Sustainable design and novel synthesis of highly recyclable magnetic carbon containing aromatic sulfonic acid: Fe3O4@C/Ph—SO3H as green solid acid promoted regioselective synthesis of tetrazoloquinazolines

Article abstract of DOI:10.1002/aoc.6346

A green and stable magnetic Fe₃O₄ core encapsulated in porous carbon shell was prepared. Then, the surface of as-synthesized Fe₃O₄@meso-C immobilized with activated 4-aminobenzenesulfonic acid to achieve Fe

Full text of DOI:10.1002/aoc.6346

Received: 19 February 2021
DOI: 10.1002/aoc.6346
Revised: 26 May 2021
Accepted: 9 June 2021
F U L L P A P E R
Sustainable design and novel synthesis of highly recyclable
magnetic carbon containing aromatic sulfonic acid:
Fe3O4@C/Ph SO3H as green solid acid promoted
regioselective synthesis of tetrazoloquinazolines
Asadollah Hassankhani1
| Behnam Gholipour2
| Nasrin Nouruzi2
| Sadegh Rostamnia3,6
|
|
Elham Zarenezhad4
| Taras Kavetskyy5,6
Rovshan Khalilov7
| Mohammadreza Shokouhimehr8
1Department of New Materials, Institute of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology,
Kerman, Iran
2Organic and Nano Group (ONG), Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh, Iran
3Organic and Nano Group (ONG), Department of Chemistry, Iran University of Science and Technology (IUST), Tehran, Iran
4Noncommunicable Diseases Research Center, School of Medicine, Fasa University of Medical Sciences, Fasa, Iran
5Department of Biology and Chemistry, Drohobych Ivan Franko State Pedagogical University, Drohobych, Ukraine
6Department of Surface Engineering, The John Paul II Catholic University of Lublin, Lublin, Poland
7Department of Biophysics and Molecular Biology, Baku State University, Baku, Azerbaijan
8Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul, 08826, South Korea
Correspondence
Asadollah Hassankhani, Department of
Abstract
New Materials, Institute of Science and
High Technology and Environmental
Sciences, Graduate University of
A green and stable magnetic Fe3O4 core encapsulated in porous carbon shell
was prepared. Then, the surface of as-synthesized Fe3O4@meso-C immobilized
with activated 4-aminobenzenesulfonic acid to achieve Fe3O4@C/
Ph SO3H. Structural, physico-chemical, and magnetic properties of synthe-
sized Fe3O4@C/Ph SO3H catalyst using various analyses such as FT-IR spec-
troscopy, TGA, XRD, SEM, TEM. EDX, and VSM were investigated. Fe3O4@C/
Ph SO3H was used as a stable and recoverable acid catalyst for regioselective
three-component synthesis of tetrazoloquinazolines under mild conditions.
This catalyst offers a green protocol of one pot due to having active SO3H
groups, reacting in mild conditions with high yield and ability to recover and
reuse without significant loss in activity.
Advanced Technology, Kerman, Iran.
Email: ahassankhani@kgut.ac.ir
Sadegh Rostamnia, Organic and Nano
Group (ONG), Department of Chemistry,
Iran University of Science and Technology
(IUST), PO Box 16846-13114, Tehran,
Iran.
Email: rostamnia@iust.ac.ir
Taras Kavetskyy, Department of Biology
and Chemistry, Drohobych Ivan Franko
State Pedagogical University, Drohobych,
PO Box 82100, Ukraine.
K E Y W O R D S
Email: taras.kavetskyy@kul.pl
Fe3O4@C/Ph SO3H, magnetic nanoparticle, mesoporous carbon, tetrazoloquinazolines,
three-component reaction
Mohammadreza Shokouhimehr,
Department of Materials Science and
Engineering, Research Institute of
Advanced Materials, Seoul National
University, Seoul, PO Box 08826, South
Korea.
Email: mrsh2@snu.ac.kr
Appl Organomet Chem. 2021;e6346.
wileyonlinelibrary.com/journal/aoc
© 2021 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.6346

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HASSANKHANI ET AL.
Funding information
Iran National foundation of Science
(INSF)
1 | INTRODUCTION
environmentally friendly, sustainable sources, and reus-
able catalysts.[10] Solid acids can be attributed to an easy
separation of catalyst from the liquid phase of reaction
mixture with minimum corrosion, easy reaction han-
dling, and good recycling for catalyst.[11,12] On the other
hand, green chemistry has led to increased research
toward synthesis of sustainable and green heterogeneous
catalysts with easy separation, especially magnetic
nanoparticles.[13]
In this work, we designed and synthesized a magnetic
porous carbon (MPC) containing sulfonic acid
(MPC/SO3H or Fe3O4@C/Ph SO3H) as a high-active,
environmentally sustainable, and recyclable catalyst by
immobilization of 4-aminobenzenesulfonic acid onto
the surface of Fe3O4@C for the synthesis of
tetrazoloquinazolines (Scheme 1).
Multi-component reactions (MCRs) have emerged
because of their valuable features such as atom economy,
straightway reaction design, and the opportunity to
manufacture target compounds by introducing several
variation elements in a single chemical event as efficient
and powerful tools in modern synthetic organic chemis-
try.[1–3] Typically, purification of products derived from
MCRs is also simple, since all the organic reagents used
are consumed and combined into the target com-
pound.[2,3] On the other hand, a MCR domino and solid
catalysts strategies are a powerful tool in which reactants
simultaneously lead to the rapid synthesis of various
complex organic molecular structures which prevented
the need for separation and purification of intermediates,
resulting in decrease of waste and reaction time and
as
a
result improves the overall performance.[4]
Tetrazolopyrimidines cover activities with a wide range
of purposes because they are a common structural motif
in pharmacologically important molecule.[5,6] The use of
these compounds have been reported in the treatment of
obesity, atherosclerosis, diabetes, hypertension, hyper-
cholesterolemia, coronary heart disease, hyperlipidemia,
depression, hypothyroidism, cardiac arrhythmias, thyroid
cancer, glaucoma, and congestive heart failure.[7–9]
Amino tetrazole is also known as part of certain drugs
such as cefazolin, Corazol, and Cefoperazone.[6]
2 | EXPERIMENTAL
2.1 | Materials and apparatus
4-aminobenzenesulfonic acid was obtained from Merck.
The other chemicals were also purchased from Sigma-
Aldrich, Merck (Germany) and Fluka (Switzerland) and
were used without further purification. Infrared Raman
(IR) spectra were obtained by a Shimadzu IR-460 spec-
1
trometer. H and 13C NMR spectra were measured on a
In recent years, due to waste minimization and atom
economy in the use of raw materials, traditional
homogeneous acid catalysts have been replaced by
Bruker DRX-500 AVANCE spectrometer at 500.13 and
125.7 MHz, respectively. Scanning Electron Microscopy
(SEM) images were recorded by a Zeiss-DSM 960A
SCHEME 1 Domino 3-CRs
synthesis of tetrazoloquinazolines
using Fe3O4@C/Ph SO3H

HASSANKHANI ET AL.
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microscope. Transition Electron Microscopy (TEM)
images were recorded on a Zeiss EM 900 TEM. The crys-
talline structure of the nanoparticles was examined by
X-Ray Diffraction (XRD) instrument (Philips-PW1800
diffractometer).
toluene-dispersed Fe3O4@C. After stirrer the mixture for
30 min at room temperature, the reaction mixture was
refluxed (open vessel reflux system) overnight to graft
sulfonyl group onto porous carbon surface of Fe3O4@C.
Finally, the Fe3O4@C/Ph SO3H was separated from the
mixture by an external magnet, and it was washed with
ethanol and then dried under vacuum at 60ꢀC for 6 h.
CHNS analysis indicates the presence of sulfur in 3.96%
in Fe3O4@C/Ph SO3H.
2.2 | Synthesis of Fe3O4 nanoparticles
Fe3O4 nanoparticles were synthesized according to our
previous method.[14] Initially, after dissolving FeCl3
(0.65 g, 4.0 mmol), sodium acetate (1.20 g), and trisodium
citrate (0.20 g, 0.68 mmol) in 20 ml pure ethylene glycol,
the mixture was stirred vigorously for 45 min under Ar
atmosphere (small glove box-absence of air). The
resulting homogenate mixture was transferred to an auto-
clave of Teflon stainless steel (100 ml capacity), sealed,
and heated for 12 h at 200ꢀC (degree rate: 2ꢀC/min under
Ar electrical Furnace). After cooling autoclave at room
temperature (degree rate: 2ꢀC/min), the resulting black
precipitate was separated magnetically. The obtained
Fe3O4 nanoparticles were washed several times with
deionized water and ethanol and then dried at 60ꢀC
under vacuum for 12 h.
2.5 | Synthesis of tetrazoloquinazolines
A mixture of benzaldehyde (1 mmol), 2-aminotetrazol
(1 mmol), and dimedone (1 mmol) was added to 3 ml
ethanol in the presence of 0.1 g of the Fe3O4@C/
Ph SO3H catalyst and stirred at 80ꢀC for 1 h. After com-
pletion of the reaction for precipitate the synthesized
product, the reaction temperature was downed to 25ꢀC.
Fe3O4@C/Ph SO3H separation using an external magnet
and then the obtained precipitate was washed with water
and dried. Finally, to achieve the final product, the crude
product was recrystallized with ethanol. All compounds
(supporting information) are known and are previously
reported in the literatures.[6,16,17]
2.3 | Synthesis of Fe3O4@C
3 | RESULTS AND DISCUSSION
The Fe3O4@C core-shell were prepared by our previous
method.[14,15] Briefly, 0.1 g of Fe3O4 as synthesized
was dispersed in 25 ml distilled water containing 2.0 g
glucose under ultrasonication for 30 min. The resulting
mixture was transferred into autoclave of 50 ml
stainless steel and heated at 200ꢀC for 12 h with a 2ꢀC/
min (note: temperature rating is important for carboniza-
tion of glucose in exact morphology; sonication of Fe3O4
is important for core-shell achievement). After cooling to
room temperature, the black solid precipitate was
collected from the solution by an external magnet and
washed several times with distilled water and ethanol.
Finally, the black product was dried under vacuum at
60ꢀC for 12 h.
In line with our continuing efforts to synthesize solid het-
erogeneous catalysts and organic compounds,[18–22]
herein, we describe the regioselective 3-CRs synthesis of
tetrazoloquinazolines via the condensation reaction
of aldehydes, 5-aminotetrazole, and dimedone or
1.3-cyclohexanedione in the presence of a novel magnetic
mesoporous carbon bonded aromatic sulfonic acid of
Fe3O4@C/Ph SO3H (Figure 1).
FTIR spectra were used to detect the changes after
encapsulation and immobilization of the SO3H groups
onto surface of Fe3O4@C. The strong peak at 579 cmÀ1 is
characteristic of Fe O vibrations, and the peak at
1,581 cmÀ1 is related to C C bond vibrations. The peak
at 3,449 cmÀ1 indicates the residual O H groups
(Figure 2a).[23–25] After sulfonation, the vibration bands
at 1,068 cmÀ1 (S═O symmetric stretching), 1,136 cmÀ1
(S═O asymmetric stretching), and 1,413 cmÀ1 (asymmet-
ric O═S═O stretching) were related to the SO3H
groups[26] (Figure 2a). The components of Fe3O4@C/
Ph SO3H synthesized were analyzed by the SEM elec-
tron dispersive spectroscopy (SEM-EDS), also which
results are indicated in Figure 2b,d. The characteristic
lines of C, N, O, Fe, and S elements indicate that the
Fe3O4 nanoparticles are coated by the carbon layer and
2.4 | Synthesis of Fe3O4@C/Ph SO3H
For the synthesis of Fe3O4@C/Ph SO3H, the synthesized
Fe3O4@C was grafted with sulfophenyl group by reduc-
tion of diazonium salt. Initially, sulfophenyl diazonium
salt was synthesized from mixing compounds containing
aminobenzenesulfonic
acid
(0.5 mmol),
NaNO2
(0.5 mmol), and 1 M HCl (1 ml) in a cooling bath of 3ꢀC.
The obtained diazonium salt was slowly poured into the

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HASSANKHANI ET AL.
FIGURE 1 Synthetic pathway of sulfonated Fe3O4@C/Ph SO3H
FIGURE 2 (a) FTIR spectra of Fe3O4, Fe3O4@C/Ph SO3H, (b) SEM-EDS analysis of Fe3O4@C, (c) XRD patterns of Fe3O4@C/
Ph SO3H, and (d) SEM-EDS analysis of Fe3O4@C/Ph SO3H
successfully sulfonated with aromatic SO3H group. The
result of this analysis could be another confirmation of
the catalyst's successful synthesis. The XRD patterns
of the as-synthesized Fe3O4@C/Ph SO3H are shown in
(Figure 2c). Six characteristic peaks matching with the
(220), (311), (400), (422), (511), and (440) were observed
for all three samples corresponding to cubic Fe3O4 phase
(JCPDSICDD copyright 1938, file number 01-1111) with
the Fd-3 m Space Group.[27] As can be seen, the relative
position and intensity of all peaks are in accordance with
the standard Fe3O4 pattern, indicating that although the
peak intensities decreased slightly during carbon
encapsulation and subsequent functionalization of MNPs
but the crystal structure did not change.
FE-SEM and TEM images were used to investigate
the size and surface morphology of the Fe3O4@C and
aromatic sulfonic acid functionalized magnetic carbon of
Fe3O4@C/Ph SO3H as shown in Figure 3. Figure 3a,b
shows FE-SEM images of Fe3O4@C after encapsulation
of magnetic into the carbon, which show that the mor-
phology of the nanoparticles is spherical and that the size
of magnetic nanoparticles is about 150–200 nm. In the
TEM images (Figures 3c,d), the core and shell structure
of Fe3O4@C are clearly defined, indicating that the Fe3O4

HASSANKHANI ET AL.
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FIGURE 3 (a, b) FE-SEM image of Fe3O4@C; (c) TEM image of Fe3O4@C and its magnified TEM (d); (e) FE-SEM image of Fe3O4@C/
Ph SO3H; and (f) comparative VSM analysis of Fe3O4@C and Fe3O4@C/Ph SO3H
nanoparticles are encapsulated by the carbon layer. The
average size of Fe3O4 nanoparticles is about 140–200 nm,
and the carbon shell thickness is about 14–15 nm, which
is in full agreement with SEM images. Figure 3e shows
FE-SEM images of Fe3O4@C/Ph SO3H after func-
tionalization of the magnetic carbon by aromatic sulfonic
acid group, which show that the morphology of the
nanoparticles is yet spherical and no changed in
particles size. As shown in Figure 3f, VSM analysis shows
super-magnetic behavior for Fe3O4 and Fe3O4@C/
Ph SO3H. For pure Fe3O4, the magnetization shifts
from À60 to +60 emu/g, while after Ph SO3H func-
tionalization, a great decrease in magnetization (À18 to
+18 emu. g) is observed.
After using a three-step synthesis route for the prepa-
ration of Fe3O4@C/Ph SO3H, as a Bronsted sulfonic acid
functionalized core-shell Fe3O4@C, its application to the
synthesis of tetraculoquinazoline using benzaldehyde
(1 mmol), 2-aminotrazole (1 mmol) in presence of the
dimedone (1 mmol) was evaluated. Initially, the reaction
progress was evaluated in water at 80ꢀC in the absence of
the catalyst, and after 24 h, no product was observed

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HASSANKHANI ET AL.
TABLE 1 Reaction optimization for the synthesis of tetrazoloquinazolinesa
Entry
1
Catalyst
Solvent
H2O
T (ꢀC)
80
Time (h)
Yielda (%)
b
-
24
4
4
4
1
1
1
1
1
1
1
1
1
1
1
1
2
AlCl3 (5 mol %)
H2O
80
trace
30
30
70
96
96
35
75
97
80
65
70
50
25
95
3
FeCl3 (5 mol %)
H2O
80
4
Cu2O (5 mol %)
H2O
80
5
Fe3O4@C/Ph SO3H (0.05 g)c
Fe3O4@C/Ph SO3H (0.1 g)c
Fe3O4@C/Ph SO3H (0.15 g)c
Fe3O4@C/Ph SO3H (0.1 g)c
Fe3O4@C/Ph SO3H (0.1 g)c
Fe3O4@C/Ph SO3H (0.1 g)c
Fe3O4@C/Ph SO3H (0.1 g)
Fe3O4@C/Ph SO3H (0.1 g)
Fe3O4@C/Ph SO3H (0.1 g)
Fe3O4@C/ph SO3H (0.1 g)
Fe3O4@C/Ph SO3H (0.1 g)
Fe3O4@C/Ph SO3H (0.1 g)
H2O
80
6
H2O
80
7
H2O
80
8
H2O
r.t
9
H2O
60
10
11
12
13
14
15
16
H2O
100
80
EtOH
CH3CN
DMF
80
80
DMSO
Toluene
Solvent-free
80
80
130
aIsolated yield.
bNo product detected.
cReaction conditions: benzaldehyde (1 mmol), 2-aminotetrazole (1 mmol), and dimedone (1 mmol) in 3 ml of solvents.
(Table 1, entry 1). Subsequently, various amounts of cata-
lyst (0.05, 0.1, and 0.15) were chosen for the reaction,
which the highest yield (96%) observed for both the 0.01
and 0.15 catalyst amounts. Therefore, 0.1 g was selected
as the optimum amount of catalysis (Table 1, entries
5–7). In the following, to further optimize the reaction
conditions, in addition to the 80ꢀC, other temperatures
such as room temperature, 60ꢀC and 100ꢀC, were also
studied. It was found that the same yield was observed
for 80ꢀC and 100ꢀC and, therefore, the 80ꢀC was selected
as the optimum temperature (Table 1, entries 6–10). In
addition, the effect of different solvents was investigated,
and it was found that water was more effective solvent
(Table 1, entries 6, 11–15). On the other hand, reaction
under solvent-free conditions requires a temperature of
130ꢀC (Table 1, entry 16).
the optimum conditions in Table 1, the use of aromatic
aldehydes including electron-deficient groups such as
4-NO2, 4-Cl, 4-Br, and 2,6-Cl2 (Table 2, entries 2–8) and
electron-rich such as 4-Me and 2,5-OMe (Table 2, entries
9 and 10) leads to synthesis of tetrazoloquinazolines at
high yields, which indicates that Fe3O4@C/Ph SO3H is
an effective catalyst for the synthesis of different
tetraclucinazoline derivatives.
In the following, the use of 1.3-cyclohexanedione was
also investigated to further increase the synthesis of
tetraclucinazoline. Similarly, acceptable results with high
yield were observed in line with the results from Table 2
for both the electron-deficient (Table 3, entries 2–8) and
electron-rich (Table 3, entries 9 and 10) aromatic ring
groups (Table 3).
The proposed mechanism for Fe3O4@C/Ph SO3H is
illustrated in Scheme 2. This catalyst with having SO3H
groups can act as acidic species (H+). Initially, the alde-
hyde was protonated in the presence of Fe3O4@C/
Ph SO3H, and in the next step, Knoevenagel
Based on the results of Table 1, the scope and general-
ity of this protocol were investigated for various aromatic
aldehydes in presence of the dimedone and
2-aminotetrazole in optimized conditions. According to

HASSANKHANI ET AL.
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TABLE 2 Three-component coupling synthesis of tetrazoloquinazolines
Entry
Ar
β-diketone
Dimedone
Dimedone
Dimedone
Dimedone
Dimedone
Dimedone
Dimedone
Dimedone
Dimedone
Dimedone
Time (h)
Yield (%)
1
2
Ph
1
1
1
1
1
1
1
1
1
1
96
90
95
95
90
95
90
95
95
92
2-Cl C6H4
4-Cl C6H4
2,4-Cl2 C6H4
4-Br C6H3
4-O2N C6H4
2-O2N C6H4
3-O2N C6H4
4-CH3 C6H4
4-OCH3 C6H4
3
4
5
6
7
8
9
10
Note: Reaction condition: aldehyde (1 mmol), 2-aminotetrazole (1 mmol), dimedone (1 mmol), and 0.1 g of Fe3O4@C/Ph SO3H in 3 ml H2O at 80ꢀC.
TABLE 3 Fe3O4@C/Ph SO3H
catalyzed the MC-synthesis of tricyclic
tetrazoloquinazolines
Entry
Ar
Ketone
Time (h)
Yield (%)
1
2
Ph
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1
1
1
1
1
1
1
1
1
1
96
95
88
92
92
95
95
90
88
90
4-Br C6H4
2-Cl C6H4
4-Cl C6H4
2,4-Cl2 C6H3
3-O2N C6H4
4-O2N C6H4
2-O2N C6H4
4-OCH3 C6H4
4-CH3 C6H4
3
4
5
6
7
8
9
10
Note: Reaction condition: aldehyde (1 mmol), 2-aminotetrazole (1 mmol), 1,3-cyclohexanedione (1 mmol),
and Fe3O4@C/Ph SO3H in 3 mL H2O at 80ꢀC.
condensation of aldehyde with dimedone resulted in the
The ability to recover and reuse the catalyst according
to the optimized conditions in Table 1 was investigated
for subsequent experiments up to 8 cycles (Figure 4a). As
shown in Figure 4b, the catalytic power and structure of
Fe3O4@C/Ph SO3H were maintained during successive
formation of a benzididine compound. After the reaction
of Michael and the addition of 2-aminetetrazole to the
reaction cycle, subsequent cyclization leads to the forma-
tion of the desired product.[16,17,28–30]

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HASSANKHANI ET AL.
SCHEME 2 The possible mechanism for the synthesis of tetrazoloquinazolines over catalysis of Fe3O4@C/Ph SO3H
FIGURE 4 (a) Reusability of Fe3O4@C/Ph SO3H in the synthesis of tetrazoloquinazolines and (b)FE-SEM image of Fe3O4@C/
Ph SO3H after 8 cycles
TABLE 4 Comparison of different methods in the synthesis of tetrazoloquinazolines
Entry
Catalyst
Conditions
Time (h)
Yield (%)/Ref
84[28]
92[29]
94[30]
83[16]
1
2
3
4
5
TsOH (10 mol%)
Solvent-free, 30 ꢀC
CH3CN, Reflux
H2O/EtOH (1:1)/100 ꢀC
iPrOH, Reflux
8
AlCl3 (20 mol%)
4
MNPs@SiO2 Pr ANDSA (0.2 g)
I2 (10 mol%)
5 min
20 min
1
Fe3O4@C/Ph SO3H (0.1 g)
H2O, 80 ꢀC
96 (this work)
cycles, which SEM pattern obtained after eight cycles also
confirms this.
Table 4 summarizes the results of our work compared
to the previously reported catalysts in the literature. As

HASSANKHANI ET AL.
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can be seen, the Fe3O4@C/Ph SO3H catalysts with
acidic sites exhibited high catalytic activity with excellent
yield (96%) in shorter time than most of the reported
works.
Mohammadreza Shokouhimehr https://orcid.org/0000-
0003-1416-6805
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The authors declare no competing interests.
AUTHOR CONTRIBUTIONS
Asadollah Hassankhani: Conceptualization; supervi-
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Sadegh Rostamnia: Supervision.
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DATA AVAILABILITY STATEMENT
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How to cite this article: A. Hassankhani,
B. Gholipour, S. Rostamnia, E. Zarenezhad,
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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.