Synthesis of Functionalized Cyclic Carbonates by One-Pot Reactions of Carbon Dioxide, Epibromohydrin, and Phenols, Thiophenols, or Carboxylic Acids Catalyzed by Ionic Liquids

Article abstract of DOI:10.1002/ejoc.201601315

The one-pot reactions of CO₂, epibromohydrin, and phenols, thiophenols, or carboxylic acids catalyzed by 1-butyl-3-[(3-hydroxyphenyl)methyl]imidazolium bromide were investigated. Three kinds of cyclic carbonates with ether, thioether, or ester groups were synthesized under mild reaction conditions in good-to-high yields. Reaction-mechanism studies indicated that the proton exchange between the alkoxide formed through the ring-opening reaction of epibromohydrin with 1-bromo-3-phenoxy-2-propanol plays a crucial role in this synthetic route. The catalyst 1-butyl-3-[(3-hydroxyphenyl)methyl]imidazolium bromide was transformed to the corresponding cyclic-carbonate-functionalized ionic liquid during the reaction. This transformation did not affect its catalytic performance in the reaction.

Full text of DOI:10.1002/ejoc.201601315

DOI: 10.1002/ejoc.201601315
Full Paper
Cyclic-Carbonate Synthesis
Synthesis of Functionalized Cyclic Carbonates by One-Pot
Reactions of Carbon Dioxide, Epibromohydrin, and Phenols,
Thiophenols, or Carboxylic Acids Catalyzed by Ionic Liquids
Shi Wu,[a] Yongya Zhang,[a] Binshen Wang,[a] Elnazeer H. M. Elageed,[a] Liangzheng Ji,[a]
Haihong Wu,*[a] and Guohua Gao*[a]
Abstract: The one-pot reactions of CO2, epibromohydrin, and through the ring-opening reaction of epibromohydrin with 1-
phenols, thiophenols, or carboxylic acids catalyzed by 1-butyl- bromo-3-phenoxy-2-propanol plays a crucial role in this syn-
3-[(3-hydroxyphenyl)methyl]imidazolium bromide were investi- thetic route. The catalyst 1-butyl-3-[(3-hydroxyphenyl)methyl]-
gated. Three kinds of cyclic carbonates with ether, thioether, or imidazolium bromide was transformed to the corresponding
ester groups were synthesized under mild reaction conditions cyclic-carbonate-functionalized ionic liquid during the reaction.
in good-to-high yields. Reaction-mechanism studies indicated This transformation did not affect its catalytic performance in
that the proton exchange between the alkoxide formed the reaction.
Introduction
strategy employs the inherent high-energy of epoxides to over-
come the thermodynamic stability of CO2 molecules. Many cat-
alytic systems including metal oxides,[6] alkali-metal salts,[7]
transition-metal halides,[8] complexes,[9] Schiff bases,[10] func-
tional polymers,[11] and ionic liquids[12] were developed to
achieve the transformation of cyclic carbonate under mild reac-
tion conditions. Recently, we have been interested in the reac-
tions of CO2, epoxides, and a third component catalyzed by
ionic liquids.[13] In particular, we found that amino-functional-
ized cyclic carbonates could be synthesized through the one-
pot reaction of CO2, epihalohydrin, and aniline.[13a] Therefore,
we envisioned that epihalohydrins would serve as ideal sub-
strates for the development of a new efficient approach to syn-
thesize various functionalized cyclic carbonates. Herein, 1-butyl-
3-[(3-hydroxyphenyl)methyl]imidazolium bromide was first ap-
plied to catalyze the reactions of CO2, epibromohydrin, and
phenols, thiophenols, or carboxylic acids (Scheme 1). By this
Cyclic carbonates are valuable organic compounds and have
been used widely as polar aprotic solvents, electrolytes for lith-
ium-ion batteries, and constituents of oils. Cyclic carbonates are
also important intermediates and raw materials in the produc-
tion of polycarbonates and polyurethanes.[1] In particular, cyclic
carbonates with different functional groups are used as mono-
mers to tailor the properties of polyesters.[2] Through the incor-
poration of different functional groups into the polymer back-
bone, polycarbonates usually show unique properties, such as
hydrophilicity, biodegradation rates, and bioadhesion.
Carbon dioxide is a main greenhouse gas, which causes cli-
mate change, and also an abundant, nontoxic, nonflammable,
readily available, and renewable carbon resource.[3] However,
the transformation of CO2 is a difficult task because CO2 is the
most oxidized state of carbon and is a thermodynamically sta-
ble molecule. The biggest obstacle to the establishment of a
transformation processes is the low energy level of CO2.[4]
Therefore, the transformation of CO2 generally requires a large
energy input, such as harsh reaction conditions or the utiliza-
tion of high-energy starting materials.
In the last decade, the cycloaddition of CO2 with epoxides
to produce five-membered cyclic carbonates has become one
of the most successful routes for the utilization of CO2.[5] This
[a] Shanghai Key Laboratory of Green Chemistry and Chemical Processes,
School of Chemistry and Molecular Engineering, East China Normal
University,
North Zhongshan Road 3663, Shanghai, 200062, China
E-mail: hhwu@chem.ecnu.edu.cn
ghgao@chem.ecnu.edu.cn
http://faculty.ecnu.edu.cn/s/376/t/3755/main.jspy
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201601315.
Scheme 1. Synthesis of functionalized cyclic carbonates through the reactions
of CO2, epibromohydrin, and phenols, thiophenols, or carboxylic acids.
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method, three kinds of functionalized cyclic carbonates with phenoxy-1,2-propylene carbonate. However, when the amount
ether, thioether, and ester groups were successfully synthesized of catalyst was more than 5.0 mmol-%, the yield of 3-phenoxy-
under mild reaction conditions.
1,2-propylene carbonate decreased dramatically (Figure 1d).
These results showed that the yields of product decreased at
Results and Discussion
Synthesis of Ether-Functionalized Cyclic Carbonates
through One-Pot Reactions of CO2, Epibromohydrin, and
Phenols
The synthesis of 3-phenoxy-1,2-propylene carbonate by the
cycloaddition of 2-(phenoxymethyl)oxirane with CO2 has been
reported widely.[14] 2-(Phenoxymethyl)oxirane is usually synthe-
sized through the reaction of phenol and epihalohydrin in the
presence of alkali (such as NaOH).[15] If the one-pot conversion
of phenol, epibromohydrin, and CO2 to 3-phenoxy-1,2-propyl-
ene carbonate could be achieved under alkali-free conditions,
the synthesis of 3-phenoxy-1,2-propylene carbonate would be
simplified. Owing to its high catalytic activity in the cyclo-
addition of CO2 with epoxides,[16a] 1-butyl-3-[(3-hydroxy-
phenyl)methyl]imidazolium bromide was used to catalyze the
model one-pot reaction of CO2, epibromohydrin, and phenol to
synthesize 3-phenoxy-1,2-propylene carbonate. A preliminary
experiment was conducted to identify the products from the
reaction mixture (Scheme 2), and 3-phenoxy-1,2-propylene
carbonate and 1,3-dibromo-2-propanol were detected by GC
after the reaction.
Scheme 2. The reaction of CO2, epibromohydrin, and phenol catalyzed by 1-
butyl-3-[(3-hydroxyphenyl)methyl]imidazolium bromide.
Effect of Various Reaction Conditions
To optimize the reaction conditions, the influence of reaction
parameters including time, temperature, CO2 pressure, and
amount of catalyst were investigated, as shown in Figure 1. As
the reaction time was prolonged from 4 to 6 h, the yield of 3-
phenoxy-1,2-propylene carbonate increased rapidly. For reac-
tion times longer than 6 h, the yield reached 74 % and did
not increase anymore (Figure 1a). As the reaction temperature
increased from 50 to 60 °C, the yield of 3-phenoxy-1,2-propyl-
ene carbonate increased gradually. However, for a further tem-
perature increase from 60 to 80 °C, the yield of the product
decreased rapidly. The appropriate reaction temperature was
60 °C (Figure 1b). For an increase of the CO2 pressure from
0.5 to 2.0 MPa, the yield of 3-phenoxy-1,2-propylene carbonate
increased initially and then decreased rapidly. The appropriate
CO2 pressure was 1.0 MPa (Figure 1c). The increase of the
amount of catalyst was beneficial to the formation of 3-
Figure 1. Effect of (a) reaction time, (b) reaction temperature, (c) CO2 pressure,
and (d) catalyst amount. Typical reaction conditions: phenol (1 mmol), epibro-
mohydrin (5 mmol), CO2 (1.0 MPa), ionic liquid (0.05 mmol), 60 °C, and 6 h.
The yields of 3-phenoxy-1,2-propylene carbonate and 1,3-dibromo-2-prop-
anol were calculated from the amount of phenol used. Circles: 3-phenoxy-
1,2-propylene carbonate. Squares: 1,3-dibromo-2-propanol.
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high temperature (>60 °C), high CO2 pressure (>1.0 MPa), or butyl-3-methylimidazolium bromide were used as the catalysts,
high catalyst amount (>5.0 mmol-%). A possible reason is that the yield of 3-phenoxy-1,2-propylene carbonate reached 62, 48,
the cycloaddition of CO2 with epibromohydrin is accelerated and 53 % respectively (Table 1, Entries 1–3). These ionic liquids
under these conditions; therefore, the epibromohydrin is con- gave lower catalytic activities than that of 1-butyl-3-[(3-hydroxy-
sumed and less is available to react with phenol. Under the phenyl)methyl]imidazolium bromide (74 % yield). These results
abovementioned reaction conditions, the byproduct 1,3-di- implied that 1-butyl-3-[(3-hydroxyphenyl)methyl]imidazolium
bromo-2-propanol formed in almost the same molar quantity bromide was a highly efficient catalyst for the reaction of CO2,
as 3-phenoxy-1,2-propylene carbonate. In addition, when epi- epibromohydrin, and phenol. Furthermore, the cyclic-carb-
chlorohydrin was used as the starting material under the opti- onate-functionalized ionic liquid, derived from the transforma-
mized reaction conditions (60 °C, 1.0 MPa CO2 pressure, and tion of 1-butyl-3-[(3-hydroxyphenyl)methyl]imidazolium brom-
5.0 mmol-% of catalyst), the yield of 3-phenoxy-1,2-propylene ide during the reaction (see the Supporting Information,
carbonate decreased to 40 %.
Scheme S1), exhibited similar catalytic performance to that of
1-butyl-3-[(3-hydroxyphenyl)methyl]imidazolium bromide, and
the yield of 3-phenoxy-1,2-propylene carbonate reached 76 %
(Table 1, Entry 4). Therefore, the transformation of 1-butyl-3-[(3-
hydroxyphenyl)methyl]imidazolium bromide did not affect its
catalytic performance in the reaction.
Reaction of CO2, Epibromohydrin, and Phenol Catalyzed
by Various Ionic Liquids
Various ionic liquids were applied to catalyze the reaction of
CO2, epibromohydrin, and phenol under the optimized reaction
conditions (Table 1). When 1-(2-hydroxylethyl)-3-methylimidaz-
olium bromide, 3-benzyl-1-butylimidazolium bromide, and 1-
Reaction-Mechanism Studies
Table 1. The catalytic activities of various ionic liquids.[a]
To investigate the reaction mechanism, three model reactions
were performed, as shown in Scheme 3. 3-Bromo-1,2-propylene
carbonate, which was obtained by the cycloaddition of CO2
with epibromohydrin, did not react with phenol (Scheme 3a).
1-Bromo-3-phenoxy-2-propanol, which was formed by the reac-
tion of phenol and epibromohydrin, did not react with CO2
(Scheme 3b). However, when epibromohydrin was added to a
mixture of 1-bromo-3-phenoxy-2-propanol and CO2, 1-bromo-
3-phenoxy-2-propanol was converted to 3-phenoxy-1,2-propyl-
ene carbonate, and 1,3-dibromo-2-propanol was obtained as a
byproduct (Scheme 3c). The yields of 3-phenoxy-1,2-propylene
carbonate and 1,3-dibromo-2-propanol reached 91 and 88 %,
respectively. These results indicated that epibromohydrin plays
an important role in the transformation of 1-bromo-3-phenoxy-
2-propanol into 3-phenoxy-1,2-propylene carbonate. It has
been reported that alkoxides form through the ring-opening
reactions of epoxides through the nucleophilic attack of anions
in ionic liquids.[16a] The generation of 1,3-dibromo-2-propanol
indicated that proton exchange had occurred between 1-
bromo-3-phenoxy-2-propanol and the alkoxide formed from
the ring-opening reaction of epibromohydrin through the nu-
cleophilic attack of a Br– ion (Scheme 4). The deprotonated 1-
bromo-3-phenoxy-2-propanol formed by proton exchange
[a] Reaction conditions: phenol (1 mmol), epibromohydrin (5 mmol), CO2
(1.0 MPa), ionic liquid (0.05 mmol), 60 °C, 6 h. [b] GC yield.
Scheme 3. Model reactions for the synthesis of 3-phenoxy-1,2-propylene carbonate.
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Scheme 4. The possible proton exchange between the 1,3-dibromo-2-propanolate anion and 1-bromo-3-phenoxy-2-propanol.
would react with CO2 to afford 3-phenoxy-1,2-propylene carb- the yields of 1a, 1b and 1c reached 85, 79, and 70 % respec-
onate.
tively. Phenols with weak electron-withdrawing groups includ-
ing chlorophenol and bromophenol (Table 2, Entries 4–7) were
also converted smoothly to the corresponding cyclic carbonates
1d–1g in yields ranging from 51–66 %. However, when phenols
with electron-donating groups, that is, 3-tert-butylphenol and
On the basis of the above analysis and previous reports,[16]
a possible reaction mechanism including two catalytic cycles is
proposed in Scheme 5. In cycle 1, epibromohydrin is initially
transformed into intermediate I through the nucleophilic attack
of the Br– ion. At the same time, phenol reacts with epibromo-
hydrin to afford 1-bromo-3-phenoxy-2-propanol in the pres-
ence of an ionic liquid. Then, equimolar amounts of 1,3-di-
bromo-2-propanol and intermediate III are generated by the
proton exchange between intermediate I and 1-bromo-3-
phenoxy-2-propanol. Thirdly, intermediate III reacts with CO2 to
afford intermediate IV. Lastly, the cyclization of intermediate
IV through an intramolecular nucleophilic attack leads to the
formation of 3-phenoxy-1,2-propylene carbonate and the re-
generation of the catalyst. In cycle 2, intermediate I that did
not take part in proton exchange reacts with CO2 to afford II.
Then, the cyclization of intermediate II through an intramolec-
ular nucleophilic attack leads to the formation of 3-bromo-1,2-
propylene carbonate and the regeneration of the catalyst.
Table 2. Reactions of CO2, epibromohydrin, and substituted phenols catalyzed
by 1-butyl-3-[(3-hydroxyphenyl)methyl]imidazolium bromide.[a]
Scheme 5. Proposed reaction mechanism.
Synthesis of Ether-Functionalized Cyclic Carbonates from
CO2, Epibromohydrin, and Substituted Phenols
To investigate the generality of this procedure, the reactions of
CO2, epibromohydrin, and substituted phenols were investi-
gated under the optimized reaction conditions (Table 2). Substi-
tuted phenols with strong electron-withdrawing groups
(Table 2, Entries 1–3) could be transformed into the correspond-
ing cyclic carbonates in high yields. When 4-nitrophenol, 4-
fluorophenol, and 3,5-difluorophenol were used as substrates,
[a] Reaction conditions: substituted phenol (1 mmol), epibromohydrin
(5 mmol), CO2 (1.0 MPa), ionic liquid (0.05 mmol), 60 °C, 6 h. [b] Isolated yield.
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4-methylphenol (Table 2, Entries 8 and 9), were used as sub- and 2f were only 58 and 50 %. These results showed that thio-
strates, the yields of the corresponding cyclic carbonates 1h phenols with electron-withdrawing groups exhibited higher ac-
and 1i were only 43 and 41 %, respectively. These results tivities than those of thiophenols with electron-donating
showed that the activities of phenols with electron-withdraw- groups owing to their stronger acidities.
ing groups were better than those of phenols with electron-
Synthesis of Ester-Functionalized Cyclic Carbonates by One-
Pot Reactions of CO2, Epibromohydrin, and Carboxylic Acids
donating groups. A possible reason is that electron-withdraw-
ing groups enhance the acidity of the phenol to promote its
reaction with epibromohydrin.
The first synthetic route to cyclic carbonates containing ester
groups was reported by Ramaiah,[17] who synthesized 3-
Table 4. Reactions of CO2, epibromohydrin, and carboxylic acids catalyzed by
1-butyl-3-[(3-hydroxyphenyl)methyl]imidazolium bromide.[a]
Synthesis of Thioether-Functionalized Cyclic Carbonates by
One-Pot Reactions of CO2, Epibromohydrin, and Thiophenols
Taking advantage of our protocol for the preparation of ether-
functionalized cyclic carbonates, we explored the reactions of
CO2, epibromohydrin, and thiophenols catalyzed by 1-butyl-3-
[(3-hydroxyphenyl)methyl]imidazolium bromide (Table 3). Sub-
stituted thiophenols with electron-withdrawing groups, that is,
2-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzene-
thiol, and 4-bromobenzenethiol (Table 3, Entries 1–4), were
transformed smoothly to the corresponding cyclic carbonates
2a–2d in 71, 75, 65, and 68 % yield, respectively. However,
when substituted thiophenols with electron-donating groups,
that is, 4-methylbenzenethiol and 2-methylbenzenethiol, were
used as substrates (Table 3, Entries 5 and 6), the yields of 2e
Table 3. Reactions of CO2, epibromohydrin, and substituted thiophenols cata-
lyzed by 1-butyl-3-[(3-hydroxyphenyl)methyl]imidazolium bromide.[a]
[a] Reaction conditions: substituted thiophenol (1 mmol), epibromohydrin
(5 mmol), CO2 (1.0 MPa), ionic liquid (0.05 mmol), 70 °C, 6 h. [b] Isolated yield.
[a] Reaction conditions: carboxylic acid (1 mmol), epibromohydrin (5 mmol),
CO2 (1.0 MPa), ionic liquid (0.05 mmol), 60 °C, 6 h. [b] Isolated yield.
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at 70 °C to afford a light yellow viscous oil in 75 % yield. 1H NMR
(400 MHz, [D6]DMSO, TMS): δ = 9.64 (s, 1 H), 9.48 (s, 1 H), 7.88 (d,
J = 8.0 Hz, 2 H), 7.20 (t, J = 8.0 Hz, 1 H), 6.84–6.80 (m, 3 H), 5.39 (s,
2 H), 4.21 (t, J = 6.0 Hz, 2 H), 1.80–1.76 (m, 2 H), 1.28–1.22 (m, 2 H),
0.89 (t, J = 8.0 Hz, 3 H) ppm. 13C NMR (100 MHz, [D6]DMSO, TMS):
δ = 157.78, 136.11, 130.00, 122.70, 122.61, 118.51, 115.61, 114.94,
51.84, 48.65, 31.25, 18.76, 13.23 ppm.
benzoyloxy-1,2-propylene carbonate through the reaction of
glycerol carbonate and potassium benzoate. Subsequently, Di-
benedetto et al.[18] reported the synthesis of cyclic carbonates
with ester groups through the esterification of glycerol carb-
onate with different acyl chlorides under alkaline conditions.
Recently, Climent et al.[19] developed a synthesis of ester-func-
tionalized cyclic carbonates through the esterification of glyc-
erol carbonate and carboxylic acid catalyzed by a Nafion–silica
hybrid.
We next explored the new synthetic method for ester-func-
tionalized cyclic carbonates through the reactions of CO2, epi-
bromohydrin, and carboxylic acids catalyzed by 1-butyl-3-[(3-
hydroxyphenyl)methyl]imidazolium bromide (Table 4). When
benzoic acids were used as the substrates, the yields of the
corresponding cyclic carbonates 3a–3g reached 90–94 %
(Table 4, Entries 1–7).
Aliphatic carboxylic acids (Table 4, Entries 8–12) were also
successfully converted into the corresponding cyclic carbonates
3h–3l in 89–94 % yield. The high yields were attributed to the
rapid generation of bromo alcohols through the reactions of
the carboxylic acids with epibromohydrin catalyzed by the ionic
liquid.[20] These results demonstrated that this procedure could
achieve the transformation of carboxylic acids into ester-func-
tionalized cyclic carbonates with high efficiency.
General Procedure for the Synthesis of 3-Phenoxy-1,2-propyl-
ene Carbonates through the One-Pot Conversion of CO2, Epi-
bromohydrin, and Phenol Catalyzed by 1-Butyl-3-[(3-hydroxy-
phenyl)methyl]imidazolium Bromide: In a typical experiment,
phenol (0.094 g, 1 mmol), epibromohydrin (0.685 g, 5 mmol), and
catalyst (0.016 g, 0.05 mmol) were added to a stainless-steel auto-
clave with an inner volume of 50 mL. The autoclave was heated at
60 °C for 2 h, the pressure of CO2 was adjusted to 1.0 MPa, and
heating was continued at 60 °C for 4 h. The autoclave was cooled
naturally to room temperature, and the remaining CO2 was re-
moved slowly. The product was analyzed by GC, and the pure prod-
uct was obtained by silica gel chromatography and characterized
by NMR spectroscopy and HRMS.
The one-pot reactions of CO2, epibromohydrin, and 4-chlorothio-
phenol or carboxylic acid were performed by similar procedures.
The difference was that the autoclave was pressurized with 1.0 MPa
of CO2 at ambient temperature and then heated for 6 h at 70 or
60 °C, respectively.
Acknowledgments
Conclusions
We thank the National Natural Science Foundation of China
(21273078, 21573072, and 21573073) and the Shanghai Lead-
ing Academic Discipline Project (project number B409) for fi-
nancial support.
Three kinds of functionalized cyclic carbonates with ether, thio-
ether, or ester groups were successfully synthesized through
the one-pot reactions of CO2, epibromohydrin, and phenols,
thiophenols, or carboxylic acids catalyzed by 1-butyl-3-[(3-
hydroxyphenyl)methyl]imidazolium bromide under mild reac-
tion conditions. The catalyst 1-butyl-3-[(3-hydroxyphenyl)-
methyl]imidazolium bromide was transformed into the corre-
sponding cyclic-carbonate-functionalized ionic liquid during
the reaction. This carbonate-functionalized ionic liquid showed
similar catalytic activity to that of 1-butyl-3-[(3-hydroxy-
phenyl)methyl]imidazolium bromide. The study of the reaction
mechanism indicated that proton exchange between an alkox-
ide and 1-bromo-3-phenoxy-2-propanol plays a crucial role in
this synthetic route.
Keywords: Carbon dioxide · Oxygen heterocycles · Ionic
liquids · Cyclic carbonates · Synthesis design
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Experimental Section
General Information: CO2 was supplied by Doumaoai with a purity
of 99.995 %. All solvents were supplied by Sinopharm Chemical Re-
agent Company. Epibromohydrin, phenol, phenylthiol derivatives,
and carboxylic acids were purchased from TCI. The NMR spectra
were recorded with Bruker Ascend 400 instruments with tetrameth-
ylsilane (TMS) as an internal standard. GC analysis was performed
with a Shimadzu GC-14B instrument equipped with a DM-1701 cap-
illary column (60 m, 0.32 mm, 0.25 μm) and a flame-ionization de-
tector. HRMS analyses were performed with a Bruker Microtof II
instrument.
1-Butyl-3-[(3-hydroxyphenyl)methyl]imidazolium Bromide: 3-
Bromomethylphenol (0.935 g, 5 mmol) and butylimidazole (4 mL)
were heated at 120 °C for 12 h. The suspension was cooled to room
temperature, washed with Et2O (3×30 mL), and dried under vacuum
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Received: October 10, 2016
Eur. J. Org. Chem. 2017, 753–759
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