Synthesis, characterization and catalytic application of Bi2S3 microspheres for Suzuki-Miyaura cross-coupling reaction and chemoselective ring opening of epoxides

Article abstract of DOI:10.1016/j.mcat.2020.111283

Bismuth sulfide (Bi₂S₃) prepared using L-cysteine, which served as both the sulfur source and the directing molecule for the formation of Bi₂S₃ as heterogeneous catalyst through solvothermal method. The prepared catalyst was examined by various techniques such as XRD, BET, FE-SEM, TEM, and TGA analysis. The results and analysis revealed that bismuth microspheres have better catalytic behavior for the preparation of biphenyl in water as a greenest solvent and for the ring opening of epoxides by nucleophiles including amines, alcohol, and thiol compared to pure Bi(NO₃)₃. 3H₂O under solvent-free condition. Moreover, the novel catalyst could be recovered and reusedat least four times without loss of its catalytic activity.

Full text of DOI:10.1016/j.mcat.2020.111283

Molecular Catalysis xxx (xxxx) xxx
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis
Synthesis, characterization and catalytic application of Bi2S3 microspheres
for Suzuki-Miyaura cross-coupling reaction and chemoselective ring
opening of epoxides
,
,
Arash Ghorbani-Choghamarania *, Zahra Taheriniab *
a Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683, Iran
b Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran
A R T I C L E I N F O
A B S T R A C T
Keywords:
Bismuth sulfide (Bi2S3) prepared using L-cysteine, which served as both the sulfur source and the directing
molecule for the formation of Bi2S3 as heterogeneous catalyst through solvothermal method. The prepared
catalyst was examined by various techniques such as XRD, BET, FE-SEM, TEM, and TGA analysis. The results and
analysis revealed that bismuth microspheres have better catalytic behavior for the preparation of biphenyl in
water as a greenest solvent and for the ring opening of epoxides by nucleophiles including amines, alcohol, and
thiol compared to pure Bi(NO3)3. 3H2O under solvent-free condition. Moreover, the novel catalyst could be
recovered and reusedat least four times without loss of its catalytic activity.
Bi2S3 microspheres
Suzuki-Miyaura cross coupling
Chemoselectivity
Ring opening of epoxides
Thermal stability
Introduction
challenging. In this sense, it is necessary to find a new approach to
conquer the difficulties. Nanoparticles (NPs) are strongly investigated
Suzuki-Miyaura cross coupling of aryl halides with phenyl boronic
because they offer an advantages of both heterogeneous and homoge-
neous catalysts, because they are sometimes called “semi--
heterogeneous” catalysts [15]. Nanoparticles easily agglomerate and
oxidize due to high surface energy in aqueous solutions; hence, it is
crucial to find a method to solve the problem [16]. In many cases, metal
nanoparticles are immobilized various solid supports. A Series of
different classes of porous organic polymer frameworks, including
conjugated microporous polymers (CMPs) [17], covalent organic
frameworks (COFs) [18], polymers of intrinsic microporosity (PIMs)
[19], and hypercrosslinked polymers (HCPs) [20], have been prepared.
Among these microparticles or microspheres have intrinsic properties
including large specific surface area [21], narrow pore size distribution
[22], high chemical stabilities [23], and low skeleton density [24]
exhibition of potential applications in coatings [25], adhesives [26],
leather finishing [27], constructions [28], biomedicines [29], catalysis
[30], paints [31], effective strategies to improve the hydrogen storage
and CO2 adsorption capacity [32], and in electronics [33]. Microspheres
–
C
acids is one of the most powerful approaches for the formation of C
bonds. In particular, for the synthesis of bi-aryl compounds, the resulting
products are widely used [1–6]. Suzuki-Miyaura coupling reaction
promoted by different palladium based catalysts [7]. Much recent at-
tentions in Suzuki-Miyaura cross- coupling has been focused on
palladium-free conditions and catalyst system including nickel [8],
copper [9], iron [10], and cobalt [11] because it is much cheaper and
more earth-abundant than the palladium containing compounds. In
order to accomplish these valuable reactions under environmentally
benign conditions, many studies focused on designing of new catalytic
systems and methodologies to cover the twelve green chemistry
principles.
Optically pure epoxides are key synthons for the generation of chiral
compounds and enantio specific ring opening of readily available
enantio enriched epoxides provides an efficient and straightforward
protocol for the wide range of highly functionalized [12,13]. Many
research have been reported for the asymmetric ring opening of epox-
ides using stoichiometric or catalytic amounts of chiral, nonracemic
reagents or catalysts under homogeneous conditions [14]. The reported
metal complex catalysts for epoxide ring opening reactions is of great
are small spherical particles, with diameters of 1 μm–1000 μm, and
depending upon the encapsulation of active drug moieties there are two
types of microspheres: microcapsules (are loosely defined as (spherical)
particles in the size range between 50 nm to 2 mm) and micro matrices
* Corresponding authors.
E-mail addresses: a.ghorbani@basu.ac.ir (A. Ghorbani-Choghamarani), z.taherinia@ilam.ac.ir (Z. Taherinia).
https://doi.org/10.1016/j.mcat.2020.111283
Received 5 September 2020; Received in revised form 17 October 2020; Accepted 20 October 2020
2468-8231/© 2020 Elsevier B.V. All rights reserved.
Please cite this article as: Arash Ghorbani-Choghamarani, Zahra Taherinia, Molecular Catalysis, https://doi.org/10.1016/j.mcat.2020.111283

A. Ghorbani-Choghamarani and Z. Taherinia
Molecular Catalysis xxx (xxxx) xxx
Scheme 1. Schematic synthesis of Bi2S3 microspheres.
[34].
Techniques such as dispersion polymerization [35], emulsion poly-
merization [36], and precipitation polymerization [37] have been used
to prepare polymer microspheres. Polymer-based chiral microspheres
[38,39] have aroused much attention recently due to their significant
application in asymmetric catalysis [40], chemoselective crystalliza-
tions [41], chiral recognitions/resolution [42] as media for high- per-
formance liquid chromatography (HPLC) and carriers for catalysis [43].
Bismuth is known as an environmentally benign element due to low
toxicity, low cost, and good stability. In the past decades, considerable
efforts have been made on the designing of effective methods to syn-
thesis various morphologies of Bi2S3 nanomaterials by using different
sulfur sources [44–48]. The different nanostructured materials of Bi2S3
such as nanorods [44,45], nanowires [46] nanotubes [48,49] and
nanobelts, [50] have been prepared. The biomolecule-assisted synthesis
method has been proven to be a novel, environmentally friendly, and
promising approach in the preparation for various nanomaterials due to
the convenient control of the morphology [51].
Fig. 1. XRD pattern of Bi2S3 microsphere.
spectroscopy), elemental mapping and nitrogen adsorption-desorption
isotherm.
As part of our ongoing research program [52] to design a green-
catalysts using (L-cysteine as an inexpensive, simple, and
environment-friendly, thiol-containing amino acid) and Bi(NO3)3. 3H2O
for formation of Bi2S3 through solvothermal method (Scheme 1).
Fig. 1 shows the XRD pattern of Bi2S3 microsphere, which major
reflections located at 27.82◦, 32.31◦, 33◦, 38◦, 39◦, 42◦, and 47◦ that
correspond to Bi2S3 crystal with a cubic phase. These results are in
agreement with the standard XRD pattern of Bi2S3 [53].
Results and discussion
In order to study the thermal stability of prepared bismuth con-
taining material, a thermogravimetric analysis performed on Bi2S3 mi-
crospheres that heated from 25 to 800 ◦C in air at a heating rate of 10 ◦C/
min (Fig. 2). Mass loss (7%) occurs at a temperature from 480ꢀ 800 ◦C, it
is attributed to decomposition of Bi2S3 microspheres.
The structure properties of the as-obtained bismuth microspheres
characterized by using a field emission scanning electron microscopy
(FESEM), Transmission Electron Microscopes (TEM), the powder X-ray
diffraction patterns (PXRD), thermogravimetric analysis (TGA), differ-
ential scanning calorimetry (DSC), EDS (Energy-dispersive X-ray
To determine the spatial distribution of elements in the Bi2S3
2

A. Ghorbani-Choghamarani and Z. Taherinia
Molecular Catalysis xxx (xxxx) xxx
microspheres, elemental mapping performed. The EDS mapping of the
Bi2S3 material is presented in Fig. 3. The EDS mapping revealedthe
presence of the Bi and S, in the powder.
The morphology and size of the products were observed by SEM and
TEM; the results were shown in Figs. 4 and 5. As shown in SEM and TEM
images in Figs. 4 and 5 the morphology of the as-obtained Bi2S3 mi-
crospheres are spherical with average diameter of around 200 nm-
0.0795
μm. It should be noted that microspheres/microcapsules in
nanometer size are usually called as nanospheres/nanocapsules to
emphasize their small size. [34]
The porous properties of the sample were investigated by measuring
the nitrogen adsorption isotherm, as shown in Fig. 6. The BET surface
area and pore volume were estimated to be 28.9 m2/g and 6.6 cm3/g
respectively, based on the N2 adsorption-desorption measurement. The
BJH pore size calculations using the adsorption branch of the nitrogen
isotherm indicate the diameter of pores are about 1.6 nm (Fig. 6).
Fig. 2. TGA thermograms of Bi2S3 microsphere.
–
Catalytic performance of the bismuth microspheres for C C cross
coupling reaction and chemoselective ring opening of epoxides.
Fig. 3. EDS mapping images of Bi2S3 microsphere.
Fig. 4. SEM images of Bi2S3 microspheres.
3

A. Ghorbani-Choghamarani and Z. Taherinia
Molecular Catalysis xxx (xxxx) xxx
Fig. 5. TEM images of Bi2S3 microspheres.
–
It must be noted we have reported homocoupling of aryl halides in
the presence of L-cysteine, recently. [54] In this research project, any
be found in Table 1, the optimum temperature for C C cross-coupling
reaction was 100 ◦C (Table 1, entry 1). To obtain the best optimal re-
action conditions, the effect of different solvents were investigated
(Table 1). The results obtained for all tested solvent (H2O, DMSO: H2O,
PEG) are shown in Table 1; it can be seen clearly that H2O is the most
effective solvent for this reaction.
–
effort to perform C C cross coupling of aryl halides with phenyl bronic
acid in the presence of L-cysteine was failed (Table 1, entry 19).
After synthesis and characterization of the Bi2S3 microsphere as
catalyst, we tested the catalytic treatment of bismuth microspheres for
the cross-coupling reaction between iodobenzene and phenylboronic
acid as model reaction to screen the solvent, bases, temperature, and
catalyst amount and the results are outlined in Table 1. In our first set of
experiments, we evaluate the performance of bismuth microspheres (65
mg) via reaction iodobenzene (1 mmol) with phenylboronic acid (1.2
mmol) and 3 equivalents of potassium tert-butoxide in DMSO as solvent.
Increasing the temperature reaction to higher temperature, afforded
the cross-coupling product with higher yield after 3 h (Table 1). As can
–
After, the different bases were evaluated for the C C cross-coupling
reaction potassium tert-butoxide gave the best yield. It was found that
the use of 65 mg of catalyst leads to 90 % of isolate yield.
With optimal condition in hand, activity of bismuth microspheres
was investigated on a series of aryl halides with different functional
–
groups for C C cross coupling reaction. Under the optimal reaction
conditions (Table 1), a variety of aryl halides reacted with phenyl-
boronic acid to achieve a variety of biphenyls (Table 2, Scheme 2). The
4

A. Ghorbani-Choghamarani and Z. Taherinia
Molecular Catalysis xxx (xxxx) xxx
Table 1
Optimization of reaction conditions for the synthesis of biphenyl.a.
Entry
Solvent
Temp.
Cat(mg)
Base
Base
Yield
(b)
(ºC)
(mmol)
(%)b
1
2
3
4
5
6
7
H2O
100
100
100
100
80
65
65
50
30
65
65
65
3
3
3
3
3
3
–
Potassium t-
butoxide
90
65
75
55
53
20
N.R
DMSO:
H2O
Potassium t-
butoxide
H2O
Potassium t-
butoxide
H2O
H2O
Potassium t-
butoxide
Potassium t-
butoxide
tert-
80
Potassium t-
butoxide
Butanol
tert-
100
–
Butanol:
H2O
8
9
DMSO
100
100
65
65
3
3
Potassium t-
butoxide
Potassium t-
butoxide
KOH
45
21
PEG
10
11
12
13
14
15
16
17
H2O
100
100
100
100
100
100
100
100
65
65
65
65
65
65
65
–
3
3
3
3
3
3
3
3
35
H2O
KF
15
H2O
Imidazole
K2CO3
25
DMSO
DMSO
DMSO
DMSO
H2O
trace
trace
N.R
N.R
N.R
Na2CO3
Na2CO3
Et3N
Potassium t-
butoxide
KOH
18
19
DMSO
100
80
L-
0.4g
3
N.R
N.R
Cysteine
L-
tert-
Potassium t-
Butanol:
H2O
Cysteine
butoxide
a
Reaction conditions:benzene iodide (1 mmol), phenylboronic acid (1.2
mmol), Base (mmol), Time (3 h), and solvent (2 mL).
b
Isolated yield.
Table 2
a
–
C
C cross coupling reaction of aryl halides and phenylboronic acid.
Entry
Ar-X
Phenylating reagent
Product
Time(h)
Yield b (%)
1
2
3
3
90
80
3
2
88
4
5
6
7
2
92
87
97
85
2.5
1.5
5
Fig. 6. The N2 gas adsorption isotherms and BJH pore size distribution of Bi2S3
microsphere.
8
4
81
coupling reactions of aryl iodides and aryl bromides provides the biaryl
compounds with good to high yields. In this study, the electronic and
steric effects on the yields and reaction rates was also evaluated. This
catalytic system showed a high activity for electron deficient and elec-
tron rich aryl halides (including 4-NO2C6H4, 4-OMeC6H4, 2-OMeC6H4,
3-OMeC6H4, 4-MeC6H4, 2-MeC6H4, 3-CF3C6H4). Electron-donating
9
10
2.5
6
79
85
11
12
13
8
71
85
80
7
8.5
–
groups show excellent catalytic activity in C C coupling reaction,
14
15
10
12
78
70
when compared toelectron-withdrawing substituents. The ortho
substituted aryl halides generated the corresponding product with
acceptable yield in longer reaction time (Table 2, compare entries 2 and
3).
aReaction conditions:benzene iodide (1 mmol), phenylboronic acid(1.2 mmol),
In the second part of this research project, another aspect of catalytic
properties of Bi2S3 microspheres was investigated in epoxide ring-
opening reaction. Initially, reaction of 2-phenyloxirane and aniline
(Scheme 3) was selected as a model reaction to obtain the best reaction
Potassium t-butoxide (3 mmol), and H2O (2 mL).
b
Isolated yield.
5

A. Ghorbani-Choghamarani and Z. Taherinia
Molecular Catalysis xxx (xxxx) xxx
Scheme 2. Bi2S3 microspheres catalyzed synthesis of biaryl.
Scheme 3. Model substrates for the ring opening reaction.
Table 3
Table 4
Optimization of the reaction conditions for the ring opening of 2-phenyloxirane
Chemoselective ring opening reaction of epoxides with various nucleophiles.
with aniline in the presence of catalytic amounts of Bi2S3 microspheres.a.
Entry
Entry
Ar-X
product
Time (h)
Yieldb (%)
Solvent
Temp. (ºC)
Cat(mg)
Time (h)
Yield(A) (%)b
1
2
95
1
2
3
4
5
6
None
None
None
None
None
None
60
60
60
60
40
25
–
24
13
95
75
55
63
48
2
3
2.5
3
92
90
30
20
10
30
30
1.5
1.5
1.5
1.5
1.5
a
Reaction conditions: 2-phenyloxirane(1 mmol), aniline(1 mmol), and Cata-
4
5
6
60min
50min
4.5
92
95
78
lyst(mg).
b
Isolated yield.
conditions the resulting data summarized in Table 3. In the absence of
the catalyst, only trace amount of amino alcohol product obtained in 24
h under solvent-free conditions at 60 ◦C (Table 3, entry 1). Then we have
tested the quantity of catalyst at 60 ◦C under solvent-free conditions for
this reaction (Table 3, entries 3–4). It was observed that the use of 30 mg
of catalyst is enough for the completion of the reaction in 2 h with 95 %
yield of amino alcohol product (Table 3, entry 1).
7
8
4.5
3.5
82
81
With optimal results in hand, the scope of the reaction has been
extended further for chemoselective ring-opening reaction of 2-phenyl-
oxirane with different alcohols (including primary and secondary ones),
thiol, and aromatic/aliphatic amine (Table 4, Scheme 4). In each case,
the catalyst showed reasonable results in term of yield (30–95 %). The
product selectivity of the isolated pure product verified by 1H-NMR
spectroscopy.
9
10min
10min
60:30
50:50
10
The possibility of catalyst recovery and recyclability is an important
object from different aspects such as environmental concerns and
commercial applicablity. In this aim, the reusability of the Bi2S3
microsphere catalyst has been investigated for the ring opening reaction
of 2-phenyloxirane by aniline. As seen from Fig. 7, the catalyst can be
efficiently recycled and reused for four consecutive cycles with negli-
gible loss of product yield.
aReaction conditions: 2-phenyloxirane (1 mmol), nucleophile (1 mmol), and
catalyst (30 mg), solvent free.
b
Isolated yield.
In order to evaluate the efficiency of Bi2S3 microsphere, we
compared the catalytic performance of our catalyst for the synthesis of
biphenyl with some of the previously reported study (Table 5).
The metal leaching of catalyst was studied using a hot filtration test.
Hot filtration technique was done for Suzuki-Miyaura cross coupling
reactions. When the reaction preceded to nearly 50 % completion, the
catalyst was separated from the reaction mixture and allowed the filtrate
to react further in exact conditions. We found that no further reaction
occurred after the separation of the catalyst after 3 h; this means that the
Bi2S3 microspheres catalyst is a heterogeneous catalyst with stable
structure.
Conclusions
In this research project, we have reported the synthesis of Bi2S3
microspheres and its catalytic application in Suzuki-Miyaura cross-
coupling reaction for the first time and chemoselective ring opening of
epoxides. The notable features of this protocol are the doing reaction
under solvent-free conditions, using H2O as a green solvent, short
6

A. Ghorbani-Choghamarani and Z. Taherinia
Molecular Catalysis xxx (xxxx) xxx
Scheme 4. Bi2S3 microspheres catalyzed ring opening of epoxides with various nucleophiles.
Ring opening of epoxides
In a typical epoxide ring-opening reaction, the catalyst, Bi2S3 mi-
crospheres (30 mg), was added into a solution of 2-phenyloxirane (1
mmol) and corresponding nucleophie. The solution was stirred at 60 ◦C
under solvent-free conditions and the progress of the reaction was
monitored using TLC. After completion of reaction, ethyl acetate (20
mL) was added and filtrated. Finally, the crude product was subjected to
column chromatography on silica gel to obtain the pure product.
Selected spectral data
Fig. 7. Catalyst recycling study for the ring opening reaction.
(R)-2-Phenyl-2-(phenylamino)ethan-1-ol 1HNMR (400 MHz, CDCl3)
(δ, ppm): 3.77 (dd, J = 4 Hz, J = 4 Hz, 1 H), 3.96 (dd, J = 4 Hz, J = 4 Hz,
1 H), 4.52 (dd, J = 4 Hz, J = 4 Hz, 1 H), 6.62 (d, J = 8 Hz, 2 H), 6.73(t, J
= 8 Hz, 1 H), 7.15 (t, J = 8 Hz, 2 H) 7.32ꢀ 7.29 (m, 2 H), 7.41ꢀ 7.39 (m, 5
H).
Table 5
–
Comparison of Bi2S3 microspheres for C C cross-coupling reaction via reaction
(1S,1′S)-2,2′-(Propane-2,2-diylbis(oxy))bis(1-phenylethan-1-ol):
1HNMR (400 MHz, CDCl3) (δ, ppm): 0.95 (s, 6 H), 3.98 (dd, J = 4 Hz, J =
4 Hz, 2 H), 4.18 (dd, J = 7.2 Hz, J = 7.2 Hz, 2 H), 4.7(s, 2 H), 5.04 (m, 2
H), 7.36ꢀ 7.32 (m, 5 H), 7.45ꢀ 7.40(m, 5 H), 13CNMR (100 MHz, CDCl3)
(δ, ppm): 21.0, 63.3, 67.9, 77.3, 127.4, 127.7, 128.0, 128.1, 128.4,
128.6, 128.8, 128.9, 129.2, 129.3.
of phenyl boronic acid and iodobenzene with previously reported procedures.
Entry
Catalyst
Yield
(%)a
Time
(h)
Ref.
1
2
Pd(II)–NHC complex
Polymer anchored Pd(II) Schiff ;
base
99
90
24
5
[55]
[56]
(R)-2-(Cinnamyloxy)-2-phenylethan-1-ol:1H NMR (400 MHz, CDCl3)
(δ, ppm): 3.78ꢀ 3.76 (m, 1 H), 4.13–4.15 (m, 3 H), 4.34ꢀ 4.18(m, 1 H),
6.37–6.39 (m, 1 H), 6.58 (s, 1 H), 6.63ꢀ 6.43 (m, 1 H), 7.29(d, J = 6.8
Hz, 2 H), 7.37(t, J = 7.4 Hz, 4 H), 7.43(d, J = 7.2 Hz, 4 H), 13CNMR (100
MHz, CDCl3) (δ, ppm): 60.4, 63.7, 82.2, 125.7, 126.1, 126.4, 127.0,
127.7, 128.2, 128.5, 128.6, 129.0, 129.7, 131.1, 132.7, 136.7, 138.5.
(R)-2-((4-Bromophenyl)thio)-1-phenylethan-1-ol: 1HNMR (400
MHz, CDCl3) (δ, ppm): 3.17 (dd, J = 8 Hz, J = 9.2 Hz, 1 H), 3.33(dd, J =
4 Hz, J = 4 Hz, 1 H), 4.21(s, 1 H), 4.78(dd, J = 3.6 Hz, J = 3.6 Hz, 1 H),
7.30ꢀ 7.29 (m, 2 H), 7.38ꢀ 7.35 (m, 5 H), 7.46(d, J = 8 Hz, 2 H),
13CNMR (100 MHz, CDCl3) (δ, ppm): 43.8, 71.8, 120.6, 125.8, 128.0,
128.1, 128.6, 131.6, 132.1, 134.4, 142.0.
3
4
Pd-MPTAT-1
95
90
85
3
[57]
This
work
Bi2S3 microspheres
aIsolated yield.
reaction time, and the high turnover frequency at room temperature,
high regio- and chemoselectivity. In addition, catalyst can be easily
recovered and reused for the subsequent run for at least 4 times with less
deterioration in its catalytic activity.
Experimental
(R)-1-Phenyl-2-(p-tolylthio)ethan-1-ol: 1HNMR (400 MHz, CDCl3)
(δ, ppm): 2.08 (s, 3 H), 2.95(s, 1 H), 3.06 (dd, J = 9.6 Hz, J = 9.6 Hz, 1
H), 3.33 (dd, J = 3.2 Hz, J = 3.2 Hz, 1 H), 4.72(m, 1 H), 7.18 (d, J = 4.4
Hz, 3 H), 7.35ꢀ 7.32 (m, 4 H), 7.38(d, J = 4.4 Hz, 2 H), 13CNMR (100
MHz, CDCl3) (δ, ppm): 21.0, 44.9, 60.4, 125.9, 127.9, 128.5, 129.9,
130.9, 131.1, 137.1, 142.2.
Synthesis of Bi2S3 microspheres
In a typical procedure, L-cysteine (1 mmol) was dissolved in 5 mL
doubly distilled water, followed by mixing 2 mmol of Bi(NO3)3⋅3H2O in
dimethylformamide (20 mL). The mixture of metal and ligand is stirred
for 10 min, then transferred into the autoclave at 160 ◦C for 15 h. The
black precipitate was formed. The solid filtrate was washed with ethyl
acetate. Finally, the precipitate was dried at 60 ◦C in the vacuum.
(R)-2-Phenyl-2-(p-tolylthio)ethan-1-ol: 1HNMR (400 MHz, CDCl3)
(δ, ppm): 2.08 (s, 3 H), 3.34(s, 1 H), 3.88 (dd, J = 6.4 Hz, J = 6.4 Hz, 1
H), 3.97(dd, J = 6.4 Hz, J = 6.4 Hz, 1 H), 4.29 (dd, J = 6.8 Hz, J = 6.8
Hz, 1 H), 7.10 (d, J = 8.4 Hz, 2 H), 7.39ꢀ 7.27 (m, 5 H), 7.38(d, J = 4.4
Hz, 2 H), 13CNMR (100 MHz, CDCl3) (δ, ppm): 21.2, 54.5, 65.0, 127.7,
128.1, 128.7, 129.7, 133.3,137.9, 139.1.
General procedure for the Suzuki reaction
A round-bottom flask was charged with an aryl halide (1 mmol),
phenylboronic acid (1.2 mmol), Bi2S3 microspheres (60 mg), and po-
tassium t-butoxide (3 mmol). The resulting mixture was stirred in H2O at
100 ◦C. The reaction was monitored by TLC. At the end of reaction, ethyl
acetate (20 mL) was added and filtrated. After concentration, the residue
was subjected to column chromatography on silica gel to yield the
desired product.
4-Methoxy-1,1′-biphenyl: 1H NMR (400 MHz, CDCl3): (δ, ppm): 3.89
(s, 3 H), 7.04 (d, J = 8 Hz, 2 H), 7.36 (t, J = 8 Hz, 1 H), 7.47 (t, J = 8 Hz, 2
H), 7.60ꢀ 7.56 (t, J = 8 Hz, 4 H).
4-Chloro-1,1’-biphenyl:1HNMR (400 MHz, CDCl3): (δ, ppm):
7.48ꢀ 7.46(m, 1 H), 7.52ꢀ 7.50 (m, 2 H), 7.64ꢀ 7.62 (t, J=4.2 Hz, 2 H),
7.76ꢀ 7.73(m, 4 H).
3′,4′-Difluoro-[1,1′-biphenyl]-4-amine: 1HNMR (400 MHz, CDCl3):
7

A. Ghorbani-Choghamarani and Z. Taherinia
Molecular Catalysis xxx (xxxx) xxx
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CRediT authorship contribution statement
[24] O. Sandin, J. Nordin, M. Jonsson, Reflective properties of hollow microspheres in
cool roof coatings, J Coat.Technol RES. 14 (2017) 817.
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microenvironmental conditions modulate adhesive material performance,
Langmuir 28 (2012), 15402.
Arash Ghorbani-Choghamarani: Supervision, Writing - original
draft. Zahra Taherinia: Data curation, Methodology.
[26] N. Haraguchi, A. Nishiyama, S.J. Itsuno, Synthesis of polymer microspheres
functionalized with chiral ligand by precipitation polymerization and their
application to asymmetric transfer hydrogenation, Polym. Sci. A. 48 (2010) 3340.
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microspheres for winter conditions, Procedia Eng. 153 (2016) 623.
Declaration of Competing Interest
¨
[28] M. Wiklund, J. Toivonen, M. Tirri, P. Hanninen, H.M. Hertz, Ultrasonic enrichment
The authors reported no declarations of interest.
of microspheres for ultrasensitive biomedical analysis in confocal laser-scanning
fluorescence detection, J. Appl. Phys. 96 (2004) 1242.
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Acknowledgment
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The authors would like to thank the research facilities of Ilam Uni-
versity, Ilam, Iran and Bu-Ali Sina University, Hamedan, Iran for the
financial support of this research project.
´
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