Nano-Pd/Chitosan Composite: An Extremely Effective Catalyst to the Synthesis of Pyrazolyl Analogues through Suzuki–Miyaura Cross-Coupling Reactions in an Aqueous Medium

Senthilkumar, M.; Manisankar, P.; Pandimurugan, R.; Vivekanand, P. A.; Periyasami, Govindasami; Harikumar, S.; Karthikeyan, Perumal; Rahaman, Mostafizur; Khanal, Santosh

doi:https://doi.org/10.1155/2023/6594464

Journal of Chemistry

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Abstract Introduction Results and Discussion Conclusion Data Availability Conflicts of Interest Acknowledgments Supplementary Materials References Copyright Related Articles

Research Article | Open Access

Volume 2023 | Article ID 6594464 | https://doi.org/10.1155/2023/6594464

Nano-Pd/Chitosan Composite: An Extremely Effective Catalyst to the Synthesis of Pyrazolyl Analogues through Suzuki–Miyaura Cross-Coupling Reactions in an Aqueous Medium

M. Senthilkumar,¹P. Manisankar,²R. Pandimurugan,³P. A. Vivekanand,⁴Govindasami Periyasami,⁵S. Harikumar,⁶Perumal Karthikeyan,⁷Mostafizur Rahaman,⁵and Santosh Khanal⁸

Academic Editor: Islam M. Al Akraa

Received02 Mar 2023

Revised08 Jun 2023

Accepted09 Jun 2023

Published27 Jun 2023

Abstract

Substituted pyrazolyl derivatives were synthesized through Suzuki cross coupling of aromatic boronic acid with heterocyclic halide using newly synthesized nano-Pd/chitosan catalyst by the water-mediated green synthesis methodology. The reactivity of the nano-Pd catalyst was highly enhanced by incorporating palladium nanoparticles with a biopolymer chitosan matrix. The synthesized nano-Pd/chitosan catalyst was studied thoroughly for its structure, morphology, and other fundamental aspects such as the size and shape by various techniques including XRD, FESEM, and EDAX analyses. The scope of the catalyst was disclosed by their great stability with remarkable reusability for Suzuki cross-coupling reaction with twelve different boronic acids under the green synthetic methodology.

1. Introduction

Generally, carbon-carbon bond in organic compounds is done through Suzuki coupling reduction reactions using palladium as catalyst [1–3]. Pyrazole skeleton functions as the backbone in various fields such as natural products, functional materials agrochemicals, and pharmaceuticals [4]. Normally, cross-coupling reactions that involve the use of organic ligand are performed in order to enhance the catalytic process and the selection of particular stereospecific reactions. In the literature for the synthesis of pyrazole derivatives, the one between aryl boronic acid and aromatic halides, named Suzuki–Miyaura cross-coupling (SM) reactions are preferred as they contain less toxic substrates [5]. Various palladium catalyst systems have been demonstrated with the following bases: Schiff bases [6], phosphorous-based ligands [7], N-heterocyclic carbene [8], amines [9], and palladacycle complexes [10]. In recent years, scientists have developed ligand-free SM reactions using simple palladium precursors such as palladium acetate, tetrakis, and dikis. Heterogeneous catalysts are pawing advantage over homogeneous catalysts because of the elimination of toxic solvents and removal, recovery, and recycling of expensive palladium precursors. To defeat aforementioned issues, the ligand-free palladium-based heterogeneous catalytic methods are developed for SM reaction [11].

In recent days, Suzuki coupling reactions were carried out using nontoxic solvents, without high temperature and tedious condition for environmentally benign methodology [12]. Researchers have been reported to use magnetic palladium catalysts for speeding up the Suzuki coupling reaction. These catalysts were either laden with Fe₃O₄ [13, 14] or modified NiFe₂O₄ with dopamine [15], modified CoFe₂O₄ with N-[3-(trimethoxysilyl) propyl] ethylenediamine [16] and allotropes of Fe₂O₃/polymer [17–20]. Some of the heterogeneous catalysts showed few disadvantages like low reactivity when compared to homogeneous forms. Similarly, the abovementioned heterogeneous catalysts also showed low reactivity which was because of palladium species discharge from the supports.

Naturally existing porphyrin ligand is used as an efficient organic ligand for preparing palladium metal complexes. Also, palladium porphyrins are of great interest owing to their high yield of intersystem crossing and long lifetime of the resulting triplet state in diverse media [21]. A convenient and efficient palladium (II)–porphyrin catalytic system is reported for their simple, stable, and high reactivity for SM coupling reactions [22–24]. An effective and highly sustainable method has been reported for the Suzuki coupling reaction of aryl halides and phenylboronic acid using in situ generated nacocellulose-supported palladium nanoparticles as heterogeneous catalysts in water [25]. Lakshmidevi et al. utilized agro waste as a sustainable and renewable medium to synthesis Pd catalyst and reported SM coupling reaction in the water medium [26, 27].

Still, there is a disadvantage can be easily rectified as palladium catalysts can be easily recovered by the way of recycling. The recovered palladium catalysts can be designed to give higher activities and selectivity. In short, heterogeneous palladium catalysts that are more efficient than their homogenous counterparts can be designed with the recycled palladium catalysts. Such targets can be achieved with the help of nanoscience which is crucial to the process.

In the present study, the synthesis of nano-Pd/chitosan catalyst has been aimed to get commercially competitive through a simple production procedure. The prepared nano-Pd/chitosan composite was utilized as a catalyst for Suzuki–Miyaura cross-coupling reactions. The nano-Pd/chitosan was studied in an aqueous solvent medium and without an organic ligand. We propose that this will be the first report to employ nano-Pd with the biopolymer chitosan composite matrix as an effective catalyst in Suzuki coupling reaction in an aqueous medium.

2. Results and Discussion

The aimed catalyst was prepared by two consecutive steps called addition in the acidic medium and reduction in the basic medium. Initially, the biopolymer chitosan solution was prepared by dissolving in 2% acidic acid solution, and the resulting gelatinous mixture was stirred vigorously and palladium chloride was added slowly. In the second step, in order to obtain Pd nanoparticles in chitosan, the gelatinous matrix was sonicated and then reduced with the addition of basic solution. At the end, the synthesized catalyst was dried well in hot air over and then characterized. The schematic catalyst preparation is presented in Figure 1.

The synthesized chitosan matrixed palladium nanoparticles were characterized thoroughly by UV-visible spectroscopy, FTIR, powder XRD, electron microscopic analysis, and thermogravimetry techniques.

2.1. UV-Visible Spectroscopy Analysis

Using double beam UV-visible spectrophotometer, the reduction of Pd²⁺ to Pd⁰ in the chitosan matrix was studied between 200 to 800 nm wavelengths. During the sonication process, in every 10 min time interval, a small portion of the reaction mixture was taken for recording UV absorption. The nanoparticles formation begins 20 min from the sonication, and the observed λ_max at 348 nm in absorption spectrum presented in Figure 2.

2.2. Fourier Transform Infrared Spectroscopy (FTIR)

The FTIR investigation was done to identify the interaction between chitosan and Pd nanoparticles, and the obtained spectra are shown in Figure 3. The peak observed at 3431 cm⁻¹ is due to the stretching vibration of the amine (-NH₂) group and the hydroxyl (-OH) group. The presence of the peak at 3436 cm⁻¹ is due to the secondary amine group present in the chitosan moiety. Likewise, -CH bending vibration and the -CONH- group are confirmed by a spectral peak at 1154 cm⁻¹ and a peak at 1078 cm⁻¹, respectively [28, 29]. In Figure 3(c), FTIR spectra show a shifting of the peak from 1654 to 1639 cm⁻¹ and 1078 to 1068 cm⁻¹ confirming the presence of nano-Pd/chitosan nanocomposites. This could be because of a strong bonding between Pd (II) and the -NH₂ group.

2.3. Morphological and Structural Studies

Scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM-EDAX) was used to evaluate the morphology and chemical composition of chitosan Figure 4 and chitosan-loaded Pd nanoparticles and the microscopic images are presented in Figure 5. The SEM images of chitosan at 2.50 Kx fold magnification shown in Figure 4(a) present an entangled layer-like structure. In Figure 4(b), a similar morphology was seen with small bright particles attached to the chitosan surface which can attribute to the aggregation of Pd nanoparticles as judged by high magnification SEM images (Figures 5(a) and 5(b)). The energy dispersive X-ray analysis (EDAX) spectrum of chitosan shows the peak corresponding to carbon, oxygen, and nitrogen. Also, the peak of palladium is also observed in the chitosan/Pd matrix as shown in Figures 4(c) and 5(c).

Identification of the crystalline structure of chitosan and nano-Pd/chitosan was carried out using XRD measurement and the results are presented in Figure 6. From the XRD patterns, it can be found that chitosan clearly shows two sharp crystalline peaks at 10° and 20°. Likewise, XRD patterns of nano-Pd/chitosan (Figure 6(b)) show the reflections peak at 2θ of 39.92°, 46.54°, and 67.90°, which are indexed to (111), (200), and (220) planes of Pd [30]. Furthermore, the observed peaks indicating the palladium is in corroboration with the JCPDS card no 87-0637. Finally, the successful preparation of Pd nanocrystals is ascertained by the absence of other diffraction peaks, an indicator of high purity. The crystal sizes that are calculated from Debye–Scherer’s equation (D = 0.94λ/β cos θ) are approximately 28 nm. The thermal behaviours of the chitosan and nano-Pd/chitosan were examined by recording the TGA thermograms which is shown in Figure 7. Three stages of weight losses are observed in TGA curves of pure chitosan. 39.1% of weight loss was observed at around 35–281°C because of the evaporation of moisture volatile contents, which constitutes the first stage. 38.8% of weight loss was found at the temperature range of 281–386°C, which indicates the formation of volatiles, which constitutes the second stage. The next stage arises at the onset of the decomposition of hydrocarbons due to which there is a weight reduction of 18.7%, and this comprises the third stage which happens at a temperature between 386 and 520°C. Finally, the remaining 3.4% weight corresponds to the residual content.

On the contrary, nano-Pd/chitosan exhibited only two stages of weight losses. Of the two, the first was noted at 350°C and the second was found in the range of 350–520°C. The first weight loss is attributed to the loss of hydrated water, and the second loss is because of the degradation of the polymer matric. Thus, the difference between pure chitosan and nano-Pd/chitosan is that a three-stage weight loss was noted in the case of pure chitosan, while two stages of decomposition was observed for the nano-Pd/chitosan nanocomposite.

In Figure 8, the DSC thermogram of nano-Pd/CS composite showed a wide range of endothermic peak between 199 and 350°C. The dehydration endothermic peak assigned to the loss of water was associated with hydrophilic groups of the chitosan composite. Unlink pure CS, the nano-Pd/CS composite in the solid state having disordered structure may have strong affinity with water. For the degradation of CS in the synthesized composite, it needs higher temperature unlike pure CS, which is clearly evident by the exothermic peak between 782 and 800°C of the DSC spectrum.

2.4. Catalytic Activity in the Suzuki Coupling Reaction That Caused C-C Bond Formation

The well-characterized nano-Pd/chitosan nanocomposite was used for Suzuki cross-coupling, and the investigation started with heterocyclic halide, aryl boronic acid, and nano-Pd/chitosan nanocomposite. The reactions were optimized by retaining the same conditions and introducing various solvents, changing concentration of catalysts, altering bases, and modifying optimum temperature, the results of the same are shown in Table 1. Initially, the concentration of the catalyst was kept unchanged. Likewise, sodium carbonate (Na₂CO₃) was used as the base and different solvents were used. The first solvent that was tested includes dioxane. This combination resulted in 35% of cross coupling of the product at 80°C at a time span of 2 h. The next solvent that was tested with the same catalyst and base was acetonitrile. This resulted in an increase in the yield of the product at 100°C with 55% cross coupling.

Almost 60% of cross coupling happened within 2 hrs when the solvent was DMF and the base was Na₂CO₃. Under the abovementioned conditions, the reaction took place at 100°C. Subsequently, when water was replaced as the solvent with the base being Na₂CO_3, at 60°C, the reaction showed 85% yield within 1 h unexpectedly. Thus, the study revealed that water is a promising solvent for high conversion, which is also a natural green solvent and is also environmentally friendly. Retaining the conditions and the catalyst of the reactions, various solvents that were changed include ethanol and toluene. Likewise, the bases that were tested include K₂CO₃, CS₂CO₃, and Et₃N. The results of the abovementioned reactions are given in Table 2. Hence, maximum yields were obtained in the presence of the nano-Pd/chitosan nanocomposite (0.02 mol %), with the base being Na₂CO₃ and the solvent being water at 60°C. By concluding the abovementioned optimization reaction, the Suzuki cross-coupling procedure involved three components, which include the innovative catalyst, nano-Pd/chitosan (0.02 mol %), (3-chloro-4,5-dihydro-1H-pyrazol-1-yl)(2-fluorophenyl)methanone 1a (1.0 mmol), and (4-cyano-3-methoxyphenyl)boronic acid (2h) (1.2 mmol). Along with the abovementioned components, the base, Na₂CO₃ (2.0 mmol), and 10 ml water (solvent) were added. This mixture was poured into a pressure tube vessel and stirred continuously at 60°C for 1 h. TLC was used to continuously monitor the reactions and their progress was noted. Ethyl acetate (10 ml) was added to the reaction mixture later when it had cooled down to room temperature. Consequently, the mixture was filtered through a sintered funnel to separate the solid catalyst. Then, the crude product was purified and recrystallized for spectroscopic analysis (Scheme 1). The proton shift (δ) values of the synthesized pyrazole analogue, 4-(1-(2-fluorobenzoyl)-4,5-dihydro-1H-pyrazol-3-yl)-2-methoxybenzonitrile (3h), are presented in Figure 9, as a representative compound, and all the synthesized pyrazole derivative spectroscopic data are presented in the experimental part.

2.5. Suzuki Cross-Coupling Reaction Mechanism with Nano-Pd/Chitosan Catalyst

The reaction mechanism involved Pd⁰/Pd²⁺ couple, is well-known, and presumed that here, the nano-Pd⁰ underwent oxidative addition with aromatic halide. The boron atom in the aromatic boronic acid was activated and polarized with the Na₂CO₃ base in H₂O and then facilitated transmetallation. The generated Pd²⁺ nanoclusters (nano-Pd²⁺/chitosan) during the oxidative addition simplified the transmetallation with organic boronic acid. Furthermore, the nano-Pd²⁺ present in nano-Pd²⁺/chitosan clusters undergo reduction to Pd⁰ during the reductive elimination reaction. As a result, the nano-Pd⁰/chitosan catalyst was recovered with its catalytic efficiency. This plausible cyclic reaction mechanism is presented in Figure 10.

In order to find the scope and limitations of different substrates and the effectiveness of the catalyst (nano-Pd/chitosan), Suzuki cross-coupling reactions were carried out with various boronic acid 2a-l (Table 2) and (3-halogen substituted-4,5-dihydro-1H-pyrazol-1-yl)(2-fluorophenyl)meethanone. The aromatic C-C bonded compounds 3a-l were obtained and all products were affirmed by spectroscopic studies and presented in the experimental part. The structure of aromatic boronic acids 2a-l and the C-C coupled product 3a-l were presented in supporting information^¥ file as Figures S1 and S2, respectively.

The major role of catalysts in environmental and industrial utilization in recycling and reusability is an important criterion for a valuable catalyst. So, the recovered and purified nano-Pd/chitosan catalyst was investigated for successive reactions under the stabilized reaction conditions described in Table 2 entry 8. The recycling nano-Pd/chitosan catalyst maintained its efficiency up to 6 consecutive cycles and then 3 to 5% decreased in the yield was observed from the 7^th cycle onwards. The catalyst ability is presented in Figure 11.

A systematic comparison of some advantageous heterogeneous Suzuki coupling protocols with the present method has been provided in Table 3. It is clear that compared to the previously reported Suzuki coupling protocol methods, the presently reporting method has its own ideal significance. Our reaction condition is completely environmentally benign with low temperature and mild basic condition, yielding high percentage of coupling product and an easy purification method. It also showed that the handling advantages of that nano-Pd/chitosan catalyst was found to be easy to separate and reuse.

3. Conclusion

In this study, a chemical precipitation method was employed to synthesize the nano-Pd/chitosan composite. The characterization of the catalyst was done using various spectroscopic techniques such as XRD, FTIR, TGA, and UV-visible. The chemical interaction of chitosan and Pd was confirmed by FTIR analysis. The range of the particle size was measured to be 20–80 nm. The nano-Pd/chitosan composite exhibits good catalytic activity towards the Suzuki coupling reaction. The various advantages of catalyst are five times recyclability, high reactivity, short time, environmentally benign solvent system, etc. The study resulted in the synthesis of biologically crucial pyrazole derivatives that are similar to that of various natural products that are known for their medicinal values. Conditions such as time of reaction, varying the solvents, and remarkable amount of catalyst were suitable for giving a maximum yield of the product. The study showed the maximum yield when the catalyst was used in water at a rate of 0.02% mol and with 1 h reaction time. NMR and HPLC were used to confirm the synthesized products.

4. Experiments

4.1. Materials

Chitosan (mol. wt. 80 kDa and 90% deacetylation) was obtained from Sigma-Aldrich, USA. Acetic acid (glacial) and palladium (II) chloride (98%) were bought from Sigma-Aldrich. Sodium hydroxide and hydrazine hydrochloride were obtained from S.D fine CHEM limited and SRL chemicals, respectively. All the chemicals used were of the AR grade and used without further purification.

4.2. Synthesis of Nano-Pd/Chitosan Catalyst

The catalyst has been synthesized with the following simplified procedure: 1.0 g of chitosan was added portionwise into a 100 mL beaker containing 25 mL of 2% acetic acid and completely dissolved. Then, 5% (w/w) of palladium chloride was added in the form of an aqueous solution to the chitosan solution. The obtained gelatinous mixture was stirred continuously to dissolve chitosan completely and it was further subjected to sonication for 30 min. 0.1 N of sodium hydroxide was added dropwise to the abovementioned mixture to increase the pH value to 9.0. The mixture was heated for about 8 hrs in a water bath maintaining the temperature at 80°C. Then, it is subjected to cooling and slowly the temperature drops down and room temperature is attained. Furthermore, palladium chloride is reduced to palladium by drop by drop addition of hydrazine hydrochloride. When the colour of the solution turns to black, it confirms the formation of Pd nanoparticles. Finally, double distilled water was used to wash the Pd nanoparticles; subsequently, they were centrifuged. The resultant particles were collected as samples, which was dried in a hot air oven before the characterization of the same was undertaken.

4.3. Characterization Techniques

FTIR spectra were recorded on a Perkin Elmer 100 FTIR spectrophotometer in the range of 4000–400 cm⁻¹ at room temperature. Thermogravimetric analysis (TGA) was recorded using TGA-V47ATA. The sample was heated in the temperature range of 30–800°C in nitrogen atmosphere with the heating rate of 10°C/min. Differential scanning calorimetry (DSC) was performed on DSC-822 and TGA-V47ATA with aluminum seal under the nitrogen atmosphere at the flow rate of 20 mL/min and at the heating rate of 10°C/min. XRD patterns were recorded at room temperature using Philips X’pert Pro X-ray powder diffractometer using CuKα radiation (λ = 1.5418 Å) at 40 mA current and 40 kV voltage. The surface morphology was observed using a field emission scanning electron microscope (Magellan XHR 400 L FESEM, FEI, Eindhoven, the Netherlands) at room temperature (20 ± 2°C) at a working distance of 4 mm with SE detection at 2 kV. UV–vis spectra were recorded using the standard quartz cell with 1 cm path length in a scanning wavelength range of 200–600 nm, with a time interval of 60 seconds at the temperature of 25°C.

4.4. General Procedure for Suzuki Cross-Coupling Reactions

The modified typical Suzuki cross-coupling reaction is presented for the synthesis of pyrazolyl analogues (3a–l). To a suspension of (3-chloro-4,5-dihydro-1H-pyrazol-1-yl)(2-fluorophenyl) methanone 1a (1b for product 3f) (1.0 mmol) in 10 mL distilled water, 1.2 mmol of aromatic boronic acid (2a–l) and 0.02 mol % of innovative catalyst nano-Pd/chitosan were added. The starting materials suspension was transferred to the pressure tube vessel and then Na₂CO₃ (2.0 mmol) was added. The reaction mixture was stirred continuously at 60°C for 1 h in the closed pressure tube vessel. After the completion of the reaction, monitored by TLC, ethyl acetate (10 mL) was added to the reaction mixture later when it was cooled down to the ambient temperature. Furthermore, the reaction mixture was filtered through a sintered funnel to separate the solid catalyst. The recovered catalyst can be used for subsequent cycles by simple purification procedure such as washing with acetone and then made to dry in desiccators. After the removal of the catalyst, the filtrate was concentrated under reduced pressure and washed with ethyl acetate (3 × 30 mL) and brain solution and then dried over Na₂SO₄. The resultant organic part was concentrated to obtain the crude product and then purified by way of flash column chromatography using CHCl₃/MeOH (9 : 1) eluent. Finally, the affirmation of the pure pyrazolyl analogues was done by spectroscopic analysis (see Scheme 2).

The structure of the synthesized compounds was accomplished with NMR, FTIR, spectroscopic analysis, and HPLC retention time with the peak area. As a representative compound, the ¹H NMR spectrum of 3H in methoxy proton resonates at δ 3.96 as a singlet. The two adjacent methylene protons in the pyrazole ring resonate as triplets. The methylene group near to electron withdrawing the keto aromatic ring resonates in the downfield at δ 4.32 as triplet compared to the adjacent methylene group of pyrazole ring. Another triplet observed at δ 3.30 corresponds to methylene proton in the five membered pyrazole ring. The aromatic region showed a multiplet peak between δ 7.20 and 7.62, integrating seven aromatic protons. The method followed for HPLC consists of TFA in water of about 0.1% and TFA in acetonitrile of 0.1%, with a flow rate of 1.5 ml per min, and column details are Atlantis d C18 with the measurement of 50 × 4.6 mm, 5 µm, and +ve mode max chromatogram has an RT (min) of 4.54% with an area of 96.70. The NMR data of all synthesized compounds with the spectra and HPLC spectrum with the retention time of synthesized C-C coupled pyrrozolyl 3a–l are presented in the supporting information file^¥.

Data Availability

The data used to support the findings of this study are included within the article.

Conflicts of Interest

The authors declare that they have no conflicts of interest.

Acknowledgments

The authors would like to show their sincere thanks to the Department of Industrial Chemistry and Physics, Alagappa University, for their help rendered in using SEM, FTIR, and XRD for analysis. The authors also thank DST-SERB (EMR/2016/000055), India, for the financial support for this research. This project was supported by Researchers Supporting Project number (RSPD2023R675), King Saud University, Riyadh, Saudi Arabia.

Supplementary Materials

The data associated with the NMR and HPLC spectra of synthesized compounds are included in the supplementary materials. (Supplementary Materials)

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Copyright © 2023 M. Senthilkumar et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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