Synthesis of nanomagnetic supported thiourea–copper(I) catalyst and its application in the synthesis of triazoles and benzamides

Article abstract of DOI:10.1002/aoc.3933

A novel nanomagnetic supported thiourea–copper(I) complex and inorganic–organic Takemoto-like hybrid nanomagnetic catalyst was designed, and synthesized. The prepared naomagnetic catalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, energy-dispersive X-ray analysis, transmission and scanning electron microscopies, thermogravimetry, nitrogen adsorption/desorption, zeta potential and vibrating sample magnetometry. Furthermore, the fabricated dual-role inorganic–organic hybrid catalyst shows a striking and robust catalytic activity for the synthesis of triazoles and benzamides through click and coupling reactions, respectively, under mild and eco-friendly reaction conditions.

Full text of DOI:10.1002/aoc.3933

Received: 25 January 2017
DOI: 10.1002/aoc.3933
Revised: 18 May 2017
Accepted: 20 May 2017
F U L L PA P E R
Synthesis of nanomagnetic supported thiourea–copper(I) catalyst
and its application in the synthesis of triazoles and benzamides
Leila Mohammadi1 | Mohammad Ali Zolfigol1
| Ardeshir Khazaei1
| Meysam Yarie1
|
Samira Ansari2 | Saeid Azizian1 | Maryam Khosravi1
1 Faculty of Chemistry, Bu‐Ali Sina
University, Hamedan 6517838683, Iran
2 Cinnagen Medical Biotechnology Research
Center, Alborz University of Medical
Science, Karaj, Iran
A novel nanomagnetic supported thiourea–copper(I) complex and inorganic–
organic Takemoto‐like hybrid nanomagnetic catalyst was designed, and synthesized.
The prepared naomagnetic catalyst was characterized using Fourier transform infra-
red spectroscopy, X‐ray diffraction, energy‐dispersive X‐ray analysis, transmission
and scanning electron microscopies, thermogravimetry, nitrogen adsorption/desorp-
tion, zeta potential and vibrating sample magnetometry. Furthermore, the fabricated
dual‐role inorganic–organic hybrid catalyst shows a striking and robust catalytic
activity for the synthesis of triazoles and benzamides through click and coupling
reactions, respectively, under mild and eco‐friendly reaction conditions.
Correspondence
Mohammad Ali Zolfigol and Ardeshir
Khazaei, Faculty of Chemistry, Bu‐Ali Sina
University, Hamedan 6517838683, Iran.
Email: zolfi@basu.ac.ir; mzolfigol@yahoo.
com; khazaei_1326@yahoo.com
Funding information
Iran National Science Foundation (INSF),
Grant/Award Number: 940124
KEYWORDS
benzamides, eco‐friendly reaction conditions, nanomagnetic catalyst, thiourea–copper(I) complex, triazoles
1 | INTRODUCTION
make them more impressive than their homogeneous
analogues.[5]
Nowadays, nanosized chemistry has manifested itself as an
evolving and developing area in modern research fields and
includes the preparation and applications of nanoparticles
as catalysts or appropriate supports.[1] Also, nanochemistry
has found a key role in the improvement of materials via
adjusting the size, shape, porosity and surface modifica-
tion.[2] A disadvantage of unsupported nanosized materials
is their aggregation during a catalytic process. Therefore, sur-
face stabilization is unavoidable. One of the most common
methods for stabilizing nanomaterials is their immobilization
onto appropriate magnetic supports in order to enhance stabi-
lization and recycling possibility.[3]
Due to many benefits such as environmentally mild
nature, excellent thermal and mechanical stability, insolubil-
ity in most common solvents, easy handling and mass pro-
duction, much attention has been paid to magnetic
nanoparticles as a superior alternative for support materials
in the field of green chemistry.[4] Also, heterogeneous
nanomagnetic‐based catalysts exhibit outstanding catalytic
reliability with high recovery and reusability potential that
Over the last decade, hybrid inorganic–organic skeleton
architectures have emerged as an influential branch in solid‐
state chemistry. As a definition, hybrid inorganic–organic
compounds are considered as materials that have both inor-
ganic and organic parts in their structures.[6] In addition,
hybrid frameworks have also been applied in gas storage, as
heterogeneous catalysts, in photoluminescence and as porous
magnets.[6–8] Therefore, reporting a new inorganic–organic
heterogeneous hybrid nanomagnetic catalyst which has all
the merits of both heterogeneous nanomagnetic systems and
hybrid materials is valuable.
In recent years, the use of thiourea (urea) organocatalysis
(Takemoto‐type catalysis) in order to accelerate and alter the
stereochemical features of organic transformations has been
well considered. A striking dimension of Takemoto‐type
catalysis is the ability of thiourea (urea) moiety to form
hydrogen‐bonding interactions in mechanistic pathways of
reactions. In addition to the importance of hydrogen‐bonding
interactions in chemical reactions, it is worth mentioning that
they play a key role in biological processes which occur in
Appl Organometal Chem. 2017;e3933.
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https://doi.org/10.1002/aoc.3933

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MOHAMMADI ET AL.
living organisms and the chemistry of life.[9–29] Therefore,
heterogenization of Takemoto‐type catalysts by grafting onto
the surface of suitable nanomagnetic supports can add merits
to them and is of importance.
Production of triazole derivatives through the common
Huisgen cycloaddition reaction by the reaction of azides
and terminal alkynes suffers from some disadvantages like
Due to the multidimensional capabilities of l,2,3‐triazoles
in the field of medicinal and industrial chemistry, much atten-
tion has been focused on these versatile heterocyclic drug
candidate materials. Triazoles have been used as bioactive
compounds, agrochemicals, dyes, photographic active com-
pounds, energetic materials and corrosion inhibitors.[30]
SCHEME 4 Preparation of amides in the presence of novel catalyst C
SCHEME 1 Some examples of high‐value molecules bearing
FIGURE 1 FT‐IR spectra of different stepwise produced materials
for the synthesis of desired catalyst C
triazole moieties[33]
SCHEME 2 Preparation of novel
nanomagnetic supported thiourea–copper(I)
complex and inorganic–organic Takemoto‐
like hybrid nanomagnetic catalyst C
SCHEME 3 Preparation of 1,2,3‐triazoles in the presence of constructed catalyst C

MOHAMMADI ET AL.
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FIGURE 2 EDX elemental analysis of the novel inorganic–organic hybrid nanomagnetic catalyst C
FIGURE 3 XRD patterns of catalyst in comparison with different stepwise prepared materials
needing a strong electron‐withdrawing group on starting
materials, elevated temperatures and long reaction times with
moderate product yields. Therefore, because of the aforemen-
tioned biological significance and also in order to overcome
the abovementioned drawbacks, the synthesis and chemistry
of l,2,3‐triazoles are well investigated in the literature.[31,32]
Scheme 1 presents some active compounds with triazole
moieties.
One of the most efficient and powerful routes for the syn-
thesis of new C–N linkages is N‐arylation reaction which pro-
ceeds through the coupling reaction of nitrogen nucleophiles
and aryl iodides, bromides and chlorides. In recent years, due
to the industrial and medicinal importance of resulting N‐aryl
heterocyclic molecules, synthesis of these valuable
compounds using metal‐catalysed processes has received
great attention. Among the metal‐catalysed systems used for
C–N bond formation, utilizing copper‐based catalysts, due
to the lower catalyst cost and toxicity, high efficiency and
compatibility with large‐scale goals is highly appealing.[34,35]
Despite the abovementioned merits, N‐arylation of amides
TABLE 1 XRD extracted data for the novel hybrid catalyst
2θ
Peak width
Size
Interplaner
Entry
(°)
(FWHM) (°)
(nm)
distance (nm)
1
2
3
4
25.5
28.4
42.2
49.9
0.22
0.16
0.30
0.40
37
51
28
21
0.35
0.31
0.21
0.18

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MOHAMMADI ET AL.
using copper‐catalysed protocols (Goldberg‐type amidation)
is limited due to some disadvantages such as needing strong
bases like NaH, necessity of high operational reaction tem-
perature, poor scope of generality, requirement for highly
polar solvents and large amount of copper reagent or nucleo-
phile. Scientific research has disclosed that using certain
organic ligands can impressively enhance the amidation reac-
tions. This issue leads to a resurgence in interest in exploring
FIGURE 4 SEM micrographs of (a, b) hybrid catalyst C and (c, d) related intermediate B. (e, f) TEM images of prepared catalyst C

MOHAMMADI ET AL.
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and developing novel and greener methods including copper‐
catalysed systems as an alternative for high‐cost palladium‐
based catalytic systems for N‐arylation reactions.[36–38]
In this report, we follow our previous efforts for present-
ing greener and more productive procedures for the synthesis
of potential bioactive species and extend our approach
towards design, synthesis and application of screening
knowledge‐based developed task‐specific nanomagnetic
reusable catalytic systems as promoters.[39] In the work
reported herein, we investigated the design and synthesis of
a
novel
inorganic–organic
Takemoto‐like
hybrid
nanomagnetic catalyst C (Scheme 2) and probed the applica-
bility of the resulting nanomagnetic core–shell catalyst for
the preparation of 1,2,3‐triazoles through a click reaction
FIGURE 6 TGA curve of novel core–shell catalyst
FIGURE 7 Magnetization curves of the catalyst in comparison with
Fe3O4 nanoparticles and compounds a and B
FIGURE 8 Zeta potential analysis for the prepared catalyst
TABLE 2 Screening reaction conditions for synthesis of triazoles
Entry
Catalyst load (g)
Solvent
—
—
Water
Water
EtOH
MeOH
MeCN
Time (h)
Yield (%)
1
2
3
4
5
6
7
0.01
0.05
0.02
0.05
0.01
0.01
0.02
5
40
60
90
92
50
50
90
5
1
0.75
8
8
1.5
aReaction conditions: bromomethylbenzene (1 mmol, 0.170 g), ethynylbenzene
(1 mmol, 0.102 g) and sodium azide (1 mmol, 0.065 g), r.t.
bIsolated yields.
FIGURE 5 (a) BET surface area analysis and (b) pore size
distribution calculated based on BJH method

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MOHAMMADI ET AL.
TABLE 3 Synthesis of desired triazole products 2a–j in presence of nanomagnetic catalyst C
Entry
Halide
Product
2a
Structure
Time (h)
Yield (%)
M.p. (°C)
1
0.5
92
129–130
2
3
2b
2c
1
90
85
144–145
98–101
1.5
4
5
2d
2e
1
90
90
70–73
0.5
150–153
6
7
2f
0.5
1.5
85
89
90–92
85–87
2 g
8
9
2 h
2i
1.5
1.5
90
88
60–63
90–92
10
2j
1
90
106–109
(Continues)

MOHAMMADI ET AL.
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TABLE 3 (Continued)
Entry
Halide
Product
2 k
Structure
Time (h)
Yield (%)
M.p. (°C)
11
7
90
104–105
aReaction condition: halides (1 mmol), alkynes (1 mmol) and sodium azide (1 mmol, 0.065 g), r.t.
bIsolated yields.
and benzamide derivatives through a C–N coupling reaction
(Schemes 3 and 4).
Based on SEM images, the size and morphology of
the prepared hybrid catalyst were investigated. From
Figure 4(a,b), it is revealed that the size of the catalyst
particles is less than 70 nm. Also, in order to study the
structure of the catalyst in more detail, TEM was used.
The images (Figure 4e,f) show that the catalyst nanoparti-
cles have a uniform spherical shape with nanometric
scales.
Based on the absorption/desorption of nitrogen, some of
the structural properties of the prepared catalyst were
obtained. The obtained BET surface area, total pore volume
and mean pore diameter of the prepared catalyst are
22.8 m2 g−1, 0.096 cm3 g−1 and 16.8 nm, respectively
(Figure 5a). The pore size distribution calculated based on
the BJH method is shown in Figure 5(b). This figure shows
the pore radius is mainly between 2 and 20 nm, which indi-
cates the catalyst is mesoporous.
2 | RESULTS AND DISCUSSION
The structure of the prepared nanomagnetic inorganic–
organic Takemoto‐like hybrid catalyst was investigated using
suitable techniques such as Fourier transform infrared (FT‐
IR) spectroscopy, X‐ray diffraction (XRD), transmission
electron microscopy (TEM) and scanning electron micros-
copy (SEM). All these methods confirmed the formation of
knowledge‐based designed catalyst and the obtained data
are discussed henceforth in detail.
In a comparative mode, as shown in Figure 1, the FT‐IR
spectra of different stepwise produced materials for the syn-
thesis of desired catalyst C were investigated in the range
400–4000 cm−1. The overall changes in the FT‐IR spectra
from Fe3O4 to the prepared catalyst can be considered as
proof for the successful construction of the desired catalyst
C.[39i] Also, the S═O stretching mode is confirmed by
observing a signal at 1650 cm − 1, and an absorption band
at 1286 cm−1 can be ascribed to the vibration of CF3
stretching mode.[40] The existence of uncoated hydroxyl
and amino groups can be verified by the broad absorption
In order to investigate the thermal stability and deter-
mine the mass loss during decomposition process of the
novel hybrid core–shell catalyst C, thermogravimetric
TABLE 4 Reaction conditions for synthesis of secondary amides 3a–f
Catalyst
load (g)
Temperature
(°C)
Yield
(%)
Entry
Solvent
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
Base
KOH
at 2800–3600 cm−1
.
1
0.01
80
80
80
80
r.t.
50
120
80
80
80
80
80
80
50
90
85
85
—
30
20
5
For elemental characterization of the prepared inorganic–
organic hybrid nanomagnetic catalyst C, energy dispersive
X‐ray (EDX) analysis was applied (Figure 2). The result from
elemental analysis verifies the existence of all expected ele-
ments comprising iron, oxygen, phosphorus, carbon, nitro-
gen, sulfur, fluorine, copper and iodine.
The obtained XRD patterns of the prepared catalyst and
its precursors are presented in Figure 3. The XRD pattern
shows that the prepared hybrid catalyst has a crystalline
nature and the related diffraction lines appear at 2θ = 25.5°,
28.4°, 42.2° and 49.9°. Furthermore, using the Scherrer equa-
tion, D = Kλ/(βcos θ), where λ is the X‐ray wavelength, K is
the Scherrer constant, β is the peak width at half maximum
and θ is the Bragg diffraction angle, the crystal size and
interplanar distance were calculated and are listed in
Table 1.
2
0.05
KOH
3
0.02
KOH
4
0.015
0.015
0.015
0.015
0.015
0.015
0.015
0.015
0.015
0.015
KOH
KOH
5
6
KOH
7
KOH
8
K2CO3
KOH
9
20
10
40
75
‐
10
11
12
13
Toluene
Toluene
MeCN
H2O
K2CO3
CsCO3
CsCO3
KOH
aReaction conditions: benzamide (1 mmol, 0.121 g), iodobenzene (1 mmol,
0.204 g), base (1 mmol).
bIsolated yields.

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MOHAMMADI ET AL.
TABLE 5 Synthesis of desired banzamide products 3a–h in presence of nanomagnetic catalyst C
Entry
Arykalide
Product
3a
Structure
Time (h)
Yield (%)
M.p. (°C)
1
12
85
150–153
2
3b
12
85
130–132
3
4
3c
24
12
60
80
250–255
220–221
3d
5
3e
12
73
159–160
6
7
3f
12
12
75
75
176–178
123–125
3 g
8
3 h
24
85
193–196
9
3a
3a
24
24
70
60
150–153
150–153
10
aReaction condition: aryl halides (1 mmol), amides (1 mmol), 80 °C.
bIsolated yields.
analysis (TGA) was conducted. The TGA plot is shown in
Figure 6. The TGA plot shows insignificant weight loss
from room temperature to about 200°C which can be attrib-
uted to evaporation of water or trapped organic solvents
during the synthesis of the catalyst. Also, a mass loss
between 280 and 350°C (about 35%) can be attributed to
the decomposition and separation of the organic–inorganic
complex anchored to the surface of Fe3O4 nanoparticles.
Therefore, the prepared hybrid catalyst preserves its cata-
lytic performance at elevated temperatures as can be
inferred from the TGA curve.
The magnetic properties of the materials used in the
prepared from Fe3O4 nanoparticles to desired catalyst C
were investigated using vibrating sample magnetometry.

MOHAMMADI ET AL.
9 of 13
The obtained results are presented in Figure 7. During the
preparation route, by anchoring different layers, the satura-
tion magnetization diminished. In the case of catalyst C,
the related profile indicates a saturation magnetization of
25.5 emu g−1 which guarantees the facile separation of
the magnetic hybrid catalyst from a reaction mixture by
applying a simple magnet.
As in the case of triazole preparation, the synthesis of
secondary amide derivatives 3a–f was screened in the
presence of the described catalyst C. For this goal, ini-
tially, we determined the optimal reaction conditions.
Therefore, for the reaction of benzamide and iodobenzene
TABLE 6 Reusability for synthesis of triazole 2a
The data obtained from inductively coupled plasma
analysis confirmed the stability of the catalyst and did
not show any meaningful leaching of Cu from the surface
of the catalyst (in the case of synthesis, the release of Cu
from the surface of the catalyst after five reuse runs is
10−6 mol% (0.015 g of catalyst consisting of 5 mol%
Cu), and in the case of triazole synthesis the leaching
of Cu from the surface of the catalyst after five reuse
runs is 2 × 10−7 mol% (0.02 g of catalyst consisting of
6.5 mol% Cu)).
To determine the surface charge of the catalyst, the
zeta potential was measured. The resulting data show that
the zeta potential for the prepared catalyst is −2.09 mV
indicating the surface charge of catalyst in nearly neutral
(Figure 8).
Entry Recycling run Reaction time (min) Isolated yield (%)
1
2
3
4
5
6
7
8
9
1
2
3
4
5
6
7
8
9
90
90
95
90
90
90
87
85
80
80
80
90
90
105
120
120
120
120
aReaction conditions: bromomethylbenzene (1 mmol, 0.170 g), ethynylbenzene
(1 mmol, 0.102 g) and sodium azide (1 mmol, 0.065 g), r.t.
After completion of investigation and confirmation of the
structure of the presented nanomagnetic core–shell catalyst
C, its catalytic activity was screened in the synthesis of
triazoles and benzamides through click and coupling
reactions, respectively, under mild and eco‐friendly reaction
conditions.
Firstly, in the case of triazole derivatives, in order to
find the best operational reaction conditions, the reaction
of bromomethylbenzene, ethynylbenzene and sodium azide
was selected as a model reaction. The reaction was carried
out at ambient temperature in various solvents including
water, ethanol, methanol and acetonitrile and in the
presence of various amounts of catalyst. The obtained data
are collected in Table 2. From the results, it can be
inferred that the optimal reaction conditions are room tem-
perature using 0.02 g of the novel Takemoto‐like catalyst
in water as solvent (Table 2, entry 3). Also, the reaction
was tested using CuI salt as the catalyst, but, in compari-
son with the prepared catalyst, the obtained data were not
satisfactory and catalyst C shows better performance than
CuI salt (20 h, 90%).
FIGURE 9 Reusability of catalyst C for synthesis of desired
product 3a
Subsequently, in order to evaluate the generality and the
versatility of the presented protocol for the preparation of
target triazoles 2a–j, three halides 1a–c were reacted with
various alkynes and NaN3 under optimized reaction condi-
tions. The data obtained are presented in Table 3. The
obtained information verifies that all desired target triazole
derivatives 2a–j are produced in relatively short reaction
times with good to excellent yields. It is worth mentioning
that the target molecules derived from phenylacetylene
derivatives show better experimental data.
FIGURE 10 Mechanistic pathway for the synthesis of target
compounds 3a–h

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MOHAMMADI ET AL.
TABLE 7 Comparison of novel nanomagnetic catalyst and other systems for synthesis of compound 2a
Entry
Reaction conditions
Thiourea supported copper(I) chloride complex (2 mol%), water, r.t.
[CuBr(PPh3)3] (0.5 mol%), neat, r.t.
Time (min)
180
Yield (%)
Ref.
[32a]
1
2
93
99
95
99
99
96
88
91
86
92
180
[32b]
[32c]
3
Copper(I) isonitrile complex (2 mol%), water, r.t.
LCO NPs/water, sonication
120
4
15
[32d]
[32e]
5
FMNPs@TD‐cu(II), EtOH–H2O/Na2CO3, 25 °C
CuNPs@agarose (0.05 mol% cu), water, 40 °C
Cu2S‐PANI (5 mol% cu), MeOH, UV
CuSO4.5H2O (5 mol%), Na ascorbate (5 mol%), MonoPhos (1.1 mol%), DMSO/H2O (1:3)
Copper(I)‐tren ([CuI] 0.05 mol%), toluene, 60 °C
Novel nanomagnetic catalyst C (0.02 g), water, r.t.
15
6
480
[32f]
7
120
[32g]
[32h]
[32i]
8
60
9
1440
30
10
This work
in 12 h, the operational temperature, solvents, bases and
amount of catalyst were investigated. The resulting data
are presented in Table 4. It can be deduced that the new
catalyst exhibited good performance for the preparation
of target compounds 3a–f in DMSO as reaction medium
at 80°C.
In the next step, with optimal reaction conditions in
hand, we investigated the efficiency and capability of the
procedure for the synthesis of secondary amide derivatives.
A good range of target molecules were obtained by the
reaction of various aryl halides and benzamide derivatives
under optimized reaction conditions with good to high
yields. The resulting data are collected in Table 5. The
obtained experimental data indicate that the coupling
reactions using aryl iodide as precursor present better
results compared with other aryl halides. Also, this
method is applicable for chlorobenzene precursor (Table 5,
entry 10).
The facile separation of a catalyst from a reaction
mixture is an outstanding merit connected with con-
structed catalysts using magnetic nanoparticles as support.
In the case of the novel nanomagnetic core–shell catalyst
C, in addition to its easy separation from a reaction mix-
ture by applying a simple external magnet, the study of
the reusability potential of the catalyst for both the pre-
sented procedures was successful. In the case of triazole
synthesis, the reusability test was performed for the
reaction of bromomethylbenzene, ethynylbenzene and
sodium azide to yield desired product 2a for nine cycles.
The obtained results confirm the versatility of catalyst C
in reusability test after nine runs as summarized in
Table 6.
The reusability of catalyst C was also examined via the
reaction of benzamide and iodobenzene for the synthesis of
desired product 3a in 12 h. After six recycles and reuses, cat-
alyst C acts as a robust catalyst for the synthesis of target
molecule 3a, and the reuse capability of the prepared catalyst
was verified (Figure 9).
As a mechanistic route for the synthesis of target mole-
cules 3a–h, at first in the nucleophilic coordination step, the
amide used throughout the reaction with base generates the
deprotonated nucleophile species which coordinate to
copper(I) to yield complex intermediate I. The reaction of
this intermediate with aryl halide leads to intermediate II.
In another mechanistic pathway, the intermediate III
through an oxidative addition of aryl halide and Cu‐based
catalyst is generated, and the second coordination process
gives the Cu(III)‐based complex II. Finally, reductive
elimination process of intermediate II yields the desired
products 3a–h and regenerates the catalyst C. It is worth
mentioning that compared with cross‐coupling reactions
catalysed by Pd(0), the oxidative addition step occurs before
the trans‐metalation step. But in the copper‐catalysed cyclic
system both of the routes of Figure 2 are acceptable (due to
unpredictability of the relative order of these two steps). A
schematic representation of the abovementioned mechanistic
aspect is portrayed in Figure 10.[41]
In order to explore the utility of the new protocol for tri-
azole synthesis in comparison with other procedures
reported in the literature, the case of target molecule 2a
was used and a comparison of data is provided in Table 7.
The collected data indicate that our presented method pro-
vides results that compare favourably with other reported
protocols.
3 | CONCLUSION
In summary, the design and synthesis of a novel inorganic–
organic Takemoto‐like hybrid nanomagnetic catalyst were
reported. Also, the application of the prepared catalyst C
was successful in the synthesis of triazoles and benzamides
through click and coupling reactions, respectively, under
mild and eco‐friendly reaction conditions. Moreover, the
catalyst shows high potential for recycling and reuse for both
mentioned reactions.

MOHAMMADI ET AL.
11 of 13
reaction mixture using an external magnet and the residue
was purified using chromatography with a mixture of ethyl
acetate and n‐hexane (50/50) as eluent system. The desired
products were obtained in good to high isolated yields as
listed in Table 6.
4 | EXPERIMENTAL
4.1 | General procedure for construction of
inorganic–organic Takemoto‐like hybrid
Nanomagnetic catalyst C (Scheme 2)
Fe3O4 nanoparticles and intermediate A were produced
according to previously reported methods.[42,43] Afterwards,
a mixture of isothiocyanate (1.84 mmol, 0.5 g) and DBU
(0.27 g, 1.84 mmol) in dry dichloromethane was added to a
dispersed solution of 0.5 g of nanomagnetic coated interme-
diate A in dry dichloromethane (2 ml) at 0°C during
20 min. In the next step, the generated mixture was shaken
for 24 h at ambient temperature to afford the desired interme-
diate B. The prepared intermediate B was washed with dry
dichloromethane and dried. Then, CuI (1 mmol, 0.19 g)
was added to intermediate B dispersed in dry dichlorometh-
ane solution. The resulting mixture was shaken for 48 h under
argon atmosphere. Finally, the resulting desired catalyst C
was collected using an external magnet and washed with
absolute ethanol (5 × 5 ml) and dried under vacuum. All
obtained spectral data confirmed the structural formation of
catalyst C.
4.4 | Selected spectral data
1‐Benzyl‐4‐(4‐methoxyphenyl)‐1H‐1,2,3‐triazole
(2b).
White solid; yield 90% (Table 4, entry 2). 1H NMR (CDCl3,
300 MHz, δ, ppm): 3.86 (s, 3H, ─OMe), 5.66 (s, 2H,
triazole‐N‐CH2), 6.97 (d, J = 7.2 Hz, 2H, Ar‐OMe), 7.28
(s, 1H, triazole‐H), 7.46 (d, J = 8.0 Hz, 2H, Ar‐OMe),
7.76–7.68 (m, 3H, ArH), 8.26 (d, J = 7.2 Hz, 2H, ArH).
13C NMR (CDCl3, 126 MHz, δ, ppm): 54.3, 55.4, 114.3,
119.0, 123.4, 127.1, 128.1, 128.8, 129.2, 134.9, 159.7.
ESI‐MS m/z: 265 (M+). Anal. Calcd for C16H15N3O (%):
C 72.43, H 5.89, N 15.82, O 6.03; found (%): C 72.50, H
5.82, N 15.84, O 6.10.
1‐(4‐Nitrobenzyl)‐4‐pentyl‐1H‐1,2,3‐triazole
(2
h).
White solid; yield 90% (Table 4, entry 8). 1H NMR
(CDCl3, 500 MHz, δ, ppm): 0.80 (t, J = 6.5 Hz, 3H,
─CH3), 1.30–1.18 (m, 4H, ─CH2), 1.62–1.53 (m, 2H,
─CH2), 5.55 (s, 2H, triazole‐N‐CH2), 7.28 (s, 1H, tri-
azole‐H), 7.31 (d, J = 8.5 Hz, 2H, Ar‐NO2), 8.13 (d,
J = 8.5 Hz, 2H, Ar‐NO2). 13C NMR (CDCl3, 126 MHz,
δ, ppm): 14.0, 22.4, 25.7, 29.1, 31.5, 53.0, 121.0, 149.5,
124.2, 128.5, 142.3, 148.0. ESI‐MS m/z: 275 (M + 1).
Anal. Calcd for C14H18N4O2 (%): C 61.30, H 6.61, N
20.42, O 11.66; found (%): C 61.15, H 6.66, N 20.47, O
11.71.
4.2 | General method for synthesis of desired
Triazole products 2a–j in presence of
Nanomagnetic catalyst C (Scheme 3)
A solution of aryl halide (1 mmol) and NaN3 (1 mmol,
0.065 g) in water (1.5 ml) was placed in a vial, then catalyst
C (0.02 g) and alkynes (1 mmol) were added to the
resulting mixture. The reaction mixture was stirred at ambi-
ent temperature for 1 h. After completion of the reactions as
monitored by TLC, the nonomagnetic catalyst C was col-
lected from the reaction mixture using an external magnet
and washed with methanol and water successively and pre-
served. Then, for extraction of the products, ethyl acetate
was added to the reaction mixture. Finally, the solvent was
removed and the crude solids obtained were purified using
CH2Cl2 and n‐hexane. The desired products were obtained
in good to excellent isolated yields as presented in
Table 4.
Ethyl 2‐(4‐phenyl‐1H‐1,2,3‐triazol‐1‐yl)acetate (2i).
White solid; yield 88% (Table 4, entry 9). 1H NMR (CDCl3,
500 MHz, δ, ppm): 1.27 (t, J = 7.0 Hz, 3H, ─OEt), 4.25 (q,
J = 7.0 Hz, ─OEt), 5.17 (s, 2H, triazole‐N‐CH2), 7.43–7.36
(m, 3H, ArH), 7.91–7.79 (m, 2H, ArH), 7.97 (s, 1H, tri-
azole‐H). 13C NMR (CDCl3, 126 MHz, δ, ppm): 14.2, 51.2,
62.6, 126.0, 128.4, 129.0, 130.6, 166.2. ESI‐MS m/z: 231
(M+). Anal. Calcd for C12H13N3O2 (%): C 62.33, H 5.67, N
18.17, O 13.84; found (%): C 62.39, H 5.61, N 18.10, O
13.82.
Ethyl 2‐(4‐(4‐methoxyphenyl)‐1H‐1,2,3‐triazol‐1‐yl)ace-
tate (2j). Colourless solid; yield 90% (Table 4, entry 10).
1H NMR (CDCl3, 500 MHz, δ, ppm): 1.26 (t, J = 7.0 Hz,
2H, ArH), 3.81 (s, 3H, ArH), 4.29 (q, J = 7.0 Hz, 2H,
─OEt), 5.16 (s, 2H, triazole‐N‐CH2), 7.04–6.82 (m, 2H,
ArH), 7.71–7.90 (m, 4H, ArH and triazole‐H).13C NMR
(CDCl3, 126 MHz, δ, ppm): 13.9, 51.0, 55.5, 62.6, 110.9,
114.4, 123.7, 127.2, 150.4, 159.8, 166.1. ESI‐MS m/z 261
(M+). Anal. Calcd for C13H15N3O3 (%): C 59.76, H 5.79, N
16.08, O 18.37; found (%): C 59.90, H 5.74, N 16.06, O
18.42.
4.3 | General method for synthesis of desired
Banzamide products 3a–h in presence of
Nanomagnetic catalyst C (Scheme 4)
To a round‐bottom flask containing a mixture of amides
(1 mmol), aryl halide (1 mmol) and KOH (1 mmol) as base
in dry DMSO (2 ml), 0.02 g of catalyst C was added. The
resulting mixture was refluxed at 80°C under argon atmo-
sphere for 12 h. After completion of the reactions as moni-
tored by TLC, the catalyst C was separated from the

12 of 13
MOHAMMADI ET AL.
Rabbani, S. Shahrokh, Appl. Organometal. Chem. 2015, 29, 809;
l) A. Maleki, M. Aghaei, N. Ghamari, Appl. Organometal. Chem.
2016, 30, 939.
1,3‐Diphenylurea (3c). Grey solid; yield 65% (Table 6,
entry 3). H NMR (CDCl3, 500 MHz, δ, ppm): 6.85 (s, b,
1
1H, amide), 7.11–7.02 (m, 2H, ArH), 7.16 (brs, 1H, amide),
7.38–7.24 (m, 8H, ArH). 13C NMR (CDCl3, 126 MHz, δ,
ppm): 110.0, 120.9, 121.8, 124.0, 124.10, 129.23, 129.38,
138.2, 156.6. ESI‐MS m/z: 212 (M+). Anal. Calcd for
C13H12N2O (%): C 73.56, H 5.70, N 13.20, O 7.54; found
(%): C 73.40, H 5.74, N 13.30, O 7.56.
N‐(4‐(Trifluoromethyl)phenyl)nicotinamide (3f). White
solid; yield 75% (Table 6, entry 6). 1H NMR (CDCl3,
500 MHz, δ, ppm): 7.55–7.39 (m, 3H), 7.88 (d, J = 8.0 Hz,
1H, pyridine‐H), 7.98 (s, 1H, Ar‐CF3), 8.26 (d, J = 8.0 Hz,
1H, pyridine‐H), 8.38 (s, 1H, pyridine‐H), 8.77 (s, 1H, pyri-
dine‐H), 9.05 (s, 1H, amide). 13C NMR (CDCl3, 126 MHz, δ,
ppm): 117.2, 121.7, 123.7, 124.07, 128.9, 131.0, 131.6,
135.9, 138.1, 147.8, 152.6, 164.6. ESI‐MS m/z: 266 (M+).
Anal. Calcd for C13H9F3N2O (%): C 58.72, H 3.33, F 1.40,
N 10.48, O 6.10; found (%): C, 58.65; H, 3.34; F, 21.46; N,
10.48; O, 6.10.
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N‐(3‐Nitrophenyl)nicotinamide (3 g). Brown solid; yield
75% (Table 6, entry 7). H NMR (CDCl3, 300 MHz, δ,
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1
12672.
ppm): 7.20 (t, J = 7.5 Hz, 1H, pyridine‐H), 7.36 (d,
J = 13.0 Hz, 2H, aromatic) 7.40 (t, J = 12.5 Hz, 1H, aromatic),
7.67 (s, 1H, Ar‐NO2), 7.80 (d, 2H, pyridine‐H), 8.55 (s, 1H,
pyridine‐H), 8.77 (brs, 1H, pyridine‐H), 9.03 (s, 1H, amide),
9.56 (s, 1H, amide). 13C NMR (CDCl3, 126 MHz, δ, ppm):
115.8, 120.1, 126.6, 129.3 × 2, 130.6, 131.4 × 2, 133.0,
136.2, 153.5, 164.3. ESI‐MS m/z: 243 (M+). Anal. Calcd for
C12H9N3O3 (%): C 59.26, H 3.73, N 17.28, O 19.73; found
(%): C 59.35, H 3.70, N 17.2, O 19.6.
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ACKNOWLEDGEMENT
We thank Bu‐Ali Sina University and Iran National Science
Foundation (INSF) for financial support (grant no. 940124)
to our research groups.
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How to cite this article: Mohammadi L, Zolfigol
MA, Khazaei A, et al. Synthesis of nanomagnetic
supported thiourea–copper(I) catalyst and its
application in the synthesis of triazoles and
benzamides. Appl Organometal Chem. 2017;e3933.
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