Novel triazole-modified chitosan@nickel nanoparticles: efficient and recoverable catalysts for Suzuki reaction

Article abstract of DOI:10.1039/c6nj03789e

We have developed an efficient strategy to prepare uniformly sized spherical NiNPs supported on chitosan surface via click chemistry. This heterogeneous catalyst has demonstrated promising catalytic activity for the Suzuki-Miyaura coupling. Furthermore, the obtained catalyst can be easily separated from the reaction mixture by centrifugation and reused several times with no significant loss of activity.

Full text of DOI:10.1039/c6nj03789e

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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ARTICLE
Novel triazole-modified chitosan @ nickel nanoparticles: efficient
and recoverable catalysts for Suzuki Reaction
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
a,b*
a
Abdol R. Hajipour
and Parisa Abolfathi
www.rsc.org/
We have developed an efficient strategy for the preparation of uniform sized spherical NiNPs supported on chitosan
surface via a “click”. This heterogeneous catalyst has demonstrated a promising catalytic activity for the Suzuki-Miyaura
coupling. Furthermore, the obtained catalyst can be easily separated from the reaction mixture by centrifugation and
reused
several
times
with
no
significant
loss
of
activity.
syntheses. Therefore, in recent years, there has been growing
interest towards heterogenization of the existing
homogeneous catalytic systems using different supports. This
strategy can provide novel recyclable and reusable solid
catalysts that facilitate the separation of the often expensive
or toxic catalyst from the reaction mixture, making the
catalytic processes valuable and cost-effective for wide
Introduction
Generally, the transition metal-catalyzed cross-coupling
reactions have played a crucial role in synthetic organic
1
chemistry. There are different types of competitive strategies
for the formation of carbon–carbon and carbon–heteroatom
2
-6
bonds in cross-coupling chemistry. Among them, palladium
is still regarded as one of the most successful method for
cross-coupling reactions in both academic and industrial
1
1
industrial applications. There have been numerous reports
on the immobilization of the homogeneous catalysts using
1
2, 13
14, 15
7
various insoluble supports such as as silica,
18, 19
polymers,
20-23
synthesis. However, the use of effective palladium-free
1
6, 17
alumina,
zeolites,
carbon nanotube
and etc.
systems has recently gathered a great deal of attention, due to
the robust demand of palladium and its limited resources.
Therefore recent attention has been focused on employing
Recently, natural materials, in particular Bio-based polymers
are one of the applicable and interesting architecture for solid
catalysts. As one kind of the widely used biopolymers, chitosan
is natural, safe, inexpensive and biocompatible polysaccharide,
which is derived from crustacean resources such as crabs,
shrimps, prawns, lobsters and cell walls of some fungi. These
polysaccharides have been widely employed for various
8
other available and cost-effective metal catalyst. Recently
nickel-based catalytic systems has emerged as
a viable
9
alternative to Pd catalyzed cross-coupling reactions. A brief
survey in the literature display that, most of these reactions
are extensively performed under homogeneous catalytic
system using various Ni sources and ligands in organic
2
4
25
applications in manufacturing processes,
agriculture,
2
6
27
28
1
0
food, biomedical, drug delivery. Chitosan has also been
extensively utilized as environmentally benign polymeric
supports for catalytic applications due to its hydrophilicity,
presence of hydroxyl and amino groups, unique three-
dimensional structure, excellent chelating property and
solvents. Despite of the significant application of the
homogeneous catalytic systems they suffer from serious
drawbacks such as the difficulty in separation of the residual
metal from the reaction mixture and the ability to recover and
reuse catalyst. These problems can cause damage to the
environment and cost for the industry, which strongly limit the
wider applicability of these systems for various organic
2
9-35
mechanical properties.
Herein, as part of our ongoing
investigations on the synthesis and applications of efficient
3
6-38
catalyst in organic synthesis,
we have prepared triazole-
modified chitosan @ nickel nanoparticles which were
synthesized by reaction of an alkynlated imino- thiophene
ligand with azide functionalized chitosan via a click chemistry,
for application in transition metal catalyzed organic reactions.
The obtained catalyst was found to be an efficient and
recyclable nanocatalyst for the Suzuki-Miyaura cross-coupling
reaction.
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Result and Discussion
Preparation and characterization of the catalysts
The synthetic route for the preparation of triazole-modified
chitosan @ nickel nanoparticles is depicted in Scheme 1. The
compound 1 was firstly prepared by a simple condensation of
4-aminophenol with thiophene-2-carbaldehyde, which is
subsequently reacted with propargyl bromide to preparation
of an alkynlated imino- thiophene ligand. In the following step,
the azide group was introduced into the chitosan surface
3
9
according to the reported procedure. Then azidated chitosan
underwent a click process with compound 2 in the presence of
active copper(I) to furnish the chitosan-triazole support.
Ultimately, the resulting triazoles were further treated with
2
NiCl in the presence of hydrazine hydrate as reducing agent to
produce the desired solid catalyst.
Fig.1 FT-IR spectra of alkynlated imino- thiophene ligand (a),
a
b
azidated chitosan (b), triazole- modified chitosan (c), triazole-
modified chitosan-Ni (d)
HO
NH
2
HO
N
O
N
S
S
1
2
OH
OH
CS
As shown in Fig. 1c, the disappearance of azide peak signifying
completion of the click reaction between compound 2 and all
O
O
N
c
d, e
HO
O
HO
O
N
NH
2
N
O
N
S
Ni
N
3
Ni
-1
n
azide groups. In addition, the characteristic peaks of 1592 cm
n
-
1
3
4
(
C=N vibration) and 1500 cm (C=C vibration of the aryl ring)
are observed. In Fig. 1d, the imine group shifts to reduced
ꢀ1
frequency (∆ν = 37 cm ) when coordination with nickel occurs.
Scheme 1 Synthesis of triazole-modified chitosan @ nickel
nanoparticles. Reaction conditions: (a) thiophene-2-
carbaldehyde, MeOH, reflux, 3 h; (b) propargyl bromide,
The above results confirm the successful attachment of imino-
thiophene ligand and subsequent coordination of nickel
nanoparticles onto chitosan. This catalyst was also
characterized by EDX, SEM, TEM, ICP and XRD analysis. The
presence of elements of C, N, O, S and Ni in the structure of
catalyst was confirmed by EDX analysis (Fig. 2). Meanwhile, the
quantitative determination of the nickel content, as
determined by ICP was obtained to be 1.37%.
O
K CO , acetone, 50 C, 24 h; (c) triflyl azide (TFA), aqueous HCl.
2
3
NaHCO , CuSO .5H O, MeOH, r.t., 5 d; (d) 2, CuI, DMF/THF
2
3
4
(1:1, V/V), r.t., 72 h; (e) NiCl /EtOH solution, 12 h, r.t., and then
2
hydrazine hydrate, r.t., 2 h.
FT-IR Spectroscopy was used to confirm the modifications of
the chitosan surface (Fig. 1). Compared to the spectrum of the
-1
unmodified chitosan, a new peak appears at 2100 cm in
azidated chitosan, which revealed the successful
immobilization of N3 moiety on the surface of chitosan.
Meanwhile, according to the results of elemental analysis, the
loading of the azide group on the chitosan surface was
-1
determined to be 0.3 mmol g .
Fig.2 EDX spectrum of catalyst
As shown in Fig. 3, X-ray diffraction spectroscopy (XRD) pattern
of catalyst that matched well with that of it (Reference code:
0
3–1051) indicate the existence of Ni (0) species on the
O
surface of chitosan substrate. The strongest peak at 2θ = 20
correspond to chitosan and other peaks in the sample at 2θ of
2
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O
O
4.5 , 51.8 and 76.7 attributed to the diffraction of (111), functionalized chitosan was also investigated by scanning
O
4
4
0
(
200) and (220) crystal planes of Ni (0).
electron microscopy (SEM). As shown in Fig. 4c, the organic
components with sphere-shaped morphology and monotonic
nanometer-sized particles exist on the surface of the chitosan.
Catalytic activity tests
After synthesis and characterization of the catalyst, the
catalytic competence of the newly designed chitosan based
nickel nanocatalyst was investigated in the Suzuki-Miyaura
reaction using 4-bromoanisole and phenylboronic acid as the
model substrates under various conditions such as base,
solvent, temperature, reaction time and catalyst loading. The
observed results are presented in table 1. The initial
experiments were carried out by running the model reaction in
the presence of K CO as base and 0.2 mol% of catalyst in
2
3
o
different solvent at 90 C. The best result is obtained when
toluene is used as solvent (Table 1, Entry 4). Noting the
importance of base in this transformation, in our next set of
experiments, the effect of various bases on the efficiency of
Fig.3 XRD pattern of catalyst
2 3
this procedure was studied. On the basis of this study, K CO
gave maximum conversion percentage. The temperature
effect for the cross-coupling reaction was also surveyed. It was
found that the improvement in reaction results was obtained
The particle size, shape and morphology of the synthesized
nanomaterial were investigated by Scanning electron
microscopy (FE-SEM) and transmission electron microscopy
o
at 90 C. As respects, in lower temperatures the desired
(
TEM) imaging techniques. As displayed in Fig 4 (A and B), TEM
product was obtained in lower yields. Further, the effect of
catalyst loading on the conversion was also studied. It was
found that the higher yield was observed when the reation
was carried out with 0.2 mol% of catalyst, while less than this
values of catalyst led to a decrease in the yield of the product.
To explore the scope and generality of the protocol, the
present study is extended to various aryl halides with
phenylboronic acid under the optimized conditions. Results
summarized in Table 2 show that aryl bromides and iodides
coupled smoothly with phenylboronic acid carrying either
electron-withdrawing or electron-releasing substituents in
relatively short reaction times. Compared with the
corresponding bromo analogues, the less active chlorobenzene
and its derivatives gave moderate to good yields and needed a
longer times. It was also found that an increasing steric
hindrance of ortho- substituted aryl halides gave lesser yield
than those obtained with para-substituted ones.
micrographs of the fresh catalyst reveals that nickel
nanoparticles have a narrow size distribution with uniform and
discrete spherical in shape. On the other hand, the DLS
measurement shows that these particles have average
diameter of 10 nm, indicating that our methodology is efficient
Reusability and heterogeneity test
The possibility of recycling of a heterogeneous catalyst is one
of the most indispensable aspects to determine its
sustainability and industrial applications. In order to study this
property, the recyclability of this system was investigated by
using bromobenzen and phenylboronic acid as model
substrates. For this purpose, at the end of the reaction, the
catalyst material was separated by centrifugation, washed
thoroughly with water and ethanol, dried and reused for
subsequent runs. The recycling experiment demonstrated that
quantitative conversion to the corresponding product was
observed for six runs (Fig. 5). This observation was further
supported by XRD and TEM analysis of the recovered catalyst.
Fig.4 TEM images of nanocatalyst (a and b), SEM photographs
of catalyst (c) A histogram representing the size distribution of
nanoparticles (d)
for the synthesis of Ni nanoparticles on the surface of chitosan
in small size which are appropriate for the catalytic
applications. The information about the surface morphology of
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A comparison of the XRD patterns of the fresh and recovered chromatograph equipped with a Varian CP SIL 5CB column: 30
catalyst reveals that both samples exhibited similar XRD m, 0.32 mm, 0.25 mm) was used for consideration of reaction
patterns even after being subjected to six runs (Fig. S1, ESIϮ). conversions and yields. Scanning electron micrographs of the
Also, TEM image of the recovered catalyst clearly shows that catalyst were taken on [FE-SEM, HITACHI (S-4160)]. The
the structure of the catalyst has no noteworthy change in acknowledgements come at the end of an article after the
comparison with fresh catalyst (Fig. S2, ESIϮ). To probe this conclusions and before the notes and references.
point that the catalyst is truly functioning in a heterogeneous
manner, a standard hot filtration test was conducted by
coupling bromobenzene and phenylboronic acid. During this
test, the solid catalyst was removed from the reaction mixture
by filtration under hot condition after 1 h and the determined
conversion was 27% (analyzed by GC). The residual solution
was then allowed to react further under similar experimental
conditions for an additional 7 h. The obtained results clearly
indicate no further increment in the conversion percentage of
the reactants. Additionally, the ICP result of the resultant
supernatant only showed 0.04 ppm of the Ni species is lost
into solution during the course of the reaction. So, these
observations approved the high catalytic activity and good
stability of the catalytic system. To compare the efficiency of
the present catalytic system with previously reported catalysts
in the Suzuki reaction, we have tabulated the results of these
catalytic systems, in Table 3. It can be clearly seen that our
catalyst is much better than the literature precedents in terms
of reaction condition, reaction time, yield, recovery and
reusability.
Table 1 Effect of different parameters for the reaction of 4-
a
bromoanisole with phenylboronic acid
b
Entry
Solvent
T(°C)
Base
CO
K2CO3
Yield
1
2
3
4
5
6
7
8
9
PEG400
EtOH
90
90
90
90
90
90
90
90
90
80
90
K
2
3
32
25
43
94
78
75
58
87
76
83
68
THF
K
2
CO
CO
CO
CO
3
3
3
3
Toluene
DMF
K
2
K
2
2
DMSO
Toluene
Toluene
Toluene
Toluene
Toluene
K
KOH
PO
NaHCO
CO
K2CO3
K
3
4
3
1
0
K
2
3
c
11
a
Reaction conditions: 4-bromoanisole (1.0 mmol), phenylboronic
acid (1.2 mmol), base (2.0 mmol), amount of catalyst (0.2 mol%),
b
time (5 h) and solvent (5.0 ml). GC yield. The amount of catalyst
c
reduced to 0.1 mol%.
Synthesis of imino-thiophene ligand (1)
Thiophene-2-carbaldehyde (10 mmol) and p-aminophenol (10
mmol) were added into 25 mL of methanol and solution was
refluxed for 3 h. Afterward, the solvent was removed and the
1
pure product 1 was obtained. Yellow crystals; H NMR (400
MHz, DMSO-d6): 9.53 (s, 1H), 8.76 (s, 1H), 7.74 (d, J = 6.8 Hz
1
H), 7.60 (d, J = 4 Hz, 1H), 7.17–7.21 (m, 3H), 6.79 (d, J = 11.6
Hz, 2H).
Synthesis of compound (2)
Fig. 5 Reusability of the catalyst
propargyl bromide 5.2 mmol) was added dropwise to a
2 3
solution of compound 1 (5 mmol) and K CO (10 mmol) in
o
acetone (10 mL), and the mixture was stirred at 50 C for 24 h
under a nitrogen atmosphere. The resulting solid was then
Experimental section
All chemical reagents were purchased from Merck Chemical
1
Company and used without further purification. H-NMR
filtered and washed several times with Et
2
O and acetone to
obtain a brown solid powder. H NMR (400 MHz, CDCl ): 8.55
s, 1H), 7.46 (d, J = 6.8 Hz, 1H), 7.43 (d, J = 4.4 Hz, 1H), 7.2 (d, J
1
3
spectra were recorded on a Bruker 400 spectrometer using
deutrated DMSO-d6 and CDCl3 as solvent and
tetramethylsilane (TMS) as internal standard. X-ray diffraction
(
=
2
8 Hz, 2H), 7.09–7.12 (m, 1H), 6.97 (d, J = 8 Hz, 2H), 4.68 (s,
H), 3.56 (s, 1H)
(XRD) powder patterns were obtained using an X’PERT MPD,
with Cu Kα radiation (40 kV, 30 mA). Transmission electron
microscopy (TEM) images were obtained using a Philips CM10
microscope. FT-IR spectroscopy (JASCO FT-IR 680-Plus
spectrophotometer) was employed for characterization of
products. Also we used Inductive coupled plasma Perkin Elmer
Optima 7300 DV. Gas chromatography (GC) (BEIFIN 3420 gas
39
Synthesis of azide-functionalized chitosan
To a solution of chitosan (0.5 g) in 0.5 M aqueous HCl. NaHCO
3
(
4 2
9.3 mmol, 20 ml), CuSO .5H O (0.09 mmol) and triflyl azide
(
TFA) solution (5.95 mmol) were added. Afterward, 15 ml of
4
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methanol was added and the solution was stirred at room high catalytic activity over six successive cycles. Additionally,
temperature for 5 days. Finally, the solid particles were filtered high catalytic activity, broad substrate scope, reusability and
and washed several time with acetone, HCl solution (5% the use of an inexpensive chitosan and nickel make it a
solution in water) and then water and finally dried at room desirable protocol from environmental and industrial view
temperature
.
point.
Preparation of imino-thiophene ligand-functionalized
chitosan via click reaction
Table 2 Suzuki cross-coupling reaction of various aryl
halides with phenylboronic acid
a
b
Entry
R
1
C
6
H
4
X
X
I
Time (h)
Yield (%)
98
Azide functionalized chitosan (0.5 g) and compound 2 (2mmol)
were mixed with CuI (0.1 mmol) in DMF/THF (1:1, V/V)
solution, and the reaction mixture was then stirred at room
temperature for 72 h. Finally, the reaction mixture was filtered
1
2
H
H
H
2.5
7
Cl
Br
Cl
I
84
3
4
96
and washed sequentially with Et
o
dried in vacuum at 60 C.
2
O, H
2
O and then acetone and
4
4-CH
9
76
3
5
4-CH3
4-CH3
3.5
6.5
5
98
Preparation of triazole-modified chitosan
nanoparticles
@
nickel
6
Br
Br
I
91
At first, chitosan (0.2 g) was dispersed into 100 mL ethanol and
1
7
4-CH
3
O
92
2
3.4 mL of 0.1 mol L- NiCl /ethanol solution dropped into the
8
4-CH O
4
98
3
above solution and stirred for 12 h at room temperature.
Then, 2 mL of hydrazine was dropwise added to the above
9
4-CH O
Cl
Br
Br
I
9
79
3
o
mixture with vigorous stirring at a temperature of 60 C. After
10
2-COCH
8
54
3
2
h, the catalyst was separated by filtration, washed several
1
1
4-COCH3
3.5
1
95
times with ethanol and deionized water, and finally vacuum
4
dried at room temperature.
1
12
4-NO
2
98
1
1
3
4
4-NO2
4-NO2
Cl
Br
7
87
3
97
Conclusions
a
Reaction conditions: aryl halide (1 mmol), phenylboronic acid
In summary, we have reported the preparation of new
functionalized chitosan with an alkynlated imino- thiophene
ligand via a “click” route. The newly designed material has
been applied as an economical and effective support for
heterogeneous nickel nanoparticle which was efficiently used
as catalysts for Suzuki cross-coupling reactions. Furthermore,
this catalytic system shows negligible leaching and maintains
(
1.2 mmol), base (2 mmol), solvent (4 ml), catalyst (0.2 mol%), 90
b
C, Isolated yield
°
Table 3 Comparison of catalytic activity of the Ni (0)/Chitosan catalyst with literature precedents using Ni
based homogeneous and heterogeneous catalysts for Suzuki-Miyaura cross coupling reaction
Entry
Catalyst
R
1
C
6
H
4
X
X
conditions
Yield (%)
9
1
o
1
Ni (0)/Chitosan
4-CH
3
Br
K
2
2
CO
3
3
, Toluene, 90 C, 6.5 h
(
(
This work)
9
5
o
2
3
Ni (0)/Chitosan
4-COCH
3
Br
Br
K
CO
, Toluene, 90 C, 3.5 h
This work)
octahedral nickel(II)
benzoylhydrazone complex
Ni(II) mounted on
42
H
Toluene, K
2
CO3 , Reflux, 8 h
, LiBr, dioxane,
180-200 C, 9h
NaOH, PCy , dioxane, 120 C, 12h
Ethylene Glycol, Cs CO , 100 C,
83
K
3
PO , PPh
4
3
43
4
5
4-CH3
Br
I
o
87
graphite (Ni/Cg)
o
44
Magnetic Fe–Ni Alloy
4-CH
3
O
3
95
o
HPMC stabilized Ni
Nanoparticles
45
2
3
6
7
4-COCH
4-NO2
3
Br
I
99
20 h
o
46
Ni-TC@ASMNP
K PO , PPh , dioxane,100 C, 10 h
98
3
4
3
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Zenmyo, H. Seike, M. Nakamura, Angew. Chem. Int. Ed.,
012, 51, 8834.
2
Acknowledgements
9
(a) F. G. –Bobes, G. C. Fu, J. Am. Chem. Soc., 2006, 128,
5360; (b) P. Leowanawat, N. Zhang, A. –M. Resmerita, B. M.
Rosen, V. Percec, J. Org. Chem., 2011, 76, 9946; (c) C. E. I.
Knappke, A. J. von Wangelin, Angew. Chem. Int. Ed., 2010,
We gratefully acknowledge the funding support received
for this project from the Isfahan University of Technology
(
IUT), IR of Iran, and Isfahan Science and Technology Town
ISTT), IR of Iran. Further financial support from the Center
4
9, 3568; (d) X. Hu, Chem. Sci., 2011, 2, 1867; (e) S. L.
(
Zultanski, G. C. Fu, J. Am. Chem.Soc., 2013, 135, 624; (f) N.
Zhang, D. J. Hoffman, N. Gutsche, J. Gupta, V. Percec, J. Org.
Chem., 2012, 77, 5956; (g)Y. –L. Xian, W.–H. Guo, G. –Z. He,
Q. Pan, X. Zhang, Angew. Chem. Int. Ed., 2014, 53, 9909; (h)
F.-S. Han, Chem. Soc. Rev., 2013, 42, 5270
of Excellence in Sensor and Green Chemistry Research (IUT)
is gratefully acknowledged.
1
0 (a) M. Xu, X. Li, Z. Sun, T. Tu, Chem. Commun., 2013, 49,
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