MOF-5/n-Bu4NBr: An efficient catalyst system for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions

Article abstract of DOI:10.1039/b902550b

The development of efficient heterogeneous catalysts for the cycloaddition of CO₂ with epoxides to produce five-membered cyclic carbonates under mild reaction conditions is of great importance. In this work, the coupling reaction of CO₂

Full text of DOI:10.1039/b902550b

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www.rsc.org/greenchem | Green Chemistry
MOF-5/n-Bu NBr: an efficient catalyst system for the synthesis of cyclic
4
carbonates from epoxides and CO under mild conditions†
2
Jinliang Song, Zhaofu Zhang, Suqin Hu, Tianbin Wu, Tao Jiang and Buxing Han*
Received 6th February 2009, Accepted 7th April 2009
First published as an Advance Article on the web 20th April 2009
DOI: 10.1039/b902550b
The development of efficient heterogeneous catalysts for the cycloaddition of CO
to produce five-membered cyclic carbonates under mild reaction conditions is of great importance.
In this work, the coupling reaction of CO with propylene oxide (PO) to produce propylene
carbonate (PC) catalyzed by MOF-5 (metal-organic frameworks) in the presence of quaternary
ammonium salts (Me NCl, Me NBr, Et NBr, n-Pr NBr, n-Bu NBr) was studied in different
conditions. It was discovered that MOF-5 and quaternary ammonium salts had excellent
2
with epoxides
2
4
4
4
4
4
synergetic effect in promoting the reaction, and the MOF-5/n-Bu
most efficient among them. The optimal temperature for the reaction was around 50 C. The
4
NBr catalytic system was the
◦
reaction could be completed in 6 h at low CO
yield of PC was not noticeable after MOF-5 was reused three times, indicating that the MOF-5
was stable. The MOF-5/n-Bu NBr catalytic system was also very active and selective for the
cycloaddition of CO with other epoxides, such as glycidyl phenyl ether, epichlorohydrin and
styrene oxide. The mechanism for the coupling reaction is also discussed.
2
pressure with very high selectivity. A decrease of the
4
2
1
8
19
Introduction
nanoparticles supported on resins, functional polymers, ion-
20
exchange resins and SiO
2
modified by quaternary ammonium
or phosphonium salts. Although heterogeneous catalysts solve
the problem of catalyst separation, most of them are active only
at high reaction temperatures (>100 C), which increases the
cost of the reaction processes. In addition, many of them need
co-solvents.
In recent years, metal-organic frameworks (MOFs), which
are formed by copolymerization of organic molecules with
metal ions or metal ion clusters, have received much attention
because of their zeolite-like properties, such as high internal
surface area and microporosity, well-ordered porous structures
and high absorption capacity. Various applications, including
gas storage, separation, magnetism and catalysis, have
been studied for the porous metal-organic frameworks. Among
these applications, using MOFs as catalysts is very attractive.
Some reactions using MOFs as catalysts have been conducted,
such as the Knoevenagel condensation reaction, Friedel–
Crafts type reaction, cyanosilylation of carbonyl compounds
and imines, isomerization, acetalization, ZnEt
to aldehydes, tetralin oxidation, aldol reaction, asym-
metric olefin epoxidation, oxidation of sulfides, asymmet-
ric hydrogenation of b-keto esters and aromatic ketones,
transesterification and photochemical reactions. In addition,
Pb supported on MOFs has been used as an effective hydro-
Carbon dioxide (CO
other hand, as a cheap, nontoxic, nonflammable and abundant
2
) is the main greenhouse gas. On the
21
C1 building block, CO
2
can be converted into many useful
◦
1
2
3
chemicals, such as dimethyl carbonate, cyclic carbonates,
4
5
6
N,N¢-disubstituted ureas, urethanes, formic acid, and so on.
In particular, five-membered cyclic carbonates derived from
the coupling reactions of CO with epoxides are promising
2
target molecules. The cyclic carbonates can be widely used
as precursors for producing polycarbonates and many fine
22
7
chemicals. Various catalysts, including homogeneous and het-
erogeneous catalysts, have been developed for the cycloaddition
of CO
2
and epoxides. Homogeneous catalysts include qua-
23
24
25
26
8
9
10
ternary ammonium and phosphonium salts, ionic liquids,
alkali metal salts, Schiff bases, salenCr(III) complexes,
salenCo(III)X complexes, Cr(III) porphyrin complexes, sale-
1
1
12
13
14
15
1
6
nAl(III) complexes, and so on. Generally, these homogeneous
catalysts are effective, and some transition metal complexes are
27
28
29
13–16
active
at mild temperatures in the presence of co-catalysts.
30
31
32
2
additions
But the separation of the catalysts from the products is difficult,
which limits the wide application of these catalysts.
In order to overcome the separation problem, many het-
erogeneous catalysts have been developed for coupling re-
33
34
35
36
37
38
39
40
41
17
actions of CO with epoxides, such as metal oxide, gold
2
42
genation catalyst.
As discussed above, many catalysts have been developed for
the coupling reaction of CO and epoxides. However, it is
still very interesting and challenging to develop heterogeneous
catalysts that are efficient under mild reaction conditions. In this
work, we conducted the reactions using MOF-5 [Zn
(BDC = benzene-1,4-dicarboxylate)], which was copolymerized
Beijing National Laboratory for Molecular Sciences (BNLMS), Centre
for Molecular Science, Institute of Chemistry, Chinese Academy of
Sciences, Beijing, 100190, China. E-mail: hanbx@iccas.ac.cn;
Fax: +86-10-62562821
2
†
Electronic supplementary information (ESI) available: X-Ray diffrac-
tion pattern, thermogram and FTIR spectrum of MOF-5. See DOI:
0.1039/b902550b
4
O(BDC)
3
1
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a
by a Zn
4
O cluster with BDC through octahedral arrays
2
Table 1 Coupling of CO and PO catalyzed by different catalysts
43
(
Scheme 1), as the heterogeneous catalyst in the presence of
c
Entry
Catalyst
Ammonium salts
None
Yield (%)
quaternary ammonium salts. It was found that the coupling
reactions could be effectively carried out at mild temperature
and low CO
inexpensive, stable, and could be easily separated and reused.
The possible catalytic mechanism is also discussed. As far as
we know, this is the first work to conduct the coupling reactions
using MOF-5 as a heterogeneous catalyst under mild conditions.
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
MOF-5
MOF-5
MOF-5
MOF-5
MOF-5
0.1
0.1
2
pressure. The catalyst was very active, selective,
Me
Me
4
NCl
NBr
4
0.25
27.1
60.2
97.6
95.2
53.7
6.5
Et
4
NBr
NBr
n-Pr
4
MOF-5
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
4
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
b
ZnCl
2
4
4
4
4
4
4
4
4
4
b
ZnO
b
BDC
1
1
1
1
1
1
None
7.2
d
e
f
MOF-5
MOF-5
MOF-5
MOF-5 (2nd)
MOF-5 (3rd)
13.9
77.6
94.5
96
96
a
Typical reaction conditions: a stainless reactor of 22 ml, 20 mmol
pressure 6
MPa, reaction temperature 50 C, reaction time 4 h. The amount of
PO with 2.5 mol% ammonium salts, 0.1 g MOF-5, CO
2
◦
b
c
ZnCl
2
, ZnO and BDC was 0.1 g. The yields were determined by GC
d
e
with an internal standard. 0.63 mol% n-Bu
n-Bu
4
NBr was used. 1.25 mol%
4
NBr was used.
f
4
NBr was used. 1.88 mol% n-Bu
the yield of PC was very low (7.2% and 6.5%, respectively)
entries 9 and 10), indicating that MOF-5 was necessary for the
reaction. Interestingly, the activity of MOF-5/n-Bu NBr was
similar to that of ZnCl /n-Bu NBr, which is a homogeneous
(
Scheme 1 The structure of the MOF-5 framework.
4
2
4
46
catalyst system for the reaction reported previously. One of the
reasons for the high catalytic activity of MOF-5 is that it is a
Results and discussion
44
porous material and has high surface area, which is favorable
for the access of reactants and ammonium salts to the active
Catalyst characterization
sites (Zn
amount of n-Bu
Increasing the amount of n-Bu
could enhance the yield of PC significantly (entries 6, 11–13).
The reusability of MOF-5 was also studied at the same
experimental conditions of entry 6 and the results are also
presented in Table 1 (entries 14, 15). It is obvious that a decrease
of the activity of the catalyst was not noticeable after being used
three times. It can be seen from the thermogram in Fig. S2 that
4
O) of MOF-5. At the same time, we found that the
NBr also had a great influence on the reaction.
NBr from 0.63 mol% to 2.5 mol%
The X-ray diffraction pattern, thermogram and FTIR spectrum
of the MOF-5 prepared in this work are given in the ESI†
4
4
(
Fig. S1–S3), which agree well with the results reported by other
44
authors.
Reaction with different catalysts
The activity of various catalysts was tested at 50 C and 6 MPa
◦
using the reaction of propylene oxide (PO) and CO to produce
2
◦
propylene carbonate (PC), and the results are summarized in
Table 1. It can be seen from Table 1 that the activity of MOF-5 de-
pends strongly on the ammonium salts used. Nearly no product
was detected without ammonium salts (entry 1). The catalyst was
active in the presence of quaternary ammonium salts, and the
yield of PC increased with an increasing length of the alkyl chain
MOF-5 began to decompose after 380 C, which is much higher
than the temperature used in this work. This provides partial
support for the good stability of the catalyst.
Effect of the CO
2
pressure on the PC yield
of the ammonium salts (entries 2–6), and n-Bu NBr was the most
4
The partition behavior of the substrates between phases may
affect the reaction rate of a biphasic reaction system. The
47
effective. This could partially result from the structures of the
quaternary ammonium ions, which probably affect the behavior
effect of the CO
5 and n-BuN
2
pressure on the catalytic activity of MOF-
Br was studied at 50 C in a pressure range of
45
◦
of the anions. The size of quaternary ammonium ions increases
4
+
+
+
+
in the following order: Me
4
N < Et
4
N < n-Pr
4
N < n-Bu
4
N .
0.4–12 MPa (total pressure of PO and CO ), and the results
2
Indeed, the bulkiness of quaternary ammonium ions forces the
bromide away from the cation. Therefore, the activity order
are shown in Fig. 1. The PC yield increased with pressure in
the range of 0.4–1.0 MPa, and remained nearly unchanged
with pressure in the range of 1.0–6.0 MPa. However, the yield
decreased as the pressure changed from 6 to 12 MPa. This
can be explained qualitatively by the effect of the pressure on
of the quaternary ammonium salts was Me
n-Pr NBr < n-Bu NBr. The solubility of quaternary ammonium
salts in the PO phase may be another reason. Our experiments
in this work showed that n-Bu NBr had the best solubility in
PO. Some other catalysts were also tested in the presence of
n-Bu NBr (entries 7–10). When the catalyst MOF-5 was not used
or benzene-1,4-dicarboxylic acid (BDC) was used as catalyst,
4
NBr < Et
4
NBr <
4
4
4
the concentrations of CO
2
and epoxides in the two phases. In
this work, it was observed that there were two phases in the
48
4
reaction system by using a view cell reported previously. The
upper phase was the vapor phase and the bottom phase was
1
032 | Green Chem., 2009, 11, 1031–1036
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Effect of the reaction temperature
Fig. 3 shows the effect of the temperature on the cycloaddition
reaction catalyzed by MOF-5 in the presence of n-Bu
4
NBr at
◦
0
.4 MPa in the temperature range of 30–70 C, with a reaction
◦
time of 4 h. At a temperature higher than 60 C, nearly all of the
PO could be converted into PC. The yield of PC decreased with
decreasing the temperature below 60 C. The figure illustrates
◦
◦
that the yield was 57% at 30 C with a reaction time of 4 h. Our
experiment also showed that the reaction could go to completion
after 11 h at this temperature.
Fig. 1 Effect of the CO
2
pressure on the PC yield. Reaction conditions:
Br, 0.1 g MOF-5, reaction
2
0 mmol PO with 2.5 mol% n-BuN
4
◦
temperature 50 C, reaction time 4 h.
the liquid phase. The reactions took place mainly in the liquid
phase because the catalyst was dispersed in this phase. In our
system, the pressure of CO
ways. First, the solubility of CO
pressure, which favoured the reaction considering that CO
a reactant. Second, the solvent power of CO to extract the
reactant increases with increasing CO pressure. In other words,
the amount of PO in the vapor becomes larger as the pressure
rises, which reduces the reaction rate. When the pressure was
very low, the yield increased as the pressure rose, indicating that
the first factor was dominant. The two factors compensated
each other in the pressure range of 1.0–6.0 MPa and the effect
of pressure on the yield was negligible. When the pressure was
higher than 6.0 MPa, the second factor became dominant and
the yield decreased with the increasing pressure.
2
affects the reaction in two opposite
in PO increases with increasing
was
2
2
2
2
Fig. 3 Effect of the reaction temperature on the PC yield. Reaction
conditions: 20 mmol PO with 2.5 mol% n-BuN Br, 0.1 g MOF-5, total
4
pressure 0.4 MPa, reaction time 4 h.
Other substrates
The coupling reactions of CO
(Scheme 2) catalyzed by MOF-5/n-Bu
2
with different epoxides
NBr were also studied,
4
The yield of PC at 0.4 MPa could reach 93% at a reaction time
of 4 h, as shown in Fig. 1. The PC yield could reach 98% when
the reaction time was prolonged to 6 h (Fig. 2). In addition, we
also conducted the reaction at 0.2 MPa and a PC yield of 95%
was obtained with a reaction time of 6.0 h, indicating that the
reaction can be conducted effectively at mild conditions.
and the results are summarized in Table 2. The data in the table
show that the catalytic system could convert all epoxides studied
to the corresponding cyclic carbonates effectively under mild
conditions. The reaction for 1b was also conducted at 6 MPa
because the reaction mixture became solid at 0.1 MPa after the
Table 2 Various carbonates synthesis catalyzed by MOF-5 in the
a
4
presence of n-Bu NBr
Entry Epoxides
1
Products
Time/h Yield (%)
3
4
56
97
b
2
3
4
12
15
93
92
Fig. 2 The influence of the reaction time on the PC yield. Reaction
conditions: 20 mmol PO with 2.5 mol% n-BuN
4
Br, 0.1 g MOF-5, total
◦
pressure 0.4 MPa, reaction temperature 50 C.
Influence of the reaction time
The influence of reaction time on the PC yield is shown in Fig. 2.
The reaction was conducted at 50 C and 0.4 MPa of total
pressure. The yield of PC increased with increasing time at the
beginning and approached 100% after a reaction time of 6 h.
a
◦
Reaction conditions: epoxide 20 mmol with 2.5 mol% n-Bu NBr, 0.1 g
4
◦
b
MOF-5, CO
pressure 6 MPa.
2
pressure 0.1 MPa, reaction temperature 50 C. CO
2
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CO
n-Bu
n-Bu
2
in the presence of catalytic amounts of MOF-5 and
NBr without using any organic solvent. In the MOF-5/
4
4
NBr catalytic system, MOF-5 and n-Bu NBr show ex-
4
cellent synergetic effect to catalyze the reactions. After easy
separation, the MOF-5 can be reused and a decrease in activity
and selectivity is not noticeable after being used three times. The
greener, inexpensive, active, selective and stable catalytic system
has potential applications for synthesizing cyclic carbonates
2
Scheme 2 Coupling of CO with different epoxides.
from CO and epoxides.
2
yield exceeded 56%. The reaction mixture was always liquid at
MPa because, as is well known, CO can reduce the melting
point of organic compounds.
6
2
Experimental
Materials
Reaction mechanism
CO
with a purity of 99.99%. Propylene oxide, epichlorohydrin,
Zn(NO O, n-Bu NBr, Me NCl and triethylamine were
)·6H
A. R. grade. Me NBr, Et NBr andbenzene-1,4-dicarboxylic acid
were C. P. grade. All the chemicals above were purchased from
Beijing Chemical Reagents Company. n-Pr NBr was A. R. grade
2
was supplied by Beijing Analytical Instrument Factory
We proposed a plausible mechanism for this chemical fixation
reaction (Scheme 3), which is similar to that of the homogenous
catalytic system with salenCo(III)X complexes as catalysts and
quaternary ammonium salts as co-catalysts. The coupling
reaction is initiated by coordination of the Zn O clusters in
3
2
4
4
4
4
14
4
4
and provided by Aldrich Chemical Company. Other epoxides
were purchased from Acros Organics. All chemicals were used
as received.
MOF-5 as a Lewis acidic site with the oxygen atom of the
epoxide, and this step can activate the epoxy ring. Secondly, the
-
Br generated from n-BuN
4
Br attacks the less-hindered carbon
atom of the coordinated epoxides, followed by the ring opening
step. Then, the oxygen anion of the opened epoxy ring interacts
Preparation and characterization of MOF-5
with the CO and this can form an alkylcarbonate anion, which is
converted into the corresponding cyclic carbonate through the
ring closing step. Meanwhile, the catalyst is regenerated. The
2
The procedure to prepare MOF-5 was similar to that re-
44
ported previously. Zn(NO
3
)·6H
2
O (1.21 g, 4 mmol), benzene-
1
,4-dicarboxylic acid (0.32 g, 2 mmol) and 40 ml N,N-
synergistic effect of MOF-5 and n-BuN Br is the main reason
4
dimethylformamide were added into a 100 ml flask equipped
for the high catalytic activity of the catalyst system under mild
conditions.
with a magnetic stirrer. The flask was put into an oil bath at
◦
6
0 C. Then, triethylamine (1.6 g) was added into the mixture.
◦
The mixture was maintained at 60 C for 4 h with stirring. The
metal-organic frameworks (MOF-5) formed was collected by
filtration and washed using N,N-dimethylformamide, and then
◦
was dried at 60 C for 12 h under vacuum.
Thermogravimetric analysis of MOF-5 was performed on a
NETZSCH STA 409 PC/PG thermogravimetric analysis system
◦
in N
2
atmosphere at a heating rate of 20 C per min. The
X-ray diffraction (XRD) patterns were collected on an X-ray
diffractometer (D/MAX-RC) operated at 40 kV and 200 mA
with Cu Ka radiation. FTIR spectra were obtained using a
Bruker Tensor 27 spectrometer, and the sample was prepared by
the KBr pellet method.
Typical procedures for the cycloadditions
All the cycloaddition reactions were conducted in a 22 ml
stainless steel reactor equipped with a magnetic stirrer. We
describe the procedure for the cycloaddition of propylene oxide
(PO) because the procedure for the reactions of other epoxides
was similar. In the experiment, MOF-5 (0.1 g), PO (20 mmol)
and desired amounts of quaternary ammonium salts were added
into the reactor. After sealing, the reactor was put into a
Scheme 3 The plausible reaction mechanism for the cycloaddition of
CO
2
4
with epoxides catalyzed by MOF-5 and n-Bu NBr.
constant-temperature air bath at a desired temperature. CO
2
was then charged into the reactor until the desired pressure
was reached, and the stirrer was started. After a certain time,
Conclusions
the reactor was placed into ice water and CO
slowly passing through a cold trap containing ethyl acetate to
absorb trace amounts of reactant and product entrained by CO
2
was released
We found that cyclic carbonates can be produced under mild
conditions in high yield from the reaction of epoxides with
2
.
1
034 | Green Chem., 2009, 11, 1031–1036
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After depressurization, the ethyl acetate in the cold trap and the
internal standard n-butanol were added into the reactor. The
reaction mixture was analyzed by a GC spectrometer (Agilent
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2
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of other epoxides were analyzed at room temperature on a
1
Bruker 400 MHz H NMR spectrometer using CDCl
3
as the
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solvent. In the experiments to test the reusability of MOF-5, the
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dimethylformamide and ethyl ether, respectively. After drying
1
1
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under vacuum for 12 h at 60 C, the catalyst was reused
1
1498.
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4
1
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4
-phenyloxymethyl-1,3-dioxolan-2-one
(2b).
H
NMR
(
CDCl
3
, 400 MHz) d (ppm) 4.16 (dd, J = 3.5, 10.5 Hz, 1H),
1
1
1
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4
2
.24 (dd, J = 4.4, 10.5 Hz, 1H), 4.54 (dd, J = 6.0, 8.4 Hz, 1H),
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H), 7.02 (t, J = 7.4 Hz, 1H), 7.31 (t, J = 8.2 Hz, 2H).
1
4
-chloromethyl-1,3-dioxolan-2-one (2c). H NMR (CDCl
3
,
4
00 MHz) d (ppm) 3.75 (dd, J = 3.6, 12.3 Hz, 1H), 3.84 (dd,
2
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.4 Hz, 1H), 5.00–5.06 (m, 1H).
1
4
-phenyl-1,3-dioxolan-2-one (2d).
H
NMR (CDCl ,
3
2
4
00 MHz) d (ppm) 4.34 (t, J = 8.2 Hz, 1H), 4.80 (t, J = 8.4 Hz,
(
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Acknowledgements
This work was supported by the National Key Basic Research
Project of China (2006CB202504) and the Chinese Academy of
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