Fe3O4@zeolite-SO3H as a magnetically bifunctional and retrievable nanocatalyst for green synthesis of perimidines

Article abstract of DOI:10.1007/s11164-019-03992-0

In the current study, a new catalytic system based on Fe₃O₄ nanoparticles immobilized on zeolite-SO₃H (Fe₃O₄@zeolite-SO₃H) is introduced. In the first stage, zeolite@SO₃H was syn

Full text of DOI:10.1007/s11164-019-03992-0

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-03992-0
Fe3O4@zeolite‑SO3H as a magnetically bifunctional
and retrievable nanocatalyst for green synthesis
of perimidines
Mehdi Kalhor1 · Zohre Zarnegar1 · Fatemeh Janghorban1 ·
S. Ahmad Mirshokraei1
Received: 6 June 2019 / Accepted: 25 September 2019
© Springer Nature B.V. 2019
Abstract
In the current study, a new catalytic system based on Fe3O4 nanoparticles immo-
bilized on zeolite-SO3H (Fe3O4@zeolite-SO3H) is introduced. In the frst stage,
zeolite@SO3H was synthesized from the reaction of zeolite-NaY with chlorosul-
fonic acid to produce zeolo sulfuric acid. Then, Fe3O4@zeolite-SO3H was prepared
via immobilizing magnetic nanoparticles on the surface of functionalized zeolite-
NaY as a support. Fe3O4@zeolite-SO3H as a multifunctional nanoplatform system
was recognized by FT-IR, FE-SEM, XRD, EDS, BET, and VSM techniques. This
nanocomposite demonstrated high activity in the catalytic synthesis of perimidine
derivatives under solvent-free conditions. Combining the advantages of solid acids
based nanocomposites and magnetic separation, this method provides an efcient
and much improved modifcation of the general synthesis of perimidines. Recycling
experiments confrmed the good stability of the nanocatalyst for six times and its
constant activity.
Keywords Fe3O4 nanoparticles · Magnetic catalyst · Sulfonated zeolite ·
Perimidine · Solvent-free conditions
Introduction
Nanomaterials are one of the most important achievements of nanotechnology.
The nanomaterials have been widely used in many felds since their unique proper-
ties compare with common materials such as unique optical, electronic, antibacte-
rial, or mechanical properties [1–9]. Recently, porous nanomaterials which include
ordered mesoporous silica, zeolites, and metal‒organic frameworks have been used for
* Mehdi Kalhor
mekalhor@gmail.com
1
Department of Chemistry, Payame Noor University, Tehran 19395-4697, Iran
Vol.:(0123456789)
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M. Kalhor et al.
synthesis of various nanocomposites. The main features for these materials are active
sites with diferent strengths, uniform channels and cavities, high adsorption capacity,
and electronic properties [10–13]. Among the various types of porous nanomaterials,
zeolites have attracted attention as heterogeneous catalysts or suitable supports because
of their interesting structure such as nonporous crystalline aluminum-containing sili-
cate, biocompatible and non-toxic nature, high thermal and chemical stability, per-
sistence in all organic solvents, no waste or disposal problems, and surface property
[14–16]. The surface feature of zeolites can be modifed chemically and physically by
surface functionalization. To enhance the catalytic property and high active surface,
zeolites can be modifed with SO3H moieties to form solid acids to be widely used as
catalysts [17, 18], as temperature tolerant proton conducting material [19], and direct
methanol fuel cell application [20]. Moreover, magnetic zeolites have shown perfor-
mances as magnetic adsorbents in water purifcation [21, 22], as a catalytic system in
degradation diethyl phthalate (DEP) in aqueous solution [23], in catalytic aquathermol-
ysis of heavy crude oil [24], and in drug delivery [25]. These magnetic separations can
provide an optional approach for recovering and reusing magnetic materials by using
external magnetic felds. Therefore, magnetic zeolo sulfuric acid can ofer as a catalytic
system to facilitate the reuse of catalyst for the synthesis of heterocycles.
Nitrogen heterocycles are of increasing importance in agro chemistry, materials sci-
ence, and medicinal chemistry. Therefore, there is continuing interest in developing
efcient, convenient, and green synthetic methods for the preparation of N-containing
heterocyclic compounds [26, 27]. Perimidines or 1H-benzo[d,e]quinazolines are one of
the most useful examples of saturated N-heterocycles, gaining increasing importance in
the pharmaceutical industry, agriculture, and synthetic chemistry [28, 29]. These cores
are used as antimicrobial and anti-infammatory activity, which explained the important
eforts devoted to the synthesis of these heterocycles [28–30]. The perimidine hetero-
cycles are synthesized through condensation reaction of 1,8-diaminonaphthalene with
various carbonyl compounds and also changing various catalysts and conditions [28,
31–34]. However, some reported methods sufer of long reaction times, use of toxic
solvents, cumbersome work-up procedures, occurrence of side reactions, and low yield.
However, there is no report of the use of magnetic zeolit-SO3H as a catalytic system in
chemical organic reactions.
Herein, we present a co-precipitation approach to fabricate Fe3O4 nanoparticles
and uniformly disperse these on the surface of SO3H-activated zeolite-NaY. Then,
we report a sustainable, green, and environmentally friendly approach to the synthe-
sis of perimidine heterocycles through cyclocondensation of aromatic aldehydes with
1,8-diaminonaphthalene, and Fe3O4@zeolite-SO3H as nanocatalyst under solvent-free
conditions (Scheme 1). The nanocatalyst was readily recycled by an external perma-
nent magnet and could be reused six times without signifcant loss of activity.
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Fe3O4@zeolite-SO3H as a magnetically bifunctional…
Scheme 1 Synthesis of perimidine heterocycles using Fe3O4@zeolite-SO3H
Experimental
Chemicals and apparatus
All chemicals were purchased from the Merck or Aldrich and used as received. The
products were identifed by comparing the physical data with those of known samples
or by their spectral data. FT-IR spectra were obtained with KBr disk on a galaxy series
FT-IR 5000 spectrometer. 1H NMR and 13C NMR spectra were recorded with a Bruker
spectrometer (400 MHz). NMR spectra were obtained in DMSO-d6 solutions and are
reported as parts per million (ppm) downfeld from Me4Si as internal standard. The
morphology of zeolitic nanostructures was studied by feld emission scanning electron
microscopy (SEM) (EVO LS 10, Zeiss, Carl Zeiss, Germany). The magnetic measure-
ment of samples was carried out in a vibrating sample magnetometer (VSM) (4 inch,
NDKF, Kashan, Iran) at room temperature. Difuse refectance spectra were acquired
on an X-ray photoelectron spectrometer (Escalab 250Xi). Nitrogen adsorption and des-
orption isotherms (BET analysis) were measured at 196 °C by a Japan Belsorb II sys-
tem after the samples were vacuum dried at 150 °C overnight.
Synthesis of Fe3O4@zeolite‑SO3H
1.5 g of zeolite-NaY was charged into the fask, and 3 mL of ClSO3H was added
dropwise at 0 °C during 30 min and stirred vigorously. When the addition was com-
pleted, the mixture was stirred for 45 min. Finally, the mixture was washed with
CH2Cl2 and H2O under sonication and dried at 50 °C to aford zeolo sulfuric acid.
Fe3O4@zeolite-SO3H was prepared according to the reported procedure in the lit-
erature [23]. For this reason, FeCl2·4H2O and FeCl3·6H2O precursors (2:1, molar
ratio) were dissolved in 25 mL of deionized water under N2 atmosphere bubbling
for 1 h. Under vigorous magnetic stirring, gradually the pH was raising by addition
20 mL of 25% NH3 solution (dropwise for 2 min). The mixture was stirred at 90 °C
for 30 min. The resultant magnetite nanoparticles were collected by an external
magnet and washed with HCl solution (0.1 M), deionized water and dried at 70 °C
in vacuum oven.
General procedure for the preparation of 2‑substituted
2,3‑dihydro‑1H‑perimidines
A mixture of aldehyde (1 mmol), 1,8-diaminonaphthalene (1 mmol), Fe3O4@zeo-
lite-SO3H (5% w/w, 0.007 g), was heated at 80 °C under solvent-free conditions.
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M. Kalhor et al.
The reaction progress was monitored by TLC. After completion of the reaction, the
mixture was dissolved EtOH and the catalyst was separated by an external magnet.
The pure products were obtained by adding crushed ice to fltrate. Characterization
data for some of the compounds are given below.
2‑(2,3‑Dichlorophenyl)‑2,3‑dihydro‑1H‑perimidine (3l)
FT-IR (KBr) (ʋmax): 3348, 3235 (N–H), 3044 (C–H), 1625, 1600, 1493, 1420, 1403,
1382, 1265 (C=C), 1182, 1161, 1043 (C–N), 835, 787, 757 (C–Cl), 603 cm−1;
1H NMR (500 MHz, DMSO-d6): δH 7.69 (d, J=8.15 Hz, 2H, H–Ar), 7.45 (t,
J=7.90 Hz, 1H, H–Ar), 7.19 (t, J=7.78 Hz, 2H, H–Ar), 7.04 (d, J=8.15 Hz, 2H,
H–Ar), 6.83 (s, 2H, NH), 6.52 (d, J=7.35 Hz, 2H, H–Ar), 7.83 (s, 1H, N–CH–N)
ppm; 13C NMR (125 MHz, DMSO-d6): δC 142.7, 141.8, 134.7, 132.1, 131.1, 130.7,
128.8, 128.6, 127.3, 116.1, 112.5, 105.0, 63.5 (N–CH–N) ppm.
2‑(5‑Nitrofuran‑2‑yl)‑2,3‑dihydro‑1H‑perimidine (3 m)
FT-IR (KBr, υmax): 3434 (N–H), 1603, 1480 (C=C), 1520, 1360 (–NO2), 1020
1
(C–N), 808, 601 cm−1; H NMR (300 MHz, DMSO-d6): δH 8.25 (d, J=7.00 Hz,
2H, H–Ar), 7.69 (s, 2H, H–Ar), 7.52–7.27 (m, 6H, H–Ar and 2NH), 5.25 (s, 1H,
N–CH–N) ppm; 13C NMR (75 MHz, DMSO-d6): δC 161.3, 150.2, 137.0, 135.5,
130.1, 128.4, 124.4, 119.2, 116.1, 114.6, 69.7 (N–C–N) ppm.
5‑(3‑(2,3‑dihydro‑1H‑perimidin‑2‑yl)‑4‑hydroxybenzyl)‑2‑hydroxybenzaldehyde
(3n)
FT-IR (KBr, υmax): 3319 (N–H), 3042, 2912, 2855 (C–H), 1655, 1600, 1498, 1418,
1
1397 (C=C), 1272, 1240, 1147 (C–O), 1027 (C–N), 814, 757 cm−1; H NMR
(500 MHz, DMSO-d6): δH 10.58 (s, 1H, OH), 10.22 (s, 1H, H-aldehyde), 9.48 (s,
1H, OH), 7.47 (s, 2H, H–Ar), 7.39–7.37 (m, 2H, H–Ar), 7.15 (t, J=7.68 Hz, 3H,
H–Ar), 6.99–6.93 (m, 4H, 2NH and H–Ar), 6.80 (d, J=8.20 Hz, 1H, H–Ar), 6.52
(d, J=8.20 Hz, 2H, H–Ar), 5.61 (s, 1H, N–CH–N), 3.85 (s, 2H, CH2) ppm; 13C
NMR (125 MHz, DMSO-d6): δC 191.9 (CHO), 177.0, 159.4 (C–O), 137.3, 136.5,
128.9, 127.2, 120.1, 117.9, 115.8, 105.1, 43.1 ppm.
Results and discussion
In continuation of our studies on the design and application of zeolitic nanocata-
lysts and magnetic catalytic systems in organic chemical processes [35–37], here we
report a green, eco-friendly, safe, practical, and efcient methodology for the prepa-
ration of perimidines using Fe3O4 nanoparticles loaded the sulfonated zeolite-NaY
as a magnetic nanocatalyst (Scheme 2).
FT-IR spectral analysis of zeolite-NaY, zeolite-SO3H, and Fe3O4@zeolite-
SO3H is shown in Fig. 1. In the spectrum of zeolite-NaY, in Fig. 1a, a broad
1 3

Fe3O4@zeolite-SO3H as a magnetically bifunctional…
band at 3459 cm−1 is related to the O–H stretching of hydrogen bonded internal
silanol groups and hydroxyl stretching of water. The absorption at 1636 cm−1 is
due to the O–H group bending mode of water. There is also a strong vibration at
1021 cm−1 and a weak absorption at 792 cm−1. The presence of vibration bands is
attributed to the symmetric and asymmetric stretching vibrations of the Si–O–Si
groups, respectively. In the FT-IR spectrum of sulfonated zeolite-NaY in Fig. 1b,
an intense and broad absorption band at 3420 cm−1 is related to S–OH stretching
vibration. The appearance of the strong peak at 1087 cm−1 is related to the Si–O
stretching vibration and the asymmetric and symmetric stretching of S=O bond.
Important peaks at 945 and 798 cm−1 are attributed to the symmetric stretching
vibration of S–O bond. The band at 455 cm−1 can be assigned to bending vibra-
tions of Si–O–Si or Al–O–Si groups for the functionalized zeolitic nanocompos-
ite. The FT-IR spectrum of Fe3O4@zeolite-SO3H in Fig. 1c reveals the presence
of all the characteristic peaks corresponding to zeolite and zeolite-SO3H. Moreo-
ver, the strong absorption band at 576 cm−1 corresponding to the Fe-O stretching
vibration of the Fe3O4 nanoparticles indicates that the magnetic nanoparticles are
supported on zeolite-SO3H.
The SEM photographs of the zeolitic nanostructures are given in Fig. 2. As shown
in Fig. 2a, the morphology of the zeolite-NaY crystal is approximately cubic and
smooth. Figure 2b shows that the SO3H activated zeolite-NaY structure is similar to
that of the pristine zeolite with a rougher surface. The SEM image of Fe3O4@zeo-
lite-SO3H in Fig. 2c shows that the roughness was increased after binding of Fe3O4
on the surface of modifed zeolite. In Fig. 2d, the magnetic ball-like nanoparticles
of 15–25 nm could clearly be found to be distributed in the surface of zeolite-SO3H.
XRD pattern of Fe3O4@zeolite-SO3H is shown in Fig. 3. The fgure shows crys-
talline peaks at 2θ° of 30.56°, 35.96°, 43.66°, 53.94°, 57.59°, 63.20°, and 74.97°
crystallographic planes of cubic iron oxide nanocrystals, respectively (Ref. Code
Fe3O4: 01–1111). These results confrmed that a signifcant amount of Fe3O4 nan-
oparticles were precipitated on the surface of zeolite-SO3H as evidenced by the
attraction of the powder particles of Fe3O4@zeolite-SO3H to magnet.
Scheme 2 The schematic pathway of the preparation of Fe3O4@zeolite-SO3H
1 3

M. Kalhor et al.
Fig. 1 FT-IR spectra for a zeolite-NaY, b zeolite-SO3H, c Fe3O4@zeolite-SO3H, and d recovered
Fe3O4@zeolite-SO3H
As shown in Fig. 4a, the N2 adsorption–desorption isotherm of zeolite-NaY
and SO3H@zeolite-Y has been displayed as types I isotherms which represents the
microporous materials. Also, by looking at their hysteresis type, it can be seen that
zeolite-NaY and SO3H@zeolite-Y have slits (layer and layer with high pores) struc-
ture and the initial nanostructure after the functionalize is still retained [38]. Also
in Fig. 4b, the N2 adsorption–desorption isotherm of Fe3O4@zeolite-SO3H can be
classifed as type IV with a hysteresis loop at a relative pressure range of 0.3–0.983
P/Po and suggests that the materials are mesoporous with type H1 of hysteresis
loops. The structure data of all these materials (BET surface area, total pore vol-
ume, and pore size) are summarized in Table 1. The BET surface area (205.56 m2/g)
and average pore diameter (6.78 nm) were recorded for Fe3O4/SO3H@zeolite-Y. The
BET surface area is decreased relative to SO3H@zeolite-Y (284.84). These results
1 3

Fe3O4@zeolite-SO3H as a magnetically bifunctional…
Fig. 2 FE-SEM image of a zeolite-NaY, b zeolite-SO3H, c and d Fe3O4@zeolite-SO3H
confrm successful supporting of Fe3O4 in the pores of SO3H functionalized zeo-
lite-NaY [39]. The Fe3O4/SO3H@zeolite-Y has a higher pore volume (6.77 nm) in
comparison with SO3H@zeolite-Y (2.35 nm), which may be due to the presence of
Fe3O4 nanoparticles through the zeolite cavities.
The EDS spectrum in Fig. 5 shows the presence of Al, Si, O, and S in Fe3O4@
zeolite-SO3H. The Al, Si, and S signals originate from the zeolite-SO3H, while the
Fe signal is obtained from the Fe3O4 nanoparticles, which confrms the existence
of Fe3O4. Moreover, the Fe content of the magnetic nanocomposite estimated by
atomic absorption spectroscopy was 4.42 mmol/g (24.71% w/w).
The magnetic behavior of Fe3O4@zeolite-SO3H was studied with a vibrating
sample magnetometer at room temperature. The magnetic hysteresis loop of mag-
netic zeolite-SO3H nanocomposites is shown in Fig. 6. The saturation magnetization
is found to be 21.30 emu g−1.
After complete characterization of functionalized zeolite-based magnetic nano-
composite, we investigated its catalytic application in the synthesis of 2-aryl
1 3

M. Kalhor et al.
(a)
3 1 1
4 4 0
5 5 1
2 2 0
4 0 0
4 2 2
5 3 3
(b)
No. Pos. [°2Th.] FWHM [°2Th.]
1
2
3
4
5
6
7
30.5586
35.9585
43.6583
53.9393
57.5951
63.2045
74.9735
0.7675
0.7675
0.8955
1.0234
0.8955
0.8955
1.8720
Fig. 3 a X-Ray difraction pattern and b the standard XRD pattern and the actual test results of for the
Fe3O4@zeolite-SO3H
perimidines. For initiating optimization of the reaction conditions, the condensation
of 4-chlorobenzaldehyde and 1,8-diaminonaphthalene was carried out as a model
reaction in the presence of Fe3O4@zeolite-SO3H. The experimental results are listed
in Table 2. It was observed that 0.007 g of magnetic nanocatalyst was enough to
1 3

Fe3O4@zeolite-SO3H as a magnetically bifunctional…
(a)
300
(b)
BJH-Plot
0.06
ADS
0.04
0.02
200
0
1
10
100
Pore diameter (nm)
100
ADS
DES
0
0
0.5
1
Relatve pressure (p/p0)
Fig. 4 a N2 adsorption/desorption isotherms of the zeolite-NaY and zeolite-SO3H; and b N2 adsorption–
desorption isotherms and volume plots of Fe3O4@zeolite-SO3H
Table 1 Porosimetery values for zeolite-NaY and its modifed structures
Samples
SaBET (m2 g−1
)
VbBJH (cm3 g−1
)
DcBJH (nm)
DdAap (nm)
Zeolite-NaY
SO3H@zeolite-Y
Fe3O4@zeolite-SO3H
619.66
284.84
205.56
0.0667
0.0532
0.03139
4.84
5.15
6.78
2.2358
2.3517
2.4214
aSpecifc surface area
bPore volume
cPore size (calculated from the adsorption branch)
dAdsorption average pore diameter (4 V/A by BET)
1 3

M. Kalhor et al.
Fig. 5 EDX spectrum of Fe3O4@zeolite-SO3H
Fig. 6 Magnetization curve for the Fe3O4@zeolite-SO3H at room temperature
catalyze the reaction to produce high yields of 2-(4-chlorophenyl)-2,3-dihydro-
1H-perimidine (3k) in shorter reaction time under solvent-free conditions at 80 °C.
As can be seen in Table 2, the results showed that the efciency and the yield of
the solventless reaction was higher at 80 °C than those obtained in the various tem-
peratures, such as 25, 50, and 100 °C. Diferent amounts of nanocatalyst were stud-
ied to fnd the best yield of the reaction. In the presence of 0.007 g of nanocata-
lyst, the highest value of yield was obtained. To compare the efciency of this new
nanocatalyst, the model reaction was tested using Fe3O4, zeolite-SO3H, and zeolite-
NaY. As indicated in Table 2, Fe3O4@zeolite-SO3H needed less reaction time and
higher yield than others. An experiment was conducted in the absence of Fe3O4@
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Fe3O4@zeolite-SO3H as a magnetically bifunctional…
Table 2 Optimizing the model reaction conditions under solvent-free conditions
Entry
Catalyst
Catalyst load- Temperature Time (min)
Yield (%)a
ing (g)
(°C)
1
2
3
4
5
6
7
8
Fe3O4@zeolite-SO3H
Fe3O4@zeolite-SO3H
Fe3O4@zeolite-SO3H
Fe3O4@zeolite-SO3H
Fe3O4@zeolite-SO3H
Fe3O4@zeolite-SO3H
Fe3O4
zeolite-SO3H
Zeolite-NaY
–
0.004
0.007
0.014
0.007
0.007
0.007
0.007
0.007
0.007
–
50
50
50
80
100
25
80
80
80
80
10
8
7
3
3
20
12
10
20
30
52
80
72
97
92
30
65
82
35
–
9
10
aIsolated yield
zeolite-SO3H. There was no efcacy for the product after 30 min. The large surface
area of zeolite-NaY and high concentration of active Brønsted acid sites in its non-
porous structure and the presence of Fe3O4 supported on the zeolite as a Lewis acid
catalyst facilitated the appropriate interaction of the reactant and the product mol-
ecules. Moreover, the magnetic nature of Fe3O4 nanoparticle supported zeolite also
allowed for facile recycling of the nanocatalyst without the use of classical separa-
tion method.
To develop the optimized conditions, other aldehyde derivatives were used for
the synthesis of 2,3-dihydro-1H-perimidines and the results are displayed in Table 3.
As observed from the results presented in this table, aromatic aldehydes contain-
ing both electron-withdrawing groups (Cl, NO2) and electron-donating groups (OH,
OMe) reacted smoothly to produce high product yields and during very short reac-
tion times.
A reasonable mechanism is proposed for the synthesis of 2-substituted peri-
midines and is disclosed in the Scheme 3. Fe3O4@zeolite-SO3H can activate the
reactant and intermediates in this reaction. Based on the literature and substrates
chemistry [42], nucleophilic attack of 1,8-diaminonaphthalene to Fe3O4@zeolite-
SO3H-activated aldehyde generated imine intermediate with the removal of water
molecule. Then, nucleophilic attack of the second amino group to nanocatalyst-acti-
vated imine intermediate is done under cyclization process to give the perimidine
product.
1 3

M. Kalhor et al.
Table 3 Synthesis of dihydroperimidine catalyzed by Fe3O4@zeolite-SO3H
–
31
31
–
–
–
–
40
–
–
–
–
31
31
31
–
–
–
–
–
–
41
31
–
–
31
1 3

Fe3O4@zeolite-SO3H as a magnetically bifunctional…
Table 3 (continued)
–
–
–
–
31
32
–
–
31
40
I
To investigate the reusability and recoverability of Fe3O4@zeolite-SO3H
nanocatalyst, it was used in model reaction under optimized conditions. For this
purpose, after the magnetic separation of the catalyst from the reaction mixture,
it washed with hot ethanol and dried at room temperature. This nanocompos-
ite was efective reusable at least six times without remarkable loss of catalytic
activity (Fig. 7). The FT-IR analysis of the reused nanocatalyst shows no change
in its structure (Fig. 1d).
Furthermore, to show the advantages of using Fe3O4@zeolite-SO3H as a mul-
tifunctional magnetic nanocatalyst in the synthesis of 3k, our catalytic method
was compared with literature resulted in reports of using various catalysts. As
shown in Table 4, most of them sufer from harsh reaction conditions such as
hazardous and toxic catalyst, long reaction times, low yields, and tedious work-
up procedures, while Fe3O4@zeolite-SO3H is green, safe, inexpensive, and eas-
ily separated from the reaction mixture by an external magnetic feld. In the
presence of this new magnetic nanocomposite [with Lewis acid (Fe3O4) and
Brønsted–Lowry acid (SO3H)], the results were better than other catalysts.
1 3

M. Kalhor et al.
Scheme 3 Proposed mechanism for the synthesis of perimidine derivatives using Fe3O4@zeolite-SO3H
97
97
95
94
92
100
90
80
70
60
50
40
30
20
10
0
89
12
7
5
4
4
3
1
2
3
4
5
6
Run
Fig. 7 Reusability of Fe3O4@zeolite-SO3H in the synthesis of 3k
1 3

Fe3O4@zeolite-SO3H as a magnetically bifunctional…
Table 4 Comparison of the catalytic efciency of Fe3O4@zeolite-SO3H with other catalysts for the syn-
thesis of 3k
Entry
Catalyst/condition
Time (h)
Yield (%)a
1
2
3
4
5
CuY-zeolite, EtOH, rt
NaY zeolite, EtOH, rt
FePO4, EtOH, rt
Ytterbium(III) trifuoromethanesulfonate, MeCN, rt
Fe3O4/SiO2/(CH2)3N+Me3Br−3 , solvent-free, 80 °C
AcOH, EtOH, rt
0.42
45-50
0.22
24
12
24
81 [31, 32]
70 [43]
80 [42]
88 [44]
93 [45]
6
52 [46]
7
8
9
10
Cu(NO3)2·2H2O, EtOH, rt
Nano-γ-Al2O3/SbCl5, solvent-free, rt
I2, EtOH, rt
0.17
0.25
0.67
0.05
83 [47]
95 [48]
84 [49]
96 (This work)
Fe3O4@zeolite-SO3H, solvent-free, 80 °C
aIsolated yield
Conclusions
In summary, bifunctional catalytic and magnetic Fe3O4@zeolite-SO3H nanohy-
brids were synthesized, through co-precipitation method. The structure of the
prepared nanocomposites has been clearly confrmed by microscopy, difraction,
and spectroscopic techniques. Then, its catalytic activity was investigated in the
synthesis of perimidine derivatives. This protocol associated with several advan-
tages such as short reaction times, high yields, utilization of a heterogeneous cat-
alyst, magnetic recovery of catalyst, and minimum pollution of the environment
makes it a useful and attractive process for the preparation of these heterocycles.
Acknowledgements We are thankful to the Payame Noor University for the partial support of this work.
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