Hydroxyl-functionalized imidazoles: Highly active additives for the potassium iodide-catalyzed synthesis of 1,3-dioxolan-2-one derivatives from epoxides and carbon dioxide

Article abstract of DOI:10.1002/cctc.201402572

4(5)-(Hydroxymethyl)imidazole and potassium iodide were identified as an efficient catalyst system for the cycloaddition of epoxides and carbon dioxide producing 1,3-dioxolan-2-one derivatives under solvent-free conditions. The high activity of the catalyst system even at 60 C was probably due to synergistic effects between potassium iodide and the substituted imidazole. Various functionalized and nonfunctionalized terminal epoxides as well as internal epoxides were converted into the corresponding cyclic carbonates in high yields (up to 99 %) under mild reaction conditions within a short reaction time. Compared with the previously reported amino alcohols e.g. triethanolamine based catalyzed synthesis of cyclic carbonates, the catalyst system described herein demonstrates a higher activity toward a broad substrate scope A perfect combination: The combination of commercially available 4(5)-(hydroxymethyl)imidazole (HMI) and potassium iodide serves as a simple and efficient catalyst system for the coupling reaction of epoxides with carbon dioxide. Several epoxides are converted into cyclic carbonates in high yields (up to 99 %) under mild and solvent-free conditions within a short reaction time. This new catalyst system demonstrates higher activity than the previously reported potassium iodide/triethanolamine (TEA) system.

Full text of DOI:10.1002/cctc.201402572

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DOI: 10.1002/cctc.201402572
Hydroxyl-Functionalized Imidazoles: Highly Active
Additives for the Potassium Iodide-Catalyzed Synthesis of
1
,3-Dioxolan-2-one Derivatives from Epoxides and Carbon
Dioxide
[
a]
Thomas Werner,* Nils Tenhumberg, and Hendrik Bꢀttner
th
Dedicated to Prof. Dr. Armin Bçrner on the occasion of his 60 birthday.
4
(5)-(Hydroxymethyl)imidazole and potassium iodide were
nal epoxides as well as internal epoxides were converted into
the corresponding cyclic carbonates in high yields (up to 99%)
under mild reaction conditions within a short reaction time.
Compared with the previously reported amino alcohols e.g.
triethanolamine based catalyzed synthesis of cyclic carbonates,
the catalyst system described herein demonstrates a higher ac-
tivity toward a broad substrate scope
identified as an efficient catalyst system for the cycloaddition
of epoxides and carbon dioxide producing 1,3-dioxolan-2-one
derivatives under solvent-free conditions. The high activity of
the catalyst system even at 608C was probably due to syner-
gistic effects between potassium iodide and the substituted
imidazole. Various functionalized and nonfunctionalized termi-
Introduction
Global climate change is closely connected to the emission of
lysts in the cycloaddition of CO to epoxides. The development
2
anthropogenic greenhouse gases. CO has been identified as
of catalyst systems for the coupling reaction of epoxides and
2
a major contributor to these emissions. In addition to the re-
duction in the CO output, the use of CO as a synthetic build-
CO , at temperatures below 1008C, low pressures, and short re-
2
action times, with readily available, inexpensive nontoxic re-
2
2
[10]
ing block is the central point of the overall CO management
agents is still an attractive topic. Methods using organocata-
lysts under mild reaction conditions (e.g., at room tempera-
ture) are rare and usually require long reaction times or involve
metal complexes as cocatalysts. We recently reported the use
of the combination of KI and triethanolamine (TEA) as a catalyst
system for the synthesis of cyclic carbonates at 908C within
2
[
1]
strategy. Hence, the use of CO as a C building block in or-
2
1
ganic synthesis and industrial processes has recently been
given great attention and is widely studied in current re-
[
2]
search. One of the most efficient methods for the chemical
fixation of CO is the coupling reaction of epoxides and CO2
2
[11]
producing cyclic carbonates. These carbonates can be used as
aprotic polar solvents, as intermediates for organic and poly-
a short reaction time of 2 h. However, the use of this catalyst
system seems to be limited to the conversion of short-chain
epoxides under the chosen reaction conditions. Long-chain ep-
oxides, such as 1,2-epoxyhexane and 1,2-epoxyoctane, were
converted into the corresponding carbonates only in moderate
yields.
[3]
meric synthesis, and as electrolytes for lithium-ion batteries.
Various homo- and heterogeneous catalysts and catalytic sys-
[
4]
tems have been developed for this transformation. However,
many of these catalyst systems suffer from low catalyst stability
or reactivity, require solvents, co-catalysts, or harsh reaction
conditions. Alkali metal salts are the most promising catalysts
for this reaction because they are abundant, inexpensive, and
nontoxic. The addition of cocatalysts or solvents is usually nec-
essary to improve the catalytic efficiency because of the low
Herein, we report the use of commercially available imida-
zoles and hydroxyl-functionalized imidazoles in combination
with readily available KI as a simple and efficient catalyst
system for the synthesis of cyclic carbonates under mild and
solvent-free reaction conditions. In contrast to KI/TEA, this new
catalyst system is also suitable for the conversion of long-chain
epoxides into the corresponding carbonates in good to excel-
lent yields.
[
5]
solubility and activity of these salts. Furthermore, there have
been frequent reports on the synergistic effect related to the
[
6]
presence of hydrogen bond donors such as cellulose, b-cyclo-
[
7]
[8]
[9]
dextrin, amino acids, and amino alcohols acting as cocata-
Results and Discussion
[
a] Dr. T. Werner, Dr. N. Tenhumberg, H. Bꢀttner
Leibniz-Institut fꢀr Katalyse e. V. an der Universitꢁt Rostock
Albert-Einstein-Strasse 29a
In our initial studies, the conversion of 1,2-butylene oxide (1a)
and CO to 1,2-butylene carbonate (2a) served as a model re-
2
1
8059 Rostock (Germany)
action for the screening of various additives in combination
with KI (Table 1). To identify a new efficient catalytic system,
E-mail: thomas.werner@catalysis.de
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201402572.
comparatively mild reaction conditions [T=908C, p(CO )=
2
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[
a]
[a]
Table 1. Screening of various additives.
Table 2. Screening of functionalized imidazole additives.
[
b]
Entry
Additive 3
Yield [%]
T=908C
T=808C
1
2
3d
3e
97
96
81
[
b]
Entry
Additive 3
Yield [%]
[
a,c,d]
1
2
none
0
74
94
3a
3b
48
3
4
5
73
73
97
3
3g
96
3c
3d
3e
[
c]
[d,e]
4
5
6
3h
3i
99
97
78
96
86
–
6
7
96
20
3j
3 f
7
3k
8
–
[
a] Reaction conditions: 25 mmol of 1a, 2.0 mol% KI, 2.0 mol% additive
, T=908C, p(CO )=10 bar, t=3 h; [b] Determined from GC analysis with
hexadecane as internal standard. Selectivity toward cyclic carbonate was
3
2
8
9
3l
99
99
95
47
ꢀ
99%; [c] 2.0 mol% KHCO
3
, 2.0 mol% KI, T=908C p(CO
2
)=10 bar, t=
)=
2
h; [d] 2.0 mol% KHCO , 2.0 mol% KI, 25 mol% H
3
2
O, T=908C, p(CO
2
10 bar, t=2 h.
3m
10
3n
99
94
10 bar (1 bar=100 kPa)] were chosen. In an initial screening,
we found that cyclic amines such as pyrrolidine (3b) and 1,8-
diazabicyclo[5.4.0]undec-7-ene (3c) demonstrate higher activity
than aliphatic amines (Table 1, entries 2–4). The use of imida-
zole (3d) and benzimidazole (3e) results in the formation of
carbonate 2a in excellent yields (96 and 97%, respectively;
Table 1, entries 5 and 6).
[
3
a] Reaction conditions: 25 mmol of 1a, 2.0 mol% KI, 2.0 mol% additive
, T=80 or 908C, p(CO )=10 bar, t=3 h; [b] Determined from GC analy-
2
sis with hexadecane as internal standard. Selectivity toward cyclic carbon-
ate was ꢀ99%; [c] In the absence of KI, the yield of 2a was 0% at 80 and
9
08C, respectively; [d] 2 mol% KCl, 2% yield of 2a; [e] 2 mol% KBr, 6%
yield of 2a.
In further investigations, different hydroxyl- and carboxyl-
functionalized imidazole derivatives 3h–m as well as the
amino acid l-proline (3g) were studied as additives (Table 2).
We envisioned a synergistic effect due to hydrogen bonding
between the oxirane and the hydroxyl functionality of the ad-
ditives 3h–m. Quantitative conversions of epoxide 1a and ex-
cellent yields (up to 99%) were obtained with various additives
was found to be a suitable additive for the synthesis of cyclic
carbonates under the chosen reaction conditions (Table 2,
entry 3), which is notable because the synthesis of cyclic carbo-
nates with use of catalytic amounts of KI and amino acids is
[8]
commonly performed at higher temperatures.
(
Table 2), which is notable because the reaction is performed
We further explored the effect of the reaction parameters in
our model reaction using 3h as an additive. The effect of the
reaction temperature on the yield of carbonate 2a was studied
in the temperature range of 25–908C (Figure 1). Low conver-
sions were observed at temperatures up to 508C. The yield of
carbonate 2a increased considerably up to 74% at 708C. A
quantitative conversion of epoxide 1a to carbonate 2a oc-
curred at 908C within a short reaction time of 3 h. At low tem-
peratures (between 50 and 708C), 3n was found to be slightly
more active than 3h.
The dependence of the yield of carbonate 2a on the reac-
tion time at an initial CO2 pressure of 10 bar and 908C is
shown in Figure 2. The conversion of epoxide 1a to product
2a proceeded quickly within the first 60 min. Notably, after
30 min, more than half of the epoxide 1a was converted into
with a transition-metal-free catalyst system under mild and sol-
vent-free conditions. Reaction temperatures above 1008C and
longer reactions times are usually required.
[
5,7,12]
To demon-
strate a better distinction of the activity of various additives,
the reaction was performed at a lower temperature (808C).
These results indicate that in contrast to unsubstituted imida-
zoles, substituted imidazoles with an additional hydroxyl
group were more active (Table 2, entries 1–5). If KCl or KBr is
used instead of KI, the yields were 2 and 6%, respectively.
Notably, 4(5)-(hydroxymethyl)imidazole (3h) and 1H-benzimi-
dazole-2-methanol (3l) demonstrated the same high catalytic
activity for the conversion of the model substrate 1a and CO2
into the cyclic carbonate 2a as did the previously reported KI/
TEA (3n) system (Table 2, entries 4, 8, and 10). In addition, 3g
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Figure 1. Effect of the reaction temperature. Reaction conditions: 25 mmol
of 1a, 2.0 mol% KI, 2.0 mol% 3h or 3n, p(CO )=10 bar, t=3 h.
2
Figure 3. Effect of the catalyst concentration. Reaction conditions: 25 mmol
of 1a, 0–2.0 mol% KI, 0–2.0 mol% 3h or 3n, KI/additive=1:1, T=908C,
2
p(CO )=10 bar, t=2 h.
pressure, the conversion of 1a was examined at 2–10 bar CO2
pressure and under isobaric conditions (Figure 4). In the pres-
sure range of 5–10 bar, there was no notable effect of pressure
on the yield of 2a. These results indicate that the synthesis of
carbonate 2a had already been performed in high yields (ꢀ
8
7%) with a constant low pressure (ꢀ3 bar). However, by per-
forming the reaction at extremely low pressures (ꢁ2 bar), con-
versions and yields decreased significantly below 16%.
Figure 2. Effect of the reaction time. Reaction conditions: 25 mmol of 1a,
.0 mol% KI, 2.0 mol% 3h or 3n, T=908C, p(CO )=10 bar.
2
2
carbonate 2a. Within 60 min, a high yield (82%) was obtained.
After 120 min, the yield increased up to 98%.
Consequently, further investigations were performed within
a short reaction time of 2 h. With respect to the yield of car-
bonate 2a, no significant difference was observed between
the additives 3h and 3n at different reaction times. The effect
of the catalyst concentration is shown in Figure 3. The best
result is obtained with equivalent amounts of KI and 3h or 3n,
respectively. As expected, the yield of carbonate 2a increases
with the increase in the concentration of the catalyst. An 80%
yield of product 2a was obtained with 1 mol% of a 1:1 mix-
ture of KI and an additive3n. An excellent yield (99%) was ob-
tained with a catalyst concentration of 2 mol% KI and 2 mol%
Figure 4. Effect of CO
2
pressure. Reaction conditions: 25 mmol of 1a,
2.0 mol% KI, 2.0 mol% 3h or 3n, T=908C, t=2 h.
No significant difference was observed between 3h and 3n
at different reaction pressures. As a result of the optimization
of the reaction conditions, both additives 3h and 3n demon-
strate a similar catalytic activity for the conversion of the
model compound 1a into the corresponding cyclic carbonate
2a.
To extend the scope of the developed catalyst system, vari-
ous epoxides 1 were converted into the corresponding carbo-
nates 2 with use of the catalyst system KI/3h under optimized
reaction conditions (Table 3). Analytically pure products were
obtained through simple filtration over silica gel, followed by
the removal of all volatiles in vacuum. High yields (ꢀ87%) of
the cyclic carbonates 2 were obtained through the conversion
3
h. In the absence of either KI or additive 3h and 3n, the de-
sired carbonate 2a was not obtained. Notably, at low catalyst
loadings (0.5 mol%), 3h demonstrated a significantly higher
activity than did 3n.
So far, the coupling reaction of epoxide 1a and CO was per-
2
formed under an initial CO pressure of 10 bar. Pressure is a sig-
2
nificant parameter with respect to safety concerns and con-
nected costs, especially for industrial plants. Hence, the conver-
sion at low pressures is desirable. To investigate the effect of
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entries 1 and 2). However, for most of the epoxides
[
a]
Table 3. Screening of functionalized imidazole additives.
1
, a slightly higher yield was obtained with KI/3h as
a catalyst. A notable effect was observed for the con-
version of long-chain epoxides such as 1,2-epoxyhex-
ane (1c), 1,2-epoxyoctane (1d), and 1,2-epoxy-5-
hexene (1i). Compared with the catalyst system KI/
3n, significantly higher yields (up to 93%) were ob-
tained for the corresponding carbonates 2c, 2d, and
[
b]
Entry
Product 2
Yield [%]
KI/3h
KI/3n
2
i with KI/3h (Table 3, entries 3, 4, and 9). We
[
c]
9
8
5
8
97 (99)
97
1
2
3
4
5
2a
2b
2c
2d
2e
assume that this is due to the lower solubility of 3n
in apolar substrates. In contrast, the same substrate
effect was less significant for 3h owing to the lower
polarity of 3h. Cyclohexene oxide (1l) and epoxi-
dized methyl oleate (1k) were tested as representa-
tives of internal epoxides. Internal epoxides are usual-
[
d]
[d]
95
55
97
92
74
ly less reactive than terminal epoxides owing to
1
1
0
5
[17–20]
steric hindrance.
Under optimized reaction con-
[
[
d]
d]
[d]
92
ditions, both catalyst systems demonstrated only
a low activity for the conversion of 1l. However,
under more rigorous reaction conditions [T=1208C,
7
6
9
1
90
83
[d]
p(CO )=50 bar, t=6 h], cyclohexene oxide (1l) was
2
converted into the corresponding carbonate 2l in
a high yield (78%) with KI/3h as a catalyst, whereas
only a moderate yield (27%) was obtained with KI/
3n (Table 3, entry 12). The conversion of 1m into the
corresponding carbonate was studied under our
standard reaction conditions used for the synthesis
of carbonated fatty acid esters. Oleochemical carbo-
nates can be used in various applications, such as the
production of potential industrial lubricants, fuel ad-
ditives, polymer plasticizers, and starting materials for
6
2 f
79
87
87
7
4
0
8
7
8
2g
2h
[
d]
[d]
94
84
59
90
93
90
9
2i
2j
[14]
polyesters and polycarbonate materials. However,
the desired cyclic carbonate 2m was formed only in
low amounts (Table 3, entry 13). In general, the cata-
lyst system KI/3h demonstrates a broader substrate
scope than KI/3n. The feasibility of catalyst recycling
was demonstrated for the model reaction under our
standard reaction conditions. In this case, 2a was
separated from the catalyst by Kugelrohr distillation.
The reused catalyst led to excellent yield (99%) in
the second cycle (entry 1).
9
9
1
9
1
0
[
[
d]
d]
[d]
99
9
9
7
8
93
99
11
2k
2l
[d]
2
7
4
78
1
1
2
3
[
[
e]
f]
[e]
2
[f]
2m
8
5
[
a] Reaction conditions: 25 mmol of 1, 2.0 mol% KI, 2.0 mol% 3h or 3n, T=908C,
p(CO )=10 bar, t=2 h; [b] Isolated yield; [c] Yield for the second cycle after the sepa-
ration of 2a through Kugelrohr distillation; [d] 1.0 mol% KI, 1.0 mol% 3h or 3n, T=
08C, p(CO )=10 bar, t=24 h; [e] T=1208C, p(CO )=50 bar, t=6 h; [f] T=1008C,
p(CO )=50 bar, t=16 h; yield determined from GC analysis.
Furthermore, we converted a number of selected
epoxides into the corresponding cyclic carbonates at
a lower temperature (608C) and only 1 mol% catalyst
2
6
2
2
(
Table 3, entries 1, 4, 5, 7, 10, and 11). Even though
2
the reaction time had to be increased to 24 h, high
yields (up to 99%) were obtained under these mild
reaction conditions (entries 10 and 11). The catalyst
system KI/3h again demonstrated higher activity than KI/3n.
of both nonfunctionalized and functionalized terminal epox-
ides (Table 1, entries 1–11). The previously reported results for
the catalyst system KI/3n are compared with the obtained re-
sults of both catalyst systems (see Table 3). During the optimi-
zation of reaction conditions, no remarkable effect was ob-
served for the conversion of short-chain epoxides, such as the
model compound 1a and propylene oxide (1b). The corre-
sponding cyclic carbonates 2a and 2b were isolated in high
yields (97 and 95%) using both additives, respectively (Table 3,
The general mechanism for the conversion of CO with ep-
2
oxide producing cyclic carbonates is well recognized and in-
volves three main elementary steps: epoxide ring opening,
CO2 insertion, and ring closure to form the five-membered
cyclic carbonate. The availability of a dissolved halogen anion
usually plays a crucial role in this reaction mechanism. Unfortu-
nately, any attempt to isolate a catalytically active species from
KI and 3h failed. NMR investigations to explain the interaction
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between 3h and KI were not successful. However, imidazolium
halides have already been described as a suitable catalyst for
[
15]
the synthesis of cyclic carbonates.
Moreover, we recently
found that the combination of KI and 1,3-bis(2,6-diisopropyl-
phenyl)imidazol-2-ylidene serves as an effective catalyst system
for the conversion of epoxides and CO into cyclic carbonates.
Scheme 2. Synthesis of the postulated active species 4.
2
Herein, we demonstrated that the reaction of the carbene
and KI in the presence of CO and small amounts of H O yields
2
2
the corresponding imidazolium iodide, which acts as a catalyst
KI/3h. Therefore, we suggest that 4 is the catalytically active
species of the catalyst system KI/3h. The addition of 25 mol%
[
16]
in this reaction. Therefore, we assumed that the reaction of
KI and 3h could also yield the corresponding 4-(hydroxymeth-
yl)-1H-imidazol-3-ium iodide (4). Therefore, we proposed the
putative reaction mechanism shown in Scheme 1. The free hy-
droxyl function of the in situ formed imidazolium iodide 4
could activate the epoxide. The activation of the epoxide by
a hydrogen bond donor accelerates the conversion with CO2.
Nucleophilic ring opening of the epoxide by the iodide leads
H O under the standard reaction conditions had no significant
2
effect on the reaction outcome, and product 2a was isolated
in 91% yield.
The formation of 4 from 3h and KI under the standard reac-
tion conditions most probably occurred in the presence of H O
2
and CO (Scheme 3). Tertiary amines form ammonium hydro-
2
gen carbonates in the presence of CO and H O in a reversible
2
2
[17]
to the corresponding halohydrin anion. Subsequent CO inser-
reaction. In a first step, we assume that the corresponding
2
tion and ring closing liberates the desired cyclic carbonate.
The corresponding halohydrin was detected by using GC–MS
after the aqueous workup of the reaction mixture. In this case,
4-(hydroxymethyl)-1H-imidazol-3-ium hydrogen carbonate (5)
is formed by the reaction of 3h and CO in the presence of
2
small amounts of H O. Subsequent exchange of the anion
2
2
a was converted in the presence of 50 mol% catalyst under
yields 4, along with the formation of potassium hydrogen car-
bonate as a byproduct. Notably, the postulated reaction
shown in Scheme 3 is an equilibrium reaction. This is most
probably the reason why we could not synthesize 4 from 3h
an argon atmosphere.
A sample of 4 was synthesized from 3h and aqueous hydro-
gen iodide (Scheme 2). The catalytic activity of 4 was proved
in the coupling reaction of 1a and CO under the reaction con-
and KI or isolate 4 under CO -free conditions.
2
2
ditions summarized in Table 3. With 4 as a catalyst, we could
convert epoxide 1a into carbonate 2a in 93% yield. This result
was comparable to the yield obtained with the catalyst system
Scheme 3. Formation of the catalytically active species 4 from 3h and KI.
Conclusions
We demonstrated that the combination of commercially avail-
able 4(5)-(hydroxymethyl)imidazole and KI serves as a simple
and efficient catalyst system for the coupling reaction of epox-
ides with CO . Several epoxides were converted into cyclic car-
2
bonates in high yields (up to 99%) under mild and solvent-free
conditions within a short reaction time. Moreover, we showed
that the developed catalyst system demonstrated higher activi-
ty than did the previously reported KI/triethanolamine system.
In addition, a plausible explanation for the high activity of the
catalyst system and the interaction of the additive 4(5)-(hy-
droxylmethyl)imidazole and KI was proposed. Overall, we
assume that this simple system is of general interest for the
synthesis of 1,3-dioxolan-2-one derivatives from epoxides and
CO2.
Scheme 1. Proposed reaction mechanism for the conversion of epoxides
1
into the corresponding carbonates 2 with the catalyst system KI/3h.
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[19]
4
-Ethyl-1,3-dioxolan-2-one (2a)
Experimental Section
According to GP1, 1a (1.81 g, 25.0 mmol) was converted into 2a in
the presence of KI (84 mg, 0.51 mmol) and 3h (49.0 mg,
All coupling reactions were performed in a 45 mL stainless steel re-
actor equipped with a magnetic stirrer. Epoxidized methyl oleate
[18]
0
9
2
.50 mmol). After removal of all volatiles, 2a (2.83 g, 24.3 mmol,
(1k) was prepared according to the method of Behr et al. All
1
7%) was obtained as a colorless oil. H NMR (400 MHz, CDCl3,
other starting materials were purchased from commercial sources
and used without further purification.
3
38C): d=1.02 (t, J =7.5 Hz, 3H), 1.69–1.87 (m, 2H), 4.08 (dd,
H,H
3
2
3
2
JH,H =8.4 Hz, J =7.0 Hz, 1H), 4.52 (dd, J =8.4 Hz, J =7.9 Hz,
H,H
H,H
H,H
13
1
1
H), 4.63–4.70 ppm (m, 1H); C{ H} NMR (100 MHz, CDCl , 238C):
3
d=8.4 (CH ), 26.9 (CH ), 69.0 (CH ), 78.0 (CH), 155.16 ppm (C=O);
3
2
2
+
+
Synthesis of 4
MS (EI): m/z (%): 116 [M ] (2), 87 [M ÀC H ] (79), 57 (14), 43 (100),
2
5
3
9 (14).
Aqueous hydrogen iodide (1.12 g, 5.0 mmol, 57 wt%) was added
slowly to a solution of 3h (0.491 g, 5.0 mmol) in 1,4-dioxane
(
10 mL). The reaction mixture was stirred at 258C for 20 h. Then,
[19]
4
-Methyl-1,3-dioxolan-2-one (2b)
the reaction mixture was extracted with ethyl acetate (10 mL) and
washed with H O (10 mL). The aqueous phase was concentrated
through evaporation, and the crude product was dried at 608C in
According to GP1, 1b (1.45 g, 25.0 mmol) was converted into 2b
in the presence of KI (83 mg, 0.50 mmol) and 3h (49 mg,
2
vacuum for 6 h. Compound 4 (1.00 g, 0.445 mmol, 89.0%) was iso-
0.50 mmol). After removal of all volatiles, 2b (2.48 g, 24.3 mmol,
1
1
lated as a colorless solid. H NMR (300 MHz, DMSO-d , 228C): d=
97%) was obtained as a colorless oil. H NMR (300 MHz, CDCl ,
6
3
3
3
3
3
2
4
1
2
.49 (d, J =8.6 Hz, 2H), 7.51 (s, 1H), 8.95 (d, J =1.3 Hz, 2H),
0.8–15.2 ppm (broad s, 2H); C{ H} NMR (75 MHz, DMSO-d ,
238C): d=1.48 (d, J =6.3 Hz, 3H), 4.02 (dd, J =8.4 Hz, J
=
H,H
H,H
H,H
H,H
H,H
13
1
3
2
6
7.2 Hz, 1H), 4.55 (dd, JH,H =8.4 Hz, JH,H =7.7 Hz, 1H), 4.80–
4.91 ppm (m, 1H); C{ H} NMR (75 MHz, CDCl , 238C): d=19.3
13
1
28C): d=55.33 (CH ), 116.09 (CH), 133.84 (CH), 134.32 ppm (CH);
2
3
À1
elemental analysis calcd (%) for C H IN O (M=226.02 gmol ): C
(CH ), 70.6 (CH ), 73.5 (CH), 155.0 ppm (C=O); MS (EI): m/z (%): 102
4
7
2
3
2
+
+
2
1
1.26, H 3.12, I 56.15, N 12.39; found: C 20.93, H 3.1, I 56.4, N
2.34.
(7) [M ], 87 (25) [M ÀCH ], 57 (100), 43 (78).
3
[19]
4
-Butyl-1,3-dioxolan-2-one (2c)
[
18]
Synthesis of 1m
According to GP1, 1c (2.51 g, 25.1 mmol) was converted into 2c in
the presence of KI (83.5 mg, 0.50 mmol) and 3h (49.1 mg,
0.50 mmol). After removal of all volatiles, 2c (3.31 g, 22.9 mmol,
Ru(acac) (acac=acetylacetonato; 80.0 mg, 0.20 mmol), dipicolinic
3
acid (668 mg, 4.0 mmol), and methyl oleate (11.8 g, 40 mmol) were
dissolved in acetonitrile (160 mL). After the addition of hydrogen
peroxide (35% aq, 12.8 g, 132 mmol), the mixture was stirred at
58C for 4 h. The resulting mixture was extracted with cyclohexane
4ꢂ200 mL). The collected cyclohexane phases were concentrated
up to 100 mL and washed with H O (50 mL). The organic phase
was dried over anhydrous MgSO , and all volatiles were evaporated
under reduced pressure. The pure product 1m (12.08 g,
7.7 mmol, 96%) was obtained as a colorless oil. H NMR (300 MHz,
1
9
2
(
8
2%) was obtained as a colorless oil. H NMR (300 MHz, CDCl3,
3
38C): d=0.91 (t, J =7.1 Hz, 3H), 1.28–1.49 (m, 4H), 1.62–1.86
m, 2H), 4.06 (dd, J =8.3 Hz, J =7.2 Hz, 1H), 4.52 (dd, J
.3 Hz, JH,H =7.9 Hz, 1H), 4.65–4.74 ppm (m, 1H); C{ H} NMR
H,H
3
2
3
=
H,H
H,H
H,H
2
(
2
13
1
(
75 MHz, CDCl , 238C): d=13.69 (CH ), 22.14 (CH ), 26.33 (CH ),
3
3
2
2
2
33.44 (CH ), 69.32 (CH ), 77.00 (CH), 155.04 ppm (C=O); MS (EI): m/z
2 2
4
(%): 87 (64), 86 (15), 71 (27), 58 (63), 57 (60), 56 (24), 55 (24), 44
29), 43 (100), 51 (50), 39 (25).
(
1
3
3
CDCl , 228C): d=0.88 (t,
.57–1.67 (m, 2H), 2.30 (t, JH,H =7.5 Hz, 2H), 2.86–2.92 (m, 2H),
.66 ppm (s, 3H); C{ H} NMR (75 MHz, CDCl , 228C): d=14.07
J
H,H
3
=6.7 Hz, 3H), 1.23–1.54 (m, 24H),
3
1
3
[20]
4
-Hexyl-1,3-dioxolan-2-one (2d)
1
3
1
3
(
2
CH ), 22.63 (CH ), 24.86 (CH ), 26.52 (CH ), 26.57 (CH ), 27.76 (CH ),
7.80 (CH ), 29.00 (CH ), 29.15 (CH ), 29.19 (CH ), 29.30 (CH ), 29.50
2 2 2 2 2
According to GP1, 1d (3.23 g, 25.2 mmol) was converted into 2d
in the presence of KI (83.0 mg, 0.50 mmol) and 3h (49.2 mg,
3
2
2
2
2
2
(
CH ), 29.52 (CH ), 31.82 (CH ), 34.02 (CH ), 51.42 (OCH ), 57.15 (CH),
0.50 mmol). After removal of all volatiles, 2d (3.19 g, 18.5 mmol,
2
2
2
2
3
1
5
2
1
7.20 (CH), 174.23 ppm (C=O); MS (EI): m/z (%): 281 (1) [MÀOCH ],
74%) was obtained as a colorless oil. H NMR (400 MHz, CDCl
3
,
3
3
64 (1), 199 (14) [C H O ], 171 (17), 155 (100) [C H O], 153 (20),
228C): d=0.87 (t, JH,H =6.9 Hz, 3H), 1.24–1.48 (m, 8H), 1.64–1.71
3 2
11
19
3
10 19
39 (19), 127 (23), 121 (10), 109 (26), 97 (34), 87 (32), 83 (32), 74
(m, 1H), 1.74–1.84 (m, 1H), 4.05 (dd,
J
H,H =8.4 Hz,
JH,H =7.2 Hz,
3
2
(
54), 69 (46), 55 (63), 43 (29), 41 (35).
1H), 4.52 (dd, JH,H =8.4 Hz, JH,H =7.9 Hz, 1H), 4.66–4.73 ppm (m,
13
1
1
H); C{ H} NMR (100 MHz, CDCl , 228C): d=13.88 (CH ), 22.35
3 3
(
7
CH ), 24.21 (CH ), 28.68 (CH ), 31.40 (CH ), 33.76 (CH ), 69.32 (CH ),
2 2 2 2 2 2
+
7.00 (CH), 155.03 ppm (C=O); MS (EI): m/z (%): 173(1) [M ], 110
+
+
General procedure (GP1) for the synthesis of cyclic carbo-
nates 2
(5), 95 (29), 87 (18) [M ÀC H ], 85 (13) [M ÀC H ], 81 (83), 68
6
13
6
13
(50), 58 (54), 57 (54), 55 (54), 43 (100), 41 (66), 39 (25).
The reactor was charged with KI (2 mol%), 3h (2 mol%), and epox-
ide 1 (25.0 mmol). The reactor was sealed and charged with CO to
[19]
2
4
-Phenyl-1,3-dioxolan-2-one (2e)
a pressure of 10 bar at 238C until the equilibrium was reached.
Then, the reactor was heated to 908C and the reaction mixture
stirred for 2 h. The reactor was cooled to ambient temperature,
According to GP1, styrene oxide (3.02 g, 25.1 mmol) was converted
into 2e in the presence of KI (84 mg, 0.51 mmol) and 3h (49 mg,
and CO was released slowly over a period of 10 min. The crude
0.50 mmol). After removal of all volatiles, 2e (3.73 g, 22.7 mmol,
2
1
product was filtered over silica gel with dichloromethane as a sol-
vent. After removal of all volatiles under vacuum, the pure cyclic
carbonate 2 was obtained.
90%) was obtained as a colorless solid. H NMR (300 MHz, CDCl ,
3
3
2
3
228C): d=4.36 (dd, J =8.6 Hz, J =7.9 Hz, 1H), 4.81 (dd, J =
8.5 Hz, J =8.3 Hz, 1H), 5.69 (t, J =8.0 Hz, 1H), 7.36–7.50 ppm
H,H
H,H
H,H
2
3
H,H
H,H
ꢁ
2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ChemCatChem 2014, 6, 3493 – 3500 3498

CHEMCATCHEM
FULL PAPERS
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1
3
1
1
(
(
(
m, 5H); C{ H} NMR (75 MHz, CDCl , 238C): d=71.1 (CH ), 78.0
22.5 mmol, 90%) was obtained as a colorless oil. H NMR (300 MHz,
3
2
4
4
CH), 125.8 (CH), 129.2 (2ꢂCH), 129.7 (2ꢂCH), 135.8 (C), 154.8 ppm
C=O); MS (EI): m/z (%): 164 (78) [M ], 119 (14), 105 (31), 91 (72),
0 (100), 89 (35), 78 (67), 77 (23), 65 (17), 51 (19).
CDCl , 238C): d=1.94 (dd, JH,H =1.5 Hz, JH,H =1.0 Hz, 3H), 4.29–
3
3 3
+
4.37 (m, 2H), 4.43 (dd, JH,H =12.6 Hz, JH,H =3.1 Hz, 1H), 4.58 (t,
3
9
JH,H =8.6 Hz, 1H), 4.95–5.02 (m, 1H), 5.64 (m, 1H), 6.13–6.15 ppm
13
1
(
m, 1H); C{ H} NMR (75 MHz, CDCl , 238C): d=18.1 (CH ), 63.4
3
3
(
1
4
CH ), 66.0 (CH ), 73.8 (CH), 127.2 (CH ), 135.1 (C), 154.4 (C=O),
66.6 ppm (C=O); MS (EI): m/z (%): 186 (24) [M ], 69 (100), 68 (38),
1 (50), 39 (24).
2
2
2
[
21]
+
4
-(4-Chlorophenyl)-1,3-dioxolan-2-one (2 f)
According to GP1, 2-(4-chlorophenyl)oxirane (3.87 g, 25.0 mmol)
was converted into 2 f in the presence of KI (83.3 mg, 0.50 mmol)
and 3h (49.5 mg, 0.50 mmol). After removal of all volatiles, 2 f
1
[10]
(
(
1
1
4.30 g, 21.7 mmol, 87%) was obtained as a colorless solid. H NMR
4-(Phenoxymethyl)-1,3-dioxolan-2-one (2k)
3
2
300 MHz, CDCl , 238C): d=4.31 (dd, JH,H =8.6 Hz, JH,H =7.8 Hz,
3
3 2 3
According to GP1, glycidyl phenyl ether (3.76 g, 25.0 mmol) was
converted into 2k in the presence of KI (83.7 mg, 0.50 mmol) and
h (50.0 mg, 0.51 mmol). After removal of all volatiles, 2k (4.53 g,
3.3 mmol, 93%) was obtained as a colorless solid. H NMR
H), 4.81 (dd, J =8.6 Hz, J =8.3 Hz, 1H), 5.66 (t, J =8.0 Hz,
H,H H,H H,H
13
1
H) 7.30–7.33 (m, 2H), 7.41–7.45 ppm (m, 2H); C{ H} NMR
3
(
75 MHz, CDCl , 238C): d=70.96 (CH), 77.20 (CH), 127.23 (2ꢂCH),
3
1
2
1
29.49 (2ꢂCH), 134.25 (C), 135.76 (CÀCl), 154.48 ppm (C=O); MS
3
2
+
(300 MHz, CDCl
3
, 238C): d=4.15 (dd,
J
H,H =10.6 Hz,
J
H,H =3.6 Hz,
(
EI): m/z (%): 198 (81) [M ], 163 (15), 139 (30), 124 (100), 119 (26),
3
2
1
5
7
H), 4.25 (dd, J =10.6 Hz, J =4.2 Hz, 1H), 4.52–4.65 (m, 2H),
.00–5.06 (m, 1H), 6.90–6.94 (m, 2H), 7.00–7.05 (m, 1H), 7.27–
H,H
H,H
112 (60), 89 (99), 75 (22), 63 (22), 50 (14).
13
1
.35 ppm (m, 2H); C{ H} NMR (75 MHz, CDCl , 238C): d=66.19
3
[19]
(
(
1
CH ), 66.81 (CH ), 74.09 (CH), 114.55 (2ꢂCH), 121.94 (CH), 129.66
2 2
2ꢂCH), 154.65 (C), 157.70 ppm (C=O); MS (EI): m/z (%): 194 (71),
07 (100), 94 (73), 79 (27), 77 (89), 66 (16), 65 (21), 51 (18), 39 (15).
4-(Chloromethyl)-1,3-dioxolan-2-one (2g)
According to GP1, epichlorohydrin (2.32 g, 25.1 mmol) was con-
verted into 2g in the presence of KI (83.3 mg, 0.50 mmol) and 3h
(
49.3 mg, 0.50 mmol). After workup, 2g (2.99 g, 21.9 mmol, 87%)
1
was obtained as a colorless oil. H NMR (400 MHz, CDCl , 238C):
d=3.69–3.83 (m, 2H), 4.40 (dd, JH,H =8.8 Hz, JH,H =5.8 Hz, 1H),
3
[20]
3
2
Cyclohexene oxide carbonate (2l)
3
2
4
.59 (dd, J =8.8 Hz, J =8.2 Hz, 1H), 4.94–5.02 ppm (m, 1H);
H,H H,H
According to GP1, cyclohexene oxide (1l) (2.47 g, 25.1 mmol) was
converted into 2l in the presence of KI (83 mg, 0.50 mmol) and 3h
1
3
1
C{ H} NMR (75 MHz, CDCl , 238C): d=43.56 (CH ), 66.94 (CH ),
3
2
2
+
7
(
4.18 (CH), 154.08 ppm (C=O); MS (EI): m/z (%): 136 (1) [M ], 87
100) [C H O ], 62 (5), 57 (5), 49 (9), 43 (26).
3 3 3
(
49 mg, 0.50 mmol) at 1208C and a CO pressure of 50 bar over
2
+
a period of 6 h. After removal of all volatiles, 2l (2.80 g, 19.7 mmol,
1
7
2
4
1
(
6
8%) was obtained as a colorless solid. H NMR (300 MHz, CDCl ,
3
38C): d=1.36–1.48 (m, 2H), 1.57–1.69 (m, 2H), 1.87–1.95 (m, 4H),
.65–4.72 ppm (m, 2H); C{ H} NMR (75 MHz, CDCl , 238C): d=
9.1 (2ꢂCH ), 26.7 (2ꢂCH ), 75.7 (2ꢂCH), 155.3 ppm (C=O); MS
EI): m/z (%): 142 (1) [M ], 97 (14), 83 (39) [C H ], 80 (32), 70 (43),
6 11
[10]
4-Vinyl-1,3-dioxolan-2-one (2h)
13
1
3
According to GP1, butadiene monoxide (1.73 g, 24.6 mmol) was
converted into 2h in the presence of KI (83.4 mg, 0.50 mmol) and
2
2
+
+
+
9 (100) [C H9 ], 57 (47), 55 (80), 54 (48), 42 (77), 41 (88).
3
h (49.6 mg, 0.50 mmol). After removal of all volatiles, 2h (2.55 g,
5
1
2
2.3 mmol, 91%) was obtained as a colorless oil. H NMR (300 MHz,
2
3
CDCl , 228C): d=4.15 (dd, J =8.5 Hz, J =7.5 Hz, 1H), 4.60 (dd,
3
H,H
H,H
2
3
JH,H =8.5 Hz, JH,H =8.1 Hz, 1H), 5.09–5.16 (m, 1H), 5.42–5.53 (m,
[22]
Carbonated methyl oleate (2m)
13
1
1
H), 5.84–5.96 ppm (m, 1H); C{ H} NMR (75 MHz, CDCl , 228C):
3
According to GP1, epoxidized methyl oleate (1m) (1.56 g,
d=69.01 (CH ), 77.29 (CH), 121.22 (CH ), 132.09 (CH), 154.71 ppm
2
2
5
0
.0 mmol) was converted into 2m in the presence of KI (16.6 mg,
(
C=O); MS (EI): m/z (%): 69 (7), 55 (9), 42 (100), 39 (51).
.10 mmol) and 3h (9.8 mg, 0.10 mmol) at 1008C and a CO pres-
2
sure of 50 bar over a period of 16 h. After the reaction, the reactor
[10]
4-(But-3-enyl)-1,3-dioxolan-2-one (2i)
was cooled to ambient temperature and CO was released slowly.
2
Hexadecane (400 mg) was added as an internal standard, and the
reaction mixture was diluted with dichloromethane (10 mL). The
catalyst was removed by purification of the reaction mixture over
silica gel column chromatography, and the resulting mixture was
analyzed by using 7890A-GC (Agilent). Pure samples of cis- and
trans-carbonated methyl oleate (2m) were obtained by purification
of the reaction mixture over silica gel column chromatography
According to GP1, 1i (2.47 g, 25.2 mmol) was converted into 2i in
the presence of KI (84 mg, 0.51 mmol) and 3h (50 mg, 0.51 mmol).
After removal of all volatiles, 2i (3.34 g, 23.5 mmol, 93%) was ob-
1
tained as a colorless oil. H NMR (300 MHz, CDCl , 238C): d=1.72–
3
3
1
8
4
.83 (m, 1H), 1.87–1.99 (m, 1H), 2.12–2.30 (m, 2H), 4.08 (dd, J
.4 Hz, J =7.2 Hz, 1H), 4.53 (dd, J =8.4 Hz, J =7.9 Hz, 1H),
.68–4.78 (m, 1H), 5.03–5.12 (m, 2H), 5.72–5.85 ppm (m, 1H);
C{ H} NMR (100 MHz, CDCl , 238C): d=28.6 (CH ), 33.0 (CH ), 69.3
=
H,H
2
3
2
H,H
H,H
H,H
using cyclohexane/ethyl acetate (10:1) as an eluent.
1
3
1
3
2
2
1
cis-Carbonated methyl oleate: H NMR (300 MHz, CDCl , 228C):
3
(
CH ), 76.3 (CH), 116.4 (CH ), 136.0 (CH), 154.9 ppm (C=O); MS (EI):
3
2
2
d=0.88 (t, JH,H =6.8 Hz, 3H), 1.22–1.44 (m, 20H), 1.46–1.75 (m,
H), 2.30 (t, J =7.5 Hz, 2H), 3.67 (s, 3H), 4.58–4.66 ppm (m, 2H);
C{ H} NMR (75 MHz, CDCl , 228C): d=14.05 (CH ), 22.60 (CH ),
m/z (%): 101 (8), 83 (21), 80 (28), 67 (19), 54 (100), 43 (99), 41 (50,
9 (53).
3
6
H,H
3
13
1
3
3
2
2
4.78 (CH ), 25.51 (CH ), 25.56 (CH ), 28.83 (CH ), 28.86 (CH ), 28.89
2
2
2
2
2
[10]
(CH
2
), 28.95 (CH
2
), 28.99 (CH
2
), 29.11 (CH
2
), 29.20 (CH
2
), 29.28 (CH ),
2
(2-Oxo-1,3-dioxolan-4-yl)methyl methacrylate (2j)
3
1.75 (CH ), 33.96 (CH ), 51.45 (OCH ), 79.88 (CH), 79.93 (CH),
2 2 3
According to GP1, glycidyl methacrylate (3.56 g, 25.0 mmol) was
converted into 2j in the presence of KI (84 mg, 0.51 mmol) and 3h
154.75 (C=O), 174.18 ppm (C=O); MS (EI): m/z (%): 357 (1), 325 (34),
294 (9), 262 (20), 239 (64), 221 (10), 181 (13), 164 (16), 155 (38), 135
(26), 121 (34), 109 (47), 95 (77), 81 (78), 69 (59), 55 (100), 43 (56), 41
(
50 mg, 0.51 mmol). After removal of all volatiles, 2j (4.18 g,
ꢁ
2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ChemCatChem 2014, 6, 3493 – 3500 3499

CHEMCATCHEM
FULL PAPERS
www.chemcatchem.org
+
(
56); HRMS (ESI): m/z calcd for C H O : 357.26355 [MH ]; found:
[7] J. Song, Z. Zhang, B. Han, S. Hu, W. Li, Y. Xie, Green Chem. 2008, 10,
20
36
5
1
337–1341.
3
57.26339.
1
[8] Z. Yang, J. Sun, W. Cheng, J. Wang, Q. Li, S. Zhang, Catal. Commun.
2014, 44, 6–9.
[9] J. S. B. Xiao, J. Wang, C. Liu, W. Cheng, Synth. Commun. 2013, 43, 2985–
trans-Carbonated methyl oleate: H NMR (300 MHz, CDCl , 228C):
d=0.85 (t, JH,H =6.8 Hz, 3H), 1.19–1.50 (m, 20H), 1.54–1.75 (m,
3
3
3
6
H), 2.28 (t, J =7.5 Hz, 2H), 3.64 (s, 3H), 4.17–4.24 ppm (m, 2H);
H,H
2
997.
1
3
1
C{ H} NMR (75 MHz, CDCl , 228C): d=13.97 (CH ), 22.50 (CH ),
3
3
2
[
10] a) M. A. Fuchs, S. Staudt, C. Altesleben, O. Walter, T. A. Zevaco, E. Dinjus,
Dalton Trans. 2014, 43, 2344–2347; b) M. A. Fuchs, C. Altesleben, S. C.
Staudt, O. Walter, T. A. Zevaco, E. Dinjus, Catal. Sci. Technol. 2014, 4,
1658–1673; c) M. E. Wilhelm, M. H. Anthofer, M. Cokoja, I. I. E. Markovits,
W. A. Herrmann, F. E. Kꢀhn, ChemSusChem 2014, 7, 1357–1360; d) C. J.
Whiteoak, N. Kielland, V. Laserna, E. C. Escudero-Adꢄn, E. Martin, A. W.
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2
2
4.48 (CH ), 24.52 (CH ), 24.69 (CH ), 28.79 (CH ), 28.84 (2ꢂCH ),
9.00 (CH ), 29.05 (CH ), 29.19 (CH ), 31.66 (CH ), 33.67 (CH ), 33.68
2 2 2 2 2
2
2
2
2
2
(
CH ), 33.85 (CH ), 51.34 (OCH ), 81.87 (CH), 81.91 (CH), 154.60 (C=
2 2 3
O), 174.05 ppm (C=O); MS (EI): m/z (%): 357 (1), 325 (35), 294 (7),
2
1
62 (17), 241 (25), 239 (32), 221 (18), 181 (11), 164 (14), 155 (24),
35 (25), 121 (34), 109 (55), 95 (86), 81 (83), 69 (60), 55 (100), 43
+
(
55), 41 (56); HRMS (ESI): m/z calcd for C H O : 357.26355 [M
20 36 5
ÀH]; found: 357.26334.
Acknowledgements
We thank the Federal Ministry of Research and Education, Ger-
many, (BMBF) for financial support (Technologien fꢀr Nachhaltig-
keit und Klimaschutz – Chemische Prozesse und stoffliche Nut-
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Keywords: alkali metals · carbon dioxide fixation · cyclic
carbonates · cycloaddition · organocatalysis
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Received: July 23, 2014
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Published online on October 10, 2014
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