New synthesis of glycerol carbonate from glycerol using sulfur-assisted carbonylation with carbon monoxide

Article abstract of DOI:10.1002/hc.20583

The glycerol carbonate synthesis from glycerol, which is an inevitable by-product of biodiesel production, was established. By combined sulfurassisted carbonylation of glycerol under 1.0 MPa of carbon monoxide at 80°C in DMF with oxidation by copper bromide(II), a facile synthetic method for glycerol carbonate in good yield was developed.

Full text of DOI:10.1002/hc.20583

Heteroatom Chemistry
Volume 21, Number 2, 2010
New Synthesis of Glycerol Carbonate from
Glycerol Using Sulfur-Assisted 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 6 January 2010; revised 29 January 2010
Also the use of 2a was investigated as monomer
ABSTRACT: The glycerol carbonate synthesis from
to produce hyperbranched aliphatic polyesters
glycerol, which is an inevitable by-product of biodiesel
(polyglycerols) [2], and glycerol carbonate (2a) has
production, was established. By combined sulfur-
a considerable possibility to be an intermediate of
assisted carbonylation of glycerol under 1.0 MPa
polycarbonate production [3].
of carbon monoxide at 80◦C in DMF with ox-
Among the synthetic methods for glycerol car-
idation by copper bromide(II), a facile synthetic
bonate (2a) from glycerol (1a), the direct synthesis
method for glycerol carbonate in good yield was devel-
of 2a by the conversion of 1a with carbon dioxide has
ꢀ
C
oped.
2010 Wiley Periodicals, Inc. Heteroatom Chem
been studied using organic tin compounds as cata-
lysts. Under the drastic reaction conditions (5.0 MPa
of CO2, 180◦C), tin dimethoxide led only to traces of
1a. However, di(n-butyl)tin dimethoxide gave a little
conversion of 1a (maximum 7%) depending on the
reaction conditions [4]. Furthermore, the catalytic
conversion of 1a with urea to 2a has been researched
in the presence of heterogeneous zinc catalysts. 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].
About 20 years ago, we found that sulfur-assisted
carbonylation with carbon monoxide of alcohols
and diols under slightly severe reaction conditions
(3.0 MPa, 80◦C) to give carbonates in good yields
[6]. Recently, we reported the sulfur-assisted car-
bonylation of diamines with carbon monoxide and
oxidation with molecular oxygen ([7] and fur-
ther references therein). However, milder reaction
conditions have been desired for the industrial
production.
21:99–102, 2010; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.20583
INTRODUCTION
The so-called “biodiesel” is a popular term for the
fatty acid methyl esters, formed from transesterifi-
cation of rapeseed oil with methanol. Biodiesel has
been developed rapidly as automotive fuels in United
States and in Europe for several years, accompanied
with the formation of a large quantity of glycerol
(1a) as by-product. Obviously, the question arises
how this additional 1a can be used wisely [1].
In 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 solvents
for many applications, for instance in colors, var-
nishes, glues, cosmetics, and pharmaceuticals [1].
Therefore, our objective has been to develop a
straightforward synthetic method for glycerol car-
bonate (2a) by the carbonylation of glycerol (1a)
with carbon monoxide and sulfur under milder re-
action conditions followed by oxidation.
Correspondence to: Takumi Mizuno; e-mail: tmizuno@
omtri.or.jp.
2010 Wiley Periodicals, Inc.
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99

100 Mizuno, Nakai, and Mihara
(1) Et3N / THF,
2.0 MPa, 80oC, 5 h
HO
OH
S
+
+
CO
HO
OH
1a
O
O
(2) CuCl2, 0.1 MPa in Air,
20oC, 16 h
O
2a: 69%
SCHEME 1 Synthesis of glycerol carbonate (2a).
RESULTS AND DISCUSSION
lamine caused a lower yield of 1a (entries 2 and
3). At the reaction temperature between 80 and
100◦C, 1a was obtained in good yields (entries
1 and 4–7). Lower pressure of carbon monoxide
led to considerably low yields (entries 8 and 9).
Using stronger base (1-methylpyrrolidine and 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU)) gave poor re-
sults to afford only tar (entries 10 and 11).
The carbonylation of 1a with carbon monoxide and
sulfur and oxidation with copper chloride(II) to pre-
pare the corresponding 2a were performed. Glyc-
erol (1a) was readily reacted with carbon monoxide
(2.0 MPa) and sulfur (3.0 equiv.) in the presence of
triethylamine (5.0 equiv.) at 80◦C for 5 h in THF sol-
vent. Then, the generated carbonothioate salt 3a in
THF was oxidized by copper chloride(II) under an
ambient pressure of air at 20◦C for 16 h. Finally,
glycerol carbonate (2a) was obtained in 69% yield
(Scheme 1). In this reaction, 2a was synthesized se-
lectively and the formation of isomeric cyclic car-
bonate (5-hydroxy-2-oxo-1,3-dioxane) was not ob-
served.
At first for the improvement of yields of 1a,
the influence of various conditions was examined
on the sulfur-assisted carbonylation of 2a with
carbon monoxide (Table 1). Longer reaction time
of carbonylation and shorter reaction time of ox-
idation, and less amount of sulfur and triethy-
Recently, we found that sulfur-assisted car-
bonylation of alcohols with carbon monoxide was
strongly accelerated by N, N-dimethylformamide
(DMF) or dimethyl sulfoxide (DMSO) [8]. There-
fore, glycerol carbonate (2a) synthesis by the use of
carbonylation of glycerol (1a) with carbon monox-
ide and sulfur in DMF and oxidation with copper
chloride(II) was checked (Table 2). Our investigation
into the sulfur-assisted carbonylation and oxidation
of 1a employing DMF as a solvent led to the suc-
cessful synthesis of 2a. Even, under lower pressure
(1.0 MPa) of carbon monoxide, glycerol carbonate
(2a) was obtained in fairly good yields (entries 1–4).
Next, the effect of oxidizers under 0.1 MPa in air
at 20◦C was examined. Copper chloride(II) and cop-
per bromide(II) gave excellent results of 2a synthe-
sis under 1.0 MPa of carbonylation (entries 4 and 5).
However, zinc compounds were shown poor results
(entries 6 and 7). Unfortunately, no formation of 2a
was observed using hydrogen peroxide (aq. 30%) as
an oxidizer (entry 8).
TABLE 1 Influence of Various Conditions on Synthesis of 1a
Temperature of Pressure of
Carbonylation, Carbonylation,
Isolated
Yield (%)
Entry
(◦C)
(Mpa)
Base
1
2
3
4
5
6
7
8
9
80
80
80
120
100
60
40
80
100
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.0
1.0
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
69
55a
34b
33
72
48
32
38
64
TABLE 2 Effect of Solvent DMF and Oxidizer
Temperature of
Pressure of
Carbonylation, Carbonylation,
Isolated
Entry
(◦C)
(Mpa)
Oxidizer Yield (%)
1
2
3
4
5
6
7
8
100
80
100
80
80
80
2.0
2.0
1.0
1.0
1.0
1.0
1.0
1.0
CuCl2
CuCl2
CuCl2
CuCl2
CuBr2
ZnBr2
Znl2
79
76
79
87
94
0
N Me
DBUd
10
11
80
80
2.0
2.0
0c
0c
Reaction conditions: Glycerol (10 mmol),
S (30 mmol), base
(50 mmol), THF (20 mL), CuCl2 (15 mmol), carbonylation for 5 h,
and oxidation for 16 h.
80
80
11
0
H2O2
aCarbonylation for 22 h and oxidation for 6 h.
bS (15 mmol), base (30 mmol).
Reaction conditions: Glycerol (10 mmol),
S (30 mmol), Et3N
cTar was formed.
(50 mmol), DMF (20 mL), Oxidizer (15 mmol), carbonylation for 5 h,
and oxidation for 16 h.
d1.8-Diazabicyclo[5.4.0]undec-7-ene.
Heteroatom Chemistry DOI 10.1002/hc

New Synthesis of Glycerol Carbonate from Glycerol Using Sulfur-Assisted Carbonylation with Carbon Monoxide 101
(1) Et3N / DMF,
1.0 MPa, 80oC, 5 h
X
OH
S
+
+
CO
OH
1a–d
O
O
(2) CuBr2, 0.1 MPa in Air,
20oC, 16 h
X
O
X= CH2OH: 94% (2a)
H: 74% (2b)
CH3: 74% (2c)
Ph: 94% (2d)
SCHEME 2 Synthesis of several cyclic carbonates (2a–d).
Several cyclic carbonates (2a–d) including glyc-
erol carbonate (2a) were synthesized by the
sulfur-assisted carbonylation with carbon monoxide
(1.0 MPa, 80◦C) and oxidation with copper bromide
(0.1 MPa in air, 20◦C) (Scheme 2). Ethylene carbon-
ate (2-oxo-1,3-dioxolane, 2b), propylene carbonate
(4-methyl -2-oxo-1,3-dioxolane, 2c), and stylene car-
bonate (2-oxo-4-phenyl-1,3-dioxolane, 2d) were ob-
tained in good to excellent yields under milder reac-
tion conditions.
Scheme 3 shows possible paths for the synthe-
sis of glycerol carbonate (2a) by the carbonylation of
glycerol (1a) followed by oxidation of the carbonoth-
ioate salt 3a. First, elemental sulfur undergoes S–S
bond fission by the reaction with anion of 1a to form
thiolate anion (4a). The reaction of 4a with car-
bon monoxide gives carbonothioate salt (3a) from
carbonylated species. The thus formed carbonoth-
ioate salt (3a) is oxidized by copper bromide(II) giv-
ing 2a via biscarbonodisulfide (5a). Indeed, biscar-
bonodisulfide formed as intermediate by oxidation
of carbonothioate salt was isolated in the carbonate
synthesis from alcohols with carbon monoxide and
sulfur [9].
CONCLUSION
In summary, a useful synthetic method for glycerol
carbonate (2a) has been developed 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 3a with
copper bromide(II) under 0.1 MPa in air at 20◦C.
From the viewpoint of making good use of 1a, which
is a by-product of biodiesel production, the present
method might give an additional field of application
on 1a.
EXPERIMENTAL
Melting points were determined on a Mettler FP
5 instrument and were uncorrected. FT-IR 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 and exact mass spectra
were measured on a JEOL JMS-600 spectrometer.
Glycerol (1a), diols 1b–d, THF, DMF, triethylamine,
1-methylpyrrolidine, DBU, sulfur (99.5%), copper
chloride(II), copper bromide(II), zinc bromide(II),
zinc iodide(II), hydrogen peroxide (aq. 30%), carbon
monoxide (99.9%), and oxygen (99.9%) were used as
purchased.
OH
OH
Et3N / DMF
+
S8
HO
OSx
4a
HO
OH
1a
Typical Procedure for the Synthesis of Glycerol
Carbonate 2a
OH
OH
O
O
OCS
3a
CO
HO
HO
OS
x
HO
In a 100-mL stainless steel autoclave, glycerol (1a)
(921 mg, 10 mmol), powdered sulfur (962 mg,
30 mmol), triethylamine (6.93 mL, 50 mmol), and
DMF (20 mL) were placed with a magnetic stir-
ring bar under an argon atmosphere. The autoclave
was then flushed three times with carbon monox-
ide and finally charged with carbon monoxide at
1.0 MPa at 20◦C. The reaction was carried out at
HO
OH
O
CuBr2
O
O
OCS
2
2a
5a
O
SCHEME 3 Proposed path for the synthesis of 2a.
Heteroatom Chemistry DOI 10.1002/hc

102 Mizuno, Nakai, and Mihara
80◦C for 5 h with vigorous stirring. After cooling
down and evacuation of carbon monoxide, copper
bromide (3.350 g, 15 mmol) was added at 20◦C un-
der air atmosphere. The reaction mixture was stirred
for additional 16 h under ambient pressure of air at
20◦C. Then, the resulting mixture was filtered (black
copper sulfide was formed), 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
given.
8, 8 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).
Stylene
carbonate
(2-oxo-4-phenyl-1,3-
dioxolane, 2d). Yield: 1.543 (94%) yield; mp
54.0◦C (Lit. [6] 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 Hz, 1H, CH2), 4.80 (t, J = 8 Hz,
1H, CH2), 5.67 (t, J = 8 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).
Glycerol carbonate (4-hydroxymethyl-2-oxo-1,3-
dioxolane, 2a). Yield: 1.114 g (94%) yield; oil [10]; IR
(neat, cm−1): ν 3444, 2931, 1790 (C O), 1403, 1179,
1
REFERENCES
1087; H NMR (d6-DMSO): δ (ppm) 3.46–3.53 (m,
1H, CH2), 3.62–3.69 (m, 1H, CH2), 4.27 (d,d, J = 6,
8 Hz, 1H, CH2), 4.48 (t, J = 8 Hz, 1H, CH2), 4.75–4.82
(m, 1H, CH), 5.23 (t, J = 6 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).
[1] Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.;
Lindner, F. Green Chem 2008, 10, 13.
[2] Rokicki, G.; Rakoczy, P.; Parzuchowski, P.; Sobiecki,
M. Green Chem 2005, 7, 529.
[3] Fukuoka, S. Chem Ind 1997, 757.
[4] Aresta, M.; Dibenedetto, A.; Nocito, F.; Pastore, C.
J Mol Catal A: Chem 2006, 257, 149.
Ethylene carbonate (2-oxo-1,3-dioxolane, 2b).
Yield: 650 mg (74%) yield; mp 35.6◦C (Lit. [6]
36.2◦C); IR (KBr, cm−1): ν 2995, 1799 (C O), 1163,
[5] Yoo, J.-W.; Mouloungui, Z. Stud Surf Sci Catal 2003,
146, 757.
[6] Mizuno, T.; Nakamura, F.; Egashira, Y.; Nishiguchi,
I.; Hirashima, T.; Ogawa, A.; Kambe, N.; Sonoda, N.
Synthesis 1989, 636.
[7] Mizuno, T.; Nakai, T.; Mihara, M. Heteroatom Chem
2009, 20, 64.
[8] Mizuno, T.; Iwai, T.; Ishino, Y. Tetrahedron 2005, 61,
9157.
[9] Mizuno, T.; Nishiguchi, I. Kagaku to Kogyo (Osaka)
1995, 69, 71; Chem Abstr 1995, 123, 8792p.
[10] Guibe, F.; Saint M’Leux, Y. Tetrahedron Lett 1981,
22, 3591.
1
1068, 773; H 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
(4-methyl-2-oxo-1,3-
dioxolane, 2c). Yield: 752 mg (74%) yield; oil [6]; IR
(neat, cm−1): ν 2987, 1791 (C O), 1389, 1184, 1053;
1H NMR (CDCl3): δ (ppm) 1.50 (d, J = 6 Hz, 3H,
CH3), 4.03 (d,d, J = 8, 8 Hz, 1H, CH2), 4.56 (d,d, J =
Heteroatom Chemistry DOI 10.1002/hc