Efficient synthesis of bis-coumarins using silica-supported preyssler nanoparticles

Article abstract of DOI:10.1080/00397910902985556

Reaction of aldehydes and 4-hydroxycoumarin in the presence of catalytic amount of silica-supported Preyssler nanoparticles led to synthesis of bis-coumarins in excellent yields. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910902985556

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Efficient Synthesis of Bis-Coumarins
Using Silica-Supported Preyssler
Nanoparticles
Majid M. Heravi a , Fatemeh Nahavandi a , Samaheh Sadjadi a ,
Hossein A. Oskooie a & Fatemeh F. Bamoharram b
a Department of Chemistry, School of Sciences , Azzahra University ,
Vanak, Tehran, Iran
b Department of Chemistry, School of Sciences , Islamic Azad
University , Mashad Branch, Mashad, Iran
Published online: 03 Feb 2010.
To cite this article: Majid M. Heravi , Fatemeh Nahavandi , Samaheh Sadjadi , Hossein A. Oskooie &
Fatemeh F. Bamoharram (2010) Efficient Synthesis of Bis-Coumarins Using Silica-Supported Preyssler
Nanoparticles, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 40:4, 498-503, DOI: 10.1080/00397910902985556
To link to this article: http://dx.doi.org/10.1080/00397910902985556
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Synthetic Communications1, 40: 498–503, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910902985556
EFFICIENT SYNTHESIS OF BIS-COUMARINS USING
SILICA-SUPPORTED PREYSSLER NANOPARTICLES
Majid M. Heravi,1 Fatemeh Nahavandi,1 Samaheh Sadjadi,1
Hossein A. Oskooie,1 and Fatemeh F. Bamoharram2
1Department of Chemistry, School of Sciences, Azzahra University, Vanak,
Tehran, Iran
2Department of Chemistry, School of Sciences, Islamic Azad University,
Mashad Branch, Mashad, Iran
Reaction of aldehydes and 4-hydroxycoumarin in the presence of catalytic amount of
silica-supported Preyssler nanoparticles led to synthesis of bis-coumarins in excellent yields.
Keywords: Bis-coumarin; heteropolyacids; recyclable catalyst
INTRODUCTION
Coumarin derivatives form an important class of compounds. These
compounds possess several types of pharmacological properties such as anticancer,
anti-HIV, anticoagulant, spasmolytic, and antibacterial activity.[1] A large number of
structurally novel coumarin derivatives have been reported to show substantial
cytotoxic activity in vitro and in vivo.
Development of methods using heteropolyacids (HPAs) as catalysts for
organic synthetic processes related to fine chemicals, such as flavors and pharmaceu-
ticals,[2] have received attention in the past decade. The catalysts based on HPAs
have many advantages over liquid acid catalysts. They are not corrosive but are
environmentally benign, presenting fewer disposal problems. Solid HPAs have
attracted much attention in organic synthesis because of their easy workup proce-
dures, easy filtration, and minimal cost and waste generation due to reuse and
recycling of the catalysts.[3]
Over the past decade, because of the unique properties of nanoparticles along
with their potential applications in different fields,[4] synthesis and characterization
of catalysts with lower dimension have became the most interesting topic of research.
As the particle size decreases, the relative number of surface atoms increases and
thus activity increases. Moreover, because of quantum size effects, nanometer-sized
particles may exhibit unique properties for a wide range of applications.[5]
Received February 7, 2009.
Address correspondence to Majid M. Heravi, Department of Chemistry, School of Sciences,
Azzahra University, Vanak, Tehran, Iran. E-mail: mmh1331@yahoo.com
498

EFFICIENT SYNTHESIS OF BIS-COUMARINS
499
Recently, these considerations raised the interest in synthesis of Keggin
nanocatalysts,[6] but the synthesis and catalytic activity of Preyssler nanocatalyst
have been largely overlooked.
In our attempt to use HPAs as catalysts in organic reactions, we recently
reported that the Preyssler type, H14[NaP5W30O110], shows strong catalytic charac-
terization.[7] Because of the unique properties of nanoparticles along with their novel
properties and potential applications in different fields,[4] we decided to immobilize
H14[NaP5W30O110] into the SiO2 nanoparticles and investigate the catalytic behavior
of this new catalyst.
Herein we report a mild, efficient, and environmentally benign procedure for
the synthesis of bis-coumarins from reaction of aldehydes and 4-hydroxycoumarin
in the presence of silica-supported Preyssler nanoparticles (H14[NaP5W30O110])=
SiO2 as an efficient catalyst (Scheme 1).
Various reaction conditions, such as different amount of catalysts, were exam-
ined to obtain the optimum reaction condition. The results of synthesis of
bis-coumarin derivatives in the presence of a catalytic amount of silica-supported
Preyssler nanoparticles are summarized in Table 1.
To optimize the amount of catalyst, the yields of two derivatives of bis-
coumarin using various amounts of catalysts (0.2, 0.3, and 0.5 mol%) were obtained.
The results for synthesis of bis-coumarin derivatives using different amounts of
silica-supported Preyssler nanoparticles are shown in Table 2. It is clear from this
table that the yields of reactions with very small amounts of catalyst are very high,
and the optimum amount of catalyst was selected as 0.3 mol% for all derivatives.
To investigate the effect of solvent on this reaction, the syntheses of two deri-
vatives of bis-coumarin have been carried out in three solvents including water, the
1:1 mixture of water=EtOH, and EtOH. The results are summarized in Table 3.
The effect of temperature on this reaction has been studied by carrying out the
synthesis of two derivatives of bis-coumarin at various temperatures (room tempera-
ture, 50ꢀC, and refluxing temperature). The results showed that increasing the
reaction temperature has no significant effect on the yields of reactions, and only
in refluxing temperature is a slight reduction in reaction time, 5 min, observed.
The optimum temperature was thus room temperature (Table 4).
To compare the efficiency of silica-supported Preyssler nanoparticles with
Preyssler-type HPAs, the reactions have been carried out in the presence of both
catalysts in the same reaction conditions. The results are summarized in Table 5.
Scheme 1. Synthesis of bis-coumarins in the presence of silica-supported Preyssler nanoparticles.

500
M. M. HERAVI ET AL.
Table 1. Synthesis of bis-coumarins in the presence of silica-supported Preyssler nanoparticles as catalyst
Mp (ꢀC)
Entry
R
Time (min)
Yield (%)a
Found
Reported[9,10]
1
2
3
4
5
6
7
H
30
25
30
20
20
20
20
92
90
90
98
96
94
96
228
242
266
252
240
233
231
228–230
242–244
265–267
252–254
240–242
232–234
230–232
4-OCH3
4-CH3
4-Cl
3-NO2
4-NO2
2-OH
aYields of isolated products.
Table 2. Results of using various amount of silica-supported Preyssler nanoparticles in synthesis of two
derivatives of bis-coumarin
Entry
R
Time (min)
Catalyst amount (mol%)
Yield (%)a
1
2
3
4
5
6
4-Cl
4-Cl
30
20
20
30
20
20
0.2
0.3
0.5
0.2
0.3
0.5
93
98
98
90
94
94
4-Cl
4-NO2
4-NO2
4-NO2
aYields refer to isolated products.
Table 3. Effect of using various solvents on the synthesis of two derivatives of bis-coumarin
Entry
R
Time (min)
Solvent
Yield (%)a
1
2
3
4
5
6
4-Cl
4-Cl
35
30
20
30
25
20
Water
Water=EtOH
EtOH
88
93
98
85
89
94
4-Cl
4-NO2
4-NO2
4-NO2
Water
Water=EtOH
EtOH
aYields refer to isolated products.
Table 4. Effect of various temperatures on the synthesis of two derivatives of bis-coumarin
Entry
R
Time (min)
Temperature (ꢀC)
Yield (%)a
1
2
3
4
5
6
4-Cl
4-Cl
20
20
15
20
20
15
25
50
80
25
50
80
99
99
4-Cl
99
94
4-NO2
4-NO2
4-NO2
94.2
94.5
aYields refer to isolated products.

EFFICIENT SYNTHESIS OF BIS-COUMARINS
501
Table 5. Comparison of efficiency of silica-supported Preyssler nanoparticles and Preyssler in the
synthesis of bis-coumarins
Entry
R
Time (min)
Catalyst
Yield (%)a
1
2
H
30
40
25
40
30
35
20
35
20
40
20
35
20
40
(H14[NaP5W30O110])=SiO2
92
88
90
82
90
85
98
90
96
90
94
88
96
89
H
H14[NaP5W30O110
(H14[NaP5W30O110])=SiO2
H14[NaP5W30O110
(H14[NaP5W30O110])=SiO2
H14[NaP5W30O110
(H14[NaP5W30O110])=SiO2
H14[NaP5W30O110
(H14[NaP5W30O110])=SiO2
H14[NaP5W30O110
(H14[NaP5W30O110])=SiO2
H14[NaP5W30O110
(H14[NaP5W30O110])=SiO2
H14[NaP5W30O110
]
3
4-OCH3
4-OCH3
4-CH3
4-CH3
4-Cl
4
]
5
6
]
7
8
4-Cl
]
9
3-NO2
3-NO2
4-NO2
4-NO2
2-OH
2-OH
10
11
12
13
14
]
]
]
aYields refer to isolated products.
As shown in this table, the yields of reactions, catalyzed by silica-supported
Preyssler nanoparticles are better than by Preyssler nanoparticles alone.
To show the merit of this method for synthesis of bis-coumarins, the compari-
son of our result for reactions of 4-nitro-benzaldehyde and 4-hydroxycoumarin using
silica-supported Preyssler nanoparticles as catalyst with those reported in previous
works has been carried out (Table 6).
As shown in this table, the synthesis of bis-coumarins in the absence of catalyst
led to long reaction times and poor yields. Using I2 as catalyst gave bis-coumarin in
good yield (95%) and short reaction time (28 min). Although I2 is an efficient catalyst
for this reaction, its required amount is 10 mol%, and there is no report based on its
reusability. Only 0.3 mol% of (H14[NaP5W30O110])=SiO2 can catalyze the reaction,
and its reusability is another advantage.
In summary, bis-coumarin derivatives were obtained from reaction of
aldehydes and 4-hydroxycoumarin in the presence of a catalytic amount of silica-
supported Preyssler nanoparticles. Using this catalyst offers advantages including
Table 6. Comparison of synthesis of one bis-coumarin derivative in various conditions
Entry
1
R
Condition
Catalyst
Time (min)
20
Yield (%)a
94
4-NO2
Stir in EtOH
at room temperature
Stir in EtOH
(H14[NaP5W30O110])=
SiO2 (0.3 mol%)
2
4-NO2
H14[NaP5W30O110
(0.3 mol%)
I2 (10 mol%)
]
30
88
at room temperature
Stir in water at 100 ꢀC
Reflux in EtOH
3
4
5
4-NO2
4-NO2
4-NO2
28
95[11]
79[12]
76[10]
—
—
240
360
Reflux in EtOH
or glacial acetic acid
aYields of isolated products.

502
M. M. HERAVI ET AL.
simplicity of operation, easy workup, good yields of products, and the recyclability
of the catalyst.
EXPERIMENTAL
All the chemicals were purchased from Merck Company. Melting points were
measured using Barnstead Electrothermal instrument. Gas chromatographic (GC)=
mass analysis was performed using an Agilent 6890 GC system, Hp-5 capillary
(30 m  530mm  1.5mm nominal). Silica-supported Preyssler nanoparticles were
prepared according the literature.[8] All compounds were known, and their physical
data were compared with those of authentic compounds and found to be
identical.[9,10]
Synthesis of Silica-Supported Preyssler Nanoparticles
A solution of Preyssler acid in a specified amount of water was added to a
solution of sodium bis(2-ethylhexyl)sulfosuccinate in cyclohexane (0.2 M). The
molar ratio of water to surfactant was selected as 3, 5 and 7. Then, tetraethoxysilan
was added into the microemulsion phase. After mixing for various times (8, 12, 18,
25, and 30 h) at room temperature, dispersed Preyssler acid=SiO2 nanostructures
were centrifuged (1500 rpm), and the particles were rinsed with acetone (four times)
and dried in a vacuum oven.
Synthesis of a-Aminonitrile Derivatives: General Procedure
A catalytic amount of silica-supported Preyssler nanoparticles (0.3 mol%) was
added to a mixture of aldehyde (1 mmol) and 4-hydroxycoumarin (2 mmol). The
mixture was stirred vigorously in EtOH at room temperature for the appropriate
reaction time. The reaction was monitored by thin-layer chromatography (TLC).
After completion of the reaction, the precipated product was separated through
filteration and washed with ethanol to give the pure product.
Table 7. Comparison of efficiency of silica-supported Preyssler nanoparticles in
synthesis of bis-coumarins after three times
Yield (%)a
Entry
R
First run
Second run
Third run
1
2
3
4
5
6
7
H
92
90
90
98
96
94
96
90
88
89
96
95
93
95
90
87
4-OCH3
4-CH3
4-Cl
88
94.5
95
3-NO2
4-NO2
2-OH
92
95
aYields refer to isolated products.

EFFICIENT SYNTHESIS OF BIS-COUMARINS
503
Recycling of the Catalyst
After filtration of the products, the catalyst could be recycled by evaporation of
the residue solution and washing with diethyl ether in each case. The recovered
catalyst could be dried and reused for the next reaction with only a slight loss in
activity. The catalyst was recovered and reused for three times in these reactions.
The obtained results are summarized in Table 7.
ACKNOWLEDGMENT
The authors are thankful to Azzahra University Research Council for the
partial financial support.
REFERENCES
1. Kostova, I.; Momekov, G.; Zaharieva, M.; Karaivanova, M. Cytotoxic activity of new
lanthanum(III) complexes of bis-coumarins. Eur. J. Med. Chem. 2005, 40, 542.
2. Heravi, M. M.; Sajadi, S.; Oskooie, H. A.; Hekmat Shoar, R.; Bamoharram, F. F. A novel
multi-component synthesis of 4-arylaminoquinazoline. Tetrahedron Lett. 2009, 50, 943.
3. Heravi, M. M.; Sajadi, S.; Oskooie, H. A.; Hekmat Shoar, R.; Bamoharram, F. F. A
direct oxidative route for the synthesis of pyrimidines using heteropolyacids. Tetrahedron
Lett. 2009, 50, 662.
4. Gorla, C. R.; Emanetoglu, N. W.; Liang, S.; Mago, W. E.; Lu, Y.; Wraback, M.; Shen, H.
Structural, optical, and surface acoustic wave properties of epitaxial ZnO films grown on
(0112) sapphire by metalorganic chemical vapor deposition. J. Appl. Phys. 1999, 85, 2595.
5. Zheng, J.; Zhang, C.; Dickson, R. M. Highly fluorescent, water-soluble, size-tunable gold
quantum dots. Phys. Rev. Lett. 2004, 93, 077402.
6. Sawant, D. P.; Vinu, A.; Jacob, N. E.; Lefebvre, F.; Halligudi, S. B. Formation of nano-
sized zirconia-supported 12-tungstophosphoric acid in mesoporous silica SBA-15: A
stable and versatile solid acid catalyst for benzylation of phenol. J. Catal. 2005, 235, 341.
7. Heravi, M. M.; Sajadi, S.; Oskooie, H. A.; Hekmat Shoar, R.; Bamoharram, F. F. Hetero-
polyacids as heterogeneous and recyclable catalysts for the synthesis of benzimidazoles.
Catal. Commun. 2008, 9, 504.
8. Heravi, M. M.; Sajadi, S.; Sajadi, S.; Oskooie, H. A.; Hekmat Shoar, R.; Bamoharram, F.
Silica-supported Preyssler nanoparticles as new catalysts in the synthesis of 4(3H)-
quinazolinones. S. Afr. J. Chem. 2009, 62, 1.
9. Manolov, I.; Maichle-Moessmer, C.; Danchev, N. Synthesis, structure, toxicological, and
pharmacological investigations of 4-hydroxycoumarin derivatives. Eur. J. Med. Chem.
2006, 41, 882.
10. Hamdi, N.; Puerta, M. C.; Valerga, P. Synthesis, structure, antimicrobial, and antioxidant
investigations of dicoumarol and related compounds. Eur. J. Med. Chem. 2008, 43, 2541.
11. Chen, Y. L.; Chen, I. L.; Chung, C. H.; Chen, P. H.; Tzeng, C. C.; Teng, C. M.; Synthesis,
antiplatelet activity, and cytotoxic evaluation of certain phenyldicoumarol derivatives.
Chin. Pharm. J. 2001, 53, 85.
12. Kidwai, M.; Bansal, V.; Mothsra, P.; Saxena, S.; Somvanshi, R. K.; Dey, S.; Singh, T. P.
Molecular iodine: A versatile catalyst for the synthesis of bis(4-hydroxycoumarin)
methanes in water. J. Mol. Catal. A: Chem. 2007, 268, 76.