Heterogeneous bimetallic Au–Co nanoparticles as new efficient catalysts for the three-component coupling reactions of amines, alkynes and CH2Cl2

Article abstract of DOI:10.1007/s11164-019-03803-6

Abstract: Propargylamines are key intermediates for the synthesis of many biologically active molecules. A new synthesis of propargylamines via a three component-coupling reactions of amines, alkynes and dichloromethane (AHA) using bimetallic nanoparticle

Full text of DOI:10.1007/s11164-019-03803-6

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-03803-6
Heterogeneous bimetallic Au–Co nanoparticles as new
efcient catalysts for the three‑component coupling
reactions of amines, alkynes and CH2Cl2
A. Berrichi1,4 · R. Bachir1 · S. Bedrane1 · N. Choukchou‑Braham1 · K. Belkacemi2,3
Received: 20 December 2018 / Accepted: 11 March 2019
© Springer Nature B.V. 2019
Abstract
Propargylamines are key intermediates for the synthesis of many biologically active
molecules. A new synthesis of propargylamines via a three component-coupling
reactions of amines, alkynes and dichloromethane (AHA) using bimetallic nanopar-
ticles Au–M (M=Cr, Cu, Co) supported on CeO2 catalysts was investigated. Bime-
tallic particles are regularly distributed on ceria and range in size from 8 to 11 nm.
Synergetic efect between gold and the second metal was demonstrated. Diferent
propargylamines were synthesized with high yields (60–85%) using Au–Co/CeO2 as
an active heterogeneous catalyst.
Graphical abstract
Extended author information available on the last page of the article
Vol.:(0123456789)
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A. Berrichi et al.
Keywords Three component-coupling · Gold · Bimetallic · Heterogeneous ·
Nanoparticles
Introduction
Propargylamines are key intermediates for the synthesis of many biologically active
nitrogen molecules such as β-lactams and therapeutic drugs [1–4].
Moreover, some propargylamines are known to be neurodegenerative protecting
groups. Rasagiline and Deprenyl are used in the treatment of dementia diseases such
as the Parkinson [5–9].
These propargylamines are often synthesized by three-component coupling reac-
tions of alkynes, amines, and a source of active methylene [10]. This way is called
A3 multicomponent reaction when aldehydes are used as a methylene source. Such
reactions can be catalyzed by gold nanoparticles [11–19].
Another strategy to synthesize propargylamines involves the activation of the
C–H bond of an alkyne and the C–X bond of a dihalomethane. This is a three-com-
ponent coupling reaction of an alkyne, a dihalomethane and an amine. This way
is called AHA multicomponent reaction. These coupling reactions are mainly cata-
lyzed by metal salts in homogeneous conditions with CuCl [20], CoBr2 [21], In2O3
[22], FeCl3 [23], K[AuCl4] [24], Ni ligands [25], silver salts [26] but few heteroge-
neous catalysts have been used [27, 28].
Gold nanoparticles deposited on reducible supports such as Fe2O3, CeO2, and
TiO2 have shown good activities in various reactions [29–33]. However, supported
gold bimetallic catalysts are not widely used. In addition, the majority of supported
bimetallic catalysts cited in the literature relate to the association of gold to noble
metals Au–Pd [34–37], Au–Pt [38–40], Au–Ag [41–44] and only a couple of pub-
lications report the association of gold to transition metals and gold Au–Fe [45],
Au–Co [46]. Furthermore, these catalysts have never been used for multicomponent
coupling reactions and particularly for the synthesis of propargylamines by the AHA
way.
In this paper, we report the synthesis of diferent propargylamines via a one-pot
three-component coupling reaction of phenylacetylene, dichloromethane and amines
(AHA) using diferent Au–M/CeO2 (M=Cu, Cr, Co) nanoparticles (Scheme 1).
A special consideration is given to Au–Co/CeO2. The catalysts are prepared by
co-DPU.
Experimental
Materials
HAuCl4·3H2O, Co(NO3)2·6H2O, Cr(NO3)3·9H2O, Cu(NO3)2·3H2O, CO(NH2)2,
AgNO3, NaBH4, and commercial ceria nano-powder (nanoparticles sizes≤20 nm)
were purchased from Sigma Aldrich.
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Heterogeneous bimetallic Au–Co nanoparticles as new efcient…
Scheme 1 AHA coupling reaction of phenylacetylene, dichloromethane and amines
Catalysts preparation
The monometallic 1%Au/CeO2 catalyst is prepared by deposition precipitation with
urea (DPU) as described elsewhere [27, 45, 47]. Bimetallic catalysts 1%Au–1%M/
CeO2 are prepared using a one pot co-deposition precipitation with the urea (CO-
DPU) method. Gold salt and the second metal salt are added on the support at the
same time. The mixture is heated up to 80 °C and kept under agitation for 16 h.
Finally, the materials are dried at 120 °C overnight.
Characterization
Difuse refectance DRUV–Vis spectroscopy measurements were carried out at room
temperature on a Lambda 800 UV–Vis spectrometer in the range of 200–800 nm.
This setup was equipped with a difuse refectance accessory set to collect the dif-
fuse refected light only. BaSO4 was used as standard.
The BET surface areas were determined from N2 adsorption isotherms at 77 K
using a Quantachrom NOVA 1000 instrument. The catalyst was outgazed in situ at
250 °C for 10 h.
FTIR spectra were recorded using a Thermo Nicolet Nexus 670 spectrometer in
absorbance mode at 32 scans with a resolution of 4 cm−1.
Transmission electron microscopy (TEM) micrographs were collected on a JEOL
JEM-1230 electron microscope.
AHA coupling
A mixture of phenylacetylene (2 mmol), amine (2.2 mmol), CH2Cl2 (1.5 mmol),
DABCO (2 mmol), catalyst (80 mg) and 3 mL of CH3CN (solvent) are loaded in a
sealed reaction 10 mL- vial. After stirring at 65 °C for 24 h, the reaction mixture is
diluted with H2O, extracted with CH2Cl2, dried over Na2SO4 and concentrated by
evaporation of solvent. This step gives the crude product, which is further purifed
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A. Berrichi et al.
by column chromatography on silica gel (acetate/hexane) to aford the correspond-
ing propargylic amine [27].
Reaction sample analysis
1H and 13C NMR spectra were recorded on a Varian Mercury 400 NMR spectrom-
eter at operating frequencies of 400 and 100 MHz, respectively, in CDCl3 as solvent.
Gas chromatography–mass spectrometry (GC–MS) was performed with a Shi-
madzu GC-2010 coupled with a GCMSQP2010. The products are known in the
literature.
1
N,N‑Diethyl‑3‑phenylprop‑2‑yn‑1‑amine H NMR (400 MHz, CDCl3) (δ ppm):
1.10–1.136 (t, 6H, 2CH3), 2.60–2.66 (q, 4H, 2CH2), 3.643 (s, 2H, CH2), 7.27–7.30
(m, 3Har), 7.41–7.43 (m, 2Har);
13C NMR (100 MHz, CDCl3) (δ ppm): 11.61(2C), 40.44(1C), 46.31(2C),
83.34(1C), 83.96(1C), 122.35(1C), 126.89(2C), 127.20 (1C), 130.69 (2C);
MS: m/z=188.089,115.027 (−HN(CH2CH3)2),
IR (ν, cm−1)=760, 689, 1198, 1320.
1
4‑(3‑phenylprop‑2‑ynyl) morpholine H NMR (400 MHz, CDCl3) (δ ppm):
2.62–2.64 (t,4Hmorpholine), 3.74–3.77 (t, 4H), 3.54 (s,2H), 7.28–7.29 (m, 3Har), 7.41–
7.43 (m, 2Har);
13C NMR (100 MHz, CDCl3) (δ ppm): 48.04(1C), 52.45(2C), 66.90(2C),
84.09(1C), 85.58(1C), 122.98(1C), 128.17(2C), 128.26(1C), 131.71(2C).
MS (m/z): 100.115 (−102, morpholine-CH2), 115.0975 (−87, morpoline),
202.1932 (100%, Μ+Η);
IR(ν, cm−1)=690, 754, 1120, 1288, 1346, 1452,1489, 1598, 2959, 3056.
1
1‑(3‑phenylprop‑2‑ynyl)pyrrolidine H NMR (400 MHz, CDCl3) (δ ppm):
1.820–1.840 (q, 4Hpyrrolidine), 2.77–2.800 (t, 4Hpyrrolidine), 3.67 (s, 2H, CH2), 7.210–
7.250 (dd, Har), 7.371–7.395 (m, Har);
13C NMR (100 MHz, CDCl3) (δ ppm): 23.89(2C), 43.70(1C), 52.48(2C),
83.79(1C), 85.39(1C), 122.82(1C), 128.3(3C), 131.77 (2C);
IR (ν, cm−1)=675, 866, 1123, 1265, 1508, 1642, 1684, 2346, 2933.
1
1‑(3‑phenylprop‑2‑ynyl)piperidine H NMR (CDCl3, 250 MHz) (δ ppm): 1.38–
1.46(m, 6Hpiperidine), 1.60–1.63 (m, 4Hpiperidine), 3.45 (s, 2H), 7.25–7.26(t, 2Har),
7.39–7.42 (m, 3Har);
13C NMR (CDCl3, 62.9 MHz) (δ ppm): 23.94(1C), 30.95(1C), 48.49(2C),
53.47(2C), 85.02(1C), 85.03(1C), 123.30(1C), 127.98(2C), 128.22(1C), 131.72(2C).
IR (ν, cm−1)=695, 753, 1158, 1366, 1452, 1736, 2347, 2800, 2804, 2943.
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Heterogeneous bimetallic Au–Co nanoparticles as new efcient…
Results and discussion
DRUV–Vis characterization
The DRUV–Vis spectra of CeO2, 1%Au/CeO2, 1%Au–1%Cu/CeO2, 1%Au–1%Co/
CeO2 and 1%Au–1%Cr/CeO2 are shown in Fig. 1. The DRUV–Vis charcteristic
bands of the diferent catalysts determined after deconvolution of the respective
spectra are summarized in Table 1. Ceria (Fig. 1a) shows a band at 216 nm cor-
responding to the charge transfer of O2− to Ce4+ and two other bands at 269 nm
and 310 nm corresponding to the charge transfer of oxygen to cation species in
a lower oxidative state [48]. These bands are also observable for 1%Au/CeO2
(Fig. 1b). Nevertheless they are shifted to higher values (269 nm 275 nm; 310 nm
321 nm) indicating metal-support interactions. Moreover, the 1%Au/CeO2 spec-
trum presents a new band at 553 nm. This band is characteristic of gold nanopar-
ticles surface plasmon resonance. In the case of the bimetallic catalysts, a net shift
of the ceria characteristic bands can be observed. The gold nanoparticles surface
plasmon resonance bands appear at 514 nm for Au–Co/CeO2 (Fig. 1c), 537 nm
for Au–Cr/CeO2 (Fig. 1d) and 516 nm for Au–Cu/CeO2 (Fig. 1e) respectively.
Fig. 1 DRUV–Vis spectra of a CeO2, b 1%Au/CeO2, c 1%Au–1%Co/CeO2, d 1%Au–1%Cu/CeO2, e
1%Au–1%Cr/CeO2
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A. Berrichi et al.
Table 1 DRUV–Vis characteristic bands of the diferent catalysts
Catalyst
Peak center Peak area Interpretation
References
[49]
CeO2
216
269
310
216
275
321
556
74
12
83
72
34
57
36
Charge transfer of O2− to Ce4+
Charge transfer of oxygen to cation species
in lower oxidative state
1%Au/CeO2
Ceria characteristic bands
[47, 50, 51]
[52–56]
Gold nanoparticle surface plasmon reso-
nance band
1%Au–1%Co/CeO2 215
197
4
131
47
Ceria characteristic bands
277
314
514
Gold nanoparticle surface plasmon reso-
nance band
414
607
699
785
38
32
33
16
90
56
67
26
Characteristic bands of Co3+ and Co2+
species
1%Au–1%Cu/CeO2 216
Ceria characteristic bands
[57–60]
[61–64]
275
324
516
Gold nanoparticle surface plasmon reso-
nance band
418
592
671
781
33
24
23
28
60
13
89
33
Characteristic bands of Cu2+
1%Au–1%Cr/CeO2 212
Ceria characteristic bands
254
302
537
Gold nanoparticle surface plasmon reso-
nance band
407
649
781
37
29
33
Characteristic bands of Cr3+, Cr6+and Cr5+
The gold nanoparticles surface plasmon resonance band shift from 553 nm
in Au/CeO2 to lower values in the bimetallic catalysts could be explained by an
interaction between Au and the second metal. Furthermore, diferent bands cor-
responding to diferent transitions in Cu, Co and Cr ions are shown.
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Heterogeneous bimetallic Au–Co nanoparticles as new efcient…
Fig. 2 FTIR spectra of a CeO2, b 1%Au/CeO2, c 1%Au–1%Co/CeO2, d 1%Au–1%Cu/CeO2, e 1%Au–
1%Cr/CeO2
Table 2 BET surface area of the
Catalyst
BET surface area Total pore volume
diferent catalysts
(m2 g−1
)
(cm3 g−1
)
1%Au/CeO2
70
47
64
64
0.142
0.126
0.124
0.123
1%Au–1%Cu/CeO2
1%Au–1%Co/CeO2
1%Au–1%Cr/CeO2
FTIR characterization
FTIR spectra of the support as well as monometallic and bimetallic catalysts are
shown in Fig. 2. A band at 1050 cm−1 related to the stretching vibration of C–O in
carbonates [65] and bands at 1250–1750 cm−1 assignable to the OCO asymmetric
and symmetric stretching vibrations are shown in the case of CeO2 and Au/CeO2
[66]. For the bimetallic catalysts the band in 2300–2350 cm−1 is attributed to CO2
(Fig. 2d–f) [67]. Two new bands are situated at 2800–3000 cm−1 related to CH3
vibration and adsorbed water [67, 68].
N2‑physisorption characterization
Nitrogen adsorption and desorption isotherms were recorded for monometallic
and bimetallic catalysts. The corresponding textural parameters are shown in
Table 2. No signifcant modifcation in BET surface area was noted by adding
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A. Berrichi et al.
Fig. 3 TEM characterization of 1%Au/CeO2 a TEM image and b size distribution histogram
Fig. 4 TEM characterization of 1%Au–1%Cr/CeO2 a TEM image and b size distribution histogram
Cr or Co to the monometallic 1%Au/CeO2 catalyst. However, Cu induces ~ 33%
decrease of this surface area.
TEM characterization
The Au and Au–M particles are nanosized (Figs. 3, 4, 5, 6). The histogram of the
particle size distribution for Au/CeO2 catalyst has a Gaussian shape (Fig. 3b).
The majority of the gold particles range from 2 to 4 nm with a mean size of
4.8 nm. The addition of the second metal induces an increase in the particles
average size up to 11 nm in the case of Cr (Fig. 4), 9 nm the case of Cu (Fig. 5)
and 8 nm the case of Co (Fig. 6).
1 3

Heterogeneous bimetallic Au–Co nanoparticles as new efcient…
Fig. 5 TEM characterization of 1%Au–1%Cu/CeO2 a TEM image and b size distribution histogram
Fig. 6 TEM characterization of 1%Au–1%Co/CeO2 a TEM image and b size distribution histogram
Table 3 Three-component coupling reaction of phenylacetylene, CH2Cl2 and diethylamine over 1% Au/
CeO2 and 1%Au–1%M/CeO2 (M=Cr, Cu, Co)
catalyst
Ph
Et2NH
CH2Cl2
Ph
CH3CN, DABCO, 65°C, 24h
NEt2
Entries
Catalysts
Yield (%)
TON
1
2
3
4
5
CeO2
1%Au/CeO2
1%Au–1%Cr/CeO2
1%Au–1%Cu/CeO2
1%Au–1%Co/CeO2
0
23
30
42
57
0
114
150
210
284
1 3

A. Berrichi et al.
Catalyst activity in AHA coupling
The results of the three-component coupling reaction of diethylamine, dichloremeth-
ane, phenylacetylene (AHA) using mono and bimetallic catalysts are shown in Table 3.
The bimetallic catalysts are more active than the monometallic one. They reached
30–57% yield (entries 3, 4, 6). The monometallic catalyst registered only 23% (entry
2) while ceria was completely inactive (entry 1). These results indicate a positive syner-
getic efect between gold and the second metal.
As Co gave the best improvement for the activity of gold nanoparticles, we investi-
gated the infuence of its content on the catalytic performance. Diferent bimetallic cat-
alysts 1%Au–x%Co/CeO2, where x was varied from 1 to 4%, were prepared and tested.
The 1%Co/CeO2 and 1%Au/CeO2 were also prepared for comparison purposes.
As highlighted in Table 4, increasing the Co loading in the bimetallic catalyst
increased markedly the reaction yield. We confrm, thus, the efect of cobalt to improve
the activity of gold nanoparticles. Indeed, by increasing Co content, the yield of propar-
gylamine increases (Table 4).
The yield obtained with the bimetallic catalysts remains signifcantly higher than the
sum of yields obtained with the two monometallic catalysts, for all cases. For instance,
the yield obtained with 1%Au–1%Co/CeO2 is circa two folds higher than that obtained
with two monometallic catalysts.
(
)
Yield 1%Au − 1%Co∕CeO2
(
57
=
= 1.7
(
)
)
23 + 10
Yield 1%Au∕CeO2 + Yield 1%Co∕CeO2
(
)
TON 1%Au − 1%Co∕CeO2
(
284
=
= 2.2
(
)
)
14 + 114
TON 1%Au∕CeO2 + TON 1%Co∕CeO2
Table 4 Three-component coupling reaction of phenylacetylene, CH2Cl2 and diethylamine catalyzed
over 1%Au–x%Co/CeO2 (x=0–4%)
1%Au-X%Co/CeO2
Ph
CH3CN,DABCO, 65°C, 24h
Et2NH
Ph
CH2Cl2
NEt2
Entries
Catalysts
Yield (%)
TON
1
2
3
4
5
1%Co/CeO2
1%Au/CeO2
1%Au–1%Co/CeO2
1%Au–2%Co/CeO2
1%Au–4%Co/CeO2
10
23
57
62
70
14
114
284
310
350
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Heterogeneous bimetallic Au–Co nanoparticles as new efcient…
Table 5 Synthesis of diferent propargylamines catalyzed by 1%Au–4%Co/CeO2
1%Au-4%Co/CeO2
Ph
HNR1R2
Ph
CH2Cl2
CH3CN, DABCO, 65 °C, 24 h
NR1R2
1a
2a-2d
3a-3d
Entry
1
Amine
Propargylamine
Yield
Yield
2%Au/CeO2[27]
TON
TON
[27]
Ph
Et2NH
NEt2
132
70
53
350
2a
3a
Ph
O
2
3
N
N
H
O
424
138
85
55
2b
3b
3c
Ph
N
N
H
67
53
334
300
132
2c
Ph
4
N
N
H
148
59
60
3d
2d
The association of gold nanoparticles and cobalt induces a positive synergetic
efect for the AHA coupling reaction.
Finally, we used various secondary amines (2a–d) while keeping phenylacety-
lene as a terminal alkyne. The 1%Au–4%Co/CeO2 was used as a catalyst for this
study. Diferent propargylamines were synthesized with high yields (67–85%)
(Table 5).
We compared the yields obtained in this study for the diferent propargy-
lamines with those obtained using 80 mg of a monometallic catalyst 2%Au/
CeO2 published elsewhere [27]. In all cases the yields obtained with bimetallic
catalyst are higher than those obtained with the monometallic catalyst (Table 5).
This confrms the positive synergy between Au and Co.
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A. Berrichi et al.
Scheme 2 Plausible mechanism for the AHA coupling reactions over Au–Co/CeO2
Mechanism
In a previous study [27] we have proposed a mechanism for this reaction using a
monometallic catalyst Au/CeO2. We still think that this mechanism is plausible in
the case of the bimetallic catalyst (Scheme 2). Indeed, in this mechanism we sug-
gested a reaction of an adsorbed phenyl acetylene and a chloro-N,NR1R2-meth-
anamine. This chloro-N,NR1R2-methanamine is produced by a reaction between
the amine and the CH2Cl2 via the formation of a chloro-N,N-R1R2-methammo-
nium chloride salt.
Conclusion
In this work, we have prepared nanosupported bimetallic catalysts Au–M/CeO2
(M = Cr, Cu, Co). Bimetallic particles are regularly distributed on ceria with sizes
ranging from 8 to 11 nm. The particles size depends on the nature of the sec-
ond metal. Furthermore, DRUV–Vis spectroscopy and FTIR showed that the CO-
DPU preparation method used in this work leads to a close interaction between
gold and the second metal. These interactions make gold NPs more stable and
more active in the bimetallic catalysts. Indeed, bimetallic catalysts are very active
in the three-component coupling reaction AHA. The activity of bimetallic cata-
lysts is always higher than the monometallic one. However, this activity depends
on the nature of the second metal. We have established the following increasing
order activity Au–Cr/CeO2 < Au–Cu/CeO2 < Au–Co/CeO2. In the case of Au–Co/
CeO2 we have demonstrated a synergetic efect between the Au and Co.
1 3

Heterogeneous bimetallic Au–Co nanoparticles as new efcient…
As Au–Co/CeO2 is the most active catalyst, we chose it to synthesize various
propargylamines by varying the starting amine. Indeed, we have synthesized sev-
eral propargylamines with good yields (60–85%). This study showed the possibil-
ity of enhancing the stability and the activity of Au NPs by adding a transition
metal (Cr, Co, Cu) using the CO-DPU method. In the other hand, this study has
opened up a new method to synthesize propragylamines by AHA with very active
heterogeneous bimetallic catalysts.
Acknowledgements We thank DGRDST and the University of Tlemcen for funding this work.
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Afliations
A. Berrichi1,4 · R. Bachir1 · S. Bedrane1 · N. Choukchou‑Braham1 · K. Belkacemi2,3
*
A. Berrichi
berrichi.amina@yahoo.fr
*
R. Bachir
redouane_bachir@hotmail.com
1
Laboratory of Catalysis and Synthesis in Organic Chemistry, Université de Tlemcen, BP 119,
Tlemcen, Algeria
1 3

Heterogeneous bimetallic Au–Co nanoparticles as new efcient…
2
Department of Soil Sciences and Food Engineering, Université Laval, Quebec-City,
QC G1V0A6, Canada
3
Centre in Green Chemistry and Catalysis (CGCC), 801 Sherbrooke Street West, Otto Maass
Building, Room 416, Montreal, QC H3A 0B8, Canada
4
Institut of Sciences and Technologie, University center- Ain Témouchent, BP 284,
46000 Ain Témouchent, Algeria
1 3