Chloromethylated polystyrene supported copper (II) bis–thiazole complex: Preparation, characterization and its application as a heterogeneous catalyst for chemoselective and homoselective synthesis of aryl azides

Article abstract of DOI:10.1002/aoc.4436

This work deals the synthesis of aryl azides catalyzed by heterogeneous copper (II) complex of 3,5–bis (2–benzothiazolyl) pyridine, [Cu (II)(BTP)(OTf)₂], immobilized on chloromethylated polystyrene, [Cu (II)(BTP)(OTf)₂]@CMP. The prepared catalyst was characterized by different analytical techniques such as X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (SEM), energy dispersive X–ray spectroscopy (EDX), elemental analysis, and FT-IR and UV–Vis spectroscopic methods. This catalytic system showed excellent activity in the synthesis of aryl azides by the reaction of aryl halides with sodium azide in the presence of catalytic amounts of [Cu (II)(BTP)(OTf)₂]@CMP. Moreover, this unique catalyst could be recovered easily and reused several times without any considerable loss of its catalytic activity.

Full text of DOI:10.1002/aoc.4436

Received: 24 January 2018
DOI: 10.1002/aoc.4436
Revised: 2 April 2018
Accepted: 26 April 2018
F U L L P A P E R
Chloromethylated polystyrene supported copper (II) bis–
thiazole complex: Preparation, characterization and its
application as a heterogeneous catalyst for chemoselective
and homoselective synthesis of aryl azides
Zahra Dehbanipour | Majid Moghadam
| Shahram Tangestaninejad
|
Valiollah Mirkhani | Iraj Mohammadpoor‐Baltork
Department of Chemistry, Catalysis
This work deals the synthesis of aryl azides catalyzed by heterogeneous copper
(II) complex of 3,5–bis (2–benzothiazolyl) pyridine, [Cu (II)(BTP)(OTf)2],
immobilized on chloromethylated polystyrene, [Cu (II)(BTP)(OTf)2]@CMP.
The prepared catalyst was characterized by different analytical techniques such
as X‐ray diffraction (XRD), thermogravimetric analysis (TGA), field emission
scanning electron microscopy (SEM), energy dispersive X–ray spectroscopy
(EDX), elemental analysis, and FT‐IR and UV–Vis spectroscopic methods. This
catalytic system showed excellent activity in the synthesis of aryl azides by the
reaction of aryl halides with sodium azide in the presence of catalytic amounts
of [Cu (II)(BTP)(OTf)2]@CMP. Moreover, this unique catalyst could be recov-
ered easily and reused several times without any considerable loss of its
catalytic activity.
Division, University of Isfahan, Isfahan,
81746–73441, Iran
Correspondence
Majid Moghadam, Department of
Chemistry, Catalysis Division, University
of Isfahan, Isfahan 81746–73441, Iran.
Email: moghadamm@sci.ui.ac.ir
Funding information
Research Council of the University of
Isfahan
KEYWORDS
aryl azide, aryl halide, bis–thiazole, copper complex, polystyrene
1 | INTRODUCTION
activity.[17,18] They also used as catalyst in few catalytic
reactions.[19–21]
An important goal in the field of catalysis is developing of
efficient catalytic systems that may be new, readily
available, mild and the catalyst easily separable from
the reaction mixture. On the other hand, in chemical
synthesis, many efforts have been focused on the develop-
ment of new catalytic systems with high activity and
selectivity.[1–4]
Recently, much attention has been devoted to the
thiazole compounds and their complexes due to their
potential applications in the fields of chemistry, biochem-
istry and pharmacology.[5–9] Also, 2–substituted
benzothiazoles have diverse biological and pharmaceuti-
cal properties such as antifungal,[10,11] antitumor,[12–14]
anti–inflammatory,[15] antiviral[16] and antimicrobial
The application of aryl azides as synthetic intermedi-
ates has attracted much attention because of their potential
applications in organic synthesis[22,23] and bioorganic
chemistry.[24] More recently they have also been applied
to prepare important components in many functional
materials such as the photo affinity labeling agents for pro-
teins,[25–29] in the synthesis of various heterocyclic com-
pounds and transition metal complexes.[24,30–38] Also they
are used as cross–linkers in photo–resistors,[39] and for
light–induced activation of polymer surfaces.[40] Despite
these widespread applications of aromatic azides, only
few synthetic methods have been reported for synthesis
of aryl and vinyl azides from readily available starting
materials.[41,42] Zhu and Ma reported a very interesting
Appl Organometal Chem. 2018;e4436.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4436

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DEHBANIPOUR ET AL.
and 100 MHz) spectra were recorded on a Bruker Avance
400 MHz spectrometer using CDCl3 as solvent. Elemental
analysis was performed on a LECO CHNS–932 analyzer.
X‐ray diffraction (XRD) analysis was carried out on a
Bruker D8 Advance instrument using Cu Kα
(λ = 1.5406 Å) radiation. Thermal gravimetric analysis
(TGA) was recorded on a Mettler TG50, under air flow
at a consistent heating of 10 °C min−1 in the range of
0–900 °C. The scanning electron micrographs were taken
on a Hitachi S–4700 field emission–scanning electron
microscope (FE–SEM). The copper content of the catalyst
was determined by a Jarrell–Ash 1100 ICP analysis.
The 3,5–bis (2–benzothiazolyl) pyridine (BTP) ligand was
synthesized and characterized as reported previously.[48,49]
SCHEME 1 Synthesis of aryl azides from aryl halides catalyzed
by [Cu (II)(BTP)(OTf)2]@CMP
procedure in the presence of copper catalyst that increase
the coupling of aryl and vinyl iodides with sodium
azide,[43] but these reactions required long reaction times
(5–30 h). Liang et al.[44] reported the synthesis of
azides under microwave irradiation using diamine ligands
in the presence of sodium ascorbate in short times
(10–120 min). Recently, Cui and Zhang[45] used a catalytic
system including Cu(0)/proline and diisopropylamine, for
synthesis of aryl azides by the reaction of aryl iodides
with sodium azide in 13–28 h. In this reaction, direct cou-
pling of inactive aryl halides with sodium azide is possible
in low yields. Completion of the reaction needed a higher
reaction temperature in which the aryl azides were
decomposed.[24,46] Recently, Cu2O/tetraethylammonium
prolinate and Proline/CuFeO2 have been reported for
conversion of aryl halides to aryl azides.[45,47]
According to the above mentioned points and by
considering the potential application of organic azides,
herein, we introduce the synthesis of aryl azides by the
reaction of aryl halides with sodium azide in the polyeth-
ylene glycol 400 (PEG–400) as solvent catalyzed by
chloromethylated polystyrene supported Cu (II) bis–thia-
zole complex (Scheme 1).
2.2 | Immobilization of 3,5–bis (2–
benzothiazolyl) pyridine (BTP) on
polystyrene
A mixture of chloromethylated polystyrene (1 g) and 3,5–
bis (2–benzothiazolyl) pyridine (BTP), (0.2 g, 0.58 mmol)
in DMF (10 ml) was prepared and stirred at 80 °C for
24 h. Then, the reaction mixture was filtered and the
resulting solid washed with CHCl3 (2 × 20 ml) and dried
in a vacuum oven at 60 °C.
2.3 | Preparation of [Cu (II)(BTP)(OTf)2]
@CMP
In a round bottom flask equipped with a condenser and a
magnetic stirrer bar, a mixture of CuBr2 (0.2 g) and
BTP@CMP (1 g) in methanol (10 ml) was refluxed for
24 h. The reaction mixture was filtered; the solid material
was washed with methanol (2 × 20 ml) and then dried in
a vacuum oven at 40 °C to afford the [Cu (II)(BTP)Br2]
@CMP catalyst. Then NaOTf (0.24 g) was added to [Cu
(II)(BTP)Br2]@CMP in dry THF and refluxed for 30 min
2 | EXPERIMENTAL SECTION
2.1 | General Remarks
The chemicals were purchased from Fluka and Merck
chemical companies. FT–IR spectra were recorded on a
JASCO 6300D spectrophotometer. The 1H NMR (400
SCHEME 2 The preparation route for
catalyst

DEHBANIPOUR ET AL.
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FIGURE 4 SEM images of [Cu (II)(BTP)(OTf)2]@CMP
FIGURE 1 FT–IR spectrum of: (a) [Cu (II)(BTP)(OTf)2]@CMP
and (b) chloromethylatedpolystyrene
to produce the [Cu (II)(BTP)(OTf)2]@CMP catalyst.
Then, the reaction mixture was filtered and the solid
material was washed with dry THF (20 ml), and dried
in a vacuum oven at 50 °C.
2.4 | General procedure for synthesis of
aryl azides
A round–bottom flask equipped with a reflux condenser
was charged with aryl halide (1 mmol), NaN3 (2 mmol),
and catalyst (0.5 mol %) and PEG–400 (5 ml) in the pres-
ent of sodium ascorbate, The reaction mixture was stirred
at 95 °C and its progress was monitored by TLC (eluent
n–hexane). After the reaction was complete, the cooled
resulting mixture was diluted by adding EtOAc/H2O;
the catalyst was separated by filtration and washed with
acetone and dried under vacuum. The organic layer was
separated, and the aqueous layer extracted with EtOAc.
Then, the organic layer was dried over anhydrous MgSO4
and the solvent was removed in vacuum to give the corre-
sponding aryl azide.
FIGURE
BTP@CMP
2
Diffuse–reflectance UV–vis spectrum of the
FIGURE 3 Diffuse–reflectance UV–vis spectrum of the [Cu (II)
(BTP)(OTf)2]@CMP
FIGURE 5 EDX spectrum of [Cu (II)(BTP)(OTf)2]@CMP

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DEHBANIPOUR ET AL.
FIGURE 6 Elemental mapping of the [Cu (II)(BTP)(OTf)2]@CMP

DEHBANIPOUR ET AL.
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The FT–IR spectrum of the BTP@CMP showed char-
acteristic band of thiazole ring at 1675 cm−1 (C=N), while
the FT–IR spectrum of polystyrene showed no band in
this region (Figure 1).
In the diffuse–reflectance UV–vis spectrum, BTP@CMP
shows two peaks at 241 and 264 nm (Figure 2).
After preparation and characterization of BTP@CMP,
the supported ligand was reacted with CuBr2 to produce
the [Cu (II)(BTP)Br2]@CMP which in turn converted to
[Cu (II)(BTP)(OTf)2]@CMP Upon reaction with NaOTf
(Scheme 2). The copper content of this catalyst, measured
by ICP analysis, was obtained to be 0.055 mmol per gram
of [Cu (II)(BTP)(OTf)2]@CMP. Upon complexation, this
π → π* intra–ligand charge transfer band respectively shifts
to 266 and 353 nm, the peak at around 748 nm was related
to the d–d transition of Cu ion in catalyst (Figure 3).
The size and surface morphologies of [Cu (II)(BTP)
(OTf)2]@CMP were studied by FE–SEM (Figure 4). As
can be seen, CMP are composed of aggregated particles.
The shape of CMP particles are spherical and have diam-
eters in the range of 42 to 75 nm. Also, the EDX detector
demonstrated the presence of carbon, nitrogen, oxygen
and sulphur atoms of the ligand. The presence of Cu
FIGURE 7 XRD of: (a) [Cu (II)(BTP)(OTf)2]@CMP and (b) the
reused catalyst
3 | RESULTS AND DISCUSSION
3.1 | Synthesis and characterization of [Cu
(II)(BTP)(OTf)2]@CMP
Scheme 2 demonstrate the preparation route for [Cu (II)
(BTP)(OTf)2]@CMP catalyst. First the ligand, 3,5–(bis
(2–benzothiazolyl))pyridine, BTP, was prepared by the
TABLE 1 Optimization of the reaction conditions in the reaction
of 4‐iodoanisole with sodium azidea
reaction
of
2–aminothiophenol
with
3,5–
pyridinedicarboxylic acid in the presence of
triphenylphosphite. Reaction of this ligand with
chloromethylated polystyrene, CMP, afforded the sup-
ported ligand, BTP@CMP. These processes were moni-
tored by elemental analysis and FT–IR spectroscopy.
The nitrogen content of BTP@CMP, by elemental analy-
sis, showed a value of about 1.31%. Based on this value,
the amount of BTP ligand supported on the polystyrene
Catalyst Amount
(mol%)
T
Time Yield
Entry Solvent
(°C) (h)
(%)b
1
PEG–400
PEG–400
H2O
–
95
95
95
95
3
3
5
5
–
2c
0.5
0.5
Trace
5
3
is about 0.31 mmolg−1
.
4
EtOH/H2O 0.5
(2:1)
40
5
6
7
DMSO
DMF
0.5
0.5
95
95
95
3
3
3
60
75
45
DMF/H2O 0.5
(3:1)
8
PEG–400
PEG–400
PEG–400
PEG–400
PEG–400
PEG–400
0.25
95
95
95
60
80
25
3
3
3
5
5
5
57
90
90
48
69
0
9
0.5
1
10
11
12
13c
0.5
0.5
0.5
aReaction conditions: aryl halide (1 mmol), NaN3 (2 mmol), [Cu (II)(BTP)
(OTf)2]@CMP as catalyst, solvent (5 ml), 95 °C.
bIsolated yield.
cWithout sodium ascorbate.
FIGURE 8 TGA curves of (a) [Cu (II)(BTP)(OTf)2]@CMP and (b)
BTP@CMP

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DEHBANIPOUR ET AL.
TABLE 2 Synthesis of aryl azides by the reaction of aryl halides with NaN3 catalysed by [Cu (II)(BTP)(OTf)2]@CMP
Entry
R
X
Product
Time (h)
Yield (%)a
1
4–OCH3
Br
4
90
2
3
4
5
6
7
4–Br
Br
Br
Br
I
4
85
90
85
92
89
85
4–NH2
4–CH3
4–OCH3
4–CH3
4–NH2
4
4
3.5
3
I
I
4
aIsolated yield.
Also, the mapping pictures obtained from SEM analy-
sis showed that all elements have been homogeneously
dispersed within the catalyst texture (Figure 6).
Powder X‐ray diffraction patterns of [Cu (II)(BTP)
(OTf)2]@CMP and reused catalyst were shown in
Figure 7. The XRD pattern of the [Cu (II)(BTP)(OTf)2]
@CMP exhibited only a very broad peak at approximately
2θ of 20°, indicating an amorphous texture of catalyst.
The XRD pattern for recycled catalyst is similar to fresh
catalyst. This similarity suggested that the structure of
recycled catalyst is preserved.
The TGA curves of BTP@CMP and [Cu (II)(BTP)Br2]
@CMP catalyst were shown in Figure 8. The BTP@CMP
had two weight loss steps in 30–800 °C temperature
range. The initial weight loss was attributed to removal
of the surface‐adsorbed water below 155 °C. An obvious
weight loss can then be observed from 400 °C to 470 °C,
SCHEME 3 The proposed mechanism
atom in the EDX of catalyst is a good indication for
attachment of copper to the thiazole ligand (Figure 5).
SCHEME 4 Chemo‐ and homoselective
synthesis of aryl azides from aryl halides

DEHBANIPOUR ET AL.
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TABLE 3 Various systems for synthesis of aryl azides from aryl
halides
checked and the best result obtained at 95 °C (entries 11–
13). Consequently, according to the experimental results,
in Table 1, it was concluded that 0.5 mol% of the catalyst,
PEG–400 as reaction medium at 95 °C are the best reac-
tion conditions for this transformation (Table 1).
Entry
Catalytic system
Time (h)
Yield (%)
1
Tetraethylammonium
prolinate/Cu2O
1.5
92[47]
After optimization of the reaction conditions, the
scope and limitations of this transformation was investi-
gated using different aryl halides (Table 2). Various aryl
iodides and bromides reacted effectively to give the corre-
sponding aryl azides with excellent yields. The results
showed that aryl iodides are slightly more reactive than
aryl bromides. In the other hand, the nature of substitu-
ent on the aryl halide has no significant effect on the
reaction rate. When aryl chlorides were used in this reac-
tion, no product was produced and they were recovered
intact from the reaction mixture.
2
3
4
CuI/L‐proline
5
93[43]
96[45]
96[53]
Cu/L‐proline/Base
CuFeO2/L‐proline/Base
24
10
which is due to the decomposition of the thiazole ligand.
Furthermore [Cu (II)(BTP)Br2]@CMP catalyst had a
weight loss step from 600 °C to 660 °C, might be caused
by the thermal decomposition of catalyst.
The actual role of sodium ascorbate is its reducing
agent nature for converting the Cu (II) to Cu (I) which
is the catalytic active species is Cu (I). To show the effect
of sodium ascorbate, a sample of catalyst was reacted
with sodium ascorbate and the filtered. This reduced cat-
alyst was used for the reaction of aryl iodide with sodium
azide. In this case, the reaction was done efficiently.
When this recovered catalyst was used with fresh starting
material (in the absence of sodium acorbate), lower
amount of the corresponding aryl azide was produced.
This shows that the presence of sodium ascorbate is cru-
cial in this reaction.
The proposed mechanism is shown in Scheme 3. In
this mechanism, the copper (II) complex is reduced to a
copper (I) complex upon reaction with sodium ascorbate.
The aryl halide is added to the copper complex via an oxi-
dative‐addition reaction. In the next step, the halide is
replaced with azide ion. In the final step, the aryl azide
is released via a reductive elimination step and released
the catalyst for the next catalytic run.
3.2 | Investigation of catalytic activity of
[Cu (II)(BTP)(OTf)2]@CMP in the
synthesis of aryl azide derivatives
After preparation and characterization of the [Cu (II)
(BTP)(OTf)2]@CMP catalyst, its catalytic activity was
investigated in the synthesis of organic azides by the reac-
tion of aryl halides with NaN3. To find the optimal reac-
tion conditions, the reaction of 4–iodoanisole (1 mmol)
with sodium azide (2 mmol) was chosen as model reac-
tion (Table 1) and the effect of different reaction parame-
ters such as solvent, catalyst amount and temperature
was investigated in this reaction (Table 1). To study the
effect of the solvent, the model reaction was carried out
in various solvents including H2O, EtOH/H2O (2:1),
DMSO, DMF, DMF/H2O (3:1) and PEG–400 in the pres-
ence of [Cu (II)(BTP)(OTf)2]@CMP. The results showed
that PEG–400 gave the best result (Table 1, entries 1–7).
Also, the effect of the catalyst amount on the yield of
the desired product was investigated, and the highest
yield was obtained using 0.5 mol% of the copper catalyst
(entries 8–10). The effect of reaction temperature was also
TABLE 4 Investigation of catalyst reusability and the amount of
copper leached after each runa
Run
Yield (%)b
Cu leached (%)c
1
2
3
4
5
92
90
90
89
89
0.1
0.03
0
0
0
aReaction conditions: aryl halide (2 mmol), NaN3 (4 mmol), [Cu (II)(BTP)
(OTf)2]@CMP (1 mol%), PEG‐400 (5 ml) at 95°C after 4 h.
bIsolated yield.
cDetermined by ICP analysis.
FIGURE 9 FT–IR spectrum of recycled catalyst

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DEHBANIPOUR ET AL.
heterogeneous catalyst was reused five consecutive times
without noteworthy loss of its activity.
3.3 | Chemo‐ and homoselectivity
The chemoselectivity (using aryl halide bearing different
halide groups) and homoselectivity (using different aryl
halide bearing similar halide group) were also
described.[50–52]
ACKNOWLEDGMENTS
The authors are grateful to the Research Council of the
University of Isfahan for financial support of this work.
To check the chemoselectivity, under the optimized
reaction conditions, a mixture of equal amounts of
4‐iodoanisole 4‐bromoanisole was selected for prepara-
tion of the 4‐methoxyphenyl azide. The results showed
that 4‐iodoanisole was more reactive that 4‐bromoanisole.
Furthermore, the homoselectivity of the presented
method was checked under the optimized reaction
conditions in the reaction of an equimolar mixture of
4‐iodoanisole and 4‐iodoaniline in which 4‐iodoanisole
was more reactive than 4‐iodoaniline (Scheme 4).
The results obtained by this catalytic system were
compared with some of those reported in the literature
(Table 3). As can be seen, this method is superior to
some previously reported methods in terms of yield and
reaction times.
ORCID
Majid Moghadam http://orcid.org/0000-0001-8984-1225
Shahram Tangestaninejad
5263-9795
http://orcid.org/0000-0001-
Iraj Mohammadpoor‐Baltork
7998-5401
http://orcid.org/0000-0001-
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How to cite this article: Dehbanipour Z,
Moghadam M, Tangestaninejad S, Mirkhani V,
Mohammadpoor‐Baltork I. Chloromethylated
polystyrene supported copper (II) bis–thiazole
complex: Preparation, characterization and its
application as a heterogeneous catalyst for
chemoselective and homoselective synthesis of aryl
azides. Appl Organometal Chem. 2018;e4436.
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