Synthesis of β-nitrostyrenes in the presence of sulfated zirconia and secondary amines

Article abstract of DOI:10.1039/c5ra17168g

A simple and efficient protocol for the synthesis of β-nitrostyrenes has been achieved by the use of sulfated zirconia-secondary amine (piperidine, pyrrolidine, proline or prolinol) cooperative systems. The condensation of different aldehydes and nitromethane demonstrates the efficiency of this process, which does not require high-temperature reactivation for the reuse of the catalytic material.

Full text of DOI:10.1039/c5ra17168g

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Carrillo, V. H. Lara and J. A. Morales-Serna, RSC Adv., 2015, DOI: 10.1039/C5RA17168G.
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Synthesis of β-nitrostyrenes in the Presence of Sulfated Zirconia
and Secondary Amines
Received 00th January 20xx,
Accepted 00th January 20xx
a
b
a*
a
R. González-Olvera, B. I. Vergara-Arenas, G. E. Negrón-Silva, D. Angeles-Beltrán, L. Lomas-
b*
b
b
b
Romero, A. Gutiérrez-Carrillo, V. H. Lara, J. A. Morales-Serna.
DOI: 10.1039/x0xx00000x
A simple and efficient protocol for the synthesis of β-nitrostyrenes has been achieved by the use of sulfated zirconia-
secondary amine (piperidine, pyrrolidine, proline or prolinol) cooperative systems. The condensation of different
aldehydes and nitromethane demonstrates the efficiency of this process, which does not require high-temperature
www.rsc.org/
reactivation
for
the
reuse
of
the
catalytic
material.
1
7
different functional groups.
1
The preparation of β-
8
Introduction
nitrostyrenes
catalysts, such as amino-functionalized MIL-101, nickel
has been achieved using heterogeneous
9
1
2
-
1
4 2
Sulfated zirconia (SO /ZrO , SZ) is a solid super acid that can
2
hydroxyapatite, amino-functionalized silicas, amine-MCM-
0
21
exist in four crystalline forms: orthorhombic, cubic, tetragonal
and monoclinic, depending on the sulfation process and
2
2
23
4
1,
diamino-functionalized FDU-mesoporous polymers,
2
4
25
2
activation temperature. The acidic property of the material
Envirocat EPZG, and zeolites. In this work, we choose to use
SZ in the tetragonal phase to generate a cooperative system
that allows us to obtain β-nitrostyrenes via the activation of an
aldehyde and nitromethane due to the Brønsted and Lewis
acid sites present in the material.
3
(Ho ≤–14) has been used to catalyse diverse organic reactions
for which the crystal structure was determined to be crucial
4
for obtaining excellent results. The most of the processes
described in the literature have focused on the use of
5
monoclinic and tetragonal catalysts that show high activities,
6
owing to their Brønsted and Lewis acid sites. The thermally
Results and discussion
driven transformation of the tetragonal phase to the
7
monoclinic phase leads to structural modifications that
First, we evaluated the ability of the tetragonal phase SZ
(
for full characterization, see ESI†) to catalyse the
change a solid containing Brønsted and Lewis acids to a solid
containing Lewis acids only; it also presents an opportunity to
apply this material to different processes, depending on the
condensation reaction between p-tolualdehyde 1a and
nitromethane using microwave heating. The model reaction
was carried out at 110 °C in toluene for 30 minutes. Under
these reaction conditions, the desired product 2a was not
obtained (Table 1, entry 1). However, when the reaction was
performed in the presence of SZ and piperidine as catalysts,
the corresponding β-nitrostyrene 2a was obtained in 85% yield
8
nature of the catalysis.
With these features in mind, our study focuses on the
effect of the crystalline structure of SZ in a condensation
process, namely, the Henry reaction, which involves the
condensation of an aldehyde with nitromethane to produce β-
nitrostyrenes. These organic compounds are useful and
(
Table 1, entry 2). This result contrasts with the yield obtained
when only piperidine was used as a catalyst (40% yield, Table
, entry 3). To evaluate other secondary amines and optimize
9
versatile building blocks that are generally used as starting
10
1
materials for the heterocyclic synthesis of compounds such
14
1
1
12
13
as pyrroles, pyrazoles, 1,2,3-triazoles, nitrochromenes,
the catalytic SZ/amine system, the reaction was performed in
the presence of pyrrolidine, proline, prolinol, morpholine and
diisopropylamine. As shown in Table 1 (entries 4 and 5), an
excellent yield was obtained using pyrrolidine and proline (90%
and 95% yield, respectively). The use of prolinol led to a β-
nitrostyrene 2a yield of 80%, while in the presence of
morpholine, the yield decreased significantly (Table 1, entry 7).
The product was not obtained when the reaction was carried
out using the SZ/diisopropylamine system. It is important to
note that the use of minor SZ concentration is reflected in the
decrease in the reaction yield.
1
5
and allylic alcohols. Furthermore, owing to the presence of a
double bond, β-nitrostyrenes are used in asymmetric
1
synthesis, and the versatile nitro group is used to obtain
6
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Based on the optimized conditions of the condensation acid catalysis takes place. To demonstrate that the monoclinic
process, the scope of the reaction with different aldehydes structure will be able to catalyse the organic reaction, the
was studied using the SZ/piperidine system (Table 2). Thus, a condensation of p-tolualdehyde 1a and nitromethane was
variety of aromatic aldehydes with various types of tested in the presence of SZ with the aforementioned
substituents underwent the reaction, leading to moderate to structure, and β-nitrostyrene was obtained in 60% yield,
good yields of the desired products 2a-m in short reaction confirming that both crystal structures can participate in the
times. The aldehydes with electron-donating groups provided reaction process.
good yields (Table 2, entries 1-4). The same trend was
observed in aldehydes with electron-withdrawing groups, with
the products 2h-2l obtained in 70-85% yield (except for 2k).
The SZ-piperidine system was also efficient for reactions of 6-
bromopiperonal and benzaldehyde, which produced the
a
Table 2. Synthesis of β-nitrostyrenes catalysed by SZ-piperidine
O
SZ (50 mg)
Amine (10 mol%)
NO2
R
H
+
CH
NO
R
3
2
Toluene
MW (30 W), 110 °C
1
b-m
2b-m
corresponding β-nitrostyrenes 2f-2g in 65%, and 70% yield,
respectively (Table 2, entries 5 and 6). Heteroaromatic
aldehyde 1m was also shown to be a good substrate to yield
the product 2m in 90% yield (Table 2, entry 12). The behaviour
of SZ-proline catalytic system during the synthesis of the same
group of β-nitrostyrenes was also evaluated. In that case, the
reactions proceeded with moderate yields with a methoxy
substituent in the aromatic ring (Table 2, entries 1-4). The
reaction did not evolve the desired product with electron-
withdrawing groups (Table 2, entries 7-11). Using
heteroaromatic aldehyde, excellent reaction yields were again
obtained (Table 2, entry 12). The use of SZ/pyrrolidine system
was abandoned because the purification on the
chromatographic column was complicated, owing to a complex
reaction mixture.
b
Entry
R
Product
Yield (%)
c
d
Pyrrolidine
Proline
50
1
2
3
4
5
3-MeOC
6
H
4
2b
2c
2d
2e
2f
85
75
60
75
65
4-MeOC6H4
3,4-(MeO)
3,4,5-(MeO)
70
2
C
6
H
3
65
3
C
6
H
2
70
50
6
7
8
9
Ph
2g
2h
2i
70
85
75
45
n.r.
n.r.
n.r.
n.r.
n.r.
65
2-BrC
4-BrC
6
6
H
4
H
4
d
4-ClC
6
H
4
2j
80
1
0
2-NO
4-NO
2
2
C
6
6
H
4
4
2k
2l
40
70
90
a
Table 1. Screening of catalysts and the optimization of reaction conditions
11
C
H
1
2
2m
O
SZ (50 mg)
Amine (10 mol%)
NO
2
H
+
CH
3 2
NO
Toluene
a
Me
MW (30 W), 110 °C Me
30 min.
Reagents: Aldehyde (1 mmol), nitromethane (3 mmol), piperidine (0.1 mmol), SZ
1
a
2a
b
(
50 mg), and toluene (1 mL). Yield of isolated product after chromatographic
c
d
b
purification. 30 minutes were necessary for the reaction. 4 h were necessary
for the reaction.
Entry
Amine
-
Yield (%)
n.r.
85
1
2
Piperidine
Piperidine
Pyrrolidine
Proline
c
3
40
4
5
6
7
8
90
95
Prolinol
Morpholine
80
40
Diisopropylamine
n.r.
a
Reagents: Aldehyde 1a (1 mmol), nitromethane (3 mmol), piperidine (0.1 mmol),
b
SZ (50 mg), and toluene (1 mL). Yield of isolated product after chromatographic
c
purification. The reaction was performed without SZ.
An analysis of SZ after the organic reaction demonstrates
that the tetragonal phase is the major crystalline structure.
However, it is also possible to identify the formation of the
monoclinic phase (Figure 1). The monoclinic phase content
increases with the number of reuses of the material without
affecting the yield of the organic reaction. The maximum
phase transformation was found after the fourth reuse (Figure
Fig. 1 SZ Powder X-ray diffraction patterns of sulphated zirconia as synthesised and
1). This behaviour leads us to believe that both crystalline
recovered in four cycles
structures participate in the reaction via their respective acid
sites. For the tetragonal phase, Lewis and Brønsted acid
catalysis is possible, while in the monoclinic phase, only Lewis
2
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cases (85%), implying that it is not necessary to use high
temperatures to reactivate the catalyst in this catalytic
process. The reaction yield decreased to 80% during the tenth
run for the material dried at 100 °C. If this material was
calcined at 500 °C under O
2
atmosphere, the yield increased to
8
5% (Figure 3). These results suggest that the reduced activity
of the catalysts during the tenth run is likely due to the
presence of organic material on the surface area; this material
is eliminated during the calcination process.
Table 4. The nitrogen adsorption–desorption analysis parameters of materials
Entry
1
Parameters
Synthesised SZ
90.75
Recovered SZ
86.15
S
BET
-1
2
(
m ·g )
Fig. 2 FT-IR spectra of SZ after pyridine desorption at different temperatures: a) dark
2
3
Pore volume
0.12
0.089
41.62
blue 50 °C, purple 100 °C, turquoise 200 °C, green 300 °C and red 400 °C.
3
-1
(cm ·g )
Pore size (Å)
52.73
The identification of the Brønsted and Lewis acid sites
present in synthesised SZ was achieved by FT-IR spectra, which
exhibited the characteristic bands of pyridinium ion at 1600,
-
1
1
540 and 1490 cm (Brønsted acid sites), and pyridine
-1
coordinated over Lewis acid sites at 1490 and 1445 cm
(Figure 2). The concentration of both types of acid sites could
be estimated from the intensities of the bands at 1540 and
-
1
1
445 cm . Those results indicated a major concentration of
Lewis acid sites (Table 3).
Table 3. Concentration of acid sites as calculated after pyridine desorption at different
temperatures
Entry
Temperature
Brønsted
Lewis
Total
B/L
-
1
-1
°C
µmolg
101
69
µmolg
179
94
Ratio
0.564
0.734
0.634
0.518
1
2
3
4
50
280
143
85
100
200
300
33
52
14
27
41
Fig. 3 Reuse of SZ dried at 100 °C and calcined at 500 °C
It is known that the monoclinic phase can be formed during
2
6
the reactivation process of material; however, in this case
where there is no reaction process, the monoclinic phase is
formed during the reaction as a consequence of the
adsorption of oxygen onto defectives sites of the SZ, as
The importance of SZ in the catalytic process is
demonstrated by the yield of the reaction carried out without
the SZ material (40%, Table 1, entry 3). Based on this result
and other studies reported in literature, in which piperidine
5
b,26
previously described.
Owing to the X-ray analysis of the
27
participated in cooperative catalysis, a putative reaction
different SZ samples after the reaction and without the use of
a reactivation process, it was possible to detect the presence
of the monoclinic phase in the material (Figure 1).
mechanism is shown in Scheme 1. The first step involves the
interaction of SZ and the aldehyde to yield an activated
intermediate,
I (immobilised at the solid/liquid interface),
2
Adsorption of N (BET method) was used to quantify and
which reacts with piperidine to yield the iminium ion II. The
27-28
reaction then proceeds as previously described:
compare the surface area and pore size of synthesised and
reused (four times) SZ. The recovered sample revealed lower
porosity and surface area than the synthesised material (Table
intermediate III is formed by reaction II with nitromethane,
followed by elimination of the secondary amine in III, also
4). It is noteworthy that, the structural change in the
catalysed by SZ, leading to the formation of b-nitrostyrene 2g
.
recovered sample, does not affect the efficiency of material in
the catalysis of the organic reaction.
In this putative reaction mechanism, it is considered that
the piperidene is not adsorbed on the SZ surface. If that
interaction were to occur, the catalytic activity of the
secondary amine could be inhibited as consequence of
neutralization process between a base and acid. It is true that
the interaction of SZ surface with amines is possible under
special conditions – a common method to determine the acid
For the reuse of material, two different reactivation
procedures were used. In the first, the material was calcined at
5
00 °C under O
procedure, the material was only dried at 100 °C in an oven for
2 h. To our delight, the reaction yield is the same in both
2
atmosphere during 3 h. In the second
1
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sites in SZ (see ESI†) – however in this case the interaction the distinction of their membership and the stipend received.
between SZ and starting materials, aldehyde and BIVA is grateful to CONACyT for her student fellowship.
nitromethane, is faster than the interaction between the
secondary amine and SZ. For these reasons, we consider that
Notes and references
the secondary amine is acting as a homogeneous component.
Moreover, it is known that under neutral conditions, the
equilibrium constant of the formation of nitronic acid from
1
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nitromethane is very small. However, under acidic conditions
(
SZ), this equilibrium can be shifted to the formation of the
3
0
nitronic acid,
owing to the acid sites of material. These
3
4
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O
I
O
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SZ
H
NO
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SZ
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g
N
H
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II
N
NO
2
H
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O
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a
7
cooperative catalysis by employing sulfated zirconia with
secondary amines that directly influence the condensation
process between an aldehyde and nitromethane (Henry
reaction). Brønsted and Lewis catalytic acid sites present in the
material allowed for the direct activation of carbonyl groups by
the formation of an iminium ion. At the same time, SZ allows
for the formation of nitronic acid, which is the C-C bond
precursor. The efficiency and operational simplicity of this
protocol was demonstrated by the reuse of the material (ten
times) with very good yields, without the requirement of
reactivation at high temperatures.
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DOI: 10.1039/C5RA17168G
Synthesis of β-nitrostyrenes in the Presence of Sulfated Zirconia and
Secondary Amines
R. GonzálezꢀOlvera, B. I. VergaraꢀArenas, G. E. NegrónꢀSilva, D. AngelesꢀBeltrán,
L. LomasꢀRomero, A. GutiérrezꢀCarrillo, V. H. Lara, J. A. MoralesꢀSerna.
A simple and efficient protocol for the synthesis of βꢀnitrostyrenes has been achieved
by the use of sulfated zirconiaꢀsecondary amine cooperative systems.
Sulfated Zirconia
O
Secondary Amine
10 mol%)
(
NO2
0-95%
R
H +
R
CH NO2
3
Toluene
MW (30 W), 110 °C,
4
30 minutes