Home Physical Sciences Magnetic nanoparticle-supported sulfonic acid as a green catalyst for the one-pot synthesis of 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles under solvent-free conditions
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Magnetic nanoparticle-supported sulfonic acid as a green catalyst for the one-pot synthesis of 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles under solvent-free conditions

  • Mahnaz Sakhdari EMAIL logo , Ali Amoozadeh and Eskandar Kolvari
Published/Copyright: October 4, 2021
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Heterocyclic Communications
From the journal Heterocyclic Communications Volume 27 Issue 1

Abstract

In this work, magnetic nanoparticle-supported sulfonic acid (γ-Fe2O3-SO3H) is used as an efficient catalyst in the synthesis of 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles in a short time (40–70 min for trisubstituted imidazoles and 30–40 min for tetrasubstituted imidazoles) and high-purity products were obtained (92–98% for trisubstituted imidazoles and 94–98% for tetrasubstituted imidazoles) in simple multicomponent reactions. The structure of these products was confirmed via FT-IR and NMR. Green and recyclable catalysts, eco-friendly and solvent-free conditions, high catalytic activity, shorter reaction time, easy recovery by an external magnet, high purity, and excellent yields are some features of these reactions.

Graphical abstract

Keywords: green chemistry; multicomponent reactions; γ-Fe2O3-SO3H; 2,4,5-trisubstituted imidazoles; 1,2,4,5-tetrasubstituted imidazoles; solvent-free conditions; recyclable catalysts

1 Introduction

Due to the effects of the chemical industry on the environment since the 1940s, fundamental changes have been carried out to increase the adoption of green chemistry principles [1,2]. Therefore, due to the significance of green chemistry goals, the use of green catalysts, especially nanocatalysts, has strongly attracted scientific interest. Owing to the properties of magnetic nanocatalysts such as large special surface area and simple separation with external magnets, [3,4,5,6,7] they play a crucial role in the removal of hazardous and toxic compounds from the environment.

Multicomponent reactions (MCRs) have applications in organic and medicinal chemistry that produce complex products from simple substances in one-pot processes. These reactions, which follow green chemistry concepts, are recognised as one of the most effective and economical methods for synthesising complex molecules in recent decades [8]. Imidazoles, one of the important heterocycles [9], can be synthesised by this method. Imidazoles have pharmaceutical and medicinal properties and are used in pesticides, dyeing, agent for resins, polymers, anion sensors, and ionic liquids [10,11]. Moreover, imidazole derivatives have been found to be anti-fungal, anti-bacterial, anti-malarial, anti-nociceptive, anti-inflammatory, anti-hypertensive, hypoxic cell therapy, imaging agents, anti-cancer, and anti-plasmodium [10,11,12]. In addition, imidazoles are an important component of natural compounds such as vitamin B12, histamine, histidine, and biotin [11].

According to the importance of green chemistry goals, in this project, we use magnetic particle-supported sulfonic acid (γ-Fe2O3-SO3H) [13] as a recyclable catalyst in the synthesis of 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles, which are valuable biologically active compounds [14], in a simple one-pot procedure from which substituted imidazoles were obtained with high efficiency and purity.

2 Results and discussion

2.1 Optimisation of reaction conditions for the preparation of substituted imidazoles

Firstly, to optimise the reaction conditions for the preparation of 2,4,5-trisubstituted imidazoles, condensation of benzil (1 mmol), ammonium acetate (5 mmol) and benzaldehyde (1 mmol) in the presence of the γ-Fe2O3-SO3H catalyst (10 mol%) under solvent-free conditions was selected as a model reaction (Scheme 1). Then, different amounts of the catalyst were studied. As shown in Table 1 entry 2a, the use of 10 mol% of the γ-Fe2O3-SO3H catalyst afforded the best efficiency (94% for trisubstituted imidazoles). Further increasing the amount of catalyst did not improve the efficiency (Table 1, entry 3a).

Scheme 1 One-pot synthesis of polysubstituted imidazoles in the presence of the γ-Fe2O3-SO3H catalyst (a: trisubstituted imidazole, b: tetrasubstituted imidazole).
Scheme 1

One-pot synthesis of polysubstituted imidazoles in the presence of the γ-Fe2O3-SO3H catalyst (a: trisubstituted imidazole, b: tetrasubstituted imidazole).

Table 1

Optimisation of catalyst amount for model reactions (a: trisubstituted imidazole, b: tetrasubstituted imidazole)

Entry Catalyst amount (mol%) Time (min) Yield (%) * Time (min) Yield (%) *
1a 1a 1b 1b
1 5 50 90 40 92
2 10 50 94 40 97
3 20 50 92 40 94
  1. *

    Yields refer to isolated products.

Secondly, we examined the effect of different temperatures on the yield, under solvent-free conditions. The highest efficiency was achieved at 100°C (94%) for the synthesis of 2,4,5-trisubstituted imidazoles (Table 2, entry 3a). As indicated in Table 2, increasing the reaction temperature from 80 to 100°C resulted in an improvement in yield from 85 to 94% (Table 2, entries 1a and 3a), but upon increasing the temperature to 120°C the reaction yield decreased to 88% due to the formation of by-products (Table 2, entry 4a). All of the reactions were monitored by TLC. Further reactions were performed at 100°C.

Table 2

Optimisation of temperature for model reactions (a: trisubstituted imidazole, b: tetrasubstituted imidazole)

Entry Temperature (°C) Time (min) Yield (%)* Time (min) Yield (%)*
1a 1a 1b 1b
1 80 50 85 40 85
2 90 50 90 40 87
3 100 50 94 40 97
4 120 50 88 40 91
  1. *

    Yields refer to isolated products.

Thirdly, the reaction was examined in various solvents. As shown in Table 3, solvent-free conditions resulted in higher yields than those obtained in any of the solvents investigated (Table 3, entry 6a).

Table 3

Solvent effect on the model reactions (a: trisubstituted imidazole, b: tetrasubstituted imidazole)

Entry Solvent Condition Yield (%)* Condition Yield (%)*
1a 1a 1b 1b
1 EtOH 10 mL/50 min/60°C 85 10 mL/40 min/50oC 80
2 MeOH 10 mL/50 min/60°C 74 10 mL/40 min/40°C 68
3 THF 10 mL/50 min/60°C 40 10 mL/40 min/60°C 55
4 DMSO 10 mL/50 min/100°C 30 10 mL/40 min/100°C 45
5 CH3CN 10 mL/50 min/60°C 50 10 mL/40 min/60°C 50
6 Solvent-free 50 min/100°C 94 40 min/100°C 97
  1. *

    Yields refer to isolated products.

For 1,2,4,5-tetrasubstituted imidazoles, a mixture of benzil (1 mmol), ammonium acetate (2 mmol), benzaldehyde (1 mmol), and aniline (2 mmol) in the presence of the γ-Fe2O3-SO3H catalyst (10 mol%) under solvent-free conditions was selected as the model reaction (Scheme 1). The catalyst loading, temperature and solvent condition optimisation steps were repeated. The best yield (97%) was obtained in the presence of 10 mol% catalyst (Table 1, entry 2b) at 100°C (Table 2, entry 3b) under solvent-free conditions (Table 3, entry 6b).

Inspired by previous reports [15,16,17], a possible mechanism for the synthesis of 2,4,5-trisubstituted imidazoles using a γ-Fe2O3-SO3H catalyst is illustrated in Scheme 2. In the process, γ-Fe2O3-SO3H as an acidic catalyst can activate the aldehyde and the 1,2-diketone, which react with ammonium acetate to form imine intermediates. Then, the imine nitrogen of imine intermediate (1) reacts with the positive carbonyl carbon of 1,2-diketone imine intermediate (2) to form carbocation (3). Finally, dehydration and the sigmatropic shift results in the 2,4,5-trisubstituted imidazole. In addition, a similar mechanism is suggested for the synthesis of 1,2,4,5-tetrasubstituted imidazoles, except that at the beginning of the reaction amine derivatives participate instead of ammonium acetate [18].

Scheme 2 Mechanism for the synthesis of trisubstituted imidazoles.
Scheme 2

Mechanism for the synthesis of trisubstituted imidazoles.

An investigation was also performed to optimise the amount of ammonium acetate used in this reaction under solvent-free conditions, and the best result was achieved with 5 mmol ammonium acetate (Table 4, entry 3).

Table 4

Optimisation of the ammonium acetate amount for model reactions (a: trisubstituted imidazole, b: tetrasubstituted imidazole)

Entry NH4OAc amount (mmol) Condition Yield (%) * Condition Yield (%) *
1a 1a 1b 1b
1 1.5 50 min/100°C 70 40 min/100°C 72
2 3 50 min/100°C 79 40 min/100°C 83
3 5 50 min/100°C 94 40 min/100°C 97
  1. *

    Yields refer to isolated products.

In the synthesis of trisubstituted imidazoles, several aromatic aldehydes with electron-withdrawing or electron-donating substituent groups were evaluated. High efficiency was achieved for substituent groups in ortho, meta or para positions of the aromatic ring (Table 5). Similar results were obtained for the synthesis of tetrasubstituted imidazoles from combinations of differently substituted aromatic aldehydes and amine derivatives (Table 6). The structure of polysubstituted imidazoles was characterized by IR and NMR.

Table 5

One-pot synthesis of trisubstituted imidazoles catalysed by γ-Fe2O3-SO3H

Compound R1 Time (min) Yield (%) * M.p. (°C)
1a C6H5 50 94 277–279 [19]
2a 4-ClC6H4 55 97 266–268 [20]
3a 2-ClC6H4 40 98 194–196 [19]
4a 4-MeOC6H4 50 98 231–233 [9]
5a 2-MeOC6H4 40 95 208–210 [20]
6a 4-FC6H4 40 95 253–255 [21]
7a 4-BrC6H4 50 96 260–262 [9]
8a 2-HOC6H4 55 90 212–214 [9]
9a 3-O2NC6H4 60 93 321–323 [22]
10a 4-O2NC6H4 60 92 241–243 [9]
11a 4-MeC6H4 70 93 232–235 [20]
12a 2,4-Cl2C6H3 65 97 173–175 [9]
13a 3-HOC6H4 50 94 261–263 [23]
14a 3-BrC6H4 50 95 303–305 [23]
15a 3,4-(MeO)2C6H3 40 96 220–222 [9]
16a 4-(Me)2NC6H4 60 92 256–258 [20]
  1. *

    Yields refer to isolated products.

Table 6

One-pot synthesis of tetrasubstituted imidazoles catalysed by γ-Fe2O3-SO3H

Compound R1 R2 Time (min) Yield (%) * M.p. (°C)
1b C6H5 C6H5 40 97 219–221 [9]
2b 2-HOC6H4 C6H5 30 98 252–254 [24]
3b 4-ClC6H4 C6H5 35 98 171–173 [9]
4b 4-MeOC6H4 C6H5 40 97 180–182 [25]
5b 4-MeC6H4 C6H5 35 96 185–187 [26]
6b 4-Br C6H4 C6H5 30 95 193–195 [27]
7b 3-HOC6H4 C6H5 25 96 186–188 [27]
8b 3-O2NC6H4 C6H5 35 95 242–245 [28]
9b 4-O2NC6H4 C6H5 40 96 196–198 [28]
10b 4-HOC6H4 C6H5 20 97 285–287 [9]
11b 3-BrC6H4 C6H5 35 95 148–150 [29]
12b 2-HOC6H4 4-MeC6H4 40 97 222–225 [9]
13b 4-MeC6H4 4-MeC6H4 40 96 196–198 [9]
14b 3-O2NC6H4 4-MeC6H4 25 97 155–157 [9]
15b 4-O2NC6H4 4-MeC6H4 30 94 220–222 [9]
16b 3-HOC6H4 4-MeC6H4 35 94 229–231 [9]
17b 4-ClC6H4 4-ClC6H4 35 95 182–185 [26]
18b 4-MeC6H4 4-ClC6H4 30 97 169–170 [26]
  1. *

    Yields refer to isolated products.

Table 7 compares the performance of γ-Fe2O3-SO3H with several other reported catalysts for the synthesis of substituted imidazoles. As one can see, high efficiency and a short time for the reaction are the features of this catalyst.

Table 7

Comparison of the γ-Fe2O3-SO3H catalyst with several catalysts for the synthesis of imidazoles

Entry Catalyst Condition for trisubstituted imidazoles Yield (%) Condition for tetrasubstituted imidazoles Yield (%)
1 [(CH2)4SO3HMIM][HSO4] [30] — — SF/140°C/150 min 88
2 SASPSPE [29] — — SF/140°C/70 min 89
3 PTSA [31] Ethanol/80°C/60 min 90 Ethanol/80°C/60 min 84
4 Y(NO3)3.6H2O [32] SF/140°C/50 min 90 — —
5 ZnO nanorods [20] H2O/reflux/150 min 80 — —
6 I 2 [12] DMSO/130°C, EtOH/100°C/1440-120 86 — —
7 This work SF/100°C/50 min 94 SF/100°C/40 min 97

After the reaction completion, the γ-Fe2O3-SO3H catalyst used can be easily separated from the products by an external magnet and reused. Therefore, the catalyst was recycled and reused several times in subsequent reactions. At the end of these reactions, the products were still obtained with satisfactory yields (Figure 1).

Figure 1 The reusability of the catalyst for model reactions (a: Trisubstituted imidazole and b: tetrasubstituted imidazole).
Figure 1

The reusability of the catalyst for model reactions (a: Trisubstituted imidazole and b: tetrasubstituted imidazole).

3 Conclusion

Here, we introduce a simple method for producing 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles, valuable heterocyclic compounds with pharmaceutical properties and medical applications, in a simple one-pot procedure with a recyclable catalyst in a green process. This project has various advantages such as a recyclable catalyst, high catalytic activity, eco-friendly solvent-free conditions, short reaction time, easy separation of catalyst by an external magnet, high-purity products, and excellent yields.

4 Experimental section

4.1 General

All chemicals used in this study were commercially available, synthesis-grade compounds, purchased from Merck or Fluka and used without any further purification. The products were identified by comparison of their melting points and spectral data with those reported in the literature. Melting points were recorded on the Electrothermal 9100 apparatus and are uncorrected. The reaction progress was monitored by TLC on commercial aluminum-backed plates of silica gel 60 F254, using ultraviolet light. FT-IR spectra were obtained with a Shimadzu 8400 spectrometer in the range 400–4000 cm−1 and the 1H NMR (500 or 300 MHz) and 13C NMR (125 or 75 MHz) spectra were recorded on a Bruker Avance 300 spectrometer in pure deuterated chloroform, with tetramethylsilane (TMS) as the internal standard.

4.2 General procedure for the synthesis of the γ-Fe2O3-SO3H catalyst

According to the reported method [13,33,34,35] for the synthesis of the desired γ-Fe2O3-SO3H catalyst, 3 g of γ-Fe2O3 nanoparticles and chlorosulfonic acid (1.163 g, 9.98 mmol) was added over a period of 30 min (Scheme 3). For comparison with the reported literature [13], the γ-Fe2O3-SO3H catalyst particles were characterized via FT-IR, XRD, TGA, XPS, TEM, titration, VSM, and DLS.

Scheme 3 Synthesis of the γ-Fe2O3-SO3H catalyst.
Scheme 3

Synthesis of the γ-Fe2O3-SO3H catalyst.

4.3 General procedure for the synthesis of 2,4,5-trisubstituted imidazoles

A mixture of benzil 1 (1 mmol), ammonium acetate (5 mmol), aromatic aldehyde (1 mmol), and the γ-Fe2O3-SO3H catalyst (10 mol%) was stirred at 100°C under solvent-free conditions for an appropriate time. The progression of the reaction was monitored by TLC. After completion of the reaction, acetone was added to the contents of the reaction vessel, the product was completely dissolved in acetone, and the catalyst was separated by an external magnet. For further purification, the solid product was recrystallised from acetone/water 9:1 (v/v) to obtain the pure product.

4.3.1 2-(4-Chlorophenyl)-4,5-diphenyl-1H-imidazole (2a)

M.p.: 266–268°C; FT-IR (KBr) ν max/cm–1: 690, 750, 830, 1,475, 1,600, 3,100, 3,400. 1H NMR (500.13 MHz, DMSO-d 6), δ/ppm: 7.25–7.82 (m, 14H, H-Ar), 12.60 (s, 1H, −NH).

4.3.2 2-(2-Methoxyphenyl)-4,5-diphenyl-1H-imidazole (5a)

M.p.: 208–210°C; FT-IR (KBr) ν max/cm–1: 690, 750, 900, 1,475, 1,600, 1,650, 3,100, 3,300. 1H NMR (500.13 MHz, DMSO-d 6), δ/ppm: 3.882 (s, 3H, OCH3), 6.862–8.025 (m, 14H, H-Ar), 11.855 (s, 1H, NH).

4.3.3 2-(2,4-Dichlorophenyl)-4,5-diphenyl-1H-imidazole (12a)

M.p.: 173–175°C; FT-IR (KBr) ν max/cm–1: 690, 900, 1,475, 1,560, 1,600, 3,100, 3,300. 1 H NMR (500.13 MHz, DMSO-d 6), δ/ppm: 7.175–7.808 (m, 13H, H-Ar), 12.658 (s, 1H, NH).

4.3.4 2-(3-Bromophenyl)-4,5-diphenyl-1H-imidazole (14a)

M.p.: 303–305°C; FT-IR (KBr) ν max/cm–1: 690, 900, 1,075, 1,475, 1,600, 1,650, 3,100, 3,300. 1H NMR (500.13 MHz, DMSO-d 6), δ/ppm: 7.234–8.314 (m, 14H, H-Ar), 12.99 (s, 1H, NH).

4.3.5 2-(3,4-Dimethoxyphenyl)-4,5-diphenyl-1H-imidazole (15a)

M.p.: 220–222°C; FT-IR (KBr) ν max/cm–1: 1475, 1,600, 1,650, 3,100, 3,400. 1 H NMR (500.13 MHz, DMSO-d 6), δ/ppm: 3.137 (s, 3H, OCH3), 3.814 (s, 3H, OCH3) 7.014–7.636 (m, 13H, H-Ar), 12.477(s, 1H, NH).

4.4 General procedure for the synthesis of 1,2,4,5-tetrasubstituted imidazoles

A mixture of benzil (1 mmol), ammonium acetate (2 mmol), aromatic aldehyde (1 mmol), amine derivative (2 mmol), and the γ-Fe2O3-SO3H catalyst (10 mol%) was stirred at 100°C under solvent-free conditions for an appropriate time. The progression of the reaction was monitored by TLC. After the completion of the reaction, acetone was added to the reaction vessel, the product was completely dissolved in the acetone, and the catalyst was separated by an external magnet. For further purification, the solid product was recrystallised from acetone/water 9:1 (v/v) to obtain the pure product.

4.4.1 1,2,4,5-Tetraphenyl-1H-imidazole (1b)

M.p.: 219–221°C; FT-IR (KBr) ν max/cm–1: 690, 900, 1,475, 1,520, 1,600, 3,100. 1H NMR (500.13 MHz, DMSO-d 6), δ/ppm: 7.23–7.61 (m, 20H, H-Ar). 13C NMR (125.76 MHz, DMSO-d 6), δ (ppm): 127.136, 129.95, 132.17, 135.87, 138.26.

4.4.2 2-(4-Methylphenyl)-1,4,5-triphenyl-1H-imidazole (5b)

M.p.: 185–187°C; FT-IR (KBr) ν max/cm–1: 690, 770, 820, 1,475, 1,500, 1,600, 2,920, 3,100. 1H NMR (500.13 MHz, DMSO-d 6), δ/ppm: 2.28 (s, 3H, CH3), 7.23–7.61 (m, 19H, H-Ar). 13C NMR (125.76 MHz, DMSO-d 6), δ (ppm): 21.22, 138.26, 138.36, 138.75, 147.29.

4.4.3 3-(1,4,5-Triphenyl-1H-imidazol-2-yl)phenol (7b)

M.p.: 186–188°C; FT-IR (KBr) ν max/cm–1: 694, 1,274, 1,494, 1,606, 3,060, 3,466. 1H NMR (500.13 MHz, DMSO-d 6), δ/ppm: 4.675 (s, 1H, OH), 6.475-7.556 (m, 19H, H-Ar).

Acknowledgements

The authors gratefully acknowledge the Semnan University Research Council for supporting this work.

  1. Funding information: The authors state no funding involved.

  2. Conflict of interest: The authors state no conflict of interest.

  3. Data availability statement: The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Received: 2020-12-17
Revised: 2021-05-07
Accepted: 2021-07-23
Published Online: 2021-10-04

© 2021 Mahnaz Sakhdari et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/hc-2020-0125
Keywords for this article
green chemistry; multicomponent reactions; γ-Fe2O3-SO3H; 2,4,5-trisubstituted imidazoles; 1,2,4,5-tetrasubstituted imidazoles; solvent-free conditions; recyclable catalysts
Creative Commons
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Articles in the same Issue

  1. Research Articles
  2. Molecular, Electronic, Nonlinear Optical and Spectroscopic Analysis of Heterocyclic 3-Substituted-4-(3-methyl-2-thienylmethyleneamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones: Experiment and DFT Calculations
  3. Lewis acid / Base-free Strategy for the Synthesis of 2-Arylthio and Selenyl Benzothiazole / Thiazole and Imidazole
  4. Synergistic promoting effect of ball milling and Fe(ii) catalysis for cross-dehydrogenative-coupling of 1,4-benzoxazinones with indoles
  5. Magnetic nanoparticle-supported sulfonic acid as a green catalyst for the one-pot synthesis of 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles under solvent-free conditions
  6. Synthesis, characteristic fragmentation patterns, and antibacterial activity of new azo compounds from the coupling reaction of diazobenzothiazole ions and acetaminophen
  7. Para toluenesulfonic acid-catalyzed one-pot, three-component synthesis of benzo[5,6]chromeno[3,2-c]quinoline compounds in aqueous medium
  8. Design and microwave-assisted synthesis of a novel Mannich base and conazole derivatives and their biological assessment
  9. Quantum chemical studies on structural, spectroscopic, nonlinear optical, and thermodynamic properties of the 1,2,4-triazole compound
  10. Design, synthesis, and biological evaluation of phenyl-isoxazole-carboxamide derivatives as anticancer agents
  11. Quantum chemistry study on the promoted reactivity of substituted cyclooctynes in bioorthogonal cycloaddition reactions
  12. Quantum chemical calculations of phenazine-based organic dyes in dye-sensitized solar cells
  13. Rapid Communications
  14. One-pot synthesis of benzofurans via heteroannulation of benzoquinones
  15. Design and development of novel thiazole-sulfonamide derivatives as a protective agent against diabetic cataract in Wistar rats via inhibition of aldose reductase
  16. Review Articles
  17. Organic electrochemistry: Synthesis and functionalization of β-lactams in the twenty-first century
  18. Some applications of deep eutectic solvents in alkylation of heterocyclic compounds: A review of the past 10 years
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