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[Msim]CuCl3: as an efficient catalyst for the preparation of 5-amino-1H-pyrazole-4-carbonitriles by anomeric based oxidation

  • Ardeshir Khazaei EMAIL logo , Ahmad Reza Moosavi-Zare EMAIL logo , Hadis Goudarzi and Mahsa Tavasoli
Published/Copyright: October 27, 2021
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 77 Issue 1

Abstract

3-Methyl-1-sulfonic acid imidazolium trichlorido copper (II) {[Msim]CuCl3} was prepared and used as a new catalyst for the preparation of 5-amino-1H-pyrazole-4-carbonitriles. In this reaction, the pyrazole ring was formed by an anomeric and vinylogous anomeric effect in the structure of the product.

Keywords: 5-amino-1H-pyrazole-4-carbonitrile; anomeric based oxidation; [Msim]CuCl3; multi-component reaction; solvent-free synthesis

1 Introduction

The pyrazole framework in medicinal and biological compounds causes various pharmacological properties such as antimicrobial [1], antitumor [2], antiviral [3], anti-inflammatory [4], analgesic [5, 6] and anti-hyperglycemic activities [7]. The multi-component reaction of aromatic aldehydes, malononitrile, and phenylhydrazine derivatives is one of the common strategies for the synthesis of these useful compounds [8]. Multi-component reactions are an important protocol in organic reactions which are carried out in one step without producing side products in order to save energy, material and solvent and revealing synthesis of the products in high yield and short reaction time [8], [9], [10], [11], [12], [13]. Multi-component synthesis of 5-amino-1H-pyrazole-4-carbonitriles previously was reported for various catalysts such as (Bim)OH [6], [4CSPy]ZnCl3 [8], CPS-CDMNPs [14], Glu@Fe3O4 [15], [HMIM]C(NO2)3 [16], sodium ascorbate [17] and BNPs-sulfamic acid [18]. But because of the medicinal, biological and industrial applications of 5-amino-1H-pyrazole-4-carbonitrile derivatives, an introduction of new methods for the synthesis of these compounds is still valuable.

Sulfonic acid functionalized imidazolium salts (SAFIS), which combine the capabilities of the imidazolium ring and acidic abilities of sulfonic acid in their structure, show an important role as catalyst for organic transformations. In the last decade, SAFIS was successfully used as a catalyst and reagent for the preparation of various organic compounds such as triarylmethanes [19], 1-amidoalkyl-2-naphthols [20, 21], benzimidazoles [22], xanthene derivatives [23, 24], dihydropyrano[2,3]pyrazoles [25], pyrido[2, 3-d:6,5-d]dipyrimidine-2,4,6,8-tetraones [26], hexahydroquinolines [27], dihydropyrimidinones [28], pyrazine derivatives [29], 1,2,4,5-tetrasubstituted imidazoles [30], amido-alkyl-phenols [31], sulfonated aromatic compounds [32], nitro aromatic compounds [33, 34], beta-amino carbonyl compounds [35] and pyrimido[4,5-b]quinoline derivatives [36].

Previously, [Msim]CuCl2 was prepared and used as a catalyst for the synthesis of bis(indolyl)methane derivatives [37]. In continuation of previous investigations, studying the application of acidic ionic liquids and salts as catalysts for the synthesis of organic compounds, we have introduced 3-methyl-1-sulfonic acid imidazolium trichlorido copper (II) {[Msim]CuCl3} as an efficient and new catalyst for the synthesis of 5-amino-1H-pyrazole-4-carbonitriles (Scheme 1).

Scheme 1: The preparation of 5-amino-1H-pyrazole-4-carbonitriles.
Scheme 1:

The preparation of 5-amino-1H-pyrazole-4-carbonitriles.

2 Results and discussion

At first, 1-methylimidazole in dry CH2Cl2 was reacted with chlorosulfonic acid at room temperature to give 3-methyl-1-sulfonic acid imidazolium chloride {[Msim]Cl} as a viscous colorless oil [20]. Then, by the reaction of [Msim]Cl with dry CuCl2 at 70 °C [Msim]CuCl3 was prepared (Scheme 2).

Scheme 2: The preparation of [Msim]CuCl3.
Scheme 2:

The preparation of [Msim]CuCl3.

In the IR spectrum of [Msim]CuCl3, the O-H stretching of the SO3H group was observed at 2100–3350 cm−1. Also, the peak considered at 1025 cm−1 could be related to –S=O and the peak observed at 1169 cm−1 could be related to vibrational modes of N-SO2 and O-SO2 bonds [34].

In the mass spectrum of [Msim]CuCl3, the molecular mass of this salt was confirmed and by energy dispersive spectroscopy (EDS), the expected elements in the structure of this compound including carbon, nitrogen, sulfur, chlorine, copper and oxygen were approved.

The morphology of [Msim]CuCl3 was studied by scanning electron microscopy (SEM). SEM analysis of [Msim]CuCl3 is displayed in Figure 1.

Figure 1: SEM micrographs of [Msim]CuCl3.
Figure 1:

SEM micrographs of [Msim]CuCl3.

Thermal gravimetric analysis (TGA) of [Msim]CuCl3 was studied in the temperature range between 25 and 600 °C. The TGA of [Msim]CuCl3 showed two steps of weight losses (Figure 2). The strongest weight loss is observed above 200 °C. Thus, [Msim]CuCl3 can be used in chemical reactions up to 200 °C without pronounced changes in its chemical structure.

Figure 2: Thermal gravimetric analysis (TGA) of [Msim]CuCl3 in the temperature range of 25–600 °C.
Figure 2:

Thermal gravimetric analysis (TGA) of [Msim]CuCl3 in the temperature range of 25–600 °C.

To study the catalytic application of [Msim]CuCl3, the catalyst was tested for the synthesis of 5-amino-1H-pyrazole-4-carbonitriles. At first, to optimize the reaction conditions, the reaction of 4-chlorobenzaldehyde, malononitrile and phenylhydrazine was considered as a model reaction and the effects of temperature, catalyst amount and various solvents, in comparison with solvent-free condition, were studied. The results were summarized in Figure 3. From the performed experiments, it can be concluded that 2 mol% of [Msim]CuCl3 at 60 °C in the absence of any solvent are the best reaction conditions for the preparation of 5-amino-1H-pyrazole-4-carbonitriles. The model reaction was also tested in the absence of catalyst which no proceeds in this reaction condition (Figure 3).

Figure 3: The effect of the catalyst amounts and temperature on the reaction between 4-chlorobenzaldehyde, malononitrile and phenylhydrazine within 5 min.
Figure 3:

The effect of the catalyst amounts and temperature on the reaction between 4-chlorobenzaldehyde, malononitrile and phenylhydrazine within 5 min.

After the optimization of the reaction conditions in order to find the efficiency and capability of the presented method, various aromatic aldehydes, containing electron withdrawing substituents, electron-releasing substituents and halogen atoms, were reacted with malononitrile and phenylhydrazine, for the synthesis of some 5-amino-1H-pyrazole-4-carbonitriles. The obtained results, including the yields and reaction times, are summarized in Table 1.

Table 1:

The preparation of 5-amino-1H-pyrazole-4-carbonitriles.

Entry Product Time (min) Yielda (%) M.p. °C (Lit.)ref
1 5 87 162–164 (164–166) [6]
2 10 83 150–151 (156–158) [14]
3 10 70 129–130 (132–134) [14]
4 5 87 142–143 (134–136) [18]
5 10 78 132–133 (144–146) [14]
6 10 81 138–141 (137–139) [17]
7 10 83 156–158 (159–160) [6]
8 5 86 115–116 (108–110) [14]
9 10 72 272–275 (275–277) [16]
10 10 82 117–120 (120–124) [14]
11 10 76 153–155 (157–158) [15]
12 5 85 128–129 (128–130) [6]
13 10 72 212–216
14 10 61 140–143

  1. aIsolated yield.

In a suggested mechanism, which is confirmed by the previous literature [8, 14], [15], [16], [17], [18], first, the aldehyde is activated with the acidic group in [Msim]CuCl3. Malononitrile is reacted with the aldehyde as Knoevenagel reaction to prepare the ciano olfine compound (I) after removing one molecule of H2O. Then, phenylhydrazine reacted with compound (I) as a Michael acceptor to prepare (II). After intramolecular nucleophilic attack of nitrogen to the C=N bond in (II), the ring is closed and (III) is obtained. By an anomeric and vinylogous anomeric effect in (III), a hydride anion could be abstracted and reacted with monocopper(II) trichloride and give a chloride ion. The chloride ion is protonated by (IV) to afford the desired product. By the reaction of monocopper(II) dichloride monohydride with released HCl, monocopper(II) trichloride is obtained and one molecule of H2 is released. In the next step, intermediate (III) was reacted with the acidic part of the catalyst and by the anomeric and vinylogous anomeric effect in (III), (IV) is prepared and one molecule of H2 was obtained. Afterward, by reaction of the sulfonate anion, in the structure of catalyst, with (IV) the desired product and the cationic part of catalyst is prepared (Scheme 3). Oxidation through the release of hydrogen gas in the ring of 1,4-dihydropyridine to prepare pyridine has been reported in the previous investigation [38]. Recently, this subject was mentioned by Zolfigol and coworkers as anomeric based oxidation, whereby the electron transfer proceeds from the heteroatom lone pair orbitals to the C–H vacant antibonding sigma orbital. The obtained hydride anion then reacts with a hydrogen cation from other resources available in the reaction, releasing H2 [39], [40], [41], [42]. Also, in the third pathway, as shown in Scheme 3, oxygen can participate in the oxidation process. In this regard, oxygen was reacted with monocopper(II) dichloride monohydride and intermediate (IV) to obtain desired product, H2O2 and monocopper(II) trichloride (Scheme 3).

Scheme 3: The proposed mechanism for the synthesis of 5-amino-1H-pyrazole-4-carbonitriles.
Scheme 3:

The proposed mechanism for the synthesis of 5-amino-1H-pyrazole-4-carbonitriles.

3 Conclusions

In summary, 3-methyl-1-sulfonic acid imidazolium trichlorido copper (II), {[Msim]CuCl3} as a new catalyst was introduced and successfully applied as a catalyst for the preparation of some 5-amino-1H-pyrazole-4-carbonitrile derivatives.

4 Experimental section

4.1 General

All chemicals were purchased from the chemical companies Merck or Fluka. The known products were identified by comparison of their melting points and spectral data with those reported in the literature.

4.2 Procedure for the preparation of [Msim]CuCl3

A round-bottomed flask (50 mL) was charged with 3-methyl-1-sulfonic acid imidazolium chloride (0.9931 g, 5 mmol), and then, dry CuCl2 (0.6722 g, 5 mmol) was added over a period of 5 min at 70 °C. Afterward, the reaction mixture was stirred for 60 min at 70 °C to prepare [Msim]CuCl3 as a brown solid.

4.3 General procedure for the synthesis of 5-amino-1H-pyrazole-4-carbonitriles

A mixture of the aromatic aldehyde, (1 mmol), malononitrile (1 mmol, 0.066 g) and [Msim]CuCl3 (0.66 g, 2 mol%) as a catalyst was added to a 25 mL round-bottomed flask connected to a reflux condenser and heated at 60 °C for 3 min. Then, phenylhydrazine (1 mmol, 0.108 g) was added to the reaction mixture and stirred at 60 °C for an appropriate time under solvent-free conditions. After the completion of the reaction, as monitored by TLC, the reaction mixture was extracted with warm ethyl acetate (10 mL) to separate the reaction mixture from the catalyst by simple filtration (the reaction mixture is soluble in warm ethyl acetate and the catalyst is insoluble). Finally, the desired product was purified by recrystallization in ethanol (90%).

4.4 Selected spectral data of compounds

4.4.1 5-Amino-3-(4-nitrophenyl)-1-phenyl-1H-pyrazole-4-carbonitrile (1)

Brown solid: m.p. = 162–164 °C; IR (KBr) = υ 1110, 1147, 1261, 1344, 1444, 1595, 3303 cm−1; 1H NMR (250 MHz, CDCl3): δ (ppm) 6.95 (1H, t, J = 7.25 Hz), 7.14 (2H, d, J = 7.50 Hz), 7.29 (2H, q, J = 7.50 Hz), 7.68 (1H, s), 7.76 (2H, d, J = 8.50 Hz), 7.98 (1H, s), 8.21 (2H, d, J = 8.75 Hz); 13C NMR (62.5 MHz, CDCl3): δ (ppm) 113.1, 121.2, 124.0, 126.2, 129.4, 133.7, 141.6, 143.5.

4.4.2 5-Amino-3-(2-hydroxynaphthalen-1-yl)-1-phenyl-1H-pyrazole-4-carbonitrile (13)

Cream solid: m.p. = 212–216 °C; IR (KBr) = υ 1169, 1258, 1304, 1534, 1604, 3026, 3322, 3440 cm−1; 1H NMR (250 MHz, CDCl3): δ (ppm) 6.94–7.05 (3H, m), 7.22–7.33 (4H, m), 7.47–7.53 (1H, m), 7.60 (1H, s), 7.72–7.80 (2H, m), 7.98 (1H, d, J = 8.00 Hz), 8.76 (1H, s), 12.04 (1H, s); 13C NMR (62.5 MHz, CDCl3): δ (ppm) 112.6, 118.9, 119.8, 120.8, 123.2, 127.0, 129.0, 129.5, 131.1, 137.8, 156.8; MS: m/z = 326.1 [M]+.

4.4.3 5-Amino-3-(2-hydroxy-5-methoxyphenyl)-1-phenyl-1H-pyrazole-4-carbonitrile (14)

Cream solid: m.p. = 140–143 °C; IR (KBr) = υ 1031, 1163, 1275, 1319, 1496, 1535, 1601, 2202, 2967, 3012, 3331, 3440 cm−1; 1H NMR (250 MHz, CDCl3): δ (ppm) 3.78 (3H, s), 6.67 (1H, s), 6.81–6.99 (5H, m), 7.28 (2H, d, J = 8.50 Hz), 7.51 (1H, s), 7.79 (1H, s), 10.42 (1H, s). 13C NMR (62.5 MHz, CDCl3): δ (ppm) 55.8, 112.6, 113.7, 116.1, 117.1, 120.9, 129.5, 140.7, 151.1, 155.8; MS: m/z = 306.11 [M]+.

5 Supporting information

IR and NMR spectra.

Corresponding authors: Ardeshir Khazaei, Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran, E-mail: ; and Ahmad Reza Moosavi-Zare, Department of Chemical Engineering, Hamedan University of Technology, Hamedan, 65155, Iran, E-mail:

Acknowledgments

The authors gratefully acknowledge the Bu-Ali Sina University for providing support to this work.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/znb-2021-0153).

Received: 2021-09-21
Accepted: 2021-10-17
Published Online: 2021-10-27
Published in Print: 2022-01-27

© 2021 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.1515/znb-2021-0153
Keywords for this article
5-amino-1H-pyrazole-4-carbonitrile; anomeric based oxidation; [Msim]CuCl3; multi-component reaction; solvent-free synthesis

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Research Articles
  4. A new phenanthrene derivative from Entada abyssinica with antimicrobial and antioxidant properties
  5. Antileishmanial, antibacterial and cytotoxicity activity of the extracts, fractions, and compounds from the fruits and stem bark extracts of Pentadesma butyracea Sabine
  6. Two 2D Co(II)/Mn(II) coordination polymers based on the quinoline-2,3-dicarboxylate ligand: synthesis, crystal structure, and fluorescence properties
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  12. A new luminescent metal-organic framework with 2,6-di(1H-imidazol-1-yl)naphthalene and biphenyl-3,4′,5-tricarboxylic acid
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  14. [Msim]CuCl3: as an efficient catalyst for the preparation of 5-amino-1H-pyrazole-4-carbonitriles by anomeric based oxidation
  15. Synthesis and structure of an asymmetrical sila[1]magnesocenophane
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