Facile synthesis of glycerol carbonate from glycerol using selenium-catalyzed carbonylation with carbon monoxide

Article abstract of DOI:10.1002/hc.20640

The commercial production of glycerol has increased considerably for several years, because of its rising inevitable formation as a by-product of biodiesel. For the effective utilization of glycerol, a new synthesis of glycerol carbonate (4-hydroxymethyl-2-oxo-1,3-dioxolane) that is used as solvents and raw material of plastics from glycerol was explored. By combined the selenium-catalyzed carbonylation of slightly excess of glycerol with carbon monoxide and potassium carbonate under 0.1 MPa at 20°C for 4 h in DMF with the oxidation of resulting selenocarbonate salt with molecular oxygen (0.1 MPa, 20 °C) for 2 h, glycerol carbonate was obtained in good yields (83-84%). However, sodium hydride to form sodium alkoxide in situ lowered the yield of glycerol carbonate. Use of triethylamine, 1-methylpyrrolidine, and DBU as bases gave poor results. Furthermore, styrene carbonate was obtained in excellent yield (90%) under similar reaction conditions. The catalytic synthesis of glycerol carbonate was also brought about in the mixed gas atmosphere (carbon monoxide:oxygen = 3:1, 0.1 MPa, 20°C). Glycerol carbonate and styrene carbonate were obtained in reasonable yields (197% and 119%, based on selenium used).

Full text of DOI:10.1002/hc.20640

Heteroatom Chemistry
Volume 21, Number 7, 2010
Facile Synthesis of Glycerol Carbonate from
Glycerol Using Selenium-Catalyzed
Carbonylation with Carbon Monoxide
Takumi Mizuno, Takeo Nakai, and Masatoshi Mihara
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku,
Osaka 536-8553, Japan
Received 11 June 2010; revised 5 August 2010
INTRODUCTION
ABSTRACT: The commercial production of glycerol
has increased considerably for several years, because
of its rising inevitable formation as a by-product of
biodiesel. For the effective utilization of glycerol, a
new synthesis of glycerol carbonate (4-hydroxymethyl-
2-oxo-1,3-dioxolane) that is used as solvents and
raw material of plastics from glycerol was explored.
By combined the selenium-catalyzed carbonylation of
slightly excess of glycerol with carbon monoxide and
potassium carbonate under 0.1 MPa at 20◦C for 4 h
in DMF with the oxidation of resulting selenocarbon-
The increase in new renewable oils that have been
used for energy applications as automotive fuels has
become a new trend in several years. The so-called
“biodiesel” is a popular term for the fatty acid methyl
esters, formed from transesterification of rapeseed
oil with methanol. Biodiesel production in the Eu-
ropean Union was estimated to be about 6 Mt in
2006 and is forecasted to increase to about 12 Mt in
2010. Biodiesel has been developed rapidly in United
States and in Europe, accompany with the formation
of a large quantity of glycerol (1a) as a by-product.
Obviously, the question arises how this additional
1a can be used wisely [1].
From a number of glycerol applications, glycerol
carbonate (4-hydroxymethyl-2-oxo-1,3-dioxolane,
2a) and its esters are very interesting derivatives
of glycerol (1a), because of their usability as sol-
vents for many applications, for instance in colors,
varnishes, glues, cosmetics, and pharmaceuticals
[1]. Also, glycerol carbonate (2a) has a considerable
possibility to be an intermediate of polycarbonate
production [2] and the use of 2a was investigated
as monomer to synthesize hyperbranched aliphatic
polyesters (polyglycerols) [3].
◦
ate salt with molecular oxygen (0.1 MPa, 20 C) for
2 h, glycerol carbonate was obtained in good yields
(83–84%). However, sodium hydride to form sodium
alkoxide in situ lowered the yield of glycerol carbonate.
Use of triethylamine, 1-methylpyrrolidine, and DBU as
bases gave poor results. Furthermore, styrene carbon-
ate was obtained in excellent yield (90%) under simi-
lar reaction conditions. The catalytic synthesis of glyc-
erol carbonate was also brought about in the mixed
gas atmosphere (carbon monoxide:oxygen = 3:1, 0.1
MPa, 20◦C). Glycerol carbonate and styrene carbonate
were obtained in reasonable yields (197% and 119%,
ꢀ
C
based on selenium used). 2010 Wiley Periodicals, Inc.
Heteroatom Chem 21:541–545, 2010; View this article on-
line at wileyonlinelibrary.com. DOI 10.1002/hc.20640
Among the synthetic methods for glycerol car-
bonate (2a) from glycerol (1a), the direct synthesis
of 2a by the conversion of 1a with carbon dioxide
has been studied using organic tin compounds (di(n-
butyl)tin dimethoxide, di(n-butyl)tin oxide, and tin
dimethoxide) as catalysts. Under the drastic re-
action conditions (5.0 MPa of CO2, 180◦C), tin
dimethoxide led only to traces of 2a. However,
Correspondence to: Takumi Mizuno; e-mail: tmizuno@
omtri.or.jp.
Contract grant sponsor: Ministry of Education, Culture, Sports,
Science and Technology, Japan.
Contract grant number: 22550144.
2010 Wiley Periodicals, Inc.
c
ꢀ
541

542 Mizuno, Nakai, and Mihara
TABLE 1 Influence of Various Conditions on Synthesis of 2a
Se Isolated
di(n-butyl)tin dimethoxide gave a little conversion of
1a (maximum 7%) depending on the reaction con-
ditions [4]. Furthermore, the catalytic conversion of
1a with urea to 2a has been researched in the pres-
ence of heterogeneous zinc catalysts (Zn(CH3C6H4-
SO3)2 and ZnSO4). At temperature 140–150◦C and a
pressure of 4.0 KPa, equimolar amounts of 1a and
urea reacted to afford 2a in good yields [5]. Also,
very recently, synthesis of 2a from 1a with dimethyl
carbonate in the presence of an uncalcined Mg-Al
hydrotalcite catalyst was reported [6].
Recently, we reported a useful synthetic method
for glycerol carbonate (2a), which has been devel-
oped by the sulfur-assisted carbonylation of glycerol
(1a) with carbon monoxide under 1.0 MPa at 80◦C in
DMF, and the oxidation of resulting carbonothioate
salts with copper(II) bromide under 0.1 MPa in air
at 20◦C [7]. However, this synthetic reaction needs
slightly severe reaction conditions and metallic oxi-
dants. About 40 years ago, our research group found
that selenium-catalyzed carbonylation with carbon
monoxide using large excess amount of alkoxides
and alcohols under mild reaction conditions (0.1
MPa, 20◦C) to give corresponding carbonates in ex-
cellent yields [8–10]. Therefore, our objective has
been to develop a straightforward synthesis for 2a
by the carbonylation of 1a with carbon monoxide
using selenium-catalyst under milder reaction con-
ditions (0.1 MPa, 20◦C) followed by oxidation with
molecular oxygen and to establish the catalytic syn-
thesis of 2a in the mixed gas atmosphere (carbon
monoxide and oxygen, 0.1 MPa, 20◦C).
Entry
Base (mmol)
(mmol) Solvent Yield (%)a
1
2
3
4
5
6
7
8
K2C03, 10
K2C03, 10
K2C03, 10
K2C03, 10
K2C03, 10
K2C03, 20
K2C03, 20
K2C03, 50
10
5
3
2
1
10
20
20
3
3
3
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
THF
22
55
84
83
61
43
45b
58b
40
9
NaH, 10
10
11
12
13
Triethylamine, 10
1-Methylpyrrolidine, 10
DBU, 10
NR
NR
c
3
3
—
K2C03, 10
NR
aYields based on selenium.
bYields based on glycerol.
c Tar was formed.
ambient pressure of molecular oxygen at 20◦C for
2 h to obtain 2a in low yield (22%) (Table 1, entry
1). In the previous results of the selenium-catalyzed
carbonylation with carbon monoxide, 20–40 equiv.
of alkoxides and alcohols was used [8,9]. Then, for
the improvement of yields of 2a, the reactions us-
ing excess equivalents of 1a and potassium carbon-
ate (2–10 equiv.) were tried (entries 2–5). The use of
3–5 equiv. of 1a and equimolecular amount of potas-
sium carbonate gave excellent results to afford 2a
in 83–84% (entries 3 and 4). Furthermore, the ef-
fects on the excess amount of catalyst selenium and
potassium carbonate were checked. Yield of 2a was
increased to 58% in the presence of 2.0 equiv. of
selenium and 5.0 equiv. of potassium carbonate (en-
try 8). In this reaction, 2a was synthesized selec-
tively and the formation of isomeric cyclic carbonate
(5-hydroxy-2-oxo-1,3-dioxane) was not observed.
Next, the influence of bases and solvent was ex-
amined on the selenium-catalyzed carbonylation of
1a with carbon monoxide (entries 9–13). In our pre-
vious report [8,9], the selenium-catalyzed carbony-
lation with carbon monoxide was established using
alkoxides and alcohols as reactants. Therefore, the
use of sodium hydride that leads to in situ forma-
tion of sodium alkoxide from 1a was tried. How-
ever, yield of 2a was lowered (entry 9). Thus, in this
RESULTS AND DISCUSSION
For the stoichiometric synthesis of glycerol carbon-
ate (2a), the carbonylation of glycerol (1a) with car-
bon monoxide, selenium, and base and the following
oxidation of resulting selenocarbonate salt (3a) with
molecular oxygen under mild conditions were exam-
ined (Scheme 1). At first, reaction of 1a with carbon
monoxide (0.1 MPa) and selenium (1.0 equiv.) in the
presence of potassium carbonate (1.0 equiv.) at 20◦C
for 4 h in DMF solvent was performed. Then, the
generated salt 3a in DMF was oxidized by under an
HO
1) Base/Solvent (20 mL),
0.1 MPa, 20oC, 4 h
OH
HO
OH
+
CO
+
Se
O
O
2) O2, 0.1 MPa, 20oC, 2h
2a
1a (10 mmol)
SCHEME 1 Stoichiometric synthesis of 2a.
O
Heteroatom Chemistry DOI 10.1002/hc

Facile Synthesis of Glycerol Carbonate from Glycerol Using Selenium-Catalyzed Carbonylation with Carbon Monoxide 543
X
1) K2CO3 (5.0 equiv.)/
OH
DMF, 0.1 MPa, 20 oC, 4 h
X= CH2OH: 83% (2a)
H: 36% (2b)
+
+
CO
Se
OH
1a–d, 5.0 equivs.
SCHEME 2 Some cyclic carbonate synthesis (2a–d).
O
O
2) O2, 0.1 MPa, 20oC, 2h
X
CH3:31% (2c)
Ph: 90% (2d)
O
cat. Se (0.1 equiv.),
K2CO3 / DMF
X
CO : O2 = 10:1, 112% (X = CH2OH)
= 5:1, 78% (X = CH2OH)
= 3:1, 197% (X = CH2OH)
119% (X = Ph)
OH
+
+
O2
CO
OH
1a,d
SCHEME 3 Catalytic synthesis of 2a,d.
O
O
0.1 MPa, 20oC, 24 h
X
2a,d
= 2:1, 69% (X = CH2OH)
O
reaction system, the troublesome in situ formation
of sodium alkoxide was unnecessary. In addition, the
carbonylation of 1-pentanol with potassium carbon-
ate as a base was performed under similar selenium-
catalyzed reaction conditions and corresponding
carbonate was not obtained at all. Using triethy-
lamine and 1-methylpyrrolidine as beses or THF sol-
vent, no reaction was caused (entries 10, 11, and
13). Stronger base (1,8-diazabicyclo[5.4.0]undec-7-
ene (DBU)) gave a poor result to afford only tar (en-
try 12).
Several cyclic carbonates (2b–d) from 5.0 equiv.
of glycols (1b–d) and potassium carbonate were
synthesized by the selenium-catalyzed carbonylation
with carbon monoxide (0.1 MPa, 20◦C) for 4 h and
oxidation with molecular oxygen (0.1 MPa, 20◦C)
for 2 h in similar manner (Scheme 2). The yields
of ethylene carbonate (2-oxo-1,3-dioxolane, 2b) and
propylene carbonate (4-methyl-2-oxo-1,3-dioxolane,
2c) were lowered. However, styrene carbonate (2-
oxo-4-phenyl-1,3-dioxolane, 2d) was obtained in ex-
cellent yield.
Then, the catalytic synthesis of glycerol carbon-
ate (2a) was also examined. Under the various ra-
tios of carbon monoxide and oxygen atmosphere
(0.1 MPa), the synthesis of glycerol carbonate (2a)
by the carbonylation of glycerol (1a) with potas-
sium carbonate in the presence of catalytic amount
of selenium (10 mol%) at 20◦C for 24 h was tried
(Scheme 3). Yield of 2a was reached 197% (based
on selenium used) using mixed gas (carbon monox-
ide:oxygen = 3:1). Under similar catalytic reaction
conditions (CO:O2 = 3:1), styrene carbonate (2d) was
given in 119% (based on selenium used).
carbonate salt 3a. First, elemental selenium under-
goes Se–Se bond fission by the reaction with an-
ion of 1a to form selenolate anion (4a). The re-
action of 4a with carbon monoxide gives seleno-
carbonate salt (3a) from carbonylated species. Be-
cause of equilibrium of 3a with anion of 1a and
carbonyl selenide, excess amounts of 1a and potas-
sium carbonate might need to synthesize 2a in high
yields. The formed 3a is oxidized by molecular oxy-
gen giving 2a and hydrogen selenide (6a) via biscar-
bonodiselenide (5a). Then, 6a was oxidized to re-
cover elemental selenium. In the carbonate synthe-
sis from alcohols with carbon monoxide and sulfur,
OH
OH
K2CO3/DMF
+
Se
HO
OSex Se
HO
OH
1a
4a
O
OH
O
OH
Sex
CO
HO
OSex SeC
HO
+
OCSe
3a
OH
3a
HO
O
Se=C=O
HO
O
OH
O2
HSeSeH
O
+
O
2a
HO
OCSe
2
O
5a
O2
Se
H2O
+
HSeSeH
H2Se
Se
Scheme 4 shows possible paths for the synthe-
sis of glycerol carbonate (2a) by the carbonylation
of glycerol (1a) followed by oxidation of the seleno-
6a
SCHEME 4 Proposed reaction path for the synthesis of 2a.
Heteroatom Chemistry DOI 10.1002/hc

544 Mizuno, Nakai, and Mihara
(C=O), 1403, 1179, 1087; 1H NMR (d6-DMSO) δ
(ppm): 3.46–3.53 (m, 1H, CH2), 3.62–3.69 (m, 1H,
CH2), 4.27 (d,d, J = 5.9, 8.4 Hz, 1H, CH2), 4.48 (t, J =
8.4 Hz, 1H, CH2), 4.75–4.82 (m, 1H, CH), 5.23 (t, J =
5.7 Hz, 1H, OH); 13C NMR (d6-DMSO) δ (ppm): 60.6,
65.8, 77.0, 155.1; MS (CI, reagent gas: methane) m/z
(%): 119 (M + H+, 100), 63 (4), 57 (37).
biscarbonodisulfide formed as intermediate was iso-
lated by oxidation of carbonothioate salt with cop-
per(II) chloride [11].
CONCLUSION
In summary, a useful synthetic method for glycerol
carbonate (2a) has been developed by the selenium-
catalyzed carbonylation of glycerol (1a) with carbon
monoxide and potassium carbonate under 0.1 MPa
at 20◦C in DMF, and the oxidation of resulting se-
lenocarbonate salt (3a) with molecular oxygen under
0.1 MPa at 20◦C. Slightly excess of 1a and potassium
carbonate gave 2a in good yields (83–84%). Also, the
catalytic reaction of glycerol (1a) was performed in
the mixed gas atmosphere (carbon monoxide:oxygen
= 3:1, 0.1 MPa, 20 ◦C) to form glycerol carbonate (2a)
in reasonable yield. From the viewpoint of making
good use of 1a, which is a by-product of biodiesel
production, the present method might give an addi-
tional field of application on 1a.
Ethylene carbonate 2b. Yield: 63 mg (36%)
yield; mp 35.6◦C, (Lit. [12] 36.2◦C); IR (KBr, cm−1)
ν : 2995, 1799 (C=O), 1163, 1068, 773; 1H NMR
(CDCl3) δ (ppm): 4.53 (s, 4H, CH2); 13C NMR (CDCl3)
δ (ppm): 64.5, 155.4; MS m/z (%): 88 (M+, 100), 73 (4),
58 (13).
Propylene carbonate 2c. Yield: 63 mg (31%)
yield; oil [12]; IR (neat, cm−1) ν: 2987, 1791 (C=O),
1389, 1184, 1053; 1H NMR (CDCl3) δ (ppm): 1.50 (d,
J = 6.2 Hz, 3H, CH3), 4.03 (d,d, J = 8.4, 8.4 Hz, 1H,
CH2), 4.56 (d,d, J = 8.4, 8.4 Hz, 1H, CH2), 4.81–4.92
(m, 1H, CH); 13C NMR (CDCl3) δ (ppm): 19.2, 70.5,
73.5, 154.9; MS m/z (%): 102 (M+, 5), 100 (11), 87
(14), 57 (100).
EXPERIMENTAL
Melting points were determined on a Mettler FP
5 instrument and were uncorrected. FTIR spectra
were recorded on a JASCO FT/IR-4100 instrument.
1H and 13C NMR spectra were obtained on a JEOL
JNM-AL300 (300 MHz, 75 MHz) instrument. Chem-
ical shifts were reported in ppm relative to tetram-
ethylsilane (δ units). Mass spectra were measured on
a JEOL JMS-600 spectrometer. Glycerol (1a), diols
1b–d, DMF, THF, potassium carbonate, sodium hy-
dride, triethylamine, 1-methylpyrrolidine, DBU, se-
lenium (99.9%), carbon monoxide (99.9%), and oxy-
gen (99.9%) were used as purchased.
Styrene carbonate 2d. Yield: 296 mg (90%)
yield; mp 54.0◦C, (Lit. [12] 56.3◦C). IR (KBr, cm−1) ν:
1775 (C=O), 1170, 1055, 759, 698; 1H NMR (CDCl3)
δ (ppm): 4.34 (t, J = 8.2 Hz, 1H, CH2), 4.80 (t, J = 8.2
Hz, 1H, CH2), 5.67 (t, J = 8.2 Hz, 1H, CH), 7.34–7.48
(m, 5H, CH); 13C NMR (CDCl3) δ (ppm): 71.1, 77.9,
125.8, 129.2, 129.7, 135.8, 154.8; MS m/z (%): 164
(M+, 100), 91 (61), 90 (91), 78 (57).
General Procedure for the Catalytic Synthesis of
Glycerol Carbonate 2a
Typical Procedure for the Stoichiometric
A mixture of glycerol (1a) (921 mg, 10 mmol), el-
emental selenium (79 mg, 1 mmol), and potassium
carbonate (1.382 g, 10 mmol) with DMF (20 mL) was
very vigorously stirred under the mixed gas (carbon
monoxide:oxygen = 3:1, 0.1 MPa). The mixed gas
was circulated at 20◦C for 24 h. The resulting pale
yellow emulsion was filtered and rinsed with t-butyl
methyl ether (100 mL). After evaporation of sol-
vents and purification by short-column chromatog-
raphy (silica gel, AcOEt), glycerol carbonate (2a) was
afforded in 197% yield (based on selenium used)
(232 mg).
Synthesis of Glycerol Carbonate 2a
A gray mixture containing glycerol (1a) (921 mg,
10 mmol), elemental selenium (237 mg, 3 mmol),
and potassium carbonate (1.382 g, 10 mmol) with
DMF (20 mL) was vigorously stirred under carbon
monoxide (0.1 MPa) at 20◦C for 4 h. Into the resulting
brown emulsion of selenocarbonate salt (3a), molec-
ular oxygen (0.1 MPa) was charged at 20◦C. The re-
action mixture was stirred for additional 2 h at 20◦C.
Then, the resulting mixture was filtered and rinsed
with t-butyl methyl ether (100 mL). After evapora-
tion of solvents and purification by short-column
chromatography (silica gel, AcOEt), glycerol carbon-
ate (2a) was given.
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Facile Synthesis of Glycerol Carbonate from Glycerol Using Selenium-Catalyzed Carbonylation with Carbon Monoxide 545
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