Polystyrene-supported basic dicationic ionic liquid as a novel, reusable, and efficient heterogeneous catalyst for the one-pot synthesis of chromene derivatives in water

Article abstract of DOI:10.1007/s11164-015-2247-3

Polystyrene-supported 1,4-bis(3-methylimidazolium-1-yl)butane dihydroxide basic dicationic ionic liquid was prepared by supporting the ionic liquid onto highly cross-linked chloromethylated polystyrene. FT-IR, SEM, TG-DTA, and elemental analysis were empl

Full text of DOI:10.1007/s11164-015-2247-3

Res Chem Intermed
DOI 10.1007/s11164-015-2247-3
Polystyrene-supported basic dicationic ionic liquid
as a novel, reusable, and efficient heterogeneous catalyst
for the one-pot synthesis of chromene derivatives
in water
1
1
Fariba Heidarizadeh
•
Narges Taheri
Received: 1 July 2015 / Accepted: 28 August 2015
Ó Springer Science+Business Media Dordrecht 2015
Abstract Polystyrene-supported 1,4-bis(3-methylimidazolium-1-yl)butane dihy-
droxide basic dicationic ionic liquid was prepared by supporting the ionic liquid
onto highly cross-linked chloromethylated polystyrene. FT-IR, SEM, TG–DTA, and
elemental analysis were employed to characterize the structure and property of the
catalyst. The results suggested that our basic dicationic ionic liquid was supported
on the surface of PS-CH Cl by a covalent bond. This basic dicationic ionic liquid
2
exhibited high catalytic activity for the one-pot synthesis of chromene derivatives in
water. The unique features of the catalyst, such as high thermal stability, recycla-
bility, excellent catalytic activity in terms of yield and reaction time, high turnover
number and turnover frequency, and also using water as a solvent, would be
potentially important for its applications in industry.
Keywords Multicomponent reaction Á Green chemistry Á Ionic liquid Á
Heterogeneous catalyst Á 4H-chromene derivatives
Introduction
In recent decades, there has been an increasing interest in developing environmen-
tally friendly greener processes, which are also economically viable [1–3]. Several
new methods and novel-designed materials have been developed in order to make
the chemical reactions cleaner and more benign. The base catalyzed reaction is an
important process in the synthesis of pharmaceutical compounds, thus complete
removing the base is very important. Moreover, as the homogenous base causes
&
Fariba Heidarizadeh
heidarizadeh@scu.ac.ir
1
Department of Chemistry, Shahid Chamran University, Ahvaz 6135743169, Iran
123

F. Heidarizadeh, N. Taheri
toxic and corrosive wastewater, finding a heterogeneous Brønsted basic catalyst in
bulk synthesis would be in high priority. There are some reports on the supported
basic materials, but they suffer drawbacks such as low loading and low thermal
stability [4, 5].
The Knoevenagel condensation and Michael reactions which are well-known
base catalyzed C–C bond-forming reactions are generally employed for the
synthesis of important compounds such as 4H-chromene derivatives. The 4H-
chomene derivatives are of considerable interest as they possess a wide range of
pharmacological properties such as spasmolytic diuretics, anticoagulant, anti-
cancer, antianaphylactic, antibacterial [6, 7], anti-fungal [8], anti-oxidant [9], anti-
leishmanial [10], anti-tumor [11], hypotensive [12] antimalarial activities [6, 7]
and anti-proliferation properties [13]. Different methods have been reported for
the synthesis of 4H-chromene derivatives. However, some of the reported methods
involve prolonged reaction time, use of stoichiometric amounts of catalyst,
hazardous solvents, unsatisfactory yields of the product or as an obstacle to
recycling the catalysts, and comparatively fewer methods have been described
using ionic liquids or supported ionic liquids. Therefore, in order to solve these
problems, a great deal of effort has been focused on the development of an
efficient catalyst for the synthesis of these compounds under green conditions. For
instance, performing safer and environmentally friendly synthetic processes is now
possible by using ionic liquids due to their unique properties, but the high cost,
difficulty in recycling and product separation, high viscosity, and moisture
sensitivity limited their further applications to the industrial scale [14]. Thus, in
order to overcome these drawbacks, immobilized ionic liquid catalysts with
heterogeneous support materials have been proposed.
In comparison with the homogeneous catalysts, heterogeneous systems present
many advantages such as fast recovery and simple recycling, higher stability of
the catalyst, and catalyst protection against destruction. Many reports on the
preparation of supported ionic liquid catalysts have been published, in which the
ionic liquids were normally immobilized onto the support materials, such as silica
gel [15–17], mesoporous silica [5, 18, 19], magnetic nanoparticles [20–22] and
polymers [23–25].
Being low cost, easy to recover and separate, and simply surface-modified,
polymeric materials have been broadly utilized among the supporting materials in
catalytic reactions [26–32]. In particular, polystyrenes such as polymeric supports
are the most common polymers for these purposes [33].
By considering all the above-mentioned points, we designed a novel supported
basic dicationic ionic liquid catalyst with high activity and selectivity combined
with simple separation from the reaction medium. This catalyst, which was prepared
through the immobilization of 1,4-bis(3-methylimidazolium-1-yl)butane dihydrox-
ide, [C (MIM) ][OH] , on polystyrene and its catalytic activity for the synthesis of
4
2
2
substituted 2-amino-4H-benzo[h]chromenes, 2-amino-4H-benzo[f]chromenes, and
-amino-4H-tetrahydrochromenein water, was studied.
2
1
23

Polystyrene-supported basic dicationic ionic liquid as a…
Experimental
General
Chloromethylated polystyrene or PS-CH Cl (200–400 mesh, 2 % divinylbenzene,
2
2-4 mmol Cl/g) was obtained from Alfaeser. All the other chemicals were
purchased from Fluka and Merck and used without further purification. All the
1
13
products are known and characterized by physical data, IR, H NMR and
NMR spectra. IR spectra were obtained on a Bomen MB:102 FT-IR spectropho-
C
1 13
tometer. H NMR and C NMR spectra were recorded on a Brucker spectrometer
at 400 and 100 MHz, respectively, in CDCl or dimethylsulfoxide (DMSO) with
3
tetramethylsilane as an internal standard. Elemental analyses were performed in a
Thermo Finnigan Flash EA 1112 CHNS-Analyzer. The polymer morphology was
examined by SEM (LEO-1455VP). Thermal stability of the functionalized
polymer was investigated by NETZSCH STA 409 PC/PG under nitrogen
atmosphere (rate of N & 1 L/h). Monitoring of the reactions and the purity
2
determination of the products were accomplished by TLC on silica gel PolyGram
SILG/UV 254 plates.
Synthesis of PS-CH IM and PS-[BrBMIM] Br [34]
2
Chloromethylated polystyrene or PS-CH Cl (2.5 g, 2 % cross-linking, 2–4 mmol/g)
2
was introduced in a round-bottomed flask of 250 mL. Then, imidazole (4 g,
60 mmol, 6 eq.) was dissolved in 25 mL of DMF and introduced into the flask and
the suspension was refluxed for 4 h. The mixture was then cooled to room
temperature. The resin was filtered and washed successively with DMF, DMF:H O
2
(
step, the synthesized PS-CH IM (1 g) was added to a round-bottomed flask. Then,
1:1), THF and finally CH Cl and then dried in a vacuum oven at 60 °C. In the next
2
2
2
1
,4-dibromobutane (10 mL) was introduced into the flask and the suspension was
refluxed at 70 °C for 4 h. The reaction mixture was then filtered and polystyrene
supported 1-(4-bromo butyl 3-methylimidazolium)bromide or PS-[BrBMIM]Br was
washed with DMF, DMF:THF (1:1), THF and CH Cl , respectively, and dried in a
2
2
vacuum oven.
Synthesis of PS-[C (MIM) ][Br]
2
4
2
The obtained PS-[BrBMIM]Br polymer (1 g) was introduced into a flask and
suspended in excess N-methylimidazole (10 mL) as solvent and reagent. The vessel
was then heated for 4 h at 80 °C in an oil bath. After this period, the desired
supported dicationic ionic liquid on polymer was collected by filtration, washed
with MeOH and CH Cl , and dried at 80 °C. The loading of the dicationic ionic
2
2
liquid was found to be 1.25 mmol/g by means of the nitrogen content obtained from
elementary analysis (Table 1).
123

F. Heidarizadeh, N. Taheri
Table 1 Elemental analysis of
PS-CH Cl, PS-CH IM and PS-
(MIM) ][Br]
Materials
C (W%)
H (W%)
N (W%)
2
2
[C
4
2
2
PS-CH
2
2
Cl
83.35
86
7.2
7.4
6.8
0.1
PS-CH
IM
6.52
7.7
PS-[C
4
(MIM)
2
][Br]
2
63.5
Preparation of supported basic dicationic ionic liquid PS-[C (MIM) ][OH]
2
4
2
[
35]
Solid potassium hydroxide (6 mmol) and PS-[C (MIM) ][Br] (1 g) were added to
2
4
2
water (15 mL), and the mixture was stirred vigorously for 1 day at ambient
temperature. The resultant solid was filtered and washed with water until the pH of
filtrate was 7, then the catalyst was washed two times with ethanol and ether, and
dried under vacuum at 60 °C for 4 h to afford PS-[C (MIM) ][OH]
4
2
2.
Determination of the capacity PS-[C (MIM) ][OH]
2
4
2
To ensure that all bromide ions were exchanged with hydroxide ions, the AgNO3
test was used, and it was found that 92 % of bromide ion were successfully
exchanged. The loading of the hydroxide anion in the catalyst was calculated by
titration with HCl (0.01 M) and found to be 2.5 mmol/g.
General procedure for the synthesis of chromene derivatives
To a suspension of equimolar (1) mixture of each of aromatic aldehyde,
malononitrile, and dimedone (or 1-naphtol or 2-naphtol) in water (5 mL), PS-
[
C (MIM ][OH] (0.04 g) was added and the mixture was heated at 80 °C for an
4
2
2
appropriate time. The progress of the reaction was monitored by TLC (n-hexane/
ethyl acetate, 4:1), for the disappearance of aldehyde. The solid was collected by
filtration, and washed with hot ethanol (2 9 10 mL) for separation of the product
from the catalyst. Evaporation of ethanol under reduced pressure gave the products,
which were purified by recrystallization in ethanol.
Selected spectral data
1
(
Table 3, entry 1): H NMR (DMSO-d , 400 MHz): d = 4.90 (1H, CH, s),
6
7
m), 7.89 (1H, J = 8.1 Hz, ArH, d), 8.25 (1H,J = 8.1 Hz, ArH, d). IR (KBr) (vmax,
.10–7.15 (1H, ArH, and 2H, NH , t), 7.19–7.34 (5H, ArH, m), 7.55–7.67 (3H, ArH,
2
-
cm ): 3450, 3340, 2200, 1670, 1590, 1480, 1395, 1310, 1230, 1120, 931, 740, 560.
1
1
(
Table 3, entry 8): H NMR (DMSO-d , 400 MHz): d = 5.30 (1H, CH, s), 6.96
6
(
ArH, m), 7.84 (1H, J = 8.1 Hz, ArH, d), 7.90–7.96 (1H, ArH, m). IR (KBr) (vmax,
2H, NH , s), 7.15–7.33 (5H, ArH, m), 7.34 (1H, J = 9 Hz, ArH, d), 7.42–7.47 (2H,
2
-
1
cm ): 3434, 3341, 2183, 1639, 1589, 1517, 1410, 1232, 1072, 1028, 814, 752, 717,
96.
6
1
23

Polystyrene-supported basic dicationic ionic liquid as a…
1
(
Table 3, entry 19): H NMR (CDCl , 400 MHz): d = 1.07 (3H, CH , s), 1.16
3
3
(
(
3H, CH , s), 2.17–2.28 (2H, CH , m), 2.45 (2H, CH , s), 3.75 (3H, –OCH , s), 4.37
3 2 2 3
-
1H, CH, s), 4.58 (2H, NH , s), 6.84–7.08 (4H, Ar–H, m). IR (KBr) (vmax, cm ):
1
2
3
457, 3326, 2968, 2157, 1657, 1381, 1216.
Recyclability of the catalyst
The recyclability of the catalyst in the reaction of 1-naphthol, benzaldehyde and
malononitrile in water at 80 °C was evaluated. In this procedure, after completion of
each reaction, hot ethanol was added and the catalyst was filtered. Then, the
recovered catalyst was washed twice in ethanol and acetone, and dried at room
temperature. Afterwards, the reused catalyst was utilized for another reaction run.
We observed that the catalytic activity of the catalyst remained unchanged within
the limits of the experimental errors for five successive runs (see Fig. 6, below).
Results and discussion
PS-[C (MIM) ][OH] preparation and its structural and morphological
4
2
2
analysis
As stated earlier, it has been demonstrated that the covalent modification of the
surface of a polymeric matrix with imidazolium subunits significantly modifies its
properties. Indeed, transfer of many of the properties of the corresponding ionic
liquid (IL) can be achieved, allowing, for instance, a controlled tuning of its polarity
[
36].
In addition, it has been observed how the exact structure and morphology of a
polymer modified with ILs units play an active role in controlling the release and
catch of the active species, their stabilization in the reaction medium, chemical, and
thermal demands under normal operating conditions, and the final catalytic
properties of the system.
Considering these facts, the immobilization of basic ionic liquid [C (MIM) ][-
4
2
OH] onto the polystyrene were done by a simple and convenient two-step reaction
2
(
Scheme 1). The first step consisted of the synthesis of novel dicationic polymer via
immobilization of IL [C (MIM) ][Br] on the polymeric backbone and in the second
4
2
2
step PS-[C (MIM) ][OH] was synthesized from [C (MIM) ][Br] by anion
2
4
2
2
4
2
metathesis reaction with KOH. The chemical structure of PS-[C (MIM) ][OH]
2
4
2
was studied using FT-IR, SEM, TG–DTG and elemental analyses.
The FT-IR spectra of the prepared PS-[C (MIM) ][OH] catalyst (Fig. 1) show
bands corresponding to the structural units of the solid polymer. Thus, the
4
2
2
immobilization of the imidazole to yield PS-CH IM polymer can be easily
2
-
monitored by the disappearance of the peak at 1265 cm which was associated
1
with the CH Cl groups (Fig. 1a), and it can also be monitored by the appearance of
2
the characteristic bands corresponding to the C=C and C=N vibrations of the
-
1
-1
imidazole moiety at 1563 cm and 1641 cm (Fig. 1b), respectively. Moreover,
123

F. Heidarizadeh, N. Taheri
N
N
Cl
DMF
HN
+
N
4
8h, reflux
1
,
PS-CH IM
4
2
4
-
h
D
PS-CH Cl
2
,
i
r
b
e
r
f
o
l
u
m
x
b
u
t
h
a
n
-
N
N
e
Br
-
-
Br
Br
4
+
N
Br
4
+
N
N
N
+
N
N
o
4
h,80 C
PS-[C (MIM) ][Br]
K
PS-[BrBMIM]Br
4
2
2
O
H
2
,
4
W
h
a
t
e
r
OH-
OH-
N
4
+
N
N +
N
PS-[C (MIM) ][OH]
4
2
2
Scheme 1 The immobilization of basic ionic liquid [C
4
2 2
(MIM) ][OH] onto the polystyrene
further reaction of the PS-CH IM with 1,4- dibromo butane led to PS-([BBMIM]Br
2
polymer.
-
1
-1
The weak bands located at 2830 cm
asymmetric and symmetric stretching vibration modes, respectively. The strong
-
peak around 1630 cm is mainly from the bending vibration of adsorbed H O.
to 2950 cm
correspond to C–H
1
2
The last step involving the reaction with methyl imidazole followed by anion
exchange is shown in Fig. 1c.
The quantity of basic dicationic ionic liquid grafted onto the polymer was
determined from CHN elemental analysis (Table 1). The amount of grafted
dicationic ionic liquid was found to be 1.25 mmol/g.
TG/DTG analysis was carried out to investigate the thermal stability of PS-
CH Cl and PS-[C (MIM) ][OH] catalyst in N atmosphere with heating rate of
2
4
2
2
2
1
0 °C/min up to 1000 °C. One can see that PS is stable up to 300 °C, and
decomposition of PS begins at 320 °C and is completed at 450 °C (Fig. 2). In the
range of 50–210 °C, a slight weight loss was observed from PS-[C (MIM) ][OH]
catalyst (Fig. 3). The weight loss was possibly attributed to the physisorbed water.
4
2
2
1
23

Polystyrene-supported basic dicationic ionic liquid as a…
2 2 4 2 2
Fig. 1 FT-IR spectra of (a) PS-CH Cl, (b) PS-CH IM, and (c) PS-[C (MIM) ][OH]
2
Fig. 2 TGA and DTG curves of PS-CH Cl
The hydrophilic structure of ionic liquid [BBMIM][OH] facilitated its adsorption
2
of more water. Moreover, some residual imidazole might be adhered to the surface
of PS-CH Cl by electrostatic adsorption. When the temperature further increased up
2
to higher than 320 °C, weight loss was obviously displayed in TGA curves of both
123

F. Heidarizadeh, N. Taheri
4 2 2
Fig. 3 TGA and DTG curves of PS-[C (MIM) ][OH]
PS-CH Cl and PS-[C (MIM) ][OH] . The reason may be that their structures were
2
4
2
2
destroyed and disordered, or the chloromethyl group and the [C (MIM) ][OH]
2
4
2
separated from the surface of the polystyrene and decomposed. Correspondingly,
sharp endothermic peaks at 330 and 440 °C appeared. Finally, it was observed that
the residue weight of PS-[C (MIM) ][OH] and PS-CH Cl was in turn about 37 and
4
2
2
2
3
possesses good stability and is a suitable catalyst for multicomponent synthesis that
2 % at 480 °C. These observations indicated that the PS-[C (MIM) ][OH]
4
2
2
occurs under 300 °C.
The structural and morphological characterizations of unmodified polystyrene
and PS-[C (MIM) ][OH] were studied by SEM images. These images show the
unmodified chloromethylated polystyrene had spherical structures (Fig. 4), but the
4
2
2
2
Fig. 4 SEM image of PS-CH Cl
1
23

Polystyrene-supported basic dicationic ionic liquid as a…
4 2 2
Fig. 5 SEM image of PS-[C (MIM) ][OH]
polystyrene microspheres (or spherical structures) had been destroyed when the
imidazole ring was supported on resins (Fig. 5). In addition, the diameters of the
undestroyed spherical particles were all in the range of 90–110 lm, the shape of
destroyed particles was irregular, and the diameter was in a wide range of
1
0–30 s lm.
Application of PS-[C (MIM) ][OH] as heterogeneous catalyst
2
4
2
for the synthesis of chromene derivatives in water
We report in this paper a highly efficient one-pot synthesis of a variety of chromene
derivatives, namely substituted 2-amino-4H-benzo[h]chromenes, 2-amino-4H-
benzo[f]chromenes, and 2-amino-4H-tetrahydrochromene, catalyzed by PS-
[
C (MIM) ][OH] in water at 80 °C (Scheme 2).
4
2
2
Initially, in order to investigate the possible catalytic activity of PS-
C (MIM) ][OH] in the synthesis of chromene derivatives, the three-component
[
4
2
2
coupling of aldehydes, malononitrile and 1-naphthol in water was chosen.
With the aim of optimizing the reaction conditions, the reaction was conducted
under different conditions in both the absence and the presence of PS-[C (MIM) ]
4
2
[
OH] (Scheme 3).The results are presented in Table 2.
2
The reaction temperature had a crucial role on the reaction yield: below 80 °C,
the reaction proceeded slowly to give relatively low yield, while no improvement
was observed above 80 °C. For yield improvement, the effect of the catalyst amount
was also studied. Increasing the catalyst amount from 0.04 to 0.07 g did not
remarkably affect the yield, while the reaction in the absence of the prepared
polymeric catalyst gave the product only 25 % yield after 4 h.
After optimizing the conditions, the scope and generality of this protocol were
examined by subjecting a broad range of aromatic aldehydes carrying either
electron-donating or withdrawing substituents, malononitrile and 1-naphthol,
2
-naphthol or dimedone using PS-[C (MIM) ][OH] as a catalyst in water at
4 2 2
8
0 °C. All the combinations reacted very well, giving moderate to excellent isolated
123

F. Heidarizadeh, N. Taheri
R
O
O
O
CN
O
4
NH2
OH
NH2
CHO
R
CN
O
5
mol%cat
CN
CN
+
H O,
80 °C
2
R
5
R
OH
CN
NH2
O
6
Scheme 2 Synthesis of
benzo[f]chromenes, and 2-amino-4H-tetrahydrochromene, catalyzed by PS-[C
a variety of substituted 2-amino-4H-benzo[h]chromenes, 2-amino-4H-
in water
4
(MIM)
2
][OH]
2
at 80 °C
NH2
CN
OH
CHO
O
CN
CN
PS-[C MIM) ][OH] 5mol%
4(
2
2
+
+
o
H O, 80 C
2
Scheme 3 Optimization of the reaction conditions
yields (80–96 %) with high purity of the desired products under optimized reaction
conditions.
It is worth mentioning that electronic effects and the nature of substituents on the
aromatic ring showed no obvious effect on this conversion,which is because they
were obtained in high yields in relatively short reaction times. The results are shown
in Table 3.
In order to show the effectiveness of the present work, we compared our results
obtained from the model reaction in the presence of PS-[C (MIM) ][OH] as a
heterogeneous catalyst with the results reported in the literature.
4
2
2
1
23

Polystyrene-supported basic dicationic ionic liquid as a…
Table 2 Optimization of reaction conditions
a
Entry
Solvent
Catalyst (gr)
Temperature (°C)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
CH
CH
2
Cl
2
0.05
0.05
0.05
0.05
–
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
80
4
35
42
38
70
25
92
92
92
85
92
81
3
CN
4
Toluene
EtOH
4
0.5
4
H
H
H
H
H
H
H
2
2
2
2
2
2
2
O
O
0.05
0.05
0.04
0.04
0.07
0.04
0.16
0.16
0.16
0.16
0.16
0.33
O
O
80
O
70
1
1
0
1
O
80
O: EtOH
80
Reaction conditions: benzaldehyde (1 mmol), malononitrile (1 mmol), and a-naphtol (1 mmol), solvent
(5 mL)
a
Yields refer to isolated pure products
The catalyst amount, reaction times or product yields and TON and TOF values
showed that our novel catalyst is more effective than those reported for other
catalytic systems (Table 4).
Proposed mechanism
A proposed mechanism to demonstrate the role of catalyst is shown in Scheme 4.
A Knoevenagel reaction, Michael addition, and intra-molecular cyclization are
involved simultaneously in the synthesis of 2-amino-4H-chromene derivatives. [45].
In the first step, the polystyrene-supported basic ionic liquid PS-[C (MIM) ]
4
2
[
OH] abstracts a proton from the active methylene group of malononitrile leading
2
to formation of carbanion. The formed carbanion of malononitrile makes a
nucleophilic attack on the carbonyl carbon atom of aromatic aldehydes, followed by
loss of a water molecule to form a-cyanocinnamonitrile derivative.
In the second step, Michael addition of 1-naphthol (2-naphthol or dimedone) to
Knoevenagel products, followed by ring closing and hydrolysis, obtained
2
-aminochromene derivatives.
In environmentally friendly methodologies, the recovery and reuse of the
prepared catalyst is highly preferable. PS-[C (MIM) ][OH] did not suffer from
4
2
2
extensive mechanical degradation and was quantitatively recovered simply by
filtration and washing with water and acetone. It could be reused for subsequent
reactions. Recycled PS-[C (MIM) ][OH] showed no significant loss of efficiency
4
2
2
with regard to yield after five successive runs (Fig. 6).
123

F. Heidarizadeh, N. Taheri
Table 3 Synthesis of substituted 2-aminochromene derivatives
Entry
Aldehyde
Naphtol or
dimedone
Product
Time Yielda
Melting
point
(
min)
(%)
(
°C)/(lit.)
1
CHO
OH
OH
NH2
O
10
92
210–211
CN
(210–212)
[
37]
2
3
4
5
CHO
NH2
5
5
96
90
90
88
231–234
CN
(230–231)
O
[
37]
NO
2
NO
2
CHO
OH
OH
OH
NH2
232–235
(232)
CN
O
[
38]
Cl
Cl
CHO
NH2
25
35
205–206
CN
(205–206)
O
[
39]
Me
Me
CHO
NH2
191–194
CN
(190–192)
O
[
37]
OMe
OMe
6
7
8
CHO
OH
OH
OH
NH2
20
5
85
95
86
236–237
Cl
CN
Cl
(235–237)
O
[
38]
CHO
NH2
208–211
CN
(210–213)
O
[
38]
NO
2
2
O N
35
170–173
169–171)
(
[
40]
1
23

Polystyrene-supported basic dicationic ionic liquid as a…
Table 3 continued
Entry
Aldehyde
Naphtol or
dimedone
Product
Time Yielda
Melting
point
(
min)
(%)
(
°C)/(lit.)
9
CHO
OH
30
90
286–288
288–289)
CN
(
(
NH2
[
39]
O
1
1
1
1
0
1
2
3
CHO
OH
OH
O N
5
5
94
91
187–188
187–188)
2
CN
NH2
NH2
NH2
NH2
[
3]
O
NO2
CHO
Cl
208–210
210–211)
CN
(
(
(
[
39]
O
Cl
CHO
OH
OH
OH
OH
Me
45
45
25
20
85
90
87
93
269–270
271–272)
CN
[
39]
O
Me
CHO
MeO
191–192
188–189)
CN
[
38]
O
OMe
1
1
4
5
CHO
Cl
Cl
271–273
CN
(270–271)
NH2
NH2
[
40]
O
CHO
NO2
239–241
(
239–241)
CN
[
38]
O2N
O
1
1
6
7
OH
40
30
92
90
224–226
226–227)
(
(
[
40]
CHO
O
228–230
225–228)
O
[
41]
O
CN
O
NH2
123

F. Heidarizadeh, N. Taheri
Table 3 continued
Entry
Aldehyde
Naphtol or
dimedone
Product
Time Yielda
Melting
point
(
min)
(%)
(
°C)/(lit.)
1
1
8
9
CHO
O
NO2
15
94
177–178
175–177)
42]
(
[
O
O
NO2
CN
O
NH2
CHO
O
Cl
25
88
207–209
208–210)
(
[
42]
O
O
Cl
CN
O
NH2
2
2
0
1
CHO
O
Me
45
50
85
80
220–222
221–222)
(
(
[
43]
O
O
Me
CN
O
NH2
CHO
O
OMe
200–202
200–201)
[
3]
O
O
O
O
OMe
CN
O
O
O
NH2
2
2
2
2
3
4
CHO
Cl
O
35
20
45
89
92
87
213–214
(215–216)
3]
Cl
CN
[
O
NH2
NO2
CHO
O
210–213
213–217)
(
(
[
3]
O2N
O
CN
NH2
O
225–228
226–227)
[
3]
O
a
Conditions: the reaction was performed by using dimedone (or 1-naphtol or 2-naphtol) (1 mmol),
aldehyde and malononitrile (1 mmol) in the presence of (5 mol %) of PS-[C (MIM ][OH] in (5 mL)
O at 80 °C
4
2
2
H
b
2
The yields refer to isolated products
1
23

Polystyrene-supported basic dicationic ionic liquid as a…
123

F. Heidarizadeh, N. Taheri
N
N
Merrifield
Resin
N
N
O
H2O
OH
CN
CN
H
O
H
CN
CN
N
N
Merrifield
Resin
Ar
N
N
CN
CN
CN
CN
N
N
Merrifield
Resin
N
N
O
OH-
OH-
Ar
H
N
N
H2O
O
Ar
H
H
CN
CN
Ar
N
N
Merrifield
Resin
N
N
O
NH2
CN
CN
O
CN
CN
CN
Ar
O
Ar
Scheme 4 Proposed mechanism for the catalyst role
Recyclability of catalyst
90
100
92
90
87
85
8
6
4
2
0
0
0
0
0
1
2
3
4
5
No. of cycles
Fig. 6 Recyclability of catalyst
Conclusion
According to the increasing need for green organic synthesis and industrial
demands, we here report the synthesis of new PS-[C (MIM ][OH] as a Brønsted-
4
2
2
type basic catalyst. It has several major advantages: (1) high thermal stability, (2)
recyclability, (3) easy isolation of the product, (4) successful application in the
multicomponent synthesis, (5) the reaction can be carried out in water, (6) the IL
unit plays an active role in controlling the release and catch of the active species,
and (7) excellent catalytic activity in terms of yield and reaction time, high turnover
number and turnover frequency.
1
23

Polystyrene-supported basic dicationic ionic liquid as a…
Acknowledgment The authors gratefully acknowledge financial support of this research by Shahid
Chamran (Ahvaz) University.
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