Histidine-catalyzed synthesis of cyclic carbonates in supercritical carbon dioxide

Article abstract of DOI:10.1007/s11426-010-4019-7

The coupling reaction of carbon dioxide with epoxides was investigated using naturally occurring α-amino acids as the catalyst in supercritical carbon dioxide and it was found that L-histidine is the most active catalyst. In the presence of 0.8 mol% of L-

Full text of DOI:10.1007/s11426-010-4019-7

SCIENCE CHINA
Chemistry
July 2010 Vol.53 No.7: 1566–1570
doi: 10.1007/s11426-010-4019-7
• ARTICLES •
Histidine-catalyzed synthesis of cyclic carbonates
in supercritical carbon dioxide
QI ChaoRong & JIANG HuanFeng*
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China
Received April 12, 2010; accepted May 10, 2010
The coupling reaction of carbon dioxide with epoxides was investigated using naturally occurring -amino acids as the catalyst
in supercritical carbon dioxide and it was found that L-histidine is the most active catalyst. In the presence of 0.8 mol% of
L-histidine at 130 °C under 8 MPa of CO2, the reaction of carbon dioxide with epoxides proceeded smoothly, affording corre-
sponding cyclic carbonates in good to excellent yields.
supercritical carbon dioxide, amino acids, epoxides, cyclic carbonates
1 Introduction
Due to oil depletion, mankind is faced with the challenge of
finding new carbon resources to get rid of oil dependence.
The combustion of fossil fuels produced large amounts of
carbon dioxide, which is the primary source of the green
house effect. Thus it is very significant to develop efficient
processes of capture, fixation and transformation of carbon
dioxide. Carbon dioxide can be employed as an abundant
and inexpensive C 1 feedstock. Recently, transformation of
carbon dioxide into valuable chemicals has drawn much
attention from governments, academic fields as well as in-
dustry fields [1–4]. The synthesis of cyclic carbonates by
the coupling reaction of CO2 and epoxides is one of the
most promising and practical methods for the utilization of
CO2 among many examples (Scheme 1). Cyclic carbonates
are valuable compounds due to their enlarged application as
aprotic polar solvents, electrolytes in secondary batteries,
and as valuable intermediates for polymer synthesis [5–7].
Compared with conventional methods using phosgene as
the starting material, the synthesis of cyclic carbonates from
Scheme 1 Synthesis of carbonate from epoxide and carbon dioxide.
epoxides and CO2 is eco-friendly and atom economic. Thus,
since Lichtenwalter and Cooper [8] first reported the syn-
thesis of cyclic carbonate from the reaction of carbon diox-
ide and epoxides in 1956, many researchers have carried out
the research in this area. Numerous homogeneous catalysts
have been reported, including metal complexes [9–17], ionic
liquids [18–21], and alkali metal salts [22, 23]. Heterogene-
ous catalysts, such as metal oxides [24, 25], silica gel or
polystyrene supported salen metal complex [26–28], sup-
ported phosphonium or ammonium salt [29–31], ion ex-
change resins [32], and ion exchange resins supported gold
nanoparticles [33], have also been developed.
Recently, we have demonstrated that in dichloromethane
most of the naturally occurring -amino acids could effec-
tively catalyze the coupling of CO2 with epoxides to yield
the corresponding cyclic carbonates in excellent yield with
high selectivity [34]. In the drive towards the development
*Corresponding author (email: jianghf@scut.edu.cn)
© Science China Press and Springer-Verlag Berlin Heidelberg 2010
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QI ChaoRong, et al. Sci China Chem July (2010) Vol.53 No.7
1567
Table 1 Coupling of propylene oxide with CO2 catalyzed by various
-amino acids a)
of more environmentally friendly route to the synthesis of
cyclic carbonates, herein we investigated the reaction of
CO2 and epoxides in supercritical carbon dioxide using
amino acids as catalysts and found that L-histidine is the
most efficient catalyst for the reaction among all the amino
acids surveyed under supercritical conditions.
Entry
1
Amino acids
glycine
Yield (%)
20
2
L-alanine
19
3
L-leucine
63
4
L-isoleucine
L-valine
62
2 Experimental
5
40
6
L-proline
51
2.1 General experimental section
7
L-phenylalanine
L-tryptophan
L-methionine
L-asparagine
L-glutamine
L-cysteine
L-serine
67
IR spectra were obtained with a Tensor-27 FTIR spec-
trometer. GC data were obtained by a GC7900 instrument
equipped with an FFAP column (30 m × 0.250 mm × 0.25
8
27
9
45
1
10
11
12
13
14
15
16
17
18
19
20
7
m). H NMR spectra were taken on a 400 MHz Bruker
5
DRX-400 spectrometer with tetramethylsilane as the inter-
nal standard and CDCl3 as the solvent. MS data were re-
corded on a Frinnigan Trace DSQ GC-MS spectrometer.
Carbon dioxide with a purity of 99.9%, epoxides and amino
acids were commercially available and used as received.
10
14
L-threonine
L-tyrosine
36
44
L-aspartic acid
L-glutamic acid
L-arginine
L-histidine
L-lysine
18
2.2 Synthesis of cyclic carbonates
15
The typical experimental procedure is as follows: propylene
oxide (20 mmol) and L-histidine (0.8 mol%) were added into
a 15 mL stainless autoclave with a magnetic stirrer, and CO2
was charged into the reactor to reach the desired pressure.
The reactor was then heated to 130 °C for desired reaction
time and the pressure was kept constant during the reaction.
After the reaction, the reactor was cooled to 0 °C, and extra
CO2 was vented slowly. The crude product was purified by
distillation. The cyclic carbonate was identified by IR,
44
100
78
a) Reaction conditions: propylene oxide (20 mmol), amino acids (0.8
mol%), CO2 pressure (8 MPa), 130 °C, 48 h.
may be due to the difference in polarity and solubility be-
tween supercritical carbon dioxide and dichloromethane.
1
GC/MS and 400 MHz H NMR. 4-Methyl-1,3-dioxolan-2-
1
3.2 Effect of CO2 pressure
one (2a): H NMR (400Hz, TMS, CDCl3),  1.48 (d, J=3.6
Hz, 3 H, CH3), 4.01 (t, J=8 .4 Hz, 1 H, CH), 4.53 (t, J=8.0
Hz, 1 H, CH), 4.81–4.86 (m, 1 H, CH); IR (film) v: 2898,
2931, 1795, 1481, 1391, 1180, 1120, 1054, cm1; MS (70 eV)
m/z (%): 102[M+], 87, 58, 57, 43 , 29.
Figure 1 shows the pressure dependence of the yield of pro-
pylene carbonate in the presence of L-histidine at 130 °C.
3 Results and discussion
3.1 Catalytic activity of different -amino acids
Twenty common -amino acids were screened in the cou-
pling reaction of CO2 with propylene oxide forming pro-
pylene carbonate and the results are shown in Table 1. We
were delighted to find that L-histidine is the most efficient
catalyst for this reaction among all the amino acids sur-
veyed under supercritical conditions. Propylene oxide could
be quantitatively transformed into propylene carbonate at
130 °C under 8 MPa of CO2 in the presence of 0.8 mol% of
histidine (Table 1, entry 19). However, other -amino acids
showed lower catalytic activity (Entries 1–18, 20), which is
different from the results obtained in dichloromethane. This
Figure 1 The effect of CO2 pressure on the yield of propylene carbonate
(PC). Reaction conditions: propylene oxide 20 mmol, L-histidine 0.8 mol%,
130 °C, 48 h.

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QI ChaoRong, et al. Sci China Chem July (2010) Vol.53 No.7
The yield increased with an increase in pressure up to 8
MPa and then dropped sharply at pressures above 12 MPa.
A similar correlation between the yield of styrene carbonate
and CO2 pressure was also found in DMF-scCO2 catalytic
system reported previously by Kawanami and coworkers
[35]. The main reason may be that at 8 MPa of CO2 pres-
sure L-histidine dissolved well into the system and led to a
high yield of propylene carbonate. While too high CO2
pressure may cause a low concentration of propylene oxide
in the vicinity of the catalyst and resulted in a decrease of
the yield.
hexene oxide was of cis stereochemistry.
In addition, although L-histidine is a chiral catalyst, no
asymmetric induction was observed. It may be because the
reaction requires high temperatures (>90 °C).
3.3 Effect of reaction time
The effect of reaction time on the yield is shown in Figure 2.
The reaction was carried out in the presence of 0.8 mol% of
L-histidine at 130 °C under 8 MPa. The results indicated that
the reaction proceeded slowly within the first 18 h and then
became fast. However, the rate of the reaction slowed down
again after 24 h. A reaction time of 48 h was necessary for
the complete conversion of propylene oxide to propylene
carbonate.
Figure 2 The effect of reaction time on the yield of propylene carbonate
(PC). Reaction conditions: propylene oxide 20 mmol, L-histidine 0.8 mol%,
130 °C, 8 MPa.
3.4 Effect of reaction temperature
The influence of reaction temperature on the yield is shown
in Figure 3. The catalytic activity of L-histidine was quite
sensitive to the reaction temperature and was low at lower
temperatures. 15% yield of propylene carbonate was ob-
tained at 90 °C. With the increase of reaction temperature
the yield increased. L-histidine showed high catalytic activ-
ity at 130 °C and gave 100% yield of propylene carbonate.
3.5 Effect of the dosage of catalysts
To optimize the dosage of catalysts, different amounts of
histidine were tested (Figure 4). The reaction could not oc-
cur in the absence of any catalyst. Increasing the load of the
catalyst the yield of propylene carbonate increased and
reached 100% in the presence of 0.8 mol% of L-histidine.
Figure 3 The effect of reaction temperature on the yield of propylene
carbonate (PC). Reaction conditions: propylene oxide 20 mmol, L-histidine
0.8 mol%, 8 MPa, 48 h.
3.6 Synthesis of various cyclic carbonates
Under the optimized reaction conditions, a variety of epox-
ides were examined for the synthesis of different cyclic
carbonates in the presence of L-histidine. As shown in Ta-
ble 2, all of the mono-substituted terminal epoxides (1a–1g)
could be transformed into the corresponding five-membered
cyclic carbonates in good to excellent yields (Table 2, en-
tries 1–7). Cyclohexene oxide (1h) could also react with
CO2 to yield the corresponding carbonate 2h in 44% yield
(Table 2, entry 8), and the lower yield could be attributed to
the effect of high steric hindrance of cyclohexene epoxide.
Figure 4 The effect of the dosage of catalysts on the yield of propylene
carbonate (PC). Reaction conditions: propylene oxide 20 mmol, 130 °C, 8
MPa, 48 h.
1
According to the H, 13C and NOESY NMR spectra of 2h,
we found that the cyclic carbonate produced from cyclo-

QI ChaoRong, et al. Sci China Chem July (2010) Vol.53 No.7
1569
Table 2 Synthesis of various cyclic carbonates in the presence of L-histidine in supercritical carbon dioxide a)
Entry
1
Epoxide
Product
Selectivity (%) b)
Yield (%) c)
100
100
2
3
99
99
95
86
4
5
6
7
8
99
98
75
77
100
100
99
100
92
44
a) Reaction conditions: epoxide 20 mmol, histidine 0.8 mol%, pressure 8 MPa, 130 °C, 48 h; b) determined by GC; c) isolated yield.
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4 Conclusions
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6
In summary, we demonstrated that among the twenty com-
mon -amino acids investigated, L-histidine is the most
active catalyst for the coupling reaction of CO2 with epox-
ides under supercritical conditions. The reaction tempera-
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