SbCl5/SiO2nanoparticles: An efficient and reusable reagent for the synthesis of 4,4′-(arylmethylene)bis(1 h -pyrazol-5-ol) derivatives in water

Article abstract of DOI:10.1080/15533174.2013.871730

An efficient and eco-friendly method for the synthesis of 4,4-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives is described by tandem Knoevenagel-Michael reaction between aromatic aldehydes and 3-methyl-1-phenyl-2-pyrazoline-5-one in the presence of nanosi

Full text of DOI:10.1080/15533174.2013.871730

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SbCl5/SiO2 Nanoparticles: an efficient and
reusable reagent for the synthesis of 4,4′-
(Arylmethylene)bis(1H-pyrazol-5-ol) derivatives in
water
Bahareh Sadeghia & Maryam Ghorbani Rada
a Department of Chemistry, Yazd Branch, Islamic Azad University, P.O. Box 89195–155, Yazd,
Iran
Accepted author version posted online: 19 Feb 2015.
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To cite this article: Bahareh Sadeghi & Maryam Ghorbani Rad (2015): SbCl5/SiO2 Nanoparticles: an efficient and reusable
reagent for the synthesis of 4,4′-(Arylmethylene)bis(1H-pyrazol-5-ol) derivatives in water, Synthesis and Reactivity in
Inorganic, Metal-Organic, and Nano-Metal Chemistry, DOI: 10.1080/15533174.2013.871730
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SbCl5/SiO2 Nanoparticles: an efficient and reusable reagent for the synthesis of 4,4´-
(Arylmethylene)bis(1H-pyrazol-5-ol) derivatives in water
Bahareh Sadeghi1, Maryam Ghorbani Rad
Department of Chemistry, Yazd Branch, Islamic Azad University, P.O. Box 89195-155, Yazd,
Iran
1 Corresponding author. E-mail: bsadeghia@gmail.com
Abstract: An efficient and eco-friendly method for the synthesis of 4,4´-(arylmethylene)bis(1H-
pyrazol-5-ol) derivatives is described by tandem Knoevenagel-Michael reaction between
aromatic aldehydes and 3–methyl-1-phenyl-2-pyrazoline-5-one in the presence of nanosilica
supported antimony pentachlorid (SbCl5/SiO2 NPs) in water. This method provides several
advantages such as environmental friendliness, shorter reaction time, waste free, simple workup
and excellent yields.
Keywords SbCl5/SiO2 NPs, aromatic aldehydes, 3–methyl-1-phenyl-2-pyrazoline-5-one, water
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INTRODUCTION
Pyrazoles and pyrazolones are important compounds that are known to possess multiple
[1-5]
biological activities, with possess anti-anxiety, antipyretic and anti-inflammatory activities
.
Furthermore, 4,4´-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives have a broad spectrum of
[7]
approved biological activity, such as anti-inflammatory [6], gastric secretion stimulatory
,
[8]
antidepressant and antibacterial [9]. The synthesis of 4,4´-(arylmethylene)bis(1H-pyrazol-5-ol)
derivatives has been reported in the presence of some catalyst such as ceric ammonium nitrate
[10]
[11]
,
sulfuric
propyltriethylenetetramine [12], xanthan sulfuric acid [13], phosphomolybdic acid [14], silica-
bonded S-sulfonic acid [15] and pyridine trifluoroacetate [16]
acid
([3-(3-silicapropyl)sulfanyl]propyl)ester
,
silica-bonded
N-
.
The use of solid acid have received considerable importance in organic synthesis [17,18] because
of their ease of handling, enhanced reaction times, greater selectivity, simple workup, and
recoverability of catalyst. Since, Antimony pentachloride is a liquid with a high specific gravity
that fumes in air and reacts with the moisture to form HCl. The handling and the usability of
SbCl5 as a liquid form is laborious and the supported form is indeed preferable. Supported SbCl5
on SiO2 nanoparticles has been prepared and has been used effectively as a catalyst. Application
of environmentally benign water and solid acid catalyst represents powerful green procedure. In
this work, the application of solid phase acidic and reusable nano catalyst (SbCl5/SiO2 NPs) have
investigated for synthesis of 4,4´-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives.
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EXPERIMENTAL
Material and instrumentation
Melting points were determined with an Electrothermal 9100 apparatus. IR spectra were
recorded on a Shimadzu IR-470 spectrometer. Elemental analyses were performed using a
Costech ECS 4010 CHNS-O analyzer at analytical laboratory of Science and Research Unite of
Islamic Azad University. The morphologies of the nanoparticles were observed using SEM of a
VEGA//TESCAN microscope with an accelerating voltage of 15 kV. The chemicals for this
work were purchased from Fluka and were used without further purification.
The dimensions of nano-SiO2 were observed with SEM (Figure 1). The stable silicagel
nanoparticles is prepared [19] and used for preparation of catalyst (SbCl5/SiO2 NPs).
FIG. 1.
Synthesis of antimony pentachlorid supported on silicagel nanoparticles
The reagent was prepared by stirring a mixture of SbCl5 (0.7 ml) and 1 g of nanosilica gel in 5
ml of chloroform for 1 h at room temperature. The slurry was filtered and washed with
chloroform. The obtained solid (SbCl5/SiO2 NPs) was dried at an ambient temperature for 2 h
and then stored in a dry container. The dimensions of nanoparticles were observed with SEM
(Figure 2). The size of parsticles are between 30-37 nm.
FIG. 2.
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General procedure for the preparation of compounds 3a-l
A mixture of 3–methyl-1-phenyl-2-pyrazoline-5-one (2 mmol), aromatic aldehyde (1 mmol),
SbCl5/SiO2 NPs (0.004 g) and H2O (5mL) was placed in a round bottom flask. The
materials were mixed and refluxed in water for the 20 min. After completion of the
reaction, the mixture was filtered to remove the catalyst. After evaporation of the solvent,
the crude product was recrystallised from hot ethanol to obtain the pure compound.
The selected spectral data:
4,4´-(Phenylmethylene)bis(3-methyl-1-phenyl-1Hpyrazol-5-ol) (3a)
Colorless powder, m.p. 171-172 ºC; IR (νmax, cm-1): 3412, 3045, 2910, 1610, 1573, 1405, 1277,
1
1015, 743; H NMR (500MHz, CDCl3): δ 2.27 (s, 6H, 2CH3), 4.91 (s, 1H, CH), 7.15 (m, 1H),
7.24 (m, 6H), 7.39 (t, 4H, J= 7.6 Hz), 7.67 (d, 4H, J= 7.6 Hz), 14.05 (br s, 2H) ppm; 13C NMR
(125 MHz, CDCl3): δ 12.0, 33.5, 121.5, 126.4, 127.8, 128.7, 129.5, 137.4, 142.5, 146.7.
RESULTS AND DISCUSSION
In continuation of previous research on the use of solid acids in organic synthesis [20-24], the
synthesis of 4,4´-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives have investigated by
condensation of 3–methyl-1-phenyl-2-pyrazoline-5-one 1 and an aromatic aldehyde 2 in the
presence of 0.004g SbCl5/SiO2 NPs catalyst.
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SCH. 1.
To optimize the reaction conditions, the reaction of benzaldehyde and 3–methyl-1-phenyl-
2-pyrazoline-5-one was used as a model reaction. The efficiency of SbCl5/SiO2 nanoparticles
is comparable with other catalysts such as ceric ammonium nitrate, sulfuric acid ([3-(3-
silicapropyl)sulfanyl]propyl)ester, silica-bonded N-propyltriethylenetetramine, xanthan
sulfuric acid, phosphomolybdic acid and silica-bonded S-sulfonic acid. According to the
obtained data, xanthan sulfuric acid and phosphomolybdic acid have more yields but xanthan
sulfuric acid has been applied (0.08 g) more amount and phosphomolybdic has lasted longer
(240 min). These results clearly show the advantages of our methodology over other protic or
Lewis acid catalyzed 4,4´-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives synthesis such as
low consumption of catalyst, shorter reaction time and excellent yields (Table 1, entry1-8). In
order to determine the optimum quantity of SbCl5/SiO2 NPs, model reaction was carried out
at reflux in water condition (Table1, entry 9-11). SbCl5/SiO2 NPs (0.004g) gave an excellent
yield in 20 min (Table1, entry 10). The above reaction was also examined in various
solvents. The best results were obtained when water was used as a solvent at reflux (Table 1,
entry 10). An interesting feature of this method is that the reagent can be regenerated at the
end of the reaction and can be used several times without losing its activity. To recover the
catalyst, after completion of the reaction, the mixture was filtered and catalyst was washed
with CHCl3 and then dries the solid residue. This process repeated for three cycles and the
yield of product 3a did not change significantly (Table 1, entry 14, 15). XRD analysis of the
fresh and recovered catalyst was taken. As it shows peaks for pure SiO2 and SbCl5 exist in
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this pattern that proof antimony pentachloride is supported on nano silica gel (Figure 3 and 4)
.
FIG. 3.
FIG. 4.
TABLE 1
To study the scope of the reaction, a series of aromatic aldehydes and 3–methyl-1-phenyl-2-
pyrazoline-5-one catalysed by SbCl5/SiO2 NPs were examined (Scheme 1). The results are
shown in Table 2. In all cases, aromatic aldehyde substituted with either electron-donating or
electron-withdrawing groups underwent the reaction smoothly and gave products in excellent
yields.
TABLE 2
All products are known and were identified by their melting points, IR spectroscopy and
elemental analyses.
CONCLUSION
In summary, a facile and mild procedure for the synthesis of 4,4´-(arylmethylene)bis(1H-
pyrazol-5-ol) derivatives have been developed by condensation reaction of aromatic aldehydes
and 3–methyl-1-phenyl-2-pyrazoline-5-one using nanosilica supported antimony pentachlorid
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(SbCl5/SiO2 NPs) as an efficient, eco-friendly and reusable heterogeneous catalyst. The main
advantages of the present synthetic protocol are mild, high yields, short reaction times and easy
reaction work up procedure.
ACKNOWLEDGEMENTS
The research Council of the Islamic Azad University of Yazd is gratefully acknowledged for
the financial support for this work.
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FIG. 1. The SEM images of SiO2 nanoparticles
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FIG. 2. The SEM images of SbCl5/SiO2 NPs
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Fig. 3. The XRD pattern of SbCl5/SiO2 NPs
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Fig. 4. The XRD pattern of recovered SbCl5/SiO2 NPs
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Ar
Me
Me
N
Me
SbCl5/SiO2 NPs
H2O, Reflux
2
+
Ar-CHO
O
N
N
N
N
N
OH
HO
Ph
Ph
Ph
1
2
3a-l
SCH. 1. The condensation of aromatic aldehydes with 3–methyl-1-phenyl-2-pyrazoline-5-one
using SbCl5/SiO2 NPs as catalyst
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TABLE 1 Comparison of the efficiency of SbCl5/SiO2 NPs with reported catalysts for the
synthesis of 3a and optimization of the reaction condition
Entry
Catalyst (amount)
Cond./Sol.
Time Yielda(%) Ref.
(min)
1
2
Ceric ammonium nitrate (5 mol%)
SASPSPEb (0.1 g)
25 ºC/H2O
80 ºC/EtOH
80 ºC/EtOH
80 ºC/EtOH
25 ºC/EtOH
80 ºC/EtOH
100 ºC/ H2O
100 ºC/H2O
100 ºC/H2O
100 ºC/H2O
100 ºC/H2O
80 ºC/EtOH
40 ºC/CH2Cl2
100 ºC/H2O
100 ºC/H2O
15
180
30
92
90
90
95
96
80
84
82
85
95
96
87
83
88
10
11
12
13
14
15
-
3
SBNPTT c (0.03 g)
4
Xanthan sulfuric acid (0.08 g)
Phosphomolybdic acid (1 mol%)
SBSSA d (0.1 g)
15
5
240
120
20
6
7
SnCl4/SiO2 NPs(0.004 g)
BF3/SiO2 NPs (0.004 g)
SbCl5/SiO2 NPs (0.002 g)
SbCl5/SiO2 NPs (0.004 g)
SbCl5/SiO2 NPs (0.006 g)
SbCl5/SiO2 NPs (0.004 g)
SbCl5/SiO2 NPs (0.004 g)
SbCl5/SiO2 NPs (0.004 g) 2nd run
8
20
-
9
20
-
10
11
12
13
14
15
20
-
20
-
20
-
20
-
20
-
SbCl5/SiO2 NPs (0.004 g) 3nd run
20
82
-
b
c
aIsolated yield, Sulfuric acid ([3-(3-silicapropyl)sulfanyl]propyl)ester, Silica-bonded N-
propyltriethylenetetramine, d Silica-bonded S-sulfonic acid,
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TABLE 2
SbCl5/SiO2 NPs catalyzed the synthesis of 4,4´-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives
Entry
Ar
Product
Yielda%
m.p./ºC
Found
171-172
199-200
Reported[Ref]
1
2
C6H5
3a
3b
3c
3d
3e
3f
3g
3h
3i
95
87
90
92
88
92
93
96
84
91
93
92
170-171[10]
198-200[11]
181-183[11]
203-204[10]
227-229[11]
210-212[11]
151-153[11]
225-227[11]
235-237[11]
215-217[11]
189-190[10]
232-233[10]
2-BrC6H4
4-FC6H4
3
182-184
203-205
229-230
208-210
152-153
224-226
236-237
217-218
189-191
230-232
4
4-MeC6H4
2-OHC6H4
4-CNC6H4
3-NO2C6H4
4-NO2C6H4
2-ClC6H4
4-ClC6H4
2-Furfuryl
2-Pyridyl
5
6
7
8
9
10
11
12
3j
3k
3l
aIsolated yield.
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