The immobilized copper species on nickel ferrite (NiFe2O4@Cu): a magnetically reusable nanocatalyst for one-pot and quick reductive acetylation of nitroarenes to N-arylacetamides

Article abstract of DOI:10.1007/s13738-019-01818-9

In this study, a green protocol for synthesis of N-arylacetamides was introduced. Magnetically, nanoparticles of the immobilized copper species on nickel ferrite, NiFe₂O₄@Cu, were synthesized and then characterized using SEM, EDX, XRD, VSM, ICP-OES, BET and XPS analyses. The XPS analysis approved that the immobilized copper species on NiFe₂O₄ only contain Cu(0) and its oxide form as CuO. The prepared nanocomposite system represented a perfect catalytic activity toward one-pot and quick reductive acetylation of various nitroarenes to the corresponding N-arylacetamides. All reactions were carried out in a mixture of H₂O–EtOH (1.5–0.5) within 2–10?min using the combination system of NaBH₄ and Ac₂O in a one-pot approach and via a two-step procedure. The utilized Cu nanocomposite was magnetically separated from the reaction mixture and reused for 5 consecutive cycles without the significant loss of its catalytic activity.

Full text of DOI:10.1007/s13738-019-01818-9

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-019-01818-9
ORIGINAL PAPER
The immobilized copper species on nickel ferrite (NiFe2O4@Cu):
a magnetically reusable nanocatalyst for one‑pot and quick reductive
acetylation of nitroarenes to N‑arylacetamides
Behzad Zeynizadeh1 · Zahra Shokri1 · Iman Mohammadzadeh1
Received: 9 October 2018 / Accepted: 26 November 2019
© Iranian Chemical Society 2019
Abstract
In this study, a green protocol for synthesis of N-arylacetamides was introduced. Magnetically, nanoparticles of the immo-
bilized copper species on nickel ferrite, NiFe2O4@Cu, were synthesized and then characterized using SEM, EDX, XRD,
VSM, ICP-OES, BET and XPS analyses. The XPS analysis approved that the immobilized copper species on NiFe2O4 only
contain Cu(0) and its oxide form as CuO. The prepared nanocomposite system represented a perfect catalytic activity toward
one-pot and quick reductive acetylation of various nitroarenes to the corresponding N-arylacetamides. All reactions were
carried out in a mixture of H2O–EtOH (1.5–0.5) within 2–10 min using the combination system of NaBH4 and Ac2O in a
one-pot approach and via a two-step procedure. The utilized Cu nanocomposite was magnetically separated from the reaction
mixture and reused for 5 consecutive cycles without the signifcant loss of its catalytic activity.
Keywords Ac2O · NaBH4 · N-arylacetamides · NiFe2O4@Cu · Nitroarenes · Reductive acetylation
Introduction
Fe3O4@SiO2@Cu–Ni–Fe–Cr LDH/Ac2O [15] and NaBH4/
CuFe2O4@SiO2@PTMS@Tu@Ni(II)/Ac2O [16] are some
of catalyst/reagent systems which have been successfully uti-
lized for direct reductive acetylation of nitroarenes to acetan-
ilide materials. Although most of the reported methods have
the own merits, however, the development and introduction
of green protocols which use the available, inexpensive and
reusable catalyst systems are a subject of more interests.
Nowadays, the capability of transition metal nanoparticles
to catalyze inter-conversion of functional groups has been
numerously documented [17–20]. In this area, the promi-
nent characteristics of copper nanoparticles including the
cheapness, ready availability, high thermal and electrical
conductivity, good mechanical hardness as well as the per-
fect catalytic activity have received much interest instead of
using the precious noble metal species [21–26]. In spite of
the great conveniences of transition metals as well as copper
nanoparticles to promote chemical reactions, they have a
strong tendency for agglomeration. Due to this, the specifc
surface area of nanoparticles and catalytic activity of the
applied catalyst systems are reduced extensively [27–30].
In order to overcome this shortcoming and prevent the use
of copper nanoparticles in over-stoichiometric manner, the
immobilization of Cu NPs on various solid supports/stabi-
lizers such as metal oxides, carbon and polymer materials,
Acetamides are the frequently used skeletons in many
biological active compounds as well as drug candidates
[1–3]. Due to this, they can be prepared generally in a
time-consuming three-step procedure involving reduction
of nitro compounds, isolation of the prepared amines and
then acetylation with an acetylating agent. In this context,
low stability of the prepared amines and yield losing of the
fnal acetamides are the issues which diminish efciency
of the titled transformation. To overcome the mentioned
drawbacks, therefore, direct reductive acetylation of nitro
functionality to acetamide could be a very useful and ef-
cient approach. The literature review shows that Zn/HOAc/
CH3COCl/Et3N [4], Sm/HOAc/Ac2O [5], Fe/AcOH [6], Fe/
RCO2H [7], Mo(CO)6/RCO2H [8], Zn/Ac2O/acidic Al2O3
[9], PtCl2(PPh3)2/SnCl4/CO [10], Ru3(CO)12/HCO2Me/
RCO2H [11], NaBH4/Pd–C/Ac2O [12], Pt/ZrO2/MeOH/
Ac2O [13], NaBH4/Fe3O4@Cu(OH)x/Ac2O [14], NaBH4/
* Behzad Zeynizadeh
bzeynizadeh@gmail.com
1
Faculty of Chemistry, Urmia University, Urmia 5756151818,
Iran
Vol.:(0123456789)
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Journal of the Iranian Chemical Society
zeolites and clay minerals have been reported [22, 31–37].
Moreover, this type of immobilization brings more catalytic
activity for the prepared catalyst system due to extreme ris-
ing of surface area and quantum level interaction of copper
species with components of the reactions [22].
was then characterized using SEM, EDX, XRD, VSM, ICP-
OES, BET and XPS analyses.
The morphology and size distribution of particles in
the prepared nanocomposite materials were investigated
by scanning electron microscopy (SEM) technique. SEM
images of NiFe2O4 (Fig. 2a, b) and NiFe2O4@Cu (Fig. 2c,
d) exhibited that morphology of two MNPs are quite difer-
ent: NiFe2O4 MNPs were constructed from roughly/irregular
and agglomerated segments resulting in a surface with low
porosity. At this construction, the particles are distributed
in the range of 10–25 nm. SEM images of NiFe2O4@Cu
MNPs also represented that through the immobilization of
copper species on the surface of NiFe2O4; morphology of
the surface was clearly modifed to an arrangement contain-
ing polygone/spherical tiny segments. At this construction,
porosity of the surface was extensively raised and the parti-
cles were distributed in the range of 10–40 nm.
Currently, the capability of spinel ferrites (MFe2O4;
M=Fe, Cu, Co, Ni, Zn, Mg and Mn) in drug delivery, pig-
ments, ferro-fuids, microwave devices, gas sensors and
catalysis has attracted the attention of numerous scientists
[38–42]. Among the well-known spinel ferrites, NiFe2O4
is a more desirable one. This magnetic material has sev-
eral advantages in terms of high thermal (up to 900 °C)
and chemical stability and unique magnetic characteristic
[43–47].
In line with the outlined strategies and continuation, our
research program directed to the application of nanocata-
lysts in organic synthesis [14–16, 23, 48–54]; herein, we
wish to investigate the immobilization of copper species on
nickel ferrite to aford magnetically nanoparticles (MNPs)
of NiFe2O4@Cu. The prepared Cu nanocomposite system
was then utilized as a superior catalyst toward one-pot and
quick reductive acetylation of various nitroarenes to N-ary-
lacetamides using NaBH4/Ac2O without the isolation of
intermediate amines (Fig. 1).
Next, the elemental composition of Ni, Fe, O and Cu in
NiFe2O4@Cu MNPs was verifed by energy-dispersive X-ray
spectroscopy (EDX) (Fig. 3). Based on this analysis, the
immobilization of copper species on the surface of NiFe2O4
was demonstrated. In addition, the actual amounts of Cu
(4.11%), Fe (30.32%) and Ni (14.35%) species in NiFe2O4@
Cu MNPs were determined by inductively coupled plasma-
optical emission spectroscopy (ICP-OES).
More investigation toward morphology and nano-struc-
tural characteristic of NiFe2O4 and NiFe2O4@Cu was also
carried out by transmission electron microscopy (TEM)
technique (Fig. 4a–h). Survey of TEM images approves
that the prepared composite systems were constituted from
nanosize particles. As well, morphology of NiFe2O4 and
NiFe2O4@Cu MNPs is quite diferent verifying the immo-
bilization of copper species on the surface of nickel ferrite.
At the next, the phase purity and crystallinity character
of nanostructured NiFe2O4 and NiFe2O4@Cu were studied
through the depicted X-ray difraction patterns of Fig. 5. The
recorded pattern in Fig. 5a shows that the appeared peaks at
2θ=30.5°, 36°, 43.5°, 54°, 57.5° and 63.5° are, respectively,
corresponded to refection planes of (2 2 0), (3 1 1), (2 2
2), (4 0 0), (5 1 1) and (4 4 0) verifying the spinel structure
of pure NiFe2O4 (JCPDS 44-1485). As well, the sharpness
appearance of signals represents the crystallinity of nano-
particles in NiFe2O4. In addition, through the Debby–Scher-
rer equation, [τ = Kλβ−1(cos θ)−1], the average size of
crystallites in NiFe2O4 was calculated 52.5 nm, whereas
K = 0.9, λ = 0.154 nm, β = 0.00412 rad, 2θ = 35.9679°,
Cos(17.98)=0.6452 rad. Calculation of the Scherrer equa-
tion for NiFe2O4@Cu MNPs resulted that the average size
of crystallites was 51.52 nm, whereas K=0.9, λ=0.154 nm,
β=0.00412 rad, 2θ=35.9841°, Cos (17.99)=0.6528 rad.
The literature review shows that the refection peaks
in XRD pattern of copper metal are corresponded to
2θ = 43.31°, 50.51° and 74.2° [23]. In XRD pattern of
Results and discussions
Synthesis and characterizations of NiFe2O4@Cu
MNPs
The study was primarily started by synthesis of magneti-
cally nanoparticles of the immobilized copper species on
nickel ferrite in a three-step procedure: (1) preparation of
NiFe2O4 MNPs by solid-state grinding of Ni(OAc)2·4H2O,
Fe(NO3)3·9H2O, NaOH and NaCl in a mortar for 50 min
at room temperature followed by washing of the prepared
nanocomposite (NiFe2O4) with deionized water, (2) sim-
ply mixing of NiFe2O4 MNPs with an aqueous solution of
CuCl2·2H2O, and (3) immobilization of copper species on
nanostructured NiFe2O4 through the reduction of Cu2+ ions
with sodium borohydride. The prepared Cu nanocomposite
NO2
NHAc
1. NiFe2O4@Cu, NaBH4
H2O-EtOH, 70 oC
2. Ac2O, 70 oC
R
R
Fig. 1 Reductive acetylation of nitroarenes with NaBH4/NiFe2O4@
Cu/Ac2O system
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Fig. 2 SEM images of NiFe2O4 (a, b) and NiFe2O4@Cu MNPs (c, d)
NiFe2O4@Cu MNPs, due to low dosage of copper spe-
cies (4.1%), the refection peaks for copper species were
appeared weakly or overlapped with the refection peaks of
NiFe2O4. It is notable that through the immobilization of
copper species, the crystallinity character of spinel NiFe2O4
was remained intact.
MNPs (37.718 emu g−1) (Fig. 6a) [55, 56]. Nevertheless,
the magnetization value for NiFe2O4@Cu MNPs is large
enough for any magnetic separation. It is also reported that
by subtracting the Ms values before and after loading of
the immobilized any species on surface of the prime mag-
netic material, the content of immobilized species could be
roughly estimated [52, 57]. Based on this idea, the calcula-
tion for Cu content (37.718‒34.584) in NiFe2O4@Cu MNPs
was 3.13%. This value is near to the actual amount of copper
content (4.11%) by ICP analysis.
The measurement for magnetic properties of NiFe2O4
and NiF2O4@Cu MNPs shows that through the immobi-
lization of diamagnetic copper species on the surface of
nickel ferrite, the magnetization (Ms) value of NiF2O4@Cu
(34.584 emu g−1) (Fig. 6b) was diminished versus NiFe2O4
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Fig. 3 EDX analysis of
NiFe2O4@Cu MNPs
In order to determine the surface area and pore size dis-
tribution of nanoparticles, the N2 absorption–desorption
analysis was also carried out on NiFe2O4 and NiFe2O4@
Cu MNPs. The results of this investigation are summarized
in Table 1. Documented data for distribution of pore sizes
reveal that both MNPs have the mesoporous characteristic
(2<D<50 nm). Moreover, the increased surface area (2.8
folds) for NiFe2O4@Cu versus NiFe2O4 MNPs approves that
porosity of the surface in NiFe2O4@Cu MNPs was highly
raised. This claim is also verifed by the illustrated SEM
images in Fig. 2c and d.
Cu system (Fig. 7e). This means that some of the copper
species are in the form of Cu2+. It is therefore indicating that
the copper metal was oxidized to copper oxide species in the
expose of air atmosphere. In this context, the signal for Cu
2p3/2 (933 eV) clearly attributed to the presence of copper
metal. The literature review shows that the boron-binding
energies for B (element), ZrB2, B-oxides and Li2B4O7 are
corresponded to 187.2, 187.8, 188.6 and 192.5 eV, respec-
tively [58]. So, the absence of any signals in XPS spectrum
of NiFe2O4@Cu in less than 250 eV is verifed that through
the reaction of NaBH4 with CuCl2·2H2O (during the prepa-
ration of nanocatalyst), the presence of any copper boride
species is quite denied.
Analysis of the surface and measuring the composition as
well chemical/electronic state of the elements in NiFe2O4@
Cu MNPs was further studied by X-ray photoelectron spec-
troscopy (XPS) technique. Illustrated spectra in Fig. 7a–e
show the results of this investigation. Based on this analysis,
the presence of Fe, Ni, O and Cu elements in NiFe2O4@Cu
system was verifed. Figure 7a shows the binding energy
signals of O 1s, Fe 2p, Ni 2p and Cu 2p for spinel struc-
ture of nickel ferrite. The detailed analysis reveals that the
nanocatalyst contains Fe3+ and Ni2+ and O2− ions. The bind-
ing energies around 529 and 533 eV are attributed to the
presence of O2− in the sample (Fig. 7b). In XPS spectrum
of Fe 2p (Fig. 7c), the signals around 714 and 723 eV are
corresponded to Fe 2p3/2 and Fe 2p1/2 showing the presence
of Fe3+ in the catalyst. In addition, XPS spectrum of Ni 2p
(Fig. 7d) indicates that the binding energies around 853 and
860 eV are corresponded to Ni 2p3/2 and Ni 2p1/2 approving
the presence of Ni2+ in the nanocomposite system. As well,
the binding energies around 936 eV (Cu 2p3/2) and 956 eV
(Cu 2p1/2) demonstrate the existence of Cu2+ in NiFe2O4@
Reductive acetylation of nitroarenes catalyzed
by NiFe2O4@Cu MNPs
After the successful synthesis and characterization of
NiFe2O4@Cu MNPs, catalytic activity of the prepared Cu
nanocatalyst was studied toward direct reductive acetylation
of nitroarenes to N-arylacetamides under diferent reaction
conditions including the change of reaction-solvent, vary-
ing the molar equivalents of reactants as well temperature
of the reaction (Table 2, entries 1‒15). Investigation of the
results exhibited that among the examined solvents, the
mixture of H2O‒EtOH (1.5:0.5 mL) represented the per-
fect efciency. In addition, using the molar equivalents of
1:2.5 (PhNO2:NaBH4) and 0.15 g of NiFe2O4@Cu MNPs
in a mixture of H2O‒EtOH (1.5:0.5 mL, 70 °C) were the
requirements to aford aniline as a sole product within 1 min
(Table 2, entry 9). After completion of the reduction, acetic
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Journal of the Iranian Chemical Society
Fig. 4 TEM images of NiFe2O4
(a–d) and NiFe2O4@Cu MNPs
(e–h)
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Journal of the Iranian Chemical Society
Fig. 5 XRD patterns of a
NiFe2O4 and b NiF2O4@Cu
MNPs
anhydride (2 mmol) was added and acetylation of aniline
was carried out at 70 °C within 2 min to aford acetanilide
in high yield. In order to clarify the infuence of NiFe2O4@
Cu MNPs on the rate of reduction (nitrobenzene to aniline),
the titled transformation was also carried out in the presence
of NiFe2O4, CuCl2·2H2O, Fe3O4 and Fe2O3 at the optimized
reaction conditions. Investigation of the results exhibited
that the later catalysts did not have the proper efciency to
promote the reduction of nitrobenzene to aniline (Table 2,
entries 16‒19).
The usefulness and generality of NaBH4/NiFe2O4@Cu/
Ac2O system were further studied toward reductive acety-
lation of structurally diverse aromatic nitro compounds to
acetanilides at the optimized reaction conditions. The results
of this investigation are summarized in Table 3.
Investigation of the results represents that all reactions
were carried out successfully within 2‒10 min to aford
acetanilide materials in high to excellent yields (Table 3).
The table also shows that 1,3-dinitrobenzene was success-
fully converted to N,N′-(1,3-phenylene)diacetamide within
8 min and 85% yield (entry 11). In the case of 3-nitrophe-
nol, the current protocol did not show any selectivity and
both amino and phenolic functionalities were acetylated in
a same reactivity to aford 3-acetamidophenyl acetate in
Fig. 6 Magnetization curves of a NiFe2O4 and b NiFe2O4@Cu MNPs
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Table 1 BET and BJH analysis of NiFe2O4 and NiFe2O4@Cu MNPs
examined conditions did not perform the acetylation of
hydroxyl groups and only the acetylation of amino groups
was taken place successfully (entries 13‒15).
Sample
Surface area
Pore size distri- Specifc pore
(m2 g−1
)
bution (nm)
volume (cm3
g−1
)
Although the exact mechanism of this synthetic protocol
is not clear, however, we think that the following mechanis-
tic pathways play a role in the formation of acetamides from
nitroarenes (Fig. 8). As seen, a nitroarene compound was
primarily reduced to the corresponding aniline derivative
with NaBH4 through the catalysis of NiFe2O4@Cu MNPs.
Then, the prepared aniline material was transformed to
NiFe2O4
NiFe2O4@Cu
5.32
14.84
48.49
34.74
3.41
1.22
90% yield (entry 10). As well, nitroarenes containing car-
bonyl and alcoholic moieties such as 3-nitroacetophenone,
3-nitrobenzaldehyde and 4-nitrobenzyl alcohol under the
Fig. 7 XPS spectra of NiFe2O4@Cu MNPs: a binding energy for whole elements, b O 1s, c Fe 2p, d Ni 2p and e Cu 2p
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Table 2 Optimization experiments for reduction of nitrobenzene to aniline
Entry
NaBH4 (mmol)
Catalyst (g)
Solvent (2 mL)
Temperature Time (min)
Conversion (%)
(°C)
1
2
3
4
5
6
7
8
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
3
2
2.5
‒
2.5
2.5
2.5
2.5
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.1)
NiFe2O4@Cu (0.15)
NiFe2O4@Cu (0.15)
‒
H2O
MeOH
H2O‒MeOH (1.5:0.5)
CH3CN
H2O‒CH3CN (1.5:0.5)
THF
70
70
70
70
70
70
70
70
70
r.t.
70
70
70
70
70
70
70
70
70
40
40
50
60
60
60
60
40
1
30
30
1
30
300
300
120
120
120
120
90
60
75
50
70
50
75
80
100
40
90
100
95
30
10
20
30
30
25
H2O‒THF (1.5:0.5)
EtOH
9
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
H2O‒EtOH (1.5:0.5)
10
11
12
13
14
15
16
17
18
19
NiFe2O4@Cu (0.15)
NiFe2O4 (0.15)
CuCl2·2H2O (0.15)
Fe3O4 (0.15)
Fe2O3 (0.15)
All reactions were carried out with 1 mmol of nitrobenzene
N-arylacetamide by the reaction of Ac2O in the presence of
Conclusions
NiFe2O4@Cu MNPs.
Magnetically, nanoparticles of the immobilized copper spe-
cies on nickel ferrite were synthesized and then character-
ized using SEM, EDX, XRD, VSM, ICP-OES, BET and
XPS analyses. The prepared Cu nanocomposite showed an
excellent catalytic activity toward direct reductive acetyla-
tion of structurally diverse aromatic nitro compounds to
N-arylacetamides in a one-pot approach. All reactions were
carried out efciently using a molar equivalents of ArNO2/
NaBH4/Ac2O (1:2.5:2) in the presence of NiFe2O4@Cu
(0.15 g) and in a mixture H2O–EtOH (1.5:0.5 mL, 70 °C)
giving the products within 2‒10 min. NiFe2O4@Cu MNPs
were easily separated by an external magnetic feld and
reused for 5 consecutive cycles without the signifcant loss
of its catalytic activity. The perfect efciency and reusability
of the nanocatalyst, quick reactions, easy work-up proce-
dure and high yield of the products as well as easy synthesis
of the nanocomposite from cost-efective materials are the
advantages which make this protocol a synthetically useful
addition to the present methodologies.
Recycling of NiFe2O4@Cu MNPs
At the next, the reusability of NiFe2O4@Cu MNPs for
reductive acetylation of nitrobenzene was studied. In this
investigation and after completion of reductive acetylation
of nitrobenzene, the nanocatalyst was separated by an exter-
nal magnet. Afterward, it was washed with ethyl acetate to
remove residual contaminants and dried in an oven. The
recycled copper nanocomposite was again used for reduc-
tive acetylation of freshly charged nitrobenzene, NaBH4
and Ac2O at the optimized reaction conditions. The given
results in Fig. 9 show that the nanocomposite can be reused
for 5 consecutive cycles without the signifcant loss of its
catalytic activity. The framework stability of NiFe2O4@Cu
MNPs and leaching of copper species from the nanocatalyst
were also investigated by measuring the copper content after
5 recovering of the nanocatalyst. The results of ICP analysis
represent that the percentage of Cu species in the fresh and
fve recycled nanocatalyst is 4.11 and 3.97%, respectively.
Based on these results, we concluded that the leaching of
Cu‐content in NiFe2O4@Cu MNPs is negligible (3.4%).
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Journal of the Iranian Chemical Society
Table 3 Reductive acetylation of nitroarenes with NaBH4/NiFe2O4@Cu/Ac2O system
Molar
Raꢀoa
Time
(min)
Yield
(%)b
Entry
1
Substrate
NO2
NO2
Product
NHCOCH3
Mp./Bp. °C [ref.]
113‒115 [14]
1:2.5:2
2
95
NHCOCH3
2
1:2.5:2
2
90
109‒110 [14]
Me
Me
NO2
NHCOCH3
NHCOCH3
3
4
1:2.5:2
1:2.5:2
2
2
93
91
65‒67 [14]
Me
Me
Me
Me
NO2
149‒151 [14]
Me
Me
Me
Me
NO2
NO2
NHCOCH3
NHCOCH3
5
1:2.5:2
6
88
182‒184 [14]
299/760 mmHg
[59]
6
7
1:2.5:2
1:2.5:4
5
2
90
88
Me
Me
Me
NO2
Me
NHCOCH3
192‒194 [60]
NHCOCH3
NHCOCH3
NH2
NO2
475/760 mmHg
[61]
8
9
1:2.5:4
1:2.5:4
1:2.5:4
2
2
2
90
92
90
H2N
H3COCHN
H3COCHN
H2N
NO2
NHCOCH3
NHCOCH3
>300 [14]
NO2
NO2
377 / 760 mmHg
[14]
10
H3COCO
HO
NHCOCH3
475/760 mmHg
[61]
11c
12c
1:4:4
8
85
88
O2N
H3COCHN
NO2
NHCOCH3
1:2.5:2
10
156‒160 [62]
HOH2C
NO2
HOH2C
NHCOCH3
13
14
1:2.5:2
1:2.5:2
6
5
92
90
120‒122 [63]
259‒260 [14]
COCH3
NO2
CH(OH)CH3
O2N
OHC
H3COCHN
HOH2C
NHCOCH3
395/760 mmHg
[64]
15
1:2.5:2
3
93
All reactions were carried out in the presence of NiFe2O4@Cu MNPs (0.15 g) and in a mixture of H2O–EtOH (1.5:0.5 mL, 70 °C)
aMolar ratio as: ArNO2/NaBH4/Ac2O
bIn these reactions, NaBH4 was added portionwise
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NaBH4 + H2O
H
H
H2
NiFe2O4@Cu
H
NH2
R
NO2
R
NO
H
NHOH
H
NO2
Fig. 9 Reductive acetylation of nitrobenzene with the recycled
H
H
NiFe2O4@Cu MNPs
R
R
R
particle was examined by measuring SEM using FESEM-
TESCAN MIRA3 instrument. TEM images were obtained
from Zeiss EM10C-100 kV transmission electron micro-
scope. X-ray photoelectron spectroscopy (XPS) was car-
ried out on Thermo Scientifc K-Alpha+ XPS instrument.
Magnetic properties of the samples were measured using a
vibration sample magnetometer (VSM, Meghnatis Daghigh
Caviar Co., Iran) under magnetic felds up to 20 kOe. The
N2 adsorption–desorption isotherms were examined on Bel-
sorp-Max, Japan. Specifc surface area of the samples was
determined using Brunauer–Emmett–Teller (BET) method.
The pore volume and pore size distribution of the nanocom-
posites were derived from desorption profles of isotherms
using Barrett–Joyner–Halanda (BJH) method. Elemental
analysis of Cu, Fe and Ni was carried out by inductively cou-
pled plasma-optical emission spectrometry (Perkin Elmer
OPTIMA 7300DV ICP-OES System). Ultrasonic irradiation
was carried out in SOLTEC SONICA 2400MH S3 (305 W).
H
H
O
O
O
NH2
O
O
O
R
H
R
H
O
N
NiFe2O4@Cu
O
O
NHCOCH3
R
Synthesis of NiFe2O4 MNPs
Fig. 8 Two-step mechanism for reductive acetylation of nitroarenes
Magnetically, nanoparticles of NiFe2O4 were synthesized
via a chemical co-precipitation method [65, 66]. A mix-
ture of Ni(OAc)2·4H2O, Fe(NO3)3·9H2O, NaOH and NaCl
with a molar ratio of 1:2:8:2, respectively, was grinded in
a mortar for 50 min at room temperature. The mixture was
then washed several times with deionized water to remove
residual contaminants (NaCl, by-product or other unreacted
materials). The nickel ferrite product was dried at 80 °C. The
resulting powder was calcinated at 800 °C for 2 h to aford
magnetically nanoparticles of NiFe2O4.
with NaBH4/NiFe2O4@Cu/Ac2O system
Experimental
Materials and instruments
All reagents and materials were purchased from chemical
companies, and they were used without further purifcation.
FT-IR and 1H, 13C NMR spectra were recorded on Thermo
Nicolet Nexus 670 and Bruker Avance 300 MHz spectrom-
eters, respectively. TLC was applied for purity determina-
tion of products and reaction monitoring over silica gel 60
F254 aluminum sheet. Powder XRD was obtained by an
X’PertPro Panalytical difractometer in 40 kV and 30 mA
with a CuKα radiation (λ = 1.5418 Å), and the difraction
patterns were recorded in 2θ = 10°‒80°. Morphology of
Synthesis of NiFe2O4@Cu MNPs
In a round-bottom fask (50 mL), a solution of CuCl2·2H2O
(0.25 g, 1.466 mmol) in deionized water (30 mL) was pre-
pared. Magnetically, nanoparticles of NiFe2O4 (1 g) was
then added, and the prepared mixture was irradiated in an
1 3

Journal of the Iranian Chemical Society
15. M. Gilanizadeh, B. Zeynizadeh, J. Iran. Chem. Soc. 15, 2821
(2018)
ultrasonic bath for 30 min. Afterward, an aqueous solution
of NaBH4 (0.11 g in 30 mL H2O) within 1 min and under N2
atmosphere was added. Due to this, magnetically nanopar-
ticles of the immobilized copper species on NiFe2O4 were
prepared. The nanoparticles were separated by magnetic
decantation and washed several times with deionized water.
Drying under air atmosphere afords NiFe2O4@Cu MNPs.
16. B. Zeynizadeh, Z. Shokri, M. Hasanpour Galehban, Appl. Orga-
nometal. Chem. 33, e4771 (2019)
17. D. Astruc, Nanoparticles and Catalysis, Chapter 1 (Wiley-VCH,
Weinheim, 2008)
18. M. Larramendy, S. Soloneski, Green Nanotechnology: Overview
and Further Prospects (IntechOpen, London, 2016)
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A general procedure for reductive acetylation
of nitroarenes
In a round-bottom fask (25 mL), a solution of nitrobenzene
(0.123 g, 1 mmol) in H2O–EtOH (1.5:0.5 mL) was prepared.
Magnetically, nanoparticles of NiFe2O4@Cu (0.15 g) were
added, and the resulting mixture was stirred for 5 min. After-
ward, NaBH4 (0.094 g, 2.5 mmol) was added and the result-
ing mixture was continued to stirring for 1 min at 70 °C.
After reduction of nitrobenzene to aniline (monitored by
TLC), Ac2O (0.204 g, 2 mmol) was added and the resulting
mixture was stirred for 1 min at 70 °C. The nanocatalyst
was separated by an external magnet, and the mixture was
extracted with EtOAc (3 × 5 mL). The organic layer was
dried over anhydrous Na2SO4. Evaporation of the solvent
afords the pure acetanilide in 95% yield (0.128 g, Table 3,
entry 1).
23. B. Zeynizadeh, M. Zabihzadeh, Z. Shokri, J. Iran. Chem. Soc. 13,
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Acknowledgements The authors gratefully appreciated the fnancial
support of this work by the research council of Urmia University. The
helpful comments of Dr. Seyed Ali Hosseini and Dr. Ali Hassanzadeh
were also acknowledged.
32. B. Zeynizadeha, S. Rahmani, RSC Adv. 9, 8002 (2019)
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