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ORIGINAL ARTICLE

Sulfated zirconia as an ecient heterogeneous and


reusable catalyst for one pot synthesis of avanones
Bashir A. Dar
a
, Nisar Ahmad
b
, Jyoti Patial
a
, Parveen Sharma
a
,
Kushal Bindu
c
, Sudip Maity
d
, Baldev Singh
a,
*
a
NPC and Catalysis Lab., Indian Institute of Integrative Medicine (CSIR), Canal Road, Jammu 180 001, India
b
Quality Control Lab., Indian Institute of Integrative Medicine (CSIR), Canal Road, Jammu 180 001, India
c
Analytical Division, Indian Institute of Integrative Medicine (CSIR), Canal Road, Jammu 180 001, India
d
CIMFR, Dhanbad, Jharkhand, India
Received 30 June 2011; accepted 27 September 2011
Available online 5 October 2011
KEYWORDS
Flavonoids;
Impregnation;
Strong acid;
Aldehydes;
Catalyst;
One pot synthesis;
Sulfated zirconia
Abstract A simple and one pot process for the synthesis of avanones in the presence of
SO
2
4
=ZrO
2
, a reusable, heterogeneous catalyst has been described. The reactions were conducted
both with and without solvent (using toluene as solvent) at 140 C with reaction times of 34 h.
Under these conditions several examples were found with very good yields (7387%) and up to
83% selectivity. The catalyst was easily recycled and reused without loss of its catalytic activity.
The present synthetic method is a simple, clean and environment friendly alternative for synthesiz-
ing substituted avanones.
2011 Production and hosting by Elsevier B.V. on behalf of King Saud University.
1. Introduction
The avanones are a class of naturally occurring polypheno-
lic compounds which are extensively distributed in vascular
plants (Lee et al., 2007). These are minor ingredients of
the human diet, (Kabalka and Mereddy, 2005; Bennardi
et al., 2007) the most abundant being the avanones.
Members of this class have been shown to display a wide
variety of biological activities, (Viuda-Martoz et al., 2008)
such as antioxidant effect, inhibition of HIV-1 proteinase,
and anticancer (Yanling et al., 2007), vasodilator, antiviral
and antiallergenic (Alan and Miller, 1996), in addition to
antimicrobial (Cushnie and Lamb, 2005; Young et al.,
2007), anti-inammatory (Pan et al., 2010) activities. The
curiosity in the biological properties of avanones has
resulted extreme synthetic efforts toward the synthesis of dif-
ferent avanones. There are number of methods available
for the synthesis of avanones and their analogs. The gen-
eral methods to obtain avanones are the cyclization of
1,3-diphenylpropane-1, 3-diones or o-hydroxychalcones (Lee
et al., 2007; Pathak et al., 2008) and Baker and Venkatar-
aman rearrangement wherein o-hydroxyacetophenone is ben-
zoylated to form the benzoyl ester (Diana et al., 2000;
*
Corresponding author. Tel.: +91 2572002/2579117/2578206/
2547493; fax: +91 2548607/2548329/2546383.
E-mail address: drbaldevsingh@yahoo.co.in (B. Singh).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
Journal of Saudi Chemical Society (2014) 18, 464468
King Saud University
Journal of Saudi Chemical Society
www.ksu.edu.sa
www.sciencedirect.com
http://dx.doi.org/10.1016/j.jscs.2011.09.015
1319-6103 2011 Production and hosting by Elsevier B.V. on behalf of King Saud University.
Balogh and Laszlo, 1993; Chisem et al., 1997). Other meth-
ods include AllanRobinson synthesis and intramolecular
Wittig strategy (Huang et al., 2003; Ganguly et al., 2005).
But these methods are not environment friendly because of
using homogeneous catalysts, such as FeCl
3
(Kumar and
Perumal, 2007), sodium acetate (Wu et al., 1989), H
2
SO
4
(Zembower and Zhang, 1998), PalladiumThiourea (Miao
and Yang, 2000), SeO
2
(Ballesteros et al., 1995), acetic acid
(Kalinin et al., 1990), DMSO (Makrandi and Kumari, 1989;
Agrawal and Soni, 2005) NiCl
2
/Zn/KI (Miyake et al., 2003),
Br
2
/CHCl
3
, NaOAc/AcOH, EtOH/HCl, clay (Varma et al.,
1998). Chemical and pharmaceutical industries are always
in search of environment friendly methodologies for organic
transformations. To overcome these problems different solid
acid catalysts, such as zeolites, clays, Al-MCM-41, oxides
like alumina (Varma et al., 1985), magnesium oxide
(Drexler and Amiridis, 2003), and supported reagents like
supported triuoromethanesulfonic acid have been used in
this transformation (Parvulescu et al., 2005). These heteroge-
neous catalysts are not only recyclable and easier to separate
from the reaction mixture, but also show better selectivity
than homogeneous catalysts. However most of them require
tedious preparation methods and the use of expensive and
toxic solvents (Wang et al., 2005; Drexler and Amiridis,
2003). It is known that sulfated zirconia an extraordinarily
acidic material that exhibits greater catalytic activity than
that of 100% sulfuric acid in several catalytic reactions
(Reddy et al., 2006) is an efcient catalyst for different func-
tional group transformations under heterogeneous conditions
and has received much attention in organic synthesis (Singh
et al., 2011). But nobody has reported this catalyst for the
synthesis of avanones to the best of our knowledge. So
herein we report the catalytic efciency of sulfated zirconia
for one pot synthesis of avanones from substituted benzal-
dehydes and substituted 2-hydroxyacetophenones
(Scheme 1).
2. Experimental
2.1. Catalyst preparation
Zirconium oxychloride ZrOCl
2
8H
2
O (Loba Chemie), ammo-
nia (25 wt%) (Loba Chemie), ammonium sulfate (NH
4
)
2
SO
4
(Loba Chemie), and sodium sulfate Na
2
SO
4
(Loba Chemie)
were of analytical grade. About 25 g of ZrOCl
2
8H
2
O was dis-
solved in 500 ml double distilled water. To this clear solution,
dilute aqueous ammonia was added drop-wise from a burette
with vigorous stirring until the pH of the solution reached
7.58. The gel mixture was stirred continuously for 30 min
and the resulting gel was washed with distilled water until free
from chloride ions and dried at 120 C for 24 h. To a ne pow-
der of zirconium hydroxide calculated amount of ammonium
sulfate was introduced by implementing the impregnation
method. The product was dried at 95 C and calcined at
550 C in air atmosphere and stored in vacuum desiccator.
2.2. Catalyst characterization
The surface and bulk properties of zirconia and sulfated zir-
conia catalyst were examined by different techniques namely
X-ray powder diffraction (Fig. 1) BET surface area and
ammonia-TPD reported elsewhere (Singh et al., 2011).
XRD patterns were recorded at room temperature on a
D8 ADVANCE (BRUKER AXS, Germany) diffractometer
using CuKa (k = 0.15418 nm) parallel beam (Gobel Mirror)
radiation which illustrates that the catalysts include two
types of zirconia phases (ZrO
2
) namely tetragonal phases
and monoclinic phases (beddeleyite). Crystallite sizes of
tetragonal and monoclinic phases are determined using
(111) planes at 2h value of 30.283 and 28.175, respectively.
The acidity of catalyst was determined by CHEMBET-3000
TPR/TPD/TPO instrument, containing a quartz reactor
(i.d. = 4 mm) and a T.C.D. detector. Prior to TPD studies;
sample was pretreated at 250 C for 2 h with continuous
ow of pure nitrogen (99.9%) then cooled to room temper-
ature. After pretreatment, the sample was saturated with
10% anhydrous ammonia gas until saturated adsorption.
The temperature was increased to 80 C and kept there for
2 h to remove the physisorbed ammonia. Finally the system
was heated from 80 to 1200 C at the rate of 10 C/min and
the desorbed gas was monitored with a T.C.D. detector. All
the ow rates were maintained at normal temperature and
pressure (NTP). All the chemicals used in this synthesis of
avanones were purchased from Sigma Aldrich; the proce-
dure for the catalytic reactions was followed from those ear-
lier reported (Wang et al., 2005).
2.3. Reaction in toluene as solvent
In a typical experiment avanone synthesis was carried out
under N
2
in a round bottomed ask equipped with a reux
condenser immersed in a thermostatted bath and stirred
magnetically. Model avanone was prepared by mixing in
15 mmol of benzaldehyde derivative and 10 mmol of substi-
tuted o-hydroxyacetophenone and heated to 140 C, 5 ml
toluene and SO
2
4
=ZrO
2
catalyst (1% mmol) was reuxed
with stirring for the indicated time (see Table 1). The reac-
tion was monitored by TLC. After completion of the reac-
tion, the catalyst was ltered and washed twice with
toluene then with dichloromethane and recycled. The
extracts were combined and washed with 1 M NaOH, then
with H
2
O, and dried with anhydrous sodium sulfate. The
R
H
O
+
O
CATALYST
OH
R'
OH
R'
O
R O
O
R
R'
intermediate
Scheme 1
Sulfated zirconia as an efcient heterogeneous and reusable catalyst for one pot synthesis of avanones 465
organic solution was concentrated in vacuum. The crude
product thus obtained was dissolved in ethyl acetate and
analyzed by GCmass spectrometry (GCMS/MS), Varian
4000 gas chromatograph (GC) FID detector and compared
with authentic samples.
2.4. Solvent-free reaction
Model avanone was prepared by mixing in 15 mmol of benz-
aldehyde derivative and 10 mmol of substituted 2-hydroxyace-
tophenone and heated to 140 C, and SO
2
4
=ZrO
2
catalyst (1%
mmol) was reuxed with stirring for the indicated time (see
Table 1). The reaction was monitored by TLC. After comple-
tion of the reaction, the catalyst was ltered and washed twice
with toluene, then with dichloromethane and recycled to check
the reusability of the catalyst. No appreciable change in the
reactivity was observed for the successive ve runs (Fig. 2).
The extracts were combined and washed with 1 M NaOH, then
with H
2
O, and dried with anhydrous sodium sulfate. The
organic solution was concentrated in vacuum. The crude prod-
uct thus obtained was dissolved in ethyl acetate for analysis by
GCmass spectrometry (GCMS/MS), Varian 4000 gas chro-
matograph (GC) FID detector and compared with authentic
samples. The products were isolated by column chromatogra-
phy and were analyzed by
1
H NMR and GC comparison with
authentic compounds.
3.
1
H NMR data of the products ((CDCl
3
) d (ppm))
3.1. 2,3-Dihydro-2-phenylchromen-4-one
3.5 (d, 2H, OCCH
2
), 5.6 (t, 1H, OCH), 7.07.9 (m, 4H, 5,
6, 7, 8-Ar-H), 7.3 (s, 5H, 2
0
, 3
0
, 4
0
, 5
0
, 6
0
-Ar-H).
3.2. 2,3-Dihydro-6-methoxy-2-phenylchromen-4-one
3.5 (d, 2H, OCCH
2
), 3.8 (s, 3H, OCH
3
), 5.6 (t, 1H, OCH),
6.87.5 (m, 3H, 5, 7, 8-Ar-H), 7.3 (s, 5H, 2
0
, 3
0
, 4
0
, 5
0
, 6
0
-Ar-H).
3.3. 6-Chloro-2,3-dihydro-2-phenylchromen-4-one
3.5 (d, 2H, OCCH
2
), 5.6 (t, 1H, OCH), 6.97.9 (m, 3H, 5,
7, 8-Ar-H), 7.3 (s, 5H, 2
0
, 3
0
, 4
0
, 5
0
, 6
0
-Ar-H).
Figure 1 XRD of SO
2
4
=ZrO
2
.
Table 1 Sulfated zirconia catalyzed synthesis of avanones in the absence of solvents at 140 C.
Reaction R R
0
Isolated yield (%) Selectivity of avanone wrt. intermediate (%)
1 H H 80 71
2 H CH
3
O 78 69
3 H Cl 83 77
4 CH
3
O CH
3
O 73 69
5 CH
3
O Cl 81 78
6 Cl CH
3
O 82 78
7 Cl H 84 81
8 NO
2
CH
3
O 84 79
9 NO
2
H 87 83
Figure 2 Recyclability of catalyst (SO
2
4
=ZrO
2
).
466 B.A. Dar et al.
3.4. 2,3-Dihydro-6-methoxy-2-(4-methoxyphenyl) chromen-4-
one
3.5 (d, 2H, OCCH
2
), 3.8 (s, 6H, OCH
3
), 5.6 (t, 1H, OCH),
6.87.5 (m, 3H, 5, 7, 8-Ar-H), 6.57.1 (s, 4H, 2
0
, 3
0
, 5
0
, 6
0
-Ar-H).
3.5. 2-(4-Chlorophenyl)-2,3-dihydro-6-methoxychromen-4-one
3.4 (d, 2H, OCCH
2
), 3.8 (s, 3H, OCH
3
), 5.6 (t, 1H, OCH),
6.87.5 (m, 3H, 5, 7, 8-Ar-H), 7.17.3 (s, 4H, 2
0
, 3
0
, 5
0
, 6
0
-Ar-H).
3.6. 6-Chloro-2,3-dihydro-2-(4-methoxyphenyl) chromen-4-one
3.4 (d, 2H, OCCH
2
), 3.8 (s, 3H, OCH
3
), 5.6 (t, 1H, OCH),
6.97.9 (m, 3H, 5, 7, 8-Ar-H), 6.87.3 (s, 4H, 2
0
, 3
0
, 5
0
, 6
0
-Ar-H).
3.7. 6-Chloro-2,3-dihydro-2-phenylchromen-4-one
3.4 (d, 2H, OCCH
2
), 5.6 (t, 1H, OCH), 6.97.9 (m, 3H, 5,
7, 8-Ar-H), 7.3 (s, 5H, 2
0
, 3
0
, 4
0
, 5
0
, 6
0
-Ar-H).
3.8. 2-(4-Chlorophenyl)-2,3-dihydro-6-nitrochromen-4-one
3.4 (d, 2H, OCCH
2
), 5.6 (t, 1H, OCH), 3.8 (s, 3H, OCH
3
),
7.38.9 (m, 3H, 5, 7, 8-Ar-H), 6.97.2 (m, 4H, 2
0
, 3
0
, 5
0
, 6
0
-Ar-H).
3.9. 2,3-Dihydro-6-nitro-2-phenylchromen-4-one
3.4 (d, 2H, OCCH
2
), 5.6 (t, 1H, OCH), 7.38.9 (m, 3H, 5,
7, 8-Ar-H), 7.3 (s, 5H, 2
0
, 3
0
, 4
0
, 5
0
, 6
0
-Ar-H).
4. Results and discussion
In view of emerging importance of avanone synthesis we
have found that SO
2
4
=ZrO
2
is an effective, convenient and
practical catalyst (Scheme 1) with excellent yields. The reac-
tion was optimized by taking entry 1 (Table 1) as a model
reaction. In addition to atmospheric conditions the reaction
was also tried in nitrogen atmosphere where better results
were obtained. It is because of the oxidation of aldehydes
to the corresponding acid in the presence of air which was
also conrmed by GCMS. However the reported results
are all under atmospheric conditions. To optimize tempera-
ture, the model reaction was carried at different temperatures
starting from room temperature up to 140 C 5. Only 4
5% yield was observed at room temperature and the yield
increases with increase in temperature, 140 C found to be
optimum beyond which there was no signicant increase in
yield. Reactions 1 and 2 (Table 1) gave better yield even at
90 C. Optimum reaction time was found between 3 and
4 h. No conversion was observed without the catalyst hence
it is concluded that for good yields the catalyst as well as
the high temperature (140 C or above) is essential which
provides the reaction sufcient energy to cross the activation
barrier to form the product. Catalyst recyclability was scru-
tinized for ve cycles without any considerable decrease of
its activity. It is evident from (Table 1) that on substituting
R with electron releasing groups there is a decrease in the
yield as well as the selectivity of the product where as reverse
is the case with electron withdrawing groups, this is because
of decrease and increase in electrophilicity and thus reactivity
of the carbonyl carbon.
5. Conclusion
In conclusion, here we report a simple, one pot and efcient
method for the synthesis of avanones using SO
2
4
=ZrO
2
a
recyclable, cheap, non-toxic and environment friendly catalyst.
The use of SO
2
4
=ZrO
2
catalysts provides very good yields, also
separation and recovery of the catalysts for further use are
easy. The catalytic activity remains constant even up to ve
consecutive reaction batches.
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