The effect of the reaction temperature was
then investigated varying from 80oC to 120oC,
using 0.2 mol% catalyst in DMF, and in the
presence of K3PO4 as the base. It was decided to
use 0.2 mol% instead of 0.5 mol% of the
bentonite-Pd2+ catalyst for the reaction as the
difference in reaction rates was not
considerable. Experimental results showed that,
within experimental errors, the reaction rate
remained almost indentical when increasing
reaction temperature from 100oC to 120oC.
Increasing reaction temperature to above 100oC
was therefore unnecessary. As expected,
decreasing the reaction temperature from 100oC
to 80oC resulted in a significant drop in the
conversion of iodobenzene, from 96% to only
66% after 7 h (Figure 4). Indeed, the
temperature range of 90oC to 120oC has been the
most commonly used for Suzuki transformation
using different types of palladium catalysts [5].
The most effective reaction temperature for the
Suzuki reaction using the bentonite-Pd2+
catalyst in this research was therefore in good
agreement with the literature.
An important point concerning the use of a
heterogeneous catalyst is its lifetime,
particularly for industrial and pharmaceutical
applications of the palladium-catalyzed Suzuki
reaction. In the best case the catalyst can be
recovered and reused before it eventually
deactivates completely. At the same time, the
512catalyst recovery can also reduce the
environmental pollution caused by heavy metals
used in the catalyst system [16, 17]. The
bentonite-Pd2+ catalyst was therefore
investigated for recoverability and reusability.
After the reaction, the catalyst was separated
from the reaction mixture by centrifugation,
washed several times with toluene, DMF, water
and ethanol to remove any physisorbed
reagents. The recovered catalyst was then dried
and reused in further reaction under identical
condition to the first run. Experimental results
showed that the bentonite-Pd2+ catalyst could be
reused in further reaction without significant
degradation in activity (Figure 5). A conversion
of approximately 90% was still achieved after 7
h for the second run. Although it was previously
reported that almost no loss of activity was
observed for reused palladium catalysts for the
Suzuki reaction in some cases, no kinetic data
was provided, and only conversions at the end of
the experiment were mentioned [18].
Unfortunately, stable activity can not be proven
by reporting only similar reaction conversions at
long times. Kinetic studies are the true test of
catalyst deactivation
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Journal of Chemistry, Vol. 46 (4), P. 509 - 514, 2008
MODIFIED BINH THUAN BENTONITE AS AN EFFICIENT AND
RECYCLABLE CATALYST FOR THE SUZUKI REACTION
BETWEEN IODOBENZENE AND PHENYLBORONIC ACID
Received 7 December 2007
PHAN THANH SoN NAM, TRuoNG NGUYeN THuY Vu, TRuoNG Vu THANH
Hochiminh University of Technology
SUMMARY
Modified Binh Thuan bentonite catalyst was prepared by exchanging with aqueous solution of
PdCl2, affording a catalyst loading of 0.14 mmol of Pd/g (ICP-MS). The Pd2+-exchanged
bentonite catalyst was assessed for its activity in the the Suzuki cross-coupling reaction between
iodobenzene and phenylboronic acid to form biphenyl as the principal product. The reaction was
performed using 0.2 mol% catalyst at 100oC in dimethylformamide (DMF) and in the presence of
K3PO4 as a base, with biphenyl being formed in a conversion of up to over 95% (GC) without
added phosphine ligands. It was also observed that the modified bentonite catalyst could be
facilely separated from the reaction mixture by centrifugation or simple filtration, and could be
reused in subsequent reactions without significant degradation in activity.
I - INTRODUCTION
Transition metal-catalyzed cross-coupling
reactions have attracted interests over the past
thirty years in organic synthesis, in particular as
convenient techniques for the formation of
carbon-carbon bonds [1]. Numerous reactions
have been developed to achieve cross-coupling,
of which the Suzuki reaction is one of the most
efficient methods for the synthesis of biaryl
derivatives [2]. These biaryl units have
exhibited practical applications in the
production of pharmaceuticals, herbicides, as
well as engineering materials such as
conducting polymers and liquid crystals [3].
Catalysts used in the standard Suzuki processes
are generally based on homogeneous palladium
phosphine complexes, which are rarely
recoverable without elaborate and wasteful
procedures, and therefore commercially
undesirable. Phosphine ligands are expensive,
toxic and generally unrecoverable. In large-
scale application, the phosphines might be a
more serious economical burden than even the
palladium itself [4]. In this context,
heterogeneous palladium catalysts have recently
emerged as a greener alternative to
homogeneous processes so that catalysts can be
recovered and reused [5].
Modified Binh Thuan bentonite catalysts
have been explored for applications in several
organic transformations, especially by Ngo Thi
Thuan and co-works. Their works have focused
on Fe3+, Al3+, Zn2+-exchanged bentonites as
solid acid catalysts for alkylation, isomerization
reactions etc [6]. We recently exchanged Binh
Thuan bentonite with Pd2+ cation and employed
this catalyst for the Heck cross-coupling
reaction of iodobenzene and styrene to produce
stilbene derivatives, and the catalyst could be
reused in subsequent reactions without
significant degradation in activity [7]. In this
paper, we wish to report the application of Pd2+-
exchanged Binh Thuan bentonite as an efficient
and recyclable catalyst for the Suzuki reaction
509
between iodobenzene and phenylboronic acid to
form biphenyl as the principal product, without
the use of any phosphine ligand. To our best
knowledge, this is the first time the Suzuki
reaction using modified Binh Thuan bentonite
catalyst has been investigated and reported in
Viet Nam.
II - EXPERIMENT
1. Catalyst preparation and characterization
The modified Binh Thuan bentonite catalyst
was prepared according to our previous report
[7]. Natural bentonite was treated with 10% HCl
aqueous solution at 70oC for 6 h to eliminate
impurities, washed several times with distilled
water until no trace of Cl- was obseved using
AgNO3 solution as indicator, dried and ground,
achieving bentonite-H+. The bentonite-H+ was
then exchanged with 0.016 M aqueous solution
of PdCl2 at 70
oC for 24 h. The solid was filtered
off under vacuum, washed several times with
distilled water until no trace of Cl- was obseved
as indicated by AgNO3 solution, dried and
ground. Particles passing through 100 mesh
sieve were then collected, achieving bentonite-
Pd2+ catalyst.
X-ray powder diffraction (XRD) patterns of
the bentonite-H+ were recorded using CuKα
radiation source on a diffractometer at Institute
of Petroleum, Petrovietnam, Ho Chi Minh City.
The surface areas of the bentonite-Pd2+ catalyst
were analyzed by BET method according to
nitrogen physisorption measurements at 77 oK,
and experiments were conducted at Analytical
Laboratory, Institute of Chemical Technology at
Ho Chi Minh City, Vietnamese Academy of
Science and Technology. The palladium loading
on the bentonite-Pd2+ catalyst was determined
using inductively coupled plasma - mass
spectroscopy (ICP-MS) measurements, and
experiments were conducted at Center of
Analytical Services and Experimentation, Ho
Chi Minh City.
2. Catalysis studies
Chemicals were purchased from Sigma-
Aldrich and Fisher, and used as received
without further purification. Unless otherwise
stated, a mixture of 4-iodobenzene (0.12 ml,
1.08 mmol), phenylboronic acid (0.1976 g, 1.62
mmol), K3PO4 (0.8628 g, 3.24 mmol), and
hexadecane (0.12 ml) as the internal standard in
dimethylformalmide (5 ml) were added to a
round-bottom flask containing the required
amount of the bentonite-Pd2+ catalyst. The flask
was heated at the required temperature with
magnetic stirring. Reaction conversions were
monitored by withdrawing aliquots (0.1 ml)
from the reaction mixture at different time
intervals, and quenching with water. The
organic components were extracted into
diethylether, dried over Na2SO4 and analyzed by
gas chromatography (GC) with reference to
hexadecane. Product identity was also further
confirmed by gas chromatography – mass
spectroscopy (GC-MS).
III - RESULTS AND DISCUSSION
Similar to our previous report where
modified Binh Thuan bentonite catalyst was
prepared for Friedel-Crafts alkylation reactions
[8], XRD patterns of the bentonite-H+ showed
that bentonite treated with 10% HCl aqueous
solution essentially contained montmorillonite.
It was also observed that calcite impurities were
almost eliminated during the course of HCl
treatment. Nitrogen physisorption measurements
of the bentonite-H+ and the bentonite-Pd2+
catalyst reported BET surface areas of 275.94
m2/g and 214.28 m2/g, respectively. Inductively
coupled plasma - mass spectroscopy (ICP-MS)
analysis of the bentonite-Pd2+ catalyst showed a
palladium loading of 0.14 mmol/g. The metal
loading observed in this research was
comparable to that of several other solid-
supported palladium catalysts in the literature
[9].
The bentonite-Pd2+ catalyst was assessed for
its activity in the Suzuki reaction initialy by
studying the coupling of iodobenzene with
phenylbornic acid to form biphenyl as the
principal product (Scheme 1). The sensitivity of
a heterogeneously catalyzed reaction to different
solvents can usually be of extreme importance,
depending on the nature of the catalyst support
material [10]. It was therefore decided to
investigate the solvent effect in the Suzuki
510
reaction, using 0.5 mol% of the bentonite-Pd2+
catalyst at 120 oC in the presence of Na2CO3 as a
base. Dimethylformalmide (DMF), isoamyl
alcohol, and p-xylene were adopted as the polar
aprotic solvent, polar protic solvent, and
nonpolar solvent, respectively. In the literature,
a number of solvents such as DMF, toluene,
dimethyl glycol, dioxane ect. worked effectively
for most of the Suzuki reactions [11].
Experimental results showed that the reaction
carried out in DMF afforded a conversion of
49% after 7 h, while the reaction in isoamyl
alcohol and p-xylene gave conversions of only
approximately 20% under the same conditions,
respectively (Figure 1). It was previously
hypothesized that DMF might be essential for
the reduction of Pd (II) to Pd (0), which was the
real active species for the coupling reaction [3].
However, the problem still remains to be solved
and needs further investigations.
I
+
B(OH)2
Pd
to
Scheme 1: The Suzuki reaction between iodobenzene and phenylboronic acid
0
20
40
60
80
100
0 1 2 3 4 5 6 7
Time (h)
C
on
ve
rs
io
n
(%
)
DMF
xylene
alcohol
Figure 1: Effect of solvents on reaction
conversions
We then decided to investigate the effect of
bases on the reaction conversions, using DMF
as the solvent at 120 oC in the presence of 0.5
mol% of the bentonite-Pd2+ catalyst. It is
generally accepted that a base is obviously
necessary to accelerate the transmetallation step
in the catalytic cycle of the Suzuki reaction [12].
The most commonly used base in the Suzuki
reaction is Na2CO3, but stronger bases such as
NaOH, K3PO4 and Ba(OH)2 were previously
reported to give better results in some cases
[13]. In this research, however, the Suzuki
reaction using Na2CO3 afforded the coupling
product in a significantly lower conversion than
reactions using CH3COONa and K3PO4 as bases
(Figure 2). After 7 h, a conversion of 76% was
obseved for the case of CH3COONa, while the
reaction using K3PO4 proceeded with up to 97%
conversion being achieved under the same
conditions. Styring and co-workers also reported
similar effects of bases in the Suzuki reaction,
where the combination of DMF as the solvent
and K3PO4 as the base exhibited dramatically
better conversion than the case of Na2CO3 [14].
Suzuki and co-workers previouly reported that
K3PO4 worked better than Na2CO3 for the case
of sterically hindered reagents in homogeneous
Suzuki reactions [15]. Although iodobenzene
and phenylboronic acid used in this research are
not sterically hindered, the similar effects of
bases might originate from the nature of the
bentonite-Pd2+ catalyst. However, futher
exploration is necessary to elucidate the
problem.
With these results in mind, we therefore
studied the effect of catalyst concentration on
reaction conversions, using DMF as the solvent
and K3PO4 as the base at 120
oC. As with
previous reports, the higher the catalyst
concentration was used, the higher the reaction
rate was observed. Almost qualtitative
conversion of iodobenzene to biphenyl was
achieved within 2 h at the palladium
511
concentration of 0.8 mol% relative to
iodobenzene. Decreasing the catayst
concentration resulted in a drop in reaction rate,
with 97% and more than 96% conversions were
obtained after 7 h at palladium concentrations of
0.5 mol% and 0.2 mol% respectively (Figure 3).
The reaction using 0.1 mol% catalyst proceeded
with slower rate, with a conversion of 94%
being achieved after 7 h. The catalyst
concentrations used in this study were
comparable to those of several previous reports
covering different aspects of the Suzuki
reaction, where the palladium concentrations
varied from less than 0.1 mol% to more than 1
mol%, depending on the nature of the catalysts
as well as the substrates [12].
0
20
40
60
80
100
0 1 2 3 4 5 6 7
Time (h)
C
on
ve
rs
io
n
(%
)
Na2CO3
CH3COONa
K3PO4
Figure 2: Effect on bases on reaction
conversions
0
20
40
60
80
100
0 1 2 3 4 5 6 7
Time (h)
C
on
ve
rs
io
n
(%
)
0.50%
0.80%
0.20%
Figure 3: Effect of catalyst concentration on
reaction conversions
0
20
40
60
80
100
0 1 2 3 4 5 6 7
Time (h)
C
on
ve
rs
io
n
(%
)
120 oC
100 oC
80 oC
Figure 4: Effect of temperature on reaction
conversions
The effect of the reaction temperature was
then investigated varying from 80oC to 120oC,
using 0.2 mol% catalyst in DMF, and in the
presence of K3PO4 as the base. It was decided to
use 0.2 mol% instead of 0.5 mol% of the
bentonite-Pd2+ catalyst for the reaction as the
difference in reaction rates was not
considerable. Experimental results showed that,
within experimental errors, the reaction rate
remained almost indentical when increasing
reaction temperature from 100oC to 120oC.
Increasing reaction temperature to above 100oC
was therefore unnecessary. As expected,
decreasing the reaction temperature from 100oC
to 80oC resulted in a significant drop in the
conversion of iodobenzene, from 96% to only
66% after 7 h (Figure 4). Indeed, the
temperature range of 90oC to 120oC has been the
most commonly used for Suzuki transformation
using different types of palladium catalysts [5].
The most effective reaction temperature for the
Suzuki reaction using the bentonite-Pd2+
catalyst in this research was therefore in good
agreement with the literature.
An important point concerning the use of a
heterogeneous catalyst is its lifetime,
particularly for industrial and pharmaceutical
applications of the palladium-catalyzed Suzuki
reaction. In the best case the catalyst can be
recovered and reused before it eventually
deactivates completely. At the same time, the
512
catalyst recovery can also reduce the
environmental pollution caused by heavy metals
used in the catalyst system [16, 17]. The
bentonite-Pd2+ catalyst was therefore
investigated for recoverability and reusability.
After the reaction, the catalyst was separated
from the reaction mixture by centrifugation,
washed several times with toluene, DMF, water
and ethanol to remove any physisorbed
reagents. The recovered catalyst was then dried
and reused in further reaction under identical
condition to the first run. Experimental results
showed that the bentonite-Pd2+ catalyst could be
reused in further reaction without significant
degradation in activity (Figure 5). A conversion
of approximately 90% was still achieved after 7
h for the second run. Although it was previously
reported that almost no loss of activity was
observed for reused palladium catalysts for the
Suzuki reaction in some cases, no kinetic data
was provided, and only conversions at the end of
the experiment were mentioned [18].
Unfortunately, stable activity can not be proven
by reporting only similar reaction conversions at
long times. Kinetic studies are the true test of
catalyst deactivation.
0
20
40
60
80
100
0 1 2 3 4 5 6 7
Time (h)
C
on
ve
rs
io
n
(%
)
1st run
2nd run
Figure 5: Study of catalyst recycling in the
Suzuki reaction
IV - CONCLUSIONS
In summary, modified Binh Thuan bentonite
catalyst was prepared by the cation exchanging
method, using aqueous solution of PdCl2. A
palladium loading of 0.14 mmol/g of bentonite
catalyst was afforded, determined by ICP –
MS. For the first time in Viet Nam, to our best
knowledge, the modified bentonite catalyst was
used as an efficient heterogeneous catalyst for
the Suzuki reaction of iodobenzene with
phenylbornonic acid to produce biphenyl as the
principal product. Using 0.2 mol% catalyst at
100 oC in DMF and in the presence of K3PO4 as
a base, the Suzuki reaction proceeded efficiently
with biphenyl being formed in a conversion of
up to over 95%, determined by GC. It was also
observed that the modified bentonite catalyst
could be facilely separated from the reaction
mixture by centrifugation or simple filtration,
and could be reused in subsequent reaction
without significant degradation in activity. Our
results here demonstrated the feasibility of
exploring Binh Thuan bentonite as a green
material to produce heterogeneous catalysts for
the Suzuki reaction as well as other useful
transition metal-catalyzed organic
transformations.
Acknowledgements: We would like to thank
researcher Bach Long Giang for the PdCl2 and
for his help with the XRD analysis.
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