Synthesis of Fe3O4?SiO2/isoniazid/Cu(II) magnetic nanocatalyst as a recyclable catalyst for a highly efficient preparation of quinolines in moderate conditions

Article abstract of DOI:10.1016/j.poly.2019.114148

This paper reports the investigation on an efficient procedure to prepare Fe₃O₄?SiO₂/isoniazid/Cu(II) as a recoverable magnetic nanocatalyst. The prepared nanocatalyst, Fe₃O₄?SiO₂/isoniazid

Full text of DOI:10.1016/j.poly.2019.114148

Journal Pre-proofs
Synthesis of Fe O @Sio /Isoniazid/Cu(II) magnetic nanocatalyst as a recyclable
3
4
2
catalyst for a highly efficient preparation of quinolines in moderate conditions
Shahram Lotfi, Ahmad Nikseresht, Nasrin Rahimi
PII:
S0277-5387(19)30585-6
DOI:
https://doi.org/10.1016/j.poly.2019.114148
POLY 114148
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
5 May 2019
2 September 2019
7 September 2019
Please cite this article as: S. Lotfi, A. Nikseresht, N. Rahimi, Synthesis of Fe O @Sio /Isoniazid/Cu(II) magnetic
3
4
2
nanocatalyst as a recyclable catalyst for a highly efficient preparation of quinolines in moderate conditions,
Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.2019.114148
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Highlighted Revised Manuscript
Synthesis of Fe O @Sio /Isoniazid/Cu(II) magnetic nanocatalyst as a
3
4
2
recyclable catalyst for a highly efficient preparation of quinolines in moderate
conditions
*
Shahram Lotfi , Ahmad Nikseresht and Nasrin Rahimi
*
Corresponding author email: sh.lotfei@gmail.com, Tel. /Fax: +98 8343724748
1

Department of Chemistry, Payame Noor University (PNU), 19395-4697 Tehran, Iran
Abstract
This paper reports the investigation on an efficient procedure to prepare
Fe @SiO /Isoniazid/Cu(II) as a recoverable magnetic nanocatalyst. The prepared
nanocatalyst, Fe @SiO /Isoniazid/Cu(II), was identified via vibrating sample magnetometer
VSM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy
dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), x-ray powder diffraction
XRD) and Fourier transform infrared (FT-IR). The nanocatalyst was applied on Friedländer
synthesis for highly efficient preparation of quinoline derivatives from α-methylene ketones and
-aminoaryl ketones under moderate conditions. This method has the advantages of short
3
O4
2
3
O
4
2
(
(
2
reaction times, good yields as well as simple catalyst separation by external magnet and solution
decanting to recover the catalyst for next cycles, with ability to be used for 4 times without
significant loss in catalytic activity.
Key words: Heterogeneous nanocatalysts; Isoniazid/Cu(II); Friedländer synthesis; Quinolines
1
. Introduction
Over the past few years, the application of heterogeneous catalysts in various organic
transformations has proved strategically essential and eco-friendly. Owing to the solubility in
reaction media, homogeneous catalysts display better catalytic activities in chemical reactions
than their heterogeneous peers, increasing the availability of catalytic active sites for the
substrate and consequently easing the reaction [1]. Nonetheless, the serious issues related to
separating the homogeneous catalysts have limited their use in industry. Therefore, it is
2

necessary to develop efficient, easy, and appropriate methods for the preparation of a wide range
of organic compounds under heterogeneous catalytic conditions.
Among various types of heterogeneous catalysts, Fe O magnetic nanoparticles have been
3
4
greatly favored owing to the fact that they are simply synthesized and surface modified and can
be recovered from the reaction mixture using a magnet. Therefore, various catalysts such as
metals and polymers can be supported on Fe O nanoparticles because they can be easily
3
4
separated out after being employed in the reaction several consecutive times [2-6]. However, the
use of magnetic particles alone causes aggregation, changing the surface and catalytic activity,
hence the necessity of a suitable covering to elude such restrictions [7]. Lately, core-shell
magnetic nanomaterials, as efficient magnetic nanocatalysts, have gained much research
attention; these nanomaterials incorporate features of magnetic cores and diverse functional
shells for various uses and have the following advantages: useful and efficient applications in
medicine [8, 9], high stability [10], comfortable surface modification [11, 12], optical properties
[
13], and environmental friendly [14]. The Fe O magnetic core–shell structure is reported in the
3 4
literature as a heterogeneous nanocatalyst for the synthesis of organic compounds [15, 16].
Today, silica is among the materials which is widely used for the shell and increases its
stability. Additionally, the surface hydroxyl functional groups (-OH) of silica provide an active
surface, simplifying the linkage of other organic functional groups for chemically modifying the
surface. This method has been successfully used to immobilize a broad variety of catalysts such
as organocatalysts, transition metal catalysts, and biocatalysts [17-20].
Heterocyclic compounds are the biggest and most diverse organic compounds in nature, widely
applied in pharmaceutical chemistry owing to their unique chemical properties [21]. Among the
significant heterocyclic aromatic compounds, quinoline derivatives are reported in different
studies due to their unique medicinal properties and potential biological activities [22]. A
reported reaction is Friedländer which involves the reaction between ketones or 2-aminoaryl
aldehydes with carbonyl compounds, capable of enolization in the presence of an acidic catalyst
[23, 24]. Nowadays, there exist several methods for the synthesis of heterocyclic compounds
such as chitosan-SO H [25], PEG-OSO H [26], HClO -SiO [26], CF COOH [27], SBA-
3
3
4
2
3
1
5/propyl-SO H [28], NaHSO /silica-gel [29] and HO SO-SiO [30, 31]. Although most of these
3 4 3 2
procedures are of significance, many have one or more of the following disadvantages: difficulty
in separating the nanocatalyst, time-consuming reaction workup, and costly reaction conditions.
3

Accordingly, it is important to provide an efficient synthesis method that can cover the
drawbacks of previous methods.
In this research, efforts were made to synthesize and characterize a new heterogeneous Cu
nanocatalyst
Fe O @SiO /ISN/Cu(II) catalyst was synthesized via decorating Cu(II) ions onto Fe O @SiO
2
(Fe O @SiO /ISN/Cu(II))
to
prepare
quinoline
derivatives.
The
3
4
2
3
4
2
3
4
nanoparticles. The catalyst was easily separated by an external magnet with no significant
decrease in catalytic activity, and was reused 4 times without a considerable reduction in the
yield of quinolines produced.
2
2
. Experimental
.1 Materials and Methods
Isoniazid, as a pharmaceutical grade material, was purchased from the DarouPakhsh
Pharmaceutical Company Tehran, Iran FeCl ·6H O, FeCl ·4H O, Cu(OAc) , TEOS (tetraethyl
.
3
2
2
2
2
orthosilicate), CPTES (3-Chloropropyltriethoxysilane), and aryl halides were obtained from
Merck. Other reagents and solvents used in this investigation were obtained from Sigma Aldrich,
Fluka or Merck Chemicals. All chemicals and solvents were used as received, without prior
purification.
Melting points were determined by a Stuart SMP melting point instrument. The Fourier
3
transform infrared (FT-IR) spectra were recorded with a Shimadzu, IR Prestige 21 spectrometer
-1
in the range of 400-4000 cm . Nanocatalysts were characterized using scanning electron
microscopy (SEM), energy dispersive spectroscopy (EDS) (Holland Philips XL300),
transmission electron microscopy (TEM) (Holland Phillips CM10), x-ray powder diffraction
XRD) (Holland Philips PW-1840), and vibrating sample magnetometer (VSM) (Meghnatis
Daghigh Kavir Co., Iran).
(
2
.2
Preparation of Fe O and Fe O @SiO magnetic nanostructures
3 4 3 4 2
Fe O and Fe O @SiO nanostructures were synthesized according to the reported methods [32].
3
4
3
4
2
For this purpose, 3g of FeCl .6H O and 1g of FeCl .4H O salts were poured into the round-
3
2
2
2
bottom flask; then, 120 mL water was added and stirring was applied vigorously for a complete
dissolution. The concentrated NH (28%) solution was then added to reach a solution pH of 11.
3
The solution under N atmosphere at 60 °C was stirred vigorously for one hour. The black
2
4

precipitate was decanted by a magnet, washed with distilled water several times, and dried at 50
C in an oven for 24 hours. In order to prepare Fe O @SiO nanostructures, 1 gr of Fe O
4
°
3
4
2
3
nanoparticles was dispersed by ultrasound in isopropyl alcohol/water solvent; next, 1.0 mL
tetraethyl orthosilicate (TEOS) and 4.80 mL NH (28%) were added to the solution at ambient
3
temperature under vigorous stirring. The final product was separated by a magnet and washed
several times with distilled H O/EtOH to remove impurities. The product was dried at 50 °C and
2
stored for the next step.
2
.3
Synthesis of the Fe O @SiO /Isoniazid/Cu(II)
3 4 2
0
.5 g of Fe O @SiO nanostructure was dispersed by ultrasonic bath in toluene solvent; after
3
4
2
that, 0.6 mL of 3-Chloropropyltriethoxysilane (CPTES) was added to the mixture and stirred
vigorously at 100 ºC for 48 hours. The precipitate (Fe O @SiO -pr-Cl) was separated by a
3
4
2
magnet that was washed several times with EtOH and dried at 60 °C in an oven for 48 hours.
Next, 0.5 g of Fe O @SiO -pr-Cl nanoparticle was dispersed by ultrasonic bath in toluene
3
4
2
solvent, and 2 mmol of isoniazid ligand was added. This mixture was stirred vigorously under
nitrogen atmosphere at 80 °C for 24 hours. The precipitate was collected by a magnet, and
washed several times with ethanol/water, dried at 40°C for 48 hours. To preparation of
Fe O @SiO /isoniazid, 0.5g of it was dispersed by ultrasonic bath in acetonitrile. Then, 50 mg of
3
4
2
Cu(OAc) salt was added to the reaction mixture and stirring was applied vigorously at 50 °C for
2
1
0 hours. The product (Fe O @SiO /Isoniazid/Cu(II)) was separated by a magnet that was
3 4 2
washed several times with distilled H O and EtOH to remove impurities; the product was dried at
2
5
0°C for 24 hours. Scheme 1, represents the synthetic trend of Fe O @SiO /Isoniazid/Cu(II).
3 4 2
2
.4 Preparation of quinolines
.2 mmol α-CH-acid, 1.0 mmol 2-aminoaryl ketone, and 0.07 g nanocatalyst were poured in a
1
bottom round flask containing ethanol solvent, and were heated and vigorously stirred until the
end of the reaction. Once the reaction was completed, understood via TLC technique, the
nanocatalyst was decanted from the reaction mixture by a magnet, which was then washed with
EtOH (about 5 mL). The final product was recrystallized by ethanol and stored for
characterization. All products were known compounds characterized by their M.p. which was
compared with literature reports.
5

3
3
3
. Results and discussion
.1 Characterization of Fe O @SiO /ISN/Cu(II) nanocatalyst
3
4
2
.1.1 FT-IR
FT-IR technique was applied to confirm the immobilization and coating of silica and other
functionalized molecules. Fig. 1 shows the FT-IR spectra of Fe O magnetic nanoparticles
3
4
(MNPs), Fe O @SiO /ISN core-shell MNPs and Fe O @SiO /ISN/Cu(II) MNPs. In Fig. 1a
3 4 2 3 4 2
-1
(
FT-IR of Fe O ), the bond at 562 cm is attributed to the vibration of Fe-O band, while the band
3
4
-1
at 3410 cm is related to the symmetrical and asymmetrical stretching vibration of hydroxyl
groups (─OHs) [33], indicating the presence of some amount of ferric hydroxide in Fe O . The
3
4
-1
band at 1620 cm is ascribed to the bending vibration of the adsorbed water. Fig. 1b displays the
FT-IR spectrum of Fe O @SiO /ISN core-shell MNPs and shows some new absorption peaks in
3
4
2
-1
comparison with Fig.1a. The sharp peak at 1079 cm is attributed to the stretching vibration
-1
bands of Si–O–Si, while the band at 959 cm is assigned to the bending vibration of the silanol
group (Si–OH) [34]. The characteristic peaks of C-H bonds are seen at 2941 and 2861 cm-1
which can be attributed to symmetric and antisymmetric stretch of CH groups. The primer of
2
isoniazid groups to the surface of Fe O @SiO MNPs is verified through the bands at 1619, 3016
3
4
2
-1
and 1399 cm assigned respectively to the C=C, aryl C-H stretches and C-N stretching of amine.
The observations indicated which isoniazid molecules as acceptor ligand were successfully
attached to the silica shell. Meanwhile, after coordination of nanocomposites with Cu(II)
-1
intensity of 1619 and 1399 cm peaks decreases that can be ascribed to the bonding interactions
between the functional groups of the nanocomposites and the Cu(II). Every band reveals that the
exterior of Fe
3
O4 nanoparticles have successfully been modified with isoniazide groups for the metal-
ligand coordination.
3
.1.2 XRD
The XRD pattern of Fe O @SiO /ISN/Cu(II) is illustrated in Fig. 2. A strong characteristic
3
4
2
diffraction was detected in the sample at 2θ of 30.12°, 35.69°, 43.39°, 54.14°, 58.02° and 63.94°
corresponding to the diffraction of (220), (311), (400), (422), (511), and (440) of the Fe O ,
3
4
implying that the modified nanoparticles were synthesized successfully without damaging the
crystal structure of Fe O core. The silica coating and functionalization with CPTES and
3
4
6

◦
Isoniazid (Fe O @SiO /ISN/Cu(II)) showed the peak at 2Ө = 16–26 , which can be due to the
3
4
2
presence of non-crystalline SiO . The presence of a broad peak is in agreement with the
2
amorphous structure of silica layer [35].
3
.1.3 VSM
The magnetic properties of Fe O @SiO /ISN/Cu(II) prepared nanocatalyst was measured by
3
4
2
VSM at ambient temperature (Fig. 3). Saturation magnetization of bare Fe O nanoparticles was
3
4
−
1
reported [34] as 61.8 emu g , and the saturation magnetization of the prepared catalyst in the
−
1
present study was 48.2 emu g (Fig. 3). These results indicate that the magnetization properties
+
2
of bare Fe O decrease when modified using Cu and the silica groups. This result demonstrated
3
4
that the prepared catalyst has good magnetic properties. Thus, the aforementioned evidence
suggested a simple and effective method of dispersing and recycling the procured catalyst form
the solution by an external magnetic force.
3
.1.4 TGA
The thermogravimetric analysis (TGA) of Fe O @SiO /ISN/Cu(II) prepared nanocatalyst is
3
4
2
shown in Fig. 4. The weight loss at about 150 °C is due to the solvent adsorbed on the surface
and inside of structures. The decomposition temperature of the organic compounds (ligand and
propyl) in the sample started at about 180°C and continued up to 600 °C. The organic molecules
were full decomposed at temperatures higher than 600 °C and the residual weight of
Fe O @SiO /ISN/Cu(II) was 90%. In other words, it can be concluded that 5% of organic
3
4
2
molecules was immobilized on the surface of Fe O @SiO /ISN/Cu(II). These results showed
3
4
2
which isoniazid and chloro propyl successfully immobilized Fe O @SiO , indicating that the
3
4
2
prepared catalyst has a good thermal stability which can be used in the reactions at high
temperatures.
3
.1.5 TEM, SEM and EDX
TEM and FESEM images were taken to determine the size and morphology of the prepared
hybrid organic-inorganic nanocatalyst (Fe O @SiO /ISN/Cu(II)). TEM was used to observe the
3
4
2
morphology of Fe O @SiO /ISN/Cu(II) catalyst. Fig. 5a shows that NPs have a core–shell
3
4
2
structure with a distinct contrast between silica shells and Fe O cores, implying that silica shells
3
4
(
Fe O @SiO ) successfully coated the hydrophilic Fe O NPs, seen as a bright gray area around
3 4 2 3 4
7

the Fe O dark core. This revealed that the true core-shell morphology was grafted on isoniazid
3
4
functionalized Fe
3
O4
@SiO NPs. The TEM image of the Fe O @SiO /ISN/Cu(II) nanocatalyst
2
3 4 2
revealed that Cu(II), with a nearly spherical morphology, was formed on the surface of the modified
Fe O nanoparticles with amino groups as organic shell. In the TEM images, the average size of the
3
4
Fe O nanoparticles was approximately 10 to 20 nm, and that of Fe O @SiO was 20 to 30 nm.
3
4
3
4
2
In addition, the FESEM image of the nanocatalyst showed that they are spherical and mono-
disperse. However, some particle aggregations were observed in the catalyst due to the magnetic
attraction between the particles (Fig. 5b). Furthermore, the energy-dispersive x-ray spectroscopy
(EDX) analysis of the nanocatalyst demonstrated the expected elements, namely Cu, C, N, Si, Fe,
and O; the spectrum and data are indicated in Fig. 6 and Table 1.
3
.2. Evaluation of Fe O @SiO /ISN/Cu(II) in the preparation of quinolines
3 4 2
The reaction of 2-amino-5-chlorobenzophenone and acetylacetone was selected to optimize
reaction conditions such as nanocatalyst dosage, solvent and temperature. First, different
amounts of the nanocatalyst (0.02, 0.05, 0.07 and 0.1 g) were optimized for a predefined reaction
time of 2 hours at 60°C (Table 2, entries 1-4). The obtained results displayed the most optimal
yield (95%) obtained with a nanocatalyst amount of 0.07 g. In the next step, the model reaction
at various temperatures (r.t, 60 and 80°C) were optimized (Table 2, entries 5 and 6). With the
increase in temperature, the reaction rate was increased. A good yield of 95% was observed at
6
0°C for 2 hours of reaction time; furthermore, the best results were obtained when ethanol was
used as reaction solvent. Further work indicated that the best results were obtained when the
reaction was carried out at 60°C, for 2 h in ethanol. Further observed was that
Fe O @SiO /ISN/Cu(II) showed higher catalytic activity compared with the corresponding
3
4
2
homogenous Fe O . In the optimized condition, different derivatives of quinolines were prepared
3
4
using different types of cyclic and noncyclic α-methylene ketones. The results are summarized in
Table 3. Good yields were observed in all derivatives, corroborating the strength of the
preparation method. As shown in Table 3, chloro and without substituents on the amino aryl
ketones did not show evident effects in terms of yields. However, the use of cyclohexanone
reduced the yield (Table 3, entry 10). As demonstrated in Fig. 7, the nanocatalyst was
successfully and efficiently recycled 4 times with 24% activity loss.
8

4
. Conclusions
In this research, the synthesis of new nanocatalyst (Fe O @SiO /ISN/Cu(II)) via
3
4
2
functionalization of silica-coated magnetic nanoparticles with Cu(OAc) was reported. To
2
investigate the structure and bonding of the synthesized nanocatalyst, TEM, FESEM, VSM,
TGA, XRD, EDS, and FT-IR techniques were applied. The core-shell nanoparticles were stable,
reusable, non-toxic and inexpensive heterogeneous nanocatalyst with great potential applications
in organic syntheses. The new nanocatalyst was used for the synthesis of quinoline derivatives
via Friedländer synthesis from α-methylene ketones and 2-aminoaryl ketones with excellent
yields and short times. Furthermore, the advantages of the introduced nanocatalyst are good
catalytic activity, easy separation by an external magnet, and good reusability for quinolines
preparation via Friedländer synthesis. The proposed nanocatalyst was also successfully applied
for the synthesis of quinoline derivatives via Friedländer synthesis with a reusability of 4 times
with a relatively low reduction in catalytic activity of 24%.
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Figure and scheme captions:
Scheme 1. Schematic diagram of Fe O @SiO /ISN/Cu(II) nanocatalyst preparation.
3
4
2
Fig. 1. FT-IR spectra of (a) Fe O , (b)Fe O @SiO /ISN and (c) Fe O @SiO /ISN/Cu(II).
3
4
3
4
2
3
4
2
Fig. 2. XRD patterns of Fe O @SiO /ISN/Cu(II) prepared nanocatalyst.
3
4
2
1
1

Fig. 3. VSM of Fe O @SiO /ISN/Cu(II) prepared nanocatalyst.
3
4
2
Fig. 4. TGA of Fe O @SiO /ISN/Cu(II) prepared nanocatalyst.
3
4
2
Fig. 5. TEM (a) and SEM (b) images of Fe O @SiO /ISN/Cu(II).
3
4
2
Fig. 6. EDX spectrum of Fe O @SiO /ISN/Cu(II) MNPs.
3
4
2
Fig. 7. Reusability of the catalyst for the synthesis of quinolines.
Table 1. EDX data of Fe O @SiO /ISN/Cu(II) MNPs (Wt %)
3
4
2
Sample
C (%) O (%)
Si (%) N (%)
17.75 3.69
Fe (%)
5.09
Cu (%) Total (%)
0.26 100
Fe O @SiO /ISN/Cu(II) 27.03 46.18
3
4
2
1
2

Table 2. Optimization of amount of catalyst and temperature of reaction a
Ph
Ph
O
Cl
Cl
O
O
O
OMe
Fe O @SiO /ISN/Cu(II)
+
3
4
2
OMe
NH2
N
1
3

Entry
Catalyst (mg)
0.02
Temperature (°C)
Time (h)
Yield (%) b
1
2
3
4
5
6
60
60
60
60
r.t
2
2
2
2
2
2
46
69
95
95
70
76
0.05
0.07
0.1
0.07
0.07
80
a
Reaction conditions: acetylaceton (1.2 mmol), 2-aminoaryl ketone (1 mmol), and the nanocatalyst.
Isolated yields.
b
Table 3. Synthesis of quinoline derivatives through Friedländer synthesis by Fe
3
O
4
@SiO
2
/ISN/Cu(II) catalyst.
Entry
Amino aryl ketone
Ketone
Product
Yieldb Mp°C
Ph
Ph
N
O
Cl
O
O
Cl
96
152
O
1
NH2
1
4

Ph
Ph
O
O
O
O
Cl
Cl
Cl
Cl
O
O
O
O
Cl
Cl
Cl
Cl
90 134
92 107
O
OMe
OEt
2
3
4
5
6
7
8
9
1
OMe
OEt
O
NH2
Ph
N
Ph
O
NH2
Ph
N
Ph
95 210
95 161
94 113
87 105
91 100
93 192
68 139
O
O
NH2
Ph
N
O
Ph
O
NH2
N
Ph
Ph
O
O
O
O
NH2
Ph
N
Ph
O
O
O
O
OMe
OEt
OMe
OEt
O
NH2
Ph
N
Ph
O
O
O
O
NH2
Ph
N
Ph
O
O
O
O
NH2
Ph
N
O
Ph
O
0
NH2
N
a
Conditions: acetylaceton deravatives (1.2 mmol) aminoaryl deravatives (1 mmol), and the nanocatalyst.
b
Yields isolated product
.
1
5

Scheme 1.
1
6

Fig. 1.
1
7

Fig. 2.
1
8

Fig. 3.
1
9

Fig. 4.
2
0

Fig. 5.
2
1

Fig. 6.
2
2

Fig. 7.
2
3

Graphical Abstract
Synthesis of Fe O @SiO /isoniazid/Cu(II) magnetic nanocatalyst as recyclable
3
4
2
catalyst for highly efficient preparation of quinolines in moderate condition
Shahram Lotfi, Ahmad Nikseresht and Nasrin Rahimi
This paper reports the study on an efficient procedure for preparation of
Fe3O4@SiO2/Isoniazid/Cu(II) as a recoverable magnetic nanocatalyst. The structure of the
synthesized nanocatalyst was investigated via different techniques namely VSM, TEM, SEM,
EDS, TGA, XRD and FT-IR. Then the nanocatalyst was applied on Friedländer reactions for a
highly efficient preparation of quinoline derivatives.
2
4