Ultrasonics Sonochemistry 17 (2010) 246–249

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

Solvent free synthesis of 1,3-diaryl-2-propenones catalyzed by commercial

acid-clays under ultrasound irradiation
Manef Chtourou, Rami Abdelhédi, Mohamed Hédi Frikha, Mahmoud Trabelsi *
Laboratory of Applied Chemistry: Heterocycles, Fats and Polymers, Faculté des sciences de Sfax, Route de Soukra Km 3,5 – BP 1171, 3000 Sfax, Tunisia

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents a novel solvent free method of synthesis of trans-chalcones. The method was based
Received 27 April 2009 on ultrasound irradiation of the reagents (aryl methyl ketones and aryl aldehydes) in presence of com-
Received in revised form 22 May 2009 mercial acid-montmorillonites as catalysts. The trans-chalcones were synthesized in high yields (85–
Accepted 4 June 2009
95%) and excellent selectivity in a short reaction time.
Available online 10 June 2009
Ó 2009 Elsevier B.V. All rights reserved.

Keywords:
Acid-montmorillonites
Solvent free
Ultrasound
trans-Chalcones

1. Introduction lyzed synthesis of chalcones and became detrimental to the

Trans-chalcones are a family of aromatic ketones with two aro-
matic groups bridged by an enone linkage (Ar–COCH@CH–Ar0 ).
These compounds are employed as such for their antineoplastic,
spasmolytic, antibiotic, bacteriostatic and bactericidal properties
or, due to their chemical flexibility, as synthons for the production
of five- and six-membered ring systems [1], or synthesized to test
their pharmacological activity [2]. Recent studies evaluated the
biological activity of chalcones and revealed them to be anti-
malarial [3,4], anti-cancer [5], anti-leishmanial [6], anti-inflamma-
tory [7], antimitotic [8], anti-tuberculosis [9], cardiovascular [10]
and cell differentiation inducing [11].
Under homogeneous conditions, these compounds are usually
prepared by base or acid catalyzed aldol condensation between
aromatic aldehydes and ketones with stoichiometric amount of
aqueous or solid sodium hydroxide [12], or catalytic amount of
p-toluenesulfonic acid [13].
Different solid catalysts have been employed to synthesize
trans-chalcones, in particular ion-exchanged mesoporous materi-
als [14], potassium hydroxide impregnated silica gel [15], and
acid-montmorillonites under solventless, but severe, conditions
[1].
Since most of the acid-catalyzed reactions required high tem-
peratures, which were responsible for generating side products,
the base-catalyzed reaction has been more widely studied. How-
ever, long reaction times were needed for the reported base-cata-
* Corresponding author. Tel./fax: +216 74 676 606.
E-mail address: Mah.Trabelsi@fss.rnu.tn (M. Trabelsi).
purity of the desired product due to side reactions such as
degradation and Michael addition [16] under basic medium. An
improved synthesis of chalcones, under ultrasound irradiation, in
alcoholic solvents gave good yields using pulverized KOH and
KF–Al2O3 as catalysts [2]. The microwave technique in the
presence of a solid catalyst has been also used for the synthesis
of these compounds [13].
Acid-montmorillonites were widely used as solid acid cata-
lysts for many organic transformations such as isomerisation
[17], alkylation [18], acylation [19], Knoevenagel reaction [20]
and aldol condensation [1]. The last reported synthesis were car-
ried out under high temperatures (130–160 °C) and needed long
reaction time and high amount of clay-catalyst to afford good
yields.
We purpose in this work the synthesis of trans-chalcones cata-
lyzed with acid-montmorillonites under ultrasound irradiation and
solventless conditions. This method allows for high yields in a
short time and at moderate temperatures reaction (100 °C) using
a reduced amount of the clay-catalyst.
2. Experimental
2.1. Materials
Four commercial acid-montmorillonites (KSF, KSF/O, K10 and
KP10) were used as catalysts for the preliminary reactions between
benzaldehyde and acetophenone. Some physicochemical proper-
ties of these clays are listed in Table 1 [21]. Acid-montmorillonites,

1350-4177/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2009.06.008
 M. Chtourou et al. / Ultrasonics Sonochemistry 17 (2010) 246–249
Table 1
Physicochemical properties of the clays catalysts [21].
Clay-catalyst Specific surface area Surface acidity
(m2 g1) (meq. H+ g1)
KSFa 10 0.74
KSF/O 117 1.05
K10 249 0.65
KP10 150 0.58
a
Free acidity: 8–12%.
aryl-benzaldehydes (98–99%) and aryl-acetophenones (98–99%)
were purchased from Fluka and used as received.
2.2. General procedure for the synthesis of trans-chalcones
For a typical synthesis, 2.5 g of KSF, 0.05 mol of aryl benzalde-
hyde and 0.05 mol of aryl acetophenone were charged in a 25 mL
glass reactor. The reaction mixture was heated in an oil bath to
100 ± 2 °C. The ultrasound probe was immersed directly in the
reactor. An ultrasonic generator (Bioblock Scientific 750 W) emits
the sound vibration into the reaction mixture. Sonification was
achieved at low frequencies of 20 kHz (amplitude of 50%). Variable
sonication times were attempted for the condensation of benzalde-
hyde and acetophenone. After cooling to room temperature, etha-
nol or dichloromethane (50 mL) was added, the reaction mixture
was filtered, and the catalyst washed with hot ethanol (50 mL).
Solvent was then evaporated and the dried crude products were
crystallized from 95% ethanol, except for nitro-chalcones, which
were crystallized from acetone, filtrated and finally dried under
vacuum for 48 h. The melting points of the isolated products were
taken on a Reichert-Heizbank apparatus. The yields of the reactions
were determined by Gas chromatography on a Shimadzu 2014-GC
apparatus using diethyl ether as solvent. The capillary column was
DB-5 and the carrier gas was Nitrogen.
2.3. Spectroscopic analysis
The FT-IR spectra were recorded, in KBr, on a Cecil CE7200 spec-
trometer. The NMR spectra of the isolated products were recorded
in solution in CDCl3 on a spectrometer type Bruker (1H at 300 MHz
and 13C at 75 MHz). The internal reference was TMS.
The spectral data of some isolated compounds, taken as repre-
sentative examples, were listed below.
2.3.1. 1,3-Diphenyl-propenone (3ab)
IR [m, cm1] 3058.1(C@C–H, Ar–H), 1662.1(C@O), 1604.9(C@C,
Ar), 1575.5; 1H NMR [d, ppm] 8.03 (2H, d, J = 7.2 Hz), 7.83 (1H, d,
JHa–Hb = 15.6 Hz), 7.55 (1H, d, JHa–Hb = 15.6 Hz), 7.52 (2H, t,
J = 8.7 Hz), and 6H between 7.42 and 7.66 ppm; 13C NMR [d,
ppm] 191.01, 145.30, 138.58, 135.25, 133.24, 131.00, 129.66,
129.31 (2C), 129.06, 128.93 (2C), 128.55, 122.44.
2.3.2. 3-(2-chlorophenyl)-1-(4-chlorophenyl)-propenone (3ec)
IR [m, cm1] 3058.8 (C@C–H, Ar–H), 1659.7 (C@O), 1599.6 (C@C,
Ar); 1H NMR [d, ppm] 8.08 (1H, d, JHa–Hb = 15.9 Hz), 7.86 (2H, d,
J = 8.7 Hz), 7.38 (2H, d, J = 9.0 Hz), 7.34 (1H, d, JHa–Hb = 15.9 Hz),
and 4H between 7.23 and 7.65 ppm; 13C NMR [d, ppm] 189.48,
141.47, 139.78, 136.62, 135.95, 133.47, 131.73, 130.74, 130.41
(2C), 129.38 (2C), 128.22, 127.52, 124.68.
2.3.3. 3-(2-methoxyphenyl)-1-(4-nitrophenyl)-propenone (3fd)
IR [m, cm1] 3077.9 (C@C–H, Ar–H), 2968.9, 2840.4, 1658.2
(C@O), 1585.9 (C@C, Ar), 1343.2 (NO2); 1H NMR [d, ppm] 3.84
(3H, s), 8.23 (2H, d, J = 8.7 Hz), 8.03 (1H, d, JHa–Hb = 15.6 Hz), 8.02
247
(2H, d, J = 9.0 Hz), 7.48 (1H, d, JHa–Hb = 15.6 Hz), and 4H between
6.90 and 7.54 ppm; 13C NMR [d, ppm] 190.07, 159.45, 150.31,
Pore diameter 143.83, 142.80, 132.90, 129.98 (2C), 129.79 (2C), 124.14, 123.72,
(Å) 122.53, 121.26, 111.75, 55.99.
50
74 2.3.4. 3-(4-chlorophenyl)-1-(4-nitrophenyl)-propenone (3gd)
56 IR [m, cm1] 3054.5 (C@C–H, Ar–H), 1664.8 (C@O), 1586.9 (C@C,
71
Ar), 1519.4, 1332.6 (NO2); 1H NMR [d, ppm] 8.35 (2H, d, J = 9.0 Hz),
8.14 (2H, d, J = 8.7 Hz), 7.79 (1H, d, JHa–Hb = 15.6 Hz), 7.46 (1H, d,
JHa–Hb = 15.9 Hz), 7.59 (2H, d, J = 8.7 Hz), 7.42 (2H, d, J = 8.7 Hz);
13
C NMR [d, ppm] 189.06, 150.54, 145.57, 143.21, 137.59 (2C),
133.19 (2C), 130.22 (2C), 129.80 (2C), 124.27 (2C), 122.06.
2.3.5. 1-(4-chlorophenyl)-3-(2-methoxyphenyl)-propenone (3fc)
IR [m, cm1] 2958.8, 2834.9, 1656.3 (C@O), 1597.9 (C@C, Ar); 1H
NMR [d, ppm] 3.82 (3H, s), 8.02 (1H, d, JHa–Hb = 15.9 Hz), 7.86 (2H,
d, J = 8.7 Hz), 7.47 (1H, d, JHa–Hb = 15.9 Hz), 7.37 (2H, d, J = 9.0 Hz),
and 4H between 6.88 and 7.53 ppm; 13C NMR [d, ppm] 190.19,
159.27, 141.32, 139.28, 137.24, 132.35, 130.34 (2C), 129.73,
129.226 (2C), 124.15, 122.74, 121.17, 111.67, 55.95.
3. Results and discussion
The preliminary reactions of aldol condensation of stoichiome-
tric amount of benzaldehyde and acetophenone were achieved
over acid-clays under ultrasound irradiation for 120 min (Scheme
1). The reactor was immersed in a water bath to maintain temper-
ature between 60 and 65 °C. The ratio of acid-clays was equal to
0.5 g/0.01 mol of each reagent in the synthesis of trans-chalcone.
As shown in Table 2, the synthesis of trans-chalcone (3) was car-
ried out in acceptable yield for the condensation of acetophenone
with benzaldehyde catalyzed by 2.5 g of KSF under ultrasound irra-
diation for 120 min.
Among the four acid-clays used, montmorillonite KSF gave the
best results, affording the trans-chalcone in 46.6% yield. KSF and
KSF/O clay-catalysts represented high surface acidities among used
clays. For this reason, these acid-clays gave the best chalcone
yields. However, the surface acidity seems not to be the single fac-
tor affecting the reaction advancement. Indeed, KSF clay gave a
better yield than KSF/O, despite the fact that it’s surface acidity
was less than that of KSF/O. Probably, the low surface area and
the free acidity of the KSF catalyst seem to have a great influence
on its catalytic activity, giving the best yields. Fig. 1 confirms these
results. Indeed, the catalytic activity of the acid-clays catalysts is
controlled by the product of their specific surface area and total
acidity. The exception occurs with KP10, where a negative correla-
Scheme 1. trans-Chalcone synthesis catalyzed by acid-montmorillonites.
Table 2
Yield of trans-chalcone over acid-clays catalysts.
Entry Clay-catalyst Yield (%)
1 None 0.0
2 Montmorillonite KP10 6.6
3 Montmorillonite K10 4.7
4 Montmorillonite KSF/0 20.0
5 Montmorillonite KSF 46.6
248 M. Chtourou et al. / Ultrasonics Sonochemistry 17 (2010) 246–249

Table 4
Effect of the reaction time on the yielda of trans-chalcone.

Time (h) 2 3 4 6
Yield (%) 46.6 56.4 67.4 80.2
a
Yields obtained at 60–65 °C and KSF ratio equal to 0.5 g/0.01 mol.

Fig. 1. Correlation between the condensation yield and the product of the specific
surface area and the surface acidity of the acid-clays.

tion can be observed between this product and the yield of the
condensation.
The effect of the KSF catalyst ratio was then studied. The same Fig. 2. Yields () and selectivity’s (h) of the aldol condensation between benzal-
model reaction (0.05 mol each reagent) was carried out using dif- dehyde and acetophenone at T = 100 °C and KSF ratio equal to 0.5 g/0.01 mol.

ferent amount of KSF clay at 60–65 °C for 240 min under ultra-
sound irradiation. The reaction time was increased to obtain
The increase of the chalcone yield at 100 °C can be explained by
better yields. Results (Table 3) showed that the maximum yield
the decrease of the reaction mixture viscosity, causing an amelio-
was obtained when the catalyst/reagents ratio is equal to 0.5 g/
ration of the reagent’s molecular diffusion and consequently accel-
0.01 mol of each reagent. A higher ratio (0.6 g/0.01 mol) seems to
erating the reaction kinetics. The input acoustic power in reaction
decrease the yield, because the reaction mixture became very vis-
medium (measured by the ultrasound generator) decreases from
cous, under solvent free conditions, thus reducing the diffusion of
35 W/cm2 at 65 °C to 26 W/cm2 at 100 °C. The decrease, at ambient
reagents molecules. This might be explained by a higher adsorp-
pressure, of the effect of ultrasound with increasing temperature
tion of reagents on clay surface. A lower KSF ratio (0.4 g/
has also been observed in other sonochemical reactions, as re-
0.01 mol) afforded reduced yield. It seems that this ratio was insuf-
ported by Entezari and Kauus [24].
ficient to catalyze the reaction and that a KSF ratio equal to 0.5 g/
However, other variables can affect ultrasound effects such as
0.01 mol was optimal in these reaction conditions.
the concentration of solids (in our case the clay-catalyst) and
In order to obtain better chalcone yield, we have carried out the
mainly the viscosity. Raso et al. [25] confirmed that at higher vis-
aldol condensation at a longer reaction time. Table 4 showed the
cosities, cavitation is more difficult to induce (i.e. a greater power
evolution of chalcone yield vs. time. Results showed that a good
input is required) and the number of cavitating bubbles per unit
yield was obtained after 6 h of ultrasound irradiation (80.2%).
volume is reduced. Duran-Valle et al. [23] reported that when
However, the reaction kinetics seems to be very slow. Indeed,
one of the phases is a solid the ultrasonic irradiation has several
increasing the reaction time from 4 to 6 h increased the reaction
additional enhancement effects, which are particularly convenient
yield only of about 13%; and a reaction time equal to 6 h under
when the solid acts as catalyst. The cavitation effects form micro-
ultrasound irradiation seems to be very high. Thus, we have
jects of liquid, which bombard the solid surface. This effect causes
thought to carry out the same model reaction at elevated temper-
the exposition of unreacted surfaces of solid, increasing the inter-
ature (100 °C). Fig. 2 showed that a faster kinetics reaction was ob-
phase surface able to react. In general, the sonication presents ben-
tained at this temperature. The reaction yield reached 80% after
eficial effects on the chemical reactivity, such as to accelerate the
only 30 min and reached its maximum (94.4%) after 60 min of
reaction, to reduce the induction period and to enhance the cata-
ultrasound irradiation. Fig. 2 showed also the high selectivity of
lyst efficiency.
the aldol condensation between benzaldehyde and acetophenone.
A very high yield was obtained after 60 min of ultrasound irra-
Indeed, no secondary products or cis-isomer were detected by
diation. This short reaction time was satisfactory under solvent
GC. The maximum obtained yield was higher than that mentioned
free reaction conditions.
by Li et al. [2] reached after 240 min of utrasonification using KF–
In order to generalize this model reaction, the reactivity of dif-
Al2O3 as catalyst. Ballini et al. [1] have obtained similar yield of
ferent aryl-benzaldehydes and methyl aryl-ketones (Scheme 2)
trans-chalcone (95%) over KSF clay-catalyst after 18 h in carrying
was tested in the same conditions: T = 100 °C, KSF ratio = 0.5 g/
out the reaction in an autoclave at 130 °C. The obtained results
0.01 mol and 60 min of ultrasound irradiation. Results of the ob-
showed that the ultrasound irradiation reduces considerably the
tained yields and selectivity’s are listed in Table 5.
reaction time even in solventless conditions. In deed, ultrasonic
Results showed that, in general, the reactions were clean and
irradiation leads to the acceleration of numerous catalytic reac-
the isolated compounds were obtained, after crystallization, in
tions as well as in homogeneous and heterogeneous systems and
pure form (IR, NMR and GC) without further purification. The
significant improvements of the yields can be realized [22]. The
yields are less than 100% due to the remaining starting reagents.
sonochemical phenomena originate from the interaction between
The chalcones formation took place with excellent selectivity. No
a suitable field of acoustic waves and a potentially reacting chem-
ical system; the interaction takes place through the phenomenon
of acoustic cavitation [23].

Table 3
Effect of the amount of KSF catalyst on the yield of trans-chalcone.

Ratio of KSF (g/0.01 mol) 0.0 0.4 0.5 0.6

Scheme 2. Schematic representation of the synthesis and chemical structures of
Yield (%) 0.0 56.0 67.4 58.2
chalcones.
 M. Chtourou et al. / Ultrasonics Sonochemistry 17 (2010) 246–249 249

Table 5
Yields and selectivity’s of the synthesised 1,3-diaryl-2-propenones.
a
Entry No (1) R1 (2) R2 Compound (3) Time (min) Yield (%) Selectivity [%] mp (°C)
1 H H 3ab 30 79.4 90.3 –
2 H H 3ab 45 91.0 95.0 –
3 H H 3ab 60 94.4 97.0 56–58
4 H H 3ab 240 95.0 98.7 –
5 H 4-Cl 3ac 60 91.2 93.5 98–100
6 H 4-NO2 3ad 60 87.5 97.9 149–150
7 2-Cl H 3eb 60 86.0 87.0 47–49
8 2-Cl 4-Cl 3ec 60 94.2 95.1 81–82
9 2-Cl 4-NO2 3ed 60 91.8 98.9 169–170
10 2-CH3O H 3fb 60 95.3 95.7 54–55
11 2-CH3O 4-Cl 3fc 60 95.2 95.4 76–78
12 2-CH3O 4-NO2 3fd 60 84.4 87.8 152–154
13 4-Cl H 3gb 60 86.0 86.9 112–113
14 4-Cl 4-Cl 3gc 60 85.3 87.3 155–156
15 4-Cl 4-NO2 3gd 60 86.3 98.2 168–170
a
Calculated as the (yield of 3/conversion of 2)  100.

competitive side reactions such as product decomposition, self
condensation, Michael addition, etc. were observed (GC). The reac-
tions of aldehydes bearing electron-donating groups such as OMe
gave the same yield as the corresponding reaction in benzaldehyde
(compare entries 3 and 10; entries 5 and 11). The presence of elec-
tron-withdrawing group such as Cl in the aldehyde afforded lower
yields (compare entries 3 and 7). The presence of an electronic
withdrawing group in the aryl methyl ketone (Cl and NO2) gave
comparable rate of condensation, even when the aldehyde contains
an electronic withdrawing group such as Cl, presumably because of
ease of formation of the corresponding enolate anion (compare en-
tries 3 and 5; and entries 7, 8 and 9).
The following representative example compared the efficiency
of the present method with that of the reported procedures. Con-
densation of benzaldehyde and 4-chlorobenzaldehyde with aceto-
phenone afforded 81 and 72% yields, respectively, after 18 h at
80 °C in DMF in the presence of Zn(bpy)(OAc)2 [26] and 75% and
69.7% yields, respectively, after 24 h at 120 °C using Bamboo char
sulfonic acid as catalyst [27]. The present method afforded 94%
and 86% yields, respectively, after 60 min under solvent free reac-
tion conditions. The condensation of benzaldehyde with 4-chloro-
acetophenone and 4-nitroacetophenone afforded 90% and 80%
yields, respectively, at ambient temperature in ethanol in the pres-
ence of LiOHH2O as catalyst [28]. The present method afforded
91.2% and 87.5% yields, respectively, under solvent free reaction
conditions. The condensation of 2-chlorobenzaldehyde with 4-
chloroacetophenone afforded 90% yield after 18 h of heating, in
an autoclave, at 130 °C in presence of KSF montmorillonite as cat-
alyst [1]. The present synthesis afforded 94.2% yield after only 1 h
of ultrasonification at 100 °C.
The physical properties were determined and structures were
confirmed by IR and NMR spectra. Inspection of 1H NMR spectral
data clearly indicated that the compounds were geometrically pure
and suggested that the ethylene moiety in the enone linkage is in
the trans-conformation (JHa–Hb = 15–16 Hz), possibly with an s-
trans-conformation around the C–C bond [29]. The stereochemistry
of chalcones follows unequivocally from the coupling constant be-
tween the a and b protons. In (E)-isomer JHa–Hb  16 Hz and in (Z)-
isomer JHa–Hb  12 Hz, as confirmed by Makham and Geiger [30].
4. Conclusion
In summary, this paper presents an improved synthesis of trans-
chalcones catalyzed by commercial acid clay (montmorillonite
KSF) under ultrasound irradiation. This method was rapid and
environmentally friendly since the synthesis was carried out under
solventless conditions. The trans-chalcones were synthesized in
good yield and excellent selectivity and the analytical analysis con-
firmed well their structures.
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