Cu(I)-anchored polyvinyl alcohol coated-magnetic nanoparticles as heterogeneous nanocatalyst in Ullmann-type C–N coupling reactions

Article abstract of DOI:10.1002/aoc.5611

In this paper, the preparation of a novel magnetic nanocatalyst (Fe₃O₄?PVA/CuCl) is described, which involves coating of polyvinyl alcohol (PVA) onto the surface of Fe₃O₄ nanoparticles and its subsequent coordination with CuCl catalyst. The nanocatalyst was characterized by various analytical methods, including Fourier-transform infrared, X-ray diffraction, inductively coupled plasma spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy, vibrating-sample magnetometry, and EDX elemental mapping. Moreover, the nanocatalyst was efficiently used in the N-arylation of amines via the formation of a carbon–nitrogen bond between the aryl halides and amines by Ullmann-type coupling reactions. The catalyst was sufficiently stable and can be reused for at least seven times in a model Ullmann reaction without remarkable alteration in its catalytic behavior. Heterogeneity of the catalyst was investigated by a hot filtration test.

Full text of DOI:10.1002/aoc.5611

Received: 15 November 2019
DOI: 10.1002/aoc.5611
Revised: 28 January 2020
Accepted: 6 February 2020
F U L L P A P E R
Cu(I)-anchored polyvinyl alcohol coated-magnetic
nanoparticles as heterogeneous nanocatalyst in Ullmann-
type C–N coupling reactions
Saba Hemmati1
| Sheida Ahany Kamangar1 | Mohammad Yousefi2
|
Mirmehdi Hashemi Salehi3 | Malak Hekmati3
1Department of Chemistry, Payame Noor
In this paper, the preparation of
a
novel magnetic nanocatalyst
University, Tehran, Iran
2Department of Chemistry, Yadegar-e-
Imam Khomeini (RAH) Shahr-e-Rey
Branch, Islamic Azad University, Tehran,
Iran
3Department of Organic Chemistry,
Faculty of Pharmaceutical Chemistry,
Tehran Medical Sciences, Islamic Azad
University, Tehran, Iran
(Fe3O4@PVA/CuCl) is described, which involves coating of polyvinyl alcohol
(PVA) onto the surface of Fe3O4 nanoparticles and its subsequent coordination
with CuCl catalyst. The nanocatalyst was characterized by various analytical
methods, including Fourier-transform infrared, X-ray diffraction, inductively
coupled plasma spectroscopy, field emission scanning electron microscopy,
energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy,
vibrating-sample magnetometry, and EDX elemental mapping. Moreover, the
nanocatalyst was efficiently used in the N-arylation of amines via the forma-
tion of a carbon–nitrogen bond between the aryl halides and amines by
Ullmann-type coupling reactions. The catalyst was sufficiently stable and can
be reused for at least seven times in a model Ullmann reaction without
remarkable alteration in its catalytic behavior. Heterogeneity of the catalyst
was investigated by a hot filtration test.
Correspondence
Mohammad Yousefi, Department of
Chemistry, Yadegar-e-Imam Khomeini
(RAH) Shahr-e-Rey Branch, Islamic Azad
University, Tehran, Iran.
Email: myousefi50@hotmail.com
Funding information
Tehran Medical Sciences, Islamic Azad
University, and Yadegar-e-Imam
Khomeini (RAH) Shahr-e-Rey Branch,
Islamic Azad University, Tehran, Iran;
Payame Noor University (PNU)
K E Y W O R D S
copper, magnetic, N-Arylation, Ullmann reaction
1 | INTRODUCTION
halide to severe reaction conditions, reasonable to poor
yields, and weak substrate generality.
Arylamines play a critical role as mediator in agro-
chemicals, drugs, natural products,[1] polymers,[2]
dendrimers,[3] pigments,[4] and electronic devices.[5]
These compounds were frequently prepared through
either coupling with organometallic substances or N–H
nucleophilic aromatic substitution, both of which
restrain their scope.[6] They are also synthesized by the
classical Ullmann-type linking with aryl halides, which
usually has some restꢀrictions such as high reaction
temperatures (150–200 C), the use of copper elements
in stoichiometric levels, insolubility of copper(I) salts
in organic solvents, sensitivity of the replaced aryl
Because of the attractive economical features of cop-
per[7] and utilization of several specific ligands such as
N,N- and N,O-bidentate compounds, many CuI-catalyzed
C–N,[8,9] C–O,[10,11] C–C,[12,13] and C–S[14] bond-forming
reactions created a renewed interest in coupling reactions
of carbon–heteroatom and its applications.[15,16] For these
coupling reactions, beneficial ligands have been discov-
ered, including amino acids,[17] diamines,[18] diimines,[7]
1,10-phenanthroline,[19] aminoarenethiolate,[20] phos-
phine
8-hydroxyquinoline,[23]
zole,[24]
glyoxal
ligands,[21]
2-aminopyrimidine-4,6-diol,[22]
(S)-pyrrolidinylmethylimida-
bis(phenylhydrazone),[25]
β-keto
Appl Organometal Chem. 2020;e5611.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5611

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HEMMATI ET AL.
SCHEME 1 Synthesis of
Fe3O4@PVA/CuCl and its application for
Ullmann C–Ncross coupling reactions
esters,[26]
2,2,6,6-tetramethylheptane-3,5-dione,[27]
nanocomposite of CuCl catalyst stabilized and supported
over polyvinyl alcohol (PVA)-coated magnetic Fe3O4 NPs.
The nanocatalyst is employed for the effective synthesis of
arylamines by C–N heterocoupling between aryl halides
and different amines in the presence of Et3N as base in
dimethylformamide (DMF) medium following Ullmann
C–N cross-coupling reactions. The most important features
of our protocol are as follows: simple procedure, use of
cheap and stable reagents, high yields, use of a novel high
surface area green material, and easily reusable catalyst
with reproducible yields in several runs (see illustration in
Scheme 1).
BINAM–Cu(II),[28] and tris-(2-aminoethyl)amine.[29]
The fabrication of heterogeneous catalysts has been
widely examined, unlike their homogeneous counterparts,
and are demonstrated to exhibit the following advantages:
simple workup, recyclability, and ease of handling.[30–34]]
Among heterogeneous catalysts, magnetite nanoparticles
(MNPs) have attracted a lot of attention because of their low
cost, stability, less toxicity, good biocompatibility, high reac-
tivity, easy isolation with an external magnet, and impor-
tantly, the small size, large surface area, and good magnetic
permeability.[35–50]
Based on our previous studies,[51] in this paper, a novel
procedure is described for the preparation of
a
FIGURE 1 Fourier-transform infrared spectra of (a) Fe3O4,
FIGURE 2 Field emission scanning electron microscopy
(b) Fe3O4@PVA, and (c) Fe3O4@PVA/CuCl. PVA, polyvinyl alcohol
image of Fe3O4@PVA/CuCl. PVA, polyvinyl alcohol

CU(I) ANCHORED POLYVINYL ALCOHOL COATED-MAGNETIC NANOPARTICLES
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(1 g) were dispersed by ultrasonic bath for 20 min. After-
ward, PVA (0.5 g, molecular weight (Mw) 72,000) was
added to the reaction solution, and the mix was mechani-
cally agitated for 24 h at 80 ꢀC. After completing the reac-
tion, the Fe3O4@PVA NPs were isolated magnetically,
rinsed with deionized water and anhydrous ethanol, and
dried at 60 ꢀC to obtain Fe3O4@PVC.
Next, 1.0 mmol CuCl was poured into 100 mL H2O and
stirred for 0.5 h. Then, 0.5 g of the prepared Fe3O4@PVA
was added and agitated at ambient temperature for 24 h.
After performing this reaction, the magnetic solid product
was separated using a magnet and washed with distilled
water and acetone, respectively, to remove undesired mate-
rials. Later, it was dried under vacuum at 60 ꢀC for 24 h to
obtain Fe3O4@PVA/CuCl. Elemental analysis of
Fe3O4@PVA/CuCl with atomic emission spectroscopy indi-
cated 0.44 mmol/g loading of copper.
FIGURE 3 Energy-dispersive X-ray spectroscopy analysis of
Fe3O4@PVA/CuCl. PVA, polyvinyl alcohol
2 | EXPERIMENTAL DESIGN
2.2 | General method for Ullmann
coupling reaction in the presence of
Fe3O4@PVA/CuCl
2.1 | Preparation of Fe3O4, Fe3O4@PVA,
and Fe3O4@PVA/CuCl nanocomposites
The magnetic Fe3O4 NPs were prepared according to our
previous work.[30] In 100 mL deionized water, Fe3O4 NPs
A solution consisting of aryl halide (1.0 mmol), amine
(1.1 mmol), Et3N (2.0 mmol), Fe3O4@PVA/CuCl
FIGURE 4 Elemental mapping of Fe3O4@PVA/CuCl shows the presence of Fe, C, O, Cl, and Cu atoms in the nanocomposite. PVA,
polyvinyl alcohol

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HEMMATI ET AL.
FIGURE 5 Transmission electron
microscopy image of Fe3O4@PVA/CuCl. PVA,
polyvinyl alcohol
(0.020 g, 0.5 mol%), and DMF (3 mL) was stirred for 8 h
at 100 ꢀC under a nitrogen atmosphere. The reaction was
accompanied by thin-layer chromatography (TLC). After
completion of the reaction, water (10 mL) and ethyl ace-
tate (10 mL) were added into the reaction mixture. First,
the catalyst was isolated using a suitable magnet and the
organic solution was extracted and dried over anhydrous
Na2SO4. Upon removing the organic solvent, a crude
product was obtained. To further purify this product,
TLC was employed.
2.3 | Procedure for recycling of the
catalyst
After the reaction time, 5 mL ethyl acetate and 10 mL
water were added to the reaction mixture and stirred for
5 min. After this time, the catalyst was separated with an
external magnet. In the next step, the recovered catalyst
was washed using EtOH 70% (5 mL) and dried under
vacuum. Then, the recovered catalyst was used for
another run.
FIGURE 6 Room temperature magnetization curve of
FIGURE 7 X-ray diffraction pattern of Fe3O4@PVA/CuCl.
Fe3O4@PVA/CuCl. PVA, polyvinyl alcohol
PVA, polyvinyl alcohol

CU(I) ANCHORED POLYVINYL ALCOHOL COATED-MAGNETIC NANOPARTICLES
5 of 9
magnetic field was applied to collect the mix, and the
separated mix was dried under vacuum. The copper con-
tent in the nanocomposite was 0.44 0.001 mmol g−1 as
predicted by inductively coupled plasma–atomic absorp-
tion spectroscopy. The catalyst was characterized by
Fourier-transform infrared (FT-IR) spectroscopy, field
emission scanning electron microscopy (FESEM),
energy-dispersive X-ray spectroscopy (EDX), elemental
mapping, transmission electron microscopy (TEM), X-ray
diffraction (XRD), inductively coupled plasma, and
vibrating-sample magnetometry (VSM).
FT-IR was utilized to examine the structure of the
synthesized Fe3O4, Fe3O4@PVA, and Fe3O4@PVA/CuCl
NPs. In the spectrum corresponding to Fe3O4 (Figure 1a),
the strong band that appeared at 582 and 637 cm−1 was
related to the Fe–O vibration and the bands at 1625 and
3408 cm−1 correspond to both the surface-adsorbed water
and hydroxyl groups.[36] In Figure 1b, the PVA-coated
Fe3O4 NPs can be seen. The adsorption peaks at 585 and
629 cm−1 correspond to those of Fe–O and bands at 1589
and 3419 cm−1 were associated with the surface-adsorbed
water and hydroxyl groups,[30] which confirmed the pres-
ence of MNPs. Moreover, the representative peaks of
FIGURE 8 X-ray photoelectron spectroscopy spectrum of
Fe3O4@PVA/CuCl in the Cu 2p region. PVA, polyvinyl alcohol
3 | RESULTS AND DISCUSSION
The catalyst was synthesized according to the stages men-
tioned in Scheme 1. Initially, the prepared magnetic
Fe3O4 NPs, based on the chemical co-precipitation
technique,[30] were coated with PVA to obtain
Fe3O4@PVA magnetic nanocomposite. Afterward, the
Fe3O4@PVA NPs were reacted with CuCl in water to
obtain Fe3O4@PVA/CuCl. Ultimately, an external
TABLE 1 Optimization of reaction parameters for amination of bromobenzene with morpholine using Fe3O4@PVA/CuCla
Entry
1
Cu (mol%)
0.5
Solvent
DMF
Toluene
EtOH
H2O
Base
T (ꢀC)
100
100
80
Yield (%)b
K2CO3
K2CO3
K2CO3
K2CO3
NaOAc
Et3N
85
40
50
25
65
95
86
75
10
80
50
35
95
85
50
0
2
0.5
3
0.5
4
0.5
100
100
100
100
100
100
80
5
0.5
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
6
0.5
7
0.5
Cs2CO3
NaOH
No base
Et3N
8
0.5
9
0.5
10
11
12
13
14
15
16
0.5
0.5
Et3N
60
0.5
Et3N
25
0.5
Et3N
120
100
100
100
0.4
Et3N
0.2
Et3N
0.0
Et3N
aReaction conditions: Bromobenzene (1.0 mmol), morpholine (1.2 mmol), catalyst, base (2 mmol), and solvent (3 mL) for 8 h.
bIsolated yield.
cDMF, dimethylformamide; PVA, polyvinyl alcohol.

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HEMMATI ET AL.
TABLE 2 N-Arylation of aryl halides using Ullmann
cross-coupling reaction in the presence of Fe3O4@PVA/CuCl
catalysta
interactions between the functional groups of the
composites and copper ions (Figure 1c).
Both
dimension
and
morphology
of
Fe3O4@PVA/CuCl were investigated by FESEM, which
indicated that the produced catalyst is nanoscale quasi-
spherical with an average diameter of approximately
10–20 nm (Figure 2). In addition, a continuous polymer
layer is seen on the catalyst surface. Besides, the field
emission scanning electron microscope equipped with
the EDX detector was utilized to confirm the presence of
PVA shell and copper species on the surface of Fe3O4
NPs, with a positive result confirming the existence of
Fe, C, and O (Figure 3). The existence of Cu and Cl
signals in EDX spectra of the nanocatalyst (Figure 3)
revealed the efficient coordination of copper ions on the
Fe3O4@PVA surface.
Moreover, the existence of Fe, C, O, Cl, and Cu was
confirmed on elemental mapping images (Figure 4),
which showed that Cu was distributed homogenously on
the Fe3O4 NPs surface.
The TEM image of the prepared catalyst is presented
in Figure 5, which indicated MNPs with dark spots. Sev-
eral of them, which are markedly more solid, appear to
be strongly accumulated. Nevertheless, most of them are
not accumulated. By contrast, PVA might be identified by
the transparent color on the TEM images. Remarkably,
the spherical MNPs, which are uniformly distributed,
confirm that PVAs effectively avoid aggregation.
Satisfactory magnetism is critical for practical applica-
tions of magnetic materials in aqueous solution. As such,
the VSM magnetization curve corresponding to
Fe3O4@PVA/CuCl NPs was obtained in which no hyster-
esis was seen. The maximal saturation magnetization of
Fe3O4@PVA/CuCl was 48.7 emu g−1. These obtained
results indicate the superparamagnetic property of this
nanocatalyst (Figure 6).
XRD analysis was implemented to investigate both
the structure and phase purity of structures. The XRD
pattern of the Fe3O4@PVA/CuCl catalyst is depicted in
Figure 7. The existence of six peaks at 2θ of 30.5ꢀ,
35.8ꢀ, 44.1ꢀ, 53.6ꢀ, 57.8ꢀ, and 63.1ꢀ corresponding to
Entry
1
Aryl halide
C6H5I
Amine
Yield (%)b
Refc
[28]
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Piperidine
Piperidine
Piperidine
Indole
96
95
60
95
92
55
96
90
95
90
95
92
55
92
90
60
85
80
[28]
[28]
[27]
[27]
[27]
[28]
[28]
[32]
[32]
[29]
[29]
[29]
[27]
[27]
[27]
[33]
[33]
2
C6H5Br
3
C6H5Cl
4
p-NCC6H4I
p-NCC6H4Br
p-NCC6H4Cl
p-CH3C6H4I
p-CH3C6H4Br
p-CH3OC6H4I
p-CH3OC6H4Br
C6H5I
5
6
7
8
9
10
11
12
13
14
15
16
17
18
C6H5Br
C6H5Cl
C6H5I
C6H5Br
Indole
C6H5Cl
Indole
C6H5I
Imidazole
Imidazole
C6H5Br
aReaction conditions: Aryl halide (1.0 mmol), amine (1.2 mmol),
Fe3O4@PVA/CuCl (0.5 mol%), and Et3N (2.0 mmol) were stirred in
dimethylformamide (3.0 mL) at 100 ꢀC for 8 h.
bIsolated yield.
cEarlier reference of the corresponding product.
dPVA, polyvinyl alcohol.
amorphous PVA at 2890 cm−1 (C–H asymmetric
stretching) and 1048 cm−1 (C–O–C stretching) presented
further evidence for the attachment of PVA on the
surface of Fe3O4 NPs. In other words, Fe3O4 NPs may
interact with PVA through the hydroxyl groups on
their surfaces. The vibration peak of Fe–O–C at
1000–1100 cm−1 also revealed the interactions between
PVA and Fe3O4 NPs.[52] Furthermore, the intensity of
bands at 3392 cm−1 was reduced as a result of bonding
FIGURE 9 Recycling of the catalyst for the
reaction of bromobenzene with morpholine

CU(I) ANCHORED POLYVINYL ALCOHOL COATED-MAGNETIC NANOPARTICLES
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FIGURE 10 Transmission electron
microscopy image of the reused
Fe3O4@PVA/CuCl catalyst after the
seventh run. PVA, polyvinyl alcohol
(2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0) is in
good agreement with standard patterns of inverse cubic
spinel magnetite (Fe3O4) crystal structure. The whole
diffraction peaks are related to the magnetic cubic
structure of Fe3O4 (JCPDS 65–3107). According to the
obtained results, the crystalline phase of Fe3O4 is not
affected by the amorphous PVA coating. There is no
peak for Cu(I).
was not produced in the absence of the catalyst (Table 1,
Entry 16). However, the introduction of the catalyst into
the reaction medium rapidly enhanced the synthesis of
the product with excellent yield. Among the various sol-
vents tested, DMF was chosen as the best solvent, and
among the examined bases, Et3N was the optimal base.
In addition, the effect of catalyst loading was evaluated
with different levels of the catalyst from 0.2 to 0.5 mol%
(Table 1, Entries 7, 14, and 15). According to the results
obtained, the optimal yield can be attained with 0.020 g
(0.5 mol%) of the catalyst (Table 1, Entry 7). Besides, the
Furthermore,
CuCl
existence
in
the
Fe3O4@PVA/CuCl nanostructure was reconfirmed by
X-ray photoelectron spectroscopy analysis by studying
binding energy range between 930 and 955 eV (Figure 8).
The analysis resolved Cu 2p spectrum into two spin–orbit
pairs with 932.2 and 952.1 eV binding energies, respec-
tively. The peak binding energy values of 932.3 eV
(Cu 2p3/2) and 952.2 eV (Cu 2p1/2) were related to cupper
ions (Cu+1) on the surface of modified Fe3O4 NPs.[53] The
Cu 2p photoelectron transitions of the Fe3O4@PVA/CuCl
catalyst were observed at 933.3 eV. The differences in Cu
2p binding energy between Fe3O4@PVA/CuCl and CuCl
were 0.5 eV. This chemical shift of the binding energy of
Cu element is induced by the coordination bonding when
Cu(I) is immobilized on Fe3O4@PVA.[54] Thus, copper
ions were successfully immobilized on the Fe3O4@PVA
support.
ꢀ
optimum temperature of reaction was 100 C (Entry 7 vs
Entries 10–12). A lower yield of the final product was
achieved at 25 ꢀC, whereas increasing the temperature to
120 ꢀC did not remarkably increase the product yield
(Table 2, Entry 13).
After optimizing the reaction conditions, it was the
turn of analyzing generality over substrate variants. In
this way, a variety of arylamine derivatives were prepared
by coupling of substituted aryl halides and secondary
amines under stabilized conditions. Different substituent
such as CH3, OCH3, and CN on bromo and iodoarenes
were very well suitable for this procedure; besides, there
was no considerable difference in the electron-
withdrawing or electron-donating effects of substituents.
Nevertheless, the chloroarenes were found to be less
reactive compared with bromo or iodo analogs, which
became evident in their yields. The results are listed in
Table 2. The isolated purified products were certified by
comparing with the standard samples.
Owing to our ongoing interest in the preparation of
novel nanocatalysts,[42] the catalytic behavior of
Fe3O4@PVA/CuCl was investigated by Ullmann cross-
coupling reactions of aryl halides with amines
(as illustrated in Scheme 1).
To find the best conditions, as a model reaction, the
reaction of bromobenzene with morpholine in the pres-
ence of Fe3O4@PVA/CuCl catalyst was selected and the
effect of different reaction factors consisting of base, sol-
vent, temperature, and the concentration of catalyst was
evaluated in detail (Table 1). As expected, case product
From a green chemical point of view, reusability of
catalyst is a critical factor. To analyze the reusability of
the prepared catalyst, the reaction of bromobenzene and
morpholine was chosen as a model reaction with a larger
batch size (2.0 mmol). After completing the reaction, the
catalyst was isolated with a suitable magnet and then

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HEMMATI ET AL.
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revealed that the catalyst could be recycled for up to
seven consecutive runs with only 5% drop in reaction
yields. This result confirmed the consistency and recycla-
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under the optimized conditions. The reaction was
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A novel magnetic nanocatalyst of CuCl anchored onto
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an eco-friendly (green), effective, and magnetically reus-
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ACKNOWLEDGEMENTS
The authors gratefully acknowledge the financial and
other support for this research provided by Payame Noor
University (PNU), Tehran Medical Sciences, Islamic
Azad University, and Yadegar-e-Imam Khomeini (RAH)
Shahr-e-Rey Branch, Islamic Azad University,
Tehran, Iran.
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ORCID
Saba Hemmati https://orcid.org/0000-0002-6161-2604
Malak Hekmati https://orcid.org/0000-0003-0790-569X
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How to cite this article: Hemmati S, Ahany
Kamangar S, Yousefi M, Hashemi Salehi M,
Hekmati M. Cu(I)-anchored polyvinyl alcohol
coated-magnetic nanoparticles as heterogeneous
nanocatalyst in Ullmann-type C–N coupling
reactions. Appl Organometal Chem. 2020;e5611.
https://doi.org/10.1002/aoc.5611