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Carousel with three slides shown at a time. Use the Previous and Next buttons to navigate three slides at a time, or the slide dot buttons at the end to jump three slides at a time. Vinyl Silanes Coupling Agent

Ronak Eisavi & Fereshteh Ahmadi

Morteza Torabi, Mohammad Ali Zolfigol, Mina Mirzaei Azandaryani

Hassan Sepehrmansourie, Mahmoud Zarei, … Sadegh Rostamnia

Mahnoush Keshavarz, Mohammad G. Dekamin, … Mohammad Nikpassand

Firouz Matloubi Moghaddam, Atefeh Jarahiyan, … Ali Pourjavadi

Zahra Alirezvani, Mohammad G. Dekamin & Ehsan Valiey

H. Rajabi-Moghaddam, MR Naimi-Jamal & M. Tajbakhsh

Reza Taheri-Ledari, Fereshteh Rasouli Asl, … Ali Maleki

Hassan Sepehrmansourie, Mahmoud Zarei, … Sadegh Rostamnia

Scientific Reports volume  13, Article number: 401 (2023 ) Cite this article

This article describes supramolecular Fe3O4/SiO2 decorated trimesic acid-melamine (Fe3O4/SiO2-TMA-Me) nanocomposite that can be prepared with features that combine properties of different materials to fabricate a structurally unique hybrid material. In particular, we have focused on design, synthesis and evaluation a heterogeneous magnetic organocatalyst containing acidic functional-groups for the synthesis of biologically important imidazole derivatives in good to excellent yields. The introduced Fe3O4/SiO2-TMA-Me nanomaterial was characterized by different techniques such as FTIR, XRD, EDX, FESEM, TEM, TGA and DTA. As a noteworthy point, the magnetic catalytic system can be recycled and reused for more than seven consecutive runs while its high catalytic activity remains under the optimized conditions.

The total synthetic approaches or even single-step reactions are being adjusted to the basic principles of green and sustainable chemistry that purpose to reduce the production of hazardous materials under various reaction conditions1,2,3. The designed-procedures for the preparation of nanomaterials including magnetic nanoparticles and their catalytic activities are entirely verified in the field of greener and atom-economic reactions especially multicomponent reactions4,5,6,7. Indeed, the use of magnetic decorated organic structures is gaining significant attention in the field of catalysis for organic transformations, mainly due to opportunities in providing new structural diversities8,9,10,11,12,13. The design and construction of new structures is achieved with the aim of improving the structural characteristics and enhancing desired catalytic performance in the definite reactions. For instance, by using diverse acidic organic functional groups with different acid strengths in the catalytic systems structure, the acidic properties of the final composition can be tuned.

Supramolecular chemistry, based on distinct interactions between small molecules as well as polymers, is a great tool to achieve superior, self-assembled molecular structures with an increased level of complexity14. According to these interactions, it is possible to prepare pseudo-supramolecular structures through sequential and predictable bonds between different organic moieties15. Further, grafting of the functionalized organic chains to the magnetic substrates is one of the best procedures for the construction of heterogeneous catalysts16 with high stability, activity and reusability17,18,19,20,21,22.

New supramolecular catalytic systems can promote the synthesis of fine chemicals through the multicomponent reaction (MCR) strategy very fast23,24,25,26. Definitely, heterocyclic scaffolds representing biological properties and medicinal applications including imidazole derivatives are an important category of such organic compunds27. Obviously, some drugs such as Daclatasvir (antiviral), Ledipasvir (antiviral), Velpatasvir (antiviral), Ketoconazole (antifungal), Clonidine (anti-hypertension), etc. have an imidazole core in their structures (Fig. 1).

Examples of medicines containing the imidazole scaffold.

In continuation of our ongoing efforts to design heterogeneous catalysts for different MCRs26,27,28,29,30,31,32,34, we wish herein to introduce preparation and fully characterization of the new magnetic Fe3O4/SiO2 decorated trimesic acid-melamine nanocomposite (Fe3O4/SiO2-TMA-Me, 1). Furthermore, its catalytic activity was investigated in the three-component synthesis of imidazole derivatives from benzil (2) or benzoin (3), aldehydes (4), and ammonium acetate (5, Fig. 2). To the best of our knowledge, there is not any report for the use of pseudo-supramolecular heterogeneous magnetic organocatalyst having acidic functional groups for the synthesis of imidazole derivatives.

Schematic preparation of the Fe3O4/SiO2-TMA-Me nanocomposite (1) for the three-component condensation of benzil (2) or benzoin (3), aldehydes (4), and ammonium acetate (5) to afford imidazole derivatives 6.

The as prepared Fe3O4/SiO2-TMA-and energy dispersive X-ray (EDX)Me nanomaterial (1) was characterized using various analytical techniques and methods such as Fourier transform infrared (FTIR) and energy dispersive X-ray (EDX) spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric (TGA), and differential thermal (DTA) analysis. The FTIR spectra of Fe3O4/SiO2, melamine (Mel) trimesic acid (TMA), melamine-trimesic acid amide (Mel-TMA) and Fe3O4/SiO2-TMA-Me solid acid (1) are show in Fig. 3.

FTIR spectra of the Fe3O4/SiO2, melamine (Mel), trimesic acid (TMA), melamine-trimesic acid amide (Mel-TMA) and Fe3O4/SiO2-TMA-Me solid acid (1).

As shown in Fig. 3, the Fe3O4/SiO2-TMA-Mel solid acid (1) presented a very strong and broad band, covering a wide range between 2800 and 3600 cm-1, for the O–H stretching vibrations of the carboxylic acid functional groups as well as Fe3O4/SiO2. Furthermore, the signals at 1730, 1710 and 1683 cm−1 are assigned to the carbonyl groups of ester, acid and amide, respectively. It should be noted that the presence of carbonyl group of ester indicates the formation of a covalent bond between the acid groups of trimesic acid and the magnetic core/shell. Furthermore, the asymmetric vibration signals of Si–O–Si and Si–OH as well as the symmetric vibration signal of Si–O–Si could be seen at 1090, 930 and 790 cm–1. In addition, the characteristic band for Fe–O stretching vibrations was observed at 560 cm−1.

The morphological features and particles size of the new magnetic nanocomposite Fe3O4/SiO2-TMA-Me nanocomposite (1) were examined by FESEM and TEM experiments (Figs. 4 and 5). The catalyst nanoparticles are approximately spherical and have been distributed with an average diameter of about 75 nm. On the other hand, TEM images (Fig. 5) obviously demonstrate decoration of core/shell magnetic nanoparticles on the trimesic acid/melamine rod-shaped structure. Also, the TEM images can be considered as a confirmation of the pseudo-supramolecular structure. Indeed, by considering this point that the Fe3O4/SiO2 is a core/shell structure, according to its preparation method, the rod-shaped particles shown in FESEM images may be attributed to the polymerized structure of melamine and trimesic acid.

FESEM images of the Fe3O4/SiO2-TMA-Me nanocomposite (1).

TEM images of the Fe3O4/SiO2-TMA-Me nanomaterial (1) in 1.0 µm and 300 nm scales.

The Energy dispersive spectroscopy (EDX) of the Fe3O4/SiO2-TMA-Me (1) is shown in Fig. 6. The EDX spectrum indicates that the introduced nanocatalyst 1 is composed of Fe, O, N and C elements.

EDX spectrum of the Fe3O4/SiO2-TMA-Me nanocomposite (1).

Also, Fig. 7 shows the XRD pattern of the Fe3O4/SiO2-TMA-Me nanomaterial (1). The XRD patterns of both melamine and trimesic acid are also illustrated for comparison as offset patterns. The diffraction peaks at 2θ values of 30.20, 35.39, 36.89, 53.31, 56.98, 73.91° can be assigned to the reflections of cubic Fe3O4 (JCPDS No. 01–088-0315) On the other hand, the well-defined high intensity diffraction signals (2θ) at 13.41, 17.95, 21.65, 22.25, 26.28, 28.90 and 29.91° are in accordance with the monoclinic crystal system of melamine (JCPDS no. 024–1654). Also, other remaining diffraction peaks can be attributed to the reflections of trimesic acid according to the JCPDS No. 00–045-1880.

XRD pattern of the Fe3O4/SiO2-TMA-Me  nanocomposite (1).

On the other hand, the TGA and DTA curves of the Fe3O4/SiO2-TMA-Me nanomaterial (1) in Fig. 8 show that the slight weight loss between 35—150 °C can be assigned to the elimination of adsorbed solvent or water molecules on its surface or trapped inside of the sample. Also, the weight losses between 150–270 °C and 270–370 °C is attributed to the partial or complete decomposition of trimesic acid moiety as well as condensation of the melamine units to melam through losing of NH3 molecules in the Fe3O4/SiO2-TMA-Me (1) structure. Moreover, the next weight loss can be interpreted by condensation of the silanols to siloxanes as well as forming more Fe −O− Fe bridges. The last step of weight loss between between 670 and 800 °C is due to complete decomposition of organic residue and remaining the inorganic Fe3O4/SiO2.

TGA/DTA curves of the Fe3O4/SiO2-TMA-Me, nanocomposite (1).

After characterization of the Fe3O4/SiO2 decorated trimesic acid-melamine (Fe3O4/SiO2-TMA-Mel) nanocomposite (1), the three-component synthesis of imidazole derivatives was chosen to examine its catalytic activity. For this purpose, the condensation of benzoin (3, 1 mmol), 4-chlorobenzaldehyde (4a, 1 mmol) and NH4OAc (5, 2.5 mmol) was selected as the model reaction for the synthesis of 6a. The reactions were optimized considering various parameters such as solvent, catalyst loading and temperature. The results are reported in Table 1.

The results of using different conditions in model reaction have been presented in Table 1. It is noteworthy that a very low yield of the desired product 6a was obtained in the absence of the Fe3O4/SiO2-TMA-Me (1) (Table 1, Entries 1–4). By using different solvents, the best result was obtained with ethanol at room temperature. In the next step, the amount of catalyst loading was optimized (Table 1, Entries 9–13). Although the reaction time using 15 or 20 mg of the catalyst loadings is slightly less than compared to 10 mg loading in EtOH under reflux conditions, no noticeable change in efficiency was seen. For this reason, the optimal amount of catalyst was chosen to be 10 mg. Furthermore, by using the introduced catalyst components separately in the model reaction, it can be concluded that the prepared nanocatalyst shows better results in proceeding the three-component synthesis of imidazole derivatives. Hence, 10 mg of catalyst Fe3O4/SiO2-TMA-Me (1) loading in EtOH under reflux conditions was selected as the optimal conditions for the next experiments.

The optimized conditions were developed to different aromatic aldehydes affording other imidazole derivatives. The results are summarized in Table 2. Noticeably, the desired products 6a–m were obtained in high to excellent yields. The obtained results obviously confirm the applicable catalytic activity of the Fe3O4/SiO2-TMA-Mel nanomaterial (1) to promote the three-component condensation of a wide range of aldehydes with benzil or benzoin and ammonium acetate (Supplementary Figure S1).

According to above results presented in Table 2, the following mechanism can be proposed for the synthesis of imidazole derivatives 6 by starting from benzil (2) or benzoin (3) catalyzed by nanocatalyst 1 (Fig. 9). First, Fe3O4/SiO2-TMA-Me solid acid (1) activates the carbonyl functional group of aldehydes (4) followed by addition of ammonia source (ammonium acetate 5) and forming imine intermediate (I) from route no.1 or aminal intermediate (III) from route no. 2. Subsequent addition of benzoin (2) and ammonia to the imine intermediate (I), followed by cyclization, air oxidation through intermediate (II) in route no. 1 or benzil (3) affords intermediate (IV). Finally, [1,5–H] shift of the intermediate (IV) affords the desired imidazole derivatives 6.

Plausible mechanism for the imidazole derivatives synthesis catalyzed by the nanocomposite Fe3O4/SiO2-TMA-Me nanocomposite (1).

One of the important advantages of Fe3O4/SiO2-TMA-Me nanomaterial (1) is that it can be magnetically separated from the reaction mixture after each run, collected, washed using acetone and n-hexane, respectively, and then reused in the subsequent model reactions. The model reaction was performed using the recycled catalyst for several times. As a result, a slight decrease in the catalytic efficiency was observed after the seventh run (Fig. 10). TEM and FESEM images as well as XRD pattern of the reused heterogeneous catalyst Fe3O4/SiO2-TMA-Me (1) have been presented in Fig. 11, which show excellent stability of the catalyst 1 under optimized reaction conditions.

Reusability of the Fe3O4/SiO2-TMA-Me heterogeneous catalyst (1) in the model reaction to afford 6a.

(a) TEM and (b) FESEM images and (c) XRD pattern of the reused Fe3O4/SiO2-TMA-Me heterogeneous acid (1) in the model reaction to afford 6a.

To evaluate the efficiency of Fe3O4/SiO2-TMA-Me acidic catalyst (1), a comparison has been made with the previously reported methods for the synthesis of imidazole derivative 6a. As shown in Table 3, the prepared nanocatalyst can compete with the  similar systems in terms of catalyst loading, reaction conditions, and catalyst reusability times.

All consumable chemicals were obtained from Merck or Aldrich chemical companies. The XRD pattern was collected by a TW 1800 diffractometer with Cu Ka radiation (λ = 1.54050 Å). The FESEM images were observed by FESEM TESCAN-MIRA3. TEM images were taken using a JEOL JEM-2100F microscope (operated at 300 kV). The analytical thin layer chromatography (TLC) experiments were performed using Merck 0.2 mm silica gel 60F-254Al-plates and n-hexane: EtOAc, (3:1, v/v %) as eluent. All compounds are known and well characterized by melting point, FTIR, 1H NMR (500 MHz), and 13C NMR (125 MHz) spectroscopy on a Bruker DRX-500 Avance instrument in DMSO-d6 at ambient temperature.

The magnetic core/shell (Fe3O4/SiO2) material was prepared according to the reported methods in literature with a slight modification50.

The mixture of trimesic acid (TMA, 3 mmol), 1-hydroxybenzotriazole (HOBT, 3 mmol) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDCI, 3 mmol) was stirred in deionized water/acetonitrile (1:1, 50 mL) for 30 min, then 1 mmol of melamine was added and the obtained mixture was stirred for 24 h at room temperature. After this time, 0.3 g prepared Fe3O4/SiO2 was mildly added and stirred for 24 h to afford the final precipitate. Afterward, the obtained solid was collected with an external magnet, washed several times using distilled water and EtOH (96%) and then dried at 45 °C for 3 h.

In a round-bottomed flask, benzoin (2, 1.0 mmol) or benzil (3, 1.0 mmol), aldehyde (4, 1.0 mmol), ammonium acetate (5, 2.5 mmol) and Fe3O4/SiO2-TMA-Me (1, 10 mg) were mixed in EtOH (5.0 mL) and stirred at room temperature. The reaction mixture was stirred for the appropriate times reported in Table 2. After completion of the reaction, the catalyst 1 was separated by an external magnet. Afterwards, H2O was added drop wise into the solution until imidazole derivatives 6 were completely precipitated. The obtained mixture was filtered off and the precipitate were washed and then dried in an oven at 70 °C for 1 h. The recycled catalyst 1 was washed with acetone and n-hexane (1 mL), respectively and then dried at 50 °C for 2 h and stored for another run.

The magnetic Fe3O4/SiO2 decorated trimesic acid-melamine pseudo-supramolecular (Fe3O4/SiO2-TMA-Me) nanocomaterial was prepared and properly characterized for the first time. The Fe3O4/SiO2-TMA-Me nanocomposite was used for the three-component condensation of benzil or benzoin, aldehydes, and ammonium acetate to afford the corresponding imidazole derivatives. Low catalyst loading, high to excellent yields of the desired products, easy and quick isolation of the products from the reaction mixture as well as reusability of the solid acidic pseudo-supramolecular nanocomposite with negligible loss of its activity are the main advantages of this method. In addition to the catalytic applications, other applications of this nanomaterial, as a pseudo-supramolecular structure, are ongoing in our laboratory and would be presented in due course.

The datasets generated and/or analyzed during the current study would be available in the Science Data Bank repository after acceptance of the manuscript.

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We are grateful for the financial support from The Research Council of Iran University of Science and Technology (IUST), Tehran, Iran (Grant No 160/20969) for their support. We would also like to acknowledge the support of The Iran Nanotechnology Initiative Council (INIC), Iran.

Pharmaceutical and Heterocyclic Compounds Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, 16846-13114, Iran

Babak Fattahi & Mohammad G. Dekamin

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B.F. worked on the topic, as his Ph.D thesis, and prepared the initial draft of the manuscript. Prof. M.G.D. is the supervisor of Mr. B.F. as his Ph.D student. Also, he edited and revised the manuscript completely.

Correspondence to Mohammad G. Dekamin.

The authors declare no competing interests.

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Fattahi, B., Dekamin, M.G. Fe3O4/SiO2 decorated trimesic acid-melamine nanocomposite: a reusable supramolecular organocatalyst for efficient multicomponent synthesis of imidazole derivatives. Sci Rep 13, 401 (2023). https://doi.org/10.1038/s41598-023-27408-7

DOI: https://doi.org/10.1038/s41598-023-27408-7

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