Efficient aromatic C-H bond activation using aluminosilicate-supported metal nanoparticles

Article abstract of DOI:10.1016/j.catcom.2014.01.022

Novel nanomaterials based on mesoporous aluminosilicate-supported nanoparticles with high surface areas have been synthesized using a mechanochemical protocol and utilized in the hydroarylation of phenylacetylene to 1,1-diarylalkenes under microwave irradiation. Fe/Al-SBA-15 exhibited a higher activity and afforded high yields of substituted alkenes in short times of reaction.

Full text of DOI:10.1016/j.catcom.2014.01.022

Efficient aromatic C-H bond activation using aluminosilicate-supported metal
nanoparticles
Reza Hosseinpour, Antonio Pineda, Angel Garcia, Antonio A. Romero,
Rafael Luque
PII:
DOI:
Reference:
S1566-7367(14)00032-6
doi: 10.1016/j.catcom.2014.01.022
CATCOM 3792
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
3 November 2013
13 January 2014
23 January 2014
Please cite this article as: Reza Hosseinpour, Antonio Pineda, Angel Garcia, An-
tonio A. Romero, Rafael Luque, Efficient aromatic C-H bond activation using
aluminosilicate-supported metal nanoparticles, Catalysis Communications (2014), doi:
10.1016/j.catcom.2014.01.022
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ACCEPTED MANUSCRIPT
Efficient aromatic C-H bond activation using aluminosilicate-supported metal
nanoparticles
Reza Hosseinpoura, b*, Antonio Pinedab, Angel Garciab, Antonio A. Romerob, Rafael Luqueb*
aTarbiat Modares University, Department of Organic Chemistry, Tehran, Iran
bDepartamento de Química Orgánica, Universidad de Córdoba, Edificio Marie-Curie (C-3),
Campus de Rabanales, Ctra. Nnal IV-A, Km 396, E14014, Cordoba, Spain, email:
q62alsor@uco.es
Abstract
Novel nanomaterials based on mesoporous aluminosilicate-supported nanoparticles with high
surface areas have been synthesized using a mechanochemical protocol and utilized in the
hydroarylation of phenylacetylene to 1,1-diarylalkenes under microwave irradiation.
Fe/Al-SBA-15 exhibited a higher activity and afforded high yields of substituted alkenes in short
times of reaction.
Keywords: supported metal nanoparticles, phenol arylation, aluminosilicates, heterogeneous
catalysis
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Introduction
Transition metal nanoparticles (NPs) have emerged as important and efficient catalysts for
organic transformations owing to their excellent physical characteristics including high surface
area, large pore volumes, and uniform pore size distribution, and their simple workups and
recyclability [1-4]. Among various nanoporous catalysts, materials with mesoporous structures
possess advantages over related microporous structures (e.g. zeolites) for various acid- or
base-catalyzed organic transformations particularly related to bulky chemicals. The stabilization
of transition metal nanoparticles onto supports via alternative methodologies including
microwave irradiation (MWI), ultrasounds (US) and ball-milling (BM) are some of the most
appealing approaches for NPs control to the design of well dispersed, small size nanomaterials
with enhanced catalytic applications [5, 6].
Arenes and heteroarenes play a key role in important functionalization processes and find
extensive applications in the chemical industry as pharmaceuticals, agrochemicals and fine
chemicals [7]. Particularly, Mizoroki–Heck-type reactions can be considered as efficient
protocols for the synthesis of vinylated compounds [7, 8]. However, the major drawback of the
Mizoroki–Heck-type reaction in the synthesis of 1,1-disubstituted alkenes relates to its poor
selectivity toward the formation of α-products [9-11]. In general, the reaction shows β-selectivity
and only a few reports have so far reported the formation of α-substituted products [12-14].
Additionally, conventional protocols for the synthesis of 1,1-disubstituted olefins involved Lewis
acid (e.g. SnCl4) catalyzed Friedel-Crafts type reactions with Bu3N in acetonitrile under reflux
conditions [15], the combination of Cu(OTf)2/TMSA (TMSA = trifluoromethanesulfonic acid)
[16], FeCl3 as homogeneous catalyst [17] as well as gallium(III) chloride [18]. Nevertheless,
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most Lewis acid catalyzed Friedel-Crafts-type reactions have their own limitations.
Homogeneous catalytic systems have inherent issues related to difficulties in recovery and
reusability of the catalysts and tedious work-up procedures. Furthermore, the utilization of
air-sensitive chemicals also restricts these methods to be carried out under inert conditions in
most cases.
In the light of these premises, the development of simple and environmentally friendly
methods able to afford 1,1-disubstituted alkenes via aromatic C-H activation still remains a
challenge in organic synthesis. Herein, we report the design of heterogeneous solid acid catalysts
based on supported metal oxide nanoparticles on SBA-15 aluminosilicates which were able to
efficiently catalyse the formation of 1,1-diarylalkenes via simple microwave-assisted
hydroarylation of phenylacetylene with phenols under mild reaction conditions (Scheme 1).
O
OH
OH
M-Al-SBA-15
+
+
H
M.W, T = 120 oC
10-60 min
1,1-diarylsubstitued alkene
Scheme 1.Hydroarylation of phenylacetylene with phenol/s catalyzed by supported nanoparticles
on aluminosilicate materials under microwave irradiation.
Experimental
Materials synthesis
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Materials were prepared in a similar way to those reported in our previous work [19, 20],
and characterised using available techniques including X-Ray Diffraction (XRD), nitrogen
physisorption, elemental analysis and surface acidity.
SBA-15 materials were prepared following the previously reported methodology by
Bonardet et al. [21]. Al-SBA-15 parent materials possessed a Si/Al ratio of 41. The supported
catalysts were subsequently prepared following our previously reported novel dry
mechanochemical approach [22]. In a typical synthesis, 0.2 g Al-SBA-15 was ground with the
needed quantity of metal precursor (FeCl2.4H2O or AgNO3) in a Retsch PM-100 planetary
ball mill using a 125 mL reaction chamber and 10 mm stainless steel balls. Milling conditions
were 10 min at 350 rpm (previously optimized conditions [22]). Upon milling, as synthesized
materials were conditioned to remove the excess of unreacted and/or physisorbed precursor and
o
directly calcined at 400 C under air for 4h. The prepared catalysts, denoted as Fe0.5%AlSBA,
Fe1%AlSBA, Fe2%AlSBA, Fe4%AlSBA, Ag1%AlSBA and Ag10%AlSBA, were characterized
by a number of techniques including X-ray Diffraction (XRD), N2physisorption, TEM and EDX.
Prior to the reaction, the Ag catalysts were activated and reduced in a flow of 50 mL/min of
hydrogen/nitrogen for 4 h at 400 ºC.
Characterization
The structure regularity of the samples was determined by XRD on a Siemens D-5000 (40
kV, 30 mA) using Cu Kα (λ=0.15418 nm) radiation. Scans were performed over a 2θ range from
10 to 80 at step size of 0.018 º with a counting time per step of 20 s.
Nitrogen adsorption measurements were carried out at 77 K using an ASAP 2000 volumetric
adsorption analyzer from Micromeritics. Samples were degassed for 24 h at 130 ºC under
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vaccum (p < 10-2 Pa) prior to adsorption measurements. Surface areas were calculated according
to the BET (Brunauer-Emmet-Teller) equation. Pore volumes (VBJH) and pore size distributions
(DBJH) were obtained from the N2 desorption branch.
TEM micrographs were recorded on a JEOL 2010HR instrument operating at 300kV fitted
with a multiscan CCD camera for ease and speed of use as well as with an EDX system. The
lattice resolution is around 0.2 nm.
The surface acidity was measured in a dynamic mode by means of a pulse chromatographic
technique of gas-phase (300 ºC) adsorption of PY (sum of Brönsted and Lewis acid sites) and
2,6-dimethylpyridine (DMPY, Brönsted sites) as probe molecules [23].
DRIFTs characterisation of surface acidity involved the titration of the acid sites with PY. The
basic probes were introduced by bubbling a stream of dehydrated and deoxygenated nitrogen
(20 mL min-1) through the liquid and into the sample chamber containing the neat (no KBr
diluted) catalyst sample at 100 ºC. Samples were equilibrated for at least 1 h at each temperature
(100, 150, 200 or 300 ºC) and reactant condition prior to collecting the spectra.
Microwave-assisted reactions
In a typical reaction, 1 mmol (0.109 mL) phenylacetylene, 1.5 mmol (0.141 g) phenol, 2 mL
solvent (cyclohexane) and 0.050 g catalyst were added to a pyrex vial and microwaved in a
pressure-controlled CEM-Discover microwave reactor for a period of time, typically between 15
to 60 min at 200 W (120 ºC, maximum temperature reached) under continuous stirring. Samples
were then withdrawn from the reaction mixture and analysed by GC and GC/MS Agilent 6890N
fitted with a capillary column HP-5 (30 m × 0.32 mm × 0.25 µm) and a flame ionisation detector
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(FID). The identity of the products was confirmed by GC-MS. The selected GC-MS program
was as follows: ramp from 60 (initial temperature) to 100ºC (1ºC/min), 5 min hold time at 100ºC
followed by a ramp from 100 to 150ºC (1ºC/min), 20 min hold time at 150ºC. The blank reaction
(in the absence of catalyst) showed negligible conversion (less than 5% conversion) was
obtained after 24 h. Response factors of the reaction products were determined with respect to
the substrates from GC analysis using standard compounds in calibration mixtures of specified
compositions. The microwave method was generally power controlled (by an infra-red probe)
where the samples were irradiated with the required power output (settings at maximum power,
300 W) to achieve different temperatures in the range of 115-120ºC.
Results and discussion
Textural and surface properties of the materials have been summarized in Table 1. Surface
acidities measured using pyridine (PY) and 2,6-dimethylpyridine (DMPY) as probe molecules
pointed to a significant increase of Lewis acidity (difference between PY-DMPY values) upon
Fe incorporation in the materials. These findings are in good agreement with previous reports
from the group [24]. In any case, ball-milling (BM) synthesized nanomaterials possessed similar
textural properties (e.g. surface areas, pore size and volumes) as compared to the parent
aluminosilicate. Interestingly, the incorporation of Ag into the SBA-15 aluminosilicate material
slightly equally increased both Lewis and Bronsted acidities, particularly for the 1%Ag material.
Metal loadings determined by ICP/MS were close to theoretical values in most cases, except for
the case of Fe0.5%/AlSBA in which a larger Fe content was observed (Table 1). Included
DRIFTs of PY for selected catalysts (Fe0.5%/AlSBA vs Fe4%/AlSBA, Figure 1) prove the
acidity of low loaded materials was preserved from low to high temperatures (100-300oC) as
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compared to a significant decrease of the acidic character for higher loaded materials (2%Fe and
over).
Figure 1. PY DRIFT spectra of Fe 0.5% /Al-SBA (left) and Fe 4% /Al-SBA (right). Bronsted
(B), Lewis (L) and a joint contribution of Bronsted + Lewis (B+L) adsorption sites can be
observed in the catalysts.
Supported Fe nanomaterials were subsequently investigated in the hydroarylation of
phenylacetylene with phenol under microwave irradiation. Reaction optimisation was conducted
in different solvents, with results shown in Table 2 (entries 1-7). The solvents screening
demonstrated that cyclohexane is the solvent of choice (entry 7).
We then investigated different nanomaterials under typically short reaction times (10-60 min)
in the same microwave-assisted model reaction in cyclohexane. Blank runs (in the absence of
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catalyst) provided no conversion in the systems, similarly to reactions run in the presence of
catalyst in conventional heating experiments (low conversion to products was obtained after 12 h
under otherwise identical conditions to those under microwave irradiation). Comparably, the
acidic Al-SBA-15 support gave an interesting 67% conversion after 60 min of reaction (Table 3).
Comparably, both Fe and Ag low loaded (< 1 wt%) systems were remarkably more active and
efficient in promoting the C-H activation to yield 74% of target product within 30 min reaction
(Table 3, entry 3).
Table 1. Textural properties [surface area (m2 g-1), pore size (nm) and pore volume (mL g-1)] and
surface acidity [measured as mmol adsorbed of probe molecule (PY or DMPY) per gram of
catalyst] of metal NPs supported on mesoporous materials and their respective supports.
Surface acidity at 300oC
(µmol base g-1)
Catalyst
Metal
Loading
(wt%)
Surface area
(m2 g-1)
Pore
PY
DMPY
(Bronsted
acidity)
size/volume
(total acidity)
(nm/mL g-1)
Al-SBA-15
--
762
630
663
645
655
512
606
6.4/ 0.6
6.3/0.48
6.3/0.61
6.3/0.50
6.8/0.52
7.5/0.46
7.7/0.57
81
77
90
96
87
90
Fe0.5%/AlSBA
Fe1%/AlSBA
Fe2%/AlSBA
Fe4%/AlSBA
Ag1%/AlSBA
Ag10%/AlSBA
0.86
1.09
2.32
3.96
0.65
11.7
150
111
141
110
126
108
116
97
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Table 2. Solvent screening in the Hydroarylation of Phenylacetylene with Fe0.5%-Al-SBA-15a
Entry
Solvent
Conversion
Selectivityc
(mol%, 1:2)
(%)b
<5
-
1
2
3
4
5
6
7
ACN
DMF
Toluene
Ethyl acetate
Ethanol
-
-
34
<5
-
28
79
63:37
0:99
-
56:44
75:25
DCM
Cyclohexane
aReaction conditions: (1 mmol, 0.109 mL) phenylacetylene, (1.5 mmol, 0.141 g) phenol, 0.05 g
catalyst, 2 mL cyclohexane, 200 W, Tmax=120 oC, Pmax=240, 60 min reaction. bGC conversion of
phenyl acetylene. cGC yield of products. Retention time [min] for phenylacetylene = 1.1, phenol
= 1.5, acetophenone = 2.1, diarylalkene = 12.5.
Selectivities to the target product were in the same range (ca. 70%) to those achieved with the
parent aluminosilicate. A series of parameters were also screened in the model reaction, namely
Fe loading and time of reaction as these provided important insights into the reaction. Generally,
an increase in Fe or Ag loading in the systems (even from 1 to 2%) led to a significant decrease
in conversion (Table 3, entries 5- 45% - vs 6- 29%-) in spite of a very similar total acidity in the
systems (Table 1).
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Table 3.Catalytic activities and selectivities to target products in the microwave-assisted reaction
of phenol with phenylacetylenea
Sel.
Sel.
Metal
Loading
(wt%)
Time of
reaction
(min)
Conversionb
(mol%)
Entry
Catalyst
(mol%)
--
(mol%)
--
Blank
Al-SBA-15
Fe0.5%/Al-SBA
Ag1%/Al-SBA
--
--
0.86
0.65
30 min
60 min
30 min
30 min
<5
67
74
75
1
2
3
4
30
30
31
69
69
68
Effect of the metal loading
Fe0.5%/Al-SBA
Fe2%/Al-SBA
Fe4%/Al-SBA
Ag1%/Al-SBA
Ag10%/Al-SBA
0.86
2.32
3.96
0.65
11.7
10 min
10 min
10 min
30 min
30 min
45
29
40
75
21
22
30
27
31
19
78
69
72
68
80
5
6
7
8
9
Evolution of conversion with time of reaction
Fe0.5%/Al-SBA
Fe0.5%/Al-SBA
Fe0.5%/Al-SBA
Ag1%/Al-SBA
Ag1%/Al-SBA
0.86
0.86
0.86
0.65
0.65
10 min
30 min
60 min
10 min
30 min
45
74
79
54
75
22
30
24
39
31
78
69
75
60
68
10
11
12
13
14
aReaction conditions: (1 mmol, 0.109 mL) phenylacetylene, (1.5 mmol, 0.141 g) phenol, 0.05 g catalyst,
2 mL of cyclohexane, 200 W, Tmax=120 oC, Pmax=240. bGC conversion of phenyl acetylene.
In terms of the effect of time of reaction, increasing times of the reaction (ca. 60 min) did not
seem to improve the conversion in the systems, which seemed to peak between 30-45 min.
(Table 3, entry 12). In all cases, selectivities to the main product were almost identical and only
slightly increased at reduced conversions. The scope of the reaction for the selected
transformation was subsequently extended to a range of challenging multi-substituted phenol
derivatives under similar reaction conditions.
Results summarized in Table 4 indicated that despite the low yields achieved in some cases for
highly structurally hindered substrates, some encouraging results (close to 50% conversion in
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some cases) could be obtained in C-H activation with selected phenols, in some cases with high
selectivities to a single product (Table 4, entry 6). Activities obtained with Ag-supported
aluminosilicates were in all cases inferior to those obtained with Fe-containing materials.
The stability and reusability of the catalyst under the investigated microwave conditions was
tested in the reaction between phenol and phenylacetylene. The optimum quantity of the best
performing system (0.05 g Fe 0.5%/AlSBA) was chosen to further evaluate the recyclability of
the catalyst and separated upon reaction completion by simple centrifugation. The recovered
catalyst (2nd use = 0.44 g, 3rd use = 0.40 g, 4th use = 0.36 g) was then washed with cyclohexane
and methanol followed by dichloromethane and dried at 100oC for 4 h.The recycled catalyst
exhibited a good conversion to the corresponding 1,1-diarylalkene under identical conditions in
subsequent runs, losing part of its initial activity after the fourth use (Fe 0.5%/AlSBA;
1st run = 79% conversion; 4th run = 58% conversion).
All results seem to indicate that particularly iron oxide nanoparticles develop an
important Lewis acidity in the materials (both Fe and Ag also develop Bronsted acid sites to
some extent, see Table 1) which is clearly responsible for the significantly improved activity of
Fe-based systems in the selected process. These results are in good agreement with the excelling
C-H activation and alkylation activities of iron oxide nanoparticle-containing materials
previously reported by the group [19, 22-24].
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Table 4.Hydroarylation of phenylacetylene with relevant phenol derivatives.a
Entry
1
Phenol derivatives
Conversion
(mol%)b
16
Selectivities
(mol%)
<5:
OH
60:
35
CH3
OH
CH3
OH
CH3
CH3
CH3
CH3
+
+
CH3
OH
CH3
Re. Time 15.3, 17.8, 21.3
70: 10:
Re.Time 1.2
OH
2
3
4
42
42
24
CH3
20
CH3
CH3
OH
OH
CH3
+
+
H3C
CH3
CH3
OH
CH3
Re. Time 13.7, 15.9, 19.5
60: 15:
Re.Time 1.2
OH
CH3
25
CH3
OH
OH
CH3
CH3
CH3
H3C
+
+
H3C
OH
CH3
Re. Time 13.5, 14.4, 15.4
90: 10
Re.Time 1.1
OH
CH3
H3C
CH3
CH3
OH
OH
CH3
+
CH3
Re. Time 12.6, 13.9
Re.Time 1.05
OH
5
6
18
49
40:
60
CH3
CH3
H3C
CH3
CH3
OH
CH3
OH
+
CH3
CH3
CH3
Re. Time 12.0, 13.9
Re.Time 1.2
OH
CH3
OH
H3C
CH3
H3C
CH3
CH3
Re. Time 16.0
Re.Time 1.1
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aReaction conditions: (1 mmol, 0.109 mL) phenylacetylene, (1.5 mmol) of phenol derivatives, 0.05 g
catalyst, 2 mL cyclohexane, 200 W, Tmax=120 oC, Pmax=240.bGC conversion of phenyl acetylene.60 min
reaction, Re.Time = Retention Times, Retention time [min] for phenol = 3.7. The order in selectivities
corresponds to the order of compounds from below.
Figure 2. Reusability studies of Fe 0.5%/AlSBA in the hydroarylation of phenylacetylene with phenol.
Reaction conditions: 1 mmol (0.109 mL) phenylacetylene, 1.5 mmol (0.141 g) phenol, 50 mg of catalyst,
o
2 mL of cyclohexane, 200 W, Tmax=120 C, Pmax=240, 60 min reaction per run. Selectivity to 1,1-
diarylalkene.
In conclusion, we have developed a range of supported metal nanoparticles on mesoporous
aluminosilicates which have been proved to be highly active and selective in the
microwave-assisted reaction of phenylacetylene with different phenols under mild reaction
conditions. The protocol was found to be amenable to various substrates and the catalysts were
reusable under the investigating conditions, preserving almost 90% of its initial activity after
three uses.
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Acknowledgments
Rafael Luque gratefully acknowledges support from the Spanish MICINN via the concession of
a RyC contract (ref. RYC 2009-04199) and fundingunderprojects P10-FQM-6711 (Consejeria de
Ciencia e Innovacion, Junta de Andalucia) and CTQ2011-28954-C02-02 (MICINN).
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Graphical Abstract
Efficient aromatic C-H bond activation using aluminosilicate-supported metal
nanoparticles
Reza Hosseinpour, Antonio Pineda, Angel Garcia, Antonio A. Romero, Rafael Luque*
O
OH
OH
M-Al-SBA-15
+
+
H
Cyclohexane
M.W, T = 120 oC
10-60 min
R
R
Major product
1,1-diarylsubstitued alkene
M = Fe, Ag
23-79 % conversion
53-78 % selectivity
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HIGHLIGHTS
Mechanochemically synthesized nanomaterials
Low loaded iron oxide and silver supported nanoparticles on aluminosilicates
High catalytic activities in the hydroarylation of phenylacetylene with phenols
Stable and highly reusable materials under microwave irradiation
17