Sulfonated rice husk ash (RHA-SO3H) as an efficient and recyclable catalyst for the Friedlander synthesis of quinolines

Article abstract of DOI:10.1007/s11164-014-1919-8

Sulfonated rice husk ash (RHA-SO₃H), as a newly reported powerful solid acid catalyst, can be efficiently used for the promotion of the preparation of substituted quinoline derivatives via the condensation reaction between 2-aminoarylketones an

Full text of DOI:10.1007/s11164-014-1919-8

Res Chem Intermed
DOI 10.1007/s11164-014-1919-8
Sulfonated rice husk ash (RHA-SO3H) as an efficient
and recyclable catalyst for the Friedlander synthesis
of quinolines
•
Farhad Shirini Mohadeseh Seddighi
Manouchehr Mamaghani
•
Received: 8 November 2014 / Accepted: 30 December 2014
Ó Springer Science+Business Media Dordrecht 2015
Abstract Sulfonated rice husk ash (RHA-SO3H), as a newly reported powerful
solid acid catalyst, can be efficiently used for the promotion of the preparation of
substituted quinoline derivatives via the condensation reaction between 2-aminoa-
rylketones and a-methylene ketones. All reactions are performed under solvent-free
conditions at 80 °C in high yields during short reaction times. Simple methodolo-
gies, easy work-up procedure, and easy preparation of the catalyst are other
advantages of this work.
Keywords Rice husk ash Á Sulfunated rice husk ash Á Solvent-free conditions Á
Friedlander synthesis Á Quinolines
Introduction
Quinolines and their derivatives are one of the most important classes of
heterocyclic compounds that occur widely in natural products. They have a wide
range of biological activities such as antimalarial [1], antibacterial [2], anti-
inflammatory [3], antihypertensive [4], antimicrobial and antioxidant [5], anti-
asthmatic [6, 7], and antiplatelet [8]. These compounds can also be used as tyrosine
kinase PDGF-RTK inhibiting agents [9]. Poly-substituted quinolines have also been
used for photonic and electronic applications in a variety of nano- and meso-
structures due to their electroluminescence and photophysical properties [10–13].
Therefore, quinoline nucleus is frequently found in several drugs (Fig. 1).
Among various procedures that have been developed and documented for the
¨
synthesis of quinoline derivatives such as Friedlander, Meth-Cohn, Pfitzinger,
F. Shirini (&) Á M. Seddighi Á M. Mamaghani
Department of Chemistry, College of Science, University of Guilan,
Post Box 1914, 41335 Rasht, I.R. Iran
e-mail: shirini@guilan.ac.ir
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F. Shirini et al.
Fig. 1 Pharmaceutically active compounds containing quinoline framework
Skraup, Doebner–Von Miller and Combes reactions [14–17], Friedlander annulation
is one of the most simple and important approaches. This reaction involves a
condensation reaction between 2-aminoarylketones and a ketone containing an
active a-methylene group. For this purpose, many homogeneous and heterogeneous
catalysts such as FeCl3Á6H2O/[bmim][BF4] [18], sulfamic acid [19], CeCl3Á7H2O
[20], HCl [21], NaHSO4ÁSiO2 [22], amberlyst-15 [23], HClO4–SiO2 [24], SiO2/I2
[25], oxalic acid [26], silica sulfuric acid under microwave irradiation [27],
dodecylphosphonic acid (DPA) [28], nano-Al2O3 [29], H3PW12O40 [30], FeCl2-
2H2O-RiHA [31], nano-flake ZnO [32], Yb(OTf)3 [33], and (BSPY)HSO4/MCM-41
[34] have been reported.
Although these procedures provide an improvement, many of these catalysts or
activators suffer from disadvantages such as long reaction times, harsh reaction
conditions, use of organic solvents and non-recoverability of the catalyst.
Furthermore, the use of homogeneous catalysts has several serious problems, such
as difficulty in the separation and recovery of the catalyst, and corrosion problems.
Therefore, introducing simple, efficient, and mild procedures using easily separable
and reusable solid catalysts to overcome these problems is still in demand.
¨
Replacement of conventional, toxic and polluting Bronsted and Lewis acid
catalysts with eco-friendly reusable heterogeneous catalysts is an area of current
interest. In this context, there has been renewed interest in the use of solid acid
catalysts for organic reactions [35]. Solid acid catalysts have many advantages
compared to traditional liquid acids, such as their efficiency, operational simplicity,
easy recyclability and recoverability, non-corrosive nature and environmental
friendliness. Therefore, solid acid catalysts can play a significant role in the
development of clean technologies.
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Sulfonated rice husk ash (RHA-SO3H) as an efficient
Recently, utilization of waste materials has been found to be of increasing
interest. Rice husk and rice husk ash could be a problem for farmers and societies,
while they can be successfully used as natural sources of amorphous silica. Several
papers have been published on the application of the modified amorphous silica
obtained from rice husk ash as the catalyst [36–38]. Although useful, the reported
method for the preparation of pure silica from rice husk ash needs various stages and
a long time [39]. On the basis of these points and our investigations, we concluded
that, under the same conditions, the use of RHA as a support for the preparation of
the catalysts is better than the use of silica, which is prepared via the precipitation
method during various stages and over a long time.
Experimental
Chemicals were purchased from Fluka, Merck, and Aldrich. All yields refer to the
isolated products. Products were characterized by comparison of their physical
constants, IR and NMR spectroscopy with authentic samples and those reported in
the literature. The purity determination of the substrate and reaction monitoring
were accompanied by TLC on silicagel polygram SILG/UV 254 plates.
Catalyst preparation (RHA-SO3H) [36]: a 50-mL suction flask charged with 3.0 g
of RHA and 10 mL CHCl3 was equipped with a constant-pressure dropping funnel
containing chlorosulfonic acid (0.7 mL) and a gas inlet tube for conducting HCl gas
into water as an adsorbing solution. Chlorosulfonic acid was added dropwise over a
period of 20 min while the reaction mixture was stirred in an ice bath (0 °C). After
addition was completed, the mixture was stirred for an additional 2 h at room
temperature. Then, the mixture was filtered and the solid residue washed with
methanol (20 mL) and dried at 70 °C for 1 h to afford RHA-SO3H (3.6 g) as an
earthy powder.
General procedure for the synthesis of quinolines: a mixture of o-aminobenzo-
phenone (1 mmol), ketone (1.2 mmol) and RHA-SO3H (80 mg) was heated at
80 °C under solvent-free conditions for the appropriate time. After completion of
the reaction as monitored by TLC (n-hexane:EtOAc, 4:1), EtOH (10 mL) was added
and the catalyst was separated. After addition of water, the product was precipitated
with high purity.
Table 1 Effect of different
Entry
Catalyst (loading)
Time (min)
Conversion
(%)
catalysts in the reaction of
2-aminobenzophenone and ethyl
acetoacetate at 80 °C under
solvent-free conditions
1
2
3
4
5
6
7
–
120
120
90
N.R.
50
AlCl3 (10 mol %)
CaCl2.2H2O (10 mol %)
FeCl3 (10 mol %)
SiO2 (80 mg)
70
90
80
90
Trace
20
RHA (80 mg)
90
RHA-SO3H (80 mg)
30
92
123

F. Shirini et al.
Selected spectral data
1
(Table 1, entry 5): m.p. 157–159 °C. IR (KBr, cm-1): m 3,045, 2,956, 1,695; H-
NMR (CDCl3, 400 MHz): d 2.22 (m, 2H), 2.71 (t, J = 6.5 Hz, 2H), 3.29 (t,
J = 6.20 Hz, 2H), 7.14 (m, 2H), 7.45 (m, 5H), 7.77 (m, 1H), 8.21 (d, J = 8.6 Hz,
1H); 13C-NMR (CDCl3, 100 MHz): d 22.4, 34.6, 42.7, 123.7, 126.2, 127.4, 127.8,
127.9, 128.0, 128.3, 131.5, 137.5, 148.5, 151.0, 162.0, 197.5.
(Table 1, entry 15): m.p. 161–163 °C. IR (KBr, cm-1): m 3,060, 2,944, 1,604,
1,572, 1,481, 1,215, 703; 1H-NMR(CDCl3, 400 MHz): d 1.71–1.83 (m, 2H),
1.92–1.96 (m, 2H), 2.58 (t, J = 6.2 Hz, 2H), 3.30 (t, J = 6.2 Hz, 2H), 7.21–7.32
(m, 4H), 7.48–7.69 (m, 3H), 7.94 (d, J = 8.6 Hz, 1H); 13C-NMR (CDCl3,
100 MHz): d 22.6, 27.7, 35.6, 124.2, 126.9, 128.1, 128.8, 128.9, 129.0, 129.5,
130.4, 131.6, 136.8, 144.9, 145.9, 129.8.
Results and discussion
In recent years, introduction of new catalysts for the promotion of organic reactions
has become an important part of our ongoing research program [40–42]. In 2013,
and in continuation of these studies, we have reported the preparation and
characterization of sulfonated rice husk ash (RHA-SO3H) in the reaction between
rice husk ash (RHA) and chlorosulfonic acid (ClSO3H), and its applicability in the
promotion of the chemoselective preparation and deprotection of 1,1-diacetates
[40], synthesis of some of bis-heterocyclic compounds [43], synthesis of formami-
dines [44] and benzimidazole derivatives [45].
On the basis of the information obtained from studies on RHA-SO3H, we
anticipated that RHA-SO3H can be used as an efficient catalyst for the acceleration
of the reactions which need the use of an acidic catalyst to speed up. So, we were
interested to investigate the applicability of RHA-SO3H in the Friedlander synthesis
of quinolines. Our investigations clarified that this solid acid catalyst is very
efficient in the requested reactions, and that all the products are obtained in good to
high yields under mild reaction conditions.
For optimization of the reaction conditions, the reaction between 2-aminoben-
zophenone and ethyl acetoacetate to its corresponding quinoline was chosen as a
model reaction and the various conditions including amount of the catalyst and ethyl
acetoacetate, solvent, and temperature were examined. Finally, the best result was
obtained using 80 mg of RHA-SO3H and 1.2 mmol ethyl acetoacetate at 80 °C
under solvent-free condition (Scheme 1). The model reaction was also carried out in
Scheme 1 Friedlander synthesis of quinolines
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Sulfonated rice husk ash (RHA-SO3H) as an efficient
the absence of catalyst and in the presence of rice husk ash as the catalyst, but the
reaction did not proceed. These results indicated that the catalyst is necessary to
produce the products. Any further increase of the catalyst amount or temperature did
not improve the reaction time or yield.
Furthermore, the X-ray fluorescence (XRF) analysis showed that RHA contains a
high value of silica content (up to 80 %) and other compositions such as Al2O3,
Fe2O3, K2O, Na2O and CaO [39]. For this purpose, and to prove the role of the
covalently bounded –SO3H groups, we used various catalysts in the reaction of
2-aminobenzophenone and ethyl acetoacetate under optimal conditions. As can be
seen in Table 1, CaCl2Á2H2O, AlCl3 and FeCl3 can partly catalyze this type of
reactions. So, the small available amounts of Ca, Fe and P in RHA can promote the
reaction, therefore the reaction proceeding in the presence of RHA is more than
SiO2. However, the completion of the reaction and reducing the reaction time using
RHA-SO3H confirms the important role of the –SO3H group in the catalyst to obtain
the best performance.
After optimization of the reaction conditions and in order to establish the
effectiveness and the acceptability of the method, we explored the protocol with a
variety of simple readily available substrates under the optimal conditions, and the
results are presented in Table 2. Various carbonyl compounds bearing one activated
a-methylene group, including 1,3-dicarbonyl compounds (ethyl acetoacetate,
methyl acetoacetate, acetylacetone and benzoyl acetone), cyclic 1,3-diketones
(5,5-dimethylcyclohexanedione (dimedone) and 1,3-cyclohexadione) and cyclic
ketones (cyclopentanone and cyclohexanone), were used in order to synthesize
quinolines. As can be seen, the reaction of 2-aminobenzophenone with cyclic
diketones took place as good as open chain analogues and afforded the respective
tricyclic quinolines (Table 2, entries 1–6). Furthermore, inactivated ketones,
cyclohexanone and cyclopenthanone, afforded the desired products in good yields
(Table 2, entries 7 and 8).
Under the optimized conditions, the above-mentioned carbonyl compounds also
reacted satisfactorily with 5-chloro-2-aminobenzophenone to produce the desired
quinolines in moderate to high yields (Table 2, entries 9–15).
To check the reusability of the catalyst, the reaction of 2-aminobenzophenone
and ethyl acetoacetate under the optimized reaction conditions was studied again.
When the reaction was completed, ethanol was added and the catalyst was separated
by filtration. The recovered catalyst was washed with dichloromethane, dried and
reused for the same reaction. This process was carried out over three runs and all
reactions ed to the desired products with high efficiency, which clearly demonstrates
practical recyclability of RHA-SO3H. Further pH analysis of the recovered catalyst
showed nearly the same loading of H? as the freshly prepared catalyst. This result
suggests that the nature of the catalyst remains intact after each run, and that
leaching of the acid species did not occur during the course of the reaction.
In order to show the efficiency of the present method, we have compared our
results obtained from the condensation of 2-aminobenzophenone with ethyl
acetoacetate catalyzed by RHA-SO3H with other results reported in the literature.
As can be seen in Table 3, this method avoids the disadvantages of other procedures
123

F. Shirini et al.
Table 2 Synthesis of quinolines catalyzed by RHA-SO3H under solvent-free conditions
Entry 2-aminoarylketone
1
Ketone
Product
Time
(min)
Yield
(%) a
m.p. (°C)
[Lit.]
30
92
100-102
100-101 [34]
2
30
89
104-106
98-100 [30]
3
25
25
25
30
30
30
40
45
45
45
45
84
90
91
90
89
90
90
89
87
86
87
110-112
110-112 [30]
4
138-140
139-140 [34]
5
157-159
158 [29]
6 b
7 b
8
191-193
192-194 [30]
133-135
133-135 [34]
142-144
142-144 [34]
9
99-101
98-99 [34]
10
11
12
13
133-135
132-134 [30]
152-154
154 [28]
185-187
186-187 [30]
208-210
207-209 [30]
14 b
45
45
84
88
96-98
97–98 [34]
15 b
161-163
162–163 [34]
a
Isolated yields
b
1.5 mmol of ketone was used
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Sulfonated rice husk ash (RHA-SO3H) as an efficient
Table 3 Comparison of the results of the reaction between o-aminobenzophenone and ethyl acetoacetate
catalyzed by RHA-SO3H with those obtained by some of the reported catalysts
Entry Catalyst
Catalyst
(loading)
Reaction
conditions
Time
(min)
Yield
(%)
Ref.
1
2
3
4
5
6
7
8
NaHSO4ÁSiO2
HClO4–SiO2
Oxalic acid
DPA
200 mg
200 mg
10 mol%
10 mol%
3 mol%
40 mg
Neat/70 °C
CH3CN/reflux
Neat/80 °C
H2O/90 °C
CHCl3/reflux
Neat/80 °C
Neat/90 °C
Neat/100 °C
3 h
2 h
2 h
140
3 h
2 h
30
95
94
91
85
98
90
88
93
[22]a,b
[24]a,b,c,d
[26]b
[28]b,d,e
[29]b,c,d
[30]b
Nano Al2O3
H3PW12O40
FeCl2Á2H2O-RiHA
(BSPY)HSO4/MCM- 70 mg
41
300 mg
[31]a
[34]b
70
9
RHA-SO3H
80 mg
Neat/80 °C
30
92
This
work
a
b
c
d
e
High catalyst loading
Long reaction time
Reflux conditions
Need to solvent
Low yield of product
such as long reaction times, excess reagents, organic solvents, reflux conditions and
low yields of the products.
Conclusion
¨
In conclusion, we have introduced a powerful Bronsted solid acid catalyst that
shows remarkable catalytic activity in Friedlander synthesis of quinolines. The
procedure has several advantages such as high reaction rates, no side reactions, ease
of preparation and handling of the catalyst, simple experimental procedure, and the
use of inexpensive and reusable catalyst. Furthermore, this process avoids problems
associated with the use of organic solvents and liquid acids, which makes it a useful
and attractive strategy in view of its economic and environmental advantages. It is
also important to note that studies on some more practical applications of the RHA-
SO3H catalyst in other organic reactions are currently underway in our laboratories.
Acknowledgment We are grateful to the University of Guilan Research Council for the partial support
of this work.
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