Fe3O4@SiO2-imid-PMAn magnetic porous nanosphere as reusable catalyst for synthesis of polysubstituted quinolines under solvent-free conditions

Article abstract of DOI:10.1002/jccs.201400380

In this research, a facile one-pot synthesis of poly-substituted quinoline derivatives has been demonstrated by using 2-aminobenzophenones and ethylacetoacetate or ketones in the presence of Fe₃O₄@SiO₂-imid-PMAⁿ

Full text of DOI:10.1002/jccs.201400380

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Fe3O4@SiO2-imid-PMAn Magnetic Porous Nanosphere as Reusable Catalyst for
Synthesis of Polysubstituted Quinolines under Solvent-free Conditions
Mohsen Esmaeilpoura* and Jaber Javidib,c*
aChemistry Department, College of Science, Shiraz University, Shiraz, Iran
bDepartment of Pharmaceutics, School of Pharmacy, Shahid Beheshti University of Medical Sciences, Tehran, Iran
cStudents Research Committee, School of Pharmacy, Shahid Beheshti University of Medical Sciences, Tehran, Iran
(Received: Sept. 9, 2014; Accepted: Dec. 26, 2014; Published Online: Apr. 16, 2015; DOI: 10.1002/jccs.201400380)
In this research, a facile one-pot synthesis of poly-substituted quinoline derivatives has been demon-
strated by using 2-aminobenzophenones and ethylacetoacetate or ketones in the presence of Fe3O4@SiO2-
imid-PMAn and Fe3O4@SiO2-imid-PMAb nanoparticles as green and reusable catalysts under sol-
vent-free conditions. The reaction proceeds efficiently in excellent yields and in a state of excellent purity.
The nanocatalysts can be recycled and reused for at least four times without noticeably decreasing in cata-
lytic activity.
Keywords: Polysubstituted quinolines; Heteropolyacides; Solvent-free; Magnetic nanocatalyst.
INTRODUCTION
Quinolines and their derivatives are very important
have significant drawbacks such as long reactions times,
harsh reaction conditions, use of toxic and corrosive re-
agents, low yields and tedious work-up. In addition, the
main disadvantage of almost all existing methods is that the
catalysts cannot be recovered during the work-up proce-
dure. Thus, the development of simple, convenient, and en-
vironmentally benign methods for the synthesis of quino-
lines is still required.
compounds because wide applications in medicinal chem-
istry, includes antibacterial, antimalarial, anti-inflamma-
tory, antiasthmatic, antihypertensive and tyrosine kinase
inhibiting agents.1-3 Also, quinoline derivatives have been
employed in the study of bioorgano-metallic and bio-
organic processes.4,5 In addition, quinolines have been
used for the preparation of nanostructures and polymers
with enhanced electronic and photonic properties.6,7
In the past decades, magnetic nanoparticles are used
extensively in a broad range of applications, such as cell la-
beling and sorting,30 drug delivery,31 magnetic resonance
imaging,32-34 sensing as well as therapeutic applications35
such as AC magnetic field-assisted cancer therapy, i.e.
hyperthermia, and PDT,36 wastewater treatment37,38 and
catalyst.39 All these technological and medical applications
require that the nanoparticles are superparamagnetic with
sizes smaller than 20 nm, with a narrow size distribution to
have uniform physical and chemical properties.40
For the synthesis of these various procedures such as
Doebner-Von Miller, Skraup, Combes, Knorr methods and
Friedlander have been developed.8-11 Among various meth-
odologies reported for the preparation of quinolines,
Friedlander annulation is one of the simplest and straight-
forward methods for the synthesis of polysubstituted quin-
olines. The Friedlander quinoline synthesis consists of a
condensation and cyclization between an aromatic 2-ami-
noaldehyde or ketone and a second carbonyl compound
containing a reactive a-methylene group in the presence of
base or acid catalysts. The Friedlander reaction can occur
in the presence of Brønsted acid catalysts such as hydro-
chloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic
acid, sulfamic acid and polyphosphoric acids,12-17 bases,18,19
lewis acids such as Y(OTf)3,20 Zr(DS)4,21 Bi(OTf)3,22 silver
phosphotungstate,23 sodium fluoride,24 ionic liquids,25 ul-
trasound irradiation,26 inorganic salt catalysts27 and micro-
wave conditions.28,29 However, many of these procedures
Recently, more attention has been paid to the mag-
netic core–shell structure due to their unique magnetic
properties. If core–shell structure composites use magnetic
catalysts with the Fe3O4 core and the SiO2 shell, the recycle
use of the catalysts can be carried out under the magnetic
field. Hence, the magnetic core–shell structure was a good
support for the catalysts.41,42
In recent years, brønsted acids such as Keggin-type
heteropolyacids (HPAs) have been used as efficient cata-
lysts for a variety of organic reactions because of their
* Corresponding author. Tel.: +98 7116137738; Fax: +98 7112286008; E-mail: m1250m551085@yahoo.com (M. Esmaeilpour),
Jaber Javidi @ gmail.com (J. Javidi)
328
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Fe3O4@SiO2-imid-PMAn Magnetic Porous Nanosphere
superacidic and redox properties, low in toxicity, highly
stable towards humidity, air stable, high proton mobility,
stronger acids than homogeneous acid catalysts and devel-
opment of clean technologies.43 Although HPAs in their
acidic form are versatile compounds, their main disadvan-
tages are high solubility in polar solvents and low surface
area (<10 m2/g). Therefore, in a homogeneous reaction the
isolation of the products and the reuse of the catalyst after
reaction become difficult.43 Therefore, in order to over-
come this problem, these materials disperse on supports
(such as silica, acidic ion-exchange resins, active carbon
and etc.) which possess large surface area. The use of sup-
port allows the heteropolyacids to be dispersed over a large
surface area and increases theirs catalytic activity.44
Therefore in this work, we wish to report a simple and
milder protocol for the synthesis of quinoline derivatives in
the presence of Fe3O4@SiO2-imid-PMAn and Fe3O4@SiO2-
imid-PMAb nanoparticles as effective catalysts via the
Friedlander method (Scheme 1).
method in our previous work.45 In a typical procedure, the mix-
ture of FeCl3.6H2O (1.3 g, 4.8 mmol) in water (15 mL) was added
to the solution of polyvinyl alcohol (PVA 15000), as a surfactant,
and FeCl2.4H2O (0.9 g, 4.5 mmol) in water (15 mL), which was
prepared by completely dissolving PVA in water followed by ad-
dition of FeCl2.4H2O. The resultant solution was left to be stirred
for 30 min in 80 oC. Then, hexamethylentetraamine (HMTA) (1.0
mol/l) was added drop by drop with vigorous stirring to produce a
black solid product when the reaction media reaches pH 10. The
resultant mixture was heated on water bath for 2 h at 60 oC and the
black magnetite solid product was filtered and washed with etha-
nol three times and was then dried at 80 oC for 10 h.Then Fe3O4
nanoparticle (0.50 g, 2.1 mmol) was dispersed in the mixture of
ethanol (50 mL), deionized water (5 mL) and tetraethoxysilane
(TEOS) (0.20 mL), followed by the addition of 5.0 mL of NaOH
(10 wt%). This solution was stirred mechanically for 30 min at
room temperature. Then the product, Fe3O4@SiO2, was separated
by an external magnet, and was washed with deionized water and
ethanol three times and dried at 80 oC for 10 h.
Preparation of H3PW12O40 nanoparticles (PMAn): PMAn
nanoparticles were prepared in our previous work.46 In a typical
procedure, 5 mmol of bulk H3PMo12O40 (PMAb) was dispersed in
50 mL n-Octane and the resulting dispersion was stirred vigor-
ously for 30 min at room temperature to form a homogeneous dis-
persion. This dispersion was transferred into a Teflon-lined stain-
less autoclave filling 80% of the total volume. The autoclave was
sealed and maintained at 150 oC for 12 h. The autoclave was then
cooled to room temperature. Finally, the resulted powder was fil-
tered and washed for several times by Octane, and dried in a vac-
uum at 80 oC for 12 h.
Synthesize poly-substituted quinoline deriv-
atives with using Fe3O4@SiO2-imid-PMAn
nanocatalyst
Scheme 1
Preparation of Fe3O4@SiO2-imid-PMAn: Fe3O4@SiO2
(1 g) was added to the solution of 3-chlorotriethoxypropylsilane
(1 mmol, 0.241 g) and imidazole (1 mmol, 0.0680 g) in p-xylene
(20 mL) and the resultant mixture was under reflux for 24 h under
nitrogen atmosphere. After refluxing for about 24 h, the mixture
was cooled to room temperature, filtered by an external magnet
and the product was washed with xylene to remove no reacted
species and dried at 70 oC for 6 h. Fe3O4@SiO2-imid (1.0 g) was
added to an acetonitrile solution of PMAn (1.0 mmol) in 20 mL
was taken in a round-bottom flask. The mixture was refluxed for
24 h under nitrogen atmosphere. After 24 h, the mixture was fil-
tered by an external magnet, washed with acetonitrile and di-
chloromethane, and dried at 70 oC for 6 h. Also, the same method
was used for the synthesis of Fe3O4@SiO2-imid-PMAb (PMAn =
nano H3PMo12O40, PMAb = H3PMo12O40).47
EXPERIMENTAL
General methods: Chemicals were purchased from the
Fluka and Merck chemical companies. The NMR spectra were re-
corded on a Bruker avance DPX 250 MHz spectrometer in chloro-
form (CDCl3) using tetramethylsilane (TMS) as an internal refer-
ence. Fourier transform infrared (FT-IR) spectra were recorded on
a Shimadzu FT-IR 8300 spectrophotometer. Elemental analysis
was done on a 2400 series Perkin-Elmer analyzer. Melting points
were determined on a Mel-Temp apparatus and are Uncorrected.
1
Therefore, all of the products were characterized by FT-IR, H
NMR and 13C NMR, and also by comparison with authentic sam-
ples.
General procedure
General Procedure for the Synthesis of quinoline deriv-
atives in the presence of magnetic nanocatalysts: A mixture of
Preparation of Fe3O4@SiO2 Core-Shell: The core–shell
Fe3O4@SiO2 nanospheres were prepared by a modified Stober
J. Chin. Chem. Soc. 2015, 62, 328-334
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Article
Esmaeilpour and Javidi
o
2-aminobenzophenone (1 mmol), ethyl acetoacetate (1.2 mmol)
and Fe3O4@SiO2-imid-PMAn (0.02 g) or Fe3O4@SiO2-imid-
PMAb (0.03 g) in solvent-free conditions was stirred at 70 ºC. The
progress of the reaction was monitored by TLC. The reaction was
followed by TLC. After completion of the reaction, ethyl acetate
was added to the solidified mixture and the insoluble catalyst was
separated by magnetic field. The filtrate was dried and organic
medium was removed with a rotary evaporator under reduced
pressure. Then, the resulting solid product was recrystallized
from ethanol to give pure product.
none and ethyl acetoacetate at 70 C (Table 1, entry 12c,
13d). Use of a higher amount of catalysts did not improve
the yield while a decrease in the amount of catalysts de-
creases the yield (Table 1). In the absence of Fe3O4@SiO2-
imid-PMAn or Fe3O4@SiO2-imid-PMAb the reaction did
not proceed even after a long reaction time (12 h) (Table 1,
entry 15).
The effect of solvent was studied by carrying out the
model reaction at different solvents under reflux condition
(Table 1, entry 1-7). The reactions were conducted in re-
fluxing toluene, CHCl3, CH2Cl2, n-Hexane, H2O, EtOH
and CH3CN as solvents and under solvent-less condition at
70 oC. As shown in Table 1, with no solvent, gave the best
results in reaction time and conversion. This observation
confirms that the solvent-free condition plays an important
role in the synthesis of quinoline derivatives and the best
rate was observed when the reaction was carried out with-
out solvent (Table 1, entry 12c, 13d). Also, the effect of tem-
perature was studied by carrying out the model reaction at
different temperatures under solvent-free condition (room
temperature, 50 oC and 70 oC) and the best results were ob-
tained at 70 oC (Table 1, entries 10c-12c, 11d-13d).
RESULTS AND DISCUSSION
In pursuit of our continued interest in the develop-
ment of solvent-free and environmentally friendly syn-
thetic protocols, we decided to explore the use of
Fe3O4@SiO2-imid-PMAn and Fe3O4@SiO2-imid-PMAb
catalysts for the synthesis of quinoline derivatives via
Friedlander condensation in good to excellent yields under
solvent-free conditions at 70 ºC.
Initially the reaction between 2-aminobenzophenone
(1 mmol) and ethyl acetoacetate (1.2 mmol), as the model
reaction was examined in the presence varying amount of
the catalysts and the results are presented in Table 1. The
best result was achieved by carrying out the reaction with
(0.02 or 0.03:1:1.2) ratio of Fe3O4@SiO2-imid-PMAn or
Fe3O4@SiO2-imid-PMAb catalysts, 2-aminobenzo-phe-
To study the generality of this process, a good range
of o-aminoaryl ketones and 1,3-diketones were condensed
to the corresponding quinoline derivatives in the presence
of catalytic amounts of Fe3O4@SiO2-imid-PMAn or
Table 1. Optimization of different proportions of Fe3O4@SiO2-imid-PMAn and Fe3O4@SiO2-imid PMAb catalysts and
also effect of solvents in the synthesis of ethyl 2-methyl-4-phenyl quinoline-3-carboxylatea
Catalystc
(gr)
Catalystd
(gr)
Entry
Solvent
Condition
Timec
Yield (%)b,c
Condition Timed
Yield (%)b,d
1
CH3CN
Ethanol
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.005
0.01
0.02
0.02
0.02
0.03
0.04
None
reflux
reflux
reflux
reflux
reflux
reflux
reflux
70 oC
70 oC
r.t
50 oC
70 oC
70 oC
70 oC
70 oC
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1 h
58
64
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.005
0.01
0.02
0.03
0.03
0.03
0.04
None
reflux
reflux
reflux
reflux
reflux
reflux
reflux
70 oC
70 oC
70 oC
r.t
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1.5 h
1 h
42
43
2
3
H2O
24
17
4
n-Hexane
CH2Cl2
78
64
5
54
49
6
CHCl3
56
46
7
Toluene
73
76
8
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
45
51
9
59
67
10
11
12
13
14
15
Trace
67
85
1.5 h
1 h
Trace
69
50 min
50 min
50 min
12 h
95
50 oC
70 oC
70 oC
70 oC
94
55 min
55 min
12 h
91
91
91
Trace
Trace
a Reaction condition: 2-aminobenzophenone (1 mmol), ethylacetoacetate (1.2 mmol).
b Isolated yield.
c Fe3O4@SiO2-imid-PMAn.
d Fe3O4@SiO2-imid-PMAb.
330
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Fe3O4@SiO2-imid-PMAn Magnetic Porous Nanosphere
Table 2. Fe3O4@SiO2-imid-PMAn and Fe3O4@SiO2-imid-PMAb catalyzed synthesis of quinolines under solvent-free conditions at 70
oCa
Time
(min)
Yield
(%)b,c
Time
(min)
Yield
(%)b,d
Entry 2-Amino ketone
Ketone
Product
m.p. (oC)
Ph
O
O
O
O
98-99
(99oC)[21]
1
2
3
Ph
NH2
OEt
CH3
50
55
45
95
96
95
55
60
55
91
91
88
OEt
N
Ph
O
O
O
O
113-114
(114-115)[48]
Ph
CH3
NH2
O
N
CH3
O
Ph
O
O
Ph
Ph
CH3
133-135
Ph
NH2
O
N
Ph
O
O
O
107-108
(107)[21]
Ph
4
OMe
CH3
60
94
60
88
OMe
NH2
O
N
Ph
O
O
O
OCH2Ph
Ph
5
6
7
8
9
50
40
45
35
35
35
90
94
92
95
91
94
60
50
60
45
40
45
86
90
89
91
90
92
90-92
OCH2Ph
N
CH3
Ph
NH2
O
O
141-143
(139-141)[48]
Ph
NH2
O
N
Ph
O
131-133
(130-132)[23]
Ph
NH2
O
N
Ph
O
O
O
157-159
(159)[21]
Ph
NH2
O
N
Ph
O
O
Ph
172-174
O
NH2
O
N
Ph
O
O
O
Cl
Cl
Cl
101-103
(101)[22]
Ph
Ph
OEt
10
OEt
NH2
N
CH3
Ph
O
O
O
O
Cl
Cl
155-157
(157)[21)]
CH3
11
12
30
45
96
96
50
55
89
90
NH2
O
N
CH3
O
Ph
O
O
Cl
216-218
(217)[21]
Ph
NH2
Ph
CH3
Ph
N
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Esmaeilpour and Javidi
O
Ph
N
O
O
O
Cl
Cl
134-136
(135)[21]
Ph
OMe
13
50
40
60
70
95
92
96
93
55
50
88
OMe
NH2
O
CH3
Ph
O
O
O
Cl
Cl
Ph
OCH2Ph
14
86
91
87
121-123
OCH2Ph
N
CH3
Ph
NH2
O
O
Cl
Cl
163-165
(165)[21]
Ph
15
80
NH2
O
N
Ph
O
Cl
Cl
Cl
106-108
(106-107)[15]
Ph
16
100
NH2
O
N
Ph
O
O
O
Cl
184-185
(185)[21]
Ph
17
50
95
100
89
NH2
N
a Reaction condition 2-aminoarylketones (1 mmol), 1,3-diketones or ketones (1.2 mmol), Fe3O4@SiO2-imid-PMAn (0.02 g) or
Fe3O4@SiO2-imid-PMAb (0.03 g), solvent-free, 70 oC.
b Isolated yield.
c Fe3O4@SiO2-imid-PMAn.
d Fe3O4@SiO2-imid-PMAb.
Fe3O4@SiO2-imid-PMAb and the related quinoline deriva-
Table 3. Comparison results of different catalysts to the
Fe3O4@SiO2-imid-PMAn and Fe3O4@SiO2-imid-PMAb
tives were obtained without observation of any by-product
in the synthesis of ethyl 2-methyl-4-phenylquinoline-3-
in good to excellent yields (Table 2). Also, cyclic ketones
carboxylatea
such as cyclopentanone and cyclohexanone underwent
Yield Literature
smooth condensation with 2-aminoarylketones to afford
the respective tricyclicquinolines (Table 2, entry 6, 7, 15,
16). In addition, this method is approximately equal effec-
tive for both cyclic and acyclic ketones. Further, it is to be
noted that highly pure products were obtained using this
simple procedure and in most cases no further purification
was needed.
A comparison among Fe3O4@SiO2-imid-PMAn and
Fe3O4@SiO2-imid-PMAb and the other catalysts, which
were reported in the literature, in the synthesis of ethyl
2-methyl-4-phenylquinoline-3-carboxylate revealed ad-
vantages of Fe3O4@SiO2-imid-PMAn and Fe3O4@SiO2-
imid-PMAb over the most of them in term of higher yield
and shorter reaction time (Table 3, entry 1,2).
Entry
Catalyst
Time
(%)
reference
1
Fe3O4@SiO2-imid-PMAn 50 min
Fe3O4@SiO2-imid-PMAb 55 min
95
91
91
90
50
60
40
80
This work
This work
This work
[49]
2
3
H3PMo12O40
H3PW12O40
P-TSOH
2 h
2 h
4
5
12 h
5 h
[49]
6
SSA
[49]
7
HClO4
12 h
240
[49]
8
NaHSO4-SiO2
[51]
9
Dodecylphosphonic acid 140 min 85
[52]
10
11
12
Zr(DS)4
3 h
90
72
95
94
[21]
CeCl3 -7H2O
[bmim][HSO4]
[53]
60 min
[50]
a Based on 2-aminobenzophenone and ethyl acetoacetate.
netic field within several minutes without the need for a fil-
tration step, and then can be readily redispersed with
slightly shake, indicating directly that the nanoparticles
possess magnetic properties (Fig. 1). Such magnetic sepa-
ration performance makes the nanoparticles more effective
and convenient in application.
According to these findings, it can be seen that
Fe3O4@SiO2-imid-PMAn and Fe3O4@SiO2-imid-PMAb
are a very efficient catalysts useful in the synthesis of quin-
oline derivatives (Table 3).
Fe3O4@SiO2-imid-PMAn magnetic catalyst dispersed
in ethyl acetate can be easily separated by external mag-
332
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Fe3O4@SiO2-imid-PMAn Magnetic Porous Nanosphere
129.0, 129.8, 129.9, 132.2, 133.3, 134.6, 136.9, 145.3,
147.6, 154.4, 197.5. FT-IR (KBr pellets, cm-1): 704, 769,
1575, 1675, 2911, 3060. C23H17NO: C, 85.4; H, 5.26; N,
4.33%, found: C, 85.12; H, 5.23; N, 4.21%. Table 2. Entry
5. White solid, m.p. 90-92 oC. 1H-NMR (250 MHZ, CDCl3):
d = 2.76 (s, 3 H, CH3), 5.03 (s, 2H, CH2), 7.08 (m, 2H, CH),
7.36 (m, 3H, CH), 7.41 (m, 2H, CH), 7.42 (m, 4H, CH),
7.44 (d, 1H), 7.71 (m, 1H, CH), 8.09 (d, 1H). 13C-NMR (63
MHz, CDCl3): d = 23.8, 67.3, 124.8, 126.2, 126.2, 126.8,
128.1, 128.1, 128.2, 128.3, 128.39, 128.67, 129.1, 130.07,
134.6, 135.3, 146.0, 147.5, 154.3, 168.1. FT-IR (KBr pel-
lets, cm-1): 762, 889, 1490, 1565, 1720, 2915, 3070. Anal.
calcd. for C24H19NO2: C, 81.58; H, 5.38; N, 3.96%, found,
C, 81.44; H, 5.28; N, 3.81%. Table 2. Entry 9. Yellow
solid, m.p. 172-174 oC. 1H-NMR (250 MHZ, CDCl3): d =
2.74 (m, 2H, CH2), 3.36 (m, 2H, CH2), 7.27 (m, 2H, CH),
7.44 (m, 4H, CH, CH), 7.73 (m, 2H, CH), 8.04 (d, 1H, CH).
13C-NMR (63 MHz, CDCl3): d = 28.4, 36.5, 123.6, 126.3,
126.4, 127.8, 128.2, 128.6, 128.8, 129.1, 130.6, 131.9,
132.9, 148.7, 151.0, 170.7, 203.3. FT-IR (KBr pellets,
cm-1): 772, 835, 1565, 1710, 2931. Anal. calcd. for
C18H13NO: C, 83.39; H, 5.02; N, 5.40%, found: C, 83.23;
H, 5.12; N, 5.21%. Table 2. Entry 14. White solid, m.p.
121-123 oC. 1H-NMR (250 MHZ, CDCl3): d = 2.66 (s, 3H,
CH3), 4.95 (s, 2H, CH2), 7.00 (m, 2H), 7.20-7.26 (m, 5H,
CH), 7.37 (m, 3H, CH), 7.46 (m, 1H, CH), 7.58 (m, 1H,
CH), 7.94 (d, 1H, CH). 13C-NMR (63 MHz, CDCl3): d =
23.7, 67.4, 125.0, 125.7, 126.9, 127.0, 127.6, 128.2, 128.3,
128.3, 128.4, 128.6, 129.0, 130.3, 130.9, 132.1, 134.4,
134.5, 145.9, 154.7, 167.7. FT-IR (KBr pellets, cm-1): 710,
740, 834, 1225, 1481, 1580, 1720, 3042, 3080. Anal. calcd.
for C24H18ClNO2: C, 74.32; H, 4.64; N, 3.61. found, C,
74.67; H, 4.85; N, 3.53.
Fig. 1. Catalyst ability to effective recovery at the end
of reactions by external magnetic field.
Fig. 2. Recyclability of Fe3O4@SiO2-imid-PMAn (A)
and Fe3O4@SiO2-imid-PMAb (B) in the synthe-
sis of ethyl 2-methyl-4-phenyl quinoline-3-car-
boxylate under solvent-free condition.
The activity of the recycle catalysts were also exam-
ined under the optimized conditions and the desired prod-
ucts were obtained in high yields after 4 runs without dis-
tinct deterioration in catalytic activity (Fig. 2).
CONCLUSIONS
In conclusion, we have demonstrated a simple, effi-
cient and straightforward synthesis of quinolines deriva-
tives by Friedlander protocol using immobilization of
phosphomolybdic acid nanoparticles on imidazole func-
tionalized Fe3O4@SiO2 as recyclable heterogeneous nano-
catalyst. The protocol offers several advantages including
easy preparation, heterogeneous nature and easy separation
of the catalyst by external magnetic field, high yields of the
products, short reaction times and operational simplicity.
Also the nanocatalyst could be successfully recovered and
recycled at least for four runs without significant loss in ac-
tivity.
ACKNOWLEDGEMENTS
Authors are grateful to the council of Iran National
Science Foundation and University of Shiraz for their un-
ending effort to provide financial support to undertake this
work.
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