One-pot synthesis of 1,4-dihydropyridines and N-arylquinolines in the presence of copper complex stabilized on MnFe2O4 (MFO) as a novel organic–inorganic hybrid material and magnetically retrievable catalyst

Article abstract of DOI:10.1002/aoc.5822

In this work, the design and synthesis of a heterogeneous catalyst based on functionalization of manganese ferrite nanoparticles encapsulated in a silica layer with Schiff base and subsequent incorporation of copper is presented. The fabricated hybrid mat

Full text of DOI:10.1002/aoc.5822

Received: 21 January 2020
DOI: 10.1002/aoc.5822
Revised: 11 April 2020
Accepted: 2 May 2020
F U L L P A P E R
One-pot synthesis of 1,4-dihydropyridines and N-
arylquinolines in the presence of copper complex stabilized
on MnFe2O4 (MFO) as a novel organic–inorganic hybrid
material and magnetically retrievable catalyst
Najmieh Ahadi1 | Akbar Mobinikhaledi1,2
| Mohammad Ali Bodaghifard1,2
1Department of Chemistry, Faculty of
In this work, the design and synthesis of a heterogeneous catalyst based on
functionalization of manganese ferrite nanoparticles encapsulated in a silica
layer with Schiff base and subsequent incorporation of copper is presented.
The fabricated hybrid material was characterized by employing Fourier-
transform infrared spectroscopy, X-ray powder diffraction, field emission scan-
ning electron microscopy, transmission electron microscopy, energy-dispersive
X-ray spectroscopy, differential thermal gravimetric analysis, vibrating sample
magnetometry and inductively coupled plasma-optical emission spectrometry
techniques. The prepared organic–inorganic hybrid material was successfully
used as an efficient and recoverable catalyst for the synthesis of
1,4-dihydropyridines and N-arylquinolines under mild and green reaction con-
ditions. The results showed that the catalyst exhibited excellent catalytic
activity under optimum reaction conditions and the desired products were
obtained in good to excellent yields. The new 1,4-dihydropyridines and N-
arylquinolines were characterized by Fourier-transform infrared spectroscopy,
1H NMR and Elemental analysis of Carbon, Hydrogen and Nitrogen (CHN)
analyses. Study of the catalyst reusability confirmed that the catalyst could be
recycled for five reaction runs with slight loss of the catalytic activity and
negligible copper leaching.
Science, Arak University, Arak,
38156-88138, Iran
2Institute of Nanosciences and
Nanotechnology, Arak University, Arak,
Iran
Correspondence
Akbar Mobinikhaledi, Department of
Chemistry, Faculty of Science, Arak
University, Arak 38156-88138, Iran.
Email: akbar_mobini@yahoo.com
Funding information
Arak University
K E Y W O R D S
1,4-dihydropyridines, copper complex, heterogeneous catalyst, magnetic organic–inorganic
nanomaterial
1 | INTRODUCTION
the subject of intense research because of their applica-
tions in various fields such as adsorption, ion exchange,
Magnetic nanoparticles have many applications in vari-
ous fields such as drug delivery, hyperthermia, magnetic
resonance imaging, cell and stem cell separation, enzyme
magnetism,[9–14]
luminescence
and
chemical
sensing.[15–18] These materials are also used as catalysts
in organic chemistry because of their exceptional proper-
ties such as thermal stability, high surface area, high
activity, low toxicity and ease of separation.[16,18–20] Mul-
ticomponent reactions have been widely used in many
immobilization,
magnetic
fluids,
sensors
and
pigments.[1–8] In recent years, the synthesis of magnetic
hybrid organic–inorganic framework materials has been
Appl Organomet Chem. 2020;e5822.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
1 of 13
https://doi.org/10.1002/aoc.5822

2 of 13
AHADI ET AL.
research areas such as medicinal chemistry and modern
organic synthesis because of time, energy and environ-
ment savings. Nitrogen-containing heterocyclic com-
pounds such as dihydropyridines and N-arylquinolines
have attracted much interest because of their numerous
biological activities. They are also used as an intermedi-
ate for the synthesis of some valuable pharmaceutical
products such as antioxidants,[21] antidiabetics,[22] anti-
tumor agents and NADH models.[21,23] The other biologi-
cal and pharmaceutical properties of these compounds
consist of blocking of calcium canals,[24] anti-inflamma-
tory[25] and analgesic properties, usefulness for the treat-
ment of cardiovascular diseases,[26,27] HIV protease
inhibition,[28] and antiplasmodial,[29] intrinsic,[30] cyto-
toxic[31] and hepatoprotective activities.[32]
Owing to wide range applications of dihydropyridines
and N-arylquinolines in pharmacology and industry,
several methods have been reported for the synthesis of
these compounds in the presence of various manganese
ferrite nanoparticles (MnFe2O4, MNPs) as catalyst.[33,34]
However, some of these methods have some limitations
such as low yield, high temperature, long reaction time
and the use of unrecyclable catalyst. Therefore, the
development of a green and simple method for synthesis
of these materials is still necessary. In view of this report,
we wish to report a clean and environmentally friendly
procedure for the synthesis of dihydropyridines using
copper complex stabilized on MFO organic–inorganic
nanohybrid material as a novel magnetically separable
catalyst.
rate of 40 ml/min. The vibration sample magnetometer
with model 730 VSM system was used at room temper-
ature to measure the magnetic properties of the pre-
pared nanostructure. Transmission electron microscopy
(TEM) measurement was carried out with a Philips
CM10 analyzer operating at 150 kV. Also, the
loading amount of Cu on MnFe2O4@SiO2–Pr–
NH@BTA@Cu(OAc)2 was determined by an inductively
coupled plasma optical emission spectrometer (Spectro
Arcos). The melting points of compounds were deter-
mined using an electrothermal digital system and are
uncorrected. Progress reactions were followed by analyt-
ical thin-layer chromatography using UV-active
aluminum-backed plates of silica gel 60F254. Infrared
spectra (IR) were obtained using KBr pellets on a
Brucker alpha series Fourier transform infrared (FT-IR)
1
spectrophotometer in the range 400–4000 cm−1. The H
and 13CNMR spectra were recorded at 300 or 400 and
75 or 100 MHz, respectively, on a Brucker Avence spec-
trometer using DMSO-d6 as a solvent.
2.2 | General procedure for the synthesis
of 1,4-dihydropyridines
To a mixture of aldehyde (1 mmol), malononitril or
ethyl-cyanoacetate (1 mmol) in EtOH (10 ml), dimedone
or indendione (1 mmol) and MnFe2O4@SiO2–Pr–
NH@BTA@Cu(OAc)2 (0.015 g) were added and stirred at
room temperature for the appropriate time (Table 2). The
completion of the reaction was followed by thin-layer
chromatography. After completion of the reaction, the
solvent was evaporated. The resulting mixture was
diluted with EtOH and the catalyst easily separated by an
external magnet. Finally, the product was recrystallized
from EtOH and water, which was then filtered and dried
in the oven.
2 | EXPERIMENTAL
2.1 | Materials and instruments
Chemical reagents and solvents were purchased from
Merk, Fulka and Aldrich chemical companies and used
without further purification. The crystal structure was
investigated for the prepared samples using a Philips
Xpert X-ray powder diffraction (XRD) diffract meter
(Cu–Kα radiation and λ = 0.15406) in the range of
Bragg angle 10–80 using 0.05 as the step length. The
morphology and size of nanoparticles were observed
with a MIRA3TESAN-XUM emission scanning electron
microscope (FE-SEM). Elemental chemical analysis
coupled with FE-SEM was used for recognition of
chemical elements of the MnFe2O4@SiO2–Pr–
NH@BTA@Cu(OAc)2 catalyst. The thermogravimetric
2.3 | Synthesis of the manganese ferrite
nanoparticles, MnFe2O4
Magnetic manganese ferrite nanoparticles (MnFe2O4)
were prepared using the co-precipitation method.[43] To a
mixture of MnCl2, 4H2O (0.5 g, 2.5 mmol) and FeCl3,
6H2O (1.35 g, 5 mmol) in a round-bottom flask (100 ml),
50 ml deionized water was added and the solution was
ꢀ
stirred for 1 h at 95 C. Subsequently, 10 ml of NH3 was
added and the brown mixture stirred for a further 1 h
under the same conditions. The magnetic precipitate was
isolated by an external magnet and washed with warm
distilled water (200 ml) and EtOH (10 ml) and then dried
at 70 ꢀC.
analysis
(TGA)
curve
for
MnFe2O4@SiO2–Pr–
NH@BTA@Cu(OAc)2 was drawn using a matter TGA
209 F3Tarsus under atmospheric pressure in the range
ꢀ
ꢀ
of 30–700 C at a heating speed of 10 C/min with flow

AHADI ET AL.
3 of 13
TABLE 2
The synthesis of dihydropyridine ansd N-arylquinolines derivatives in the presence of MNP@BSAT@Cu(OAc)2 (10 mg)
nanoparticles as a catalyst
1a– 2a– 3a–
Time
Product (min)
Yield
(%)
Melting point (ꢀC)
obtained
Melting point (ꢀC)
reported
Entry Carbonyl
b
b
b
1
3-NO2-C7H5O
4-Cl-C7H5O
2-Cl-C7H5O
2,4-diCl2-C7H5O
4-Br-C7H5O
C7H6O
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1a
1a
1a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2b
2b
2b
2b
2b
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
3b
3b
3b
3b
3b
3b
6a
6b
6c
6d
5e
6f
20
20
40
30
29
30
70
60
60
20
90
15
14
15
30
25
45
95
95
90
93
86
94
87
88
88
95
92
92
83
87
80
94
83
228–230
240–242
205–206
230–233
245–246
203–204
249–250
255–256
257–259
255–257
>300
229–231[35]
245–246[36]
207–209[37]
244–245[38]
255–257[36]
205–206[38]
256–257[35]
256–258[38]
260–262[39]
2
3
4
5
6
7
2-OMe-C7H5O
4-OMe- C7H5O
4-Me
6g
6 h
6i
8
9
10
11
12
13
14
15
16
17
C7H6O
6j
—
—
Indoline-2,3-dione
4-Cl-C7H5O
3-NO2-C7H5O
4-NO2-C7H5O
6k
7a
7b
7c
7d
7e
7f
269–270
265–267
270–271
272–274
237–238
241–243
268–269[40]
268–269[41]
275–276[40]
4-OH,3-NO2-C7H4O 1a
—
—
Terphetaldehyde
4-CH3-C7H5O
1a
1a
243–245[42]
aIsolated yields, aromatic aldehyde or indoline-2,3-dione (1 mmol), dimedone or 1H-indene-1,3(2H)-dione (1 mmol), ethylacetate or
malononitrile (1 mmol) and ammonium acetate or aniline (1.5 mmol) in the presence of MNP@BSAT@Cu(OAc)2 (10 mg) as catalyst, EtOH
(5 ml) at room tempareture.
2.4 | Preparation of silica-coated MNPs
(MnFe2O4@SiO2 MNPs)
for 30 min. Then, APTS (0.14 ml) was added and the
resulting suspension sonicated for another 10 min. The
mixture was refluxed for 24 h at 110 C and the obtained
ꢀ
The Stöber method was used for preparation of silica-
coated MNPs (MnFe2O4@SiO2 MNPs).[44] MnFe2O4 (1 g)
was added to a mixture of H2O (3 ml), EtOH (20 ml) and
ammonium hydrate 25% (0.8 ml). The mixture was soni-
cated for 30 min and tetraethylortosilicate (0.07 ml)
added and sonicated for another 30 min. Afterwards, the
mixture was stirred for 12 h at room temperature. The
obtained product was isolated by an external magnet,
washed with distilled water and EtOH and then dried at
70 ꢀC.
precipitate was separated by an external magnet and
washed several times with toluene and dried for 7 h at
80 ꢀC.
2.6 | Preparation of triazine dichloride-
functionalized silica-coated magnetic
nanoparticles (MnFe2O4@SiO2–Pr–NH–
TDCl2)
MnFe2O4@SiO2–Pr–NH–TDCl2 was prepared according
to the reported method in the literature.[46] Firstly, a mix-
ture of MnFe2O4@SiO2–Pr–NH2 nanoparticles (1 g), dry
THF (4 ml) and Et3N as a base in a round-bottomed flask
(25 ml) was sonicated for 10 min. Then, cyanuric chloride
(0.19 g) was added and stirred for 24 h at room tempera-
ture. The resulting solid was isolated by an external mag-
net. For withdrawing unreacted cyanuric chloride, the
resulting solid was washed several times with THF
(10 ml) and CH3Cl (10 ml) and dried at 50 ꢀC.
2.5 | Functionalization of MnFe2O4@SiO2
MNPs with (3-aminopropyl)triethoxysilane
(MnFe2O4@SiO2–Pr–NH2 MNPs)
Functionalization of MnFe2O4@SiO2 MNPs with
(3-aminopropyl)triethoxysilane (APTS) was performed by
the method used by Salemi et al.[45] MnFe2O4@SiO2
(0.5 g) was sonicated in 10 ml toluene under ultrasound

4 of 13
AHADI ET AL.
2.7 | Preparation of triazine diamine-
functionalized silica-coated MnFe2O4
nanoparticles (MnFe2O4@SiO2–Pr–NH–
TDA)
(s, 1H, CH), 6.95–7.03 (m, 4H, HAr), 9.03 (s, 1H, NH)
ppm.13C NMR: δ = 194.7, 167.3, 149.8, 145.3, 145.2, 134.9,
128.7, 127.8, 110.5, 104.2, 59.4, 50.7, 35.8, 32.6, 29.6, 26.9,
21.0, 18.7, 14.6 ppm. Anal. calcd for C22H27NO3: C, 74.76;
H, 7.70; N, 3.96%. Found: C, 74.80; H, 7.80; N, 3.90%.
MnFe2O4@SiO2–Pr–NH–TDA was prepared by the
reported method.[47] The MnFe2O4@SiO2–Pr–NH–TDCl2
(1 g) was sonicated in dioxane (50 ml) in a round-bottom
flask (100 ml) for 10 min. Then, 15 mꢀl ammonia (25%)
was added and refluxed for 24 h at 80 C in an oil bath.
Finally, the prepared functionalized MNPs were sepa-
rated by an external magnetic field, washed with dioxane
and dried at 50 ꢀC.
2.10.2 | Ethyl 4-(4-bromophenyl)-
2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydroquinoline-3-carboxylate (6e)
IR (KBr) (νmax, cm−1): 3276, 3206, 3077, 2961, 2933, 1702,
1
1648, 1605, 1490, 1381, 1215, 842. H NMR (300 MHz,
DMSO-d6): δH = 0.82 (s, 3H, CH3), 1.00 (s, 3H, CH3), 1.12
(t, 3H, J = 7.1 Hz, CH3), 1.94–2.44 (m, 4H, CH2), 2.29 (s,
3H, CH3), 3.96 (q, 2H, J = 7.1 Hz, CH2), 4.82 (s, 1H, CH),
7.08–7.39 (m, 4H, HAr), 9.12 (s, 1H, NH) ppm. Anal. calcd
for C21H24BrNO3: C, 60.29; H, 5.78; Br, 19.10; N, 3.35%.
Found: C, 60.30; H, 5.68; Br, 19.20; N, 3.44%.
2.8 | Preparation of MNP–BSAT
nanoparticles
MNP– Bis Salicylaldehydetriazine (BSAT) nanoparticles
were prepared using a previously reported procedure.[48]
Firstly, MnFe2O4@SiO2–Pr–NH–TDCl2 (1 g) was soni-
cated in EtOH (40 ml) in round-bottom flask for 15 min.
Then, salicylaldehyde (2 ml) was added and refluxed for
24 h. At the last step, the precipitated solid material
was isolated by an external magnet. Unreacted
salicylaldehyde was removed by washing with EtOH and
n-hexane. The solid material was dried at 70 ꢀC.
2.10.3 | Ethyl 2,7,7-trimethyl-5-oxo-
4-phenyl-1,4,5,6,7,8-hexahydroquinoline-
3-carboxylate (6f)
IR (KBr) (νmax, cm−1): 3284, 3205, 3077, 2961, 2932, 1700,
1643, 1606, 1487, 1381, 1213. 1H NMR (300 MHz, DMSO-
d6): δH = 0.82 (s, 3H, CH3), 1.00 (s, 3H, CH3), 1.12 (t, 3H,
J = 7.1 Hz, CH3), 1.94–2.44 (m, 4H, CH2), 2.29 (s, 3H,
CH3), 3.96 (q, 2H, J = 7.09 Hz, CH2), 4.88 (s, 1H, CH),
7.08–7.39 (m, 5H, HAr), 9.12 (s, 1H, NH) ppm. Anal. calcd
for C21H25NO3: C, 74.31; H, 7.42; N, 4.13%. Found: C,
74.11; H, 7.22; N, 3.97%.
2.9 | Preparation of Cu-decorated MNP–
BSAT nanoparticles
The Cu-decorated MNP–BSAT nanoparticles were
prepared via the reported method.[49] The MNP–BSAT
nanoparticles (1 g) were sonicated in EtOH (40 ml) in a
round-bottom flask (100 ml) for 15 min. The Cu(OAc)2
(2 mmol, 0.398 g) was then added and the mixture was
refluxed for 24 h at 80 ꢀC using an oil bath. The obtained
solid was separated by an external magnet, washed with
EtOH and water and dried at 70 ꢀC in an oven.
2.10.4 | Ethyl 2-methyl-5-oxo-4-phenyl-
4,5-dihydro-1H-indeno[1,2-b]pyridine-
3-carboxylate (6j)
IR (KBr) (νmax, cm−1): 3267, 3229, 3083, 3024, 2903, 1705,
1
1671, 1606, 1584. H NMR (300 MHz, DMSO-d6): δH
=
1.48 (t, 3H, J = 7.2 Hz, CH3), 2.25 (s, 3H, CH3), 4.33 (q, 2H,
J = 7.0 Hz, 4.59 (s, 1H, CH), 6.93–7.41 (m, 9H, HAr), 9.99
(s, 1H, NH) ppm. Anal. calcd for C22H19NO3: C, 76.50; H,
5.54; N, 4.06%. Found: C, 76.39; H, 5.34; N, 3.98%.
2.10 | Spectra and physical data
2.10.1 | Ethyl 2,7,7-trimethyl-5-oxo-4-(p-
tolyl)-1,4,5,6,7,8-hexahydroquinoline-
3-carboxylate (6i)
2.10.5 | Ethyl 2-methyl-20,5-dioxo-
1,5-dihydrospiro[indeno[1,2-b]pyridine-4,30-
indoline]-3-carboxylate (6k)
IR (KBr) (νmax, cm−1): 3278, 3208, 3078, 2959, 1701, 1647,
1
1605, 1492, 1380, 1281. H NMR (300 MHz, DMSO-d6):
δH = 0.84 (s, 3H, CH3), 1.00 (s, 3H, CH3), 1.14 (t, 3H,
J = 7.1 Hz, CH3), 1.96–2.44 (m, 4H, CH2), 2.24 (s, 3H,
CH3), 2.29 (s, 3H, CH3), 3.96 (q, 2H, J = 7.1 Hz, CH2), 4.79
IR (KBr) (νmax, cm−1): 3342, 3253, 3215, 3164, 3068, 2963,
1713, 1705, 1676, 1641, 1519. 1H NMR (300 MHz,

AHADI ET AL.
5 of 13
DMSO-d6): δH = 1.50 (t, 3H, J = 12.0 Hz, CH3), 2.57 (s,
3H, CH3), 4.37 (q, J = 12.0 Hz, 2H, CH2), 6.81–7.70 (m,
8H, HAr), 10.29 (s, 1H, NH), 10.37 (s, 1H, NH) ppm. Anal.
calcd for C23H18N2O4: C, 71.49; H, 4.70; N, 7.25%.
Found: C, 71.31; H, 4.42; N, 7.62%.
(m, 9H, HAr). Anal. calcd for C25H25N3O: C, 78.30; H,
6.57; N, 10.96%. Found: C, 78.43; H, 6.32; N, 10.90%.
3 | RESULTS AND DISCUSSION
3.1 | Characterization of MNP–
2.10.6 | 2-Amino-4-(4-hydroxy-
3-nitrophenyl)-7,7-dimethyl-5-oxo-1-phenyl-
1,4,5,6,7,8-hexahydroquinoline-
3-carbonitrile (7d)
BSAT@Cu(OAc)2 nanoparticles catalyst
The MNP@BSAT@Cu(OAc)2 nanoparticles were used
for the synthesis of 1,4-dihydropyridine derivatives. Cu-
decorated MNP–BSAT nanoparticles were prepared via
the method illustrated in Scheme 1. Firstly, MnFe2O4
nanoparticles were prepared via the co-preparation
method,[50] and then coated with an SiO2 layer[32] and
APTS, respectively, to afford MnFe2O4@SiO2–Pr–NH2
(1). The reaction of cyanuric chloride with
MnFe2O4@SiO2–Pr–NH2 in toluene gave MNP@TCl2 (2)
IR (KBr) (νmax, cm−1): 3464, 3324, 3215, 2958, 2890, 2179,
1
1652. H NMR (300 MHz, DMSO-d6): δH = 0.99 (s, 3H,
CH3), 1.15 (s, 3H, CH3), 1.96 (d, J = 17.4 Hz, 1H, CH2),
2.25 (d, J = 15.1 Hz, 1H, CH2), 2.78 (s, 2H, CH2), 4.75 (s,
1H, CH), 5.75 (s, 2H, NH2), 7.42–8.01 (m, 8H, HAr), 11.17
(brs, 1H, OH). 13C NMR: δ = 195.3, 151.8, 151.3, 150.9,
138.3, 136.5, 134.5, 130.7, 130.3, 119.9, 115.8, 111.7, 59.9,
49.6, 41.4, 35.8, 32.3, 29.5, 26.5 ppm. Anal. calcd for
C24H22N4O4: C, 66.97; H, 5.15; N, 13.02%. Found: C,
67.78; H, 5.05; N, 12.8%.
nanoparticles.
Consequently,
MNP@TDA
(3)
nanoparticles were prepared by reaction of NH3 and
MNP@TCl2 nanoparticles, which then changed to
MNP@BSAT (4) by reaction with salicylaldehyde.
Finally, Cu-decorated MNP@BSAT nanoparticles (5),
were constructed by reaction of MNP@TBSA with
2.10.7 | 2-Amino-4-[4-(2-amino-3-cyano-
6,6-dimethyl-8-oxo-4-phenyl-
1,4,5,6,7,8-hexahydronaphthalen-1-yl)
phenyl]-7,7-dimethyl-5-oxo-1-phenyl-
1,4,5,6,7,8-hexahydroquinoline-
3-carbonitrile (7e)
Cu(OAc)2
in
EtOH.
MNP@BSAT@Cu(OAc)2
nanoparticles were characterized by FT-IR spectroscopy,
FE-SEM, TGA, XRD, vibrating sample magnetometry,
energy dispersive X-ray (EDX) and inductively coupled
plasma atomic emission spectroscopy (ICP–OES)
analyses.
The FT-IR spectra of MnFe2O4 (a), MnFe2O4@SiO2
(b), MnFe2O4@SiO2–Pr–NH2 (c), MNP@TCl2 (d),
IR (KBr) (νmax, cm−1): 3468, 3236, 3061, 2957, 2181, 1644.
1H NMR (300 MHz, DMSO-d6): δH = 0.74 (s, 3H, CH3),
0.87 (s, 3H, CH3), 1.01 (s, 6H, CH3), 1.74 (d, J = 16.0 Hz,
2H, CH2), 2.04 (s, 2H), 2.16 (d, J = 16.0 Hz, 2H, CH2),
2.37 (s, 2H, CH2), 4.68 (s, 2H, 2CH), 5.3 (s, 4H, 2NH2),
7.12–7.57 (m, 14H, HAr). 13C NMR: δ = 195.3, 160.6,
151.5, 150.7, 136.7, 130.6, 129.6, 127.2, 124.8, 123.4, 97.1,
66.8, 50.6, 36.3, 34.9, 32.7, 29.3, 28.4 ppm. Anal. calcd for
C42H40N6O2: C, 76.34; H, 6.10; N, 12.72%. Found: C,
76.54; H, 6.01; N, 12.9%.
MNP@TDA
(e),
MNP@BSAT
(f)
and
MNP@BSAT@Cu(OAc)2 (g) nanoparticles are presented
in Figure 1. The absorption band around 580 cm−1 was
assigned to Fe–O stretching (Figure 1A-e). In addition,
the broad band at 3100–3500 cm−1 was attributed to OH
stretching (Figure 1A-g), which covered the characteristic
absorption band of NH stretching (Figure 1c–e). In addi-
tion, the absorption band at 1620 cm−1 was due to OH
twisting (Figure 1A-g). The strong absorption band at
1091 cm−1 and absorptions at 954, 815 and 459 cm−1 orig-
inated from asymmetric stretching, symmetric stretching
in plane bending and rocking mode for the Si–O–Si
group, respectively (Figure 1B-g). These data confirm that
SiO2 was immobilized on the surface of MnFe2O4 MNPs.
The weak absorption band at 2950 cm−1 related to CH
symmetric and asymmetric stretching modes (Figure 1c–
g), and the bands indicated at 1490–1620 cm−1 confirmed
the existence of CN in heterocyclic rings. In addition, the
bond at 1430 cm−1 was in support of the C–C bond of
heterocyclic rings (Figure 1e–g). These results confirmed
the formation of MNP@BSAT. Figure 1g represents the
2.10.8 | 2-Amino-7,7-dimethyl-5-oxo-
1-phenyl-4-(p-tolyl)-
1,4,5,6,7,8-hexahydroquinoline-
3-carbonitrile (7f)
IR (KBr) (νmax, cm−1): 3458, 3333, 3217, 2956, 2926, 2178,
1
1654. H NMR (300 MHz, DMSO-d6): δH = 0.99 (s, 3H,
CH3), 1.14 (s, 3H, CH3), 1.94 (d, J = 10.5 Hz, 1H, CH),
2.26 (d, J = 14.7 Hz, 1H, CH), 2.43 (s, 2H, CH2), 2.77 (s,
3H, CH3), 4.68 (s, 1H, CH), 5.57 (s, 2H, NH2), 7.41–7.85

6 of 13
AHADI ET AL.
SCHEME 1 Preparation of
MNP@BSAT@Cu(OAc)2 nanocatalyst
FT-IR spectrum of MNP@BSAT@Cu(OAc)2. The absorp-
tion bands at 1411, 1543 and 1211 cm−1 show that Cu is
decorated with C=N and C-O, respectively.[51,52]
thickness was evaluated in the range of 5–11 nm. It can
be found from the SEM images that the size of the cata-
lyst particles is in the nanometer range according to the
TEM images.
Figure 2 depicts the XRD of MnFe2O4 (a) and
MNP@BSAT@Cu(OAc)2 (b) nanoparticles. Patterns
show that nanoparticles have a crystalline structure at
2θ = 61.77, 56.12, 52.47, 42.52, 35.02 and 29.27, which are
attributed to intensities of 333, 422, 311, 400, 311 and
200 respectively. This can be assigned to the planes of
MnFe2O4 (JCPDS card no. 1964-73 Standard). The broad
peak at 2θ = 18–20 in the pattern (b) proves the presence
of amorphous SiO2 and shows that the MnFe2O4 nano-
particle is successfully coated with the silica layer. Using
the Williamson–Hall equation [D = 0.9 λ/β cos (θ) + 2Aε
sin(θ)] (Supplementary Information), the average size of
the crystals was estimated to be 28 nm.[53]
Furthermore,
the
EDX
spectra
for
MNP@BSAT@Cu(OAc)2 and MnFe2O4@SiO2–Pr–NH2
are shown in Figure 3b, c, which proves the presence of
Mn, Fe, O, Si, Cu,
N
and
C
elements for
MNP@BSAT@Cu(OAc)2 and the presence of Mn, Fe, O,
Si, N and C elements for MnFe2O4@SiO2–Pr–NH2.
Increasing the intensity of the Si peak relative to those of
Mn and Fe (Figure 3b, c), and also the presence of the Cu
signal in the EDX spectrum (Figure 3c) illustrates that
magnetic core was successfully functionalized. Using the
results obtained in the EDX analysis, the column diagram
(Figure 3D) was drawn up as a comparison between
Weight percent (W%) elements. Increasing the intensity of
N element in the EDX analysis confirmed the successful
functionalization of MNPs. Comparison of the data
showed the Si absorption to be higher than that of Mn and
The
morphology
and
shape
of
MNP@BSAT@Cu(OAc)2 catalyst were investigated by
FE-SEM (Figure 3a) and TEM (Figure 3e). According to
the FE-SEM images with the magnifications of 200 and
500 nm, MNP@BSAT@Cu(OAc)2 were spherical parti-
cles with the average size of 22 nm. The black spots and
colorless parts in the TEM image correspond to MnFe2O4
core and silica layer, respectively. According to the TEM
images, the sizes of the catalyst particles were <30 nm. In
addition to the TEM images, the typical silica shell
Fe.
The
N/Cu
ratio
(N/Cu
=
6)
in
MNP@BSAT@Cu(OAc)2 obtained by EDX and micro-
analysis (C 10.09, H 0.52, N 2.5%) confirmed the proposed
structure of this nanocatalyst.
The magnetic property of MnFe2O4 (a) and
MNP@BSAT@Cu(OAc)2
(b)
nanoparticles
was

AHADI ET AL.
7 of 13
FIGURE 1 (A) Fourier transform infrared
(FT-IR) spectroscopy for MnFe2O4 (a),
MnFe2O4@SiO2 (b), MnFe2O4@SiO2–Pr–NH2
(c), MNP@TCl2 (d), MNP@TDA (e),
MNP@TBSA (f), MNP@BSAT@Cu(OAc)2 (g).
(B) Expanded (d–g) spectra
FIGURE 2 The X-ray diffraction pattern
(XRD) of MnFe2O4 (a) and
(b) MNP@BSAT@Cu(OAc)2 nanoparticles
estimated at a field of ( 8000 Oe) at room temperature
by vibrating sample magnetometry analysis (Figure 4).
The S-shape curve shows the superparamagnetic
property of these nanoparticles. The magnetic satura-
tions of MnFe2O4 (a) and MNP@BSAT@Cu(OAc)2
(b) weree 33 and 17 (emu/g), respectively. The

8 of 13
AHADI ET AL.
FIGURE 3 Emission scanning
electron microscope (FE-SEM) and
transmission electron microscopy
(TEM) images of
MNP@BSAT@Cu(OAc)2, and energy
dispersive X-ray (EDX) analysis for
MNP@BSAT@Cu(OAc)2 and
MnFe2O4@SiO2–Pr–NH2
ꢀ
emanent
magnetizations
for
MnFe2O4
and
2.08% at temperature T > 200 C in curve (a) and 3% in
MNP@BSAT@Cu(OAc)2 were 1.5 and 1 Oe (left inset
of Figure 4), and also the coercivities for MnFe2O4 and
MNP@BSAT@Cu(OAc)2 were 40 and 30 emug, respec-
tively. The reduction of the magnetic property indi-
cates that the MnFe2O4 surface was successfully coated
by organic groups. The catalyst was separated using a
magnet field as shown in Figure 4 (the right inset).
The TGA analyses for MnFe2O4 (a) and
MNP@BSAT@Cu(OAc)2 (b) nanoparticles are shown in
Figure 5. The curve (a) shows a weight loss of 8.74% in two
steps for MnFe2O4 nanoparticles and the curve (b) shows a
weight loss of 18.89% in three steps for
MNP@BSAT@Cu(OAc)2 nanoparticles. A weight loss of
curve (b) is associated with the removal of organic solvents
and surface hydroxyl groups. The second step for MnFe2O4
(curve a) at 200 < T < 800 ꢀC shows a weight loss of 6.66%,
which is related to the deformation of the nanoparticle.
The second step for MNP@BSAT@Cu(OAc)2 (curve b) at
ꢀ
200 < T < 500 C shows a weight loss of 10%, which is
attributed to the removal of organic groups on the surface
of the nanoparticle. The third step, a reduction of 5.3% at
T < 500, is related to the deformation of the nanoparticles.
The catalytic study of MNP@BSAT@Cu(OAc)2 mag-
netic nanoparticles was initially started to find the opti-
mized conditions for synthesis of 1,4-dihydropyridines
via three-component condensation of dimedone (1 mmol,

AHADI ET AL.
9 of 13
FIGURE 4 Vibrating sample
magnetometry analyses of MnFe2O4 (a) and
MNP@BSAT@Cu(OAc)2 (b)
MNP@TDA, MNP@TBSA; Table 1, entries 12–16). The
reaction was also performed in the absence of a catalyst
and low yield of product was obtained in a prolonged
reaction time (Table 1, entry 9). So, the best conditions
were achieved when the reaction was carried out at room
temperature in the presence of 10 mg of hybrid
nanocatalyst [MNP@BSAT@Cu(OAc)2] in EtOH as a sol-
vent (Table 1, entry 7).
Encouraged by the obtained results and the develop-
ment of this simple procedure for synthesis of
1,4-dihydropyridines and N-arylquinolines, the reaction
was carried out in the presence of various aldehydes and
ketones bearing electron-withdrawing or electron-
donating substituents (Scheme 3 and Table 2) under opti-
mized conditions. As the results show, the yield of the
reaction with aldehydes bearing electron-withdrawing
groups is higher, which is due to there being a more
FIGURE 5 Thermogravimetric analysis analyses for MnFe2O4
(a) MNP@BSAT@Cu(OAc)2 (b) nanoparticles
0.14 g), ethyl acetoacetate (1 mmol, 0.13 ml), benzalde-
hyde (1 mmol, 0.11 ml) and ammonium acetate
(1.5 mmol, 0.12 g) as a model reaction (Scheme 2,
Table 1). Firstly, the model reaction was optimized via
variety solvents and solvent-free conditions in the pres-
ence of MNP@BSAT@Cu(OAc)2 (Table 1, entries 1–4).
Ethanol was a suitable solvent for the reaction (Table 1,
entry 1). Then, the amount of MNP@BSAT@Cu(OAc)2
as catalyst was investigated (Table 1, entries 1, 5 and 6).
The results show that 10 mg MNP@BSAT@Cu(OAc)2
was the optimal value (Table 1, entries 1, 8 and 9). Fur-
ther, the temperature was optimized for the model reac-
tion (Table 1, entries 1, 7 and 10). The efficiency and
reaction time with increasing temperature from room
ꢀ
temperature to 80 C did not changed obviously. Room
temperature was selected as the optimum temperature
(Table 1, entry 7). Finally, the catalytic activity of
MNP@BSAT@Cu(OAc)2 was compared with that of
SCHEME 2 The model reaction for the synthesis of ethyl
2,7,7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-
3-carboxylate
other
magnetic
nanoparticles
(MnFe2O4,
MnFe2O4@SiO2, MnFe2O4@SiO2–Pr–NH2, MNP@TCl2,

10 of 13
AHADI ET AL.
TABLE 1
The optimization of reaction conditions for synthesis of ethyl
2,7,7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate (6f)
Entry
1
Catalyst (mg)
Solvent
EtOH
H2O
Temperature (ꢀC)
Time (min)
Yielda (%)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (10 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (10 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (10 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (10 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (15 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (5 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (10 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (5 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (15 mg)
MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (10 mg)
—
50
30
65
60
45
30
90
30
30
30
30
260
30
30
30
30
30
95
65
70
75
94
90
94
87
94
90
40
45
56
40
76
80
2
50
3
EtOH/H2O (1:1)
—
50
4
50
5
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
50
6
50
7
r.t.
r.t.
r.t.
80
8
9
10
11
12
13
14
15
16
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
MnFe2O4@SiO2–Pr–NH@BSTA (10 mg)
MnFe2O4@SiO2–Pr–NH@TCl2 (10 mg)
MnFe2O4@SiO2–Pr–NH2 (10 mg)
MnFe2O4@SiO2 (10 mg)
MnFe2O4 (10 mg)
aIsolated yield, dimedone (1 mmol, 0.14 mg), ethyl acetoacetate (1 mmol, 0.13 ml), benzaldehyde (1 mmol, 0.11 ml) and ammonium acetate
(1.5 mmol, 0.12 mg), MnFe2O4@SiO2–Pr–NH@BSTA@Cu(OAc)2 (10 mg) as catalyst, EtOH (10 ml) at room temperature.
activate carbonyl group of these aldehydes compared
with that of ketones or aldehydes with electron-donating
groups. The efficiency of this catalyst for preparation of
the N-arylquinolines is comparable with the values
reported in the literature (Table 3). The comparison of
the catalytic activity of prepared hybrid nanocatalyst
[MNP@BSAT@Cu(OAc)2] with Yb (OTf)3, ANP and
ZnO showed that this catalyst had a better reaction time
and efficiency. Easy separation by an external magnet is
one of the advantages of this catalyst over nonmagnetic
nanoparticles such as Yb (OTF)3, ZnO and Cu(OTf)2. As
the results show, the greater efficiency of
MNP@BSAT@Cu(OAc)2 nanocatalyst for synthesis of
these compounds in EtOH as a solvent led to shorter
reaction times and higher yields.
The recovery and reusability of catalysts for commer-
cial, industrial applications and green chemistry is very
important. In view of these points, the recyclability and
reusability of nanocatalyst, MNP@BSAT@Cu(OAc)2,
were investigated for synthesis of ethyl 2,7,7-trimethyl-
5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-
SCHEME 3 The synthesis of 1,4-dihydropyridines and N-
arylquinolines in the presence of MNP@BSAT@Cu(OAc)2

AHADI ET AL.
11 of 13
TABLE 3
Comparison of MNP@BSAT@Cu(OAc)2 catalyst with other reported catalysts for synthesis of ehyl
2,7,7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate (6f)
Entry
Conditions
Catalyst
Time
6 min
20 min
5 h
Yield (%)
1
2
3
4
5
6
7
Solvent free, 50 ꢀC
Solvent free, 80 ꢀC
EtOH, r.t.
Fe3O4
89[38]
90[39]
90[54]
88[55]
92[56]
Mn@PMO-IL
Yb (OTf)3
ANP
EtOH, r.t.
4 h
EtOH, 80 ꢀC
ZnO
1 h
MW (200 W), EtOH, 100 ꢀC
Cu(OTf)2
MNP@BTAT@Cu(OAc)2
150 min
30 min
95[57]
EtOH, r.t.
94 [this work]
Abbreviation: ANP; Threo-(1S,2S)-2-amino-1-(4' -nitrophenyl)-1,3-propanediol, (Mn@PMO-IL); Manganese-containing periodic mesoporous organosilica with
ionic-liquid framework, W; Watt, Yb(OTf)3; Ytterbium(III) trifluoromethanesulfonate
3-carboxylate (6f) as a the model reaction (Scheme 2)
under optimized conditions. After completion of the reac-
tion, 10 ml of hot ethanol was added to the reaction and
the catalyst was easily separated by an external magnet.
The catalyst was washed with ethanol several times and
dried in the oven, then used again in the model reaction.
The catalyst could perform the model reaction for five
runs without significant loss in its activity (Figure 6a).
The structure of recycled catalyst after five runs was con-
sidered by FT-IR (Figure 6b), XRD (Figure 6c), EDX
(Figure 6d) and TEM (Figure 6f). The analyses clearly
confirmed that the structure of MNP@BSAT@Cu(OAc)2
showed no specific change after five runs. The amount of
copper leaching in the MNP@BSAT@Cu(OAc)2 catalyst
FIGURE 6 (a) Results for
recyclability of hybrid nanocatalyst in
the model reaction during five runs and
(b) FT-IR spectra, (c) XRD, (d) EDX,
(e) comparative column diagram (W%)
for fresh catalyst and recycled catalyst,
and (f) TEMfor recycled catalyst

12 of 13
AHADI ET AL.
SCHEME 4 Plausible mechanism for the synthesis of 1,4-dihydropyridines
after five runs was compared with that in the fresh cata-
lyst by employing ICP–OES analysis. The result showed
that the amount of copper leaching into the solvent was
negligible (1.87 × 10−3 for fresh catalyst and 1.82 × 10−3
reused catalyst). This consideration prove that the syn-
thesized hybrid nanocatalyst [MNP@BSAT@Cu(OAc)2]
has good stability and reusability during five runs.
yield and purity under green reaction conditions. The
catalyst could be recovered and reused without consider-
able reduction of its catalytic activity. The simple experi-
mental procedures, short reaction times, good to
excellent yields, ease of separation and reusability of the
catalyst, good thermal and chemical stability , and envi-
ronmentally benign conditions were the advantages of
this method.
A
suggested mechanism for synthesis of
dihydropyridines is shown in Scheme 4. The Cu(II) ion
may acts as a Lewis acid and activate the carbonyl group
of aldehyde or ketone for the condensation reactions. The
nucleophilic attack of the enol form of β-ketone on the
activated carbonyl group by catalyst afforded
compound A, which was followed by a Michael addition
by enolized ethylacetoacetate to produce B. The subse-
quent nucleophilic attack of ammonium acetate on car-
bonyl groups of B and tautomerization gave the desired
dihydropyridine as a final product.[58]
ACKNOWLEDGEMENTS
We thank the Arak University research council for pro-
viding partial support for this research.
ORCID
Akbar Mobinikhaledi https://orcid.org/0000-0002-9732-
7282
Mohammad Ali Bodaghifard https://orcid.org/0000-
0001-9732-4746
REFERENCES
4 | CONCLUSION
[1] D. Ni, W. Bu, E. B. Ehlerding, W. Cai, J. Shi, Chem. Soc. Rev.
2017, 46, 7438.
[2] Z. Hedayatnasab, F. Abnisa, W. M. A. W. Daud, Mater. Des.
2017, 123, 174.
[3] M. Arvand, S. Hemmati, Sensor. Actuat B – Chem. 2017,
238, 346.
[4] K. Ulbrich, K. Hola, V. Subr, A. Bakandritsos, J. Tucek,
R. Zboril, Chem. Rev. 2016, 116, 5338.
[5] S. J. Kim, B. Lewis, M. S. Steiner, U. V. Bissa, C. Dose,
J. A. Frank, Contrast. Media. Mol. I 2016, 11, 55.
[6] Y. Cao, L. Wen, F. Svec, T. Tan, Y. Lv, Chem. Eng. J. 2016,
286, 272.
In summary, Cu complex grafted successfully onto the
surface
of
magnetic
nanoparticles
and
the
[MNP@BSAT@Cu(OAc)2] was fabricated as an organic–
inorganic hybrid material and characterized by FT-IR,
SEM, TEM, XRD, elemental chemical analysis, TGA–
Differential gravimetric analysis (DTG) and ICP–OES
analyses. This hybrid nanomaterial as a heterogeneous
catalyst exhibited excellent catalytic activity in the syn-
thesis of 1,4-dihyropyridine and N-arylquinoline deriva-
tives. The desired products were constructed in high
[7] I. A. Adelere, A. Lateef, Nanotechnol. Rev. 2016, 5, 567.

AHADI ET AL.
13 of 13
[8] L. Luo, S. Pu, J. Tang, X. Zeng, M. Lahoubi, Appl. Phys. Lett.
2015, 106, 193507.
[38] A. Khazaei, A. R. Moosavi-Zare, H. Afshar-Hezarkhani,
V. Khakyzadeh, RSC Adv. 2014, 4, 32142.
[9] P. J. Hagrman, D. Hagrman, J. Zubieta, Angew. Chem. Int. Ed.
1999, 38, 2638.
[39] M. Nasr-Esfahani, D. Elhamifar, T. Amadeh, B. Karimi, RSC
Adv. 2015, 5, 13087.
[10] M. Eddaoudi, D. Moler, H. Li, B. Chen, T. Reineke,
M. O'Keeffe, O. M. Yaghi, Acc. Chem. Res. 2001, 34, 319.
[11] G. Férey, Chem. Mater. 2001, 13, 3084.
[40] S. K. Singh, K. N. Singh, Monatsh. Chem. 2012, 143, 805.
[41] X.-S. Wang, M.-M. Zhang, H. Jiang, C.-S. Yao, S.-J. Tu, Tetra-
hedron 2007, 63, 4439.
[12] M. E. Davis, Nature 2002, 417, 813.
[13] D. R. Xiao, E. B. Wang, H. Y. An, Y. G. Li, Z. M. Su, C. Y. Sun,
Chem. A – Eur. J. 2006, 12, 6528.
[14] H. Y. Lee, J. Park, M. S. Lah, J.-I. Hong, Cryst. Growth Des.
2008, 8, 587.
[42] S. Gao, C. H. Tsai, C. Tseng, C.-F. Yao, Tetrahedron 2008, 64,
9143.
[43] Z. Rashid, H. Naeimi, A.-H. Zarnani, M. Nazari, M.-
R. Nejadmoghaddam, R. Ghahremanzadeh, RSC Adv. 2016, 6,
36840.
[15] S. S. Han, H. Furukawa, O. M. Yaghi, W. A. Goddard Iii,
J. Am. Chem. Soc. 2008, 130, 11580.
[44] F. Dehghani, A. R. Sardarian, M. Esmaeilpour, J. Organomet.
Chem. 2013, 743, 87.
[16] H. J. Choi, M. Dinca, J. R. Long, J. Am. Chem. Soc. 2008, 130,
7848.
[45] H. Salemi, B. Kaboudin, F. Kazemi, T. Yokomatsu, RSC Adv.
2016, 6, 52656.
[17] S. S. Kaye, A. Dailly, O. M. Yaghi, J. R. Long, J. Am. Chem.
Soc. 2007, 129, 14176.
[46] N. Sohrabi, N. Rasouli, M. Torkzadeh, Chem. Eng. J. 2014,
240, 426.
[18] M. Dinca, J. R. Long, J. Am. Chem. Soc. 2007, 129, 11172.
[19] D. Azarifar, R. Asadpoor, O. Badalkhani, M. Jaymand,
E. Tavakoli, M. Bazouleh, ChemistrySelect 2018, 3, 13722.
[20] D. Azarifar, O. Badalkhani, Y. Abbasi, M. Hasanabadi, J. Iran.
Chem. Soc. 2017, 14, 403.
[21] N. Edraki, A. R. Mehdipour, M. Khoshneviszadeh, R. Miri,
Drug Discov. Today 2009, 14, 1058.
[22] J. Briede, D. Daija, M. Stivrina, G. Duburs, Cell Biochem.
Funct. 1999, 17, 89.
[23] R. P. Herrera, Organocatalytic transfer hydrogenation and
hydrosilylation reactions, in Hydrogen Transfer Reactions, (Vol.
374), Switzerland: Springer International Publishing, 2016, 105.
[24] G. D. Henry, Tetrahedron 2004, 29, 6043.
[47] M. A. Bodaghifard, S. Asadbegi, Z. Bahrami, J. Iran. Chem.
Soc. 2017, 14, 365.
[48] A. Rezaei, H. Khani, M. Masteri-Farahani, M. K. Rofouei,
Anal. Meth. 2012, 4, 4107.
[49] M. Esmaeilpour, J. Javidi, F. N. Dodeji, M. M. Abarghoui,
J. Mol. Catal A Chem. 2014, 393, 18.
[50] H. Naeimi, Z. Rashid, A.-H. Zarnani, R. Ghahremanzadeh,
New J. Chem. 2014, 38, 5527.
[51] S. Q. Memon, N. Memon, A. Mallah, R. Soomro,
M. Y. Khuhawar, Curr. Anal. Chem. 2014, 10, 393.
[52] A. Mishra, M. Soni, Metal-based Drug 2008, 875410, 2008.
[53] N. Ahadi, M. A. Bodaghifard, A. Mobinikhaledi, Appl.
Organomet. Chem. 2019, 33, e4738.
[25] S. Bahekar, D. Shinde, Acta Pharm. 2002, 52, 281.
[26] F. Bossert, H. Meyer, E. Wehinger, Angew. Chem. Int. Ed. Engl.
1981, 20, 762.
[27] S. Cosconati, L. Marinelli, A. Lavecchia, E. Novellino, J. Med.
Chem. 2007, 50, 1504.
[54] L.-M. Wang, J. Sheng, L. Zhang, J.-W. Han, Z.-Y. Fan, H. Tian,
C. T. Qian, Tetrahedron 2005, 61, 1539.
[55] S.-J. Song, Z.-X. Shan, Y. Jin, Synth. Commun. 2010, 40, 3067.
[56] F. M. Moghaddam, H. Saeidian, Z. Mirjafary, A. Sadeghi,
J. Iran. Chem. Soc. 2009, 6, 317.
[28] A. Hilgeroth, Min-Rev. Med. Chem. 2002, 2, 235.
[29] P. Beagley, M. A. Blackie, K. Chibale, C. Clarkson, R. Meijboom,
J. R. Moss, P. J. Smith, H. Su, Dalton Trans. 2003, 3046.
[30] Y. Sawada, H. Kayakiri, Y. Abe, T. Mizutani, N. Inamura,
M. Asano, C. Hatori, I. Aramori, T. Oku, H. Tanaka, J. Med.
Chem. 2004, 47, 2853.
[57] K. K. Pasunooti, C. Nixon Jensen, H. Chai, M. L. Leow, D.-
W. Zhang, X.-W. Liu, J. Combin. Chem. 2010, 12, 577.
[58] H. Alinezhad, S. M. Tavakkoli, Res. Chem. Intermediates 2015,
41, 5931.
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
[31] Z. Ma, Y. Hano, T. Nomura, Y. Chen, Bioorg. Med. Chem. Lett.
2004, 14, 1193.
[32] K. S. Atwal, G. C. Rovnyak, S. D. Kimball, D. M. Floyd,
S. Moreland, B. N. Swanson, J. Z. Gougoutas, J. Schwartz,
K. M. Smillie, M. F. Malley, Med. Chem. 1990, 33, 2629.
[33] G. Mohammadi Ziarani, S. Mousavi, N. Lashgari, A. Badiei,
M. Shakiba, Iran.J. Chem. Chem Eng. 2013, 32, 9.
[34] M. A. Zolfigol, A. G. Choghamarani, M. Shahamirian,
M. Safaiee, I. Mohammadpoor-Baltork, S. Mallakpour,
M. Abdollahi-Alibeik, Tetrahedron Lett. 2005, 46, 5581.
[35] A. Zare, F. Abi, A. R. Moosavi-Zare, M. H. Beyzavi,
M. A. Zolfigol, J. Mol. Liq. 2013, 178, 113.
How to cite this article: Ahadi N,
Mobinikhaledi A, Bodaghifard MA. One-pot
synthesis of 1,4-dihydropyridines and N-
arylquinolines in the presence of copper complex
stabilized on MnFe2O4 (MFO) as a novel organic–
inorganic hybrid material and magnetically
retrievable catalyst. Appl Organomet Chem. 2020;
e5822. https://doi.org/10.1002/aoc.5822
_
_
ꢀ
[36] R. S¸ims¸ek, U. B. Ismailoglu, C. S¸afak, I. Sahin-Erdemli, Il
Farmaco 2000, 55, 665.
[37] M. Tajbakhsh, H. Alinezhad, M. Norouzi, S. Baghery,
M. Akbari, J. Mol. Liq. 2013, 177, 44.