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Proceeding Paper

Cobalt (II) Complex on Nanodiamond-Grafted Polyethyleneimine@Folic Acid: An Extremely Effective Nanocatalyst for Green Synthesis of 5-Substituted 1H-Tetrazole Derivatives †

by
Zahra Nasri
,
Arezoo Ramezani
and
Hossein Ghafuri
*
Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114, Iran
*
Author to whom correspondence should be addressed.
†
Presented at the 28th International Electronic Conference on Synthetic Organic Chemistry (ECSOC-28), 15–30 November 2024; Available online: https://sciforum.net/event/ecsoc-28.
Chem. Proc. 2024, 16(1), 86; https://doi.org/10.3390/ecsoc-28-20132
Published: 14 November 2024
(This article belongs to the Proceedings of The 28th International Electronic Conference on Synthetic Organic Chemistry)
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Abstract

:
In this paper, a novel, cost-effective, and green methodology has been investigated for the preparation of cobalt (II) nanoparticles supported on a nanodiamond-carbon-structure grafted polyethyleneimine@folic acid (ND-g-PEI@FA@Co(II)) nanocomposite. Some of the physicochemical characteristics of the synthesized efficient heterogeneous nanocatalyst, including bond formation and functional groups, percentage of elements, crystalline phase, and surface morphology were studied using techniques such as Fourier transform infrared spectroscopy (FT-IR), Energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-SEM). Following the principles of green chemistry, this nanocatalyst has been used in the production of 5-substituted 1H-tetrazole derivatives using different benzaldehyde derivatives, sodium azide, and malononitrile agents in ethanol eco-friendly solvent with high efficiency. The mechanism of tetrazole synthesis is carried out through cascade condensations, such as Knoevenagel condensation, 1,3-dipolar cycloaddition, and tautomerization reactions. The main advantages of the ND-g-PEI@FA@Co(II) nanocatalyst include facile preparation, easy separation, minimal consumption of catalyst for a multicomponent reaction (MCR), the use of cheap and recyclable materials, excellent product yield, and reusability up to four times with good efficiency. The substrate used in this heterogeneous catalyst (ND) with appropriate thermal stability, abundant availability in large quantities, and non-toxicity are prominent features of the synthesized nanocomposite.

1. Introduction

Tetrazoles are a group of heterocyclic compounds with a five-membered ring structure containing four nitrogen atoms and one carbon atom attached to the main structure of the molecule [1,2]. Concerning biological properties, tetrazole derivatives have antifungal [3], antibacterial [4], antiviral, anti-inflammatory, anticancer [5,6,7,8], antitubercular [9], antiHIV [10], antidiabetic, and antihypertensive activities. In addition, tetrazole derivatives are also used for the production of medicines needed by patients who have immunodeficiencies [11]. Therefore, the synthesis of tetrazoles is of special importance. Tetrazoles are synthesized through a multicomponent reaction between aldehydes or nitriles and sodium azide in three steps [12,13,14]. Compared to nitriles, aldehydes have attracted more attention from researchers due to their lower toxicity and greater accessibility [15,16]. Meanwhile, the use of an excellent and suitable catalyst to increase the product efficiency and reaction rate in the synthesis of tetrazole derivatives can be very important.
Among the nanomaterials that have been reported for the synthesis of tetrazoles by other researchers, boehmite-based nanoparticles (NPs) [17], magnetic NPs, copper-based NPs [18], MCM-41-based NPs [19], carbon-based NPs, ZnO NPs, and nanocomposites are worth a mention [20].
From the point of view of green chemistry, catalysts must have outstanding features such as high selectivity and efficiency, good stability, high recyclability, and excellent activity. In this work, a nanocatalyst based on a nanodiamond carbon substrate was prepared. During recent years, carbon materials have been developed in different directions and different types of carbons have emerged at the nanoscale, including nanotubes, fullerene, graphene, non-graphite nanostructures, and nanodiamonds [21]. The coordination number of nanodiamond carbon atoms is 4, and they have quasi-zero-dimensional and quasi-one-dimensional structures. Recently, these nanoparticles have attracted a lot of attention in scientific and industrial fields due to their special characteristics. Compared to other nanoparticles, nanodiamond has very versatile surface chemistry, which can be tuned to create different chemical and physical properties by adjusting and controlling the reaction, leading to an increased stability and compatibility with the environment, etc. This surface feature in nanodiamonds has led to its wide applicability in catalysts.
Nanodiamonds have a high thermal conductivity, chemically active surface, and spherical structure, which makes them useful for improving polymer properties and preparing nanocomposite coatings [22]. These compounds have high mechanical strength, electrochemical resistance, and high chemical stability against corrosion and can be produced in large quantities at a low cost. Among other advantages of these nanoparticles, we can mention the large relative surface area and its non-toxicity [23].
In this research, a nanodiamond substrate was grafted with polyethyleneimine (PEI) polymer. PEI was added to the catalyst in order to increase stability and strength and create many active sites for better metal complexation. In the next step, folic acid (FA) was attached to the substrate as a result of the amidation reaction, and finally, cobalt (II) metal was coordinated with active groups. This catalyst was used for the synthesis of 5-substituted 1H-tetrazole derivatives with excellent efficiency and a suitable solvent.

2. Experimental

2.1. Reagents and Apparatus

All chemicals were purchased from Merck or Aldrich (St. Louis, MO, USA) with high purity and utilized as received without further purification. The functional groups were investigated by a Fourier transform infrared (FT-IR) spectrometer (S8400, Shimadzu, Japan). The percentage of elements was recorded by energy dispersive X-ray spectroscopy (EDS) analysis (Numerix DXP-P10X model, equipped with EDS detector). The phase and crystallinity of the ND-g-PEI@FA@Co(II) nanocomposite were identified using an X-ray diffraction (XRD) pattern (D8 Advance, Bruker, Berlin, Germany). The morphology and surface image were monitored by a field emission scanning electron microscope (FE-SEM) analyzer (TESCAN-MIRA3).

2.2. Preparation of ND-g-PEI

Initially, 0.5 g of ND was placed into the furnace at 450 °C for 5 h at rate of 1 °C/min. In the second step, the oxidized ND (0.3 g), 0.31 g of N,N′-dicyclohexylcarbodiimide (DCC), and 0.4 g of N-hydroxysuccinimide (NHS) were poured into a round-bottom flask and 10 mL of DMSO solvent was added. This mixture was stirred at room temperature for 24 h. After 24 h, 1.0 g of PEI was added and the reaction mixture was stirred for 8 h. In order to separate the ND-g-PEI nano polymer, it was centrifuged and then dried inside at 60 °C for 24 h.

2.3. Preparation of ND-g-PEI@FA

In this step, 0.265 g of FA powder, 0.31 g of DCC, and 0.4 g of NHS were added to 10 mL of DMSO and stirred at room temperature for 24 h. Next, 1.0 g of ND-g-PEI nano polymer was added to the mixture and stirred under the previous conditions for 12 h. The ND-g-PEI@FA nanocomposite was washed with EtOH and dried in an oven at 60 °C for 24 h.

2.4. Preparation of ND-g-PEI@FA@Co(II)

To complex the cobalt (II) on the prepared ND-g-PEI@FA nanocomposite, 0.5 g of ND-g-PEI@FA was dispersed in 10 mL of EtOH for 30 min. Additionally, 0.5 g of Co(OAc)2 was dissolved in 10 mL of deionized water and the resulting solution was added to the dispersed nanocomposite. The reaction mixture was refluxed at 80 °C for 24 h. After the completion of the reaction, the catalyst was washed once using EtOH solvent and dried at 70 °C (Scheme 1).

2.5. General Procedure for the Synthesis of 5-Substituted 1H-Tetrazole Derivatives

For this purpose, benzaldehyde derivatives (1a–e, 1 mmol), malononitrile (2, 1 mmol), NaN3 (3, 1.2 mmol), and 40 mg of the ND-g-PEI@FA@Co(II) nanocomposite were added to a round-bottom flask and stirred in a mixture of EtOH and H2O green solvent at a ratio of 1:1 for 4 h. The reaction progress was controlled by the thin-layer chromatography (TLC) technique. After completion, the reaction mixture was diluted using HCl (10 mL, 2 M), and the catalyst was separated by filtration. EtOAc (10 mL) was added to the solution under filtration and decanted. The EtOAc was evaporated and the final product was recrystallized for further purification with the mixture of H2O and EtOH (Scheme 2).

2.6. Spectral Data

(E)-3-(2-Chlorophenyl)-2-(1H-tetrazol-5-yl) acrylonitrile (4a). FT-IR (KBr, cm−1): 3420, 2926, 2222, and 1564. Observed Mp (°C): 165–167 (Figure 1).

3. Results and Discussion

3.1. FT-IR Spectroscopy

The FT-IR spectra of oxidized ND (ND-COOH) are shown in Figure 2a. The stretching vibrations in the range of 3628–3010 cm−1 are attributed to the O–H bonds of carboxylic acid groups. Also, the adsorption bands at 2914 and 2848, 1708, and 1222 cm−1 are related to the asymmetric and symmetric vibrations of the aliphatic C–H groups, stretching vibration of C=O carboxylic acid, and C–O bond in the oxidized ND structure.
As indicated in Figure 2b, the broad peak appearing at 3659 to 3104 cm−1 is related to the stretching vibrations of the O–H and N–H bonds. Furthermore, the adsorption bands at 2917 and 2850 cm−1 are related to the asymmetric and symmetric vibrations of the –CH2– groups. Also, the characteristic peaks at 1651, 1630, 1023, and 954 cm−1 are attributable to the stretching vibrations of the C=O functional group resulting from the nucleophilic attack of the amine groups present in PEI on the carboxylic acid groups present in oxidized ND and the formation of the amide bond, the bending vibration of –NH– in the PEI structure [24,25], the stretching vibration of C–N, and the wagging of the –NH2 groups in PEI, respectively [26,27].
In Figure 2c, the FT-IR spectrum of the ND-g-PEI@FA nanocomposite can be observed. The adsorption peaks in the range of 3654 to 3223 cm−1 belong the to O–H bonds of the carboxylic acid functional group of the FA and NH bonds of PEI and FA. On the other hand, the stretching vibrations at 2927 and 2850 cm−1, 1708, 1623, 1437, and 1313, and 1089 cm−1 correspond to the asymmetric and symmetric vibrations of –CH2–, the stretching vibration of carboxylic acid (C=O), the stretching vibration mode of the C=O bond of the amide group, the benzene ring stretching vibration of FA, and the C–O bonds of carboxylic acid in the FA structure [28].

3.2. EDS Analysis

The EDS spectrum of the synthesized ND-g-PEI@FA@Co(II) nanocomposite is shown in Figure 3. The peaks representing carbon (54.97%), nitrogen (11.64%), oxygen (29.76%), sulfur (0.86%), and cobalt (2.78%) confirm the nanocomposite formation.

3.3. XRD Pattern

The XRD pattern of the synthesized ND-g-PEI@FA@Co(II) nanocatalyst was monitored, as shown in Figure 4. The characteristic peaks at 2θ = 21.89° and 43.80° are related to the oxidized ND structure (JSPDS card No.: 96-110-0920). On the other side, the peaks at 2θ = 7.62°, 14.60°, 17.23°, and 28.8° can be attributed to the crystalline structure of folic acid (JCPDS card No: 96-222-0898) [29]. Also, the Co(II) XRD pattern appears at 2θ = 15.35° and 33.1° (JCPDS card No.: 96-410-5685) [13,30]. PEI has an amorphous structure and does not appear in the XRD pattern for this nanocatalyst [31,32].

3.4. FE-SEM Analysis

Figure 5 shows the FE-SEM images of the ND-g-PEI@FA@Co(II) nanocomposite. The FE-SEM images show that the ND nanoparticles are spherical, relatively uniform, and have a regular distribution on the surface. In addition, it can be seen from these images that the folic acid coating increases the particle size.

3.5. Optimization of Reaction Conditions for the Synthesis of 5-Substituted 1H-Tetrazole Derivatives

As determined in Table 1, to obtain the optimal conditions for the synthesis of 5-substituted 1H-tetrazole derivatives, various parameters were investigated such as catalyst dosage, solvent, and reaction temperature. The multicomponent reaction between 4-chlorobenzaldehyde (1b) (1 mmol), malononitrile (2) (1 mmol), and NaN3 (3) (1.2 mmol) was carried out in the presence of the ND-g-PEI@FA@Co(II) nanocatalyst under different conditions. The progress of the reaction was evaluated using a TLC technique. Based on the results in Table 1 (entries 1–4), the synthesis reaction of the tetrazole derivatives was carried out in catalyst-free conditions with different solvents, but no product was obtained in the reaction time. In entries 8–12, reactions were performed using different amounts of nanocatalyst, and the best efficiency was obtained for the quantity of 40 mg of nanocatalyst. Next, in entries 13–15, the effect of solvent on product efficiency was investigated, and the best result was obtained with a mixture of H2O and EtOH as a green solvent. Finally, the impact of temperature on the synthesis reaction of tetrazole derivatives was evaluated in entries 16–18. According to the obtained results, the best conditions for the synthesis of 3-(4-cholorophenyl)-2-(1H-tetrazole-5-yl) acrylonitrile (4b) using the ND-g-PEI@FA@Co(II) nanocatalyst can be seen in Table 1 (entry 14).
As shown in Table 2 for the synthesis of different tetrazole derivatives, various aldehydes with different electron donor and electron acceptor groups were used in the presence of nanocatalysts under optimized conditions; the structure and melting point are specified in Table 2.

3.6. The Plausible Mechanism for the Synthesis of 5-Substituted 1H-Tetrazole Derivatives

The mechanism of tetrazole synthesis involves cascade condensations, such as Knoevenagel condensation, 1,3-dipolar cycloaddition, and tautomerization reactions. First, CH acid (malononitrile) and benzaldehyde are activated using a nanocatalyst, and with the nucleophilic attack of malononitrile on the electrophilic group of the aldehyde, intermediate (III) is formed, which is obtained by the Knoevenagel condensation and intermediate (IV). In the next step, as a result of nucleophilic cyclization, NaN3 attacks one of the nitrile groups (C≡N), and intermediate (V) is produced. Finally, as a result of tautomerization and adding HCl (2 M), the 5-substituted 1H-tetrazole product (VII) is synthesized [37,38,39,40,41]. (Scheme 3)

3.7. Reusability of ND-g-PEI@FA@Co(II) Nanocatalyst

To emphasize the importance of the reuse of the ND-g-PEI@FA@Co(II) nanocatalyst in the production process of tetrazole derivatives, the catalyst was investigated. After separating the catalyst, it was washed using water and ethanol and then dried in an oven at 60 °C. The catalyst was reused four times. According to the results in Figure 6, the reaction efficiency demonstrated a slight decrease (from 97% to 81%).
In Table 3, the efficiency of the prepared nanocatalyst in the synthesis of tetrazole was compared with that of different catalysts. In this work, the nanocatalyst was able to perform the tetrazole synthesis reaction in a short period of time using a green and environmentally friendly solvent with acceptable efficiency, which shows the importance of this nanocatalyst compared to other catalysts.

4. Conclusions

In conclusion, a new and suitable nanocatalyst based on a nanodiamond carbon substrate and polyethylene imine polymer with abundant amine groups was prepared for a quick and green synthesis of tetrazole derivatives. Among the outstanding features of this work, of note is the use of environmentally friendly raw materials, the use of green and affordable solvents, and the stability and acceptable recyclability of the synthesis.

Author Contributions

Z.N.: laboratory works and author; A.R.: laboratory works and author; H.G.: responsible writer. All authors have read and agreed to the published version of the manuscript.

Funding

We are grateful for the financial support from the research council of Iran University of Science and Technology (IUST), Tehran, Iran.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available upon request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

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Chemproc 16 00086 sch001
Scheme 1. Preparation steps for ND-g-PEI@FA@Co(II) nanocomposite.
Scheme 1. Preparation steps for ND-g-PEI@FA@Co(II) nanocomposite.
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Scheme 2. Multicomponent reaction for synthesis of 5-substituted 1H-tetrazole derivatives.
Scheme 2. Multicomponent reaction for synthesis of 5-substituted 1H-tetrazole derivatives.
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Figure 1. The FT-IR of (E)−3−(2−chlorophenyl) −2−(1H-tetrazol−5−yl) acrylonitrile.
Figure 1. The FT-IR of (E)−3−(2−chlorophenyl) −2−(1H-tetrazol−5−yl) acrylonitrile.
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Figure 2. The FT-IR spectra of (a) oxidized ND, (b) ND-g-PEI, and (c) ND-g-PEI@FA nanocatalyst.
Figure 2. The FT-IR spectra of (a) oxidized ND, (b) ND-g-PEI, and (c) ND-g-PEI@FA nanocatalyst.
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Figure 3. The EDS analysis of ND-g-PEI@FA@Co(II) nanocatalyst.
Figure 3. The EDS analysis of ND-g-PEI@FA@Co(II) nanocatalyst.
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Figure 4. The XRD pattern of ND-g-PEI@FA@Co(II) nanocatalyst.
Figure 4. The XRD pattern of ND-g-PEI@FA@Co(II) nanocatalyst.
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Figure 5. The FE-SEM images of the ND-g-PEI@FA@Co(II) nanocatalyst (a–d).
Figure 5. The FE-SEM images of the ND-g-PEI@FA@Co(II) nanocatalyst (a–d).
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Scheme 3. The proposed mechanism of the synthesis of 5-substituted 1H-tetrazole derivatives by ND-g-PEI@FA@Co(II) nanocatalyst.
Scheme 3. The proposed mechanism of the synthesis of 5-substituted 1H-tetrazole derivatives by ND-g-PEI@FA@Co(II) nanocatalyst.
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Figure 6. Reusability of the ND-g-PEI@FA@Co(II) nanocatalyst.
Figure 6. Reusability of the ND-g-PEI@FA@Co(II) nanocatalyst.
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Table 1. Optimization of reaction conditions for synthesis of 5-substituted 1H-tetrazole derivatives.
Table 1. Optimization of reaction conditions for synthesis of 5-substituted 1H-tetrazole derivatives.
EntryCatalystCatalyst Dosage (mg)SolventT (°C)Time (h)Yield (%)
1------EtOHr.t4N. R. a
2------Toluener.t4N. R.
3------DMFr.t4N. R.
4------EtOH/H2Or.t4N. R.
5ND-COOH40EtOH/H2O100460
6ND-g-PEI40EtOH/H2O100472
7ND-g-PEI@FA40EtOH/H2O100470
8ND-g-PEI@FA@Co(II)10EtOH/H2O80480
9ND-g-PEI@FA@Co(II)20EtOH/H2O80487
10ND-g-PEI@FA@Co(II)30EtOH/H2O80489
11ND-g-PEI@FA@Co(II)40EtOH/H2O80491
12ND-g-PEI@FA@Co(II)50EtOH/H2O80490
13ND-g-PEI@FA@Co(II)40EtOH80490
14ND-g-PEI@FA@Co(II)40TolueneReflux430
15ND-g-PEI@FA@Co(II)40DMFReflux450
16ND-g-PEI@FA@Co(II)40EtOH/H2O70478
17ND-g-PEI@FA@Co(II)40EtOH/H2O90495
18ND-g-PEI@FA@Co(II)40EtOH/H2O100497
Reaction conditions: 4-Chlorobenzaldehyde (1b) (1 mmol), malononitrile (2) (1 mmol), NaN3 (3) (1.2 mmol), and nanocomposite. a No Reaction.
Table 2. Synthesis of different tetrazole derivatives in the presence of the ND-g-PEI@FA@Co(II) nanocatalyst.
Table 2. Synthesis of different tetrazole derivatives in the presence of the ND-g-PEI@FA@Co(II) nanocatalyst.
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EntryAldehyde (1a–m)Product (4a–m)Time (h)Yield (%)Mp (°C)
ObservedLiterature
1Chemproc 16 00086 i002Chemproc 16 00086 i003494174–175175–177 [33]
2Chemproc 16 00086 i004Chemproc 16 00086 i005497165–167165–168 [33]
3Chemproc 16 00086 i006Chemproc 16 00086 i007491169–171168–170 [34]
4Chemproc 16 00086 i008Chemproc 16 00086 i009487188–190189–191 [35]
5Chemproc 16 00086 i010Chemproc 16 00086 i011485159–160159–161 [36]
Reaction conditions: benzaldehyde derivatives (1a–e) (1 mmol), malononitrile (2) (1 mmol), NaN3 (3) (1.2 mmol), nanocatalyst (40 mg), and a mixture of EtOH/H2O (10 mL).
Table 3. Comparison of results by ND-g-PEI@FA@Co(II) nanocatalyst with various catalysts.
Table 3. Comparison of results by ND-g-PEI@FA@Co(II) nanocatalyst with various catalysts.
EntryCatalystSolventTime (h)Yield (%)Ref.
1Cu-P.bis(OA)@FeB-MNPsPEG297[1]
2Co(II)-diazido intermediateDMSO1299[12]
3Fe3O4@HT@AEPH2-Co(II)H2O195[16]
4Co-(PYT)2@BNPsPEG298[13]
5ND-g-PEI@FA@Co(II)EtOH/H2O497This work
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Nasri, Z.; Ramezani, A.; Ghafuri, H. Cobalt (II) Complex on Nanodiamond-Grafted Polyethyleneimine@Folic Acid: An Extremely Effective Nanocatalyst for Green Synthesis of 5-Substituted 1H-Tetrazole Derivatives. Chem. Proc. 2024, 16, 86. https://doi.org/10.3390/ecsoc-28-20132

AMA Style

Nasri Z, Ramezani A, Ghafuri H. Cobalt (II) Complex on Nanodiamond-Grafted Polyethyleneimine@Folic Acid: An Extremely Effective Nanocatalyst for Green Synthesis of 5-Substituted 1H-Tetrazole Derivatives. Chemistry Proceedings. 2024; 16(1):86. https://doi.org/10.3390/ecsoc-28-20132

Chicago/Turabian Style

Nasri, Zahra, Arezoo Ramezani, and Hossein Ghafuri. 2024. "Cobalt (II) Complex on Nanodiamond-Grafted Polyethyleneimine@Folic Acid: An Extremely Effective Nanocatalyst for Green Synthesis of 5-Substituted 1H-Tetrazole Derivatives" Chemistry Proceedings 16, no. 1: 86. https://doi.org/10.3390/ecsoc-28-20132

APA Style

Nasri, Z., Ramezani, A., & Ghafuri, H. (2024). Cobalt (II) Complex on Nanodiamond-Grafted Polyethyleneimine@Folic Acid: An Extremely Effective Nanocatalyst for Green Synthesis of 5-Substituted 1H-Tetrazole Derivatives. Chemistry Proceedings, 16(1), 86. https://doi.org/10.3390/ecsoc-28-20132

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