Solvent-free synthesis of propargylamines catalyzed by an efficient recyclable ZnO-supported CuO/Al2O3 nanocatalyst

Article abstract of DOI:10.1002/aoc.4625

An efficient nanocatalyst of ZnO-supported CuO/Al₂O₃ (CuO/ZnO/Al₂O₃ nanocatalyst) was prepared by the co-precipitation method and characterized by scanning electron microscopy, energy-dispersive X-ray spectrosco

Full text of DOI:10.1002/aoc.4625

Received: 30 May 2018
DOI: 10.1002/aoc.4625
Revised: 10 September 2018
Accepted: 11 September 2018
F U L L P A P E R
Solvent‐free synthesis of propargylamines catalyzed by an
efficient recyclable ZnO‐supported CuO/Al2O3 nanocatalyst
Zohreh Sotoudehnia | Jalal Albadi
| Ahmad Reza Momeni
Department of Chemistry, Faculty of
An efficient nanocatalyst of ZnO‐supported CuO/Al2O3 (CuO/ZnO/Al2O3
nanocatalyst) was prepared by the co‐precipitation method and characterized
by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray
powder diffraction and Brunauer–Emmett–Teller surface area analysis. CuO/
ZnO/Al2O3 nanocatalyst proved to be a very efficient catalyst on the synthesis
of propargylamines under solvent‐free conditions in high yields. Moreover, the
catalyst can be recyclable without reducing catalytic activity up to five times.
Science, Shahrekord University,
Shahrekord, Iran
Correspondence
Jalal Albadi, Department of Chemistry,
Faculty of Science, Shahrekord University,
Shahrekord, Iran.
Email: jalal.albadi@gmail.com;
albadi@sku.ac.ir
Funding information
KEYWORDS
Shahrekord University
aldehyde, CuO/ZnO/Al2O3 nanocatalyst, phenylacetylene, propargylamines, solvent‐free conditions
1 | INTRODUCTION
loading of Cu and ZnO as well as a relatively lower amount
of Al2O3, has been used most widely in steam reforming of
Propargylamines have attracted a lot of attention due to
their medicinal and biological properties, such as
antiparkinson,[1] anti‐Alzheimer,[2] anti‐apoptotic[3] and
bovine plasma amine oxidase inhibitors.[4] Propargylamine
derivatives are useful synthetic intermediates in organic
synthesis, and are also significant structural elements in
natural products and therapeutic drug molecules, as well
as for the synthesis of polyfunctional amino deriva-
tives.[5,6] Due to the importance of propargylamines, vari-
ous catalytic procedures have been reported for the
synthesis of these compounds. According to previous
reports, various metal‐based catalysts, including Ag, Fe,
Li, Ni, Pd, In and Au, have been reported for the synthesis
of propargylamines.[7–16] In this view, copper and zinc
catalysts are the most important for the synthesis of
propargylamine derivatives, and good results have been
achieved in the presence of these catalysts.[17–28]
In previous researches, the use of hybrid metal oxide
catalysts has attracted a lot of attention both in industry
and in organic chemistry. To increase the performance
and reducibility of copper‐based catalysts, most studies
have focused on using a suitable promoter and synthesis
procedure.[29] Among these catalysts, Cu/ZnO/
Al2O3(CZA), as the commercial catalyst that contains high
methanol reaction.[30] Various factors, such as synthesis
procedure and appropriate promoters, can competently
effect the physicochemical and catalytic properties of these
catalysts. ZnO is identified as an operative promoter for the
improvement of reducibility and distribution of copper
particles that can effect the spreading and redox properties
of the copper species as well as being responsible for better
metal support interaction.[31] Moreover, Al2O3 as a consti-
tution promoter has a good effect on the CuO/ZnO cata-
lysts reactivity, and was added to the CuO/ZnO catalysts
to increase the surface area, mechanical resistance and
thermal stability.[32] On the other hand, in recent years,
increasing attention has been focused on the catalytic
application of nanocatalysts. Catalytic systems using
nanocatalysts, such as hybrid metal oxide catalysts, have
resulted in various important advantages, such as good
properties, high stability, dispersity of the particles, supe-
rior activity and catalyst recyclability.
Based on the literature, the catalytic application of ZnO‐
supported CuO/Al2O3 (CuO/ZnO/Al2O3 nanocatalyst) has
not been studied on organic synthesis reactions, particu-
larly for the synthesis of propargylamines. In previous
researches, we have reported the catalytic activity of
various nanocatalysts on the organic synthesis
Appl Organometal Chem. 2018;e4625.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4625

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SOTOUDEHNIA ET AL.
reactions.[33–36] In an extension of our research, herein, we
wish to report the preparation and characterization of an
efficient recyclable kind of ZnO‐supported CuO/Al2O3
nanocatalyst (Cu/ZnO/Al2O3 nanocatalyst) as well as its
catalytic activity on the synthesis of propargylamines
under solvent‐free conditions (Scheme 1).
and crystallinity of the catalyst. The Scherrer equation
was used to determine the average crystallite size of the
sample. The BET surface area was tested by N2 adsorp-
tion–desorption method. The investigation was carried
out using an automated gas adsorption analyzer (Tristar
3020, Micromeritics). The sample was purged with nitro-
gen gas for 3 h at 300ºC by a VacPrep 061 degas system
(Micrometrics).
2 | EXPERIMENTAL
2.1 | General
2.4 | General procedure
Chemicals were purchased from Merck and Fluka.
The nanocatalyst was prepared by the co‐precipitation
method, and characterized by scanning electron micros-
copy (SEM), energy‐dispersive X‐ray spectroscopy (EDS),
X‐ray powder diffraction (XRD) and Brunauer–Emmett–
Teller (BET) surface area study. All obtained products
were characterized by comparison of their physical and
spectroscopic properties with those reported in the litera-
ture. NMR spectra were recorded on a Bruker Advance
400 MHz. Yields refer to isolated pure products.
In a round‐bottom flask, a heterogeneous mixture of alde-
hydes (1 mmol), amine (1 mmol) and phenylacetylene
(1.2 mmol) Cu/ZnO/Al2O3 nanocatalyst (0.05 g) was
stirred at 80°C for the appropriate times (mentioned in
Table 3) under solvent‐free conditions. The improvement
of the reaction was monitored by thin‐layer chromatogra-
phy (TLC). After reaction completion, the reaction mix-
ture was allowed to cool at room temperature. Then hot
chloroform was added and the catalyst was separated.
The solvent was evaporated under reduced pressure and
the residue was purified by silica gel column chromatog-
raphy to obtain the pure corresponding propargylamines.
The spectral and analytical data for the new prepared
compound are as follows:
2.2 | Catalyst preparation
The catalyst was prepared through a co‐precipitation pro-
cess, by adding Na2CO3 solution (0.5 M) drop‐wise into a
mixture of Cu (NO3)2·3H2O (0.03 M), Zn (NO3)3·6H2O
(0.03 M) and aluminum nitrate (0.03 M) solutions under
strong stirring. The obtained suspension was aged at
pH 8.5 for 15 min at 50°C, then filtered and washed with
warm deionized water. The precipitates were dried for 12
h at 100°C, followed by calcination at 300°C for 3 h to
obtain the CuO/ZnO/Al2O3 nanocatalyst.
1
Table 3, entry 9: Oil; H NMR (CDCl3, 400 MHz), δ
(ppm): 1.34–1.54 (m, 6H), 2.47 (br, 4H), 4.68 (s, 1H),
4.96 (s, 2H), 6.87 (d, 2H), 7.21–7.43 (m, 10H), 7.45 (d,
2H). 13C NMR (CDCl3, 100 MHz), δ (ppm): 24.48, 26.13,
50.58, 61.78, 70.05, 86.28, 87.76, 114.36, 127.57, 128.01,
128.11, 128.33, 128.64, 129.81, 131.85, 137.09, 158.31.
Elem. Anal. Found: C, 85.09%; H, 7.19% N, 3.73% (calcd
for C27H27NO: C, 85.00%; H, 7.13%; N, 3.67%).
2.3 | Catalyst characterization
3 | RESULTS AND DISCUSSION
3.1 | Catalyst characterization results
The morphology of the nanocatalyst was studied using
SEM by a JEOL JSM‐6500F device, equipped with
an EDS analytical system to study the existence of
different components of the catalyst. The XRD study
was performed using an X‐ray diffractometer, Cu‐Kα
monochromatized radiation source and a nickel filter
(Panalytical X'Pert‐Pro), in order to explore the structure
Figure 1 represents the SEM images of the Cu/ZnO/Al2O3
nanocatalyst with different magnifications. An aggrega-
tion of the Al2O3 and CuO nanoparticles was observed
on the surface of ZnO support. The sizes of these
nanoaggregates with different shapes are less than 20
nm. As a quantitative proof, the EDS (Figure 1d) analysis
has been performed, and presented the content of ZnO
support greater than 75% by weight.
The XRD pattern of the CuO/ZnO/Al2O3 nanocatalyst
was shown in Figure 2. The peaks centered at about 2θ =
31.9, 2θ = 34.76, 2θ = 56.84, 2θ = 69.18 corresponded to
the 100, 002, 110 and 200 crystalline planes of ZnO sup-
port, respectively.[37] The peaks observed at 2θ = 36.58,
2θ = 47.86 and 2θ = 63.32 may be related to 111, 202
and 113 planes of CuO, respectively.[38] It is valuable to
SCHEME 1 Synthesis of propargylamines catalyzed by Cu/ZnO/
Al2O3 nanocatalyst

SOTOUDEHNIA ET AL.
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FIGURE 1 Scanning electron microscopy (SEM) micrographs and energy‐dispersive X‐ray spectroscopy (EDS) analysis results of the CuO/
ZnO/Al2O3 nanocatalyst
The N2 adsorption–desorption isotherms of the ZnO
support and CuO/ZnO/Al2O3 nanocatalyst are presented
in Figure 3. As can be seen, thin hysteresis loops between
p/p0 = 0.3–0.8 and p/p0 = 0.3–0.85 appeared in the iso-
therms of the support and nanocatalyst, respectively.
According to the IUPAC recommendation, these N2‐
isotherms, type III, can be attributed to the metal oxides
with a non‐porous structure.[38,39] As represented in
Figure 3a, the capacity of the nanocatalyst for adsorption
of the inert N2 is greater than that of the support in the
relative pressure range below 0.8.
The BET and Barrett–Joyner–Halenda methods were
employed to evaluate the specific surface area (m2 g−1
)
FIGURE 2 The X‐ray powder diffraction (XRD) of the CuO/
ZnO/Al2O3 nanocatalyst
and porosity of the support and nanocatalyst, respec-
tively. The pattern of pore width distribution and struc-
tural characteristics of the support and catalyst were
shown in Figure 3b and Table 1, respectively. As seen
from Figure 3b, a wide pore size distribution for both
the ZnO support and the ZnO‐supported nanocatalyst
CuO‐Al2O3 with a maximum are at about 30 and 24
nm, respectively. It is obvious from Figure 3b that the
pore sizes of support and nanocatalyst are in the range
of mesoporous and macroporous structures. Thus, this
observation indicates the formation of the non‐porous
structure of metal oxides that co‐precipitate together.[38]
The low pore size, high surface area and total pore vol-
ume of the CuO/ZnO/Al2O3 nanocatalyst with respect
note that the peaks related to different phases of Al2O3 as
α, δ, θ and γ, δ, θ appeared at about 2θ = 36.58 and 2θ =
47.86.[33] This XRD interpretation can be stated, because
the percentages of Al2O3 (10% w/w) and CuO (5% w/w)
in the target nanocatalyst are nearly close. As seen, the
CuO/ZnO/Al2O3 nanocatalyst was synthesized by co‐pre-
cipitation of three metal oxide phases, so that the peak
overlapping is inevitable, and subsequently influences
the detailed interpretation of the given XRD pattern.
However, the XRD data indicated the presence of three
metal oxide crystals in the composite nanocatalyst.

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SOTOUDEHNIA ET AL.
FIGURE 3 (a, b) The N2 adsorption/desorption of ZnO support and CuO/ZnO/Al2O3 nanocatalyst, (c, d) pore width distribution of the
ZnO and CuO/ZnO/Al2O3 nanocatalyst
TABLE 1 Structural parameters of the support and the nanocatalyst
BET surface area
Total pore volume
(cm3 g−1
)
Average pore
width (nm)
Catalyst
(m2 g−1
)
ZnO
38.93
50.22
0.161
0.173
22.62
17.64
CuO/ZnO/Al2O3
BET, Brunauer‐Emmett‐Teller.
to the ZnO support may be due to the incorporation of
the Al2O3 phases in the nanocatalyst.[39]
The reaction was also checked at different temperatures.
The results showed that 80°C is appropriate for the reac-
tion, and increasing temperature does not affect the speed
of the reaction and yield of the desired product. It was
found that in the absence of the catalyst the reaction
failed to form the corresponding product even after 18
h. Therefore, the effect of the catalyst amount on the
reaction was also examined. Moreover, the reaction
was also investigated in the presence of various amounts
of raw materials. The outcomes indicated that the
best results were achieved from the reaction of 4‐
nitrobenzaldehyde, piperidine and phenylacetylene (with
1:1:1.2 mol ratios), in the presence of CuO/ZnO/Al2O3
nanocatalyst (0.05 g), under solvent‐free conditions at
80°C (Table 2). Increasing the amount of catalyst did
not have a particular effect on the yield of product and
reaction time. Moreover, the obtained results in water
and ethanol as solvent resulted in the corresponding
3.2 | Catalytic activity
According to reports on the use of copper and zinc cata-
lysts on the synthesis of propargylamines, we decided to
prepare and use a hybrid catalyst of these metals. After
preparation and characterization of CuO/ZnO/Al2O3
nanocatalyst, we considered the optimal conditions for
the synthesis of propargylamines. For this purpose, ini-
tially, reaction of 4‐bromobenzaldehyde, piperidine and
phenylacetylene was selected as a pattern reaction and
various parameters were studied on the process of this
reaction. Parameters such as solvent, temperature, cata-
lyst and raw materials amounts were studied. Various
solvents such as water, ethanol, acetonitrile, toluene, as
well as solvent‐free conditions were carefully studied.

SOTOUDEHNIA ET AL.
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TABLE 2 Optimization of the reaction conditions
Entry
Solvent
Condition
Catalyst (g)
Time (h)
Yield (%)a
1
2
2
3
4
5
CH3CN
Toluene
EtOH
reflux
reflux
reflux
reflux
80°C
0.05
0.05
0.05
0.05
0.05
0.05
4
Trace
60
2
4
Trace
Trace
90
H2O
4
Solvent‐free
Solvent‐free
1.5
1.5
100°C
90
aIsolated yields. Reaction conditions: 4‐bromobenzaldehyde (1 mmol), piperidine (1 mmol) and phenylacetylene (1.5 mmol).
product in lower yield. It is obvious that the catalytic
activity of the CuO/ZnO/Al2O3 nanocatalyst is limited
by the solvation, so that the product yields were increased
in solvent‐free medium. In water and ethanol as solvent,
there can be nucleophilic competition with amine. It also
interferes with the presence of protons in the formation
of copper salt with phenylacetylene. In acetonitrile, a
by‐product was detected. There may be an interaction
between the catalyst and acetonitrile, and then it has
been nucleophilic attacked by amine. Thus, all of the
reactions were performed in the presence of CuO/ZnO/
Al2O3 nanocatalyst (0.05 g), under solvent‐free conditions
at 80°C.
TABLE 3 Synthesis of propargylamines catalyzed by CuO/ZnO/
Al2O3 nanocatalyst
Entry
R
Amine
Time (h)
Yield (%)a
1
H
piperidine
piperidine
piperidine
piperidine
piperidine
piperidine
piperidine
piperidine
piperidine
piperidine
morpholine
morpholine
morpholine
morpholine
morpholine
morpholine
1.5
1.5
2
94
93
94
91
92
93
89
86
88b
90
89
92
93
92
87
91
2
4‐Br
3
4‐Cl
4
2‐Cl
2.5
1.5
2
5
4‐NO2
3‐NO2
4‐OH
2‐OH
4‐OCH2Ph
4‐OMe
4‐Cl
6
7
2
8
2
After optimization, we explored the possibility
of CuO/ZnO/Al2O3 nanocatalyst on the synthesis of dif-
ferent propargylamines under optimized conditions. The
results are shown in Table 3.
9
2
10
11
12
13
14
15
16
2
2
2‐Cl
2.5
1.5
2
As shown in Table 3, various aromatic aldehydes
carrying both electron‐donating or ‐withdrawing substitu-
ents, secondary amines and phenylacetylene gave high
yields of products with good performance. Aromatic
aldehydes possessing electron‐donating substituents
such as OH, OMe or Me groups afforded the desired prod-
ucts in high yields. Moreover, a new product was synthe-
sized from 4‐benzyloxybenzaldehyde, piperidine and
phenylacetylene in good yield, and characterized by phys-
ical properties and spectroscopic data (Table 3, entry 9).
Excellent yields of propargylamines were found while
aromatic aldehydes containing electron‐withdrawing
groups such as NO2, Cl or Br were employed as the sub-
strates (Table 3). Also, in these reactions, both piperidine
and morpholine responded well and showed good results.
Moreover, the duration of the reactions in this procedure
is low and the desired products were obtained at short
reaction times.
4‐NO2
3‐NO2
4‐OH
4‐OMe
2.5
2
aIsolated pure products.
bNew compound. Reaction conditions: aldehyde (1 mmol), amine (1 mmol),
phenylacetylene (1.5 mmol), CuO/ZnO/Al2O3 nanocatalyst (0.05 g), under
solvent‐free condition. Products were characterized by comparison of their
spectroscopic data (NMR and IR) and melting points with those reported
in the literature.[12,21,25]
the presence of Al2O3, no product was obtained. Also,
in the presence of their combinations, corresponding
products were synthesized in lower yields and longer
times than CuO/ZnO/Al2O3 nanocatalyst (Table 4).
A
probable mechanism of the synthesis of
The model reaction was checked with individual salts
(ZnO, CuO and Al2O3) and with their combinations. The
results revealed that in the presence of CuO and ZnO,
prepared products were obtained in much lower yields
and high reaction times. Moreover, excess amounts of
the catalyst need to be used for reaction completion. In
propargylamines catalyzed by CuO/ZnO/Al2O3
nanocatalyst is shown in Scheme 2. At first, CuO/
ZnO/Al2O3 nanocatalyst activated the C‐H bond of
phenylacetylene to afford the desired acetylidine com-
plex. Also, nucleophilic attack of amine to the activated
aldehyde (by CuO/ZnO/Al2O3 nanocatalyst), followed

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SOTOUDEHNIA ET AL.
TABLE 4 Comparision study between CuO/ZnO/Al2O3 nanocatalyst ZnO, CuO, Al2O3, and with their combinations for the synthesis of
propargylamines
Entry
Catalyst
Catalyst amount (g)
Time (h)
Yield (%)a
1
2
2
3
CuO
0.05
0.05
0.05
0.05
5
5
5
4
30
25
–
ZnO
Al2O3
Combinationsb
50
aIsolated yields.
bCombination of CuO, ZnO and Al2O3, Reaction conditions: 4‐bromobenzaldehyde (1 mmol), piperidine (1 mmol) and phenylacetylene (1.5 mmol), under sol-
vent‐free condition.
the convenient recyclability of the Cu/ZnO/Al2O3
nanocatalyst, and consequently confirm its potential role
on the organic synthesis reactions (Table 5).
The XRD pattern of the recycled catalyst after being
used seven consecutive times was compared with the
XRD pattern of the catalyst before the reaction for the
SCHEME 2 The proposed mechanism for the synthesis of
propargylamines catalyzed by CuO/ZnO/Al2O3 nanocatalyst
by H2O removal, provides iminium ion. Then, the
acetylidine complex was added to iminium ion to give
the corresponding propargylamine.
The reusability of the Cu/ZnO/Al2O3 nanocatalyst
was also studied in the reaction between 4‐
bromobenzaldehyde, piperidine and phenylacetylene
under optimized conditions (Table 5). After the reaction
completion, which was monitored by TLC, the catalyst
was separated by filtration and washed with hot chloro-
form. Then, it was dried and stored for the following
reaction run. This process was carried out seven times
without significant loss of activity. These results prove
TABLE 5 Recyclability study of CuO/ZnO/Al2O3 nanocatalyst
Run
1
2
3
4
5
6
7
Time (h)
1.5
93
1.5
93
1.5
93
2
2
2.5
90
3
FIGURE 4 The X‐ray powder diffraction (XRD) pattern (a) and
scanning electron microscopy (SEM) image (b) of the recycled
CuO/ZnO/Al2O3 nanocatalyst
Yield (%)a
92
90
89
aIsolated pure products.

SOTOUDEHNIA ET AL.
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TABLE 6 Comparison study between CuO/ZnO/Al2O3 nanocatalyst with some other catalysts used for the synthesis of propargylamines
Entry
Catalyst
Condition
Time (h)
Yield (%)a
Reference
[7]
1
2
3
4
5
6
Ag‐NPs@mmt
toluene/100°C
toluene/100°C
solvent‐free/80°C
toluene/100°C
water/100°C
2
95
80
95
96
93
94
[19]
[20]
[21]
[25]
CuSBA‐15(42) catalys
Cu salen
6
2.5
6
Cu@MOF‐5‐C
zinc titanate nanopowder
Cu/ZnO/Al2O3 nanocatalyst
5
solvent‐free/80°C
1.5
This research
aIsolated yield.
synthesis of product 1. As seen from Figure 4a, the inten-
sity of some peaks was reduced but the crystal structure
of the catalyst remained. Comparison of the SEM image
of the used catalyst (Figure 4b) with fresh catalyst
showed more agglomeration of the catalyst particles in
the used catalyst.
ORCID
Jalal Albadi http://orcid.org/0000-0002-9914-9133
REFERENCES
[1] J. J. Chen, D. M. Swope, J. Clin. Pharmacol. 2005, 45, 878.
In order to show the quality of the present method,
Table 6 compares the results of the synthesis of
propargylamine by reaction of benzaldehyde, piperidine
and phenylacetylene catalyzed by Cu/ZnO/Al2O3
nanocatalyst with some of the reported methods in the
literature. In contrast with other reported catalysts, Cu/
ZnO/Al2O3 nanocatalyst accelerates the reaction very
effectively in less time and gives the corresponding
products in high yields under solvent‐free conditions.
The catalyst can be recovered simply by filtration and
can be reused for seven runs without significantly
diminishing its activity. Moreover, the reaction in the
presence of some other catalysts has been reported in
organic toxic solvents and required longer reaction times
(Table 6).
[2] I. Bolea, A. Gella, M. Unzeta, J. Neural. Transm. 2013, 120,
893.
[3] W. Maruyama, T. Yamamoto, K. Kitani, M. C. Carrillo, M.
Youdim, M. Naoi, Mech. Ageing Dev. 2000, 116, 181.
[4] H. B. Jeon, L. M. Sayre, Biochem. Biophys. Res. Commun. 2003,
304, 788.
[5] V. A. Peshkov, O. P. Pereshivko, E. V. Van der Eycken, Chem.
Soc. Rev. 2012, 41, 3790.
[6] K. Layek, R. Chakravarti, M. LakshmiKantam, H.
Maheswaran, A. Viru, Green Chem. 2011, 13, 2878.
[7] S. J. Borah, D. K. Das, Catal. Lett. 2016, 146, 656.
[8] B. Sreedhar, A. S. Kumar, P. S. Reddy, Tetrahedron Lett. 2010,
51, 1891.
[9] S. D. Dindulkar, B. Kwan, K. T. Lim, Y. T. Jeong, J. Chem. Soc.
2013, 125, 101.
[10] J. Safaei‐Ghomi1, S. H. Nazemzadeh, Catal. Lett. 2017, 147,
1696.
4 | CONCLUSION
[11] D. A. Kotadia, S. S. Soni, Appl. Catal. A: Gen. 2014, 488, 231.
[12] R. Manikandan, P. Anitha, P. Viswanathamurthi, J. G.
In conclusion, we have reported the preparation and
characterization of an efficient recyclable nanocatalyst
of ZnO‐supported CuO/Al2O3 as well as its application
on the synthesis of propargylamines. All reactions were
carried out under solvent‐free conditions and correspond-
ing products were obtained in high yields. Cu/ZnO/Al2O3
nanocatalyst showed excellent performance, recyclability
and stability on the synthesis of propargylamines. It was
simply separated from the reaction mixture and catalyzed
reactions up to seven times.
Malecki, Polyhedron 2016, 119, 300.
[13] M. Rahman, A. K. Bagdi, A. Majee, A. Hajra, Tetrahedron Lett.
2011, 52, 4437.
[14] V. Kar‐Yan Lo, K. Ka‐Yan Kung, M.‐K. Wong, C.‐M. Che,
J. Organomet. Chem. 2009, 694, 583.
[15] A. Feiz, A. Bazgir, Catal. Commun. 2016, 73, 88.
[16] R. Magg, A. Bello, C. Oro, G. Sartori, L. Soldi, Tetrahedron
2008, 64, 1435.
[17] M. Mirabedini, E. Motamedi, M. Z. Kassaee, Chin. Chem. Lett.
2015, 26, 1085.
[18] J. Safaei‐Ghomi, S. H. Nazemzadeh, H. Shahbazi‐Alav, Res.
Chem. Intermed. 2017, 43, 7375.
ACKNOWLEDGMENTS
The authors are grateful to the research council of
Shahrekord University for the support of this research.
[19] M. Srinivas, P. Srinivasu, S. K. Bhargava, M. L. Kantam, Catal.
Today 2013, 208, 66.

8 of 8
SOTOUDEHNIA ET AL.
[20] M. Tajbaksh, M. Farhang, H. R. Mardani, R. Hosseinzadeh, Y.
[34] J. Albadi, M. Jalali, A. R. Momeni, Res. Chem. Intermed. 2018,
44, 2395.
Sarrafi, Chin. J. Catal. 2013, 34, 2217.
[21] S. Cheng, N. Shang, C. Feng, S. Gao, C. Wang, Z. Wang, Catal.
Commun. 2017, 89, 91.
[35] J. Albadi, A. Alihosseinzadeh, A. Razeghi, Catal. Commun.
2014, 49, 1.
[22] M. Mominul Islam, A. S. Roy, S. Manirul Islam, Catal. Lett.
2016, 146, 1128.
[36] J. Albadi, A. Alihosseinzadeh, A. Mansournezhad, Synth.
Commun. 2015, 45, 877.
[23] E. Ramu, R. Varala, N. Sreelatha, S. R. Adapa, Tetrahedron Lett.
2007, 48, 7184.
[37] J. Chauhan, N. Shrivastav, A. Dugaya, D. Pandey, J. Nanomed.
Nanotechnol. 2017, 8, 429.
[24] K. V. V. Satyanarayana, P. Atchuta Ramaiah, Y. L. N.
Murty, M. Ravi Chandra, S. V. N. Pammi, Catal. Commun.
2012, 25, 50.
[38] C.‐L. Chiang, K.‐S. Lin, Int. J. Hydrogen. Energ. 2017, 42, 23
526.
[39] M. Jalali, A. Aliakbar, Int. J. Environ. Anal. Chem. 2015, 96, 542.
[25] C. Mukhopadhyay, S. Rana, Catal. Commun. 2009, 11, 285.
[26] B. Kodicherla, P. C. Perumgani, M. R. Mandapati, Appl.
Organomet. Chem. 2014, 28, 756.
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.
[27] Q. Zhang, J.‐X. Che, W.‐X. Gao, J.‐C. Ding, H.‐Y. Wu, Appl.
Organomet. Chem. 2010, 24, 809.
[28] M. M. Khakzad Siuki, M. Bakavoli, H. Eshghi, Appl.
Organomet. Chem. 2018, 32.
[29] J.‐P. Shen, C. Song, Catal. Today 2002, 77, 89.
[30] K. M. Eblagon, P. H. Concepción, H. Silva, A. Mendes, Appl.
Catal. B: Environ. 2014, 154, 316.
How to cite this article: Sotoudehnia Z, Albadi
J, Momeni AR. Solvent‐free synthesis of
propargylamines catalyzed by an efficient
recyclable ZnO‐supported CuO/Al2O3
[31] F. Ahmadi, M. Haghighi, H. Ajamein, J. Mol. Catal. B: Chem.
2016, 421, 196.
[32] P. H. Matter, D. J. Braden, U. S. Ozkan, J. Catal. 2004, 223, 340.
nanocatalyst. Appl Organometal Chem. 2018;e4625.
https://doi.org/10.1002/aoc.4625
[33] J. Albadi, A. Alihosseinzadeh, M. Jalali, A. Mansournezhad,
Appl. Organomet. Chem. 2018, 32.