Propylsulfonic acid functionalized nanozeolite clinoptilolite as heterogeneous catalyst for the synthesis of quinoxaline derivatives

Article abstract of DOI:10.1016/j.cclet.2015.04.037

In this work, the natural nanozeolite clinoptilolite (Nano CP) was successfully functionalized by propylsulfonic acid and applied as efficient heterogeneous catalyst for the synthesis of quinoxaline derivatives in aqueous media. The nanocatalyst was chara

Full text of DOI:10.1016/j.cclet.2015.04.037

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Chinese Chemical Letters
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Original article
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Propylsulfonic acid functionalized nanozeolite clinoptilolite as
heterogeneous catalyst for the synthesis of quinoxaline derivatives
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Q1 Seyed Meysam Baghbanian
Department of Chemistry, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
In this work, the natural nanozeolite clinoptilolite (Nano CP) was successfully functionalized by
propylsulfonic acid and applied as efficient heterogeneous catalyst for the synthesis of quinoxaline
derivatives in aqueous media. The nanocatalyst was characterized by various techniques such as CHN,
XRD, FT-IR, BET, TGA/DTA, SEM, TEM and TEM-EDS. The results show its applicability as green, reusable
and promising catalyst in organic synthesis. It was found that the nanocatalysts could be recycled and
reused eight times without significant loss of catalytic activities.
Received 5 March 2015
Received in revised form 12 April 2015
Accepted 23 April 2015
Available online xxx
Keywords:
ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
Clinoptilolite
Heterogeneous catalyst
Nanozeolite
Propylsulfonic acid
Quinoxalines
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1. Introduction
these catalysts are low selectivity and using expensive or toxic 31
materials for the synthesis of them on a large scale [16]. Acid 32
9
Quinoxaline derivatives are important components of pharma-
cologically active compounds, including antiviral, antibacterial,
anti-inflammatory, anti-protozoal, askinase inhibitors, anticancer
and anthelmintic agents [1]. In addition, quinoxaline derivatives
are reported for their application in dyes, organic semiconductors,
rigid subunits in macrocyclic receptors or molecular recognition,
efficient electroluminescent materials, chemically controllable
switches [2,3]. Generally, quinoxalines are synthesized by the
condensation of aryl 1,2-diamines with 1,2-dicarbonyl compounds
in MeOH/AcOH [4]. There are several methods for the formation of
the quinoxaline ring system in the presence of various catalysts
have been reported [5–15]. However, all these methods have some
drawbacks in the light of current working performance such as
application of toxic reagents, or reagents which are very expensive
and less accessible, thermally unstable and formation of side
products.
treatment causes a modification in morphology of nanozeolite CP 33
by the destruction of channel-blocking impurities and the 34
development of secondary porosity [17]. Therefore, acid treatment 35
increases the number of Si–OH groups, which can be used for the 36
immobilization process. To explore its capability, we intended to 37
investigate on the functionalization of natural nanozeolite 38
clinoptilolite by propylsulfonic acid and applied as catalyst for 39
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the synthesis of quinoxalines.
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2. Experimental
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All chemicals such as 3-mercaptopropyltrimethoxysilane 42
(MPTS), hydrogen peroxide (33 wt%) were purchased from Merck 43
Chemical Company. The raw zeolite material was an Iranian 44
commercial clinoptilolite (Afrandtooska Company) obtained from 45
deposits in the region of Semnan (ca. 1 $ per kg). All the other 46
solvents and chemicals were obtained from analytical reagent 47
grade chemicals unless specified otherwise and purchased from 48
Nanozeolite clinoptilolite is attractive in material supports
because of the excellent properties such as ease of availability of
the natural, inexpensive, high specific surface area, large pore
volumes, good thermal and chemical stability, and non-toxicity.
Although many kinds of zeolites were used as catalysts or catalysts
supports such as HB, A, NaY, X, Y and ZSM-5, the main drawbacks of
Merck Company.
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2.1. Synthesis of activated Nano CP
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The nanozeolite clinoptilolite (5 g) was taken into a 250 mL 51
round bottom flask and 100 mL 4 mol/L sulfuric acid was added to 52
it. The flask mixture was refluxed for 1 h. After cooling, the 53
E-mail address: s.m.baghbanian@iauamol.ac.ir.
http://dx.doi.org/10.1016/j.cclet.2015.04.037
1001-8417/ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: S.M. Baghbanian, Propylsulfonic acid functionalized nanozeolite clinoptilolite as heterogeneous
catalyst for the synthesis of quinoxaline derivatives, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.04.037

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S.M. Baghbanian / Chinese Chemical Letters xxx (2015) xxx–xxx
Table 1
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supernatant was discarded and the activated nanozeolite CP was
repeatedly washed with deionized water (250 mL) until the
solution became neutral and finally dried in oven at 80 8C
overnight to obtain the white solid product. The activated
nanozeolite CP was designated as AT-Nano CP.
Optimization of reaction conditions for the synthesis of quinoxaline 3a.a
Entry
Solvent
Catalyst (g)
Temp. (8C)
Time (min)
Yield (%)b
1
2
H2O
–
25
25
80
25
25
25
25
50
80
25
25
25
25
120
80
60
30
15
10
20
15
15
30
45
50
45
Trace
30
55
85
90
95
95
95
95
85
65
35
40
H2O
Nano CP [0.01]
Nano CP [0.01]
NZ-PSA[0.004]
NZ-PSA [0.008]
NZ-PSA [0.01]
NZ-PSA [0.02]
NZ-PSA [0.01]
NZ-PSA [0.01]
NZ-PSA [0.01]
NZ-PSA [0.01]
NZ-PSA [0.01]
NZ-PSA [0.01]
3
H2O
4
H2O
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2.2. Synthesis of propylsulfonic acid functionalized AT-Nano CP (NZ-
PSA)
5
H2O
6
H2O
7
H2O
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63
64
65
66
67
68
69
70
AT-Nano CP (2 g) was taken into a 50 mL round bottom flask.
MPTS (2 mL) was dissolved in toluene (4 mL) and added slowly
under vigorous stirring condition. The resulting mixture was
stirred at 80 8C for 8 h. The mixture was then filtered and washed
with toluene (4 mL) and double distilled water (5 mL) before
drying at 100 8C. The oxidation was carried out by contacting the
sample (1.0 g) with a solution of hydrogen peroxide (33 wt%) at
room temperature and stirred for 12 h. The solid was then filtered,
washed abundantly with distilled water, following by drying at
100 8C for overnight.
8
H2O
9
H2O
10
11
12
13
EtOH
DMF
Toluene
CH2Cl2
a
Reaction conditions: benzene-1,2-diamine (1 mmol), benzil (1 mmol) and
solvent (5 mL).
b
Isolated yields.
order to optimize the reaction conditions, the catalytic efficiency
was studied with various amounts of nano NZ-PSA in the model
reaction (entries 4–6). The results reveal that 0.01 g of NZ-PSA
provided the best effects in terms of economy of catalyst charge
and purity of products (entry 6). Moreover, higher amounts of the
catalyst (0.02 g) did not improve the yield and the reaction time
(entry 7). The role of solvents in the reaction was also screened. As
shown in Table 1, entries 10–13, it was found that water is a
suitable solvent to produce the target products in high to excellent
yields and relatively short reaction time in comparison with other
solvents. Also, we carried out the model reaction at various
temperatures ranging from 25 8C to 80 8C (entries 7–9). The results
demonstrate that increase in the reaction temperature did not
affect the product yield and reaction time. Consequently, the best
results were afforded by the reaction of these components in water
(5 mL) in the presence of 0.01 g of NZ-PSA at room temperature
obtaining quinoxaline 3a in a 95% yield (entry 6).
To assess the generality of this approach for the synthesis of
quinoxalines, various substituted 1,2-diketones were reacted with
structurally and electronically diverse o-phenylenediamines, and
the results are summarized in Table 2, 3a-j. It was observed that
electron-donating groups had no significant effect on the reaction
results (3b,g,h,i). Moreover, other 1,2-diketones such as 9,10-
phenanthraquinone (3c,h,i), acenaphthoquinone (3d,g), and
indantrione (3e,f) were examined in this reaction and correspond-
ing quinoxalines were produced in the short time and excellent
yield. In following to further explore the potential of this protocol,
we also examined the synthesis of quinoxalines using another
reactant, phenacyl bromide derivatives instead of 1,2-diketones
under similar reaction conditions (Table 2). Results demonstrate
that all p-chloro and bromophenacylbromide were reacted with o-
phenylenediamines to provide the corresponding products in good
yields (5a-i).
The reaction was clean and the products were obtained in high
yields without the formation of any by-products. All the products
prepared were known compounds and their structures were
characterized with use of the spectral methods (1H NMR and 13C
NMR) and comparison with authentic samples (Supporting
information). The recyclability of the catalyst for reactions was
investigated for the synthesis of quinoxaline under the optimized
reaction conditions. The catalyst was recovered by filtration
technique after each experiment and washed with hot distilled
ethanol (2 mL) twice and drying at 80 8C in an oven to provide an
opportunity for recycling experiments. The separated nanocatalyst
was reused successively eight times without any significant loss of
activity (Fig. S7 in Supporting information). The strong interaction
of MPTS grafted on the surface of AT-Nano CP could be the reason
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2.3. General procedure for the synthesis of quinoxalines
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A mixture of aromatic o-diamine (1 mmol), 1,2-dicarbonyl
compounds or phenacyl bromides (1 mmol) and NZ-PSA (0.01 g)
in 5 mL of water was stirred at room temperature for an
appropriate time (Table 2). The progress of the reaction was
monitored by TLC. After completion of the reaction, the catalyst
was filtered off. The solvent was evaporated under reduced
pressure and the pure product was obtained without any further
purification and their spectroscopic data are shown in supporting
information.
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3. Results and discussion
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The nanozeolite CP was prepared according to a simple method
developed recently by our group [18a] and subsequently activated
with 4 mol/L sulfuric acid. The activated nanozeolite CP was
designated as AT-Nano CP. AT-Nano CP was reacted with MPTS in
toluene at 80 8C to afforded propylsulfonic acid functionalized
nanozeolite CP (NZ-PSA). Afterwards, the NZ-PSA was character-
ized by various techniques such as CHN, XRD, FT-IR, BET, TGA/DTA,
SEM, TEM and TEM-EDS (Supporting information). After synthesis
and characterizations of NZ-PSA, the catalytic activities of these
nanocatalyst were explored for the synthesis of quinoxaline
derivatives. In order to determine the optimum reaction condi-
tions, the reaction of benzene-1,2-diamine 1a (1 mmol) with
benzil 2a (1 mmol) was examined as a model reaction in water at
room temperature (Scheme 1).
The model reaction was carried out in the presence of different
catalytic amounts of nanozeolite CP and NZ-PSA the results are
presented in Table 1. In the absence of catalyst, only a trace amount
of desired product was obtained even after in longer reaction time
(entry 1). The results show that both nanocatalysts could promote
the reaction, but NZ-PSA catalyst is significantly more effective
than nanozeolite CP in the synthesis of quinoxaline 3a and it
provides better results with high yields and short reaction times. In
Scheme 1. The model reaction for the synthesis of quinoxaline 3a.
Please cite this article in press as: S.M. Baghbanian, Propylsulfonic acid functionalized nanozeolite clinoptilolite as heterogeneous
catalyst for the synthesis of quinoxaline derivatives, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.04.037

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Table 2
Synthesis of quinoxalines 3 and 5 catalyzed by NZ-PSA.a
a
Reaction conditions: o-Phenylenediamines (1 mmol), 1,2-diketones or phenacyl bromides (1 mmol), water (5 mL) and NZ-PSA (0.01 g), 25 8C.
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for the repetitive use of the catalyst in a greater number of catalytic
runs with high yield.
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In summary, propylsulfonic acid functionalized nanozeolite CP
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efficient heterogeneous catalyst for the synthesis of quinoxaline
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Please cite this article in press as: S.M. Baghbanian, Propylsulfonic acid functionalized nanozeolite clinoptilolite as heterogeneous
catalyst for the synthesis of quinoxaline derivatives, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.04.037