An Efficient Microwave-Assisted Synthesis Method of Novel Bi2O3 Nanostructure and Its Application As a High-Performance Nanocatalyst in Preparing Benzylidene Barbituric Acid Derivatives

doi:10.21203/rs.3.rs-966810/v1

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An Efficient Microwave-Assisted Synthesis Method of Novel Bi₂O₃ Nanostructure and Its Application As a High-Performance Nanocatalyst in Preparing Benzylidene Barbituric Acid Derivatives

https://doi.org/10.21203/rs.3.rs-966810/v1

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In this study, controllable and optimal microwave irradiation has been used to synthesize the novel nanostructures of Bi₂O₃ under environmental conditions. The final products had a thermal stability of 210 °C, an average particle size distribution of 85 nm, and surface area of 783 m²/g. The high thermodynamic stability of Bi₂O₃nanostructures were confirmed by TG and DSC analyses. The nanostructure nature of compounds, most importantly, the use of effective, cost effective and rapid synthesis route of microwave have created significant physiochemical properties in the Bi₂O₃ products. These unexpected properties have made the possibility of potentials application of these products in various fields, especially in nanocatalyst applications. It is well-documented that, as Lewis acid, bismuth nanocatalyst exhibits a great catalytic activity for the green synthesis of some bio-active barbituric acid derivatives using precursors with electron-donating or –withdrawing nature in high yields (80-98%). After incorporating this catalyst into the aqueous media, all the reactions were completed within 2-3 min at room temperature. The main advantages of this method are practical facility, the availability of starting materials, and low costs besides the catalyst reusability. Additionally, the catalyst synthesis process may be carried in the aqueous media during a short period with medium to high yields. The obtained results have opened a new window for development of a novel nanocatalyst with practical application.

Nanoscience

Bi2O3 nanostructure

Efficient synthesis route

Novel catalyst

Benzylidene barbituric acid

Bi₂O₃ nanostructures are one of the most important products from transition metal oxides [1]. These structures, because of having special properties, attracted particular attention to themselves in recent decade [2]. Among their extraordinary properties, the dielectric, piezoelectric, corrosion resistance, environmental compatibility and low-cost properties can be mentioned [3–5]. The surface and physic-chemical natures of Bi₂O₃ is such that electron transfers are easily exchanged between photo-generated and electron-hole pairs and as a result, these compounds can be used as a critical nanostructure in various fields [6, 7].

Metal oxide nanostructures are produced by various methods, among which hydrothermal [8], ultrasonic [9], sol-gel and other conventional methods [10] can be mentioned. Many of these methods require specific conditions that not only cause the reactions under controlled conditions, but also leave many environmental impacts.

In order to overcome these problems, the microwave route has been proposed as an effective method to prepare of various structures. Among the advantages of this method, it can be mentioned that the time duration of the synthesis process is reduced. The reactions are also carried out under low temperature, and carbon dioxide emission is reduced compared to other methods. In addition, the major difference in using microwave irradiation compared to other conventional methods is that in the usual methods, at first, heat is irradiated to the surface of the material and then it is transmitted to the inside of the bulk. But in microwave methods, electromagnetic energy directly enters the structure of material. As a result of homogeneous irradiation of heat, the optimum use of energy is made, which creates desirable physiochemical properties in the structure.

As a cyclic-amide, barbituric acid is the raw material in the synthesis of barbiturates. The mixtures of the derivatives of this material with alkyls and aryls exhibits hypnotic and seductive effects [11] Several derivatives of 5-arylidene barbituric acid have been more concerned as the raw material, which encompass the intermediate in the synthesis of benzyl barbituric derivatives [12] as well as heterocyclic compounds [13] asymmetrical disulphides [11] oxadiazaflavines [14]. Moreover, these derivatives have been extensively exploited in the pharmaceutical industry as anesthetics and central nervous system depressants [15, 16], local anaesthetic ,antispasmodic, sedative, hypnotic [17], antimicrobial, antifungal, antitumor [18], anticonvulsant [19] and anticancer [20], as well as complex and salt formation reagent [21–25], analgesic, bronchodilator, vasodilator, anti-parkinsonian, antimalarial and anti-allergic agents [26–30].

Various synthetic methods have been introduced for the preparation of 5-arylidene barbituric acid derivatives, in which different catalysts, including solvent free grinding using NH₂SO₃H [31] microwave irradiation [32] an infra-red promoted route [33] and condensation using ionic liquid media [34] are employed.

Although some researchers have reported this reaction with the use of no catalyst [35, 36], the following catalysts are used and introduced in this regard: [DABCO](SO₃H)₂Cl₂ [37], [DABCO] (SO₃H)₂(HSO₄)₂ [38], p- nanoporous MMT-HClO₄ [39], dodecylbenzenesulfonic acid (DBSA) [40], FeCl₃.6H₂O [41] ethylammonium nitrate [42], silico-tungstic acid [43], amino-sulfonic acid [31], NaOH/fly ash [44], sodium p-toluene sulfonate (NaPTSA) [45], CoFe₂O₄-NPs [46], non-catalyst/infrared irradiation [33], BF₃/nano γ-Al₂O₃ [47] succinimidinium N-sulfonic acid hydrogen sulfate ([SuSA-H]HSO₄) [48], basic alumina [49], Verjuice [50], sulfonic acid functionalized nanoporous silica (SBA-Pr-SO₃H) [37], copper oxide nanoparticles (CuO-NPs) [51], aminosulfonic acid (NH₂SO₃H) [31], 2-amino-3-(4-hydroxyphenyl) propanoic acid (L-tyrosine) [52], CoFe₂O₄ nanoparticles [46], sodium acetate (CH₃COONa) [53], 1-n‐butyl‐3‐methylimmidazolium tetrafluoroborate ([bmim]BF₄) [34], polyvinyl pyrrolidone stabilized nickel nanoparticles (PVP-Ni-NPs) [54], cetyltrimethyl ammonium bromide (CTMAB) [55], ethyl ammonium nitrate (EAN) [42], ZrO₂/SO₄⁻² [56], sodium p-toluene sulfonate (NaPTSA) [45], Ce₁MgxZr_1−xO₂ (CMZO) [57], taurine [58]. The methods adopted to produce these heterocyclic compounds have been useful and effective; however, the methods also have their own disadvantages and drawbacks, including expensive catalysts and reagents, harsh conditions for the catalyst synthesis, the use of contaminated organic solvents and/or corrosive inorganic acids, tedious laboring, non-reusability of the catalyst, and the need for extra amounts of this reagent or the others as well as the incorporation of self-condensation and bis-addition.

Using water as the reaction medium, in addition to providing the advantage of organic synthesis in an aqueous medium, directs the procedure toward a more environmentally-benign path. Moreover, in situ reductant generation decreases the purification steps and the waste generation, which facilitates the procedure and makes it more practical.

Cobalt nanocatalyst has been utilized successfully so that it leads to the desirable results in the synthesis of arylidene barbituric acid derivatives.

In this work, novel nanostructures of Bi₂O₃ products are prepared under microwave irradiations with ideal physiochemical properties. For this purpose, final nanostructures were characterized by relevant analyses, and the microwave process was optimized to select the desired products. Finally, the practical application of these nanostructures was investigated in the nanocatalyst reaction of preparation benzylidene barbituric acid derivatives.

Chemicals and reagent

Al₂O₃.4SiO. H₂O (MW: 224.145 g/mol, 99.99%), Bi (NO₃)₃.5H₂O (MW: 485.0715 g/mol, 99.98%) as well as barbituric acid and aromatic aldehyde derivatives were supplied from Merck Chemical Company. The as-received materials were used with no purification.

Material characterization

The thermodynamic behavior of the Bi₂O₃ nanostructures were analyzed with 5 K/min using Thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC) system (Netzsch QMS403C). The X-ray diffraction (XRD) patterns of the samples were analyzed on XPert PRO PANalytical diffractometer using CuKa radiations. XRD was performed at 2theta range of 10–90. The surface morphology of Bi₂O₃ nanocatalyst was evidenced from the scanning electron microscopy (SEM, Hitachi, S-4800, 25 15 kV). The Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) measurements were applied using Micrometrics ASAP2010analyzer to calculate the surface area and pore-size distributions of crystals scratched from the Bi₂O₃ nanostructures. The magnetic hysteresis loops were recorded using vibrating sample magnetometer (Changchun Yingpu, VSM-300). FT-IR spectroscopy were performed by a Perkin-Elmer FT-IR 240-C spectrophotometer (KBr). ¹³C NMR and ¹H NMR (400 MHz) spectra were obtained by a Bruker Av-400 spectrometer in DMSO-d₆ using tetramethylsilane (TMS) as the internal standard. Melting points were measured using Electrotermal 9100 apparatus and were then corrected. The progress of reactions was assessed using thin layer chromatography (TLC), and the products were identified based on their melting points and IR spectra, in comparison to the authentic samples and those reported in the literature. The reaction yields were estimated with regard to the isolated products.

Catalyst preparation

In order to synthesize of Bi₂O₃ nanostructures, the solutions including 2 mmol Bi (NO₃)₃.5H₂O in 10 mL ethylene glycol (Sol. a), and 2 mmol Al₂O₃.4SiO.H₂O in 10 mL ethylene glycol (Sol. b) were separately prepared under environmental conditions. The obtained solution (Sol. a and Sol. b) was stirred at temperature of 60°C for a period of 20 min. The obtained mixture has been entered into a microwave reactor and has been placed under the optimal conditions of 120 W for time duration of 15 min at microwave temperature of 26°C. Calcinations` procedure were then performed on the sample so that a pure Bi₂O₃ nanostructure was created. At the end, the products were washed three times with distilled water to eliminate impurities existing in the structure. Also, in order to dry the products, they have been placed in the oven up to 80° C. After 2 h, the primary nuclei related to the formation of Bi₂O₃ nanocrystals were formed.

General procedure for the preparation of benzylidene barbituric acid derivatives: A mixture of barbituric acid (1 mmol), aldehyde (1 mmol) and 20 W% (0.029 g) Bi₂O₃ nanocatalyst in water (10 mL) was stirred at room temperature. The completion of the reaction was monitored by TLC [ethyl acetate: n-hexane (4:6)]. To gain pure benzylidene barbituric acid derivatives, when the reaction was completed, the mixture was filtered, and the solid retentate was washed three times with 10 mL water.

Charactrization of Bi₂O₃ nonocatalyst

Thermodynamic and nanocrystalline behaviors

Figure 1a. shows the thermodynamic behaviour of Bi₂O₃ samples from environment temperature up to 700°C. Based on TG analysis, four observable peaks have been presented. The peak at temperature of 60°C was related to evaporation of surface water. In the second stage (91°C), the impurities and solvents trapped in the network were vanished. In order to create a pure Bi₂O₃ sample, it was better to heated up the samples to this temperature range. A considerable weight reduction occurred within the temperature of 214°C, which can be attributed to the destruction of the B₂O₃ sample. The remaining sample components also collapsed at 368°C.

Based on DSC curve, the presence of endothermic peaks showed the energies required for weight reduction of the Bi₂O₃ sample components in each one of the mentioned stages. Since each one of the DSC peaks was in accordance with the TG data, therefore, the product had not undergone phase change in the above temperature range [59]. These results were consistent with the XRD data that confirmed the presence of pure single phase in the Bi₂O₃ sample.

The XRD patterns of the nanostructures have been presented in Figure 1b. The diffracted peaks indicated that the sample has been indexed in the BCC system with the Bi₂O₃ crystalline phase (JCPDS No. 34-0097) [60].

Based on the results, no peaks related to the presence of impurity or the formation of multiple phases has been observed, which confirmed the successful synthesis of the pure structure of Bi₂O₃ samples. The presence of some sharp peaks indicated that the samples had a high crystalline structure [61]. As a result, the effective microwave route affected the formation of Bi₂O₃ nanocatalyst with high purity and significant crystalline percentages (Fig. 1).

Morphology And Size Distribution

The morphology and particle size distribution of Bi₂O₃ sample with various magnifications have been shown in Figure 2a and b. According to these images, the SEM micrographs confirmed the formation of Bi₂O₃ crystals with tiny sizes. The size of crystals was in the nanometric range, which was in accordance with the XRD results. Also, SEM results showed that the surface morphology of both samples was plate-like nanostructures and particles have been distributed uniformly without any evidence of agglomeration. In addition, the Bi₂O₃ samples showed a dense surface with good connections between the crystals (Fig. 2).

Textural and magnetic properties

The N₂ adsorption/desorption isotherm and the porosity of Bi₂O₃ nanocatalyst synthesized under optimal conditions of microwave irradiation has been exhibited in Figure 3a and b, respectively. According to classical isotherms [62], Bi₂O₃ sample had the adsorption/ desorption behavior similar to the type IV isotherms, which indicated the mesoporous size distribution for them [63]. Based on the BJH method, the Bi₂O₃ samples also had an average pore size distribution of 4 nm, which was in accordance with the type IV isotherms. According to the results obtained from BET technique, the sample had a surface area of about 783 m²/g [64], which was considerable compared to the previous samples. The increase of surface area and porosity of the products can be attributed to the desirable conditions of nucleation, growth of crystals, as well as the effective impact of microwave synthesis parameters (Fig. 3) [65].

Figure 4 exhibits the magnetic hysteresis of the Bi₂O₃ nanostructures prepared by microwave route under optimal condition. The saturation magnetization of this novel nanocatalyst is about 65/4 emu/g. Also, it displays a small coercivity along with narrow hysteresis that confirmed the soft magnetic properties for this samples. This can be related to the results of small crystalline size of Bi₂O₃ nanostructure that approved the inversely relation between coercivity and size distribution by D6 [66].

Synthesis of benzylidene barbituric acid using Bi₂O₃ nanoparticles

This project mainly aimed to synthesize recyclable bismuth oxide nanoparticles using a facile, high-performance and pro-environmental method. The nanoparticles were used as the catalyst in the production process of the arylidene barbituric acid derivatives (Scheme 1).

The performance of Bi₂O₃ nanocatalyst was investigated using barbituric acid (2) and 4-chlorobenzaldehyde (1j), as the model substrate. In order to optimize the reaction conditions, various weight percentage of catalyst and diverse solvents were exploited.

Firstly, the model reaction was performed solvent-free with no catalyst. As expected, the reaction did not happen noticeably. In addition, in another test, no reaction happened in the absence of the solvent and the presence of the catalyst (Table 1, Entry 1, 2). Afterwards, with the use of the catalyst (20 Wt%) and several solvents, which were different in terms of polarity and protic nature, such as methanol, ethanol, C₂H₅OH/H₂O, chloroform, toluene, dichloromethane, and acetonitrile, the reaction was re-assessed. Monitoring the reaction revealed that the polar solvents such as methanol, ethanol, and acetonitrile were much effective than the non-polar ones. This might be attributed to the much better dispersion of the catalyst as well as much better solubility of the reagents in the polar solvents. In the next experiment, water as a green solvent was used and the reaction progress was assessed. It was found out that the synthesis of arylidene barbituric acid catalyzed by Bi₂O₃ nanostructure was progressed with higher yields (Table 1).

Table 1

Synthesis of 3j in the presence of different solvents and amounts of catalyst
Entry	Catalyst (W%)	Solvent	Time (h/min)	Temp.	Yield (%)
1	----	-----	N.R	r.t.	---
2 3	Bi₂O₃ 20% ----	----- H₂O	N.R 24 h	r.t. r.t.	--- 33
4	Bi₂O₃ 20%	H₂O	2 min	r.t.	91
5	Bi₂O₃ 20%	EtOH	3 min	r.t.	40
6	Bi₂O₃ 20%	EtOH/H₂O (1:1)	3 min	r.t.	36
7	Bi₂O₃ 20%	CH₃OH	3 min	r.t.	35
8	Bi₂O₃ 20%	CH₃CN	3 min	r.t.	32
9	Bi₂O₃ 20%	CHCl₃	3 min	r.t.	24
10	Bi₂O₃ 20%	CH₂Cl₂	3 min	r.t.	23
11	Bi₂O₃ 20%	C₇H₈	3 min	r.t.	18
12	Bi₂O₃ 5%	H₂O	2 min	r.t.	73
13	Bi₂O₃ 10%	H₂O	2 min	r.t.	87
14	Bi₂O₃ 15%	H₂O	2 min	r.t.	89
15	Bi₂O₃ 25%	H₂O	2 min	r.t.	58
16	Bi₂O₃ 30%	H₂O	2 min	r.t.	52
17	Bi₂O₃ 35%	H₂O	2 min	r.t.	46

Optimizing the consumption of Bi₂O₃ nanocatalyst showed that its concentration plays a decisive role in the reaction efficiency as such increasing the catalyst concentration from 5 to 20 W% raised the product yield. On the other hand, the catalyst concentrations above 20 W% reduced the yield. Consequently, the optimum level of the catalyst was set as 20 W% for the reaction at room temperature (Table 1).

After optimizing the catalyst, the reactions of different aldehydes with both electron-donating and withdrawing substitutions were studied. It was noticed that the nanocatalyst can catalyze their conversion to the corresponding products in high yields during short reaction time. In fact, electron-donating and withdrawing functional groups on the aromatic ring of aldehydes have no considerable effect on their reaction’s yields (Table 2).

Table 2

benzylidene barbituric acid derivatives obtained via the Knoevenagel condensation of benzaldehyde derivatives and barbituric acid using Bi₂O₃ nanocatalyst
Entry	Ar	X	Product	Time (min)	Yield (%)^a	\(\frac{\varvec{m}.\varvec{p}. (?)}{\varvec{O}\varvec{b}\varvec{s}\varvec{e}\varvec{r}\varvec{v}\varvec{e}\varvec{d} \varvec{R}\varvec{e}\varvec{p}\varvec{o}\varvec{r}\varvec{t}\varvec{e}\varvec{d} }\)	Ref
1	2-OHC₆H₄-	O	3a	3	93	248-250 249-250	[39]
2	4-MeOC₆H₄-	O	3b	3	97	295-297 294-297	[67]
3	2-MeOC₆H₄-	O	3c	3	90	267-269 268-269	[39]
4	P-(Me)₂NC₆H₄-	O	3d	3	97	277-279 278-279	[39]
5	C₆H₅CH=CH-	O	3e	3	95	267-268 268	[67]
6	4-OHC₆H₄-	O	3f	3	98	>300 >300	[67]
7	2-NO₂C₆H₄-	O	3g	3	97	271-274 271-273	[67]
8	4-NO₂C₆H₄-	O	3h	3	76	269-271 268-270	[39]
9	2-ClC₆H₄-	O	3i	3	96	250-252 249-251	[67]
10	4-ClC₆H₄-	O	3j	3	94	298-300 298-300	[67]
11	3-NO₂C₆H₄-	O	3k	3	94	227-229 226-228	[67]
12 13 14 15	C₆H₅- 3,4,5-(OCH₃)₃C₆H₂- 2,4-Cl₂C₆H₃- 4-OH-3-OCH₃C₆H₃-	O O O O	3l 3m 3n 3o	3 3 3 3	96 98 95 97	250-252 249-252 249-250 238-250 268-270 265-270 292-293 293-294	[67] [69] [57] [57]
^a Isolated yield.

Compared to our previous reports on the production of benzylidene barbituric acid in the presence of Co₃O₄ nanocatalyst at 90°C, the results of this experiment are quite remarkable and promising in terms of the reaction conditions (i.e., aqueous medium, room temperature and short periods of time). In most cases, the magnet was stopped as soon as the catalyst was introduced into the reaction medium, and in most cases the reaction was completed in less than 3 minutes.

All the products were identified by infrared (IR) spectroscopy, and their melting points were compared with the reference data. For more certainty, the structure of the product “3m, 3n and 3o” was verified using ¹H NMR spectroscopy as well.

For compound 3m, the main absorption peaks in FT-IR spectrum were appeared at the wavenumbers of 1654, 1733, 1751, 3240 and 3629 cm⁻¹, which are attributed to C=C bond, two groups of C=O stretching vibration, sp² C-H stretching and the secondary N-H stretching, respectively. In ¹H NMR spectral analyses of this compound it was observed that two characteristic singlets in 𝛿 11.37 and 11.24 ppm for the NH groups of pyrimidine ring and other singlets at 𝛿 8.27 and 7.84 ppm due to aromatic protons and CH=C olefin proton and aromatic protons respectively. Also, two signals for the methoxy groups appeared in 𝛿 3.79 and 3.82 ppm. It indicated that barbituric acid was added successfully to 3,4,5-trimethoxy benzaldehyde and the compound “3m” was prepared.

5-(3,4,5-trimethoxybenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (3m): Yield 98%. MP = 249-250 \(℃\). IR (KBr, cm⁻¹): 3629, 3240, 1751, 1733, 1654. ¹H NMR (400 MHz, CDCl₃) δ: 3.79 (s, OCH₃), 3.82 (s, 2 OCH₃), 7.84 (s, H-Ar), 8.27 (s, 1H, CH=C), 11.24 (s, NH), 11.37 (s, NH).

5-(4-hydroxy-3-methoxybenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (3o): Yield 97%, MP = 293-294. IR (KBr, cm⁻¹): 3277, 1748, 1696, 1664. ¹H NMR (400 MHz, CDCl₃) δ: 3.83 (s, CH₃O), 6.90 (d, J = 8.4 Hz, ArH), 7.81 (dd, J = 8 Hz, 1.8 Hz, H-Ar), 8.47 (d, J = 2 Hz, H-Ar), 8.22 (s, H-Ar), 10.56 (s, OH), 11.14 (s, NH), 11.26 (s, NH).

5-(2,4-dichlorobenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (3n): Yield 95%. MP = 268-270 \(℃\). IR (KBr, cm⁻¹): 3218, 1741, 1675. ¹H NMR (400 MHz, CDCl₃) δ: 7.48 (dd, J = 8.4, 2 Hz, H-Ar), 7.53 (dd, J = 8.4, 2 Hz, H-Ar), 7.81 (d, J = 2 Hz, H-Ar), 8.21 (s, 1H, CH=C), 11.29 (s, NH), 11.49 (s, NH).

To investigate the potential of this catalytic procedure and to fulfill the requirements of green chemistry, the catalyst reusability was evaluated with regard to the model reaction. The product of each step was dissolved in warm ethyl acetate, and the catalyst was subsequently recovered by centrifuging. In order to remove tars more efficiently from the catalyst surface, it was rinsed with H₂O twice and then used with no further purification in the next run. On the other hand, the solvent was removed by evaporation, and the product residue was gathered. The yields of four successive cycles from the first to fourth runs at room temperature were 98%, 95%, 93%, and 90%, respectively (Table 3). The results show no significant decrease in the performance of the recovered catalyst compared to the fresh state; hence, the catalyst could be reused several times successively.

Table 3

Reusability of the catalyst in the preparation of 5-benzylidene barbituric acid derivative of 4-chlorobenzaldehyde
Run	Yield of 3n (%)
First of renewed catalyst	98
Second of renewed catalyst	95
Third of renewed catalyst	93
Fourth of renewed catalyst	90

The possible mechanism of barbituric acid and aryl aldehyde reaction, known as “Knoevenagel condensation”, is illustrated in scheme 2. The barbituric acid structure first converts to the enol form (keto-enol tautomerism in the first step) and it then attacks to the aldehyde (second step) activated by Bi₂O₃ nanocatalyst as a Lewis acid. Finally, the dehydration process leads to the final product (last step).

Comparison of the catalytic ability

With the aim of demonstrating the potential and the performance of the proposed method in preparing this type of compound, the method was compared with some other previously reported methods. Table 4 summarizes the results of the comparison. It can be noticed that this novel method is superior to many others, especially in terms of reaction time, catalyst reusability, and bio-environmental considerations.

Table 4

Comparison of various methods for the synthesis of (thio)barbituric acid
Entry	Catalyst	Amount of catalyst	Conditions	Time (min)	Yield (%)	Ref
1	BF₃/nano-ᵞ-Al₂O₃	60 mg	Ethanol/r.t.	30	84	[48]
3	PVP-Ni Nps	100 mg	Ethylene glycole, 50\(℃\)	10-15	93	[55]
4	[bmim]BF₄	0.2 mL	Grinding-laying	120	78	[35]
5	EAN	2 mL	r.t.	180	83	[43]
7	CH₃COONa	100 mol%	Grinding	10	91	[54]
8	CMZO	200 mg	EtOH, 60-70\(℃\)	60	85	[58]
9	P-Dodecylbenzene sulfonic acid (DBSA)	30 mol%	H₂O, reflux	67	62	[41]
10	[H₂-pip][H₂PO₄]₂	5 mol%	H₂O/EtOH (1:1) 80°C	20	96	[68]
11	Taurine	20 mol%	H₂O, 90\(℃\)	9	96	[59]
12	FeCl₃.6H₂O	15 mol%	H₂O, reflux	35	80	[42]
13	NPs MMT-HClO₄	10 mg	H₂O, 70\(℃\)	4	94	[40]
14	NaPTSA/r.t.	50 mol%	r.t.	4	92	[46]
15	Verjuice	10 mL	60\(℃\)	7	96	[51]
16	CoFe₂O₄ NPs	1 mol%	H₂O, EtOH/r.t.	2-6	94-80	[47]
17	[SuSA-H]HSO₄	5 mol%	H₂O/ r.t.	2-12	80-98	[49]
18	Co₃O₄ nanocatalyst	20 W%	H₂O/ r.t.	3-25	98	[69]
19	Bentonite (Al₂O₃.4SiO.H₂₎	25 mol%	90\(℃\)/H₂O	5-25	90-98	[70]
20	Bi₂O₃ nanocatalyst	20 W%	H₂O/r.t.	3	98	This work

In this work, an effective strategy of the microwave route has been proposed to synthesize Bi₂O₃ nanostructures with single phase over a short period of time and with optimal energy. This cost effective, efficient, and environment friendly route has created controlled properties of products that affected their catalytic applications. The results of the related analyses indicated that the Bi₂O₃ samples had, high thermal stability, narrow particle size distribution, and a desirable surface area. These properties differentiated the Bi₂O₃ nanocatalysts developed in this study from the previous samples. The results showed that the application of optimal conditions of the microwave irradiation also affected the catalytic efficiency of the Bi₂O₃ products.

So, the prepared Bi₂O₃ nanocatalyst is introduced as an efficient nanocatalyst to catalyze the synthesis of benzylidene barbituric acid derivatives. Short reaction time, facile work-up process, recyclability of the catalyst, economical advantage and aquatic medium make this method promising. This method is attractive due to its safe and environment-friendly process.

Acknowledgements

The author express appreciation to the Islamic Azad University (Kerman Branch), for supporting this investigation.

Authors’ contributions

E.Sh. proposed the ideas, analyzed the result data and reviewed and edited the manuscript, M.Y. completed the experiment, analyzed the result data and wrote the manuscript, S.A and D.Gh played the role of consultant in the research stages. This article has been read by all authors and agreed to be published.

Funding

The authors received no specific funding for this work.

Conflict of interest

The authors declare that they have no conflict of interest.

Availability of Data and Supporting Materials

A The datasets supporting the conclusions of this article are included within the article and All data are fully available without restriction.

Competing interests

The authors declare that they have no competing interests.

Author details

Department of Chemistry, Kerman Branch, Islamic Azad University, Kerman, Iran.

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GraphicalAbstract.docx
Scheme01.png
Scheme 1. Synthesis of arylidene barbituric acid derivatives using Bi2O3 nanocatalyst under optimized conditions
Scheme02.png
Scheme 2. Proposed mechanism for the synthesis of arylidene barbituric acid derivatives in the presence of Bi2O3 nanocatalyst

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An Efficient Microwave-Assisted Synthesis Method of Novel Bi₂O₃ Nanostructure and Its Application As a High-Performance Nanocatalyst in Preparing Benzylidene Barbituric Acid Derivatives

Status:

Version 1

Abstract

Figures

Introduction

Experimental

Chemicals and reagent

Material characterization

Catalyst preparation

Results And Discussion

Charactrization of Bi₂O₃ nonocatalyst

Thermodynamic and nanocrystalline behaviors

Textural and magnetic properties

Synthesis of benzylidene barbituric acid using Bi₂O₃ nanoparticles

Comparison of the catalytic ability

Conclusion

Declarations

References

Supplementary Files

Status:

Version 1

An Efficient Microwave-Assisted Synthesis Method of Novel Bi2O3 Nanostructure and Its Application As a High-Performance Nanocatalyst in Preparing Benzylidene Barbituric Acid Derivatives

Status:

Version 1

Abstract

Figures

Introduction

Experimental

Chemicals and reagent

Material characterization

Catalyst preparation

Results And Discussion

Charactrization of Bi2O3 nonocatalyst

Thermodynamic and nanocrystalline behaviors

Textural and magnetic properties

Synthesis of benzylidene barbituric acid using Bi2O3 nanoparticles

Comparison of the catalytic ability

Conclusion

Declarations

References

Supplementary Files

Status:

Version 1

An Efficient Microwave-Assisted Synthesis Method of Novel Bi₂O₃ Nanostructure and Its Application As a High-Performance Nanocatalyst in Preparing Benzylidene Barbituric Acid Derivatives

Charactrization of Bi₂O₃ nonocatalyst

Synthesis of benzylidene barbituric acid using Bi₂O₃ nanoparticles