Design, synthesis and characterization of a urea-bridged periodic mesoporous organosilica supporting Cu nanoparticles (Cu@APS-TDU- PMO) as highly efficient and recoverable catalyst for the synthesis of tetrazole derivatives

doi:10.21203/rs.3.rs-1528468/v1

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Design, synthesis and characterization of a urea-bridged periodic mesoporous organosilica supporting Cu nanoparticles (Cu@APS-TDU- PMO) as highly efficient and recoverable catalyst for the synthesis of tetrazole derivatives

https://doi.org/10.21203/rs.3.rs-1528468/v1

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In this work, a new mesoporous periodic organosilica is introduced with urea-bridges obtained by the reaction of amino group of (3-aminopropyl) triethoxysilane and 2,4-toluene diisocyanate (APS-TDU-PMO). The obtained PMO-APS-TDU was found to be an appropriate support for loading of Cu(II) nanoparticles to afford Cu@APS-TDU-PMO. Uniformity and mesoporosity of both synthesized nanomaterials including PMO-APS-TDU and Cu@PMO-APS-TDU were characterized by different techniques such as FTIR, EDX, TGA, XRD, FESEM, BET, and TEM. Furthermore, the prepared Cu@APS-TDU-PMO was also used, as a heterogeneous and recyclable catalyst, for the synthesis of tetrazole derivatives through cascade condensation, concerted cycloaddition and tautomerization reactions. Indeed, the main advantages of this Cu@APS-TDU-PMO is its simple preparation and high catalytic activity as well as proper surface area which enable it to work under solvent-free conditions. Also, the introduced Cu@APS-TDU-PMO heterogeneous catalyst showed good stability and reusability for five consecutive runs to address more green chemistry principles.

Urea-bridged periodic mesoporous organosilica (APS-TDU-PMO)

Cu(II) supported on urea-bridged PMOs (Cu@APS-TDU-PMO)

Tetrazole derivatives

Green Chemistry

Mesoporous silica nanomaterials are widely used in materials science for various applications and as special blocks for making various valuable materials. Mesoporous silica nanomaterials have been extensively studied and used for various applications including catalysis, ion exchange, adsorption, molecular sieving, and even as templates for synthetic conductive carbon nanowires ^1–20 due to their special properties such as large specific surface, high pore volume, uniform and tunable pores, high stability, and low cost ^21–28. Significant research efforts in recent years have been devoted to the development of periodic mesoporous organosilica (PMO) for applications in diverse fields. PMOs were first reported in 1999 ^29–38. PMOs are hybrid porous materials with high surface area and large porosity obtained by sol-gel method from an organo-bridged alkoxysilane in the presence of a surfactant ^39–44. The porous framework of PMOs is created by organic functional groups covalently binding to siloxane domains. In contrary to SBA-15 and MCM-41 which can only be functionalized at the surface by grafting methods, ^45,46 different organic functionalities of organic-bridged silica precursor can be included in the silica framework ^47–49. PMOs have some advantages over periodic mesoporous silica (PMS) materials including mechanical stability, hydrophobic pore wall, and high concentration of organic functional group in the framework, which have led to applications in different fields such as hydrophobic drug carriers, ⁵⁰ adsorbents, ^51,52 biological/biomedical supports, ⁵³optical applications ⁵⁴ solid chromatographic phases ⁵⁵ and catalysis. ^56–61 It is essential to use suitable catalytic systems for the preparation medically and ecologically very important compounds. Therefore, catalytic systems can be used for these purposes. The catalytic system consists of homogeneous and heterogeneous types. Also, heterogeneous catalysts have received more attention due to their many advantages such as easy separation from the reaction mixture, recyclability and less contamination in the final product. Among the various metal nanoparticles, copper nanoparticles are of particular importance due to their high conductivity, easy access, low cost, and tremendous copper potential to replace precious metals such as platinum,

gold, and silver. Immobilization of copper(II) on organic and inorganic ligands is one of the best methods for the production of heterogeneous catalysts with high stability, high activity and high load. Due to the use of copper complexes in various chemical reactions, such as the hydroboration reactions, ^62,63 direct addition of terminal alkynes to imines, ^64,65 alkyne-azide cycloaddition, ⁶⁶ allylic alkylation reactions ⁶⁷ and β-boration of α,β-unsaturated esters, ⁶⁸ special attention has been paid to copper complexes as catalysts for these reactions. The catalytic synthesis of heterocyclic compounds, such as tetrazole derivatives, has received much attention in recent times ^69–72. Tetrazole derivatives are an important class of nitrogen-rich heterocyclic nucleus with widespread use as potential drug nuclei and compounds such as Lasortan, Irbesartan, and Tomelukast which have been developed into drugs ^73–80. In addition, application of tetrazole derivatives as important compounds in synthetic organic chemistry, ^81,82 catalysis and energetic applications,⁸³ materials chemistry, ⁸⁴ and as ligands in coordination chemistry ⁸⁵ have led to the development of various efficient synthesis methods. Tetrazole derivatives are most commonly synthesized by [3 + 2] cycloaddition method ^86–93. Also, attempts for the production of tetrazole derivatives through new methods have led to the use of 2-benzylidenemalononitrile and sodium azide. This paper reports the synthesis of novel periodic mesoporous organosilica prepared by the reaction of amino group of (3-aminopropyl) triethoxysilane and 2,4-toluene diisocyanate (APS-TDU-PMO) with walls having urea bridges for Cu nanoparticles loading (Cu@APS-TDU-PMO, 1). Also, the synthesized PMO was used as a highly efficient and recoverable catalyst for the synthesis of tetrazole derivatives via three-component addition of aldehydes, malononitrile, and sodium azide (Scheme 1).

The prepared Cu@APS-TDU-PMO (1) was characterized by FTIR, TEM, SEM, XRD, BET, EDX and TGA techniques.

FTIR spectrum of the synthesized PMO and Cu@APS-TDU-PMO (1) are shown in Fig. 1. The absorption band at 3414 cm^-1 is attributed to N-H stretching. Two sharp absorption bands at 2928 cm^-1and 2862 cm^-1 are assigned to the asymmetric and symmetric stretching of aliphatic C-H bonds, respectively. The absorption bands at 1682 cm^-1 and 1654 cm^-1 correspond to C=O bond stretching of the urea. The band at 1544 cm^-1 can be assigned to the stretching vibration of the C=C bond. Two absorption bands at 1192 cm^-1 and 1092 cm^-1 are related to the Si-O-Si bonds (Fig. 1a). Also, the absorption band of Cu is clearly observed at 700-800 cm^-1 (Fig. 1b).

Thermal gravimetric analysis (TGA) curve (Fig. 2) shows that the weight loss slightly below 100 °C can be assigned to the elimination of adsorbed surface water. Weight loss between 200-300 °C is due to the degradation of small amounts of the unextracted surfactant (P123). Also, weight loss between 300-600 °C is attributed to the removal of the bridge from the Cu@APS-TDU-PMO (1) structure.

FESEM and TEM images show that the Cu@APS-TDU-PMO (1) is composed of a large number of interwoven rods with 40.54-59.13 nm in width. It can also be seen that the morphology of PMO was mostly preserved after deposition of Cu nanoparticles (Fig. 3). TEM images also demonstrate the honeycomb arrangement of mesopores and tubular mesochannels in the Cu@APS-TDU-PMO (1) structure, confirming the formation of a hexagonal mesoporous structure.

There is a peak at 2θ=1.35° in the low-angle XRD pattern, indicating the mesoporous structure of Cu@APS-TDU-PMO (1, Fig. 4a). Also, the wide-angle diffraction signal at 2θ of 20-30°, which is characteristic of mesoporous structures, is observed in the wide-angle XRD pattern of Cu@APS-TDU-PMO (1, Fig. 4b). The diffraction peaks at 2θ of 44.30°, 50.30°, and 75° can be assigned to the reflections of Cu (marked with ●).

EDX analysis confirms the presence of C, N, O, Si, and Cu elements in the Cu@APS-TDU-PMO (1) structure (Fig. 5).

The N₂ adsorption-desorption isotherm for Cu@APS-TDU-PMO (1) represents type IV isotherm commonly observed for mesoporous silica structures (Fig. 6). The calculated BET surface area was approximately 276 m² g^-1 which was retained even after the deposition of Cu nanoparticles. The average pore size was about 5.74 nm (Table 1).

Table 1 Structural parameters of the Cu@APS-TDU-PMO (1) determined from nitrogen sorption experiments.

Sample

Pore diameter (nm)

Surface area (m² g^-1)

Vp (cm³ g^-1)

Cu@APS-TDU-PMO (1)

5.74

276

0.17

Catalytic application of the Cu@APS-TDU-PMO (1) for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives

The catalytic performance of the prepared Cu@APS-TDU-PMO (1) was investigated for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives. To determine theoptimal reaction conditions for the three components of aromatic aldehyde (2), malononitrile (3), and sodium azide (4), the reaction was conducted using different solvents, temperatures, and catalyst loadings. The optimized reaction conditions are shown in Table 2. Initially, the reaction was performed under different conditions without catalyst. The obtained data showed that the reaction efficiency was negligible after 120 min (Entry 1-7). Then, the reaction was performed in EtOH, DMF, and solvent-free in the presence of 50 mg of catalyst, which solvent-free condition was more efficient (Entry 8-10). The results showed that the optimum amount of catalyst is 30 mg for the reaction, and a lower amount of catalysts leads to reduced efficiency of the reaction (Entry 11-13). Therefore, 30 mg of the catalyst in solvent-free conditions at 110 °C was selected as the optimal reaction condition for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives.

Table 2 Optimal condition for synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives^a (5a-i).


Entry	Catalyst	Catalyst loading (mg)	Solvent	Temperature (°C)	Time (h)	yield of (%) 5a
1	-	-	Solvent-Free	r.t.	120	Trace
2	-	-	H₂O	r.t.	120	Trace
3	-	-	DMF	r.t.	120	30
4	-	-	EtOH	r.t.	120	20
5	-	-	EtOH	Reflux	120	20
6	-	-	DMF	Reflux	120	40
7	-	-	Solvent-Free	110	120	45
8	Cu@APS-TDU-PMO (1)	50	EtOH	Reflux	50	38
9	Cu@APS-TDU-PMO (1)	50	DMF	Reflux	50	65
10	Cu@APS-TDU-PMO (1)	50	Solvent-Free	110	50	90
11	Cu@APS-TDU-PMO (1)	30	Solvent-Free	110	50	97
12	Cu@APS-TDU-PMO (1)	20	Solvent-Free	110	50	70
13	Cu@APS-TDU-PMO (1)	10	Solvent-Free	110	50	55

^aReaction conditions: aldehydes (2a, 1 mmol), malononitrile (3, 1 mmol), sodium azide (4, 1.2 mmol) and Cu@APS-TDU-PMO (1, 0.03 g) under different conditions.

Benzaldehyde with electron-withdrawing and electron-donating groups was used for the synthesis of 2-(1H- Tetrazol-5-yl) acrylonitrile derivatives, the results of which are summarized in Table 3.

Table 3 Scope of the 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives catalysed using Cu@APS-TDU-PMO (1)^a.

Entry	Substrate (2)	product	Time (min)	Yield (%)
1			50	97
2			52	93
3			55	92
4			60	89
5			60	91
6			56	93
7			53	92
8			56	89
9			52	92

^aReaction conditions: aldehydes (2a, 1 mmol), malononitrile (3, 1 mmol), sodium azide (4, 1.2 mmol) and Cu@APS-TDU-PMO (1, 0.03 g) under different conditions.

The proposed mechanism for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives

The proposed mechanism for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives is shown in scheme 2. Initially, the carbonyl group of aromatic aldehyde and the nitrile group of malononitrile are activated by the Cu@APS-TDU-PMO (1) catalyst. The Knoevenagel condensation reaction between the aromatic aldehyde and the malononitrile results in intermediate (I) formation. Then, Cu from the catalyst activates N of the intermediate (I), leading to [3+ 2] cycloaddition reaction between intermediate (I) and sodium azide. Subsequently, the catalyst was separated from intermediate (II) using an aqueous solution of HCl (acidic conditions) to obtain intermediate (II). Finally, 2-(1H-tetrazol-5-yl) acrylonitrile derivative as a more desirable tautomer was created via the tautomerization of intermediate (II).

Comparison of the catalytic activity of Cu@APS-TDU-PMO (1) catalyst

Table 4 compares the catalytic activity of Cu@APS-TDU-PMO (1) with other catalysts reported in the literature for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives. Specific properties of Cu@APS-TDU-PMO (1) catalyst, such as high efficiency, low catalyst loading, short reaction time, elimination of corrosive or expensive reagents, and reusability, make it superior to other reported catalysts.

Table 4 compares the catalytic activity of Cu@APS-TDU-PMO (1) with other catalysts reported.

Entry	Catalyst	Catalyst loading	Tempereture(°C)	Time (min)	References
1	Nano-NiO	0.06 mmol	70	360	⁹⁴
2	Fe₃O₄@APTMS-DFX	0.03 g	120	60	⁹⁵
3	Cu-MCM-41	0.03 g	140	720	⁹⁶
4	Mesoporous ZnS	1 mmol	120	36 h	⁹⁷
5	Cu@APS-TDU-PMO (1)	0.03 g	110	30	This work

Recyclability of Cu@APS-TDU-PMO (1)

Performing chemical reactions using recyclable and reusable catalysts is a significant issue in terms of green chemistry and environmental protection. In this study, recyclability of the catalyst was also investigated. For this purpose, the catalyst was separated from the reaction mixture using filtration, then washed with EtOH, and dried at 60 °C. The recycled catalyst was used in four consecutive reactions under optimal conditions for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives. As shown in Fig. 7, the catalytic activity of Cu@APS-TDU- PMO (1) was slightly decreased from 97 % to 85 %.

Materials and Instrumentation

All chemicals were purchased from Merck or Aldrich. Characterization of the new Cu@APS-TDU-PMO (1) was performed by FESEM (TESCAN-MIRA3), TEM (Philips EM 208S), FTIR (Shimadzu 8400S), BET (ASAP 2020 micromeritics), and TGA Bahr Company STA 504). XRD patterns of the mesoporous silica nanosphere were obtained using TW 1800 diffractometer with Cu_Ka radiation (λ = 1.54050 Å). ¹H NMR (500 MHz, Bruker DRX-500 Avance spectrometers in DMSO) spectral were compared with those obtained from authentic samples or reported in the literature. Distilled water was used in all experiments.

General procedure for the preparation of 1,3-bis(3-(triethoxysilyl)propyl) urea bridge

First, (3-aminopropyl) triethoxysilane (APS, 6.52 mL) was added dropwise to 2,4-toluene diisocyanate (2 mL) and the mixture was stirred under solvent-free condition at 75°C for 4 h. Then, the mixture was cooled down to room temperature and stirred for 12 h to obtain a white gel. Subsequently, CHCl₃ (10 mL) was added to the white gel and a clear solution was obtained, then hexane (10 mL) was added to it and a white precipitate was obtained which was separated by filtration and washed with hexane and dried at 70 °C.

General procedure for the preparation of PMO

P123 (4 g) as a surfactant was dissolved in 150 mL HCl (2M) and heated to 40 °C under stirring for 4 h. Then, the white powder (3.5 g) prepared above was dissolved in CHCl₃ and with TEOS (11.8 mL) added dropwise and simultaneously to the solution of P123 and HCl and stirred for 24 h at 40 °C and then aging for 48 h at 100 °C. Eventually, washed with EtOH (5 mL) and hexane (5 mL) and dried at 80 °C. The surfactant was extracted by a Soxhlet via EtOH-acidic. Finally, it was dried at 100 °C for 12 h.

General procedure for the preparation of Cu@APS-TDU-PMO (1)

Cu(OAc)₂ (0.5 g) was dissolved in 5 mL distilled water and this solution was added slowly to the suspension of PMO-APS-TDU (0.5 g) in 10 mL distilled water. The solution was stirred at room temperature for 24 h. Finally, the resulting solid was collected, washed with H₂O and EtOH, and dried at 60 °C for 5 h (Scheme 3).

General procedure for the preparation of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives

Cu@APS-TDU-PMO (1, 0.03 g), aromatic aldehyde (2a-i, 1 mmol), malononitrile (3, 1 mmol), and NaN₃(4, 1.20 mmol) were heated to 110 °C under solvent-free conditions. The reaction development was monitored by TLC. After completion of the reaction, the reaction mixture dissolved in HCl (2M, 15 mL) and the catalyst was separated by filtration, then the resulting solution was extracted with EtOAc (3×10 mL). Finally, the solvent evaporated under reduced pressure and the desired product was recrystallized with EtOH-H₂O to afford the pure product. The recovered catalyst was reused for subsequent cycles without a loss of performance.

The FTIR, ¹HNMR and ¹³CNMR data of tetrazole derivatives

3‑(2‑Chlorophenyl)‑2‑(1H‑tetrazole‑5‑yl) acrylonitrile (5b)

FTIR (KBr, cm^-1): 3420 (NH), 2221 (CN), 1564 (C=C).; ¹HNMR (500MHz, CDCl₃): δ (ppm) 7.58–7.59 (2H, d, CH-Ar), 7.61–7.69 (1H, t, J= 7.20 Hz, CH-Ar), 8.13–8.14 (1H, d, CH-Ar), 8.54(1H, s, CH), 13.22 (br s, NH).; ¹³CNMR (75 MHz, CDCl₃) δ (ppm) 80.14, 116.80, 129.17, 129.88, 130.73, 131.97, 134.39, 135.19, 147.04, 159.07, 161.37.

3‑(4‑Methoxyphenyl)‑2‑(1H‑tetrazole‑5‑yl) acrylonitrile (5g)

FTIR (KBr, cm^-1): 3146 (NH), 2224 (CN), 1586 (C=C).; ¹HNMR (500MHz, CDCl₃): δ (ppm) 3.82 (3H, s, OCH3), 7.09–7.11 (1H, d, CH-Ar), 7.96–7.99 (1H, d, CH-Ar), 8.21 (1H, s, CH), 13.70 (br s, NH). ¹³CNMR (75 MHz, CDCl₃) δ (ppm) 56.02, 93.70, 115.25, 116.55, 125.21, 132.61, 147.97, 155.85, 162.91.

In conclusion, 2,5-toluenediisocyanate-based Cu@APS-TDU-PMO (1) with Cu nanoparticle loading was synthesized on the surface of pore wall. The synthesized Cu@APS-TDU-PMO (1) was characterized by using FTIR, EDX, TGA, XRD, FESEM, BET, and TEM techniques. It showed unique characteristics such as porous structure with adjustable pore size, high thermal stability, large surface area, and uniform pore size distribution. The synthesized Cu@APS-TDU-PMO (1) was efficiently used as a promising and recyclable catalyst for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives. In addition, the catalyst can be easily separated by filtration and used several times without significant reduction in catalytic activity. Other

Availability of data and materials

The datasets generated and/or analysed during the current study would be available in the Science Data Bank repository after acceptance of the manuscript.

Acknowledgements

We are grateful for the financial support from The Research Council of Iran University of Science and Technology (IUST), Tehran, Iran (Grant No 160/20969) for their support. We would also like to acknowledge the support of The Iran Nanotechnology Initiative Council (INIC), Iran.

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Schemes 1, 2 and 3 are available in Supplementary Files section.

No competing interests reported.

Scheme01.png
Scheme 1. Cu@APS-TDU-PMO (1) for the three-component condensation of aldehydes (2a-i), malononitrile (3), and sodium azide (4).
Scheme02.png
Scheme 2. The proposed mechanism for the synthesis of 2-(1H-Tetrazol-5-yl) acrylonitrile derivatives.
Scheme03.png
Scheme 3. General procedure for the preparation of Cu@APS-TDU-PMO (1).
SupportingInformation3.docx

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Design, synthesis and characterization of a urea-bridged periodic mesoporous organosilica supporting Cu nanoparticles (Cu@APS-TDU- PMO) as highly efficient and recoverable catalyst for the synthesis of tetrazole derivatives

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