RESEARCH ARTICLE

 

Improvement of the catalytic activity of an Algerian clay by acid treatment under solvent and solvent-free conditions for 3,4-dihydropyrimidin-2(1H)-one synthesis

 

 

Lamia Bouchenka^I, ; Farida Bouremmad^I; Fatiha Belferdi^II; Samira Maane^III; Musa Mutlu Can^IV; Mousa Amayreh^V; Mehmet Ali Gulgun^VI

^ILaboratory of Interaction between Materials and Environment (LIME), Faculty of Sciences and Technology, University of Jijel, Jijel, Algeria
^IILaboratory of Pharmacology and Phytochemistry, Faculty of Sciences and Technology, University of Jijel, Jijel, Algeria.
^IIIDepartment of Chemistry, Faculty of Sciences, Ferhat Abbas Setif-1 University, Algeria
^IVRenewable Energy and Oxide Hybrid Systems Laboratory, Department of Physics, Faculty of Science, Istanbul University, Vezneciler, Istanbul, Turkey
^VChemistry Department, Faculty of Applied Sciences, Palestine Technical University - Kadoorie (PTUK), Tulkarm, Palestine
^VISabanci University, FENS, Orhanli Tuzla, Istanbul, Turkey

 

 

---

ABSTRACT

This work aims to study the effects of acid treatment on the structural and catalytic properties of Algerian montmorillonite. Acid activation of montmorillonite is carried out by sulfuric acid (H₂SO₄) at different concentrations under controlled conditions. The structural changes of the montmorillonite are investigated by XRD, FTIR, XRF, and BET techniques. The results of the proposed study indicated that acid activation causes significant changes in the structure of the samples. This leads to an increase in specific surface area and pore volume. The FTIR spectrum of adsorption of pyridine on montmorillonite showed an increase of the acidic sites depending on the concentration of the treatment solution. The activated montmorillonite is then used as a heterogeneous acid catalyst for the synthesis of dihydropyrimidinone molecule (DHPM) by Biginelli reaction using different solvents, and under solvent-free conditions. It was found that the reaction under solvent-free conditions simplifies the preparation process and gives excellent yields (92%, 8 h), in addition, it is an environmentally friendly process and deals with green chemistry. In this work, the importance of the order of introduction of the reagents is proven, thus allowing us to propose a reaction mechanism.

Keywords: Heterogeneous catalysis, Green chemistry, Montmorillonite, Biginelli reaction

---

 

 

INTRODUCTION

The Biginelli reaction allows obtaining the dihydropyrimidinones (DHPMs) molecules and their derivatives which have various pharmacological and therapeutic properties.¹ DHPMs molecules exhibit antibacterial, antiviral, anti-inflammatory, antitumor, antiepileptic, antifungal as well as antioxidant activities.^2-4 In addition, DHPMs were also used as modulators of calcium channels in cardiovascular disease.⁵

The classical Biginelli procedure developed in 1893 by the Italian chemist Pietro Biginelli, aimed to prepare DHPMs by a single operation of cyclo-condensation reaction with three reagents. This reaction consists of the mixture of aldehyde, ethyl acetoacetate, and urea where ethanol was used as a solvent, under strongly acidic conditions (HCl) while heating at reflux. The main drawbacks of the conventional synthesis are the requirement of prolonged reaction times with low yields and severe reaction conditions.^6,7 Furthermore, the traditional catalysts used are toxic and difficult to separate from the reaction medium; which, is a significant obstacle to the regeneration step. To overcome the mentioned drawbacks, researchers are developing new strategies for the classical synthesis to produce DHPMs in good yields.^7,8 Recently, a series of operating protocols have been proposed⁹ such as the use of microwave or ultrasound irradiation,^9,10 the use of various homogeneous and heterogeneous catalysts like Lewis acids,¹¹ Brönsted acids,⁴ ionic liquids,¹² organo-catalysts,^13,14 nano-catalysts,¹³ transition metal salts and hetero-poly acids.^15,16

Montmorillonite has been successfully used in various fields, and continues to attract the attention of many researchers, especially in heterogeneous catalysis for organic synthesis.¹⁷ This interest is justified by its numerous advantages such as its low cost, abundance in nature, cation exchange capacity, its high specific surface area,^18-20 as well as its non-toxic and non-corrosive characteristics.²¹ Moreover, it is reusable and acts as a Lewis/Brönsted acid.²¹ All the above advantages make the montmorillonite one of the most important clay minerals.

Montmorillonite is a 2:1 phyllosilicate formed by stacking octahedral and tetrahedral layers so that an octahedral layer is interposed between two tetrahedral layers.^22-24 Properties of montmorillonite can be improved by several physicochemical treatments,²⁵ such as organic, inorganic and organometallic intercalation,¹⁹ heat treatment, and acid activation.²⁶ The acid activation method allows the replacement of exchangeable interlayer cations by H⁺ at low acid concentrations, and the destruction of octahedral and tetrahedral layers at high acid concentrations. Furthermore, different modifications occurred during the acid attack such as volume of the pores, specific surface area, number and/or the nature of active site were observed notably on the crystal lattice.^26-28

The proposed work deals with green chemistry by applying heterogeneous catalysis and solvent-free conditions. An Algerian montmorillonite is used as a solid acid catalyst for the preparation of the DHPM (Scheme 1). We investigated the effect of the acid treatment of the Algerian montmorillonite on the yield of the Biginelli reaction. Therefore, we highlighted the effect of other parameters such as the mass of the catalyst, the solvent, the solvent-free conditions, and the introduction order of the reagents, which allows us to propose a mechanism for the reaction. Finally, the development method is a simple, efficient and environmentally friendly catalytic system to synthesize DHPM in high yields.

 

 

MATERIALS AND METHODS

Materials and characterization methods

The clay raw material used in this study is an Algerian montmorillonite, obtained from the deposits of Hammam Boughrara in Maghnia in western Algeria, marketed by the national company of useful substances and non-ferrous materials (ENOF).

Sulfuric acid (95%, VWR Chemicals), benzaldehyde (99%, Sigma-Aldrich), ethyl acetoacetate (99%, Sigma-Aldrich), urea (99%, Sigma-Aldrich), methanol (99%, Honeywell Riedel-de-Haën™), ethanol (99%, VWR Chemicals), acetonitrile (99.9%, Merck), cyclohexane (99.8%, Sigma-Aldrich) and acetic acid ( 99.5%, Honeywell Fluka™) were used in the current research activity without further purification.

To evaluate the structural changes of montmorillonite after acid activation, different characterization techniques were used (XRD, FTIR, FRX, and BET). The recording of the diffractograms of the samples were carried out using a D8 Advance Bruker AXS diffractometer with CuKa radiation equipped with a curved graphite monochromator. The data were collected in the 29 range of 5-80° with a step interval of 0.03° per second.

The specific surface area of sodium montmorillonite and activated montmorillonite, at different concentrations, was determined by BET method using the Micro metrics 3 Flex Adsorption Analyzer (Version 4.03). The samples were analyzed under a nitrogen atmosphere (adsorption-desorption isotherm at 77 K). Before the measurement, the samples were heated at 200 °C for 2h. The total pore volume was deduced from the amount of nitrogen gas adsorbed at P/P₀ = 0.95. FTIR spectra were obtained by a Shimadzu Fourier Transform Infrared Spectrophotometer (FTR-8400S) over a range of 500 cm^-1 to 4000 cm^-1. The elemental composition of the studied samples was determined by X-ray fluorescence (XRF) using a ZSX Primus spectrometer. All reactions were controlled by analytical thin-layer chromatography (TLC). The melting point of DHPMs was determined with a BÜCHI-B540 melting meter and the 1H NMR spectra were recorded with an Advance Bruker spectrometer (300 MHz) using CDCl₃ as solvent. Chemical shifts are conducted in parts per million (δ, ppm).

Catalyst preparation

The clay was activated by a sulfuric acid solution at different concentrations (1 mol/L, 2 mol/L, and 3 mol/L) at 60 °C and under stirring for 24 h, clay proportions were 20 g for 250 mL of solution. The clay/acid mixture was then separated by filtration; this process was repeated 4 times. The solid precipitate is washed with distilled water to eliminate the excess sulfuric acid. The precipitate was dried at 100 °C for 24 h in oven, crushed and then stored in a dry place. The activated montmorillonite, at different concentrations, was designated Mt-1M, Mt-2M and Mt-3M, and the sodium montmorillonite was designated by Mt-Na.

Biginelli reaction for the synthesis of the DHPM

The Biginelli reaction occurred in a 50 mL sample trial, where benzaldehyde (5 mmol), urea (6.25 mmol), ethyl acetoacetate (12 mmol), and montmorillonite (20% of benzaldehyde amount) were mixed in two ways. For the first one with 5 mL of solvent, while the second without solvent. The mixture is heated to 80 °C at reflux with stirring for 8 h.

At the end of the reaction, the mixture is washed with hot methanol, the filtrate is collected, and the methanol is removed at 65 °C. To obtain an analytically pure product, the product was recrystallized in ethanol. Compounds obtained, using this procedure, have been identified by: melting points, FTIR and 1H-NMR.

 

RESULTS AND DISCUSSION

Characterization of catalyst

X-ray diffraction (XRD)

Figure 1 depicts the XRD spectra, for sodium montmorillonite and activated montmorillonite, at different concentrations of sulfuric acid.

 

 

The characteristic peaks for Mt-Na are located at 29 = 6.21°, 20°, 35° and 62°; they are attributed to reflections (001), (020), (200,130) and (060,330),respectively.²⁹ We can also note the existence of certain impurities such as quartz at 29 = 21°, 26°, 50°, and 68°.^30,31 The main peak of sodium montmorillonite is at 29 = 6.21° and gives the interfoliar space distance d₀₀₁ = 14 Å.

The XRD spectra reveal very significant structural changes due to the acid attack. For all concentrations, the characteristic peak of montmorillonite (001) completely disappeared. As the protons penetrate the montmorillonite sheets, they replace the exchangeable cations in the interfoliar space and attack the OH groups of the tetrahedral and octahedral sheets. This leads to the dissolution of the central atoms and the destruction of the chemical bonds as well as the disappearance of the basal spacing. The disappearance of the peaks at 29 = 20°, 35°, and 62° for the three catalysts clearly confirms that the two-dimensional montmorillonite lattice is completely lost by attack with sulfuric acid. Also, it is important to mention that the peaks at 29 = 26° and 50° characterizing quartz, are present in the three catalysts but with different intensities, which shows the formation of silica due to the acid activation process.

Nitrogen adsorption (BET)

Figure 2 shows the nitrogen adsorption-desorption isotherms for sodium montmorillonite and treated montmorillonite at different acid concentrations. Table 1 summarizes the results of BET surface area and total pore volumes. According to the IUPAC classification, the adsorption-desorption isotherm of various catalysts is of type II. It has been described in the case of macro-porous solids^32,33 and non-porous solids.³³ The adsorption isotherm of sodium montmorillonite represents an H4-type hysteresis loop characteristic of sheet-shaped particles with slit pores.³⁴ While, after acid activation, isotherms show a significant increase in the volume of adsorbed nitrogen.

 

 

 

 

This could be attributed to the formation of new pores due to acid treatment.¹⁹ The below isotherms show an H3 type hysteresis loop which generally defines mesoporous materials with microstructure mainly composed from capillary pores.^35-37 Sodium montmorillonite presents a low specific surface area of 33 cm² g^-1, which reaches a maximum of 310 cm² g^-1 for the Mt-1M and then decreases to 192 cm² g^-1 and 219 cm² g^-1 for the Mt-2M and Mt-3M, respectively (Table 1). We observed an increase in surface area of Mt-1M; and this could be attributed to the exfoliation and/or destruction of adjacent layers of the multi-segmented clay due to acid attack, as well as the dissolution of structural cations from octahedral layer which leads to formation of new pores.^19,20 Surface area of Mt-2M and Mt-3M clays were decreased; and this could be attributed to pore clogging associated with the formation of mineralized phases which resist acid attack.^19,38 The specific surface area of the Mt-3M is greater than that of the Mt-2M which means that the mineralized phases formed at the 2 M concentration are also attacked, thus causing the creation of new cavities in the structure of Mt-3M.

Infrared Spectroscopy (FTIR)

FTIR spectra of the studied samples are shown in Figure 3. The data in Table 2 summarize the vibrational modes of characteristic bands of montmorillonite.

 

 

 

 

From Figure 3, the absorption bands at 3620 cm^-1, 979 cm^-1, 915 cm^-1, and 839 cm^-1 are attributed to the vibrations of hydroxyl groups bound with the cations Al³+ and Mg²+. After acid activation, all the above absorption bands were completely disappeared. This disappearance can be explained by the phenomenon of leaching of cations Al³⁺ and Mg²⁺ structuring the octahedral layer. An increase in the intensity ofthe bands at 1089 cm^-1 and 788 cm^-1 is also noticed after the acid treatment, especially for the Mt-1M. This increase indicates the formation of three-dimensional structures of Si-O-Si units.⁴²

The infrared results are in good agreement with those of: XRD (the increase of the intensity of characteristic peaks of quartz), XRF (increase in the percentage of silica and decrease in the percentage of cations structuring the octahedral layer) and BET (increase of surface area due to the dissolution of the octahedral layer).

Catalysts acidity analysis

Acidic properties of raw and treated montmorillonite were investigated using FTIR spectra of pyridine adsorbed on the material (Figure 4). The results are shown in the region of 1600-1400 cm^-1, as this region gives more information about the type of acidity in the material. Also three bands can be seen in Figure 4; the peak around 1540 cm^-1 corresponds to pyridine adsorbed on the Brönsted acid sites, the peak around 1450 cm^-1 is attributed to pyridine adsorbed on the Lewis acid sites and the band around 1490 cm^-1 is due to the vibrations of the H-linked pyridine which involves the two types of acid sites, this band is then characteristic of the total acidity of the material.⁴³ The spectra clearly shows that the intensities of characteristic peaks of different types of acids, increase with the concentration of the acid treatment solution, thus we can affirm that Mt-3M has a greater number of acid sites responsible for the catalytic properties. This improves its reactivity as it is well known that in heterogeneous catalysis, the catalyst efficiency depends strongly on the number of active surface sites.

 

 

X-Ray Fluorescence (XRF)

XRF is a non-destructive analytical technique used for qualitative and quantitative determination of the chemical composition of materials. The results of elemental chemical analysis given in Table 3, provides the percentage of oxide weight of Mt-Na, Mt-1M, Mt-2M and Mt-3M. They reveal that silicon and aluminum are the main constituents of natural montmorillonite. After acid activation, data in Table 3 clearly indicate considerable changes in the contents of oxides constituting the montmorillonite. The percentages of oxides decreased significantly in the case of Mt-1M, while the percentages of silicon, potassium and titanium increased. The decrease in the fractions of aluminum, iron and magnesium can be attributed to leaching of Al⁺³, Fe⁺² and Mg⁺² cations structuring the octahedral layer, which leads to the dissolution of this layer.⁴⁴ A considerable reduction was also observed in the contents of interfoliar cations (Na⁺ and Ca²⁺) translating the phenomenon of cationic exchange of these two cations by the H+ protons of the acid solution.¹⁹ For the Mt-2M, a slight variation has been noticed in the composition of the clay and this is due to the passivation phenomenon of montmorillonite.²⁸ Indeed at this concentration, montmorillonite becomes more resistant to acid attack because of the formation of insoluble mineralogical phases containing silicon, potassium and titanium precipitated on the fragments of the non-destroyed silicates and which are protected against any new acid attack.^19,28 In reference of Mt-3M, the structure of montmorillonite is destroyed and this can be explained by the sharp decrease in the percentages of interfoliar cations and cations structuring octahedral layer. The XRF results are in good agreement with the results obtained by BET analysis; the specific surface area increases for Mt-1M due to the leaching of the octahedral cations. While it decreases for Mt-2M due to the formation of insoluble mineralogical phases containing silicon, potassium and titanium, leading to the blockage of the clay pores then it increases for Mt-3M, due to complete destruction of montmorillonite structure.

 

 

Characterizations of 3, 4-dihydropyrimidin-2(1 H)-one (DHPM)

The characteristics of the final product are as follows: T_f = 206 °C.^45,46 IR (KBr) v: 3233, 3101, 2940, 1718, 1697, 1595, 1218 cm^-1. 1H NMR (300 MHz, CDCl₃) δ: 1.22 (t, 3H), 2.36 (s, 3H), 4.07 (q, 2H), 5.29 (s, 1H), 5.91 (s, 1H), 7.09-7.21 (m, 5H), 8.28 (s, 1H).

Catalytic activity

Firstly, the reaction was conducted without catalyst and then various catalysts were used to test their effects on the reaction yield and time.

Effect of solvent on catalytic reaction

The reaction progress in the presence of the three catalysts Mt-1M, Mt-2M and Mt-3M with an amount of 20 wt% of benzaldehyde for 8 h was investigated (Table 4). As can be seen in Table 4, the reaction yield was higher in the presence of catalyst and tended to increase with the montmorillonite treatment concentration of sulfuric acid. This confirms that the reaction yield is influenced by the acidity of the clay and not by the specific surface area. Also, the nature of the solvent plays an important role in the synthesis of DHPMs. The reaction using cyclohexane provided a yield of 92%, whereas the acetic acid and acetonitrile gave lower yields of 89% and 74%, respectively (Mt-3M). This difference in yield can be explained by the phenomenon of specific interaction between the solvent and the catalyst.

Parametric studies

From an economic and ecological point of view, the process of solvent-free reactions remains a goal to be achieved. In this perspective, we have examined the reaction under solvent-free conditions and only for the Mt-3M, which presented better yields (Table 4).

Effect of catalyst dose

The considered doses of catalyst are 20%, 40%, and 60% (Table 5). The results show that, increasing the catalyst load from 20% to 40% effectively improves the reaction yield, this can be explained by the increase in the number of catalytic sites and consequently the catalyst can bind more reagent molecules, therefore it will be more efficient. Note that the best yield is obtained with a catalyst percentage of 40%. This value was estimated as the optimal load. While, when the dose of 60% is used, the mixture becomes pasty, with high density, difficult to stir, this minimize the catalyst-reagent contacts, and consequently the yield decreases.

 

 

Effect of the introduction order of the reagents

In heterogeneous catalysis, the adsorption step is decisive in the catalytic act because it can modify the nature of the reagents and this can decrease or increase their reactivity. Therefore, the order of introduction of the reagents becomes paramount. To see the effect of this step in our case study, we carried out three different orders distributed on six processes according to Table 6.

• Order 1: Put the three reagents with the Mt-3M clay at the same time under stirring.

• Order 2: Put two reagents with the Mt-3M clay under stirring and after 2 h, add the 3rd reagent.

• Order 3: Put one of the three reagents with the Mt-3M clay under stirring and after 2 h, add the two remaining reagents. Note that, as urea is solid, it cannot be stirred with solid montmorillonite. Therefore, this order contains just two processes of starting with benzaldehyde and ethyl acetoacetate, respectively.

Table 6 reveals that the introduction order of the reagents is highly important. The best reaction yields are obtained with process 0 and process 4. These results are directly related to the adsorption step of the reagents and/or the intermediates which may result from their interactions. Note that when the reagents are introduced according to process 1, process 3 and process 5, the yields are low.

From the literature, three main mechanisms have been proposed for the Biginelli reaction (Iminium, Enamine and Knoevenagel mechanisms).⁴⁷ As process 0 and process 4 have the best yields (Table 6), we propose, in Scheme 2, a mechanism based on the enamine pathway for the Biginelli reaction catalyzed by montmorillonite (Mt-3M). The first step corresponds to the adsorption of benzaldehyde 1 on montmorillonite, the addition of urea 2 and ethyl acetoacetate 3 leads to their condensation thus giving the intermediate enamine 4 catalyzed and stabilized by montmorillonite, this intermediate reacts with the adsorbed benzaldehyde to give intermediate 5, after intramolecular cyclisation and dehydration, dihydropyrimidinone (DHPM) is obtained.

 

 

Catalyst recyclability

The efficiency of a heterogeneous catalyst is highly dependent on its regeneration and repetitive use. Generally, catalysts can be regenerated by several ways, such as high temperature calcination and chemical cleaning. Microwaves and ultrasound can also significantly intensify the regeneration process.^48,49 In this respect, the Mt-3M clay used under optimized reaction conditions is regenerated by simple filtration, and washed several times with hot ethanol, and then dried at 90 °C for 24 h. The final product was reused for three further catalytic cycles (Figure 5). After the third recovery of the catalyst, the reaction yield was reduced to 76%. This could be attributed to the accumulation of reagents or organic compounds resulting from the reaction on the montmorillonite surface.

 

 

Comparison of the catalytic performance

To appreciate the results obtained in the proposed work, we performed some comparisons with other recently published works from literature, as shown in Table 7. The comparison covers temperature, solvent, reaction time and yield. It confirms that the present protocol using Algerian montmorillonite activated with sulfuric acid is one of the most effective protocols for the synthesis of DHPMs.

 

 

A comparison of our process with published works mentioned in Table 7 shows the following:

• In the first work referenced,⁵⁰ a synthetic catalyst with solvent is used, while our catalyst is natural and abundant, moreover the process we propose is solvent-free, which makes it less expensive and more ecological.

• The second work referenced⁵ used a synthetic catalyst while ours is natural and gives comparable performance, which makes our product more competitive because it is less expensive, abundant and more ecological.

• The third work referenced⁸ used a toxic acid as a homogeneous catalyst with hard separation from the reaction medium in addition to its toxicity, which makes our product much more efficient.

• Finally, compared to the fourth work referenced,⁵¹ our process is much more efficient whether in terms of temperature, reaction time or yield.

 

CONCLUSION

To carry out the Biginelli reaction efficiently, a series of experiments were performed using Algerian montmorillonite as a solid acid catalyst under different conditions. The catalyst was easily prepared by a simple ion exchange with a sulfuric acid solution. This exchange process leads to the leaching of Al³+, Mg+² and Fe+³ cations structuring the octahedral layer; this is accompanied by an increase in the specific surface area and surface acidity of the activated montmorillonite. The reaction carried out in absence of any catalyst gave low yields for relatively long reaction times, which justifies the importance of the catalyst. The results obtained in the presence of activated clay, clearly show that the acidity of the clay is the parameter which influences the yield.

The nature of the solvent plays an important role in the Biginelli reaction while the reaction without solvent gives good yields. It makes the DHPMs preparation process safer and eco-friendly. The effect of the catalyst dose is also to be considered as well as the introduction order of the reagents. Furthermore, we have shown that the studied clay is reusable and keeps its catalytic reactivity after three regeneration tests.

 

ACKNOWLEDGEMENTS

The authors thank the universities of Biskra and Sétif in Algeria, for kind collaboration and their support in the characterization of the samples.

 

ORCIDS

Lamia Bouchenka: https://orcid.org/0000-0002-8475-084X

Farida Bouremmad: https://orcid.org/0000-0001-9211-7182

Fatiha Belferdi: https://orcid.org/0000-0001-6080-2652

Samira Maane: https://orcid.org/0000-0003-3292-7639

Musa Mutlu Can: https://orcid.org/0000-0002-6593-3202

Mousa Amayreh: https://orcid.org/0000-0001-7030-8391

Mehmet Ali Gulgun: https://orcid.org/0000-0002-7096-6252

 

REFERENCES

1. Suppan T, Mahendran HP, Jeyaraj S, Mohanta K, Bhattacharjee RR. Phosphotungstic acid-Jeffamine* hybrid catalyst for one-pot Biginelli reaction starting from benzyl alcohol. Appl Catal A Gen. 2020;603:117734. https://doi.org/10.1016/j.apcata.2020.117734        [ Links ]

2. Kouachi K, Lafaye G, Pronier S, Bennini L, Menad S. Mo/y-Al₂O₃ catalysts for the Biginelli reaction. Effect of Mo loading. J Mol Catal A Chem. 2014;395:210-216. https://doi.org/10.1016/j.molcata.2014.08.025        [ Links ]

3. Bendi A, Rao GD, Sharma N, Singh MP. CoFe₂O₄/Cu (OH)₂ Nanocomposite: Expeditious and Magnetically recoverable heterogeneous catalyst for the four component Biginelli/Transesterification reaction and their DFT Studies. Results Chem. 2021;3:100202. https://doi.org/10.1016/j.rechem.2021.100202        [ Links ]

4. Keciek A, Paprocki D, Koszelewski D, Ostaszewski R. Evaluation of alcohols as substrates for the synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones under environmentally friendly conditions. Catal Commun. 2020;135:105887. https://doi.org/10.1016/jxatcom.2019.105887        [ Links ]

5. El-Yazeed WA, Abou El-Reash Y, Elatwy L, Ahmed AI. Novel bimetallic Ag-Fe MOF for exceptional Cd and Cu removal and 3, 4-dihydropyrimidinone synthesis. J Taiwan Inst Chem Eng. 2020;114:199-210. https://doi.org/10.1016/j.jtice.2020.09.028        [ Links ]

6. Davarpanah J, Sayahi MH, Ghahremani M, Karkhoei S. Synthesis and characterization of nano acid catalyst derived from rice husk silica and its application for the synthesis of 3, 4-dihydropyrimidinones/thiones compounds. J Mol Struct. 2019;1181:546-555. https://doi.org/10.1016/j.molstruc.2018.12.113        [ Links ]

7. Santos MC, Uemi M, Gonçalves NS, Bizeto MA, Camilo FF. Niobium chloride in 1-n-butyl-3-methylimidazolium chloride ionic liquid as a catalyst for biginelli reaction. J Mol Struct. 2020;1220:128653. https://doi.org/10.1016/j.molstruc.2020.128653        [ Links ]

8. Mathapati SR, Prasad D, Atar AB, Nagaraja BM, Jadhav AH. Phosphorofluoridic Acid as an Efficient Catalyst for One Pot Synthesis of Dihydropyrimidinones under Solvent Free and Ambient Condition. Mater Today. 2019;9:661-668. https://doi.org/10.1016/j.matpr.2018.10.390        [ Links ]

9. Sharma UK, Sharma N, Kumar R, Sinha AK. Biocatalysts for multicomponent Biginelli reaction: bovine serum albumin triggered waste-free synthesis of 3, 4-dihydropyrimidin-2-(1 H)-ones. Amino Acids. 2013;44(3):1031-1037. https://doi.org/10.1007/s00726-012-1437-1        [ Links ]

10. Pramanik M, Bhaumik A. Phosphonic acid functionalized ordered mesoporous material: a new and ecofriendly catalyst for one-pot multicomponent Biginelli reaction under solvent-free conditions. ACS Appl Mater Interfaces. 2014;6(2):933-941. https://doi.org/10.1021/am404298a        [ Links ]

11. De Souza RO, da Penha ET, Milagre HM, Garden SJ, Esteves PM, Eberlin MN, Antunes OAC. The three-component Biginelli reaction: a combined experimental and theoretical mechanistic investigation. Chem Eur J. 2009;15(38):9799-9804. https://doi.org/10.1002/chem.200900470        [ Links ]

12. Elhamifar D, Hosseinpoor F, Karimi B, Hajati S. Ionic liquid-based ordered mesoporous organosilica-supported copper as a novel and efficient nanocatalyst for the one-pot synthesis of Biginelli products. Microporous Mesoporous Mater. 2015;204:269-275. https://doi.org/10.1016/j.micromeso.2014.11.011        [ Links ]

13. Fard MAD, Ghafuri H, Rashidizadeh A. Sulfonated highly ordered mesoporous graphitic carbon nitride as a super active heterogeneous solid acid catalyst for Biginelli reaction. Microporous Mesoporous Mater. 2019;274:83-93. https://doi.org/10.1016/j.micromeso.2018.07.030        [ Links ]

14. Pandey J, Anand N, Tripathi RP. L-Proline catalyzed multicomponent reaction of 3, 4-dihydro-(2H)-pyran, urea/thiourea, and aldehydes: Diastereoselective synthesis of hexahydropyrano pyrimidinones (thiones). Tetrahedron. 2009;65(45):9350-9356. https://doi.org/10.1016/j.tet.2009.09.002        [ Links ]

15. Phukan A, Borah SJ, Bordoloi P, Sharma K, Borah BJ, Sarmah PP, Dutta DK. An efficient and robust heterogeneous mesoporous montmorillonite clay catalyst for the Biginelli type reactions. Adv Powder Technol. 2017;28(6):1585-1592. https://doi.org/10.1016/j.apt.2017.03.030        [ Links ]

16. Boumoud T, Boumoud B, Rhouati S, Belfaitah A, Debache A, Mosset P. An efficient and recycling catalyst for the one-pot three-component synthesis of substituted 3, 4-dihydropyrimidin-2 (1H)-ones. E-J Chem. 2008;5(4):688-695. https://doi.org/10.1155/2008/132879        [ Links ]

17. Belferdi F, Bouremmad F, Shawuti S, Gulgun MA. Effect of the Exchanged Cation in an Algerian Montmorillonite Used as a Heterogeneous Catalyst for Biginelli Reaction. Acta Chim Slov. 2021;68:355-362. https://dx.doi.org/10.17344/acsi.2020.6300        [ Links ]

18. Sadjadi S, Koohestani F. Bentonite with high loading of ionic liquid: A potent non-metallic catalyst for the synthesis of dihydropyrimidinones. J Mol Liq. 2020;319:114393. https://doi.org/10.1016/j.molliq.2020.114393        [ Links ]

19. Horri N, Sanz-Pérez ES, Arencibia A, Sanz R, Frini-Srasra N, Srasra E. Effect of acid activation on the CO₂ adsorption capacity of montmorillonite. Adsorption. 2020;26:793-811. https://doi.org/10.1007/s10450-020-00200-z        [ Links ]

20. Zeynizadeh B, Rahmani S, Ilkhanizadeh S. Strongly proton exchanged montmorillonite K10 (H+-Mont) as a solid acid catalyst for highly efficient and environmental benign synthesis of biscoumarins via tandem Knoevenagel-Michael reaction. Polyhedron. 2019;168:48-56. https://doi.org/10.1016/j.poly.2019.04.034        [ Links ]

21. Hechelski M, Ghinet A, Louvel B, Dufrénoy P, Rigo B, Daïch A, Waterlot C. From conventional Lewis acids to heterogeneous montmorillonite K10: eco-friendly plant-based catalysts used as green Lewis acids. ChemSusChem. 2018;11(8):1249-1277. https://doi.org/10.1002/cssc.201702435        [ Links ]

22. Yotsuji K, Tachi Y, Sakuma H, Kawamura K. Effect of interlayer cations on montmorillonite swelling: Comparison between molecular dynamic simulations and experiments. Appl Clay Sci. 2021;204:106034. https://doi.org/10.1016/j.clay.2021.106034        [ Links ]

23. Bhatti UH, Sultan H, Min GH, Nam SC, Baek IH. Ion-exchanged montmorillonite as simple and effective catalysts for efficient CO₂ capture. J Chem Eng. 2021;413:127476. https://doi.org/10.1016/j.cej.2020.127476        [ Links ]

24. Peng K, Wang H, Gao H, Wan P, Ma M, Li X. Emerging hierarchical ternary 2D nanocomposites constructed from montmorillonite, graphene and MoS₂ for enhanced electrochemical hydrogen evolution. Chem Eng J. 2020;393:124704. https://doi.org/10.1016/j.cej.2020.124704        [ Links ]

25. Mao J, Lv G, Zhou R. Effect ofacid-treated and hexadecyltrimethylammonium bromide-modified montmorillonites on adsorption performance of mycotoxins. Environ Sci Pollut Res. 2020;27(4):4284-4293. https://doi.org/10.1007/s11356-019-07118-2        [ Links ]

26. Boudriche L, Calvet R, Hamdi B, Balard H. Effect of acid treatment on surface properties evolution of attapulgite clay: an application of inverse gas chromatography. Colloids Surf A Physicochem Eng. 2011;392(1):45-54. https://doi.org/10.1016/j.colsurfa.2011.09.031        [ Links ]

27. Angaji MT, Zinali AZ, Qazvini NT. Study of physical, chemical and morphological alterations of smectite clay upon activation and functionalization via the acid treatment. World j nano sci eng. 2013;3:161-168. http://dx.doi.org/10.4236/wjnse.2013.34019        [ Links ]

28. Bendou S, Amrani M. Effect of hydrochloric acid on the structural of sodic-bentonite clay. J Miner Mater Charact Eng. 2014;2:404-413. http://dx.doi.org/10.4236/jmmce.2014.25045        [ Links ]

29. Maiti S, Pramanik A, Chattopadhyay S, De G, Mahanty S. Electrochemical energy storage in montmorillonite K10 clay based composite as supercapacitor using ionic liquid electrolyte. J Colloid Interface Sci. 2016;464:73-82. https://doi.org/10.1016/j.jcis.2015.11.010        [ Links ]

30. Maged A, Kharbish S, Ismael IS, Bhatnagar A. Characterization of activated bentonite clay mineral and the mechanisms underlying its sorption for ciprofloxacin from aqueous solution. Environ Sci Pollut Res. 2020;27(26):32980-32997. https://doi.org/10.1007/s11356-020-09267-1        [ Links ]

31. Penchah HR, Ghaemi A, Godarziani H. Eco-friendly CO₂ adsorbent by impregnation of diethanolamine in nanoclay montmorillonite. Environ. Sci. Pollut. Res. 2021;28:55754-55770. https://doi.org/10.1007/s11356-021-14920-4        [ Links ]

32. Zang S, Zhang G, Qiu W, Song L, Zhang R, He H. Resistance to SO₂ poisoning of V₂O₅/TiO₂-PILC catalyst for the selective catalytic reduction of NO by NH₃. Chinese J Catal. 2016;37(6):888-897. https://doi.org/10.1016/S1872-2067(15)61083-X        [ Links ]

33. Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F, Rouquerol J, Sing KSW. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl Chem. 2015;87(9-10):1051-1069. https://doi.org/10.1515/pac-2014-1117        [ Links ]

34. Horri N, Sanz-Pérez ES, Arencibia A, Sanz R, Frini-Srasra N, Srasra E. Amine grafting of acid-activated bentonite for carbon dioxide capture. Appl. Clay Sci. 2019;180:105195. https://doi.org/10.1016/j.clay.2019.105195        [ Links ]

35. Bhorodwaj SK, Dutta DK. Heteropoly acid supported modified Montmorillonite clay: An effective catalyst for the esterification of acetic acid with sec-butanol. Appl Catal A-Gen. 2010;378(2):221-226. https://doi.org/10.1016/j.apcata.2010.02.026        [ Links ]

36. Huang G-Q, Song Y-H, Liu C, Yang JM, Lu J, Liu ZT, Liu ZW. Acid activated montmorillonite for gas-phase catalytic dehydration of monoethanolamine. Appl Clay Sci. 2019;168:116-124. https://doi.org/10.1016/j.clay.2018.10.019        [ Links ]

37. Zarnaghash N, Rezaei R, Hayati P, Doroodmand MM. Selective ultrasonic assisted synthesis of iron oxide mesoporous structures based on sulfonated melamine formaldehyde and survey of nanorod/sphere, sphere and core/ shell on their catalysts properties for the Biginelli reaction. Mater Sci Eng C. 2019;104:109975. https://doi.org/10.1016/j.msec.2019.109975        [ Links ]

38. Kooli F, Liu Y, Al-Faze R, Al Suhaimi A. Effect of acid activation of Saudi local clay mineral on removal properties of basic blue 41 from an aqueous solution. Appl Clay Sci. 2015;116:23-30. https://doi.org/10.1016/j.clay.2015.07.044        [ Links ]

39. Ali M, Attia AA, Taha M, El-Maadawy M, Abo-Raia A, Abouria A. Application of acid activated bentonite for efficient removal of organic pollutants from industrial phosphoric acid: kinetic and thermodynamic study. SPE Middle East Oil and Gas Show and Conference, Manama, Bahrain, 18-21 March 2019. https://doi.org/10.2118/194719-MS        [ Links ]

40. Baghdadli MC, Meghabar R, Belbachir M. Acid-Activated Algerian Montmorillonite as Heterogeneous Catalysts for Cationic Polymerization of Styrene. Asian J Chem. 2016;28(6):1197. https://doi.org/10.14233/ajchem.2016.19620        [ Links ]

41. Luna FMT, Cecilia JA, Saboya RMA, Barrera D, Sapag K, Rodríguez-Castellón E, Cavalcante C. Natural and modified montmorillonite clays as catalysts for synthesis of biolubricants. Materials. 2018;11(9):1764. https://doi.org/10.3390/ma11091764        [ Links ]

42. Elfadly A, Zeid I, Yehia F, Abouelela M, Rabie A. Production of aromatic hydrocarbons from catalytic pyrolysis of lignin over acid-activated bentonite clay. Fuel Process Technol. 2017;163:1-7. https://doi.org/10.1016/j.fuproc.2017.03.033        [ Links ]

43. Sliwa M, Samson K, Ruggiero-Mikoiajczyk M, Zelazny A, Grabowski R. Influence of montmorillonite K10 modification with tungstophosphoric acid on hybrid catalyst activity in direct dimethyl ether synthesis from syngas. Catalysis letters. 2014;144(11):1884-1893. https://doi.org/10.1007/s10562-014-1359-5        [ Links ]

44. Khoualdia B, Loungou M, Elaloui E. Optimized Activation of Bentonite for Adsorption of Magnesium and Cadmium from Phosphoric Acid. WORLD. 2018;3(4):83-91. https://doi.org/10.11648/j.wjac.20180304.11        [ Links ]

45. Prakash S, Elavarasan N, Venkatesan A, Subashini K, Sowndharya M, Sujatha V. Green synthesis of copper oxide nanoparticles and its effective applications in Biginelli reaction, BTB photodegradation and antibacterial activity. Adv Powder Technol. 2018;29(12):3315-3326. https://doi.org/10.1016/j.apt.2018.09.009        [ Links ]

46. Farhadi A, Takassi MA, Enjilzadeh M, Davod F. Synthesis of Some Biginelli-type Products: Nano Alumina Sulfonic acid (NASA) Catalyzed under Solvent-free Condition. J App Chem Res. 2018;12(1):48-57.         [ Links ]

47. Sahota N, AbuSalim DI, Wang ML, Brown CJ, Zhang Z, El-Baba TJ, Cook SP, Clemmer DE. A microdroplet-accelerated Biginelli reaction: mechanisms and separation of isomers using IMS-MS. Chem Sci. 2019;10(18):4822-4827. https://doi.org/10.1039/C9SC00704K        [ Links ]

48. Jou C-JG, Lo CC. Using a microwave-induced method to regenerate platinum catalyst. Sustain Enviro Res. 2017;27:279-282. https://doi.org/10.1016/j.serj.2017.06.005        [ Links ]

49. Sulman MG. Effects of ultrasound on catalytic processes. Russ Chem Rev. 2000;69:165-177. https://doi.org/10.1070/RC2000v069n02ABEH000543        [ Links ]

50. Rahimi S, Soleimani E. Synthesis of 2-substituted benzimidazole, coumarin, benzo [b][1, 4] oxazin and dihydropyrimidinone derivatives using core-shell structured Fe₃O₄@ SiO₂-ZnCl₂ nanoparticles as an effective catalyst. Results Chem. 2020;2:100060. https://doi.org/10.1016/j.rechem.2020.100060        [ Links ]

51. Slimi H, Moussaoui Y, ben Salem R. Synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones/thiones via Biginelli reaction promoted by bismuth (III) nitrate or PPh₃ without solvent. Arab J Chem. 2016;9:S510-S514. https://doi.org/10.1016/j.arabjc.2011.06.010        [ Links ]

 

 

Received 28 February 2023
Revised 28 September 2023
Accepted 25 October 2023

 

 

* To whom correspondence should be addressed. Email: bouchenkalamia@gmail.com