Copper nanoparticles incorporated on a mesoporous carbon nitride, an excellent catalyst in the Huisgen 1,3-dipolar cycloaddition and N-arylation of N-heterocycles

Article abstract of DOI:10.1002/aoc.3914

Cu nanoparticles with average particles size around 10?nm were incorporated on the surface of a mesoporous carbon nitride support. The XRD and N₂ adsorption isotherms show that it maintains a hexagonal mesoporous structure with a high surface a

Full text of DOI:10.1002/aoc.3914

Received: 13 January 2017
DOI: 10.1002/aoc.3914
Revised: 21 April 2017
Accepted: 6 May 2017
F U L L PA P E R
Copper nanoparticles incorporated on a mesoporous carbon
nitride, an excellent catalyst in the Huisgen 1,3‐dipolar
cycloaddition and N‐arylation of N‐heterocycles
Siyavash Kazemi Movahed1 | Parinaz Salari1 | Melika Kasmaei1 | Mahsa Armaghan2 |
Minoo Dabiri1
| Mostafa M. Amini1
1 Faculty of Chemistry, Shahid Beheshti
University, Tehran 1983969411, Islamic
Republic of Iran
2 Department of Chemistry, Science and
Research Branch, Islamic Azad University,
Tehran, Islamic Republic of Iran
Cu nanoparticles with average particles size around 10 nm were incorporated on the
surface of a mesoporous carbon nitride support. The XRD and N2 adsorption
isotherms show that it maintains a hexagonal mesoporous structure with a high
surface area (600.03 m2 g−1). The embedded Cu nanoparticles exhibit extremely
high catalytic performance in two different kinds of organic reactions. The Huisgen
1,3‐dipolar cycloaddition and N‐arylation of N‐heterocycles were all accomplished.
Correspondence
Minoo Dabiri, Faculty of Chemistry, Shahid
Beheshti University, Tehran 1983969411,
Islamic Republic of Iran.
KEYWORDS
arylation, cycloaddition, heterogeneous catalysis, mesoporous materials, nanoparticles
Email: m‐dabiri@sbu.ac.ir
Funding information
Research Council of Shahid Beheshti Uni-
versity; Iranian National Science Foundation,
Grant/Award Number: 94028845
1 | INTRODUCTION
hydrogenation of aromatic carboxylic acids,[4b] photocata-
lytic hydrogen evolution,[4c] Friedel–Crafts reaction,[4d] oxy-
Recently, metal NPs have been widely explored to under-
stand their physicochemical properties. Their favorable
properties are impressed by quantum effects, high surface
energy and large surface area to volume.[1] Among the
metal nanoparticles, Cu NPs have received considerable
public interest, which may be due to their excellent
optical, electrical and thermal properties. Cu NPs were
assumed cost‐effective as compared to noble metals like
Ag, Au, Pd and Pt. Recently, Cu NPs have attracted
considerable attention in different catalytic reactions such
as the azide − alkyne cycloaddition via click chemistry,
coupling reactions, reduction reactions, oxidation reactions,
‘one‐pot’ multicomponent reactions, miscellaneous reac-
tions, etc.[2]
gen reduction reaction[4e] and photocatalytic CO2 reduction.
[4f]
The success of MCN materials is mainly attributed to
their unique combination of multiple physicochemical prop-
erties such as large specific surface area, (~200 m2 g−1), large
pore volumes (≥0.5 cm3 g−1), surface active sites, high sta-
bility, tunable porosity and a high nitrogen content.[5,6] The
abundant nitrogen functionalities on the surface sites can
modify the electronic structure of the carbon matrix and
strength the interaction between carbon and guest molecules.
Additionally, these functionalities be usually regarded as
favorable anchor sites for enhancing particle nucleation and
reducing the particle size which allow its direct use as hetero-
geneous catalysts.[3,7]
As shown in Scheme 1, MCN has been successfully pre-
pared by using the SBA‐15 material as a hard template
through a simple polymerization reaction between ethane‐
1,2‐diamine (EDA) and perchloromethane (PCM). Subse-
quently, the resulting composite is heat‐treated in a nitrogen
Recently, mesoporous carbon nitride (MCN) materials
have been investigated as heterogeneous catalysts for various
chemical transformations.[3] For instance, they have been
examined
for
dye
photocatalytic
degradation,[4a]
Appl Organometal Chem. 2017;e3914.
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Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.3914

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KAZEMI MOVAHED ET AL.
SCHEME 1 Schematic illustration of Cu NPs‐MCN nanocomposite preparation
flow to carbonize the polymer. The MCN is recovered after
digestion of the silica mold in sodium hydroxide. Finally,
the incorporation of small and well dispersed Cu NPs onto
the MCN framework is conducted by reduction of copper
nitrate with L‐ascorbic acid as a reducing agent to yield the
CuNPs‐MCN nanocomposite.
was treated under ultrasonic condition for 30 min. L‐ascorbic
acid (5 mmol) was gradually added to the solution and stirred
for 24 h. The resulted precipitation was collected by centrifu-
gation, washed with H2O (5 × 10 ml) and EtOH (3 × 10), and
dried at 100 °C. The ICP‐AES analysis gave the actual Cu
contents as 3.6 wt.% for Cu NPs‐MCN nanocomposite.
2 | EXPERIMENTAL
2.1 | Synthesis of MCN
2.3 | Preparation of cu NPs‐SBA‐15
nanocomposite
The SBA‐15 (100 mg) was dispersed in 20 ml of H2O.
Cu(NO3)2.3H2O 2O (0.5 mmol) was added to the solu-
tion, the mixture was treated under the ultrasonic condi-
tion for 30 min. L‐ascorbic acid (5 mmol) was
gradually added to the solution and stirred for 24 h.
The resulted precipitation was collected by centrifugation,
washed with H2O (5 × 10 ml) and EtOH (3 × 10), and
dried at 100 °C. The ICP‐AES analysis gave the actual
Cu contents as 5.3 wt.% for Cu NPs‐SBA‐15
nanocomposite.
The mesoporous SBA‐15 silica was prepared by the
method as described elsewhere.[8,9] The calcined SBA‐15
(0.5 g) was added to a mixture of EDA (1.35 g) and
PCM (3 g). The resultant mixture was stirred at 90 °C
for 6 h. Then, the obtained dark solid mixture was put in
an oven for 12 h. The resulting composite (a template‐car-
bon nitride polymer) was heat‐treated in a nitrogen flow at
600 °C with a heating rate of 3.0 °C min−1 and kept at
600 °C for 5 h to carbonize the polymer.[10] The MCN
was recovered after digestion of the SBA‐15 mold in 1 N
NaOH solution (EtOH:H2O 50:50 (v:v)) at 80 °C, by cen-
trifugation, washed several times with EtOH and H2O, and
dried at 100 °C.
2.4 | Preparation of CMK‐3 nanocomposite
The CMK‐3 was prepared via a hard temple method.[11]
First, 1.25 g of sucrose and 2.7 ml of H2SO4 were dis-
solved in 5 mL ol H2O. Then, 1 g of SBA‐15 was impreg-
nated with the above solution and the mixture was
transferred to an oven and maintained at 100 °C for 6 h
and then at 160 °C for another 6 h. The obtained powder
was then impregnated again with a solution obtained by
2.2 | Preparation of cu NPs‐MCN
nanocomposite
The MCN (100 mg) was dispersed in 20 ml of H2O. Cu(NO3)
2.3H2O (0.5 mmol) was added to the solution, the mixture

KAZEMI MOVAHED ET AL.
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dissolving sucrose (0.8 g) and H2SO4 (0.05 ml) in H2O
(5 ml). The mixture was then treated again at 100 and
160 °C. Finally, the carbonization was completed at 900 °
C in a nitrogen flow. The SBA‐15 mold was digested with
1 N NaOH solution (EtOH:H2O 50:50 (v:v)) at 80 °C.
After centrifugation and washing with EtOH, the carbon
product was dried at 120 °C.
3 | RESULTS AND DISCUSSION
3.1 | Characterization
The SEM images of MCN and Cu NPs‐MCN are shown in
Figure 1a‐b. The MCN exhibits a tubular structure with
uniform particles, which the diameters are about 300 nm,
being highly similar to those of the parent SBA‐15 template
that shows the successful replication process of MCN from
2.5 | Preparation of cu NPs‐CMK‐3
nanocomposite
The CMK‐3 (100 mg) was dispersed in 20 ml of H2O. Cu
(NO3)2.3H2O (0.5 mmol) was added to the solution, the mix-
ture was treated under the ultrasonic condition for 30 min. L‐
ascorbic acid (5 mmol) was gradually added to the solution
and stirred for 24 h. The resulted precipitation was collected
by centrifugation, washed with H2O (5 × 10 ml) and EtOH
(3 × 10) and dried at 100 °C. The ICP‐AES analysis gave
the actual Cu contents as 3.8 wt.% for Cu NPs‐CMK‐3
nanocomposite.
2.6 | General procedure for the
multicomponent 1,3‐dipolar cycloaddition
A mixture of Cu NPs‐MCN nanocomposite (0.5 mol % of
Cu), an organic halide (1.0 mmol), phenylacetylene
(1.0 mmol) and sodium azide (1.2 mmol) in EtOH:H2O
(1:1; 3 mL) were heated at 60 °C for 10 h. The reaction
was monitored by thin layer chromatography (TLC). After
the completion of the reaction, the heterogeneous mixture
was cooled to r.t. and ethyl acetate was added to the flask
and the catalyst was separated by centrifugation. The organic
layer was dried over MgSO4 and concentrated under reduced
pressure to give the corresponding 1,2,3‐triazole. The
obtained triazole was purified by recrystallization from
EtOH.
2.7 | General procedure for N‐Arylation of
N‐heterocycles
A mixture of Cu NPs‐MCN nanocomposite (2.5 mol % of
Cu), K3PO4 (1.5 mmol), N‐heterocycle (1.0 mmol), an aryl
halide (1.0 mmol), and DMF (3 mL) under air was stirred
for 4 h at 120 °C. The reaction was monitored by thin layer
chromatography (TLC). After the completion of the reaction,
the heterogeneous mixture was cooled to r.t., diluted with
Ethyl acetate (3 × 10 ml), and the catalyst was separated by
centrifugation. The organic layer was concentrated under
reduced pressure to give the corresponding coupled product.
The Obtained N‐arylated of heterocycle was purified by
recrystallization from EtOH.
FIGURE 1 SEM images of a) MCN and b) cu NPs‐MCN
nanocomposite; c) corresponding quantitative EDS element mapping
of cu

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KAZEMI MOVAHED ET AL.
FIGURE 3 a) Full range XPS spectrum of MCN, b) N 1 s core level
region XPS spectra of MCN, c) Full range XPS spectrum of cu NPs‐
MCN nanocomposite, d) N 1 s and e) cu 2p, core level regions XPS
spectra of cu NPs‐MCN nanocomposite, respectively
FIGURE 2 a‐b) TEM images and c) HAADF image of cu NPs‐MCN
nanocomposite

KAZEMI MOVAHED ET AL.
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SBA‐15.[12] The morphology of MCN do not change after
the incorporation Cu NPs onto the MCN framework
(Figure 1b). Additionally, the density and distribution of
copper on the Cu NPs‐MCN nanocomposite is evaluated by
energy dispersive X‐ray spectroscopy (EDS) mapping. The
Cu NPs are uniformly distributed and anchored along the
heterogeneous mesoporous surface of the MCN (Figure 1c).
The TEM images of Cu NPs encapsulated MCN is shown
in Figure 2a‐b. The HAADF image of Cu NPs‐MCN com-
posite shows that the copper nanoparticles are on the surface
of MCN (Figure 2c).
The electronic properties of MCN and Cu NPs‐MCN
composites are probed by XPS analysis (Figure 3). The bind-
ing energies are calibrated based on the C1s peak at 284.5 eV
as a reference. The high‐resolution XPS spectrum of N 1 s
core level for MCN composite displays main peaks at 397.9
and 399.9 eV (Figure 3b). The peak at 397.9 eV corresponds
to nitrogen atoms bonded with the graphitic carbon atoms,[10]
while the peak at 399.9 eV corresponds to N atoms trigonally
bonded to two sp2 carbon atoms and one sp3 carbon atom in
an amorphous C‐N network or to all sp2 carbons.[13] After the
conjugation of the copper nanoparticles on MCN, these bind-
ing energies shift to higher value 398.5 and 400.2 eV. These
result show that the copper nanoparticles bonded the nitrogen
atoms in MCN.[14] The high‐resolution XPS spectrum of Cu
2p is shown in Figure 3e, the two peaks at 933.9 and
953.8 eV, are assigned to Cu 2p3/2 and Cu 2p1/2, respectively.
This indicates that supported copper species are kept in a
zero‐valent chemical state.[15]
FIGURE 5 Nitrogen adsorption/desorption isotherms of MCN and
cu NPs‐MCN
TABLE 1 Screening of the reaction conditionsa
The XRD patterns of the MCN and Cu NPs‐MCN com-
posites are shown in Figure 4. The diffraction peaks for the
Cu NPs are scarcely detected, resulting from the small size
of Cu NPs.[16] The small angle XRD patterns of MCN and
Cu NPs‐MCN composites show the three characteristic
peaks, the highly‐ordered two‐dimensional hexagonal
mesostructure with the space group of p6mm at 2θ = 1.6°,
2.6° and 3.8° corresponding to (11−0), (110) and (200) crys-
tallographic planes, respectively.[10] The diffraction peaks at
Entry Solvent
Catalyst (mol% of cu) Temp. (°C) Yieldb (%)
1
2
3
4
5
CH2Cl2
CH3CN
EtOH
Cu NPs‐MCN (0.5)
Cu NPs‐MCN (0.5)
Cu NPs‐MCN (0.5)
Cu NPs‐MCN (0.5)
Cu NPs‐MCN (0.5)
60
60
60
60
60
59
72
90
84
98
H2O
EtOH/
H2O
6
EtOH/
H2O
Cu NPs‐MCN (0.5)
Cu NPs‐MCN (0.25)
Cu NPs‐SBA‐15 (0.5)
Cu NPs‐CMK‐3 (0.5)
MCNc
50
60
60
60
60
75
56
7
EtOH/
H2O
8
EtOH/
H2O
73
9
EtOH/
H2O
88
10
EtOH/
H2O
28c
abenzyl bromide, (1.0 mmol), phenylacetylene (1.0 mmol), sodium azide
(1.2 mmol), solvent (3 mL), 10 h.
bIsolated yield. MCN (0.05 g)
ctwo 1,4‐ and 1,5‐ regioisomers (1:1).
FIGURE 4 The high angle XRD patterns of MCN and cu NPs‐MCN
(inset: Low angle)

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KAZEMI MOVAHED ET AL.
2θ = 44 and 64° correspond to the stainless steel sample
holder of powder diffractometer.
of the 1,2,3‐triazole family have indeed shown interesting
biological and biochemical activities, such as anti‐allergic,
anti‐bacterial, anticancer, antiviral and anti‐HIV. Addition-
ally, 1,2,3‐triazoles are found extensive use in herbicides,
fungicides, corrosion inhibitions, photostabilizers, and lubri-
cants and dyes.[19,20] Recently, the copper catalysis discov-
ered for this transformation, which accelerates the reaction
up to 10 million times, placed it in a category of its own
and has enabled many novel applications.[20]
The porous nature of MCN and Cu NPs‐MCN
composites are evaluated by nitrogen physisorption measure-
ments. The prepared composites showed type IV N2 adsorp-
tion–desorption isotherms which are characteristic of
mesoporous materials based on the IUPAC classification.[17]
The BET total surface areas of MCN, and Cu NPs‐MCN
composites are found to be 567.09 and 600.03 m2 g−1
,
respectively (Figure 5). From these results, it can be con-
cluded that the Cu NPs act as spacers between MCN roads
thereby preventing their aggregation.[18]
As the initiating point of our exploration, the reaction
between phenylacetylene, sodium azide and benzyl bromide
as a model reaction was chosen to show the feasibility of
the strategy and optimize the reaction conditions (Table 1).
By using Cu NPs‐MCN (0.5 mol% of Cu) as the catalyst,
the reaction was tested for employing various solvents such
as CH2Cl2, CH3CN, EtOH, H2O and the mixture of EtOH/
H2O (Table 1, Entries 1–5). The best results were obtained
by using the mixture of EtOH/H2O as solvent in the model
reaction (Table 1, entry 5). A lower reaction temperature
decreased the yield of the reaction (Table 1, entry 6). As
can be seen from the Table 1, the optimized amount of cata-
lyst in the reaction was obtained to be 0.5 mol% of Cu
(Table 1, entries 5 and 7). In order to study the effect of the
3.2 | The catalytic activity of cu NPs‐MCN
nanocomposite toward the multicomponent 1,3‐
dipolar cycloaddition
After the careful investigation of the prepared Cu NPs‐MCN
nanocomposite, it was employed in the multicomponent 1,3‐
dipolar cycloaddition of phenylacetylene, sodium azide and
different organic halides. This reaction has found broad appli-
cations in various disciplines including materials science,
chemical biology, and medicinal chemistry. Several members
TABLE 2 Multicomponent 1,3‐dipolar cycloaddition catalyzed by cu NPs‐MCN nanocompositea
Entry
Organic halide
Product
Yieldb (%)
1
98
2
3
98
94
4c
78
86
5c
1a
aOrganic halide, (1.0 mmol), phenylacetylene (1.0 mmol), sodium azide (1.2 mmol), 10 h
bIsolated yield.
cReaction time = 16 h.

KAZEMI MOVAHED ET AL.
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TABLE 3 Reusability of the cu NPs‐MCN nanocomposite in multi-
component 1,3‐dipolar cycloaddition
support and the role of nitrogen doping in the carbon frame-
work, the array of copper catalysts were prepared (Table 1,
entries 8–9). We used Cu NPs‐SBA‐15 and Cu NPs‐CMK‐
3 in the model reaction. The observed yields of triazole in
both cases were surprisingly inferior. The addition of the
nitrogen in the support leads to an increase in the triazole
yield. Probably, the nitrogen atoms in the carbon framework
can act as a ligand for Cu NPs. For comparison, the model
reaction was conducted in the presence of MCN as a catalyst
for 10 h at 60 °C in EtOH/H2O, which cycloaddition products
were isolated without regioselectivity and in 28% yield
(Table 1, entry 10).
Reaction cycle
1st
2nd
3rd
4th
5th
6th
7th
8th
Yieldb (%)
98
98
98
97
97
97
97
96
abenzyl bromide, (6.0 mmol), phenylacetylene (6.0 mmol), sodium azide
(7.2 mmol), Cu NPs‐MCN nanocomposite (0.5 mol% of Cu), EtOH/H2O
(18 mL), 10 h and Temp. = 60 °C
bIsolated yield.
With the optimized conditions in hand, the scope of the
reaction was explored by reacting various halides in the
mixture of EtOH/H2O at 60 °C, using Cu NPs‐MCN nano-
composite (0.5 mol% of Cu) (Table 2). Different substituents
such as p‐NO2 and p‐Br of benzyl bromide were equally
−
effective toward the nucleophilic substitution of N3
,
followed cycloaddition (Table2, entries 2 and 3). A non‐acti-
vated alkyl halide (n‐decyl bromide) and benzyl chloride also
participated in the reaction and produced the corresponding
triazoles in moderate yields, although the prolongation of
reaction time was needed (Table 2, entries 4 and 5).
Reusability is an important characteristic of the heteroge-
neous catalysis which should be examined in catalytic
reactions. Therefore, we performed a reusability test for the
Cu NPs‐MCN catalyst in the multicomponent 1,3‐dipolar
cycloaddition of benzyl bromide, phenylacetylene and
sodium azide under the optimized conditions. After the
completion of the reaction, the catalyst was easily separated
by centrifugation from the reaction solution and washed with
ethyl acetate (3 × 10 mL) and EtOH (2 × 10 mL), and used
for the next run. This process was repeated for the eight
cycles. After eight cycles, Cu NPs‐MCN nanocomposite
was still stable and active, and provide 96% yield (Table 3).
Furthermore, no significant change was observed in the
morphology of Cu NPs‐MCN after the eight runs, which is
concluded by the TEM image given in Figure 6.
FIGURE 6 TEM image of cu NPs‐MCN reused after eight cycles in
multicomponent 1,3‐dipolar cycloaddition between of benzyl bromide,
phenylacetylene and sodium azide
TABLE 4 Screening of the reaction conditionsa
Entry
Base
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
Cs2CO3
K2CO3
K3PO4
Solvent
EtOH
H2O
Temp.
reflux
reflux
120
Yieldb (%)
47
1
3.3 | The catalytic activity of cu NPs‐MCN
nanocomposite toward N‐arylation of N‐
heterocycles
2
trace
65
3
NMP
4
CH2Cl2
DMSO
DMF
reflux
120
trace
72
5
N‐arylazoles are ubiquitous in bioactive compounds, natural
products, pesticides, pharmaceuticals, dyes, polymers,
ionic liquids and N‐heterocyclic carbenes.[21] Thus, the
development of a novel, efficient, simple and practical
method for N‐arylation of heterocycles is an important end
in the modern organic synthesis.[22]
6
120
98
7
DMF
110
72
8
DMF
120
98
9
10c
DMF
120
64
DMF
120
Trace
aImidazole (1 mmol), 1‐bromo‐4‐nitrobenzene (1 mmol), Cu NPs‐MCN nano-
composite (2.5 mol% of Cu), base (1.5 mmol), solvent (3 mL), 4 h.
bIsolated yield.
cMCN (0.05 g)
Inspired by the high activity and stability of Cu NPs‐MCN
nanocomposite, the Ullmann C‐N cross‐coupling was further
used as another model reaction to test the further performance
of Cu NPs‐MCN nanocatalyst. In our initial experiment,

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KAZEMI MOVAHED ET AL.
TABLE 5 Cu NPs‐MCN nanocomposite catalyzed N‐arylation of N‐heterocycles
Entry
Aryl halide
N‐heterocycle
Product
Yield (%)
1
98
2
3a
98
3
4
5
3a
3a
91
79
75
2a
6
7
2a
2a
68
94
8
2a
2a
2a
98
73
72
86
9
10
11
12
3a
3a
4c
98
(Continues)

KAZEMI MOVAHED ET AL.
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TABLE 5 (Continued)
Entry
Aryl halide
N‐heterocycle
3a
Product
Yield (%)
13
4d
4a
94
14
15
3a
3a
98
65
4c
aAryl halide (1 mmol), N‐heterocycle (1 mmol), Cu NPs‐MCN nanocomposite (2.5 mol% of Cu) K3PO4 (1.5 mmol), DMF (3 ml), 4 h and Temp. = 120 °C.
bIsolated yield.
TABLE 6 Reusability of the cu NPs‐MCN nanocomposite in
imidazole and 1‐bromo‐4‐nitrobenzene were chosen as the
model substrates to optimize reaction conditions including
bases, solvents and reaction temperatures, and the results are
presented in Table 4. The results indicate that the base, solvent
and temperature significantly influence on the product yield.
The reaction was not done when this reaction was carried out
with MCN as the catalyst (Table 4, Entry 10).
Ullmann cross coupling of bromobenzene and imidazolea
Reaction cycle
1st
2nd
3rd
4th
5th
6th
7th
8th
Yieldb (%)
91
91
90
87
85
82
80
77
aImidazole (6 mmol), bromobenzene (6 mmol), Cu NPs‐MCN nanocomposite
(2.5 mol% of Cu) K3PO4 (9 mmol), DMF (18 ml), 4 h and Temp. = 120 °C
With these results in hand, the N‐arylation of various
substituted aryl halides bearing electron‐donating and elec-
tron‐withdrawing groups with imidazole were chosen to
explore the scope and the generality of the reaction (Table 5
, entries 1–4). These reactions were done effectively and gave
good yields. Other N‐heterocycles such as indole, 1,2,4‐tri-
azole, 5‐phenyl‐2H‐tetrazole, benzotriazole, and benzimid-
azole reacted with 1‐bromo‐4‐nitrobenzene under standard
experimental conditions and provided products with 68–
98% yields (Table 5, entries 5–10). The 1‐iodo‐2‐
methylbenzene as a hindered substrate converted to the corre-
sponding product with a moderate yield (Table 5, entry 11).
Furthermore, chlorobenzene had lower reactivity in com-
parison with bromobenzene and iodobenzene (Table 5,
entry 15).
TABLE 7 Comparison of efficiency of various copper catalysts in
Ullmann cross‐coupling reaction of bromobenzene and imidazole
Yield Time
Catalyst
Condition
(%)
(h)
Ref.
Cu NPs‐MCN
(2.5 mol%)
K3PO4, DMF,
120 °C
91
4
This work
[23]
[24]
[25]
[26]
CuFAP (12.5 mol%) K2CO3, DMSO,
110 °C
90
85
99
31
10
24
30
24
CuNPs/MagSilica
(10 mol%)
K2CO3, DMF,
152 °C
Cu(II)‐NaY (10 mol K2CO3, DMF,
%)
120 °C
CuPc (10 mol%)
KOH, DMSO,
90 °C
We performed a reusability test for the Cu NPs‐MCN
catalyst in the Ullmann cross‐coupling of bromobenzene
and imidazole under the optimized conditions. The Cu NPs‐
MCN catalyst was stable during the catalytic reaction and
easily separated by centrifugation the reaction solution at
the end of the reaction. A new batch of coupling reactions
was started by using the separated Cu NPs‐MCN catalyst
and this process was continued up to the eight cycles. As seen
in the Table 6, Cu NPs‐MCN was still active and provide
77% yield in 4 h after eight runs.
bromobenzene and imidazole. Clearly, the present catalyst
exhibited a simple, high effective, less time‐consuming
method for the C‐N coupling reaction.
4 | CONCLUSIONS
In conclusion, we have successfully demonstrated that Cu
NPs‐MCN nanocomposite is a novel, simple, effective and
reusable heterogeneous catalyst for the Huisgen 1,3‐dipolar
cycloaddition and N‐arylation of N‐heterocycles taking a
The Table 7 provides a comparison of the present
method with other reported copper heterogeneous catalytic
systems in the Ullmann cross coupling reaction between

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KAZEMI MOVAHED ET AL.
[11] S. Jun, S. H. Joo, R. Ryoo, M. Kruk, M. Jaroniec, Z. Liu, T.
short reaction time leading to good yields under aerobic
conditions without using any external ligands or additives
as promoters. In order to study the effect of the support and
the role of N‐doping in the carbon framework, the array of
copper catalysts were prepared. We used Cu NPs‐SBA‐15
and Cu NPs‐CMK‐3 in the model reaction. The results show
that the addition of the nitrogen in the support leads to an
increase in the triazole yield. Probably, the nitrogen atoms
in the support can act as a ligand for Cu NPs. The reusability
is high, and the catalyst can be recycled for several times
without the considerable loss of activity.
Ohsuna, O. Terasaki, J. Am. Chem. Soc. 2000, 122, 10712.
[12] L. Zhang, H. Wang, Z. Qin, J. Wang, W. Fan, RSC Adv. 2015,
5, 22838.
[13] A. Vinu, K. Ariga, T. Mori, T. Nakanishi, S. Hishita, D. Golberg,
Y. Bando, Adv. Mater. 2005, 17, 1648.
[14] I. I. Perepichka, M. A. Mezour, D. F. Perepichka, R. B. Lennox,
Chem. Commun. 2014, 50, 11919.
[15] S. K. Movahed, M. Dabiri, A. Bazgir, Appl. Catal. A 2014, 488, 265.
[16] J. Hermannsdorfer, R. Kempe, Chem–Eur. J. 2011, 17, 8071.
[17] K. S. W. Singh, D. H. Everett, R. A. W. Haul, L. Moscou, R. A.
Pierotti, J. Rouquerol, T. Siemieniewska, Pure Appl. Chem. 1985,
57, 603.
ACKNOWLEDGEMENTS
[18] R. B. Rakhi, W. Chen, D. Cha, H. N. Alshareef, J. Mater. Chem.
2011, 21, 16197.
We gratefully acknowledge financial support from the
Research Council of Shahid Beheshti University and the Ira-
nian National Science Foundation (Proposal No: 94028845).
[19] M. Meldal, C. W. Tornøe, Chem. Rev. 2008, 108, 2952.
[20] a) G. C. Tron, T. Pirali, R. A. Billington, P. L. Canonico, G. Sorba,
A. A. Genazzani, Med. Res. Rev. 2008, 28, 278; b) H. B. Jalani, A.
Ç. Karagöz, S. B. Tsogoeva, Synthesis 2017, 49, 29.
REFERENCES
[21] a) K. Morimoto, R. Ogawa, D. Koseki, Y. Takahashi, T. Dohi, Y.
Kita, Chem. Pharm. Bull. 2015, 63, 819; b) D. Yang, B. An, W.
Wei, L. Tian, B. Huang, H. Wang, ACS Comb. Sci. 2015, 17, 113.
[1] P. Deka, R. C. Deka, P. Bharali, New J. Chem. 2014, 38, 1789.
[2] a) R. A. Soomro, S. T. H. Sherazi, Sirajuddin, N. Memon, M. R.
Shah, N. H. Kalwar, K. R. Hallam, A. Shah, Adv. Mat. Lett.
2014, 5, 191; b) M. B. Gawande, A. Goswami, F.‐X. Felpin, T.
Asefa, X. Huang, R. Silva, X. Zou, R. Zboril, R. S. Varma, Chem.
Rev. 2016, 116, 3722.
[22] S. Pan, J. Liu, H. Li, Z. Wang, X. Guo, Z. Li, Org. Lett. 2010, 12,
1932.
[23] M. L. Kantam, G. T. Venkanna, C. Sridhar, K. B. S. Kumar,
Tetrahedron Lett. 2006, 47, 3897.
[3] S. Elavarasan, B. Baskar, C. Senthil, P. Bhanja, A. Bhaumik, P.
[24] F. Nador, M. A. Volpe, F. Alonso, G. Radivoy, Tetrahedron 2014,
70, 6082.
Selvam, M. Sasidharan, RSC Adv. 2016, 6, 49376.
[4] a) L. Luo, A. Zhang, M. J. Janik, K. Li, C. Song, X. Guo, Appl.
Surf. Sci. 2017, 396, 78; b) H. Jiang, X. Yu, R. Nie, X. Lu, D.
Zhou, Q. Xia, Appl. Catal. A: General 2016, 520, 73; c) Q. Han,
B. Wang, J. Gao, Z. Cheng, Y. Zhao, Z. Zhang, L. Qu, ACS Nano
2016, 10, 2745; d) Q. Yang, W. Wang, Y. Zhao, J. Zhu, Y. Zhu, L.
Wang, RSC Adv. 2015, 5, 5497; e) Y. Zhou, H. Xue, T. Wang, H.
Guo, X. Fan, L. Song, W. Xia, H. Gong, Y. He, J. Wang, J. He,
Chem. – Asian J. 2017, 12, 60; f) J. Mao, T. Peng, X. Zhang, K.
Li, L. Yea, L. Zan, Catal. Sci. Technol. 2013, 3, 1253.
[25] M. L. Kantam, B. P. C. Rao, B. M. Choudary, R. S. Reddy, Synlett
2006, 2006, 2195.
[26] Q. Huang, L. Zhou, X. Jiang, X. Qi, Z. Wang, W. Lang, Chinese J.
Catal. 2014, 35, 1818.
SUPPORTING INFORMATION
Additional Supporting Information may be found online in
the supporting information tab for this article.
[5] G. P. Mane, D. S. Dhawale, C. Anand, K. Ariga, Q. Ji, M. A.
Wahab, T. Mori, A. Vinu, J. Mater. Chem. A 2013, 1, 2913.
[6] C. Liang, Z. Li, S. Dai, Angew. Chem. Int. Ed. 2008, 47, 3696.
How to cite this article: Kazemi Movahed S, Salari
P, Kasmaei M, Armaghan M, Dabiri M, Amini MM.
Copper nanoparticles incorporated on a mesoporous
carbon nitride, an excellent catalyst in the Huisgen 1,3‐
dipolar cycloaddition and N‐arylation of N‐
[7] a) K. K. R. Datta, B. V. S. Reddy, K. Ariga, A. Vinu, Angew. Chem.
Int. Ed. 2010, 49, 5961. b) H. Wang, T. Maiyalagan, X. Wang, ACS
Catal. 2012, 2, 781.
[8] D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F.
Chmelka, G. D. Stucky, Science 1998, 279, 548.
heterocycles. Appl Organometal Chem. 2017;e3914.
https://doi.org/10.1002/aoc.3914
[9] R. Tayebee, M. M. Amini, M. Ghadamgahi, M. Armaghan, J. Mol.
Catal. A 2013, 366, 266.
[10] A. Vinu, Adv. Funct. Mater. 2008, 18, 816.