Magnetic Nanoparticle Anchored Deep Eutectic Solvents as a Catalyst for the Etherification and Amination of Naphthols

Article abstract of DOI:10.1002/adsc.201800743

Herein, we introduce a reusable catalyst consisting of a deep eutectic solvent made up of choline chloride and p-toluene sulfonic acid (pTSA) covalently immobilized on magnetic nanoparticles (MNPs) as an agent for chemoselective direct ipso etherification and amination of naphthols. The bonding of the DES to the surface of the nanoparticles has increased the catalytic activity of the DES and also has simplified catalyst recovery from the reaction mixture. The MNP bound DES particles with an average size of 12±2 nm was characterized by FTIR, PXRD, HRTM, TGA, and VSM. For 16 tested etherification reactions, the functionalized magnetite nanoparticle catalyst gave an average yield of 84%; for 5 tested aminations the average yield was 77%. For all 23 tested reactions the yield was above 70% and pTSA Br?nsted acid loading was only 0.45 mol%. The catalytic performance could be attributed to the dispersion of the nanoparticles, strong DES-support interactions and interactions of the hydrogen donor species with naphthols. This work is the first catalytic examination of PDES covalently bonded on MNPs as a platform for organic transformations. (Figure presented.).

Full text of DOI:10.1002/adsc.201800743

Title: Magnetic Nanoparticle Anchored Deep Eutectic Solvents as a
Catalyst for the Etherification and Amination of Naphthols
Authors: Parisa Zamani, John Ozdemir, Yumi Ha, Mourad Benamara,
Andrian Kuchuk, Tengjiao Wang, Jingyi Chen, Ahmad
Khosropour, and Hassan Beyzavi
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800743
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10.1002/adsc.201800743
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Magnetic Nanoparticle Anchored Deep Eutectic Solvents as a
Catalyst for the Etherification and Amination of Naphthols
Parisa Zamani,† John Ozdemir,‡ Yumi Ha,‡ Mourad Benamara,§ A. V. Kuchuk,§
Tengjiao Wang,‡ Jingyi Chen,‡ Ahmad R. Khosropour,*,†,‡ and M. Hassan Beyzavi*,‡,§
†Department of Chemistry, University of Isfahan, Isfahan, 81746-73441, Iran. Email: khosropour@chem.ui.ac.ir
‡Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, Arkansas 72701, United States.
Email: beyzavi@uark.edu
§Institute for Nano Science and Engineering, University of Arkansas, Fayetteville, Arkansas 72701, United States.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201#
Abstract. Herein, we introduce a reusable catalyst
consisting of a deep eutectic solvent made up of choline
chloride and p-toluene sulfonic acid (pTSA) covalently
immobilized on magnetic nanoparticles (MNPs) as an
agent for chemoselective direct ipso etherification and
amination of naphthols. The bonding of the DES to the
surface of the nanoparticles has increased the catalytic
activity of the DES and also has simplified catalyst
recovery from the reaction mixture. The MNP bound
DES particles with an average size of 12±2 nm was
characterized by FTIR, PXRD, HRTM, TGA, and VSM.
For 16 tested etherification reactions, the functionalized
magnetite nanoparticle catalyst gave an average yield of
84%; for 5 tested aminations the average yield was 77%.
For all 23 tested reactions the yield was above 70% and
pTSA Brønsted acid loading was only 0.45 mol%. The
catalytic performance could be attributed to the
dispersion of the nanoparticles, strong DES-support
interactions and interactions of the hydrogen donor
species with naphthols. This work is the first catalytic
examination of PDES covalently bonded on MNPs as a
platform for organic transformations.
Current methods established for C–O bond-
formation include O-arylations that employ transition-
metal-catalyzed cross-coupling, diaryliodonium salts,
benzynes, phenol alkylations, etc. (Scheme 1a).[4]
A
nucleophilic aromatic substitution reaction (SNAr) to
functionalize aryl C–OH bond is an effective strategy
because the transformation would not require prior
functionalization of the –OH group and water would
be produced as the only byproduct.[5] Given the utility
of the products, access to several functional
derivatives could be achieved by employing
heteroatoms with O- and N-centered nucleophiles.[6]
The current methodologies for C–O bond formation,
suffer from toxic reagents (i.e., alkylating agents),
complicated catalysts, expensive transition-metal
catalyst, and harsh reactions conditions (i.e., strong
corrosive acids or utilizing microwave irradiation).[7]
Deep eutectic solvents (DESs) are liquid catalysts
formed through the establishment of hydrogen bonds
between hydrogen bond donors (HBD) and hydrogen
Keywords:
Deep
eutectic
solvents
(DESs),
Etherification, Amination, pTSA; Naphthol, Magnetic
nanoparticles
Introduction
As a result of alkyl-aryl and aryl-aryl ethers being
crucial constituents in the pharmaceutical,
agrochemical, and high-tech industries (Figure 1)
development of new catalysts and convergent
approaches to produce these ethers with greater
economic efficiency and without harmful effects to
the health or environment of the user are being
investigated. [1-3]
1
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10.1002/adsc.201800743
Advanced Synthesis & Catalysis
Figure 1. Biologically and agrochemically active aryl ether
compounds.
particles exposed to acids and aqueous solutions limit
their extensive applications.[18] To overcome these
limitations and simultaneously improve potential
functionalization, the surface of these MNPs can be
coated by a protection layer such as biocompatible
organic species (surfactants and polymers) or
inorganic layers (silica, carbon or metals).[19] In the
past twenty years many publications have focused on
the preparation of magnetic core-shell structures by
coating a polymer shell around preformed MNPs.[20]
In this work the catalytic activity of the deep
eutectic solvent mixture of choline chloride and pTSA
was expanded to etherification or amination of
naphthol with various alcohols or amines (Scheme
1b). Concomitantly we have designed, synthesized
and characterized the first type of magnetic
nanoparticle anchored deep eutectic solvent resulting
in a catalyst which can be separated from the finished
reaction mixture by application of a magnetic field.
Results and Discussions
The catalytic study began with the preparation of
DES anchored nanoparticle catalyst as illustrated in
Figure 2. Vinyltrimethoxysilane (VS) and Fe3O4
nanoparticles were sonicated in an alkaline ethanol-
water solution to produce VS surface functionalized
Fe3O4 (MNPs-VS). Glycidyl methacrylate (GMA)
containing an epoxy functional group was then
applied as a monomer for in situ polymerization in the
presence of MNPs-VS, giving new NPs (MNPs-
GMA) with a core-shell scaffold. This construction
protected the iron oxide core from leaching and
further oxidation under high temperatures in the
atmosphere. The MNPs-CCL were fabricated by
reaction of MNPs-GMA with ChCl in the presence of
Scheme 1. Previous and presented aryl ether syntheses
routes.
bond acceptors (HBA) and show environmentally
benign features.[8] The eutectic mixture of quaternary
ammonium salt choline chloride (ChCl) and the
hydrogen bond donor p-tolunesulfonic acid (pTSA) as
a catalyst for the dehydration of fructose to 5-
hydroxymethylfurfural involving the formation of a
new intramolecular C–O bond has been shown to be
viable.[9] Investigations into the separation of
aromatic, aliphatic and phenol compounds from
solutions of DESs is an ongoing are of research with
challenges created by the ionic properties of DESs.[10]
Functionalized magnetic nanoparticles show high
dispersion in many solvents but can be easily
separated from solution by application of a magnetic
field and have been investigated as anchors for
catalytically relevant moieties.[11,12] Magnetic iron
oxide nanoparticles have been studied for applications
in biomedicine and bioengineering applications,
including bio-labelling, DNA detection, tumor
therapy, magnetic resonance imaging (MRI), and
magnetically guided targeted drug delivery
highlighting the nontoxic nature of the material.[13-17]
It should be noted that the spontaneous erosion,
oxidation, and aggregation of pure nano-Fe3O4
1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU)
in
aqueous solution at room temperature. The MNPs-
CCL were then treated with pTSA leading to MNPs-
CCL/TSA.
2
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10.1002/adsc.201800743
Advanced Synthesis & Catalysis
Data (ICDD), Powder Diffraction Files, Card No. 01-073-
9877).
Figure 2. Synthetic route of MNPs-CCL/TSA.
As shown in Figure 4, the experimental Bragg
peaks from planes with different Miller indices and
their intensity ratio correlated with those measured for
the reference Fe3O4 cubic phase. This indicates a pure
cubic crystalline structure of NPs with lattice
parameter ~ 0.832 nm. The lateral coherence length
was directly deduced from the full width at half
maximum (β) of the peaks using Scherrer equation
0.9 휆
(퐷 =
), where λ=0.15418 nm is the wavelength
훽푐표푠휃
of the XRD source and θ is the peak position. Thus,
by considering that the broadening of the Bragg peaks
results from pure size effects, the mean size of the
catalyst was about 12±2 nm.
Figure 3. IR spectra of a) MNPs-VS, b) MNPs-GMA, c)
MNPs-CCL, and d) MNPs-CCL/TSA.
The morphology of the catalyst was investigated by
HRTEM using an FEI Titan 80-300 TEM fitted with
CEOS image corrector. Figure 6 shows a typical
HRTEM image of the nanoparticles. Atomic planes
are visible in the image confirming their crystalline
nature. Most of the particles have a spherical shape
while a low density of them exhibit facets. A
statistical analysis of their size distribution was
conducted using HRTEM images obtained under the
same conditions. As illustrated in the histogram, their
size ranges are from 10 to 20 nm with an average
value of 14 nm, which appear aggregated. This result
is consistent with that obtained using XRD. The inset
represents the FFT (or SAED Pattern) of the image,
which can be used to identify a specific family of
planes similarly to an electron diffraction pattern
analysis. The inset contains spots which correspond to
real space distances of 0.295nm, 0.255nm, 0.175nm.
These correspond well with the interplanar distances
of (220), (311) and (511) planes of the nanoparticles.
TGA of MNPs-CCL/TSA displayed acceptable
thermal stability up to 270 °C with a 5.67% loss in
mass by 190 °C and a total loss of 30.8% mass upon
evaporation of all organic species from the
nanoparticles at 270 °C (Figure 5).
Figure 3 illustrates Fourier transform infrared (FT-
IR) spectra of MNPs-CCL/TSA. The bands at 437,
566, 1048, 1409, 1601 and 3434 cm-1 are the
characteristic absorptions of vinyl silane, providing
evidence for the constitution of the silica shell (Figure
3a). The MNP’s Fe–O peak appears at 556 cm-1.
Peaks located at 1724, 1735 and 1740 cm-1 arise from
the C=O functional groups (Figure 3b, c, and d
respectively). The intense and broad absorptions near
1048, 3249, and 3400 cm-1 are assigned to the –OH
moieties. The absorption peak at 1130 cm-1
corresponds to a choline C–N bond (Figure 3c). Alkyl
C–H stretches are found at 2860 and 2958 cm-1.
The particle size of MNPs-CCL/TSA was
elucidated by TEM analyses. The crystallinity of
MNPs-CCL/TSA was studied by PXRD in the ranges,
10 to 90° 2θ (Figure 4). The Bragg reflection peaks
are observed at 30°, 35°, 43°, 53°, 57°, 63° 2θ, which
were assigned to the (222), (311), (400), (422), (511)
and (440) planes corresponding to the cubic crystal
structure of Fe3O4. The two broad diffraction peaks at
10° and 23° 2θ suggest the stacking of the linkage
planes.
100
5.06%
95
90
25.8
85
80
75
70
65
Figure 4. Powder X-ray diffraction spectra of MNPs-
CCL/TSA. Peaks from the reference Fe3O4 cubic phase are
denoted as blue bars (International Centre for Diffraction
30
130
230
330
430
530
Temeperature (°C)
3
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10.1002/adsc.201800743
Advanced Synthesis & Catalysis
Figure 7. Magnetization curves of a) nano-Fe3O4, b)
MNPs-VS, and c) MNPs-CCL/TSA.
Figure 5. TGA of MNPs-CCL/TSA.
This reduction in saturation arises due to the surface
coating of the Fe3O4 nanoparticles with the dense
polymer layer during the synthetic pathway of the
CCL/TSA based catalyst. The superparamagnetic
behavior of the synthesized nanoparticles guarantees
facile and efficient separation of catalyst from the
reaction mixture by simply using an external magnet.
The surface area measurements were run. We
observed a surface area of ca. 9 m2 g–1 (as, BET), total
pore volume (p/p0 = 0.980) 3.34 × 10–2, and mean
pore diameter of 15 nm. (see SI for additional info).
Next, the performance and efficacy of the prepared
nanoparticles were tested in the nucleophilic
substitution of aryl C–OH bonds via a variety of O-,
and N-centered nucleophiles. To achieve the optimum
reaction conditions, we chose the reaction between 2-
naphtol (1a) and 1-hexanol (2a) as the model reaction
to optimize the amount of catalyst, temperature, and
solvent (Table 1). The reaction did not proceed in the
absence of the catalyst (Table 1, entry 1) or even with
the loading of 0.45 mol% of TSA (Table 1, entry 2).
For comparison, using only ChCl/TSA (DES-based
choline chloride: TSA) or CCL/TSA as the
homogeneous catalysts gave 10% and 43% yields
respectively (Table 1, entries 3 and 4). Further
investigation showed that nanomaterials such as
ChCl/MNPs, MNPs-VS, and MNPs-GMA are not
efficient for these transformations (Table 1, entries 5–
7). Running the reaction at 120 °C for 12 h without
solvent in the presence of 20 mg of magnetically
separable MNPs-CCL/TSA (containing 0.45 mol%
pTSA) generated the desired product 3a in 90%
isolated yield. (Table 1, entry 8). The conversions
were hindered using solvents such as propylene
carbonate (PC) or toluene and gave yields of less than
35% (Table 1, entries 9 and 10). Decreasing the
amount of the catalyst to 10 mg reduced yields of the
desired product 3a to 40% and increasing the amount
of MNPs-CCL/TSA did not improve the yield (Table
1, entries 14 and 15). This improved catalytic activity
might be due to the higher surface areas of the
heterogeneous nanoparticles.
Figure 6. a) HRTEM image, b) the inset represents the
FFT pattern, and c) particle size distribution histogram of
MNPs-CCL/TSA.
The magnetic properties of the nanoparticle
catalyst were compared with Fe3O4 NPs, VS-MNPs
and MNPs-CCL/TSA using VSM analysis (Figure 7).
The prepared samples MNPs-VS, MNPs-CCL/TSA
are
superparamagnetic,
and
the
saturation
magnetization values are 28.1 emug-1 and 12.2 emug-1
respectively.
80
a)
Table 1. Optimization of the Reaction Conditions.a)
60
b)
40
20
c)
0
-10000
-5000
0
5000
10000
-20
-40
-60
-80
T
Time
(h)
Yield
(%)c)
Entry
catalyst
solventb
(̊
C)
d
1
2
3
4
-
-
-
-
120
120
120
120
12
12
12
12
-
-
TSAe
ChCl/TSAe
CCL/TSAe
4
10
43
H (Oe)
4
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10.1002/adsc.201800743
Advanced Synthesis & Catalysis
ChCl/MNPsf
VS-MNPsf
GMA-MNPsf
5
6
7
8
9
10
11
12
13
14
15
-
120
120
120
120
120
120
110
130
120
120
120
12
12
12
12
12
12
12
12
24
12
12
10
respectively (Table 2, entries 17 and 19–21). The
scale-up potential of this reaction was also
investigated utilizing 2 g of 2-naphthol and 4 g of 2a,
which generated the product 3a in 85% yield.
d
-
-
-
d
-
90
35
20
76
92
93
40
90
MNPs-CCL/TSA
MNPs-CCL/TSA
MNPs-CCL/TSA
MNPs-CCL/TSA
MNPs-CCLTSA
MNPs-CCL/TSA
MNPs-CCL/TSAg
-
PC
toluene
Table 2. Screening of SNAr reaction of alcohols and
amines with naphthols in the presence of MNPs-
CCL/TSA.a)
-
-
-
-
-
MNPs-CCL/TSAh
a)
Reaction conditions: 1a (1.0 mmol), 2a (3.0 mmol) and
catalyst (20 mg, (containing 0.45 mol% pTSA)) were
b)
c)
d)
mixed; 2 mL; Yield of the purified product;
No
e)
f)
conversion;
0.45 mol% of pTSA.
20 mg of the
nanoparticle (containing 0.45 mol% pTSA); g) 10 mg of the
catalyst; h) 30 mg of the catalyst.
Using the optimal conditions established for the
reaction of 2-naphtol (1a) and 1-hexanol (2a) a
variety of alcohols or amines, for the synthesis of the
corresponding products through SNAr reaction of
naphthols were screened (Table 2). Primary alcohols,
including 1-hexanol (2a), 1-heptanol (2b), 1-octanol
(2c) and 2-chloroethanol (2e), were treated with 2-
naphthol (1a) and the substitution products, 3a, 3b, 3c
and 3e respectively gave 90%, 95%, 91% and 82%
yields of analogous ethers (Table 2, entries 1–3 and
5). When hexane-1,6-diol was applied as
a
nucleophile and reacted with 2d and 2k; the
chemoselective mono-etherification reaction was
observed and the corresponding products (3d and 3k)
were obtained in 82% and 78% yields respectively
(Table 2, entries 4 and 11). Chiral alcohols such as
(+)-menthol and (+)-citronellol were also tested as
nucleophiles and generated the products 3f and 3g in
78% and 77% respectively (Table 2, entries 6 and 7).
Furthermore,
the
derivatives
of
2,3-
dihydronaphtho[2,3-b][1,4]dioxine were synthesized
via condensation reaction of naphthalene-2,3-diol
with various 1,2-diols such as ethane-1,2-diol (2h),
butane-2,3-diol (2i) and propane-1,2-diol (2j) and
products 3h, 3i and 3j were produced in 93%, 98%
and 94% yields (Table 2, entries 8–10). Also, 1-
naphthol was found equally viable in this
transformation. 1-Naphthol reacted with different
primary alcohols 2l, 2m, 2n, and 2o as well as
hindered secondary alcohol 2p and generated the
corresponding products 3l, 3m, 3n and 3o with 86%,
79%, 75% and 78% yields (Table 2, entries 12–16).
Next, we decided to extend the scope of this protocol
by using amines as nucleophiles with the previously
reported reaction conditions and catalyst loading. As
shown in Table 2, aniline employed as a nucleophile
and successfully gave 3r in 81% yield. (Table 2, entry
18). 4-methoxyaniline, p-anisidine, 2-nitroaniline, and
3-nitroaniline were reacted with 2-naphthol to furnish
3q, 3s, 3t and 3u in 80%, 79%, 74% and 70% yields,
5
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10.1002/adsc.201800743
Advanced Synthesis & Catalysis
phenol and phenol derivates with hexanol were
attempted. We also ran a reaction between ortho-
aminoaniline and naphthalene-2,3-diol, however,
none of the reactions were successful or efficient,
except for p-nitrophenol which gave 25% yield of the
product (3v). (Table S1, Scheme S1)
The extraordinary catalytic performance could be
attributed to dispersion of the nanoparticles, stronger
PDES-support interactions and interaction of
hydrogen
donor
species
with
naphthols.
Mechanistically, we belive that the mechanism of the
reaction is similar to the previous report, which is
catalyzed via the keto tautomer intermediate
formation of the naphthol skeleton. It is proposed
that, the addition−elimination mechanism is prefered
over the traditional SNAr.[4i]
Finally, the reusability of MNPs-CCL/TSA was
also evaluated in the synthesis of 3b as a model. After
completion of the reaction, the catalyst was separated
from the reaction mixture by an external magnet,
washed with EtOH, air-dried and reused directly in a
template for the next run without further purification.
After six cycles of reasoning the catalyst for 3b as a
relatively challenging system, the reaction bears a
95
94
90
84
100
50
0
75
1
2
3
Runs
4
5
TON = 8.4, and TOF = 0.12 h-1.
Figure 8. Reusability of MNPs-CCL/TSA.
As illustrated in Figure 8, the catalyst displayed
high but slowly decreasing activity in continuous
cycles, which might be attributed to the leaching of
pTSA during the reaction and recovery process. The
elemental analysis illustrated 17% leaching for pTSA
after five runs for the catalyst. This protocol could be
considered as a robust way to a chemoselective direct
etherification and amination of naphthols. Easy
purification of the products and high recyclability of
the catalyst are other main advantages of the
presented process.
Conclusions
a)
Reaction conditions: 1 (1.0 mmol), 2 (3.0 mmol) and
In conclusion, we have revealed here a reusable
magnetic nanoparticle catalyst based on the covalent
bonding of ChCl /pTSA on the MNPs, for
nucleophilic substitution of hydroxyl groups of aryl
alcohols by O- and N-centered nucleophiles. The
present methodology provides prominent advantages
MNPs-CCL/TSA (20 mg, (containing 0.45 mol% pTSA)).
Yield of the purified product.
(naphthalene-2,3-diol).
b)
c)
1 (6 mmol). d1
The catalytic reaction of quinolin-8-ol, 1-
nitrosonaphthalen-2-ol, 2-nitrosonaphthalen-1-ol,
6
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10.1002/adsc.201800743
Advanced Synthesis & Catalysis
polymer microspheres and choline chloride. The magnetic
nanoparticles were isolated with external magnet during
each washing step and were kept for further application.
to previously reported catalysts for aryl ether bond
formation including economic viability, easy
preparation, and separation, high catalytic activity,
stability, and reusability.
Synthesis of MNPs-CCL/TSA: ChCl-MNPs (0.24 g) and
0.2 g of PA were added to round bottom flask and stirred
for 2 hours at 80 ⁰ C. Then 100 ml de-ionized (DI) water
was added to the above mixture and shaken at 80 ⁰ C for
16 hours. The brownish product was rinsed several times
with ethanol and water and collected magnetically from
solution mixture. The desired MNPs-CCL/TSA dried at
50–60 ⁰ C and used for nucleophiles substitution of
naphthyl C–OH bonds. The contents of choline chloride
and p-toluene sulfonic acid on MNPs were determined by
the elemental analysis as follows: choline chloride: 1.9%
and p-Toluene sulfonic acid: 3.88%.
Experimental Section
General remarks. All starting materials such as
various alcohols, substituted anilines, glycidyl methacrylate
(GMA), choline chloride (ChCl), trimethoxy vinyl silane
(VS), p-toluene sulfonic acid (PA), iron (II) chloride
tetrahydrate (FeCl2.4H2O), iron (III) chloride hexahydrate
(FeCl3.6H2O), and ammonium hydroxide were purchased
from Merck and Sigma-Aldrich companies. All solvents
were obtained from commercial sources and used without
further purifications. XRD diffraction patterns of PA-ChCl-
MNPs were matched to JCPDS Card No. 76-1849 to
elucidate miller indices and confirm the crystal structure of Synthesis of 2-hexyloxynaphthalene (3a). 2-Naphthol 1a
1
to Fe3O4. All of the products characterized by H and 13C
(144 mg, 1.0 mmol), 1-hexanol 2a (306 mg, 3.0 mmol),
and catalyst PA-ChCl-MNPs (20 mg, (containing 0.45
NMR spectra, and FT-IR spectrophotometric. The novel
magnetically nanoparticles (PA-ChCl-MNPs) were mol% pTSA)) were taken into round bottom flask. The
determined by FT-IR, VSM, HRTEM, PXRD, TGA and reaction mixture was stirred at 120 ⁰ C for 12 hours. The
EDX techniques. The magnetic properties of novel progress of the reaction was monitored by TLC (eluent: n-
nanoparticles were determined in a vibrating sample hexane/ethyl acetate, 2:1). After completion of the reaction,
1
the crude was directly purified by silica-gel column
magnetometer (VSM, RDK-415E, Japan). H NMR and
13C NMR spectra were recorded on a 400MHz NMR and chromatography using 2% (v/v) ethyl acetate/ n-hexane
100 MHz NMR spectrometer respectively at room solution to obtain the corresponding product 3a as a
temperature in CDCl3 solution.
colorless liquid in 90% yield (205 mg).
Synthesis of vinyl silane coated iron oxide magnetic
nanoparticles (VS-MNPs). 0.415 g iron oxide magnetic
nanoparticles were added in 100 ml of de-ionized (DI)
water in 3- neck round bottom flask and stirred vigorously
under the protection of N2, and the pH value was adjusted
to 8-9 by adding certain amount of 1 M ammonium
hydroxide solution. Then 4 ml of trimethoxy vinyl silane
was added slowly into the above solution. The dispersion
was ultrasonicated for 120 min at 80 ⁰ C to ensure
homogeneity. The obtained light brownish product was
separated magnetically from solution and washed
repeatedly with ethanol and water to remove the excess
NH3•H2O and TMOVS. The purified product was dried
under vacuum for further application.
ACKNOWLEDGMENT
M. H. B. gratefully acknowledges the financial support through
the startup funds from the University of Arkansas. A. R. K.
gratefully thanks the Center of Excellence of Chemistry and the
Research Council of the University of Isfahan (CECUI) for
financial support of this work. We thank L. Whisenhunt for the
help with the measurement of optical rotations of the chiral
compounds.
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Synthesis of core-shell magnetic nanoparticles (GMA-
MNPs). To the water solution including 0.415 g VS-
MNPs, 0.025 g ammonium persulfate and 0.316 ml
glycidyl methacrylate (GMA) monomer were added and
the mixture was stirred for 24 hours at 80 ⁰ C. Then the
brownish black polymeric microspheres collected by
external magnet and washed with ethanol and water for
several times. The obtained solid sample was dried under
vacuum for further use.
Synthesis of amino-functionalized core-shell magnetic
nanoparticles (ChCl-MNPs). Choline chloride (ChCl) (2
g) was added into 100 ml of aqueous solution containing
0.483 g of the polymeric microspheres coated iron oxide
magnetic nanoparticles (GMA-MNPs) and stirred
vigorously. Next, 4 ml of 1 M DBU solution was added to
the dispersion and continued for 6 hours at room
temperature. The corresponding ChCl-MNPs were washed
3 times with ethanol and water to remove the excess
7
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10.1002/adsc.201800743
Advanced Synthesis & Catalysis
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Advanced Synthesis & Catalysis
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9
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