Copper nanoparticles supported on starch micro particles as a degradable heterogeneous catalyst for three-component coupling synthesis of propargylamines

Article abstract of DOI:10.1039/c5ra22292c

Novel copper nanoparticles supported on starch micro particles (CuNPs@MS) were prepared successfully and characterized by SEM, EDX, TEM, SAED, TGA, XPS, and XRD analyses. The easily synthesized and thermally stable CuNPs@MS have been applied as a green, d

Full text of DOI:10.1039/c5ra22292c

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Journal Name
RSCPublishing
ARTICLE
Copper Nanoparticles Supported on Starch Micro
Particles as a Degradable Heterogeneous Catalyst for
Three-Component Coupling Synthesis of
Propargylamines
Cite this: DOI: 10.1039/x0xx00000x
Received 00th January 2012,
Accepted 00th January 2012
Mohammad Gholinejad,*a Fariba Saadati,b Shahram Shaybanizadeh,b Biji Pullithadathilc
DOI: 10.1039/x0xx00000x
Novel copper nanoparticles supported on starch micro particles (CuNPs@MS) was prepared
successfully and characterized by SEM, EDX, TEM, SAED, TGA, XPS, and XRD analyses.
The easy synthesized and thermally stable CuNPs@MS has been applied as green, degradable,
and eco-friendly catalyst in three component reaction of amines, aldehydes and alkynes for
preparation of diverse propargylamines. Reactions were performed under heterogeneous
conditions and catalyst were successfully recycled for five consecutive runs with small
decrease in activity.
www.rsc.org/
Introduction
have been reported for A3 coupling reactions under
Transition metal catalyzed reaction of an aldehyde, an alkyne,
and an amine (A3 coupling)1 is important and easy method to
access propargylamines compared to the traditional methods
such as reaction of less commercially available propargyl
halides with amines2 or using stoichiometric amounts of lithium
or magnesium acetylides with imines.3 The obtained
propargylamines are important synthetic intermediates for the
synthesis of divers nitrogen- containing biologically active
compounds and potential therapeutic agents.4 In recent years
application of different transition metals such as gold,5 indium,6
iron,7 zinc,8 Cu/Ru,9 iridium,10 silver,11 and nickel12 through C-
H bond activation of terminal alkynes have been reported.
However, since copper catalysts precursors are cheap,
available, and highly reactive, many A3 coupling reactions
have been reported using copper as a source of heterogeneous
heterogeneous condition. Recently, we have also reported
periodic mesoporous organosilica (PMO) supported gold20 and
copper21 nanoparticles as efficient catalysts in A3 coupling
reactions.
In recent years, using ecofriendly and biodegradable materials
as supports for stabilization of metal nanoparticles has attracted
great attention.22 Along this line, we have reported agarose as
naturally abandon and cheap biopolymer for stabilization of
palladium and copper nanoparticles and their applications in Pd
catalyzed
carbon-carbon23
and
Huisgen
1,3-dipolar
cycloaddition reactions.24 Among the different natural
polymers, starch is most common carbohydrate consisting of a
large number of glucose units linked by glycosidic bonds with
complete biodegradability,25 low cost and renewability26 and
can be regenerated from carbon dioxide and water by
photosynthesis in plants.24 In continuation with our interest on
heterogeneous copper catalysts and A3 coupling reaction,
herein, we wish to report copper nanoparticles supported on
starch micro particles as green and sustainable catalyst in three
component coupling of amines, aldehydes and alkynes.
or homogeneous catalysts.13 As
a
mentioned, since
application in
propargylamines have extensive
pharmaceutically active compounds, contamination of product
with toxic metal is not desirable and using heterogeneous
catalysts with high turnover number and recyclable ability is
highly attractive for A3 coupling reaction.
Along this line different heterogeneous copper catalysts
supported on different solid supports such as Fe3O4,14 MCM-
41,15 SiO2,16 montmorillonite,17 zeolites,18 mesoporous Cu/Al19
Results and discussion
Prepared starch micro particles was dissolved and sonicated in
deionized water and after addition of aqueous solution of
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ARTICLE
DOI: 10.1039/C5RA22292C
Cu(OAc)2.H2O, final starch supported copper nanoparticles was TEM image of CuNPs@MS confirmed presence of copper
obtained by addition of NaBH4 as a reducing agent at 30 °C. nanoparticles in average size of 15-20 nm supported on starch
The obtained material is referred as CuNPs@MS throughout micro particles (Figure 4a and 4b). Figure 4c shows the selected
the text of this article. Copper loading on the CuNPs@MS was area diffraction pattern (SAED) analysis with prominent ring
determined using ICP analysis to be 0.25 mmolg-1. pattern corresponding to Cu. The diffraction pattern shows
Thermogravimetric analysis of prepared CuNPs@MS showed prominent rings with interplanar spacing values of 0.20, 0.18,
three main weight losses between 25-700 °C. First weight loss 0.12 and 0.109 nm corresponding to (111), (200), (220) and
(25-120) is related to physisorbed water and organic solvents (311) planes respectively for Cu with fcc structure (JCPDS no.
and second and third ones are related to decomposition of 04-0836). Thus the diffraction analysis shows the presence of
starch polysaccharide structure. This diagram confirms thermal Cu in the cubic structures.
stability and negligible structure leaching of CuNPs@MS up to
300 °C (Figure 1).
Fig 1. Thermogravimetric diagram of the CuNPs@MS
Scanning electron microscope (SEM) image of CuNPs@MS
showed presence of highly uniform and micro sized starch
particles (Figure 2a). Also, the presence of copper and carbon
in the structure of CuNPs@MS was confirmed by energy-
dispersive X-ray spectroscopy (EDX) (Figure 3) obtained from
SEM analysis.
Fig.4 (a) and (b) TEM images of CuNPs@MS in different magnifications; (c) SAED
analysis of the CuNPs@MS; (d) TEM images of reused catalyst after 3rd run.
X-ray crystallography of prepared material (Figure 5a) showed
both (111) phases for Cu2O (JCPDS no. 05-0667) and Cu
(JCPDS no. 04-0836) at 2ϴ values of 36.3 and 43.2
respectively confirming presence of both Cu(0) and Cu(I)
species in catalyst structure.24
Fig. 2 (a) SEM image of the catalyst; (b) SEM image of reused catalyst after 3rd
run.
Fig. 3 EDX spectrum of CuNPs@MS
2 | J. Name., 2012, 00, 1-3
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Fig. 5 (a) XRD pattern of the catalyst; (b) XRD pattern of reused catalyst after 3rd
run.
2
CH3CN
EtOH
1,4-dioxane
DMSO
THF
30
30
30
30
30
30
60
60
60
60
60
60
60
60
60
60
60
60
20
20
20
20
20
20
20
20
20
20
20
20
18
14
8
21
12
6
3
Furthermore, the X-ray photoelectron spectrum (XPS) spectra,
for Cu 2p3/2 of the prepared material showed two main peak at
933.5 and 935.6 eV related to metallic Cu and Cu2O species
respectively (Figure 6).27
4
5
0
6
41
11
65
45
55
10
30
96
90
76
50
84b
71c
64d
7
DMF
8
CH3CN
EtOH
H2O
9
10
11
12
13
14
15
16
17
18
19
DMSO
1,4-dioxane
THF
Fig 6. XPS spectrum of the CuNPs@MS
The Brunauer Emmett Teller (BET) surface area of the
CuNPs@MS was determined by physisorption of nitrogen (N2)
to be 68 m2g-1.
The catalytic activity of prepared CuNPs@MS was tested in
three component coupling reaction of amine, aldehyde and
alkyne for the preparation of propargylamines. In order to find
optimized reaction conditions, reaction of benzaldehyde,
piperidine and phenylacetylene in the presence of 0.3 mol%
catalyst was selected as the model reaction and effect of solvent
and reaction temperature were studied. Study of reaction in
different solvents such as H2O, CH3CN, EtOH, 1,4-dioxane,
DMSO, DMF, and THF at room temperature afford low yields
with highest yield using THF (Table 1, entries 1-7). Increasing
reaction temperature to 60 °C improved reaction yields (Table
1, entries 8-13). However, best isolated yield was obtained
using THF as a solvent within 20 h (Table 1, entry 13). Results
of Table 1 indicated that decreasing reaction time caused drops
in reaction yields (Table 1, entries 14-16). Also, it was found
that using low amounts of copper catalyst, desired products
were obtained in lower isolated yields (Table 1, entries 17-19),
therefore; 0.3 mol% of catalyst was selected as suitable amount
for this reaction. It was worth mentioning that according to the
thermal stability of the catalyst which was 300 °C, catalyst can
easily tolerate finding optimized reaction conditions.
THF
THF
THF
THF
20
20
20
THF
THF
aReaction conditions: benzaldehyde (1 mmol), piperidine (1.5 mmol)
phenylacetylene (1.2 mmol), catalyst (0.3 mol %) and solvent 1.5 mL.
bUsing 0.18 mol% catalyst. c Using 0.12 mol% catalyst. dUsing 0.06 mol%
catalyst
With the optimized reaction conditions in hand, various
aldehydes including either electron releasing or withdrawing
groups such as Me, OMe, Br and Cl as well as benzaldehyde
and 1-naphtaldehyde were reacted efficiently with
phenylacetylene and different amines such as piperidine,
morpholine, and pyrrolidine (Table 2). Also, reaction of
furfural as a heterocyclic aldehyde with piperidine and
phenylacetylene were procced efficiently and desired product
was obtained in excellent yield (Table 2, entry 12). Furthermore
reaction of butanal and heptanal as the aliphatic aldehydes with
morpholine and phenylacetylene were performed well and
afford desired products in excellent yields (Table 2, entries
17,18). We have also studied reactivity of diphenylamine with
benzaldehyde and phenylacetylene under optimized reaction
conditions. However, result indicated that reaction did not
proceed and starting material were intact.
Table 1. Screening of different solvents and temperatures for the reaction of
benzaldehyde, phenylacetylene and piperidine.a
O
N
CuNPs@MS (0.3 mol%)
H
+
+
N
H
THF, 60 °C
Entry
Solvent
H2O
Temp.
(°C)
30
Time (h)
20
Yield(%)
30
1
Table 2. Reactions of structurally different aldehydes with amines and phenylacetylene.a
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DOI: 10.1039/C5RA22292C
NR2
CuNPs@MS (0.3 mol%)
THF, 60 °C, 20 h
Ar
ArCHO
+
+ R2NH
Isolated Yield
(%)a
ArX
Michael acceptor
Product
Entry
O
H
96
1
N
H
N
1a
O
H
95
2
N
1b
O
O
H
95
3
N
O
N
H
1c
CH3
O
H
95
4
N
H
N
H3C
1d
CH3
O
H
94
5
N
H3C
1e
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DOI: 10.1039/C5RA22292C
CH3
O
O
H
94
92
90
6
7
8
N
O
N
H
H3C
1f
Cl
O
H
N
H
N
Cl
1g
Cl
O
O
H
N
N
H
Cl
O
1h
Br
O
H
94
91
88
9
N
H
N
Br
1i
O
H
N
10
N
H
1j
O
H
O
O
N
11
N
H
1k
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O
O
H
93
12
O
N
H
N
1l
Cl
Cl
91
13
N
H
N
1m
OCH3
O
O
H
96
14
N
O
N
H
H3CO
1n
O
H3C
H
CH3
89
15
N
H
N
1o
Cl
O
H
92
16
N
H
N
Cl
1p
O
O
94
17
H
N
N
H
O
1q
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DOI: 10.1039/C5RA22292C
O
O
90
18
H
N
O
N
H
1
r
a Reaction conditions: Aldehyde (1 mmol), amine (1.5 mmol), phenylacetylene (1.2 mmol), catalyst (0.3 mol %) and THF 1.5 mL.
Proposed mechanism for the reaction is the same with well-
28
known mechanism for A3 coupling reaction (Figure 7).21,
Reaction proceed via the activation of the Csp-H bond of the
terminal alkyne by the CuNPs@MS. Then, alkynyl-Cu
intermediate react with the immonium ion generated in situ
from the reaction of aldehyde and secondary amine to produce
the corresponding propargylic amine product, and regenerate
the active CuNPs@MS species for further reactions.
Ph
H
Fig. 8 Recycling of catalyst for the reaction of benzaldehyde, pipridine and
phenylacetylene
Cu
SEM (Figure 2b) and TEM (Figure 4d) images of the catalyst
after 3rd run showed preserve of catalyst structure during the
reaction. Furthermore, XRD analysis of reused catalyst after 3rd
run showed copper nanoparticle states were intact within the
reaction (Figure 5b).
Starch
Ph
NR2
H2O
+
Ar
ArCHO+R2NH
ArCH NR2
Ph
Fig. 7 Proposed reaction mechanism using CuNPs@MS
Conclusions
Recyclabity of heterogeneous catalysts is important factor from
the economical and sustainable chemistry stand points. Along
this line we have studied recyclibity of catalyst for the reaction
of benzaldehyde, pipridine and phenylacetylene under
optimized reaction conditions. After completion of the reaction
in each run catalyst was separeted by centifugation and reused
in another reaction batch. Result of this study indicated that the
catalyst is recyclable for five conscutive runs with small drops
in catalytic activity (Figure 8). The slow decrease in reaction
yields during recycling process is may reslut of strong
intraction between Cu NPs and available free hydroxy groups
of starch particles. This result was confirmed by ICP analysis of
reaction solution after five reaction cycle which showed small
leaching of copper species (1.4%) to reaction medium.
In conclusion, in this study we have used micro starch particles
as a cheap, abandon, green support for stabilization of copper
nanoparticles. The new material was characterized using
different technics and applied as an efficient catalyst in three
component coupling reaction of amines, aldehydes and alkynes.
Using this catalyst, various aldehydes reacted with different
amines and phenylacetylene under heterogeneous conditions.
The catalyst was recyclable and recycled for five consecutive
runs with small decrease in reactivity.
Experimental:
All chemicals were purchased from Sigma-Aldrich, Acros and
Merck Chemical Companies and were used without further
purification. Column chromatography was carried out on silica
gel 60 Merck (230-240 mesh) in glass columns (2 or 3 cm
diameter) using 15-30 grams of silica gel per one gram of the
1
crude mixture. H NMR was recorded at 250 MHz and 13C
NMR was recorded at 62.5 MHz in CDCl3 using TMS as
internal standard. X-ray diffraction (XRD) was recorded on
Philips X'PertPro. The size of the particles of the catalyst was
determined by transmission electron microscopy using Philips
CM-120 instrument.
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Preparation of starch micro particles:29 1.25 gr corn starch
was dissolved in 25 mL distilled water at room temperature and
25 mL acetone was added. The high molecular weight starch
separated and then dissolved in 25 mL distilled water with a
stirring rate of 750 rpm and pH of the new solution was
adjusted at 2.5. Starch particles were obtained by addition of 75
mL acetone. For stabilization of particles a cross-linking agent
glutaraldehyde (0.25 ml) was added and system stirred at 750
rpm for 12 h. Then, the acetone was evaporated and material
was dried over oven at 50 C.
4
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e
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,
g
5
(a
Preparation of CuNPs@MS: Mixture of starch micro particles
(0.5 gr) in 15 mL H2O was sonicated for 60 min. Then,
Cu(OAc)2.H2O (0.025gr, 0.1mmol) which already dissolved in
4 mL H2O gradually added to suspension and stirred for 2h at
room temperature. Then, NaBH4 (0.4 mmol, 0.015 gr) which
already dissolved in 6 mL H2O was added drop wise under
argon atmosphere and reaction mixture stirred at 750 rpm for
48 h at 30 °C. The catalyst was collected after filtration, washed
with water (3×10 ml), and dried in oven at 60°C.
b
8
c
d
4
e
,
,
f
g
h
General procedure for A3 coupling reaction: The catalyst
(12 mg, 0.3 mol%) was added to a mixture of aldehyde (1
mmol), phenylacetylene (1.2 mmol) and amine (1.5 mmol) in
THF (1.5 mL) and the mixture was stirred at 60 °C for 20 h
under argon atmosphere. After the complication of reaction, the
solvent evaporated under reduced pressure. The crude product
was obtained by column chromatography (EtOAc, hexane) to
afford propargylamines in high to excellent yields. All products
were known and confirmed by 1H NMR, 13C NMR.
(i
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(a
Notes and references
b
aDepartment of Chemistry, Institute for Advanced Studies in Basic
Sciences (IASBS), P. O. Box 45195-1159, Gavazang, Zanjan 45137-
6731, Iran. Email: gholinejad@iasbs.ac.ir
c
3
11
(a
5
bDepartment of Chemistry, Faculty of Science, University of Zanjan, P.O.
Box 45195-313, Zanjan, Iran
cNanotech Research, Innovation and Incubation Center, PSG Institute of
Advanced Studies, Coimbatore-641 004, India
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Page 10 of 10
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DOI: 10.1039/C5RA22292C
Graphical abstract
Starch supported Cu NPs as a degradable heterogeneous catalyst for A3
coupling reaction