Chitosan supported 1-phenyl-1H-tetrazole-5-thiol ionic liquid copper(II) complex as an efficient catalyst for the synthesis of arylaminotetrazoles

Article abstract of DOI:10.1016/j.molliq.2021.117398

A recyclable functional hybrid catalyst was prepared via a simple method using chitosan as a linear polysaccharide and an ionic liquid. In this work, the synthesis of chitosan supported 1-phenyl-1H-tetrazole-5-thiol ionic liquid copper(II) complex (CS@Tet

Full text of DOI:10.1016/j.molliq.2021.117398

Journal of Molecular Liquids 341 (2021) 117398
Contents lists available at ScienceDirect
Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Chitosan supported 1-phenyl-1H-tetrazole-5-thiol ionic liquid copper(II)
complex as an efficient catalyst for the synthesis of arylaminotetrazoles
Mahmoud Nasrollahzadeh a, , Narjes Motahharifar , Zahra Nezafat , Mohammadreza Shokouhimehr
⇑
a
a
b
a
Department of Chemistry, Faculty of Science, University of Qom, Qom 37185-359, Iran
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
b
a r t i c l e i n f o
a b s t r a c t
Article history:
A recyclable functional hybrid catalyst was prepared via a simple method using chitosan as a linear
polysaccharide and an ionic liquid. In this work, the synthesis of chitosan supported 1-phenyl-1H-
tetrazole-5-thiol ionic liquid copper(II) complex (CS@Tet-IL-Cu(II)) was investigated. The synthesized
CS@Tet-IL-Cu(II) was characterized using XRD, EDS, elemental mapping, STEM, FT-IR, TG/DTA, ICP-MS
and TEM analyses. CS@Tet-IL-Cu(II) was applied as an effective and novel catalyst in the synthesis of ary-
Received 17 April 2021
Revised 12 August 2021
Accepted 25 August 2021
Available online 30 August 2021
3
laminotetrazoles via the cycloaddition reaction of arylcyanamides and NaN in DMF solvent. The exper-
Keywords:
imental results indicated that the type of substituents on arylcyanamides could affect the type of
products (A or B isomer). The arylcyanamides with electron withdrawing and donating groups can pro-
duce isomer A (5-arylamino-1H-tetrazole) and isomer B (1-aryl-5-amino-1H-tetrazole), respectively. In
addition, CS@Tet-IL-Cu(II) can be reused five times with no noteworthy loss of performance.
Ó 2021 Elsevier B.V. All rights reserved.
Arylaminotetrazole
Arylcyanamide
Chitosan
CS@Tet-IL-Cu(II)
Heterogeneous catalyst
Ionic liquid
1
. Introduction
In recent years, tetrazole compounds have made many contri-
azide sources, expensive reagents, and homogeneous catalysts,
harsh reaction conditions as well as tedious workup, low yield,
and production of a mixture of different isomers [21].
butions to chemistry, medicine, and pharmaceuticals. Tetrazoles
can be applied as isosteres of carboxylic acids, ligands in a variety
of complexes, as well as explosives in different propellants [1–5].
Tetrazole anions are ten times more lipophilic than carboxylate
anions, which is an important feature in the design of different
drug molecules to penetrate cell membranes [6–8]. In addition,
tetrazoles are applied as herbicides, plant growth regulators, and
fungicide stabilizers in agriculture [9–11]. Tetrazole is a 5-
membered ring with special properties including high acidity and
enthalpy of formation as well as high N number. In addition, tetra-
zoles are very stable [12–14]. Various tetrazole derivatives have
been successfully used as efficient compounds in the preparation
of N-containing compounds [15,16]. Tetrazole containing com-
pounds have various applications; especially in medicine, such as
antihypertensive drugs and antitumor agents [17,18].
Recently, arylaminotetrazoles have been synthesized by the
[2 + 3] cycloaddition reaction of monosubstituted cyanamides
and sodium azide (NaN ). Due to some advantages of heteroge-
3
neous catalysts, researchers have used them in the synthesis of
arylaminotetrazoles [22–26].
Heterogeneous catalysts are one of the most promising com-
pounds for different reactions. One of the most significant steps
in the fabrication of heterogeneous catalysts is to select a suitable
support for the decoration of metal nanoparticles or complexes
[27–34]. Natural polymers or biopolymers, for example cellulose,
alginate, starch, gum, chitin, and chitosan are the most promising
compounds, which are broadly applied as efficient supports in
the synthesis of heterogeneous catalysts. In recent years, among
the various biopolymers, chitosan has attracted a lot of attention
due to its many benefits. In fact, chitosan is a hydrophobic and lin-
ear polysaccharide, which is prepared by deacetylation of chitin in
an alkaline solution. Chitin, which is the most abundant polysac-
charide after cellulose, is obtained from the exoskeletons of
shrimp, crabs, and squid (Fig. 1). In addition, chitosan is a cationic
polysaccharide with some advantages including biodegradability,
accessibility, biocompatibility, and none-toxicity. These advan-
tages make chitosan a suitable and biodegradable choice for the
preparation of heterogeneous catalysts [21].
There are some methods for the preparation of arylaminotetra-
zoles. Due to the many benefits and applications of arylaminotetra-
zoles, there are several methods to synthesize them (Scheme 1)
[
19,20]. Some of the methods shown in Scheme 1 for the synthesis
of aminotetrazoles have drawbacks including the use of non-safe
⇑
Corresponding author.
E-mail address: mahmoudnasr81@gmail.com (M. Nasrollahzadeh).
https://doi.org/10.1016/j.molliq.2021.117398
167-7322/Ó 2021 Elsevier B.V. All rights reserved.
0

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Scheme 1. Different methods for the synthesis of aminotetrazoles.
Ionic liquids (ILs), which are a novel class of eco-friendly, safe
solvents composed mainly of ions, are applied in various applica-
tions; especially in catalysis. In other words, ILs can play different
roles as catalysts, reagents, reaction media, and solvents. Nowa-
days, the use of ILs as catalysts is very much considered by
researchers because they have many benefits such as high thermal
stability, recyclability, and exceptional solvation properties
a relatively inexpensive catalyst, generality, efficiency, short reac-
tion time, simplicity, easy work-up procedure, reusability of the
catalyst, straightforward isolation of the products, and the high
yield of products are the advantages of this protocol.
2
. Experimental
[
35,36].
An efficient heterogeneous metal ionic liquid catalyst (CS@Tet-
2.1. Tools and chemicals
IL-Cu(II)) by 1-phenyl-1H-tetrazole-5-thiol has been designed and
characterized in this work. In other words, 1-phenyl-1H-tetrazole-
All chemicals were obtained from Merck and Aldrich Chemical
Co. Chitosan (De-acetylation degree: 85%, molecular weight:
0,000–80,000 Da (medium), particle dimension: powder with a
5
-thiol ionic liquid Cu(II) complex has been supported on chitosan
5
using (3-chloropropyl)trimethoxysilane. To the best of our knowl-
edge, this is the first report on the synthesis of a tetrazole based
ionic liquid stabilized on the surface of chitosan. Although there
are several reports concerning imidazole based ionic liquids [28],
very few ionic liquid based tetrazoles have been synthesized
mesh size of 80, soluble in 1% acetic acid) was supplied by Nano
Novin Polymer (NNP) Co. Company. The structure of the synthe-
sized heterogeneous catalyst was characterized using FT-IR, XRD,
TEM, FESEM, and EDS analyses. The products were characterized
1
13
by FT-IR, HNMR, and CNMR. The FT-IR and NMR spectra were
recorded using Perkin-Elmer 781 and Bruker spectrophotometer
and Avance DRX-400 and 600 MHz, respectively. The morphology
and size of the prepared catalyst were obtained by TEM using JEM-
F200 JEOL, and FESEM, Hitachi S-4700 instruments. The XRD and
TG/DTA analyses were performed using Philips PW 1373 diffrac-
tometer and STA 1500 Rheometric-Scientific, respectively. The ele-
mental contents of the catalyst were determined by inductively
coupled plasma optical emission spectrometry (ICP-MS, Perkin
Elmer, Optima 8000).
[
29,37,38]. However, it is noteworthy that there are no reports
on the synthesis of ionic liquids using 1-phenyl-1H-tetrazole-
-thiol. Therefore, this report could create a new route for the
5
synthesis of ionic liquid based tetrazoles. Next, the prepared
CS@Tet-IL-Cu(II) was applied in the preparation of arylaminotetra-
zole derivatives by [2 + 3] cycloaddition reaction of a wide range of
substituted arylcyanamides and NaN in DMF solvent (Scheme 2).
3
The results show that the CS@Tet-IL-Cu(II) has excellent catalytic
activity and the products are obtained in good yields. The use of
2

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Fig. 1. Schematic representation of the preparation of chitosan from chitin.
2.2. Synthesis of ionic liquid (Tet-IL)
2.5. Synthesis of arylaminotetrazoles
In a 150 mL flask, 5 mmol of 1-phenyl-1H-tetrazole-5-thiol and
3
In a 50 mL flask, 1 mmol of arylcyanamides, 1.5 mmol of NaN ,
5
mmol of (3-chloropropyl)trimethoxysilane (TMOS) were added
0.05 g of CS@Tet-IL-Cu(II), and 7 mL of DMF were added and the
mixture obtained was stirred at 120 °C for an appropriate time
(the reaction progress was monitored by TLC). Upon the comple-
tion of the reaction, the reaction mixture was cooled and
CS@Tet-IL-Cu(II) was removed from the reaction medium via filtra-
tion. The reaction mixture was then treated with 25 mL of HCl and
to 50 mL of ethanol and the reaction mixture was subjected to
reflux conditions. Reaction progress was followed by TLC. After
2
of 1,4-butane sultone were then added dropwise to the reaction
mixture and stirring was continued for 8 h (Tet-IL).
0 h, the reaction temperature was reduced to 50–55 °C. 5 mmol
2
5 mL of ethyl acetate while being vigorously stirred. The organic
layer was separated from the mixture and the aqueous layer was
over-extracted using 25 mL of ethyl acetate. Finally, the separated
organic layers were washed with water, followed by the removal of
solvent, and crystallization in ethanol for further purification.
2
.3. Synthesis of CS@Tet-IL-Cu(II)
Firstly, in a 250 mL flask, 1.5 g of chitosan (CS) were added to
Tet-IL, prepared in the previous stage, and the resulting mixture
was refluxed for 24 h. When the reaction was over, the reaction
mixture was cooled and the resulting precipitate (CS@Tet-IL) was
separated from the reaction mixture by filtration, washed several
times with ethanol, and then dried. In the next stage, in a 150 flask,
3
. Results and discussion
3.1. Characterization of CS@Tet-IL-Cu(II)
a mixture of 1.2 g of CS@Tet-IL and 0.4 g of CuCl
4 h. The resulting precipitate (CS@Tet-IL-Cu(II)) was then sepa-
rated by filtration and dried after washing with ethanol
Scheme 3).
2
was refluxed for
CS@Tet-IL-Cu(II) structure was confirmed using XRD, EDS, ele-
2
mental mapping, TEM, STEM, FT-IR, ICP-MS and TG/DTA analyses.
Fig. 2 displays the XRD pattern of CS@Tet-IL-Cu(II). The peak
observed in 2h = 20° is related to the presence of chitosan in the
synthesized catalyst, which matches the XRD pattern reported in
the literature [40]. Due to the uniform distribution of copper parti-
cles in the synthesized catalyst, the peak corresponding to the cop-
per particles is not visible.
(
2.4. Synthesis of arylcyanamides
Different arylcyanamides were produced according to literature
methods [39].
The chemical compositions of CS@Tet-IL and CS@Tet-IL-Cu(II)
were determined using EDS and elemental mapping analyses.
3

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Scheme 2. Schematic representation of synthesis of arylaminotetrazoles using CS@Tet-IL-Cu(II).
Scheme 3. Synthetic pathway for the preparation of CS@Tet-IL-Cu(II) catalyst.
Fig. 2. XRD pattern of CS@Tet-IL-Cu(II).
4

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Fig. 3. EDS spectra and elemental mapping analysis of a) CS@Tet-IL and b) CS@Tet-IL-Cu(II).
5

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Fig. 3 (continued)
Fig. 3 displays the EDS spectra of the CS@Tet-IL and CS@Tet-IL-Cu
II). The EDS analysis of the catalyst was carried out by a Cu grid
TEM analysis was applied to determine the particle size. Fig. 4
displays the TEM images of CS@Tet-IL and CS@Tet-IL-Cu(II). As
shown in Fig. 4, the copper complex is evenly distributed on the
surface of chitosan ionic liquid. The average size of a copper com-
plex is about 10 nm. The STEM images of CS@Tet-IL and CS@Tet-IL-
Cu(II) are displayed in Fig. 5, which confirm the homogenous
assembly of the synthesized catalyst.
(
to hold the sample. As shown in Fig. 3 (a), copper is not observed
in the CS@Tet-IL elemental mapping. EDS and elemental mapping
of the CS@Tet-IL-Cu(II) confirmed the presence of the C, O, Si, Cu
and N in the structure of CS@Tet-IL-Cu(II) (Fig. 3 (b)). The
CS@Tet-IL-Cu(II) elemental mapping confirmed the uniform
distribution of copper particles on the CS@Tet-IL surface. The con-
tent of the Cu within CS@Tet-IL-Cu(II), as determined using ICP-
MS, was 0.6 wt%.
Fig. 6 shows the FT-IR spectra of CS@Tet-IL and CS@Tet-IL-Cu
À1
(II). As observed, the peak in the range of 3200–3500 cm
is
related to NH and OH of chitosan. Furthermore, the peaks at
6

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Fig. 4. TEM images of CS@Tet-IL (top) and CS@Tet-IL-Cu(II) (bottom).
Fig. 5. STEM images of (left) CS@Tet-IL and (right) CS@Tet-IL-Cu(II).
À1
2
886, 1624 and 1152 cm correspond to the tensile vibrations of
autonomic TG/DTA were carried out from 40 °C to 700 °C. Fig. 7
(a, b) shows the comparative weight loss of CS@Tet-IL and
CS@Tet-IL-Cu(II). For both samples, the weight loss observed at
temperatures below 200 °C is due to the release of water or organic
solvents in the structure. In addition, in both samples, the weight
loss in the temperature range of 200–500 °C corresponds to the
3
3À
C-H (sp ) bonds, C = N bonds of tetrazole and SO , respectively,
which confirms the presence of tetrazole and IL in the structure
of the synthesized CS@Tet-IL-Cu(II).
Thermogravimetric (TG) and differential thermal analysis (DTA)
tests in airflow (120 mL/min) at a heating rate of 2 °C/min on an
7

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Fig. 6. FT-IR spectra of CS@Tet-IL and CS@Tet-IL-Cu(II).
decomposition of chitosan and 1-phenyl-1H-tetrazole-5-thiol
functionalized ionic liquid. As shown in Fig. 7 (b), another
decomposition stage is observed after 600 °C, which is related to
the decomposition of the prepared catalyst.
containing electron withdrawing and donating groups produce iso-
mer A (5-arylamino-1H-tetrazole) and isomer B (1-aryl-5-amino-
1H-tetrazole), respectively.
The advantage of our method over other methods is that
depending on the arylcyanamide used in the cycloaddition reac-
tion, the product will be either isomer A or B, while other methods
3.2. Catalytic application of CS@Tet-IL-Cu(II) in the synthesis of
3 3 2
using HN , glacial acetic acid, and FeCl -SiO yield an isomeric mix-
arylaminotetrazoles
ture (Scheme 4) [3,25]. In other words, our method is regiospecific.
This is in concordance with the reports previously published
regarding the synthesis of arylaminotetrazoles using natrolite zeo-
The synthesized CS@Tet-IL-Cu(II) was applied as an efficient
catalyst in the [2 + 3] cycloaddition reaction of arylcyanamides
3 4 3 4 2
lite, Ag/Fe O nanocomposite, and Fe O @SiO -aminotet-Cu(II) cat-
and NaN
3
in DMF solvent for the synthesis of arylaminotetrazoles.
using
alyst [22–24]. The reported protocols have disadvantages such as
the production of the mixtures of isomers [3,25], use of hydrazoic
acid as a highly toxic and explosive compound, harsh reaction con-
ditions, long reaction times, low yield, difficulty of work up due to
the application of homogeneous catalysts, in situ generation of
hydrazoic acid, difficulties in preparation and availability of the
Natrolite zeolite [23] as a local and natural catalyst and also
The cycloaddition of 4-chlorophenylcyanamide and NaN
3
CS@Tet-IL-Cu(II) was chosen as a model reaction to optimize the
reaction conditions. Since cycloaddition reactions are performed
at high temperatures, DMF was selected as the most suitable sol-
vent. Different amounts of the catalyst were used to perform this
reaction, the results of which are summarized in Table 1. The reac-
tion does not occur in the absence of a catalyst (Table 1, entry 1). As
displayed in Table 1, the most significant result is obtained in the
reaction of 1 mmol of 4-chlorophenylcyanamide with 1.5 mmol
3 4
Euphorbia peplus Linn leaf extract for the synthesis of Ag/Fe O
nanocomposite [22]. Compared to other reported catalysts,
CS@Tet-IL-Cu(II) avoids the previously reported problems and per-
forms the best. To the best of our knowledge, this is the first report
wherein an ionic liquid based tetrazole has been immobilized on
the chitosan surface as an effective support.
Based on previous reports [22–24], a mechanism is proposed for
the synthesis of arylaminotetrazole derivatives, as displayed in
Scheme 5. The products were obtained via the guanidine azide
intermediates.
3
of NaN in the presence of 0.05 g of CS@Tet-IL-Cu(II) in DMF sol-
vent (Entry 4). When the amount of catalyst is slightly increased,
the product yield does not significantly increase (Entry 5). How-
ever, decreasing the amount of the catalyst significantly reduces
the product yield (Entry 3).
To prepare arylaminotetrazoles, various types of aryl-
cyanamides with electron donating and withdrawing groups were
used (Table 2). Our results indicate that various arylcyanamides
with different electron donating and withdrawing groups form
arylaminotetrazole derivatives in high yields. In addition, the
results show that cyanamides with electron donating groups are
more reactive. On the other hand, as shown in Table 2, the cycload-
dition reaction time of arylcyanamides containing electron-
donating groups is shorter than that of arylcyanamides with elec-
tron withdrawing groups. According to Table 2, arylcyanamides
The chemical structures of the synthesized arylaminotetrazoles
1
derivatives (A and B isomers) were confirmed using FT-IR, HNMR,
1
3
and CNMR spectroscopy (Fig. 8). In the FT-IR spectra of the syn-
thesized A and B isomers, the peaks corresponding to NH and NH
2
1
are observed. In the HNMR spectrum of A isomer, two NH peaks
are observed corresponding to the NH of the amine connected to
the aryl group and NH of the tetrazole ring. However, the HNMR
1
8

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Fig. 7. TG/DTA analysis of (a) CS@Tet-IL and (b) CS@Tet-IL-Cu(II).
of B isomer shows one peak for the NH
2
group. Fig. 8 shows the 13-
the
catalyst,
the
cycloaddition
reaction
of
2-
CNMR spectrum of 5-(3-bromophenyl)amino-1H-tetrazole. As
observed in the Figure; both isomers have peaks in the 154–158
region associated with the tetrazole ring.
chlorophenylcyanamide with NaN
3
using CS@Tet-IL-Cu(II) in
DMF solvent was selected as the model reaction. After the reaction
is over; CS@Tet-IL-Cu(II) is separated from the reaction mixture by
filtration, washed several times with ethanol, dried and applied for
the next cycle. As shown in Scheme 6, CS@Tet-IL-Cu(II) can be used
for up to 5 consecutive cycles with no significant reduction of cat-
alytic performance. The XRD pattern, TEM images, and elemental
mapping of the CS@Tet-IL-Cu(II) after 5 cycles display that the
3.3. Reusability of the CS@Tet-IL-Cu(II)
One of the significant features of heterogeneous catalysts is
their ability to be recycled and reused. To test the recyclability of
9

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Table 1
a
Optimization of reaction conditions for the synthesis of 5-(4-chlorophenyl)amino-1H-tetrazole.
Entry
Catalyst (g)
Time (min)
Yieldb (%)
1
2
3
4
5
0
120
60
40
30
30
0
0.01
0.03
0.05
0.07
66
78
85
85
a
Reaction conditions: 4-chlorophenylcyanamide (1 mmol), NaN
Isolated yield.
3
(1.5 mmol), DMF (7 mL), catalyst, 120 °C.
b
physical and chemical features such as chemical composition, size,
and shape have not changed (Fig. 9). To check the heterogeneity of
this catalyst, which is an important factor, the filtrate of each cycle
was also analyzed by ICP-MS technique. Very low copper contam-
ination was observed during these experiments. Copper leaching
after the recycling tests was investigated and ICP-MS analysis
showed that copper leaching was negligible (~0.1%).
laminotetrazole derivatives. The structure of the synthesized
CS@Tet-IL-Cu(II) was confirmed using XRD, FT-IR, EDS, elemental
mapping, STEM, TG/DTA, ICP-MS and TEM analyses. The prepared
CS@Tet-IL-Cu(II) performs well in the synthesis of arylaminotetra-
zole derivatives even after 5 consecutive cycles. Our method for the
synthesis of arylaminotetrazole derivatives is effective. It has many
advantages such as the application of high performance heteroge-
neous catalysts, no use of toxic and explosive compounds such as
3
NH , formation of high efficiency products, and single isomer (iso-
mer A or B).
4
. Conclusion
In this study, a chitosan supported metal ionic liquid has been
successfully synthesized. Chitosan supported 1-phenyl-1H-
tetrazole-5-thiol ionic liquid copper(II) complex has been prepared
using (3-chloropropyl)trimethoxysilane (CS@Tet-IL-Cu(II)). The
prepared CS@Tet-IL-Cu(II) has been applied as a novel and effective
heterogeneous catalyst in the [2 + 3] cycloaddition reaction of aryl-
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
3
cyanamides with NaN in DMF as a solvent for the synthesis of ary-
10

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Table 2
a
Synthesis of arylaminotetrazole derivatives in the presence of CS@Tet-IL-Cu(II).
Yieldb (%)
86
TON
TOF (min
9109
À1
)
Entry
1
Arylcyanamide
Product
Time (min)
20
182176
2
25
83
175821
7033
3
4
5
6
20
20
20
20
83
82
85
86
175821
173703
180058
182176
8791
8685
9003
9109
7
8
9
30
40
30
45
45
30
20
83
81
85
85
83
85
86
175821
171584
180058
180058
175821
180058
182176
5860
4289
6002
4001
3907
6002
9109
1
1
1
1
0
1
2
3
1
4
20
85
180058
9003
a
Reaction conditions: Arylcyanamide (1 mmol), NaN
Isolated yield.
3
(1.5 mmol), DMF (7 mL), CS@Tet-IL-Cu(II) (0.05 g), 120 °C.
b
11

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Scheme 4. Synthesis of 5-arylamino-1H-tetrazole (isomer A) and 1-aryl-5-amino-1H-tetrazole (isomer B) under different reaction conditions.
Scheme 5. The proposed mechanism for the synthesis of arylaminotetrazoles.
12

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Fig. 8. FT-IR (top), 1HNMR (center) and 13CNMR (below) spectra of 5-(3-bromophenyl)amino-1H-tetrazole.
13

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
Fig. 8 (continued)
Scheme 6. Reusability of the CS@Tet-IL-Cu(II).
14

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
6
5
4
3
2
1
00
00
00
00
00
00
0
1
0
20
30
40
50
60
70
80
90
2
(degree)
Fig. 9. XRD pattern, TEM images, and elemental mapping of the recycled CS@Tet-IL-Cu(II).
15

M. Nasrollahzadeh, N. Motahharifar, Z. Nezafat et al.
Journal of Molecular Liquids 341 (2021) 117398
[
21] N. Motahharifar, M. Nasrollahzadeh, A. Taheri-Kafrani, R.S. Varma, M.
Acknowledgments
Shokouhimehr, Magnetic chitosan-copper nanocomposite:
A
plant
assembled catalyst for the synthesis of amino-and N-sulfonyl tetrazoles in
eco-friendly media, Carbohydr. Polym. 232 (2020) 115819.
The supports provided by the University of Qom are
appreciated.
[22] M. Sajjadi, M. Nasrollahzadeh, S. Mohammad Sajadi, Green synthesis of Ag/
Fe nanocomposite using Euphorbia peplus Linn leaf extract and evaluation
3 4
O
of its catalytic activity, J. Colloid Interface Sci. 497 (2017) 1–13.
23] M. Nasrollahzadeh, D. Habibi, Z. Shahkarami, Y. Bayat, A general synthetic
method for the formation of arylaminotetrazoles using natural natrolite
zeolite as a new and reusable heterogeneous catalyst, Tetrahedron 65 (51)
(2009) 10715–10719.
References
[
[
[
[
1] H. Zhao, Z.-R. Qu, H.-Y. Ye, R.-G. Xiong, In situ hydrothermal synthesis of
tetrazole coordination polymers with interesting physical properties, Chem.
Soc. Rev. 37 (1) (2008) 84–100.
2] X.-M. Zhang, Y.-F. Zhao, H.-S. Wu, S.R. Batten, S. Weng Ng, Syntheses and
structures of metal tetrazole coordination polymers, Dalt. Trans. (26) (2006)
[24] M. Nasrollahzadeh, M. Sajjadi, H.A. Khonakdar, Synthesis and characterization
of novel Cu(II) complex coated Fe @SiO nanoparticles for catalytic
performance, J. Mol. Struct. 1161 (2018) 453–463.
[25] D. Habibi, M. Nasrollahzadeh, Silica-supported ferric chloride (FeCl
3
O
4
2
3
170, https://doi.org/10.1039/b518052j.
3 2
-SiO ): an
3] A.R. Modarresi-Alam, M. Nasrollahzadeh, Synthesis of 5-arylamino-1H (2H)-
tetrazoles and 5-amino-1-aryl-1H-tetrazoles from secondary arylcyanamides
in glacial acetic acid: a simple and efficient method, Turk. J. Chem. 33 (2009)
efficient and recyclable heterogeneous catalyst for the preparation of
arylaminotetrazoles, Synth. Commun. 40 (2010) 3159–3167.
[26] M. Maham, M. Khalaj, Synthesis of thiotetrazoles and arylaminotetrazoles
2
67–280.
2
using rutile TiO nanoparticles as a heterogeneous and reusable catalyst, J.
Chem. Res. 38 (8) (2014) 502–506.
[
4] Z.P. Demko, K.B. Sharpless, Preparation of 5-substituted 1H-tetrazoles from
nitriles in water, J. Org. Chem. 66 (24) (2001) 7945–7950.
[27] M. Ghasemi, A. Khataee, P. Gholami, R.D.C. Soltani, A. Hassani, Y. Orooji, In-situ
electro-generation and activation of hydrogen peroxide using a CuFeNLDH-
CNTs modified graphite cathode for degradation of cefazolin, J. Environ.
Manage. 267 (2020) 110629.
[28] S. Sadjadi, M.M. Heravi, S.S. Kazemi, Ionic liquid decorated chitosan hybridized
with clay: A novel support for immobilizing Pd nanoparticles, Carbohydr.
Polym. 200 (2018) 183–190.
[29] M. Nasrollahzadeh, Z. Nezafat, N.S. Soheili Bidgoli, N. Shafiei, Use of tetrazoles
in catalysis and energetic applications, Recent developments, Mol. Catal. 513
(2021) 111788.
[
5] T. Jin, F. Kitahara, S. Kamijo, Y. Yamamoto, Copper-catalyzed synthesis of 5-
substituted 1H-tetrazoles via the [3+ 2] cycloaddition of nitriles and
trimethylsilyl azide, Tetrahedron Lett. 49 (17) (2008) 2824–2827.
6] C.-X. Wei, M. Bian, G.-H. Gong, Tetrazolium compounds: synthesis and
applications in medicine, Molecules 20 (2015) 5528–5553.
[
[
[
[
7] E.A. Popova, R.E. Trifonov, V.A. Ostrovskii, Tetrazoles for biomedicine, Russ.
Chem. Rev. 88 (6) (2019) 644–676.
8] V.A. Ostrovskii, R.E. Trifonov, E.A. Popova, Medicinal chemistry of tetrazoles,
Russ. Chem. Bull. 61 (4) (2012) 768–780.
9] B.S. Jursic, B.W. Leblanc, Preparation of tetrazoles from organic nitriles and
sodium azide in micellar media, J. Heterocycl. Chem. 35 (1998) 405–408.
[30] P. Mehdizadeh, Y. Orooji, O. Amiri, M. Salavati-Niasari, H. Moayedi, Green
synthesis using cherry and orange juice and characterization of TbFeO
3
[
[
[
10] Y.-T. Li, W.-Q. Yao, S. Zhou, J.-X. Xu, H. Lu, J. Lin, X.-Y. Hu, S.-K. Zhang, Synthesis,
fungicidal activity, and 3D-QSAR of tetrazole derivatives containing
phenyloxadiazole moieties, Bioorg. Med. Chem. Lett. 34 (2021) 127762.
11] J. He, B. Li, F. Chen, Z. Xu, G. Yin, Tungstates: Novel heterogeneous catalysts for
the synthesis of 5-substituted 1H-tetrazoles, J. Mol. Catal. A Chem. 304 (2009)
ceramic nanostructures and their application as photocatalysts under UV light
for removal of organic dyes in water, J. Clean. Prod. 252 (2020) 119765.
[31] S.h. Jafari, S. Azizian, B. Jaleh, Adsorption kinetics of methyl violet onto TiO
2
nanoparticles with different phases, Colloids Surf. A Physicochem. Eng. Asp.
384 (1-3) (2011) 618–623.
[32] Y. Orooji, M. Ghanbari, O. Amiri, M. Salavati-Niasari, Facile fabrication of silver
iodide/graphitic carbon nitride nanocomposites by notable photo-catalytic
performance through sunlight and antimicrobial activity, J. Hazard. Mater. 389
(2020) 122079.
1
35–138.
12] M.S. Pino-Gonzalez, A. Romero-Carrasco, S. Calvo-Losada, N. Oña-Bernal, J.J.
Quirante, F. Sarabia, Synthesis of tetrazole fused azepanes and quantum
chemical topology study on the mechanism of the intramolecular
cycloaddition reaction, RSC Adv. 7 (79) (2017) 50367–50371.
[33] Y. Orooji, R. Mohassel, O. Amiri, A. Sobhani, M. Salavati-Niasari, Gd
ZnO nanocomposites: green sol-gel auto-combustion
2
ZnMnO
synthesis,
6
/
[
[
[
13] L.M.T. Frija, M.L.S. Cristiano, A. Gómez-Zavaglia, I. Reva, R. Fausto, Genesis of
rare molecules using light-induced reactions of matrix-isolated tetrazoles, J.
Photochem. Photobiol. C Photochem. Rev. 18 (2014) 71–90.
14] D. Ichinari, A. Nagaki, J.-I. Yoshida, Generation of hazardous methyl azide and
its application to synthesis of a key-intermediate of picarbutrazox, a new
potent pesticide in flow, Bioorg. Med. Chem. 25 (23) (2017) 6224–6228.
characterization and photocatalytic degradation of different dye pollutants
in water, J. Alloys Compd. 835 (2020) 155240.
[34] P. Gholami, L. Dinpazhoh, A. Khataee, Y. Orooji, Sonocatalytic activity of
biochar-supported ZnO nanorods in degradation of gemifloxacin: synergy
study, effect of parameters and phytotoxicity evaluation, Ultrason. Sonochem.
55 (2019) 44–56.
[35] I.M.N. Vold, K.M. Vårum, E. Guibal, O. Smidsrød, Binding of ions to chitosan-
selectivity studies, Carbohydr. Polym. 54 (4) (2003) 471–477.
[36] F. Xiao, F. Zhao, Y. Zhang, G. Guo, B. Zeng, Ultrasonic electrodeposition of gold-
platinum alloy nanoparticles on ionic liquid-chitosan composite film and their
application in fabricating nonenzyme hydrogen peroxide sensors, J. Phys.
Chem. C 113 (3) (2009) 849–855.
15] A.R. Modarresi-Alam, F. Khamooshi, M. Rostamizadeh, H. Keykha, M.
1
Nasrollahzadeh, H.-R. Bijanzadeh, E. Kleinpeter, Dynamic
H
NMR
spectroscopic study of the restricted S-N rotation in aryl-N-(arylsulfonyl)-N-
(
(
triphenylphosphoranylidene) imidocarbamates, J. Mol. Struct. 841 (1–3)
2007) 61–66.
[
16] B. Gutmann, T.N. Glasnov, T. Razzaq, W. Goessler, D.M. Roberge, C.O. Kappe,
Unusual behavior in the reactivity of 5-substituted-1H-tetrazoles in
a
resistively heated microreactor, Beilstein J. Org. Chem. 7 (2011) 503–517.
[37] G. Aridoss, K.K. Laali, Highly efficient synthesis of 5-substituted 1H-tetrazoles
catalyzed by Cu-Zn alloy nanopowder, conversion into 1,5- and 2,5-
disubstituted tetrazoles, and synthesis and NMR studies of new tetrazolium
ionic kiquids, Eur. J. Org. Chem. 2011 (31) (2011) 6343–6355.
[38] G.-H. Tao, Y. Guo, Y.-H. Joo, B. Twamley, J.M. Shreeve, Energetic nitrogen-rich
salts and ionic liquids: 5-aminotetrazole (AT) as a weak acid, J. Mater. Chem.
18 (2008) 5524–5530.
[39] R.J. Crutchley, M.L. Nakicki, Pentaammineruthenium(III) complexes of neutral
and anionic (2,3-dichlorophenyl)cyanamide: a spectroscopic analysis of ligand
to metal charge-transfer spectra, Inorg. Chem. 28 (1989) 1955–1958.
[40] S. Kumar, J. Koh, Physiochemical, optical and biological activity of chitosan-
chromone derivative for biomedical applications, Int. J. Mol. Sci. 13 (5) (2012)
6102–6116.
[
17] T. Tanaka, T. Okuda, Y. Yamamoto, Characterization of the CYP3A4 active site
by homology modeling, Chem. Pharm. Bull. 52 (7) (2004) 830–835.
18] S.M. Bayomi, M.A. Moustafa, A.R. Maarouf, M.H. Abutaleb, Design, synthesis,
biological activity and molecular modeling of new heterocyclic tetrazole
derivatives, J. Am. Sci. 12 (1) (2016) 40–56.
[
[
19] R. Yella, N. Khatun, S.K. Rout, B.K. Patel, Tandem regioselective synthesis of
tetrazoles and related heterocycles using iodine, Org. Biomol. Chem. 9 (9)
(
2011) 3235, https://doi.org/10.1039/c0ob01007c.
[
20] P. Nimnual, J. Tummatorn, B. Boekfa, C. Thongsornkleeb, S. Ruchirawat, P.
Piyachat, K. Punjajom, Construction of 5-aminotetrazoles via in situ generation
of carbodiimidium ions from ketones promoted by TMSN
4 (9) (2019) 5603–5613.
3
/TfOH, J. Org. Chem.
8
16