Fe3O4?L-arginine magnetic nanoparticles: A novel and magnetically retrievable catalyst for the synthesis of 1′3-diaryl-2N-azaphenalene

Article abstract of DOI:10.1002/jccs.201800274

The catalytic activity of l-arginine-coated nano-Fe₃O₄ particles (Fe₃O₄?l-arginine) proves they are a novel magnetic catalyst without the use of heat and reflux for the synthesis of 1,3-diaryl-2-N-azaphenalene d

Full text of DOI:10.1002/jccs.201800274

Received: 10 August 2018
Revised: 4 January 2019
Accepted: 6 January 2019
DOI: 10.1002/jccs.201800274
A R T I C L E
Fe3O4@L-arginine magnetic nanoparticles: A novel
and magnetically retrievable catalyst for the synthesis
of 103-diaryl-2N-azaphenalene
Asghar Eftekhari1 | Naser Foroughifar2 | Malak Hekmati1 | Mahdi Khobi3
1Department of Organic Chemistry, Faculty of
The catalytic activity of L-arginine-coated nano-Fe3O4 particles (Fe3O4@L-argi-
Pharmaceutical Chemistry, Tehran Medical
Sciences, Islamic Azad University, Tehran, Iran
nine) proves they are a novel magnetic catalyst without the use of heat and reflux
for the synthesis of 1,3-diaryl-2-N-azaphenalene derivatives and n-acyl-1,3-diaryl-
2-N-azaphenylene derivatives in a one-pot pseudo-five-component condensation
reaction of compounds of 2,7-naphthalene diol, aldehydes, and ammonia deriva-
tives (ammonium acetate or ammonium hydrogen phosphate) and solvent (water
and alcohol) with high yield and short reaction times, economical, and simple
workup. The structure and magnetic properties of the obtained nanoparticles were
characterized via Fourier transform infrared spectroscopy (IR) and field emission
scanning electron microscopy (FE-SEM). The results demonstrated that the average
size of the synthesized magnetite nanoparticles is about 21 nm. In addition, the het-
erogeneous catalyst can be easily recovered magnetically and can be reused for fur-
ther runs without significant loss of its catalytic activity.
2Department of Chemistry, Tehran North Branch,
Islamic Azad University, Tehran, Islamic Republic
of Iran
3Department of Medicinal Chemistry, Faculty of
Pharmacy and Pharmaceutical Sciences Research
Center, Tehran University of Medical Sciences,
Tehran, Islamic Republic of Iran
Correspondence
Naser Foroughifar, Department of Chemistry,
Tehran North Branch, Islamic Azad University,
Tehran, Islamic Republic of Iran.
Email: n_foroughifar@yahoo.com
Funding information
Islamic Azad University
KEYWORDS
azaphenalene, multicomponent, nanocatalysts, one-pot
potentials and very low negative reduction potentials and
are, thus, extremely promising antioxidants in biological sys-
1
| INTRODUCTION
Multicomponent reactions (MCRs) are of increasing impor-
tance in organic and medicinal chemistry. MCRs are
particularly useful to generate diverse chemical libraries of
drug-like molecules for biological screening.[1–6]
Nevertheless, development and discovery of new MCRs
is still in demand. The Biginelli, Ugi, Passerini, and Man-
nich reactions are some examples of MCRs.[7]
The Betti procedure can be interpreted as an extension of
Mannich condensation, with formaldehyde replaced by an
aromatic aldehyde, the secondary amine replaced by ammo-
nia, and the C–H acid replaced by an electron-rich aromatic
compound such as 2-naphthol.[8]
Azaphenalenyl, a heteroatomic modification of the phe-
nalenyl system, is an important building block in the synthe-
sis of organic multifunctional electronic and magnetic
materials. Azaphenalene derivatives have very low oxidation
tems, several alkaloid-based compounds with a tricyclic aza-
phenalene core have been isolated from a variety of ladybird
species; the most prominent of these are precoccinelline,
murine, and hippodamine. Because of their high biological
activity, scarce natural supply, and difficult, only small-
scale, isolation from natural sources, synthesis of this hetero-
cyclic nucleus is currently of major importance.[9–14]
The heterogeneous catalysts composed of hybrid organic
and inorganic materials have recently garnered interest from
researchers as they possess the advantages of both homoge-
neous and heterogeneous catalysts. Many investigations
have focused on heterogeneous catalysts, especially mag-
netic nanoparticles (MNPs), for example, Fe3O4 nanoparti-
cles. This issue is due to their unique physical, electronic,
and magnetic properties, including high-level area, low
© 2019 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J Chin Chem Soc. 2019;1–8.
http://www.jccs.wiley-vch.de
1

2
EFTEKHARI ET AL.
toxicity, good stability, ease of preparation, and recycling by
means of an external magnetic field.[15,16]
MNPs (Fe3O4) are widely used in basic science and cata-
lysts. Noncoated Fe3O4 MNPs have high chemical activity,
and are quickly oxidized in air (especially), usually resulting in
loss of magnetism and magnetite dispersibility. Therefore, pro-
viding a suitable surface coating and developing some effec-
tive protection strategies (to form core/shell structured
materials) to keep the stability of Fe3O4 MNPs is very impor-
tant. In recent years, MNPs of iron oxide (Fe3O4) have been
widely used as heterogeneous catalysts in organic reactions
because they are cheap, available, less toxic, recyclable, and
easy to separate from the reaction solution using a
magnet.[16–21]
The significant merits of the catalyst were related to its
facile recyclability using an external magnetic field, reusabil-
ity for at least five reaction cycles, excellent activity, high
stability, mild reaction conditions, and high isolated yields
of the products.[22]
We have developed a facile, rapid, and efficient method
for synthesis of 1,3-diaryl-2-azaphenalene derivatives in
good to high yield via Fe3O4@L-arginine as a nanocatalyst.
L-Arginine-coated MNPs (Fe3O4@L-arginine) were prepared
by chemical coprecipitation of FeCl3ꢀ6H2O and FeCl2ꢀ4H2O
salt solutions in the presence of L-arginine and used for this
reaction.[23]
Our recent studies focussed on the development of prac-
tical, safe, and environmentally friendly procedures for some
important transformations.[1,24–28]
SCHEME 2 Synthesis pathway of n-acyl-1,3-diaryl-2-N-azephenylene
diffraction (XRD), and field emission scanning electron
microscopy (FE-SEM).
Spectrum 4a shows the FT-IR spectrum of Fe3O4 nano-
particles at a stretching vibration of around 3,402 and
579 cm−1, which combines the contributions from both sym-
metrical and asymmetrical modes of the surface hydroxyl
groups and Fe–O bonds of iron oxide, respectively (Figure 1).
FE-SEM images of Fe3O4@L-arginine nanoparticles are
shown to determine the size of morphology (Figure 2). The
diameter of particles is about 21 nm in a spherical shape.
The crystal structure of Fe3O4 @L-arginine nanoparticles
is evaluated using the XRD technique (Figure 3). The pat-
terns indicate a crystallized structure at 2θ: 18.2, 30.0, 35.4,
43.08, 53.7, 57.1, and 62.7, which shows diffraction peaks,
corresponding to (485), (297), (253), (210), (171), (161),
and (148), respectively. According to the standard sample
Fe3O4 (JCPDS file no. 98-007-7842), the peaks of MNPs in
the XRD model are corresponded. The average crystal size
of nanoparticle Fe3O4@L-arginine is assessed using Debye–
Scherrer's formula (D = K λ/β cos θ). The crystal size of
MNPs is about 21 nm in the range determined using FE-
SEM analysis. Figure 3 demonstrates a pattern of count
peaks. According to the standard sample Fe3O4 (Ref. code
no. 00.019.0629) and coesite (Ref. code no. 00.001.1111),
the peaks of Fe3O4@L-arginine nanoparticles in XRD model
are corresponded.
We found a simple and efficient procedure for the syn-
thesis of novel 1,3-diphenyl-2-azaphenalene derivatives
from the condensation of 2,7-naphthalenediol, aromatic alde-
hydes, and ammonia derivatives (ammonium acetate or
ammonium hydrogen phosphate) in a mixture of EtOH–H2O
(3:1) in the presence Fe3O4@L-arginine nanocatalyst as an
efficient catalyst with recycling potential and reusability.
(Schemes 1 and 2).
2.2 | Synthesis and characterization of 103-diaryl-2N-
azaphenalene catalyzed by Fe3O4@L-arginine
To optimize the reaction conditions, 9-Dihydroxy-1,3-di
(2-methoxyphenyl)-2,3-dihydro-2-zaphenalene (A5) was
prepared as a model compound in different amounts of cata-
lyst, different solvents, through which the reaction of
2,7-naphthalene diol (1 mmol), aromatic benzaldehyde
(2 mmol), and ammonia derivatives (ammonium acetate or
ammonium hydrogen phosphate,1.2 mmol) was examined.
The results are shown in Table 1.
2
| RESULTS AND DISCUSSION
2.1 | Characterization of the Fe3O4@L-arginine
catalyst
Fe3O4@Larginine nanoparticles were characterized using
Fourier transform infrared (FT-IR) spectroscopy, X-ray
First, the model reaction was performed using several
solvents. In the second step, we examined the amount of
catalyst.
It is evident from Table 1 (entry 10) that applying more
than the specified quantity of catalyst did not have a positive
effect on the yield of product.
SCHEME 1 Synthesis pathway of 1,3-diaryl-2-N-azaphenalene

EFTEKHARI ET AL.
3
FIGURE 1 Comparison of FT-IR spectra of Fe3O4 and Fe3O4@L-arginine
FIGURE 2 The SEM Image of Fe3O4 and Fe3O4@L-arginine
As shown in Table 1, the best result was obtained using
50 mg of the Fe3O4@L-arginine catalyst in Ethanol–H2O as
a safe solvent with a proportion of 3:1 (Table 1, entry 8).
The conditions optimized for the production of the
1,3-diaryl-2-N-azaphenalene derivatives and n-acyl-1,-
3-diaryl-2-N-azephenylene derivatives were evaluated in the
absence and presence of the Fe3O4@L-arginine as a catalyst.
The reaction of aromatic aldehydes carrying either electron-
donating or electron-withdrawing substituents with ammonia
derivatives (ammonium acetate or ammonium hydrogen
phosphate) is carried out (Table 2).
From these results, we see that all reactions proceeded to
afford the corresponding products in good yields.
FIGURE 3 The XRD spectra of Fe3O4 and Fe3O4@L-arginine
A possible mechanism for the synthesis of n-acyl-1,-
3-diaryl-2-N-azephenylene is shown in Scheme 2. According
to this scheme, condensation compounds are tautomers and
can be converted to intermediate schiff base with a cycloaddi-
tion reaction (Similar mannich reaction) producing keto–enol
tautomeric derivatives of n-acyle-1,3-di-aryl azaphenalene.
Then, this Intermediate reacted with ethyl acetate (Which is
produced by the reaction of ethanol and acetic acid), and pro-
duces n-acyl-1,3-diaryl azaphenalene (Scheme 3).
The magnetic resonance multiplicity of the core has been
marked as single (s), dual (d), triple (t), quaternary (q), mul-
tiple (m), and broad (br). Tetramethyl silane (TMS) has also
been used as an internal standard.
2.2.1
| 4,9Dihydroxy-1,3-di(2-methoxyphenyl)-2,3-dihydro-
2-azaphenalene:(A5)
The received spectra indicate desired products have been
produced. To prove, interpretation two products (A5 and B4
) have been evaluated.
Products are identified by their physical properties and
1
their spectral data (IR, H-NMR, 13C-NMR) or by compar-
ing them with reliable samples. The vibrational transfer fre-
quencies are in the wave number unit (1 cm) and the
intensity of the absorbing bands has been marked as; strong
(s), medium (m), weak (w), shoulder (sh), and broad (br).

4
EFTEKHARI ET AL.
TABLE 1 Optimization of reaction conditions for preparation of 103-diaryl-2N-azaphenalene derivatives
Entry
1
Catalyst (mg)
—
Solvent
Temp. (ꢁC)
Reflux
Reflux
Reflux
Reflux
r.t.
Time
Yield A5 (%)
EtOH
7 hr
57
53
60
72
81
76
84
90
79
90
86
90
20
75
2
—
1 EtOH:1 H2O
2 EtOH:1 H2O
3 EtOH:1 H2O
EtOH
7 hr
3
—
7 hr
4
—
7 hr
5
Fe3O4@L-arginine(50)
Fe3O4@L-arginine(50)
Fe3O4@L-arginine(50)
Fe3O4@L-arginine(50)
Fe3O4@L-arginine(25)
Fe3O4@L-arginine(75)
Fe3O4@L-arginine(50)
Fe3O4@L-arginine(50)
Fe3O4(50)
30 min
30 min
30 min
30 min
30 min
30 min
15 min
45 min
30 min
30 min
6
1 EtOH:1 H2O
2 EtOH:1 H2O
3 EtOH:1 H2O
3 EtOH:1 H2O
3 EtOH:1 H2O
3 EtOH:1 H2O
3 EtOH:1 H2O
3 EtOH:1 H2O
3 EtOH:1 H2O
r.t.
7
r.t.
8
r.t.
9
r.t.
10
11
12
13
14
r.t.
r.t.
r.t.
r.t.
L-arginine(50)
r.t.
TABLE 2 Multicomponent one-pot synthesis of 103-diaryl-2N-azaphenalene derivatives
Without catalyst
With catalyst
M.p. (ꢁC)
Found
Entry
1
Product
B1
Ar
R
Time (hr)
Yield (%)
76
Time (min)
Yield (%)
92
Reported [ref]
208–209[9]
C6H5
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
5
7
6
6
8
9
8
10
6
8
7
5
6
8
6
7
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
207–208
218–220
212–214
216–217
194–196
205–207
186–188
225–227
258–259
214–216
204–206
202–203
204–206
191–193
230–232
215–216
[7]
2
B2
4-ClC6H4
3-HOC6H4
4-HOC6H4
4-NO2C6H4
N,N-Di MeC6H4
2-NO2C6H4
2-BrC6H4
2-MeC6H4
2-ClC6H4
2-MeOC6H4
C6H5
44
71
—
3
B3
36
83
—
4
B4
47
72
216–217[9]
5
B5
64
85
—
—
—
—
—
6
B6
55
81
7
B7
54
86
8
B8
29
73
9
B9
73
91
[7]
10
11
12
13
14
15
16
B10
B11
A1
42
71
—
73
85
—
70
87
202–203[1]
204–206[1]
—
A2
4-HOC6H4
2-NO2C6H4
2-MeC6H4
2-MeOC6H4
H
35
68
A3
H
62
93
A4
H
72
85
—
A5
H
72
90
215–216[1]
The infrared spectrum of this compound exhibits broad and
strong adsorption in the 3,300–3,100 cm−1 region of the ten-
sile vibrations of the N–H and O–H bonds. Characteristics
of tensile vibrations of C-H aromatics in the region of
3,063 cm−1 and tensile vibrations of aliphatic C–H have
appeared in the 2,939 cm−1 area. Also, the absorption asso-
ciated with the tensile vibrations of C–O links in the
1,243 cm−1 area appears to be a strong peak.
related to the proton numbers 4 and 5 of the naphthol ring,
and the dual peak appearing in the region 6.39 ppm is
related to the proton numbers 3 and 6, and the peaks of other
aromatic hydrogens are found in the region 6.39–7.14 ppm.
The peaks related to the aliphatic hydrogens of the pyridine
ring appear in the region 5.46 ppm, and the aliphatic hydro-
gens of methoxy groups appear in the region 3.77 ppm as
single branch. The carbon nuclear magnetic resonance spec-
trum (13C-NMR) of compound A5 shows 14 carbon, the
peaks related to aromatic carbon connected to methoxy
groups appear in the region 157.37 ppm and the peaks
related to aromatic carbon connected to hydroxy groups
appear in the region 150.38 ppm. In the spectrum of this
compound, there are two types of aliphatic carbon, the peak
The proton Nuclear Magnetic Resonance Spectrum (1H-
NMR) of the A5 compound exhibits a single branch peak in
the area 9.06 ppm that relates to Phenolic OH groups. The
peak of N–H appears in the area 2.662 ppm as a broad spec-
trum, these two peaks disappeared in the spectrum obtained
for D2O. The dual peak appearing in the region 7.57 ppm is

EFTEKHARI ET AL.
5
hydrogens are found in the regions 6.63 and 6.88 ppm. The
peaks related to the aliphatic hydrogens of the pyridine ring
appear in the region 5.18 ppm and the aliphatic hydrogens
of methoxy groups appear in the region 1.191 ppm as a sin-
gle branch.
The carbon nuclear magnetic resonance spectrum 13C-
NMR of compound A4 shows 13 carbon, the peak related to
the carbonyl group (C = O) can been seen in the region
172.74 ppm and the peaks related to aromatic carbon con-
nected to hydroxy groups appear in the regions 156.72 and
150.97 ppm. In the spectrum of this compound, there are
two types of aliphatic carbon, the peak appearing in the
region 21.69 ppm is related to the aliphatic carbon of meth-
oxy groups and the peak appearing in the region 53.35 ppm
is related to the aliphatic carbon of the piperidine ring.
SCHEME 3 The most probable mechanism for synthesis of N-acyl-
1,3-diaryl-2-azaphenalene derivatives
2.3 | Recovery and reusability of catalyst
The reusability of magnetic catalysts is one of their notewor-
thy advantages. In this study, the reusability of the
Fe3O4@L-arginine catalyst was investigated in the synthesis
of the 1,3-diaryl-2-N-azaphenalene derivatives. After com-
pletion of the reaction, the catalyst could be easily separated
from the reaction mixture with the assistance of an external
magnetic force and was washed with ethanol and dried at
60 C for 1 hr. The catalytic activity of Fe3O4@L-arginine
was examined for five runs.
appearing in the region 55.86 ppm is related to the aliphatic
carbon of methoxy groups, and the peak appearing in the
region 47.85 ppm is related to the aliphatic carbon of the
piperidine ring.
2.2.2
| N-acetyl-4,9-dihydroxy-1,3-di(4-hydroxyphenyl)-
2,3-dihydro-2-azaphenalenes(B4)
3
| EXPERIMENTAL
3.1 | General
All chemicals purchased from Merck or Fluka, and used
without further purification.To measure melting points, used
capillary tubes on an electrothermal digital apparatus. IR
spectra were recorded by the TENSOR 27, FT-IR 5000 in
The infrared spectrum of this compound exhibits broad and
strong adsorption bands in the 3,300–3,100 cm−1 region of
the tensile vibrations of the O–H bond, which have appeared
broadly due to the formation of hydrogen bonds. Also, a
sharp peak appears in the 3,630 cm−1 area, which is related
to the free O–H Phenol. Absorption bands related to the ten-
sile vibrations of the carbonyl group C=O appeared in the
region of 1,623 cm−1 and the tensile vibrations of the bond
C=C aromatic appeared in the 1,511 cm−1 region as a strong
peak. Also, the absorption related to the tensile vibrations of
the C–O bonds appeared in the 1,246 cm−1 region as a
strong peak.
1
KBr. HNMR and 13C-NMR spectra were obtained on Bru-
ker 125 MHz spectrometers using DMSO-d6 as a solvent
with TMS as an internal standard. The progress of the reac-
tion was monitored by thin-layer chromatography (TLC)
using n-hexane/EtOAc as an eluent. Nanoparticles were
characterized using an X-Pert Pro MPD XRD diffractometer
(Cu-Kα, k = 0.154056 nm) over the range 2θ = 10–80
using 0.04 as the step length. The scanning electron micro-
scope measurement was obtained using a Hitachi S-4700
field emission-scanning electron microscope (FE-SEM).
The 1H-NMR of the B4 compound exhibits a broad
spectrum with a four-hydrogen integral in the region
8.92 ppm that relates to phenolic OH groups. The dual peak
appearing in the region 7.58 ppm is related to proton num-
bers 4 and 5 of the naphthol ring. The dual peak appearing
in the region 7.01 ppm is related to proton numbers 3 and
6 of the naphthol ring, and the peaks for other aromatic
3.2 | General procedure for “1,3-diaryl-2-N-
azaphenalene and N-acyl-1,3-diaryl-2-N-azephenylene”
without the presence of a catalyst
Products of aldehydes, 2,7-naphthalene-diol, and ammonia
derivatives are prepared in a MCR, one-Pot, and under sol-
vent conditions.

6
EFTEKHARI ET AL.
The chemicals used are from Merck, Aldrich, and
Fuluca, or were synthesized in the laboratory.
ethanol (3:1) in a balloon, in an unheated condition, and it is
stirred for an hour. Then the mixture was kept for an hour
without moving. We followed the reaction progression
with TLC.
After completion of the reactions, 20 mL of saturated
NaCl was added to the reaction mixture and stirred for
60 min at room temperature. The precipitate was thinned
and washed with water and then dried. The product was
washed with 20 mL ethyl acetate-hexane in a 4:1 ratio and
dried at 100ꢁC under vacuum for 4 hr.
A mixture of aldehyde (2 mmol), 2,7-naphthalene diol
(1 mmol), ammonia derivatives (ammonium hydrogen sul-
fate or ammonium acetate) (2 mmol), and 4 mL of water-
ethanol in a 1:3 ratio was prepared and used for this study.
We followed the reaction progression with TLC.
After completion of the reactions, 20 mL of saturated
NaCl was added to the reaction mixture and stirred for
60 min at room temperature. The precipitate was thinned
and washed with water and then dried.
It can be seen that products are produced in less time and
with a better efficiency without the use of heat and reflux
conditions. The reaction time and efficiency values are listed
in Table 2.
The crude product was washed with 20 mL ethyl
ꢁ
acetate-hexane in a 4:1 ratio and dried at 100 C under vac-
uum for 4 hr.
To expand the reaction above after a suitable initial
result, reactions with various derivatives of aldehyde, such
as deadly electron groups (such as halide and nitro) and
donor electron groups (such as methyl), were investigated.
The duration and efficiency for each of the products are
reported in Table 1.
In the second step, the amount of catalyst required was
investigated. These studies have shown that the best result is
achieved using 100 mg of the catalyst, which when used
more does not have a significant effect on the reaction per-
formance (duration and efficiency).
The model reaction was repeated in the presence of L-
arginine and naked Fe3O4 separately as a catalyst. The
results showed that the yield of the reaction is lower than
that of arginine-coated Fe3O4. The results were inserted in
the following table, entries. Naked Fe3O4 showed no appro-
priate efficiency for the model reaction. Although the reac-
tion was successfully performed in the presence of pure
arginine, arginine-coated Fe3O4 was selected as the best cat-
alyst due to its simple recovery and reuse compared with
homogeneous arginine.
3.3 | Preparation of Fe3O4@L-arginine nanocatalyst
To synthesize this nanocatalyst,
a mixture of salts
FeCl3.6H2O (5 mmol) and FeCl2.4H2O (2.5 mmol) was dis-
solved in 100 mL of deionized water. Then, 2 mg of L-
arginine and 30 mL of ammonia solution were added to
male 25 % solution until the pH of the solution reaches 11.
The above combination was kept under reflux conditions for
ꢁ
6 hr at 100 C. The Fe3O4@L-arginine nanocatalyst was
The reaction with aliphatic aldehydes such as ethanal,
propanal, and hexanal was evaluated under optimized condi-
tions. Unfortunately, the observations of the reaction mixture
by TLC showed few small points that could not be sepa-
rated, ultimately we stopped the reaction.
separated from the aqueous solution by an external magnet
and eventually washed and dried for 24 hr (Scheme 4).[22]
The quality of the synthesized nanocatalyst was proved
using FTIR, XRD, and SEM analyses.
The reaction between two different aromatic aldehydes
(2-methoxybenzaldehyde and 2-nitrobenzaldehyde) was also
evaluated under the optimized condition. Interestingly, the
major product of the two symmetrical combinations is con-
sidered appropriate.
3.4 | Synthesis of compounds in the presence of
Fe3O4@L-arginine nanocatalyst
At first, we added 100 mg of the synthesized nanocatalyst
into a mixture of aldehyde (2 mmol), 2,7-naphthalene diol
(1 mmol), and ammonia derivatives (ammonium hydrogen
sulfate or ammonium acetate) (2 mmol), and 4 mL of water-
4
| SELECTED SPECTRAL DATA
4.1 | A5:4,9Dihydroxy-1,3-di(2-methoxyphenyl)-
2,3-dihydro-2-azaphenalene
IR (KBr): νmax = 3,493, 3,271–2,939, 1,624, 1,599, 1,514,
1,243, 1,026, 832, and 749 cm. 1H NMR (500 MHz,
DMSO-d6): δ = 9.06 (s, 2H, disappeared on D2O
exchange), 7.57 (d, J = 8.5, 2H), 7.14 (t, J = 7.6, 2H), 6.98
(d, J = 8.7, 2H), 6.85 (d, J = 7.5, 2H), 6.65(t, J = 7.6, 2H),
6.39 (d, J = 8.7, 2H), 5.56 (s, 2H), 3.77 (s, 6H), and 2.66
(br, 1H, disappeared on D2O exchange). 13C NMR
(125 MHz, DMSO-d6): δ = 157.4, 150.3, 132.9, 131.4,
SCHEME 4 Synthesis pathway of Fe3O4@L-arginine

EFTEKHARI ET AL.
7
128.5, 127.9, 122.7, 120.2, 120.3, 115.1, 114.9, 111.2, 55.8,
and 47.8.
5 | CONCLUSIONS
Finally, we were able to carry out an efficient reaction, one-
pot, low-time, and high efficiency, without the use of heat
and reflux for the production of derivatives of 1,3-diaryl-
2-n-azaphenalene and n-acyl-1,3-diaryl-2-n-azaphenylene
from a mixture of five compounds of 2, 7-naphthalene diol,
aldehydes, ammonia derivatives (ammonium acetate or
ammonium hydrogen phosphate), and solvent (water
and alcohol) in the presence of Fe3O4@L-arginine
nanocatalysts.
As shown in Table 1, on the nanoscale, the reaction time
is, on average, one-fifth of the time when the catalyst is not
used, while the efficiency of the reactions is improved by
20–50%. It also saves energy due to nonuse of heat, and the
synthesis of compounds makes economical.
4.2 | B1:N-acetyl-4,9-dihydroxy-1,3-di(phenyl)-
2,3-dihydro-2-azaphenalene
IR (KBr): νmax = 3,300–3,000, 2,818, 2,708, 1,626, 1,585,
1,516, 1,431, 1,396, 1,327, 1,273, 1,130, 1,028, 881, 736,
699, and 671 cm−1; 1H NMR (500 MHz, DMSO-d6):
δ = 9.01 (br, 2H, disappeared on D2O exchange), 7.56 (d,
J = 7.7 Hz, 2H), 7.21(t, J = 7.6, 4H), 7.16(t, J = 7.6, 2H),
7.08 (d, J = 7.0 Hz, 4H), 6.86 (d, J = 8.7 Hz, 2H), 5.19 (s,
2H), and 1.91 (s, 3H); 13C NMR(125 MHz, DMSO-d6):
δ = 172.5, 150.5, 145.2, 132.2, 128.3, 128.1, 127.7, 126.6,
122.7, 116.2, 115.2, and 53.9.
In addition, Fe3O4 was considered as a nanocatalyst
because of the availability, low toxicity, recyclability, and
easy separation of the reaction solution. The catalyst can be
used five times without losing its function.
4.3 | B4:N-acetyl-4,9-dihydroxy-1,3-di
(4-hydroxyphenyl) -2,3-dihydro-2-azaphenalenes
The Fe3O4@L-arginine nanocatalyst was characterized
using FT-IR spectroscopy, XRD, and FESEM.
IR (KBr): νmax = 3,630, 3,319, 3,211, 3,015, 2,823, 2,696,
1,623,1,604, 1,543, 1,511, 1,429, 1,309, 1,246, 1,174, 1,130,
836, 773, and 657 cm−1; 1H NMR (500 MHz, DMSO-d6):
δ = 8.92 (br, 4H , disappeared on D2O exchange), 7.58 (d,
J = 7.4 Hz, 2H), 7.01–6.88 (m, 6H), 6.63–6.50 (m, 4H), 5.18
(s, 2H), and 1.90 (s, 3H); 13C NMR(125 MHz, DMSO-d6):
δ = 172.74, 156.72, 150.9, 132.2, 131.75, 129.59, 128.12,
122.5, 115.3, 115.1, 114.8, 53.3, and 21.6.
ACKNOWLEDGMENTS
We gratefully acknowledge the Department of Organic
Chemistry, Faculty of Pharmaceutical Chemistry, Tehran
Medical Sciences, Islamic Azad University, Tehran, Iran.
ORCID
Naser Foroughifar https://orcid.org/0000-0003-0562-
4.4 | B9:N-acetyl-4,9-dihydroxy-1,3-di
3015
(2-methylphenyl)-2,3-dihydro-2-azaphenalene
IR (KBr): νmax = 3,271–2,968, 1,624, 1,511, 1,411, 1,316,
1,039, 840, 758, and 699 cm−1. 1H NMR (500 MHz,
DMSO-d6): δ = 9.11 (br, 2H, disappeared on D2O
exchange), 7.55 (d, J = 8.5, 2H), 7.09 (t, J = 7.6, 2H), 6.96
(d, J = 8.7, 2H), 6.91 (m, 2H), 6.84 (m, 4H), 5.15 (s, 2H),
2.20 (s, 6H), and 1.91 (S, 3H). 13C NMR (125 MHz,
DMSO-d6): δ = 172.4, 150.5, 144.9, 136.99, 132.1, 128.9,
128.6, 127.6, 127.32, 125.45, 122.7, 116.3, 115.2, 53.89,
21.6, and 21.5.
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How to cite this article: Eftekhari A, Foroughifar N,
Hekmati M, Khobi M. Fe3O4@L-arginine magnetic
nanoparticles: A novel and magnetically retrievable
catalyst for the synthesis of 103-diaryl-2N-azaphena-
lene. J Chin Chem Soc. 2019;1–8. https://doi.org/10.
1002/jccs.201800274
[27] N. Foroughifar, A. Mobinikhaledi, M. A. Bodaghi Farad, H. Moghanian,
S. Ebrahimi, M. Kalhor, Synth. Commun. 2009, 39, 1166.