Application of [Fe3O4@SiO2@(CH2)3Py]HSO4 ? as heterogeneous and recyclable nanocatalyst for synthesis of polyhydroquinoline derivatives

Article abstract of DOI:10.1002/aoc.5101

Four-component condensation reaction of aromatic aldehydes, dimedone, ethyl acetoacetate and ammonium acetate in the presence of a catalytic amount of ionic liquid on silica-coated Fe₃O₄ nanoparticles as a heterogeneous, recyclable a

Full text of DOI:10.1002/aoc.5101

Received: 18 April 2019
DOI: 10.1002/aoc.5101
Revised: 12 June 2019
Accepted: 15 June 2019
F U L L P A P E R
−
Application of [Fe3O4@SiO2@(CH2)3Py]HSO4 as
heterogeneous and recyclable nanocatalyst for synthesis of
polyhydroquinoline derivatives
Sami Sajjadifar
| Zahra Azmoudehfard
Department of Chemistry, Payame Noor
University, PO Box 19395‐4697, Tehran,
Iran
Four‐component condensation reaction of aromatic aldehydes, dimedone,
ethyl acetoacetate and ammonium acetate in the presence of a catalytic
amount of ionic liquid on silica‐coated Fe3O4 nanoparticles as a heterogeneous,
recyclable and very efficient catalyst provided the corresponding
polyhydroquinoline derivatives in good to excellent yields in ethanol under
Correspondence
Sami Sajjadifar, Department of Chemistry,
Payame Noor University, PO Box 19395‐
4697, Tehran, Iran.
−
reflux condition. The [Fe3O4@SiO2@(CH2)3Py]HSO4 catalyst was character-
Email: sami.sajjadifar@gmail.com
ized using various techniques such as scanning electron microscopy, powder
X‐ray diffraction, thermogravimetric analysis, vibrating sample magnetometry
and Fourier transform infrared spectroscopy. Furthermore, the recovery and
reuse of the catalyst were demonstrated seven times without detectable loss
in activity.
Funding information
Payame Noor University Research
Council
KEYWORDS
[Fe3O4@SiO2@(CH2)3Py]HSO4−, aldehydes, dimedone, ethyl acetoacetate, polyhydroquinoline
1 | INTRODUCTION
β‐ketoester and ammonia).[9] However, this method
has some disadvantages like the harsh conditions of
Multicomponent reactions play an important role in mod-
ern synthetic organic chemistry because of the discovery of
compounds in medicinal chemistry or combinatorial
chemistry.[1] The advantages of these multicomponent
reactions include allowing compounds to be synthesized
in a few steps, formation of new bonds in one pot with high
atom economy, simplified purification, reduction of by‐
products formed and ease of workup.[2]
Polyhydroquinoline derivatives are important com-
pounds in organic chemistry due to their various pharma-
ceutical properties and biological activities such as
cardiovascular, hepatoprotective, bronchodilator, vasodi-
lator, geroprotective, antitumour and antiartherosclerotic
activities.[3–8] Despite of a variety of applications for
polyhydroquinoline derivatives, very few approaches have
been established for the synthesis of these compounds.
Substituted polyhydroquinolines are usually prepared by
cyclization reactions (Hantzsch ring closure of aldehydes,
the reaction, tedious workup procedure, low yields, use
of large quantities of volatile organic solvent and
long eaction times. In recent years, more efficient
catalysts have been reported for the synthesis of
polyhydroquinolines, such as baker's yeast,[10]
Ce(NH4)2(NO3)6,[11] glycine,[12] grinding,[13] hafnium
(IV) bis(perfluorooctanesulfonyl)imide complex in
fluorous media,[14] Ni0.35Cu0.25Zn0.4Fe2O4 magnetic nano-
particles (MNPs),[15] Hy‐Zeolite,[16] Cu–S‐(propyl)‐2‐
aminobenzothioate,[17] L‐proline and derivatives,[10] metal
triflates,[18] molecular iodine,[19] Fe3O4–adenine–Ni,[20]
4,4′‐(butane‐1,4‐diyl)bis(1‐sulfo‐1,4‐diazabicyclo[2.2.2]
octane‐1,4‐diium)tetrachloride,[21] PTSA,[22] solar thermal
energy,[23] MCM‐41@Serine@Cu(II),[24] MNPs/DETA‐
SA,[25] Ni‐Cu‐Mg Fe3O4 MNPs,[26] ILOS@Fe/TSPP,[27]
alginic acid,[28] Ni@IL‐OMO,[29] V‐TiO3[30] and melamine
trisulfonic acid.[31] Furthermore, soluble metal catalysts
often require a tedious catalyst separation step. The search
Appl Organometal Chem. 2019;e5101.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5101

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SAJJADIFAR AND AZMOUDEHFARD
for alternative catalysts based on heterogeneous, cheap
and environmentally benign metals is thus an increasingly
important task.
products were dried at 40 °C to afford Fe3O4
nanoparticles.
In a 250 ml flask, Fe3O4 nanoparticles (2 g) were
dispersed in 50 ml of distilled water and 20 ml of ethanol
for 20 min. Then, poly(ethylene glycol) 400 (PEG)
(3.36 g), 10 ml of aqueous NH3 (25%) and tetraethyl
orthosilicate (TEOS; 2 ml) were added to the mixture
for 38 h. The obtained brown MNPs were separated from
solution using a powerful magnet and rinsed with etha-
nol. Finally, the products were dried at room temperature
for 48 h to afford Fe3O4@SiO2.
In a 250 ml flask, Fe3O4@SiO2 (1.5 g) was dispersed in
50 ml of toluene for 30 min. (3‐Chloropropyl)
trimethoxysilane (2.5 ml) was added to Fe3O4@SiO2
under vigorous stirring and nitrogen protection at 40 °C
for 8 h. The obtained MNPs were separated from solution
using a powerful magnet and rinsed with ethanol.
Finally, the products were dried at 50 °C for 48 h to afford
Fe3O4@SiO2@(CH2)3‐Cl.
These heterogeneous catalysts are recyclable, non‐
toxic, cleaner and involve easier workup methods.
Recently, MNPs have shown great potential via recycling
and recovery of the catalysts using an external magnetic
field.[32] Coating of MNPs prevents their aggregation in
solution and enhances chemical stability.[33] Also, the
design of ionic liquid allows for the creation of additional
functionalities into the ionic liquid structure with
physical or chemical properties. The combination of func-
tionalized ionic liquid and MNPs provides suitable
heterogeneous systems.[34]
In the work reported herein, we tried to synthesize a
novel catalyst by immobilization of an ionic liquid on
silica‐coated MNPs as a support. Thus, we report the syn-
thesis of polyhydroquinolines in the presence of the mag-
netic nanocatalyst.
In a 250 ml flask, Fe3O4@SiO2@(CH2)3‐Cl (5 g)
dispersed in 50 ml of toluene and pyridine (2 ml)
were added under reflux conditions for 12 h. The obtained
MNPs were separated from solution using a powerful
magnet and rinsed with CH2Cl2. Finally the products
were dried to afford [Fe3O4@SiO2@(CH2)3Py]Cl−. Then
[Fe3O4@SiO2@(CH2)3Py]Cl− (5 g) was dispersed in 10 ml
of CH2Cl2, and H2SO4 (1 ml) was added dropwise and
stirred under reflux conditions for 24 h. The obtained
MNPs were separated from solution using a powerful
2 | MATERIALS AND METHODS
2.1 | General
The reagents and solvents used in this work were
obtained from commercial companies and were used
without further purification. Analytical TLC was per-
formed using Merck silica gel GF254 plates. All products
are known and were characterized by comparison of their
spectral (NMR) and physical data with those of authentic
samples. X‐ray diffraction (XRD) patterns were recorded
with a Philips X’pert powder X‐ray diffractometer (Co
Kɑ radiation = 0.1540 nm), scanning at 2 min−1 from
10° to 100°. Scanning electron microscopy (SEM) images
were recorded with a TESCAN MIRA3. Thermogravimet-
ric analysis (TGA) was conducted with a Shimadzu DTG‐
60 instrument. NMR spectra were recorded with a Bruker
FX 400Q NMR spectrometer. The supermagnetic proper-
ties of the nanocatalyst were measured with a vibrating
sample magnetometry (VSM) instrument (MDKFD) oper-
ating at room temperature.
magnet and rinsed with ethanol. Finally the products were
−
dried to afford [Fe3O4@SiO2@(CH2)3Py]HSO4
.
2.3 | General procedure for preparation of
polyhydroquinolines
A mixture of aldehyde (1 mmol), dimedone (1 mmol),
ethyl acetoacetate (1 mmol), ammonium acetate
−
(1.2 mmol) and [Fe3O4@SiO2@(CH2)3Py]HSO4 (25 mg)
in ethanol (5 ml) was stirred under reflux condition for
the appropriate time. The progress of the reaction was
monitored by TLC. After completion of the reaction, the
catalyst was separated via an external magnetic. The
reaction mixture was dissolved in ethyl acetate and
poured into water. The resulting precipitate was filtered
and was purified by recrystallization from ethanol to
afford the desired compound in pure form.
2.2 | General procedure for preparation of
−
novel [Fe3O4@SiO2@(CH2)3Py]HSO4
Fe3O4 nanoparticles were synthesized according to
reported literature.[35] FeCl3⋅6H2O (0.216 mol, 5.84 g)
and FeCl2⋅4H2O (0.0108 mol, 2.17 g) were dissolved into
100 ml of deionized water at 80 °C followed by addition
of 10 ml of aqueous NH3 (25%) under vigorous stirring
and nitrogen protection. The obtained MNPs were sepa-
rated from solution using a powerful magnet and rinsed
three times with 200 ml of deionized water. Finally, the
3 | RESULTS AND DISCUSSION
3.1 | Characterization
Fe3O4 nanoparticles were coated using TEOS. The
successfully generated Fe3O4@SiO2 nanostructure was

SAJJADIFAR AND AZMOUDEHFARD
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−
SCHEME 1 Preparation of [Fe3O4@SiO2@(CH2)3Py]HSO4 and its application for the synthesis of polyhydroquinoline derivatives
modified using (3‐chloropropyl)trimethoxysilane and pyr-
To investigate the presence of organic structure on the
Fe3O4 MNPs, TGA was performed. The TGA curve of
[Fe3O4@SiO2@(CH2)3Py]HSO4 shows a mass loss of
idine. This was followed by sulfonation with H2SO4 to
−
−
afford [Fe3O4@SiO2@(CH2)3Py]HSO4 with a core–shell
nanostructure as
nanocatalyst (Scheme 1). The catalytic activity of
[Fe3O4@SiO2@(CH2)3Py]HSO4 was investigated for the
a
novel ionic liquid magnetic
the organic functional groups as it decomposes upon
heating. The TGA curve shows a small amount of weight
−
synthesis of polyhydroquinoline derivatives.
The synthesized [Fe3O4@SiO2@(CH2)3Py]HSO4− cata-
lyst was characterized using SEM, powder XRD, TGA,
VSM and Fourier transform infrared (FT‐IR) spectroscopy.
SEM images were applied to verify the nanostructure of
[Fe3O4@SiO2@(CH2)3Py]HSO4−. The nanostructure mor-
phology exhibited a spherical shape and the average
particle size of the catalyst was about 14–21 nm
(Figure 1).
−
FIGURE 2 TGA of [Fe3O4@SiO2@(CH2)3Py]HSO4
FIGURE 3 Powder XRD pattern of [Fe3O4@SiO2@(CH2)3Py]
HSO4
−
−
FIGURE 1 SEM image of [Fe3O4@SiO2@(CH2)3Py]HSO4

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SAJJADIFAR AND AZMOUDEHFARD
loss below 100 °C corresponding to removal of adsorbed
solvents. The mass loss of about 30% of organic functional
groups has been reported to desorb at temperatures above
200 °C. A weight loss at about 500 °C is related to the
phase changes of Fe3O4 MNPs (Figure 2).
dard Fe3O4 XRD pattern[36] (Figure 3). The crystallite
size was determined from Scherrer's equation, D = kλ/
β cos θ, and it was found to be about 20 nm.
The magnetic property of the nanocatalyst was investi-
gated using VSM. The magnetization curve for the
−
Powder XRD is an effective technique used to
identify the magnetite crystal phase in the
[Fe3O4@SiO2@(CH2)3Py]HSO4 nanoparticles is shown
in Figure 4. From the VSM analysis, the saturation mag-
−
−
[Fe3O4@SiO2@(CH2)3Py]HSO4 nanocatalyst. The XRD
netization of [Fe3O4@SiO2@(CH2)3Py]HSO4 is about
diffraction pattern of [Fe3O4@SiO2@(CH2)3Py]HSO4
15.12 emu g−1, which is much lower than that of bare
Fe3O4 nanoparticles (about 39.1 emu g−1) reported in
−
shows several peaks at 2θ = 30.2°, 35.6°, 43.3°, 54.1°,
57.4° and 63.1°, which are assigned to the (220), (311),
(400), (422), (511) and (440) crystallographic faces of mag-
netite. This pattern is in good agreement with the stan-
the literature[17]
Figure
nanoparticles, Fe3O4@SiO2, Fe3O4@SiO2@(CH2)3‐Cl,
[Fe3O4@SiO2@(CH2)3Py]Cl−
and
.
5
shows the FT‐IR spectra of Fe3O4
−
[Fe3O4@SiO2@(CH2)3Py]HSO4 nanoparticles. The FT‐
IR spectrum of Fe3O4 nanoparticles (Figure 5a) shows
a strong band at 3383 cm−1, which corresponds to
OH bonds linked to the surface of iron atoms. Bands
of stretching vibration of Fe&bond;O bonds appear at
TABLE 1 Influence of solvent in synthesis of
polyhydroquinolinea
Entry
Solvent
Time (min)
Yield (%)b
1
2
3
4
5
6
H2O
90
90
90
90
90
90
41
84
46
32
98
71
PEG
MeCN
EtOAc
EtOH
−
FIGURE 4 VSM analysis of [Fe3O4@SiO2@(CH2)3Py]HSO4
Solvent‐free
aConditions of reaction: benzaldehyde (1 mmol), dimedone (1 mmol), ethyl
acetoacetate (1 mmol), ammonium acetate (1.2 mmol), catalyst (25 mg), sol-
vent (5 ml) and 80 °C.
bIsolated yield.
TABLE 2 Influence of temperature and amount of catalyst in
synthesis of polyhydroquinolinea
Amount of
catalyst (mg)
Temperature
(°C)
Time
(min)
Yield
(%)b
Entry
1
2
3
4
5
6
7
10
15
20
25
30
25
25
Reflux
Reflux
Reflux
Reflux
Reflux
60
90
90
54
69
80
98
99
64
29
90
90
85
100
100
40
aConditions of reaction: benzaldehyde (1 mmol), dimedone (1 mmol), ethyl
acetoacetate (1 mmol), ammonium acetate (1.2 mmol), catalyst and EtOH
(5 ml).
FIGURE
5
FT‐IR spectra of (a) Fe3O4 nanoparticles, (b)
Fe3O4@SiO2, (c) Fe3O4@SiO2@(CH2)3‐Cl, (d)
[Fe3O4@SiO2@(CH2)3Py]Cl− and (e) [Fe3O4@SiO2@(CH2)3Py]
−
HSO4 nanoparticles
bIsolated yield.

SAJJADIFAR AND AZMOUDEHFARD
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−a
TABLE 3 Synthesis of polyhydroquinolines in presence of [Fe3O4@SiO2@(CH2)3Py]HSO4
Entry
Aldehyde
Product
Time (min)
Yield (%)b
M.p. (°C)
203–204[37]
1
90
98
2
3
4
5
6
7
80
100
140
105
85
95
91
90
93
95
83
245–246[38]
257–259[37]
230–231[37]
175–178
252–253[37]
180
303–306
8
9
125
115
90
90
230–232[39]
198–199[40]
(Continues)

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SAJJADIFAR AND AZMOUDEHFARD
TABLE 3 (Continued)
Entry
Aldehyde
Product
Time (min)
Yield (%)b
M.p. (°C)
10
70
90
243–244[38]
aConditions of reaction: benzaldehyde (1 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol), ammonium acetate (1.2 mmol), catalyst (25 mg), EtOH
(5 ml) and reflux condition.
bIsolated yield.
444 and 579 cm−1 in all the FT‐IR spectra. The presence
of (3‐chloropropyl)trimethoxysilane is confirmed by
a characteristic peak at 1070–1100 cm−1 which is
ascribed to the Fe&bond;O&bond;Si stretching vibration
and C&bond;H stretching vibration band appears at
a model reaction under various conditions. The effects
of solvent, catalyst amount and temperature were exam-
ined. Initially, we used solvents such as H2O, PEG,
MeCN, EtOAc and EtOH. EtOH was the most effective
solvent for this reaction, and the polyhydroquinoline
was obtained in 98% yield (Table 1, entry 6).
2973 cm−1
.
In the next stage, the effects of temperature and
amount of catalyst in the progress of the reaction were
examined. According to Table 2, the best result was
obtained under reflux conditions. Meanwhile, the
amount of catalyst showed a significant effect on the
product yield. Best results were obtained in the presence
of 25 mg of catalyst (Table 2, entry 4).
3.2 | Catalytic studies
After characterization of the catalyst, to find the optimal
−
conditions,
[Fe3O4@SiO2@(CH2)3Py]HSO4
as
a
nanocatalyst was examined in the synthesis of
polyhydroquinoline derivatives. In this respect, the
cyclocondensation of benzaldehyde, dimedone, ethyl
acetoacetate and ammonium acetate was investigated as
To generalize this methodology, we synthesized a
series of polyhydroquinolines in the presence
−
of [Fe3O4@SiO2@(CH2)3Py]HSO4
as homogeneous
SCHEME 2 Plausible reaction
mechanism of [Fe3O4@SiO2@(CH2)3Py]
HSO4−‐catalysed polyhydroquinoline
synthesis

SAJJADIFAR AND AZMOUDEHFARD
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FIGURE 6 Recycling experiment of
−
[Fe3O4@SiO2@(CH2)3Py]HSO4 in
condensation of benzaldehyde, dimedon,
ethyl acetoacetate and ammonium acetate
catalyst under reflux conditions. Many types of aldehydes
having electron‐donating and electron‐withdrawing
moieties were used to obtain the corresponding
polyhydroquinolines (Table 3).
In Scheme 2, a plausible reaction mechanism involving
the [Fe3O4@SiO2@(CH2)3Py]HSO4− catalyst is presented.
The first step is protonation of the carbonyl group in alde-
hyde. The role of the catalyst comes in the Knoevenagel‐
type condensation of aldehydes with active methylene
compounds and in the Michael‐type addition of intermedi-
ates to give final product.
and then dried under vacuum and recycled in further reac-
tions. As shown in Figure 6, the catalyst was used for over
seven runs without any significant loss of activity.
To show the benefits of our procedure in
comparison with other reported catalysts, we
summarize several reported catalysts for the
preparation of polyhydroquinolines in Table 4. Synthesis
of
polyhydroquinolines
in
the
presence
of
−
[Fe3O4@SiO2@(CH2)3Py]HSO4 showed higher yield
and good reaction time compared to other catalysts
reported in the literature.
The recyclability of the catalyst was examined for
the reaction of benzaldehyde with dimedon, ethyl
acetoacetate and ammonium acetate as a model reaction
in ethanol using 25 mg of [Fe3O4@SiO2@(CH2)3Py]
4 | CONCLUSIONS
−
An effective [Fe3O4@SiO2@(CH2)3Py]HSO4 catalysis
−
HSO4 catalyst. Upon completion of the reaction,
was formulated for the synthesis of polyhydroquinolines
with benzaldehyde, dimedon, ethyl acetoacetate and
ammonium acetate. The Fe3O4 MNPs were prepared
and further ionic liquid was immobilized on their surface.
This catalyst was characterized using TGA, XRD, SEM
and VSM techniques. This catalyst can be recovered and
reused seven times. All products were obtained in good
yields and high purity. The high yields, operational ease,
practicality and applicability to a number of substrates
render this method as a valuable substitute to other previ-
ously utilized approaches.
−
[Fe3O4@SiO2@(CH2)3Py]HSO4
was
conveniently
removed from the product using an external magnet, and
the remaining solution was decanted. The recovered cata-
lyst was washed using ethanol to remove residual product
TABLE 4 Comparison results for [Fe3O4@SiO2@(CH2)3Py]
−
HSO4 with those for other catalysts
Time Yield
Entry Catalyst
(min) (%)a Ref.
[41]
1
2
3
4
5
6
7
8
Pd‐SBTU@Fe3O4
90
240
150
120
95
98
90
89
97
92
94
89
98
[42]
[17]
[43]
[44]
[45]
[46]
GSA@MNPs
Cu‐SPATB/Fe3O4
Fe3O4‐SA‐PPCA
Cu (II)/L‐His@Fe3O4
Boehmite‐SSA
ACKNOWLEDGMENTS
Financial support from Payame Noor University Research
Council is gratefully acknowledged.
215
300
90
Ga(OTf)3
ORCID
[Fe3O4@SiO2@(CH2)3Py]
This
work
−
HSO4
Sami Sajjadifar https://orcid.org/0000-0001-8661-1264

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SAJJADIFAR AND AZMOUDEHFARD
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