Novelty of Claisen-Schmidt condensation of biomass-derived furfural with acetophenone over solid super base catalyst

Article abstract of DOI:10.1039/c4ra09194a

Valorization of biomass into value added chemicals and products using green technologies has been a subject matter of several papers. Claisen-Schmidt condensation of furfural with acetophenone to produce the α,β-unsaturated keto compound, 3-(furan-2-yl)-1

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Novelty of Claisen-Schmidt condensation of
biomass-derived furfural with acetophenone
over solid super base catalyst
Cite this: DOI: 10.1039/x0xx00000x
Ganapati D. Yadav,*and Akhilesh R. Yadav
Received 00th January 2014,
Accepted 00th January 2014
Valorization of biomass into value added chemicals and products using green technologies
have been a subject matter of several papers. Claisen-Schmidt condensation of furfural with
acetophenone to produce α, β-unsaturated keto compound, 3-(furan-2-yl)-1-phenylprop-2-en-1-
one, is commercially attractive since it is used in pharmaceutical industry and can be
hydrogenated to give high quality diesel fuel. In the current work, preparation and
DOI: 10.1039/x0xx00000x
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characterization of 5-15% w/w Al O3 on CaO was done using FT-IR, TGA, XRD, SEM,
2
EDXS, TPD and nitrogen BET. It was used in the reaction of furfural with acetophenone and
its activity and selectivity were compared with other catalysts in a batch reactor at 120 ˚C. 15%
w/w Al O /CaO was the best catalyst. It was 100% selective towards the formation of 3-(furan-
2
3
2
-yl)-1-phenylprop-2-en-1-one. The catalyst is robust and can be reused without loss of
activity. The kinetics of the reaction follows Langmuir-Hinshelwood-Hougen-Watson
mechanism with weak adsorption of all species leading to typical second order kinetics. The
apparent energy of activation is 12.5 kcal/mol.
Introduction
towards development, characterization and application of solid base
2
7-30
catalysts.
In terms of catalytic activity under mild and greener
Chalcones
have diverse biological activities and possess
conditions, solid superbase catalysts are much superior to the
antioxidant, antimicrobial, antimalarial,
antileishmanial, anti-
31
conventional homogeneous catalysts. Of late, increasing attention
1
-9
inflammatory, antitumor and antibacterial activity. The existence
of α, β-unsaturated keto function in chalcones is responsible for
their antimicrobial activity, which may be altered depending on the
nature and position of substituent on the aromatic ring. Structure
activity relationships of various alkoxylated and hydroxylated
chalcones have been reported for antimalarial activity. Chalcones
bearing non-natural substituents have been synthesized during recent
years and some derivatives find use as sweeteners, drugs, and
sunscreen agents. Traditionally, chalcones are synthesized via
Claisen-Schmidt condensation using homogeneous basic catalysts
is focused on development of novel basic solid materials via
different synthetic routes, which may be useful for several important
32,33
base-catalyzed reactions.
Catalytic dehydration of sugar under
3
ambient conditions gives furfural as one of the products, which is a
precious platform molecule for manufacturing chemicals and
1
0
[34]
fuels. Hydrogenation of furfural gives linear C -C adducts which
5
6
35
have very poor performance as fuel. The conversion of furfural
into high quality fuel by aldol condensation with acetone followed
1
1
by hydrogenation and deep hydrogenation was reported by Dumesic
36,37
and co-workers.
As stated earlier, substantial information is
such as NaOH, KOH and Ca(OH) . It is well known that such
2
available on homogeneous catalyzed synthesis of chalcones; but very
few reports have disclosed activity of heterogeneous base catalysts
for the said synthesis. Recently some papers have reported synthesis
catalysts are beset with many drawbacks such as catalyst recovery,
waste treatment and disposal resulting in high cost and a large E-
1
2-15
factor.
As a potential alternative, heterogeneous catalysts have
of furfural based chalcones by homogeneous route, which are not
also been used for Claisen-Schmidt condensation, including Lewis
acids, Brønsted acids, and solid bases.
used for the creation of a combinatorial library of chalcones.
Organolithium bases in apolar solvent were also used. However,
most of these methods require expensive reagents and toxic solvents
to overcome heat and mass transfer problems in liquid phase
reactions. Solid acid catalysts have been explored extensively for a
variety of organic transformations, apart from their major bulk use in
FCC in refineries, whereas limited efforts have been devoted
38-42
only inefficient but also brown processes.
As per our
1
6-24
These reactions have been
understanding there is no information on heterogeneous base
catalyzed synthesis of furfural based chalcones. Recently our group
has demonstrated activity and selectivity of calcined hydrotalcite
2
5
2
6
supported on hexagonal mesoporous silica (CHT/HMS) in
43,44
selectivity engineered base catalyzed reactions.
Herein for the
first time, we report a simple and convenient method for preparation
of solid super base and reusable catalyst for the synthesis of furfural
based chalcones. Its performance is compared with several other
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catalysts to bring out its novelty. The catalyst was prepared by sol- method. Surface area measurement and pore size distributions
gel method and thoroughly characterized by various analytical
techniques such as FTIR, TPD, SEM, XRD, EDX, TGA and
nitrogen BET pore analysis. Effects of various parameters affecting
the reaction rate and conversions were investigated to deduce
kinetics of the reaction. The overall process is clean and green.
analysis were done, after pretreating the sample under high
vacuum at 300 °C for 4 h, by nitrogen adsorption on a
Micromeritics ASAP 2010 instrument at an adsorption
temperature of 77 K. Basic site density was measured by
temperature programmed desorption of CO , pre-adsorbed at
2
room temperature in a Micromeritics -2920 TPR/TPD analyser.
Experimental
o
o
Samples were treated in N at 120 C for 1 h, cooled to 27 C
2
and then exposed to 10 % v/v CO /He stream for 1 h. Weakly
Chemicals
2
adsorbed CO was removed by purging the samples with He at
The following chemicals were procured from firms of repute
and used without further purification. Calcium oxide,
aluminium nitrate, magnesium nitrate, stronsium nitrate,
acetophenone, furfural and decane were obtained from S.D.
Fine Chemicals Ltd, Mumbai, India. The catalysts used for the
reaction were dried at 120 ºC for 2 h before use. Calcined
hydrotalcite (CHT) with different amount of magnesium
loading, calcined hydrotalcite on HMS (CHT/HMS) and
hydrated hydrotalcite (HHT) were prepared by well established
2
room temperature. The temperature was then increased at the
0
0
rate of 10 C/min from 27 to 700 C; the amount of CO2
chemisorbed and its desorption profile were then measured.
A TCD detector was used to measure the ammonia desorption
profile. The elemental composition of prepared catalyst and its
textural property were obtained by Energy Dispersive X-ray
Spectroscopy (EDXS) on a KEVEX X-ray spectrometer and
scanning electron micrograph.
4
3-45
procedures reported earlier by our laboratory.
Experimental set up
All experiments were performed in a stainless Parr autoclave of
capacity 100 cm equipped with a four blade-pitched turbine
Catalyst Preparation
3
Al O /CaO catalyst was prepared by sol-gel method. The
2
3
3
impeller. The temperature could be maintained at ±1 °C of the
desired value with the help of in-built PID controller. The
instrument was also equipped with a speed regulator that could
maintain the speed at ±5 rpm of the desired speed.
Predetermined quantities of reactants and the catalyst were
charged into the autoclave and the temperature was raised to the
desired value. Once the temperature was attained, an initial
sample was withdrawn. Further samples were taken at periodic
intervals. It took 15 min to get the reaction temperature to reach
required amount of Ca(OH) 2 was dispersed in 250 cm of
water. Then 6.6227 g of Al (NO ) .9H O in 50 cm of water
was added drop wise in the above solution. After complete
addition, the solution was stirred for 1 h and refluxed for 24 h at
3
3
3
2
120 °C. The solution was filtered and dried at 120 °C for 12 h
and was subjected to calcination at 700 °C to get the desired
catalyst. Thus, 5-15% w/w Al O /CaO was prepared by this
2
3
method using appropriate quantities of the reagents. Similarly,
5% w/w Al O supported on SrO and MgO were prepared.
1
2
3
1
20 °C and until then the reaction volume was not agitated. A
HT(Hydrotalcite) was prepared by a standard procedure. A
solution of 1 mol magnesium nitrate (Mg(NO ) .6H O) and 0.5
typical standard experiment contained 0.01 mol furfural and
3
2
2
3
0.02 mol acetophenone with 0.0127 g/cm catalyst loading, 120
mol aluminium nitrate (Al(NO ) .6H O) was prepared by
3
3
2
°
C temperature, agitated at 1000 rpm in ethanol solvent.
dissolving the corresponding salts in distilled water. The
solution was then co-precipitated by the addition of 50%
aqueous solution of 3.5 mol NaOH and Na CO (anhydrous
Acetophenone was taken in excess and the conversion was
based on disappearance of limiting reactant furfural.
2
3
0
.943 mol) in distilled water. The addition took about 4 h and
Method of analysis of reaction mixture
Clear liquid samples were withdrawn from the reaction mass
periodically and analyzed by gas chromatography on a Chemito
was carried out carefully with vigorous stirring at room
temperature or below 35 °C. During the addition, the pH of the
solution was maintained between 9 and 10. The slurry was
cooled to room temperature, filtered and washed with deionized
water until the pH of the wash water was 7. After drying at 100
8
610 model, SE-30 stainless steel packed column. The injector
and detector temperatures were programmed from 100 °C to
80 °C with a ramp rate of 10 °C /min. Nitrogen was used as
o
2
C for 24 h, the solids were calcined at 723 K for 12 h to get
3
4
3
the carrier gas at a flow of 0.5 cm /s. Quantitative results were
obtained through calibration by using synthetic mixtures of
reactants and products. The conversion was based on decrease
in concentration of limiting reactant furfural. The reaction
products were confirmed by GC-MS.
CHT(Calcined hydrotalcite).
Catalyst Characterization
IR spectra of the samples pressed in KBr pellets were obtained
with a Perkin Elmer instrument at a resolution of 2 cm
between 4000 cm and 350 cm , and in each case, the samples
-
1
-
1
-1
were referenced against a blank KBr pellet. Powder X-ray Results and discussion
diffraction (XRD) patterns were obtained by using Cu Kα
Scheme 1 depicts Claisen-Schmidt condensation of furfural
with acetophenone. Preliminary experiments showed that
among all synthesized catalysts, 15% w/w Al O /CaO was the
radiation (λ= 1.540562). Samples were step-scanned from 1 to
0 in 0.045 steps, with a stepping time of 0.5 s. The textural
characterization of CaO and 5-15% Al O loaded CaO were
4
2
3
2
3
determined by physisorption of nitrogen BET surface area best in both virgin and reused forms and hence its full
measurements (Micromeritics ASAP). The pore size characterization is reported here (Table 1).
distribution was calculated from the adsorption curve by BJH
2
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amount of –OH groups which are still present at the surface.
-
1
The small peak at 1638 cm indicates water bending on the
4
8
surface due to physically adsorbed water from atmosphere.
XRD studies
The X-ray diffraction (XRD) patterns of uncalcined and
calcined 15% w/w Al O / CaO are shown in Figure 2. The
strong diffraction peaks for CaO were seen in the catalyst
2
3
Scheme1:Claisen-Schmidt condensation of 2-furfural with
acetophenone.
calcined at 700 °C. The peaks for Ca(OH) were also observed
2
in the XRD profile of uncalcined sample. Calcination at 700 °C
leads to decomposition of calcium hydroxide into calcium
oxide. The calcined material shows major diffraction peaks at
Table 1. Effect of Al O loading on CaO: Activity of fresh and
reused catalysts in reaction of furfural with acetophenone
2
3
3
2.2°, 37.4°, 53.9°, 63.2° and 67.5° which are characteristic
Catalyst
Conversion,%
Fresh catalyst Reused catalyst
2 h
peaks of CaO (JCPDS card No. 00-037-1497).
1
h
1 h
2 h
CaO
58
50
88.5 30.3
90.3 41.8
55.6
76.0
5
1
1
% w/wAl O /CaO
2 3
0% w/wAl O /CaO
65
100
100
59.1
70.5
92.1
100
2
3
5% w/wAl O /CaO
71.5
2
3
Reaction conditions: Furfural-0.01 mol, Acetophenone-0.02 mol,
3
Catalyst loading 0.012 g/cm , Speed of agitation-1000 rpm,
Temperature -120 °C, solvent-ethanol, Internal standard-n-Decane-
2
00 µL
Catalyst characterization
FT-IR spectra of uncalcined and calcined 15% w/w Al O on CaO
2
3
are given in Figure 1 to determine the type of groups present in
catalyst. In the case of uncalcined material, the sharp band at 3643
-
1
Fig. 2 XRD analysis of catalyst 15% w/w Al O /CaO
2
3
cm is attributed to the stretching of hydrogen bonded to CaO and
-
1 45
its bending mode at 712 cm .
5
0
The results match with those of Matsuhashi et al. The XRD
patterns of both uncalcined and calcined catalysts show that
there is not
Matsuhashi et al.
aluminium alkoxide on the surface of metal hydroxide in ethyl
a single peak corresponding to CaAl O .
2 4
4
9,50
have reported that decomposition of an
Uncalcined
5
0
acetate is a better way to deposit alumina on metal oxides.
Calcined
Figure 2 distinctly shows peaks for gibbsite phase of aluminium
hydroxide. When the material was further calcined at 700 °C,
the gibbsite phase was transformed into boehmite phase
(
JCPDS card no. 21-13070). In the case of 15% w/w
+
3
Al O /MgO, high fraction of the Al ions are in octahedral
sites, probably due to substitution of Mg ions by Al ions.
Deposition of a layer of Al O on the surface of CaO was
2
3
+
2
+3
49
2
3
4
9,50
expected as per literature.
5% w/w Al O /CaO was very stable beyond 700 ° according
1
2
3
to the TGA analysis (Figure 3). However, the loss in weight
from 200 to 550 C can be explained. A loss of about 3.9%
o
Fig. 1 FTIR of catalyst 15% w/w Al O /CaO
2
3
weight was observed due to moisture present in the catalyst and
-
1
The weak band observed at 1120 cm and strong band at 474
also removal of CO from the carbonate species used in the
2
-
1
46
-2
cm is due to Al-O bond. Asymmetric stretching of CO is
indicated by two bands at 1448 cm and 1414 cm . The weak
band at 874 cm is due to out of plane bending of CO3
After calcination, the intensity of most of the bands is greatly
3
preparation. The weight loss below 200 °C was due to the loss
of interlayer water and physically absorbed moisture. The next
weight loss at 300 °C is attributed to hydroxyl group from the
-
1
-1
-
1
-2 47,48
.
brucite-like layer of calcium hydroxide. Another loss close to
-
1
reduced. The broad band at 3423 cm is due to a sizeable
-2
5
00 °C is because of CO and CO3 removal. The catalyst is
2
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4
9,50
very much stable above 550 °C.
low strength due to presence of hydroxyl groups and medium and
strong basic sites due to basic oxygen atoms present on the surface
Fig. 3 TGA of 15% w/w Al O /CaO catalyst
2
3
BET surface area analysis
Fig. 4 N adsorption ASAP of calcined catalyst 15% w/w
2
Al O /CaO
2
3
The catalyst shows characteristic type IV adsorption isotherms with
well defined steps in nitrogen adsorption and desorption isotherms
(Figure 4). There is a hysteresis in the adsorption-desorption
isotherm at relative pressure (p/p ) in the range of 0.4-0.94. The
o
physical properties of CaO and 5 to 15% w/w Al O /CaO catalysts
2
3
are shown in Table 1. There is a slight decrease in the surface area
and pore volume of the CaO as the Al O loading increases which
2
3
suggest that aluminium oxide is being generated on the surface of
CaO. The growth of crystalline Al O on the CaO is also supported
2
3
by XRD and FTIR. The average pore diameter 15% w/w Al O /CaO
2
3
is found to be 11.0 nm. The explanation is in accordance with
5
2
IUPAC classification. The textural characteristics of catalyst with
different loading of alumina on the calcium oxide are described in
Table 2.
Table 2. Textural characteristics of catalyst with different
loading of Al O on CaO
2
3
Catalyst
S
Dav
[A°]
Vtotal
[cm g ]
BET
2
-1 [a]
[b]
3 -1 [c]
[
m g ]
CaO
55.61
49.51
43.96
92.6
89.2
90.0
0.15
0.13
0.12
Fig. 5 CO - TPD of 15% w/wAl O /CaO
2
2
3
5
1
1
% w/w Al O /CaO
2 3
0% w/w Al O /CaO
of the catalyst. The two strong peaks at 394 °C and 665 °C
2
3
3
3
correspond to 33.82 cm /g and 47.29 cm /g of CO which was
5% w/w Al O /CaO
62.85
95.4
0.18
2
2
3
a
b
adsorbed at STP, respectively. These two peaks are responsible
for generation superbasicity in the catalyst.
BET surface area of various catalysts, Average pore diameter
(
c
4 V/A)° by BET, BJH pore volume.
SEM of catalyst
CO - TPD analysis of 15% w/wAl O /CaO
2
2
3
The particle morphology SEM at various magnifications for
uncalcined and calcined 15% w/w Al O on CaO is shown in
2
3
CO -TPD was done for calcined 15% w/w Al O /CaO sample Figure 6. The SEM result also supports formation of large
2
2
3
(Figure 5). There are basic sites of different strength consisting of particle of Ca(OH)2 with smooth planes and high degree of
4
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crystallinity, and incorporation of aluminium hydroxide on the Claisen-Schmidt condensation of furfural with acetophenone for
surface of calcium hydroxide in uncalcined sample (Figure 6A synthesis of 3-(furan-2-yl)-1-phenylprop-2-en-1-one was chosen to
and B). After calcination at 700 °C very rough surface was
revealed (Figure 6C and D). The particle size was in the range
of 1-5 µm.
Table 3. EXDS analysis
Element
O
Weight / %
30.73
62.97
6.30
Atomic / %
51.51
42.21
6.28
Ca
Al
Total
100
100
study the efficacy of a variety of catalysts (Scheme S1 in
Supplementary Material). The effects of various catalysts on the
yield of the product were studied.
Catalyst Screening
Fig. 6 SEM of uncalcined (A, B) and calcined catalysts (C, D)
Aluminium hydroxide was present on the surface as hexagonal
plates like particles before calcination, whereas after calcination
Fig. 8 Efficacy of various catalysts.
Reaction conditions: Furfural-0.01 mol, Acetophenone-0.02 mol,
3
Catalyst loading- 0.012 g/cm , Speed of agitation-1000 rpm,
Temperature -120 °C, solvent-ethanol, Internal standard-n-Decane-
2
00 µL, Time – 2 h.
Fig. 7 EDXS analysis of 15% w/w Al O /CaO
2
3
Various catalyst prepared by sol-gel method were screened under
otherwise similar conditions. The activity of CaO, 15% w/w Al O
2
3
supported on CaO, MgO and SrO, hydrated hydrotalcite (HHT),
calcined hydrotalcite (CHT) with different ratio of Mg:Al, are given
in order to study the effect of mole ratio of Mg:Al on catalytic
activity of CHT. For instance, CHT (3:1) stands for Mg:Al ratio in
the CHT. Concentration profiles were monitored for each catalyst
and the initial activity was calculated. The initial activity was the
highest for 15% w/w Al O /CaO and it gave maximum conversion
the structure was disturbed with an irregular morphology (Figure 6).
Figure 7 gives EDXS analysis of 15% w/w Al O /CaO after
calcination at 700 °C which shows the incorporation of alumina on
surface of CaO (Table 3).
2
3
Catalytic application
2
3
of 98.5% within 2 h for furfural to acetophenone mole ratio 1:2 at
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3
1
20 °C at a catalyst loading of 0.0127 g/cm based on total volume
of liquid (Figure 8). Pure calcium oxide obtained by calcination of
Ca(OH) at 700 °C gives 88.5% conversion in the same time but it
2
has got very poor reusability. Therefore it was not selected for
[
53]
further study. Hattori et al. have reported CaO and SrO as efficient
catalysts for self condensation of furfural (called Tishchenko
reaction to give 2-furylmethyl-2-furancarboxylate) at 80 °C.
However, in the current work there was no self condensation over
1
5% w/w Al O /CaO. The activity of other alumina loaded catalyst
2 3
was found to be very low (Figure 8). Uncalcined hydrotalcite with
Mg: Al (3:1) gives 16.8% conversion whereas calcined hydrotalcite
gives 13.4% conversion of the limiting reactant. We have also tested
two calcined hydrotalcite (CHT) catalysts with mole ratio of Mg: Al
as 5:1 and 9:1. Hardly 2% increase in the conversion was observed
for CHT with Mg: Al ratio 9:1 as compared to Mg: Al ratio 5:1.
Effect of loading of Al O and reusability after 1 and 2 h reaction
2
3
times is also given in Table 1 for all catalysts. The activity and
reusability of 15% w/w Al O /CaO was found to be the best. These
2
3
49,50
results are in agreement with Matsuhashi and co-workers.
it can be concluded that loading of alumina on calcium oxide
enhances its activity, stability and reusability of catalyst. Therefore Reaction conditions: Catalyst-15%w/w Al O /CaO, Furfural-
Hence
Fig. 9 Efficacy of reusability of catalyst
2
3
1
5% w/w Al O /CaO was selected for further investigation. Various 0.01 mol, Acetophenone-0.02 mol, Catalyst loading 0.012
2
3
3
g/cm , Speed of agitation-1000 rpm, Temperature -120 °C,
parameters affecting rate of reaction and kinetic model of the
reaction is given in supporting information.
solvent-ethanol, Internal standard-n-Decane-200 µL. Time- 2 h
In conclusion we have developed a simple, efficient, and
environmentally benign method for the liquid phase Claisen-
Schmidt condensation of furfural with acetophenone to produce
Catalyst reusability
The reusability of 15% w/w Al O /CaO was tested by
conducting 4 runs (Figure 9). After each run the catalyst was
filtered and refluxed for 2 h with 50 cm of ethanol in order to
remove any adsorbed material from the pores. It was filtered
and dried in an oven at 120 ºC for 2 h. Since there are losses of
particles during filtration due to attrition, the actual quantity of
catalyst used in next batch was almost 4-5% less than the
previous batch. The volume of reaction mixture was adjusted to
2
3
3-(furan-2-yl)-1-phenylprop-2-en-1-one.
3
Acknowledgements
G.D.Y. received support from R.T. Mody Distinguished
Professor Endowment and as J.C. Bose National Fellow from
Department of Science and Technology, Government of India.
A.R.Y. thanks UGC for providing JRF under its BSR in Green
Technology.
3
make up the catalyst loading of 0.0127 g/cm . It was observed
that there is only marginal decrease in the conversion. Thus, the
catalyst was active and reusable (Table 1).
Notes and references
a
Department of Chemical Engineering, Institute of Chemical
Technology,Matunga, Mumbai 400 019, India.Fax: 91-22-3361-1002;
Tel:91-22-3361-1001
Conclusions
15 % w/w Al O /CaO was synthesized and fully characterized
2 3
gdyadav@yahoo.com,gd.yadav@ictmumbai.edu.in (G.D.Yadav);
gdyakhilesh@gmail.com (A.R. Yadav)
by FT-IR, XRD, surface area analysis, TGA, SEM, EDXS, and
CO -TPD. The catalyst possesses excellent activity and 100%
2
†
Electronic Supplementary Information (ESI) available:
selectivity for the Claisen-Schmidt condensation of
furfuraldehyde with acetophenone. It gives the best result at a
3
catalyst loading of 0.0127 g/cm , furfural to acetophenone mole 1.R. J. Anto, K. Sukumaran, G. Kuttan, M. N. A. Rao, V. Subbaraju, R.
ratio of 1:2, speed of agitation 1000 rpm and temperature of
20 °C. Since no side reaction such as aldol condensation or
Tishchenko reaction was observed and the only coproduct is
water, our methodology fits into the principles of green
chemistry toward development of atom economical and
Kuttan, Cancer Lett. 1995, 97, 33.
1
2
3
. J. Vaya, P. A. Belinky, M. Aviram, Free Radic. Biol. Med. 1997, 23,
3
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Table of Contents Entry
Novelty of Claisen-Schmidt condensation of biomass-
derived furfural with acetophenone over solid super
base catalyst
Ganapati D. Yadav,*and Akhilesh R. Yadav
1
5% w/w Al O /CaO is an excellent and reusable
2
3
catalyst for 100% selective condensation furfural with
acetophenone to produce 3-(furan-2-yl)-1-phenylprop-
2
-en-1-one.
8
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