Fe3O4@MCM-41@Zn-Arg: as a novel, magnetically recoverable and ecofriendly nanocatalyst for the synthesis of disulfides, sulfoxides and 2,3-dihydroquinazolin?4(1H)?ones

Article abstract of DOI:10.1080/24701556.2020.1802750

The direct supporting of Zn-arginine complex on magnetic core-shell nanostructures (Fe₃O₄@MCM-41@Zn-Arg) was reported as a novel, heterogeneous and excellent nanocatalyst, which applied for the oxidation reaction of sulfides to sulfoxides, oxidative coupling of thiols to their corresponding disulfides and the synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives under mild conditions. The structure of the catalyst was studied by X-Ray diffraction, Fourier transform-infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, atomic absorption spectroscopy, and vibrating sample magnetometry techniques. The simple experimental procedure, very good catalytic activity, low cost, and excellent recycling are the noteworthy features of the currently employed heterogeneous catalytic system.

Full text of DOI:10.1080/24701556.2020.1802750

Inorganic and Nano-Metal Chemistry
ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/lsrt21
Fe O @MCM-41@Zn-Arg: as a novel, magnetically
3
4
recoverable and ecofriendly nanocatalyst for
the synthesis of disulfides, sulfoxides and 2,3-
dihydroquinazolin‑4(1H)‑ones
Mohsen Nikoorazm & Zahra Erfani
To cite this article: Mohsen Nikoorazm & Zahra Erfani (2020): Fe O @MCM-41@Zn-Arg: as
3
4
a novel, magnetically recoverable and ecofriendly nanocatalyst for the synthesis of disulfides,
sulfoxides and 2,3-dihydroquinazolin‑4(1H)‑ones, Inorganic and Nano-Metal Chemistry, DOI:
10.1080/24701556.2020.1802750
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INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2020.1802750
Fe O @MCM-41@Zn-Arg: as a novel, magnetically recoverable and
3
4
ecofriendly nanocatalyst for the synthesis of disulfides, sulfoxides
and 2,3-dihydroquinazolin-4(1H)-ones
Mohsen Nikoorazm and Zahra Erfani
Department of Chemistry, Faculty of Science, Ilam University, Ilam, Iran
ABSTRACT
ARTICLE HISTORY
The direct supporting of Zn-arginine complex on magnetic core-shell nanostructures
Received 27 March 2020
Accepted 12 July 2020
3 4
(Fe O @MCM-41@Zn-Arg) was reported as a novel, heterogeneous and excellent nanocatalyst,
which applied for the oxidation reaction of sulfides to sulfoxides, oxidative coupling of thiols to
their corresponding disulfides and the synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives
under mild conditions. The structure of the catalyst was studied by X-Ray diffraction, Fourier trans-
form-infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, atomic
absorption spectroscopy, and vibrating sample magnetometry techniques. The simple experimen-
tal procedure, very good catalytic activity, low cost, and excellent recycling are the noteworthy
features of the currently employed heterogeneous catalytic system.
KEYWORDS
core-shell nanostructures;
magnetic; sulfoxides;
disulfides; 2,3-
dihydroquinazolin-4(1H)-one
Introduction
nanoparticles which have the advantages of both mesopo-
rous and magnetic nanoparticles has undoubtedly gained
much interest for practical applications.
Sulfoxides and disulfides are important compounds due
to their properties and reactivity and play an important role
The target of science is recently shifted toward preserving
the environment, thus in green catalytic reactions, the recov-
ery and reusability of catalysts is an important factor for
[14]
[
1–3]
ecological and economic demands.
Compared to hetero-
in various medical, biological, and nanotechnological appli-
geneous catalysis, in homogeneous catalysis, the activity and
selectivity of the catalyst is better, but the difficulty of cata-
lyst separation from the final product creates economic and
environmental barriers.
recoverable and efficient supports for the immobilization of
homogeneous catalysts in order to combine the advantages
[15,16]
cations.
In particular, sulfoxides are valuable synthetic
intermediates for the production of a range of chemically
and biologically active molecules including psychotropic and
vasodilators antibacterial, anti-atherosclerotic, anti-ulcer,
[
4,5]
Nanoparticles could be used as
[17–19]
anti-hypertensive anti-fungal and anti-atherosclerotic.
Likewise, disulfides are essential moieties of biologically
active compounds for peptide and protein stabilization
[
6]
of both homogeneous and heterogeneous catalysis. Among
different nanoparticles, mesoporous silica, especially MCM-
anions, and they are also used in sulphenylation of enolates
4
1, because of their high surface area for catalyst loading,
[20,21]
and other anions.
2, 3-dihydroquinazolin-4(1H)-one
nontoxic content, thermal and mechanical stability, high dis-
persion of the active phases, tunable pore size and ease of
surface modification seems to be good heterogeneous sup-
port for the immobilization of homogeneous catalysts.
However, mesoporous silica powders because of their small
sizes are difficult to separate by filtration techniques. This
drawback can be overcome using magnetic core-shell nano-
structures as ideal heterogeneous supports. Due to simple dihydroquinazolin- 4(1H)-one derivatives,
derivatives are an important class of heterocyclic compounds
[
22]
[23]
with antihyperlipidemic,
antihypertensive,
anti-
[
24]
[25]
[26]
parkinsonism,
anti-microbial,
anti-inflammatory,
[
7–10]
[
27]
and bronchodilator
activities are extensively used in
chemical and pharmaceutical industries. Although a wide
variety of reagents and catalysts have been reported for oxi-
dation of organosulfur compounds and the synthesis of 2,3-
[
28–32]
there are
recovery and reusability, high surface area, low cost, non- several disadvantages which accompany with these methods
toxic, readily available, coupling with organic ligands and such as use of toxic chemicals, heavy metal contamination,
inorganic compounds such as silica, Fe O magnetic nano- harsh conditions, long reaction times, overoxidation, prob-
3
4
particles have been widely used as core of the catalyst sup- lematic removal and recovery of the expensive catalyst, tedi-
[
11–13]
port.
The consolidation of the advantages of magnetic ous workup and low product yields. Herein, in this study,
Fe O core with mesoporous silica shell to develop novel we wish to report a new and convenient method for the oxi-
3
4
magnetic
core-shell
nanostructure
Fe O @MCM-41 dation of sulfides, oxidative coupling of thiols and the
3 4
CONTACT M. Nikoorazm
e_nikoorazm@yahoo.com
Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran.
Supplemental data for this article can be accessed on the publisher’s website.
ß 2020 Taylor & Francis Group, LLC

2
M. NIKOORAZM AND Z. ERFANI
3 4
Scheme 1. Synthesis of Fe O @MCM-41@Zn-Arg.
3 4 2 2
Scheme 2. Proposed mechanism for the oxidation of sulfides and oxidative coupling of thiols in the presence of Fe O @MCM-41@Zn-Arg using H O

INORGANIC AND NANO-METAL CHEMISTRY
3
3 4 3 4
Figure 1. XRD patterns of (a) small angle of Fe O @MCM-41 (b) wide angle of Fe O @MCM-41@Zn-Arg.
3 4 3 4 3 4 3 4
Figure 2. FT-IR spectra of (a) Fe O (b) Fe O @MCM-41(c) Fe O @MCM-41@Arg and (d) Fe O @MCM-41@Zn-Arg.

4
M. NIKOORAZM AND Z. ERFANI
3 4 3 4
Figure 3. SEM images of (a) Fe O @MCM-41 and (b) Fe O @MCM-41@Zn-Arg.
3 4
Figure 4. The EDS spectrum of Fe O @MCM-41@Zn-Arg.
synthesis of 2,3-dihydroquinazolin- 4(1H)-one derivatives (XRD), super magnetic properties, thermogravimetric
under mild conditions in the presence of Fe O @MCM- analysis(TGA), and IR spectra of samples were recorded with
3
4
4
1@Zn-Arg as a novel, ecofriendly and reusable nanocatalyst.
FESEM-TESCAN MIRA3, Holland Philips X’pertX-ray powder
diffraction (XRD) diffr actometer, Vibrating Sample
Magnetometer(VSM) MDKFD, Shimadzu DTG-60 instrument,
and disk on a VRTEX 70 model BRUKER, respectively.
Experimental section
Materials
Preparation of Fe O @MCM-41@Zn-Arg
3
4
All the materials and solvents used in this work were purchased
from Merck, Fluka or Sigma-Aldrich companies and used with- Magnetic nanostructure Fe O @MCM-41 was synthesized by
3
4
out further purification. Also, SEM images, X-ray diffraction a chemical co-precipitating method similar to our previously

INORGANIC AND NANO-METAL CHEMISTRY
5
3 4
Figure 5. TGA/DTA curves of Fe O @MCM-41@Zn-Arg.
ethanol (20 mL) for 30min. Then, the suspension was centri-
fuged and the solid was redispersed in a solution mixture of
deionized water (10 mL), ethanol (20 mL), and NH (0.5 mL).
3
The system was kept under vigorous mechanical stirring for
3
0 min, and then tetraethylorthosilicate (TEOS) (0.03 g)
was added drop wise. Subsequently, the mixture was kept
under well-mixed conditions at room temperature for 6 h.
The coated nanoparticles (Fe O @nSiO ) were collected
3
4
2
by magnetic separation, washed with ethanol and deion-
ized water for several times. Then, the coated
Fe O @nSiO nanoparticles were dispersed in a solution
3
4
2
composed of ethanol (30 mL), deionized water (40 mL),
NH (0.6 mL) and CTAB (0.15 g). After mechanical stir-
3
ring at room temperature for 30 min, 0.4 g of TEOS was
added dropwise to the solution and kept under stirring at
room temperature for 6 h. The solid products were sepa-
3 4
Figure 6. Magnetic curve of Fe O @MCM-41@Zn-Arg.
rated, washed with plenty of ethanol/deionized water and
Initially, the magnetic Fe O cores were dried in a vacuum oven at 80 C for 12 h. Finally, to
[
33]
ꢁ
reported work.
3
4
prepared using chemical coprecipitation method. Typically, remove organic template CTAB, ethano l(100 mL) and
ꢀ
1
FeCl .4H O (0.8 g) and FeCl .6H O (2 g) were completely dis- 2 mol L
HCl (5 mL) were added to 0.1 g of obtained
2
2
3
2
solved in 10mL of deionized water under nitrogen atmos- product, then the mixture was kept under mechanical stir-
phere. The resulting solution was added dropwise to 100 mL ring at room temperature, for 48 h. The solid products
ꢀ
1
of 1.0 mol L aqueous ammonia solution containing 0.4 g of were separated by magnetic separation and dried in a vac-
ꢁ
cetyltrimethylammonium bromide (CTAB) under sonication uum oven at 80 C for 24 h.
and nitrogen atmosphere with continuous stirring for 30 min,
the black precipitate (Fe O nanoparticles) was isolated by was performed by refluxing of Fe
The modification of Fe O @MCM-41 with L-Arginine
3 4
O
4
@MCM-41 (1 g) and L-
3
4
3
ꢁ
magnetic decantation, washed thoroughly with deionized Arginine (2 g, 11 mmol) in deionized water at 90 C for 24 h,
ꢁ
water, and finally dried at 80 C under vacuum. For the prep- under N
atmosphere. The resulting solid (Fe
O
3
@MCM-
4
2
aration of core–shell structured Fe O @MCM-41, 0.5 g of the 41@L-Arginine) was separated by an external magnet,
3
4
magnetic Fe O nanoparticles were ultrasonically dispersed in washed with distilled water and dried in an oven overnight.
3
4

6
M. NIKOORAZM AND Z. ERFANI
3 4
Table 1. Optimization of oxidative coupling of 4- methylthiophenol using Fe O @MCM-41@Zn-Arg under various conditions.
a
Entry
Amount of catalyst (mg)
Amount of oxidant (mL)
Solvent
Ethanol
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
9
None
20
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.3
6h
45
45
45
45
45
45
45
45
45
Trace
96
96
86
92
88
86
94
78
Ethanol
15
10
Ethanol
Ethanol
15
n-hexane
15
15
15
Acetonitrile
Dichloromethane
Ethyl acetate
15
H
2
O
10
15
Ethanol
82
Reaction conditions: 4-methylthiophenol (1 mmol), H
Isolated yield.
2
O
2
(0.4 mL) and catalyst (15 mg) in EtOH (3 mL) at room temperature.
a
2 2 3 4
Table 2. Oxidative coupling of thiols into disulfides with H O in the presence of a catalytic amount of Fe O @MCM-41@Zn-Arg in EtOH at room temperature.
a
ꢁ
M. P. ( C) [Ref.]
Entry
1
Substrate
Product
Time (min)
65
Yield (%)
93
[
40]
67–69
[
41]
2
45
96
40–42
[
41]
3
4
65
70
92
90
174–176
[
42]
42]
86–89
58–60
[
5
70
96
[
[
34]
41]
6
7
8
55
45
70
95
97
98
Oil
Oil
[
34]
278–281
[
34]
9
60
50
93
94
134–136
[
41]
1
0
90–92
Reaction conditions: substrate (1 mmol), H
Isolated yield.
2
O
2
(0.4 mL) and catalyst (15 mg) in EtOH (3 mL) at room temperature.
a
ꢁ
In the last step, the obtained Fe O @MCM-41@L-Arginine The reaction mixture was refluxed at 80 C for 24 h. Finally,
3
4
(
(
0.5 g) was dispersed in 30 mL ethanol, and then Zn the synthesized nano solid (Fe O @MCM-41@Zn-Arg) was
3 4
NO ) .6H O (0.25 g) was added to the reaction mixture. separated from the suspension by an external magnet,
3
2
2

INORGANIC AND NANO-METAL CHEMISTRY
7
Table 3. Optimization of oxidation of sulfides to the corresponding sulfoxides using Fe
3
O
4
@MCM-41@Zn-Arg under various conditions.
a
Entry
Amount of catalyst (mg)
Solvent
Amount of oxidant (mL)
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
9
None
15
15
15
15
15
15
10
8
Solvent free
Solvent free
Ethanol
Ethyl acetate
Acetonitrile
Dichloromethane
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.3
6h
90
90
90
90
90
90
90
90
90
Trace
98
90
85
88
64
45
88
82
H
2
O
Solvent free
Solvent free
Solvent free
1
0
15
86
Reaction conditions: Methyl phenyl sulfide (1 mmol), H2O2 (0.4 mL) and catalyst (15 mg) under solvent-free at room temperature.
a
Isolated yield.
washed with absolute ethanol, and dried under vacuum at
room temperature (Scheme 1).
The crystalline structure of the Fe O @MCM-41@Zn-Arg
3 4
was determined by powder X-ray diffraction (XRD). XRD
patterns of (a) small angle of Fe O @MCM-41 (b) wide-
3
4
angle of Fe O @MCM-41@Zn-Arg is shown in Figure 1.
3
4
General procedure for the oxidative coupling of thiols
ꢁ
ꢁ
ꢁ
The characteristic peaks at 2h ¼ 30.44 , 35.59 , 43.39 ,
ꢁ
ꢁ
ꢁ
To the mixture of the thiol (1 mmol) and Fe O @MCM- 53.74 , 57.29 and 62.79 which are in agreement with
3
4
4
1@Zn-Arg (15 mg) in ethanol (3 mL), H O (0.4 mL) was standard patterns of inverse cubic spinel magnetite (Fe O )
3 4
2
2
[
34]
added and stirred at room temperature. After completion of crystal structure,
show the presence of magnetite core in
ꢁ
the reaction (monitored by TLC), the catalyst was separated the structure. The broad peak at 2h ¼ 20–30 corresponds to
[
35]
from the mixture by an external magnet and the product amorphous silica.
Low angle XRD pattern for the
[
33]
was extracted with ethyl acetate and the solvent was Fe
O @MCM-41 is shown in our previously reported,
4
3
removed by simple evaporation to give pure disulfides.
2
the silica mesoporous structure exhibited a strong peak at
ꢁ
h ¼ 2.52 corresponded to the characteristic of hexagonal
ꢁ
ꢁ
ordering and two characteristic peaks at 2h ¼ 3.9 and 4.44
General procedure for the oxidation of sulfides
which are characteristic peaks of MCM-41.
The FT-IR spectra of Fe O , Fe O @MCM-41,
A
mixture of sulfide (1 mmol), H O (0.4 mL), and
3
4
3 4
2
2
Fe O @MCM-41@ Arg, Fe O @MCM-41@Zn-Arg are
Fe O @MCM-41@Zn-Arg (15 mg) was stirred under solvent-
3
4
3 4
3
4
shown in Figure 2. In FT-IR spectrum of the Fe O nano-
free condition at room temperature for appropriate time and
the progress of the reaction was monitored by TLC. After
completion of the reaction, the catalyst was separated by mag-
net and product was extracted with ethyl acetate. Finally,
ethyl acetate was evaporated to give the pure sulfoxides.
3
4
particles (Figure2 a) the Fe–O stretching vibration is
observed in terms of two strong absorption bands near 580
ꢀ
1
ꢀ1
and 444 cm ; also characteristic peaks at 3200–3500 cm
corresponding to symmetrical and asymmetrical modes of
O–H bonds on the surface of magnetic nanoparticles. In
ꢀ
1
Figure 2 b, the band at 461 cm correspondings to bending
Si-O–Si and characteristic peaks at 800 and 1081 cm cor-
responding to symmetric and asymmetric stretching of Si-
General procedure for the synthesis of 2,
ꢀ1
3-dihydroquinazolin- 4(1H)-one derivatives
O–Si vibrations respectively. The appearance of the
A
mixture of aldehyde (1 mmol), 2-aminobenzamide
ꢀ
1
ꢀ
(C ¼ N) (1662 cm ) band and presence of a peak around
(
(
1 mmol) in the presence of Fe O @MCM-41@Zn-Arg
3 4
20 mg) as a catalyst, was stirred in H O as solvent at 90 C
ꢀ1
ꢁ
2925 cm
corresponding to the aliphatic C-H stretching
2
vibration of the methylene group, shows that L-Arginine
was supported on the Fe O @MCM-41 surface (Figure2 c).
for the appropriate time.
After completion of the reaction (monitored by TLC),
the catalyst was separated from the mixture by an external
magnet. Then, the resulting mixture was dissolved
in hot ethanol, filtered and dried. The pure 2,3-dihydro-
quinazolin-4(1H)-ones were obtained by recrystallization
in ethanol.
3 4
The Fe O @MCM-41@Ar exhibits a ꢀ(C ¼ N) stretch at
3
ꢀ
4
1
1
662 cm , while in the Fe O @MCM-41@Zn- Arg, this
3 4
band shifts to the lower frequency and appears at
ꢀ
1
1
632 cm , which indicates the formation of the coordin-
ation binding between the ligand and the metal ion.
Figure 3 shows the scanning electron microscopy (SEM)
images of Fe O @MCM-41 and Fe O @MCM-41@Zn-Arg.
3
4
3
4
Results and discussion
This study showed the morphologies of the Fe O @MCM-
3
4
The prepared new heterogeneous catalyst was characterized 41 and Fe O @MCM-41@Zn-Arg are uniform spherical par-
3 4
by SEM, EDS, XRD, TGA, AAS, VSM and FT-IR spectros- ticles with uniform nanometer size.
copy. The results obtained indicate that Zn-arginine com-
The energy dispersive spectrum (EDS) of the catalyst
plex was successfully immobilized onto the surface of confirms the presence of Fe, Zn, O, Si, and N species
magnetic core-shell nanostructures.
in the catalyst (Figure 4).

8
M. NIKOORAZM AND Z. ERFANI
3 4
Table 4. Oxidation of various sulfides to sulfoxides in the presence of Fe O @MCM-41@Zn-Arg.
a
ꢁ
M. P. ( C) [Ref.]
Entry
1
Substrate
Product
Time (min)
100
Yield (%)
93
[
43]
133–135
[
34]
2
3
45
60
96
92
Oil
[
34]
oil
[
44]
34]
4
5
1200
90
80
98
67–68
[
31–32
[
41]
6
7
10
70
94
93
Oil
[
34]
120–122
[
45]
8
9
480
88
116–117
[
33]
70
25
92
94
oil
[
37]
1
0
103–105
a
2 2
Reaction conditions: substrate (1 mmol), H O (0.4 mL) and catalyst (15 mg) under solvent-free at room temprature Isolated yield.
Also, atomic absorption spectroscopy (AAS) shows that three weight losses. The first mass loss about 2% below
ꢁ
the amount of zinc determined on the Fe O @MCM- 200 C corresponds to the removal of physically adsorbed
3
ꢀ1
4
ꢀ
4
4
1@Zn-Arg was found to be 1.56 ꢂ 10 mole g
.
solvent and water inside the pores channels. The second
The thermal stability of Fe O @MCM-41@Zn-Arg was mass loss occurs at the region of 200–550 C mainly
ꢁ
3
4
studied by thermogravimetric analysis (TGA) (Figure 5). related to the decomposition of the organically modified
The TGA of Fe O @MCM-41@Zn-Arg sample shows moieties on Fe O @MCM-41@Zn-Arg. the third mass loss
3
4
3
4

INORGANIC AND NANO-METAL CHEMISTRY
9
Table 5. Optimization of the reaction conditions for synthesis of 2,3-dihydro- phenyl sulfide was chosen as a model compound and exam-
quinazolin-4(1H)-ones via the condensation of 4-chlorobenzaldehyde with
ined in the presence of different amount of catalyst, hydrogen
anthranilamide as a model reaction for 120 min.
peroxide (H O ) as well as in the presence and absence of
2 2
ꢁ
a
Entry Catalyst (mg) Temperature ( C)
Solvent
Time (min) Yield (%)
various solvents. The results can be seen in Table 3. As shown
in Table 3, the suitable reaction condition was obtained when
Fe O @MCM-41@Zn-Arg (15 mg) and H O (0.4 mL) as a
1
2
3
4
5
6
7
8
9
1
1
a
None
10
15
20
25
20
20
20
20
90
90
90
90
90
90
90
90
90
80
70
H
H
H
H
H
PEG
EtOH
2
2
2
2
2
O
O
O
O
O
10 h
120
120
120
120
120
120
120
120
120
120
Trace
58
84
96
96
92
94
45
30
3
4
2 2
green oxidant, under solvent-free conditions at room tempera-
ture for 90 min was selected. After optimization of the reaction
conditions, a variety of sulfides with different functional
groups were successfully employed to prepare the correspond-
ing sulfoxides with excellent chemoselectivity in high to
excellent yields with short reaction time. Because of mild
conditions of described heterogeneous systems, there is any
overoxidation to sulfone for oxidation of sulfides was not
observed. The results are shown in Table 4.
DMF
1,4-dioxane
0
1
20
20
H
H
2
O
O
82
75
2
Isolated yield
ꢁ
appears at 550–800 C as a result of the decomposition of
the silanol groups.
The mechanism of oxidation of sulfides and oxidative
coupling of thiols in the presence of Fe O @MCM-41@Zn-
3
4
The magnetic properties of the Fe O @MCM-41@Zn-Arg
3
4
[46]
Arg is shown in Scheme 2 . Based on these mechanisms,
reaction of H O with this catalyst leads to the intermediate
were studied using vibrating sample magnetometer (VSM)
at room temperature. The saturation magnetization (Ms)
observed for Fe O @MCM-41@Zn-Arg was found to be
2
2
A which is converted to active oxidant B. In the next step,
nucleophilic attack of the sulfide or thiol on this intermedi-
ate gives cation C or C which produce the final products.
3
4
ꢀ
1
2
2.06 emu g (Figure 6).
1
2
We finally studied the catalytic properties of
Evaluation of the catalytic activity of Fe O @MCM-
Fe O @MCM-41@Zn-Arg for the synthesis of 2, 3-dihydro-
3
4
3
4
4
1@Zn-Arg
quinazolin-4(1H)-one derivatives. In order to optimize reac-
tion conditions, the reaction of 4-chlorobenzaldehyde
(1 mmol) and 2-aminobenzamide (1 mmol) under varying
conditions, for example, using different amounts of catalyst,
temperature and nature of solvents have been performed.
In continuation of our interest in the different organic transfor-
mations,
and oxidative coupling of thiols and synthesis of 2,3-dihydro-
quinazolin- 4(1H)-one derivatives in the presence of catalytic
amounts of Fe O @MCM-41@Zn-Arg are reported.
[36–39]
herein, our studies in the oxidation of sulfides
For this propose various solvents such as H O, EtOH, 1,4-
2
3
4
dioxane, PEG, and DMF were examined. Since this nanoca-
In our initial screening experiments, the catalytic activity
of complex was evaluated in oxidative coupling of thiols to
their corresponding disulfides. In order to get the best
experimental conditions, 4-methylthiophenol was selected as
model substrate and a series of experiments were performed
with the variation of the amount of catalyst, hydrogen
peroxide and nature of the solvent system. As shown in
Table 1, in the absence of catalyst, (Table 1, entry 1), the
yield and reaction times were quite undesirable. However,
when similar oxidative coupling was conducted in the pres-
ence of different amounts of catalyst (Table 1, entries 2–4),
the best results in terms of yield, were obtained only with
talyst is much reactive in H O compared with other sol-
2
vents, H O was selected as a solvent for this reaction. Also,
2
it was found with increasing the amount of the catalyst
from 10 to 20 mg the yield of the product increases, above
2
0 mg no further increase in the product yield was observed.
Therefore, as shown in Table 5, the best results were
ꢁ
obtained in H O using 20 mg of catalyst at 90 C .
2
The scope and generality of this method was investigated in
the reaction of various types of aldehydes (with both electron-
donating and electron-withdrawing substituents such as -CH3,
-
OCH , -OCH CH , -Br, -Cl, -F, and –NO) with 2-aminoben-
3 2 3
zamide and the corresponding 2, 3-dihydroquinazolin-4(1H)-
ones were obtained in the excellent yields (Table 6).
1
5 mg of Fe O @MCM-41@Zn-Arg (Table 1, entry 3).
3 4
Among the tested solvents, such as (water, ethanol, aceto-
nitrile, n-hexane, ethyl acetate, dichloromethane) ethanol
was chosen as the best solvent for this reaction. To investi-
Based on our experimental results, we propose the fol-
lowing mechanism to account for the Fe O @MCM-41@Zn-
3
4
[
52]
Arg catalyzed the three-component reaction (Scheme 3).
gate the effect of different amount of hydrogen peroxide the
,
The carbonyl group in aldehyde was activated by the cata-
lyst. Then the anthranilamide reacted with the activated
aldehyde and the intermediate I is formed. After dehydra-
tion of intermediate I, the imine intermediate II is gener-
ated. Finally, the intramolecular cyclization of imine
intermediate II produced the final product.
reaction was performed using different amounts of H O
2
2,
and the results showed that 0.4 mL of H O is the best.
2
2
As shown in Table 2, the wide range of thiols were con-
verted to their corresponding products in the present of
Fe O @MCM-41@Zn-Arg as a catalyst in ethanol at room
3
4
temperature and all products were obtained in high yields
with short reaction times.
After successfully synthesizing a series of disulfide, we
turned our attention toward the synthesis of sulfoxides com-
Recyclability of the catalyst
pounds using Fe O @MCM-41@Zn-Arg and hydrogen perox- The reusability of the Fe O @MCM-41@Zn-Arg catalyst was
3
4
3 4
ide. In order to determine the best reaction conditions methyl studied in the reaction of 4- methylthiophenol in oxidative

1
0
M. NIKOORAZM AND Z. ERFANI
Table 6. Synthesis of 2, 3-dihydroquinazolin-4(1H)-ones catalyzed by Fe
3
O
4
@MCM-41@Zn-Arg.
a
ꢁ
M.p. ( C) [Ref.]
Entry
Product
Time (min)
120
Yield (%)
97
[
47]
1
222–224
[
47]
47]
2
3
140
150
89
90
188–190
168–170
[
[
47]
4
110
94
230–232
[
47]
5
6
7
100
120
140
94
96
88
196–198
200–203
195–198
[
48]
[
49]
[
50]
50]
8
9
80
96
92
210–212
190–192
[
120
[
51]
1
0
100
94
204–206
a
ꢁ
reaction conditions: substrate (1 mmol), anthranilamide (1 mmol) and 20 mg of catalyst in water at 90 C.
Isolated yield.
b

INORGANIC AND NANO-METAL CHEMISTRY
11
Scheme 3. Proposed mechanism for the synthesis of quinazolinones
coupling of thiol reaction (a), methyl phenyl sulfide in
the oxidation of sulfides (b) and 4-chlorobenzaldehyde
for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones (c)
under optimized conditions. After completion of each run,
the catalyst was separated by the assistance of an external
magnet and washed with ethyl acetate, and then dried
for the next run. As shown in Figure 7, the catalyst was
reused for at least six times without a considerable decrease
in its catalytic activity.
In order to find the leaching of the catalyst, the amount of
Zn in catalyst was determined by AAS after six times recycled.
ꢀ
4
The amount of Zn in catalyst was found to be 1.47ꢂ 10 mol
ꢀ
1
g
based on AAS for catalyst after 6 runs reused.
In order to investigate the efficiency of this procedure,
Figure 7. Reusability of Fe
disulfide (columns a), sulfoxide (columns b) and 2,3-dihydroquinazolin-4(1H)-one
columns c).
3 4
O @MCM-41@Zn-Arg catalyst for the preparation of
(
we compared the results on the oxidation of the methyl
TABLE 7. Comparison of Fe
3
O
4
@MCM-41@Zn-Arg for oxidation of methyl phenyl sulfide and oxidative coupling of 4-methylbenzenethiol
and synthesis of 2-(4-chlorophenyl)-2,3-dihydroquinazolin-4(1H)-one, with previously reported procedure.
Entry
Substrate
Catalyst
Time (min)
Yield (%)
Ref.
1
2
3
4
5
6
7
8
9
Methylphenylsulfide
Methylphenylsulfide
Methylphenylsulfide
Methylphenylsulfide
4-methylthiophenol
4-methylthiophenol
4-methylthiophenol
4-methylthiophenol
Fe
3
O
4
@MCM-41@ Zn-Arg
90
165
180
270
25
98
85
98
93
97
70
99
96
96
89
87
80
This work
[
[
[
53]
54]
55]
Bromide ion
Ion Exchange Resin
NBS
Fe
Fe3O4@Tryptophan-Fe
[bmim][SeO (OCH )]
Co-Salophen
Fe @MCM-41@ Zn-Arg
2-(N-morpholino)ethanesulfonc acid
3
O
4
@MCM-41@ Zn-Arg
This work
[56]
[20]
[57]
80
2
3
120
180
120
180
420
300
4-ClC
4-ClC
4-ClC
4-ClC
H
6 4
H
6 4
H
6 4
H
6 4
CHO
CHO
CHO
CHO
3
O
4
This work
[31]
[32]
[58]
10
11
12
SiO
KAl(SO
2
–FeCl
3
4
2
)2.E12H O

1
2
M. NIKOORAZM AND Z. ERFANI
phenyl sulfide(entries 1–4) and oxidative coupling of 4-
methylthiophenol (entries 5–8) and synthesis of 2-(4-chloro-
phenyl)-2,3-dihydroquinazolin-4(1H)-one (9-12) with the
previously reported procedures in the literature (Table 7). It
is obvious that described procedure in this study clearly
shows good reaction time and higher yield than the other
catalysts which have been reported previously.
2
Reactions in H O or PEG. RSC Adv. 2016, 6, 43205–43216.
DOI: 10.1039/C6RA02967A.
7
.
Nikoorazm, M.; Ghorbani-Choghamarani, A.; Mahdavi, H.;
Esmaeili, S. Efficient Oxidative Coupling of Thiols and
Oxidation of Sulfides Using UHP in the Presence of Ni or Cd
Salen Complexes Immobilized on MCM-41 Mesoporous as
Novel and Recoverable Nanocatalysts. Microporous Mesoporous
Mat 2015, 211, 174–181. DOI: 10.1016/j.micromeso.2015.03.011.
Omidi, F.; Behbahani, M.; Kalate Bojdi, M.; Shahtaheri, S. J.
Solid Phase Extraction and Trace Monitoring of Cadmium Ions
in Environmental Water and Food Samples Based on Modified
Magnetic Nanoporous Silica. J. Magn. Magn. Mater 2015, 395,
8
.
.
Conclusions
213–220. DOI: 10.1016/j.jmmm.2015.07.093.
In summary, an environmentally friendly, magnetically
recoverable and novel nanostructural catalyst was prepared
for the oxidative coupling of thiols to their corresponding
disulfides in ethanol with H O as oxidant and oxidation of
9
Rostamizadeh, S.; Zekri, N. An Efficient, One-Pot Synthesis of 2-
Amino-4H-Chromenes Catalyzed by (a-Fe 2 O 3)-MCM-41-
Supported Dual Acidic Ionic Liquid as a Novel and Recyclable
Magnetic Nanocatalyst.
329–2341. DOI: 10.1007/s11164-015-2152-9.
0. Kefayati, H.; Jirsaray Bazargard, S.; Vejdansefat, P.; Shariati, S.;
Kohankar, M. Fe MCM-41-SO H@[HMIm][HSO ]: an
Res. Chem. Intermed. 2016, 42,
2
2
2
sulfides to the sulfoxides under solvent-free condition and
1
1
1
the synthesis of 2,3 dihydroquinazolin-4(1H)-one derivatives
3
O
4
@
3
4
ꢁ
in water at 90 C. The designed catalyst exhibited good cata-
Effective Magnetically Separable Nanocatalyst for the Synthesis
of Novel Spiro [Benzoxanthene-Indoline] Diones. Dyes Pigm.
lytic activity in all cases and could be recovered easily and
reused for several times. High efficiency, the simplicity in
operation, simple and inexpensive procedure, easy purifica-
tion, mild conditions, short reaction times, high yields of
products and easy separation make this procedure
more attractive.
2
016, 125, 309–315. DOI: 10.1016/j.dyepig.2015.10.034.
1. Ghorbani-Choghamarani, A.; Azadi, G. Synthesis and
Characterization of Sulfamic Acid-Functionalized Nanoparticles
and Study of Its Catalytic Activity for the Oxidation of Sulfides
to Sulfoxides. Croat. Chem. Acta 2016, 89, 49–54. DOI: 10.5562/
cca2776.
3 4
2. Abdollahi-Alibeik, M.; Rezaeipoor-Anari, A. Fe O @ B-MCM-41:
A New Magnetically Recoverable Nanostructured Catalyst for the
Synthesis of Polyhydroquinolines. J. Magn. Magn. Mater. 2016,
Funding
3
98, 205–214. DOI: 10.1016/j.jmmm.2015.09.048.
We gratefully acknowledge Ilam University Research Council for par- 13. Zhang, F.; Jin, J.; Zhong, X.; Li, S.; Niu, J.; Li, R.; Ma, J. Pd
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1
4. Nemati, F.; Sabaqian, S. Nano-Fe
3
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