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ChemistrySelect doi.org/10.1002/slct.202003890
z Catalysis
Fe(III)/Bentonite as a Heterogeneous Catalyst for the
Synthesis of 3,4-dihydropyrimidin-2-(1H)-ones
Lakha V Chopda[a] and Pragnesh N. Dave*[a, b]
Fe(III) immobilized over natural bentonite (bent) using the
impregnation method. Prepared catalysts were well character-
ized by XRD, FT-IR and FeSEM. The catalytic activity of three
catalysts 10, 20 and 30 % Fe(III)/bent evaluated for the synthesis
of 3,4-dihydropyrimidin-2(1H)-ones known as Biginelli reaction.
The catalyst 30 % Fe(III)/bent exhibited a high yield of the
Highlights
* 10, 20 and 30 % Fe(III) were supported over bentonite clay.
The catalysts are well characterized by (XRD), FT-IR, FeSEM
and EDS. All charactization method showed that Fe
supported over bentonite.
* The used catalysts were screened for Biginelli reaction for
synthesis dihydropyrimidones.
* 30 % Fe(III)/bent exhibited high yield of product towards
model Biginelli reaction between benzaldehyde, ethylacetoa-
cetate and urea in ethanol.
* 30 % Fe(III)/bent exhibited high yield of product in CH3CN,
DMF and solvent free- condition.
* The catalyst 30 % Fe(III)/bent applied for synthesis of variety
of dihydropyrimodone in good yield in CH3CN.
* Reusability studies show that no great decline in activity
after 5th cycle.
Introduction
Biginelli reaction is a three component reaction of aldehydes, 1,
3-dicarbonyl compounds and urea/thiourea accessible to 3, 4-
dihydropyrimidin-2(1H)-ones/thiones (DHPMS/DHPMTHs) in the
presence of acidic catalyst. This reaction first developed by
Pietro Biginelli in the presence of catalytic amount of HCl in
ethanol that provided 3, 4-dihydropyrimidin-2(1H)-ones/thiones
in low to moderate yield (20–60 %).[1–4] Dihydropyrimidin-2(1H)-
ones/thiones displayed variety of biological activity.[5–7] Hence,
several homogeneous catalysts especially Lewis acids such as
BiCl3, Bi(OTf)3, Bi(NO3)3, CeCl37H2O, Cu(OTf)2, CuCl22H2O/
CuSO45H2O, Fe(NO3)39H2O, Fe(OTs)36H2O, GaCl3, Hf(OTf)4, In
[a] L. V Chopda, Prof. Dr. P. N. Dave
Department of Chemistry, KSKV Kachchh University, Bhuj, India
[b] Prof. Dr. P. N. Dave
Department Of Chemistry, Sardar Patel University, Vallabh Vidyanagar,
India
E-mail: pragnesh7@yahoo.com
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.202003890
ChemistrySelect 2020, 5, 14161 – 14167
product towards the synthesis of a variety of dihydropyrimi-
dones (DHPMs). The high yield of dihydropyrimidone (DHPM)
was obtained in model reaction in ethanol, acetonitrile, DMF
and solvent - free condition. The reusability test indicated that
6 % of yield of product decreased after 5th cycle.
(OTf)3, RuCl3, SbCl3, SnCl22H2O, Sr(OTf)2, TiCl4, Yb(OTf)3, ZnCl2,
ZrCl4 and ZrCl4 or ZrOCl28H2O[8–27] subsequently were devel-
oped to enhance the yield of product. All mentioned catalysts
improved the yield of product but most of them are expensive;
difficult to remove from solution consequently metal traces can
be remained in the final product and reusability are the key
issues. To address these problems, heterogeneous catalysts are
extensively employed for this reaction which displayed good
activity and reusability and facilitated easy separation of
product.[28–30] Various Lewis acids are supported over different
kind of solid support for this reaction. These are
FeCl3@nanopore silica, Lewis acids (ZnCl2,AlCl3,GaCl3,InCl3 and
FeCl3) @MCM-41 & montmorrionolite K 10 clay, ZnCl2 over silica,
Cu@PMO-IL, MoO3@Al2O3, HBF4-SiO2, SbCl3@Al2O3, LaCl3-graph-
ite, Mo/γ-Al2O3, CuCl2-SiO2, SnCl4 & TiCl4@SiO2, FeCl3@Al-MCM-
41, FeCl3@PANI, Nafion-Ga, Yttria-Zirconia, ZrO2-pillared clay,
Ce@MCM-41, Ps-AlCl3, metalsalts@NaY, SnCl2@nanoSiO2, Mg/Fe
hydrotalcite, ZnCl2, CuCl2, NiCl2, and CoCl2 doped hydroxyapa-
tite, ZnCl2, CuCl2 and NiCl2 doped fluorapatite, SOCl2@ silica gel
and recently work on HClO4-Al2O3 were devised for Biginelli
reaction.[31–55] These reported catalyst exhibited very good yield
towards DHPMS/DHPMTHs with good reusability. Bentonite
belongs to the family of smecitie which contains one octahe-
dral sheet and two silica sheets (2 : 1 or tetrahedral-octahedral-
tetrahedra (TOT) mineral) that form layer through van der waals
force and has the general formula as Rx(H2O)4{(Al2-
x,Mgx)2[(Si,Al)4O10](OH)2}, R is the exchangeable cations of alkali
and alkaline earth metals between layers.[56–61] Apart from this,
it possesses both Lewis and Bronsted acidity,[56,62,63] thus it was
explored as a heterogeneous catalyst in organic synthesis.[62]
The other unique properties made it a favorable support for
immobilization of metals nanoparticles,[57,59,64] metal oxides,[65,66]
metal salts[56,60,63,67] and other modification of bentonite for
various application.[68–76] Bentonite is widely distributed in the
Kachchh region of India and mainly sodium and calcium
bentonite are found in this area. In the field of synthetic
organic chemistry, bentonite based material explored as
catalyst. FeCl3/bentonite for the synthesis of (E)-1-(2,4-dimeth-
ylthiazol-5-yl)-3-phenylprop-2-en-1-ones under solvent-free
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conditions, Cu-bentonite for the synthesis of benzimidazoles,
benzoxazoles and benzothiazoles, vanadium-chromium-ben-
tonite used as catalyst for epoxidation of cyclohexene, H2SO4
activated bentonite, bentonite functionalized by propyl sulfonic
acid and ionic liquid 8B@bentonite for esterification reaction,
montmorillonite KSF for pyrano and furanoquinolines and
CTMAB-bentonite for synthesis of 3,4-dihydropyrano[c]chro-
mene derivatives.[77–84] In the literature, a very few examples
available on bentonite based catalyst for Biginelli reaction
which include montmorillonite KSF catalyst, bentonite clay,
montmorillonite KSF assisted by microwave, activated mont-
morrilonite, bentonite-PS-SO3H, Fe(III)-montmorillonite K10,
TiO2-pillared montmorillonite, Co@imine-Na + -MMT, ionic
liquid@bentonite and including our reported work on
H4[W12SiO40]/bent & H3[PW12SiO40]/bent.[85–95] In this work, we
developed Fe(III)/bent as a heterogeneous catalyst for synthesis
of 3,4-dihydropyrimidin-2-(1H)-ones.
Result and Discussion
XRD analysis
The XRD patterns of raw bentonite and impregnation of
different loading of Fe(III) to bentonite are shown in Figure 1.
The characteristic peak (basal spacing) of d001 refection of
bentonite appears at 2θ = 7.09°.[88,96–99] After loading of Fe(III),
this main diffraction peak shifted to lower angle as percentage
of Fe(III) increased from 10 to 20 to 30 % (4.96°, 4.70° and 4.56°).
The corresponding d-spacing is shown in Table no.1. The
increased in d-spacing signifies that Fe(III) incorporated into
interlayer space of bentonite[100,101] by replacing of interlayer
cations Na and Ca. The intense peak at 2θ = 20.91° in raw
bentonite attributes to its SiO2 crystalline nature.[102] The
intensity of this peak decreased in all three samples and almost
vanished in 30 % Fe(III)/bent. It showed that crystallinity of SiO2
turned to amorphous nature[88,96,102] as similar observation made
by us in our previous work.[93,94] Other diffraction peaks of
bentonite observe at 2θ = 19.9°, 26.6°, 28.58°, 36.0°, 42.5° and
61.7°.[103–106] The peaks at 2θ = 20.91°, 26.6°, 36.0° and 42.5°
Figure 1. XRD pattern of 10, 20 and 30 % Fe(III)/bent.
ChemistrySelect 2020, 5, 14161 – 14167
reflect that bentonite contains ample amount of quartz and no
peak has seen at 31.30° represent for cristobalite.[103] It shows
that bentonite does not bear cristobalite. The low intensity
peak at 61.7° reveals about octahedral sheet in bentonite[105]
which remains intact in all three samples. It indicates that no
distraction occurred in octahedral sheet after supporting of Fe
(III) while in our reported work, this peak almost disappeared as
percentage TSA & TPA increased in bentonite which could led
to some distraction in octahedral sheet.[93,94] A new peaks
30.81°, 38.67°, 44.54°, 67.07°, 67.47° and 80.53 can be assigned
to Fe(III) over bentonite and some peaks such as 38.67°, 67.07°,
67.47° and 80.53° are not detected at higher loading (20 & 30 %
Fe(III)/bent). This could be indicated that as loading increased
Fe(III) homogeneously deposited over bentonite.
FT-IR analysis
FT-IR spectra of raw bentonite and 10, 20 and 30 % Fe(III)/bent
are shown in Figure 2. In the raw bentonite, a strong band at
1006.84 cm 1 corresponds to Si O stretching vibrations and
bending vibration of Al Al OH appears at 921 cm 1.[100,101,107]
Bands of Si O Al and Si O Si attribute between 521–
800 cm 1.[108,109] The bands at 876 and 793 cm 1 could be
associated with Si-O Al and Si O Si bending vibrations
respectively. The bands at 671 cm 1 can be assigned to
combine Al O and Si O out of plane vibrations.[107] The peaks
observe at 3623 cm 1 and 3508 cm 1 ascertain to stretching
vibration of a surface hydroxyl group attached to bentonite
and stretching vibration of H O H of adsorbed water
respectively.[96,99] The band at 1640 cm 1 relates to bending
vibration of O H (surface of bentonite) and H O H of
adsorbed water.[110] The FT-IR spectra of 10, 20 and 30 % Fe(III)/
bent have a similar pattern that of raw bentonite. The only
difference is that the intensity of Si O stretching vibrations
decreased after loading of Fe(III) and shifted to higher wave
number. It is in good agreement to XRD results in which
intensity of d001 reflection peak decreased after loading of Fe
(III). This could be provided evidence of presence of Fe(III) over
bentonite. No characteristic bands of Fe(III) observe in all three
Figure 2. FT-IR of 10, 20 and 30 % Fe(III)/bent.
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ChemistrySelect doi.org/10.1002/slct.202003890

samples which signify that Fe(III) homogeneously distributed bent catalysts is quite differing from that of raw bentonite. Fe-
over bentonite. SEM images of Fe(III)/bent (Figure 3b to 3d), where no hexagon
shape of raw bentonite is shown. It shows that Fe(III) is
homogeneous distributed over surface of bentonite. EDS
FeSEM-EDS analysis
analysis of three samples confirms presence of Fe in bentonite
Fe-SEM images of raw bentonite and 10, 20 and 30 % of Fe(III)/ (Figure S1 (b–d). Detailed analysis of the EDS of four catalysts is
bent are shown in Figure 3a–3d respectively. Fe-SEM image of shown in Table S1 (b–d) respectively.
raw bentonite exhibit hexagon shape with an average particle
size around 200 nm. The surface morphology of 10–30 % Fe(III)/
Catalytic activity
The model reaction was chosen between benzaldehyde, ethyl-
acetoacetate and urea in 2 : 2 : 2.4 mmol ratio of reactants
respectively using, 10, 20 and 30 % of Fe(III)/bent. The reaction
performed in the presence of 0.09 g amount of catalysts in
ethanol at 80 °C. The yield of corresponding DHPM achieved in
Scheme 1. Model Biginelli reaction in the presence of Fe(III)/bent.
54, 68 and 84 % by 10, 20 and 30 % Fe(III)/bent respectively for
7 h of reaction time as shown in Table 2 (entry 1 to 3). The % of
Fe(III) was increased in catalyst led to enhance the yield of
product (Table S1 (b–d)). In addition, effect of amount of
catalyst of 30 % Fe(III)/bent was carried out to find optimum
amount of catalyst required for the reaction. The yield of
desired product was achieved in 89 and 94 % at 0.1 and 0.15 g
of catalyst as shown in Table 2 (entry 4 & 5). 0.2 g of catalyst
showed 94 % yield of product. It showed that higher amount
(0.2 g) did not enhance the yield of product (Table 2, entry 6).
Hence 0.15 g of catalyst found to be sufficient amount of
catalyst to catalyze the reaction. Further, using 0.15 g of
catalyst, reaction was performed in acetonitrile (80 °C), DMF
(90 °C), methanol (60 °C) and solvent-free conditions (80 °C). The
yield of product was 95, 88, 60 and 90 % in acetonitrile, DMF,
methanol and solvent-free conditions respectively as repre-
sented in Table 2 (entry 7–10). Catalyst 30 % Fe(III)/bent
required to high loading (0.15 g) than our reported work on
Figure 3. FeSEM images of bent, 10, 20 & 30 % Fe(III)/bent. 30 %TSA/bent and 30 %TPA/bent (0.09 g) catalysts.[93,94] Various
DHPMs are prepared using 0.15 g of catalyst in acetonitrile for
7 h of reaction time as shown in Table 3.The DHPMs are
Table 1. D-spacing of 10, 20 and 30 % Fe(III)/bent. obtained in good to high yield of products.
Sr No d-spacing (nm) Reusability test of 30 % Fe(III)/bent has been conduct in
order to check its efficiency. Catalyst displayed 95, 92, 91, 91
Bentonite 1.245
10 % Fe(III) /bent 1.782
and 89 % yield of product after 1st, 2nd, 3rd, 4th and 5th cycles
20 % Fe(III) /bent 1.878 respectively. The 6 % of yield of product decreased after 5th
30 % Fe(III) /bent 1.939 round. Leaching test was performed using hot filtration

Table 2. Model Biginelli reaction in the presence of 10, 20 & 30 % Fe(III)/bent.

No. Catalyst Solvent Temperature (°C) Amount of catalyst (g) Yield

1 10 % Fe(III)/bent Ethanol 80° 0.09 54 %

2 20 % Fe(III)/bent Ethanol 80° 0.09 68 %
3 30 % Fe(III)/bent Ethanol 80° 0.09 84 %
4 30 % Fe(III)/bent Ethanol 80° 0.1 89 %
5 30 % Fe(III)/bent Ethanol 80° 0.15 94 %
6 30 % Fe(III)/bent Ethanol 80° 0.2 94 %
7 30 % Fe(III)/bent Acetonitrile 80° 0.15 95 %
8 30 % Fe(III)/bent DMF 90° 0.15 88 %
9 30 % Fe(III)/bent Methanol 60° 0.15 60 %
10 30 % Fe(III)/bent Solvent- free 80° 0.09 90 %

Reaction conditions: Benzaldehyde (2 mmol), ethylacetoacetate (2 mmol), urea (2.4 mmol), solvent (25 ml), temperature 80 °C and reaction time 7 h.
M.P. of compound : 204–206 (205-206).[109]

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Table 3. Synthesis of DHPMs using 30 % Fe(III)/bent.
Reaction conditions: Benzaldehyde (2 mmol), ethylacetoacetate (2 mmol),
urea (2.4 mmol), acetonitrile (25 ml), temperature 80 °C and reaction time
7 h.
M.P. of compounds: 1: 230–232 (233–235)[111] 2: 214–216 (215–216)[110] 3:
214–217 (215–216)[112] 4: 200–203 (200–201)[112] 5: 176–180 (177–179)[111] 6:
256–260(255–256)[113] 7: 208–211 (210)[112] 8: 226–230 (227–228)[112] 9: 210–
214 (213–214)[112] 10: 183–185 (184–186)[114] 11: 206–209 (206–208)[114] 12:
202–204(204–205)[115] 13: 203–206 (205–206)[112] 14: 210–212 (210–211).[112]
method in order to confirm whether Fe leached out or not. The
model reaction performed under optimized conditions and
after half & hour catalyst removed by filtration reaming reaction
mixture was kept for 24 h. After 24 h, concerning product was
obtained in 25 %. It confirmed that Fe was not leached out.
Plausible reaction mechanism and comparison of catalyst
The possible reaction mechanism of 30 % Fe(III)/bent catalyst
can be envisaged and displayed in Figure 5. Generally,
bentonite is usually neutral or weakly basic in nature which is
attributed to presence of intercations Na and Ca in the form of
oxide.[116,117] After immobilization of Fe(III), these cations (Na
and Ca) interchanged with Fe(III) as evident by XRD by
increasing d-spacing. The pH of Fe(III)/bent could be decreased
that of raw bentonite. The nature of Fe(III)/bent is acidic. Belaidi
et al measured the acidity of AAC (acid-activated clay-
bentonite), Cr-AAC and 5 V/Cr-AAC materials by pyridine
adsorption method.[79] Bronsted and Lewis/Bronsted acids sites
of Cr-AAC and 5 V/Cr-AAC increased than AAC and prakash et
al also studied the effect of acidity of Al3 + Mont(100), Al3 +
Mont(200) and Al3 + Mont(400) as prepared different condi-
tions for esterification reaction between propionic acid and p-
cresol.[118] Catalysts Al3 + -Mont(100), Al3 + -Mont(200) and Al3 +
-Mont(400) exhibited 88 %, 56 % and negligible activity. It
revealed that increased temperature led to decrease the
Bronsted acidity concentration due to loss of water from
montmorillonite clay. These both reported work support our
assumption about acidic nature of Fe(III)/bent as preparation
and reaction temperature around 100 °C. In the proposed
reaction mechanism, carbonyl group first activated by Fe(III)/
bent same in the case of acid catalyze reaction[119] produces
electrophilic centre at carbonyl carbon. Nucleophilic attacks by
urea or ethylacetoacetate led to form iminium I or Knoevenagel
II intermediates. These intermediates could be rate-determining
step in this reaction. Iminium I or Knoevenagel II intermediates
react with ethylacetoacetate and urea respectively. Imine
intermediate I reacts with ethyacetoacetate furnished inter-
mediate III and Knoevenagel intermediate reacts to urea
produces intermediate IV. Both intermediates undergo cycliza-
tion to form intermediate V which finally generates dihydropyr-
imidone. In a comparison of intermediates I & II, intermediate I
prefers over II because of high nucleophilicity of urea than
ethylacetoacetate, hence proposed reaction mechanism of
30 % Fe(III)/bent is line with proposed by Kappe, Johnson and
Hu means iminium pathway.[4] The third possible reaction
mechanism was proposed in the literature for this reaction. It is
occurring through enamine. It happens by nucleophilic attack
of urea to ethylacetoacetate but possibility of this pathway is

Table 4. Comparison of catalyst.

Entry Catalyst Conditions Amount catalyst Time Yield (%) Ref

(min)
[31]
1 FeCl3/nanopore silica (1 : 1 : 1.2) 400 W 180 °C(solvent-free) 0.05 g 15 75
5 FeCl3/MCM-41 (1 : 1 : 1.2) 400 W 180 °C(solvent -free) 0.05 g 15 78
6 FeCl3/SBA-15 (1 : 1 : 1.2) 400 W 180 °C(solvent free) 0.05 g 15 82
7 FeCl3/VSB-15 (1 : 1 : 1.2) 400 W & 180 °C(solvent- free) 0.05 g 15 92
[32]
8 FeCl3/MCM-41 (1 : 1 : 1.3) 700 W(solvent-free) 0.03 g 3 89
9 FeCl3/montmorillonite 700 W(solvent-free) 0.03 g 3 70
K 10(1 : 1 : 1.3)[a]
[42]
10 Fe(III)/Al-MCM-41(2 : 2 : 3) Reflux(acetonitrile) 0.03 g 240 85
[43]
11 FeCl3/PANI(1.8 : 1.8 : 2.3) Reflux(acetonitrile) 0.2 g 1440 83
[90]
12 Fe(III)/montmorrillonite K10(1 : 1 : 1) Grinding(pulverizing) 0.1 g 10 92
13 Present work 80 °C(acetonitrile) 0.09 g 420 95 –
(2 : 2 : 2.4)

Reactants (Benzaldehyde: Ethylacetoacetate: Urea) ratio in mmol

[a] indicated used 4-methoxy benzaldehyde instead of benzaldehyde.

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Acknowledgements

We acknowledge Panjab University and VGEC Chandkheda for

utilizing their characterization facility.

Conflict of Interest
The authors declare no conflict of interest.

Keywords: Support catalyst · Bentonite · Heterogeneous

catalysis · Lewis acid · Dihydropyrimidones

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