A Thermomorphic Polyethylene-Supported Imidazolium Salt for the Fixation of CO2 into Cyclic Carbonates

Article abstract of DOI:10.1002/adsc.202000032

An imidazolium catalyst supported on thermomorphic polyethylene (PE) was prepared from 1-methylimidazole and polyethylene iodide (PE?I). The catalyst was characterized by ¹H and ¹³C NMR, SEC and MALDI-ToF mass spectrometry. Its catalytic activity was evaluated in the ring-opening of epoxides with carbon dioxide to give cyclic carbonates under solvent-free conditions. The catalyst proved to be active at low catalyst loading (down to 0.1 mol%) and allows the reaction to occur at low CO₂ pressure (1–5 bar) and moderate temperature (100 °C). A range of terminal and internal epoxides was converted to the corresponding cyclic carbonates with high yields and selectivities. The recyclability of the catalyst was studied and no significant loss of activity was observed after 5 runs. (Figure presented.).

Full text of DOI:10.1002/adsc.202000032

Title: A Thermomorphic Polyethylene-Supported Imidazolium Salt for
the Fixation of CO2 into Cyclic Carbonates
Authors: Kévin Grollier, Nam Duc Vu, Killian Onida, Ayman Akhdar,
Sebastien Norsic, Franck D'Agosto, Christophe Boisson, and
Nicolas Duguet
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000032
Link to VoR: http://dx.doi.org/10.1002/adsc.202000032

Advanced Synthesis & Catalysis
10.1002/adsc.202000032
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
A Thermomorphic Polyethylene-Supported Imidazolium Salt
for the Fixation of CO into Cyclic Carbonates
2
a
a
a
a
b
Kevin Grollier, Nam Duc Vu, Killian Onida, Ayman Akhdar, Sébastien Norsic,
b
b
a,
Franck D’Agosto, Christophe Boisson, and Nicolas Duguet *
a
Université de Lyon, Université Claude Bernard Lyon 1, CNRS, INSA-Lyon, CPE-Lyon, Institut de Chimie et Biochimie
Moléculaires et Supramoléculaires, ICBMS, UMR 5246, Equipe CAtalyse, SYnthèse et ENvironnement (CASYEN),
Bâtiment
Dr Nicolas Duguet: +33(0) 472 448 507, nicolas.duguet@univ-lyon1.fr
Université de Lyon, Univ. Lyon 1, CPE Lyon, CNRS UMR 5265, Laboratoire de Chimie Catalyse Polymères et Procédés
C2P2), Equipe LCPP, Bat 308F, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne, France.
Lederer,
1
rue
Victor
Grignard,
F-69622
Villeurbanne
cedex,
France.
b
(
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. An imidazolium catalyst supported on (1-5 bar) and moderate temperature (100°C). A range of
thermomorphic polyethylene (PE) was prepared from 1- terminal and internal epoxides were converted to the
methylimidazole and polyethylene iodide (PE-I). The catalyst corresponding cyclic carbonates with high yields and
1
13
was characterized by H and C NMR, SEC and MALDI-ToF selectivities. The recyclability of the catalyst was studied and
mass spectrometry. Its catalytic activity was evaluated in the no significant loss of activity was observed after 5 runs.
ring-opening of epoxides with carbon dioxide to give cyclic
carbonates under solvent-free conditions. The catalyst proved Keywords: Polyethylene; Organocatalysis; carbon dioxide;
to be active at low catalyst loading (down to 0.1 mol%) and epoxides; cyclic carbonates
2
allows the reaction to occur at low CO pressure
oxidized
state
engendering
an
important
Introduction
thermodynamic stability. Consequently, the utilization
of a catalyst is mandatory to activate it. A lot of
catalytic systems have been described in the literature
Carbon dioxide is the most important waste
produced by human activities due to the massive
utilization of fossil resources for the production of
energy and raw materials. Moreover, carbon dioxide,
as a greenhouse gas, has an important impact on the
[16]
for the preparation of carbonates from CO
2
.
Metal-
[
17]
based catalysts such as Metal-Organic Frameworks,
[18]
[19]
[20]
[21]
Salen,
salophen,
porphyrin,
scorpionate,
[
22]
triphenolate
complexes usually offer excellent
[1]
climate change but also on the biodiversity due to the
activities with a low catalyst loading. Alternatively,
metal-free approaches have been reported in the
acidification of the oceans.[ In February 2018, a high
2]
concentration of 408 ppm of CO
2
(World average) was
[
23]
literature
mainly
such
and imidazolium
organocatalytic systems based on polyols
using
single-component
reported.[ One way to decrease this concentration is
3]
[24]
organocatalysts
as
ammonium,
salts or other
[4]
the capture and storage of carbon dioxide, notably
[25]
[26]
[5]
phosphonium,
using Metal-Organic Frameworks (MOFs).
An
[27]
and
amongst
New organocatalysts have also emerged
alternative way is to use CO as a non-toxic, cheap and
2
[28]
[29]
polyphenols,
DBU-derived salts,
[6]
abundant C1 building block. For instance, CO is
2
[23]
others.
such as squaramides,
mainly used for the direct carboxylation of organic
[30]
[31]
ascorbic acid,
and boron-based systems.
recently, metal-free and halide-free catalysts have also
organic
substrates,[ for incorporation into heterocycles and
for methylation reactions.[9] Additionally, carbon
dioxide is already used to produce urea on an industrial
scale (120 Mt/year).[ Another industrial application
is the synthesis of propylene carbonate from propylene
7]
[8]
[32]
[33]
scorpionates,
More
[34]
been developed, highlighting the intense research
efforts on this topic. Organocatalysts are usually
inexpensive but often require a higher catalyst loading
than metal-based catalysts. Another drawback of
organocatalysts is related to their difficult separation
from the reaction mixture, thus compromising the
recycling. To avoid this issue, supported versions have
been described using various insoluble supports such
10]
oxide and CO
2
with 100% atom economy. Generally,
[11]
cyclic carbonates can be used as non-toxic solvents,
[
12]
electrolytes for lithium batteries and as precursors
[13]
for the preparation of polycarbonates
and non-
isocyanates polyurethanes (NIPUs).[14] These different
applications make the preparation of cyclic carbonates
[35]
[36]
as polystyrene,
cellulose
silica
or biopolymers such as
a very active field.[ The carbon of CO
is at the most
15]
2
[37]
[38]
and
chitosan.
Many
other
1
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Advanced Synthesis & Catalysis
10.1002/adsc.202000032
heterogeneous systems were also reported to
[39]
efficiently catalyse the reaction. However, except in
some cases,[ the catalytic activity of supported
catalysts is usually lower than their non-supported
40]
[41]
versions, mainly due to diffusion problems. In this
context, thermomorphic polyethylene (PE) could be a
good alternative to insoluble supports due to its
original physical properties. Thermomorphic PE is
solid at room temperature but becomes liquid above its
melting temperature (about 100-120°C) and could be
solubilized in aromatic solvents (around 80-90°C).
This property permits an easier recycling of the
catalyst while keeping a good activity, thus offering
Scheme 2. Preparation of catalyst 1.
The complete conversion of PE-I has been proved
1
by H NMR and 3-methyl-1-polyethyleneimidazolium
iodide 1 was obtained in 92% isolated yield. Catalyst
the benefits of both homogeneous and heterogeneous
1
13
catalysts.[
42]
Only two catalysts supported on
1
was characterized by H and C NMR, SEC and
1 13
MALDI-ToF mass spectroscopy. From H and
C
thermomorphic PE were described in the literature.
Beirgbreiter et al. reported a ruthenium-based catalyst
supported on PE for the olefin ring-closing
metathesis[ and Boisson, Thieuleux et al. described
an iridium-based catalyst grafted on PE for the D/H
exchange.[ To the best of our knowledge, end-
functionalized thermomorphic PE has never been used
as support for organocatalysts. Herein, we report the
synthesis and characterization of an imidazolium
NMR spectra, the apparition of the characteristic
proton at 9.79 ppm and carbon at 138.0 ppm (spectrum
in ESI) clearly indicate the formation of the
imidazolium core (Figure 1).
43]
44]
organocatalyst
polyethylene for the preparation of cyclic carbonates
using CO (Scheme 1).
supported
on
thermomorphic
2
2
Scheme 1. Synthesis of carbonates from CO using a
thermomorphic PE-supported organocatalyst.
1
Figure 1. H NMR (TCE/C
6
D
6
2:1v/v, 500 MHz, 363 K, 128
scans) of the polyethylene-supported imidazolium.
Results and Discussion
A functionality of about 92% was calculated based
on the proton integrations (calculation method detailed
First, polyethylene iodide (PE-I) was prepared by
polymerization of ethylene in the presence of a
neodymium complex[ and was obtained with 92%
functionalization (the remaining 8% are non-
functionalized PE). An number average degree of
in ESI). A DP
n
of 42 was also calculated based on
45]
NMR data (ESI) which gave an average molar mass of
-1
M = 1385 g mol . In regards to the precursor PE-I, the
n
slightly higher DP measured for 1 can be explained by
n
the loss of a fraction of low molar mass polymer
polymerization (DP ) of 36 was obtained from the
n
during the purification of the product. The SEC of 1
NMR analysis of the PE-I (see ESI). Due to the fact
that PE derivatives are not soluble in any solvent at
room temperature, no purification by column
chromatography can be done. So, the challenge of
using this material is to obtain quantitative
functionalization. The thermomorphic catalyst was
synthesized at 120°C from commercially available 1-
methylimidazole (6 equiv.) and PE-I (Scheme 2).
(
performed at high temperature in trichlorobenzene)
was also carried out but the results could not be
exploited unambiguously due to the presence of the
charged imidazolium core as sometimes observed for
[46]
PE chains carrying charged end group.
MALDI-
ToF mass spectrometry (MALDI-ToF MS) of the
same sample is also given in Figure 2. Three different
populations can be observed. The red one corresponds
to catalyst 1; for a DP of 20, a mass of 699.75 m/z was
required (C48
H
95
2
N ) and a mass of 699.7 m/z was
experimentally found (Figure 2a and 2b). The two
other populations (blue and green curves) correspond
to two fragments with a loss of mass of 14 Da and 12
Da, respectively. The loss of 14 Da would result from
2
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Advanced Synthesis & Catalysis
10.1002/adsc.202000032
the cleavage of the N-CH
3
and the loss of 12 Da could
(Figure 2, b and c). However, the average molar mass
of the polymer could not be accurately determined by
MALDI-ToF MS. Indeed, the chains that are
vaporized are condition-dependent,
only short chains were analyzed.
result from the fragmentation of the imidazolium core
+
+
(
M - CH + H ). The accordance between experimental
[46],[47]
and calculated isotopic abundance of the catalyst for a
DP=20 confirms the nature of the red population
in our case,
Imidazolium supported on PE (n=20)
c)
90
80
70
60
50
40
30
20
10
0
699
700
701
702
703
704
(m/z)
b)
a)
Figure 2. a) MALDI-ToF MS of catalyst 1. b) Zoom between 670-740 m/z. c) Theoretical isotopic abundance (calculated
by IsoPro) for the 699.7 m/z peak (DP=20).
In addition, MALDI-ToF MS is not quantitative as
attested by the discrepancies between the quantitative
Figure 3. a) Catalyst 1 at room temperature. b) Catalyst 1 at
110°C (after being melt around 120°C, then cooled to
110°C).
1
functionalization of PE-I observed by H NMR and the
presence of additional populations resulting from
fragmentation during MALDI-ToF MS analyses.
Overall, all analysis confirmed the expected structure
of the thermomorphic PE supported imidazolium 1.
Finally, the thermomorphic character of catalyst 1 was
investigated. At room temperature, the catalyst is a
white solid (Figure 3, a) but it becomes liquid above
Advantageously,
this
thermomorphic
organocatalyst can be synthesized through a single-
step operation on a multi-gram scale.
The catalytic activity of 1 was evaluated for the
1
10°C when heated neat (Figure 3, b). This behaviour
formation of cyclic carbonates from CO and epoxides.
2
correlates well with the DSC data showing that the
catalyst is a crystalline material, which has a fusion
temperature of about 115°C (at peak) and a
crystallisation temperature of about 104°C (at peak)
The optimization of the reaction parameters was
carried out using the ring-opening of styrene oxide 2
(SO) into styrene carbonate 3 (SC) as a model reaction
(Table 1). A fixed temperature of 100°C was chosen to
fully exploit the thermomorphic character of the
catalyst. At this temperature, the polymer-supported
organocatalyst and the reagents are completely
miscible. Moreover, all the reactions were performed
(
see ESI).
in solvent-free conditions. At 20 and 10 bar of CO ,
2
the conversion of SO 2 was almost complete after 4
hours using only 1 mol% of catalyst. The selectivity
was >99%, thus giving a yield of SC 3 of about 95-
9
7% (Table 1, entries 1-2). Then, in order to determine
the limits of the catalytic activity, the catalyst loading
was decreased from 1 to 0.1 mol%, but these
conditions did not permit to reach more than 85% yield
(
Table 1, entries 3-5). By increasing the reaction time
to 16 hours, almost quantitative yields (96-97%) can
3
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Advanced Synthesis & Catalysis
10.1002/adsc.202000032
be reached using 0.4 and 0.2 mol% of catalyst while
only 78 % of SC was obtained for 0.1 mol% (Table 1,
entries 3-5, results in brackets). From these results, we
decided to keep the catalyst loading at 0.4 mol% for
further optimization in order to apply robust conditions
to a wide range of epoxides.
reached 99% in all cases. Epichlorohydrin was fully
converted to give carbonate 6 with 86% yield.
Similarly, epifluorohydrin and epibromohydrin were
successfully converted to carbonates 7-8 with 99 and
92% isolated yield, respectively. The reaction was also
carried out on a range of terminal epoxides bearing a
linear alkyl chain. With propylene oxide and 1,2-
epoxybutane, the conversion was full and carbonates
Table 1. Optimization of the reaction conditions for the
opening of SO into SC.a
9-10 were isolated with moderate yields (62-69%).
Under the standard conditions, the conversion of 1,2-
epoxyhexane and 1,2-epoxyoctane only reached 75
and 78%, respectively. These results show that the
increase of the alkyl chain length slightly decreases the
catalytic activity, probably due to the combination of
steric and solubility issues. Increasing the catalyst
loading to 1 mol% allowed to fully convert these two
epoxides and the corresponding carbonates 11-12 were
isolated with 92% yield. The presence of a double
bond is well tolerated and carbonate 13 was isolated
with 81% yield. Finally, a bis-epoxide was converted
to bis-carbonate 14 with an excellent 97% isolated
yield. Noteworthy, bis-carbonates are excellent
building-block for the preparation of non-isocyanate
polyurethanes (NIPUs).
Entry
1 (mol %)
p
CO
2
t (h) Yield (%)b
(
bar)
1
2
3
4
5
6
7
8
1
1
20
10
10
10
10
5
4
95
4
4
4
4
16
16
16
97
c
0.4
0.2
0.1
0.4
0.4
0
85 (96)
74 (97)c
42 (78)c
96
d
1
10
88
traces
a)
Reaction conditions: 45-mL stainless steel autoclave,
b)
epoxide 2 (1.05 g, 8.74 mmol), 100°C.
determined by H NMR of the crude reaction mixture.
Selectivity is always >99%. c) 16 hours of reaction. d)
Yields were
1
2
Balloon of CO .
Moreover, a similar yield of 96% was obtained by
using only 5 bar of CO (Table 1, entry 6).
Interestingly, the reaction can also proceed smoothly
under 1 atmosphere of CO (balloon) using 0.4 mol%
of catalyst 1 to give SC with 88% yield (Table 1, entry
). Finally, a blank experiment was performed without
2
2
7
any catalyst and only traces of carbonate 3 was
observed, thus confirming the importance of the
catalyst to promote the reaction (Table 1, entry 8).
Subsequently, the optimized conditions [0.4 mol%
of 1, neat, 100°C, 16h, 5 bar of CO ] were applied for
2
the formation of cyclic carbonates from a range of
terminal epoxides (Figure 4).
First, styrene oxide gave carbonate 3 with 89%
isolated yield. Glycidol was fully converted, but the
selectivity of carbonate 4 did not reach more than 45%
due to the formation of a polymer. Indeed, at high
temperature in the presence an acidic proton, glycidol
can easily polymerize to polyethers, as already
reported in the literature.[ Considering that glycerol
48]
[49]
carbonate 4 is a very promising building-block, the
reaction has been conducted at slightly lower
temperature (90°C). However, no improvement of the
selectivity was obtained under these conditions. To
Figure 4. Evaluation of the substrate scope using terminal
epoxides. Reaction conditions: 45-mL stainless steel
autoclave, epoxides (1 equiv.), catalyst 1 (0.4 mol%), neat,
circumvent
this
problem,
1,2-epoxy-3-
100°C, 16 h, p(CO
2
) = 5 bar. a Using 1 mol% of 1. b 0.4
phenoxypropane was used as a starting material and
the corresponding carbonate 5 was obtained with 95%
isolated yield. For the other terminal epoxides, the
catalytic system was highly selective (>99%) toward
the formation of cyclic carbonates and the NMR yield
mol% of catalyst / epoxide function was used. Yields were
1
determined by H NMR of the crude reaction mixture.
Isolated yields are given in brakets. All selectivities are >
99 % except for glycidol (45%).
4
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Advanced Synthesis & Catalysis
10.1002/adsc.202000032
The conversion of more challenging substrates such
presence of cis/trans-isomers (in similar ratio) in the
starting material. The reaction was also performed on
cyclooctene oxide, however, the corresponding
carbonate 19 was only obtained with 10% yield.
Finally, for cyclododecene oxide, no traces of
carbonate 20 has been detected even after 72 hours. It
should be noted that such behaviour has already been
as 1,2-disubstituted and cyclic epoxides was next
studied using catalyst 1 (Figure 5). First, the reaction
was carried out on trans-stilbene oxide under the
standard conditions, but only up to 5% of the
corresponding carbonate was obtained. Not
surprisingly, the reactivity of internal epoxides is
usually lower compared to the terminal ones as
reported in the literature.[ As a result, the reaction
conditions were hardened to reach a satisfying
conversion of trans-stilbene oxide (see Table S1 in
[52]
reported before.
The lower reactivity can be
50]
explained by a preferred twisted conformation of the
fused 8- or 12-membered ring, making the ring-
opening more difficult or even impossible under the
chosen reaction conditions.
ESI). Using 4 mol% of 1 and increasing the CO
2
pressure to 10 bar, the conversion of trans-stilbene
The mechanism of the epoxide ring opening into
carbonates with imidazolium salts is already well-
known and relatively well described in the
oxide reached 82% after 40 hours. However, carbonate
1
5 was obtained with only 71% selectivity. Indeed, the
[23c]
presence of 2-phenylacetophenone has been observed
literature.
In catalyst 1, the iodide is a good
1
by H NMR, and was formed with 24%. The formation
candidate to open the epoxide as it is a good
nucleophilic and non-basic counter-anion. Moreover,
the presence of the PE chain can enhance this
nucleophilicity: the combination of steric effects and
the non-polar properties of the chain allows a better
dissociation of the imidazolium ion pair. Indeed, it has
been previously reported that the number of carbons of
the linear alkyl chain carried by the imidazolium core
of this ketone could be explained by a Meinwald
rearrangement[
51]
catalyzed by the imidazolium
species. A similar rearrangement was also observed
starting from cis-stilbene oxide and the corresponding
carbonate 15 was obtained with comparable yield
(
62%) and selectivity (71%). Using the same
conditions, high conversions of cyclopentene and
cyclohexene oxides were reached and cyclic
carbonates 16-18 were obtained high yields (85-90%).
[
26b]
has an influence in term of reactivity.
From methyl
to dodecyl, it was observed that the longer the chain,
[53]
the more reactive the catalyst. To verify that this
phenomenon is also true in our case, a comparison
between catalyst 1 and a shorter analogue 21 was
performed using styrene oxide 2 as a model substrate.
The reaction was carried out with 0.4 mol% of catalyst
at 100°C under 10 bar of CO (Scheme 4).
2
Scheme 4. Comparison of catalysts 21 and 1. The selectivity
is >99% for these two reactions. Conversion and selectivity
1
were determined by H NMR of the crude reaction mixture.
With 1-butyl-3-methylimidazolium iodide 21, the
conversion reached 75%, while using catalyst 1, it
increased to 85%. This significant difference of
reactivity confirms the positive influence of the long
PE alkyl chain. Moreover, for the systems that
incorporate long alkyl chains, the miscibility of 1 with
Figure 5. Evaluation of the substrate scope using internal
epoxides. Reaction conditions: 45-mL stainless steel
autoclave, epoxide (1 equiv.), catalyst 1 (4 mol%), neat,
1
00°C, 40 h, p(CO
2
) = 10 bar. a 72 h reaction. NR: No
1
Reaction. Yields were determined by H NMR of the crude
reaction mixture. All selectivities are > 99 % except for
trans- and cis-stilbene oxides (71%). Isolated yields
obtained after purification by column chromatography are
presented in brakets.
the other reactants (epoxides and CO ) may
2
significantly improve, giving better overall kinetics.
Herein, we demonstrate the advantages of the PE
supported organocatalyst: while its recovery is eased
by the insolubility of PE at low temperature, this
supported version is more reactive than the
homogeneous one, which is in sharp contrast with the
[41]
It should be noted that carbonate 18 was obtained as
a 43:57 mixture of diastereoisomers due to the
lower reactivity expected from a supported catalyst.
5
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Advanced Synthesis & Catalysis
10.1002/adsc.202000032
The recyclability of catalyst 1 was investigated
using styrene oxide as a model substrate (Figure 6).
After each reaction, the catalyst was filtered,
washed and dried before re-use. The results show that
both the conversion (93-95%) and the selectivity
(
99%) were maintained over five runs, thus indicating
100
that neither deactivation nor degradation of the catalyst
occurred under these conditions. To further verify this,
1
the H NMR of the used catalyst after five runs was
80
60
40
20
0
also performed and compared with those of the fresh
catalyst (see ESI). Satisfyingly, no detectable sign of
degradation was observed, thus highlighting its high
robustness and stability.
In order to further highlight the reactivity of catalyst
1
, its performances were compared with selected
recent
homogeneous
and
heterogeneous
[54]
organocatalytic systems (Table 2).
For better
comparison, the reaction was carried out with
propylene oxide using 0.4 mol% of catalyst 1 at 100°C
1
for 4 hours. Under these conditions, the H NMR yield
Run #1
Run #2
Run #3
Run #4
Run #5
of propylene carbonate 9 reached 79%, thus giving a
-1
TON of 198 and a TOF of 49 h (Table 2, entry 1).
These results are comparable with the catalytic
Figure 6. Study of the recyclability of catalyst 1. Reaction
conditions: 45-mL stainless steel autoclave, catalyst 1 (1
mol%), styrene oxide 2 (1.05 g, 8.74 mmol), neat, 100°C,
performances of phosphorus ylide-CO
2
adducts
[55]
reported by Lu (Table 2, entry 2). This demonstrates
that
thermomorphic
polyethylene-supported
4
2
h, p(CO ) = 10 bar. Blue: conversion. Grey: selectivity.
organocatalyst 1 exhibit similar performances that
1
Conversions and selectivities were determined by H NMR
of the crude reaction mixture.
homogeneous single component organocatalysts.
Table 2. Comparison of catalytic activites with selected (supported-)organocatalytic systems.a
Entry Catalytic system
S.M.
Cat.
loading conditions
mol%)
Reaction
Conv./
Yield
TON
TOF
(h )
Recycling
-1
(
(
%)
1
2
3
4
5
6
7
8
9
PE-Im
This work
PO
0.4
neat, 100°C, 4h
p(CO ) = 5 bar
79b
78b
85b
99c
99d
88b
96c
99b
100b
198
156
42
49
5 runs (SO)
2
CO
2
-Phosphorus ylides PO
0.5
neat, 100°C, 4h
p(CO ) = 20 bar
39
Homogeneous
Homogeneous
12 runs (EH)
6 runs (ECH)
5 runs (SO)
adducts,
Lu, (2015)
Squaramides / TBAI
Kleij, (2017)
2
[
55]
EH
PO
PO
SO
SO
PO
ECH
2 / 2
1
neat, 80°C, 0.5 h
p(CO ) = 10 bar
85
[
30a]
2
PS-Resorcinarenes
neat, 80°C, 18h
p(CO ) = 5 bar
99
5.5
2
[
28c]
Kleij, (2017)
FIP-Im
2
5
neat, 80°C, 10h
p(CO ) = 10 bar
20
[
56]
Ji, (2018)
2
PE-Im
This work
0.4
neat, 100°C, 16h
p(CO ) = 1 bar
220
9.6
198
250
14
2
[HDBU]I
Dove, (2019)
10
neat, 70°C, 4h
p(CO ) = 1 bar
2.4
16.5
10.4
6 runs (AGE)
5 runs (ECH)
4 runs (SO)
[
29c]
2
COF-JLU7 / TBAB
Liu, (2018)
0.5 / 5
0.4 / 1
neat, 80°C, 12h
p(CO ) = 1 bar
[
57]
2
P-Dop / TBAI
D’Elia/Crespy,
neat, 60°C, 24h
p(CO ) = 1 bar
2
[
58]
(
2019)
6
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Advanced Synthesis & Catalysis
10.1002/adsc.202000032
a)
Reaction conditions and data as reported in original papers. SM: Starting material, EH: 1,2-epoxyhexane, PO: Propylene
b) 1
c)
d)
oxide, SO: Styrene oxide, ECH: Epichlorohydrin, AGE: Allyl Glycidyl Ether. H NMR yield, Conversion, GC yield.
General procedure for the ring-opening of terminal
Better results were reported by Kleij using
epoxides: The epoxide (9 mmol, 1 equiv) and catalyst 1 (0.4
squaramides
but
in
the
presence
of
mol%) were added in a 45-mL stainless steel autoclave with
a magnetic stirrer, then the autoclave was sealed and the air
tetrabutylammonium iodide co-catalyst (Table 2, entry
[30a]
3
).
For other comparison, fully recyclable,
was removed by a CO
with CO
2
flux. The autoclave was charged
2
(5-20 bar) and the reactor was heated at 100°C.
heterogeneous organocatalytic systems28c]such as
[
After the reaction was complete (4-16 hours), the mixture
was cooled to 0°C (ice bath), and the reactor was opened
when it was cold to avoid any loss of material. The crude
polystyrene-supported
resorcinarenes
and
[
56]
functional ionic polymers (FIP-Im)
gave TOF
-1
1
values of 5.5 and 2 h , respectively (Table 2, entries
sample was analyzed by H NMR. After addition of EtOAc
to the residue, the catalyst was filtered and the filtrate was
concentrated under reduced pressure to give the desired
carbonates without any further purification.
4
-5). The results obtained with catalyst 1 under
atmospheric CO were also compared with other
2
recyclable organocatalytic systems working under
similar conditions. Using styrene oxide as substrate, a
General procedure for the ring-opening of internal
epoxides: The epoxide (5 mmol, 1 equiv) and catalyst 1 (4
mol%) were added in the 45-mL autoclave with a magnetic
stirrer, then the autoclave was sealed and the air was
-1
TON of 220 and a TOF of 14 h were obtained with 1
Table 2, entry 6). By comparison, DBU salts reported
(
-1
by Dove gave a TON of 9.6 and a TOF of 2.4 h for
removed by a CO
2
flux. The autoclave was charged with
[29c]
the same substrate at 70°C (Table 2, entry 7).
CO (10 bar) and the reactor was heated at 100°C. After 40
2
hours, the mixture was cooled to 0°C (ice bath), and the
reactor was opened when it was cold to avoid any loss of
Similar results can also be achieved using covalent
organic frameworks COF-JLU7 in the presence of
tetrabutylammonium bromide as a co-catalyst, as
reported by Liu (Table 2, entry 8).[57] Finally, high
TON and TOF were recently reported by D’Elia and
Crespy by using dopamine-functionalized polymer
nanoparticules in combination with TBAI under mild
1
material. The crude sample was analyzed by H NMR. After
addition of EtOAc to the residue, the catalyst was filtered
and the filtrate was concentrated under reduced pressure.
The residue was purified by column chromatography to give
the desired carbonates.
Procedure for the recycling of the catalyst: The recycling
of the catalyst was carried out following to the general
procedure for terminal epoxides, using catalyst 1 (1 mol%)
[58]
conditions (60°C) (Table 2 , entry 9).
Overall, our results show that thermomorphic-
polyethylene-supported organocatalyst 1 can compete
with other homogeneous organocatalysts in terms of
activity while being fully recyclable.
2
in the presence of CO (10 bar) at 100°C for 4 hours. After
the reaction was complete, EtOAc (30 mL) was added into
the crude mixture, then the suspension was filtered through
paper membrane (0.1 m). The resulting solution was
concentrated under reduced pressure to give the desired
product (93-97% yield) and the solid catalyst was dried
under vacuum at 40°C for 4 h before reusing for the next run
without any further purification. About 90-95% of the
catalyst was recovered after each run. There are some
unavoidable mechanical losses during the filtration step.
Conclusion
In conclusion, we have reported the first
imidazolium
organocatalyst
supported
on
thermomorphic PE. This catalyst was synthesized in
one-step from polyethylene iodide and 1-
methylimidazole and was obtained with 92% yield on
Acknowledgements
The Institut de Chimie de Lyon (ICL) is acknowledged for funding
the “PE-Organocat” project that allows us to get preliminary
results. The authors thank the French National Agency for
Research for financial support through a Ph.D. grant to K.O.
1
a gram scale. The catalyst was characterized by H and
1
3
C NMR, SEC and MALDI-ToF MS. The reactivity
of the catalyst has been studied on the synthesis of
cyclic carbonates from CO and epoxides. The catalyst
works under low CO pressure (1-10 bar) and moderate
(
ANR-19-CE07-0006-ThermoPESO). The Auvergne-Rhône-Alpes
region is acknowledged for a partial support (SCUSI 2017009361
1) for Master 2 studies to A.A. The authors also thank the SAS
2
2
0
temperature (100°C) at low loading (0.4-4 mol%).
Under these conditions, a range of terminal and
internal epoxides was converted to the corresponding
cyclic carbonates with high yields and selectivities.
Contrary to typical supported organocatalysts, the use
of thermomorphic polyethylene as support enhances
the catalytic activity. The recyclability of the catalyst
has been studied and validated over five runs. Finally,
we demonstrate that thermomorphic polyethylene is an
excellent support for organocatalysts, which, with an
improved reactivity and an excellent recyclability,
combines the benefits of homogeneous and
heterogeneous catalysis.
PIVERT for a Ph.D. grant to N.D.V. (GENESYS program: project
WP3P21-Bioaldehydes). This work was performed in partnership
with the SAS PIVERT, within the frame of the French Institute for
the Energy Transition (Institut pour la Transition Energétique
(ITE) P.I.V.E.R.T. (http://www.institut-pivert.com)) selected as an
Investment for the Future (“Investissements d’Avenir”). This work
was supported, as part of the Investments for the Future, by the
French Government under the reference ANR-001-01. F.D. and
C.B. thanks the French National Agency for Research for the ANR
LISIP-15-LCV4-005 funding. The authors would like to thank F.
Delolme (UMR 5086, IBCP, Lyon, France) for MALDI-ToF MS
analyses and the Centre Commun de RMN de Lyon (A. Baudoin,
E. Chefdeville, C. Gilbert) for NMR analyses.
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