Fe3O4@HA-Cu(OAc)2 nanocomposite as a nanomagnetic water-compatible catalyst for efficient synthesis of 1,2,3-triazoles in water

doi:10.21203/rs.3.rs-4849421/v1

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Fe₃O₄@HA-Cu(OAc)₂ nanocomposite as a nanomagnetic water-compatible catalyst for efficient synthesis of 1,2,3-triazoles in water

https://doi.org/10.21203/rs.3.rs-4849421/v1

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A new Humic acid-based nanomagnetic copper(II) composite was prepared and used as an eco-friendly recoverable catalyst for the synthesis of 1,4-disubstituted 1,2,3-triazoles via the three-component click reaction of alkyl halide, sodium azide, and terminal alkyne in good to excellent yield. A simple magnetic copper acetate composite preparation using humic acid, Fe3O4@HA-Cu(OAc)2, was reported and characterized by SEM, TEM, XRD, EDX, VSM, AAS, and FT-IR. The catalyst shows high catalytic potential in a one-pot three-component click reaction for synthesizing 1,2,3-triazoles. The nanomagnetic Fe3O4@HA-Cu(OAc)2 demonstrates highly efficient, stable, compatible with oxygen/water and recyclable copper (II), and cost-effectiveness advantages catalyst. An external magnetic field easily recovers the catalyst, and therefore, time and energy are saved since no filtration or decantation technique was needed. According to high dispersibility in water, nanomagnetic Fe3O4@HA-Cu(OAc)2 can be utilized as a highly efficient catalyst.

Biological sciences/Biochemistry

Physical sciences/Chemistry

Physical sciences/Materials science

Copper (II) acetate

Magnetic nanocomposite

Humic acid

Fe3O4@HA-Cu(OAc)2

3-triazole

In chemical synthesis, click chemistry is a class of simple, atom-economy reactions commonly used for joining two molecular entities of choice. Click chemistry is not a single specific reaction, but describes a way of generating products that follow examples in nature, which also generates substances by joining small modular units. In many applications, click reactions join a biomolecule and a reporter molecule. Click chemistry is not limited to biological conditions: the concept of a "click" reaction has been used in chemo proteomic, pharmacological, biomimetic, and molecular machinery applications ¹. However, they have been notably useful in detecting, localizing, and qualifying biomolecules. As an attractive example of click chemistry, note that 1,2,3-triazoles have received considerable attention owing to their properties such as high dipole moment, strong hydrogen bonding ability, and high chemical stability ².

A triazole is a heterocyclic compound featuring a five-membered ring of two carbon and three nitrogen atoms with the molecular formula C₂H₃N₃. Many triazoles are versatile, biologically active compounds commonly used as fungicides and plant retardants. Lastly, the many free lone pairs in triazoles make them useful as coordination compounds, although not typically as haptic ligands.

1,2,3-Triazoles, also known as vicinal triazoles, are usually prepared following (3+2) cycloaddition protocols. A common technique for unsubstituted triazoles is the Huisgen azide-alkyne 1,3-dipolar cycloaddition: an azide and an alkyne react at high temperatures to form a ring.

Metal catalysts are employed to selectively prepare a desired isomer. In the copper-catalyzed (CuAAC), copper(I) salts are selected for the formation of 1,4-disubstituted 1,2,3-triazoles. One such catalyst is CuBr (PPh₃)₃, which is relatively stable towards oxidation even at elevated temperatures and can produce triazoles with a broad range of substituents either in solvent ³, ⁴ or under neat ⁵ reaction conditions.

It should be mentioned that in metal-free conditions ⁶ or transition metals such as Cu ^7-16, Ru, Ag ¹⁷, Au, etc. can catalyze the 1,3-dipolar cycloaddition of an azide and an alkyne, to form 1,2,3-triazole ^13,18. In this regard, the most popular metal catalyst for this reaction is a copper source in polar solvents ¹⁹. Copper catalysts are drawing a great deal of attention, which is due to their accessibility, cheapness, and low-toxicity properties ²⁰. Due to these characteristics, copper nanoparticles have generated a great deal of interest, especially in the field of catalysis. The introduction of a new copper-based catalyst over the past two decades has changed this situation as it enables the reaction to be promoted in mild conditions. The reaction scope has also been greatly expanded, rendering this copper-based cross-coupling attractive for both academia and industry.

Since the recovery of copper catalysts is a challenge for scientists who want to develop sustainable production processes, heterogenization is applied to facilitate the recovery and recycling of the catalyst. In this respect, inorganic and organic supports are used to heterogenized copper, whilst keeping the inherent activity of the catalytic copper to allow its separation and recovery ²¹. One of the most interesting supports for heterogenization is magnetic nanoparticles (MNPs) which have extensive attention due to their unique properties ²². Also, carbon-based magnetic composites have drawn much attention since they are environmentally friendly, highly efficient, abundant, and diverse.

Humic acid-derived carbon-based catalysts are based on Humic acid being a renewable source of carbon material, from trees to advanced carbon-based catalysts ²³. Lignin is the second most abundant biopolymer on earth after cellulose, that is a carbon-rich (approximately 55–66%) renewable resource that when oxidized under pressure, lignin is converted to humic acid-like compounds ²⁴ which has a lot of functional groups on its surface including phenolic, carboxylic, hydroxylic, and amid groups causing high efficiency in organic synthesis.

Considering the high abundance and accessibility of humic acid, here in this study, we report a novel preparation of copper(II) acetate magnetic nanocomposite, Fe₃O₄@HA-Cu(OAc)₂, in mild, with an eco-friendly method. Fe₃O₄@HA-Cu(OAc)₂ is successfully presented as a highly efficient recoverable biocatalyst for click synthesis of 1, 2, 3-triazoles derivatives via a three-component condensation of terminal alkynes, alkyl halide, and sodium azide in water at room temperature. The organic part of humic acid affects the solubility of the substrates in water and also has a lot of excellent functional groups to support and stabilize Cu(OAc)₂ for activating the substrate molecules simultaneously to conduct triazole synthesis in water efficiently.

Simple formation of Humic acid- copper(II) acetate and magnetic nanoparticles were achieved from the reaction of respective iron (II) and iron (III) metal salts in water containing Humic acid as a support agent to achieve Fe₃O₄@HA and then stirred the Fe₃O₄@HA in water solution of Cu(OAc)₂. It is believed that Humic acid plays a role of support to keep control of the particle's growth to generate nano-sized powders of magnetic nanoparticles and also has a lot of excellent functional groups to stabilize and disperse Cu on the surface.

Characterization of materials

Scanning electron microscope (FESEM) and transmission electron microscopy (TEM): The morphologies of Fe₃O₄@HA-Cu(OAc)₂ are shown in FESEM images in Fig. 2.

It can be seen that copper acetate and magnetic nanoparticles have successfully been grown on the surface of the Humic acid. The Humic acid structure with hydroxyl groups can provide a higher absorber contact to promote the easier growth of copper acetate and magnetic nanoparticles on the surface. The copper acetate and magnetic nanoparticles were evenly coated on the humic acid, and the size and structure were relatively uniform. TEM analysis of the Humic acid-copper (II) acetate magnetic nanocomposite shows the spherical morphology of the material with a diameter of about 10–12 nm (Fig. 3).

X-ray diffraction (XRD)

The XRD spectra of the iron oxide (Fe₃O₄), magnetically humic acid (Fe₃O₄@HA), and ( Humic acid-copper acetate magnetic nanocomposite (Fe₃O₄@HA-Cu(OAc)₂) are displayed in Fig. 4 shows the XRD pattern of synthesized Humic acid-copper acetate magnetic nanocomposite, which contains iron oxide (Fe₃O₄; JCPDS file 111-731) ²⁵ (Fig. 4). Humic acid is affected by the broadening of diffraction peaks at 2Ɵ=10–20. X-ray diffraction pattern of pure Fe₃O₄ (Fe₃O₄; JCPDS file 019–0629) ²⁶ has the highest peak at ~33°corresponding to the (104) plane, which is an indication of the formation of magnetite. The main diffraction peaks are located at 33°, 35°, 43°, 54°, 57°, and 63°, assigned to the magnetite peaks who having rhombohedral structure with R3c space group. According to our target which produces the recoverable copper (II), in the following, the copper (II) acetate magnetic nanocomposite properties, are investigated via EDX, and FTIR analysis.

Energy-dispersive X-ray (EDX) spectroscopy and Atomic absorption spectroscopy (AAS):

The EDX analysis confirms the presence of carbon, oxygen, iron, and copper (Fig. 5). The presence of the carbon and oxygen peaks refers to the basic structures of humic acid. The two peaks of iron and oxygen assert the fabrication of the magnetic nanoparticles. The quantitative results of copper (II) acetate magnetic nanocomposite are summarized in Table 1.

Table 1. The quantitative results of copper (II) acetate magnetic nanocomposite.
Elm	Line	W%	A%
C	Ka	20.33	41.29
O	Ka	24.35	37.13
Al	Ka	01.21	01.09
Au	Ka	09.14	01.13
Fe	Ka	39.63	17.31
Cu	Ka	05.33	02.05
Matrix		Correction	ZAF

Atomic absorption spectroscopy (AAS) was conducted to investigate the amount of Cu content supported on Fe₃O₄@HA-Cu(OAc)₂. According to the AAS analysis, the loading amount of copper in Fe₃O₄@HA-Cu(OAc)₂ was determined to be 1.88 mmol g⁻¹. Thus, the synthesized nanoparticles have a high capacity to form chelates with the Cu species which could be attributed to the presence of a good functional group on humic acid. According to this the calculated turnover number of catalyst (TON) was 51.06 which is a high TON.

Vibrating sample magnetometer (VSM) analysis

The VSM analysis shows the magnetic properties of magnetic humic acid and humic acid-copper acetate magnetic (Fe₃O₄) nanocomposite at room temperature (Fig. 6). It shows that not much has changed in saturation magnetization (magnetic humic acid: 0.17 emug^-1, humic acid-copper acetate magnetic: 0.17 emug^-1).

Fourier-transform infrared spectra (FTIR)

The FTIR spectroscopy is an important tool to show the structural characterization of the units of humic acid. As shown in Fig. 7 the spectra in region 3000–3700 cm^-1 show the highest amount of hydroxyl groups available on the surface. The peaks at 1424 cm^-1 and 1559 cm^-1 are assigned to the carboxylic group and the peaks at 2856 cm^-1 and 2923 cm^-1 are assigned to the aliphatic C-H of humic acid. Besides, the peak at 572 cm^-1 is assigned to Fe^_O stretching vibration in the magnetic part and the peak at 448 cm^-1 is assigned to copper acetate ²⁷. This evidence confirms that humic acid copper acetate is completely supported by fe₃O₄.

Catalytic Activity of copper (II) acetate magnetic nanocomposite in click synthesis of 1, 2, 3-triazoles

After succeeding in preparing and characterizing nano magnetically Fe₃O₄@HA-Cu(OAc)₂, it was applied to three component click synthesis of 1, 2, 3-triazoles to show catalytic potential and various catalyst loading, solvents, and temperatures was optimized for the model reaction of benzyl bromide, phenylacetylene, and sodium azide (Tables 2). The model reaction was carried out easily in the presence of 0.01 g of Fe₃O₄@HA-Cu(OAc)₂ and the best conditions were selected when the reaction was performed in sole water at room temperature to yield the corresponding 1, 2, 3-triazole in 100% conversion (Table 2, entry 4) and 96% isolated yield (Table 3, entry 1). Besides, the reaction was performed in a shorter reaction time when the temperature increased to 50 ^˚C and 70 ^˚C (entries 11 and 12).

Table 2. The optimization results were obtained for the synthesis of 1-benzyl-1,2,3-triazole.
Entry	Catalyst (g)	Solvent (mL)	Temp. (^﮿C)	Time (h)	Conversion (%)`
1	0.01	H₂O/EtOH 50% (1)	10	24	100
2	0.01	EtOH (1)	10	12	80
3	0.01	H₂O (1)	10	10	100
4	0.01	H₂O (1)	25	1.7	100
5	0.01	EtOH (1)	25	2.24	80
6	0.01	Acetonitrile (1)	25	12	100
7	0.01	H₂O/EtOH 50% (1)	25	2	100
8	0.01	PEG 200 (1)	25	24	90
9	0.008	H₂O (1)	25	2.15	100
10	0.005	H₂O (1)	25	2.5	100
11	0.01	H₂O (1)	50	1	100
12	0.01	H₂O (1)	70	0.7	100
13	0.01	H₂O (1.5)	25	2.15	100
14	0.01	H₂O (0.5)	25	2.45	100

The high catalytic activity, stability, and reusability of copper (II) acetate magnetic nanocomposite in water allow us to extend the model reaction to synthesize a series of 1,2,3-triazole derivatives (Table 3). Aromatic alkynes in comparison to the aliphatic one show higher activity due to the stable complex with copper (II). On the other hand, to show the wide catalytic activity of copper (II) acetate magnetic nanocomposite, it was also investigated in the β-hydro-1H-1,2,3-triazole synthesis reaction. In all cases, after consuming the limited alkyl halide or epoxide, ethanol was added to the reaction mixture to solve the corresponding product and separated the catalyst by an external magnet. The pure corresponding product was achieved after reducing the solvent a recrystallization in water in good to excellent yield.

Comparison study of catalytic Activity

To comprehend the efficacy and potency of Fe₃O₄@HA-Cu(OAc)₂ nanocomposite, the present catalytic system was compared with several previously reported methods for the synthesis of 1-benzyl-1,2,3-triazole. The copper (II) acetate magnetic nanocomposite catalyst exhibits high catalytic activity as compared to other reports, which is attributed to the availability of more active and stable copper (II) stabilized with hydroxyl groups on humic acid (Table 4). Moreover, the reusability of copper (II) acetate magnetic nanocomposite is found to be significantly easier as compared to some other copper (II) and copper (I)-based catalytic systems that separated with an external magnet easily from the reaction mixture.

Table 4. Comparison study of the catalytic activity of different copper catalysts for the synthesis of 1,2,3-triazole.
Catalyst	Solvent	Temp (^﮿C)	Time (h)	Yield (%)
CuI [copper(I) iodide] ¹⁰	Toluene	110	72	67
Cu⁰/Fe₃O₄⁷	DMSO	80	0.5	62-96
Ag₂SO₄ ¹⁷	DMF	70	0.67	76
I₂⁶	DMSO	100	12	86
Cu (OTf)₂ ¹³	DMF/AcOH (4:1)	110	14	96
CuFe₂O₄ ⁹	H₂O	70	6	87
CuO ¹¹	THF/H₂O (24:1)	60	24	96
Fe₃O₄@TiO₂/ Cu₂O ¹²	H₂O	100	0.3	89
Cu-Apatite ⁸	H₂O	100	1.5	99
This study	H₂O	Room temperature	1.7	96

A novel and stable copper (II) acetate magnetic nanocomposite was easily prepared, which displays the best catalytic performance for click synthesis of 1, 2, and 3-triazole derivatives at room temperature, with excellent yields. Humic acid acts as a carbon-based material for nano-magnetic preparation. Since the catalyst can recover easily from the reaction mixture by an external magnetic field, time and energy are saved concerning filtration or decantation techniques. The reactions proceeded in water at room temperature. Reusability experiments exhibited that the copper (II) acetate magnetic nanocomposite after four runs shows the same catalytic ability. Moreover, the effects of reaction temperature on catalytic performance were investigated. Since the copper (II) acetate magnetic nanocomposite is highly stable and easily achieved by this method efforts are currently being made to apply it to other organic reactions.

Humic acid-copper (II) acetate magnetic nanocomposite preparation:

The aqueous dispersed solution of humic acid (10 mL, 0.5 wt%) was added into Fe²⁺and Fe³⁺ aqueous solution (3 mmol, 0.596 g, and 4.75 mmol, 0.77 g respectively) under an ultrasonic bath. Then the ammonia solution (30%) was added fast under argon gas at 60^˚C to the pH of the solution was raised to 10. The magnetic humic acid was separated with an external magnet washed with water several times and transferred to an 80 ^˚C oven for 15 h. Magnetic humic acid (1 g) and copper acetate monohydrate (2 mmol) were added to methanol under an ultrasonic bath and stirred overnight. The composite was separated by an external magnet and dried for 12 h at 80 ^˚C in the oven. (Fig. 1). The copper (II) acetate magnetic nanocomposite was characterized by SEM, TEM, XRD, EDX, VSM, AAS, and FTIR analyses.

1-benzyl-1,2,3-triazole derivatives synthesis:

Nano Fe₃O₄@HA-Cu(OAc)₂ (0.01 g) was added to a stirring mixture of the alkyne (1.1 mmol), alkyl halide (1 mmol), and NaN₃ (1.1 mmol, 0.072 g) in deionized water (1 mL). The reaction mixture was stirred at room temperature and the progress of the reaction was monitored by TLC (n-hexane: ethyl acetate, 80:20). After completion of the reaction, ethanol (4 mL) was added to the reaction mixture, and the catalyst was separated by a permanent magnet from the reaction mixture. The pure 1-aryl-1,2,3-triazole products were obtained after evaporation of the solvent and crystallized in water and ethanol as highly pure powder compounds with good to excellent yields (Table 2).

β-hydroxy-1,2,3-triazole derivatives synthesis:

Nano Fe₃O₄@HA-Cu(OAc)₂ (0.01 g) was added to a stirring mixture of alkyne (1.1 mmol), epoxide (1 mmol, ), NaN₃ (1.1 mmol) in water (1 mL). The reaction mixture was stirred with a magnetic stirrer at room temperature and followed by TLC (n-hexane: ethyl acetate, 70: 30). After completion of the reaction, ethanol (4 mL) was added and the catalyst was separated by a permanent magnet from the reaction mixture. The β-hydroxy-1,2,3-triazole was obtained after the concentration of the reaction mixture under diminished pressure in oil form. The pure β-hydroxy-1,2,3-triazole products were obtained after recrystallization in water and ethanol, with good to excellent yields (Table 2).

Humic acid- copper (II) acetate magnetic nanocomposite reusability:

To study the reusability of Fe₃O₄@HA-Cu(OAc)₂ nanocomposite, the model reaction of benzyl bromide, phenylacetylene, and sodium azide proceeded efficiently, in the presence of the catalyst (Fig. 8). Fe₃O₄@HA-Cu(OAc)₂ (0.01 g) was added to a stirring mixture of phenylacetylene (1.1 mmol), benzyl bromide (1 mmol), and NaN3 (1.1 mmol) in water (1 mL) and stirred at room temperature until verification of the completion of the reaction (1.7 h). Ethanol (5 mL) was added to the reaction mixture to solve precipitated corresponding 1, 2, 3-triazole, and Fe₃O₄@HA-Cu(OAc)₂ was magnetically recovered by placing a permanent magnet in the reactor wall. Fe₃O₄@HA-Cu(OAc)₂ was washed with ethanol (5 mL) and dried at r.t for 12 h. The same catalyst was used in 4 cycles for the 1-benzyl-1,2,3-triazole synthesis reaction. The advancement of using humic acid- copper (II) acetate magnetic nanocatalyst includes easy separation by a magnetic field without any sedimentation techniques, efficient catalytic and recycling potentials with a negligible amount of leaching of the metal, create an eco-friendly media at room temperature with excellent yields.

Characterization:

All commercially available chemicals were obtained from Merck and Fluka Chemical Companies, and used without further purification unless otherwise stated; solvents were distilled before their use. The method mentioned below synthesized the humic acid- copper (II) acetate magnetic nanocomposite and 1, 2, and 3-triazoles derivatives.

The x-ray diffraction (XRD) analysis was accomplished on the dried samples (2 h at 110°C), applied with a Lynxeyes detector and using a BRUKER diffractometer (D8 advance, with a Cu Kα radiation λ= 1.54086 A). The energy-dispersive X-ray spectroscopy (EDX) data were performed via the ESCALAB 250 device and the monochromatic source was Al (Kα line=1486.6 eV) for 500 μm surface diameter of the sample. In the following, the calibration of photoelectron spectra was at 284.8 eV for C1s carbon in the C-C component. The magnetic data analysis (VSM) was carried out by a Lake Shore 7300 vibrating sample magnetometer. The Thermo Scientific Trace 1300 device was used for gas chromatography analysis, armed with an EI ionization source and an ISQ-QD detector. On the other hand, for the hydrogen and carbon magnetic resonance (¹HNMR and ¹³CNMR) analyses, we used the Bruker 400 AVANCE which was matched with a dual Z probe at 400 and 100 MHz. For this reason, the internal standard solvent was CDCl₃ (7.26 ppm for 1H and 77.16 ppm for 13C). Besides, Fourier transform infrared spectroscopy (FTIR, PerkinElmer, USA) was applied to specify the products (mid-infrared region 4000–400 cm^-1). Also, the attenuated total reflection (ATR) method helped us directly measure some of the samples. The thin-layer chromatography (TLC) method followed the progress of the reactions on silica-gel Polygram.

Acknowledgments

A.A.J. thanks the Research Council of Yazd University for financial support.

Conflict of Interests

The authors declare no conflict of interest.

Authors’ contributions

B.A. is a Ph.D. student. She has worked on the manuscript's subject in the laboratory and A.A.J. helps as supervisor. B.A. wrote the manuscript and A.A.J. edited the manuscript.

Competing interests

The author(s) declare no competing interests.

Supplementary information

The supplementary information includes the hot filtration method (Fig. S1), AAS analysis (Fig. S2), and FT-IR and NMR spectra of products.

Funding

Yazd University

Availability of data and materials

All data is provided in the manuscript or cited in the references.

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Table 3 is available in the Supplementary Files section.

No competing interests reported.

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Fe₃O₄@HA-Cu(OAc)₂ nanocomposite as a nanomagnetic water-compatible catalyst for efficient synthesis of 1,2,3-triazoles in water

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