Synthesis and characterization of spinel FeAl2O4 (hercynite) magnetic nanoparticles and their application in multicomponent reactions

Article abstract of DOI:10.1007/s11164-019-03930-0

The spinel ferrite FeAl₂O₄ (hercynite) MNPs (magnetic nanoparticles) were applied as a reusable catalytic system for the one-pot synthesis of benzo[a]pyrano[2,3-c] phenazine and polyhydroquinoline derivatives via a multicomponent rea

Full text of DOI:10.1007/s11164-019-03930-0

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-03930-0
Synthesis and characterization of spinel FeAl2O4
(
hercynite) magnetic nanoparticles and their application
in multicomponent reactions
Arash Ghorbani‑Choghamarani1 · Masoud Mohammadi · Lotf Shiri ·
1
1
Zahra Taherinia1
Received: 26 March 2019 / Accepted: 8 July 2019
©
Springer Nature B.V. 2019
Abstract
The spinel ferrite FeAl O (hercynite) MNPs (magnetic nanoparticles) were applied
2
4
as a reusable catalytic system for the one-pot synthesis of benzo[a]pyrano[2,3-c]
phenazine and polyhydroquinoline derivatives via a multicomponent reaction under
green reaction conditions. The structure of the prepared nanocatalyst has been char-
acterized by XRD, FTIR, SEM, EDS, BET, and VSM techniques. The FeAl O
2
4
MNPs act as Lewis acids and oꢀer several advantages such as high yields of prod-
ucts, short reaction times, and easy workup procedure. Moreover, the recycled nano-
catalyst was used at least four times without signiꢁcant loss of its activity.
Keywords FeAl O · Hercynite · Magnetic nanoparticles · Benzo[a]pyrano[2,3-c]
2
4
phenazine · Polyhydroquinoline
Introduction
Multicomponent reactions (MCRs) have been widely used as an outstanding pathway
for the chemical synthesis due to several advantages such as atom economy, mild reac-
tion conditions, low costs of reagents and catalysts, minimization of by-products, short
reaction times, and high chemoselectivity [1–6]. Therefore, the designing of novel mul-
ticomponent reactions is an important and attractive task. Phenazines are a large class
of well-known natural and synthetic nitrogen-containing heterocyclic compounds [7].
They are an important class of biologically active heterocyclic compounds with tryp-
anocidal [8, 9], fungicidal [10], antiplatelet [11], antitumor [12], and antiparasitic activ-
ities properties [13]. Moreover, they have been employed as useful materials for the
preparation of dyestuꢀs [14], pesticides [15], and antibiotics [16]. Polyhydroquinoline
*
Arash Ghorbani-Choghamarani
arashghch58@yahoo.com; a.ghorbani@ilam.ac.ir
1
Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran
Vol.:(012
1
3456789)
3

A. Ghorbani-Choghamarani et al.
derivatives demonstrate a diverse array of biological and pharmacological properties
including antitubercular properties [17], anticancer [18], neurotropic [17], platelet anti-
aggregation [17], and antidiabetic activities [19]. Several methods have been reported
for the synthesis of polyquinolines and phenazines [20–37]; however, in spite of their
valuable advantages and potential utility, some of these methods suꢀer for some disad-
vantages including unrecoverability of the catalyst, strong acidic conditions, long reac-
tion times, low yield of products, diꢂcult workup, and harsh reaction conditions.
In recent years, the improvement in nanotechnology led to an increasing insist for
multifunctional materials owing to simplicity in operation [38–40], remarkable recycla-
bility [41], high surface area of catalysts [42, 43], and eco-friendly nature [44]. In this
regard, solid catalysts and magnetic composite nanoparticles are interesting for indus-
trial [45] and biomedical applications [46] and, especially, in catalysis studies as a mag-
netically separable catalyst [47]. Among the various magnetic nanoparticles, Fe O has
3
4
been widely considered as a catalyst [48, 49]. In general, the spinel ferrite nanoparti-
cles (AB O , B=Co, Fe, Ni, Mn, Mg, Al, Zr, Zn, etc.) alloy (Fe–Co, Fe–Pt, Fe–Ru,
2
4
etc.) and multifunctional nanoparticles have higher performance than the monometallic
catalysts [39, 49–55]. Diꢀerent experimental methods for the synthesis of spinel fer-
rites have been reported in the researches, such as sol–gel [56], electrodeposition [57],
reaction sintering [58], mechanochemical [59], single-step solution combustion [60],
co-precipitation [49, 61–64], thermal decomposition [65], hydrothermal [66], electro-
chemical [67], and solvent deꢁcient [68]. Although in the most of these methods, spi-
nel FeAl O nanoparticles are achieved in the desired or required sizes and microstruc-
2
4
tures, they are diꢂcult to apply on larger scales due to their expensive and complicated
procedures, high reaction temperatures, long reaction times, toxic reagents and by-
products, and their potential harm to the environment [69]. Among these procedures,
co-precipitation method is an easy, versatile, and low-cost method for the preparation
of FeAl O nanoparticles. Co-precipitation is a rapid, easy, and economical process
2
4
that oꢀers a series of advantages such as controlled crystallite size, high limpidness, no
agglomeration of the particles, and stable particle surface along with homogeneity [63,
7
0–74]. In this work, co-precipitation technique using FeCl ·4H O and Al(NO ) ·9H O
2 2 3 3 2
as inexpensive, non-toxic, and available reagents has been applied for the preparation of
FeAl O MNPs in green reaction media.
2
4
In the development of greener and sustainable processes for the organic synthesis,
FeAl O MNPs was applied as a catalyst for the preparation of benzo[a]pyrano[2,3-
2
4
c] phenazine and polyhydroquinoline derivatives using expensive, green, and avail-
able materials. The presence of iron oxide in the catalyst causes the magnetic prop-
erty. The catalyst composition was characterized by XRD, FTIR, SEM, EDS, BET,
and VSM techniques, and the reactions process and mechanism were also discussed.
Experimental section
Chemicals
All reactants were purchased from Merck and Aldrich chemical companies and used
without further puriꢁcation. Fourier transform infrared (FTIR) was recorded as KBr
1
3

Synthesis and characterization of spinel FeAl O …
2
4
pellets on a VRTEX 70 model Bruker FTIR spectrophotometer. Powder XRD was
collected with a PHILIPS and model PW1730. S Magnetic measurements were
taken using a SQUID vibrating sample magnetometer (VSM) MDKFD operating at
2
5 °C.
Typical procedure for the synthesis of FeAl O MNPs
2
4
The FeAl O was prepared via a chemical co-precipitation method [49]. Initially,
2
4
FeCl ·4H O (0.795 g) and Al(NO ) ·9H O (0.375 g) (2:1 mol) were dissolved in
2
2
3 3
2
water (100 mL) under N atmosphere at 80 °C. Then, 10 mL of NaOH solution
2
(
0.2 M) was added dropwise for 10 min into the stirring mixture. (The pH of solu-
tion was found to be 12.) After 30-min stirring of mixture, the FeAl O MNPs were
2
4
collected using an external magnet and precipitate was washed a few times with
deionized water. The obtained precipitate was dried at 75 °C overnight.
Typical procedure for the synthesis of benzo[a]pyrano[2,3‑c] phenazines
A solution of 2-hydroxynaphthalene-1,4-dione (1 mmol), benzene-1,2-diamine
(
1 mmol), and FeAl O MNPs (40 mg) in PEG-400 was stirred for 15 min at
2
4
1
00 °C. After completion of the ꢁrst step of reaction (monitored by TLC), benzal-
dehyde (1.0 mmol) and malononitrile (1.5 mmol) were added into the reaction mix-
ture and stirred for an appropriate time at 100 °C, and the progress of the reaction
was monitored by TLC (n-hexane/ethyl acetate: 6:4). After completion of the reac-
tion, the mixture was cooled down to room temperature, and the catalyst was sepa-
rated by applying an external magnet. The obtained products were extracted with
ethyl acetate (15 mL). The organic layer was successively washed with water, dried
over Na SO (1.5 g), and ꢁltered. The solvent was removed by rotary evaporator
2
4
and raw product puriꢁed by column chromatography (silica gel, hexane/ethyl ace-
tate) to obtain desired pure products in reasonable yields (75–90%). All the products
reported here are known compounds and the melting point and spectroscopic data
matched literature values.
Typical procedure for the synthesis of polyhydroquinolines
A solution of ammonium acetate (1.2 mmol), aldehyde (1 mmol), ethyl acetoacetate
(
1 mmol), dimedone (1 mmol), and FeAl O MNPs as a catalyst (40 mg) in ethanol
2 4
(
3 ml) was stirred at 80 °C for an appropriate time, and the progress of the reaction
was monitored by 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. Then, the solvent evapo-
rated and all products were recrystallized from ethanol. The pure polyhydroquino-
line derivatives were obtained in excellent yields (86–96%).
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3

A. Ghorbani-Choghamarani et al.
Representative NMR data
3
2
‑Amino‑1‑(4‑Cl‑phenyl)‑1H‑benzo[a]pyrano[2,3‑c] phenazine‑2‑carbonitrile (entry
1
, Table 2) Mp: 286–289 °C. H NMR (400 MHz, DMSO-d ) δ (ppm): 5.50 (s, 1H,
6
CH), 7.29 (d, 2H, J=8.2 Hz, NH ), 7.44 (m, 4H, Ar–H), 8.06–7.88 (m, 4H, Ar–H),
2
8
.15 (m, 1H, Ar–H), 8.32–8.23 (m, 1H, Ar–H), 8.45 (d, J=7.9 Hz, 1H, Ar–H), 9.23
(
d, J=7.9 Hz, 1H, Ar–H).
3
‑Amino‑1‑(4‑NO ‑phenyl)‑1H‑benzo[a]pyrano[2,3‑c]
phenazine‑2‑carbonitrile
2
1
(
(
(
entry 6, Table 2) Mp: 279–280 °C. H NMR (300 MHz, DMSO-d ) δ (ppm): 5.37
6
s, 1H, CH), 7.24 (d, J=8.4, 2H, NH ), 7.37 (d, J=8.02, 4H, Ar–H), 7.94–7.85
2
m, 7.4, 4H, Ar–H), 8.02 (d, J=2.8, 1H, 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).
Results and discussion
In continuing of our previous studies for catalytic applications of spinel ferrites
MNPs [49], in this research, we decided to demonstrate the preparation of a FeAl O
2
4
MNP as an eꢂcient and recoverable nanocatalyst in multicomponent reactions.
Catalyst characterization
The XRD patterns of the FeAl O MNPs are presented in Fig. 2. As it can be seen,
2
4
the catalyst structure was justiꢁed by the XRD patterns by the peak positions at
θ=30.59, 32.15, 35.99, 43.65, 45.87, 54.11, 57.61, 63.27, 71.81, 74.65, and 75.70,
which are related to (2 0 0), (0 3 1), (3 1 1), (4 0 0), (1 1 0), (4 2 2), (1 1 1), (4 4 0),
6 2 0), (5 3 3), and (1 1 1) reꢃections, respectively. All peaks have been conꢁrmed
the formation of spinel-type FeAl O MNPs. Also, appearing a peak at 2θ values of
2
(
2
4
5
4.11 corresponds to the spinel structure of ferrite particles [75–77]. More impor-
tantly, the presence of Al in the structure was conꢁrmed by the peak positions at
2
θ=32.15, 45.87, 54.11, and 75.70, which is related to aluminum oxide. In addi-
tion, the absence of any signals of impurities in the XRD pattern conꢁrms the high
purity level of the prepared FeAl O MNPs. Crystalline size of FeAl O MNPs in
2
4
2
4
the nanocomposites was calculated from XRD data using Scherer’s formula. The
particle size obtained from XRD data was found to be 45.35 nm (Fig. 1).
The structure of FeAl O MNPS was analyzed by Fourier transform infrared
2
4
(
FTIR) spectroscopy. As it can be seen, the presence of vibration bands in 447, 579,
−1
3
428 cm are due to Fe–O, and OH bonds, respectively. Also, a weak adsorption
−1
band around 722 cm is related to Al–O bond [78] (Fig. 2).
The morphology of FeAl O MNPs was studied by SEM analysis. Figure 3 shows
2
4
that the FeAl O particles formed in approximately spherical shape with an average
2
4
size of 50–70 nm.
1
3

Synthesis and characterization of spinel FeAl O …
2
4
Fig. 1 XRD pattern of the FeAl O4
2
The EDS analysis exhibits the existence of Al, Fe, and oxygen in the prepared
nanocatalyst (Fig. 4). Also, the purity of the FeAl O MNPs was conꢁrmed by the
2
4
absence of any signals of other elements in the in the EDS pattern.
The Brunauer–Emmett–Teller (BET) surface areas of FeAl O MNPs were inves-
2
4
tigated using the nitrogen adsorption/desorption method. As shown in Fig. 5. The
2
−1
BET speciꢁc surface area is 50.815 m g .
The magnetization curve of synthesized FeAl O MNPs is shown in Fig. 6. The
2
4
saturation magnetization of FeAl O MNPs was found to be~43 emu/g, which
2
4
1
3

A. Ghorbani-Choghamarani et al.
Fig. 2 FTIR spectra of FeAl O MNPs
2
4
demonstrated the superparamagnetic properties of FeAl O MNPs, indicating the
2
4
catalyst could be separated from the reaction mixture by an external magnetic ꢁeld.
Catalytic study
After the successful synthesis and characterization of FeAl O MNPs, their catalytic
2
4
activity has been examined in the multicomponent reactions. Synthesis of benzo[a]
pyrano[2,3-c] phenazine and polyhydroquinoline derivatives was chosen to evalu-
ate the catalytic eꢂciency of the prepared nanocatalyst. Initially, we have started
our experiments by the synthesis of benzo[a]pyrano[2,3-c] phenazine derivatives
(
Scheme 1).
In order to optimize reaction conditions, the combination of benzene-1,2-di-
amine, 2-hydroxynaphthalene-1,4-dione, malononitrile, and 4-chlorobenzaldehyde
was chosen as a model reaction. The eꢀect of various reaction parameters includ-
ing solvent, temperature, and amounts of the catalyst was screened to achieve high
catalytic eꢂciency and yield. The results are summarized in Table 1. In order to
reduce the formation of by-products, initially the 2-hydroxynaphthalene-1,4-dione
and benzene-1,2-diamine were mixed and stirred and then 4-chlorobenzaldehyde
and malononitrile were added to this mixture.
First, the eꢀect of solvents was considered. Surprisingly, PEG was the most suit-
able solvent to reach the desired product (Table 1). Then, the eꢀects of reaction tem-
perature were evaluated on the model reaction. Among the various screened tem-
peratures (e.g., 25, 50, 80, and 100 °C), 100 °C was the most eꢀective temperature
1
3

Synthesis and characterization of spinel FeAl O …
2
4
Fig. 3 SEM pattern of FeAl O
2
4
MNPs
Fig. 4 EDS pattern of FeAl O MNPs
2
4
1
3

A. Ghorbani-Choghamarani et al.
Fig. 5 Nitrogen adsorption–desorption isotherms of the FeAl O MNPs
2
4
(
Table 1, entry 2). Then, the inꢃuence of the catalyst loading on the outcome of
reaction was studied with diꢀerent amounts of catalyst. Obtained results revealed
that 40 mg of the catalyst is the most eꢀective amount (Table 1, entry 1). As given in
Table 1, entry 8, the reaction was not completed in the absence of the catalyst even
after 24 h. Eventually, PEG at 100 °C in the presence of 40 mg of FeAl O MNPs
2
4
was found to be the best choice for the described multicomponent reaction.
With optimal conditions in hand, we investigated generality and the substrates
scope of the described reaction by using the series of aromatic aldehyde to react
with 2-hydroxynaphthalene-1,4-dione and benzene-1,2-diamine (Table 2). The
results are summarized in Table 2. Based on the obtained results, we found that all
reactions produced the corresponding benzo[a]pyrano[2,3-c] phenazine in good to
1
3

Synthesis and characterization of spinel FeAl O …
2
4
Fig. 6 VSM of FeAl O MNPs
2
4
Scheme 1 Synthesis of benzo[a]pyrano[2,3-c] phenazine
excellent yields (75–90%) and also aldehydes including electron-withdrawing moie-
ties increased the rate of combination.
Moreover, this catalytic procedure was used for the preparation of 3-amino
spirobenzo [c] pyrano[3,2-a] phenazine. In this aim, 2-hydroxynaphthalene-1,4-di-
one (1 mmol), benzene-1,2-diamine (1 mmol), and malononitrile (1 mmol) were
mixed with isatin (1 mmol) under obtained optimal reaction conditions to yield
corresponding product (Table 2, entry 9). It was observed that aromatic aldehydes
showed higher activities than isatin (Table 2, entries 1–8).
The suggested reaction mechanism for the described combination is depicted
in Scheme 2 based on the previously reported reaction pathway [35]. Initially,
1
3

A. Ghorbani-Choghamarani et al.
Table 1 Optimization for the
synthesis of 2-amino-1-(4-
chlorophenyl)-1H-benzo[a]
pyrano[2,3-c] phenazine-3-
carbonitrile
Entrya Cat. (mg) Solvent Temp. (°C) Time (h) Yieldb (%)
1
2
3
4
5
6
7
8
9
1
1
40
40
40
40
40
40
40
–
PEG
DMSO 100
100
3
3
3
3
3
3
3
24
3
3
90
65
20
48
Trace
39
57
Trace
31
45
H O
100
100
25
50
80
100
100
100
100
2
DMF
PEG
PEG
PEG
PEG
PEG
PEG
PEG
10
20
30
0
1
3
65
a
Reaction conditions: 2-hydroxynaphthalene-1,4-dione (1 mmol),
benzene-1,2-diamine (1 mmol), 4-chlorobenzaldehyde (1 mmol),
malononitrile (1 mmol), FeAl O nanocatalyst, and solvent (2 mL)
2
4
b
Isolated yield
intermediate 3 was formed from the Schiꢀ-base condensation of benzene-1,2-di-
amine and 2-hydroxynaphthalene 1,4-dione in the presence of FeAl O MNPs.
2
4
Sequentially, a possible intermediate 7 was formed via Michael addition of 6 with
2
-benzylidenemalononitrile. (Intermediate 6 was formed via the Knoevenagel
condensation of aldehyde with malononitrile.) Finally, intermolecular cyclization
of intermediate 7 produced a ꢁnal product 8.
Afterward, to show the more capability of FeAl O MNPs, we decided
2
4
to examine their eꢀect on the synthesis of polyhydroquinoline derivatives
(
Scheme 3).
We started the study of this synthesis by the combination of ammonium acetate
1.2 mmol), dimedone (1 mmol), p-Cl-benzaldehyde (1 mmol), and ethyl acetoac-
(
etate (1 mmol) to optimize the reaction conditions as given in Table 3.
When the reaction was conducted at 25 and 50 °C, the observed yield was very
low (Table 3, entries 10, 11). In addition, the reaction yield and reaction rate increase
by increasing the reaction temperature and the amount of the catalyst. The ideal tem-
perature for the reaction was found to be reꢃux conditions in ethanol. Finally, the
best results were obtained with 40 mg of catalyst in EtOH as a solvent under reꢃux
conditions (Table 3). Under the optimized conditions, reactions of diꢀerent aromatic
aldehydes have been investigated to obtain a wide range of corresponding polyhyd-
roquinoline derivatives (Table 4). The results are summarized in Table 4.
A plausible mechanism for the multicomponent synthesis of polyhydroquinolines
on the basis of previous reports [82] is depicted in Scheme 4. Based on this mecha-
nism, the FeAl O MNPs play a role as a Lewis acid catalyst in the Knoevenagel
2
4
condensation of aldehydes with active methylene compounds (dimedone or ethyl
acetoacetate) to produce an α,β-unsaturated compound; in the next step, FeAl O
2
4
MNPs were catalyzed by the Michael addition of intermediates to obtain the polyhy-
droquinoline (Scheme 4).
1
3

Synthesis and characterization of spinel FeAl O …
2
4
Table 2 Synthesis of benzo[a]pyrano[2,3-c] phenazine derivativesa
Entry Aldehyde
Product
Time Yieldb M.P
(
h)
(%)
Measured Reported
1
4
85
287–288 288–291
[
37]
2
3
90
286–289 286–288
36]
[
3
4
5
80
88
292–294 295 [36]
273–275 273 [36]
4.5
5
4
87
247–249 >250 [34]
1
3

A. Ghorbani-Choghamarani et al.
Table 2 (continued)
Entry Aldehyde
Product
Time Yieldb M.P
h) (%)
(
Measured Reported
6
7
8
2
75
90
83
85
279–280 281–283
[
37]
4
284–287 282–285
79]
[
4.5
5.5
270–273 275 [36]
9
254–256 >250 [22]
a
Reaction conditions: 2-hydroxynaphthalene-1,4-dione (1 mmol), benzene-1, 2-diamine (1 mmol), aro-
matic aldehyde or isatin (1.0 mmol), malononitrile (1 mmol), catalyst (40 mg), and PEG (2 mL)
Isolated yield
b
1
3

Synthesis and characterization of spinel FeAl O …
2
4
Scheme 2 Proposed mechanism for the synthesis of benzo[a]pyrano[2,3-c] phenazine
Scheme 3 Synthesis of polyhydroquinolines
Table 3 Optimization
Entrya
b
Cat. (mg)
Solvent
EtOH
Temp. (°C)
Yield (%)
for the synthesis of
polyhydroquinolines
1
2
3
4
5
6
7
8
9
40
40
40
40
40
30
20
10
–
Reꢃux
80
80
80
80
Reꢃux
Reꢃux
Reꢃux
Reꢃux
50
96
65
30
48
68
73
57
38
13
68
37
H O
2
PEG
DMSO
–
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
1
0
40
40
1
1
25
a
Reaction conditions: 4-chlorobenzaldehyde (1.0 mmol), dime-
done (1 mmol), ethyl acetoacetate (1 mmol), ammonium acetate
(
1.2 mmol), catalyst, and solvent (3 mL)
Isolated yield. Time 3 h
b
1
3

A. Ghorbani-Choghamarani et al.
Table 4 Synthesis of polyhydroquinoline derivativesa
Entry Aldehyde
Product
Time
min)
Yield M.P
b
(
(%)
Measured Reported
1
30
50
45
96
90
93
244–246 243–245 [80]
192–194 252–255 [81]
256–258 251–252 [82]
2
3
4
5
45
70
95
87
202–204 203–205 [80]
230–232 231–234 [46]
1
3

Synthesis and characterization of spinel FeAl O …
2
4
Table 4 (continued)
Entry Aldehyde
Product
Time
min)
Yield M.P
b
(
(%)
Measured Reported
223–225 225–227 [80]
6
80
89
7
40
92
247–249 249–251 [80]
8
9
30
45
86
90
232–235 231–233 [80]
178–180 180–182 [80]
a
Reaction conditions: aromatic aldehyde (1.0 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol),
ammonium acetate (1.2 mmol), catalyst (40 mg), and EtOH (3 mL)
Isolated yield
b
Catalyst recyclability
The recoverability of a catalyst is one of the outstanding properties of catalysts
or catalytic systems. Therefore, the reusability of FeAl O MNPs was consid-
2
4
ered for the synthesis of polyhydroquinolines by the reaction of ammonium
acetate, p-Cl-benzaldehyde ethyl acetoacetate, and dimedone. At the end of the
1
3

A. Ghorbani-Choghamarani et al.
Scheme 4 Proposed mechanism for the synthesis of polyhydroquinolines
reaction, FeAl O MNPs were simply recovered from the mixture with the help
2
4
of an external magnet. The separated catalyst was washed with ethyl acetate and
used for another run. The results showed that this catalyst is reusable up to four
times without loss of its activity (Fig. 7).
Hot ꢀltration
The heterogeneity of FeAl O MNPs in the reaction mixture was studied using
2
4
the hot ꢁltration test. The hot ꢁltration test was performed for the synthesis of
polyhydroquinolines in the model reaction under the optimal reaction condi-
tions. After 15 min (half reaction time), the reaction was terminated, and corre-
sponding product was obtained in 51% of yield. Then, the reaction was repeated,
and at the half time of the reaction, the catalyst was separated by magnetic sep-
aration and the reaction mixture was allowed to react further (in the absence
of catalyst). We found that only a trace conversion (< 4%) of the condensation
reaction was performed on the heating of the catalyst-free solution for another
1
5 min. This means that this nanocatalyst is completely heterogeneous.
1
3

Synthesis and characterization of spinel FeAl O …
2
4
Fig. 7 Catalyst recycling study
for the synthesis of polyhydro-
quinolines
Conclusions
In this study, spinel ferrite FeAl O nanoparticles were synthesized, and their perfor-
2
4
mance as a magnetic nanocatalyst for the one-pot synthesis of benzo[a]pyrano[2,3-
c] phenazine and polyhydroquinoline derivatives was considered. The most out-
standing advantages of this catalyst are reasonable yields of desired products, short
reaction time, low cost of starting materials for the preparation of the catalyst, mild
reaction media, and versatile workup procedure. Moreover, catalyst could be sepa-
rated easily using a magnet and reused many times without signiꢁcant loss of its
catalytic activity.
Acknowledgements The authors thank the research facilities of Ilam University, Ilam, Iran, for ꢁnancial
support of this research project.
References
1
2
3
4
5
.
.
.
.
.
V. Estevez, M. Villacampa, J.C. Menendez, Chem. Soc Rev. 39, 4402 (2010)
B. Groenendaal, E. Ruijter, R.V.A. Orru, Chem. Commun. 43, 5474 (2008)
D.J. Ramón, M. Yus, Angew. Chemie Int. Ed. 44, 1602 (2005)
R.C. Cioc, E. Ruijter, R.V.A. Orru, Green Chem. 16, 2958 (2014)
M. Zakeri, M.M. Nasef, E. Abouzari-Lotf, A. Moharami, M.M. Heravi, J. Ind. Eng. Chem. 29, 273
(
2015)
6
7
.
.
M.A. Mironov, Russ. J. Gen. Chem. 80, 2628 (2010)
L. Myhren, G. Nygaard, G. Gausdal, H. Sletta, K. Teigen, K. Degnes, K. Zahlsen, A. Brunsvik, Ø.
Bruserud, S. Døskeland, F. Selheim, L. Herꢁndal, Mar. Drugs 11, 332 (2013)
C. Neves-Pinto, V.R.S. Malta, M. Do, C.F.R. Pinto, R.H.A. Santos, S.L. De Castro, A.V. Pinto, J.
Med. Chem. 45, 2112 (2002)
8
9
.
.
A. Ghorbani-Choghamarani, R. Sahraei, Z. Taherinia, Res. Chem. Intermed. 45, 3199 (2019)
1
1
0. Z. Xiong, J. Niu, H. Liu, Z. Xu, J. Li, Q. Wu, Bioorg. Med. Chem. Lett. 27, 2010 (2017)
1. F. Guilhon-Simplicio, C.C.D.S. Pinheiro, G.G. Conrado, G.D.S. Barbosa, P.A. Dos Santos, M.D.M.
Pereira, E.S. Lima, J. Ethnopharmacol. 140, 282 (2012)
1
1
2. G.W. Rewcastle, W.A. Denny, B.C. Baguley, J. Med. Chem. 30, 843 (1987)
3. W. Blankenfeldt, A.P. Kuzin, T. Skarina, Y. Korniyenko, L. Tong, P. Bayer, P. Janning, L.S. Thom-
ashow, D.V. Mavrodi, Proc. Natl. Acad. Sci. U.S.A. 101, 16431 (2004)
1
4. F. Dickens, H. Mcilwain, Biochem. J. 32, 1615 (1938)
1
3

A. Ghorbani-Choghamarani et al.
1
1
1
1
5. T.F.C. Chin-A-Woeng, G.V. Bloemberg, B.J.J. Lugtenberg, New Phytol. 157, 503 (2003)
6. Y. Wang, S.E. Kern, D.K. Newman, J. Bacteriol. 192, 365 (2010)
7. G.B. Dharma Rao, S. Nagakalyan, G.K. Prasad, RSC Adv. 7, 3611 (2017)
8. S.C. Jadhvar, H.M. Kasraliker, S.V. Goswami, A.V. Chakrawar, S.R. Bhusare, Res. Chem. Intermed.
4
3, 7211 (2017)
1
9. S.M. Vahdat, F. Chekin, M. Hatami, M. Khavarpour, S. Baghery, Z. Roshan-Kouhi, Chin. J. Catal.
3
4, 758 (2013)
2
2
2
2
0. A. Yazdani-Elah-Abadi, R. Mohebat, M. Lashkari, Polycycl. Aromat. Compd. 6638, 1 (2017)
1. J. Safaei-Ghomi, F. Eshteghal, H. Shahbazi-Alavi, Appl. Organomet. Chem. 32, e3987 (2018)
2. A. Hasaninejad, S. Firoozi, Mol. Divers. 17, 499 (2013)
3. M.A. Ghasemzadeh, B. Mirhosseini-Eshkevari, M.H. Abdollahi-Basir, Appl. Organomet. Chem. 33,
e4679 (2019)
2
2
2
4. R. Mohebat, P. Dehgan, A. Yazdani-Elah-Abadi, J. Chin. Chem. Soc. 65, 1259 (2018)
5. W. Blankenfeldt, J.F. Parsons, Curr. Opin. Struct. Biol. 29, 26 (2014)
6. A. Yazdani-Elah-Abadi, R. Mohebat, M. Maghsoodlou, R. Heydari, Polycycl. Aromat. Compd. 38,
9
2 (2018)
2
2
2
3
7. A. Chaudhary, J.M. Khurana, Res. Chem. Intermed. 44, 1045 (2018)
8. R. Mohebat, A. Mojahedi, A. Yazdani-Elah-Abadi, Org. Prep. Proced. Int. 50, 424 (2018)
9. S. Molaei, S. Javanshir, Green Chem. Lett. Rev. 11, 275 (2018)
0. A. Yazdani-Elah-Abadi, M.T. Maghsoodlou, R. Mohebat, R. Heydari, Chin. Chem. Lett. 28, 446
(
2017)
3
3
3
3
1. F. Khorami, H.R. Shaterian, Res. Chem. Intermed. 41, 3171 (2015)
2. N. Guttenberger, W. Blankenfeldt, R. Breinbauer, Bioorg. Med. Chem. 25, 6149 (2017)
3. R. Bharti, T. Parvin, Mol. Divers. 20, 867 (2016)
4. J. Gao, M. Chen, X. Tong, H. Zhu, H. Yan, D. Liu, W. Li, S. Qi, D. Xiao, Y. Wang, Y. Lu, F. Jiang,
Comb. Chem. High Throughput Screen. 18, 960 (2015)
3
3
3
5. H.R. Shaterian, F. Moradi, M. Mohammadnia, Comptes Rendus Chim. 15, 1055 (2012)
6. H.R. Shaterian, M. Mohammadnia, J. Mol. Liq. 177, 162 (2013)
7. S.L. Wang, F.Y. Wu, C. Cheng, G. Zhang, Y.P. Liu, B. Jiang, F. Shi, S.J. Tu, ACS Comb. Sci. 13,
1
35 (2011)
3
8. N. Pradhan, S. Singh, N. Ojha, A. Shrivastava, A. Barla, V. Rai, S. Bose, Biomed Res. Int. 365672
(
2015)
3
4
9. Q. Pu, M. Kazemi, M. Mohammadi, Mini. Rev. Org. Chem. 16, 5775 (2019)
0. A. Ghorbani-Choghamarani, M. Mohammadi,. R. H. Hudson, T. Tamoradi, Appl. Organomet.
Chem. 33, e4977 (2019)
4
4
4
1. S. Chaturvedi, P.N. Dave, N.K. Shah, J. Saudi Chem. Soc. 16, 307 (2012)
2. P.G. Tratnyek, R.L. Johnson, Nano Today 1, 44 (2006)
3. W. Riedel, L. Thum, J. Möser, V. Fleischer, U. Simon, K. Siemensmeyer, A. Schnegg, R.
Schomäcker, T. Risse, K.-P. Dinse, J. Phys. Chem. C 122, 22605 (2018)
4. L.F. Gladden, Chem. Eng. J. Biochem. Eng. J. 56, 149 (1995)
4
4
5. O.K. Bishoge, L. Zhang, S.L. Suntu, H. Jin, A.A. Zewde, Z. Qi, J. Environ. Sci. Heal. Part A Toxic/
Hazardous Subst. Environ. Eng. 53, 537 (2018)
4
4
6. M. Yarie, M.A. Zolꢁgol, Y. Bayat, A. Asgari, D.A. Alonso, A. Khoshnood, RSC Adv. 6, 82842
(
2016)
7. M.E. De Sousa, M.B. Fernández Van Raap, P.C. Rivas, P.C. Mendoza Zélis, P. Girardin, G.A.
Pasquevich, J.L. Alessandrini, D. Muraca, F.H. Sánchez, J. Phys. Chem. C 117, 5436 (2013)
8. J. Xu, J. Sun, Y. Wang, J. Sheng, F. Wang, M. Sun, Molecules 19, 11465 (2014)
4
4
5
9. A. Ghorbani-Choghamarani, M. Mohammadi, Z. Taherinia, J. Iran. Chem. Soc. 16, 411 (2019)
0. K.P. Naidek, F. Bianconi, T.C.R. da Rocha, D. Zanchet, J.A. Bonacin, M. das Graças Fialho Vaz,
M.A. Novak, J. Colloid Interf. Sci. 358, 39 (2011)
5
5
1. S.N. Sun, C. Wei, Z.Z. Zhu, Y.L. Hou, S.S. Venkatraman, Z.C. Xu, Chin. Phys. B 23, 37503 (2014)
2. S.A. Oskoui, A. Niaei, H.-H. Tseng, D. Salari, B. Izadkhah, S.A. Hosseini, ACS Comb. Sci. 15, 609
(
2013)
5
3. J. Basak, N. Hardia, S. Saxena, R. Dixit, R. Dwivedi, S. Bhadauria, R. Prasad, Ind. Eng. Chem. Res.
4
6, 7039 (2007)
5
5
5
4. P.B. Bhat, F. Inam, B.R. Bhat, ACS Comb. Sci. 16, 397 (2014)
5. R. Klimkiewicz, K. Przybylski, J. Baran, W. Miśta, Ind. Eng. Chem. Res. 48, 6291 (2009)
6. M. Azam, A. Nairan, S. Riaz, S. Naseem, Mater. Today Proc. 2, 5150 (2015)
1
3

Synthesis and characterization of spinel FeAl O …
2
4
5
5
5
6
7. F. Mukhtar, Z.N. Kayani, S. Riaz, S. Naseem, Ceram. Int. 44, 9550 (2018)
8. J. Chen, L. Yu, J. Sun, Y. Li, W. Xue, J. Eur. Ceram. Soc. 31, 259 (2011)
9. P.M. Botta, E.F. Aglietti, J.M. Porto López, Mater. Chem. Phys. 76, 104 (2002)
0. R. Mistri, S. Maiti, J. Llorca, M. Dominguez, T.K. Mandal, P. Mohanty, B.C. Ray, A. Gayen, Appl.
Catal. A Gen. 485, 40 (2014)
6
6
6
6
6
6
1. M.S. Samadi, H. Shokrollahi, A. Zamanian, Mater. Chem. Phys. 215, 355 (2018)
2. B. Atashkar, A. Rostami, A. Rostami, M.A. Zolꢁgol, Appl. Organomet. Chem. 33, e4691 (2019)
3. M. Kazemi, M. Ghobadi, A. Mirzaie, Nanotechnol. Rev. 7, 43 (2018)
4. S. Gupta, M. Lakshman, J. Med. Chem. Sci. 2, 51 (2019)
5. G. Singh, S. Chandra, Int. J. Hydrogen Energy 43, 4058 (2018)
6. Z. Rouhani, J. Karimi-Sabet, M. Mehdipourghazi, A. Hadi, A. Dastbaz, Environ. Nanotechnol.
Monit. Manag. 11, 100 (2019)
6
6
6
7. Y. Zhang, L. Yuan, X. Zhang, J. Zhang, Z. Yue, L. Li, Appl. Surf. Sci. 410, 99 (2017)
8. K.N. Nithyayini, M.N.K. Harish, K.L. Nagashree, Electrochim. Acta 317, 701 (2019)
9. M. Goodarz Naseri, E.B. Saion, H. Abbastabar Ahangar, A.H. Shaari, M. Hashim, J. Nanomater. 10,
1
(2010)
7
7
7
7
7
7
7
7
0. S. Nasrin, F.-U.-Z. Chowdhury, S.M. Hoque, J. Magn. Magn. Mater. 479, 126 (2019)
1. K. Wu, J. Li, C. Zhang, Ceram. Int. 45, 11143 (2019)
2. N. Masunga, O.K. Mmelesi, K.K. Kefeni, B.B. Mamba, J. Environ. Chem. Eng. 7, 103179 (2019)
3. M. Amiri, M. Salavati-Niasari, A. Akbari, Adv. Colloid Interf. Sci. 265, 29 (2019)
4. L. Shiri, S. Zarei, M. Kazemi, D. Sheikh, Appl. Organomet. Chem. 32, e3938 (2018)
5. S. Chen, H. Lu, Y. Wu, Y. Gu, F. Li, C. Morlay, J. Nanoparticle Res. 18, 255 (2016)
6. H. Rahmani-Boldaji, M. Saeri, S. Otroj, H. Shariꢁ, Mater. Sci. 24, 301 (2018)
7. M.A.A. Daghetta, M. Dapiaggi, L. Pellegrino, B. Pastore, L. Pagliari, C.V Mazzocchia, in
ICHEAP12 12TH Int. Conf. Chem. Process Eng., edited by Pierucci, S and Klemes, JJ (AIDIC
SERVIZI SRL, VIA Giuseppe Colombo 81/A, Milano, MI 20133, Italy, 2015), p. 1741
8. Y. Dong, H. Lu, J. Cui, D. Yan, F.X. Yin, D.Y. Li, Ceram. Int. 43, 16094 (2017)
9. A.Y.E. Abadi, M.T. Maghsoodlou, R. Heydari, R. Mohebat, Res. Chem. Intermed. 42, 1227 (2016)
0. K. Mohammadi, F. Shirini, A. Yahyazadeh, Res. Chem. Intermed. 42, 2047 (2016)
1. T. Tamoradi, M. Ghadermazi, A. Ghorbani-Choghamarani, Catal. Lett. 148, 857 (2018)
2. A. Ghorbani-Choghamarani, M. Mohammadi, T. Tamoradi, M. Ghadermazi, Polyhedron 158, 25
7
7
8
8
8
(
2019)
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