Efficient Conversion of Epoxides into Carbonates with CO 2 and a Single Organocatalyst: Laboratory and Kilogram-Scale Experiments

Article abstract of DOI:10.1055/s-0039-1691405

Cheap and readily available 2-aminopyridine and related compounds can be used as organocatalysts for the conversion of epoxides into cyclic carbonates. This reaction gives high conversions under solvent-free conditions and is amenable to a kilogram-scale

Full text of DOI:10.1055/s-0039-1691405

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Georg Thieme Verlag Stuttgart · New York
2019, 30, A–F
letter
A
en
Synlett
R. Azzouz et al.
Letter
Efficient Conversion of Epoxides into Carbonates with CO and a Sin-
2
gle Organocatalyst: Laboratory and Kilogram-Scale Experiments
Rabah Azzouza,c
O
Viviana Contreras Morenob
Clara Herasme-Grullonb
O
O
CO2
7 examples
46 – 100 % yields
O
R
R
Vincent Levachera
Lionel Estelb
cheap catalyst
efficient conversions
lab to kg scale
cat.
N
NH2
Alain Ledouxb
Salim Derrouiched
Francis Marsaisc
Laurent Bischoff*a
a
Normandie Université, UNIROUEN, INSA Rouen, CNRS, COBRA
UMR 6014, 76000 Rouen, France
laurent.bischoff@univ-rouen.fr
Normandie Universit é , INSA Rouen, UNIROUEN, LSPC, EA4704,
b
7
6000 Rouen, France
c
VFP Therapies R&D, 1 Rue Tesnière, 76130 Mont Saint-Aignan,
France
Veolia Recherche & Innovation, Centre de Recherche de Maisons-
Laffitte, 78603 Maisons-Laffitte, France
d
Received: 28.08.2019
Accepted after revision: 25.11.2019
Published online: 09.12.2019
put, requiring high pressures and temperatures to yield di-
methylcarbonates.4 The latter are precursors of diphenyl
DOI: 10.1055/s-0039-1691405; Art ID: st-2019-d0454-l
carbonate, a useful surrogate for phosgene in the industrial
preparation of polycarbonate materials. A representative
example consists of the use of cerium oxide as a catalyst.
These energetic considerations have led several groups
to focus on the reaction of carbon dioxide with molecules of
higher reactivity, thus avoiding the requirement for an ex-
ternal source of energy. For instance, unstable carbamates
can be trapped with electrophilic reagents and thus con-
Abstract Cheap and readily available 2-aminopyridine and related
compounds can be used as organocatalysts for the conversion of epox-
ides into cyclic carbonates. This reaction gives high conversions under
solvent-free conditions and is amenable to a kilogram-scale conversion
under mild conditions.
Key words epoxides, cyclic carbonates, carbon dioxide, organocataly-
sis, aminopyridine
5
sumed in a stoichiometric amount. In particular, the reac-
tivity of epoxides is interesting, since these incorporate
both electrophilic carbon and subsequent nucleophilic oxy-
gen atoms. Thus, in the presence of appropriate catalysts,
Increasingly over recent years, efforts have been made
to reduce the industrial production of carbon dioxide and
thus avoid its effects on climate change. Besides the capture
CO can be inserted into reactive epoxides to yield the cor-
2
1
followed by geological or ocean storage of CO , several dif-
responding cyclic carbonates, or, in some cases, directly
2
ferent products arising from its utilization have been de-
scribed. For instance, carbon dioxide can be reduced to pro-
provide polycarbonates.6
For this purpose, several catalytic systems have been
described over the last decade.7 The main strategies ex-
plored to date are summarized in Scheme 1. Dual activation
is often required to achieve high conversions under atmo-
spheric pressure. In the epoxide-activation strategy, open-
ing with a halide and resulting formation of a transient ha-
logeno (bromo and iodo) intermediate results in both the
release of a nucleophilic alkoxide with a remaining C–X
electrophilic bond. This preliminary opening pathway rep-
resents the most commonly encountered form of epoxide
activation. However, when a halide ion containing catalyst
such as tetrabutylammonium bromide is used, either high
pressures and temperatures are required, or the assistance
2
duce formic acid derivatives, carbon monoxide, or metha-
3
nol, products that are highly valuable energetic materials,
since formic acid can further release hydrogen and metha-
nol can be used directly as a fuel. In the present study, we
were interested in the preparation of cyclic carbonates, via
incorporation of carbon dioxide into epoxides. Cyclic car-
bonates such as ethylene or propylene carbonate are known
as industrial solvents and, from a general viewpoint, dialkyl
carbonates are high-value starting materials for the synthe-
sis of polycarbonates through transesterification with diols.
Due to the high chemical stability of carbon dioxide, its
direct esterification with methanol involves high energy in-
©
2019. Thieme. All rights reserved. Synlett 2019, 30, A–F
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

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R. Azzouz et al.
Letter
of a Lewis acid is employed, in order to stabilize the strong
basic alkoxide ion before its reaction with carbon dioxide.
This electrophilic activation and stabilization can be ob-
tained either via H-bond formation from an alcohol moiety
or with various metal catalysts.8,9
However, in the case of industrial combustion exhausts, the
removal of water will add an energy-consuming step. In ad-
dition, the cost of these reagents is generally too high for in-
dustrial applications.
2-Aminopyridine is a relatively inexpensive compound
(
ca. 15 $/kg), easily accessible by the Chichibabin reaction of
i) pathway A : H bond or Lewis acid / halide epoxide co-activation
X
15
sodium amide with pyridine. It can exist as both tautom-
eric forms, and, in contrast to 2-hydroxy and 2-thiopyri-
dines, 2-aminopyridine mostly exists mainly as the 2-ami-
R1
R1
X
R1
X–
O–
O
X–
O
O–
16
M+
no- rather than 2-iminopyridine tautomer. Having a pKa
H
O
H
O
M+
value of 6.9, it is less basic than DBU or deprotonated NHCs,
thus avoiding its acido-basic reaction with carbon dioxide
and concomitant formation of hydrogen carbonate salt. It
has a moderate toxicity and a good chemical stability to-
wards water and most organic solvents. Owing to the elec-
tron-withdrawing properties of the pyridine nucleus, the
amino group has a limited nucleophilic character, thus pro-
tecting this moiety from alkylation with epoxides or air ox-
idation, as observed in the case of many amines.
Lewis acid
R2
R2
hydrogen bond
X
R1
CO2
CO2
O
–O
R1
O
O
O
O
ii) pathway B : strong nucleophilic CO2 activation (Nu = DBU, NHC...)
Experiments conducted in NMR solvents (CDCl , DMSO,
or acetonitrile) provided no evidence of the formation of
3
R1
R1
R1
the CO adduct with 2-aminopyridine. Thus, we believe that
O
2
+Nu CO2–
Nu + CO2
O–
Nu
O
O
O
O
a limited amount of 2-aminopyridine/CO complex is pres-
2
+
ent; nevertheless, exhibiting sufficient reactivity to lead to
the opening of the epoxide. Interestingly, when the reaction
is carried out in a glass reactor, the formation of a precipi-
Nu
O
iii) our work : mild CO2 activation with stabilized adduct
tate is noticed when CO under pressure is applied. This
2
H
H
precipitate disappears during the course of the reaction. We
believe that the sole pyridine nitrogen atom is not nucleo-
N+
N
H
N
N
H
O
O-
philic enough to react with CO , as may occur in the case of
2
nucleophilic activation
H-bond stabilization
DMAP or DBU. Thus, a hydrogen bond with the vicinal 2-
amino group is required for carbamate stabilization. In-
deed, as described in the literature,7 co-catalysis using
both a phenol as the H-bond donor and DMAP as the nucle-
ophilic catalyst has been described. In our case, the catalyst
can be responsible for both activations (see Scheme 2). This
is supported by the fact that 2-dimethylaminopyridine
proved to be barely reactive under the same conditions;
whereas 2-methylaminopyridine remained an effective cat-
alyst, underlining the role of the hydrogen bond with the
Scheme 1 Different modes of CO activation
2
,17
Cooperative catalysis has been explored with both
Lewis acid metal catalysis with halide as counterion, and H-
bond donors such as diphenolic ligands, e.g. salophen. Cat-
ionic, organic solvent-soluble phosphonium salts, bearing
an ortho-phenol group for H-bond activation of the epox-
9
9
b,c
ide, and bromide counterion have been described. Hirose
9e
and co-workers also used organocatalysts encompassing
both an alcohol as H-bond donor and nucleophilic assis-
tance by iodide. Nucleophilic organocatalysts are also an ef-
NH or NHMe substituent.
2
10
ficient way to catalyze epoxide opening. Many catalytic
systems can be supported on montmorillonite clay or nat-
CO2
1
1
H
+H
N+
N
NH2
N
H
N
N
H
12a
12b
ural or synthetic macromolecules. Most of these sys-
tems afford good results but often involve high costs and
structural or surface analyses to ensure reproducible reac-
tions.
O
O–
O
O–
O
R
Another mechanistic strategy consists of activating CO2
12a
O
with strong nucleophiles such as amidines or guanidines;
H
+
O
O
N
N+
H
even NHCs can be employed.13 Unfortunately, strong nucle-
ophiles also behave as fairly strong bases. Indeed, the reac-
N
NH2
R
O
O
O–
tion of CO with DBU was thoroughly studied and shown to
2
be particularly sensitive to moisture, enabling the transfor-
14
mation of CO into hydrogen carbonate if water is present.
Scheme 2 Catalysis of epoxide carbonatation with aminopyridine
2
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2019. Thieme. All rights reserved. Synlett 2019, 30, A–F

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R. Azzouz et al.
Letter
The catalytic properties of 2-aminopyridine were first
examined using epichlorohydrin as a model substrate, on a
Table 1 Influence of the Temperature with Different Catalysts
18
a
5
mL scale. Epichlorohydrin is a widely used synthon,
Yield (%) with catalyst
mostly prepared as a monomer for epoxy paints.
Temp 2-Aminopyridine 2-Methylaminopyridine 2-Aminopyrimidine
(°C)
The corresponding cyclic carbonate is a high-value in-
termediate, especially if considered as a monomer for high-
ly functionalized polycarbonates. This preliminary work
was aimed at determining which catalyst amongst the 2-
aminopyridine analogues would be most suitable for this
reaction. In this set of experiments, we used a large amount
2
5
0
0
8
25
90
5
28
81
0
25
66
4
6
a
Isolated yields.
of catalyst, under 12 bar pressure of CO , in order to exhibit
2
the catalytic properties of the catalysts even with low activ-
ities (Scheme 3).
ed, low concentrations of catalyst decreased the yields. Sur-
prisingly, 2-methylaminopyridine remained effective at 2.5
mol%; whereas 2-aminopyridine only afforded a modest
O
52% yield under the same conditions. When decreasing to
O
0.5 equiv catalyst
O
O
1% ratio, we still noticed catalytic activity, although with
low yields, except with 2-aminopyrimidine, which did not
catalyze the reaction in such a concentration (Table 2).
Cl
CO2, 12 bar, 45 °C, 16 h
1a
Cl
N
Catalyst none
CO2
O
N
NH2
N
NHMe
N
NMe2
N
NH2
O
catalyst
0 bar, 60 °C, 16 h
O
O
Cl
1
Yield (%)
3
95
75
46
61
Cl
Scheme 3 Catalyst comparison (isolated yields)
Scheme 5 Catalyst loading
These results clearly show the importance of the cata-
lyst itself since, with no catalyst, barely any reaction oc-
curred. The hydrogen bond also seemed crucial, the lowest
yield being obtained using 2-dimethylaminopyridine. 2-
Aminopyrimidine can also catalyze this reaction, though
less efficiently. Further examinations of catalytic activities
were only performed with N–H bearing catalysts.
Table 2 Yields Obtained with Various Catalyst Concentrations
Yield (%) with catalyst
Catalyst 2-Aminopyridine 2-Methylaminopyridine 2-Aminopyrimidine
(
mol%)
Then the same reaction was conducted under 10 bar of
10
5
90
69
52
34
81
82
78
20
67
35
34
0
CO over 16 h, at various temperatures (Scheme 4). We ob-
2
served a rapid increase in reaction above 40 °C; however,
we did not wish to use temperatures higher than 60 °C in
order to avoid side reactions such as degradation of the epi-
chlorohydrin. In the absence of catalyst, only traces of cyclic
carbonate were observed. 2-Aminopyridine remained the
most active catalyst, though 2-methylaminopyridine and 2-
aminopyrimidine also gave good yields at 60 °C (Table 1).
2.5
1
Having these results in hand, we wished to extend the
scope of this transformation. Amongst commercially avail-
able, suitably substituted epoxides that would lead to useful
monomers in polycarbonate chemistry, we focused on gly-
cidol, glycidyl ethers, and phenyloxirane.
CO2
0.5 equiv catalyst
0 bar, temp, 16 h
O
O
In each case, we revisited the reaction conditions, espe-
cially the catalyst loading, the reactivities of the epoxides
exhibiting strong differences. Glycidol is an important
chemical intermediate, its carbonate represents a particu-
larly interesting monomer for polycarbonate synthesis.
When we studied carbonate formation from glycidol
(Scheme 6), we observed an unexpected reactivity of glyci-
dol even if no catalyst is present. This may be due to self-
activation by means of hydrogen bonding with the alcohol
moiety. Pleasingly, the reactivity proved higher in the pres-
ence of the catalyst, as listed in Table 3.
O
O
Cl
1
Cl
Scheme 4 Role of the temperature
As an important feature towards the possibility of in-
dustrial development, we next examined the catalyst load-
ing, still working at 60 °C under 10 bar of CO2 pressure
(Scheme 5). These results clearly indicate that there is no
requirement for high concentrations of catalyst, good yields
being obtained even at 5 mol% loading although, as expect-
©
2019. Thieme. All rights reserved. Synlett 2019, 30, A–F

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R. Azzouz et al.
Letter
Table 3 Synthesis of Glycidyl Carbonate under Various Conditions
Yield (%) with catalyst
Conditions
No catalyst
2-Aminopyridine
2-Methylaminopyridine
2-Aminopyrimidine
20 bar, 50 mol% cat., 45 °C
20 bar, 10 mol% cat., 45 °C
10 bar, 5 mol% cat., 40 °C
10 bar, 5 mol% cat., 25 °C
60
19
1.2
36
80
90
80
87
70
80
80
78
83
78
76
78
CO2
O
aminopyridine as catalyst, we could reduce the operating
conditions at laboratory scale. To verify the applicability of
the reaction at large scale by only using an organocatalyst,
different operating conditions were evaluated and opti-
mized to maximize the amount and the quality of the prod-
uct obtained.
O
catalyst
O
O
HO
conditions
16 h
1
b
OH
Scheme 6 Carbonation of glycidol
These results confirm the high catalytic activity of 2-
aminopyridine, which remains the most efficient catalyst in
this reaction, with 87% yield being obtained at room tem-
perature with a 5 mol% catalyst loading under 10 bar pres-
sure of CO2.
Having these results in hand, we examined the reactivi-
ty of other commercially available epoxides having suffi-
ciently high boiling points for reactions at 70–85 °C. We fo-
cused on 2-aminopyridine, which allowed the formation of
carbonates from every epoxide. Surprisingly, phenyloxirane
only gave a moderate yield, while having a high propensity
for epoxide opening. Bisglycidyl ether also lead to moderate
yield of dicarbonate (62%), along with monocarbonate. Oth-
er epoxides gave good yields of carbonate formation, espe-
cially allyl glycidyl ether, which provided the carbonate in
quantitative yield (Figure 1).
The reactions between CO and epichlorohydrin (ECH)
2
were carried out in a stainless-steel stirred tank reactor (1.5
L) at a range of temperatures (50–110 °C) and pressures be-
low 5 bar (Figure 2). The temperature in the reactor was
maintained constant thanks to a carrier fluid circulating
through a jacket. The accuracy of the temperature regula-
tion inside of the reactor was ±0.1 °C. Stirring allowed the
temperature and composition of the liquid phase to be kept
homogeneous and improved the mass transfer. A reservoir
of gas allowed continuous feeding into the reactor. The
amount of gas feed was controlled by regulating the pres-
sure inside the stirred tank. Before every reaction, a vacu-
um was established to eliminate air contained in the reac-
tor. The reactions were carried out under solvent-free con-
ditions.
O
O
O
O
O
O
O
O
O
O
Ph
5 °C, 16 h
OPh
7
85 °C, 16 h
75 °C, 16 h
46% 1c
96% 1d
100% 1e
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
4
8
5 °C, 6 h
70 °C, 16 h
62% 1g
82% 1f
Figure 1 Other carbonates prepared under 20 bar CO , 10 mol% 2-
2
aminopyridine
Figure 2 Stirred reactor diagram. T: temperature; P: pressure; C:
chamber; j: jacket; r: reactor.
Finally, with the aim of validating future industrial de-
velopment, we examined the reactivity of epichlorohydrin
in the presence of CO and 2-aminopyridine at 1 kg scale.
The current commercial methods allowing production of
cyclic carbonates require temperatures above 150 °C and
Reactions performed at lab scale showed good conver-
sions and yields at temperatures above 50 °C and concen-
trations of catalyst lower than 10 mol%. We observed the
behavior of the reaction at pilot scale, by evaluating tem-
2
high pressures of CO between 50 bar and 80 bar. Using 2-
2
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R. Azzouz et al.
Letter
peratures of between 50 °C and 110 °C. The pressure of the
reaction and catalyst concentration were fixed to 5 bar and
The effect of CO pressure on the reaction rate was ob-
served at the optimal temperature of 80 °C and 5.0 mol% of
2
5
mol%, respectively.
2-aminopyridine, the pressure of CO into the reactor being
2
Figure 3 shows the conversion of epichlorohydrin, and
varied from 1 bar to 5 bar. Figure 5 shows the variation of
carbonate formation over time at these pressures. Using 2-
aminopyridine as catalyst, a relatively insignificant effect of
additional information is given in Figure 4, which demon-
strates the effect of temperature on the concentration of
carbonate produced over time. At temperatures lower than
CO pressure was observed on the production rate of car-
2
6
0 °C, the production of the carbonate was quite slow, reac-
bonate. A similar effect has also been noticed, but at higher
pressures when, below 150 bar, there was no effect on the
formation rate of dimethyl carbonate from CO2 and eth-
ylene oxide.20
tion taking more than 6 h with conversions lower than 30%.
At temperatures above 70 °C, conversions were higher than
80% with a reaction time below 5 h. We observed signifi-
19
cant induction periods at temperatures lower than 70 °C.
Indeed, we detected an optimal operating point over 80 °C
at pilot scale with a conversion and yield of around 90%,
which was comparable to that obtained at laboratory scale.
At temperatures higher than 90 °C, we observed a decrease
in carbonate formation, which could be explained by ther-
mal degradation of the catalyst.
Figure 5 Effect of pressure on carbonate production over time at
80 °C and 5 mol% of 2-aminopyridine
The conversions and yields were similar to that ob-
tained at 5 bar (ca. 90%). Under these conditions, we could
minimize the pressure of the reaction without any conse-
quence on the reaction performance.
According to the studies performed at laboratory scale,
catalyst concentrations from 2.5 mol% to 10 mol%, could be
used with success to obtain the cyclic carbonate at a tem-
perature of 60 °C. However, at pilot scale, the reaction re-
quires a higher temperature to obtain similar yields. Ac-
cording to our study, we observed an optimal conversion at
Figure 3 Effect of pressure on carbonate production over time at
80 °C bar and 5 mol% of 2-aminopyridine
80 °C. This temperature was used to study the performance
of the catalyst. Two different concentrations of catalyst (5
mol% and 7 mol%), were used during these reactions, and
the pressure of CO was fixed at 5 bar.
2
Figure 6 shows the evolution of carbonate concentration
over time according to the two catalyst concentrations
used. An insignificant variation on the dynamic behavior of
carbonate formation was detected during the reaction.
However, a slight difference was observed for the induction
period. The concentration of carbonate was slightly lower
when the concentration of catalyst was 7% mol. The yield of
the reaction decreased to around 6%, but the overall conver-
sion of epichlorohydrin remained relatively stable. We pro-
pose some catalyst degradation could occur during the last
phases of the reaction, possibly due to the high temperature
Figure 4 Effect of temperature on carbonate production over time at
bar and 5 mol% of 2-aminopyridine
5
(80 °C) and the higher concentration of catalyst (7 mol%).
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Letter
Meyer, L. A., Ed.; Cambridge University Press: Cambridge, 2005,
4
42.
2) Oldenhof, S.; van der Vlugt, J. I.; Reek, J. N. H. Catal. Sci. Technol.
016, 6, 404.
3) (a) Porosoff, M. D.; Yanb, B.; Chen, J. G. Energy Environ. Sci. 2016,
, 62. (b) Albo, J.; Alvarez-Guerra, M.; Castano, P.; Irabien, A.
(
(
2
9
Green Chem. 2015, 17, 2304.
(4) Tundo, P.; Selva, M. Acc. Chem. Res. 2002, 35, 706.
(5) Yoshida, M.; Komatsuzaki, Y.; Ihara, M. Org. Lett. 2008, 10, 2083.
(6) Darensbourg, D. J.; Mackiewicz, R. M. J. Am. Chem. Soc. 2005,
127, 14026.
(
(
(
7) Büttner, H.; Longwitz, L.; Steinbauer, J.; Wulf, C.; Werner, T. Top
Curr. Chem. (Z) 2017, 375.
8) Comerford, J. W.; Ingram, I. D. V.; North, M.; Wu, X. Green Chem.
2
015, 17, 1966.
9) (a) Castro-Osma, J. A.; Lamb, K. J.; North, M. ACS Catal. 2016, 6,
012. (b) Wu, X.; Chen, C.; Guo, Z.; North, M.; Whitwood, C. ACS
5
Catal. 2019, 9, 1895. (c) Toda, Y.; Komiyama, Y.; Kikuchi, A.;
Suga, H. ACS Catal. 2016, 6, 6906. (d) Liu, S.; Suematsu, N.;
Maruoka, K.; Shirakawa, S. Green Chem. 2016, 18, 4611.
Figure 6 Effect of catalyst concentration on carbonate production
over time at 80 °C and 5 bar CO2
(e) Wang, L.; Zhang, G.; Kodama, K.; Hirose, T. Green Chem.
2
016, 18, 1229. (f) North, M.; Pasquale, R. Angew. Chem. Int. Ed.
This result showed that, at pilot scale, the temperature
had an impact more significant on the reaction perfor-
mance compared to the catalyst concentration at the condi-
tions studied. Under appropriate conditions, we could use a
relatively low concentration of catalyst and obtain good
yields and conversions.
This whole set of experiments allow us to conclude that
the laboratory-scale reaction of epichlorohydrin with car-
bon dioxide can be carried out with high reliability on a pi-
lot scale, thus paving the way towards an industrial process.
In terms of sustainable chemistry, this constitutes an addi-
tional example of synthesis of cyclic carbonates from epox-
ides, with a very simple and readily available organocata-
lyst, exhibiting low basicity and avoiding hydrogen carbon-
ate formation. Importantly, carbonates having both reactive
moieties such as glycidyl or epichlorohydrin carbonates,
available through this phosgene-free preparation, are of
great interest in the manufacturing of polymers.
2009, 48, 2946. (g) Clegg, W.; Harrington, R. W.; North, M.;
Pasquale, R. Chem. Eur. J. 2010, 16, 6828.
(
(
(
10) Cokoja, M.; Wilhem, M. E.; Anthofer, M. H.; Herrmann, W. A.;
Kühn, F. E. ChemSusChem 2015, 8, 2436.
11) Verma, S.; Kureshy, R. I.; Roy, T.; Kumar, M.; Das, A.; Khan, N. H.;
Abdi, S. H. R.; Bajaj, H. C. Catal. Commun. 2015, 61, 78.
12) (a) Sun, J.; Cheng, W.; Yang, Z.; Wang, J.; Xu, T.; Xin, J.; Zhang, S.
Green Chem. 2014, 16, 3071. (b) Beckman, E. J.; Munshi, P. Green
Chem. 2011, 13, 376.
(13) Kayaki, Y.; Yamamoto, M.; Ikariya, T. Angew. Chem. Int. Ed. 2009,
8, 4194.
4
(
14) (a) Perez, E. R.; Santos, R. H. A.; Gambardella, M. T. P.; de
Macedo, L. G. M.; Rodrigues-Filho, U. P.; Launay, J.-C.; Franco, D.
W. J. Org. Chem. 2004, 69, 8005. (b) Heldebrant, D. J.; Jessop, P.
G.; Thomas, C. A.; Eckert, C. A.; Liotta, C. L. J. Org. Chem. 2005, 70,
5335.
(15) Chichibabin, A. E.; Zeide, O. A. Zhur. Russ. Fiz. Khim. Obshch.
(J. Russ. Phys. Chem. Soc.) 1914, 46, 1216.
16) Stefaniak, L. Org. Magn. Reson. 1979, 12, 379.
(
(
17) (a) Shen, Y.-M.; Duan, W.-L.; Shi, M. Adv. Synth. Catal. 2003, 345,
337. (b) Metcalfe, I. S.; North, M.; Pasquale, R.; Thursfield, A.
Energy Environ. Sci. 2010, 3, 212.
(18) Azzouz, R.; Bischoff, L.; Levacher, V.; Estel, L.; Ledoux, A.;
Derrouiche, S.; Contreras Moreno, V.; Marsais, F.
Funding Information
(
19) An open glass Schlenk tube was charged with epichlorhydrin (5
mL, 61.8 mmol), 2-aminopyridine (580 mg, 6.18 mmol), and a
magnetic stir bar. It was placed in a stainless-steel autoclave,
then pressurized with carbon dioxide to 10 bar pressure. It was
heated under stirring at 60 °C (internal temperature) for 16 h.
After cooling, the carbonate was purified by filtration through a
short pad of silica, eluting with diethyl ether, followed by evap-
oration of the solvent to yield 7.58 g of carbonate (90%).
This work has been partially supported by INSA Rouen, Rouen Univer-
sity, CNRS, EFRD, European INTERREG IV A France (Channel), and
Labex SynOrg (Grant No. ANR-11-LABX-0029). Rabah Azzouz is grate-
ful to FEDER BIOFLUORG, and Viviana Contreras Moreno is grateful to
Veolia Recherche et Innovation for financial support.()
Supporting Information
4
-(Chloromethyl)-1,3-dioxolan-2-one (1a)
1
Supporting information for this article is available online at
Pale-yellow liquid. H NMR (300 MHz, CDCl ):  = 4.95–5.05 (m,
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https://doi.org/10.1055/s-0039-1691405.
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1 H), 4.59 (t, J = 8.4 Hz, 1 H), 4.38–4.44 (m, 1 H), 3.71–3.80(m, 2
13
H). C NMR (75 MHz, CDCl ):  = 154.6, 74.6, 67.0, 44.2.
3
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20) Cui, H.; Wang, T.; Wang, F.; Gu, C.; Wang, P.; Dai, Y. Ind. Eng.
References and Notes
Chem. Res. 2004, 43, 7732.
(1) IPCC, 2005: IPCC Special Report on Carbon Dioxide Capture and
Storage; Metz, B.; Davidson, O.; de Coninck, H. C.; Loos, M.;
©
2019. Thieme. All rights reserved. Synlett 2019, 30, A–F