Efficient synthesis of β-aminoketones catalyzed by Fe3O4@ quillaja sapogenin/Ni (II) as a novel magnetic nano-catalyst

Article abstract of DOI:10.1002/aoc.5834

A new nano-magnetic core–shell Fe₃O₄@quillaja sapogenin/Ni (II) was synthesized and characterized thoroughly using various tests including energy-dispersive X-ray spectroscopy (EDS), Brunauer–Emmett–Teller (BET), thermo-gravimetric analysis (TGA), high-resolution transmission electron microscopy (HR-TEM), vibrating sample magnetometer (VSM), Fourier transform infrared (FT-IR) spectroscopy, inductively coupled plasma (ICP), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The achievements demonstrated that the proposed agents were beneficial to synthesis the derivatives of β-aminoketone. Moreover, it was possible to recover the catalyst by means of simple magnetic decantation quickly. Besides, no reduction in the activity of the catalyst occurred, even though it was utilized in various reactions.

Full text of DOI:10.1002/aoc.5834

Received: 29 February 2020
DOI: 10.1002/aoc.5834
Revised: 8 April 2020
Accepted: 18 April 2020
F U L L P A P E R
Efficient synthesis of β-aminoketones catalyzed by Fe O @
3
4
quillaja sapogenin/Ni (II) as a novel magnetic nano-catalyst
1
2
1
Majid Heidarpour | Hossein Anaraki-Ardakani
| Neda Hasanzadeh
|
1
Ayeh Rayatzadeh
1
Department of Chemistry, Ahvaz Branch,
A new nano-magnetic core–shell Fe O @quillaja sapogenin/Ni (II) was
Islamic Azad University, Ahvaz, Iran
3 4
2
Department of Chemistry, Mahshahr
synthesized and characterized thoroughly using various tests including
energy-dispersive X-ray spectroscopy (EDS), Brunauer–Emmett–Teller (BET),
thermo-gravimetric analysis (TGA), high-resolution transmission electron
microscopy (HR-TEM), vibrating sample magnetometer (VSM), Fourier trans-
form infrared (FT-IR) spectroscopy, inductively coupled plasma (ICP), X-ray
diffraction (XRD) and scanning electron microscopy (SEM). The achieve-
ments demonstrated that the proposed agents were beneficial to synthesis
the derivatives of β-aminoketone. Moreover, it was possible to recover the
catalyst by means of simple magnetic decantation quickly. Besides, no reduc-
tion in the activity of the catalyst occurred, even though it was utilized in
various reactions.
Branch, Islamic Azad University,
Mahshahr, Iran
Correspondence
Hossein Anaraki-Ardakani, Department
of Chemistry, Mahshahr Branch, Islamic
Azad University, Mahshahr, Iran.
Email: hosseinanaraki@yahoo.com
K E Y W O R D S
3 4
green chemistry, nano Fe O , nickel (II) chloride, quillaja saponin, three-component
1
| INTRODUCTION
a heterogeneous MNPs support for organic-based
[
6,7]
catalysts.
Among different nanoparticles, Fe O
3 4
Considering specific merits of heterogeneous catalysts,
many research activities have been made in recent years
by chemists to utilize this catalyst. Easy storage, as well
as easy handling, and also the ability to be recovered
and reproduced in an easy way, can be mentioned as
nanoparticles widely studied by researchers as the core
magnetic support owing to its specific properties
such as strong magnetic properties, high chemical
stability, being abundant, effortless preparation via co-
[
8,9]
precipitation, and low toxicity.
It should be noted
[1,2]
some of their advantages.
A big section of these cata-
that pure Fe O4 nanoparticles, with the high surface
3
lysts is profound intrant the supporting material, and
thus reactants have finite accessibility to the catalytic
area to volume ratio, are highly chemically active and
[
10]
suffer from an inherent instability.
They are very
[3]
sites. But with the use of nanometer scales, the ener-
getic level of these catalysts increases and can be
completely dispersed in solutions and produce homoge-
sensitive to oxidation and tend to aggregate spontane-
ously when exposed to acids and aqueous solutions. In
order to surmount these limitations, it is essential to
protect the surface of nanoparticles by an external
[4,5]
neous conditions.
[
11,12]
In this area, MNPs are known as efficient nano-
support because they are recovered from the mixture
by a magnet, which is more convenient and efficient
than the filtration or centrifugation approach. In recent
layer made out of carbon and silica.
Recently, many researchers try is to produce cata-
lysts by covering magnetic nanoparticle iron oxide
with organic materials initiate in plants. The Licorice
plant, Quillaja Saponaria (sapogenin), is one of those
years, Fe O4 MNPs have been utilized commonly as
3
Appl Organomet Chem. 2020;e5834.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
1 of 13
https://doi.org/10.1002/aoc.5834

2
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HEIDARPOUR ET AL.
organic materials which are a huge evergreen plant
with leathery and bright leaves. They also have thick
bark and are originally from Peru, China, and the
2 | EXPERIMENTAL
2.1 | General
[13]
semi-arid regions of Chile.
Generally, sapogenin
widely found in terrestrial plants like the bark of
quillaja and marine animals. Investigating the chemi-
cal structure of sapogenin is concluded in that
sapogenins are steroids having extremely broad
applications related to cancer, blood circulation sys-
All chemicals utilized in this work were provided from
Aldrich and Merck companies and used without
further purification. An electrothermal apparatus was
implemented to measure the melting points of utilized
chemicals in the laboratory. FT-IR spectra were detected
[14–16]
−1
tem, and some other clinical issues.
Sapogenin
in a range between 4,000 and 400 cm by Perkin Elmer
used in industry is provided from the outer layer
quillaja trunk.
apparatus. In order to monitor the progress of reactions,
thin-layer chromatography (TLC) test was conducted
under UV light to visualize the process well enough. TLC
papers were provided in Merck. A Philips XRD apparatus
was utilized to analyze the powder of product via Cu/Kα
radiation, the wavelength of which was 1.54 Å.
In recent years, extracts of natural plants have exten-
sively exploited as foam-making materials in beverages,
emulsifiers in food and Medicine, and soaking agents in
[17]
photography.
Sapogenin is dominantly composed of
cellulose, a part of which is hydrophobic, the other par is
hydrophilic. Functional groups existing in the hydro-
philic part of the sapogenin make it capable of chemical
modifications. Therefore, sapogenin can be used in order
to bond various functional groups to synthesis polymeric
TGA experiments were done by a LINSEIS MODEL
1600 PT. The apparatus is commonly used for thermal
analysis purposes with a heating rate of 5 C/min under
ꢀ
ambient pressure. The magnetic properties of the sample
were identified through vibrating sample magnetometer
under room temperature.
[18]
catalysts.
1
13
Among the family of cellulose derivatives, the
building of the quillaja sapogenin (QS) in particular
is appealing because it contains a mixture of major
properties of quillaja sapogenin with incredible features
of materials. Owing to the presence of OH groups in
its polymeric tissue, it will be applied as an effective
coating for iron nanoparticles, and then obtained by
engaging an active metal halide at the Core-
H and C NMR spectra were studied by a Bruker
DRX-500 Avance spectrometer. DMSO-d6 solution by
TMS was utilized as the internal standard. A Mira III
apparatus was implemented to obtain SEM. EDX analysis
was performed for the mapping of the nanocomposites
elements. It should be mentioned that a 10 mA layer of
gold was utilized to cover the surface of the sample two
minutes before the test.
[19]
shell surface.
Munnich type reactions were conducted to form C-C
bonds in the synthesis process. Compounds of the β-
aminoketones, which are necessary intermediates
in herbal products, were provided through the mentioned
3 | METHODS
3.1 | Fe O MNPs preparation
3
4
[17,20]
process.
Previously, a portion of the β-aminoketone's com-
MNPs precipitated in the alkali solution of Fe (III) and
ꢀ
pounds had already been catalyzed by H PW O
Fe (II) (molar ratio 2:1) at 80 C via the standard co-
3
12 30
[
21]
[22]
[32]
(
hetero poly acids),
carbon-based solid acid,
dia-
precipitation method reported by Liu et al.
[
23]
[24]
[25]
ryliodonium (III),
BiNO3,
citric acid,
proline and
Cu/NH -SBA-15,,
ionic liquid (carboxyl-functionalized poly)
The mentioned catalysts for this purpose,
FeCl .6H O (10 mmol, 2.7 g) and FeSO .7H O
3
2
4
2
[
26,27]
[28]
[29]
solution,
InCl3
CFPIL).
calixarenes,
(10 mmol, 1.39 g) were gradually poured in a 100 ml sam-
2
[
30]
ple of distilled water, which had already been deoxygen-
[31]
ꢀ
(
ated. The mixture was vigorously dispersed at 80
C
despite having some advantages, have also some disad-
vantages, including time consuming reaction process,
a small yield of products, harmfulness, and low effi-
ciency in the recovery process. Thus, it seems essential
to replace them with other ones without owing to
these disadvantages.
under nitrogen gas protection. Afterward, a 7.5 mm sam-
ple of ammonium hydroxide was added to the dispersed
mixture swiftly.
The reaction mixture was suddenly incorporated with
ammonium hydroxide by a volume of 7.5 ml. Finally, the
2+
3+
base was added to the aqueous phase of Fe /Fe for-
ming black precipitations, which were MNPs. The pro-
cess was preceded for another 1 hr, and the aqueous
phase was cooled down to ambient temperature. Black
precipitations were isolated via an external magnet. After
In this report, we synthesis and characterize
nano-Fe O @Qs/Ni (II) as a bio-based, magnetic, and
3
4
effective heterogeneous catalyst for the synthesis of
β-aminoketones.

HEIDARPOUR ET AL.
3 of 13
gathering them from the aqueous phase, they were
washed by water and dried in a vacuum 4 times.
3.6 | 3-(4-Bromo-phenylamino)-
3-(4-chloro-phenyl)-1-phenyl-propan-1-one
[33,34]
(Table 3, entry 4i)
ꢀ
−1
3
.2 | Preparation of nano-Fe O @ Quillija
Mp 171–173 C, IR (KBr, cm ): 751, 1,082, 1,300, 1,511,
3
4
Sapogenin
1,599, 1,682, 3,376; Analyses:Calcd, For C H BrClNO:
C,60.82; H,4.13; N,3.38; Found: C, 60.87; H,4.17; N,
3.31%. H NMR(300 MHz, CDCl ): δ = 7.92(s,2H),
21
17
1
A mixture of synthesized nano-Fe O (1.5 g) and Quillaja
3
4
3
Saponin (2.5 g) in 30 ml ethanol was stirred for 20 min at
ambient temperature. After the reaction, the products
were removed by a magnet and dried at room tempera-
ture, 3.96 g of product were obtained.
7.87(d,J = 1.4 Hz, 1H), 7.58(m, 2H), 7.46(t,J = 7.82 Hz,
2H), 7.38–7.27(m, 2H), 7.19–7.15(m, 2H), 6.43–6.40(m,
13
2H), 4.92(br, 1H), 4.65(s, br, 1H), 3.45(m, 2H). ( CNMR,
75 MHz, CDCl ): δ = 197.8, 145.7, 140.9, 136.4, 133.7,
3
1
4
33.2, 131.8, 129.05, 128.8, 128.1, 127.7, 115.4, 109.8, 54.2,
4.9 ppm.
3
.3 | Preparation of nano-Fe O @ Quillija
3 4
Sapogenin/Ni (II)
3
.7 | 3-(4-Bromo-phenylamino)-1-phenyl-
The obtained nano-Fe O powder (0.15 g) and quillaja
3-p-tolyl-propan-1-one (Table 3, entry 4j)
3
4
saponin (0.3 g) and NiCl .6H O (1 g) were dispersed in an
2
2
ꢀ
−1
ethanol sample (10 ml) via stirrer at ambient temperature
for half of an hour. After the reaction, the solvent was
evaporated at room temperature to be obtained in good
yields. Afterward, its magnetic properties were analyzed.
In the next step, products were washed via ethanol again.
Mp 175–177 C, IR (KBr, cm ): 761, 1,092, 1,312, 1,398,
1,513, 1,603, 1,673, 3,060, 3,395; Analyses:Calcd, For
C H BrNO: C, 67.01; H, 5.11; N, 3.55%; Found: C,
67.11; H, 5.18; N, 3.58%; H NMR (300 MHz, CDCl ):
δ = 7.94–6.43(m,13H), 6.40(m,1H), 4.91(m,1H), 3.60(d,d,
J = 12, J = 4.5 Hz,1H), 3.34–3.22(d,d,J = 12,J = 4.5 Hz,
22
20
1
3
13
1H), 2.23(s,3H). ( CNMR, 75 MHz, CDCl ): δ= 198.5,
3
3
.4 | β-aminoketones' synthesizing
136.1, 134.8, 129.84, 129.80, 129.6, 129, 128.9, 128.7,
128.1, 127.8, 120.8, 114, 54.4, 46.4, 21 ppm.
procedure
A mixture of aromatic aldehydes (1 mmol), amines
(
(
1 mmol), ketones (1.1 mmol), and nano-Fe O @Qs/Ni
II) (0.07 g) was mixed in EtOH (15 ml) at room condi-
3.8 | 3-(4-nitro-phenylamino)-1-phenyl-
3-p-tolyl-propan-1-one (Table 3, entry 4 k)
3
4
tions. After the end of the reaction, which was recognized
by TLC, the synthesized catalyst was gathered with a
magnet, and the mixture was then warmed to achieve the
crude product. Finally, the crude product was purified by
ethanol/acetone crystallization; the following compounds
were achieved.
ꢀ
−1
Mp 163–165 C, IR (KBr, cm ): 767, 861, 1,223, 1,313,
1,513, 1,599, 1,670, 3,026, 3,391; Analyses: Calcd, For
C H N O : C, 73.32; H, 5.59; N, 7.77%; Found: C,
22
20 2 3
1
73.38; H, 5.51; N, 7.81%; H NMR (300 MHz, CDCl ): δ =
7.98–6.58(m,13H), 5.12(m,1H), 4.35(s,1H), 3.72(m,1H),
3.39(m,1H), 2.24(s,3H). ( CNMR, 75 MHz, CDCl ):
3
13
Spectral data of the purified products 4 h-m.
3
δ = 197.85, 152.2, 138.2, 138, 137.6, 135.25, 129.75, 128.8,
128.4, 128.15, 127.7, 126.6, 112.1, 53.9, 45.55, 21.05 ppm.
3
1
.5 | 3-(4-Bromo-phenylamino)-
,3-diphenyl-propan-1-one (Table 3,
entry 4 h)
3.9 | 4-(4-Bromo-phenyl)-1,3-diphenyl-
-phenylamino-butan-2-one (Table 3,
entry 4 l)
4
ꢀ
−1
Mp 177–179 C, IR (KBr, cm ): 768, 858, 1,067, 1,311,
,515, 1,606, 1,677, 2,888, 3,412. Analyses:Calcd, For
C H BrNO: C, 66.33; H, 4.77; N, 3.68; O, 4.21%.
1
ꢀ
−1
Mp 124–126 C, IR (KBr, cm ): 658, 703, 753, 1,504,
21
18
1
Found: C, 66.36; H, 4.80; N, 3.64%. H NMR(300 MHz,
1,605, 1,707, 3,436; Analyses: Calcd, For C H BrNO: C,
28
24
CDCl ): δ = 7.97–6.61(m,14H), 6.35(d,J = 6 Hz,1H),
71.49; H, 5.14; N, 2.98% Found: C, 71.58; H, 5.29; N,
3
13
1
5
.11(m,1H), 3.54(m,2H). ( CNMR,75 MHz,CDCl3):
δ = 198.1, 146.9, 141.6, 137.9, 133.1, 131.9, 128.6,
28.43, 128.4, 127.6, 126.1 116.9, 116.8, 55.14, 44.5 ppm.
2.78%, H NMR (300 MHz, CDCl ) δ = 7.36–7.17 (m,
3
10 H), 6.97–6.94 (m, 4H), 6.75–6.5 (m, 3H), 6.29 (d,
J = 7.67 Hz, 2H), 4.94 (d, Anti, J = 9.97 Hz, 0.92 H), 4.85
1

4
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HEIDARPOUR ET AL.
2
+
3+
(
d, syn, J = 4.81 Hz, 0.08 Hz), 4.13 (d, syn, J = 7.3 Hz,
Fe and Fe ions' co-precipitation, and then the prod-
uct of the first step was stirred with Quillaja Sapogenin.
Afterwards, it was utilized as a magnetic support in order
0
1
1
1
5
.09 H), 4.09 (d, anti, J = 10.16 Hz, 0.91 H), 3.73 (s, br,
1
3
H), 3.39 (s, 2H). ( CNMR, 75 MHz, CDCl ): δ = 204.7,
3
46.8, 141.15, 134.3, 132.6, 131.6, 129.6, 129.4, 129.1,
28.9, 128.7, 128.5, 127, 121.2, 118.1, 113.9, 113.5, 64.4,
8.9, 50.45 ppm.
to bond NiCl (Scheme 1).
2
The synthesized catalyst, nano-Fe O @Qs/Ni (II), is
3
4
characterized by FT-IR (Fourier transform infrared spec-
troscopy), XRD (X-ray diffraction), VSM (vibrating sam-
ple magnetometer), ICP (inductively coupled plasma),
EDX (Energy-dispersive X-ray spectroscopic analysis),
BET (Brunauer–Emmett–Teller), SEM (scanning electron
microscopy), HR-TEM (high-resolution transmission elec-
tron microscopy), and TGA (thermogravimetric analysis).
The results obtained from FT-IR spectroscopy of
(A) nano-Fe O , (B) nano-Fe O @Qs, (C) nano-
Fe O @Qs/Ni(II) are presented in Figure 1. An intensive
3 4
band observed in 585 cm through FT-IR spectra of the
nano-Fe O4 disclosed the presence of Fe-O stretching
vibrations. Furthermore, the wideband between 3,300
and 3,500 cm− is an indication of the presence of the
O-H bond stretching vibration.
3
4
.10 | 4-(4-Chloro-phenyl)-1,3-diphenyl-
-phenylamino-butan-2-one (Table 3,
entry 4 m)
ꢀ
−1
Mp 170–171 C, IR (KBr, cm ): 684, 700, 759, 1,511,
1
7
3
7
1
,608, 1,705, 3,443; Analyses: Calcd, For C H ClNO: C,
28 24
3
4
3 4
8.95; H, 5.68; N, 3.29% Found: C, 78.78; H, 5.41; N,
1
−1
.43% H NMR (300 MHz, CDCl ) δ = 7.36–7.27 (m,7H),
3
.2–7.17 (m, 3H), 7.07–6.95 (m, 3H), 6.75 (d, J = 1.35 Hz
H), 6.72 (d, J = 1.89 Hz, 1H), 6.64–6.58 (m, 1H), 6.37
d, J = 7.6 Hz, 1H), 6.30 (d,d, J = 8, J = 0.83 Hz,2H),
3
1
(
4
.97(d, anti, J = 10.15 Hz, 0.82H), 4.86 (d, syn,
J = 7.4 Hz 0.18H), 4.49 (s, br, 1H), 4.11 (d, syn,
J = 7.4 Hz, 0.18H), 4.08 (d, anti, J = 10.15 Hz, 0.82H),
Presence of Fe-O stretching vibration regarding the
absorption of nano- Fe O @Qs, Quillija Sapogenin
3
4
13
3
1
1
5
.39 (s, 2H). ( CNMR, 75 MHz, CDCl ): δ = 204.8,
(B) indicates that Quillija Sapogenin covers the magnetic
3
−
1
46.8, 140.6, 134.3, 132.6, 131.6, 129.6, 129.4, 129.1,
28.9, 128.7, 128.5, 127, 121, 117.7, 113.9, 113.65, 64.4,
8.9, 50.5 ppm.
nano-Fe O . Wideband at 3383 cm , which has resulted
3 4
from the presence of OH group, in conjunction with the
absorption bands around 2,925 cm− illustrates the
1
stretching vibrations of the C–H bonds. A band at
1
619 cm− denotes to the bending vibrations of H–O–H.
1
−
1
4
| RESULTS AND DISCUSSION
The absorption band between 1,065 and 1,100 cm illus-
trates the existence of the C–O bonds.
Nano-Fe O @Qs/Ni (II) was prepared through a two-step
The FT-IR spectra of the nano-Fe O @Qs/Ni
(II) (C) demonstrate a band at 415 cm that can be
3
4
3 4
−
1
process. The first step was synthesize of nano-Fe O by
3
4
3 4
SCHEME 1 Preparation of nano-Fe O @Qs/Ni (II)

HEIDARPOUR ET AL.
5 of 13
corresponded by O–Ni–O bending vibrations. The band
studied by means of high angle X-ray diffraction analysis
(XRD) (Figure 2).
at 615 cm− correspondings to stretching vibrations of
1
−1
ꢀ
Fe–O groups. The 1,626 cm band demonstrates the
The bare Fe O illustrates peaks at 2 = 30.3832 ,
3
4
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
presence of H–O–H bending vibrations. Bands around
35.7926 , 42.7498 , 52.6881 , 56.3598 , 61.64866 with
FWHM equal to 0.4722, 0.4722, 0.4723, 0.7873, 0.6298
and 0.6298 demonstrates the cubic structure of the
high-pure Fe O explained by other researchers
1
2
,921 cm− refer to the stretching vibration of C–H, the
stretching vibrations of O–H bonds have been recognized
−
1
at 3375 cm .
3
40]
4
[
In comparison with nano-Fe O @Qs, bonding Ni
(Figure 2A).
3
4
(
II) to the Qs shifts Fe–O stretching vibrations to lower
The same peaks were obtained from the XRD pattern
of nano-Fe O @Qs, which illustrates the preservation of
−1
−1
wave range (from 626 cm to 615 cm ) (Figure 1).
3
4
Structure and purity of the nano-Fe O (A), nano-
the structure of the crystalline spinel ferrite core while
cellulose coating process.
3
4
Fe O @Qs (B), and nano-Fe O @Qs/Ni (II)(C) are
3
4
3 4
FIGURE 1 FT-IR spectra of
(
a) nano-Fe
3
O
4
, (b) nano-Fe
3 4
O @Qs,
(
c) nano-Fe
3 4
O @Qs/Ni (II)
3 4 3 4 3 4
FIGURE 2 XRD patterns of the (a) nano-Fe O , (b) nano-Fe O @Qs, (c) nano-Fe O @Qs/Ni (II)

6
of 13
HEIDARPOUR ET AL.
ꢀ
ꢀ
ꢀ
Furthermore, other peaks at 2 = 19.8 and 21.3 ,
denote to the sapogenin cover on nano-Fe O (Figure 2
800 C is related to metals and some organic compounds
(Figure 3).
3
4
B). The XRD outputs of nano-Fe O @Qs/Ni (II) are an
To evaluate the elemental concentration of nano-
Fe O @Qs, an EDS test was performed. As shown in
Figure 4, the results of EDS nano Fe O @Qs demonstrate
3 4
3
4
indication of the amorphous structure.
3
4
ꢀ
ꢀ
ꢀ
ꢀ
Peaks observed at 2 = 12.5 , 19 , 21 , 27 were also
observed in the Fe O @Qs (Figure 2. C). The diffrac-
the existence of C, Fe, and O. Moreover; EDS experiment
outputs confirmed that the nano- Fe O and quillaja were
3
4
ꢀ
ꢀ
ꢀ
ꢀ
tion peaks at 2 = 16.6 , 49.1 , 53.6 , 55.73 demonstrate
3
4
the NiCl core. A sharp peak around 2 = 37 indicates
combined (Figure 4).
2
the existence of nano-Fe O @Qs and bonding of Ni to
Qs shell.
The presence of the desired elements in nano-
Fe O @Qs/Ni (II) was approved by EDX analysis
3
4
3
4
Thermo-gravimetric analysis (TGA) has been con-
ducted at temperatures between 0 to 800 C (Figure 3).
(energy-dispersive X-ray spectroscopy) (Figure 5). EDX
outputs obviously confirmed the existence of Fe, Cl,
Ni, O, C elements in the synthesized catalyst.
ꢀ
(
A) illustrates TGA data of nano-Fe O @Qs. The curve
3 4
indicates three phases of mass-loss. Firstly, the mass
loss occurred from 20 to 135 C was very low (about
The magnetic characteristics of the nano-Fe O (A),
nano-Fe O @Qs (B), and nano-Fe O @Qs/Ni (II) were
3 4 3 4
3
4
ꢀ
1
2.64%) and was related to inter-crystalline water and
evaluated at ambient temperature by a VSM analysis,
which is presented in Figure 6.
solvents' vapor. The second and third steps refer to the
mass loss resulted from weight loss due to the decom-
position of quillaja sapogenin molecules from the for-
mation of cellulose compounds. In the second step,
3
1
6
The whole of the results shows superparamagnetic
behavior. Therefore, the saturation magnetization of
nanoparticles is approximately 70.0 emu/g (Figure 6a) and
[41–44]
5.27% mass loss was observed in temperatures between
is far less than its bulk counterparts (92.0 emu/g).
The nano-Fe O @Qs/Ni (II) magnetization was lower
ꢀ
70 and 510 C. The third mass loss occurred from
3
4
ꢀ
ꢀ
40 C to 800 C.
than 30.0 emu/g. This might result from the presence of a
.
The TGA (B) is related to nano-Fe O @Qs/Ni (II).
The curve shows two mass-loss steps. Firstly, a weight
Sapogenin and Ni shells as double layers around nano-
Fe O core.
3
4
3
4
ꢀ
ꢀ
loss (39.49%) from 90 C to 416 C is related to the
removal of moisture and solvent and some organic com-
pounds of the catalyst. Subsequently, and other weight
The morphology and size of the nano-Fe O @Qs/Ni
3
4
(II) were investigated by scanning electron microscopy
(SEM). indicates that the dimensions of nano-Fe O @Qs/Ni
3
4
ꢀ
loss steps, the main weight loss (39.85%) from 422 C to
(II) are between 21 and 44 nm (Figure 7).
FIGURE 3 Thermal
gravimetric analysis pattern of
a) nano-Fe @Qs, (b)
nano-Fe @Qs/Ni (II)
(
3 4
O
3 4
O

HEIDARPOUR ET AL.
7 of 13
FIGURE 4 EDS diagram of
nano-Fe O @Qs
3 4
FIGURE 5 EDS diagram of
nano-Fe @Qs/Ni (II)
3 4
O
HR-TEM images were prepared to study the morpho-
logical characteristics of the catalyst, which are illus-
trated in Figures 8a and b.
HR-TEM test results convey the message that the
shape of Fe O @Qs/Ni (II) MNPs is a sphere with a size
3
4
range between 21 and 44 nm. Images shown in Figure 8
illustrates that a layer of Qs with a thickness of 8 nm is
formed around Fe O MNPs as a core-shell after being
3
4
modified by Qs.
Furthermore, based on Figure 8, the average diameter
for Fe O @Qs/Ni (II) is 33 nm.
3
4
Figure 9 illustrates the isotherms of N adsorption–
2
desorption on nano-Fe O @Qs and nano-Fe O @Qs/Ni (II).
3
4
3 4
The catalyst sample classifies as mesoporous mate-
rials, according to IUPAC, because it exhibits the IV type
behavior. The total surface area of Fe O @Qs was
FIGURE 6 Magnetization loops of (a) nano-Fe
nano-Fe @Qs and (c) nano-Fe @Qs/Ni (II)
3 4
O , (b)
3
4
2
−1
3
O
4
3
O
4
reduced from 8.9317 to 3.1174 m g after adsorbing

8
of 13
HEIDARPOUR ET AL.
3 4
FIGURE 7 SEM image of synthesized nano-Fe O @Qs/Ni (II)
FIGURE 8 (a). HR-TEM of synthesized catalyst at 50 nm scale. (b). HR-TEM of synthesized catalyst at 100 nm scale
FIGURE 9
isotherms of nano-Fe
Fe @Qs/Ni (II) (b)
N
2
adsorption–desorption
3 4
O
@Qs (a), nano-
3 4
O

HEIDARPOUR ET AL.
9 of 13
Ni. Therefore, it can be said that the decrease in the
amount of pore volume results from adsorption on Ni
complex on Qs surface. Results obtained from this test
show that because of the existence of a high volume
of organic materials presents in the inner surface of
Fe O (Figure 9). The surface characteristics of the cata-
between aromatic ketones, aromatic amines, and aro-
matic aldehydes (Scheme 2).
Initially, to optimize the reaction conditions reaction of
acetophenone, benzaldehyde, and aniline was chosen as a
model reaction. First, the model reaction was performed
using nano-Fe O , nano-Fe O @Qs, or nano-Fe O @Qs/Ni
3
4
3
4
3
4
3 4
lyst are tabulated in Table 1. In order to depict the mag-
netic characteristics of the prepared catalyst, nano-
Fe O @Qs/Ni (II) is dispersed in ethanol, which leads to
(II) as the catalyst. We found that nano-Fe O @Qs/Ni
3 4
(II) acted as a highly efficient catalyst for this reaction
(Table 2, entry 5). Also, only a trace amount of the product
was formed in the absence of a catalyst (Table 2, entry 1).
Then the model reaction was carried out in various solvent
with nano-Fe O @Qs/Ni (II) as a catalyst at ambient
3
4
a dark aqueous phase. By means of an external magnet,
the nano-Fe O @Qs/Ni (II) was totally gathered on one
3
4
side of the container. (Figure 10).
3
4
We have examined the catalytic activity of nano-
Fe O @Qs/Ni (II) for the preparation of β-aminoketone
temperature, and ethanol was recognized as the best
solvent (Table 2, entry 5).
3
4
derivatives via a one-pot three-component reaction
Afterward, optimization of catalyst amounts was car-
ried out in the model study by using different amounts
of the nano-Fe O @Qs/Ni (II). The higher yield was
3
4
obtained by increasing the amount of catalyst from
.01 g to 0.1 g. However, further increase of the molar
TABLE 1
3 4
Surface properties of nano-Fe O @Qs and
0
nano-Fe @Qs/Ni (II)
3 4
O
amount of the catalyst from 0.07 g to 0.1 g did not signif-
icantly increase the yield of the product (Table 2,
entry4). Hence, the optimum concentration of nano-
Fe O @Qs/Ni (II) NPs was selected 0.07 in the model
Pore diam by
BJH method
(m /g) (nm)
SBET
Pore vol
(cm /g)
2
3
Sample
3
4
Nano-Fe
Nano-Fe
3
3
O
O
4
4
@Qs
8.9317
3.1174
1.98
1.61
0.067303
0.012749
reaction. It was found that the best condition is using
.07 g of the catalyst with ethanol at room temperature
@Qs/Ni
0
(
II)
(
Table 2, entry4).
The efficiency and generality of the reaction were
investigated through various ketones, aromatic amines,
and aldehydes. The results are summarized in Table 3.
The most probable mechanism for the synthesis of β-
aminoketones was shown in Scheme 3.
Based on the results discussed before, it can be said
that bonds between initially magnetic nano-catalyst and
the carbonyl functional group of aldehyde (2) activate it
for a nucleophilic rash toward amines (3), which leads
intermediate (5) to be formed. Afterward, the intermedi-
ate loses a mole of water, and consequently, converts to
imine (6). Then the enol, which has been formed via
tautomerization of ketones (1) in the presence of nano-
catalyst, reacts with imine. The fruit of the latest reaction
is the final product (4) (Scheme 3).
FIGURE 10 Photographs of aqueous suspension of nano-
Fe @Qs/Ni (II) before (a) and after (b) magnetic capture
3 4
O
SCHEME 2 One-pot Mannich reaction of aromatic ketones, aromatic aldehydes and aromatic amines catalyzed by nano-Fe
II) at room temperature
3 4
O @Qs/Ni
(

10 of 13
HEIDARPOUR ET AL.
TABLE 2
The optimization of condition for the reaction of aniline, benzaldehyde and acetophenone
ꢀ
[a]
Entr
Catalyst(g)
Solvent-Temp( C)
EtOH-Reflux
EtOH-Reflux
EtOH-Reflux
EtOH-Reflux
EtOH-r.t.
Time(h)
Yield (%)
1
2
3
4
5
6
7
8
9
-
10
Trace
45
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
Nano-Fe
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
(0.1)
8
@QS(0.1)
6
75
@QS/Ni (II)(0.1)
@QS/Ni (II)(0.1)
@QS/Ni (II)(0.1)
@QS/Ni (II)(0.1)
@QS/Ni (II)(0.1)
@QS/Ni (II)(0.1)
@QS/Ni (II)(0.01)
@QS/Ni (II)(0.03)
@QS/Ni (II)(0.05)
@QS/Ni (II)(0.07)
@QS/Ni (II)(0.09)
@QS/Ni (II)(0.07)
@QS/Ni (II)(0.07)
4
91
4
93
MeOH-r.t.
5
65
CH
3
CN-r.t.
5
70
H
2
O-r.t.
5
Trace
55
HOAC-r.t.
EtOH-r.t.
EtOH-r.t.
EtOH-r.t.
EtOH-r.t.
EtOH-r.t.
EtOH-r.t.
EtOH-r.t.
5
1
1
1
1
1
1
1
0
1
2
3
4
5
6
4
55
4
70
4
85
4
93
4
93
2 2.30
2
93
89
a
isolated Yield.
TABLE 3
Entry
3 4
β-aminoketone preparation by nano-Fe O @Qs/Ni (II)
ꢀ
ꢀ
ketone
R
1
R
2
Time (h)
Yield (%)
anti/syn
mp. ( C)
lit. mp. ( C)
[
[
[
35]
36]
37]
4
4
4
4
4
4
4
4
4
4
4
4
4
a
b
c
d
e
f
Acetophenone
H
H
2.30
4
93
91
90
93
91
82
84
95
90
88
86
85
86
-
164–165
161–162
167–168
171–172
167–169
46–148
165–168
160–161
165–168
170–171
168–170
148–150
132–133
Acetophenone
4-OCH
4-OCH
H
3
3
4-CH
3
-
Acetophenone
H
3
-
[
38]
Acetophenone
4-Cl
H
2.30
2.20
2
-
[
[
[
39]
39]
39]
1,3-diphenylpropan-2-one
1,3-diphenylpropan-2-one
1,3-diphenylpropan-2-one
Acetophenone
H
99/1
4-F
H
91/9
j
4-OCH
H
3
H
3
99/1
131–133
177–179
171–173
175–177
163–165
124–126
170–171
h
4-Br
4-Br
4-Br
2.30
2.40
3
-
[This work]
[This work]
[This work]
[This work]
[This work]
[This work]
i
j
Acetophenone
4-Cl
-
Acetophenone
4-CH
4-CH
4-Br
3
-
k
Acetophenone
3
4-NO
2
3
-
l
1,3-diphenylpropan-2-one
1,3-diphenylpropan-2-one
H
2.30
2.20
92/8
82/18
m
4-Cl
H
Reaction conditions; aniline (1 mmol), aldehyde (1 mmol), acetophenon (1.1 mmol) or 1,3-diphenylpropan-2-one (1.1 mmol); catalyst
0.07 g).
(
5
| REUSABILITY AND LEACHING
The synthesized catalyst was washed with ethanol and
then was dried at ambient temperature in vacuum con-
dition. The wash and dry process were conducted four
times. Then the washed sample was used in reaction
cycles. As well-depicted in Figure 11, the catalyst is
capable of being reused up to 4 runs to achieve a yield
of 80 to 93%. Moreover, the ICP test results of virgin cat-
alyst show that the concentration of Ni in the catalyst is
STUDY OF THE CATALYST
The most paramount feature of the novel catalyst is
reusability. This feature was investigated in a model
reaction of Acetophenone, Benzaldehyde, and aniline in
optimization reaction conditions, after finished the reac-
tion, the catalyst was separated via an external magnet.

HEIDARPOUR ET AL.
11 of 13
SCHEME 3 Mechanism for
formation of β-aminoketones in the
presence of nano-Fe3O4@Qs/Ni (II)
FIGURE 11 The recycling experiment of
nano-Fe
3 4
O @Qs/Ni (II) in the synthesis of β-
aminoketones reaction
3
1
.63 × 10− mol/g. The same test was conducted on the
achieved after the reaction half-time (90 min); in this
way, the catalyst was recovered, and after filtration of
the mixture, the reaction was to proceed until 3 hours
(reaction ending time). It was observed that 50% of the
product was yielded. As a result, these experiments vali-
date that the synthesized catalyst is strong against
leaching (Figure 11).
recovered catalyst as well. It was disclosed that a very
small amount of Ni molecules got lost after reaction
because the Ni concentration in recovered catalyst
−
3
−3
−3
decreased to 1.63 × 10 , 1.61*10 , 1.6*10 , and
3
1
.59*10− mol/g after being recovered for first to fourth
time, respectively.
Hot filtration experiment was conveyed in the cou-
pling of 4-Bromoaniline 4-methyl benzaldehyde by
acetophenone to examine the leaching of the catalyst. In
this study, 49% of yield product was procured after a
half-time reaction. Moreover, the same result was
Finally, the efficiency and generality of this method
were assessed by comparison with already synthesized
catalysts. Comparison results are illustrated in Table 4.
Based on the data shown in Table 4, nano-Fe O @Qs/Ni
3
4
(II) is an efficient catalyst.

12 of 13
HEIDARPOUR ET AL.
TABLE 4
3 4
Efficiency comparison of nano-Fe O @Qs/Ni (II) with other catalysts
ꢀ
[b]
Entry
Catalyst
Amount
10 mol%
10 mol%
15 mol%
0.1 g
Temperature ( C)
Time(h)
yield (%) Ref
[
[
[
[
[
[
[
[
[
[
24]
23]
45]
22]
21]
31]
46]
47]
48]
25]
1
2
3
4
5
6
7
8
9
BiNO
3
25
25
25
25
25
25
30
25
25
25
25
4
89
83
92
90
76
70
75
86
92
90
Diaryliodonium (III)
Saccharose
24
9
Carbon-based solid acid
3.45
18
5
H
3
PW12
O
30
0.691 g
CFPIL-1
PS-SO
Al (CH
0.032 g
3
H
0.08 g
24
8
3
SO
3
)
3
.4H
2
O
0.5 mmol
1.63 mol %
20 mol%
0.07 g
[CellFemBen]CSA/EtOH
Citric acid
5
1
1
0
1
10
2.30
nano-Fe
3
O
4
@Qs/Ni (II)
93 [present work]
a
Reaction conditions: benzaldehyde (1 mmol); aniline (1 mmol); acetophenone (1.1 mmol).
Isolated yields.
b
[
8] X. Zheng, S. Luo, L. Zhang, J.-P. Cheng, Green Chem. 2009,
1, 455.
6
| CONCLUSIONS
1
[
9] Y. Jiang, C. Guo, H. Xia, I. Mahmood, C. Liu, H. Liu, J. Mol.
Catal. B: Enzym. 2009, 58, 103.
In summary, we have preparation and characterization
of nano-Fe O @Qs/Ni (II) as a nanomagnetic catalyst for
3
4
[10] L. M. Rossi, N. J. S. Costa, F. P. Silva, R. Wojcieszak, Green
Chem. 2014, 6, 2906.
[11] K. R. Rohit, M. R. Phadatarec, B. B. Sinha, D. M. Sakatee,
A. V. Ghulef, G. S. Ghodake, N. G. Deshpandea, V. J. Fulari,
J. Taiwan Inst. Chem. Eng. 2019, 95, 357.
12] C. S. Gill, B. A. Price, C. W. Jones, J. Catal. 2007, 251, 145.
13] P. V. Chavan, K. S. Pandit, U. V. Desai, M. A. Kulkarni,
P. P. Wadgaonkar, RSC Adv. 2014, 4, 42137.
14] A. Shaabani, A. Rahmati, Z. Badri, Cat. Com. 2008, 1, 13.
15] M. Syamala, Org. Prep. Proced. Int. 2009, 41, 1.
the synthesis of β-aminoketone derivatives via a one-pot
three-component reaction of ketones, aromatic alde-
hydes, and aromatic amines in ethanol at room tempera-
ture. Fast reaction rate, good yields, and mild reaction
conditions are the most significant advantages of this
methodology. Furthermore, the catalyst can easily be sep-
arated and reused for more runs.
[
[
[
[
ACKNOWLEDGEMENTS
[16] S. Balakrishnan, A. Rajendran, R. Kulandaivelu,
All authors appreciate the laboratory facilities provided
by Ahvaz Branch, Islamic Azad University, Ahvaz, Iran.
S. Narayanan, T. S. Nellaiappan, J. the Australian Cer. Soc.
2
019, 55, 953.
17] Y. C. Teo, J. J. Lau, M. C. Wu, Tetrahedron: Asymmetry 2008,
9, 186.
[
[
1
ORCID
18] S. K. Aghdam, A. Moslemizadeh, M. Madani, M. Ghasemi,
Hossein Anaraki-Ardakani https://orcid.org/0000-0002-
K. Shahbazi, M. K. Moraveji, Chem. Eng. Res. Des. 2019,
0
512-8033
147, 570.
[
19] A. Moslemizadeh, S. K. Aghdam, K. Shahbazi,
REFERENCES
S. Zendehboudi, J. Mol. Liq. 2017, 247, 269.
[
1] M. Chenguang, S. Hongqin, Z. Shixia, H. Peng, Z. Xiaoyan,
C. Yun, L. Hongling, J. Comp. Inter. 2019, 26, 537.
[20] S. A. Soldatova, N. M. Kolyadina, A. T. Soldatenkov,
A. V. Malkova, Russ. J. Org. Chem. 2019, 55, 479.
[
[
2] N. Mizuno, M. Misono, Chem. Rev. 1998, 98, 199.
3] A. Y. Leung, Encyclopedia of Common Natural Ingredients
Used in Foods, Drugs, and Cosmetics, Wiley, NY 1980.
[21] N. Azizi, L. Torkiyan, M. R. Saidi, Org. Lett. 2006, 8, 2079.
[22] A. Davoodnia, A. Tavakoli-Nishaburi, N. Tavakoli-Hoseini,
Bull. Korean Chem. Soc. 2011, 32, 635.
[
[
[
[
4] M. A. A. El-Remaily, A. M. Abu-Dief, Tetrahedron 2015, 71,
[23] Y. Zhang, J. Han, L. Zhen-Jiang, RSC Adv. 2015, 5, 25485.
[24] S. S. Mansoor, K. Aswin, K. Logaiya, S. P. N. Sudhan, J. Saudi
Chem. Soc. 2015, 19, 379.
[25] V. B. Ningdale, U. N. Chaudhar, K. A. Shaikh, J. Comp. Inter.
2014, 7, 86.
[26] R. Duthaler, Angew. Int. Ed. Engl. 2003, 42, 975.
[27] A. Sasaoka, M. I. Uddin, A. Shimomoto, Y. Ichikawa,
M. Shiro, H. Kotsuki, Tetrahedron: Asymmetry 2006, 17, 2963.
2
579.
5] M. A. A. El-Remaily, A. M. Abu-Dief, R. M. El-Khatib, Appl.
Organomet. Chem. 2016, 30, 1022.
6] A. M. Abu-Dief, I. F. Nassar, W. H. Elsayed, Appl. Organomet.
Chem. 2016, 30, 917.
7] A. A. Marzouk, A. M. Abu-Dief, A. A. Abdelhamid, Appl.
Organomet. Chem. 2018, 32, e3794.

HEIDARPOUR ET AL.
13 of 13
[
28] E. Akceylan, M. Yilmaz, Polycyclic Aromat. Compd. 2016,
6, 801.
29] S. A. A. Vandarkuzhali, B. Viswanathan, M. P. Pachamuthu,
[43] W. S. Mohamed, M. Alzaid, M. S. M. Abdelbaky, Z. A. S. García-
Grand, A. M. Abu-Dief, Nanomaterials 2019, 9, 1602.
[44] C. Toyos-Rodríguez, J. Calleja-García, L. Torres-Sánchez,
A. López, A. M. Abu-Dief, A. Costa, L. Elbaile, R. D. Crespo,
J. S. Garitaonandia, E. Lastra, J. A. García, F. J. García-Alonso,
J. Nanomaterials 2019, 10, Article ID 2464010.
[45] M. R. Mousavi, N. Hazeri, M. T. Maghsoodlou, S. Salahi,
S. M. Habibi-Khorassani, Chin. Chem. Lett. 2013, 24, 411.
[46] S. Iimura, D. Nobutou, K. Manable, S. Kobayashi, Chem.
Commun. 2003, 14, 1644.
3
[
S. C. Kishore, J. Inorganic and Organome Poly Mater 2020,
3
0, 359.
[
[
30] T. P. Loh, S. C. Chen, Org. Lett. 2002, 4, 3647.
31] A. G. Khiratkar, K. R. Balinge, K. J. Bhansali, P. R. Bhagat,
Res. Chem. Intermed. 2018, 44, 787.
[
32] X. Liu, Z. Ma, J. Xing, H. Liu, J. Magn. Magn. Mater. 2004,
2
70, 1.
33] K. Ghodrati, E. Dezfoolinezhad, R. Badri, New J. Chem. 2016,
0, 4575.
[
[47] M. Wang, Z.-G. Song, H. Jiang, Org Prepa and Proce Intern
2009, 41, 315.
4
[
[
34] N. Kakesh, S. Sayyahi, R. Badri, C. R. Chim. 2018, 21, 1023.
35] M. T. Maghsoodlou, N. Khorshidi, M. R. Mousavi, N. Hazeri,
S. M. Habibi-khorassani, Research on Chem Inter 2014, 41,
[48] S. Khanapure, M. Jagadale, D. Kale, S. Gajare, G. Rashinkar,
Aust. J. Chem. 2019, 72, 513.
7
497.
36] F. Dong, L. Jun, Z. Xin-Li, L. Zu-Liang, Catal. Lett. 2007,
16, 76.
37] Y. Dai, B. D. Li, H. D. Quan, C. X. Lu, Chin. Chem. Lett. 2010,
1, 31.
38] L. Wang, J. Han, J. Sheng, H. Tian, Z. Fan, Cat. Com. 2005,
, 201.
[
[
[
[
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
1
2
6
39] F. Nemati, A. S. Fakhaei, A. Amoozadeh, Y. Saeidi-Hayeniaz,
Synth. Commun. 2011, 41, 3695.
How to cite this article: Heidarpour M, Anaraki-
Ardakani H, Hasanzadeh N, Rayatzadeh A.
Efficient synthesis of β-aminoketones catalyzed by
Fe O @ quillaja sapogenin/Ni (II) as a novel
[
[
40] J. H. Jang, H. B. Lim, Microchem. J. 2010, 94, 148.
41] A. M. Abu-Dief, M. S. Abdelbaky, D. Martínez-Blanco,
Z. Amghouz, S. García-Granda, Mater. Chem. Phys. 2016, 174.
42] E. M. M. Ibrahim, L. H. Abdel-Rahman, A. M. Abu-Dief,
A. Elshafaiea, S. K. Hamdan, A. M. Ahmed, Mater. Res. Bull.
3
4
magnetic nano-catalyst. Appl Organomet Chem.
020;e5834. https://doi.org/10.1002/aoc.5834
[
2
2
018, 99, 103.