Immobilized ionic liquid on the zeolite: its characterization and catalytic activity in the synthesis of coumarins via Pechmann reaction

Article abstract of DOI:10.1007/s13738-020-01950-x

In this work, in the first step, the 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium chloride ([MTMSPIm]Cl) is immobilized on HY and NaY zeolites as an acidic catalyst. The synthesized catalysts were well characterized by different methods such as FTIR, TGA, XRD, BET, SEM, EDX and ICP. The characterizations of catalysts indeed show the ionic liquid supported on amine-functionalized zeolites. Also, the result shows the micro-/mesoporous structure for catalysts which have been emerged as an important class of catalytic materials. The micro-/mesocatalyst ([MTMSPIm]Cl@zeolite) was used as an acidic catalyst to synthesize coumarins via Pechmann reaction in solvent-free condition. The effect of different factors such as catalyst amount, solvent and time was investigated. Finally, catalyst can be easily separated and reused for the next reactions at least for five runs without any significant changes in yield and structure of the catalyst. Comparison of modified zeolite with [MTMSPIm]Cl shows higher yield and selectivity and mild condition related to other works.

Full text of DOI:10.1007/s13738-020-01950-x

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-020-01950-x
ORIGINAL PAPER
Immobilized ionic liquid on the zeolite: its characterization
and catalytic activity in the synthesis of coumarins via Pechmann
reaction
Mojgan Zendehdel1,2 · Soheila Khaghaninejad1,2 · Fatemeh Tavakoli1,2 · Shiva Ganji1,2
Received: 20 December 2019 / Accepted: 4 May 2020
©
Iranian Chemical Society 2020
Abstract
In this work, in the frst step, the 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium chloride ([MTMSPIm]Cl) is immobi-
lized on HY and NaY zeolites as an acidic catalyst. The synthesized catalysts were well characterized by diꢀerent methods
such as FTIR, TGA, XRD, BET, SEM, EDX and ICP. The characterizations oꢁ catalysts indeed show the ionic liquid sup-
ported on amine-ꢁunctionalized zeolites. Also, the result shows the micro-/mesoporous structure ꢁor catalysts which have
been emerged as an important class oꢁ catalytic materials. The micro-/mesocatalyst ([MTMSPIm]Cl@zeolite) was used as
an acidic catalyst to synthesize coumarins via Pechmann reaction in solvent-ꢁree condition. The eꢀect oꢁ diꢀerent ꢁactors
such as catalyst amount, solvent and time was investigated. Finally, catalyst can be easily separated and reused ꢁor the next
reactions at least ꢁor fve runs without any signifcant changes in yield and structure oꢁ the catalyst. Comparison oꢁ modifed
zeolite with [MTMSPIm]Cl shows higher yield and selectivity and mild condition related to other works.
Keywords ([mtmspim]cl@zeolite) · Micro-/mesostructure · Ionic liquids · Pechmann reaction
Introduction
criteria to minimize the amount oꢁ ILs in the reactions [2].
We know homogenous catalysts have some limited use,
because usually separating them ꢁrom the reaction prod-
ucts is diꢂcult, which may lead to environmental and eco-
nomic problems, especially in the case oꢁ expensive and
toxic catalyst. Recently, to overcome these limitations, the
immobilization oꢁ ionic liquid onto some solid supports
such as polymer, complex, magnetite nanoparticles, gra-
phene and mesoporous materials has been developed [3–5].
Zeolites are crystalline microporous aluminosilicate which
have Brøonsted and Lewis sites, act as solid acid catalysts
and are used as a support ꢁor heterogeneous catalyst [6–9].
Although zeolites have many advantages, diꢀusion limita-
tions not only lead to a negative inꢃuence on catalytic activ-
ity but can also cause a loss in selectivity and a reduction
in the liꢁetime oꢁ the catalyst. Then, recently, signifcant
eꢀorts have been made to prepare micro-/mesoporous zeo-
lite materials [10]. Literature review shows that in some
work, composites oꢁ zeolite and ILs were prepared [11–13],
but a micro-/mesostructure oꢁ zeolite by immobilization oꢁ
ILs on it has not been reported yet.
In the past decades, interest in ionic liquids (ILs) has been
increased ꢁor organic reactions due to their unique proper-
ties such as solubility, very low vapor pressure, low toxic-
ity, high chemical and thermal stabilities, which are oꢁten
named as green solvents [1]. Also, ILs show good cata-
lytic activity and high selectivity as a homogeneous cata-
lyst ꢁor organic reaction. But ionic liquids are very expen-
sive, and many eꢀorts are made on the basis oꢁ economic
*
Mojgan Zendehdel
m-zendehdel@araku.ac.ir; mojganzendehdel@yahoo.com
Soheila Khaghaninejad
S-khaghani@araku.ac.ir
Fatemeh Tavakoli
F-tavakoli20@phd.araku.ac.ir
Shiva Ganji
shivaganji1369@gmail.com
1
2
Department oꢁ Chemistry, Faculty oꢁ Science, Arak
University, Arāk 38156-8-8349, Iran
Coumarins and their derivatives are widely applied in
many areas, ꢁor example as drug in present-day and modern
medicine, biology, polymer sciences [14], also as inhibitor
Institute oꢁ Nanosciences and Nanotechnology, Arak
University, Arāk, Iran
Vol.:(0
1
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3

Journal of the Iranian Chemical Society
oꢁ platelet aggregation, antibacterial, anticancer, inhibitor
conditions via Pechmann reaction. Our study showed that
the [MPIm]Cl@HY zeolite was very eꢀective and could
be recovered and reused several times without signifcant
decrease in its eꢂciency (Scheme 1).
oꢁ steroid ꢀ reductase and inhibitor oꢁ HIV-1 protease [15,
1
6]. Also coumarins have been used as optical brightening
agents, laser dyes and ꢃuorescent markers [17].
There are some classical methods which are used ꢁor the
synthesis oꢁ coumarin such as Pechmann reaction [18], Kno-
evenagel condensation [19], Wittig reactions [20], Perkin
Experimental
[
21], Reꢁormatsky [22], Wittig [19, 23], Claisen rearrange-
ment [24] and ꢃash vacuum pyrolysis [25].
All materials and solvents were purchased ꢁrom Aldrich or
Merck, while NaY Zeolite was purchased ꢁrom Iran zeolite
Company (Tehran, Iran). X-ray powder diꢀraction patterns
were recorded on an X-ray diꢀractometer (Philips 1840)
with radiation oꢁ Cu-Kα at room temperature. Energy-dis-
persive X-ray spectroscopy (Oxꢁord X-max) and Fourier
transꢁorm inꢁrared (FTIR) spectroscopy were perꢁormed
with a Galaxy series FTIR 5000 spectrometer. Thermo-
gravimetric analyses (TGA and DTA) were perꢁormed using
a Diamond Pyris TM, TG/DT 6300 instrument, ꢁrom 30
to 600 °C at a heating rate oꢁ 10 °C/min under Ar ꢃow.
The feld emission scanning electron microscope (FESEM)
photographs oꢁ the samples were obtained using a Zeiss
Sigma-VP FESEM instrument. BET apparatus (ASAP
2020 V3.04 E with adsorption oꢁ nitrogen at 76.34 °K) was
The Pechmann reaction with very simple starting materi-
als (phenols, β-ketoesters and acid catalysts) is one oꢁ the
simplest and direct methods ꢁor the synthesis oꢁ coumarins
[
26]. Literature review showed that the synthesis oꢁ cou-
marin via Pechmann reaction has been done in the presence
oꢁ some solid acid catalysts such as nafon, natural zeolite,
amberlyst 15, ionic liquid, cation-exchanged resin, and
Graphite/montmorillonite K10 [27, 28].
Along this work, we graꢁted an imidazolium-type ionic
liquid 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium
chloride [MTMSPIm]Cl, which is pre-ꢁunctionalized with
a trimethoxysilylpropyl group on the surꢁace oꢁ HY and NaY
zeolite and characterized by XRD, FTIR, SEM, EDAX, BET
and TGA methods. Then, inorganic/organic hybrid catalyst
was used ꢁor the preparation oꢁ coumarins under diꢀerent
Scheme 1 Synthesis oꢁ cou-
marins via Pechmann reaction
Scheme 2 The preparation oꢁ
[
MTMSPIm]Cl@HY catalyst
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1
used. HNMR spectra were obtained on a Bruker Avance
3
00 MHz spectrometer.
Preparation of 1‑methyl‑3‑(3‑trimethoxysilylpropyl)
imidazolium chloride grafted on zeolite ([MTMSPIm]
Cl@HY and NaY zeolite)
The synthesis oꢁ methyl propylimidazolium chloride
immobilized to zeolite ([MPIm]Cl@HY) has been done
in three main steps (Scheme 2).
In the frst step, ꢁor the preparation oꢁ HY, 2 g oꢁ NaY
zeolite was added to 200 mL oꢁ NH Cl solution (0.002 M)
4
and stirred ꢁor 24 h. Then, solid was fltered, washed with
water and calcined at 300 °C ꢁor 5 h to remove NH .
3
In the second step, 3-chloropropyltrimethoxysi-
lane (CPTS, 1 mmol) was added to 1-methylimidazole
Fig. 1 FTIR oꢁ NaY (a), HY (b), [MPIm]Cl@NaY (c), [MPIm]Cl@
(
1.2 mmol) at 88 °C in dry toluene and reꢃuxed ꢁor 30 h
HY (d)
under nitrogen atmosphere. Then, the brown-colored paste
was added to 0.4 g oꢁ HY zeolite in 50 mL dry toluene and
reꢃuxed ꢁor 24 h under nitrogen atmosphere. Finally, the
solid powder was fltered and then dried and characterized
Fig. 2 SEM oꢁ [MPIm]Cl@NaY (a, b) and [MPIm]Cl@HY (c, d) with 50, 100, 200 kx magnifcation, e, f EDX oꢁ [MPIm]Cl@NaY (e) and
MPIm]Cl@HY (f)
[
by FTIR, XRD, BET, SEM and EDX, and TGA methods.
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Synthesis of coumarin
109.7, 22.0. IR, ʋ (KBr disc): up to 3000 (OH broad),
−
1
1
690 cm . Mp 183–185 °C.
In a typical reaction method, diꢀerent amounts oꢁ prepared
catalyst were added to a mixture oꢁ resorcinol derivative
(
(
1 mmol) and ethyl acetoacetate (1 mmol) in a round ꢃask
250 mL) and stirred at 130 °C without the presence any
Results and discussion
solvent. The advancement oꢁ the reaction was considered
by TLC. Aꢁter completion oꢁ the reaction, the mixture oꢁ
reaction was dissolved in hot toluene (3 × 5 mL) and then
the catalyst was separated. Finally, the solvent was evapo-
rated and then product was re-crystallized ꢁrom a mixture
The FTIR spectra ꢁor pure and ꢁunctionalized HY and NaY
zeolite by [MPIm]Cl are shown in Fig. 1a–d, which exhibit
characteristic bonds related to the asymmetric stretching
−
1
oꢁ Al–O–Si at about 1018–1030 cm and the symmet-
ric stretching and bending ꢁrequency bands oꢁ Al–O–Si
−
1
oꢁ EtOH/H O. In order to reuse the catalyst, it was washed
ꢁramework oꢁ zeolite at ca.747 and 439 cm , respectively
[29]. The FTIR spectroscopy oꢁ [MPIm]Cl@HY and
NaY (Fig. 1c, d) show the new broad absorption bands at
2
with hot toluene and diethyl ether. All samples were evalu-
ated via FTIR and NMR.
1
−1
−1
7
-Hydroxy-4-methylcoumarin: H-NMR± (DMSO d6):
1573 cm and 1458 cm (C=N and C=C stretching) and
−
1
2
3
.65 (s, 3H, Me), 6.4 (s, 1H, olefnic CH), 6.9–7.7 (m,
the bands at 1956, 2955 cm (aliphatic C–H stretching)
1
−1
H, aromatic protons), OH is unobserved. 1530; H NMR
and 3151 cm (unsaturated C–H stretching), respectively
(
(
CDCl3) d 2.39 (3H, s), 3.28 (br s, 1H), 6.06 (s, 1H), 6.8
which confrmed the presence oꢁ [MPIm]Cl in the surꢁace
oꢁ zeolite [24], which confrmed the presence oꢁ [MPIm]
Cl in the surꢁace oꢁ zeolite [30].
1
3
s, 1H), 6.82 (d, 1H), 7.44 (d, 1H). C NMR (CDCl3):
d¼161.7, 159.6, 152.6, 151.80, 128.9, 113.9, 112.5, 111.5,
Scanning electron microscopy images oꢁ [MPIm]Cl@
NaY and [MPIm]Cl@HY are shown in Fig. 2a–d. They
indicate that the morphology oꢁ zeolite HY crystals with-
out ꢁormation oꢁ separate amorphous phase is obtained by
average size oꢁ about 400 nm (Fig. 2a, b). The ꢁunction-
alized zeolite morphology shows that some grooves and
voids took place on the surꢁace oꢁ zeolite, which may be
the evidence ꢁor the overgrowth oꢁ the mesoporous phase
in the sample (Fig. 2c, d). These results are the same as
other results in the literature [31].
Table 1 EDX oꢁ [MPIm]Cl@NaY and [MPIm]Cl@HY
Compounds
Si/Al
C/N
O
Cl
NaY
2.83
2.80
2.78
–
3.02
3.10
39.87
44.02
44.12
–
3.92
3.90
[
[
MPIm]Cl@NaY
MPIm]Cl@HY
a
b
c
d
Calculated by the BET method
Calculated by the t-plot method
Obtained at a relative pressure oꢁ 0.99
Calculated by the BJH method
The EDX (Fig. 2e, ꢁ) and elemental analysis results in
Table 1 ꢁor [MPIm]Cl@NaY and [MPIm]Cl@HY indicate
Fig. 3 Adsorption–desorption curves and BJH oꢁ [MPIm]Cl@NaY (a) and [MPIm]Cl@HY (b)
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Table 2 Brunauer–Emmett–Teller (BET) surꢁace area and the volume oꢁ samples
2
Smicrob (m /g)
2
2
c
3
Vmicrob (cm /g)
3
Vmesod (cm /g)
3
Sample
SBET (m /g)
Smeso (m /g)
V c (m /g)
dBJH (nm)
t
NaY zeolite
530.30
367.30
153.20
522
330.82
110.39
8.30
36.48
42.81
0.50
0.45
0.37
0.45
0.30
0.29
0.05
0.15
0.08
2.25
1.29
1.29
[MPIm]Cl@NaY
MPIm]Cl@HY
[
that a Si/Al and C/N molar ratios are about 2.8 and 3,
respectively. These results establish the presence oꢁ alu-
minosilicate and imidazolium agents in the samples [32].
the decreasing oꢁ surꢁace area may be due to blocking oꢁ
the zeolite pores and accessible cages ꢁunctional groups
and which mesophase aꢁter ꢁunctional by [MPIm]Cl [27,
33]. The BJH shows the distribution oꢁ pore size oꢁ the
related materials to be about 1–100 nm and confrms the
presence oꢁ catalyst with broad size and two ranges.
Figure 4a–d shows the powder X-ray diꢀraction (XRD)
patterns oꢁ pure NaY and HY zeolites aꢁter ꢁunctionalized by
[MPIm]Cl group. In the wide angle range, all samples show
characteristic reꢃection related to Y zeolite, and aꢁter ꢁunc-
tionalized with [MPIm]Cl group, the intensity oꢁ reꢃection
due to decreasing crystallinity oꢁ microporous phase was
reduced. Also, low-angle range XRD patterns containing
N adsorption–desorption curves oꢁ NaY and HY zeo-
2
lites ꢁunctionalized by [MPIm]Cl are shown in Fig. 3a,
b. The behavior oꢁ NaY and HY zeolite aꢁter introducing
ionic liquid were typical ꢁor a microporous solid (type I)
but in the two cases small hysteresis loop between (0.4
and 0.9) ꢁor P/P . Brunauer–Emmett–Teller (BET) sur-
0
ꢁ
ace area and among the volume oꢁ samples summarize
in Table 2. The reduction in surꢁace area and pore volume
2
related to pure NaY zeolite (S
= 530.30 m /g) confrms
BET
the presence oꢁ ionic liquid on the surꢁace oꢁ zeolite. Also,
(
100), (110) and (200) peaks with low intensity correspond-
ing to hexagonal pore symmetry oꢁ MCM-41 (Fig. 5a, b)
confrm the presence oꢁ mesoporous phase with small order
which is also observed in the SEM and BET results [31].
Thermogravimetric analysis oꢁ [MPIm]Cl@NaY and
[
MPIm]Cl@HY is shown in Fig. 6a, b. Four weight loss
steps took place in the TGA/DTA diagrams. In the frst step,
ꢁ
rom 25 to 150 °C, 7.60% and 7.15% weight loss can be seen
related to the physical desorption oꢁ the water molecules in
the [MPIm]Cl@NaY and [MPIm]Cl@HY, respectively. The
Fig. 4 XRD oꢁ NaY (a), HY (b), [MPIm]Cl@NaY (c), [MPIm]Cl@
Fig. 5 Low angle range oꢁ XRD ꢁor [MPIm]Cl@NaY (a), [MPIm]
HY (d)
Cl@HY (b)
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Journal of the Iranian Chemical Society
Fig. 6 Thermogravimetric analysis oꢁ [MPIm]Cl@NaY (a) and [MPIm]Cl@HY (b)
second step oꢁ about 220 °C in two cases is associated with
the loss oꢁ ꢁree water molecules that are inside the pores or
water molecules which by hydrogen bonding are linked with
Si–O and Al–O groups and established. In the third step aꢁter
For optimization reaction conditions, frstly we considered
the reaction oꢁ resorcinol (1 mmol) with ethyl acetoacetate
(EAA, 1 mmol) in the presence oꢁ diꢀerent amounts oꢁ syn-
thesized catalyst (0.02–0.2 g) at 130 °C. The progress oꢁ the
treatment was monitored by TLC (n-hexane/EAc) method.
The results are demonstrated in Table 3, which show that
the yield oꢁ reaction is trace without using catalyst and then
catalyst plays a special role in the preparation oꢁ coma-
rin. Entries 1–8 illustrate that with the increase in catalyst
amount due to increasing acidic sites, the yield oꢁ reaction
increased, but aꢁter 0.18 g (entry 8), no signifcant change
can be observed. To consider the eꢀect oꢁ catalyst nature,
the beꢁore study shows the activities oꢁ some zeolites such
as H-Y(US), H-ZSM-5 due to diꢀusion limitations in porous
2
20 °C with 16.27% and 17.05% weight loss, the mass decline
around 400 °C can be attributed to the decomposition oꢁ
MPIm]Cl agent. Also, the small endothermic peaks oꢁ about
[
3
30–370 °C in DTG can correspond to the dehydration oꢁ
the hydroxyl groups inside the micro- and meso-phases [34].
Catalyst activity
In this section, we examined the acidic rule oꢁ catalyst ꢁor the
preparation oꢁ coumarin compounds via Pechmann reaction.
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Table 3 Optimization oꢁ the conditions oꢁ reaction ꢁor the preparation oꢁ 7-hydroxy-4-methylcoumarin
HO
O
O
HO
OH
O
O
Diffrent catalysts and condition
+
OEt
Entry
Catalyst type (catalyst amount (g))
Solvent
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
[MTMSPIm]Cl@HY-Z (0.04)
[MTMSPIm]Cl@HY-Z (0.06)
[MTMSPIm]Cl@HY-Z (0.08)
[MTMSPIm]Cl@HY-Z (0.1)
[MTMSPIm]Cl@HY-Z (0.12)
[MTMSPIm]Cl@HY-Z (0.14)
[MTMSPIm]Cl@HY-Z (0.16)
[MTMSPIm]Cl@HY-Z (0.18)
[MTMSPIm]Cl@HY-Z (0.2)
[MTMSPIm]Cl@HY-Z (0.18)
[MTMSPIm]Cl@HY-Z (0.18)
[MTMSPIm]Cl@HY-Z (0.18)
[MTMSPIm]Cl@HY-Z (0.18)
Without Catalyst
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
8
6:30
5
3:45
3:5
3
2:45
2:30
2:30
2:30
2:30
2:30
2:30
2:30
2:30
2:30
2:30
2:30
22.0
28.5
40.0
51.0
62.5
68.0
85.0
96.5
95.8
57.5
91.0
80.0
68.5
Trace
38.5
30.0
40.0
81.0
10
11
12
13
14
15
16
17
18
H O
2
THF
CH CN
3
DMF
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
Solvent ꢁree
HY-Z (0.18 g)
NaY-Z (0.18 g)
[MTMSPIm]Cl
[MTMSPIm]Cl@NaY-Z
Reaction conditions: resorcinol (1mmol), EAA (1 mmol), temperature = 130 °C, stirred in oil bath
zeolite which are very low ꢁor preparation oꢁ coumarin ꢁrom
resorcinol; entries 15 and 16 confrmed this subject [35]. But
result oꢁ catalyst shows with ꢁunctionalized zeolite, a micro-/
mesostructure was created based on other works; these kinds
oꢁ catalysts with bigger porous size and higher stability are
suitable ꢁor entering bulk molecule and increasing the yield
and liꢁetime oꢁ the catalyst [36].
ꢁound in the molecule oꢁ solvents [37–39]. To consider the
importance oꢁ problems ꢁor green chemistry, the creation
oꢁ solvent-ꢁree conditions ꢁor reaction is advantageous,
which avoids the use oꢁ environmental hazardous and toxic
solvents in this work.
Furthermore, in order to show the excellent catalytic
activity, we studied the reaction oꢁ diꢀerent activated phe-
nols with [MTMSPIm]Cl@HY-Z catalyst EAA, which
shows clean and aꢀorded exclusive coumarins in high yields
in relatively short times (Table 4).
The entries 8 and 18 show that ꢁunctionalized acidic
ꢁ
orm oꢁ zeolite (HY) is the better catalyst related to NaY
zeolite; it seems combination oꢁ Brøonsted acid sites
because introducing hydrogen group to zeolite and nucleo-
philic group to ILs increased catalyst activity.
Although the careꢁul mechanism is not recognized, based
on other work [26] a plausible mechanism to the ꢁormation
oꢁ coumarin catalyzed by [MTMSPIm]Cl@zeolite is shown
in Scheme 3. In the frst step, [MTMSPIm]Cl@zeolite acti-
vated the hydroxyl oꢁ phenolic groups and protonated EAA
and phenolic groups and then resorcinol made nucleophilic
attack to the carbonyl group. The transesterifcation occurred
between reactants at two sites, and [MTMSPIm]Cl@zeolite
In the next step, to consider the eꢀect oꢁ solvents on
the preparation oꢁ cumarin with ꢁunctionalized zeolite by
ionic liquid and yield in the optimum conditions, some
polar solvents were used (entries 10–13). The result shows
that with the use oꢁ polar solvent, the yield oꢁ reaction
decreased compared to the solvent-ꢁree condition; it seems
the interaction between solvents and ionic liquid deacti-
vated ILs sites to ꢁormation oꢁ coumarin; in the case oꢁ
water, this eꢀect is very high. As described in the litera-
ture, in the wet media ionic liquids, hydrolytically unstable
reagents are stabilized due to the ꢁact that the water is in
the ꢁorm oꢁ isolated molecules rather than aggregates as
absorbed proton again. In the next steps, EtOH and H O
2
removing and coumarin derivatives were synthesized. The
catalytic activity oꢁ micro/mesostructure [MTMSPIm]
Cl@zeolite comprised with other reported heterogeneous
catalysts ꢁor combination oꢁ resorcinol and ethyl acetoac-
etate which prepared coumarin that shows in this work the
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Journal of the Iranian Chemical Society
Table 4 Synthesis oꢁ diꢀerent kinds oꢁ coumarin using [MTMSPIm]Cl@HY-Z as a catalyst
OH
O
O
[
MTMSPIm]Cl@HY-Z
+
OEt
X
o
X
O
O
1
30 C, Solventless
X=Ph,NO ,Me,H
2
Entry
Product
M.p
Yield (%)
54.26
1
1
56–159
53 [40]
OH
O
O
1
49–150
89.35
82
OH
O N
151–154 [41]
2
O N
2
O
O
O
O
1
1
74–177
OH
77–179 [42]
O N
2
NO2
NO2
1
1
83–186
87
OH
83–185 [41]
O
O
NO2
1
1
31–133
92
50
OH
OH
31–132 [43]
Me
O
O
Me
8
8
4–85
1 [44]
O
O
condition oꢁ reaction (amount oꢁ catalyst, yields, time and
temperature oꢁ reaction) are very mild and eco-ꢁriendly due
to solvent ꢁree condition (Table 5).
ꢁacile reusability oꢁ the catalyst. To study the reusability oꢁ
the [MPIm]Cl@HY, the fltered catalyst was washed with
hot toluene and diethyl ether and then reused on the opti-
mum condition (resorcinol (1 mmol), catalyst (0.18 g), time
150 min and temperature 130 °C) without obvious loss oꢁ
catalytic activity. The results are presented in Fig. 7, and
also the XRD and FTIR show no change (Fig. 8a, b) in the
crystallinity oꢁ [MPIm]Cl@HY zeolite, which confrm the
high stability ꢁor micro-/mesoporous structure catalyst.
As expected, the Pechmann reaction strongly depends on
the temperature. Iꢁ the reaction temperature was reduced
ꢁ
rom 130 to 100 and 80 °C, the yield oꢁ cumarin decreased
even aꢁter 5 h oꢁ reaction time to over 0.18 g oꢁ [MTMSPIm]
Cl@HY-Z ꢁrom 96.5 to 53 to 33.5%, respectively.
One oꢁ the great advantages oꢁ this catalyst is simple
separation by using fltration, which can easily lead to the
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Journal of the Iranian Chemical Society
Scheme 3 Proposal mechanism
ꢁ
or the preparation oꢁ coumarin
derivatives in the presence oꢁ
HY-IL catalyst via Pechmann
reaction
Table 5 Comparison
Catalyst
Catalyst amount
Time (h)
Yield (%)
Tempera-
ture (°C)
Reꢁ
oꢁ catalytic activity oꢁ
[
MTMSPIm]Cl@HY-Z with
other heterogeneous catalysts
Without catalyst (solvent)
Al-MCM-41 (Si/Al=25) (solvent)
PW/Al-MCM-41 (solvent)
_
0.5 g
0.5 g
0.5 g
100 mmol
100 mmol
0.078 g
0.12 mmol
0.5 mmol
0.18 g
5:83
4
4
1
4
4
2
12
2
2:30
89
73
75
67.5
100
93
75
62
78
[45]
[46]
[46]
[47]
[48]
[48]
[49]
[50]
[51]
–
175
175
400
200
200
85
80
60
130
Al-MCM-41 (Si/Al=104) (solvent)
SiO /sulꢁated (20%) (solvent)
2
TiO /sulꢁated (20%) (solvent)
2
Acidic ionic liquid (solvent)
[
[
bmim]HSO ionic liquid (solvent)
bmim.Cl] [NbCl ] (solvent)
4
34
96.5
x
5 Y
This work (solvent ꢁree)
Reported reaction conditions: the substrates are resorcinol and ethyl acetoacetate
Conclusion
In conclusion, an extremely eꢂcient method has been devel-
oped ꢁor the preparation oꢁ immobilized [MPIm]Cl in NaY
and HY zeolite, which is characterized by diꢀerent meth-
ods ꢁor confrmation oꢁ a micro-/mesoporous structure. The
micro-/mesoporous structure oꢁ zeolite has a number oꢁ advan-
tages with respect to both zeolites and mesoporous materials.
This kind oꢁ catalyst improves the reactant molecules diꢀu-
sion inside the crystal, increases availability oꢁ active sites,
reduces diꢀusion path oꢁ the reactant and coke precursor mol-
ecules and mesoporous materials with higher hydrothermal
stability and acidity. The micro-/meso[MPIm]Cl@zeolite as
a recyclable catalyst under solvent-ꢁree conditions with an
Fig. 7 Recycling oꢁ the catalyst
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Journal of the Iranian Chemical Society
Fig. 8 XRD pattern (A) and
FTIR (B) beꢁore (a) and aꢁter
(
b) recycling
environmentally benign nature was used ꢁor the synthesis oꢁ
coumarins via Pechmann reaction. The high yield and simple
and clean experimental way confrmed that the combination
oꢁ tunable pore and acid sites in zeolite and nucleophilic group
oꢁ ILs is useꢁul ꢁor organic reaction. Also, the result show that
hierarchical catalyst can be used sometimes without signifcant
change in yield and structure oꢁ the catalyst.
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oꢁ Excellence in the Chemistry Department oꢁ Arak University and
zeolite and porous materials committee oꢁ Iranian Chemical Society
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