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. 2023 May 17;8(21):18479–18490. doi: 10.1021/acsomega.2c06651

Application of Nanomagnetic Metal–Organic Frameworks in the Green Synthesis of Nicotinonitriles via Cooperative Vinylogous Anomeric-Based Oxidation

Bashirullah Danishyar †, Hassan Sepehrmansourie †, Hossein Ahmadi †, Mahmoud Zarei ‡,*, Mohammad Ali Zolfigol †,*, Mojtaba Hosseinifard §
PMCID: PMC10233831  PMID: 37273641

Abstract

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In the current study, we synthesized a new nanomagnetic metal–organic framework Fe3O4@MIL-53(Al)-N(CH2PO3)2 and characterized it using various techniques. This nanomagnetic metal–organic framework was used for the synthesis of a wide range of nicotinonitrile derivatives as suitable drug candidates by a four-component reaction of 3-oxo-3-phenylpropanenitrile or 3-(4-chlorophenyl)-3-oxopropanenitrile, ammonium acetate (NH4OAc), acetophenone derivatives, and various aldehydes including those bearing electron-donating, electron-withdrawing, and halogen groups, which afforded desired products (27 samples) via a cooperative vinylogous anomeric-based oxidation (CVABO) mechanism under solvent-free conditions in excellent yields (68–90%) and short reaction times (40–60 min). Increasing the surface-to-volume ratio, easy separation of the catalyst using an external magnet, and high chemical and temperature stability are the advantages of the described nanomagnetic metal–organic frameworks.

Introduction

Nowadays, a new class of porous materials has been developed by linking metal ions with organic compounds as ligands. This class of porous compounds grown in 3D space constitute metal–organic frameworks (MOFs).1−3 By selecting the appropriate metal, ligand, and reaction conditions, the particle size, pore structure, and morphology can be designed and adjusted.4,5 Metal–organic frameworks (MOFs) as multivariate materials have been widely used in drug delivery, biotechnology, magnetic resonance imaging (MRI), adsorption and desorption, gas separation, catalysis, and photocatalysis.6−10 Despite many applications, nanomagnetic particles (Fe3O4) are used as suitable cores in catalysts.11 The high stability and high surface-to-volume ratio will lead to an amazing integration between nanomagnetic materials and metal–organic frameworks (MOFs). According to the abovementioned facts, nanomagnetic metal–organic frameworks are easily separated from the reaction by an external magnetic field.12 Furthermore, the advantage of heterogeneous catalysts over homogeneous ones is their easy separation and recovery in organic reactions.13,14 Many methods have been reported for the synthesis of nanomagnetic metal–organic frameworks as heterogeneous catalysts.15−17 Recently, we introduced metal–organic frameworks and other molecules with phosphorous acid pendent groups (N-C-(PO3H2)2),18−20 melamine,21 glycoluril,22 carbon quantum dots (CQDs),23 and mesoporous materials (SBA-15)24 as novel heterogeneous catalysts in the preparation of biologically active organic compounds.

In recent research, N-heterocyclic compounds such as nicotinonitriles or triaryl pyridines have been considered for the preparation of various biologically active compounds with antiviral, antibacterial, anticonvulsant, and antioxidant properties, which are also useful in the treatment of breast and lung cancer (Figure 1).25−27 Furthermore, changing substitutions at various ring positions of pyridine can also enhance the biological activities of nicotinonitriles.28,29 Therefore, research and development are necessary and important in the synthesis of new compounds with N-scaffold compounds.

Figure 1.

Figure 1

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Structure of medicinal compounds containing nicotinonitrile.

In the past, J.T. Edward introduced the anomeric effect (AE) concept to explain the chemical stability and mechanism in organic synthesis.30 When sharing of electrons occurs through double bonds, it is called the vinylogous anomeric effect (VAE).31,32 Although different kinds of anomeric effects have been reported in the literature, in this study, cooperative VAE is our main interest (Scheme S1). Recently, we reviewed the influence of AE in chemical processes.33,34 Also, we introduced the concept of anomeric-based oxidation (ABO) as a driving force in the synthesis of susceptible molecules.35,36 Besides, this concept has been presented in the oxidation and/or reduction of NADP+/NADPH or NAD+/NADH systems via hydride transfer.37 The development of the cooperative vinylogous anomeric-based oxidation (CVABO) concept is our research interest.

Based on the feature mentioned herein, we wish to synthesize novel nicotinonitrile derivatives via the condensation of 3-oxo-3-phenylpropanenitrile or 3-(4-chlorophenyl)-3-oxopropanenitrile, aldehyde, acetophenones, and ammonium acetate using Fe3O4@MIL-53(Al)-N(CH2PO3)2 as a nanomagnetic and porous catalyst (Scheme 1).

Scheme 1. Preparation of Nicotinonitriles Using Fe3O4@MIL-53(Al)-N(CH2PO3)2 as the Nanomagnetic Metal–Organic Framework.

Scheme 1

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Experimental Section

Preparation of Nanomagnetic Metal–Organic Frameworks Based on Al

According to the previously reported literature, MIL-53(Al)-NH2 and MIL-53(Al)-N(CH2PO3H2)2 were synthesized.20 Then, in a 50 mL round-bottomed flask, a mixture of MIL-53(Al)-N(CH2PO3H2)2 (0.65 g) and Fe3O4 (0.5 g) was stirred in toluene (15 mL) as a solvent at 80 °C for 12 h. After cooling the reaction mixture, the composite was separated by an external magnet. Finally, the pure Fe3O4@MIL-53(Al)-N(CH2PO3)2 was washed with ethanol (3 × 10 mL) and collected using an external magnet (Scheme 2).

Scheme 2. Preparation of Fe3O4@MIL-53(Al)-N(CH2PO3)2.

Scheme 2

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General Procedure for the Preparation of Nicotinonitrile Derivatives

According to the previously reported procedure, 3-oxo-3-phenylpropanenitrile and 3-(4-chlorophenyl)-3-oxopropanenitrile were prepared as starting materials (Scheme 3).38 In a 20 mL round-bottomed flask, a mixture of starting materials (1 mmol), aldehydes (1 mmol), acetophenones (1 mmol), ammonium acetate (1.5 mmol, 0.115 g), and Fe3O4@MIL-53(Al)-N(CH2PO3)2 (20 mg) were stirred at 110 °C in solvent-free conditions. The progress of the reaction was followed by the TLC technique (n-hexane/ethyl acetate 1:1). After the completion of the reaction, the catalyst was separated from the reaction mixture by adding hot ethanol (20 mL) and using an external magnet. The precipitate was cooled and dried after filtration. The pure product was obtained by washing several times with ethanol (Scheme 1).

Scheme 3. Preparation of 3-Oxo-3-phenylpropanenitrile and 3-(4-Chlorophenyl)-3-oxopropanenitrile.

Scheme 3

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Results and Discussion

Al-based metal–organic framework catalysts functionalized with phosphorous acid have been previously reported by our research group.20 In a previous report, the metal–organic framework MIL-53(Al)-NH2 was synthesized using an electrochemical method. By applying various analyses, its structure was well established, and the obtained results were in good agreement with previously reported methods. Linking phosphorous acid tags with the prepared Al-based MOFs produced its corresponding post-modified form MIL-53(Al)-N(CH2PO3H2)2 as a porous acidic catalyst. Subsequently, the magnetic properties of Fe3O4 were used to create a new magnetic catalyst. By combining Al-based metal–organic frameworks functionalized with phosphorous acid and Fe3O4, we synthesized a novel nanomagnetic metal–organic framework Fe3O4@MIL-53(Al)-N(CH2PO3)2 (Scheme 2). In this report, the solvothermal method was used to prepare Al-based MOFs to show the diversity of the method for the synthesis of the described MOFs. In addition to being porous and having phosphorous acid groups, this catalyst has magnetic properties and can be easily separated from the reaction medium after the reaction is completed using an external magnet. For confirming the structure and morphology of the catalyst, various techniques such as energy-dispersive X-ray spectroscopy (EDS), N2 adsorption–desorption isotherms (BET), FT-IR spectroscopy, XRD, SEM elemental mapping, vibrating sample magnetometry (VSM), thermal gravimetry (TG), and derivative thermal gravimetry (DTG) were used. Synthesis of pyridines with various substitutions to yield biologically active candidates is our main research interest. In addition, the synthesis of susceptible molecules for the development of the anomeric-based oxidation concept is our other research target. Here, we tried to combine both of the abovementioned research interests.

The FT-IR spectra of the intermediate material, substrate, and catalyst are compared in Figure 2. According to the FT-IR spectra, the functional groups of MIL-53(Al)-NH2 match with previously reported results.20,39 The peaks at 3503 and 3384 cm–1 in MIL-53(Al)-NH2 indicate the NH2 functional group. The broad peak at 2700–3600 cm–1 indicates the acidic OH of PO3H2 and the Fe3O4 functional group in the catalyst. The adsorption bands at 1020–1180 cm–1 are related to P–O bond stretching. Also, the absorption band at 598 cm–1 is linked to the stretching vibration of the Fe–O group in Fe3O4. The changes of MIL-53(Al)-NH2, MIL-53(Al)-N(CH2PO3H2)2, and Fe3O4@MIL-53(Al)-N(CH2PO3)2 were detected in the synthesis of catalyst.

Figure 2.

Figure 2

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FT-IR spectra of MIL-53(Al)-NH2, MIL-53(Al)-N(CH2PO3H2)2, and Fe3O4@MIL-53(Al)-N(CH2PO3)2.

The morphology of Fe3O4@MIL-53(Al)-N(CH2PO3)2 was studied using XRD, EDX spectroscopy, and SEM techniques. For this purpose, a comparative XRD analysis of Fe3O4@MIL-53(Al)-N(CH2PO3)2 and MIL-53(Al)-NH2 was performed, as shown in Figure 3. According to the XRD spectra, the structure of MIL-53(Al)-NH2 matches well with previously reported studies.20,39 The peaks corresponding to the regions of 2θ = 8.84, 10.44, 15.58, 18.04, 20.64, 26.99, and 48.28° indicate MIL-53(Al)-NH2, and these peaks are also present in the final catalyst. On adding Fe3O4, the peaks of this compound at 2θ = 18.19, 30.09, 35.54, 43.14, 53.64, 57.39, 62.99, and 74.44° corresponding to the Fe3O4 diffraction lines (111), (220), (311), (400), (422), (511), (440), and (533) were included,40 indicating the proper addition of Fe3O4 to MIL-53(Al)-NH2. The XRD pattern of the catalyst shows that it has a crystalline nature. The size of the crystal and average interplaner distance were calculated by the Scherer equation and the Bragg equation, which are determined to be in the range of 6.8–13.4 nm. The results are shown in Table S1.

Figure 3.

Figure 3

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XRD patterns of MIL-53(Al)-NH2 and Fe3O4@MIL-53(Al)-N(CH2PO3)2.

In another investigation, the scaffold catalyst was composed of C, N, O, Al, Fe, and P according to the energy-dispersive X-ray spectroscopy (EDX) technique (Figure 4). Also, the distribution of elements including C (red), N (blue), O (green), Al (yellow), Fe (gray), and P (orange) on the surface of the catalyst was investigated and verified by SEM elemental mapping (Figure 4). Therefore, energy-dispersive X-ray (EDX) spectroscopy and SEM elemental mapping of all of the expected elements confirm the uniform distribution of the elements on the surface.

Figure 4.

Figure 4

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Energy-dispersive X-ray (EDX) analysis and elemental mapping of C (red), N (blue), O (green), Al (yellow), Fe (gray), and P (orange) atoms for Fe3O4@MIL-53(Al)-N(CH2PO3)2.

Also, the scanning electron microscopy (SEM) technique was used to determine the morphology and particle size of the Fe3O4@MIL-53(Al)-N(CH2PO3)2 catalyst, as shown in Figure 5. A comparison of the SEM images of Fe3O4@MIL-53(Al)-N(CH2PO3)2 and MIL-53(Al)-NH2 shows that the morphology has not changed after functionalization. According to SEM images, the particles of Fe3O4@MIL-53(Al)-N(CH2PO3)2 were uniform in size, with good dispersion performance and no agglomeration.

Figure 5.

Figure 5

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SEM images of (a, b) MIL-53(Al)-NH2 and (c, d) Fe3O4@MIL-53(Al)-N(CH2PO3)2.

The nitrogen adsorption–desorption isotherm (BET) of Fe3O4@MIL-53(Al)-N(CH2PO3)2 is shown in Figure S1. This isotherm shows that the addition of Fe3O4 to MIL-53(Al)-N(CH2PO3H2)2 reduces the pore size and surface area up to 58.40 m2/g. Also, the total pore volume of Fe3O4@MIL-53(Al)-N(CH2PO3)2 is reduced to 0.248 cm3/g.20 The pore size distribution of Fe3O4@MIL-53(Al)-N(CH2PO3)2 based on the BJH method is shown in Figure S1. The mean pore diameter of Fe3O4@MIL-53(Al)-N(CH2PO3)2 is 17.02 nm.

To study the thermal stability of nanomagnetic metal–organic frameworks, thermogravimetric (TG) and derivative thermogravimetric (DTG) analyses were performed (Figure 6). Three stages of weight loss for Fe3O4@MIL-53(Al)-N(CH2PO3)2 are observed. The first weight loss is related to the evaporation of organic solvents at 100 °C. The main weight loss at 350 °C can be assigned to the decomposition of the material including MIL-53(Al)-N(CH2PO3H2)2.

Figure 6.

Figure 6

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Thermogravimetric (TG) and derivative thermogravimetric (DTG) analyses of Fe3O4@MIL-53(Al)-N(CH2PO3)2.

In continuity, magnetic measurement of Fe3O4@MIL-53(Al)-N(CH2PO3)2 and Fe3O4 was performed using vibrating sample magnetometry (VSM) technique (Figure 7). According to the curves shown in Figure 7, magnetic measurements were performed for Fe3O4@MIL-53(Al)-N(CH2PO3)2 33.20 μg–1 and Fe3O4 66.5 μg–1. This decrease is due to the coating of Fe3O4 nanoparticles by MIL-53(Al)-N(CH2PO3H2)2.

Figure 7.

Figure 7

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Vibrating sample magnetometry (VSM) of Fe3O4 and Fe3O4@MIL-53(Al)-N(CH2PO3)2.

After the successful synthesis and characterization of Fe3O4@MIL-53(Al)-N(CH2PO3)2, it was used for the preparation of nicotinonitrile derivatives. The abovementioned catalyst was applied for the multicomponent reaction of 3-oxo-3-phenylpropanenitrile (1 mmol, 0.145 g), acetophenone (1 mmol, 0.120 g), 4-chlorobenzaldehyde (1 mmol, 0.140 g), and ammonium acetate (1.5 mmol, 0.115 g) as a model reaction via a cooperative vinylogous anomeric-based oxidation. The model reaction was tested using different amounts of catalysts, solvents, and temperatures. The results of the obtained products are summarized in Table 1. The best parameters for the synthesis of nicotinonitrile were achieved in the presence of Fe3O4@MIL-53(Al)-N(CH2PO3)2 (20 mg) at 110 °C under solvent-free conditions (entry 1, Table 1). The model reaction was also tested using different organic solvents such as n-hexane, MeOH, EtOH, CH3CN, CH2Cl2, EtOAc, DMF, CHCl3, and water (5 mL), the results obtained for which did not improve entries 12–20 in Table 1. Results show that Fe3O4@MIL-53(Al)-N(CH2PO3)2 is suitable for the preparation of nicotinonitrile derivatives. Besides, the model reaction was tested for the preparation of the target reaction under N2 and Ar atmospheres for confirming anomeric-based oxidation (ABO). The reaction was successfully performed in the absence of any oxygen molecules.

Table 1. Effect of Different Amounts of Catalyst, Temperature, and Solvent on the Synthesis of Fused Nicotinonitrile Derivatives.

entry solvent time (min) cat. (mg) temp. (°C) yield (%)
1   50 20 110 85
2   80 10 110 70
3   120 5 110 30
4   65 15 110 45
5   60 30 110 82
6   180   110 15
7   180 20 25  
8   120 20 50 25
9   100 20 80 42
10   65 20 100 72
11   50 20 120 80
12 n-hexane 180 20 reflux  
13 EtOH 120 20 reflux 72
14 MeOH 120 20 reflux 65
15 DMF 100 20 110 70
16 CH2Cl2 180 20 reflux  
17 CHCl3 180 20 reflux  
18 CH3CN 120 20 reflux 42
19 EtOAc 180 20 reflux  
20 H2O 120 20 reflux 27
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After the optimization of the reaction conditions, the efficiency and applicability of Fe3O4@MIL-53(Al)-N(CH2PO3)2 were studied for the preparation of nicotinonitriles. The results summarized in Tables 2 and 3 indicate that starting materials (3-oxo-3-phenylpropanenitrile or 3-(4-chlorophenyl)-3-oxopropanenitrile) and various aldehydes including those bearing electron-donating, electron-withdrawing, and halogen groups afforded desired products (1b–14b) and (1c–13c) in excellent yields (68–90%) and short reaction times (40–60 min).

Table 2. Synthesis of Nicotinonitrile Derivatives (1b–14b) Using Fe3O4@MIL-53(Al)-N(CH2PO3)241,42.

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Table 3. Synthesis of Nicotinonitrile Derivatives (1c–13c) Using Fe3O4@MIL-53(Al)-N(CH2PO3)2.

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In the suggested mechanism, the starting material [(3-oxo-3-phenylpropanenitrile or 3-(4-chlorophenyl)-3-exopropanenitrile)] is activated by the catalyst. The enol form of the starting material and activated aldehyde produced intermediate I. On the other hand, the ammonia generated from ammonium acetate reacts with activated acetophenone to form intermediate II. Then, the reaction between intermediates I and II leads to intermediate III. Subsequently, intermediate III creates intermediate IV by an intramolecular reaction and loss of one molecule of H2O. In the last stage of the reaction mechanism, intermediate IV is converted into the final product through two possible paths A and/or B, via a cooperative vinylogous anomeric-based oxidation mechanism, releasing H2 or H2O2 (Scheme 4).34,35,43 Also, to investigate the activation of aldehyde by the catalyst, p-chlorobenzaldehyde was reacted with Fe3O4@MIL-53(Al)-N(CH2PO3)2 at room temperature. Then, the FT-IR spectra of the reaction mixtures were examined. The absorption band of C=O of p-chlorobenzaldehyde at 1693 cm–1 shifted to 1693, 1695, 1701, and 1705 cm–1 in the presence of MIL-53(Al)-NH2, Fe3O4, MIL-53(Al)-N(CH2PO3H2)2, and Fe3O4@MIL-53(Al)-N(CH2PO3)2, respectively (Figure S2).

Scheme 4. Proposed Mechanism for the Synthesis of Nicotinonitriles Using Fe3O4@MIL-53(Al)-N(CH2PO3)2.

Scheme 4

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Following the optimal synthesis of nicotinonitrile derivatives by Fe3O4@MIL-53(Al)-N(CH2PO3)2, we tested 3-oxo-3-phenylpropanenitrile (1 mmol, 0.145 g), acetophenone (1 mmol, 0.120 g), 4-chlorobenzaldehyde (1 mmol, 0.140 g), and ammonium acetate (1.5 mmol, 0.12 g) as model reactions using various inorganic and organic catalysts (solid acids, nanomagnetic liquids, and ionic liquids). According to the results shown in Table 4, it can be concluded that Fe3O4@MIL-53(Al)-N(CH2PO3)2 exhibits the best performance compared to other catalysts. To prove the recyclability of the catalyst, we tested the model reaction under optimal conditions. The results in Figure 8 show that the Fe3O4@MIL-53(Al)-N(CH2PO3)2 catalyst can be reused up to five times without a noticeable change in its catalytic activity. To prove the stability of the catalyst, FT-IR and XRD analyses were performed, and the corresponding spectra of fresh and reused catalysts are compared in Figures S3 and S4. The pattern of the reused catalyst is the same as the profile of the fresh catalyst without apparent loss of crystallinity. Also, Fe and Al loadings at the synthesized MOF were determined by ICP analysis. For this purpose, ICP results confirmed that the synthesized magnetic porous catalyst contains 6862.80 × 10–6 mol/g Al and 3183.46 × 10–6 mol/g Fe.

Table 4. Evaluation of Various Catalysts for the Synthesis of Nicotinonitriles in Comparison with Fe3O4@MIL-53(Al)-N(CH2PO3)2.

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entry catalyst amount of catalyst time (min) yield (%)
1 SSA44 20 mg 100 30
2 NaOH 20 mol % 150 32
3 Fe3O4 20 mg 120 trace
4 p-TSA 20 mol % 120 35
5 pipyridine 20 mol % 100 trace
6 nano-SB-[PSIM]Cl45 20 mg 180  
7 GTBSA46 20 mol % 120 55
8 APVPB47 20 mg 100 40
9 [Py-SO3H]Cl48 20 mol % 80 48
10 [PVI-SO3H]Cl49 20 mg 180 28
11 Et3N 20 mol % 120 32
12 GTMPA22 20 mol % 120 55
13 NaHSO4 20 mol % 60 77
14 Fe3O4 20 mg 120 trace
15 MIL-53(Al)-NH2 20 mg 120 25
16 MIL-53(Al)-N(CH2PO3H2)2 20 mg 60 80
17 Fe3O4@MIL-53(Al)-N(CH2PO3)2, this work 20 mg 50 85
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Figure 8.

Figure 8

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Recyclability of Fe3O4@MIL-53(Al)-N(CH2PO3)2 for the synthesis of nicotinonitrile derivatives.

Conclusions

In conclusion, a new nanomagnetic metal–organic framework Fe3O4@MIL-53(Al)-N(CH2PO3)2 was prepared and introduced via a post-modification method. The synthesized nanomagnetic metal–organic framework was fully characterized by FT-IR, SEM elemental mapping, EDX, XRD, SEM, TGA–DTG, N2 adsorption–desorption, BJH, and VSM. It was used in the preparation of nicotinonitrile derivatives as biologically active candidates with a high yield and short reaction time. The recyclability and reusability of the presented catalyst, green conditions, and easy work-up are major advantages of the described methodology.

Acknowledgments

The authors thank the Bu-Ali Sina University and Iran National Science Foundation (INSF) (Grant Number 4004528) for financial support.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.2c06651.

  • Spectral data of nicotinonitriles, different kinds of anomeric effects, XRD data and N2 adsorption–desorption isotherms of the catalyst, FT-IR spectra of p-Cl-benzaldehyde in the presence of different stages of the catalyst, and comparison of FT-IR and XRD spectra of the fresh and reused catalyst (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao2c06651_si_001.pdf (4.2MB, pdf)

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