

96

toluene, Ar, 100 °C toluene, N2, 110 °C solvent-free, 120 °C DCE, 70 °C

4

42

6

90

3

99

12

90

solvent-free, 70 °C toluene, 110 °C solvent-free, 110 °C CH3CN, reflux H2O, 100 °C

7

91

2 150 min

95 93

6 16

70 54

2

95

solvent-free, 100 °C

Figure 8. Recycling experiment of Fe3O4@SiO2-Se-T/CuI.

Fe3O4@SiO2-Se-T/CuI without considerable decrease in its catalytic efficiency or copper leaching can be reused for at least five consecutive cycles. These results clearly demonstrate that the synthesized nanocatalyst is very active and stable during the reaction runs.

4. CONCLUSIONS In summary, we developed a novel, efficient, and recoverable base metal nanomagnetic catalyst through covalent anchoring of CuI complex containing organoselenium ligand onto silica coated magnetic nanoparticles modified with (3-aminopropyl)triethoxysilane (Fe3O4@SiO2-Se-T/CuI). The structure of the resulting catalyst was fully authenticated by various techniques including FT-IR spectroscopy, XRD, TGA, FE-SEM, EDX, VSM, XPS, AAS, and ICP-OES. This new air- and moisturestable heterogeneous nanocatalyst was employed for the A3 coupling reaction. Broad access of aldehydes, amines, and alkynes was successful to create the relevant products in good to high yields. Additionally, the catalyst can be conveniently separated from the reaction media with an external magnet and recycled for at least five successive cycles without appreciable decrease in the catalytic property. High chemical and thermal stabilities, excellent durability, convenient recoverability and reusability of catalyst, mild reaction conditions, broad substrate scope, good yields, and short reaction times are main advantages of this catalytic process which make it a potential candidate for addressing many of the challenges of green chemistry. Moreover, this is the first report of applying heterogeneous copper catalyst containing organoselenium ligand in A3 coupling reaction and further investigations for the development of metal catalysis to other selenium-

a

Magnetic CuO nanoparticles supported on graphene oxide. bCopper supported on periodic mesoporous organosilica (PMO) ionic liquid. c Copper nanoparticles supported on graphene. dNanoparticles supported on metal−organic framework derived nanoporous carbon. e Zeolite-Y encapsulated Cu(I). fpip = (2-picolyliminomethyl) pyrrole anion. gHydroxyapatite supported copper.

systems can produce the corresponding product in high yield, the newly synthesized Fe3O4@SiO2-Se-T/CuI shows better performance than most of the reported catalyst systems in terms of the following reaction conditions: loading of catalyst (entries 6 and 9−11), solvent (entries 1, 3, 4, 7, and 9−11), reaction time (entries 1−7 and 9−11), and temperature (entries 4−5, 8, and 9), as well as easy separation and simple H


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containing ligands are currently taking place in our laboratory. Their application will be presented in due course.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.iecr.9b03843.

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Effect of different studied parameters on A3 product yield using Fe3O4@SiO 2-Se-T/CuI as catalyst; A3 coupling of different aldehydes, secondary amines, and terminal alkynes in the presence of Fe3O4@SiO2-Se-T/ CuI catalyst (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: (+98)(23)31533171. Fax: (+98)(23)333654110. ORCID

Firouzeh Nemati: 0000-0002-9446-8936 Author Contributions

The manuscript was written through the contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful to the Research Council of the University of Semnan for financial support of this project. REFERENCES

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