Fe3O4@MCM-41@ZrCl2: A novel magnetic mesoporous nanocomposite catalyst including zirconium nanoparticles for the synthesis of 1-(benzothiazolylamino)phenylmethyl-2-naphthols

Article abstract of DOI:10.1002/aoc.6212

The present article reports the synthesis of a new magnetic mesoporous nanocomposite with core–shell structure, formulated as Fe₃O₄@MCM-41@ZrCl₂. The prepared reagent was successfully characterized using different types of

Full text of DOI:10.1002/aoc.6212

Received: 12 April 2020
DOI: 10.1002/aoc.6212
Revised: 4 July 2020
Accepted: 8 July 2020
F U L L P A P E R
Fe3O4@MCM-41@ZrCl2: A novel magnetic mesoporous
nanocomposite catalyst including zirconium nanoparticles
for the synthesis of 1-(benzothiazolylamino)phenylmethyl-
2-naphthols
Reyhaneh Pourhasan Kisomi1 | Farhad Shirini1
| Mostafa Golshekan2
1Department of Chemistry, College of
The present article reports the synthesis of a new magnetic mesoporous
nanocomposite with core–shell structure, formulated as Fe3O4@MCM-
41@ZrCl2. The prepared reagent was successfully characterized using different
types of methods. The combination of unique properties of MCM-41 as an
inimitable mesoporous compound, satisfying magnetic nature of the Fe3O4
magnetic nanoparticles and substantial catalytical applications of zirconium,
caused the favorable efficiency of the intended nanocomposite in the synthesis
of 1-(benzothiazolylamino)phenylmethyl-2-naphthols via a multicomponent
condensation reaction of 2-aminobenzothiazole, 2-naphthol, and aromatic
aldehydes in absence of solvent in good to high yields (70–90%). Green condi-
tions of the reactions, easy separation, practicability, product purity, reusability
of the catalyst, affordability, and environmentally profits are the considerable
advantages of this protocol.
Sciences, University of Guilan, Rasht, Iran
2Medical Biotechnology Research center,
School of Paramedicine, Guilan
University of Medical Sciences, Rasht,
Iran
Correspondence
Farhad Shirini, Department of Chemistry,
College of Sciences, University of Guilan,
Rasht 41335-19141, Iran.
Email: shirini@guilan.ac.ir
Funding information
Research Council of the University of
Guilan
K E Y W O R D S
1-(benzothiazolylamino)phenylmethyl-2-naphthols, Fe3O4@MCM-41@ZrCl2, magnetic
nanoparticles (MNPs), MCM-41, zirconium
1 | INTRODUCTION
absorption,[25–27] and so forth.[28] Moreover, in order to
make such compounds more applicable in terms of recy-
In spite of significant advances in the field of mesoporous
materials and the growing expansion of new types of
them,[1–8] the first and foremost member of M41S called
MCM-41 still has attracted growing research attention
owing to its chemical versatility.[9–13] Its capabilities,
especially in the field of catalytic activity, all come from
its unique properties, such as high surface area
(ꢀ1000 m2 g−1), narrow pore size distribution, uniform
pore size, and the possibility of adjusting the diameter of
the pores between 2 and 10 nm. These features result in
high thermal stability and the possibility of using it in a
wide range of applications such as catalization,[13–15]
clability, use of magnetic nanoparticles (MNPs) for the
preparation of nanocomposites is so helpful leading to
their simple recovery by using an external magnetic field,
which increases their performance in the next
reuses.[29–32] In this regard, iron oxides especially Fe3O4
are preferable because of their good magnetic properties
compared with other MNPs, high resistance to degrada-
tion and lower toxicity.[33,34]
In order to obtain interesting and remarkable
catalytic capabilities from these magnetic mesoporous
nanocomposites, modification of their surface by stabiliza-
tion of metal nanoparticles on their structure is one of the
best selections.[14,32,35–39] This method is also a useful way
isolation,[16–18]
photocatalysis,[19–21]
sensors,[22–24]
Appl Organomet Chem. 2021;35:e6212.
wileyonlinelibrary.com/journal/aoc
© 2021 John Wiley & Sons, Ltd.
1 of 15
https://doi.org/10.1002/aoc.6212

2 of 15
POURHASAN KISOMI ET AL.
of preventing the accumulation of metal nanoparticles. In
this field, zirconium (IV)-based nanoparticles are one of
the most useful cases because of their commercial availabil-
ity, low price, and low toxicity.[40] Also these compounds
represent a good Lewis acid behavior and high catalytic
activity characteristics,[41–43] which come from a high
coordinating ability due to the higher charge-to-size
value of Zr4+ compared with most of the metal ions.[44,45]
Incorporation of Zr (IV) nanoparticles into the framework
of mesoporous materials not only enhances their catalytic
applicability but also increases their thermal and hydro-
thermal stability. On the other hand, this process makes
them stable against moisture and corrosiveness and also be
easy to handle.[46–48]
2 | EXPERIMENTAL
2.1 | Materials
All chemicals including FeCl3Á6H2O, FeCl2Á4H2O,
tetraethylorthosilicate (TEOS), cetyl trimethylammonium
bromide (CTAB), NaOH, NaF, ZrCl4, 2-aminobenzothiazole,
2-naphthol, and aldehydes were bought with high purity
from Merck chemical company (Munich). All solvents were
provided from Merck (Munich), and with the aim of the
minimization of the absorption of the atmosphere moisture,
besides getting distilled before being used, they were saved
sealed in airtight containers as well.
The
extensive
and
significant
role
of
2-aminobenzothiazole core, as a privileged scaffold, in
pharmaceutical, biological, and industrial chemistry is
undeniable.[49–58] Among these types of compounds,
1-(benzothiazolylamino)phenylmethyl-2-naphthols have two
biologically active components, 2-aminobenzothiazole and a
Betti's base. Betti's base, a structure called 1-(α-aminoalkyl)-
2-naphthols with two active amino and hydroxyl groups,
plays a major role in synthetic chemistry due to the
possibility of C–C bond formation under mild laboratory
conditions.[58] These benefits have navigated numerous
efforts to synthesize 1-(benzothiazolyl amino)phenylmethyl-
2- naphthols employing various catalysts such as
sodium dodecyl sulfate (SDS),[59] NaHSO4.H2O,[60] hetero-
polyacid (HPA),[61] maltose,[62] 3-methyl-1-(4-sulfonic acid)
propylimidazolium hydrogen sulfate [(CH2)3SO3HMIM]
[HSO4],[63] fumaric acid,[64] oxalic acid,[58] ɤ-aminobutyric
2.2 | Characterization techniques
All products were characterized by comparing their phys-
ical constants, and also infrared (IR) and nuclear mag-
netic resonance (NMR) spectra with authentic samples
and those reported in the literature. The pureness mea-
surement of the substrate and reaction monitoring was
appended by thin-layer chromatography (TLC) on a silica
gel Polygram SILG/UV 254 plate. Melting points measur-
ing were achieved using an electrothermal IA9100 melt-
ing point apparatus in capillary tubes. The pelletized
samples of the synthesized nanocomposite were distin-
guished via Fourier transform infrared spectroscopy
(FT-IR) measurements by Brucker Alpha series in the
range of 400–4000 cm−1. Investigation on crystal phases
and crystallinity of the synthesized MNPs were fulfilled
by X-PERT instrument with CuKα radiation of Sharif
University of Technology (Iran) in the range of 0.7ꢁ–80ꢁ
(2É). Transmission electron microscopy (TEM) images
were prepared with a Zeiss-Sigma VP device from Oxford
instruments company (England). The energy dispersive
spectrometer (EDS) was performed on a TESCAN MIRA
II (Czech) device to detect the presence of elements.
Absorption–desorption nitrogen gas isoterms and surface
area (SBET) were determined using a BELSORP-mini II
device at a temperature of 77ꢁK. The samples were out-
gassed at 373ꢁK and 1 mPa for 12 h before adsorption
measurements.
acid
NH3(CH2)5NH3BiCl5.[67]
(GABA),[65]
phosphate
fertilizers,[66]
and
Although all reports have their own credits, some
defects such as toxicity and expensiveness of the catalyst,
environmental pollution, challenging synthesis, inacces-
sible reactions, long-term reaction times, and undesirable
yields are still notable. Therefore, further research is
needed to find greener and more economical methods. In
continuation of our prior reports on the application of
different acidic and basic catalysts, especially meso-
porous, zirconium-based, and supported reagents in
organic transformations,[46,68–76] and in order to over-
come the above mentioned restrictions, we intended to
prepare a diverse range of 1-(benzothiazolylamino)
phenylmethyl-2-naphthols through a three-component
2.3 | Preparation of the catalyst
2.3.1 | Preparation of Fe3O4-MNPs
condensation
reaction
of
2-aminobenzothiazole,
2-naphthol, and a variety of aldehydes in the presence of
a new magnetic mesoporous nanocomposite formulated
as Fe3O4@MCM-41@ZrCl2. This reagent is synthesized
via a simple method and characterized using different
types of techniques.
The synthesis of Fe3O4-MNPs was fulfilled according to
our previous method with slight modification.[77] Accord-
ingly, 6.3-g FeCl3Á6H2O, 4.0-g FeCl2Á4H2O, and 1.7-mL

POURHASAN KISOMI ET AL.
3 of 15
HCl (12 mol L−1) were mixed in 50 mL of deionized
water in a beaker. Then, the solution was degassed with
argon gas and heated to 80ꢁC in a reactor. Concurrently,
250 mL of a 1.5 mol L−1 ammonia solution was gently
added to the solution under argon gas protection and vig-
orous stirring (1000 rpm). After completion of the reac-
tion, the resultant black solid of Fe3O4-MNPs was
separated from the reaction medium using an external
magnet followed by washing four times with 500-mL
double distilled water. Eventually, the black powder of
Fe3O4-MNPs was achieved.
times and then dried at 100ꢁC. Thus, the desired
mesoporous magnetic nanocomposite was achieved
(Scheme 1).
2.4 | General procedure for the synthesis
of 1-(benzothiazolylamino)phenylmethyl-
2-naphthols (See supporting information)
A mixture of 2-aminobenzothiazole (1 mmol), 2-naphthol
(1 mmol), aromatic aldehyde (1 mmol), and the prepared
nanocatalyst (0.05 g) was heated in an oil bath at 100ꢁC
under neat conditions. The reaction progress was investi-
gated by TLC using a mixture of n-hexane:ethyl acetate
(2:1) solvents until the completion of the reaction. After
completion of the reaction, ethanol (10 mL) was added to
the reaction vessel, and the catalyst was separated from
the mixture by an external magnet. The solvent was evap-
orated from the residue, and the product was purified by
recrystallization from ethanol. The spectral data of some
compounds are as follows:
2.3.2 | Preparation of Fe3O4@MCM-41
magnetic nanocomposites
To synthesize Fe3O4@MCM-41, we followed the
method described by Saadatjoo et al.[78] Typically, a
mixture of 50 mL of deionized water, 5 mL of ammo-
nia solution (2.5 M), and 1.5 g of the synthesized
Fe3O4-MNPs was sonicated for 30 min. Then, 10 mL
of tetraethyl orthosilicate (TEOS), 0.9 g of sodium
hydroxide (NaOH), and 0.19 g of sodium fluoride
(NaF) were added to it and stirred vigorously for 2 h.
Afterwards, 3 g of cetyltrimethylammonium bromide
(CTAB) was added to the mixture and stirred for 2 h
again. After this time, the mixture was transferred to
an autoclave with hydrothermally treating in an oven
at 100ꢁC for 48 h under static conditions. The acquired
sediment was separated by an external magnet and
washed several times with distilled water and dried at
100ꢁC. Lastly, in order to eliminate the surfactant, the
as-synthesized Fe3O4@MCM-41 was calcined at 300ꢁC
for 3 h. At this step, the nanocomposite was obtained
in the form of an orange powder with a magnetic
feature.
Table 1, Entry 13: IR (neat) ν = 3315, 3052, 1589,
1540, 1441, 1321, 1263 cm−1
;
1H NMR (DMSO-d6,
400 MHz): δ = 7.02–7.95 (m, 18H), 8.99 (s, 1H), 10.24
(s, 1H) ppm; 13C NMR (DMSO-d6, 100 MHz): δ = 118.6,
119.0, 119.5, 121.5, 121.6, 122.9, 124.4, 125.5, 125.9,
126.02, 126.6, 126.78, 126.80, 127.9, 128.17, 128.22,
129.09, 129.14, 130.2, 131.2, 132.3, 132.7, 133.2, 140.7,
152.4, 153.8, 166.9 ppm.
Table 1, Entry 14: IR (neat) ν = 3356, 3056, 1592,
1543, 1445, 1323, 1262 cm−1
;
1H NMR (DMSO-d6,
400 MHz): δ = 7.24–7.77 (m, 26H), 8.81 (s, 2H), 10.14 (br,
2H) ppm; 13C NMR (DMSO-d6, 100 MHz): δ = 118.1,
118.5, 118.8, 119.0, 121.3, 121.4, 122.8, 125.9, 125.9, 126.4,
127.2, 129.0, 129.9, 130.0, 131.2, 132.5, 140.8, 152.5, 153.6,
153.6, 166.7 ppm.
Table 1, Entry 15: IR (neat) ν = 3375, 1581, 1540,
1
1443, 1329, 1261 cm−1; H NMR (DMSO-d6, 400 MHz):
2.3.3 | Preparation of magnetic
mesoporous nanocomposites including
zirconium nanoparticles Fe3O4@MCM-
41@ZrCl2
δ = 2.22 (s, 3H, CH3), 7.02–7.80 (m, 15H), 8.80 (s, 1H),
10.15 (br, 1H) ppm; 13C NMR (DMSO-d6, 100 MHz):
δ = 21.7, 119.3, 121.4, 121.4, 122.9, 123.7, 123.7,
125.9, 126.0, 126.8, 126.9, 127.1, 127.4, 127.5, 128.4, 128.5,
129.1, 130.0, 131.2, 132.6, 137.5, 143.0, 152.6, 153.6,
166.8 ppm.
For the synthesis of Fe3O4@MCM-41@ZrCl2 magnetic
nanocomposite, we followed the procedure reported by
Kamali and Shirini[46] with minor modification.
Typically, to a mixture of 0.5 g of ZrCl4 in 15 mL of
chloroform, 0.5 g of the calcined Fe3O4@MCM-41
nanocomposite was added. The resulting slurry
was continuously stirred at room temperature for 24 h.
The gained sediment was separated using an external
magnet and washed with chloroform for several
Table 1, Entry 16: IR (neat) ν = 3310, 1620, 1593,
1
1535, 1502, 1440 cm−1; H NMR (DMSO-d6, 400 MHz):
δ = 3.81 (d, J = 22.81 Hz, 1H), 3.88 (d, J = 22.81 Hz, 1H),
7.05–7.97 (m, 18H), 8.88 (s, 1H), 10.21 (s, 1H) ppm; 13C
NMR (DMSO-d6, 100 MHz): δ = 53.8, 118.6, 118.9, 119.0,
119.4, 120.1, 120.2, 121.4, 121.5, 122.9, 123.2, 125.3, 125.5,
125.9, 126.8, 127.0, 127.2, 127.6, 129.1, 129.1, 130.1, 131.3,
132.7, 139.9, 141.3, 142.0, 152.6, 153.7, 166.8 ppm.

4 of 15
POURHASAN KISOMI ET AL.
SCHEME 1 Preparation of
Fe3O4@MCM-41@ZrCl2 nanocomposite
3 | RESULTS AND DISCUSSION
3.1 | Characterization of the catalyst
3.1.1 | FT-IR analysis
prosperous removal of the surfactant. In both spectra
(b and c), the appeared bands at 465, 890, and 1,080 cm−1
are indexed as characteristic absorptions of MCM-41
structure resulted from the symmetric and asymmetric
bending and stretching vibrations of Si–O–Si bonds.[80] In
addition, the attendance of 560 cm−1 vibration band at all
the magnetic synthesized materials confirms the presence
of Fe3O4 nanoparticles. It is notable that because of
overlapping of the vibration bands of Zr–O–Si with the
asymmetric vibration bands of Si–O from sylanol groups
at 960 cm−1, this band is not observable.[72]
The FT-IR spectra of Fe3O4 (a), Fe3O4@MCM-41 [before
and after removal of the template (b,c)], ZrCl4 (d) and
Fe3O4@MCM-41@ZrCl2 (e) are indicated in Figure 1.
Obviously, in comparison, the absorption band at
560 cm−1 is attributed to the vibrations of the Fe–O bond
in bare MNPs (spectrum a).[79] As can be seen, in all
spectra, the absorption bands related to the stretching
and bending vibrations of the O–H bond appeared at
3446 and 1640 cm−1, respectively. Strong bands at 2850
and 2920 cm−1 in spectrum (b) are related to the symmet-
ric and asymmetric vibrations of the CH2 groups of
the surfactant, respectively. The potential decrease of the
intensity of such bands in the spectrum (b) verifies the
3.1.2 | Powder XRD analysis
The X-ray diffraction (XRD) patterns of the Fe3O4
@
MCM-41 nanocomposite at low and wide angle region
(Figure 2) show the peaks that can be assigned to the
structure of Fe3O4 MNPs and the MCM-41 mesoporous

POURHASAN KISOMI ET AL.
5 of 15
TABLE 1 Optimization of the amounts of the catalyst, temperature, and solvent in the reaction of 2-aminobenzothiazole (1 mmol),
2-naphthol (1 mmol), and 4-chlorobenzaldehyde (1.1 mmol) in the presence of Fe3O4@MCM-41@ZrCl2 nanocomposite as the catalyst
Entry
Amounts of the catalyst (g)
Solvent
Temperature (ꢁC)
Time (min.)
Conversions
1
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.04
0.05
0.06
0.05
0.05
0.05
0.05
-
r.t.
90
90
90
90
90
90
90
90
15
15
90
90
90
45
Not completed
Trace
2
-
50
3
-
100
50
Trace
4
H2O
Not completed
Trace
5
H2O
100
50
6
EtOH
Not completed
Trace
100 (85)a
100 (90)a
100 (87)a
7
EtOH
100
100
100
100
100
100
100
100
8
-
-
-
-
-
-
-
9
10
11b
12c
13d
14e
Trace
Not completed
Not completed
100 (70)a
aIsolated yields.
bFe3O4.
cFe3O4@MCM-41.
dMCM-41.
eZrCl2.
Standards (JCPDS No. 19-692).[81] By surveying the repre-
sented pattern of Figure 2a, manifestly, a sharp and well-
defined diffraction peak is available at 2É = 2.63, which
corresponded to the peak (100), and the weaker peak at
2É = 4.65 validates the peak (110), as the characteristics
of mesoporous materials, and verifies the existence of
hexagonal structure.[82,83] After introducing of ZrCl4, as
can be seen in Figure 2b, the mentioned nanocomposite
revealed
a strong undeniable diffraction peak at
2É = 2.55ꢁ, representative of the Bragg plane reflection
(100), and the weaker one at 4.65ꢁ, indexed as (110)
reflection, indicating the preservation of the regular
mesoporous structure of MCM-41 after incorporation of
the zirconium nanoparticles on this mesoporous support.
As a more accurately description, the stabilization of zir-
conium metal nanoparticles resulted in the reduction of
the intensity of peaks, especially of (100) plane and their
relative shift towards the lower angle region, while the
overall diffraction patterns of the indexed appeared peaks
originated from the mesoporous material structure in the
desired nanocomposite have been completely preserved.
FIGURE 1 The Fourier transform infrared spectroscopy
(FT-IR) spectra of (a) Fe3O4, (b,c) Fe3O4@MCM-41 before and after
of the template removing, (d) ZrCl4, and (e) Fe3O4@MCM-
41@ZrCl2 nanocomposite
material. As clearly shown, in wide angle degree, the
characteristic peaks of the Fe3O4 structure appeared at
2É = 30.43ꢁ, 35.61ꢁ, 43.47ꢁ, 53.7ꢁ, 57.22ꢁ, and 63.03ꢁ
and established the presence of Fe3O4 in the structure
of the synthesized nanocomposite. These data are
corresponding with the XRD pattern of the standard
Fe3O4 from Joint Committee on Powder Diffraction
3.1.3 | BET analysis
The nitrogen adsorption/desorption isotherms of the
Fe3O4@MCM-41@ZrCl2 mesoporous nanocomposite

6 of 15
POURHASAN KISOMI ET AL.
FIGURE 2 (a) Wide angle X-ray
diffraction (XRD) patterns of
Fe3O4@MCM-41, (b) low angle XRD
patterns of Fe3O4@MCM-41, and
(c) Fe3O4@MCM-41@ZrCl2 mesoporous
nanocomposite
FIGURE 3 The N2 adsorption/
desorption isotherm of
(a) Fe3O4@MCM-41 and
(b) Fe3O4@MCM-41@ZrCl2
mesoporous nanocomposite
before and after the stabilization of the zirconium
nanoparticles are shown in Figure 3. By investigation in
the obtained diagrams, it is deduced that both isotherms
correlate with type IV (in the IUPAC classification),
accompanied by the absorption–desorption hysteresis in
3.1.4 | EDX analysis
The results of the energy dispersive X-ray (EDX) analysis
derived from the magnetic mesoporous nanocomposite
comprising zirconium nanoparticles (Fe3O4@MCM-
41@ZrCl2) are presented in Figure 4, indicating the pres-
ence of all the expected elements (Fe, Si, O, and Zr). This
confirms the successful loading of zirconium-based
nanoparticles on the mesoporous nanocomposite
structure.
ꢁ
the relative pressure region (P/P = 0.3–1), which is
expectable as the characteristic of the ordered meso-
porous materials isotherm.[84] The obtained Brunauer–
Emmet–Teller (BET) surface areas, total pore volume,
and Barret–Joyne–Halendu (BJH) mean pore diameter
were estimated 694.32 m2 g−1, 0.699 cm3 g−1, and
4.02 nm, respectively. After loading ZrCl4, as it is shown
in Figure 3b, the surface area and the residual total pore
volume of the Fe3O4@MCM-41@ZrCl2 mesoporous
nanocomposite were determind to be 271.11 m2 g−1 and
0.278 cm3 g−1, respectively. The relative diminution of
the surface area and total pore volume is affected by the
occupancy of the stabilized metal nanoparticles in the
structure of the mesoporous material and as sufficient
evidence confirms the prospering synthesis of the men-
tioned nanocomposite.[85] Although after ZrCl4 impreg-
nation, the BET surface area and total pore volume were
lessened, high surface areas and total pore volume were
perceived in Fe3O4@MCM-41@ZrCl2, and as a result, it
could be deduced that well-organized Fe3O4@MCM-
41@ZrCl2 mesoporous nanocomposite with a high
enough surface area could be achieved using this
method.
3.1.5 | TEM analysis
The TEM analysis of the catalyst is performed and
illustrated in Figure 5. Accordingly, there are the
spherical-like nanoparticles that are structured of dark
MNPs cores surrounded by amorphous silica shells
owning metals nanoparticles. The synthesized magnetic
mesoporous nanocomposites are perceptibly agglomer-
ated affected by the magnetic nature of the synthesized
nanoparticles.
3.1.6 | VSM analysis
In order to clarify the magnetic behavior of the
synthesized magnetic mesoporous nanocomposite, in

POURHASAN KISOMI ET AL.
7 of 15
FIGURE 4 The energy dispersive X-ray (EDX) profiles of
Fe3O4@MCM-41@ZrCl2 nanocomposite
FIGURE 6 The magnetic hysteresis curves of
(a) Fe3O4@MCM-41 and (b) Fe3O4@MCM-41@ZrCl2
nanocomposites
3.2 | Catalytic activity
After identification of the prepared novel magnetic
mesoporous nanocomposite, evaluation of its catalytic
role was the subsequent step. In this line, preparation
of a series of 1-(benzothiazolylamino)phenylmethyl-
2-naphthols via a three-component condensation reac-
tion of 2-aminobenzothiazole, 2-naphthol, and different
types of aromatic aldehydes, in the presence of
Fe3O4@MCM-41@ZrCl2, was intended. At first and in
order to determine the best reaction conditions, the effect
of different parameters such as amounts of the catalyst,
temperature, solvent, and also solvent-free conditions on
the reaction of 2-aminobenzothiazole (1 mmol),
2-naphthol (1 mmol), 4-chlorobenzaldehyde (1 mmol), as
the model reaction, was investigated. The related out-
comes are given in Table 1, illustrating that the most
suited conditions are as shown in Scheme 2 (Table 1,
Entry 9). In addition to investigating the effect of diverse
aforementioned parameters on the promotion of the
model reaction, and in order to further establishing the
capability of the introduced catalyst to catalyze this trans-
formation, the reaction progress was studied in the pres-
ence of Fe3O4, Fe3O4@MCM-41, MCM-41, and ZrCl2
separately. Based on the obtained data, Fe3O4
nanoparticles slightly proceeded with the reaction while
MCM-41and Fe3O4@MCM-41 were more effective due to
a large number of hydroxy groups on the high surface
area of the mesostructured moiety relative to the magne-
tite nanoparticles. The use of zirconium nanoparticles
caused the reaction to proceed completely, which is
FIGURE 5 The transmission electron microscopy (TEM)
image of Fe3O4@MCM-41@ZrCl2 nanocomposite
addition to the conventional distinguishing test of its
magnetic feature by applying a magnetic stirrer bar, the
vibrating-sample magnetometry (VSM) analysis was per-
formed, too. In this line, the obtained magnetic hysteresis
curves of MNPs are exhibited in Figure 6 stating about
38 and 7 emu g−1 as the estimated amount of saturation
magnetization value (Ms) for Fe3O4@MCM-41 and
Fe3O4@MCM-41@ZrCl2 nanoparticles, respectively.
Based on a reasonable justification, the observed decrease
in Ms value is evidence of loading nonmagnetic metal
nanoparticles on the magnetic mesoporous support
while it should be pointed out that the obtained
magnetization value of the final catalyst is sufficiently
as high as it could be magnetically separated using a
conventional magnet.

8 of 15
POURHASAN KISOMI ET AL.
reasonably due to the acidic nature of the utilized metal
nanoparticles that is the main factor in advancing the
reaction (as shown in the proposed mechanism
illustrated in Scheme 3). But in comparison with the
introduced catalyst, the much higher density of
zirconium nanoparticles stabilized on the surface of the
mesostructured support increases the acidic strength of
the entire catalyst, leading to boosted yields of the target
product and enhanced reaction rate.
In order to a more comprehensive and more accurate
evaluation of the catalytic capability of the novel
introduced catalyst in the 1-(benzothiazolylamino)
phenylmethyl-2-naphthols beget,
a comparison with
the performance of other reported catalysts in the synthesis
of 1-((benzo[d]thiazol-2-ylamino)(4-chlorophenyl)methyl)
naphthalen-2-ol (Entry 2, Table 2) was performed in
Table 3. This comparison reveals that the introduced cata-
lyst in this project has an adequate ability to generate the
desired product at an acceptable time with a very good
yield. Accordingly, Fe3O4@MCM-41@ZrCl2 can be stated
as a beneficial catalyst in terms of great activity, low con-
sumption of organic solvents, adaptability with the envi-
ronment, easy separation via an external magnetic field,
satisfactory yields of the products, and acceptable reaction
times compared with the other reported systems.
To comprehend the reaction proceeding in the presence of
the catalyst discussed, a credible mechanism is outlined in
Scheme 3. According to the proposed mechanism, the reaction
proceeds via activating the carbonyl group of the aldehyde
by the Lewis acidic catalyst Fe3O4@MCM-41@ZrCl2 followed
by nucleophilic attack of 2-naphthol on the activated carbonyl
of the aldehyde leading to the formation of the intermediate
(I). In the next step, the addition of 2-aminobenzothiazole
to this intermediate results in the production of the
intermediate (II) and ultimately the main product.
Accordingly,
different
derivatives
of
1-(benzothiazolylamino)phenylmethyl-2-naphthols using
a variety of aromatic aldehydes were prepared. The
results of this survey, along with the time, yield, and
melting point of each sample, are exhibited in Table 2.
Based on the information given in this table, it is
ascertained that, under the selected conditions, the target
compounds are obtained at short reaction times with
satisfactory yields. After completion of the reaction, a
scanty amount of the products lost during the work-up
process, and isolated yields got less than conversion
yields while the utilized magnetic nanocomposite can
be almost completely isolated from the reaction media.
This fact is manifested in Figure 7, so that in the
proximity of an external magnet, Fe3O4@MCM-
41@ZrCl2 nanocomposite was easily separated from its
aqueous suspension in a few seconds.
SCHEME 2 Synthesis of
1-(benzothiazolylamino)phenylmethyl-
2-naphthols derivatives catalyzed by
Fe3O4@MCM-41@ZrCl2 nanocomposite
SCHEME 3 A plausible
mechanism for the preparation of
1-(benzothiazolylamino)
phenylmethyl-2-naphthols
derivatives catalyzed by
Fe3O4@MCM-41@ZrCl2
nanocomposite

POURHASAN KISOMI ET AL.
9 of 15

10 of 15
POURHASAN KISOMI ET AL.

POURHASAN KISOMI ET AL.
11 of 15

12 of 15
POURHASAN KISOMI ET AL.

POURHASAN KISOMI ET AL.
13 of 15
3.3 | Reusability of the catalyst
magnetically, washed with ethanol, dried at 50ꢁC in air,
and finally tested for its activity in the next run. As shown
in Figure 8, this process was repeated at least for 4 times
with the scant change in the reaction times and yields.
Moreover, after comparing the spectra of the
as-synthesized catalyst with the recovered one in the
laboratory, showing no significant differences, we came to
this conclusion that the stability of the structure of the pre-
pared catalyst is good enough.
In order to show the recyclability of the catalyst
the
preparation
of
1-((benzo[d]thiazol-2-ylamino)
(4-chlorophenyl)methyl)naphthalen-2-ol was investigated
again. After completion of the reaction, ethanol was added
to the mixture, and the catalyst was separated
FIGURE 7 Photographs of an aqueous suspension of
Fe3O4@MCM-41@ZrCl2 magnetic nanocomposite before (a) and
after (b) magnetic capture
FIGURE 8 Reusability of Fe3O4@MCM-41@ZrCl2
nanocomposite in the synthesis of 1-((benzo[d]thiazol-2-ylamino)
(4-chlorophenyl)methyl)naphthalen-2-ol
TABLE 3 Comparison of the efficiency of Fe3O4@MCM-41@ZrCl2 nanocomposite with other reported catalysts in the reaction of
2-aminobenzothiazole, 2-naphthol, and 4-chlorobenzaldehyde
Time
(min.)
Yield
(%)
Entry Catalyst
Amount
Conditions
Ref.
1
2
3
HPA
LiCl
0.12 g
H2O/ultrasonic/40ꢁC 110
90
92
39
55
Javanshir et al.[61]
Shaabani and Rahmati[86]
Hosseinian et al.[60]
0.5 g/0.071 mol H2O/90ꢁC
360
120
30
ZnCl2
0.1 mol
0.1 mol
Solvent-free/70ꢁC
[(CH2)3SO3HMIM]
[HSO4]
Solvent-free/100ꢁC
Solvent-free/70ꢁC
Solvent-free/70ꢁC
Shaterian and
Hosseinian[63]
4
5
Zn(OAc)2.2H2O
0.1 mol
0.1 mol
35
60
62
65
Hosseinian and
Shaterian[60]
ZrO2
Hosseinian and
Shaterian[60]
6
7
YbCl3
Fe2O3
0.2 mol
0.1 mol
H2O/100ꢁC
360
60
40
43
Kumar et al.[59]
Solvent-free/70ꢁC
Hosseinian and
Shaterian[60]
8
MgCl2
0.1 mol
Solvent-free/70ꢁC
19
71
Hosseinian and
Shaterian[60]
9
Sc(OTf)3
0.2 mol
0.1 mol
H2O/100ꢁC
60
53
55
62
Kumar et al.[59]
10
Al(H2PO4)3
Solvent-free/70ꢁC
Hosseinian and
Shaterian[60]
11
12
DABCO
0.1 mol
0.05 g
Solvent-free/70ꢁC
Solvent-free/100ꢁC
120
15
40
90
Hosseinian and
Shaterian[60]
Fe3O4@MCM-41@ZrCl2
This work

14 of 15
POURHASAN KISOMI ET AL.
[7] P. Panahi, N. Nouruzi, E. Doustkhah, H. Mohtasham, A.
Ahadi, A. Ghiasi-Moaser, S. Rostamnia, G. Mahmoudi, A.
Khataee, Ultrason. Sonochem. 2019, 58, 104653.
[8] K. Madasamy, S. Kumaraguru, V. Sankar, S. Mannathan, M.
Kathiresan, New J. Chem. 2019, 43, 3793.
4 | CONCLUSION
In the present study, the synthesis and identification of a
novel nanocomposite consists of MNPs and masoporous
materials containing zirconium element were intended.
In fact, the increased catalytic efficiency was achieved
via the use of Fe3O4 magnetic nanoparticles for the possi-
bility of easy separation, MCM-41 as a masoporous silica
compound with the aim of providing a greater surface
area and zirconium derivatives as the effective metal
nanoparticles to gain more catalytic activity. In this
regard, Fe3O4@MCM-41@ZrCl2 as a new magnetic
mesoporous nanocomposite was successfully identified
according to different analyses and exhibited satisfactory
catalytic activity in begetting diverse range of
1-(benzothiazolylamino)phenylmethyl-2-naphthols deriv-
atives. The green conditions, great yields, practicability,
operational ease, product purity, stability, affordability,
recyclability, and environmentally profits are the consid-
erable advantages of this protocol.
[9] J. A. S. Costa, R. A. de Jesus, D. O. Santos, J. F. Mano, L. P. C.
~
Romao, C. M. Paranhos, Microporous Mesoporous Mater. 2020,
291, 109698.
[10] D. R. Do Carmo, P. F. P. Barbosa, L. R. Cumba, Silicon 2020,
12, 1111.
[11] M. Golshekan, F. Shirini, Silicon 2020, 12, 747.
[12] W. Kaewprachum, S. Wongsakulphasatch, W. Kiatkittipong,
A. Striolo, C. K. Cheng, S. Assabumrungrat, J. Environ. Chem.
Eng. 2020, 8, 102920.
[13] A. Na Rungsi, A. Luengnaruemitchai, N. Chollacoop, S.-Y.
Chen, T. Mochizuki, H. Takagi, Y. Yoshimura, Appl. Catal., A
2020, 590, 117351.
[14] H. Filian, A. Kohzadian, M. Mohammadi, A. Ghorbani-
Choghamarani, A. Karami, Appl. Organomet. Chem. 2020, 34, e5579.
[15] M. Nikoorazm, M. Mohammadi, M. Khanmoradi, Appl.
Organomet. Chem. 2020, n/a, e5704.
[16] K. Kawahara, S. Kohiki, T. Yoshitomi, S. Nishi, H. Shimooka,
M. Mitome, Y. Bando, T. Shishido, M. Oku, Mater. Lett. 2008,
62, 3682.
ACKNOWLEDGMENTS
[17] X. Chu, Y.-Y. Le, Q. Zhu, K. Fan, W.-L. Dai, Appl. Surf. Sci.
2011, 257, 8605.
[18] M. A. Florea, B. Purcareanu, A. Bicu, V. Drumea, C. E. Gird,
M. Grigoroscuta, D. E. Mihaiescu, G. Vasilievici, L. Olariu,
IOP Conference Series: Materials Science and Engineering 2019,
572, 012008.
[19] W. Jia, T. Liu, Q. Li, J. Yang, Catal. Today 2019, 335, 221.
[20] S. Esmaeili, M. A. Zanjanchi, H. Golmojdeh, S. Shariati, Micro-
porous Mesoporous Mater. 2020, 292, 109714.
[21] L. Luo, J. Ma, H. Zhu, J. Tang, Nanoscale 2020, 12, 7339.
[22] S. Kunchakara, M. Dutt, A. Ratan, J. Shah, V. Singh, R. K.
Kotnala, J. Porous, Mater. 2019, 26, 389.
We are thankful to the Research Council of the Univer-
sity of Guilan for the preparation of feasibility of doing
this research.
AUTHOR CONTRIBUTIONS
Reyhaneh Pourhasan Kisomi: Formal analysis; inves-
tigation; validation; visualization. Mostafa Golshekan:
Conceptualization; validation.
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are
available in the supplementary material of this article.
[23] S. Kunchakara, A. Ratan, J. Shah, R. K. Kotnala, V. Singh,
J. Mater. Sci.: Mater. Electron. 2019, 30, 15646.
[24] M. Dutt, A. Kaushik, M. Tomar, V. Gupta, V. Singh, J. Porous,
Mater. 2020, 27, 285.
[25] V. Rizzi, E. A. Prasetyanto, P. Chen, J. Gubitosa, P. Fini, A.
Agostiano, L. De Cola, P. Cosma, J. Mol. Liq. 2019, 273, 435.
[26] S.-Y. Cheng, Y.-Z. Liu, G.-S. Qi, J. Nanomater. 2020, 2020,
6187656.
[27] P. Shao, H. Chen, Q. Ying, S. Zhang, Energ. Fuel. 2020, 34, 2089.
[28] G. Q. Lu, X. S. Zhao, Nanoporous Materials: Science and Engi-
neering, Imperial College Press, London 2004.
[29] J. P. Dhal, T. Dash, G. Hota, J. Porous, Mater. 2020, 27, 205.
[30] Y. Deng, X. Xu, R. Wang, Y. Zhao, Waste Biomass Valoriz.
2020, 11, 1491.
[31] W. Li, F. Fu, Microporous Mesoporous Mater. 2020, 298,
110060.
[32] S. Abaeezadeh, D. Elhamifar, M. Norouzi, M. Shaker, Appl.
Organomet. Chem. 2019, 33, e4862.
[33] Y. Kobayashi, M. Horie, M. Konno, B. Rodríguez-González,
L. M. Liz-Marzán, J. Phys. Chem. B 2003, 107, 7420.
[34] K. Ojaghi Aghbash, N. Noroozi Pesyan, H. Batmani, Appl.
Organomet. Chem. 2019, 33, e5227.
ORCID
Farhad Shirini https://orcid.org/0000-0002-0768-3241
REFERENCES
[1] N. Noroozi Pesyan, G. Rezanejade Bardajee, E. Kashani, M.
Mohammadi, H. Batmani, Res. Chem. Intermed. 2020, 46, 347.
[2] H. Sepehrmansouri, M. Zarei, M. A. Zolfigol, A. R. Moosavi-
Zare, S. Rostamnia, S. Moradi, Mol. Catal. 2020, 481, 110303.
[3] M. Nikoorazm, M. Khanmoradi, M. Mohammadi, Appl.
Organomet. Chem. 2020, 34, e5504.
[4] J. C. Mansano Willig, G. Granetto, D. Reginato, F. R. Dutra,
É. F. Poruczinski, I. M. de Oliveira, H. A. Stefani, S. D. de
Campos, É. A. de Campos, F. Manarin, G. V. Botteselle, RSC
Adv. 2020, 10, 3407.
[5] H. Alinezhad, M. Cheraghian, S. Ghasemi, J. Organomet.
Chem. 2020, 907, 121069.
[6] W.-J. Sun, E.-Q. Gao, Appl. Catal., A 2019, 569, 110.

POURHASAN KISOMI ET AL.
15 of 15
[35] R. Hajian, A. Ehsanikhah, Chem. Phys. Lett. 2018, 691, 146.
[36] Z. Roosta, A. Izadbakhsh, A. M. Sanati, S. Osfouri, J. Porous,
Mater. 2018, 25, 1135.
[37] E. Karakhanov, A. Maximov, A. Zolotukhina, V. Vinokurov,
E. Ivanov, A. Glotov, Catalysts 2020, 10.
[38] T. Sun, M. Gong, Y. Cai, S. Xiao, L. Zhang, Y. Zhang, Z. Xu, D.
Zhang, Y. Liu, C. Zhou, Res. Chem. Intermed. 2020, 46, 459.
[39] W.-H. Zhang, J.-L. Shi, L.-Z. Wang, D.-S. Yan, Mater. Lett.
2000, 46, 35.
[40] A. Yamaguchi, M. Yokoyama, A. Suzuki, Y. Iwasawa, H.
Sakai, M. Yuasa, M. Abe, Phys. Scr. 2005, 834.
[64] M. Maghsoodlou, M. Karima, M. Lashkari, B. Adrom, N.
Hazeri, Bulg. Chem. Commun. 2016, 48, 369.
[65] M. Fardpour, A. Safari, S. Javanshir, Green Chem. Lett. Rev.
2018, 11, 429.
[66] O. Zimou, B. Malek, A. Elhallaoui, T. Ghailane, R. Ghailane,
S. Boukhris, N. Habbadi, A. Hassikou, A. Souizi, Bulletin of
Chemical Reaction Engineering & Catalysis 2019, 14, 238.
[67] Z. Benzekri, S. Sibous, H. Serrar, A. Ouasri, S. Boukhris, R.
Ghailane, A. Rhandour, A. Souizi, J. Mol. Struct. 2020, 1202, 127308.
[68] F. Shirini, M. A. Zolfigol, A. Pourhabib, Russ. J. Org. Chem.
2003, 39, 1191.
[41] Q. Guo, S. Rao, J. Xu, S. Ren, Chemistry Bulletin/Huaxue
Tongbao 2014, 77, 353.
[69] F. Shirini, M. Ali Zolfigol, E. Mollarazi, Synth. Commun. 2005,
35, 1541.
[42] L. Sadighnia, B. Zeynizadeh, S. Karami, M. Abdollahi, J. Chin.
Chem. Soc. 2019, 66, 535.
[70] F. Shirini, M. Ali Zolfigol, E. Mollarazi, Synth. Commun. 2006,
36, 2307.
[43] S. Kumar, A. Singh, P. K. Singh, H. Miyaoka, V. Kain, Y.
Kojima, Int. J. Hydrogen Energy 2020, 45, 14413.
[44] A. K. Chakraborti, R. Gulhane, Synlett 2004, 2004, 627.
[45] Z.-H. Zhang, T.-S. Li, Curr. 2009, 13, 1.
[46] F. Kamali, F. Shirini, Appl. Organomet. Chem. 2018, 32, 3972.
[47] X. X. Wang, F. Lefebvre, J. Patarin, J.-M. Basset, Microporous
Mesoporous Mater. 2001, 42, 269.
[71] F. Shirini, M. A. Zolfigol, A. Safari, J. Chem. Res. 2006,
2006, 154.
[72] F. Kamali, F. Shirini, New J. Chem. 2017, 41, 11778.
[73] R. Pourhasan-Kisomi, F. Shirini, M. Golshekan, Appl.
Organomet. Chem. 2018, 32, 4371.
[74] R. Pourhasan-Kisomi, F. Shirini, M. Golshekan, J. Nanosci.
Nanotechnol. 2019, 19, 3859.
[48] X. Yang, L. Zhou, C. Chen, J. Xu, Mater. Chem. Phys. 2010,
120, 42.
[75] M. Haghighat, F. Shirini, M. Golshekan, J. Mol. Struct. 2018,
1171, 168.
[49] Y. Oba, N. Yoshida, S. Kanie, M. Ojika, S. Inouye, PLoS One
2014, 8, 84023.
[76] M. Haghighat, F. Shirini, M. Golshekan, J. Nanosci.
Nanotechnol. 2019, 19, 3447.
[50] M. C. Van Zandt, M. L. Jones, D. E. Gunn, L. S. Geraci, J. H.
Jones, D. R. Sawicki, J. Sredy, J. L. Jacot, A. T. DiCioccio, T.
Petrova, A. Mitschler, A. D. Podjarny, J. Med. Chem. 2005, 48,
3141.
[51] E. R. Atkinson, F. E. Granchelli, J. Pharm. Sci. 1976, 65, 618.
[52] S. N. Manjula, N. Malleshappa Noolvi, K. Vipan Parihar, S. A.
Manohara Reddy, V. Ramani, A. K. Gadad, G. Singh, N.
Gopalan Kutty, C. Mallikarjuna Rao, Eur. J. Med. Chem. 2009,
44, 2923.
[77] M. Golshekan, S. Shariati, N. Saadatjoo, RSC Adv. 2014, 4, 16589.
[78] N. Saadatjoo, M. Golshekan, S. Shariati, H. Kefayati, P. Azizi,
J. Mol. Catal. A: Chem. 2013, 377, 173.
[79] S. Ghafoor, S. Ata, J. Chil. Chem. Soc. 2017, 62, 3588.
[80] W. Xie, X. Zang, Food Chem. 2016, 194, 1283.
[81] M. Aliahmad, N. N. Moghaddam, Mater. Sci-Poland 2013,
31, 264.
[82] T. F. Parangi, R. M. Patel, U. V. Chudasama, Bull. Mater. Sci.
2014, 37, 609.
[53] C. G. Mortimer, G. Wells, J.-P. Crochard, E. L. Stone, T. D.
Bradshaw, M. F. G. Stevens, A. D. Westwell, J. Med. Chem.
2006, 49, 179.
[83] M. Nikoorazm, F. Ghorbani, A. Ghorbani-Choghamarani, Z.
Erfani, Phosphorus, Sulfur Silicon Relat. Elem. 2018, 193, 552.
[84] T. Chen, X. Peng, H. Dai, J. Porous, Mater. 2016, 23, 987.
[85] S. Luo, G. Fan, M. Luo, J. Li, G. Song, J. CO2 Util. 2016, 14, 23.
[86] A. Shaabani, A. Rahmati, E. Farhangi, Tetrahedron Lett. 2007,
48, 7291.
ꢀ
[54] C. Rodríguez-Rodríguez, N. Sánchez de Groot, A. Rimola, A.
ꢀ
Alvarez-Larena, V. Lloveras, J. Vidal-Gancedo, S. Ventura, J.
Vendrell, M. Sodupe, P. González-Duarte, J. Am. Chem. Soc.
2009, 131, 1436.
[87] M. Seddighi, F. Shirini, M. Mamaghani, C. R. Chim. 2015,
18, 573.
[55] C. Desai, K. Desai, Orient. J. Chem. 2000, 16, 311.
[56] M. Yamaguchi, D. Pratt, M. Aimi, Y. Ishiwata, Hair Dye Com-
position, Google Patents, 2009.
SUPPORTING INFORMATION
Additional supporting information may be found online in
the Supporting Information section at the end of this article.
[57] D. Fajkusova, M. Pesko, S. Keltosova, J. Guo, Z. Oktabec, M.
Vejsova, P. Kollar, A. Coffey, J. Csollei, K. Kralova, J.
Jampilek, Bioorg. Med. Chem. 2012, 20, 7059.
[58] M. T. Maghsoodlou, M. Karima, M. Lashkari, B. Adrom, J.
Aboonajmi, J. Iran. Chem. Soc. 2017, 14, 329.
How to cite this article: Pourhasan Kisomi R,
Shirini F, Golshekan M. Fe3O4@MCM-41@ZrCl2:
A novel magnetic mesoporous nanocomposite
catalyst including zirconium nanoparticles for the
synthesis of 1-(benzothiazolylamino)phenylmethyl-
2-naphthols. Appl Organomet Chem. 2021;35:
e6212. https://doi.org/10.1002/aoc.6212
[59] A. Kumar, M. S. Rao, V. K. Rao, Aust. J. Chem. 2010, 63, 1538.
[60] A. Hosseinian, H. R. Shaterian, Phosphorus, Sulfur Silicon
Relat. Elem. 2012, 187, 1056.
[61] S. Javanshir, A. Ohanian, M. M. Heravi, M. R. Naimi-Jamal,
F. F. Bamoharram, J. Saudi, Chem. Soc. 2014, 18, 502.
[62] B. Adrom, M. T. Maghsoodlou, N. Hazeri, M. Lashkari, Res.
Chem. Intermed. 2015, 41, 7553.
[63] H. R. Shaterian, A. Hosseinian, Res. Chem. Intermed. 2015,
41, 793.