Synthesis and characterization of a novel Fe3O4@SiO2/bipyridinium dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of β-azidoalcohols, β-cyanohydrins, and

Article abstract of DOI:10.1016/j.crci.2015.06.019

β-Azidoalcohols, β-cyanohydrins, and β-acetoxy alcohols have been synthesized in the presence of a Fe₃O₄@SiO₂/bipyridinium nanocomposite (Fe₃O₄@SiO₂/BNC) as a novel magnetic and recyclable

Full text of DOI:10.1016/j.crci.2015.06.019

G Model
CRAS2C-4120; No. of Pages 10
C. R. Chimie xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Comptes Rendus Chimie
www.sciencedirect.com
Full paper/Memoire
Synthesis and characterization of a novel Fe O @SiO /
3
4
2
bipyridinium dichloride nanocomposite and its application
as a magnetic and recyclable phase-transfer catalyst in
the preparation of
b-azidoalcohols, b-cyanohydrins,
and
b-acetoxy alcohols
a,
a
b
Ali Reza Kiasat *, Fatemeh Chadorian , Seyyed Jafar Saghanezhad
a
Chemistry Department, Faculty of Sciences, Shahid Chamran University, Ahvaz 61357-4-3169, Iran
b
ACECR-Production Technology Research Institute, Ahvaz, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
b
-Azidoalcohols,
b
-cyanohydrins, and
b
-acetoxy alcohols have been synthesized in the
Received 5 June 2015
Accepted after revision 23 June 2015
Available online xxx
presence of a Fe
3
O
4
@SiO /bipyridinium nanocomposite (Fe O @SiO /BNC) as a novel
2
3
4
2
magnetic and recyclable phase-transfer catalyst (PTC) in water. The catalyst was
characterized with FT–IR, SEM, XRD, VSM, and TGA. This methodology offers several
advantages, including easy work-up procedure, excellent regioselectivity, high yields,
short reaction times, recyclable catalyst, easy separation of the catalyst through an external
magnet and eco-friendly procedure.
Keywords:
Ring opening reaction
Epoxide
ß 2015 Acad e´ mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
b-Azidoalcohols
b-Acetoxy alcohols
b-Cyanohydrins
Magnetic nanocatalyst
1
. Introduction
ꢀ
ꢀ
organic materials such as small molecules and surfac-
tants, polymers, ionic liquids and biological molecules;
inorganic materials such as silica, metals and nonmetals,
metal oxides and sulfides [5,6].
Due to their simplicity of synthesis and their recycla-
bility, magnetic-nanoparticle-supported catalysts, espe-
cially iron oxide nanoparticles such as magnetite (Fe
and maghemite ( -Fe ) have been greatly utilized in
3 4
O )
g
2
O
3
Because of simple experimental operations, mild
organic reactions, including hydrogenation and reduction,
oxidation, hydroformylation, C–C coupling, asymmetric,
biocatalytic, olefin metathesis, and other catalytic reac-
tions [1–4]. Different catalysts have been immobilized on
magnetic nanoparticles (MNPs), including:
reaction conditions, inexpensive, environmentally benign
reagents and solvents and large-scale reaction, phase-
transfer catalysis (PTC) is a very useful approach [7]. One
practical limitation of the phase-transfer method, howev-
er, is that many of the catalysts used promote the
formation of stable emulsions [8]. Immobilization of the
phase-transfer catalyst on an insoluble magnetic support
can provide a simple solution to this problem.
b
-Azido alcohols are compounds of interest in organic
*
Corresponding author.
E-mail address: akiasat@scu.ac.ir (A.R. Kiasat).
synthesis as either precursors of vicinal amino alcohols or
http://dx.doi.org/10.1016/j.crci.2015.06.019
631-0748/ß 2015 Acad e´ mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
1
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3 4 2
O @SiO /bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
2
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
in the chemistry of carbohydrates, nucleosides, lactames,
and oxazolines [9]. Generally, azidohydrins are prepared
through ring opening reactions of epoxides by using
different azides in suitable solvents. Even though the
classical protocol uses sodium azide and ammonium
chloride, the azidolysis reaction requires a long reaction
time (12–48 h) and the azidohydrin is often accompanied
by isomerization, epimerization, and rearrangement of
products [10].
operating from 1 to 30 kV. Thermal stability of the
¨
supported catalyst was examined using a BAHR, SPA
503 Thermo-gravimetric Analyzer (TGA) at a heating rate
À1
of 10 8C.min
950 8C.
over the temperature range from 40 to
3 4
2.2. General procedure for the preparation of nano-Fe O
Nano-Fe
coprecipitation method [23]. A 500-mL round-bottom flask
was charged with FeCl O (3.1736 g, 16 mmol) and
Á4H
FeCl O (7.57 g, 28 mmol) and dissolved in 320 mL of
Á6H
deionized water. The mixed solution was stirred under
nitrogen at 80 8C for 1 h, then 40 mL of NH O (25%) were
3 4
O was prepared via an improved chemical
Although a few reagents and catalysts have been
reported recently for the conversion of epoxides to
azido alcohols, -cyanohydrins, and -acetoxy alcohols
11–18], disadvantages such as long reaction times, low
b
-
2
2
b
b
3
2
[
yields of products, difficulty in the preparation and/or the
storage of reagents or catalysts, tedious workup, and, in
most cases, low regioselectivity, clearly identify a need for
introducing new methods for such functional group
transformations.
3
ÁH
2
injected into the reaction mixture rapidly, which was
stirred under a nitrogen atmosphere for another 1 h and
then cooled to room temperature. The precipitated
particles were washed five times with hot water and
In continuation of our effort toward the synthesis of
novel catalysts, and their application in organic synthesis
3 4
separated by magnetic decantation. Finally, nano-Fe O
was dried under vacuum at 70 8C.
[
19–24], an Fe
3 4 2
O @SiO /bipyridinium nanocomposite
(
Fe @SiO /BNC) has been introduced as a novel hetero-
3
O
4
2
2.3. General procedure for the preparation of N-N-
geneous phase-transfer catalyst for the one-pot prepara-
tion of -azido alcohols, -cyanohydrins, and -acetoxy
alcohols in aqueous medium (Scheme 1).
bis(triethoxysilylpropyl)-4,4-bipyridinium dichloride
+
2
À
b
b
b
precursor, (TEOS)
2
BiPy 2Cl
In a 25-mL three-neck round-bottom flask, bipyridine
(8 mmol, 1.25 g) was added to DMF (5 mL), and stirred to
make a clear solution. To this solution, (3-chloropropyl)-
triethoxy silane (16 mmol, 3.18 g) was added dropwise,
and the mixture was stirred at 90 8C for 72 h under an
2
. Experimental
.1. General
All commercially available chemicals were purchased
2
argon atmosphere. Afterwards, the white solid, (TEOS)
BiPy 2Cl , was filtered and washed with methanol. This
solid was dried for 2 h in an oven at 90 8C [27].
2
+
2
À
from Fluka and Merck companies and used without further
purification. The products were characterized by their
physical constant and comparison with authentic samples.
Reaction monitoring was accomplished by TLC on silica gel
polygram SILG/UV 254 plates. The IR spectra were
recorded on a BOMEM MB-Series 1998 FT–IR spectropho-
tometer using KBr pellets for the samples and the catalyst
in the range between 4000 and 400 cm . H and C NMR
spectra were recorded in CDCl and DMSO-d on a Bruker
Advanced DPX 400 MHz spectrometer using TMS as
internal standard. The SEM analyses were carried out
2.4. General procedure for the preparation of Fe
BNC
3 4 2
O @SiO /
3 4
In a 250-mL round-bottom flask, 2 g of Fe O nano-
À1
1
13
particles were dispersed in a solution of 40 mL of distilled
water and 120 mL of ethanol via an ultrasonic bath for
15 min. Afterwards, 3 mL of ammonia (25%) were added. In
3
6
+
2
À
the next step, (TEOS) BiPy 2Cl (5 g) was added to the
2
using
a
LEO 1455VP Scanning Electron Microscope,
suspension. While stirring, 1.5 mL of TEOS in 40 mL of
OH
NaN3
N3
°
R
Water, 90 C
β−azido alcohols
OH
CN
O
(Fe O @SiO /BNC)
3 4 2
NaCN
°
R
Water, 90 C
R
β−cyanohydrins
OH
NaOAc
OAc
°
R
Water/EtOH, 90 C
β−acetoxy alcohols
Scheme 1. (Color online). One-pot preparation of
3 4 2
b-azido alcohols, b-cyanohydrins, and b-acetoxy alcohols using Fe O @SiO /BNC as a catalyst.
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3 4 2
O @SiO /bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
3
°
MeO
OMe
Si OMe
OMe
DMF, 90 C
2
(MeO) Si
(CH )
Cl +
N
N
3
2 3
MeO Si
MeO
N
N
7
2h
Cl
Cl
+2
À
Scheme 2. Preparation of (TEOS) BiPy 2Cl .
2
ethanol was added dropwise to the suspension. After 48 h
of stirring at room temperature, the desired catalyst,
3. Results and discussion
Fe
3
O
4
@SiO
2
/BNC, was separated via an external magnet
In the first step, Fe
3 4
O magnetic nanoparticles were
and was washed repeatedly with ethanol. Then the catalyst
prepared via the well-known coprecipitation method.
was dried at 60 8C for 2 h.
Afterwards,
N-N-bis(triethoxysilylpropyl)-4,4-bipyridi-
+
2
2
nium dichloride, (TEOS) BiPy 2Cl, as a precursor was
2.5. General procedure for the preparation of
b
-azido
prepared by the reaction of bipyridine and (3-chloropro-
alcohols in the presence of Fe @SiO /BNC in water
3
O
4
2
pyl) triethoxy silane in DMF at 90 8C for 72 h (Scheme 2). In
+
2
À
the next step, (TEOS) BiPy 2Cl and TEOS were added to
2
A 25-mL round-bottom flask was charged with epoxide
1 mmol), sodium azide (3 mmol), Fe @SiO /bipyridine
0.03 g) and 5 mL of deionized water and was heated at
0 8C in an oil bath for a specific time (10–50 min). After
completion of the reaction, which was indicated by TLC
TLC n-hexane/ethyl acetate (5:1)] (see Table 2), the
the suspension of magnetite nanoparticles in the presence
of ammonia to prepare the silica shell containing
bipyridinium units through a sol–gel method (Scheme 3).
(
(
9
3
O
4
2
3 4 2
To study the structure of Fe O @SiO /BNC, its charac-
terization was accomplished with FT–IR, SEM, TGA, VSM
and XRD techniques.
[
catalyst was separated utilizing an external magnet. The
product was extracted with diethyl ether (3 Â 10 mL), the
organic phase was concentrated and dried using
The
(TEOS)
In the spectra of Fe
FT–IR
BiPy 2Cl and Fe
spectra
of
@SiO
nanoparticles and of Fe
Fe
/BNC were recorded.
@SiO
3
O
4
nanoparticles,
+
2
À
2
3
O
4
2
3
O
4
3
O
4
2
/
CaCl
2
. After evaporation of the solvent under reduced
BNC, the characteristic peak corresponding to the stretch-
ing of the Fe–O bond is evident. Peaks in the range from
pressure with a rotary evaporator, the
were obtained with 88–95% yield.
b-azido alcohols
À1
+2
À
990 to 1200 cm in the spectra of (TEOS)
Fe @SiO /BNC is due to symmetrical and unsymmetrical
2
BiPy 2Cl and
3
O
4
2
2
.6. General procedure for the preparation of
b
-cyanohydrins
stretching vibrations of the Si–O bond, which verifies the
presence of silica shell around the magnetic nanoparticles.
The hydroxyl groups on the surface of the silica shell and
in the presence of Fe @SiO /BNC in water
3
O
4
2
A
25-mL round-bottom flask was charged with
epoxide (1 mmol), sodium cyanide (3 mmol), Fe @-
SiO /BNC (0.05 g) and 5 mL of deionized water and was
also the absorbed water show stretching vibration peaks of
À1
3
O
4
the O–H bond in the 3200–3600 cm
region. The
2
stretching peaks due to the aromatic moiety are evident
À1
refluxed in an oil bath for a specific time (20–40 min).
After completion of the reaction, which was indicated by
TLC [TLC n-hexane/ethyl acetate (5:1)] (see Table 3), the
catalyst was separated utilizing an external magnet. The
product was extracted with diethyl ether (3 Â 10 mL), the
organic phase was concentrated and dried using
in the 1400–1600 cm region. The bending vibration of
À1
water is seen at 1640 cm (Fig. 1).
After successful verification of the structure by record-
ing the FT–IR spectrum, it was decided to record the SEM
image of the catalyst. According to the SEM image,
although the particles have coagulated, the size of the
nanocomposite particles is under 100 nm (Fig. 2).
2
CaCl . After evaporation of the solvent under reduced
pressure with a rotary evaporator, the
were obtained with 85–95% yield.
b
-cyanohydrins
3 4 2
To evaluate the thermal stability of Fe O @SiO /BNC,
thermogravimetric analysis (TGA) was conducted. Accord-
ing to the TGA diagram, the grafted copolymer is stable up
to 250 8C (Fig. 3).
2.7. General procedure for the preparation of
b-acetoxy
alcohols in the presence of Fe @SiO /BNC in water
3
O
4
2
A mass loss of a ca. 6% is seen at 200 8C, which can be
attributed to the elimination of water. After 250 8C, it
seems that the organic part starts to decompose and a mass
loss of about 20% is seen in the range from 250 to 600 8C.
Further weight loss in the range between 650 and 800 8C
A
25-mL round-bottom flask was charged with
epoxide (1 mmol), sodium acetate (8 mmol), Fe @-
SiO /BNC (0.07 g) and 5 mL of aqueous ethanol (50:50);
the mixture was refluxed in an oil bath for a specific time
25–90 min). After completion of the reaction, which
was indicated by TLC [TLC n-hexane/ethyl acetate (5:1)]
as indicated in Table 4), the catalyst was separated
3 4
O
2
can be attributed to the phase transition from Fe
3
O
4
to FeO
(
[28].
The X-ray diffraction pattern of Fe O @SiO /BNC was
3 4 2
(
recorded (Fig. 4). It can be seen that the positions and the
intensity of the diffraction peaks are consistent with the
standard pattern for JCPDS Card No. (19–629) for magne-
utilizing an external magnet. The product was extracted
with diethyl ether (3 Â 10 mL), the organic phase was
concentrated and dried using CaCl
2
. After evaporation of
tite, with six peaks at 2u = 30.5, 35.8, 43.4, 53.8, 57.5, and
the solvent under reduced pressure with
evaporator, the -acetoxy alcohols were obtained with
8–92% yield.
a
rotary
63.18.
b
In order to investigate the magnetic properties of
@SiO /BNC, a vibrating sample magnetometer (VSM)
7
Fe
3
O
4
2
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3 4 2
O @SiO /bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
4
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
3 4 2
Scheme 3. Preparation of Fe O @SiO /BNC.
+2
À
3 4 2 3 4 2
Fig. 1. (Color online.) FTIR spectra of nano-Fe O (a); (TEOS) BiPy 2Cl (b); and Fe O @SiO /BNC (c).
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3 4 2
O @SiO /bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
5
3 4 2
Fig. 5. VSM curve of Fe O @SiO /BNC.
3 4 2
Fig. 2. (Color online.) SEM image of Fe O @SiO /BNC.
decided to evaluate its catalytic activity as a phase-transfer
catalyst in the ring opening of epoxides.
In the beginning, a model reaction of phenyl glycidyl
ether (1 mmol) and sodium azide (2–3 mmol) in the
was used. The saturation magnetization of Fe
BNC was 33.8 emu/g (Fig. 5).
3 4 2
O @SiO /
3 4 2
After successful characterization of Fe O @SiO /BNC
using FT–IR, SEM, TGA, VSM and XRD techniques, it was
3 4 2
presence of Fe O @SiO /BNC in 5 mL of deionized water
3 4 2
Fig. 3. (Color online.) TGA diagram of Fe O @SiO /BNC.
3 4 2
Fig. 4. (Color online.) X-ray diffraction pattern of Fe O @SiO /BNC.
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3 4 2
O @SiO /bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
6
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
Table 1
azide attack is directed by electronic effects and the
reaction is thought to be pseudo S 1. In the other cases, due
to steric hindrance of bulky groups, the unsubstituted
carbon is more accessible to the azide attack and the
Optimization of reaction conditions for the preparation of
b
-azido alcohol
N
from phenyl glycidyl ether, in the presence of Fe
medium.
3 4 2
O @SiO /BNC in aqueous
Entry
NaN
mmol)
3
Nanocomposite
(g)
Temperature
Time
reaction proceeds with a S
After the success of Fe
-azido alcohols, we decided to explore the catalytic
activity of this catalyst in the preparation of -cyanohy-
N
2 mechanism.
(
(8C)
(min)
3
O
4
@SiO /BNC in the preparation
2
1
2
3
4
5
6
7
8
2
2
3
3
3
3
3
3
0.07
0.1
90
90
90
90
90
90
60
r.t
60
50
of
b
b
0.03
0.05
0.07
–
50
drins. Subsequently, the ring opening of epoxides (1 mmol)
was conducted with sodium cyanide (3 mmol) in the
50
50
360
240
300
3 4 2
presence of Fe O @SiO /BNC (0.05 g) as the magnetic PTC
0.07
0.07
at 90 8C in aqueous medium. In the FT–IR spectrum, the
stretching vibration of the cyanide group is obvious at
In all cases the time indicates the total conversion except for entries 6 and
, which the reaction did not complete.
À1
2
253 cm (Fig. 7).
8
All epoxides reacted almost equally well to afford the
corresponding
Table 3).
With the same method, we decided to explore the
catalytic activity of this catalyst in the preparation of
acetoxy alcohols. Thus, the ring opening of epoxides
(1 mmol) was conducted with sodium acetate (8 mmol) in
b-cyano hydrins in high to excellent yields
(
was conducted under different conditions. According to
TLC, the optimized amount of reactants and of the catalyst
was found: 3 mmol of sodium azide and 0.03 g of the
catalyst complete the reaction at 90 8C in a minimum time
b
-
(Table 1).
3 4 2
the presence of Fe O @SiO /BNC (0.07 g) as the magnetic
In the FT–IR spectrum, the stretching vibration of azide
group is obvious at 2106 cm (Fig. 6).
PTC in a 50:50 mixture of ethanol/water under reflux
conditions. In the FT–IR spectrum, the stretching vibration
of carbonyl group is obvious at 1719 cm (Fig. 8).
À1
À1
In the next step, with optimum conditions in hand
(
5
1 mmol epoxide: 3 mmol azide: 0.03 g Fe
mL of deionized water at 90 8C), the generality and
synthetic scope of this coupling protocol were demon-
strated by synthesizing a series of -azido alcohols (Table
) in 10 to 50 min with 88–95% yield.
A glimpse to Table 2 makes clearly evident the
3
O
4
@SiO
2
/BNC:
All epoxides reacted almost equally well to afford the
corresponding
yields (Table 4).
Due to the importance of green chemistry and catalyst
recycling, the recyclability of Fe @SiO /BNC was asses-
b-acetoxy alcohols in high to excellent
b
2
3
O
4
2
sed in the reaction of phenyl glycidyl ether with the azide
anion. The result is shown in Fig. 9. The activity of the
nanocomposite is slightly decreased after 4 times of reuse.
generality of this methodology. Different functional
groups, including ether, ester and double bond, are easily
tolerated in the reaction conditions. The results clearly
indicate the high regioselectivity of epoxide ring-opening
by the azide anion. Steric and electronic effects direct
regioselectivity; for example, in styrene oxide, the phenyl
group acts as an electron-donating group via resonance,
which in turn stabilizes the carbocation. As a result, the
3 4 2
To demonstrate the superiority of Fe O @SiO /BNC over
the reported catalysts, the azidolysis reaction of styrene
oxide was considered as a representative example (Table
5). In all of these cases (except for entry 1, 2), a low yield of
the desired product was obtained. It is also noteworthy to
mention that all of the reported procedures required long
Fig. 6. (Color online.) FT–IR spectrum of 2-hydroxy-3-phenoxy propyl azide.
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3 4 2
O @SiO /bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
7
Table 2
Preparation of
b-azido alcohols from corresponding epoxides and sodium azide in the presence of Fe
3 4 2
O @SiO /BNC in aqueous medium at 90 8C.
Entry
1
Epoxide Product
Time (min)
15
Yield (%)
95
2
50
95
3
4
10
10
91
92
5
6
10
20
89
90
7
20
30
88
90
a
8
a
Due to low boiling point of 1,2-epoxy butane, the reaction was conducted at 60 8C.
Fig. 7. FT–IR spectrum of 2-hydroxy-pentanenitrile.
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3
O
4
@SiO
2
/bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
8
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
Table 3
Preparation of
3 4 2
b-cyano hydrins from corresponding epoxides and sodium cyanide in the presence of Fe O @SiO /BNC in aqueous medium at 90 8C.
Entry
1
Epoxide Product
Time (min)
40
Yield (%)
94
2
20
95
3
4
25
25
92
87
5
6
25
30
95
91
7
20
40
85
90
a
8
O
a
Due to low boiling point of 1,2-epoxy butane, the reaction was conducted at 60 8C.
Fig. 8. FT–IR spectrum of 3-acetoxy-2-hydroxy-propylmethacrylate.
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3
O
4
@SiO
2
/bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
9
Table 4
Preparation of
b-acetoxy alcohols from corresponding epoxides and sodium acetate in the presence of Fe
3
O
4
@SiO
2
/BNC in ethanol/water (50:50) under
reflux conditions.
Entry
1
Epoxide
Product
Time (min)
90
Yield (%)
92
2
35
90
3
4
30
30
87
85
5
6
30
50
82
78
7
25
45
88
79
a
8
a
Due to low boiling point of 1,2-epoxy butane, the reaction was conducted at 60 8C.
Table 5
Comparison of azidolysis of styrene oxide with other reported methods in the literature.
Entry
Catalyst
LiClO
Solvent
CH CN
Temperature (8C)
Time (h)
Yield (%)
Ref
1
2
3
4
5
6
7
8
9
4
3
80
70
5
92
90
85
85
85
80
85
85
95
[25]
NH Cl
(TBA)
4
MeOH–H
CH CN–H
2
O
5
[25]
4
PFe11MO39Á3H
2
O
3
2
O
80
4.5
0.5
1.5
1
[26]
Dowex–PEG
PEG300
H
2
O
100
60
[19]
PEG300
[20]
SiO
2
–PEG
H
H
H
H
2
O
2
O
2
O
2
O
100
90
[23]
a
MPTC
0.5
1.5
0.25
[24]
Network polymer
80
[22]
Fe
3
O
4
@SiO
2
/BNC
90
This work
a
Multi-site phase-transfer catalyst.
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3
O
4
@SiO
2
/bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of

G Model
CRAS2C-4120; No. of Pages 10
1
0
A.R. Kiasat et al. / C. R. Chimie xxx (2015) xxx–xxx
Acknowledgments
We are grateful to the Research Council of Shahid
Chamran University for financial support.
References
[
[
[
[
1] Y. Zhu, L.P. Stubbs, F. Ho, R. Liu, C.P. Ship, J.A. Maguire, N.S. Hosmane,
Chem. Cat. Chem. 2 (2010) 365–374.
2] S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L.V. Elst, R.N. Muller,
Chem. Rev. 108 (2008) 2064–2110.
3] V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.-M. Basset,
Chem. Rev. 111 (2011) 3036–3075.
4] M.B. Gawande, P.S. Branco, R.S. Varma, Chem. Soc. Rev. 42 (2013) 3371–
3
393.
Fig. 9. (Color online.) Reusability of the nanocomposite in the reaction of
[
[
[
[
[
5] C.W. Lim, I.S. Lee, Nano Today 5 (2010) 412–434.
6] W. Wu, Q. He, C. Jiang, Nanoscale Res. Lett. 3 (2008) 397–415.
7] H.E.S. Ali, Catal. Commun. 8 (2007) 855–860.
8] H. Mahdavi, B. Tamami, React. Funct. Polym. 64 (2005) 179–185.
9] S.W. Chen, S.S. Thakur, W. Li, C.K. Shin, R.B. Kawthekar, G.J. Kim, J. Mol.
Catal. A Chem. 259 (2006) 116–120.
phenyl glycidyl ether with the azide anion.
[10] F. Fringuelli, O. Piermatti, F. Pizzo, L. Vaccaro, J. Org. Chem. 64 (1999)
reaction times (except for entries 4, 7). These results
6094–6096.
[11] A.R. Kiasat, S. Nazari, J. Davarpanah, C. R. Chimie 17 (2014) 124–130.
[12] B. Tamami, H. Mahdavi, Tetrahedron Lett. 42 (2001) 8721–8724.
[13] M.N. Soltani Rad, S. Behrouz, Mol. Divers 17 (2013) 9–18.
[14] G. Sabitha, R.S. Babu, M.S.K. Reddy, J.S. Yadav, Synthesis 15 (2002)
clearly demonstrate that Fe
more efficient catalyst for this reaction.
3 4 2
O @SiO /BNC is an equally or
2
254–2258.
[15] F. Kazemi, A.R. Kiasat, S. Ebrahimi, Synth. Commun. 33 (2003) 999–
004.
16] N. Iranpoor, H. Firouzabadi, M. Shekarize, Org. Biolmol. Chem. 1 (2003)
24–727.
4
. Conclusion
1
[
In conclusion, a novel Fe
3
O
4
@SiO
2
/BNC, has been
magnetic and
recyclable phase-transfer catalyst in the preparation of
-azidoalcohols, -cyanohydrins, and -acetoxy alcohols
7
synthesized and its application as
a
[17] S.W. Chen, S.S. Thakur, W. Li, C.K. Shin, R.B. Kawthekar, G.J.J. Kim, Mol.
Catal. A Chem. 259 (2006) 116–120.
[
18] B. Mombani Godajdar, A.R. Kiasat, M. Mahmoodi Hashemi, J. Mol. Liq.
83 (2013) 14–19.
[19] A.R. Kiasat, R. Badri, B. Zargar, S. Sayyahi, J. Org. Chem. 73 (2008) 8382–
385.
b
b
b
1
was investigated. The catalyst was characterized with FT–
IR, SEM, XRD, VSM and TGA. According to the experimental
results, the regioselective ring opening reaction of
epoxides, in the presence of azide, cyano and acetate
anions in aqueous medium, leads to the corresponding
products in a short reaction time and with high yields. This
methodology offers several advantages, including an easy
work-up procedure, excellent regioselectivity, high yields,
short reaction times, recyclability of the catalyst, easy
separation of the catalyst through an external magnet; it is
also an eco-friendly procedure.
8
[
[
20] A.R. Kiasat, M. Zayadi, Catal. Commun. 9 (2008) 2063–2067.
21] A.R. Kiasat, S. Sayyahi, Catal. Commun. 11 (2010) 484–548.
[22] A. Mouradzadegun, A.R. Kiasat, P. Kazemian Fard, Catal. Commun. 29
(2012) 1–5.
[
[
23] A.R. Kiasat, M. Fallah-Mehrjardi, J. Iran. Chem. Soc. 6 (2009) 542–546.
24] A.R. Kiasat, R. Mirzajani, H. Shalbaf, M. Fallah-Mehrjardi, J. Chin. Chem.
Soc. 56 (2009) 594–599.
[25] M. Chini, P. Crotti, F. Macchia, Tetrahedron Lett. 31 (1999) 5641–5644.
[26] B. Yadollahi, H. Danafar, Catal. Lett. 113 (2007) 120–123.
[27] A. Bashti, A.R. Kiasat, B. Mokhtari, RSC Adv. 5 (2015) 25816–25823.
[28] O. Rahman, S.C. Mohapatra, S. Ahmad, Mater. Chem. Phys. 132 (2012)
196–202.
Please cite this article in press as: Kiasat AR, et al. Synthesis and characterization of a novel Fe
3 4 2
O @SiO /bipyridinium
dichloride nanocomposite and its application as a magnetic and recyclable phase-transfer catalyst in the preparation of