The immobilized Ni(II) species on thiourea functionalized copper ferrite: a reusable nanocatalyst for synthesis of biscoumarins under solvent-free conditions

Article abstract of DOI:10.1007/s13738-020-01878-2

In this study, nanoparticles of CuFe₂O₄@SiO₂@PTMS@Tu@Ni(II) as the reusable magnetic catalyst were prepared. Synthesis of the Ni(II)–CuFe₂O₄ system was carried out through a five-step procedure includ

Full text of DOI:10.1007/s13738-020-01878-2

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-020-01878-2
ORIGINAL PAPER
The immobilized Ni(II) species on thiourea functionalized copper
ferrite: a reusable nanocatalyst for synthesis of biscoumarins
under solvent‑free conditions
Behzad Zeynizadeh1 · Morteza Hasanpour Galehban · Zahra Shokri
1
1
Received: 2 February 2019 / Accepted: 12 February 2020
©
Iranian Chemical Society 2020
Abstract
In this study, nanoparticles of CuFe O @SiO @PTMS@Tu@Ni(II) as the reusable magnetic catalyst were prepared. Syn-
2
4
2
thesis of the Ni(II)–CuFe O system was carried out through a ꢀve-step procedure including the preparation of CuFe O
2
4
2
4
as the prime magnetic core, layering of silica, 3-chloropropyltrimethoxysilane and thiourea and ꢀnally the immobilization
of Ni(OAc) ·4H O. The prepared nanocomposite system was then characterized using FT-IR, SEM, EDX, XRD, VSM,
2
2
ICP-OES and TGA/DSC analyses. Catalytic activity of CuFe O @SiO @PTMS@Tu@Ni(II) was further studied toward
2
4
2
synthesis of biscoumarin materials by a domino Knoevenagel–Michael reaction of 4-hydroxycoumarin with aromatic and
heterocyclic aldehydes under solvent-free conditions (70 °C) within 15–30 min. The applied nanocomposite system was
easily and magnetically separated from the reaction mixture and reused for six consecutive cycles without the signiꢀcant
loss of its catalytic activity.
Keywords Biscoumarins · CuFe O · Knoevenagel–Michael · Ni(II) · Thiourea
2
4
Introduction
to prevent aggregation of nanoparticles and preserve their
original characteristics. In this area, the application of car-
bon materials [10–12], polymers [13–16], zeolites [17–19],
resins [20], metal oxides [21, 22] and clay minerals [23–25]
was successfully reported for the titled strategy.
Transition metal elements and their complexes due to
prominent biological properties such as antifungal and anti-
bacterial activities as well as the applicability in sensors,
optoelectronics, magnetic devices and drug delivery sys-
tems have attracted the considerable interest of numerous
scientists [1–7]. Consequently, nanomaterials containing
transition metals due to inherent electronic conꢀguration
and high surface energy of the existing metals and the huge
surface area to volume ratio have the eligibility to consider
as the more eꢁcient catalyst systems to promote chemical
reactions [8]. Despite this, they have a strong tendency for
agglomeration to produce bulk counterparts. In this situa-
tion, the surface area of nanoparticles (NPs) and catalytic
activity of the applied catalyst systems are intensively
decreased [9]. Overcoming of these drawbacks needs, the
immobilization of transition metals NPs on solid supports
Nowadays, the usefulness of spinel ferrites with a general
formula of MFe O (M=Fe, Cu, Co, Ni, Zn, Mg and Mn) in
2
4
pigments, gas sensors, ferroꢂuids, drug delivery and cataly-
sis has gained the considerable interests in academic and
industrial points of view [26–32]. Among the spinel ferri-
tes, CuFe O is a more desirable transition bimetallic oxide.
2
4
Because, this magnetic material has the advantages in terms
of high thermal stability (up to 900 °C), unique magnetic
characteristic and synergic chemical reactivity of copper and
iron to catalyze transformation of functional groups [33–38].
Over the past years, coumarins have been considered as
the prominent biological active materials [39–44]. Among
the coumarins, biscoumarin materials also exhibited the
signiꢀcant pharmacological activities such as antibacterial
[
45–47], antifungal [47], anti-inꢂammatory [48], antico-
*
Behzad Zeynizadeh
agulant [49], antitumor [50], anti-HIV [51–53], cytotoxic,
enzyme [47, 54, 55] and urease [56] inhibition, radical
scavenger and chain-breaking anti-oxidants [57]. Synthesis
of biscoumarin materials is usually carried out through a
bzeynizadeh@gmail.com
1
Faculty of Chemistry, Urmia University, Urmia 5756151818,
Iran
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1
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Journal of the Iranian Chemical Society
domino Knoevenagel–Michael reaction of 4-hydroxycou-
marin with aromatic aldehydes in the presence of a promoter
Nicolet Nexus 670. Magnetic property of the samples was
determined using vibrating-sample magnetometer (VSM,
Meghnatis Daghigh Caviar Co., Iran) under magnetic ꢀelds
up to 20 kOe. Morphology of the particles was examined via
the obtained SEM images from FESEM-TESCAN MIRA3
instrument. Chemical composition of the samples was deter-
mined by EDX analysis. X-ray diꢃraction (XRD) analysis
was carried out on X’PertPro Panalytical diꢃractometer in
40 kV and 30 mA with a CuKα radiation (λ = 1.5418 Å).
Elemental analysis of Cu and Ni species was carried out by
inductively coupled plasma–optical emission spectrometry
(ICP-OES, Optima 7300D). The irradiation of ultrasound
was carried out on SOLTEC SONICA 2400MH S3 (305 W).
system. The literature review shows that using ZnCl [58],
2
Zn(proline) [59], I [60], n-Bu NBr [61], P4VPy-CuO NPs
2
2
4
[
62], sulfated titania [63], phosphotungstic acid [64], silica
gel [65], silica sulfuric acid NPs [66], silica-supported Prey-
ssler NPs [67], silica-bonded N-propylpiperazine sodium
n-propionate [68], silica-supported sodium hydrogen sul-
fate and indion 190 resin [69], p-toluenesulfonic acid [70],
sulfonated rice husk ash (RHA-SO H) [71], sodium dodecyl
3
sulfate (SDS) [72], n-dodecylbenzene sulfonic acid (DBSA)
[
73], propane-1,2,3-triyl-tris (hydrogen sulfate) [74], tri-
ethylammonium hydrogen sulfate [75], graphene oxide
nanosheets [76], mesoporous acid-activated montmorillon-
ite K10 [77], nano Fe O @ZrO –H PO [78], mesoporous
Synthesis of CuFe O @SiO MNPs
3
4
2
3
4
2
4
2
FeTUD-1 [79], task-speciꢀc ionic liquids [80], benzimida-
zolium-based SO H-functionalized ionic liquids [PSebim]
Magnetically nanoparticles of CuFe O were primarily
2 4
3
[
[
OTf] [81], tetramethylguanidium-based ionic liquids [82],
synthesized via a chemical co-precipitation method using
FeCl ·6H O and CuCl ·2H O [36]. Then, layering of sil-
MIM(CH ) SO H][HSO ] [83] has been successfully uti-
2
4
3
4
3
2
2
2
lized to promote the synthesis of biscoumarin materials.
Although most of the reported methods have the own
advantages/shortcomings; however, the development of
environmentally friendly methods is one of the subjects of
green chemistry and therefore motivates new challenges
toward synthesis of biscoumarin materials. Therefore, in line
with the outlined strategies and continuation of our research
programs directed to the immobilization of transition metals
species on magnetic materials [37, 38, 77, 84–94], herein,
we wish to introduce the synthesis and characterization of
magnetically nanoparticles (MNPs) of CuFe O @SiO @
ica was carried out on nanocores of CuFe O . For doing,
2 4
the obtained CuFe O MNPs (1.5 g) in deionized water
2
4
(20 mL) were sonicated for 30 min. Subsequently, isopro-
panol (200 mL), PEG-400 (5.36 g), distilled water (20 mL),
aqueous ammonia (10 mL, 25 wt%) and tetraethyl orthosili-
cate (TEOS, 2 mL) were, respectively, added to the prepared
suspension. The mixture was stirred at room temperature
for 28 h. The resulting CuFe O @SiO MNPs were mag-
2
4
2
netically separated, washed with distilled water and aqueous
ethanol 96% and then dried under air atmosphere.
2
4
2
PTMS@Tu@Ni(II). At the next, catalytic activity of the pre-
pared nanocomposite system was investigated toward one-
pot Knoevenagel–Michael reaction of 4-hydroxycoumarin
with aromatic and heterocyclic aldehydes under solvent-free
conditions (Fig. 1).
Preparation of CuFe O @SiO @PTMS@Tu@Ni(II)
2
4
2
MNPs
Magnetically nanoparticles of CuFe O @SiO (1.7 g) were
2
4
2
dispersed in absolute EtOH (120 mL). 3-Chloropropyltri-
methoxysilane (3.4 mL) was then added and the resulting
mixture was irradiated by ultrasound for 60 min. The mix-
Experimental
ture was continued to stir under reꢂux and N atmosphere
2
for 20 h. The prepared nanoparticles of CuFe O @SiO @
2
4
2
General
PTM-Cl were washed with distilled water and aqueous etha-
nol 96% and then dried under air atmosphere.
All substrates and solvents were purchased from chemi-
cal companies in high quality and they were used with-
Next, the magnetic nanoparticles of CuFe O @SiO @
2
4
2
PTM-Cl (1 g) in absolute EtOH (50 mL) were dispersed
1
13
out further puriꢀcation. H, C NMR and FT-IR spectra
were recorded on 300 MHz Bruker Avance and Thermo
by sonication for 20 min. K CO (2.5 mmol) and thio-
2
3
urea (2.5 mmol) were added and the resulting mixture was
Fig. 1 Synthesis of biscou-
marin materials catalyzed by
CuFe O @SiO @PTMS@Tu@
2
4
2
Ni(II) MNPs
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Journal of the Iranian Chemical Society
stirred under reꢂux conditions for 20 h (N atmosphere). The
heated in an oil bath (70 °C). After completion of the reac-
tion within 15 min (monitored by TLC), EtOAc was added
and the resulting mixture was stirred for 5 min. The nanocat-
alyst was magnetically separated from the reaction mixture.
Evaporation of the solvent under reduced pressure followed
by recrystallization of the crude product from hot EtOH
aꢃords the pure biscoumarin 3,3′-(phenylmethylene)-bis(4-
hydroxy-2H-chromen-2-one) in 95% yield (Table 2, entry 1).
2
obtained CuFe O @SiO @PTMS@Tu MNPs were washed
2
4
2
with distilled water and aqueous ethanol 96% and then dried
under air atmosphere.
Finally, the magnetic nanoparticles of CuFe O @SiO @
2
4
2
PTMS@Tu (1 g) were sonicated in absolute EtOH (25 mL)
and were mixed with an aqueous solution of Ni(OAc) ·4H O
2
2
(
0.5 g in a mixture of EtOH:H O/2:2 mL). The resulting
2
mixture was stirred under reꢂux conditions for 20 h. The
obtained nanoparticles of CuFe O @SiO @PTMS@Tu@
2
4
2
Ni(II) were magnetically separated, washed with distilled
Results and discussion
water and aqueous ethanol 96% and then dried at 50 °C.
Synthesis of CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
2
4
2
A typical procedure for synthesis of biscoumarin
materials
The study was started by synthesis of CuFe O @SiO @
2
4
2
PTMS@Tu@Ni(II) MNPs via a five-step procedure
In an experimental tube, a mixture of benzaldehyde
(Fig. 2): (i) magnetically nanoparticles of CuFe O
2
4
(
1 mmol), 4-hydroxycoumarin (2 mmol) and CuFe O @
was prepared through a chemical co-precipitation of
2
4
SiO @PTMS@Tu@Ni(II) MNPs (10 mg) was stirred and
FeCl ·6H O and CuCl ·2H O in an aqueous solution
2
3
2
2
2
Fig. 2 Synthetic diagram of CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
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4
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Journal of the Iranian Chemical Society
of NaOH, (ii) layering of silica around nanocores of
CuFe O using tetraethyl orthosilicate (TEOS), (iii) sur-
FT‑IR analysis
2
4
face-linking of CuFe O @SiO with 3-chloropropyltri-
Fourier transform infrared spectroscopy as a primarily
tool was used for functional groups and structural elu-
cidation of CuFe O , CuFe O @SiO @PTMS@Tu and
2
4
2
methoxysilane (PTMS-Cl), (iv) linking of thiourea with
the immobilized 3-chlorotrimethoxysilane on CuFe O
2
4
2
4
2
4
2
@
SiO and (v) immobilization of Ni(OAc) ·4H O on
CuFe O @SiO @PTMS@Tu@Ni(II) MNPs. In FT-IR
2
2
2
2 4 2
CuFe O @SiO @PTMS@Tu giving the nanocomposite
spectrum of CuFe O MNPs (Fig. 3a), the bands at 460
2 4
2
4
2
−
1
of CuFe O @SiO @PTMS@Tu@Ni(II). In continuation,
and 583 cm are attributed to bending vibration of Cu–O
and Fe–O bonds, respectively. As well, a broadband around
2
4
2
characterization of the Ni(II)–CuFe O system was car-
2
4
−
1
ried out using FT-IR, SEM, EDX, XRD, VSM, ICP-OES
3426 cm is devoted to the stretching vibration of the
adsorbed water or surface hydroxyl groups [95]. In FT-IR
spectrum of CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
and TGA/DSC analyses.
2
4
2
−
1
(
Fig. 3b), a broad absorbance at 583 cm is devoted to
Fig. 3 FT-IR spectra of (a) CuFe O and (b) CuFe O @SiO @PTMS@Tu@Ni(II), (c) CuFe O @SiO @PTMS@Tu and (d) thiourea
2
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2
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Journal of the Iranian Chemical Society
bending vibration of Cu–O, Fe–O and Ni–O. The layering
of silica around nanocores of copper ferrite and the linkage
of propylsiloxy groups are also veriꢀed by a strong absorb-
−
1
ance band at 1080 cm . Consequently, two bands around
−
1
1
422 and 1605 cm are also deꢀned to symmetric and
asymmetric vibrations of C=S in thiourea [96]. Compar-
ing the FT-IR spectrum of CuFe O @SiO @PTMS@Tu@
2
4
2
Ni(II) (Fig. 3b) with that of CuFe O @SiO @PTMS@Tu
2
4
2
(
Fig. 3c) shows that the peak pattern of both spectra is the
same; however, intensity of the peaks around 3432 and
−
1
2
924 cm showing the stretching vibrations of NH and
2
the aliphatic propyl groups, respectively, was increased.
Through the immobilization of Ni(II) species, in addition,
−
1
a little shifting (1–3 cm ) of the signals to lower frequen-
cies in FT-IR spectrum of CuFe O @SiO @PTMS@Tu@
2
4
2
Ni(II) is observable. In this context, FT-IR spectrum of
thiourea (Fig. 3d) representing the signal position of NH ,
2
C–N and C=S bonds demonstrates that the immobiliza-
tion of thiourea on the surface of CuFe O @SiO @PTMS
2
4
2
MNPs was successfully taken place. Based on this evalu-
ation, therefore, the immobilization of thiourea, propyl-
siloxy and silica layer on nanocores of CuFe O was suc-
2
4
cessfully veriꢀed.
SEM analysis
Next, the porosity and surface morphology of CuFe O @
2
4
SiO @PTMS@Tu@Ni(II) MNPs was studied using scan-
2
ning electron microscopy (SEM) technique. Illustrated
images in Fig. 4 show that surface of Ni(II)–CuFe O
2
4
MNPs has the extreme porosity; however, to some extent,
the agglomeration of nanoparticles was led to the for-
mation of bulk segments. The nanoparticles have harsh/
irregular shapes and they are distributed in the range of
1
5–34 nm.
EDX and ICP‑OES analysis
In continuation, the elemental proꢀle of CuFe O @SiO @
2
4
2
PTMS@Tu@Ni(II) MNPs was also determined by energy-
dispersive X-ray (EDX) analysis. Depicted graph in Fig. 5
shows that all the required elements (C, N, O, Fe, Si, Cu,
S and Ni) are present in composition of the nanocatalyst,
and therefore, it demonstrates the successful preparation of
CuFe O @SiO @PTMS@Tu@Ni(II) MNPs. Consequently,
2
4
2
the exact amount of Ni (19.9%) and Cu (9.7%) was deter-
mined using inductively coupled plasma–optical emission
spectroscopy (ICP-OES).
XRD analysis
At the next, the phase purity and crystallinity character
of CuFe O and CuFe O @SiO @PTMS@Tu@Ni(II)
Fig. 4 SEM images of CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
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4
2
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Journal of the Iranian Chemical Society
Fig. 5 EDX spectrum of
CuFe O @SiO @PTMS@Tu@
2
4
2
Ni(II) MNPs
Fig. 6 XRD patterns of (a) CuFe O and (b) CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
2
4
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Journal of the Iranian Chemical Society
MNPs were studied using X-ray diꢃraction (XRD) analysis
decreased, it was enough for any magnetic separation.
It is also concluded that, because of the existing of hys-
teresis loop of magnetization, the prepared laboratory
samples of CuFe O and CuFe O @SiO @PTMS@Tu@
(
Fig. 6). The XRD pattern of CuFe O (Fig. 6a) represents
2 4
the signals at 2Ɵ=19.01°, 30.2°, 35.8°, 43.3°, 54.3°, 57.9°
and 62.6° corresponding to the reꢂection planes of (1 1 1),
2
4
2
4
2
(
2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0), respec-
Ni(II) MNPs have the characteristic of soft ferromagnetic
tively. Comparison of the pattern with the standard one of
cubic spinel CuFe O (JCPDS 77–0010) [97] illustrates
materials [98].
2
4
the prepared laboratory sample of copper ferrite has the
TGA and DSC analysis
impurity of CuO and Fe O . Thus, the phase purity of the
2
3
CuFe O sample was slightly downed; however, its crystal-
Thermogravimetric (TGA) and differential scanning
calorimetric (DSC) of CuFe O @SiO @PTMS@Tu@
2
4
linity character, based on the signal shapes, is high. More-
2
4
2
over, comparing the XRD pattern of CuFe O @SiO @
Ni(II) MNPs were illustrated in Fig. 8. The figure shows
that via the process of dehydration at the programma-
ble heating (30–800 °C) as well as removing of organic
moiety, fragmentation and calcination, mass losing of the
nanocomposite system was carried out. Observation of
the results represented that through the raising of tem-
perature (10 °C/min), overall mass losing of CuFe O @
2
4
2
PTMS@Tu@Ni(II) (Fig. 6b) with the laboratory sample
of CuFe O (Fig. 6a) represents that during the layering of
2
4
SiO @PTMS@Tu moiety and anchoring Ni(II) species,
2
the cubic spinel structure of CuFe O remained intact. The
2
4
pattern analysis also shows that the crystallinity character
and phase purity of the Ni(II)–CuFe O and CuFe O are
2
4
2
4
2
4
the same. In this context, the average crystallite size of
SiO @PTMS@Tu@Ni(II) MNPs is 16.17%. In addition,
2
CuFe O @SiO @PTMS@Tu@Ni(II) MNPs (based on
the DSC graph of Ni(II)–CuFe O system shows that
2
4
2
2
4
the Debye–Scherrer equation) was calculated 54.35 nm,
while λ = 0.1542 nm, 2Ɵ = 35.783°, FWHM = 0.2558°,
β = 0.00446 rad).
the main mass losing of the nanocatalyst was carried
out at 323 °C. These data clearly show that the prepared
CuFe O @SiO @PTMS@Tu@Ni(II) MNPs has high
2
4
2
thermal stability.
VSM analysis
Synthesis of biscoumarin materials catalyzed
by CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
Magnetic properties of CuFe O and CuFe O @SiO @
2
4
2
4
2
2
4
2
PTMS@Tu@Ni(II) MNPs were determined using vibrat-
ing-sample magnetometer (VSM) analysis in an applied
magnetic field up to 20 KOe. Based on this analysis
After the successful synthesis and characterization of
CuFe O @SiO @PTMS@Tu@Ni(II) MNPs, catalytic
2
4
2
(
Fig. 7), the saturation magnetization (Ms) values of
activity of the prepared nanocatalyst was further studied
toward one-pot the Knoevenagel–Michael reaction of
4-hydroxycoumarin with aromatic aldehydes. To optimize
reaction conditions, therefore, the condensation reaction
of 4-hydroxycoumarin with benzaldehyde was selected
as the model reaction and the inꢂuence of parameters
including the change of reaction-solvent and temperature,
using solvent-free conditions and varying the amount of
nanocatalyst were studied therein (Table 1). Investigation
of the results exhibited that among the examined condi-
tions, using benzaldehyde (1 mmol), 4-hydroxycoumarin
CuFe O and CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
2
4
2
4
2
−
1
were determined 13.49 and 5.45 emu g , respectively.
Comparison of the Ms values clearly shows that during
the layering of magnetic nucleuses with nonmagnetic spe-
cies, the saturation magnetization of the final nanocom-
posite was notably decreased. Although the value was
(
2 mmol) and the Ni(II)–CuFe O MNPs (10 mg) under
2 4
solvent-free conditions (70 °C) were the requirements to
carry out the titled transformation within 15 min and in
high yield. Therefore, the conditions mentioned in entry
1
3 (Table 1) were selected as the optimum parameters. It
is also notable that performing of the model reaction in
the presence of CuFe O MNPs (20–40 mg) did not show
2
4
any better results under reꢂux and solvent-free conditions
within 120 min (Table 1, entries 1 to 4).
Next, the catalytic activity and usefulness of CuFe O @
2
2
4
SiO @PTMS@Tu@Ni(II) MNPs were further studied
Fig. 7 Magnetization curves of (a) CuFe O and (b) CuFe O @
2
4
2
4
SiO @PTMS@Tu@Ni(II) MNPs
toward one-pot the Knoevenagel–Michael reaction of
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Journal of the Iranian Chemical Society
Fig. 8 TGA and DSC analyses
of CuFe O @SiO @PTMS@
2
4
2
Tu@Ni(II) MNPs
Table 1 Optimization experiments for synthesis of 3,3′-(phenylmethylene)-bis(4-hydroxy-2H-chromen-2-one) via the condensation reaction of
-hydroxycoumarin (2 mmol) with benzaldehyde (1 mmol)
4
Entry
Catalyst
Catalyst
mg)
Solvent
(mL)
Temperature
Time
(min)
Conversion
(%)
o
(
( C)
1
2
3
4
5
6
7
8
9
CuFe O4
40
20
20
20
70
70
70
70
70
70
70
20
10
10
Solvent-free
Solvent-free
70
70
120
120
120
120
120
120
120
120
120
120
120
15
80
80
0
50
90
70
50
10
0
2
CuFe O4
2
CuFe O4
H O
Reꢂux
Reꢂux
Reꢂux
Reꢂux
Reꢂux
Reꢂux
Reꢂux
Reꢂux
Reꢂux
70
2
2
CuFe O4
EtOH
2
CuFe O @SiO @PTMS@Tu@Ni(II)
H O
2
4
2
2
CuFe O @SiO @PTMS@Tu@Ni(II)
EtOH
2
4
2
CuFe O @SiO @PTMS@Tu@Ni(II)
MeOH
CH Cl
2
4
2
CuFe O @SiO @PTMS@Tu@Ni(II)
2
4
2
2
2
CuFe O @SiO @PTMS@Tu@Ni(II)
n-Hexane
2
4
2
10
11
12
13
14
CuFe O @SiO @PTMS@Tu@Ni(II)
CH CN
0
2
4
2
3
CuFe O @SiO @PTMS@Tu@Ni(II)
EtOAc
50
100
100
40
2
4
2
CuFe O @SiO @PTMS@Tu@Ni(II)
Solvent-free
Solvent-free
Solvent-free
2
4
2
CuFe O @SiO @PTMS@Tu@Ni(II)
70
r.t.
15
60
2
4
2
CuFe O @SiO @PTMS@Tu@Ni(II)
2
4
2
4
-hydroxycoumarin with structurally diꢃerent aromatic,
as furfural and thiophene-1-carbaldehyde as the same of
aromatic aldehydes were also successfully performed the
titled reaction within 25 min and in 92–95% yields. Conse-
quently, all attempts to examine the reaction of 4-hydroxy-
coumarin with formaldehyde as an aliphatic aldehyde were
also unsuccessful.
heterocyclic and aliphatic aldehydes at the optimized reac-
tion conditions (Table 2).
Investigation of the results represents that aromatic
aldehydes including electron releasing and withdrawing
functionalities were easily participated in the condensa-
tion reaction using the Ni(II)–CuFe O MNPs (10 mg)
In continuation, the suitability of this syn-
thetic method was highlighted by compari-
son of the obtained result for synthesis of
2
4
to aꢃord biscoumarin materials within 15–30 min and in
high yields. In this context, heterocyclic aldehydes such
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Journal of the Iranian Chemical Society
Table 2 Synthesis of
biscoumarin materials catalyzed
by CuFe O @SiO @PTMS@
2
4
2
Tu@Ni(II) MNPs
Entry
RCHO
Time (min)
Yield (%)
1
15
95
2
3
4
5
20
20
25
20
92
92
93
92
6
7
8
9
20
30
20
15
15
15
93
93
94
96
95
96
1
1
0
1
1
1
1
2
3
4
25
25
30
95
93
93
1
1
1
5
6
7
25
25
60
92
95
0
All reactions were carried out with the molar ratio of aldehyde (1 mmol), 4-hydroxycoumarin (2 mmol)
and the Ni(II)–CuFe O MNPs (10 mg) under solvent-free conditions (70 °C)
2
4
3
,3′-(phenylmethylene)-bis(4-hydroxy-2H-chromen-2-one)
the present work represents the outstanding result than the
previous systems.
catalyzed by CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
2
4
2
with those of reported for other protocols. Table 3 shows
that in terms of the yield, reaction time and reusability of
the nanocatalyst as well as beneꢀts of solvent-free condition,
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Journal of the Iranian Chemical Society
Table 3 Comparison of the synthesis of 3,3′-(phenylmethylene)-bis(4-hydroxy-2H-chromen-2-one) with CuFe O @SiO @PTMS@Tu@Ni(II)
2
4
2
MNPs and other reported systems
Entry
Catalyst
Time (min)
Yield (%)
Condition
Reusability
Ref.
1
2
3
4
5
6
7
8
9
CuFe O @SiO @PTMS@Tu@Ni(II)
I2
15
27
30
15
20
60
20
30
70
25
150
60
15
25
12
120
95
93
95
96
93
95
92
90
82
92
93
87
80
95
97
96
H O/70 °C
6
–
–
5
5
8
–
3
–
–
5
–
4
6
4
2
Present work
[60]
[61]
[63]
[64]
[65]
[66]
[69]
[70]
[71]
[72]
[73]
[76]
[77]
[78]
[81]
2
4
2
2
H O/100 °C
2
n-Bu NBr
H O/100 °C
4
2
Sulfated titania
Phosphotungstic acid
Silica gel
H O/80 °C
2
H O/80 °C
2
H O/reꢂux
2
Silica sulfuric acid NPs
NaHSO /SiO
H O/reꢂux
2
Toluene/100 °C
4
2
p-Toluenesulfonc acid
H O/reꢂux
2
10
11
12
13
14
15
16
RHA-SO H
Solvent-free/80 °C
3
Sodium dodecyl sulfate
H O/60 °C
2
n-Dodecylbenzene sulfonic acid
Graphene oxide nanosheets
Acid-activated montmorillonite
nano Fe O @ZrO –H PO
H O/40 °C
2
H O/reꢂux
2
H O/r.t.
2
H O/reꢂux
3
4
2
3
4
2
[PSebim][OTf] as IL (ionic liquid)
IL/70 °C
Although the exact mechanism of this synthetic
Ni(II)–CuFe O MNPs were magnetically separated from
2 4
method is not clear, a depicted mechanism in Fig. 9 shows
the promotion role of CuFe O @SiO @PTMS@Tu@
the reaction mixture, washed with EtOH and then dried
under air atmosphere. The vessel of reaction was again
charged with the fresh benzaldehyde, 4-hydroxycoumarin
and the recycled Ni(II)–CuFe O MNPs to run the con-
2
4
2
Ni(II) MNPs in one-pot the Knoevenagel–Michael reac-
tion of aromatic/heterocyclic aldehydes with 4-hydrox-
ycoumarin. The figure shows that via activation of the
aldehyde by the Ni(II)–CuFe O MNPs, nucleophilic
2
4
densation reaction for a second time. Figure 10 represents
that CuFe O @SiO @PTMS@Tu@Ni(II) MNPs can be
2
4
2
4
2
attack of 4-hydroxycoumarin with the aldehyde affords
reused for six consecutive cycles without the significant
loss of catalytic activity. Moreover, VSM (Fig. 11), FT-IR
(Fig. 12) and EDX (Fig. 13) spectra of CuFe O @SiO @
3
-(benzylidene)chroman-2,4-dione (I). Consequently, the
Michael reaction of 4-hydroxycoumarin (second mole-
cule) with the prepared intermediate (I) produces the final
biscoumarin material.
2
4
2
PTMS@Tu@Ni(II) MNPs after first recycling step rep-
resent that the magnetic property and structure of the
Ni(II)–CuFe O MNPs remained intact. In this context,
2
4
Recycling of CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
the framework stability of the Ni(II)–CuFe O MNPs was
2
4
2
2 4
also examined by measuring Ni-content before and after
first/second recycling steps of the nanocatalyst. The ICP-
OES analysis represents that the percentage of Ni spe-
cies in the fresh, first and second recycling steps of the
nanocatalyst is 19, 18.99 and 18.68%, respectively. Based
on these results, it is concluded that the leaching of Ni
species in CuFe O @SiO @PTMS @Tu@Ni(II) MNPs
The green aspect of the Knoevenagel–Michael reaction of
benzaldehyde with 4-hydroxycoumarin in the presence of
CuFe O @SiO @PTMS@Tu@Ni(II) MNPs was further
2
4
2
investigated by examining the reusability of the nano-
composite at the optimized reaction conditions. In this
area, once the condensation reaction was completed, the
2
4
2
is negligible.
1
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Journal of the Iranian Chemical Society
Fig. 9 A proposed mecha-
nism for the promotion role of
CuFe O @SiO @PTMS@Tu@
2
4
2
Ni(II) MNPs
Fig. 10 Reusability of CuFe O @SiO @PTMS@Tu@Ni(II) MNPs
2
4
2
Fig. 11 Magnetization curve of CuFe O @SiO @PTMS@Tu@Ni(II)
2
4
2
Conclusion
MNPs after ꢀrst recycling
In this paper, we have synthesized magnetically nanoparti-
cles of the immobilized Ni(II) species on thiourea function-
alized copper ferrite: CuFe O @SiO @PTMS@Tu@Ni(II).
DSC analyses. Catalytic activity of the Ni(II)–CuFe2O4
MNPs was investigated toward one-pot the Knoeve-
nagel–Michael reaction of 4-hydroxycoumarin with aro-
matic/heterocyclic aldehydes under solvent-free conditions
2
4
2
The prepared nanocatalyst system was then characterized
using FT-IR, SEM, EDX, XRD, VSM, ICP-OES, TGA and
(70 °C) giving biscoumarin materials within 15–30 min and
1
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Journal of the Iranian Chemical Society
6
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