Silica gel modified with tetraalkylammonium halides as an available and efficient catalyst for the synthesis of cyclic organic carbonates from epoxides and CO2

Article abstract of DOI:10.1007/s11172-019-2637-6

Silica gel with the additives of tetraalkylammonium halides serves as an efficient catalyst for the solvent-free insertion of carbon dioxide into epoxides (10–56 atm of CO₂, 105–100 °C), leading to cyclic carbonates with quantitative conversion

Full text of DOI:10.1007/s11172-019-2637-6

1866
Russian Chemical Bulletin, International Edition, Vol. 68, No. 10, pp. 1866—1868, October, 2019
Siliсa gel modified with tetraalkylammonium halides as an available
and efficient catalyst for the synthesis of cyclic organic carbonates
from epoxides and СО2
S. E. Lyubimov,а M. V. Sokolovskaya, B. Chowdhury, A. V. Arzumanyan, R. S. Tukhvatshin,
а
b
а
а
а
а
а
а
L. F. Ibragimova, A. A. Tyutyunov, V. A. Davankov, and A. M. Muzafarov
аA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
2
8 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 6471. E-mail: lssp452@mail.ru
b
Department of Applied Chemistry, Indian Institute of Technology (Indian School of Mines),
Dhanbad, 826004, India.
E-mail: biswajit72@iitism.ac.in
Silica gel with the additives of tetraalkylammonium halides serves as an efficient catalyst for
the solvent-free insertion of carbon dioxide into epoxides (10—56 atm of CO , 105—100 °С),
2
leading to cyclic carbonates with quantitative conversion.
Key words: cyclic carbonates, silica gel, epoxides, carbon dioxide, carbon dioxide fixation.
Processing of carbon dioxide into practically signifi-
Results and Discussion
cant organic compounds is an actual problem of modern
chemistry.1 This problem is not only environmentally
substantiated, since CO2 is one of the main compo-
nents of greenhouse gas, but also interesting in practi-
cal terms because it is available and non-toxic. At the
For initial testing, we selected two types of silica gel
for column chromatography as catalysts, differing in par-
ticle sizes (SG1, 0.06—0.2 mm; SG2, 0.04—0.063 mm).
The silica gels were tested in the addition of CO to cyclo-
2
same time, CO is characterized by high thermodynamic
hexene oxide (1), which leads to cyclohexene carbonate
(2) (Scheme 1). At an initial pressure of 56 atm and heat-
ing to 105 °С, the reaction, as it turned out, did not occur
(Table 1, entries 1 and 2). Taking into account the postu-
2
inertness with respect to the main classes of organic
compounds, which complicates the development of the
2
corresponding catalysts. One of the most striking ex-
1
1
amples of the direct insertion of CO into an organic
lated reaction mechanism, which requires the presence
of a halide ion to ensure the occurrence of the process, we
modified silica gel with the tetrabutylammonium iodide
additives. In this case, both catalysts provided high conver-
sion (entries 3 and 4), with SG2 silica gel with a smaller
2
molecule is its catalytic coupling with epoxides to form
cyclic organic carbonates.3 The latter are used as aprotic
polar solvents, fuel additives, electrolytes for lithium-
ion batteries, anti-caking agents, as well as monomers
for the production of polycarbonates and polyureth-
anes.5 Despite the industrial success of this reaction,
the development of efficient inexpensive catalysts com-
bining the ability to quickly complete the reaction at
low temperatures and pressures of carbon dioxide con-
,4
particle size being more efficient. Note that Bu NI itself
4
—8
in the absence of silica gel does not catalyze the process
under the same conditions. When Bu NI was replaced
4
with the more common bromide Bu NBr, the conversion
4
was also high (cf. entries 4 and 5). An increase in the
9
—19
tinues. The catalysts for this reaction are very diverse,
content of the Bu NBr additive leads to even more com-
4
for example, transition and non-transition metal com-
plexes (including exotic ones based on Sc, Sm, Y, La, Re),
modified carbon nanotubes, crown ether complexes,
modified molecular sieves, ionic liquids based on am-
monium, imidazolium, and phosphonium systems, as
well as polyols.
In the present work, we show that cheap silica gel used
for column chromatography and modified with tetraalkyl-
ammonium halide additives can efficiently and quantita-
tively convert different epoxides to carbonates.
plete conversion (cf. entries 5 and 6). The study of the
effect of CO pressure on the rate of the process showed
2
that its efficiency practically does not decrease at a pressure
of 20 or even 10 atm (entries 7 and 8). The use of Bu NCl
4
as an additive gave a less acceptable result compared to
the corresponding bromide or iodide, however, an increase
in the content of chloride Bu NCl clearly had a positive
4
effect on the rate of the process (entries 9 and 10). The
effect of Et NCl with shorter alkyl substituents is close to
4
that of Bu NCl (entry 11). Finally, for the Bu NBr•SG2
4
4
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1866—1868, October, 2019.
066-5285/19/6810-1866 © 2019 Springer Science+Business Media, Inc.
1

Catalyst for cyclic carbonates
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 10, October, 2019
1867
system a quantitative conversion of cyclohexene oxide (1)
to carbonate 2 was achieved by a slight increase in tem-
perature from 105 to 110 °С (entry 12).
To sum up, we have proposed the most available at
present catalyst for the synthesis of cyclic carbonates from
the corresponding epoxides. The catalyst consists of widely
used column chromatography silica gel and available
quaternary ammonium salt Bu NBr. Note that this sim-
4
Scheme 1
plest catalytic system allows one to carry out the reaction
without solvent, providing quantitative conversion of
epoxides to carbonates, regardless of the steric and elec-
tronic factors of the starting substrates.
Experimental
1H, 13С and 19F NMR spectra were recorded on Bruker
Avance 400 spectrometer (400.13, 100.61, and 376.5 МHz).
Silica gel SG1 (0.06—0.2 mm, 60 Å, Acros Organics), SG2
Cat is the catalyst.
(
0.04—0.063 mm, 60 Å, Merck), cyclohexene oxide (1), 2-(chloro-
Using this simple catalyst (Bu NBr•SG2) and the
optimized conditions, we studied the addition of CO to
other epoxides 3a—h (Scheme 2). In all the cases, the
corresponding carbonates 4a—h were obtained in quanti-
tative yield.
4
methyl)oxirane (3a), 2-(phenoxymethyl)oxirane (3e), and 2-phen-
yloxirane (3h) are commercially available reagents. 2-(Fluoro-
methyl)oxirane (3b), 2-(2,2,2-trifluoroethyl)oxirane (3c), 2-[(penta-
fluorophenyl)methyl]oxirane (3d), 2-(N,N-diethylaminomethyl)-
oxirane (3f), and 4-(oxirane-2-ylmethyl)morpholine (3g) were
obtained according to procedures described earlier.2
2
0—24
Synthesis of carbonates 2 and 4а—h from epoxides. The cor-
responding silica gel (18 mg), tetraalkylammonium halide
Scheme 2
(
3—6 mg) (see Table 1 and Scheme 2) were placed in a 10-mL
autoclave, followed by the addition of epoxide 1 or 3а—h
0.2 mL). The autoclave was filled with CO (initial pressure 10,
(
2
2
0, or 56 atm) and heated to the required temperature in
a thermostat. After completion of the reaction, the autoclave was
cooled, decompressed, and opened, dichloromethane (2 mL)
was added to the residue, the mixture was filtered through a short
layer of silica gel, the solvent was evaporated, and the reac-
tion mixture was analyzed by NMR. The spectral characteristics
of carbonates 2 and 4a,b,e—h correspond to the literature
R = CH Cl (a), CH F (b), CH CF (c), CH C F (d), CH OPh (e),
2
2
2
3
2
6
5
2
CH NEt2 (f), (morpholin-4-yl)methyl (g), Ph (h)
2
1
0,22,25,26
data.
Reagents and conditions: i. CO (initial pressure 56 atm), 3 (0.2 mL),
2
4-(2,2,2-Trifluoroethyl)-1,3-dioxolan-2-one (4c). A white
powder, m.p. 63 °C. Found (%): C, 35.26; H, 3.04. C H F O .
NBu Br (6 mg), SG2 (18 mg), 110 °C, 24 h.
4
5
5
3
3
1
Calculated (%): C, 35.31; H, 2.96. H NMR (CDCl ), δ:
3
2
4
.51—2.64 (m, 1 H); 2.74—2.87 (m, 1 H); 4.25 (t, 1 Н, J = 8.0 Hz);
Table 1. Insertion of CO2 into the molecule of cyclohexene
oxide (1)
13
.68 (t, 1 Н, J = 8.0 Hz); 4.98—5.05 (t, 1 H). C NMR (CDCl ),
3
δ: 38.06 (q, J = 29.0 Hz); 68.78 (s); 70.50 (q, J = 3.0 Hz); 124.45
1
9
(
q, J = 277.15 Hz); 153.74. F NMR (CDCl ), δ: –63.84.
3
Entry
Catalyst
T/°C P/atma
t/h Conversion
4
-[(Pentafluorophenyl)methyl]-1,3-dioxolan-2-one (4d).
(
%)
A white powder, m.p. 133 °C. Found (%): C, 44.71; H, 1.96.
1
C10H F O . Calculated (%): C, 44.79; H, 1.88. H NMR
5
5
3
1
2
3
4
5
6
7
8
9
SG1
105
105
105
105
105
105
105
105
105
105
105
110
56
56
56
56
56
56
20
10
56
56
56
56
24
24
24
24
24
24
24
24
24
24
24
24
0
0
(
400.13 МHz, CDCl ), δ: 3.12—3.27 (m, 2 H); 4.25 (t, 1 Н,
3
SG2
b
J = 8.0 Hz); 4.62 (t, 1 Н, J = 8.0 Hz); 4.92—4.98 (m, 1 H).
Bu NI •SG1
70
89
4
1
3
b
C NMR (75.5 МHz, CDCl ), δ: 26.83 (CH ); 68.62 (CH —O);
3
2
2
Bu NI •SG2
4
2
3
b
74.53 (CH—O); 107.99 (dt, ipso-C, J
C—F
= 18.3 Hz, J
C—F
=
Bu NBr •SG2
86
4
= 3.8 Hz); 137.69 (ddddd, m-C—F, 1J
= 253.8 Hz,
c
C—F
Bu NBr •SG2
95
4
2
2
3
4
c
JC—F = 17.4 Hz, J
C—F
= 12.7 Hz, J
C—F
= 4.9 Hz, J
C—F
= 13.3
= 247.6
=
Bu NBr •SG2
93
4
1
2
c
= 1.9 Hz); 140.90 (dtt, p-C—F, J
Hz, J
Hz, J
C—F
= 254.8 Hz, J
C—F
Bu NBr •SG2
92
4
3
1
b
C—F
C—F
= 5.4 Hz); 145.45 (dddd, 2 o-C—F, J
C—F
Bu NCl •SG2
35
4
2
3
3
c
= 15.6 Hz, J
C—F
= 8.1 Hz, J
C—F
= 3.0 Hz); 153.92
1
1
1
0
1
2
Bu NCl •SG2
54
4
1
9
c
(C=O). F NMR (376.50 МHz, CDCl ), δ: –(160.87—160.67)
3
Et NCl •SG2
50
4
c
(m, 2 F); –153.56 (t, 1 F, J = 22.6 Hz); –141.92 (dd,
Bu NBr •SG2
100
4
2
F, J = 7.53 Hz, J = 22.6 Hz).
a
b
c
Initial pressure before heating.
Alk NHal (3 mg)+ SG1 or SG2 (18 mg).
This work was financially supported by the Russian
Science Foundation (Project No. 19-43-02031).
4
Alk NHal (6 mg) + SG2 (18 mg).
4

1868
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 10, October, 2019
Lyubimov et al.
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Received June 17, 2019;
in revised form June 26, 2019;
accepted July 4, 2019
1