La complex supported on magnetic nanoparticles: green, efficient, novel and reusable nanocatalyst for the synthesis of 5-substituted tetrazoles and the oxidation reactions in neat condition

Article abstract of DOI:10.1007/s13738-019-01646-x

In the present work, we were interested in the synthesis of green and novel magnetic nanocatalyst by anchoring La complex on Fe₃O₄. The nanocatalyst was successfully synthesized and characterized by FT-IR, SEM, TGA, XRD, EDX, and ICP techniques. The designed procedure shows many benefits such as short reaction time, high yield, excellent purity, eco-friendly catalyst, easy workup and easy recovery from the reaction mixture by external magnet. [Figure not available: see fulltext.].

Full text of DOI:10.1007/s13738-019-01646-x

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-019-01646-x
ORIGINAL PAPER
La complex supported on magnetic nanoparticles: green, efficient,
novel and reusable nanocatalyst for the synthesis of 5-substituted
tetrazoles and the oxidation reactions in neat condition
Taiebeh Tamoradi1 · Asrin Irandoust1 · Mohammad Ghadermazi1
Received: 26 October 2018 / Accepted: 22 February 2019
© Iranian Chemical Society 2019
Abstract
In the present work, we were interested in the synthesis of green and novel magnetic nanocatalyst by anchoring La complex
on Fe3O4. The nanocatalyst was successfully synthesized and characterized by FT-IR, SEM, TGA, XRD, EDX, and ICP
techniques. The designed procedure shows many benefits such as short reaction time, high yield, excellent purity, eco-friendly
catalyst, easy workup and easy recovery from the reaction mixture by external magnet.
Keywords Fe3O4 · La · Green · Novel · 5-Substituted tetrazoles · Sulfoxides · Disulfides
Introduction
During recent years, the use of reusable homogenous cata-
lysts has been limited in organic synthesis due to their irk-
some isolation and regeneration from reaction mixture as
well as economic and industrial point of view [1–3]. Use
* Taiebeh Tamoradi
of heterogeneous catalysts has been one of the important
t.tabss@yahoo.com
routes towards environmental sustainability and industrial
* Mohammad Ghadermazi
process development. In this regard, various materials such
mghadermazi@yahoo.com
as organic polymers, magnetic nanoparticles, activated car-
1
bon, boehmite, carbon nanotubes, clays and molecular sieves
Department of Chemistry, Faculty of Science, University
of Kurdistan, Sanandaj, Iran
Vol.:(0123456789)
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Journal of the Iranian Chemical Society
(MCM-41, SBA-15, etc) have been proposed as competent
heterogeneous support by the immobilization of homog-
enous precursors over them [4–8]. Magnetic nanoparticles
(MNP) have been evolved as one of the important supports
facilitating the access of substrates to active sites, easy
admittance for surface functionalization, high dispersion,
excellent chemical and thermal stability, easy synthesis and
effortless separation by external magnet [9–12]. It should
be mentioned that various catalysts reported oxidation reac-
tions, the synthesis of N-containing heterocyclic compounds
and one-pot three-component reaction [13–21]. Up to date,
the use of metal catalysts including La has not been shown
in previous reports for the synthesis of N-containing het-
erocyclic compounds in the short reaction time and good to
excellent yields.
of nanostructures was determined by SEM using FESEM
(TESCAN MIRA3) and powder X-ray diffraction (XRD)
measurements using Co radiation source with a wave-
length=1.78897 Å, 40 kV, respectively. Melting points of
5-substituted tetrazoles, disulfides and sulfoxides were deter-
mined with an electrothermal 9100 apparatus. Thermal sta-
bility of the material was performed by TGA measurement
in a Shimadzu DTG-60 instrument and Fourier transform
infrared (FT-IR) spectra of all samples were recorded in a
Bruker VERTEX 80 v instrument.
Preparation of Fe3O4@Tryptophan–La nanocatalyst
The Fe3O4 nanoparticles were synthesized following a pre-
viously reported method by Ghorbani-Choghamarani et al.
[23]. The surface modification of Fe3O4 was performed by
refluxing a mixture of 1.0 g of MNP powder and 1.5 g of
tryptophan in distilled water (30 mL) for 24 h. After the
reaction, complexed product was separated by an external
magnet, and washed with ethanol/water and dried to afford
Fe3O4@Tryptophan. Then Fe3O4@Tryptophan–La nanocat-
alyst was obtained by mixing 1.0 g Fe3O4@Tryptophan and
1.08 g La (NO3)3.H2O in 30 mL absolute ethanol at reflux
condition for 16 h.
In the last few years, superparamagnetic Fe3O4 nanopar-
ticles being functionalized with different metal complexes
have been used as heterogeneous catalysts in the oxidation
and synthesis of 5-substituted tetrazoles [22–26]. 5-Substi-
tuted tetrazoles, sulfides and disulfides are versatile organic
reagents and are important constituents in biological pro-
cesses, and chemical and pharmaceutical industries. The
oxidation products of sulfides and thiols have received
considerable importance in industry, pharmaceuticals and
agrochemicals. They find important application in the devel-
opment of sensors, oil-sweetening processes, as vulcanizing
agents, etc. [27–32].
General procedure for the oxidation reactions
Tetrazole compounds, a nitrogen-rich heterocycle, have
plenty of uses in catalysis technology, as ligands in coordina-
tion chemistry, heterocyclic chemistry, material sciences, as
effective stabilizers of metallopeptide structures in organo-
metallic chemistry and stable surrogates for carboxylic acids
in known active molecules [33].
To a stirred suspension of Fe3O4@Tryptophan–La in H2O2
(0.5 mL) at room temperature, sulfide or thiol (1.0 mmol)
was added under solvent-free condition. After the comple-
tion of reaction (monitored by TLC), the catalyst was sepa-
rated using a magnet and the reaction mixture was concen-
trated to get pure sulfoxide or disulfide derivatives.
Now, based on the ground of this plethora of applica-
tions, we have opted to report an efficient and convenient
methodology for the synthesis of 5-substituted tetrazoles,
disulfides and sulfoxides catalyzed over a novel material,
the La complex of tryptophan, supported on nanomagnetic
Fe3O4. There has been no report on the La complex sup-
ported on Fe3O4 nanoparticles for the aforementioned syn-
thesis as yet.
General procedure for the synthesis of 5‑substituted
tetrazoles
To a stirred suspension of Fe3O4@Tryptophan–La (0.006 g)
in H2O (2 mL) aryl nitrile (1.0 mmol) and sodium azide
(1.2 mmol) was added and heated at 100 °C. After the com-
pletion of reaction (monitored by TLC), the catalyst was sep-
arated by magnet and then the reaction mixture was diluted
with HCl (4 N, 10 mL). Finally, the resultant organic layer
was extracted with ethyl acetate and concentrated to obtain
corresponding tetrazoles.
Experimental
Materials and physical measurements
Selected spectral data
All solvents and materials were purchased from Merck
and Sigma-Aldrich and used without further purification.
The elemental analysis and La content were determined
by energy-dispersive X-ray spectroscopy (EDAX) and
inductively coupled plasma-optical emission spectrom-
etry (ICP-OES), respectively. The surface morphology
Methyl phenyl sulfoxide 1H NMR (400 MHz, CDCl3, ppm):
δH =2.64 (s, 3H), 7.53–7.72 (m, 2H), 7.65–7.69 (m, 3H).
5-(2-Chlorophenyl)-1H-tetrazole 1H NMR (400 MHz,
DMSO, ppm): δH =7.64 (t, J=6 Hz, 1H), 7.77 (t, J=6 Hz,
1H), 7.84 (d, J=6.4 Hz, 1H), 7.92 (d, J=6.3 Hz, 1H).
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Journal of the Iranian Chemical Society
1
5-(4-Nitrophenyl)-1H-tetrazole H NMR (400 MHz,
DMSO, ppm): δH =8.21–8.25 (m, 2H), 8.40–8.43 (m, 2H).
Results and discussion
Catalyst preparation
As shown in Scheme 1, Fe3O4@Tryptophan–La catalyst was
prepared by reaction between Fe3O4@Tryptophan as green
ligand and La.
Catalyst characterization
After the successful synthesis of the nanocatalyst, it was
confirmed by SEM, FT-IR, EDX, XRD, TGA, ICP and VSM
techniques. The FT-IR spectra of Fe3O4, Fe3O4@Tryptophan
and Fe3O4@Tryptophan–La nanoparticles were recorded in
the range 400–4000 cm− 1. As shown in Fig. 1, the O–H
and Fe–O stretching vibrations appeared at approximately
3400–3500 and 580 cm−1, respectively, which confirms the
presence of Fe3O4 in all the samples. In the spectrum of
Fe3O4@Tryptophan, the characteristic absorption bands
Fig. 1 FT-IR spectrum of Fe3O4 (green), Fe3O4@Tryptophan (blue),
Fe3O4@Tryptophan–La catalyst (red)
Scheme 1 Synthesis of Fe3O4@
Tryptophan–La catalyst (red)
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Journal of the Iranian Chemical Society
Fig. 2 SEM images of Fe3O4
(a) and Fe3O4@Tryptophan–La
catalyst
Fig. 3 EDX spectrum of Fe3O4@Tryptophan–La
around 2853–2922 and 1622 cm−1 corresponded to that of
aliphatic C–H and C=N stretching vibrations, respectively.
SEM images of the Fe3O4 and Fe3O4@Tryptophan–La
catalyst are shown in Fig. 2. As shown in images, Fe3O4
and Fe3O4@Tryptophan–La nanoparticles were made up of
uniform spherical particles. Also, based on the synergistic
effects theory, obtained morphology assisted to maximize
the simultaneous increase of the catalyst efficiency and fre-
quency of molecular interactions (higher yields) or decreas-
ing activation energy of the rate-determining step (lower
times).
Fig. 4 The TGA diagram of Fe3O4@Tryptophan–La
to be about 15% of the Fe3O4@Tryptophan–La catalyst and
a weight loss in the temperature range 200–550 °C is due to
the decomposition of chemisorbed functional groups onto
the surface of Fe3O4 nanoparticle (Fig. 4).
Vibrating sample magnetometer curve of the coated
Fe3O4 nanoparticles with La complex at room temperature
is shown in Fig. 5 and mentioned parameters of the Fe3O4
and Fe3O4@Tryptophan–La nanoparticles were 73 and
47.1 emu g−1, respectively. The decrease is due to the load-
ing of La complex on the Fe3O4 surface.
The energy-dispersive X-ray spectroscopy (EDX) analysis
of Fe3O4@Tryptophan–La nanocatalyst confirmed the pres-
ence of Fe, O, N, C and La species in the obtained catalyst
(Fig. 3), and the La content in the material was obtained to
be 0.27 mmol g−1.
Figure 6 illustrates the X-ray diffraction analysis (XRD)
pattern of Fe3O4, Fe3O4@Tryptophan and Fe3O4@Trypto-
phan–La. The X-ray diffraction analysis (XRD) patterns of
all samples show diffraction peaks at 2θ = 30.69°, 35.95°,
43.93°, 54.12°, 59.53°, 63.78° corresponding to (2 2 0), (3
The quantitative determination of the organic groups on
the surface of Fe3O4 nanostructure was determined by TGA
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Journal of the Iranian Chemical Society
O
S
Fe O
4@Tryptophan-La
3
S
rt
,
2
H
O
Solvent-Free,
2
R1
R2
R1
1a-1i
R2
2a-2i
Scheme 2 Fe3O4@Tryptophan–La catalyzed the oxidation of sulfide
to sulfoxide
Table 1 Optimization of oxidation of sulfides to the corresponding
sulfoxides using Fe3O4@Tryptophan–La nanoparticles under various
conditions
Entry Solvent
H2O2 Catalyst (mg) Time (min) Yield (%)a
Fig. 5 Magnetization curves for Fe3O4 (blue) and Fe3O4@Trypto-
phan–La (red)
1
2
3
4
5
6
7
Solvent free 0.5
3
7
5
5
5
5
5
60
8
10
25
35
75
90
78
98
98
83
92
90
41
Solvent free 0.5
Solvent free 0.5
Solvent free 0.4
Ethanol
Ethyl acetate 0.5
Acetonitrile 0.5
0.5
aIsolated yields
Then we tested the catalytic activity of Fe3O4@Trypto-
phan–La in the oxidation of a wide range of sulfides with
different functional groups (Table 2) and a plausible mecha-
nism was proposed for the mentioned reaction in Scheme 3
[6].
Fig. 6 XRD patterns of Fe3O4 (a), Fe3O4@Tryptophan (b) and
Fe3O4@Tryptophan–La (c)
To investigate the behavior of the catalyst in other reac-
tions, we designed various experiment parameters for
the optimization of reaction conditions such as solvent,
amount of catalyst and H2O2 by the oxidation of 4-meth-
ylbenzenethiol as a model reaction (Scheme 4), and the best
results were indicated in the presence of 0.007 Fe3O4@Tryp-
tophan–La and 0.5 mL H2O2 under solvent-free condition for
the mentioned reaction (Table 3).
1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0) planes of magnetite
phase (JCPDS#01-075-0449) of Fe3O4, which crystallized in
the cubic system. Also, the XRD patterns of Fe3O4@Tryp-
tophan and Fe3O4@Tryptophan–La indicated that the Fe3O4
phase has not been changed during the modifications [22].
Then we tested the catalytic activity of Fe3O4@Trypto-
phan–La in the oxidation of a wide range of thiols under the
optimized condition (Table 4), and a plausible mechanism
was proposed for the mentioned reaction in Scheme 5 [6].
Also, we designed various experiments for the synthe-
sis of 5-(3-nitrophenyl)-1H-tetrazole to optimize the reac-
tion conditions such as solvent, temperature and amount of
catalyst (Scheme 6) and the best results were shown with
0.006 g of Fe3O4@Tryptophan–La and H2O as green solvent
at 80 °C (Table 5).
Catalytic studies
After synthesis and characterization of the catalyst, we
decided to test the catalytic activity of Fe3O4@Trypto-
phan–La for the synthesis of sulfides (Scheme 2), disulfides
(Scheme 4) and 5-substituted tetrazoles (Scheme 6). Initially,
we designed various experiments to optimize the reaction
conditions such as solvent, amount of catalyst and H2O2 by
the oxidation of methylphenyl sulfide to methylphenyl sul-
foxide as a model reaction. The best results were obtained in
the presence of 0.005 Fe3O4@Tryptophan–La catalyst and
0.5 mL H2O2 under solvent-free condition for the mentioned
reaction (Table 1).
To generalize the scope of the reaction, a series of aro-
matic substituted nitriles was chosen for the synthesis of
tetrazole derivatives under the optimized conditions as
shown in Table 6 and then proposed a mechanism for syn-
thesis of mentioned compound (Scheme 7) [13].
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Journal of the Iranian Chemical Society
Table 2 Oxidation of sulfides
to sulfoxides in the presence of
Fe3O4@Tryptophan–La
Entry Substrate
Product Time (min) Yield (%)a TON TOF (h-1) M.p. (°C)
1
2
3
4
5
6
7
8
9
Dipropylsulfide
Diethylsulfide
Dibenzylsulfide
Benzylphenylsulfide
Tetrahydrothiophene
Ethylphenylsulfide
Diphenylsulfide
3,3′-Thiodipropionic acid 2h
Methylphenylsulfide 2i
2a
2b
2c
2d
2e
2f
25
30
15
40
5
10
20
20
10
91
94
85
93
94
90
92
81
98
674
696
630
689
696
667
681
600
726
1620
1393
2518
1044
8385
41,667
2065
1818
4537
Oil [34]
Oil [34]
125 [22]
118 [22]
Oil [34]
Oil [24]
60 [23]
2g
207 [31]
Oil [22]
aIsolated yield
techniques. The results indicate that the catalyst can be
recycled without any significant change in its structure.
Fe3O4
O
S
R1 R2
O
O
NH
La
NH
Catalyst leaching study
NH2
O
R2
Fe3O4
O
The amounts of La leaching were studied by checking the
La loading amount before and after recycling of the cata-
lyst by ICP-OEIS technique. Based on ICP-OES analysis
of the prepared catalyst, the exact amount of La loaded
on modified magnetic nanoparticles for the conversion of
methylphenyl sulfide to the methylphenyl sulfoxide at least
for six consecutive cycles is 0.19 mmol g−1. Since leach-
ing of metal from the support surface is very negligible
for these reactions, the catalytic activity has been slightly
decreased.
Fe3O4
La
H2N
NH2
O
S
O
O
R1
O
S+
R2
R1
La
R1
S
HN
R2
O
H
HN
L a
O
O
H
2O2
La
NH2
O
O
H2N
HN
Fe3O4
O
O
Fe3O4
It should be noted that two reactions of oxidation of
methylphenyl sulfide under optimized reaction conditions
were investigated to perform hot filtration experiment.
In the first reaction, we found the yield of product under
optimized conditions in half time of the reaction was 60%.
Simultaneously, in the second reaction, the same reaction
was repeated, but in the half time of the reaction, the cata-
lyst was separated from the reaction mixture by filtration
process and allowed to react further under identical reac-
tion conditions. Noteworthy, the yield of reaction in this
stage was 66% which confirmed that leaching of metal has
not occurred.
Scheme 3 Proposed mechanism for oxidation of sulfides in the pres-
ence of Fe3O4@Tryptophan–La as catalyst
R3
Fe
O
4@Tryptophan-La
3
R3
S
S
SH
R3
rt
,
2
H
O
Solvent-Free,
2
4a-4g
3a-3g
Scheme 4 Fe3O4@Tryptophan–La catalyzed the oxidation of thiols
to disulfides
Comparison of the catalyst
The reusability of the prepared catalyst was tested in
all three reactions, the oxidation of methyl phenyl sulfide,
coupling of 4-methylthiophenol and 5-(4-nitrophenyl)-
1H-tetrazole, and it was observed that we could use it for six
consecutive runs of the mentioned reactions without much
decrease in activity (Fig. 7).
The oxidation of methylphenyl sulfide and 4-methylben-
zenethiol and synthesis of 2-(1H-tetrazol-5-yl)phenol in
our protocol have been compared with previously reported
methods and we feel delighted in the predominance of our
methodology in comparison to other methods in terms of
ease of operation, short reaction time, commercial availabil-
ity of materials and high yield (Table 7).
The nature of the recovered catalyst was investigated
by XRD pattern (Fig. 8), TGA (Fig. 9) and SEM (Fig. 10)
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Journal of the Iranian Chemical Society
Table 3 Optimization of
oxidative coupling of thiols
to disulfides using Fe3O4@
Tryptophan–La under various
conditions
Entry
Solvent
H2O2
Catalyst (mg)
Time (min)
Yield (%)a
M.p. (°C)
1
2
3
4
5
6
7
Solvent free
Solvent free
Solvent free
Solvent free
EtOH
Ethyl acetate
Acetonitrile
0.5
0.5
0.5
0.4
0.5
0.5
0.5
3
7
5
7
7
7
7
45
10
25
20
60
80
95
52
95
90
92
89
75
83
41–43 [22]
41 [22]
39–41 [22]
42 [22]
41 [22]
40–42 [22]
40 [22]
aIsolated yields
Table 4 Oxidative coupling of
thiols to disulfides using H2O2
in the presence of Fe3O4@
Tryptophan–La
Entry Substrate
Product Time (min) Yield (%)a TON TOF (h-1) M.p. (°C)
1
2
3
4
5
6
7
4-Methylbenzenethiol
Naphthalene-2-thiol
2-Mercaptobenzoic acid 4c
Benzo[d]thiazole-2-thiol 4d
2-Mercaptoethanol
Benzo[d]oxazole-2-thiol 4f
Benzyl mercaptan 4g
4a
4b
10
25
95
35
35
30
30
95
93
96
83
76
84
92
503
492
508
439
402
444
467
3144
1183
321
753
689
888
934
40 [22]
130 [22]
270–272 [24]
174 [24]
Oil [22]
4e
90 [34]
55–57 [22]
aIsolated yields
S
CN
S
R
N
HN
R
H
R
S
H
N
N
NH
Fe
3
O
4@Tryptophan-La
Fe3O4
O
N
80 o
C
O
H
2O,
NaN
,
3
R
NH2
O
NH2
La
R
R
Fe3O4
S+
O
La
O
6a-6h
5a-5h
H
Fe3O4
O
H
2O2
Scheme 6 Fe3O4@Tryptophan–La catalyzed the one-pot synthesis of
O
5-substituted tetrazoles
R
La
S
O
Fe3O4
NH
O
H2N
NH
H
Table 5 Optimization of reaction conditions for the synthesis of
5-substituted 1H-tetrazole derivatives in the presence of Fe3O4@
Tryptophan–La
Entry Solvent Temp (oC) Catalyst (mg) Time (min) Yield (%)a
O
NH2
S
La
O
Fe3O4
R
H
O
O
La
H2N
+
O
H
2O
1
2
3
4
5
6
7
8
PEG
EtOH
DMSO 80
H2O
H2O
H2O
H2O
H2O
80
80
6
6
6
6
8
4
6
6
10
15
10
7
93
90
92
94
96
84
88
95
O
H
N
H
80
80
80
60
100
6
Scheme 5 Proposed mechanism for the oxidation of thiols in the
17
12
6
presence of Fe3O4@Tryptophan–La as catalyst
Conclusion
aIsolated yields
In conclusion, we report a novel material, the Fe3O4@
Tryptophan–La catalyst, achieved by anchoring lantha-
num onto the surface of Fe3O4. Synthesis of the nano-
material was demonstrated by versatile chemical and
physical techniques. The catalytic behavior of this nano-
structured material was investigated as a recyclable system
for the synthesis of 5-substituted tetrazoles and oxidation
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Journal of the Iranian Chemical Society
Table 6 Synthesis of
Entry Substrate
Product Time (min) Yield (%)a TON TOF (h-1) M.p. (°C)
5-substituted 1H-tetrazole
derivatives in the presence of
Fe3O4@Tryptophan–La under
optimized reaction conditions
1
3
4
5
6
7
8
9
Phthalonitrile
3-Nitrobenzonitrile
2-Chlorobenzonitrile
2-Hydroxybenzonitrile 4d
4-Hydroxybenzonitrile 4e
4-Chorobenzonitrile
4-Nitrobenzonitrile
Benzonitrile
4a
4b
4c
30
7
84
94
86
95
98
89
90
91
518
580
531
586
605
549
555
562
1036
4974
640
1409
1833
732
204 [24]
155–157 [34]
180 [22]
222 [22]
236 [24]
259 [34]
224 [34]
211 [34]
50
25
20
45
10
95
4f
4g
4h
3469
35
aIsolated yields
N
N
NH
N
N
La
H2N
NH
N
N
O
O
Fe3O4
Ph
Ph
RCN
HN
NaN3
H+
HN
NH
NH2
La
Na N
N
N
N
O
O
Fe3O4
O
O
NH2
Fe3O4
La
Ph
Fig. 8 XRD pattern of the recovered Fe3O4@Tryptophan–La
C
N
Ph
N
N
Na
N
Scheme 7 The proposed mechanism of synthesis of 5-substituted-
1H-tetrazole derivatives in the presence of Fe3O4@Tryptophan–La as
catalyst
Fig. 9 The TGA diagram of the recovered Fe3O4@Tryptophan–La
reactions in neat condition. The most attractive features of
this protocol include commercial availability of reagents,
simple workup procedure, high yield in short time, ease
of separation via magnet, and reusability of the catalyst.
Fig. 7 Reusability of Fe3O4@Tryptophan–La in the oxidation of
methyl phenyl sulfide (a), coupling of 4-methylbenzenethiol (b) and
5-(4-nitrophenyl)-1H-tetrazole (c)
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Journal of the Iranian Chemical Society
Fig. 10 SEM images of the
recovered catalyst at different
magnifications
Table 7 Comparison of
Fe3O4@Tryptophan–
Entry
Substrate
Catalyst
Time (min)
Yield (%)a
La for the oxidation of
methylphenylsulfide and
4-methylbenzenethiol and
synthesis of 2-(1H-tetrazol-5-yl)
phenol with previously reported
procedure
1
2
3
4
5
6
7
8
Methylphenylsulfide
Methylphenylsulfide
Methylphenylsulfide
Methylphenylsulfide
Methylphenylsulfide
Methylphenylsulfide
Methylphenylsulfide
4-Methylbenzenethiol
4-Methylbenzenethiol
4-Methylbenzenethiol
4-Methylbenzenethiol
4-Methylbenzenethiol
Benzonitrile
Fe3O4–adenine–Ni
VO–2A3HP–MCM-41
Zr-oxide@MCM-41
2NaBO3.4H2O(I)/KBr
Fe3O4
Fe3O4@Tryptophan
Fe3O4@Tryptophan–La
VO-salen–MCM-41
Cd-salen–MCM-41
Fe3O4
Fe3O4@Tryptophan
Fe3O4@Tryptophan–La
CoY zeolite
Fe3O4/ZnS HNSs
Fe3O4
55
120
300
120
10
10
10
120
150
10
10
10
840
1440
95
95
95
98 [34]
96 [35]
98 [36]
57 [37]
Trace
Trace
98 [this work]
95 [38]
98 [39]
Trace
9
10
11
12
13
14
15
16
17
Trace
95 [this work]
90 [40]
81 [41]
Trace
Trace
91 [this work]
Benzonitrile
Benzonitrile
Benzonitrile
Benzonitrile
Fe3O4@Tryptophan
Fe3O4@Tryptophan–La
aIsolated yields
Acknowledgements We gratefully acknowledge the support of this
3. T. Tamoradi, M. Ghadermazi, A. Ghorbani-Choghamarani, Syn-
thesis of polyhydroquinoline, 2, 3-dihydroquinazolin-4 (1H)-one,
sulfide and sulfoxide derivatives catalyzed by new copper complex
supported on MCM-41. Catal Lett. 148, 857–872 (2018). https://
doi.org/10.1007/s10562-018-2311-x
work by University of Kurdistan.
References
4. J. Davarpanah, A.R. Kiasa, Synthesis and characterization of
SBA-polyperoxyaCID: AN efficient heterogeneous solid peroxy-
acid catalyst for epoxidation of alkenes. Catal Commun. 46, 75–80
(2014). https://doi.org/10.1016/j.catcom.2013.11.022
1. A. Jabbari, M. Nikoorazm, A. Ghorbani-Choghamarani, A. Jab-
bari, A facile preparation of palladium Schiff base complex sup-
ported into MCM-41 mesoporous and its catalytic application in
Suzuki and Heck reactions. J. Porous. Mater. 23, 967–975 (2016).
https://doi.org/10.1007/s10934-016-0154-7
5. M.A. Zolfigol, M. Yarie, Fe3O4@TiO2@O2PO2(CH2)NHSO3H as
a novel nanomagnetic catalyst: application to the preparation of
2-amino-4,6-diphenylnicotinonitriles via anomeric-based oxida-
tion. Appl. Organometal. Chem. 31, e3598 (2017). https://doi.
org/10.1002/aoc.3598
2. S.M. Baghbanian, S. Khaksar, S.M. Vahdat, M. Farhang, M.
Tajbakhsh, One-step, synthesis of Hantzsch esters and polyhydro-
quinoline derivatives using new organocatalyst. Chin. Chem. Lett.
21, 563–567 (2010). https://doi.org/10.1016/j.cclet.2009.12.011
6. A. Heidari, H. Younesi, Z. Mehraban, Removal of Ni(II),
Cd(II), and Pb(II) from a ternary aqueous solution by amino
1 3

Journal of the Iranian Chemical Society
functionalized mesoporous and nanomesoporous silica. J.
Chem. Eng. 153, 70–79 (2009). https://doi.org/10.1016/j.
cej.2009.06.016
Environ. Chem. Lett. 14, 195–199 (2016). https://doi.org/10.1007/
s10311-016-0558-2
21. A. Maleki, M. Aghaei, R. Paydar, Highly efficient protocol for the
aromatic compounds nitration catalyzed by magnetically recycla-
ble core/shell nanocomposite. J. Iran. Chem. Soc. 14, 485–490
(2017). https://doi.org/10.1007/s13738-016-0996-6
7. A. Benhamou, M. Baudu, Z. Derriche, J.P. Basly, Aqueous heavy
metals removal on amine-functionalized Si-MCM-41 and Si-
MCM-48. J. Hazard. Mater. 171, 1001–1008 (2009). https://doi.
org/10.1016/j.jhazmat.2009.06.106
22. T. Tamoradi, B. Mehraban-Esfandiari, M. Ghadermazi, A. Ghor-
bani–Choghamarani, Immobilization of a nickel complex onto
8. D. Saberi, M. Sheykhan, K. Niknam, A. Heydari, Preparation
of carbon nanotube-supported α-Fe2O3@CuO nanocomposite:
a highly efficient and magnetically separable catalyst in cross-
coupling of aryl halides with phenols. Catal. Sci. Technol 3,
2025–2031 (2013). https://doi.org/10.1039/C3CY00082F
9. T. Tamoradi, A. Ghorbani-Choghamarani, M. Ghadermazi,
Fe3O4–adenine–Zn: a novel, green, and magnetically recoverable
catalyst for the synthesis of 5-substituted tetrazoles and oxidation
of sulfur containing compounds. New J. Chem 41, 11714–11721
(2017). https://doi.org/10.1039/C7NJ02337E
functionalized Fe
3O4 nanoparticles: a green and recyclable cata-
lyst for synthesis of 5-substituted 1H-tetrazoles and oxidation
reactions. Res. Chem. Intermed. 44, 1363–1380 (2018). https://
doi.org/10.1007/s11164-017-3172-4
23. A. Ghorbani-Choghamarani, Z. Darvishnejad, B. Tahmasbi, Schiff
base complexes of Ni, Co, Cr, Cd and Zn supported on magnetic
nanoparticles: as efficient and recyclable catalysts for the oxida-
tion of sulfides and oxidative coupling of thiols. Inorg. Chim. Acta
435, 223–231 (2015). https://doi.org/10.1016/j.ica.2015.07.004
24. A. Ghorbani-Choghamarani, L. Shiri, G. Azadi, The first report on
the eco-friendly synthesis of 5-substituted 1H-tetrazoles in PEG
catalyzed by Cu(II) immobilized on Fe3O4@SiO2@L-arginine
as a novel, recyclable and non-corrosive catalyst. RSC Adv. 6,
32653–32660 (2016). https://doi.org/10.1039/C6RA03023H
25. A. Ghorbani-Choghamarani, B. Tahmasbi, P. Moradi, Palladium–
S-propyl-2-aminobenzothioate immobilized on Fe3O4 magnetic
nanoparticles as catalyst for Suzuki and Heck reactions in water
or poly(ethylene glycol). Appl. Organomet. Chem. 30, 422–430
(2016). https://doi.org/10.1002/aoc.3449
10. M.A. Zolfigol, M. Kiafar, M. Yarie, A. Taherpour, M. Saeidi-
Rad, Experimental and theoretical studies of the nanostructured
{Fe3O4@SiO2@(CH2)3Im}C(CN)3 catalyst for 2-amino-3-cyan-
opyridine preparation via an anomeric based oxidation. RSC Adv.
6, 50100–50111 (2016). https://doi.org/10.1039/C6RA12299J
11. J. Davarpanah, A.R. Kiasat, Catalytic application of silver
nanoparticles immobilized to rice husk-SiO2-aminopropylsi-
lane composite as recyclable catalyst in the aqueous reduction
of nitroarenes. Catal. Commun. 41, 6–11 (2013). https://doi.
org/10.1016/j.catcom.2013.06.020
12. M.A. Zolfigol, V. Khakyzadeh, V.A.R. Moosavi-Zare, A. Ros-
tami, A. Zare, N. Iranpoor, M.H. Beyzavi, R. Luque, A highly
stable and active magnetically separable Pd nanocatalyst in aque-
ous phase heterogeneously catalyzed couplings. Green Chem. 15,
2132–2140 (2013). https://doi.org/10.1039/C3GC40421H
13. A. Maleki, P. Ravaghi, M. Aghaei, H. Movahed, A novel magneti-
cally recyclable silver-loaded cellulose-based bionanocomposite
catalyst for green synthesis of tetrazolo[1,5-a]pyrimidines. Res.
Chem. Intermed. 43, 5485–5494 (2017). https://doi.org/10.1007/
s11164-017-2941-4
26. T. Tamoradi, A. Ghorbani-Choghamarani, M. Ghadermazi,
Synthesis of a new Pd(0)-complex supported on magnetic nano-
particles and study of its catalytic activity for Suzuki and Stille
reactions and synthesis of 2,3-dihydroquinazolin-4(1H)-one deriv-
atives. Polyhedron 145, 120–130 (2018). https://doi.org/10.1016/j.
poly.2018.01.016
27. M. Hajjami, L. Shiri, A. Jahanbakhshi, Zirconium oxide com-
plex-functionalized MCM-41 nanostructure: an efficient and reus-
able mesoporous catalyst for oxidation of sulfides and oxidative
coupling of thiols using hydrogen peroxide. Appl. Organometal.
Chem. 29, 668–673 (2015). https://doi.org/10.1002/aoc.3348
28. A. Ghorbani-Choghamarani, P. Moradi, B. Tahmasbi, Ni–S-meth-
ylisothiourea complexes supported on boehmite nanoparticles and
their application in the synthesis of 5-substituted tetrazoles. RSC
Adv. 16, 56638–56646 (2016). https://doi.org/10.1039/C6RA0
8026J
14. A. Maleki, An efficient magnetic heterogeneous nanocata-
lyst for the synthesis of pyrazinophorpyrazine macrocycles.
Polycycl. Aromat. Compd. 38, 402–409 (2018). https://doi.
org/10.1080/10406638.2016.1221836
15. A. Maleki, J. Rahimi, O.M. Demchuk, A.Z. Wilczewska, R.
Jasiński, Green in water sonochemical synthesis of tetrazolopy-
rimidine derivatives by a novel core-shell magnetic nanostructure
catalyst. Ultrason. Sonochem. 43, 262–271 (2018). https://doi.
org/10.1016/j.ultsonch.2017.12.047
29. A. Ghorbani-Choghamarani, P. Zamani, Ammonium bromide as
an effective and viable catalyst in the oxidation of sulfides using
nitro urea and silica sulfuric acid. J. Iran. Chem. Soc. 8, 142–148
(2011). https://doi.org/10.1007/BF03246211
16. A. Shaabani, A. Maleki, A.H. Rezayan, A. Sarvary, Recent pro-
gress of isocyanide-based multicomponent reactions in Iran.
Mol. Divers. 15, 41–68 (2011). https://doi.org/10.1007/s1103
0-010-9258-1
30. M. Bagherzadeh, M. Zare, Chapter one—developments in tetra-
zole chemistry. Adv. Heterocyclic Chem. 123, 1–62 (2017). https
://doi.org/10.1016/bs.aihch.2016.12.003
17. A. Shaabani, A. Maleki, Green and efficient synthesis of quinoxa-
line derivatives via ceric ammonium nitrate promoted and in situ
aerobic oxidation of a a -hydroxy ketones and a α-keto oximes in
aqueous media. Chem. Pharm. Bull. 56, 79–81 (2008). https://doi.
org/10.1248/cpb.56.79
31. N. Moeini, T. Tamoradi, M. Ghadermazi, A. Ghorbani-
Choghamarani, Ni–S-methylisothiourea complexes supported on
boehmite nanoparticles and their application in the synthesis of
5-substituted tetrazoles. RSC Adv. 6, 56638–56646 (2016). https
://doi.org/10.1039/C6RA08026J
18. A. Maleki, Green oxidation protocol: selective conversions of
alcohols and alkenes to aldehydes, ketones and epoxides by using
a new multiwall carbon nanotube-based hybrid nanocatalyst via
ultrasound irradiation. Ultrason. Sonochemistry. 40, 460–264
(2018). https://doi.org/10.1016/j.ultsonch.2017.07.020
19. A. Maleki,·T. N. Kari, Leaking-Free, Green, double core/shell,
palladium-loaded magnetic heterogeneous nanocatalyst for selec-
tive aerobic oxidation. Catal. Lett. 148, 2929–2934 (2018). https
://doi.org/10.1007/s10562-018-2492-3
32. M. Esmaeilpour, J. Javidi, F. Nowroozi Dodeji, M. Mokhtari,
Abarghoui, Facile synthesis of 1- and 5-substituted 1H-tetrazoles
catalyzed by recyclable ligand complex of copper(II) supported on
superparamagnetic Fe
3O4@SiO2 nanoparticles. J. Mol. Catal. A
393, 18–29 (2014). https://doi.org/10.1016/j.molcata.2014.06.001
33. F. Abrishami, M. Ebrahimikia, F. Rafiee, Synthesis of 5-substi-
tuted 1H-tetrazoles using a recyclable heterogeneous nanonickel
ferrite catalyst. Appl. Organomet. Chem. 29, 730–735 (2015).
https://doi.org/10.1002/aoc.3358
20. A. Maleki, R. Rahimi, S. Maleki, Efficient oxidation and epoxi-
dation using a chromium(VI)based magnetic nanocomposite.
34. T. Tamoradi, M. Ghadermazi, A. Ghorbani-Choghamarani, A.
Ghorbani-Choghamarani, Ni(II)-Adenine complex coated Fe3O4
1 3

Journal of the Iranian Chemical Society
nanoparticles as high reusable nanocatalyst for the synthesis of
polyhydroquinoline derivatives and oxidation reactions. Appl.
Organomet. Chem. 32, e3974 (2018). https://doi.org/10.1002/
aoc.3974
38. A. Jabbari, H. Mahdavi, M. Nikoorazm, A. Ghorbani-Choghama-
rani, Oxovanadium(IV) salicylidene Schiff base complex anchored
on mesoporous silica MCM-41 as hybrid materials: a robust cata-
lyst for the oxidation of sulfides. J. Porous. Mater. 22, 1111–1118
(2015). https://doi.org/10.1007/s10934-015-9986-9
35. M. Nikoorazm, A. Ghorbani-Choghamarani, M. Khanmoradi,
Immobilization of a vanadium complex onto functionalized
nanoporous MCM-41 and its application as a catalyst for the sol-
vent-free chemoselective oxidation of sulfide to sulfoxide. Appl.
Organomet. Chem. 30, 236–241 (2016). https://doi.org/10.1002/
aoc.3422
39. M. Nikoorazm, A. Ghorbani-Choghamarani, H. Mahdavi, H.S.M.
Esmaeili, Efficient oxidative coupling of thiols and oxidation of
sulfides using UHP in the presence of Ni or Cd salen complexes
immobilized on MCM-41 mesoporous as novel and recoverable
nanocatalysts. Microporous Mesoporous Mater. 211, 174–181
(2015). https://doi.org/10.1016/j.micromeso.2015.03.011
40. U.B. Patil, K.R. Kumthekar, J.M. Nagarkar, A novel method
for the synthesis of 5-substituted 1H-tetrazole from oxime and
sodium azide. Tetrahedron Lett. 53, 3706–3709 (2012). https://
doi.org/10.1016/j.tetlet.2012.04.093
36. M. Hajjami, L. Shiri, A. Jahanbakhshi, Zirconium oxide complex-
functionalized MCM-41 nanostructure: an efficient and reusable
mesoporous catalyst for oxidation of sulfides and oxidative cou-
pling of thiols using hydrogen peroxide. Appl. Organomet. Chem.
29, 668–673 (2015). https://doi.org/10.1002/aoc.3348
37. A. Dhakshinamoorthy, K. Pitchumani, Clay-supported ceric
ammonium nitrate as an effective, viable catalyst in the oxidation
of olefins, chalcones and sulfides by molecular oxygen. Catal.
Commun. 10, 872–878 (2009). https://doi.org/10.1016/j.catco
m.2008.12.025
41. L. Lang, H. Zhou, M. Xue, X. Wang, Z. Xu, Mesoporous ZnS
hollow spheres-catalyzed synthesis of 5-substituted 1H-tetrazoles.
Mater. Lett. 106, 443–446 (2013). https://doi.org/10.1016/j.matle
t.2013.05.067
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