Supported benzimidazole-salen Cu(II) complex: An efficient, versatile and highly reusable nanocatalyst for one-pot synthesis of hybrid molecules

Article abstract of DOI:10.1002/aoc.4446

A novel and efficient nanocatalyst consisting of benzimidazole-salen Cu(II) complex on surface-modified silica (BS-Cu(II)@SiO₂) was prepared. The heterogeneous nanocatalyst was characterized by FESEM, TEM, EDX, FT-IR, XRD, ICP, and TGA. The nanocatalyst was used for the one-pot synthesis of some target hybrid molecules. An efficient four component C–H bond activation/[3?+?2] cycloaddition and condensation/cyclization/aromatization sequence toward triazole-benzimidazole derivatives is disclosed. This methodology provides a general and rapid synthetic route to some new triazole-benzimidazole hybrids under mild reaction conditions. In addition, the heterogeneous nanocatalyst can be easily separated from the reaction mixture and used several times without noticeable leaching or loss of its catalytic activity. We believe this interesting one-pot reaction as well as benzimidazole-salen Cu(II) complex pave the way to the design and synthesis of other new hybrid molecules and metal catalysts, respectively.

Full text of DOI:10.1002/aoc.4446

Received: 17 February 2018
DOI: 10.1002/aoc.4446
Revised: 22 April 2018
Accepted: 9 May 2018
F U L L P A P E R
Supported benzimidazole‐salen Cu(II) complex:
An efficient, versatile and highly reusable nanocatalyst for
one‐pot synthesis of hybrid molecules
Hashem Sharghi
| Mahdi Aberi | Pezhman Shiri
Department of Chemistry, Shiraz
University, Shiraz 71454, I. R. Iran
A novel and efficient nanocatalyst consisting of benzimidazole‐salen Cu(II)
complex on surface‐modified silica (BS‐Cu(II)@SiO2) was prepared. The het-
erogeneous nanocatalyst was characterized by FESEM, TEM, EDX, FT‐IR,
XRD, ICP, and TGA. The nanocatalyst was used for the one‐pot synthesis of
some target hybrid molecules. An efficient four component C–H bond activa-
Correspondence
Hashem Sharghi, Department of
Chemistry, Shiraz University, Shiraz,
71454, I. R. Iran.
Email: shashem@chem.susc.ac.ir
tion/[3
+ 2] cycloaddition and condensation/cyclization/aromatization
Funding information
Shiraz University Research Council
sequence toward triazole‐benzimidazole derivatives is disclosed. This method-
ology provides a general and rapid synthetic route to some new triazole‐benz-
imidazole hybrids under mild reaction conditions. In addition, the
heterogeneous nanocatalyst can be easily separated from the reaction mixture
and used several times without noticeable leaching or loss of its catalytic activ-
ity. We believe this interesting one‐pot reaction as well as benzimidazole‐salen
Cu(II) complex pave the way to the design and synthesis of other new hybrid
molecules and metal catalysts, respectively.
KEYWORDS
benzimidazole‐salen Cu(II) complex, cyclization reactions, heterogeneous catalyst, hybrid molecules,
nanoparticles
1 | INTRODUCTION
arresting of metal nanoparticles in different regions of
these macromolecules. From our point of view, this kind
Today, due to the low cost and environmentally benign
properties, copper nanoparticles have been attracting
the attention of organic synthetic chemists.[1] The copper
is stabilized with different ligands which are finally sup-
ported on solid supports. Many types of ligands (includ-
ing dithioethane,[2] L‐proline,[3] 1,10‐phenanthroline,[4]
of molecules should be preferred to others even
dendrimeric materials[8] due to their excellent properties,
easy way of their synthesis, various metal trapping sites
and also their cost‐effectiveness.
N‐Heterocyclic compounds[9] are one of the often
incorporated planar cores in agrochemistry, materials sci-
ence, medicinal chemistry, optics, and other emerging
areas. Since a series of drugs (including albendazole,
omeprazole, thiabendazole, lansoprazole, pantoprazole,
telmisartan, astemizole, candesartan cilexetil, and
mebendazole) have been introduced via optimization of
substituents around the benzimidazole nucleus, many
researches have focused on their facile synthesis.[10] Some
patents and papers[11] have been published for the
tris
(triazolyl)methanol,[5]
and
1H‐pyrrole‐2‐
carbohydrazide[6]) have been attached on solid materials
and applied in laboratory or industrial processes. On the
other hand, one of the most important factors must be
considered in developing new catalysts is to enhance the
capacity of metal absorption of solid supports by using
complexation in two or multi‐functionalized ligands as
stabilizers.[7] The novel features of these structures permit
Appl Organometal Chem. 2018;e4446.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4446

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SHARGHI ET AL.
synthesis and investigation of biochemistry properties of
benzimidazole‐linked 1,2,3‐triazole derivatives, as
well.[12]
The ‘domino reaction’, ‘cascade reaction’, and ‘tan-
dem reaction’ are several terminologies to describe
multi‐step reactions that are adopted in a single vessel.[13]
One‐pot processes have been used extensively in syn-
thetic organic chemistry for a long time. It is therefore
important to note that these synthetic strategies can
reduce chemical waste, save time, and simplify practical
aspects. F. Alonso et al. have reported sustainable,
environmentally benign, and one‐pot procedure for
1,2,3‐triazoles from organic halides, aryldiazonium salts,
anilines, or epoxides using supported copper nanoparti-
cles. The research group has also reported β‐
methylsulfanyl‐1,2,3‐triazoles in a one pot manner from
alkenes.[1c] There is a micro review which focuses on
the advantages of the multicomponent syntheses of
fluorophores.[14]
SCHEME 1 Synthesis of ligand C
microscope (FESEM), transmission electron microscopy
(TEM), energy dispersive X‐ray (EDX) analysis, FT‐IR
spectroscopy, powder X‐ray diffraction (XRD) and induc-
tively coupled plasma (ICP).
FESEM and TEM images were used to study the sur-
face morphology of the BS‐Cu(II)@SiO2 According to
the images of FESEM, the average particle size of this
nanocatalyst was calculated to be less than 40 nm
(Figure 1).
With these considerations in mind and our ongoing
interest in designing and synthesizing copper based cata-
lysts as well as heterogeneous catalysts,[13d, 15] we aim to
demonstrate the synthesis of BS‐Cu(II)@SiO2 and evalu-
ate its applications in one pot reactions towards N‐hetero-
cycles synthesis.
TEM images were employed to further characteriza-
tion of the structure and morphology of BS‐Cu(II)
@SiO2, as well. This analysis is similar to that found in
the FESEM data (Figure 2).
2 | RESULTS AND DISCUSSION
Our study was initiated by the synthesis of BS‐Cu (II)
@SiO2 as reusable nanocatalyst in several steps. In this
regard, 2‐hydroxybenzaldehyde and paraformaldehyde
was added to concentrated hydrochloric acid at 5–10 °C.
The resulting mixture was stirred for 2 days at room temper-
ature to produce 5‐(chloromethyl)‐2‐hydroxybenzaldehyde
A.[16] Also, 2‐(1H‐benzo [d]imidazol‐2‐yl) phenol B was
synthesized from salicylaldehyde and o‐phenylenediamine
at room temperature in the presence of catalyst
(Scheme 1).[17]
We also conducted EDX analysis to detect the chemi-
cal composition of BS‐Cu(II)@SiO2. In the spectrum, Si,
N, O, C and Cu peaks confirm the chemical modification
of the nanocatalyst (Figure 3).
Further characterization of nanocatalyst BS‐Cu(II)
@SiO2 was achieved using FT‐IR spectroscopy. The new
nanocatalyst was approved by the comparison of the
FT‐IR spectra of BS‐Cu(II)@SiO2 and D. According to
the previously reported manuscripts,[18] D exhibits the ν
(C=N) stretching band of imine nitrogens of Schiff base
and aromatic ring at around 1647 cm−1. The shift of the
ν (C=N) stretching band to around 1630 cm−1 suggests
the coordination of ligand to the copper ion (Figure 4).
Figure 5 shows XRD pattern of BS‐Cu(II)@SiO2. The
spectrum shows peak at 2θ around 13° which is related
to the silica gel support.[15e] Since the amount of Cu spe-
cies is very low relative to solid material, the diffraction
peaks are weak. Therefore, the concentration of Cu loading
(4.09% w/w) in the supported benzimidazole‐salen matrix
was determined using the ICP data.
5‐(Chloromethyl)‐2‐hydroxybenzaldehyde
A
was
reacted with 2‐(1H‐benzo [d]imidazol‐2‐yl) phenol B
to form 2‐hydroxy‐5‐((2‐(2‐hydroxyphenyl)‐1H‐benzo
[d]imidazol‐1‐yl)methyl) benzaldehyde C as shown in
Scheme 2. This prepared ligand C was covalently anchored
on amino‐functionalized silica solid support in ethanol
under reflux conditions for five hours. In next step, the sup-
ported benzimidazole‐salen Cu(II) complex (BS‐Cu(II)
@SiO2) was prepared by the reaction of ligand on amino‐
functionalized silica solid support D and Cu(OAc)2.H2O
in ethanol under reflux condition for seven hours.
TGA experiment was carried out under nitrogen flow
from room temperature to 700 °C. As can be seen in
Figure 6, the TGA curve displays two‐stage decomposi-
tion. The first weight loss corresponds to adsorbed water
The resulting BS‐Cu(II)@SiO2 as a nanocatalyst (E)
was characterized using different spectrometric tech-
niques including field emission scanning electron

SHARGHI ET AL.
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SCHEME 2 Proposed structure for
silica supported benzimidazole‐salen
copper(II) complex as a nanocatalyst (BS‐
Cu(II)@SiO2)
FIGURE 1 Field emission scanning electron microscope (FESEM) image of the silica supported benzimidazole‐salen copper(II) complex
and organic solvents in the BS‐Cu(II)@SiO2. The second
decomposition step takes place between 180–700 °C. This
peak can be related to the decomposition of the organic
functionalized part on the surface of silica. The TGA pro-
file also confirms high thermal stability of BS‐Cu (II)
@SiO2 (Figure 6). The DTG analysis is also shown in
Figure 6.
A new method for copper‐catalyzed synthesis of some
new benzimidazole‐triazole hybrids from organic halides,
epoxides or boronic acide 1, 4‐(prop‐2‐yn‐1‐yloxy)

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SHARGHI ET AL.
FIGURE 2 TEM images for the silica supported benzimidazole‐salen copper(II) complex
FIGURE 3 Energy dispersive X‐ray spectrum (EDX) of the BS‐
Cu(II)@SiO2
benzaldehyde derivatives 2, o‐phenylenediamines 3 and
FIGURE 4 FT‐IR spectra of (a) supported benzimidazole‐salen D
and (b) BS‐Cu(II)@SiO2 E
sodium azide was discovered through a C–H bond activa-
tion/[3 + 2] cycloaddition and condensation/cyclization/
aromatization sequence (Scheme 3).
2.1 | Synthesis of 1,4‐disubstituted‐1,2,3‐
triazole‐1H‐benzo[d]imidazole hybrids
from benzyl halides, 4‐(prop‐2‐yn‐1‐yloxy)
benzaldehyde, sodium azide, and o‐
phenylenediamines
For our initial screening experiments, the 1,3‐dipolar
cycloaddition process between benzyl bromide 1a, 4‐
(prop‐2‐yn‐1‐yloxy) benzaldehyde 2a, and sodium azide
in the presence of BS‐Cu(II)@SiO2 as nanocatalyst and
H2O (1.0 ml) as solvent at room temperature was applied
to explore the viability of obtaining 1,4‐disubstituted
1,2,3‐triazole intermediate. After forming triazole
FIGURE 5 XRD patterns of BS‐Cu(II)@SiO2 as a nanocatalyst
intermediate, o‐phenylenediamines 3a was added but
the condensation/cyclization/aromatization transforma-
tion failed to take place (Scheme 4).

SHARGHI ET AL.
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instead of only water. In order to establish the optimum
reaction conditions, the condensation/cyclization/aroma-
tization transformation of triazole intermediate with o‐
phenylenediamine 3a was studied considering various
factors including different cosolvents, catalyst loadings
and temperatures. It was found that the continuation of
the reaction is largely dependent on the nature of the
cosolvent. Lower yields were obtained for desired product
when using cosolvents such as CHCl3, H2O, CH3CN
DMF, DMSO, THF, CH3OH and dioxin, whereas higher
yield was achieved in EtOH (Table 1 entries 1–10). In
the next step, different amounts of cosolvent was also
investigated in the condensation/cyclization/aromatiza-
tion reaction of triazole intermediate with o‐
phenylenediamine 3a using BS‐Cu(II)@SiO2 (5.0 mol %)
at room temperature. The best results were obtained
using 1:9 v/v mixture of water/ethanol. As shown in the
Table 1 (entries 10–13), when the amount of the
cosolvent was reduced, the yield of the hybrid product
decreased, whereas raising the amount of cosolvent did
not lead to an appreciable increase of the yield. In the
next step, loading levels of the BS‐Cu(II)@SiO2 were
screened and the lowest catalyst loading in the synthesis
of benzimidazole‐triazole hybrid 4a was 5.0 mol %
FIGURE 6 TG and DT analysis of BS‐Cu(II)@SiO2 as
nanocatalyst
a
The axillary effect of various organic solvents was also
checked at room temperature during this process. By
using a 1:9 v/v mixture of water/ethanol instead of only
water, the rate of the condensation/cyclization/aromati-
zation transformation was enhanced and, consequently,
the yield increased startlingly. According to the litera-
ture,[17] loss of water during the formation of Schiff base
is the major reason for using a mixture of water/ethanol
SCHEME 3 A new method for copper‐catalyzed synthesis of some new benzimidazole‐triazole hybrids
SCHEME 4 Synthesis of 1,4‐
disubstituted‐1,2,3‐triazole‐1H‐benzo[d]
imidazole hybrids from benzyl bromide
(1a), 4‐(prop‐2‐yn‐1‐yloxy)benzaldehyde
(2a), sodium azide, and benzene‐1,2‐
diamines (3a)

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SHARGHI ET AL.
TABLE 1 Copper catalyzed synthesis of benzimidazole‐triazole hybrid 4a from triazole intermediate and o‐phenylenediamine 3a under
various conditions
Entry
Cosolvent (mL)
Catalyst (mol %)
Temperature (°C)
Time (h)
Yield (%)a
1
‐
5
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
40
60
24
12
12
12
12
12
12
12
12
6
<10
40
2
DMSO (5)
CH3CN (5)
THF (5)
5
3
5
55
4
5
18
5
H2O (5)
5
<10
<10
<10
15
6
DMF (5)
5
7
CHCl3 (5)
Dioxin (5)
Methanol (5)
Ethanol (5)
Ethanol (7)
Ethanol (9)
Ethanol (11)
Ethanol (9)
Ethanol (9)
Ethanol (9)
Ethanol (9)
Ethanol (9)
5
8
5
9
5
68
10
11
12
13
14
15
16
17
18
5
77
5
6
85
5
6
89
5
6
89
2.5
7
6
68
6
89
10
5
6
89
5
89
5
4
89
aIsolated yield.
(Table 1 entries 12, 14–16). We next turned our attention
to the investigation of the temperature effect. Although
the reaction is carried out at room temperature, it can
also be accelerated by increasing the reaction tempera-
ture, as well (Table 1 entries 12, 17, 18).
According to Table 1, the reaction was performed well
by using 5.0 mol % of nanocatalyst in 10.0 ml of water/
ethanol (9:1 v/v) as the appropriate solvent at room tem-
perature. The reaction was completed within 6 h with the
best outcome.
To improve economic profile, the catalyst recyclability
was also studied. The nanocatalyst can be readily
removed from the reaction mixture by simple centrifuga-
tion and used seven times without noticeable leaching or
loss of its catalytic activity. After centrifugation, the
recovered nanocatalyst was dried and then used for
another successive reaction run (Figure 7).
FIGURE 7 Heterogeneous nanocatalyst recyclability studies for
the synthesis of benzimidazole‐triazole hybrid 4a from triazole
intermediate and o‐phenylenediamine 3a at room temperature
To determine whether or not leaching of the catalyst
occurs, the heterogeneous catalyst was stirred for 6 h in
EtOH at room temperature. The catalyst was separated
and the solvent was used for the synthesis of benzimid-
azole‐triazole hybrid 4a from triazole intermediate and
o‐phenylenediamine 3a under the optimized conditions
for 12 h. As no product was detected, it was concluded
that no copper leaching took place. Moreover, the ICP
analysis shows the same results for BS‐Cu(II)@SiO2 after
reusing the catalyst for at least seven times.
The scope and limitation of this one pot four compo-
nent [3 + 2] cycloaddition and condensation/cyclization/
aromatization sequence catalyzed by BS‐Cu(II)@SiO2
was explored using a series of organic halides, epoxides,
or boronic acide 1, 4‐(prop‐2‐yn‐1‐yloxy) benzaldehyde
derivatives 2, o‐phenylenediamine derivatives 3 and

SHARGHI ET AL.
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SCHEME 5 Synthesis of benzimidazole‐β‐hydroxy triazole hybrid 4b from o‐phenylenediamine 3a, 4‐(prop‐2‐ yn‐1‐yloxy)benzaldehyde
2a, styrene oxide 1b and NaN3.
NaN3. The reaction of benzyl halides 1a, 2, 3, and NaN3
afforded the desired hybrid products 4a‐4e, as expected.
phenylenediamine 3a, and NaN3 under optimized reac-
tion conditions, low amount of desired product 4b was
formed (Scheme 5).
To improve the yield of the reaction, some modifica-
tions to the above‐optimized experimental procedure were
required to convert the organic epoxides to hybrid com-
pounds, as well. In continuation of our studies, hybrid
products were also produced by the transformation of 4‐
2.2 | Synthesis of β‐hydroxy‐1,4‐
disubstituted‐1,2,3‐triazole‐1H‐benzo[d]
imidazole hybrids from epoxides, 4‐(prop‐2‐
yn‐1‐yloxy) benzaldehyde, sodium azide,
and o‐phenylenediamines
(prop‐2‐yn‐1‐yloxy)
benzaldehyde
2a
and
o‐
phenylenediamine 3a to benzimidazole intermediate in
ethanol (5.0 ml) at room temperature. The click transfor-
mation of them to benzimidazole‐β‐hydroxy triazole
In an attempt to investigate this one‐pot four‐component
sequential cyclization processes between styrene oxide
1b,
4‐(prop‐2‐yn‐1‐yloxy)
benzaldehyde
2a,
o‐
SCHEME 6 Synthesis of benzimidazole‐triazole derivatives by using phenylboronic acid.

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SHARGHI ET AL.
TABLE 2 Synthesis of benzimidazole‐triazole hybridsa and b
.
hybrid molecule 4b was also performed well at room tem-
perature by adding 5.0 ml water as cosolvent and styrene
oxide 1b. The reaction provided outstanding results in the
case of benzimidazole‐β‐hydroxy triazole derivatives 4j‐4o.
satisfaction, the azidonation reaction occurred smoothly
with 5.0 mol % catalyst in methanol (2.0 ml) at room tem-
perature.[19] On other hand, benzimidazole intermediate
formation reaction was separately performed at room
temperature in ethanol (5.0 ml), too. After these two were
mixed, water (5.0 ml) was added. Finally the reaction was
stirred until the reaction was completed (Scheme 6). All
results are shown at Table 2.
2.3 | Synthesis of 1,4‐disubstituted‐1,2,3‐
triazole‐1H‐benzo[d]imidazole hybrids
from phenylboronic acid, 4‐(prop‐2‐yn‐1‐
yloxy) benzaldehyde, sodium azide, and o‐
phenylenediamines
3 | CONCLUSIONS
In addition, we explored the synthesis of these benzimid-
azole‐triazole derivatives by using phenylboronic acid
instead of benzyl halides or epoxides. To our great
In summary, BS‐Cu(II)@SiO2 has been successfully syn-
thesized in several steps and characterized by field emis-
sion
scanning
electron
microscope
(FESEM),

SHARGHI ET AL.
9 of 14
transmission electron microscopy (TEM), energy disper-
sive X‐ray (EDX) analysis, FT‐IR spectroscopy, powder
X‐ray diffraction (XRD) and inductively coupled plasma
(ICP) and thermal gravimetric analysis (TGA). This
new, versatile, efficient and novel catalytic system pro-
vides a procedure that enables the synthesis of triazole‐
benzimidazole hybrid molecules in one‐pot while
displaying good functional group tolerance.
salicylaldehyde (150 mmol) and praformaldehyde
(10.0 g; 333 mmol). The resulting emulsion was further
stirred for 48 h. The mixture was washed carefully with
saturated aqueous NaHCO3 and separated out by
extracting with ethyl acetate to give white crystalline
solid which used for next step without further
purification.
1
81% yield, mp: 66–68 °C; H NMR (CDCl3, 250 MHz)
This system shows several advantages including syn-
thesis of complex molecules using commercially available
starting materials, having easy work up without needing
for purification of intermediates, and carrying out under
mild conditions.
δ10.93 (s, 1H), 9.80 (s, 1H), 7.39–7.50 (m, 2H), 6.89 (d,
J = 8.4 Hz, 1H), 4.50 (s, 2H); 13C NMR (CDCl3,
62.9 MHz) δ= 196.2, 161.6, 137.7, 133.9, 129.2, 120.3,
118.3, 45.0; IR (KBr cm−1) 3737, 2866, 1654, 1481, 1380,
1269, 1149, 1006, 771, 675, 574; Mass m/z (%): 171 (M+
+1, 5.3), 170 (M+, 19.0), 135 (100.0), 105 (11.6), 77
(23.1), 51 (23.5).
4 | EXPERIMENTAL
4.1 | Instrumentation, analysis and
starting material
4.3 | Procedure for the synthesis of 2‐(1H‐
benzo[d]imidazol‐2‐yl) phenol (B)[17]
Chemical materials and solvents were purchased from
Fluka, Sigma‐Aldrich and Merck Companies and used
without further purification. The used aminopropyl silica
gel was also obtained from Fluka. NMR spectra were
recorded in CDCl3 or DMSO‐d6 solvents on a Bruker
Avance DPX‐250 (1H‐NMR 250 MHz and 13C NMR
62.9 MHz) spectrometer. IR spectra were obtained using
a Shimadzu FT‐IR 8300 spectrophotometer. Characteriza-
tion and surface morphology of the nano‐catalyst were
performed with a MIRA3 TESCAN SEM, operating at
20.0 kV. TEM images were obtained with a transmission
electron microscopy (TEM, Zeiss‐EM10C, 80 kV). The
energy dispersive X‐ray (EDX) analysis was done using
SIRIUS SD EDX analyser. Mass spectra were determined
at 70 or 20 ev on a Shimadzu GCMS‐QP 1000 EX instru-
ments. By a Büchi‐535 circulating oil melting point appa-
ratus, melting points were obtained in open capillary
tubes. Characterization of the catalyst was obtained using
X‐ray diffraction (XRD, D8, Advance, Bruker, axs). TGA
of the sample was performed under a nitrogen atmo-
sphere with a Netzsch STA 409 PC/PG instrument. The
inductively coupled plasma (ICP) analysis data were
obtained using a Varian Vista‐pro analyser. The purity
of substrates and reaction monitoring were determined
by TLC on silica gel PolyGram SILG/UV 254 plates. The
column chromatography was performed in glass columns
on short columns of silica gel 60 (70–230 mesh).
A mixture of salicylaldehyde (1.0 mmol) and o‐
phenylenediamine (1.0 mmol) was stirred in 5.0 ml of
EtOH in the presence of catalytic amount of previously
reported catalysts at room temperature for the suitable
time. After removal of the solvent, the residue was puri-
fied by silica gel column chromatography employing n‐
hexane/ethyl acetate (10:1) as eluent.
1H NMR (DMSO‐d6, 250 MHz): δ13.07 (s, 1H), 8.02 (d,
J = 7.8 Hz, 1H), 7.63–7.67 (m, 2H), 7.25–7.45 (m, 3H),
6.97–7.04 (m, 2H); 13C NMR (DMSO‐d6, 62.9 MHz): δ=
157.9, 151.6, 131.7, 126.1, 123.2, 122.4, 119.1, 117.9,
117.1, 112.5, 111.5.
4.4 | Procedure for the synthesis of 2‐
hydroxy‐5‐((2‐(2‐hydroxyphenyl)‐1H‐benzo
[d]imidazol‐1‐yl)methyl) benzaldehyde (C)
A solution of 2‐(1H‐benzo [d]imidazol‐2‐yl) phenol B
(1.0 mmol) and triethylamine (1.2 mmol) in 2.0 ml of
DMF was added to a solution of 5‐(chloromethyl)‐2‐
hydroxybenzaldehyde A (1.0 mmol) in 2.0 ml of DMF.
The reaction mixture was allowed to stir for 12 h at
80 °C. The product was precipitated using cold water.
The precipitate was filtered off and purified by silica gel
column chromatography employing n‐hexane/ethyl ace-
tate 5:1 as eluent.
Pale yellow, yield 91%, mp: 223–235 °C; 1H NMR
(DMSO‐d6, 250 MHz) δ= 10.72 (s, 2H), 10.14 (s, 1H),
7.66–7.70 (m, 1H), 7.33–7.46 (m, 4H), 7.11–7.25 (m, 3H),
7.03 (d, J = 8.0 Hz, 1H), 6.84–6.94 (m, 2H), 5.40 (s, 2H);
13C NMR (DMSO‐d6, 62.9 MHz) δ= 190.7, 160.0, 156.0,
151.7, 141.9, 134.8, 134.7, 131.5, 130.8, 127.6, 126.8,
122.5, 122.0, 119.2, 118.7, 117.5, 116.2, 110.8, 46.8; IR
(KBr cm−1) 3443, 3044, 2528, 1655, 1593, 1485, 1455,
4.2 | Procedure for the synthesis of 5‐
(chloromethyl)‐2‐hydroxy‐benzaldehyde
(A)[16]
To a vigorously stirred solution of precooled (5–10 °C)
concentrated hydrochloric acid (100 ml) were added

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SHARGHI ET AL.
1380, 1338, 1270, 1211, 1148, 1074, 1037, 1006, 980, 839,
816, 766, 752, 745, 674, 541. Anal. Calcd for C21H16N2O3
(344.12): C, 73.24; H, 4.68; N, 8.13; found: C, 73.35; H,
4.77; N, 8.01.
column chromatography over silica gel employing n‐hex-
ane/ethyl acetate (5:1) as eluent.
4.8 | General procedure for the synthesis
of benzimidazole‐triazole hybrids (4) from
epoxide derivatives (1), 4‐(prop‐2‐yn‐1‐
yloxy) benzaldehyde derivatives (2), o‐
phenylenediamine derivatives (3) and
sodium azide
4.5 | Procedure for the synthesis of ligand
on amino‐functionalized silica solid
support (D)
2‐hydroxy‐5‐((2‐(2‐hydroxyphenyl)‐1H‐benzo
[d]
For each reaction, 4‐(prop‐2‐yn‐1‐yloxy) benzaldehyde 2
(1.0 mmol) and o‐phenylenediamine 3 (1.0 mmol) were
stirred in ethanol (5.0 ml) at room temperature in the
presence of BS‐Cu (II)@SiO2 (5.0 mol %) at room temper-
ature for 6 hr. Progress of reactions was monitored by
TLC using n‐hexane/ethyl acetate (8:1). After forming
the benzimidazole intermediate, epoxide 1 (1.0 mmol),
sodium azide (1.2 mmol) and 5.0 ml H2O were added to
the mixture and stirred for 5 hr at room temperature.
The reaction was monitored by TLC. After completion
of the reaction, the whole reaction mixture was centri-
fuged for 5 min to separate the nanocatalyst. The recov-
ered nanocatalyst was washed with ethanol and water,
vacuum dried, and stored for another consecutive reac-
tion runs. Evaporation of the solvent gave the crude prod-
uct, which was purified by column chromatography over
silica gel employing n‐hexane/ethyl acetate (5:1) as
eluent.
imidazol‐1‐yl)methyl) benzaldehyde C (1.0 mmol) in eth-
anol (10.0 ml) was added to 3‐aminopropyl functionalized
silica gel (1.0 g) in ethanol (10.0 ml) and stirred under
reflux conditions for five hours. The solid product was
centrifuged and washed several times with ethanol. Then,
the obtained solid was dried under vacuum at 60 °C.
4.6 | Procedure for the synthesis of
supported benzimidazole‐salen Cu(II)
complex
For synthesis of supported benzimidazole‐salen Cu(II)
complex (BS‐Cu(II)@SiO2), a mixture of ligand on
amino‐functionalized silica solid support D (1.2 g) and
Cu(OAc)2.H2O (1.0 mmol) was added to ethanol
(50 ml). The mixture was then refluxed for seven hours.
The solid product was centrifuged and washed several
times with ethanol and water. Then, the solid products
were dried under vacuum at 60 °C.
4.9 | General procedure for the synthesis
of benzimidazole‐triazole hybrids (4) from
boronic acide (1c), 4‐(prop‐2‐yn‐1‐yloxy)
benzaldehyde derivatives (2), o‐
phenylenediamine derivatives (3) and
sodium azide
4.7 | General procedure for the synthesis
of benzimidazole‐triazole hybrids (4) from
benzyl halide derivatives (1), 4‐(prop‐2‐yn‐
1‐yloxy) benzaldehyde derivatives (2), o‐
phenylenediamine derivatives (3) and
sodium azide
For each reaction, 4‐(prop‐2‐yn‐1‐yloxy) benzaldehyde 2
(1.0 mmol) and o‐phenylenediamine 3 (1.0 mmol) were
stirred in ethanol (5.0 ml) at room temperature in the
presence of BS‐Cu (II)@SiO2 (5.0 mol %) for 6 h. Prog-
ress of reactions was monitored by TLC using n‐hex-
ane/ethyl acetate (8:1). Then, a mixture of boronic
acide 1c (1.0 mmol), sodium azide (1.2 mmol) and
nanocatalyst E (5.0 mol %) was separately stirred in
methanol (2.0 ml) at room temperature for 12 h.[19]
After completion of each reaction, these two were mixed
and H2O (5.0 ml) was added to the mixture. The
reaction was monitored by TLC. After completion of
the reaction, the whole reaction mixture was centrifuged
for 5 min to separate the nanocatalyst. The recovered
nanocatalyst was washed with ethanol and water,
vacuum dried, and stored for another consecutive
reaction runs. Evaporation of the solvent gave the crude
For each reaction, benzyl halide 1 (1.0 mmol), 4‐(prop‐2‐
yn‐1‐yloxy) benzaldehyde 2 (1.0 mmol) and sodium azide
(1.2 mmol) were stirred in 1.0 ml of H2O in the presence
of BS‐Cu(II)@SiO2 (5.0 mol %) at room temperature for
5 h. Progress of reactions was monitored by TLC using
n‐hexane/ethyl acetate (8:1). After forming the triazole
intermediate, o‐phenylenediamine 3 (1.0 mmol) in
9.0 ml ethanol was added to the mixture and stirred for
6 h at room temperature. The reaction was monitored
by TLC. After completion of the reaction, the whole reac-
tion mixture was centrifuged for 5 min to separate the
nanocatalyst. The recovered nanocatalyst was washed
with ethanol and water, vacuum dried, and stored for
another consecutive reaction runs. Evaporation of the sol-
vent gave the crude product, which was purified by

SHARGHI ET AL.
11 of 14
product, which was purified by column chromatography
over silica gel employing n‐hexane/ethyl acetate (5:1)
as eluent.
4.13 | (2‐(4‐((1‐Benzyl‐1H‐1,2,3‐triazol‐4‐yl)
methoxy)phenyl)‐1H‐benzo[d]imidazol‐5‐
yl)(phenyl) methanone (4d)
Pale yellow; mp 221–223. 1H NMR (DMSO‐d6, 250 MHz):
δ= 13.125 (s, 1H), 8.316 (s, 1H), 8.136 (d, J = 8.7 Hz, 2H),
7.864–7.959 (m, 1H), 7.743 (d, J = 6.7 Hz, 3H), 7.518–
7.648 (m, 5H), 7.291–7.350 (m, 4H), 7.220 (d,
J = 8.7 Hz, 2H), 5.607 (s, 2H), 5.230 (s, 2H). 13C NMR
(DMSO‐d6, 75 MHz): δ = 143.19, 138.67, 136.451,
132.51, 131.24, 129.91, 129.27, 128.89, 128.68, 128.47,
125.33, 124.80, 122.78, 121.74, 118.73, 115.77, 114.33,
111.70, 61.75, 53.37. IR (KBr): 3422, 3120, 1794, 1618,
1491, 1838, 1319, 1278, 1247, 1178, 1816, 1051, 891, 833,
708. Anal. Calcd for C30H23N5O2 (485.55): C, 74.21; H,
4.77; N, 14.42; found: C, 74.47; H, 4.84; N, 14.63.
4.10 | 2‐(4‐((1‐Benzyl‐1H‐1,2,3‐triazol‐4‐yl)
methoxy)phenyl)‐1H‐benzo[d]imidazole
(4a)
Pale brown; mp 248–250. 1H NMR (DMSO‐d6, 250 MHz):
δ= 12.734 (s, 1H), 8.310 (s, 1H), 8.091 (d, J = 8.7 Hz, 2H),
7.618 (d, J = 6.5 Hz, 1H), 7.461 (d, J = 7.2 Hz, 1H), 7.295–
7.362 (m, 4H), 7.136–7.203 (m, 5H), 5.607 (s, 2H), 5.213 (s,
2H). 13C NMR (DMSO‐d6, 75 MHz): δ = 189.85, 151.74,
143.26, 136.46, 129.27, 128.68, 128.47, 125.29, 123.46,
122.31, 115.63, 61.70, 53.36. IR (KBr): 3433, 3083, 2875,
2516, 2132, 2044, 1794, 1610, 1447, 1244, 1175, 1011,
874, 749. Anal. Calcd for C23H19N5O (381.44): C, 72.42;
H, 5.02; N, 18.36; found: C, 72.73; H, 5.79; N, 18.01.
4.14 | 2‐(2‐((1‐Benzyl‐1H‐1,2,3‐triazol‐4‐yl)
methoxy)phenyl)‐1H‐benzo[d]imidazole
(4e)
Yellow; mp 152–153.1H NMR (DMSO‐d6, 250 MHz): δ=
12.283 (s, 1H). 8.253–8.290 (m, 2H), 7.577–7.613 (m,
2H), 7.083–7.314 (m, 10H), 5.601 (s, 2H), 5.515 (s, 2H).
13C NMR (DMSO‐d6, 75 MHz): δ = 155.85, 143.70,
136.41, 131.59, 130.44, 129.24, 128.67, 128.37, 124.78,
122.41, 121.95, 119.34, 114.48, 62.68, 53.38. IR (KBr):
3421, 3255, 3058, 1598, 1458, 1304, 1281, 1251, 1227,
1164, 1127, 1057, 1034, 847, 809, 744. Anal. Calcd for
C23H19N5O2 (381.44): C, 72.42; H, 5.02; N, 18.36; found:
C, 72.48; H, 5.27; N, 18.44.
4.11 | 2‐(4‐((1‐Benzyl‐1H‐1,2,3‐triazol‐4‐yl)
methoxy)phenyl)‐5‐methyl‐1H‐benzo[d]
imidazole (4b)
Pale brown; mp 172–174. 1H NMR (DMSO‐d6, 250 MHz):
δ= 12.586 (s, 1H), 8.307 (s, 1H), 8.083 (d, J = 8.5 Hz, 2H),
7.480 (d, J = 8.2 Hz, 1H), 7.266–7.401 (m, 6H), 7.182 (d,
J = 8.7 Hz, 2H), 6.956 (d, J = 7.5 Hz, 1H), 5.607 (s, 2H),
5.211 (s, 2H), 2.396 (s, 3H). 13C NMR (DMSO‐d6,
75 MHz): δ = 159.71, 143.28, 136.46, 129.27, 128.67,
128.46, 128.38, 125.28, 123.66, 115.58, 61.70, 53.37,
21.81. IR (KBr): 3437, 2873, 2053, 1611, 1459, 1315,
1276, 1234, 1188, 1053, 1026, 832, 811, 717. Anal. Calcd
for C24H21N5O (395.47): C, 72.89; H, 5.35; N, 17.71; found:
C, 73.05; H, 5.40; N, 17.98.
4.15 | 2‐(4‐((1‐Phenyl‐1H‐1,2,3‐triazol‐4‐yl)
methoxy)phenyl)‐1H‐benzo[d]imidazole
(4f)[12]
Pale yellow; mp 222–224. 1H NMR (DMSO‐d6, 250 MHz):
δ= 12.744 (s, 1H), 8.986 (s, 1H), 8.136 (d, J = 9.0 Hz, 2H),
7.884–7.930 (m, 2H), 7.486–7.624 (m, 5H), 7.246 (d,
J = 8.70 Hz, 2H), 7.128–7.180 (m, 2H), 5.330 (s, 2H). 13C
NMR (DMSO‐d6, 75 MHz): δ = 159.81, 151.73, 144.13,
137.04, 130.43, 129.31, 128.54, 123.60, 123.52, 120.69,
115.67, 61.65. IR (KBr): 3156, 3008, 2885, 1610, 1499,
1477, 1450, 1438, 1243, 1217, 1181, 1023, 1004, 835, 749.
Anal. Calcd for C22H17N5O (367.14): C, 71.92; H, 4.66;
N, 19.06; found: C, 72.08; H, 4.71; N, 19.34.
4.12 | 2‐(4‐((1‐Benzyl‐1H‐1,2,3‐triazol‐4‐yl)
methoxy)‐3‐methoxyphenyl)‐1H‐benzo[d]
imidazole (4c)
1
Yellow; mp 212–215. H NMR (DMSO‐d6, 250 MHz): δ=
12.764 (s, 1H), 8.305 (s, 1H), 7.702–7.774 (m, 2H), 7.606–
7.640 (m, 1H), 7.480–7.506 (m, 1H), 7.141–7.401 (m,
8H), 5.613 (s, 2H), 5.194 (s, 2H), 3.839 (s, 3H). 13C NMR
(DMSO‐d6, 75 MHz): δ = 151.86, 149.66, 149.38, 143.25,
136.47, 129.27, 128.67, 128.48, 125.42, 123.75, 119.58,
114.05, 110.43, 62.17, 56.02, 53.35. IR (KBr): 3425, 3202,
3150, 1607, 1501, 1478, 1466, 1454, 1430, 1331, 1268,
1247, 1162, 1049, 1428, 835, 813, 744, 709. Anal. Calcd
for C24H21N5O2 (411.47): C, 70.06; H, 5.14; N, 17.02;
found: C, 70.12; H, 5.53; N, 17.82.
4.16 | 2‐(3‐Methoxy‐4‐((1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)methoxy)phenyl)‐1H‐benzo[d]
imidazole (4 g)
Pale yellow; mp 226–228. 1H NMR (DMSO‐d6, 250 MHz):
δ= 12.000 (s, 1H), 8.968 (s, 1H), 7.910 (d, J = 8.5 Hz, 2H),

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SHARGHI ET AL.
7.741–7.898 (m, 2H), 7.450–7.621 (m, 5H), 7.367 (d,
J = 8.2 Hz, 1H), 7.152–7.187 (m, 2H), 5.295 (s, 2H),
3.866 (s, 2H). 13C NMR (DMSO‐d6, 75 MHz):
δ = 149.68, 149.39, 144.06, 137.01, 130.42, 129.56,
129.32, 129.20, 123.69, 122.46, 120.69, 119.68, 114.06,
110.49, 62.02, 56.06. IR (KBr): 3261, 1707, 1599, 1499,
1470, 1328, 1290, 1267, 1241, 1149, 1010, 878, 846, 746.
Anal. Calcd for C23H19N5O2 (397.44): C, 69.51; H, 4.82;
N, 17.62; found: C, 68.88; H, 4.91; N, 17.63.
128.50, 127.67, 126.53, 125.89, 124.86, 123.45, 122.34,
115.61, 66.74, 63.56, 61.81. IR (KBr): 3415, 3142, 3091,
1754, 1611, 1500, 1479, 1440, 1255, 1190, 1053, 834, 739.
Anal. Calcd for C24H21N5O2 (411.47): C, 70.06; H, 5.14;
N, 17.02; found: C, 70.27; H, 5.20; N, 17.21.
4.20 | 2‐(4‐((4‐(5‐Methyl‐1H‐benzo[d]
imidazol‐2‐yl)phenoxy)methyl)‐1H‐1,2,3‐
triazol‐1‐yl)‐1‐phenylethanol (4 k)
1H NMR (CDCl3, 250 MHz): δ= 12.598 (s, 1H), 8.471 (s,
1H), 8.082 (d, J = 8.5 Hz, 2H), 7.423 (d, J = 7.7 Hz, 1H),
7.317–7.344 (m, 6H), 7.195 (d, J = 8.5 Hz, 2H), 6.973 (d,
J = 8.0 Hz, 1H), 5.813 (dd, J1 = 9.0 Hz, J2 = 4.7 Hz,
1H), 5.357 (t, J = 4.7 Hz, 2H), 5.221 (s, 2H), 4.254–4.356
(m, 1H), 3.967–4.050 (m, 1H), 2.395 (s, 1H). 13C NMR
(CDCl3, 75 MHz): δ = 163.19, 159.54, 151.32, 143.03,
136.40, 131.96, 131.86, 130.13, 128.82, 128.55, 128.32,
127.10, 125.88, 123.73, 123.61, 115.02, 114.72, 114.18,
66.94, 64.10, 61.89, 21.57. IR (KBr): 745, 849, 1058, 1259,
1455, 1605, 3145, 3414. Anal. Calcd for C25H23N5O2
(425.49): C, 70.57; H, 5.45; N, 16.46; found: C, 70.60; H,
5.57; N, 16.59.
4.17 | 5‐Chloro‐2‐(4‐((1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)methoxy)phenyl)‐1H‐benzo[d]
imidazole (4 h)[12]
Pale yellow; mp 254–256. 1H NMR (DMSO‐d6, 250 MHz):
δ= 8.980 (s, 1H), 8.117 (d, J = 8.7 Hz, 2H), 7.889–7.919
(m, 2H), 7.460–7.625 (m, 5H), 7.270 (d, J = 9.0 Hz, 2H),
7.185 (dd, J = 8.5 Hz & 2.0 Hz, 1H), 5.334 (s, 2H). 13C
NMR (DMSO‐d6, 75 MHz): δ = 160.23, 153.02, 144.05,
137.03, 130.43, 129.57, 129.32, 128.83, 126.83, 123.55,
122.76, 122.6, 120.69, 115.78, 61.68. IR (KBr): 3404,
3259, 1609, 1490, 1306, 1247, 1180, 1121,. 1052, 923,
829, 800, 752. Anal. Calcd for C22H16ClN5O (401.85): C,
65.76; H, 4.01; N, 17.43; found: C, 65.91; H, 4.24; N,
17.50.
4.21 | 1‐(4‐((4‐(1H‐Benzo[d]imidazol‐2‐yl)
phenoxy)methyl)‐1H‐1,2,3‐triazol‐1‐yl)‐3‐
phenoxypropan‐2‐ol (4 l)
4.18 | 5‐Chloro‐2‐(3‐methoxy‐4‐((1‐phenyl‐
1H‐1,2,3‐triazol‐4‐yl)methoxy)phenyl)‐1H‐
benzo[d]imidazole (4i)
1H NMR (CDCl3, 250 MHz): δ = 7.637 (d, J = 3.50, 1H),
7.546 (t, J = 7.75, 1H), 7.234–7.342 (m, 1H), 7.095–7.161
(m, 3H), 6.953–7.006 (m, 2H), 6.826 (t, J = 7.50, 1H),
6.660–6.736 (m, 5H), 4.789 (s, 2H), 4.421–4.509 (m, 1H),
4.244–4.265 (m, 2H), 3.817–3.930 (m, 3H). 13C NMR
(CDCl3, 75 MHz): δ = 53.29, 61.77, 68.39, 69.94, 114.91,
115.03, 121.31, 123.52, 126.21, 129.95, 129.99, 131.72,
136.64, 142.724, 143.07, 154.10, 158.76, 158.85, 159.63.
Anal. Calcd for C25H23N5O3 (485.55): C, 68.01; H, 5.25;
N, 15.86; found: C, 68.25; H, 5.07; N, 15.93.
Pale yellow; mp 231–233. 1H NMR (DMSO‐d6,
250 MHz): δ= 12.900 (s, 1H), 8.964 (s, 1H), 7.920 (d,
J = 7.5 Hz, 2H), 7.745 (d, J = 10.5 Hz, 2H), 7.451–
7.620 (m, 5H), 7.367 (d, J = 8.2 Hz, 1H), 7.184 (d,
J = 8.5 Hz, 1H), 5.293 (s, 2H), 3.856 (s, 2H). 13C NMR
(DMSO‐d6, 75 MHz): δ = 149.69, 149.66, 144.02, 137.02,
130.42, 129.56, 129.31, 126.67, 123.71, 123.28, 122.60,
120.69, 119.89, 114.05, 110.54, 62.05, 56.08. IR (KBr):
3428, 3159, 1600, 1460, 1431, 1328, 1276, 1257, 1161,
1052, 926, 833, 804, 762. Anal. Calcd for C23H18ClN5O2
(431.88): C, 63.97; H, 4.02; N, 16.22; found: C, 64.08;
H, 4.35; N, 16.41.
4.22 | 2‐(4‐((2‐(1H‐Benzo[d]imidazol‐2‐yl)
phenoxy)methyl)‐1H‐1,2,3‐triazol‐1‐yl)‐1‐
phenylethanol (4 m)
Yellow; mp 192–195. 1H NMR (DMSO‐d6, 250 MHz):
δ = 12.241 (s, 1H), 8.453 (s, 1H), 8.262–8.297 (m, 1H),
7.531–7.660 (m, 2H), 7.424–7.430 (m, 2H), 7.088–7.307
(m, 8H), 5.831 (q, J = 4.50, 1H), 5.525 (s, 2H), 5.335 (t,
J = 5.50, 1H), 4.221–4.326 (m, 1H), 3.951–4.036 (m, 1H).
13C NMR (DMSO‐d6, 75 MHz): δ = 149.43, 143.17,
137.70, 131.63, 130.42, 129.14, 128.75, 127.59, 124.33,
121.99, 119.32, 119.07, 114.52, 112.22, 66.77, 63.58,
62.84. IR (KBr): 3418, 3249, 1601, 1462, 1446, 1284,
1253, 1131, 1095, 1076, 847, 811, 744. Anal. Calcd for
4.19 | 2‐(4‐((4‐(1H‐Benzo[d]imidazol‐2‐yl)
phenoxy)methyl)‐1H‐1,2,3‐triazol‐1‐yl)‐1‐
phenylethanol (4j)
1
Yellow; mp 241–244. H NMR (DMSO‐d6, 250 MHz): δ=
12.745 (s, 1H), 8.476 (s, 1H), 8.110 (d, J = 8.2 Hz, 2H),
7.520–7.605 (m, 2H), 7.141–7.348 (m, 9H), 5.800–5.851
(m, 1H), 5.352 (t, J = 4.5 Hz, 2H), 5.229 (s, 2H), 4.256–
4.400 (m, 1H), 3.985–4.032 (m, 1H). 13C NMR (DMSO‐
d6, 75 MHz): δ = 159.93, 142.71, 137.77, 129.17, 128.79,

SHARGHI ET AL.
13 of 14
[2] M. Tavassoli, A. Landarani‐Isfahani, M. Moghadam, S.
Tangestaninejad, V. Mirkhani, I. Mohammadpoor‐Baltork,
Appl. Catal., A 2015, 503, 186.
C24H21N5O2 (411.47): C, 70.06; H, 5.14; N, 17.02; found:
C, 70.18; H, 5.24; N, 17.29.
[3] C. You, F. Yao, T. Yan, M. Cai, RSC Adv. 2016, 6, 43605.
[4] Y. Lin, M. Cai, Z. Fang, H. Zhao, Tetrahedron 2016, 72, 3335.
4.23 | 2‐(4‐((4‐(1H‐Benzo[d]imidazol‐2‐yl)‐
2‐methoxyphenoxy)methyl)‐1H‐1,2,3‐
triazol‐1‐yl)‐1‐phenylethanol (4n)
[5] E. Ozkal, S. Ozcubukcu, C. Jimeno, M. A. Pericas, Catal. Sci.
Technol. 2012, 2, 195.
[6] B. Yang, Z. Mao, X. Zhu, Y. Wan, Catal. Commun. 2015, 60, 92.
Pale brown; mp 185–188. 1H NMR (DMSO‐d6, 250 MHz):
δ = 7.134–7.180 (m, 2H), 5.789–5.844 (m, 1H), 5.349 (t,
J = 5.25, 1H), 5.189 (s, 2H), 4.249–4.353 (m, 1H), 3.954–
4.037 (m, 1H), 3.837 (s, 3H). 13C NMR (DMSO‐d6,
62.9 MHz): δ = 151.86, 149.68, 149.48, 142.68, 137.81,
129.16, 128.77, 127.69, 126.54, 125.00, 123.76, 122.71,
122.64, 122.04, 119.60, 119.02, 114.07, 111.51, 110.45,
66.72, 63.59, 62.30, 56.02. IR (KBr): 3412, 3149, 1606,
1449, 1267, 1179, 1155, 1029, 1007, 850, 812, 742. Anal.
Calcd for C25H23N5O3 (441.49): C, 68.01; H, 5.25; N,
15.86; found: C, 68.42; H, 5.31; N, 16.03.
[7] J. Šebestík, M. Reiniš, J. Ježek, Biomedical Applications of
Peptide‐, Glyco‐ and Glycopeptide Dendrimers, and Analogous
Dendrimeric Structures, Springer Vienna, Vienna 2012 99.
[8] N. El Brahmi, S. El Kazzouli, S. Mignani, M. Bousmina, J. P.
Majoral, Tetrahedron 2013, 69, 3103.
[9] a) P. Singla, V. Luxami, K. Paul, RSC Adv. 2014, 4, 12422. b) P.
Singla, V. Luxami, K. Paul, Bioorg. Med. Chem. 2015, 23, 1691.
c) L. Mohammadi, M. A. Zolfigol, A. Khazaei, M. Yarie, S.
Ansari, S. Azizian, M. Khosravi, Appl. Organomet. Chem
2018, 32, e3933. d) H. Sharghi, J. Aboonajmi, M. Mozaffari,
M. M. Doroodmand, M. Aberi, Appl. Organomet. Chem. 2018,
32, e4124. e) A. Khalafi‐Nezhad, M. Shekouhy, H. Sharghi, J.
Aboonajmi, A. Zare, RSC Adv. 2016, 71, 67281. f) H. Sharghi,
P. Shiri, M. Aberi, Mol. Diversity 2014, 18, 559. g) H. Sharghi,
M. Aberi, M. Khataminejad, P. Shiri, Beilstein J. Org. Chem.
2017, 13, 1977.
4.24 | 2‐(4‐((4‐(1H‐Benzo[d]imidazol‐2‐yl)
phenoxy)methyl)‐1H‐1,2,3‐triazol‐1‐yl)
cyclohexanol (4o)[20]
[10] a) Y. Bansal, O. Silakari, Med. Chem. 2012, 20, 6208. b) B.
Narasimhan, D. Sharma, P. Kumar, Med. Chem. Res. 2012, 21,
269.
1H NMR (DMSO‐d6, 250 MHz): δ = 8.223 (s, 1H), 8.102
(d, J = 8.7 Hz, 2H), 7.530–7.567 (m, 2H), 7.147–7.231
(m, 4H), 5.199 (s, 2H), 4.98 (s, 1H), 3.98–4.26 (m, 2H),
2.475–2.489 (m, 2H), 1.690–1.979 (m, 4H), 1.171–1.321
(m, 2H). 13C NMR (DMSO‐d6, 62.9 MHz) δ = 159.51,
151.20, 141.50, 139.11, 128.02, 123.91, 122.64, 121.89,
115.03, 114.69, 71.27, 65.84, 61.30, 34.74, 31.86, 24.36,
23.72. IR (KBr): 745, 833, 1,077, 1,178, 1,248, 1,441,
1,499, 1,613, 2,855, 2,933, 3,151, 3,415. Anal. Calcd for
C22H23N5O2 (389.19): C, 67.85; H, 5.95; N, 17.98; found:
C, 67.87; H, 5.91; N, 17.98.
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Wang, X. Han, Z. Zhou, Expert Opin. Ther. Pat. 2015, 25, 595.
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3605. d) H. Sharghi, P. Shiri, Synthesis 2015, 26, 1131. e) S.
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ACKNOWLEDGEMENT
[15] a) H. Sharghi, M. Aberi, P. Shiri, Appl. Organomet. Chem. 2017,
31, e3761. b) H. Sharghi, P. Shiri, M. Aberi, Synthesis 2014, 46,
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Shiri, J. Iran. Chem. Soc 2018, Inpress, doi: https://doi.org/
10.1007/s13738‐018‐1308‐0
The financial support of this work was prepared by the
Shiraz University Research Council and the Iran National
Elite Foundation.
ORCID
[16] a) Z. Li, S. Wu, H. Ding, D. Zheng, J. Hu, X. Wang, Q. Huo, J.
Guan, Q. Kan, New J. Chem. 2013, 37, 1561. b) M. M. Islam, P.
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Hashem Sharghi http://orcid.org/0000-0001-6772-3332
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How to cite this article: Sharghi H, Aberi M,
Shiri P. Supported benzimidazole‐salen Cu(II)
complex: An efficient, versatile and highly reusable
nanocatalyst for one‐pot synthesis of hybrid
molecules. Appl Organometal Chem. 2018;e4446.
https://doi.org/10.1002/aoc.4446
[20] H. Sharghi, M. Aberi, M. M. Doroodmand, J. Iran. Chem. Soc.
2012, 9, 189.
SUPPORTING INFORMATION
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