Pd-SBT@MCM-41: As an efficient, stable and recyclable organometallic catalyst for C-C coupling reactions and synthesis of 5-substituted tetrazoles

Article abstract of DOI:10.1002/aoc.3848

A palladium S-benzylisothiourea complex was anchored on functionalized MCM-41 (Pd-SBT@MCM-41) and applied as efficient and reusable catalyst for the synthesis of 5-substituted 1H–tetrazoles using [2?+?3] cycloaddition reaction of various organic nitriles with sodium azide (NaN₃) in poly(ethylene glycol) (PEG) as green solvent. Also this catalyst was applied as an versatile organometallic catalyst for Suzuki cross-coupling reaction of aryl halides and phenylboronic acid (PhB(OH)₂) or sodium tetraphenyl borate (NaB(Ph)₄). This nanocatalyst was characterized by thermal gravimetric analysis (TGA), X-ray Diffraction (XRD), scanning electron microscopy (SEM), inductively Coupled Plasma (ICP) and N₂ adsorption–desorption isotherms techniques. Recovery of the catalyst is easily achieved by centrifugation for several consecutive runs.

Full text of DOI:10.1002/aoc.3848

Received: 21 January 2017
DOI: 10.1002/aoc.3848
Revised: 20 March 2017
Accepted: 26 March 2017
F U L L PA P E R
Pd‐SBT@MCM‐41: As an efficient, stable and recyclable
organometallic catalyst for C‐C coupling reactions and synthesis
of 5‐substituted tetrazoles
Mohsen Nikoorazm
| Arash Ghorbani‐Choghamarani
| Massoud Ghobadi | Shokofeh Massahi
Department of Chemistry, Faculty of
Science, Ilam University, P. O. Box
A palladium S‐benzylisothiourea complex was anchored on functionalized MCM‐41
Pd‐SBT@MCM‐41) and applied as efficient and reusable catalyst for the synthesis of
‐substituted 1H–tetrazoles using [2 + 3] cycloaddition reaction of various organic
nitriles with sodium azide (NaN ) in poly(ethylene glycol) (PEG) as green solvent.
6
9315516, Ilam, Iran
(
5
Correspondence
Mohsen Nikoorazm, Department of
Chemistry, Ilam University, P.O. Box
3
Also this catalyst was applied as an versatile organometallic catalyst for Suzuki
6
9315516, Ilam, Iran.
cross‐coupling reaction of aryl halides and phenylboronic acid (PhB(OH) ) or sodium
2
Email: e_nikoorazm@yahoo.com
tetraphenyl borate (NaB(Ph) ). This nanocatalyst was characterized by thermal
4
Funding information
Ilam University
gravimetric analysis (TGA), X‐ray Diffraction (XRD), scanning electron microscopy
(
SEM), inductively Coupled Plasma (ICP) and N adsorption–desorption isotherms
2
techniques. Recovery of the catalyst is easily achieved by centrifugation for several
consecutive runs.
KEYWORDS
mesoporous MCM‐41, organometallic catalyst, palladium, Suzuki reaction, tetrazoles
1
| INTRODUCTION
stability in high temperature, relatively hydrophobic nature
[
15]
and versatile separation from reaction media.
Large
Recently, heterogeneous catalysts have used in various organic
specific surface area of MCM‐41 that possesses a lot of silanol
[1]
reactions and industrial processes. Because heterogeneous
catalysts have several advantages such as: stability,
groups leads to simple modification of its surface by other
[
16,17]
functional groups.
Also high specific pore volume (up
[
2–4]
recoverability and recyclability.
However, they have
to 1.3 ml/g) of MCM‐41 allows anchoring of huge
[
3]
enormous drawbacks, such as lack of activity and selectivity.
molecules such as organic ligands and metal complexes into
[
18]
This drawback can be overcome by nanomaterials, because
nanomaterials have high surface area resulting to high activity
hexagonal channels.
Furthermore, high thermal stability
of this nanostructural compound allows doing organic
[
3,4]
[19]
and selectivity.
Generally, various nano materials have
reaction in high temperatures. On the other hand, tetrazoles
been employed to fabricate heterogeneous palladium catalysts
are an important class of heterocycles with wide range of
applications in medicinal chemistry, coordination chemistry,
catalytic science technology and in material chemistry.
[
5]
[6]
such as graphene,
graphitic carbon nitride
metal
[
1,7]
[8]
[9]
[10]
[20–23]
oxides,
ionic liquids, clay, boehmite nanoparticles,
[
11,12]
molecular sieves (SBA‐15 and MCM‐41),
organic frameworks,
metal–
Among them,
Recently tetrazoles and their derivatives (such as Valsartan
and Losartan) were used in drugs and they are used for anti
HIV drug candidate, antiviral, antibacterial and anticancer
[
13]
[14]
and polymers.
mesoporous silica such as MCM‐41 is great and useful
material for the heterogenization of homogeneous catalysts
because of some unique properties such as large specific
[
22,23]
agents.
Also, C‐C coupling reactions have become a
powerful strategy for the preparation of complicated organic
compounds, natural products, preparation of advanced
2
surface area (>1000 m /g), ease of functionalization,
[
24–28]
homogeneous hexagonal pore arrays with pore diameters,
materials and biologically active compounds.
The
Appl Organometal Chem. 2017;e3848.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.3848

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NIKOORAZM ET AL.
Suzuki cross coupling reaction is one of the powerful methods
for the preparation of pharmaceuticals, polymers, herbicides,
K CO (3 mmol), and Pd‐SBT@MCM‐41 (0.010 g) were
2
3
transformed into a 50 ml reaction flask containing 5 ml
of PEG‐400 as solvent and stirred at 80°C. The progress
of the coupling reaction was monitored by TLC. After
completion of the reaction, catalyst was separated and
washed with diethyl ether. The reaction mixture was
extracted with water and diethyl ether and organic layer
dried over anhydrous sodium sulfate (Na SO ) (1.5 g).
[28]
liquid crystals and ligands for catalysis.
In continuation of
[
29,30]
our studies,
herein, we report synthesis and
characterization of Pd‐SBT@MCM‐41 as an efficient, sta-
ble and reusable nanostructural catalyst for the preparation
of 5‐substituted 1H–tetrazole derivatives and C‐C coupling
reactions.
2
4
Finally, evaporation of the solvent gives pure biphenyl
derivatives.
2
2
| EXPERIMENTAL
.1 | Preparation of catalyst
3
| RESULT AND DISCUSSION
The mesoporous MCM‐41 was prepared according to
[30]
the previously reported procedure.
Typically, 2 ml
3.1 | Catalyst preparation
of (3‐choloropropyl)triethoxysilane (CPTES) was added
to 25 ml of toluene containing 2 g of MCM‐41. The reac-
tion mixture was stirred with magnetic stirrer for 24 h at
Initially, the MCM‐41 material has been prepared and
functionalized with 3‐choloropropyltriethoxysilane (CPTES)
[31]
according to the previous reported procedure.
The
40°C. The product was separated out, washed with etha-
immobilization of S‐benzylisothiourea on MCM‐41
SBT@MCM‐41) was performed by substituting replaceable
nol and dried at 50°C. Then the resulting product
(
(
MCM‐41‐(SiCH CH CH Cl) ) (1 g) added to toluene
2
2
2
x
NH of ligand with supported‐terminal choloro groups of
organic‐modified MCM‐41. Finally, the catalyst was pre-
(20 ml) and S‐benzyl isothiourea (2 mmol) and potassium car-
bonate (K CO ) (2 mmol) were added also to this mixture and
2
3
pared by reaction of SBT@MCM‐41with Pd(OAc) , subse-
2
stirred under reflux conditions for 24 h. The resulting
SBT@MCM‐41 was washed with ethanol to remove
unreacted S‐benzyl isothiourea. Finally Pd‐SBT@MCM‐41
was prepared by mixing a solution of palladium acetate (Pd
quently by reduction of Pd(II) to Pd (0) (Scheme 1). This
catalyst characterized by X‐ray diffraction (XRD), scanning
electron microscopy (SEM), thermogravimetric analysis
(
TGA) and N adsorption–desorption isotherms, and induc-
2
(
OAc) ) (0.25 g) in ethanol (20 ml) with SBT@MCM‐41
2
tively coupled plasma atomic emission spectroscopy
ICP‐OES).
(0.5 g) for 24 h under reflux conditions. Subsequently sodium
(
borohydride (0.4 mmol) was added to this mixture and kept
under reflux for another 2 h. The resulting catalyst was fil-
tered, washed by ethanol and dried at 50°C.
3.2 | Catalyst characterization
The SEM and TEM images of the catalyst were shown in
Figures 1 and 2. The Pd‐SBTU@MCM‐41 was observed
using SEM imaging and found to be spherical with mean
diameter of 80 ± 20 nm (Figure 1). Also, the catalyst sam-
ple clearly exhibits a well‐ordered hexagonal type of array
2
5
.2 | General procedure for the synthesis of
‐substituted 1H–tetrazole derivatives
A mixture of sodium azide (1.4 mmol), benzonitrile
(
(
1 mmol), and 0.03 g of Pd‐SBT@MCM‐41 in PEG‐400
3 ml) magnetically stirred at 120°C. After completion of
the reaction (observed by tin layer chromatography (TLC)),
the reaction mixture was cooled down to room temperature,
and catalyst was separated by simple filtration and hydro-
chloric acid (HCl) (4 N, 10 ml) was added to the filtrated.
The products extracted with ethyl acetate (3 × 10 ml). The
organic solvent was dried over anhydrous sodium sulphate
(1.5 g), and evaporated to give the corresponding solid
product.
2
.3 | General procedure for the Suzuki
reaction
A mixture of aryl halide (1 mmol), phenylboronic acid
(1 mmol) or sodium tetraphenyl borate (0.5 mmol),
SCHEME 1 Synthesis of Pd‐SBT@MCM‐41

NIKOORAZM ET AL.
3 of 9
FIGURE 1 SEM image of Pd‐SBT@MCM‐41
of regular hexagonal arrangement in TEM micrographs
before (Figure 2a) and after (Figure 2b) of coordination of
palladium. Also, TEM image revealed more accurate infor-
mation on the morphology and particles size of the palla-
dium nanoparticles. As shown in TEM image, most of the
Pd particles are supported on MCM‐41 with an average
diameter about 4 ± 1 nm (Figure 2b). In order to estimate
the exact amount of palladium loaded on the mesoporous
catalyst, ICP‐OES analysis was performed. The Pd amount
FIGURE 2 TEM image of (a) SBTU@MCM‐41 and (b) Pd‐
SBTU@MCM‐41
of immobilized catalyst on MCM‐41 was found to be
.0018 mol g−
1.
0
In order to determine the percentage of organic moieties
onto MCM‐41, the TGA analysis of Pd‐SBT@MCM‐41was
performed. TGA curves of MCM‐41 and Pd‐SBT@MCM‐
41 are shown in Figure 3. The TGA curve of MCM‐41
showed a 3% weight loss from 25–250°C, which is related
to desorption of water and silanol groups. TGA curve of
Pd‐SBT@MCM showed a two‐step of weight loss. The first
step of weight loss from 25–200°C (about 5%), is due to the
FIGURE 3 TGAdiagram of MCM‐41 (a) and Pd‐SBT@MCM‐41 (b)
[32]
removal of the adsorbed solvents,
and the second weight
loss in the range of 200–400°C (approximately 23%) is
related to the decomposition of supported organic spacers
on the MCM‐41.
[
34]
silica, as expected in MCM‐41 structure.
The XRD
pattern of Pd‐SBT@MCM‐41 sample shows that upon
post‐synthetic grafting of palladium complex inside the
channels of MCM‐41, the d110 and d200 refractions were
no longer observed. This result could be attributed to lower
local order and increasing in the wall thickness of support
The small angle powder X‐ray diffraction patterns for
MCM‐41 and Pd‐SBT@MCM‐41 are exhibit in Figure 4.
XRD pattern of MCM‐41 sample illustrate typical peaks cor-
responding to diffraction at (100), (110) and (200) planes
[33]
[35]
which are due to the hexagonal channel arrays.
highest peak observed for all the samples (corresponding to
0 0 plane) indicated the regular order of the mesoporous
The
materials.
The N2 adsorption–desorption isotherms of MCM‐41
and Pd‐SBT@MCM‐41 are shown in Figure 5. According
1

4
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NIKOORAZM ET AL.
ethanol), temperature, amount of NaN and catalyst were
3
examined in the [2 + 3] cycloaddition reaction of
benzonitrile with NaN . The result of this study is summa-
3
rized in Table 1. As shown in Table 1, 0.03 g of Pd‐
SBT@MCM‐41, 1.4 mmol of NaN in PEG‐400 at 120°C
3
was found to be the best conditions for the synthesis of 5‐
substituted 1H–tetrazoles.
After optimization of the reaction condition, the catalytic
activity of Pd‐SBT@MCM‐41 was extend for various nitriles
and the obtained results are summarized in Table 2. As
shown in Table 2, benzonitriles with both electron‐with-
drawing and electron‐donating substituents have been suc-
cessful converted to corresponding tetrazoles in good
yields. Interestingly, malononitrile and terephthalonitrile
afforded the mono cycloaddition products (Table 2,
entries 10, 11).
FIGURE 4 XRD pattern of MCM‐41 (a) and Pd‐SBT@MCM‐41 (b)
Also, we examined the catalytic activity of Pd‐
SBT@MCM‐41 in the Suzuki cross coupling reaction of aryl
halides with PhB(OH) or NaB(Ph) (Scheme 3).
2
4
It is well known the Suzuki cross‐coupling reaction is
considerably affected by the nature of catalyst, the added
base and type of solvent. Therefore, the proper choice
of reaction conditions is very important to do this
reaction.
FIGURE 5 Nitrogen adsorption–desorption isotherms of MCM‐41
a) and Pd‐SBT@MCM‐41 (b)
(
In order to optimize the reaction conditions, the effect of
different parameters such as kind of solvent and base, tem-
perature and the amount of Pd‐SBT@MCM‐41 were exam-
to the IUPAC classification all MCM‐41 samples have
ined in the reaction of iodobenzene and PhB(OH) as a
type IV isotherms; this indicates that the synthesized
2
[
36]
model reaction (Table 3). When, 0.005 g of catalyst was
used in model reaction, the corresponding biphenyl product
was isolated in 46% yield after 70 min. When the amount
of catalyst has been increased from 0.005 to 0.008 g, biphe-
nyl was obtained in 69% yield after 70 min and the best
samples have mesoporous structure.
The surface area
2
−1
of MCM‐41 decreased from 1371.8 to 286.2 m g and
average pore volume decreased from 1.52 to 0.61 Cm g
3
−
1
for Pd‐SBT@MCM‐41. On the other hand, an increase
of the wall thickness occurred, which is show the grafting
of palladium complex inside the pore channels of
MCM‐41.
perfomance was obtained when 0.010
g
of Pd‐
SBT@MCM‐41 was used. Moreover, the model reaction
was carried out in the absence of catalyst: moderate yield
of the product was obtained after long time (5 h). Also, the
3
.3 | Catalytic study of Pd‐SBT@MCM‐41
coupling of iodobenzene with PhB(OH) was examined in
2
various solvent such as DMSO, PEG‐400, DMF, ethanol
and water (Table 3, entries 3–7). Studies of solvent effect
on the activity of catalyst reveal that the model reaction
could proceed better in PEG‐400 (Table 3, entry 3). The
effect of various bases and temprature (Table 3, entries
After synthesis and characterization of described catalyst, its
catalytic properties was examined in the synthesis of
tetrazoles via [2 + 3] cycloaddition reaction of nitriles with
sodium azide (Scheme 2).
In order to optimize reaction conditions, various
parameters such as solvent (PEG, dimethylsulfoxide
7–11) on the performance of catalyst was also studied and
the best results were obtained at 80°C using 3 mmol of
(DMSO), N,N‐dimethylformamide (DMF), water and
K CO .
2
3
After the optimization of the reaction conditions, we
extended the catalytic activity of Pd‐SBT@MCM‐41 for
other aryl halide including electron‐donor and electron‐with-
drawing functional groups (Table 4). Various aryl iodides,
aryl bromides and aryl chlorides were successfully coupled
with phenylboronic acid and corresponding biphenyls were
obtained in good to excellent yields. However, the
SCHEME 2 Synthesis of 5‐substituted 1H–tetrazoles catalysed by
Pd‐SBT@MCM‐41

NIKOORAZM ET AL.
5 of 9
TABLE 1 Optimization of reaction conditions for synthesis of 5‐substituted 1H–tetrazole derivatives in the presence of Pd‐SBT@MCM‐41
Entry
Catalyst (mg)
Solvent
NaN
3
(mmol)
Temperature (°C)
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
9
30
30
30
35
25
20
30
30
30
30
30
PEG
1.2
120
120
8
60
63
96
97
56
40
93
95
22
31
66
PEG
1.3
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
8
PEG
120
8
PEG
120
6.75
8
PEG
120
PEG
120
8
DMF
DMSO
ethanol
water
PEG
120
6
120
6.2
8
Reflux
Reflux
100
1
1
0
1
8
8
a
Isolated yield.
TABLE 2 Synthesis of 5‐substituted 1H–tetrazole derivatives in the presence of Pd‐SBT@MCM‐41
a
Entry
Nitrile
benzonitrile
Product
Time (h)
Yield (%)
M.P. (°C)
1
2
3
4
5
6
7
8
9
5‐phenyl‐1H‐tetrazole
8
4
96
92
93
88
86
88
87
90
90
214–216
217–219
232–234
174–176
148–151
130–132
263–265
180–182
225–227
114‐117
253–256
260–263
4‐nitrobenzonitrile
4‐hydroxybenzonitrile
4‐acetylbenzonitrile
3‐nitrobenzonitrile
3‐chlorobenzonitrile
4‐bromobenzonitrile
2‐chlorobenzonitrile
2‐hydroxybenzonitrile
malononitrile
5‐(4‐nitrophenyl)‐1H–tetrazole
5‐(4‐hydroxyphenyl)‐1H–tetrazole
5‐(4‐acetylphenyl)‐1H–tetrazole
5‐(3‐nitrophenyl)‐1H–tetrazole
5‐(3‐chlorophenyl)‐1H–tetrazole
5‐(4‐bromophenyl)‐1H–tetrazole
5‐(2‐chlorophenyl)‐1H–tetrazole
5‐(2‐hydroxyphenyl)‐1H–tetrazole
2‐(1H–tetrazol‐5‐yl)acetonitrile
4‐(1H–tetrazol‐5‐yl)benzonitrile
5‐(4‐chlorophenyl)‐1H–tetrazole
5
24
8.5
8
14
4
6
b
10
11
12
24
7
76
terephthalonitrile
80
91
4‐chlorobenzonitrile
8
a
Isolated yield has been obtained using nitrile (1 mmol), NaN3 (1.4 mmol) in PEG‐400 (2 ml) in the presence of Pd‐SBT@MCM‐41 (0.03 g) at 120°C,
b
the reaction has been carried out at 130°C.
completing reaction including aryl chlorides was slower than
aryl iodides and bromides ones.
We also applied optimized reaction conditions for the
coupling of aryl halides with sodium tetraphenyl borate.
SCHEME 3 C‐C coupling reaction catalysed Pd‐SBT@MCM‐41

6
of 9
NIKOORAZM ET AL.
TABLE 3 Optimization of reaction conditions for C‐C coupling reaction in the presence of Pd‐SBT@MCM‐41
Entry
Catalyst (mg)
Solvent
Base
Temperature (°C)
Time (min)
Yield (%)a
1
2
3
4
5
6
7
8
9
‐
5
PEG
K
K
K
K
K
K
K
K
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
80
80
80
80
80
80
80
80
80
80
80
60
300
70
70
60
45
50
60
60
70
70
70
70
‐
46
69
98
94
92
64
69
46
15
32
66
PEG
8
PEG
10
10
10
10
10
10
10
10
10
PEG
DMF
DMSO
Ethanol
Water
PEG
3
Et N
1
1
1
0
1
2
PEG
NaOEt
KOH
PEG
PEG
2 3
K CO
a
Isolated yield.
TABLE 4 C‐C coupling reaction in the presence of Pd‐SBT@MCM‐41
a
Entry
Aryl halide
Iodobenzene
Phenylatig reagent
Time (min)
Yield (%)
M.P. (°C)
1
2
3
4
5
6
7
8
9
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
2
2
2
2
2
2
2
2
2
2
2
60
70
98
91
93
96
92
97
95
93
92
87
88
97
95
90
90
94
96
67–68
42–44
Oil
4‐Iodotoluene
2‐Iodotoluene
300
175
70
4‐Iodoanisole
81–84
64–67
41–44
112–114
82–84
72–74
111–114
80–83
66–68
42–43
80–83
66–69
41–44
112–114
Bromobenzene
4‐Bromotoluene
4‐Bromonitrobenzene
4‐Bromobenzonitrile
4‐Bromochlorobenzene
4‐Chloronitrobenzene
4‐Chlorobenzonitrile
Iodobenzene
90
50
45
45
10
11
12
13
14
15
16
17
250
280
65
NaB(Ph)
NaB(Ph)
NaB(Ph)
NaB(Ph)
NaB(Ph)
NaB(Ph)
4
4‐Iodotoluene
4
4
4
4
4
80
4‐Iodoanisole
180
80
Bromobenzene
4‐Bromotoluene
4‐Bromonitrobenzene
100
45
(Continues)

NIKOORAZM ET AL.
7 of 9
TABLE 4 (Continued)
Entry
Aryl halide
Phenylatig reagent
Time (min)
Yield (%)a
M.P. (°C)
18
19
20
4‐Bromobenzonitrile
4‐Bromochlorobenzene
4‐Chloronitrobenzene
NaB(Ph)
NaB(Ph)
NaB(Ph)
4
4
4
60
60
90
93
89
81–84
72–73
275
110–113
a
Isolated yield.
In this regard, wide range of aryl halides with electron‐
donor and electron‐withdrawing functional groups reacted
with sodium tetraphenyl borate and the corresponding
biphenyl was obtained in the good to excellent yields
(Table 4, entries 12–20). Therefore, these results revealed
that this methodology is effective for a wide range of aryl
halides and phenylboronic deriavatives.
A plausible catalytic cycle for this C–C bond coupling
reaction in the presence of Pd‐SBT@MCM‐41 was shown
[
10,37,38]
in Scheme 4.
The reusability of the Pd‐SBT@MCM‐41 was studied
in coupling of iodobenzene with PhB(OH) and synthesis
2
of 5‐phenyl‐1H‐tetrazole (Figure 6). As shown in
Figure 6, the catalyst was reused over 6 times without
any significant palladium leaching or loss of its catalytic
activity. The average isolated yield for 6 successive cycles
FIGURE 6 Recyclability of Pd‐SBT@MCM‐41 in the (a) coupling
of iodobenzene with PhB(OH) and (b) synthesis of 5‐phenyl‐1H‐
2
tetrazole
in coupling of 4‐Iodotoluene with PhB(OH) and synthe-
2
sis of 5‐phenyl‐1H‐tetrazole is 91% and 91.3%
respectively, which clearly demonstrates the practical recy-
clability of this catalyst.
Also, to examine if Pd is leaching out from the catalyst
during reactions, the amount of palladium in Pd‐
SBT@MCM‐41 was determined by ICP‐OES. The amount
of Pd in Pd‐SBT@MCM‐41 was found to be 1.63 × 10
−
3
−1
mol g after 4 times recycled. This amount was compa-
−3
−1
rable with fresh catalyst (1.85 × 10 mol g ). The obtained
result confirmed that the palladium leaching is negligible in
these reactions.
In order to indicate the efficiency of this catalyst, the
obtained results for synthesis of the 5‐phenyl‐1H‐tetrazole
in the presence of Pd‐SBT@MCM‐41 was compared with
previously reported methods for this cycloaddition reac-
tion (Table 5). As shown in Table 5, Pd‐SBT@MCM‐
4
1 has a better catalytic activity in synthesis of 5‐
substituted 1H–tetrazoles. Also Pd‐SBT@MCM‐41 is
comparable with previously reported catalysts in terms
of non‐toxicity, price, stability, catalyst recycling and easy
separation.
SCHEME 4 Plausible mechanism for the C‐C coupling reaction in
the presence of Pd‐SBT@MCM‐41

8
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NIKOORAZM ET AL.
TABLE 5 Comparison results of Pd‐SBT@MCM‐41 with other catalysts for synthesis of 5‐phenyl‐1H‐tetrazole
a
Entry
Catalyst
CoY zeolite
Cu–Zn alloy nanopowder
B(C
Fe
Mesoporous ZnS
Condition
Time (h)
Yield (%)
Ref.
[
[
[
[
[
[
[
[
[
22]
39]
40]
41]
42]
43]
44]
45]
46]
1
2
3
4
5
6
7
8
9
DMF, 120°C
DMF, 135°C
DMF, 120°C
DMF, 120°C
DMF, 120°C
14
10
8
90
95
94
81.1
86
86
82
79
90
96
6 5 3
F )
3
O
4
/ZnS HNSs
24
36
8
LiB(N
CuFe
FeCl
Nano ZnO/Co
Pd‐SBT@MCM‐41
3
)
4
NH4OAc (15 mg), DMF/MeOH (9/1), 120°C
DMF, 120°C
2
O
4
12
12
12
8
3
–SiO
2
DMF, 120°C
3
O
4
DMF, 120–130°C
1
0
Peg, 120°C
This work
a
Isolated yield.
[
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4
| CONCLUSION
[
2
015, 165, 661.
Covalently functionalization of Pd‐SBT complex onto the
MCM‐41 surface was successfully achieved by post‐synthetic
grafting procedure. A novel and highly efficient method was
developed for synthesis of 5‐substituted 1H–tetrazole
derivatives by treatment of nitriles with sodium azide in the
presences of Pd‐SBT@MCM‐41 as catalyst. Also, a simple
and efficient procedure for Suzuki cross‐coupling reaction
between aryl halides and PhB(OH) or NaB(Ph) ) in the
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2
4
presence of Pd‐SBT@MCM‐41 in PEG‐400 as green solvent
was developed. This new protocol has the advantage of easy
availability, easy handling, high stability and reusability of
the catalyst, short reaction times, simple experimental and
work up procedure.
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This work was supported by the research facilities of Ilam
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How to cite this article: Nikoorazm M, Ghorbani‐
Choghamarani A, Ghobadi M, Massahi S. Pd‐
SBT@MCM‐41: As an efficient, stable and recyclable
organometallic catalyst for C‐C coupling reactions and
synthesis of 5‐substituted tetrazoles. Appl
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4
35] F. Havasi, A. Ghorbani‐Choghamarani, F. Nikpour, Microporous
Mesoporous Mater. 2016, 224, 26.
Organometal Chem. 2017;e3848. https://doi.org/
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0.1002/aoc.3848
36] A. Mathew, S. Parambadath, S. S. Park, C. S. Ha, Microporous
Mesoporous Mater. 2014, 200, 124.