An efficient and recyclable catalytic system for carbon–sulfur coupling reaction and synthesis of 5-substituted 1H-tetrazoles

Article abstract of DOI:10.1080/17415993.2017.1408809

In this research paper, efficient and economical protocols for the synthesis of symmetrical sulfides and 5-substituted 1H-tetrazoles have been reported using Fe₃O₄@SBTU@Ni(II) as a heterogeneous and recoverable nanocatalyst. The noticeable features of this catalytic system are: operational simplicity, environmentally benign, easier work-up procedure, green and efficient synthetic entry to excellent yield of products in a high reusability and applicability to various starting materials and, therefore, cost efficiency.

Full text of DOI:10.1080/17415993.2017.1408809

Journal of Sulfur Chemistry
ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: http://www.tandfonline.com/loi/gsrp20
An efficient and recyclable catalytic system for
carbon–sulfur coupling reaction and synthesis of
5-substituted 1H-tetrazoles
Arash Ghorbani-Choghamarani, Zahra Moradi & Gouhar Azadi
To cite this article: Arash Ghorbani-Choghamarani, Zahra Moradi & Gouhar Azadi (2017): An
efficient and recyclable catalytic system for carbon–sulfur coupling reaction and synthesis of 5-
substituted 1H-tetrazoles, Journal of Sulfur Chemistry, DOI: 10.1080/17415993.2017.1408809
To link to this article: https://doi.org/10.1080/17415993.2017.1408809
Published online: 23 Dec 2017.
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Date: 26 December 2017, At: 02:18

JOURNAL OF SULFUR CHEMISTRY, 2017
https://doi.org/10.1080/17415993.2017.1408809
An efficient and recyclable catalytic system for carbon–sulfur
coupling reaction and synthesis of 5-substituted 1H-tetrazoles
Arash Ghorbani-Choghamarani, Zahra Moradi and Gouhar Azadi
Department of Chemistry, Faculty of Science, Ilam University, Ilam, Iran
ABSTRACT
ARTICLE HISTORY
In this research paper, efficient and economical protocols for the syn-
thesis of symmetrical sulfides and 5-substituted 1H-tetrazoles have
been reported using Fe3O4@SBTU@Ni(II) as a heterogeneous and
recoverable nanocatalyst. The noticeable features of this catalytic
system are: operational simplicity, environmentally benign, easier
work-up procedure, green and efficient synthetic entry to excellent
yield of products in a high reusability and applicability to various
starting materials and, therefore, cost efficiency.
Received 3 June 2017
Accepted 18 November 2017
KEYWORDS
Symmetrical sulfides;
sulfur-transfer reagent;
5-substituted 1H-tetrazoles;
Fe3O4@SBTU@Ni(II);
recoverable
KOH, DMSO, 130°C, Cat.
X
Cat.
R
R
S
R
+
S
Ni
N
S
Y
NH2
NH
Y=NH NH ,CH
2
2
3
O
O
Si
Fe O
N
N
3
4
O
HN
N
R
CN
R
+
NaN3
Cat.
PEG,130°C,Cat.
1. Introduction
Carbon–heteroatom bond-forming reactions are widely used in industry and academia,
pharmaceutical research, materials synthesis and process development. Among them, the
CONTACT Arash Ghorbani-Choghamarani
a.ghorbani@ilam.ac.ir
Department of Chemistry, Faculty of Science,
Ilam University, P.O. Box 69315516, Ilam, Iran
©
2017 Informa UK Limited, trading as Taylor & Francis Group

2
A. GHORBANI-CHOGHAMARANI ET AL.
carbon–sulfur bond formation is one of the significant organic transformations and power-
ful tools for the synthesis of value-added thioethers [1]. Among thioethers, diaryl sulfides
are of great significance due to their broad spectrum of therapeutic activities; also, they
can be employed for diverse clinical applications in the treatment of cancer [2], HIV, and
Alzheimer’s [3] and Parkinson’s diseases [4]. The cross-coupling reactions of aryl halides
with thiols are one of the most important synthetic methods for the preparation of these
valuable materials, but in this case, the main limitations are still the use of volatile and foul-
smelling thiols as substrates, which leads to the serious safety and environmental problems.
In addition, thiols are prone to form undesired disulfides and can act as metal deactivators
[
5]. In order to solve the above-mentioned problems, various novel odorless procedures for
making the C–S bond have been developed by different research groups [6–20]. However,
these odorless protocols suffer from some disadvantages such as the use of homogeneous
catalysts, long reaction time, harsh reaction conditions, metal contamination of the final
product and non-recyclability of the catalyst. Thus, the introduction of new catalytic sys-
tems for this transformation is still a challenge. To make the catalytic processes green and
sustainable, considerable efforts have been devoted to carrying out the C–S coupling reac-
tions. The problems that connected with the homogeneous catalysts can be solved using
heterogenization of homogeneous catalysts. Heterogenization is commonly achieved by
entrapment or grafting of the active molecules on the surfaces or inside the pores of a
solid support such as silica and alumina [21]. Among different catalyst supports, magnetic
nanoparticles (MNPs) have attracted increasing attention because of their facile separation
from the reaction mixture using an external magnet. Magnetic separation of MNPs is easy,
economical and saves time and energy. Moreover, MNPs such as Fe O have a high surface
3
4
area, excellent thermal and chemical stability and surface modification ability period. Also,
they offer an additional advantage of being magnetically separable, thereby eliminating the
requirement of catalyst filtration after completion of the reaction [22–25].
Based on the above consideration, in this research, we first prepared Fe O @SBTU
Ni(II) as novel and recoverable nanocatalyst and then its application for the syn-
3
4
@
thesis of diaryl/alkyl sulfides using thioacetamide and thiosemicarbazide as a sulfur-
transfer reagent has been studied. Also, considering the highly prominent pharmacological
activities and medicinal chemistry applications of tetrazoles as well as in material sci-
ence (including propellants and explosives), Parveen et al., Sharghi et al. and Sreedhar
et al. [26–28] described that a heterogeneous nanocatalyst was applied for the synthe-
sis of these compounds via a [3+2] cycloaddition reaction between nitriles and sodium
azide.
2. Results and discussion
At the outset of experiments, we synthesized SBTU@Ni(II) as shown in Scheme 1.
Initially, grafting of 3-chloropropyltrimethoxysilane on the surface of Fe O4 mag-
3
netic nanoparticles was performed. Then, the reaction of the grafted MNPs with S-
benzylthiuronium sulfate has been achieved to Fe O @SBTU. Finally, Fe O @SBTU
3
4
3
4
reacted with Ni(NO ) .6H O to achieve target nanocatalyst (Scheme 1).
3
2
2
In the next step, synthesized catalyst was characterized using different techniques such
as Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM),
VSM, TGA and X-ray diffraction (XRD). The XRD pattern of Fe O @SBTU@Ni(II) is
3
4

JOURNAL OF SULFUR CHEMISTRY
3
Scheme 1. Synthesis of Fe3O4@SBTU@Ni(II).
Figure 1. XRD pattern of Fe3O4@SBTU@Ni(II).
shown in Figure 1. The position and relative intensities of all peaks verify standard XRD
pattern of Fe O , indicating retention of the crystalline cubic spinel structure during
3
4
functionalization of MNPs.
Figure 2 shows the SEM image of Fe O @CPTES (a), Fe O @SBTU (b) and the SEM
3
4
3
4
images (c) and EDS analysis of the synthesized Fe O @SBTU@Ni(II). SEM has been used
3
4
to study the structure and morphology of the catalyst. As shown in Figure 2, nanoparticles

4
A. GHORBANI-CHOGHAMARANI ET AL.
Figure 2. SEM image of Fe3O4@CPTES (a), Fe3O4@SBTU (b) and the SEM images (c) and EDS analysis of
the synthesized Fe3O4@SBTU@Ni(II).

JOURNAL OF SULFUR CHEMISTRY
5
Figure 3. FT-IR spectra of Fe3O4 (a), Fe3O4@CPTES (b), Fe3O4@SBTU (c) and Fe3O4@SBTU@Ni(II) (d).
are nearly spherical with more than 7 nm in size. Also, the EDS analysis results confirm
the elemental composition of the nanoparticles and the existence of Ni in the prepared
nanocatalyst.
Figure 3 shows the FT-IR spectra of both unfunctionalized and functionalized MNPs.
−
1
The Fe–O and O–H stretching vibrations were observed near 581 and 3433 cm , respec-
tively. The significant feature observed in Figure 3(b) is the appearance of the peaks at
−
1
−1
−1
1
(
009 cm (Si–O stretching), 1624 cm (C−9−N stretching), and 2829 and 2887 cm
–CH stretching). In the FT-IR spectrum of Fe O @SBTU ((spectrum c), the existence of
2
3
4
−
1
S-benzylthoiurea group was identified from C−9−N vibrations that appear at 1620 cm
−
1
and this band was shifted to (1629 cm ) in the Fe O @SBTU@Ni(II) spectrum (spec-
3
4
trum d). The results show that SBTU@Ni(II) was successfully attached to the surface of
the Fe O nanoparticles.
3
4
TGA curves of Fe O and Fe O @SBTU@Ni(II) nanocatalyst are shown in Figure 4.
3
4
3
4
The initial weight loss up to 150°C is due to residual water and the decomposition of
the organic moieties started after 250°C. These results were confirmed that organic lay-
ers have been anchored to the surface of magnetic nanoparticles. Also, atomic absorption
spectroscopy was employed to determine the exact amount of Ni in Fe O @SBTU@Ni(II),
3
4
−4
which was found to be 0.9 × 10 mol/g.
Figure 5 shows the magnetic hysteresis curve of the Fe O @SBTU@Ni(II), which
3
4
exhibits a superparamagnetic behavior. With superparamagnetic property, the catalyst
can be easily recovered by applying an external magnetic field. The measured satura-
tion magnetization value (Ms) of the Fe O @SBTU@Ni(II) was found to be around
3
4
3
0 emu/g.
N adsorption–desorption isotherms are used as a macroscopic average measurement
2
for exploring the surface area, pore diameter and pore volume of the material. The N2
adsorption/desorption isotherm of the final catalyst are shown in Figure 4. The specific

6
A. GHORBANI-CHOGHAMARANI ET AL.
Figure 4. TGA curves of Fe3O4 and Fe3O4@SBTU@Ni(II).
Figure 5. VSM analysis of Fe3O4@SBTU@Ni(II).
Table 1. Textural properties of synthesized materials obtained by nitrogen adsorption–desorption
analysis.
3
3
2
VTotal (cm /g)
.1603
Vm (cm /g)
DBJH (nm)
SBET (m /g)
Sample name
Catalyst
0
25.228
4.82
109.8
surface areas and pore volumes were determined by application of the BET equation and
the numerical data are listed in Table 1 (Figure 6).
After characterization, the catalytic application of Fe O @SBTU@Ni(II) was investi-
3
4
gated in the synthesis of diaryl/alkyl sulfides using thioacetamide and thiosemicarbazide
as a new sulfur-transfer reagents. In the first step, the effect of solvent and catalyst

JOURNAL OF SULFUR CHEMISTRY
7
Figure 6. The N2 adsorption/desorption isotherm for Fe3O4@SBTU@Ni(II).
loading was studied (Table 2). At the beginning, all reactions were performed at 130°C.
The study showed that the reaction was strongly affected by the amount of the catalyst
and sulfur-transfer reagent. As shown in Table 2, in both catalytic systems, the yield of
products increases with increasing the amount of catalyst. The catalyst efficiency was by
solvent. As can be seen from Table 2, DMSO was the best solvent and afforded the prod-
uct with excellent yields. Also, the reaction was evaluated in the presence of different
bases. From the base screening, KOH was found to be the most effective one (Table 2,
entries 4, 15).
With the optimal reaction conditions in hand, we examined the scope of the coupling
reaction using different aryl halides (Scheme 2). The results are summarized in Table 3.
As shown in Table 3, the process was very efficient and afforded good yields for the target
products. It is important to note that when we used the aryl with Cl and Br substituents,
the reaction only proceeds in Br position. Also, aryl chloride showed less reactivity than
aryl iodides and bromides, and the products were obtained in moderate yields.
The suggested mechanism for this transformation is shown in Scheme 3. Initially, aryl
halide reacts with Ni nanoparticles to form intermediate (I) and then coupling reac-
tion of the aryl halide with thioacetamide or thiosemicarbazide produces compound (II),
which is transformed into thiol anion in the presence of KOH. Then, thiol anion reacts
with intermediate (I) to afford corresponding sulfide and acetamide or semicarbazide as
by-products.
After successful synthesis of diaryl/alkyl sulfides, we turned our attention towards the
synthesis of 5-substituted 1H-tetrazoles via a cycloaddition reaction of various organic
nitriles with sodium azide. In the first stage of the study, we tried to seek the optimal
amount of catalyst for the model reaction (Scheme 4). Then, the effect of solvent and tem-
perature was considered. As shown in Table 4, the best reaction conditions for the synthesis
−4
of these compounds were 40 mg (4.24 × 10 mol%) of Fe O @SBTU@Ni(II) at 120°C in
3
4
PEG as a green solvent.

8
A. GHORBANI-CHOGHAMARANI ET AL.
Table 2. The effect of solvent and catalyst loading in the synthesis of diaryl/alkyl sulfides.a
Thiosemicarbazide
(mmol)
Thioacetamide
(mmol)
b
Entry
Cat. (mg)
Solvent
Base
KOH
KOH
KOH
KOH
KOH
KOH
KOH
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
1
1
1
–
–
–
–
–
–
–
–
–
–
–
–
1
36
40
45
50
50
50
50
50
50
50
50
50
16
20
25
30
30
30
30
30
30
30
30
30
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
6.5
5
4
2.5
8
4.5
3.5
3.5
9
2.5
2.5
2.5
12
7
5.5
3.5
3.5
3.5
10
8
69
72
86
88
63
1
0.5
0.8
1
1
1
1
1
1
–
–
–
–
–
–
–
–
–
–
–
–
81
N.R.
N.R.
70
N.R.
N.R.
N.R.
69
76
85
94
N.R.
N.R
57
63
82
N.R.
N.R.
N.R.
PEG
KOH
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
NaOH
Na2CO3
K2CO3
NaOEt
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
NaOH
Na2CO3
K2CO3
NaOEt
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
1
1
1
1
1
PEG
0.5
0.7
1
1
1
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
16
3.5
3.5
3.5
1
Note: N.R., no reaction.
a
Rection conditions: KOH (1 gr) and Solvent (3 mL) at 130°C.
Isolated yield.
b
Scheme 2. Synthesis of symmetrical sulfide catalyzed by Fe3O4@SBTU@Ni(II).
After optimization of reaction conditions, we screened a range of commercially available
organic nitriles for this cycloaddition reaction (Table 5). As shown in Table 5, the cycload-
dition reaction of various organic nitriles with sodium azide was successful and afforded
to the desired products in good to excellent yields (Scheme 5).
Eventually, to show the possibility of magnetic recycling of described nanocatalyst syn-
thesis of 2-(1H-tetrazol-5-yl)phenol was considered in five consequence runs. As shown
in Figure 7, the catalyst can be recycled five times by magnetic separation without major
loss of its catalytic activity.
3. Conclusion
In summary, in this study, we introduced new catalytic systems for the synthesis of
aryl/alkyl sulfide using thiosemicarbazide and thioacetamide as sulfur-transfer reagents.
The reactions generated a variety of diaryl sulfides in moderate to high yields and were

JOURNAL OF SULFUR CHEMISTRY
9
Table 3. Synthesis of diaryl/alkyl sulfides using thioacetamide and thiosemicarbazide.a
Thiosemicarbazide
Thioacetamide
Entry
1
Ar-X
Product
Yield (%) Time (h) Yield (%) Time (h)
m.p. (Ref)
90
4
94
3.5
Colorless liquid [29]
2
3
88
59
2.5
5
89
69
1.5
5
Colorless liquid [29]
Colorless liquid [29]
4
5
57
89
3.5
3
57
93
2
4
159–161 [30]
44–46 [29]
6
7
8
59
69
80
2
4.5
5
65
74
75
1.5
4.5
4
68–72 [29]
Yellow liquid [29]
Yellow liquid [29]
9
62
85
6
3
66
85
6
Yellow liquid [29]
Oil yellow [29]
10
1.5
1
1
2
64
60
2
65
60
1.5
2
159–161 [30]
44–47 [31]
1
1.5
a
Reaction condition: aryl halides (1 mmol), thiosemicarbazide or thioacetamide (1 mmol), KOH (1 g) and DMSO (3 mL).
Isolated yield.
b
applicable to various aryl iodides and bromides. Using commercially available, cheap
and chemically stable sulfur source, elimination of volatile and foul-smelling thiols as
substrate and using heterogenous recoverable nanocatalyst for this transformation are
the main advantages of this protocol. Also in this paper, 5-substituted 1H-tetrazoles
were prepared via a cycloaddition reaction of various organic nitriles with sodium azide,
which generated a diverse range of 5-substituted 1H-tetrazoles of in good to excellent
yields.

10
A. GHORBANI-CHOGHAMARANI ET AL.
Scheme 3. Proposed mechanism for the synthesis of sulfides.
Scheme 4. Synthesis of 5-(3-chlorophenyl)-1H-tetrazole.
Table 4. Screening of different parameter for one-pot synthesis of diphenyl sulfide.a
b
Entry
Cat (mg)
Solvent
Temperature (°C)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
a
30
40
50
40
40
40
40
40
PEG
PEG
PEG
DMF
H2O
DMSO
PEG
120
120
120
120
120
120
80
8
89
93
93
49
N.R.
58
5.5
5.5
5.5
5.5
5.5
5.5
5.5
45
62
PEG
100
Reaction condition: 3-chlorobenzonitrile (1mmol), NaN3 (1.2 mmol).
Isolated yield.
b
4. Experimental
4
.1. Preparation of Fe O @CPTES
3
4
3
-Chloropropyltriethoxysilane (CPTES) (1 g) was added to a suspension of Fe O (1 g)
3 4
in n-hexane (25 mL) and the mixture was refluxed for 24 h under N atmosphere. Then,
2
the resulting solid was collected by magnetic separation, washed with anhydrous ethanol
several times and dried under vacuum in an oven at 60°C overnight. The resulting material
was denoted as Fe O @CPTES.
3
4

JOURNAL OF SULFUR CHEMISTRY
11
Table 5. Synthesis of different structurally 5-substituted-1H-tetrazoles in the presence of
a
Fe3O4@SBTU@Ni(II).
Entry
1
Substrate
Product
Time (h)
5.5
Yield (%)b
93
m.p. (Ref)
132–133 [32]
2
3
4
15
12
4
94
93
92
225–226 [31]
217–220 [32]
149–151 [32]
5
6
10
15
91
88
263–265 [32]
260–262 [32]
7
7
94
253 [32]
8
9
9
6
87
91
212–214 [32]
211–214 [32]
(
continued).

12
A. GHORBANI-CHOGHAMARANI ET AL.
Table 5. Continued.
Entry
Substrate
Product
Time (h)
30
Yield (%)b
91
m.p. (Ref)
10
173–175 [32]
11
8
90
181–183 [32]
a
Reaction condition: aryl halides (1 mmol), thiosemicarbazide or thioacetamide (1 mmol), KOH (1 g) and DMSO (3 mL).
Isolated yield.
b
Scheme 5. Synthesis of 5-substituted-1H-tetrazoles compounds.
Figure 7. Recycling experiments for the synthesis of 2-(1H-tetrazol-5-yl)phenol.
4
.2. Preparation of Fe O @SBTU@Ni(II)
3 4
Fe O @CPTES (1 g) was dispersed in 15 mL n-hexane by ultrasonication under nitrogen
3
4
atmosphere. Next, S-benzylthiuronium sulfate (2.5 mmol) and triethylamine (3.5 mmol)
was added to the mixture under reflux conditions for 20 h. Functionalized MNPs
coated SBTU was washed with 30 mL of ethanol and then dried at 60°C. Afterwards,
Fe O @SBTU (1 g) was dispersed in 20 mL dry ethanol and Ni(NO ) ·6H O (2.5 mmol)
3
4
3 2
2
was added and the mixture was refluxed for 20 h. The resulting nanocomposites (nomi-
nated as Fe O @SBTU@Ni(II) were magnetically collected, washed with ethanol and dried
3
4
under vacuum (Scheme 1).

JOURNAL OF SULFUR CHEMISTRY
13
4
.3. General procedure for the synthesis of sulfides
In a 10 mL round-bottomed flask, a mixture of thioacetamide or thiosemicarbazide
1 mmol), KOH (1 g), aryl/alkyl halide (1 mmol) and Fe O @SBTU@Ni(II) (30 mg using
(
3
4
thioactamide and 50 mg using thiosemicarbazide) in DMSO was stirred at 130°C for an
appropriate time. After completion of the reaction, CH Cl was added to the mixture and
2
2
the catalyst separated by a magnetic field; the filtered washed with water several times and
dried with anhydrous Na SO . Then, the organic solvent was evaporated to give the crude
2
4
solid product. In some cases, the crude product purified by preparative TLC.
4
.4. General procedure for the synthesis of 5-substituted-1H-tetrazoles derivatives
In a round-bottomed flask, a mixture of nitrile (1 mmol) and sodium azide (1.2 mmol) in
the presence of 40 mg of Fe O @SBTU@Ni(II) was stirred at 120°C in PEG for an appro-
3
4
priate time (monitored by TLC). Then, the reaction mixture was cooled down to room
†
temperature. After mag netic separation of catalyst, HCl (4 N, 10 mL) was added to the
filtrate and the product extracted with ethyl acetate (2 × 10 mL). The organic layer was
washed with water several times, dried with anhydrous Na SO and concentrated to give
2
4
the crude solid crystalline product.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
The authors acknowledge Ilam University, Ilam, Iran for financial support of this work.
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