Gold Nanoparticles Supported on Imidazole-Modified Bentonite: Environmentally Benign Heterogeneous Catalyst for the Three-Component Synthesis of Propargylamines in Water

Article abstract of DOI:10.1002/cplu.201800162

Gold nanoparticles supported on imidazole-modified bentonite, Bent@Im@Au NPs, has been developed for the first time as an effective heterogeneous catalyst for the synthesis of propargylamines under mild reaction conditions in water at a loading of 0.07 mol % of Au. Various techniques such as X-ray diffraction, high-resolution transmission electron microscopy, Fourier transform infrared spectroscopy, and element mapping by scanning electron microscopy were used to determine the physicochemical properties of the catalysts. The new gold catalyst was found to be highly active providing high to excellent yields of A3 coupling products via the reactions of various aldehydes, having electron-withdrawing as well as electron-donating substituents, with different amines and alkynes. The catalysts can be easily recovered and reused without significant loss of activity and the recycled catalyst was characterized.

Full text of DOI:10.1002/cplu.201800162

Accepted Article
Title: Gold Nanoparticles Supported on Imidazole Modified Bentonite:
Environmentally Benign Heterogeneous Catalyst for A3 Synthesis
of Propargylamines in Water
Authors: Mohammad Gholinejad, Reza Bonyasi, Carmen Najera,
Fariba Saadati, Maedeh Bahrami, and Neda Dasvarz
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10.1002/cplu.201800162
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Gold Nanoparticles Supported on Imidazole Modified Bentonite:
Environmentally Benign Heterogeneous Catalyst for A3 Synthesis
of Propargylamines in Water
Mohammad Gholinejad,*[a,b] Reza Bonyasi,[c] Carmen Najera,*[d] Fariba Saadati,[c] Maedeh Bahrami,[a]
Neda Dasvarz[a]
Abstract: Gold nanoparticles supported on imidazole modified
bentonite, Bent@Im@Au NPs, has been developed for the first time
as an effective heterogeneous catalyst for the synthesis of
propargylamines under mild reaction conditions in water with using
0.07 mol% of Au. Various techniques such as X-ray diffraction, high
resolution transmission electron microscopy, Fourier-transform
infrared spectroscopy and element mapping by scanning electron
microscopy were used to determine the physicochemical properties
of the catalysts. The new gold catalyst was found to be highly active
towards achieving the high to excellent yield of the A3 coupling
products via the reactions of various electron withdrawing as well as
electron donating aldehydes with different amines and alkynes. The
catalysts can be easily recovered and reused without a significant
loss of activity and the reused catalyst was characterized.
waste and increase safety, is the catalytic coupling reaction of
aldehydes, amines and terminal alkynes (A3 coupling) via C―H
activation of alkynes for the synthesis of propargylamines.[7]
Recently, many transition-metal catalysts such as Ir,[8] Ag,[9]
Cu,[7] a Cu–Ru bimetallic system,[9] Fe,[11] Zn,[12] and In [13] have
been suggested as new catalysts for the preparation of
propargylamines. Because of the well-recognized catalytic
properties of gold(I) and (III) in recent years, gold based
catalysts are recognized as efficient catalysts in various organic
transformations.14 One of the most interesting studied
applications of gold catalysts was in A3 coupling reaction via
gold activation of the sp C-H bond.15 Along this line, in recent
years different various gold catalysts have been introduced for
A3 coupling reaction under homogeneous conditions.[16] In spite
of the high price of gold and problem of recycling of
homogeneous catalysts, less examples of heterogeneous
recyclable gold catalysts have been described for A3 coupling
reaction.[17,18]
Introduction
Selection of support and suitable functionalization are important
factors for design of efficient heterogeneous catalysts. Different
organic and inorganic materials such as polymers, magnetic and
silica based compound were used for stabilization of metal
nanoparticles. Clay minerals having different properties such as
mechanical and thermal stability, high surface area and ion
exchange capacity, and economical price are promising
supports for the preparation heterogeneous catalysts.[19] Among
the different clay minerals, bentonite is a naturally occurring
materials which is formed by volcanic ash. Bentonite comprises
mainly of crystalline clay minerals belonging to the smectite
group, which are hydrous aluminum silicates containing Fe, Mg,
Na, and Ca elements.[20] Recently, surface modifications of clay
with new ligands have received considerable attention because
it allows the formation of new organo-clays with desired
properties.[21] Along this line bentonite-supported catalysts have
been applied to several types of organic reactions.[22] However
to date very limited bentonite-supported gold catalysts have
been essayed in organic reactions[23] and there is no report
dealing with bentonite-supported gold catalyst applied in A3
coupling reaction.
Propargylamines are important units in biologically active
intermediates in the production of pharmaceuticals and natural
products.[1] For example propargylamines moieties have
applications in the synthesis of anti-Alzheimer, anti-Parkinson,
and anti-depressant drugs.[2] Traditional methods for the
synthesis of propargylamines include reaction of stoichiometric
amounts of lithium or magnesium acetylides with imines[3] and
reaction of only few commercially available propargyl halides
with amines.[4] However, these methods require highly dry
solvents, inert atmosphere and the use of stoichiometric
amounts of organometallic reagents which inhibit the application
of these methods in large scale operations.[5]
In recent years, multicomponent reactions (MCRs) receive
increasing attention since they provide easy and rapid access to
large group of organic compounds with diverse substitution
patterns.[6] One of the best examples of MCRs which reduce
[a]
[b]
Mohammad Gholinejad, Maedeh Bahrami
Department of Chemistry, Institute for Advanced Studies in Basic
Sciences (IASBS), P. O. Box 45195-1159, Gavazang, Zanjan
45137-6731, Iran
E-mail: gholinejad@iasbs.ac.ir
Mohammad Gholinejad
Herein, we report for the first time a novel gold nanoparticle
supported on poly imidazole modified bentonite is an efficient,
simple and sustainable catalyst in the three-component coupling
reaction of aldehydes, amines and terminal alkynes at low
catalyst loading and under mild reaction conditions in water.
Research Center for Basic Sciences & Modern Technologies
(RBST), Institute for Advanced Studies in Basic Sciences (IASBS),
Zanjan 45137-66731, Iran
[c]
[d]
Reza Bonyasi, Fariba Saadati
Department of Chemistry, Faculty of Science, University of Zanjan,
P. O. Box 45195-313, Zanjan, Iran
Carmen Najera
Departamento de Química Orgánica and Centro de Innovación en
Química Avanzada (ORFEO-CINQA). Universidad de Alicante,
Apdo. 99, E-03080-Alicante, Spain
Email: cnajera@ua.es
Supporting information for this article is given via a link at the end of
the document.
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Results and Discussion
For the preparation of bentonite-supported gold nanoparticles
(NPs), bentonite was allowed to react with acryloyl chloride in
dry THF. The successful attachment of acryloyl was pursued
through FTIR spectroscopy showing the carbonyl stretching
bond at 1735 cm-1 (Figure 1 in supporting information). In the
next step, the resulting solid 1 was treated with vinylimidazole in
the presence of benzoyl peroxide as initiator. Finally to the
bentonite modified polyimidazole 2 was added NaAuCl4·2H2O
and NaBH4 in water. The obtained new gold composite 3 is
referred as Bent@Im@Au NPs through the text. Content of
nitrogen and gold have been determined by elemental analysis
and atomic absorption spectroscopy to be 1.1 and 0.02 mmol/g,
respectively.
Figure 1. FESEM images of Bent@Im@Au.
EDX-map analysis of Bent@Im@Au showed the presence of
highly uniform and dispersed Au as well as N and C species in
the structure (Figure 2 in supporting information). Also, total map
image of the Bent@Im@Au showed that the Au nanoparticles
are located very uniformly without any agglomeration (Figure 3
in supporting information). In addition, the presence of different
elements such as C, N, O, Mg, Ca, Na, Al, Si, and Au was
proved in the structure (Figure 4, supporting information). High-
Resolution Transmission Electron Microscopy (HRTEM) images
from Bent@Im@Au showed small and uniform Au NPs in
around 1-2 nm size which are stabilized in the solid surface
(Figure. 2).
Scheme 1. Preparation of Bent@Im@Au NPs.
Field emission scanning electron microscopy (FESEM) images
of Bent@Im@Au showed presence of gold nanoparticles (bright
points) stabilized on sheets of bentonite (Figure 1).
Figure 2. TEM images of Bent@Im@Au in different magnification
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X-ray powder diffraction (XRD) of Bent@Im@Au was also
studied (Figure 5 in the Supporting Information). However, due
to low loading weight of Au on the support and also the overlap
of bentonite peaks 22z,24 with Au NPs, this diffractogram did not
show any significant peaks for Au NPs. Therefore we studied X-
ray photoelectron spectroscopy (XPS) of Bent@Im@Au for Na,
Ca, Al, N, Si, and Au elements. XPS spectrum in Na 1s confirms
the presence of Na(I) in the structure of bentonite by showing a
peak at 1072.5 eV (Figure 3a).[25] XPS study in the Ca 2p region
showed a doublet peak centered at 347.1 and 351.1 eV related
to the Ca(II) in the solid structure (Figure 3b).[26] The core-level
photoelectron spectrum of Al 2p between 72-76 eV was
deconvoluted into two main peaks at 74.2 and 74.70 eV, which
are related to Al(III) in Al-OH and Al2O3 forms (Figure 3c).[27] The
binding energy (BE) value of Si 2p in silanol (Si-OH) and silicone
oxygen (Si-O) bond appeared at 102.4 and 103.1eV,
respectively (Figure 3d).[27a] In order to confirm the presence of
the imidazole group, XPS analysis for N1s region was studied
indicating the presence of two peaks at 398.9 and 401.05 eV
which can be attributed to the C=N and C–N bonds of the
imidazole (Figure 3e).[28] Finally the XPS spectrum in the Au 4f
region showed two intense doublets at 83.4 and 87.2 eV
corresponding to Au(0) and 85.1 and 88.6 eV related to Au(I)
species (Figure 3f). These results confirm that during the final
catalyst preparation step most of ionic Au was successfully
reduced to metallic form.
the effect of different factors such as solvent, reaction
temperature and catalyst amount (Table 1). Using 0.07 mol%
catalyst loading at 50 °C in different solvents such as CH3CN,
EtOH, THF, DMF, toluene, and H2O gave high to quantitative
yields for the reaction (Table 1, entries 1-6). For further
optimization studies we selected water as the best green solvent
and performed reaction using 0.07 and 0.05 mol% of catalyst 3.
Under these reaction conditions, 100 and 90% yield were
obtained respectively (Table 1, entries 7 and 8). Therefore, we
selected 0.07 mol% catalyst as the optimum amount. Also, using
0.07 mol% of catalyst and lowering the reaction time and
temperature, gave lower yields for the reaction (Table 1, entries
9 and 10). It should be noted that reaction in the absance of gold
using bentonite and imidazole functinalized bentonite (2) failed
to proceed (Table 1, entries 11 and 12). Also reactions using
bentonite supported Au before addition of NaBH4 and
bentonite supported Au reduced with hydrazine gave low
yield (Table 1, entries 13 and 14).
Table 1. Optimization of the reaction conditions for the reaction of
benzaldehyde, piperidine and phenylacetylene catalyzed by
Bent@Im@Au[a]
O
N
H
N
Bent.Im@Au NPs
Solvent, T
H
+
+
Entry
1
Catalyst (mol%)
Solvent
CH3CN
EtOH
THF
Yield (%)b
100
95
0.1
0.1
0.1
0.1
0.1
0.1
0.07
0.05
0.07
0.07
-
2
3
84
4
DMF
Toluene
H2O
100
100
100
100
90
5
6
7
H2O
8
H2O
9
H2O
61c
52d
0e
10
11
12
13
14
H2O
H2O
-
H2O
0f
Figure 3. XPS spectrum of Bent@Im@Au NPs (3) in a) Na1s, b) Ca 2p, c)
Al2p, d) Si2p, e) N1s and Au 4f regions.
0.07
0.07
H2O
19g
26h
H2O
The catalytic activity of Bent@Im@Au NPs was examined in the
three-component A3 reaction of amines, aldehydes and alkynes.
For this purpose, initially reaction of benzaldehyde, piperidine
and phenylacetylene was selected as model reaction to study
[a]Reaction conditions: benzaldehyde (1 mmol), piperidine (1.5 mmol),
phenylacetylene (1.5 mmol) and solvent (2 mL) for 1 d.
[b] Isolated crude yields determined by 1H NMR.
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propargylamines were obtained in high to excellent isolated
[c] Reaction performed during 12 h.
[d] Reaction performed at 25 °C
yields
(Table
2,
entries
1-10).
Reaction
of
3-
thiophenecarbaldehyde as heterocyclic aldehyde took place well
without poisoning or deactivation of the catalyst (Table 2, entry
11). Furthermore, reaction of aromatic and aliphatic aldehydes
with other secondary amines such as morpholine, pyrrolidine
and dimethylamine occurred efficiently affording the
corresponding propargylamines in high to excellent yields (Table
2, entries 12-19). It should be noted reaction of pentanal and
heptanal as aliphatic aldehydes with morpholine or piperidine
and phenylacetylene performed effectively and desired products
obtained in 81 and 89% isolated yields respectively (Table 2,
entries 20 and 21). Furthermore reaction of 1-octyne as aliphatic
alkyne with benzaldehyde and piperidine proceed well and the
corresponding product was obtained in 85% isolated yields
(Table 2, entry 22).
[e] Reaction using 35 mg bentonite as catalyst
[f] Reaction using 35 mg (3) as catalyst
[g] Reaction using bentonite supported Au (0.07 mol%) without reducing
agent
[h] Reaction using bentonite supported Au (0.07 mol%) with hydrazine
as reducing agent.
Having the optimized reaction conditions in hand, reactions of
various aldehydes with secondary amines and alkynes were
studied (Table 2). The obtained results indicated that the
reactions of different aromatic aldehydes containing electron-
donating and -releasing groups such as Cl, Br and Me as well as
1-naphtaldehyde and biphenyl-4-carboxaldehyde with piperidine
and phenylacetylene proceed effectively and the corresponding
Table 2. The reactions of different aldehydes, amines and alkynes in the presence of Bent@Im@Au as catalyst.[a]
R1
Bent@Im@Au NPs
(0.07 mol%)
NR2
R3
R2 NH +
2
R1CHO
2
+
R3
H2O, 50 °C
Entry
R1CHO
R22NH
Product
Isolated yield [b]
92
1
90
2
3
93
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84
4
5
90
6
7
8
89
84[c]
85
9
81[d]
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O
H
10
90
N
S
11
82
N
12
88
13
84[c]
N
O
Cl
90
14
15
88[c]
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16
87
17
82[c]
83[c]
18
HN(CH3)2
19
94
20
81
O
21
89
H
N
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22
85
[a] Reaction conditions: aldehyde (1 mmol), amine (1.5 mmol), alkyne (1.5 mmol), H2O (2 mL), catalyst (35 mg, containing 0.07 mol% Au), and during
1 d.
[b] Isolated yields after column chromatography.
[c] Reaction timeIs 30 h
Au@MIL-10118j
120/4
85/8
1,4-dioxane
H2O
-
5.7a
83
Comparison catalytic activity of Bent@Im@Au catalyst with
othersupported gold catalyst in A3 coupling reaction of 4-
NP@Au/NNN-
pincer18k
0.07
methylbenzaldehyde, piperidine and phenylacetylene as
a
Fe3O4@Au18l
100/24
50/24
Toluene
H2O
10
63
90
common substrate (Table 3), showed overall efficiency of the
presented catalyst (Bent@Im@Au). Also, It should be noted that
in compared to our previous reports regarding A3 coupling
reaction,[7b,17i,18f-g] novel Bent@Im@Au catalysed reactions under
mild and greener reaction conditions (50 °C in water). Briefly, the
advantages of the catalyst are described below. 1) Bentonite
was modified for the first time with poly imidazole with very
simple methode; 2) Poly imidazole modified bentonite was used
for the stabilization of gold NPs; 3) The new material was used
for the first time as the catalyst in A3 coupling reaction; 4) In
comapred to other previous Au catalysts and our reported Au or
Cu catalysts, reactions proceed efficiently under mild reaction
conditions in water.
Bent@Im@Au
0.07
[a] 60 mg catalyst containing 4.96 wt% gold
Since the recovering and reusing of heterogeneous catalysts are
very important aspects for sustainable chemistry and
economical stand points, we studied recycling of the catalyst in
the model reaction of benzaldehyde, piperidine and
phenylacetylene under optimized reaction conditions. For this
purpose, in each run after 24 h, catalyst was separated by
centrifugation and after washing with ethyl acetate and drying
was used in another reaction batch. Results showed this catalyst
3 was recyclable for 7 runs with small decrease in activity
(Figure 4).
Table 3. Comparison catalytic activity of Bent@Im@Au with other
reported Au catalysts in A3 coupling reaction
O
N
H
N
Catalyst
H
+
+
Solvent, T
Me
Me
Au
mol%
Catalyst
T(°C)/t(h)
Solvent
Yield
16l
Au38(SC2H4Ph)24
80/5
60/11
100/24
60/18
75/12
80/24
80/24
80/7
Solvent-free
CHCl3
0.01
0.2
0.04
1
84
88
81
95
83
89
75
54
Au@PMO-IL17i
NAP-Mg-Au(0)17f
MNP@PILAu18a
Au NPs17n
Toluene
H2O
CH3CN
Toluene
H2O
10
18d
Au25(PET)18
0.1
2
Figure 4 Recycling of the catalyst for the reaction of benzaldehyde, piperidine
and phenylacetylene.
Au@HS-MCM18e
IRMOF-3-LA-Au18h
1,4-dioxane
1.7
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FESEM mages of the reused catalyst after 7 runs showed very
similar pattern to fresh catalyst (Figure 5). However, TEM
images of reused catalyst after 7 runs showed presence of
mostly uniform nanoparticles and sligtly aggrigate form. (Figure
6).
Figure 5 FESEM images of reused catalyst after 7 runs.
Figure 6 TEM images of reused catalyst after 7 runs.
In addition, XPS analysis of the reused catalyst showed stability
and the presence of imidazole group in the structure. On the
other hand, the XPS spectrum in the Au 4f region indicates the
presence of Au(0) as a sole species in the reused catalyst
structure, it means that during the A3 reaction all of the ionic Au
species were reduced to Au(0) (Figure 7). Atomic absorption
spectroscopy of the reused catalyst after seven runs showed the
amount of leaching of Au was 2.7%.
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were added at 0 °C under argon atmosphere. Then the mixture was
stirred for 24 h at room temperature and was subjected to centrifugation.
The obtained isolated solid was washed with distilled water (2×15 mL)
and ethanol (2×15 mL) and then dried in an oven at 70 °C giving product
1. For introducing the imidazole group, product 1 (1 g) was dissolved in
EtOH (20 mL) and the mixture was deoxygenated by bubbling argon for 5
min. Then, N-vinilimidazole (10 mmol, 0.9 mL) and benzoyl peroxide (8
mg) were added and the mixture was stirred at 80 °C for 24 h. The
resulting suspension was centrifuged and the resulting solid (2) was
washed with water (15 mL) and ethyl acetate (3×15 mL) and dried at 60
ºC.
Preparation of Bent@Im@Au NPs (3)
NaAuCl4·2H2O (0.03 mmol, 12 mg) was dissolved in H2O (1 mL) and
bentonite (800 mg), which was previously sonicated in H2O (10 mL), was
added. Then, an aqueous solution of NaBH4 (0.3 mmol, 11 mg in 1 mL
water) was added slowly and the mixture was stirred for 24 h at room
temperature under argon atmosphere. The resulting solid was separated
with centrifugation, and washed with water (3×10 mL) and ethyl acetate
(3×10 mL) and finally dried at 60 °C. Atomic absorption spectroscopy
General procedure for the synthesis of propargylamines
Figure 7 XPS analysis of reused catalyst after 7 runs a) N1S and b) Au 4f
regions.
To a 5 mL flask, the catalyst (35 mg, containing 0.07 mol% Au), aldehyde
(1 mmol), amine (1.5 mmol), phenylacetylene (1.5 mmol) and H2O (2 mL)
were added and the mixture was stirred at 50 °C for 24 h. After the
complication of reaction, the crude products were extracted using ethyl
acetate (4×5 mL). Further purification was performed by column
chromatography on silica gel using hexane and ethyl acetate as eluent.
All products were characterized by 1H NMR and 13C NMR.
Conclusions
The new bentonite supported Au catalyst, Bent@Im@Au,
prepared by a very simple method and characterized by different
techniques. The catalyst showed good activity in synthesis of
propargylamines via A3 coupling reaction in water at 50 °C. Both
aromatic and aliphatic aldehydes and alkynes were reacted
effectively with different amines. Using centrifuge separation,
catalyst was recovered and reused for seven consecutive runs
with small decrease of activity.
Acknowledgements
The authors are grateful to Institute for Advanced Studies in
Basic Sciences (IASBS) Research Council and Iran National
Science Foundation (INSF-Grant number of 95844587) for
support of this work. C. Nájera is also thankful for financial
support to the Spanish Ministerio de Economía y Competitividad
(MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-
REDC), the Spanish Ministerio de Economía, Industria y
Competitividad, Agencia Estatal de Investigación (AEI) and
Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects
Experimental Section
General
All chemicals were purchased from Sigma-Aldrich, Acros, and Merck
companies and were used without further purification. All 1H and 13C
NMR were recorded on a Bruker 400 and 250 MHz spectrometer at 400
MHz and 62.5 MHz, respectively. Chemical shifts were given as δ values
with reference to tetramethylsilane (TMS) as the internal standard. FT-IR
spectra were recorded on a Bruker Vector 22. Transmission electron
microscopy (TEM) was performed by JEOL JEM-2010 instrument.
Scanning electron microscopy (SEM) was performed by Hitachi S3000N.
Energy dispersive X-ray analysis (EDX) results were obtained using Carl
Zeiss Sigma instrument. The content of gold in the catalyst was
determined using Varian atomic absorption spectrometry. X-Ray
diffraction was performed using Bruker D8-Advance.
CTQ2016-76782-P
Generalitat Valenciana (PROMETEOII/2014/017) and the
University of Alicante.
and
CTQ2016-81797-REDC),
the
Keywords: Bentonite • Gold• A3 coupling • Water •
Heterogeneous
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Mohammad Gholinejad,*[a,b] Reza
Bonyasi,[c] Carmen Najera,*[d] Fariba
Saadati,[c] Maedeh Bahrami,[a] Neda
Dasvarz[a]
Page No. – Page No.
Gold Nanoparticles Supported on
Imidazole Modified Bentonite:
Environmentally Benign
Heterogeneous Catalyst for A3
Synthesis of Propargylamines in
Water
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