A Highly Active, Recyclable and Cost-Effective Magnetic Nanoparticles Supported Copper Catalyst for N-arylation Reaction

Article abstract of DOI:10.1007/s10562-019-02929-x

Abstract: The immobilization of a copper complex by covalent anchoring of 2-hydroxybenzophenone on the surface of amine-functionalized magnetic nanoparticles was reported. The structure and morphology of the catalyst was characterized by different techniques such as Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron micrograph (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), vibrating sample magnetometer (VSM) and inductively coupled plasma (ICP) spectroscopy. This efficient and cost effective catalyst was applied in the N-arylation reaction and the products were obtained in good to excellent yields in short reaction times. The cost-effective catalyst demonstrated high stability, which could be facilely separated from the reaction mixture by applying an external magnet and recycled at least four times with only a slight decrease in its activity. Graphic Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-019-02929-x

Catalysis Letters
https://doi.org/10.1007/s10562-019-02929-x
A Highly Active, Recyclable and Cost‑Efective Magnetic Nanoparticles
Supported Copper Catalyst for N‑arylation Reaction
Razieh Zahedi1 · Zahra Asadi1 · Fahimeh Dehghani Firuzabadi1
Received: 11 May 2019 / Accepted: 3 August 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
The immobilization of a copper complex by covalent anchoring of 2-hydroxybenzophenone on the surface of amine-func-
tionalized magnetic nanoparticles was reported. The structure and morphology of the catalyst was characterized by difer-
ent techniques such as Fourier-transform infrared spectroscopy (FT-IR), X-ray difraction (XRD), transmission electron
micrograph (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), vibrating sample
magnetometer (VSM) and inductively coupled plasma (ICP) spectroscopy. This efcient and cost efective catalyst was
applied in the N-arylation reaction and the products were obtained in good to excellent yields in short reaction times. The
cost-efective catalyst demonstrated high stability, which could be facilely separated from the reaction mixture by applying
an external magnet and recycled at least four times with only a slight decrease in its activity.
Graphic Abstract
Keywords Heterogeneous · Magnetic materials · Catalytic properties · NFG-arylation reaction
1 Introduction
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-019-02929-x) contains
supplementary material, which is available to authorized users.
The N-arylation coupling reaction is the most powerful and
widely used method for the construction of C–N bond which
is one of the most important areas of research in synthetic
organic chemistry [1]. The N-aryl nitrogen heterocycles are
unique building blocks in numerous biologically important
natural compounds [2–5] pharmaceuticals [6–9] and indus-
trial applications [10].
* Zahra Asadi
zasadi@shirazu.ac.ir
1
Department of Chemistry, College of Sciences, Shiraz
University, Shiraz 71454, Iran
Vol.:(0123456789)
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R. Zahedi et al.
Recently, remarkable improvement has been made on
the transition-metal-catalyzed N-arylation reaction. These
researches have particularly focused on Cu-promoted Ull-
mann [11–16] or Pd-mediated Buchwald-Hartwig coupling
reactions [17–22]. Due to the high cost of palladium, less
costly metals become more desirable. Since copper is an
inexpensive and available metal, its use is highly demanded
to develop new catalyst systems [23]. However, in order to
promote N-arylation reaction by Cu catalysts, often high
temperature (125–220 °C) and large amounts of catalyst
are required [24]. Consequently, by using suitable bidentate
chelating ligands such as N,N-, O,O-, and N,O-chelators,
the reaction outcome can be improved [25, 26]. On the other
hand many catalysts used in N-arylation reaction are homo-
geneous that sufer from drawbacks associated with the sepa-
ration and recovery of the catalysts. To solve these problems,
homogeneous catalysts are typically immobilized on various
insoluble supports, rendering them heterogeneous in nature
[27–33]. The efciency of heterogeneous catalyst systems
can be improved by using nanosized catalysts because of
their small size and high surface area. However, the sup-
porting nanocatalysts such as TiO2 nanoparticles [34], ionic
liquids [35], carbon nanotubes [36], SBA-15 [37], MCM-41
[38, 39] or some polymers [40] have disadvantages such as
tedious workup processes, difcult and expensive separation
of catalyst from the reaction mixture. Moreover, some of
these supports need high temperature for calcination or time
consuming and boring conditions for their preparation. Thus,
the use of magnetic nanoparticles (MNPs) as a catalyst sup-
port appears to be the most logical solution: their insoluble
and superparamagnetic nature enables simple and efcient
separation of the catalysts from the reaction mixture with the
help of an external magnet [41–43].
to 12. The reaction temperature was reduced and kept at
63 °C for 1 h. The black solid product was isolated by exter-
nal magnet, washed with distilled water and ethanol for sev-
eral times and dried in the vacuum.
2.2 Synthesis of Fe3O4@SiO2 Core–Shell
Microspheres
2.0 g Fe3O4 nanoparticles were suspended in 70 mL ethanol
and 10 mL distilled water by sonication for 25 min. Then,
5 mL of aqueous solution of ammonia (NH3·H2O, 25%) and
4 mL of tetraethylorthosilicate (TEOS) were slowly added
and the mixture stirred for further 24 h. The coated NPs were
magnetically collected and rinsed with ethanol and deion-
ized water, respectively.
2.3 Synthesis of Amine Functionalized Fe3O4@SiO2
(AS‑MNPs)
The Fe3O4@SiO2 (1.0 g) was dispersed in dry toluene
(50 mL) with ultrasonicating for 30 min. To the result-
ing suspension, 1.5 mL of (3-aminopropyl)triethoxysilane
(APTES) was added and the mixture was refuxed for 24 h
under N2 atmosphere. The mixture was subjected to mag-
netic decantation and the obtained solid was washed with
toluene and ethanol for several times.
2.4 Immobilization of Schif Base Ligand
on AS‑MNPs (HB@AS‑MNPs)
1.0 g of AS-MNPs and an ethanolic solution (30 mL) of
2-hydroxybenzophenone (2.0 mmol, 0.4 g) was refuxed
overnight under N2 atmosphere. The solid product was sep-
arated magnetically, washed with ethanol and dried under
vacuum.
In continuing our eforts to develop economical and eco-
friendly synthetic pathways for coupling reactions [44–46],
in the present work, we would like to introduce a new het-
erogeneous magnetic reusable catalyst supported imine
copper complex for the N-arylation reaction. This system is
of interest as it possesses several advantages, such as short
reaction time, high yields, simple separation and reusability
of the catalyst.
2.5 Synthesis of Cu‑HB@AS‑MNPs Catalyst
1.0 g of as-synthesized HB@AS-MNPs was dispersed
in 40 mL absolute ethanol, followed by the addition of
copper(II) acetate. The mixture was stirred under refux
for 24 h under an inert (N2) atmosphere. The catalyst was
collected by a magnetic bar and washed three times with
ethanol. The Cu-HB@AS-MNPs catalyst was obtained with
loading of 1.48 mmol of Cu per gram determined by ICP.
2 Experimental
2.1 Synthesis of Fe3O4
2.6 General Procedure for N‑arylation Reaction
Catalyzed by Cu‑Catalyst
Fe3O4 magnetic nanoparticles (MNPs) were synthesized
according to a previously reported method [47]. 3.0 g
FeCl3·6H2O and 2.1 g FeCl2·4H2O were added to 500 mL
deionized water and stirred under the continuous fow of
nitrogen at 83 °C. Then, sodium hydroxide (10 wt%) was
added dropwisely to the solution until the pH value reached
Amine (1.0 mmol) was added to a suspension of aryl halide
(1.0 mmol), K2CO3 (2.0 mmol), and Cu catalyst (0.047 g,
7 mol%) in DMSO (3.0 mL) in a 10 mL reaction fask. The
reaction mixture was stirred at 130 °C and monitored by
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A Highly Active, Recyclable and Cost‑Efective Magnetic Nanoparticles Supported Copper…
TLC to determine completion of the reaction. Subsequently,
the catalyst was separated magnetically and the reaction
mixture was diluted with ethyl acetate (20 mL). The sol-
vent was evaporated under reduced pressure to get the crude
product and the product was purifed by column chromatog-
raphy on silica using n-hexane and ethyl acetate.
of the catalyst particles was 15 nm. In order to verify the
existence of all expected elements in the Cu-HB@AS-MNPs
catalyst EDX analysis was employed. The results confrmed
the attachment of copper complex on the surface of MNPs
and the components of the catalyst were Fe, Si, N, C, O and
Cu elements (Fig. 1c). The exact quantity of copper loaded
on the Cu-HB@AS-MNPs catalyst was measured using ICP.
The ICP analysis of the catalyst indicated that 1.48 mmol/g
of copper was loaded onto the nanomagnetic catalyst.
Successful functionalization of the MNPs can be
determined from the FT-IR spectroscopic technique. The
FT-IR spectra of Fe3O4, Fe3O4@SiO2, AS-MNPs, HB@
AS-MNPs and Cu-HB@AS-MNPs catalyst are exhibited
in Fig. 2. The IR spectra of bare Fe3O4 (Fig. 2a) illustrated
the absorption band at 590 cm−1 attributed to Fe–O bond
vibration [48, 49] and a broad band at 3452 cm−1 assigned
to the presence of OH groups on the surface of the MNPs
[50]. FT-IR spectra of Fe3O4@SiO2 (Fig. 2b) showed spe-
cifc peaks for Si–O–Si bond at 1087 cm−1 and 790 cm−1,
which confrmed the presence of silica phase [51]. In the
FT-IR spectra of AS-MNPs (Fig. 2c), additional peaks
due to N–H stretching vibration and NH2 bending mode
3 Results and Discussion
3.1 Characterization of Cu‑HB@AS‑MNPs Catalyst
The process for the preparation of Cu-HB@AS-MNPs cata-
lyst is shown in Scheme 1. Fe3O4 particles were synthesized
by the co-precipitation of Fe3+ and Fe2+ salt and coated with
a thin layer of silica using a sol–gel process to give Fe3O4@
SiO2. The resulting silica-coated MNPs were then modifed
with (3-aminopropyl) triethoxysilane (APTES) to obtain
amine functionalized MNPs (AS-MNPs). Subsequently,
AS-MNPs was reacted with 2-hydroxybenzophenone in
ethanol to aford HB@AS-MNPs. Finally, HB@AS-MNPs
was treated with copper(II) acetate in ethanol to aford the
desired Cu-HB@AS-MNPs catalyst. The catalyst was char-
acterized by SEM, TEM, EDX, CHN, FT-IR, ICP, XRD
and VSM.
of free NH2 group were seen at 3481 and 1677 cm−1
,
respectively [52, 53]. Furthermore, the absorption band
corresponding to C-H band of propyl group from APTES
was appeared at 2985 and 2862 cm−1 [54, 55]. In Fig. 2d,
a characteristic peak at 1670 cm−1 was related to C=N
stretching vibrations of HB@AS-MNPs, which afrmed
that 2-hydroxybenzophenone was successfully immobi-
lized on the surface of functionalized silica [56, 57]. In the
FT-IR spectrum of Cu-HB@AS-MNPs (Fig. 2e), due to
The size and morphology of the synthesized catalyst were
characterized using TEM and SEM. The TEM images dis-
played a dark Fe3O4 core surrounded by a gray silica shell
with a thickness of about 4 nm (Fig. 1a). SEM image indi-
cated that the synthesized Cu-HB@AS-MNPs had uniform-
ity and a spherical morphology (Fig. 1b). The average size
OH
O
(EtO)3Si
NH2
TEOS
Fe3O4
Fe3O4
SiO2
Fe3O4
SiO2
OH
OH
O
Si
NH2
dry toluene, reflux
O
AS-MNPs
2-hydroxybenzophenon
ethanol
reflux
O
O
O
Cu+
O
Si
N
O
Si
N
OH
Fe3O4
SiO2
Fe3O4
SiO2
O
O
Cu(OAc)2
ethanol/ reflux
Cu-HB@AS-MNPs
Scheme 1 A schematic illustration for the synthesis of Cu-HB@AS-MNPs catalyst
HB@AS-MNPs
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R. Zahedi et al.
Fig. 1 TEM (a), SEM (b), and EDX pattern of Cu-HB@AS-MNPs catalyst (c)
the binding of azomethine nitrogens to the metal ion, the
absorption peak of C=N was shifted to a lower frequency
at 1636 cm−1.
negligible shifts. The sharp peaks of HB@AS-MNPs did
not change in the XRD pattern of Cu-HB@AS-MNPs cata-
lyst, confrming that the structure of the catalyst did not
deform after metalation (Fig. 3b).
To investigate the composition and crystallinity of HB@
AS-MNPs and Cu-HB@AS-MNPs; XRD technique was
used. As shown in Fig. 3a, b the position and relative inten-
sities of all peaks in the XRD pattern of MNPs were in good
conformity with the face centered cubic (fcc) Fe3O4, indicat-
ing retention of the crystalline structure during functionali-
zation of MNPs. The MNPs demonstrated six characteristic
difraction peaks at 2θ = 30.3º, 35.6º, 43.2º, 53.1º, 57.2º,
and 63.0º due to (220), (311), (400), (422), (511) and (440),
respectively [58, 59].
Magnetization properties of HB@AS-MNPs and
Cu-HB@AS-MNPs were investigated by VSM in the
employed magnetic feld from − 8500 to +8500 Oe. The
magnetization curves indicated that both HB@AS-MNPs
and Cu-HB@AS-MNPs were superparamagnetic at room
temperature and could be efciently separated from the
reaction mixture using an external magnet (Fig. 4a, b). The
saturation magnetization of HB@AS-MNPs and Cu-HB@
AS-MNPs were 46 and 33 emu g−1, respectively. The
decrease in the magnetization value of Cu-HB@AS-MNPs
indicated the successful attachment of Cu on the surface
of HB@AS-MNPs.
Furthermore, a broad peak at 2θ < 20 was assigned to
amorphous state SiO2 shells [60]. By adding Cu(OAc)2 to
HB@AS-MNPs, these characteristic peaks appeared with
1 3

A Highly Active, Recyclable and Cost‑Efective Magnetic Nanoparticles Supported Copper…
3.2 N‑arylation of Amines with Aryl Halides
Catalyzed by Cu‑HB@AS‑MNPs
To evaluate the applicability of Cu-HB@AS-MNPs cata-
lyst in the N-arylation reaction, the reaction conditions
were surveyed by using iodobenzene and benzimidazole
(2a) as model substrates. The initial attempt was focused on
the coupling reaction of 2a (1.0 mmol) with iodobenzene
(1.0 mmol) using 10 mol% of Cu catalyst in DMF at 135 °C
(Table 1, entry 1), and the desired N-arylated product was
obtained 92% of the yield. Then, diferent parameters such as
solvent, base, temperature and catalyst amount were exam-
ined to obtain the optimal reaction conditions. The infuence
of the solvent on the reaction was investigated and good
yield was obtained with DMF and DMSO (Table 1, entries
1, 2). In order to increase the sustainability of the method
and owing to the awful environmental efect of DMF, DMSO
was chosen as the most suitable solvent. Other solvents such
as, DMA, PEG and H2O/TBAB (tetrabutyl ammonium bro-
mide, as a surfactant) were found to be inferior (Table 1,
entries 3–5). Moreover, in the absence of solvent, 70% yield
of product was observed (Table 1, entry 6). We also screened
the use of various bases such as K2CO3, CH3COONa, KOH
Fig. 2 FT-IR spectra of Fe3O4 (a), Fe3O4@SiO2 (b), AS-MNPs (c),
HB@AS-MNPs (d), and Cu-HB@AS-MNPs catalyst (e)
t
and BuOK (Table 1, entry 2, entries 7–9) and the results
clearly indicated that K2CO3 was the best one (Table 1, entry
2).Three diferent catalyst amounts were tested. By using
5 mol% and 7 mol% of Cu-catalyst, 80% and 90% of prod-
ucts were obtained, respectively (Table 1, entries 10, 11).
Since the yield of the product did not change remarkably
upon decreasing the catalyst amount from 10 to 7 mol%,
7 mol% of Cu-catalyst was chosen as the catalyst amount. It
should be noted that no coupling product was observed in
the absence of the Cu catalyst, confrming the necessity of
using the Cu-HB@AS-MNPs as catalyst for the N-arylation
reaction (Table 1, entry 12). Also, some tests were carried
out at several temperatures and it was found that by increas-
ing the temperature from 100 to 130 °C, the yield increased
from 60 to 90% (Table 1, entries 13–15). However, at 140 °C
no signifcant reaction progress compared to 130 °C was
observed (Table 1, entry 16). Therefore, 130 °C is a suitable
temperature to push this reaction forward (Table 1, entry
15). As a result the entry 15 of Table 1 was selected as opti-
mized conditions for N-arylation reaction using Cu-HB@
AS-MNPs catalyst.
Fig. 3 XRD patterns of HB@AS-MNPs (a) and Cu-HB@AS-MNPs
catalyst (b)
Having the optimized reaction conditions in hand, the
scope of this reaction with various functionalized iodoben-
zenes and amines was explored (Scheme 2). As shown in
Scheme 2, the coupling reactions were accomplished with
high to excellent yields (80–95%). The N-arylation reac-
tion was efciently promoted for aryl iodides with benzi-
midazole to give the corresponding coupling products up to
92% yield (Fig. 3a–c). Good yield of product was obtained
for bromobenzene in longer time (Fig. 3a). Extending this
Fig. 4 VSM curves of HB@AS-MNPs (a) and Cu-HB@AS-MNPs
(b)
1 3

R. Zahedi et al.
Table 1 Optimization of the N-arylation reaction between iodobenzene (1.0 mmol) and benzimidazole catalyzed by Cu-HB@AS-MNPs catalyst
N
H
I
N
N
catalyst
+
base, solvent
N
1a
2a
3a
Entry
Solvent
Catalyst amount (mol%) Bases
Temperature (℃)
Yield (%)a
1
2
3
4
5
6
7
8
DMF
DMSO
DMA
PEG(200)
H2O/TBAB
None
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
10
10
10
10
10
10
10
10
10
5
7
–
7
7
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
CH3COONa
KOH
130 °C
130 °C
130 °C
130 °C
Refux
130 °C
130 °C
130 °C
130 °C
130 °C
130 °C
130 °C
100 °C
115 °C
130 °C
140 °C
92
90
60
60
75b
70
30
40
60
80
90
–
9
tBuOK
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
10
11
12
13
14
15
16
60
70
90c
92
7
7
Reaction conditions: iodobenzene (1.0 mmol), benzimidazole (1.0 mmol), base (2.0 mmol), solvent (3.0 mL), Cu-HB@AS-MNPs (7 mol%,
0.047 g), 130 °C, 4 h
aIsolated yields
b2.0 mmol of TBAB was used
cThe optimum conditions for N-arylation reaction
chemistry to include pyrazole as substrate was also quite
successful. The reaction of pyrazole with aryl halides led
to the synthesis of products containing the biological active
fragments (Fig. 3d–f). In the reaction of benzimidazole and
pyrazole with substituted iodobenzene, electron-donating
group (CH3) on the aryl halide depressed the efciency of
the reactions to some extent (Fig. 3c, f). However, electron-
withdrawing aryl halide (1-iodo-4-nitrobenzene) underwent
in the coupling reactions well to aford the products in higher
yields (Fig. 3b, e, h). In addition, hydrazobenzene reacted
with iodobenzene and 4-nitroiodobenzene to give new sym-
metrical products in high yields (Fig. 3g, h). The optimized
reaction conditions were also applied to the cross coupling
of diphenylcarbazide with iodobenzene and a new product
containing four functional groups was synthesized (Fig. 3i).
The products were characterized by 1H NMR.
completion of the reaction, the catalyst was separated magneti-
cally, successively washed with deionized water, ethanol and
ethyl acetate and reused four times under the same reaction
conditions. As shown in Fig. 5 only a slight decreasing in the
catalytic activity was observed after each run. The FT-IR spec-
tra of the reused catalyst (Fig. 6) confrmed that the structure
of the catalyst was remained unchanged after recovery.
After four runs in N-arylation reaction, the TEM image
demonstrated that the morphology and the size of the recov-
ered catalyst was almost the same as that of freshly prepared
catalyst (Fig. 7).
On the basis of these experiments, in can be concluded that
the Cu-HB@AS-MNPs catalyst was stable and heterogeneous
in practice.
Moreover, the reusability of Cu-HB@AS-MNPs cata-
lyst was examined due to the potential benefts in commer-
cial applications. In this regard, the reaction of iodobenzene
with benzimidazole was chosen as the model reaction. After
1 3

A Highly Active, Recyclable and Cost‑Efective Magnetic Nanoparticles Supported Copper…
R1
N
X
R1
R2
catalyst (7 mol%)
R2
+
HN
DMSO, K2CO3
130 °C
3a-3i
X=I, Br
N
N
N
N
N
N
O2N
H3C
3c
5h, 90%
3a
3b
1h, 92%
X=I, 3h, 90%
X=Br, 8h, 75%
N
N
O2N
N
H3C
N
N
N
3d
3e
3f
3h, 90%
5h, 95%
4h, 90%
O2N
O
N
N
N
N
N
N
N
N
NO2
3h
3g
1h, 90%
7h, 91%
3i
24h, 80%
Scheme 2 Summary of the N-arylation reaction of aryl iodides with amines under the optimized conditions. Reaction conditions: aryl iodide
(1.0 mmol), amines (1.0 mmol), base (2.0 mmol), solvent (3.0 mL), Cu-HB@AS-MNPs (7 mol%, 0.047 g), 130 °C
100
80
60
40
20
0
90
89
86
83
82
1
2
3
4
5
Run
Fig. 5 The reusability of the Cu-HB@AS-MNPs for reaction between
Fig. 6 FT-IR spectra of the Cu-HB@AS-MNPs catalyst after fve
benzimidazole and iodobenzene under the optimized conditions
runs
1 3

R. Zahedi et al.
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In summary, we have prepared a retrievable and sustainable
nano magnetic catalyst (Cu-HB@AS-MNPs) used for a vari-
ety of organic transformations such as N-arylation reaction
in good to excellent yields. In order to decrease the harmful
efect of toxic solvents, DMSO with low toxicity was chosen
as the solvent of this reaction. The attractive features of this
catalyst compared to other reported catalysts are the use of
low cost metal center, high yield, short reaction time for
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catalyst efcient after four cycles. Notably, magnetic separa-
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