Preparation of 2,3-diarylthiazolidin-4-one derivatives using barium molybdate nanopowders

Article abstract of DOI:10.1080/15533174.2014.988227

Barium molybdate (BaMoO₄) nanopowder was successfully synthesized via a simple precipitation route without any surfactant. The prepared nanopowder was applied for the facile synthesis of 2,3-diarylthiazolidin-4-one derivatives using cyclization

Full text of DOI:10.1080/15533174.2014.988227

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Preparation of 2,3-diarylthiazolidin-4-one derivatives
using Barium molybdate nano powders
Hadi Taghrira & Majid Ghashangb
a 1Department of Chemistry, Science and Research Branch, Islamic Azad university, Arak, Iran
b 2Department of Chemistry, Faculty of Sciences, Najafabad Branch, Islamic Azad University,
Najafabad, Esfahan, Iran; P.O. Box: 517
Accepted author version posted online: 09 Mar 2015.
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To cite this article: Hadi Taghrir & Majid Ghashang (2015): Preparation of 2,3-diarylthiazolidin-4-one derivatives using
Barium molybdate nano powders, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, DOI:
10.1080/15533174.2014.988227
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Preparation of 2,3-diarylthiazolidin-4-one derivatives using Barium molybdate nano
powders
Hadi Taghrir1 and Majid Ghashang *,2
1Department of Chemistry, Science and Research Branch, Islamic Azad university, Arak, Iran.
2Department of Chemistry, Faculty of Sciences, Najafabad Branch, Islamic Azad University,
Najafabad, Esfahan, Iran; P.O. Box: 517; E-mail: ghashangmajid@gmail.com (Majid Ghashang)
Abstract
Barium molybdate (BaMoO4) nano-powder was successfully synthesized via a simple
precipitation route without any surfactant. The prepared nano-powder was applied for the facile
synthesis of 2,3-diarylthiazolidin-4-one derivatives using cyclization reaction of aromatic
aldehydes, aromatic amines and thioglycolic acid under ambient condition.
Keywords: thioglycolic acid; thiazolidin-4-one; Barium molybdate (BaMoO4); 2,3-
diarylthiazolidin-4-one
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Introduction
Barium molybdate (BaMoO4) has attracted much attention due to their unique structure and
potential applications. The more attraction of barium molybdate is due to its attractive
photoluminescence (PL) property [1-7]. BaMoO4 existing in the scheelite structure, has a high
potential for applications in many fields, such as optical fibers, light-emitting diodes, lanthanide
activated lasers, and scintillation detectors [1-7]. Various techniques for the preparation of
BaMoO4 were reported including Czochralski technique [6], spontaneous crystallization method
[8] Complex Polymerization Method (CPM) [9], simple precipitation method [10], reverse
microemulsions [11], microwave-assisted hydrothermal [12], EDTA-mediated route [13] and
calcinations method [14]. However, the preparation and evaluation of the catalytic properties of
BaMoO4 in organic transformations have not been focused. Thus the present work concentrates
on the homogeneous precipitation, preparation and application of BaMoO4 nanopowder as an
efficient catalyst in the synthesis of a variety of 2,3-diarylthiazolidin-4-one derivatives (Scheme
1).
The heterocycles containing thiazolidin-4-ones are of great interest and have been preclinically
shown to be useful because they have associated with a diverse range of interesting biological
activities, such as anticancer [15], anti- HIV [16], antimalarial [17], tuberculostatic [18],
antihistaminic [19], anticonvulsunt [20], antibacterial [21], and antiarrythmic [22].
Therefore, construction of new methods for the preparation of thiazolidin-4-ones still holds great
interest. A variety of synthetic methods have been developed for constructing such thiazolidin-4-
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ones and among them the cyclo-condensation reaction of aldehydes, amines and thioglycolic
acid has been more versatile [23-32].
Based on the above information’s and due to our interest in developing the synthetic
methodologies for the construction of heterocyclic compounds [33-38], herein, a detailed
account of our focused attention toward construction of the thiazolidin-4-one derivatives was
reported, via a cyclo-condensation reaction of aldehydes, amines and mercaptoacetic acid in the
presence of BaMoO4 nanopowder as catalyst (Scheme 1).
Experimental
Reagents and Instrumentation:
All reagents were purchased from Merck and Aldrich and used without further purification. All
yields refer to isolated products after purification. The NMR spectra were recorded on a Bruker
Avance DPX 400 MHz instrument. The spectra were measured in DMSO-d6 relative to TMS
(0.00 ppm). Elemental analysis was performed on a Heraeus CHN-O-Rapid analyzer. TLC was
performed on silica gel polygram SIL G/UV 254 plates. The powder X-Ray diffraction patterns
were measured with D8, Advance, Bruker, axs, diffractometer using CuKα irradiation. FE-SEM
was taken by a Hitachi S-4160 photograph to examine the shape and size of BaMoO4 nano-
particles.
Preparation of BaMoO4 nano-powder: To an aqueous solution of BaCl2 (10 mmol BaCl2 in 50
mL of water) sodium molybdate (10 mmol dissolved in 50 mL of EtOH/H2O (50/50) + triethyl
ammonium chloride (15 mmol) + 5 mL NH3 (aqueous solution 37%)) was added drop-wise with
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vigorously stirring at room temperature. After the dropping process was completed, the resultant
mixture was aged for 30 min. The accessed precipitates were separated from the mother liquor
by filtrating and were washed with distilled water for several times, then were dried at 100 °C.
The BaMoO4 nano-particles were slightly ground for analysis.
General procedure: To a mixture of aldehyde (1 mmol), aromatic amine (1 mmol) and
thioglycolic acid (1 mmol) in ethanol (5 mL), BaMoO4 nano-powder (0.17 mmol) as a catalyst
was added and the mixture was stirred for appropriate time at room temperature (Table 2).
Progress of the reaction was monitored by TLC. Upon completion, the solvent was concentrated
and the reaction mixture was diluted in CH2Cl2, the catalyst was isolated by simple filtration, and
the crude product was crystallized in n-hexane / ethyl acetate to afford the pure product.
Selected data:
2-(4-hydroxyphenyl)-3-p-tolylthiazolidin-4-one (Table 2, Entry 7): 1H-NMR (400 MHz, CDCl3):
2.27 (s, 3H), 3.71 (d, J = 12.4 Hz, 1H), 3.82 (d, J = 12.4 Hz, 1H), 5.14 (s, 1H), 6.70-7.14 (m,
6H), 7.73 (d, J = 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ = 20.6, 34.0, 52.3, 115.7, 120.8,
129.7, 130.8, 148.7, 157.2, 159.3, 160.7, 170.4 ppm; Found: C, 67.36; H, 5.35; N, 5.02
C16H15NO2S; requires: C, 67.34; H, 5.30; N, 4.91%].
Results and discussion
In order to determine the crystalline structure and phase composition of the BaMoO4 nano-
powder, X-ray diffraction (XRD) analysis using Cu-Kα radiation was applied (Figure 1). The
XRD pattern of BaMoO4 nano-powder exhibited diffraction pattern characteristics of the
tetragonal structure with pronounced 26.67, 27.27, 32.52, 34.37, 36.42, 38.52, 43.42, 46.32,
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48.27, 53.47, 54.62, 67.62 and 69.62 peaks (Figure 1). The average crystallite diameter of the as
prepared powder was determined by XRD, using from the highest peak of the BaMoO4 phase (2θ
at around 26.67), according to the Scherrer equation. The average crystalline size estimated by
using the Scherrer formula from the highest peak of the XRD was 80 nm and was determined
with the use of the following equation:
Where K is taken as 0.9, λ is the wavelength of X-ray used, β is the full width half maximum of
the prominent peak and θ is the glancing angle.
The average crystalline size of the BaMoO4 nano-powder was characterized by field emission
scanning electron microscopy (FE-SEM). Figure 2 shows the FE-SEM micrographs of the
BaMoO4 nano-particles. Based on the FE-SEM observation, the BaMoO4 nano-particles contain
spherical or ellipsoidal shapes. The particle sizes were mainly distributed in the range of 60 to
120 nm. The size of about 50 particles of BaMoO4 was measured and the average particle size
was obtained as 83 nm.
Figure 3 shows grain size distributions of BaMoO4 nano-powders. The powder milled for 2h and
sonicated in ethanol for1h had monomodal distributions with median particle size.
A comparison between the particle size distributions of BaMoO4 samples measured by different
techniques, including Cyclic microwave irradiation, Complex polymerization method (CPM),
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Precipitation method, Hydrothermal Synthesis using domestic microwave with the present study
was done and the results are summarized in Table 1. It is shown that particle size obtained with
the present work is comparable with those of reported literature.
As a preliminary test reaction, catalytic conversion of three-component condensation of
benzaldehye, 4-methyl aniline and thioglycolic acid to 2-phenyl-3-p-tolylthiazolidin-4-one was
examined (Scheme 2).
To find optimize the reaction conditions, the reaction was carried out by the using of different
solvents (Table 2, Entries 1-7) or solvent-free condition (Table 2, Entry 8). Among the solvent
screened, ethanol was found to be the best promoter in terms of reaction times and yields (Table
2, Entry 5).
For find the optimized amount of BaMoO4, the reaction was carried out by varying amount of
the catalyst (Table 2, Entries 9-12). Maximum yield was obtained when 0.17 mmol of catalyst
was used (Table 2, Entry 5). A further increase in the amount of BaMoO4 nano-powder in
mentioned reaction did not have any significant effect on the product yield. Under the standard
conditions, no reaction was observed in the absence of a catalyst. This shows that the catalyst is
essential for the product formation (Table 2, Entry 13). The results are summarized in Table 2.
Next, the scope and efficiency of this procedure was explored for the synthesis of a wide variety
of substituted 2,3-diarylthiazolidin-4-one derivatives (Scheme 1, Table 3).
As expected, this reaction proceeded smoothly and the desired products were obtained in good
yields. In general, aromatic aldehydes and aromatic amines were well tolerated in this reaction
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system (Table 3). Based on the obtained results, the electronic effects and the steric effects of the
substituents both in amines and aldehydes played significant role in the yields of products.
Aromatic aldehyde systems that possessed substitutions at the ortho, meta or para positions had
the yield, however, aromatic aldehydes containing electron-donating groups gave higher yields
than that with electron-withdrawing groups. When ortho-substituted aldehydes (Table 3, Entry 4)
were used in this process, the corresponding product was obtained in good yields. Electron
donating group on the amine was able to facilitate the transformation by giving evidently higher
yield of products than the entries using halogen atom functionalized anilines (Table 3).
The work-up procedure is very clear-cut; that is the products were isolated and purified by
simple filtration and recrystallization from n-hexane / ethyl acetate.
In order to estimate the efficiency and generality of this methodology, the obtained results in the
synthesis of 2,3-diphenyl thiazolidin-4-one using BaMoO4 nanopowder as catalyst has been
compared with those of the previously reported methods. The results are summarized in Table 4.
It was found that the present method is convincingly superior to the reported methods with
respect to reaction time and the yield of the product.
Our attention was then turned to the possibility of recycling the catalyst from the reaction media
since the recovery and reuse of the catalyst are highly preferable for a greener process. At the
completion of the reaction, the reaction mixture was poured into CHCl3 and stirred for 5 min.
The solid catalyst separated was filtered via simple filtration, dried and reused for subsequent
reactions. The reusability of the catalyst was investigated by using benzaldehye, 4-methyl aniline
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and thioglycolic acid as model substrates. After 10 recycles, the catalyst still had a high activity
and gave the corresponding product in good yield (Figure 4).
Conclusion
The nanopowder structure, BaMoO4, prepared by a simple precipitation method, was used as an
efficient catalyst for the preparation of 2,3-diarylthiazolidin-4-one derivatives. It was stated that
the use of 0.17 moles of BaMoO4 as catalyst for the catalytic condensation reaction of aromatic
aldehydes, aromatic amines and thioglycolic acid under ambient condition provides high yields
of products. Certainly, the simplicity of the accommodated catalytic system makes it suitable for
further research and practical applications.
Acknowledgments
We are thankful to the Najafabad Branch, Islamic Azad University research council for partial
support of this research
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Table 1: Particle size distribution of BaMoO4 nano-powder compared with those of reported
literatures.
Entry
Method
Particle size
30-75
Reference
1
2
3
Cyclic microwave irradiation
Complex polymerization method (CPM)
Precipitation method
4
40-50 nm
9
10
31.52 ± 4.65 nm
4
5
Hydrothermal Synthesis using domestic 0.7-3.1 µm
microwave
39
-
This work
83 nm
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Table 2: Optimization of the reaction conditions in the synthesis of 2-
phenyl-3-p-tolylthiazolidin-4-one (Scheme 2)
Entry
T (°C)
Solvent (5 mL)
Catalyst
(mmol)
Yield
(%)a
1
2
0.17
0.17
0.17
0.17
0.17
0.17
0.17
0.17
0.34
0.09
0.05
0.03
-
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
n-Hexane
CH2Cl2
Et2O
-
25
30
51
88
85
75
68
86
80
45
27
-
3
4
EtOAc
EtOH
MeOH
CH3CN
-
5
6
7
8
9
EtOH
EtOH
EtOH
EtOH
EtOH
10
11
12
13
a Isolated Yields, reaction time: 2 h
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Table 3: Synthesis of 2,3-diarylthiazolidin-4-one derivatives using BaMoO4 nano-
powder as catalyst (Scheme 1)
Entry
Aldehyde
Amine
Time
(h)
Yield
(%)a
1
Benzaldehyde
4-Methylaniline
4-Methylaniline
4-Methylaniline
4-Methylaniline
4-Methylaniline
4-Methylaniline
4-Methylaniline
4-Methoxyaniline
4-Methoxyaniline
4-Methoxyaniline
4-Methoxyaniline
2
2
88
2
4-Methylbenzaldehyde
4-Chlorobenzaldehyde
2-Chlorobenzaldehyde
3-Nitrobenzaldehyde
4-Methoxybenzaldehyde
4-Hydroxybenzaldehyde
2-Chlorobenzaldehyde
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
2-Methylbenzaldehyde
85
74
68
77
84
71
60
56
61
71
3
2.5
4
4
5
3.5
2
6
7
3
8
4
9
4
10
11
3.5
2.5
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12
13
14
15
4-Methoxybenzaldehyde
4-Methylbenzaldehyde
Benzaldehyde
4-Methoxyaniline
4-Methoxyaniline
4-Chloroaniline
Aniline
2
2
80
87
57
81
3
Benzaldehyde
2h
aIsolated yields. All known products have been reported previously in the literature
and were characterized by comparison of NMR spectra with authentic samples [25-
32].
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Table 4: Comparison results of BaMoO4 with other catalysts reported in the literature
Entry
Catalyst
Condition
Yield Reference
(%)a
1
2
Bi(SCH2COOH)3
H2SO4
Solvent-free; 70 °C; 2h
Toluene, 100 °C; 5 h
Toluene, 100 °C; 5 h
Toluene, 100 °C; 5 h
Toluene, 100 °C; 5 h
Toluene, 100 °C; 5 h
Toluene, 100 °C; 5 h
Toluene, 100 °C; 5 h
Toluene, 100 °C; 5 h
Ethanol; r.t.; 2 h
75
34
32
24
48
15
8
30
31
3
P-TsOH
31
4
MsOH
31
5
HClO4-TiO2
Acidic Al2O3
TiO2
31
6
31
31
7
8
Amberlite
Zeolite type Y
BaMoO4
36
41
81
31
9
31
10
This work
aIsolated Yield; based on the preparation of 2,3-diphenyl thiazolidin-4-one
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Figure 1: XRD pattern of BaMoO4 nano-particles
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Figure 2: FE-SEM micrographs of BaMoO4 nano-particles
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Figure 3: Particle size distribution of BaMoO4 nano-particles
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Figure 4: Rusability of BaMoO4 nano-powder
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O
BaMoO4
O
N Ar
Ar'
+ Ar-NH2 + Ar'-CHO
OH
S
HS
EtOH, r.t.
Scheme 1: Preparation of 2,3-diarylthiazolidin-4-one derivatives
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O
NH2
BaMoO4
O
N
S
+ Ph-CHO +
HS
OH
Ph
Scheme 2: Preparation of 2-phenyl-3-p-tolylthiazolidin-4-one
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