Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247

https://doi.org/10.1007/s11144-018-1495-9

Alkaline–modified montmorillonite K10: an efficient

catalyst for green condensation reaction of aromatic
aldehydes with active methylene compounds

Manef Chtourou1 · Achraf Lahyani1 · Mahmoud Trabelsi1

Received: 5 October 2018 / Accepted: 5 November 2018 / Published online: 12 November 2018
© Akadémiai Kiadó, Budapest, Hungary 2018

Abstract
An efficient and reusable catalyst, alkaline–modified Montmorillonite K10, has
been developed and used in the Knoevenagel condensation. A series of condensa-
tion reactions based on ultrasound irradiation of different types of active methylene
compounds and a variety of aromatic aldehydes showed the high efficiency of the
prepared catalyst. This protocol has notable advantages, such as being eco-friendly,
the ease of the work-up and reuse of the catalyst. The isolated compounds were syn-
thesized in high yields (83–100%) in a short reaction time and were obtained, after
crystallization, in pure form (IR, NMR and GC) without further purification. When
ethyl cyanoacetate was used as active methylene compound, the reaction is highly
stereoselective with only E geometry.

Keywords Alkaline modification · Knoevenagel condensation · Montmorillonite

K10 · Ultrasound irradiation

Introduction

The Knoevenagel condensation is one the well-known reactions in organic chemis-

try in order to form carbon–carbon bond from aldehydes and active methylene com-
pounds. The obtained functionalized alkenes are important components in flavor,
perfumes, pharmaceuticals, coumarin derivatives, cosmetics and polymers. These
compounds are also used in the synthesis of chemical intermediates such as car-
bocyclic as well as heterocyclic compounds of biological significance [1], calcium
antagonists [2] and anti-hypertensive drugs. The Knoevenagel adducts are also use-
ful intermediates for further transformations, such as Diels–Alder and Michael addi-
tions [3].

* Mahmoud Trabelsi
Mah.Trabelsi@fss.rnu.tn
1
Laboratory of Organic Chemistry, Faculty of Sciences of Sfax, University of Sfax, Route de
Soukra Km 3.5, BP 1171, 3000 Sfax, Tunisia

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238 Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247

Under homogeneous conditions, the Knoevenagel condensation is usually

catalyzed by weak bases like primary, secondary, tertiary amines [4], ethylene
diamine [5], dimethylamino-pyridine [6] and ammonium salts [2]. The recov-
ery of the conventional catalysts is difficult and their utilization is associated
with environmental pollution. From the view point of green chemistry, the use
of toxic solvents and homogeneous catalysts is desirable. The development of
environmentally friendly solid catalysts has known a great growing interest [7].
Solid catalysts provide high yield and selectivity along with waste reduction,
easier catalyst recovery and possible reusability and safer and easier operation
methods. Various solid catalysts and solid-supported catalysts have been applied
to Knoevenagel condensation such as anion–exchange resin [8, 9], alkaline earth
oxides [10], alkali-exchanged zeolites [11], calcined hydrotalcites [12], sulfate
promoted zirconia [13], magnesium perchlorate [3], diphosphate [14], MgO/
ZrO2 composite oxide [15], robust C ­ eZrO4 [16], Ru(OH)x supported on poly-
ethylenimine modified magnetic nanoparticles coated with silica [17] and clays
[18, 19]. The last reported synthesis used commercial acid-montmorillonites as
catalysts and was carried out under high temperatures and needed long reaction
time.
Acid–activated clays have been widely used as catalysts in many organic
transformations [20–22]. There are few works that described the preparation
and the utilization of alkaline–modified clays as catalysts in organic chemistry
[23–27]. The base modification of the clay serves two purposes. First, it neutral-
izes substantially all of the acid sites (OH sites) within the clay and replaces
them with their conjugate basic sites (­O−). Second, the treatment impregnates
the clay with cations from the base [24, 26].
We purpose in this work the use of NaOH-modified Montmorillonite K10 as
catalyst in the Knoevenagel condensation. This method is based on ultrasound
irradiation of the reaction mixture at ambient temperature and uses ethanol as
eco-compatible solvent, allowing for high yields in a short reaction time.

Experimental

Catalyst preparation

To 20 g of montmorillonite K10 was added 200 mL of 2 M NaOH aqueous solu-

tion in a 500 mL reactor equipped with a vapor condenser. The dispersions were
heated under reflux and magnetic stir for 3 h. The resulting alkaline clay, noted
A-K10, was recovered by filtration, washed three times by 100 mL of hot dis-
tilled water and finally dried at 100 ± 5 °C. This catalyst was characterized using
energy dispersive X-ray spectroscopy (EDX) attached to a scanning electron
microscope for elemental composition and SEM images, XRD (X’Pert Pro PAN-
alytical diffractometer) with Cu K ­ α1 radiation (40 kV and 40 mA). The original
montmorillonite K10 was also characterized using the same methods.

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Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247 239

General procedure for the condensation of aryl aldehydes with ethyl

cyanoacetate and malonitrile

For a typical synthesis, 10 mmol of aromatic aldehyde and 10 mmol of malonitrile

or ethyl cyanoacetae were dissolved in 2 mL of absolute ethanol in a 10 mL glass
reactor.
0.15 g of clay-catalyst was then added and the reactor was placed in a water bath.
The ultrasound probe was immersed directly in the reactor. An ultrasonic genera-
tor (Bioblock Scientific 750 W) emits the sound vibration into the reaction mixture.
Sonification was achieved at low frequencies of 20 kHz (amplitude of 30%) and the
water bath temperature (r.t) was controlled by the addition and remove of water.
Variable sonication times were attempted for the condensation of benzaldehyde and
malonitrile or ethyl cyanoacetae. Dichloromethane (10 mL) was added, the reaction
mixture was filtered, and the catalyst washed with dichloromethane (20 mL) and
dried at 100 ± 5 °C for further reuse times. Solvent was then evaporated and the
dried crude products were crystallized from absolute ethanol, 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 dichlorometh-
ane as solvent. The capillary column was DB-5 and the carrier gas was Nitrogen.
The conversion of the aromatic aldehydes was calculated as follows: Conversion
(wt%) = 100 × [initial wt%−final wt%]/initial wt%.

Spectroscopic analysis

The FT-IR spectra were recorded, in KBr, on a Cecil CE7200 spectrometer. The
­ DCl3 on a spec-
NMR spectra of the isolated products were recorded in solution in C
trometer 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 representative
examples, were listed below:

2-(4–chlorobenzylidene) malononitrile (entry 13): White, crystalline solid.

IR [ν, ­cm−1] 3032.9, 2922.9, 2227.4, 1636.1, 1584.9, 1406.8; 1H NMR [δ, ppm]
7.89 (d, 2H aromatic, J = 8.4 Hz), 7.76 (s, 1H alkenic), 7.54 (d, 2H aromatic,
J = 8.7 Hz); 13C NMR [δ, ppm] 158.7, 141.6, 132.2, 130.5 (2C), 129.6 (2C),
113.8, 112.7, 83.7.
2-(2–methoxybenzylidene) malononitrile (entry 10): Yellow, crystalline solid.
IR [ν, ­cm−1] 3045.8, 2928.8, 2221.5, 1578.1, 1463.9, 1369.0; 1H NMR [δ, ppm]
8.31 (s, 1H alkenic), 8.19 (d, 1H aromatic, J = 8.1 Hz), 7.60 (d, 1H aromatic,
J = 7.5 Hz), 7.08 (d, 1H aromatic, J = 7.5 Hz), 7.01 (d, 1H aromatic, J = 8.4 Hz),
3.94 (s, 3H aliphatic); 13C NMR [δ, ppm] 159.3, 154.9, 137.0, 129.2, 121.6,
120.5, 114.8, 113.4, 111.9, 81.6, 56.4.
Ethyl (E) 2-cyano-3-(2–chlorophenyl)-2-propenoate (entry 3): White, crystalline
solid.

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240 Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247

IR [ν, c­ m−1] 2994.6, 2223.2, 1731.0, 1609.5, 1467.6; 1H NMR [δ, ppm] 8.69 (s,
1H alkenic), 8.24 (d, 1H aromatic, J = 7.2 Hz), 7.50 (d, 2H aromatic, J = 7.5 Hz),
7.43 (d, 1H aromatic, J = 7.5 Hz), 4.41 (q, 2H aliphatic, J = 7.2 Hz), 1.42 (t, 3H
aliphatic, J = 7.2 Hz); 13C NMR [δ, ppm] 162.2, 151.6, 136.8, 134.1 (2C), 130.7,
130.2, 127.8, 115.2, 106.5, 63.3, 14.5.
Ethyl (E) 2-cyano-3-(4–nitrophenyl)-2-propenoate (entry 4): Yellow, crystalline
solid.
IR [ν, c­m−1] 3037.0, 2999.0, 2853.3, 2225.8, 1720.0, 1616.7, 1593.5, 1515.8,
1347.3; 1H NMR [δ, ppm] 8.36 (d, 2H aromatic, J = 9.0 Hz), 8.32 (s, 1H alkenic),
8.15 (d, 2H aromatic, J = 8.7 Hz), 4.43 (q, 2H aliphatic, J = 7.2 Hz), 1.43 (t, 3H
aliphatic, J = 7.2 Hz); 13C NMR [δ, ppm] 161.8, 152.1, 150.0, 137.3, 131.9 (2C),
124.7 (2C), 114.9, 107.7, 63.7, 14.5.

Results and discussion

Characterization of catalysts

The chemical composition of K10 and A-K10 obtained using energy-dispersive

spectrometry (EDS) are presented in Table 1. Results showed that sodium and cal-
cium percentages were increased after alkaline modification of K10 (from 0.29 to
4.96% and from 0.20 to 1.07%). However, the silica percentage was decreased from
32.51 to 21.82%. These results can be explained by the substitution of ­Si4+ with
­Al3+ and A­ l3+ with F
­ e2+ or M
­ g2+ that give the lattice a net negative charge which is
balanced by alkali and alkali earth cations (usually N ­ a+ and ­Ca2+) located between
the layer [28]. However, EDS is indicative of mainly the surface species; hence,
more evidence for confirming the intercalation should be obtained by X-ray diffrac-
tion [29].
The X-ray diffraction patterns of parent K10 and A-K10 are shown in Fig. 1. In
general, the XRD pattern of A-K10 was virtually unchanged as compared to that
of parent clay to indicate the satisfactory retention of the crystallinity as well as
that no delamination occurred during the base modification [29]. The peak at 8.9°
corresponding to a basal spacing of 9.92 Å is typical to collapsed 2:1 phyllosili-
cates which matches with the diffraction pattern of a mica and phengite [26]. The
same diffraction pattern is detected in A-K10 with decreasing peak intensity. After
sodium intercalation, the basal spacing was increased from 9.92 Å for K10 to 12.6 Å
and 15.1 Å for A-K10. The (001) reflection (d = 12.6 Å) was the characteristic of a
sodium smectite, d = 15.1 Å could as well correspond to a sodium smectite [26, 30].

Table 1  Chemical composition [wt %] O Si Al Ca Mg Na K Ti Fe

of Montmorillonite K10 and
alkaline modified K10 K10 51.66 32.51 10.37 0.20 1.41 0.29 0.92 0.31 2.33
A-K10 52.96 21.82 11.22 1.07 1.47 4.96 1.23 0.44 4.82

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Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247 241

Fig. 1  X-ray diffraction patterns of montmorillonite K10 and the alkaline modified K10 (A-K10)

The increase of Na percentage from 0.29 to 4.96% (Table 1) was in correlation with
the increase of the basal spacing from 9.92 to 12.6 Å.
Fig. 2 shows the comparison between SEM images of parent K10 and A-K10.
It reveals that majority of the particles in both samples had a lamellar morphol-
ogy with a composition similar to 2:1 phyllosilicate that corresponds with the mica

Fig. 2  SEM images for a montmorillonite K10 and b alkaline modified K10 (A-K10)

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242 Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247

phase as observed under XRD. The images show that the modified clay had mostly
similar morphology to the parent clay consisting mainly of flake-shaped particles
which were somehow similar to a layered structure of smectite clay [26]. In conclu-
sion, layered nature seemed to prevail after sodium intercalation into K10.

Catalytic activity

A series of preliminary tests between the stoichiometric amount of benzaldehyde

and ethyl cyanoacetate or malonitrile (10 mmol) over A-K10 clay catalyst (0.25 g)
under ultrasound irradiation were realized to optimize the main experimental param-
eters involved in the conduct of the condensation. In order to elucidate the effect of
ultrasound irradiation on the Knoevenagel condensation, comparative essays using
conventional method were realized. Results (Table 2) showed that the ultrasonifica-
tion allows reducing considerably the reaction time.
The sonication presents beneficial effects on the chemical reactivity, such as to
accelerate the reaction, to reduce the induction period and to enhance the catalyst
efficiency. Duran–Valle et al. [31] claimed that the cavitation effect causes the expo-
sition of the unreacted surfaces of the solid catalyst increasing the interphase surface
able to react.
The alkaline modified K10 afforded 100% condensation yields due to its basic
character, manifested by a relatively important Na percentage (4.96%). Montmoril-
lonite K10 exhibited poor catalytic activity due to its acidic character since it had
both Bronsted and Lewis acidic sites [32]. It seems that the catalytic activity of the
clay-catalyst was controlled by their sodium content, traducing the level of basic
sites ­(O−) and consequently the strength of the basic properties of the prepared clay
catalyst [24]. The acidic or basic nature of montmorillonite structure was mostly
influenced by its specific character of having combined water (structurally bound
OH form or loosely bound ­H2O). Thus, the base modification had neutralized most
of the acid sites within the clay and replaced them with their conjugate basic sites
­(O−) and impregnated the clay with cations [32].
Results showed also that faster kinetics reactions, between malonitrile and
benzaldehyde, were obtained when compared with those of the condensation of

Table 2  Effect of ultrasound irradiation on Knoevenagel condensation over K10 and A-K10 catalysts
Catalyst Substrate Magnetic stir (r.t) Ultrasound irradiation (r.t)
Time Yield (%) Time (min) Yield (%)

None Ethyl cyanoacetate 60 0

K10 Ethyl cyanoacetate 60 3
A-K10 Ethyl cyanoacetate 24 h 96 60 100
2h 57 30 100
10 77
Malonitrile 30 min 72 30 100
2h 94 10 100

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Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247 243

Fig. 3  Effect of A-K10 catalyst ratio on the yield of ethyl α-cyanocinnamate. Experimental conditions:
0.01 mol each reagent, T = 25–30 °C and 30 min of ultrasound irradiation

Fig. 4  The yield of ethyl

α-cyanocinnamate after four
cycles of use of A-K10 catalyst.
Experimental conditions:
catalyst ratio = 0.15 g/0.01 mol
each reagent, T = 25–30 °C and
30 min of ultrasound irradiation

benzaldehyde with ethyl cyanoacetate. This result can be explained by the better
electron withdrawing ability of malonitrile, as reported by Postole et al. [33]. Cli-
ment et al. [34] confirmed that the rate controlling step of the condensation reaction
on basic solids is the attack by the carbanion intermediate on the carbonyl group of
benzaldehyde.
The effect of catalyst ratio was then studied. The same reaction model (0.01 mol
each reagent) was carried out using different amounts of A-K10 catalyst at 25–30 °C
for 30 min under ultrasound irradiation. As shown in Fig. 3, the maximum yield was
obtained when the catalyst/reagent ratio is equal to 0.15 g/0.01 mol of each reagent.
From this ratio the yield remains constant.
The reusability of the base-modified clay A-K10 was also studied on four con-
secutive reaction cycles for the synthesis of ethyl α-cyanocinnamate for 30 min of
ultrasound irradiation. The recovered catalyst was used, after washing with dichlo-
romethane (20 mL) and drying at 100 ± 5 °C, under the conditions same as those
in the first run. The results in Fig. 4 showed that the condensation yield decreased
slowly from 100 to 92% after four reuses times. These results confirmed that the
prepared catalyst exhibited good and nearly consistent catalytic activity since it was
slowly deactivated. The deactivation of the activity of AK10 in the reaction could
be mainly attributed to the state change of some basic sites from ­O− to acid sites
OH due to the reaction conditions (presence of water as product of the condensation

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244 Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247

Scheme 1  Schematic representation of the condensation reaction of aromatic aldehydes with active
methylene compounds

Table 3  Knoevenagel condensation of aldehydes with ethyl cyanoacetate and malonitrile

Entry Ar Z Time (min) Conversion (%) GC yield (%) melting point (°C)

Found Reported

1 C6H5 CO2Et 30 100 100 54–55 50–51 [36]

2 2-CH3OC6H4 CO2Et 30 82 88 74–75 72–74 [9]
3 2-ClC6H4 CO2Et 30 92 92 58–59 52–53 [37]
4 4-NO2C6H4 CO2Et 30 100 100 172–173 168–169 [36]
5 4-ClC6H4 CO2Et 30 97 98 91–92 89–90 [38]
6 4-CH3O ­C6H4 CO2Et 30 78 83 86–87 85–86 [9]
7 3,4-(CH3O)2 ­C6H3 CO2Et 30 92 95 148–149 –
8 3,4,5-(CH3O)3C6H2 CO2Et 30 83 88 81–82 –
9 C6H5 CN 10 100 100 80–82 82–83 [38]
10 2-CH3OC6H4 CN 10 100 100 82–84 85–86 [9]
11 2-ClC6H4 CN 10 100 100 94–96 94–96 [37]
12 4-NO2C6H4 CN 10 100 100 160–161 159–160 [37]
13 4-ClC6H4 CN 10 100 100 162–163 161–162 [38]
14 4-CH3OC6H4 CN 10 100 100 112–114 114–115 [9]
15 3,4-(CH3O)2C6H3 CN 10 100 100 142–143 –
16 3,4,5-(CH3O)3C6H2 CN 10 100 100 140–141 –

reaction). Beavers and Culp [24] confirmed that the base cation is in the form of
chemically bound ions, not merely adsorbed, because they remain in the catalyst
after several washings with solvent. The ­Na+ cation remains separate, largely within
the interstitial cavity bound by ionic forces in order to balance the negative charge of
the basic sites ­(O−) but physically too large to fit into the clay’s layer structure. The
resulting forced charge separation serves to further increase the basicity and further
enhance the unusual basic properties of the catalyst.

Generalization of the reaction model

Owing to its high catalytic activity, the alkaline–modified clay was used as cata-
lyst for a series of condensation reactions carried out using different types of active
methylene compounds and a variety of aryl aldehydes (Scheme 1).
Results of the obtained yields are presented in Table 3. Results showed that,
in general, the reactions were clean and the isolated compounds were obtained,

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Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247 245

after crystallization, in pure form (IR, NMR and GC) without further purifica-
tion. The yields are less than 100% due to the remaining starting reagents. When
ethyl cyanoacetate was used as active methylene compound, the reaction is highly
stereoselective with only E-geometry. The (E)-stereochemistry of the molecules
was assigned on the basis of the chemical shift values of the β-vinylic protons
(8.02–8.69 ppm) [35]. The excellent selectivity’s for the synthesized compounds,
confirmed that no competitive side reactions such as product decomposition, Can-
nizzaro condensation, etc. were observed (GC).
As a general view, the aromatic aldehydes bearing electron-withdrawing groups
reacted more easily in comparison with those containing electro-donating groups
(compare entries 3, 4 and 5; entries 2, 6 and 8).
The following representative examples compared the efficiency of our method
with those of some reported procedures. The Knoevenagel condensation of benza-
ldehyde and 4-chlorobenzaldehyde with malonitrile afforded 92% and 84% yields
after 24 h at 160 °C in the presence of montmorillonite KSF [19], 93% and 65%
yields after 20 min at 60 °C in the presence of MgO/ZrO2 composite oxide as cata-
lyst [15], 89% and 88% yields after 180 and 120 min under heat using SO2−
4 /ZrO2 as
catalyst [13] and 82% and 81% yields under reflux of ethanol using ­CexZn1−xO2 as
catalyst for 50–60 min [33]. The A-K10 catalyst allowed affording 100% yields at
room temperature after only 10 min of ultrasound irradiation.
The condensation of 2-chlorobenzaldehyde with ethyl cyanoacetate afforded
75% yield after 90 min at 60 °C using MgO/ZrO2 composite oxide as catalyst
[15]. The A-K10 catalyst afforded 92% yield at room temperature after 30 min of
ultrasonification.
The condensation of benzaldehyde and 4-nitrobenzaldehyde with ethyl cyanoac-
etate afforded 80% and 88% yields after 90 min at 60 °C [15] and 78% and 85%
yields under reflux of ethanol [33]. The present method afforded 100% yields after
30 min of ultrasound irradiation.

Proposed mechanism

The basic sites ­(O−) on clay catalyst surface produce a carbanion from activated
methylene compound as shown in Scheme 2, the conjugated base generated here
is stable due to conjugation with the cyano-group. This anion makes a nucleophilic
attack on the carbonyl-carbon atom of the aromatic aldehyde to form the final prod-
uct by simple dehydration.

Conclusion

This paper presents the utilization of alkaline-modified Montmorillonite K10 as

catalyst for Knoevenagel condensation. The prepared catalyst showed efficient and
consistent catalytic activity for several reactions cycles. The synthesis method was
rapid, safe, easy and environmentally friendly since it was carried out under ultra-
sound irradiation, at room temperature and uses ethanol as eco-compatible solvent.

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246 Reaction Kinetics, Mechanisms and Catalysis (2019) 126:237–247

Scheme 2  The proposed mechanism of Knoevenagel condensation catalyzed by A-K10

The products of the condensation reaction were synthesized in excellent yields and
selectivity’s and the spectroscopic analysis confirmed well their structures.

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