Synthesis of a new Ni complex supported on CoFe2O4 and its application as an efficient and green catalyst for the synthesis of bis(pyrazolyl)methane and polyhydroquinoline derivatives

Article abstract of DOI:10.1039/d0nj00223b

Effective research in green chemistry requires new and applicable synthetic techniques. In this regard, for the first time, a green method is reported for the immobilization of iminodiacetic acid-Ni complex on the surface of CoFe₂O₄

Full text of DOI:10.1039/d0nj00223b

View Article Online
View Journal
NJC
New Journal of Chemistry
Accepted Manuscript
A journal for new directions in chemistry
This article can be cited before page numbers have been issued, to do this please use: T. Tamoradi, S. M.
Mousavi and M. Mohammadi, New J. Chem., 2020, DOI: 10.1039/D0NJ00223B.
Volume 42
Number
March 2018
Pages 3963-4776
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
6
21
NJC
New Journal of Chemistry
rsc.li/njc
A journal for new directions in chemistry
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
rsc.li/njc

Page 1 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
Synthesis of new Ni complex supported on CoFe O and its application as an efficient
DOI: 10.1039/D0NJ00223B
2
4
and green catalyst for the synthesis of bis(pyrazolyl)methane and polyhydroquinoline
derivatives
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Taiebeh Tamoradi, a, Seyedeh Masoumeh Mousavi,b Masoud Mohammadi
c
a
Department of Chemistry, Islamic Azad University, Izeh, Iran.
e-mail: t.tabss@yahoo.com
b
College of Environmental, Karaj, Iran.
c
Department of Chemistry, Faculty of Science, Ilam University, Ilam, Iran
Abstract
Effective research in green chemistry require to new and applicable synthetic
techniques. In this regard, for the first time, a green method was reported for
immobilization of iminodiacetic acid-Ni complex on the surface of CoFe O magnetic
2
4
nanoparticles. This obtained nanoparticle was characterized by chemical and physical
techniques such as Fourier-transform infrared spectroscopy (FTIR), X‐ray Diffraction
(
XRD), energy-dispersive X-ray analysis (EDX), inductively coupled plasma - optical
emission spectrometry (ICP-OES), scanning electron microscopy (SEM), X-ray mapping
and thermal gravimetric analysis (TGA) techniques. In addition, The catalytic activity
of prepared nanocomposite was examined in the synthesis of polyhydroquinoline and
bis(pyrazolyl)methane derivatives in green conditions. It was be observed that all
products were obtained in short reaction times and good to excellent yields. More
importantly, the catalyst was easy recovered and recycled by magnetic field for five
successive times without noticeable decrease in its catalytic activity.

Address correspondence to Department of Chemistry, Islamic Azad University, Izeh, Iran; e-
mail: t.tabss@yahoo.com (T. Tamoradi).

New Journal of Chemistry
Page 2 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
Keywords:
Ni,
Magnetic
nanoparticles,
Green,
polyhydroquinoline,
DOI: 10.1039/D0NJ00223B
bis(pyrazolyl)methane
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
.
Introduction
Green chemistry provided twelve principles, which has been work at the molecular level 1–6.
This important review has attracted widespread interest in reduce or eliminate the use and
generation of hazardous chemical products 7–9. Future trends in this field are discussed with the
challenge of using the green chemistry in design of ecofriendly catalysts in important organic
synthesis10,11. The use of greener nanoscience is a proactive approach to advancing applications
and reducing implications of nanotechnology 2,7,12–15. Recently studies show that the risks of
toxic materials of chemical processes and reaction pathways have been minimized by using
nanotechnology in the control of green chemistry 7,16–20. Nanotechnology were extensively
developed because its application in multidisciplinary field such as engineering, biology,
physics, and chemistry21,22. Recent years have witnessed increased attentions on the use of
nanotechnology in the water purification, targeted delivery of anticancer drugs, electronics,
catalyst and imaging contrast agents 7,10,23–25. Recently studies were shown that nanomaterials
with their outstanding properties such as unique shapes, nanometric-size, particle size
distribution and high surface to volume ratio, have extensively attracted attentions in important
organic synthesis as catalyst 7,26–30
.
Recently, magnetic nanoparticles were extensively used as catalytic supports in chemical
synthesis 2,7,31,32. In this regard, CoFe O MNPs have been developed because of their
2
4
properties such as storage devices, magnetic polystyrene nanocomposites, permanent magnets,
ferrofluids, magnetic recording, supercapacitor, drug carrier, biomedicine, electronics,
catalysis, sensors and pigments etc 26,33–36
.

Page 3 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
On other hand, N-contain heterocycle compounds have received profound attention due
to their inevitable role in various fields i.e. organic synthesis, material science,
photography, information recording systems and explosives, organometallic chemistry,
medicinal chemistry, ligands in coordination chemistry, ability to modulate calcium
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
channels and treatment of cardiovascular diseases 7,17,22,37–41
.
In order to synthesis of N-contain heterocycle compounds, many heterogeneous
catalysts based on supports including carbon 15,42, ionic liquids 43,44, spinel ferrite
7,21,22,45,46,
molecular sieves (SBA-15 and MCM-41) 17,47, Boehmite , and polymers
has been used. Nevertheless, due to their simple and easy recycling, spinel ferrite
MNPs, especially cobalt ferrite nanoparticles such as magnetite (CoFe O ) is a suitable
16
48–
50
2
4
support for different catalysts.
In this regard, a novel magnetic nanocatalyst was prepared by anchoring Ni complex on
the surface of CoFe O MNPs and its catalytic activity was examined in the synthesis
2
4
of polyhydroquinoline and bis(pyrazolyl)methane derivatives by one-pot
multicomponent reactions. The use of Ni complex and magnetic nanoparticles as green
materials is one of outstanding properties of this nanocatalyst. Moreover, High surface
area, convenient recovery and reusability for several times without any significant loss
of activity, inexpensive and chemically stable reagents, good reaction times and simple
practical methodology; makes this protocol both attractive and economically viable.
2
.
Experimental
.1. Materials
For the synthesis of catalyst CoCl .6H O, FeCl .6H O, Ni(NO ) and iminodiacetic
2
2
2
3
2
3 2
acid, were purchased from Sigma-Aldrich. Also, all reagents and solvents in organic
synthesis were obtained from Merck and used without further purification.

New Journal of Chemistry
Page 4 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
2
.2. Characterization methods
The particle size and morphology of the nanostructures were studied using a FESEM-
TESCAN MIRA3 microscope equipped with EDX. FT-IR spectra of all samples were
acquired by KBr disc using a VRTEX 70 model BRUKER FT-IR spectrophotometer.
The powder XRD of the catalyst weredone using Co Kα radiation (λ= 1.78897 Å) with
operating at 40 keV, and a cathode current of 40 Ma in the scanning range of 2θ = 5 to
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
8
0.
2
.3. Synthesis of CoFe O @IDA-Ni MNPs nanocatalyst
2
4
The CoFe O MNPs were prepared by the coprecipitation technique as it was previously
2
4
4
6
reported by our group . Then, 1.5 mL of (3-Chloropropyl)trimethoxysilane (CPTMS)
and 1 g of CoFe O were dissolved in 20 mL toluene under stirring conditions.
2
4
Subsequently, the reaction mixture was refluxed for 24 hour. The final product was
separated by an external magnet and washed with hexane and dried in oven at 70 °C to
CoFe O @CPTMS MNPs product. Afterwards, the obtained CoFe O @CPTMS MNPs
2
4
2
4
(
0.1 g) was dispersed in 25 mL toluene by sonication for 30 min. and, then, 0.33 g of
iminodiacetic acid and 1.5 mL of triethylamine were added to the reaction mixture
which was stirred under the N atmosphere at reflux conditions for 48 h. The final
2
powder was separated by an external magnet and washed with ethanol/deionized water
and dried in oven at 70 °C to give CoFe O @IDA MNPs. Finally, in order to prepare
2
4
CoFe O @IDA-Ni organometallic complex, the obtained CoFe O @IDA MNPs (0.1 g) was
2
4
2
4
dispersed in 30 mL ethanol by sonication for 30 min. Ni(NO ) was added to the reaction
3
2
mixture which was stirred under the N atmosphere at reflux conditions (80 °C) for 16 h
.
2
Subsequently, the reaction mixture was cooled to room temperature and, then, the final
CoFe O @IDA-Ni MNPs were isolated, using an external magnet, from the reaction mixture,
2
4

Page 5 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
washed by ethanol/water to remove the remaining impurities and, finally, dried in an oven at
7
0°C for 8 h.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
.4. General procedure for the synthesis of polyhydroquinolines
A mixture of Aromatic aldehyde (1mmol), ammonium acetate (1.2 mmol), dimedone (1 mmol)
and ethyl acetoacetate (1 mmol) the perecence of CoFe O @IDA-Ni MNPs (35 mg) was
2
4
dissolved in ethanol (3 mL) and then, stirred under reflux conditions for an appropriate time.
The progress of the reaction was monitored by thin-layer chromatography (TLC) (acetone : n-
hexane 3:7). After completion of the reaction, hot ethanol (10 mL) was added to the reaction
vessel and the catalyst was separated using an external magnet and washed with ethyl acetate
and acetone. Then, the solvent evaporated and all products were recrystallized from ethanol.
The pure polyhydroquinoline derivatives were obtained in excellent yields (88-98%).
2
.5. General procedure for the synthesis of bis(pyrazolyl)methanes
A mixture of ethyl acetoacetate (2 mmol), phenylhydrazine (2 mmol), and aldehyde(1 mmol)
in the presence of CoFe O @IDA-Ni MNPs (50 mg) was dissolved in DMSO (3mL) and
2
4
then, stirred at of 80 °C for an appropriate time. The progress of the reaction was monitored by
thin-layer chromatography (TLC). Upon the completion of the reaction, the mixture was cooled
down to room temperature and the catalyst was separated by the magnetic seperation and
washed with ethyl acetate and acetone, then, the reaction mixture was extracted with water and
ethyl acetate. The organic layer was dried over Na SO . Afterward, the solvent was evaporated,
2
4
and the resulting precipitate was recrystallized from hot ethanol (95%) to give the pure product.

New Journal of Chemistry
Page 6 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
2
.6.
Selected spectral data
After successful synthesis of bis(pyrazolyl)methane and polyhydroquinoline derivatives, some
1
13
of the obtained products have been identified by H NMR, C NMR. Also, melting point of
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
all products were compared with authentic literatures. These melting point of products are in
good agreement with authentic literatures.
1
Table 2 Product 1 : H NMR (400 MHz, DMSO-d ) δ (ppm): 5.50 (s, 1H, CH), 7.29 (d, 2H, J = 8.2
6
Hz, NH ), 7.44 (m, 4H, Ar-H), 8.06- 7.88 (m, 4H, Ar-H), 8.15 (m, 1H, Ar-H), 8.32-8.23 (m, 1H, Ar-
2
H), 8.45 (d, J = 7.9 Hz, 1H, Ar-H), 9.23 (d, J = 7.9 Hz, 1H, Ar-H).
1
Table 2 Product 14 : HNMR (300 MHz, DMSO-d ) δ (ppm): 5.37 (s, 1H, CH), 7.24 (d, J=
6
8
.4, 2H, NH ), 7.37 (d, J=8.02, 4H, Ar-H), 7.94-7.85 (m, 7.4, 4H, Ar-H), 8.02 (d, J=2.8, 1H,
2
Ar-H), 8.18-8.15 (m, 1H, Ar-H), 8.36 (d, J = 7.78, 1H, Ar-H), 9.1 (d, J=7.67, 1H, Ar-H).
1
Table 4 Product 2 : H NMR (500 MHz; DMSO-d ): δ (ppm) 2.26 (s, 6H, 2CH ), 4.92 (s, 1H,
6
3
CH, methine), 7.16-7.22 (m, 4H, Ar-H), 7.28 (d, J = 8.5 Hz, 2H, Ar-H), 7.38 (t, J = 8.0 Hz, 4H,
1
3
Ar-H), 7.65 (d, J = 7.8 Hz, 4H, Ar-H), 12.46 (br, 1H, OH), 13.84 (s, 1H, OH); C NMR (125
MHz; DMSO-d ): δ (ppm) 12.2, 33.2, 121.2, 126.3, 128.7, 129.6, 129.8, 131.2, 137.9, 141.8,
6
1
46.9.
1
Table 4 Product 3 : H NMR (500 MHz; DMSO-d ): δ (ppm) 2.23 (s, 6H, 2CH ), 5.04 (s,
6
3
1H, CH, methine), 7.08 (t, J = 7.3 Hz, 1H, Ar-H), 7.18 (t, J = 7.2 Hz, 2H, Ar-H), 7.28 (t, J =
7
7
.3 Hz, 1H, Ar-H), 7.37 (t, J = 7.9 Hz, 4H, Ar-H), 7.51 (d, J = 7.9 Hz, 1H, Ar-H), 7.63 (d, J =
.9 Hz, 4H, Ar-H), 7.76 (d, J = 6.5 Hz, 1H, Ar-H), 12.43 (br, 1H, OH), 13.71 (s, 1H, OH);
1
3
C NMR (125 MHz; DMSO-d ): δ (ppm) 12.6, 34.8, 104.5, 121.0, 123.3, 126.1, 127.9,
6
128.8, 129. 4, 131.0, 133.3, 137.6, 141.5, 146.7.
1
Table 4 Product 7 : H NMR (500 MHz; DMSO-d ): δ (ppm) 2.34 (s, 6H, 2CH3), 3.67 (s, 3H,
6
OCH ), 3.70 (s, 3H, OCH ), 4.91 (s, 1H, CH, methine), 6.84 (d, J = 10.0 Hz, 1H, Ar-H), 6.86
3
3
(d, J = 10.0 Hz, 1H, Ar-H), 6.93 (s, 1H, Ar-H), 7.23 (t, J = 7.3 Hz, 2H, Ar-H), 7.44 (t, J = 7.9
13
Hz, 4H, Ar-H), 7.73 (d, J = 7.9 Hz, 4H, Ar-H), 11.68 (br, 1H, OH), 14.11 (s, 1H, OH); C

Page 7 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
NMR (125 MHz; DMSO-d ): δ (ppm) 12.2, 33.5, 56.0, 105.4, 112.1, 112.2, 119.8, 121.1,
6
1
26.0, 129.4, 135.5, 137.9, 146.7, 147.8, 148.9.
1
Table 4 Product 10 : H NMR (500 MHz; DMSO-d6): δ (ppm) 2.28 (s, 12H, 4CH ), 4.86 (s,
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
13
2
H, CH, methine), 7.16-7.67 (m, 24H, Ar-H), 12.43 (br, 2H, OH), 14.09 (s, 2H, OH); C NMR
(125 MHz; DMSO-d6): δ (ppm) 12.1, 33.3, 121.1, 126.0, 127.4, 129.3, 140.5, 146.7.
3
3
. Results and discussion
.1. Catalyst charactrization
After preparation of CoFe O @IDA-Ni MNPs (Scheme 1) from available and green
2
4
materials, the structure of this nanocatalyst was characterized by FT-IR, XRD, EDX, ICP-OES,
SEM, X-ray mapping and TGA techniques.
NaOH
CPTMS
Dionized water
N , Reflux 1 h
Toluene
CoFe O @CPTMS MNPs
FeCl3.6H2O
CoCl2.6H2O
2
CoFe O MNPs
2
4
2
4
O
R
O
Iminodiacetic Acid Toluene
OEt
N
H
Ni(NO3)2
O
O
+
OH
OEt
EtOH, Reflux
+
H
R
O
CoFe O @IDA MNPs
2
4
CoFe O @IDA-Ni MNPs
+
2
4
NOHAc
CHO
O
EtO
O
OH HO
2
+
OH2
Ph
Ph
N
N
N
N
+
Cl
2 PhHN NH2
Cl

New Journal of Chemistry
Page 8 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
2 4
Scheme 1. Synthesis of CoFe O @IDA-Ni MNPs.
The FT-IR spectra of CoFe O and CoFe O @IDA-Ni MNPs was performed in the 400–4000
2
4
2
4
-1
−1
cm in Fig. 1. Two strong absorption band in around 3400-3500 and 580 cm in both of
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
1
samples contributed to O-H and Fe-O stretching vibrations, respectively . These data clearly
proved the successful synthesis of CoFe O nanoparticles. According to the spectra of
2
4
CoFe O @IDA-Ni MNPs, the presence of absorption bands around 2850-2950 and 1720 cm-1
2
4
is attributed to aliphatic C-H stretching vibration and C=O stretching vibration,
respectively16,52. Therefore, immobilization of IDA-Ni complex on CoFe O was clearly
2
4
verified by FT-IR spectra.
C
2 4 2 4
Fig. 1 FT-IR spectrum of CoFe O (a) and CoFe O @IDA-Ni MNPs (b).
The powder X-ray diffraction (XRD) of nanocomposite was performed to investigation of
structural and textural properties (Fig. 2). It was be found that a highly crystalline cubic system
of CoFe O can be observed with presence of seven sharp diffraction peaks at diffraction angles
2
4
2θ = 3521.9, 35.4, 41.3, 50.8, 63.9, 67.8 and 74.3 related to (1 1 1), (2 2 0), (3 1 1), (4 0 0), (4
2), (5 1 1), and (4 4 0) reflections, respectively 51,53. which are in agreement with the standard
2
4
6
patterns of CoFe O crystal structure .
2
4

Page 9 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2 4
Fig.2 XRD pattern of CoFe O @IDA-Ni MNPs.
As observed in Fig. 3, the presence of Fe, Co, Si, C, O, N and Ni specie in the structure of
CoFe O @IDA-Ni nanocomposite was confirmed by the energy-dispersive X-ray spectroscopy
2
4
(EDX) analysis. These observations show that Ni complex immobilized on the surface of
-3
-1
CoFe O . The quantitative amount of Ni active sites was obtained to be 1.11 ×10 mol.g using
2
4
the ICP-OES technique.

New Journal of Chemistry
Page 10 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2 4
Fig. 3 EDX spectrum of CoFe O @IDA-Ni MNPs.
Also, Morphology of magnetic nanocatalyst was studied by FE-SEM (Fig. 4). The images of
this nanocomposite shows that the shape of nanoparticle is uniform nanometer in quasi-
spherical with a range of diameter about 25 nm. Therefore, high active sites are available for
immobilization of Ni on the surface of CoFe O nanoparticles.
2
4

Page 11 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Fig. 4 SEM images of CoFe
O
2 4
@IDA-Ni MNPs at 2μ (a), 1μ (a) and 500 nm (c) and 200 nm (d)
magnifications.
In addition, nanoparticle probes with EDX atomic mapping analysis (Fig. 5). C, N, Co, Fe, O
and Ni species were well distributed in the nanocomposite. On the other hand, the existence of
C, N, O and Ni species in the composite further confirms the successful immobilization IDA-Ni
complex on magnetic nanoparticles.

New Journal of Chemistry
Page 12 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2 4
Fig. 5 The X-ray map analysis of CoFe O @IDA-Ni MNPs.
Thermo‐gravimetric analysis (TGA) of CoFe O @IDA-Ni MNPs is presented (Fig. 6). The first
2
4
weight loss below 200 °C corresponds to the removal of the physically and chemically
adsorbed solvents or surface hydroxyl groups, and the second weight loss in the range of
2
00‐600 °C is related to the decomposition of the organic layers on the surface of CoFe O .
2
4
TGA curve of the CoFe O @IDA-Ni nanocatalyst shows a weight loss more than 9% from 200
2
4
to 600 °C, resulting from the decomposition of immobilized organic spaces on the CoFe O
2
4
surface.

Page 13 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Fig. 6. TGA curve of CoFe O @IDA-Ni MNPs.
2
4
3
.2.
Catalytic studies
After characterization of the synthesized CoFe O @IDA-Ni, its catalytic activity was
2
4
evaluated in multicomponent reactions (including the synthesis of polyhydroquinoline and
bis(pyrazolyl)methane derivatives). Initially, the catalytic properties of CoFe O @IDA-Ni
2
4
were examined in in four component Hantzsch synthesis of polyhydroquinoline derivatives.
To find the best conditions for the Hantzsch reaction, the four component reaction of
dimedone (1 mmol), 4-chlorobenzaldehyde (1 mmol), ethyl acetoacetate (1 mmol) and
ammonium acetate (1.2 mmol) under different conditions was selected as the model reaction
(
Scheme 2), then the effect of various parameters such as catalyst concentration, temperature
and solvent investigated on the model reaction. It was be found that the best conditions were
obtained in the presence of 35 mg of the catalyst in EtOH under reflux conditions (Table 1).

New Journal of Chemistry
Page 14 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
Cl
O
O
H
Catalyst
O
O
O
Cl
Solvent, 
+
OEt
O
O
N
H
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
NH OAc
4
OEt
Scheme 2 Optimization of reaction conditions for the Hantzsch synthesis of polyhydroquinolines in
the presence of CoFe O @IDA-Ni MNPs.
2
4
2 4
Table 1 Optimization for the Synthesis of polyhydroquinolines in the presence of CoFe O @IDA-
Ni MNPs.
Entrya
Catalyst
Cat.(mg)
Solvent
Temp.(ºC)
Time.(min)
Yielda
%)
(
1
CoFe O @IDA-Ni
-
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
80
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
N.R
27
2
4
2
CoFe O @IDA-Ni
0.5
10
15
20
25
30
35
35
35
35
35
35
35
35
35
35
2
4
3
CoFe O @IDA-Ni
37
2
4
4
CoFe O @IDA-Ni
51
2
4
5
CoFe O @IDA-Ni
68
2
4
6
CoFe O @IDA-Ni
84
2
4
7
CoFe O @IDA-Ni
95
2
4
8
CoFe O @IDA-Ni
98
2
4
9
CoFe O @IDA-Ni
H
2
O
67
2
4
10
11
12
13
CoFe O @IDA-Ni
EtOH: H
2
O (1:1)
82
2
4
CoFe O @IDA-Ni
Solvent free
Solvent free
Solvent free
PEG-400
EtOH
52
2
4
CoFe O @IDA-Ni
100
83
2
4
CoFe O @IDA-Ni
120
90
2
4
1
1
1
1
4
5
6
7
CoFe O @IDA-Ni
80
84
2
4
CoFe O @IDA-Ni
25
Trace
53
2
4
CoFe O @IDA-Ni
EtOH
50
2
4
CoFe O @IDA-Ni
EtOH
60
78
2
4

Page 15 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
1
8
CoFe O @IDA-Ni
35
EtOH
70
30
91
2
4
a
Isolated Yield.
After the optimization of reaction conditions, a wide variety of polyhydroquinoline were
prepared under optimized conditions (Scheme 3). Besides, all products were obtained in short
reaction times and good to excellent yields in which authenticated by comparing with standard
samples. The obtained results have been summarized in Table 2.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
O
O
R
H
O
O
R
+
Catalyst
O
OEt
EtOH, 80°C
N
O
O
H
NH OAc
4
OEt
2 4
Scheme 3. Synthesis of various polyhydroquinoline derivatives in the presence of CoFe O @IDA-Ni
MNPs.
Table 2. Synthesis of polyhydroquinoline derivatives polyhydroquinolines in the presence of
CoFe
2
O
4
@IDA-Ni MNPs.
M.P
Time
Yield
(%)
Entry
aldehyde
product
b
(min)
Measured
242-245
Reported
Cl
2
43-245 54
30
98
O
O
O
1
H
H
OEt
Cl
N
H
Me
O
2
52–255 55
50
94
253-255
Me
O
O
2
OEt
N
H

New Journal of Chemistry
Page 16 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
O
OMe
2
51-252 17
H
45
96
91
89
93
251-253
214–216
189–192
141–143
MeO
MeO
F3C
O
O
O
O
3
4
5
6
OEt
OEt
OEt
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
N
H
OMe
O
MeO
O
16–218 56
2
1
1
2
H
60
45
45
OMe
N
H
CF3
O
88–190 56
40–142 56
03–205 54
H
O
N
H
CN
O
H
NC
O
O
O
O
OEt
OEt
N
H
O
O
H
H
35
60
97
91
201–204
229–231
7
8
N
H
OH
O
231-234 57
O
OEt
OH
N
H

Page 17 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
O
OH
2
2
2
25–227 54
49–251 54
31–233 54
H
55
93
224–226
HO
O
O
9
OEt
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
N
H
Br
O
H
45
95
249–251
O
O
O
1
1
Br
OEt
OEt
N
H
O
Br
O
H
30
88
231–233
1
2
Br
N
H
F
O
H
45
91
180–183
O
O
13
F
1
80–182 54
OEt
N
H
NO2
O
H
50
95
242–244
O N
2
O
O
1
4
241–243 54
OEt
N
H
O
NO2
76–177 56
1
H
15
O
O
3
0
91
172–175
OEt
NO2
N
H

New Journal of Chemistry
Page 18 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
O
OH
HO
67-169 56
1
H
O N
16
2
3
0
88
168-170
O
O
NO2
OEt
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
N
H
O
NMe2
H
7
5
93
262–264
Me N
O
O
261–263 54
2
1
7
OEt
N
H
a
Reaction conditions: aromatic aldehyde (1.0 mmol), dimedone (1mmol), ethyl acetoacetate (1 mmol), and ammonium
acetate (1.2 mmol), catalyst (35 mg) and EtOH (3 mL).
b
Isolated yield.
A plausible mechanism for the multicomponent synthesis of polyhydroquinolines on the basis
of previous reports has been depicted in Scheme 4.
NH OAc
4
O
O
HOAc
NH2
H
+
O
NH3
O
Ar
EtO
O
Ar
H
O
O
Ar
O
O
OEt
O
N
H
EtO
NH3
O
Ar
O
O
HOAc
+
H
OEt
O
H
NH2
Ar
NH OAc
4

Page 19 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
2 4
Scheme 4. Proposed mechanism for the synthesis of polyhydroquinolines in the presence of CoFe O @IDA-
Ni MNPs.
Next, the catalytic activity of CoFe O @IDA-Ni for the synthesis of 4,4'-(arylmethylene)-bis-
2
4
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives via one-pot, multi-component domino
Knoevenagel condensation– Michael addition–cyclization Reactions was investigated. For this
purpose, the domino reaction of ethyl acetoacetate (2 mmol), phenylhydrazine (2 mmol), and
aldehyde (1 mmol) was selected as the model reaction to optimize the reaction conditions
(
Scheme 5). then the effect of various parameters such as catalyst concentration, temperature
and solvent investigated on the model reaction. It was be found that the best reaction conditions
were obtained in the presence of 50 mg of the catalyst in DMSO as solvent at 80 °C (Table 3).
OH HO
Ph
Ph
N
N
CHO
Cl
EtO
PhHN NH2 + 2
N
N
O
O
Catalyst
Solvent, 
2
+
Cl
Scheme 5 Optimization of reaction conditions for the synthesis of 4,4'-((4-
chlorophenyl)methylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) in the presence of
CoFe O @IDA-Ni MNPs.
2
4
Table 3. Optimization of the reaction condition for the preparation of 4,4'-((4-
Chlorophenyl)methylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ol)
Entry
Catalyst
Temperature
(oC)
Time
(min)
Yielda
(%)
Cat.(mg)
Solvent
1
2
3
-
-
5
DMSO
DMSO
DMSO
80
80
80
1 day
45
Trace
CoFe O @IDA-Ni
2
4
3
5
1
4
CoFe O @IDA-Ni
10
45
2
4

New Journal of Chemistry
Page 20 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
039/D0NJ00223B
9
4
5
6
7
8
9
CoFe O @IDA-Ni
20
DMSO
DMSO
DMSO
DMSO
80
80
80
80
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
2
4
DOI: 10.1
7
CoFe O @IDA-Ni
30
40
50
50
50
50
50
50
50
50
50
50
50
50
2
4
8
9
7
5
CoFe O @IDA-Ni
2
4
CoFe O @IDA-Ni
2
4
98
NR
Trace
83
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
CoFe O @IDA-Ni
2
4
H O
2
80
Reflux
Reflux
Reflux
80
CoFe O @IDA-Ni
2
4
H O
2
10 CoFe O @IDA-Ni
2
4
Acetonitrile
EtOH
11 CoFe O @IDA-Ni
2
4
74
1
1
1
1
2
3
4
5
CoFe O @IDA-Ni
2 4
PEG-400
DMF
70
CoFe O @IDA-Ni
2
4
80
88
CoFe O @IDA-Ni
2
4
Solvent free
80
49
CoFe O @IDA-Ni
2
4
Solvent free
DMSO
120
73
16 CoFe O @IDA-Ni
2
4
2
4
6
7
5
0
0
5
NR
67
1
1
1
7
8
9
CoFe O @IDA-Ni
DMSO
DMSO
DMSO
2
4
CoFe O @IDA-Ni
2
4
82
CoFe O @IDA-Ni
50
2
4
91
aIsolated yield
The conditions thus optimized were applied in the synthesis of 4,4'-(arylmethylene)-bis-(3-
methyl-1-phenyl-1H-pyrazol-5-ol) derivatives (Scheme 6) and all products obtained in good to
excellent yields and short reaction times (Table 4).
OH HO
Ph
Ph
CHO
EtO
N
N
O
O
Catalyst (50 mg)
N
N
PhHN NH2
+
+
DMSO, 80°C Reflux
Cl
2
mmol
2 mmol
1 mmol
Cl
Scheme 6. Synthesis of various 4,4'-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives in the
presence of CoFe @IDA-Ni MNPs..
2
O
4

Page 21 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
Table 4. Preparation of 4,4'-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives catalyzed by
a
CoFe
2
O
4
@IDA-Ni MNPs.
Time
(min)
M.P. (ºC)
Entry
aldehyde
Product
Yield (%)b
Measured literature
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
O
H
Me
Me
1
70–172
1
35
97
169-171
212-214
5
8
N
N
N
N
Ph
Ph
Ph
OH HO
Cl
O
H
Me
Me
213–215
2
Cl
45
98
5
9
N
N
N
N
Ph
OH HO
O
Br
Me
H
O
Me
198–200
3
4
45
45
97
96
198-200
200-203
6
0
Br
N
N
N
N
Ph
Ph
Ph
OH HO
Me
H
Me
Me
202–204
5
8
Me
N
N
N
N
Ph
OH HO
OMe
O
H
Me
Me
173–175
5
MeO
45
92
172-174
5
9
N
N
N
N
Ph
Ph
Ph
OH HO
OH
O
H
Me
Me
153–155
6
HO
40
90
154-155
5
9
N
N
N
N
Ph
OH HO

New Journal of Chemistry
Page 22 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
O
OMe
MeO
Me
H
Me
194–196
7
MeO
60
94
193-196
5
9
OMe
N
N
N
N
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Ph
Ph
OH HO
O
NO2
H
Me
Me
225–227
8
9
O N
2
30
60
89
92
224-226
151-153
60
N
N
N
N
Ph
Ph
Ph
Ph
OH HO
NO2
O
H
Me
Me
1
51-153
6
1
N
N
N
N
NO2
OH HO
Ph
Ph
N
N
H
O
H
OH HO
N
N
Me
Me
2
14–216
1
0
180
88
213-215
60
O
Me
Me
N
N
N
N
Ph
Ph
OH
HO
a
Reaction conditions: 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (1 mmol), aldehyde (2 mmol), catalyst (50 mg),
in DMSO at 80 °C.
Isolated yield.
b
Proposed mechanism for synthesis of bis(pyrazolyl)methanes using CoFe O @IDA-Ni MNPs,
2
4
has been shown in Scheme 7.

Page 23 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
Ph-NHNH2
-
H O
2
HN
NH
O
O
..
O
Me
OEt
Ph
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
OEt
O
O
Me
OEt
Ph
N N
O
Me + EtOH
(I)
Me
Me
O
Ar
Ph
N N
Me
Me
N
Ar
N
N
HO
Me
O
N
N
N
N
Ph
Ph
(II)
OH
(IV)
N
Ph
Ph
OH HO
Knoevenagel
condensation
bis(pyrazolyl)methanes
Ar
H
Ph
O
addition
Ph
Ph
Michael
Me
N N
N N
N N
Me
O
Me
HO
Ar
(
I)
(II)
(III)
Scheme 7. Proposed mechanism for the synthesis of bis(pyrazolyl)methanes in the presence
of CoFe O @IDA-Ni MNPs.
2
4
3
.3.
Reusability study of catalyst
The easy recovery of catalyst is very important in terms of sustainable and economic chemistry
viewpoints. Therefore, recovery and reusability of CoFe O @IDA-Ni was evaluated in the
2
4
synthesis of ethyl-4-(4-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3
carboxylate and 4,4'-((4-Chlorophenyl)methylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ol)

New Journal of Chemistry
Page 24 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ00223B
(
Fig. 7). The results were shown the high stability and high reusability of catalyst under
working conditions.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2 4
Fig.7 Reusability of CoFe O @IDA-Ni MNPs in the in the synthesis of ethyl-4-(4-chlorophenyl)-2,7,7-
trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3 carboxylate (a) and 4,4'-((4-Chlorophenyl)methylene)bis(3-
methyl-1-phenyl-1H-pyrazol-5-ol) (b).
`
3
.4. Hot filtration
The stability of CoFe O @IDA-Ni MNPs in the reaction was tested using the hot filtration test.
2
4
The hot filtration test was performed in the synthesis of ethyl-4-(4-chlorophenyl)-2,7,7-
trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3 carboxylate under optimal reaction
conditions. At the first, after 15 min (half reaction time), the corresponding product obtained
in 59 % of yield. Then, the reaction was repeated, and at the half time of the reaction, the
catalyst was separated and the reaction mixture was allowed to react further (in the absence of
catalyst). It was be found that only a trace conversion (<2%) of the condensation reaction was
performed upon the heating of the catalyst-free solution for another 15 min. These observation
shows the high stability of catalyst.
3
.5. Leaching study
In order to investigation of the leaching of Ni into the reaction media, ICP-OES analysis was
performed. In this case, the Ni content in the reaction media in synthesis of ethyl-4-(4-
chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3 carboxylate, as the

Page 25 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
representative example was found to be 0.89% in which show the negligible leaching of Ni
during the reaction process.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
.6. Comparison
As it can be seen in the Table 5 and 6, the efficiency of synthesis prepared catalyst in the
synthesis of 4,4'-((4-Chlorophenyl)methylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) and
ethyl-4-(4-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3 carboxylate
derivatives was compared with literature. It should be noted in the terms of reaction
temperature, yield and time factors this method was better than the other catalysts.
Table 5. Comparison of the synthesis of 4,4'-((4-Chlorophenyl)methylene)bis(3-methyl-1-
phenyl-1H-pyrazol-5-ol) in the presence of Ni-IDA-MNPs with previously reported
procedure.
Time
(min)
Yield
(%)
Catalyst
Aspirin
Conditions
Ref.
entry
a
1
2
EtOH/H O,
62
63
30
5
92
97
6
0 °C
2
3
AP-SiO
2
CH
3
CN, r.t
Solvent-free,
6
6
4
5
DCDBTSD
40
8
80
96
8
0 °C
4
5
Solvent-free,
2 4
CuFe O
8
0 °C
Solvent-free,
50 °C
6
6
[
Pyridine–SO3H]Cl
8
94
6
7
6
6
7
8
SASPSPE
EtOH, Reflux
Acetonitrile,
132
20
85
90
Ni‑guanidine@MCM‑41 NPs
8
0 °C
8
DMSO, 80
This
work
Ni-IDA-MNPs
45
98
°
C
a
Isolated yield.
Table 6. Comparison of the synthesis of ethyl-4-(4-chlorophenyl)-2,7,7-trimethyl-5-
oxo-1,4,5,6,7,8-hexahydroquinoline-3 carboxylate in the presence of CoFe
Ni MNPs with previously reported procedure.
2 4
O @IDA-

New Journal of Chemistry
Page 26 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Yield (%)a
View Article Online
Entry
catalyst
Time (min)
Ref.
DOI: 10.1039/D0NJ00223B
1
6
9
NiFe
FeAl
2
2
O
O
4
4
3
90
2
3
4
5
6
7
8
2
7
2
0
180
90
98
95
96
95
95
Cu-SPATBA/Fe
Pd‐SBTU@Fe
Fe ‐Adenine‐Ni
3
O
4
65
140
145
15
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
71
72
73
3
O
4
3
O
4
III
Ru @CMC/Fe
Fe -SA-PPCA
@D-NH-(CH
3 4
O
7
4
120
3
O
4
Fe
SO
3
O
4
2
)
4
-
75
76
77
90
86
92
92
92
3
H
9
Fe
3
O
4
-TEDETA-Br
3
120
10
Fe
3
O
4
2 2 3
@SiO @(CH ) Im}
2
0
C(CN)
3
1
1
1
2
7
7
8
8
SBA-15@Glycine- Ni
SBA-15@Glycine-Cu
110
100
94
97
92
1
1
3
4
17
79
3
5
SBA-15@AMPD-Co
Nicotinic acid
5
1
5
Ni-IDA-MNPs
3
0
98
This work
a
Isolated yield.
4
.
Conclusion
In this study, a new and magnetic nanocatalyst was successful designed by anchoring of
iminodiacetic acid-Ni complex on the surface of CoFe O nanoparticles. Catalyst was named
2
4
CoFe O @IDA-Ni and its structure was charactrized by FTIR, XRD, EDX, ICP-OES, SEM,
2
4
X-ray mapping and TGA techniques. Then, its catalytic activity was tested in the synthesis of
in the synthesis of polyhydroquinoline and bis(pyrazolyl)methane derivatives. In all case,
products obtained in short reaction time and high yield. Easy separation, the use of green,
inexpensive and available materials, chemical and physical stability, easy work-ups and high
catalytic activity are outstanding properties of reported method.

Page 27 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ00223B
Acknowledgements
We gratefully acknowledge the support of this work by Tehran University.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
References
1
2
3
S. Chaturvedi, P. N. Dave and N. K. Shah, J. Saudi Chem. Soc., 2012, 16, 307–325.
C. W. Lim and I. S. Lee, Nano Today, 2010, 5, 412–434.
S. Zarin, Z. Aslam, A. Zahir, M. S. Kamal, A. G. Rana, W. Ahmad and S. Ahmed, J.
Iran. Chem. Soc., 2018, 15, 2689–2701.
4
5
F. R. Moghadam, S. Azizian, E. Kianpour, M. Yarie, M. Bayat and M. A. Zolfigol,
Chem. Eng. J., 2017, 309, 480–488.
O. Volkov, R. Macías, N. P. Rath and L. Barton, Appl. Organomet. Chem., 2003, 17,
4
09–420.
6
7
8
M. Batzill and U. Diebold, Prog. Surf. Sci., 2005, 79, 47–154.
M. Kazemi and M. Mohammadi, Appl. Organomet. Chem., 2020, 34, e5400.
R. Huirache-Acuña, R. Nava, C. Peza-Ledesma, J. Lara-Romero, G. Alonso-Núez, B.
Pawelec and E. Rivera-Muñoz, Materials (Basel)., 2013, 6, 4139–4167.
W. Al Zoubi and Y. G. Ko, Appl. Organomet. Chem., 2017, 31, e3574.
M. Kazemi, S. M. Nasr, Z. Chen and M. Mohammadi, Mini. Rev. Org. Chem., 2019,
9
10
1
6, 1–11.
1
1
Q. Pu, M. Kazemi and M. Mohammadi, Mini. Rev. Org. Chem., 2019, 16, 5775–5791.
F. Feizpour, M. Jafarpour and A. Rezaeifard, Catal. Letters, 2018, 148, 30–40.
M. Kalhor, S. Banibairami and S. A. Mirshokraie, Green Chem. Lett. Rev., 2018, 11,
12
1
3
3
34–344.

New Journal of Chemistry
Page 28 of 34
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
1
4
M. Abdollahi, H. Atashi, F. F. Tabrizi and M. Mansouri, J. Iran. Chem. Soc., 2017, 14,
DOI: 10.1039/D0NJ00223B
2
45–256.
E. Yilmaz, Y. Tut, O. Turkoglu and M. Soylak, J. Iran. Chem. Soc., 2018, 15, 1721–
731.
15
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
1
1
1
1
6
7
8
9
A. Ghorbani-Choghamarani, M. Mohammadi, R. H. E. Hudson and T. Tamoradi, Appl.
Organomet. Chem., 2019, 33, e4977.
A. Ghorbani-Choghamarani, M. Mohammadi, T. Tamoradi and M. Ghadermazi,
Polyhedron, 2019, 158, 25–35.
H. Veisi, R. Azadbakht, F. Saeidifar and M. R. Abdi, Catal. Letters, 2017, 147, 976–
986.
M. Khanmoradi, M. Nikoorazm and A. Ghorbani-Choghamarani, Catal. Letters, 2017,
1
47, 1114–1126.
D. Azarifar, S. M. Khatami, M. A. Zolfigol and R. Nejat-Yami, J. Iran. Chem. Soc.,
014, 11, 1223–1230.
A. Ghorbani-Choghamarani, M. Mohammadi and Z. Taherinia, J. Iran. Chem. Soc.,
019, 16, 411–421.
20
2
2
2
2
1
2
3
2
A. Ghorbani-Choghamarani, M. Mohammadi, L. Shiri and Z. Taherinia, Res. Chem.
Intermed., 2019, 45, 5705–5723.
C. M. Marson, Chem. Soc. Rev., 2012, 41, 7712–7722.
24
M. Kooti and M. Afshari, Catal. Letters, 2012, 142, 319–325.
L. Chen, A. Noory Fajer, Z. Yessimbekov, M. Kazemi and M. Mohammadi, J. Sulfur
Chem., 2019, 40, 451–468.
2
5
26
M. Kazemi, M. Ghobadi and A. Mirzaie, Nanotechnol. Rev., 2018, 7, 43–68.
M. Arghan, N. Koukabi and E. Kolvari, J. Iran. Chem. Soc., 2019, 16, 2333–2350.
W. Sun, W. Yang, Z. Xu and Q. Li, ACS Appl. Nano Mater., 2018, 1, 5035–5043.
2
2
7
8

Page 29 of 34
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
2
9
A. Zhou, R. M. Guo, J. Zhou, Y. Dou, Y. Chen and J. R. Li, ACS Sustain. Chem. Eng.,
DOI: 10.1039/D0NJ00223B
2
018, 6, 2103–2111.
30
H. Filian, A. Kohzadian, M. Mohammadi, A. Ghorbani-Choghamarani and A. Karami,
Appl. Organomet. Chem., 2020, n/a, e5579.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
1
M. N. Chen, L. P. Mo, Z. S. Cui and Z. H. Zhang, Curr. Opin. Green Sustain. Chem.,
2
019, 15, 27–37.
3
3
3
2
3
4
M. Mahmoudi, A. Simchi and M. Imani, J. Iran. Chem. Soc., 2010, 7, S1–S27.
E. Yilmaz and M. Soylak, J. Iran. Chem. Soc., 2017, 14, 2503–2512.
S. T. Fardood, A. Ramazani and S. Moradi, J. Sol-Gel Sci. Technol., 2017, 82, 432–
439.
3
5
P. Dolcet, S. Diodati, F. Zorzi, P. Voepel, C. Seitz, B. M. Smarsly, S. Mascotto, F.
Nestola and S. Gross, Green Chem., 2018, 20, 2257–2268.
F. Vetr, Z. Moradi-Shoeili and S. Özkar, Appl. Organomet. Chem., ,
DOI:10.1002/aoc.4465.
36
3
3
3
4
7
8
9
0
M. A. Zolfigol and M. Mokhlesi, J. Iran. Chem. Soc., 2008, 5, S91–S96.
F. Shirini and M. P. Lati, J. Iran. Chem. Soc., 2017, 14, 75–87.
A. Rahmati and N. Pashmforoush, J. Iran. Chem. Soc., 2015, 12, 993–1036.
A. Khalafi-Nezhad, F. Panahi, R. Yousefi, S. Sarrafi and Y. Gholamalipour, J. Iran.
Chem. Soc., 2014, 11, 1311–1319.
41
R. Saini and N. Dharawath, J. Iran. Chem. Soc., 2018, 15, 2183–2192.
R. H. Fath and S. J. Hoseini, Appl. Organomet. Chem., 2018, 32, e3964.
P. K. Khatri and S. L. Jain, Catal. Letters, 2012, 142, 1020–1025.
L. Han, M. S. Park, S. J. Choi, Y. J. Kim, S. M. Lee and D. W. Park, Catal. Letters,
4
4
2
3
44
2
012, 142, 259–266.
4
5
M. Mohammadi and A. Ghorbani-Choghamarani, New J. Chem., 2020, 44, 2919–