Efficient one-pot synthesis of bis(4-hydroxycoumarin)methanes in the presence of sulfonic acid functionalized nanoporous silica (SBA-Pr-SO 3H)

Article abstract of DOI:10.1002/jccs.201200530

An efficient and simple method for the synthesis of bis(4-hydroxycoumarin) methanes has been achieved through a one-pot condensation of aryl aldehydes and 4-hydroxycoumarin in the presence of nanoporous solid acid catalyst of SBA-Pr-SO3H with pore size of

Full text of DOI:10.1002/jccs.201200530

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Efficient One-Pot Synthesis of Bis(4-hydroxycoumarin)methanes in the Presence of
Sulfonic Acid Functionalized Nanoporous Silica (SBA-Pr-SO H)
3
a,
Ghodsi Mohammadi Ziarani, * Alireza Badiei, Masoomeh Azizi and Negar Lashgari
b
a
a,b
a
Department of Chemistry, Alzahra University, P.O. Box 1993891176, Tehran, Iran
School of Chemistry, College of Science, University of Tehran, P.O Box 14155-6455, Tehran, Iran
b
(Received: Oct. 12, 2012; Accepted: Dec. 21, 2012; Published Online: Jan. 28, 2013; DOI: 10.1002/jccs.201200530)
An efficient and simple method for the synthesis of bis(4-hydroxycoumarin)methanes has been achieved
through a one-pot condensation of aryl aldehydes and 4-hydroxycoumarin in the presence of nanoporous
3
solid acid catalyst of SBA-Pr-SO H with pore size of 6 nm. Excellent yields, short reaction times, reus-
ability of the catalyst and simple workup are advantages of this synthetic procedure.
Keywords: Bis(4-hydroxycoumarin)methanes; Nanocatalyst; Sulfonic acid functionalized SBA-15.
2
(TBAB), and phosphotungstic acid. Recently, new kind
1
22
INTRODUCTION
Coumarins constitute an important class of pharma-
1
cological agents which are known for their anti-coagulant,
of solid acids based on sulfonic groups contained in meso-
23-25
26-28
structured MCM-41
and SBA-15 materials
have
2
anti-fungal, anti-inflammatory, anti-bacterial, anti-oxi-
3
4
emerged. Surface modification of the SBA-15 leads to ma-
terials with high surface area, narrow pore size distribution,
high accessibility of acid centers and relative high acid
strength. Sulfonic acid functionalized SBA-15 showed
5
6
dant, and anti-tumor activities. The development of
coumarin scaffolds for the drug discovery has recently
7
drawn much attention. Recent reports describe that 4-hy-
,8
2
9-31
9
,10
high catalytic activity in a number of organic reactions.
droxycoumarin derivatives such as dicoumarol,
ethyl
12
11
Furthermore, immobilization of different nanoparticles on
3
biscoumacetate, and bis(4-hydroxycoumarin)methanes
2,33
SBA-15 as a silicate support has been reported, too.
In
(
Figure 1) exhibit diverse biological activities. Complexes
14,15
and cerium
1
of neodymium (III), lanthanum (III),
3
our continued interest towards the application of nano-
1
III) with bis(4-hydroxycoumarin)methanes were also
6
porous heterogeneous solid catalysts to the synthesis of
3
(
4-37
heterocyclic compounds,
we have decided to use SBA-
synthesized by reaction of corresponding salts with the lig-
ands and the cytotoxic screening of complexes was carried
out.
Pr-SO H as an efficient nano catalyst in the synthesis of
3
bis(4-hydroxycoumarin)methanes.
The synthesis of bis(4-hydroxycoumarin)methanes
was achieved through the reaction of 4-hydroxycoumarin
and various aldehydes using different conditions such as
RESULTS AND DISCUSSION
In this work, we report a mild and efficient procedure
for the synthesis of bis(4-hydroxycoumarin)methanes from
the condensation reaction of aldehydes and 4-hydroxy-
1
7
18
microwave irradiation, sonication, and in the presence
of different catalysts such as sodium dodecyl sulfate
1
SDS), molecular iodine, tetrabutylammonium bromide
9
20
3
coumarin in the presence of SBA-Pr-SO H as a highly effi-
(
cient heterogeneous acid catalyst (Scheme I).
Scheme I Synthesis of bis(4-hydroxycoumarin)meth-
anes using SBA-Pr-SO
nano acid catalyst
3
H as an efficient
In order to optimize the reaction conditions, the reac-
Fig. 1. 4-Hydroxycoumarin derivatives.
tion of benzaldehyde and 4-hydroxycoumarin as a model
*
Corresponding author. Tel: +982188041344; Fax: +982188041344; E-mail: gmziarani@hotmail.com; gmohammadi@alzahra.ac.ir
J. Chin. Chem. Soc. 2013, 60, 499-502
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499

Article
Ziarani et al.
Table 1. Solvent effect on the synthesis of compound 1a
and 4-hydroxycoumarin in the presence of solid acid cata-
lyst in the first step and a Michael addition of second mole-
cule of 4-hydroxycoumarin in the second stage to form the
desired product.
[
a]
Entry
Solvent
Time (min)
Yield (%)
1
2
3
4
EtOH
Neat
100
No reaction
70
80
-
H O
2
86
97
We have also compared the efficiency of various cata-
lysts in the synthesis of 3,3¢-benzylidene-bis-(4-hydroxy-
coumarin) as the model of reaction (Table 3). The high
yield of products and short reaction times demonstrated
EtOH:H O (1:1)
2
25
[
a]
Isolated yield.
3
that SBA-Pr-SO H with its distinct features such as the
reaction, was carried out in three solvents including H
EtOH, and EtOH/H O (1:1) and also under solvent-free
system in the molar ratio of 1:2. The best result was ob-
tained in 97% yield after 25 min in EtOH/H O using 0.02 g
SBA-Pr-SO H as catalyst (Table 1). Using this reaction
2
O,
pore size of 6 nm, acts as an efficient nano-reactor in this
reaction (Figure 2).
2
The SBA-15 as a new nanoporous silica can be pre-
pared by using commercially available triblock copolymer
2
3
4
2,43
Pluronic P126 as a structure directing agent.
A sche-
H was
conditions, a range of bis(4-hydroxycoumarin)methane de-
rivatives were synthesized in 92-99% yields and the results
were summarized in the Table 2. Different aromatic alde-
hydes bearing electron-withdrawing and electron-donating
substituents were successfully used in this reaction and
high yields of products were obtained. After completion of
the reaction (monitored by TLC), the crude product was
dissolved in hot ethanol, the heterogeneous solid catalyst
was removed from the reaction mixture by simple filtra-
tion, and after cooling of the filtrate, the pure crystals of
products were obtained. The recovered catalyst washed
consequently with diluted acid solution, water and acetone,
and dried under vacuum. The reusability of the catalyst was
investigated under optimized conditions for the synthesis
of the model compound. The process of recycling was com-
pleted four times and no significant decrease in activity
was observed. The yields for the four runs were found to be
matic illustration for the preparation of SBA-Pr-SO
3
shown in Figure 3. The calcined SBA-15 silica was func-
tionalized with (3-mercaptopropyl)trimethoxysilane (MPTS)
and then, the thiol groups were oxidized to sulfonic acid by
hydrogen peroxide. The surface of the catalyst was ana-
lyzed by different methods such as TGA, BET and CHN
methods. The morphology of catalyst was verified by the
SEM and TEM images (Figure 4). It was found that mor-
phology of solid was saved without change during the sur-
face modifications. On the other hand, the TEM image
(
Figure 4 right) reveals the parallel channels, which resem-
ble the pores configuration of SBA-15. This indicates that
9
7%, 91%, 87%, and 80%, respectively.
The most probable mechanism of this reaction in-
Fig. 2. SBA-Pr-SO3H acts as a nano-reactor.
cludes a fast Knoevenagel condensation between aldehyde
Table 2. The SBA-Pr-SO H catalyzed the synthesis of bis(4-hydroxycoumarin)methanes in
3
EtOH/H O
2
[
a]
Entry
Ar
Product Time (min) Yield (%)
M.p (°C)
M.p (Lit.)
2
2
2
2
3
2
2
2
2
3
0
1
2
3
4
5
6
7
8
9
C H
6
1a
1b
1c
1d
1e
1f
25
30
28
30
25
30
30
32
30
37
97
98
94
98
92
99
98
98
98
97
230-232
252-253
123-125
230-232
266-268
240-242
253-255
220-222
229-230
199-200
228-230
252-254
120-124
232-234
265-267
242-244
254-256
222-224
230-232
197-198
5
0
0
0
8
0
0
0
0
8
4-ClC H
6
4
3-NO C H
2
6
4
4
4
4-NO C H
2
6
4-CH C H
3
6
4-OCH C H
4
3
6
2-OHC H
6
1g
1h
1i
4
4-OHC H
6
4
C H CH=CH-
5
6
1
0
2,4-(OCH ) C H
3
1j
3
2
6
[
a]
Isolated yield.
500
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J. Chin. Chem. Soc. 2013, 60, 499-502

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Synthesis of Bis(4-hydroxycoumarin)methanes
Table 3. Comparison of efficiency of various catalysts in synthesis of 3,3'-benzylidene-bis(4-hy-
droxycoumarin) 1a in recent years
Entry
Catalyst
Solvent
Condition
Time
Yield (%)
Ref.
3
9
1
2
0
1
1
2
3
4
5
6
MnCl .4H O
2
H O
2
Stir. at 100 °C
Reflux
30 min
25 min
20 min
2 h
99
92
93
84
92
97
2009
2009
2010
2010
2010
2
2
2
4
4
TBAB
H O
2
Phosphotungstic acid
[bmim]BF4
H O
2
80 °C
-
Heating (60-70 °C)
r.t
H [NaP W O110])/SiO2
5
EtOH
30 min
25 min
14
30
SBA-Pr-SO H
3
H O/EtOH
2
Reflux
This work
2
kV while TEM was carried out on a Tecnai G F30 at 300 kV.
Synthesis and functionalization of SBA-15
The nanoporous compound SBA-15 was synthesized and
3
functionalized according to our previous report and the modi-
4
fied SBA-15-Pr-SO H was used as nanoporous solid acid catalyst
3
in the following reaction.
Fig. 3. Schematic illustration for the preparation of
SBA-Pr-SO H.
General procedure for the preparation of bis(4-hy-
droxycoumarin)methanes
3
A mixture of aryl aldehyde (1 mmol), 4-hydroxycoumarin
(
(
(
3 2
2 mmol), and SBA-Pr-SO H (0.02 g) in mixture of H O/EtOH
1:1) (5 mL) was stirred at reflux. After completion of the reaction
monitored by TLC), the mixture was cooled and filtered. The
crude product was dissolved in hot ethanol and then the catalyst
was removed by filtration. The filtrate was cooled and concen-
trated to provide the pure crystals of bis(4-hydroxycoumarin)
methanes. All compounds were known, and their physical data
Fig. 4. SEM image (left) and TEM image (right) of
SBA-Pr-SO H.
3
(
mp, IR, NMR) were compared with those reported in the litera-
ture. The catalyst was washed subsequently with diluted acid so-
lution, distilled water and then acetone, dried under vacuum and
re-used for several times without loss of significant activity.
Spectroscopic data for selected examples are shown below.
3,3¢-Benzylidene-bis(4-hydroxycoumarin) 1a
the pore of SBA-Pr-SO
steps reactions.
3
H was not collapsed during two-
H with pore size of 6 nm
In conclusion, SBA-Pr-SO
3
was proved to be an efficient heterogeneous nanoporous
solid acid catalyst in the one-pot synthesis of bis(4-hy-
M.p = 230-232 °C; IR (KBr): 3424, 3073, 2968, 2925,
-1 1
2725, 2601, 1659, 1612, 1563, 1527, 1346, 1100, 763 cm ; H
droxycoumarin)methanes in EtOH/H
2
O. The reasonable
reaction time, excellent yields of products, simple workup
procedure, and environmentally friendly conditions are
main advantages of this method.
NMR (250 MHz, CDCl ): d 6.44 (s, 1H), 7.2–7.26 (m, 5H), 7.32
3
(t, J = 7.5 Hz, 2H), 7.48 (d, J = 7.5 Hz, 2H), 7.67 (t, J = 7.5 Hz,
2H), 7.85 (d, J = 7.5 Hz, 2H).
3
,3¢-(4-Chlorobenzylidene)-bis(4-hydroxycoumarin) 1b
EXPERIMENTAL
M.p = 252-253 °C; IR (KBr): 3423, 3072, 2933, 2726,
-
2682, 2608, 1668, 1609, 1562, 1488, 1350, 1306, 1094, 763 cm ;
1
All chemicals were obtained commercially and used with-
out further purification. IR spectra were recorded from KBr disks
using a FT-IR Bruker Tensor 27 instrument. Melting points were
measured by using the capillary tube method with an electro ther-
1
3
H NMR (250 MHz, CDCl ): d 6.28 (s, 1H), 6.77 (d, J = 7.5 Hz,
2H), 7.08 (d, J = 7.5 Hz, 2H), 7.35 (s, 4H), 7.83 (d, J = 7.5 Hz,
2H), 7.37 (d, J = 7.5 Hz, 2H).
1
mal 9200 apparatus. The H NMR (250 MHz) was run on a Bruker
3,3¢-(4-Methylbenzylidene)-bis(4-hydroxycoumarin) 1e
DPX, 250 MHz spectrometer using TMS as an internal standard
M.p = 266-268 °C; IR (KBr): 3418, 2916, 2855, 2728,
-1 1
2685, 2615, 1669, 1608, 1564, 1306, 1092, 762 cm ; H NMR
(
CDCl
3
solution). SEM analysis was performed on a Philips XL-
3
0 field-emission scanning electron microscope operated at 16
(250 MHz, CDCl ): d 2.47 (s, 3H), 6.24 (s, 1H), 6.46 (d, J = 7.5
3
J. Chin. Chem. Soc. 2013, 60, 499-502
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501

Article
Ziarani et al.
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ACKNOWLEDGEMENTS
We gratefully acknowledge for the financial support
from the Research Council of Alzahra University and the
University of Tehran.
2
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© 2013 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2013, 60, 499-502