Preparation and characterization of magnetically separable MgFe2O4/Mg(OH)2 nanocomposite as an efficient heterogeneous catalyst for regioselective one-pot synthesis of β-chloroacetates from epoxides

Article abstract of DOI:10.1002/aoc.4520

Magnetically separable MgFe₂O₄/Mg(OH)₂ nanoparticles were fabricated and characterized using various techniques. These nanoparticles were used as a new catalyst for regioselective one-pot synthesis of β-chloroacetates from epoxides in the presence of NiCl₂?6H₂O and acetic anhydride. All reactions were carried out in ethanol at room temperature within 22–80?min giving the β-chloroacetates in high to excellent yields. The nanocatalyst was easily separated using an external magnet and reused several times without any significant loss of efficiency or magnetic property.

Full text of DOI:10.1002/aoc.4520

Received: 26 April 2018
DOI: 10.1002/aoc.4520
Revised: 14 June 2018
Accepted: 30 June 2018
F U L L P A P E R
Preparation and characterization of magnetically separable
MgFe2O4/Mg(OH)2 nanocomposite as an efficient
heterogeneous catalyst for regioselective one‐pot synthesis
of β‐chloroacetates from epoxides
Shadi Hassanzadeh | Ronak Eisavi
| Mojtaba Abbasian
Department of Chemistry, Payame Noor
Magnetically separable MgFe2O4/Mg(OH)2 nanoparticles were fabricated and
characterized using various techniques. These nanoparticles were used as a
new catalyst for regioselective one‐pot synthesis of β‐chloroacetates from epox-
ides in the presence of NiCl2⋅6H2O and acetic anhydride. All reactions were
carried out in ethanol at room temperature within 22–80 min giving the
β‐chloroacetates in high to excellent yields. The nanocatalyst was easily sepa-
rated using an external magnet and reused several times without any signifi-
cant loss of efficiency or magnetic property.
University, Tehran, Iran
Correspondence
Ronak Eisavi, Department of Chemistry,
Payame Noor University, PO Box 19395‐
3697, Tehran, Iran.
Email: roonak.isavi@gmail.com
KEYWORDS
β‐chloroacetates, epoxides, MgFe2O4/Mg(OH)2, nanocomposite
1 | INTRODUCTION
compounds[19,20] such as lipid mediators,[21–23] marine
natural compounds[24,25] and a specific group of enzymes
One‐pot synthesis as a green and simple method in which
several transformations are carried out in the same reac-
tion vessel provides unique advantages such as simple
work‐up procedures, fewer purification steps and increas-
ing of product yields.
named halohydrin dehalogenases. Also, β‐haloesters as
protected halohydrins with easily removable protecting
groups are essential building blocks in the synthesis of
natural products,[26,27] carbohydrates, steroids[28,29] and
bioconjugate structures of importance to drug design-
ing,[30,31] gene therapy,[32] membranology[33] and
enzymology.[34,35]
Recently, magnetic nanoparticles due to their easy
magnetic separation property[1–4] have received special
attention in biomedicine,[5–7] biosensors, biochips[8] and
material sciences.[9–11] However, the use of these mate-
rials always shows adsorption problems, because they
have a strong tendency of self‐aggregation and fewer
functional groups.[12,13] Nanostructures containing cores
of magnetic ferrites provide a helpful solution for effi-
ciency improvement of nanoferrites.[14] These nanoparti-
cles are stable in air and easily separable catalysts[15]
which have attracted much attention in organic reac-
tions,[16] drug targeting, magnetic cell separation and
magnetic sealing in recent years.[17,18]
Although ring‐opening of epoxides to β‐halohydrins
has been extensively studied in recent years, the conver-
sion of epoxides to β‐chloroesters has been rarely studied.
Synthesis of β‐chloroesters from epoxides has been
reported with TiCl4/EtOAc/imidazole,[36] trimethylsilyl
halides/pyridine/TFAA,[37] tBuCH2COCl/BiCl3
and
[38]
acyl chlorides in combination with CrO2Cl2,[39] CoCl2,[40]
Bu2SnCl2/Ph3P,[41] hexaalkylguanidinium chloride,[42]
LiClO4,[43] Zn,[44] Bi (NO3)3⋅5H2O[45] and TMSCl‐
SnCl2.[46] Some of these procedures suffer from disadvan-
tages such as high temperatures, long reaction times, the
use of harmful reagents, low efficiency and regioselec-
tivity, formation of by‐products, incapability of catalyst
β‐Halohydrins are some of the most important inter-
mediates for the synthesis of biologically active
Appl Organometal Chem. 2018;e4520.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4520

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HASSANZADEH ET AL.
recycling and the risk of metal remaining in the obtained
product in pharmaceutical synthesis. Therefore, in order
to overcome these problems and in connection with our
recent works on nanoferrites,[47–49] we describe here a
green and efficient method for the regioselective one‐pot
synthesis of β‐chloroacetates from epoxides with nickel
chloride and acetic anhydride in the presence of a cata-
lytic amount of MgFe2O4/Mg(OH)2 magnetic nanoparti-
cles in ethanol solvent at room temperature.
2.3 | Synthesis of MgFe2O4/Mg(OH)2
Nanocomposite
In a two‐neck round‐bottom flask, a solution of Mg
(NO3)2⋅6H2O (1.28 g, 5 mmol) in distilled water (30 ml)
was prepared and then MgFe2O4 (0.85 g, 4.3 mmol)
was added. The mixture was stirred vigorously for
15 min and followed by dropwise addition of NaOH
solution (2 M) in order to alkalize the mixture up to
pH ~ 12. The stirring of alkali mixture was continued
at room temperature for 24 h. The dark brown
MgFe2O4/Mg(OH)2 nanocomposite was separated using
a magnet, washed with distilled water and then dried
under air atmosphere.
2 | EXPERIMENTAL
2.1 | Instrumentation and Materials
All materials were purchased from Merck and Aldrich
with the best quality and they were used without further
purification. The synthesized nanocatalyst was character-
ized using X‐ray diffraction (XRD) with a Bruker D8
Advance diffractometer with graphite‐monochromatized
Cu K αradiation (λ= 1.54056 Å) at room temperature.
Scanning electron microscopy (SEM) images were
obtained using an FESEM‐TESCAN. The magnetic prop-
erty of the synthesized nanocatalyst was measured using
a vibrating sample magnetometry (VSM) instrument
(Meghnatis Daghigh Kavir Co., Kashan Kavir, Iran) at
room temperature. Transmission electron microscopy
(TEM) images were recorded using an EM10C 100 kV
series microscope from Zeiss (Germany). Energy‐disper-
sive X‐ray spectrometry (EDS) analysis was conducted
with a MIRA3 FE‐SEM microscope (TESCAN, Czech
Republic) equipped with an EDS detector (Oxford Instru-
2.4 | One‐pot Synthesis of β‐Chloroacetates
Catalysed by MgFe2O4/Mg(OH)2
Nanocomposite: A General Procedure
In a round‐bottomed flask equipped with a magnetic stir-
rer, a solution of epoxide (1 mmol), NiCl2⋅6H2O (0.47 g,
2 mmol) and Ac2O (0.51 g, 5 mmol) in EtOH (2 ml) was
prepared. MgFe2O4/Mg(OH)2 nanocomposite (0.02 g,
0.07 mmol) was then added to the solution and the
resulting mixture was stirred magnetically for
22–80 min at room temperature. The progress of the reac-
tion was monitored by TLC using n‐hexane–EtOAc (10:4)
as an eluent. After completion of the reaction, in order to
neutralize the reaction mixture, an aqueous solution of
NaHCO3 (10%, 10 ml) was added and followed by stirring
for additional 10 min. The magnetic nanocatalyst was
separated using an external magnet and accumulated
for the next run. The reaction mixture was extracted with
EtOAc (3 × 5 ml) and then dried over anhydrous Na2SO4.
After evaporating the organic solvent and short‐column
chromatography of the obtained crude product over silica
gel, pure β‐chloroacetate was obtained as a pale yellow
oil (80–98% yield). The collected MgFe2O4/Mg(OH)2
nanoparticles were washed with distilled water and dried
for the next cycle. All products are known compounds
and were characterized by comparison of their spectra
1
ments, UK). Fourier transform infrared (FT‐IR) and H
NMR/13C NMR spectra were recorded with Thermo
Nicolet Nexus 670 FT‐IR and 300 MHz Bruker Avance
spectrometers, respectively. The products were character-
ized using their spectra data and comparison with the
data reported in the literature. All yields refer to isolated
pure products.
2.2 | Preparation of MgFe2O4
Nanoparticles
1
(FT‐IR, H NMR and 13C NMR) with those of valid sam-
ples.[36,41,43] These data are given in the supporting
information.
MgFe2O4 nanoparticles were prepared by a solid‐state
procedure. Briefly, in a mortar, Mg(CH3COO)2⋅4H2O, Fe
(NO3)3⋅9H2O, NaOH and NaCl were mixed in a molar
ratio of 1:2:8:2 and ground together for 50 min. The reac-
tion started quickly along with the release of heat. The
mixture colour changed from blue to brown after 4 min.
Then the mixture was washed with double‐distilled water
several times. After removing the additional salts by
washing, the product was dried at 80 °C for 2 h. The pro-
duced powder was calcined at 300, 500, 700 and 900 °C
for 2 h to obtain final magnesium nanoferrite.
3 | RESULTS AND DISCUSSION
3.1 | Synthesis and Characterization of
Magnetic Nanocatalyst
MgFe2O4/Mg(OH)2 nanoparticles were synthesized in a
two‐step procedure. Nano‐MgFe2O4 was first prepared
by
a
solid‐state reaction of inorganic reagents

HASSANZADEH ET AL.
3 of 11
Mg(CH3COO)2⋅4H2O, Fe (NO3)3⋅9H2O, NaCl and NaOH
(Scheme 1). In order to decompose and completely
remove the excess salts used in the preparation of
nanoferrite and produce the MgFe2O4 nanoparticles with
high crystallinity, phase purity and increased saturation
magnetization (Ms), the obtained powder was calcined
at various temperatures (300 to 900 °C).[4,50] Then,
MgFe2O4 was added to an aqueous solution of
Mg(NO3)2⋅6H2O and followed by dropwise addition of
NaOH solution under vigorous stirring and a brown sus-
pension was prepared (Scheme 2). The obtained
nanocatalyst was characterized using FT‐IR spectroscopy,
XRD, SEM, EDS, TEM and VSM.
3.2 | Catalyst Characterization
3.2.1 | XRD analysis
The XRD patterns of nano‐Mg(OH)2, ferromagnetic
MgFe2O4 nanoparticles and MgFe2O4/Mg(OH)2 are
displayed in Figure 1. The main peaks located at 2θ=
30.47°, 35.82°, 43.48°, 53.77°, 57.32°, 62.88°, 71.36° and
74.35° are assigned to the diffraction of MgFe2O4 crystal
with spinel structure. This pattern is in agreement with
that of pure spinel MgFe2O4 in the standard data (JCPDS
no. 01–036‐0398). The average crystallite size of the
MgFe2O4 sample was calculated using the Scherrer equa-
tion (38 nm). In the XRD pattern of MgFe2O4/Mg(OH)2,
all the peaks of MgFe2O4 and Mg(OH)2 are observed. The
sharp peaks at 2θ= 18.49°, 38.21°, 50.99°, 58.85°, 68.37°
and 75.08° correspond to hexagonal phase of magnesium
hydroxide crystal, which are very close to those of stan-
dard data (JCPDS no. 84–2164). The peaks at 62.53° and
72.50° for magnesium hydroxide overlap with the 62.88°
and 71.36 peaks of MgFe2O4.
SCHEME 1 Synthesis of MgFe2O4 nanoparticles
SCHEME 2 Synthesis of MgFe2O4/
Mg(OH)2 nanoparticles
FIGURE 1 XRD patterns of (a) nano‐
Mg(OH)2, (b) nano‐MgFe2O4 and (c)
MgFe2O4/Mg(OH)2 nanocomposite

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HASSANZADEH ET AL.
3.2.2 | VSM analysis
3.2.3 | SEM analysis
Figure 2 shows magnetization curves of MgFe2O4 and
MgFe2O4/Mg(OH)2 nanoparticles at room temperature.
The narrow cycles and hysteresis loops show the behav-
iour of soft ferromagnetic particles with low coercivity.
Also, the decrease of saturation magnetization (Ms) from
48.82 emu g−1 of MgFe2O4 to 23.95 emu g−1 of MgFe2O4/
Mg(OH)2 is related to the presence of Mg(OH)2.
The morphology of the synthesized nanoparticles was
investigated using the SEM technique. Figure 3 shows
SEM images of MgFe2O4/Mg(OH)2 nanocomposite that
confirm the presence of irregular nanoparticles with
diameters ranging from 23 to 39 nm.
3.2.4 | FT‐IR spectroscopy
Figure 4 shows the FT‐IR spectra of MgFe2O4, Mg(OH)2
and MgFe2O4/Mg(OH)2 nanoparticles. The sharp and
strong absorption band at 3697 cm−1 is related to the
O─H stretching vibrations in the crystal structure of
Mg(OH)2.[51] The broad absorption peaks at 3436 and
1647 cm−1 correspond to the stretching and bending
modes of hydroxyl group in surface adsorbed water,
respectively. A broad band at 1509 cm−1 is attributed to
the O─ H bending vibrations in Mg(OH)2. The formation
of tetrahedral–octahedral structures of the metal oxide
FIGURE 2 Magnetization curves of (a) MgFe2O4 nanoparticles
and (b) MgFe2O4/Mg(OH)2 nanoparticles
FIGURE 3 SEM images of MgFe2O4/Mg(OH)2

HASSANZADEH ET AL.
5 of 11
FIGURE 4 FT‐IR (KBr) spectra of (a)
MgFe2O4, (b) Mg(OH)2 and (c) MgFe2O4/
Mg(OH)2
(Fe─ O and Mg─ O) is confirmed by the absorption
bands at around 400–600 cm−1 [48]
.
3.2.5 | EDS analysis
The chemical composition of the MgFe2O4/Mg(OH)2 nano-
composite was determined using EDS analysis. In the EDS
spectrum, Fe, O and Mg signals are observed (Figure 5).
3.2.6 | TEM analysis
TEM images of the MgFe2O4/Mg(OH)2 nanocomposite
are shown in Figure 6. As can be seen from the images,
FIGURE 5 EDS spectrum of MgFe2O4/Mg(OH)2
FIGURE 6 TEM images of MgFe2O4/Mg(OH)2

6 of 11
HASSANZADEH ET AL.
two sizes of particles are clearly distinguishable, with dif-
ferences in their colour and morphology. The larger black
spots with hexagonal shape were attributed to the
Mg(OH)2 particles.
3.3 | Conversion of Epoxides to
β‐Chloroacetates with NiCl2⋅6H2O
Catalysed by MgFe2O4/Mg(OH)2
Nanocomposite
In order to optimize the reaction conditions, we investi-
gated the simultaneous one‐pot chlorination and acetyla-
tion of styrene oxide with NiCl2⋅6H2O and Ac2O under
various reaction conditions (Scheme 3). Based on a litera-
ture survey, amount of catalyst, amount of reactants, tem-
perature, solvents and reaction time were studied as
experimental factors. Table 1 summarizes the results.
The best result was obtained using styrene oxide
(1 mmol), nickel chloride (2 mmol) and acetic anhydride
SCHEME 3 Conversion of epoxides to β‐chloroacetates with
NiCl2⋅6H2O catalysed by MgFe2O4/Mg(OH)2 nanocomposite
TABLE 1 Nano‐MgFe2O4/Mg(OH)2‐catalysed reaction of styrene oxide with NiCl2⋅6H2O and Ac2O under various conditionsa
Ac2O
(mmol)
MgFe2O4/
Mg(OH)2 (g)
NiCl2⋅6H2O
(mmol)
Time
(min)
Conversion
(%)b
Yield
(%)c
Entry
Conditions
1
5
3
3
3
3
3
3
1
2
4
5
10
5
5
5
5
5
5
5
5
5
5
5
5
—
2
2
2
2
2
1
3
2
2
2
2
2
1
2
2
2
2
2
2
2
2
2
2
2
EtOH/r.t.
60
10
0
100
100
100
100
100
100
100
100
100
100
100
100
80
0
75
75
70
79
73
79
75
77
82
87
88
81
69
60
77
73
78
60
Trace
51
65
20
50
2
0.01
0.01
0.005
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
EtOH/65 °C
EtOH/r.t.
3
70
4
EtOH/r.t.
80
5
EtOH/r.t.
40
6
EtOH/r.t.
60
7
EtOH/r.t.
35
8
EtOH/r.t.
66
9
EtOH/r.t.
50
10
11
12
13
14
15
16
17
18
19
20
21
22
23d
24e
EtOH/r.t.
35
EtOH/r.t.
30
EtOH/r.t.
15
EtOH/r.t.
40
Solvent‐free/r.t./grinding
Solvent‐free/r.t.
Solvent‐free/oil bath (70 °C)
Solvent‐free/oil bath (90 °C)
CH3CN/r.t.
CHCl3/r.t.
30
240
360
120
120
60
70
90
100
100
70
n‐Hexane/r.t.
EtOAc/r.t.
120
120
40
40
60
H2O/r.t.
80
EtOH/r.t.
60
50
EtOH/r.t.
60
80
aAll reactions were carried out with 1 mmol of styrene oxide.
bConversion of less than 100% was determined on the basis of the recovered epoxide.
cIsolated yields.
dCatalysed by MgFe2O4.
eCatalysed by Mg(OH)2.

HASSANZADEH ET AL.
7 of 11
a
TABLE 2 Conversion of epoxides to β‐chloroacetates with NiCl2⋅6H2O and Ac2O catalysed by nano‐MgFe2O4/Mg(OH)2
Entry
Epoxide (a)
β‐Chloroacetate (b)
Time (min)
Yield (%)b
Ref.
[36]
1
30
87
[43]
2
3
75
40
83
85
[36]
[36]
4
5
6
7
22
27
80
60
98
91
82
97
[36]
[36]
[41]
[36]
[43]
[36]
8
29
24
60
89
80
80
9
10
[36]
[36]
11
12
60
40
85
92
aAll reactions were carried out with 1 mmol of epoxide in the presence of NiCl2⋅6H2O (1 mmol), Ac2O (5 mmol) and nano‐MgFe2O4/Mg(OH)2 (0.02 g,
0.077 mmol, 7.7 mol%) in ethanol at room temperature.
bYields refer to isolated pure products.
(5 mmol) in the presence of nano‐MgFe2O4/Mg(OH)2
(0.02 g, 0.077 mmol, 7.7 mol%) as catalyst in ethanol sol-
vent at room temperature (Table 1, entry 11). The pres-
ence of a catalytic amount of the nanoparticles was
essential to accomplish the reaction. It is worth noting
that in the absence of catalyst, the reaction did not pro-
ceed even after 60 min (entry 1). The quantity of catalyst
was optimized using various amounts of MgFe2O4/
Mg(OH)2 (0.005, 0.01 and 0.02 g), and the best result
was obtained with 0.02 g of catalyst. An increase in the
amount of catalyst from 0.01 to 0.02 g not only acceler-
ated the rate of reaction but also increased the product
yield. This showed that the catalyst concentration plays
a consequential role in the optimization of the product
yield (entries 3–5).
FIGURE
7
Recycling of nano‐MgFe2O4/Mg(OH)2 in the
conversion of styrene oxide to 2‐chloro‐2‐phenylethylacetate
The effect of temperature on the reaction was studied
by comparing the obtained results from performing the
reaction at room temperature and 65 °C. The results
showed that the higher temperature led to a decrease in
the reaction time but did not increase the product yield
(entries 2 and 3).

8 of 11
HASSANZADEH ET AL.
yield (entry 8). The molecules of ethanol solvent are com-
peting with the resulting chlorohydrin from the ring
opening of epoxide for reaction with acetic anhydride to
produce the corresponding ester and subsequently reduc-
ing the amount of acyl groups in the reaction mixture. So,
in order to increase the product yield and reduce the reac-
tion time, we had to use an additional amount of acetic
anhydride (5 mmol). Greater amounts of Ac2O did not
improve the yield of product (entry 12).
In order to highlight the effect of solvent on the proce-
dure efficiency, the model reaction was also investigated
under solvent‐free conditions. In the absence of solvent,
the reaction was not complete even under grinding in
the mortar (entries 14 and 15).
Furthermore, the reaction was carried out under oil
bath conditions (70 and 90 °C). The obtained results were
not satisfactory under solvent‐free conditions at various
high temperatures (entries 16 and 17).
The effect of solvent was investigated by performing
the reaction in various solvents such as water, n‐hexane,
acetonitrile, chloroform and ethanol (entries 18–22).
Ethanol was selected as the best solvent for
β‐chloroacetylation of epoxides under optimized condi-
tions. The results showed that in comparison with etha-
nol, the reaction times were longer and the yields of
product were considerably lower in all other solvents.
Ethanol as a polar and protic organic solvent is more
effective and facilitates the ring opening of epoxides by
nucleophilic reagents. The non‐polar solvents such as
n‐hexane were not able to facilitate the reaction. The
chloroacetylation of styrene oxide was executable in ace-
tonitrile as a polar solvent but the reaction time was long
(120 min). Ethyl acetate and chloroform were not identi-
fied as appropriate solvents due to low product yields.
We also investigated the β‐chloroacetylation of sty-
rene oxide using bare MgFe2O4 and Mg(OH)2 nanoparti-
cles (entries 23 and 24). The yields of these reactions
were far less than those of reactions using the
MgFe2O4/Mg(OH)2 composite catalyst. These results
indicate that the interactions between the Mg(OH)2 and
MgFe2O4 nanoparticles may increase the catalytic activity
of MgFe2O4/Mg(OH)2.
FIGURE 8 (a) Magnetization curve, (b) XRD pattern and (c) FT‐
IR (KBr) spectrum of recovered MgFe2O4/Mg(OH)2
Various amounts of nickel chloride (1, 2 and 3 mmol)
were also examined in the conversion of styrene oxide to
2‐chloro‐2‐phenylethylacetate, and the quantity of 2 mmol
was chosen as the optimum option (entries 5–7).
In this reaction, acetic anhydride was used as an acet-
ylating agent. Increasing the amount of acetic anhydride
from 1 to 5 mmol reduced the reaction time and
enhanced the product yield (entries 8–11). The desired
reaction was also accomplished using 1 mmol of Ac2O,
but at a longer reaction time and with a lower product
To establish the generality and diversity of the pre-
sented method in the preparation of β‐chloroacetates
SCHEME 4 Proposed mechanism for
conversion of epoxides to β‐chloroacetates
with NiCl2⋅6H2O and Ac2O catalysed by
nano‐MgFe2O4/Mg(OH)2

HASSANZADEH ET AL.
9 of 11
from epoxides, the conversion of various epoxides bearing
aryl, alkyl and allyl substituted groups was further stud-
ied under optimized conditions. Table 2 presents the
results relating to the capability of this synthetic method.
Regioselective ring opening and chloroacetylation of
various epoxides containing electron‐releasing or
electron‐withdrawing groups were carried out efficiently
in ethanol at room temperature, and the corresponding
β‐chloroacetates were produced in high to excellent
yields.
of hydroxyl functional groups on the surface of the
nanocatalyst. The hydroxyl groups are capable of activat-
ing the epoxide ring through formation of hydrogen
bonds with oxygen and facilitating the ring opening of
oxirane. On the other hand, the coordination of oxygen
in epoxide with magnesium also catalyses the opening
of oxirane ring especially in a protic solvent medium.
The regioselective cleavage of epoxides bearing alkyl
and allyl groups by chloride ion proceeded from less hin-
dered carbon of the epoxide ring via SN2 type of mecha-
nism (β‐cleavage); however, aryl‐substituted epoxides
prefer to be opened from the more hindered position
via SN1 type of mechanism (α‐cleavage). In the case of
aryl‐substituted epoxides, the positive charge on the
aryl‐substituted position is stabilized by mesomeric
effects of aryl ring, while in the transformation of
alkylated epoxides to the corresponding β‐chloroacetates,
the steric factor plays the key role. In this reaction,
nickel chloride is just used as the source of chloride
nucleophile for the chlorination of ring‐opened epoxide
and does not have any catalytic effect because it is not
able to promote the reaction in the absence of the
nanocatalyst (Table 1, entry 1).
3.4 | Recycling of Nano‐MgFe2O4/Mg(OH)2
The recycling of the green nanocatalyst was investigated
under the optimized reaction conditions (Table 2, entry 1).
The nanoparticles were easily accumulated by applying
an external magnetic field, washed with distilled water
and, after drying, reused seven times without any signifi-
cant loss of activity (Figure 7). The structure of the recov-
ered catalyst was confirmed using XRD, FT‐IR and VSM
analyses after three runs (Figure 8).
3.5 | Proposed Mechanism for Conversion
of Epoxides to β‐Chloroacetates with
NiCl2⋅6H2O and Ac2O Catalysed by
MgFe2O4/Mg(OH)2 Nanocomposite
3.6 | Comparison of Catalytic Activities of
MgFe2O4/Mg(OH)2 and Other Catalysts
Although the exact mechanism of this reaction is not still
clear, a possible mechanism is presented in Scheme 4.
The coating of MgFe2O4 using Mg(OH)2 was carried out
in order to reduce the self‐aggregation tendency of
MgFe2O4 nanoparticles and also to increase the amount
The advantages of the presented synthetic method were
manifested by comparison of β‐chloroacylation of styrene
oxide with methods reported in the literature (Table 3).
From viewpoints of perfect regioselectivity, short reaction
times, mild and eco‐friendly conditions, recoverability,
TABLE 3 Comparison of catalytic activity of MgFe2O4/Mg(OH)2 with that of various other catalysts reported for β‐chloroacylation of
styrene oxidea
Entry
Catalyst system
Acylation reagent
Conditions
Product
Time (h)
Yield (%)
Ref.
1
2
3
4
5
6
7
8
9
MgFe2O4/Mg(OH)2
TiCl4/imidazole
Co (II)Cl2
Ac2O
EtOH/r.t.
I
0.5
3.5
1
87
This work
[36]
EtOAc
r.t.
I + II
95 (4:96)
[40]
[41]
[42]
[42]
[44]
[43]
[52]
PhCOCl
PhCOCl
MeCOCl
PhCOCl
MeCOCl
MeCOCl
Ac2O
CH3CN/r.t.
I + II
80 (96:4)
nBu2SnCl2/Ph3P
Benzene/60 °C
Solvent‐free/50 °C
Solvent‐free/100 °C
Petroleum ether/N2/28 °C
EtOAc/r.t.
I
24
3
63
PBGSiCl
II
80
PBGSiCl
II
5
70
Zn
I
2
84
LiClO4
I
3
68
(n‐Hexyl)4NCl
Solvent‐free/reflux
I + II
8
79 (19:81)
aAll reactions were carried out with 1 mmol of styrene oxide.

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HASSANZADEH ET AL.
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4 | CONCLUSIONS
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The preparation of eco‐friendly MgFe2O4/Mg(OH)2 nano-
composite has been developed as a novel and efficient
heterogeneous magnetic catalyst in the one‐pot conver-
sion of structurally diverse epoxides to β‐chloroacetates
with nickel chloride and acetic anhydride in ethanol at
room temperature. The mentioned protocol offers several
benefits such as reusability and easy separation of the cat-
alyst from the reaction medium, perfect regioselectivity,
low temperature, short reaction times, high product
yields and simple work‐up procedure.
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The financial support of this work by the Research
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SUPPORTING INFORMATION
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