Propylene carbonate synthesis from propylene glycol, carbon dioxide and benzonitrile by alkali carbonate catalysts

Article abstract of DOI:10.1016/j.catcom.2012.08.030

The synthesis of propylene carbonate from propylene glycol and carbon dioxide in the presence of various catalysts has been reported. Benzonitrile has been used as both solvent and dehydrating agent. Under optimal conditions, the best results were obtained in the presence of alkali carbonate catalysts. The propylene carbonate yield could reach up to 20% with a propylene-1,2-glycol conversion of 44%.

Full text of DOI:10.1016/j.catcom.2012.08.030

Catalysis Communications 29 (2012) 58–62
Contents lists available at SciVerse ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Propylene carbonate synthesis from propylene glycol, carbon dioxide and
benzonitrile by alkali carbonate catalysts
E. Da Silva a, W. Dayoub a, G. Mignani b, Y. Raoul c, M. Lemaire a,
⁎
a
Laboratoire Catalyse, Synthèse et Environnement, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), CNRS, UMR 5246, Université Claude Bernard Lyon 1,
bat. CPE, 43 boulevard du 11 novembre 1918, 69622, Villeurbanne, France
b
RHODIA, Centre de Recherche et de Technologie de Lyon (CRTL), 85 avenue Frères Perret, 69190, Saint-Fons, France
SOFIPROTEOL, 11 rue de Monceau CS 60003, 75378 Paris cedex 08, France
c
a r t i c l e i n f o
a b s t r a c t
Article history:
The synthesis of propylene carbonate from propylene glycol and carbon dioxide in the presence of various
catalysts has been reported. Benzonitrile has been used as both solvent and dehydrating agent. Under opti-
mal conditions, the best results were obtained in the presence of alkali carbonate catalysts. The propylene
carbonate yield could reach up to 20% with a propylene-1,2-glycol conversion of 44%.
© 2012 Published by Elsevier B.V.
Received 14 November 2011
Received in revised form 24 July 2012
Accepted 28 August 2012
Available online 19 September 2012
Keywords:
Alkali carbonate
Carbon dioxide
Homogeneous
Glycol carbonate
Dehydrating agent
1. Introduction
carbonate and propylene carbonate can be obtained by direct carbon-
atation of ethylene glycol (EG) or propylene glycol (PG) in the presence
The formation of polyol carbonate from carbon dioxide is probably
one of the most interesting pathways in terms of synthetic method
and atom economy [1]. New syntheses for the conversion and valori-
zation of polyols [2–4] have been realized and especially for the
formation of glycerin carbonate [5] as a main compound of battery elec-
trolyte, surfactant, intermediate reactant and propylene carbonate as
new green solvents or triphosgene substitute [6]. The carbonatation of
diols gave low yields due to the presence of water molecules formed
during the reaction [7,8] and thus inducing a possible catalyst poisoning
and a reversible reaction (Scheme 1).
Due to the difficulty of this synthetic route and the urgent need
for enhancing new methodologies, efforts on direct carbonatation
of monoalcohols or glycol derivatives have been done. Methods for
the synthesis of DMC from carbon dioxide and orthoesters [9,10] or ac-
etal derivatives [11–13] have been developed by Sakakura et al. using
organotin compounds as catalysts. Nowadays, tin catalysts remain as
the best catalysts for DMC production from carbon dioxide but the pro-
cess has not been applied for industrial process due to harsh conditions:
high temperature, high pressure, until 300 atm. and the use of tin cata-
lysts. The role of Sn-catalysts or other metal oxides in the synthesis
of DMC has been widely detailed in the literature [14–18]. About glycol
derivatives, the synthesis of five-membered rings such as ethylene
of carbon dioxide. He et al. described an effective synthesis of propylene
carbonate with remarkable selectivity catalyzed by organotin com-
pounds [19]. However, conversion and yield are very low and show
the limit of using tin catalyst. Another example was described in the
presence of magnesium catalysts and scCO2 without any solvent or ad-
ditives showing high selectivity but a very low yield [20]. Recently, the
formation of carbonate compounds from carbon dioxide and alcohol
compounds has been done by using dehydrating reagent to remove
water produced during the reaction. Acetonitrile is a nitrile solvent
commonly used as a dehydrating agent giving acetamide and acetic
acid in the presence of water molecules. Several works tend to optimize
the reaction conditions in the presence of this solvent. The first example
of propylene or ethylene carbonate has been obtained using cerium
based catalysts or a mixture of cerium and zirconium oxides and carbon
dioxide in supercritical media showing high selectivity but limited by
reaction equilibrium [21,22]. Alkali carbonates were used to catalyze
propylene carbonate synthesis from PG and CO2 with a conversion of
30–40% and a selectivity of average 60% for PC [23]. A series of zinc
oxide [24] or modified acetate catalysts [25] present similar results
than those described with alkali carbonates. Related with the basicity
of catalysts, a series of organic bases such as TBD (triazabicyclodecene),
DBU (diazabicycloundecene) and TEA (triethylamine) were employed
for PC synthesis where the yield reached average 15% with 60% of selec-
tivity [26]. Under optimal conditions performed by various groups,
acetonitrile remains a major drawback due to its cost, low boiling
⁎
Corresponding author. Tel.: +33 4 72 43 14 07; fax: +33 4 72 43 14 08.
E-mail address: marc.lemaire@univ-lyon1.fr (M. Lemaire).
1566-7367/$ – see front matter © 2012 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.catcom.2012.08.030

E. Da Silva et al. / Catalysis Communications 29 (2012) 58–62
59
2.4. GC and NMR analyses
All reaction media were analyzed by gas chromatography
(SHIMADZU GC-14A) equipped with a temperature-programmed
injector. The injector temperature was maintained at 250 °C. The
compounds were separated on a RESTEK Stabilwax column (30 m
long, i.d. 0.32 mm, 0.5 μm) as polar stationary phase (Crossbond®
Carbowax® polyethyleneglycol). The column temperature was main-
tained at 40 °C for the first minute and then raised up to 250 °C by
15 °C/min. Nitrogen was employed as vector gas. The outlet of the
column was connected to a hydrogen flame ionization detector main-
tained at 250 °C. CR6-A Chromatopac integrator was used for data ac-
quisition. Samples were prepared in THF or ethanol. GC–MS were
measured with focus DSQ electronic ionization with stabilwax column.
The characterization of PGB molecules has been done by nuclear mag-
netic resonance. NMR spectra were recorded with a Bruker ALS or
DRX 300 spectrometer (1H: 300 MHz, 13C: 75 MHz).
Scheme 1. Direct carbonatation of glycol derivatives.
point, its toxicity and high polarity. Moreover such nitrile is weakly
compatible with CO2 system. In this article, we describe a synthetic
route of formation of propylene carbonate from PG and CO2 over dif-
ferent sources of heterogeneous or homogeneous catalysts. Acetoni-
trile is substituted by benzonitrile and other industrially available
nitrile or dinitrile acting as both solvent and dehydrating agent. As
reported for CO2-expanded ethanol, benzonitrile can increase the
solubility of carbon dioxide in propylene glycol at high temperature
and pressure [27]. PC yield was improved and the reaction condi-
tions in Benzonitrile+CO2 +Propylene Glycol were optimized. The
reactions were investigated in details by GC and GC/MS analyses.
We have reported the mechanism by identifying intermediate and
byproduct compounds. This is the first example reported of propyl-
ene carbonate formation in the presence of benzonitrile.
3. Results and discussion
3.1. PC synthesis from PG and C6H5CN
As shown Scheme 2, the synthetic route to alkylene carbonate is
based on: (step 1) direct carbonatation of glycol derivatives and water
formation; benzonitrile was hydrated to benzamide in the presence of
water molecules; (step 2) the benzonitrile could be easily regenerated
from benzamide by flash vacuum pyrolysis as described by McNab
[28]. In our work, we focused on the optimization of step 1 using
propylene glycol as reference.
2. Experimental part
2.1. Chemical reagents
Propylene-1,2-glycol (Acros, 99%) was dried at 110 °C at 100 mbar
during 4 h and stored under nitrogen. Propylene-1,3-glycol (Acros,
99%), ethylene glycol (Acros, 99%), phenol (Acros, 99+%), octane-
1,2-diol (Aldrich, 98%), and pentafluorophenol (Acros, 99+%) were
used for reaction without further purification. All the products
were purchased: benzamide (purity 99%), adiponitrile, glutaronitrile,
succinonitrile, cyanamide and isobutyronitrile having a purity >98%
from Acros; benzonitrile (99+%), tetrahydrofuran and ethanol in
p.a. grade from Sigma-Aldrich; carbon dioxide from Air Liquide France
(purity 99.998%, moisture 3 ppm, oxygen 2 ppm, 4.95 MPa).
Propylene carbonate is synthesized in the presence of propylene
glycol (100 mmol) and benzonitrile (100 mmol) under CO2 super-
critical conditions at 10 MPa, 448 K for 18 h in the presence of cata-
lytic amount of various catalysts (5% mol). As detailed in Scheme 1,
benzamide is formed by the hydration of benzonitrile in the presence
of water molecules provided from the following reaction: PG+CO2
gives PC+H2O. Depending on the reaction conditions, ester
2.2. Preparation of catalysts
Anhydrous alkali carbonates were obtained from various industri-
al companies and directly used without further purification. Metal
oxides were given by Rhodia Electronics and Catalysis (La Rochelle,
France) and calcinated at 500 °C during 2 h (increment rate 2 °C/min
during 4 h) using a Nabertherm apparatus.
2.3. Reaction apparatus and conditions
Reactor was previously heated at 150 °C during 2 h to remove water
molecules and cooled down at room temperature under carbon dioxide
atmosphere. The reaction was carried out in a 100 mL stainless-steel
reactor provided by PARR instrument. The autoclave is equipped with
a mechanical stirrer, internal thermal probe and a manometer up to
20 MPa. A solution of PG (100 mmol) and benzonitrile (100 mmol)
was stirred at 1000 rpm in the presence of catalysts (5%mol) as a typical
process. Carbon dioxide was introduced into the reactor to replace air at
5 MPa at room temperature. The mixture was heated at 175 °C showing
8 MPa pressure. The 10 MPa pressure is adjusted with a pump. Reaction
was stopped after 18 h by cooling down the reactor to room tempera-
ture and then slowly depressurized. Tetraethyleneglycol was added to
the crude mixture as an internal standard for quantitative analysis.
The reaction mixture was analyzed by GC apparatus using tetrahydrofu-
ran or ethanol as solvent.
Scheme 2. Synthesis of PC from PG and CO2.

60
E. Da Silva et al. / Catalysis Communications 29 (2012) 58–62
Scheme 3. Eq. (1): hydrolysis of benzamide to benzoic acid; Eq. (2): formation of two monoesters from benzoic acid and PG.
derivatives from propylene glycol such as PG-1-B (propylene glycol-
1-benzoate) and PG-2-B (propylene glycol-2-benzoate) were also
observed and characterized by GC–MS technique. To confirm the pres-
ence of ester derivatives, we synthesized PGB with a ratio of 40/60 for
PG-1-B and PG-2-B following the procedure described in the literature
[29]. The PGB formation can be explained by esterification process be-
tween benzoic acid and PG as shown in Scheme 3. However, benzoic
acid as benzamide hydration product has never been observed in reac-
tion mixture and only an esterified product was obtained.
As shown in Fig. 1, the synthesis of PC in the presence of benzonitrile
is quite selective showing PGB and benzamide as byproducts. All peaks
have been characterized and analyzed by GC–MS. A broad peak is ob-
served for both PGB having approximately the same retention time.
The yield and ratio of each product were analyzed by GC and the results
are summarized in Table 1. Without addition of nitrile solvent, propyl-
ene carbonate formation is not observed at all, pointing out that
dehydrating agent is essential for catalysis. In addition, benzamide
was not detected in the absence of PG demonstrating that it was formed
in the presence of water molecules provided from PC synthesis. In the
absence of carbon dioxide, no PC formation and PG conversion were ob-
served assuming that carbonate group was provided from CO2 and not
from carbonate catalysts. The best result is observed using 5%mol of po-
tassium carbonate giving 20% and 24% of yields for PC and PGB, respec-
tively (Table 1, entry 1). The conversion of PG reached 44% with TON
of 4. Extending the reaction time until 62 h (entry 2), PG conversion in-
creased partially up to 57% showing limitations of the reaction. Nowa-
days, this value is the best conversion reported but PC selectivity
dropping from 45% to 33%. To enhance the PC selectivity, ammonium
carbonate was added into the reaction system to afford benzamide hy-
dration [23] and not to produce PGB (entry 4). Unfortunately in this
case, no significative effect was shown. At 473 K, PC yield drops until
9% with a low selectivity reaching 20% (entry 3). That implied a possible
demixing between benzonitrile and supercritical carbon dioxide and/or
an unstability of propylene carbonate at high temperature.
Replacing potassium carbonate by a more basic one such as cesi-
um carbonate (entry 6), similar result was observed in terms of con-
version, yield and selectivity for both products. Using 15%mol of
catalyst (entry 7), the activity of cesium carbonate decreased serious-
ly where PC yield was only 13%. The yield dropped in comparison to
that obtained with 5%mol of catalyst. The quantity of PG was not
enough to solubilize all the carbonate catalyst giving a heterogeneous
mixture and decreasing the mass transfer process.
Moreover, alkali carbonates such as sodium or lithium carbonates
have little solubility in benzonitrile/PG mixture showing a very low
activity for PC synthesis (entries 8–9). The reaction activity can be re-
sumed by the basicity and the size of counterion where high activity
is done in the following order: K≈Cs>Na>Li. To raise basicity of
Table 1
PC synthesis from PG and CO2 under standard conditions.
Entry Cat.
PGconv Yield
Yield
PGB
(%)
Selectivity
PC
(%)
Selectivity
PGB
(%)
TON
(%)
PC
(%)
1
2
3
4
5
6
7
8
K2CO3
K2CO3
K2CO3
K2CO3
44
57a
45b
38c
30d
44
31e
22
6
1
2
1
2
20
19
9
13
13
17
13
8
24
38
36
25
18
28
18
14
2
45
33
20
34
42
37
42
36
–
55
67
80
66
58
63
58
64
–
4.0
3.8
1.8
2.6
2.6
3.4
2.6
1.6
0.8
–
K2CO3
Cs2CO3
Cs2CO3
Na2CO3
Li2CO3
MgCO3
CaCO3
9
4
10
11
12
13
Traces Traces
Traces Traces
Traces Traces
Traces Traces
–
–
–
–
–
La2(CO3)3
Al2(CO3)3
–
–
–
–
–
–
Reaction conditions: PG (100 mmol), Benzonitrile (Bn, 100 mmol), 5% mol catalyst,
CO2 10 MPa, temperature 448 K, time 18 h; YPGB=yield of PG-1-B+PG-2-B; yield
(Y) and conversion determined by GC; TON (turn-over number)=(mol of substrate
converted to propylene carbonate/mol of catalyst).
a
62 h reaction time.
Reaction done at 473 K.
5%mol of (NH4)2CO3 was added.
5%mol 18-crown-6 was added.
b
c
Fig. 1. GC-chromatogram (stabilwax column) of reaction mixture done in THF under
standard conditions. Retention times are omitted for clarity and double line represents
the solvent.
d
e
15%mol catalyst.

E. Da Silva et al. / Catalysis Communications 29 (2012) 58–62
61
K2CO3, 18-crown-6 ether was added to the reaction (entry 5) but no
increasing performance was observed.
than this achieved for PC but suggested that the formation of alkylene
carbonate is easier when the molecule presents both primary and
secondary alcohols. For higher polyol such as glycerol having three
hydroxyl groups, we never observed the formation of glycerin carbon-
ate under these conditions. Recently, Tomishige et al. used benzonitrile
to substitute acetonitrile for direct carbonatation of monoalcohols
(methanol, ethanol, propanol, isopropyl and benzyl alcohols) to
dialkyl carbonate in the presence of CeO2 as catalyst [32,33]. In our
work, we were also interested on direct transformation of phenol
to diphenylcarbonate (DPC) as phosgene substitute. DPC has never
been seen under our experimental conditions. Pentafluorophenol was
also used to increase solubility in CO2 but no conversion was observed.
Using di- or trivalent carbonates such as magnesium, calcium, alu-
minum or lanthanum (entries 10–13) leads to a very low conversion
and only traces of PC were detected by GC analysis. Several metal ox-
ides such as La2O3, Al2O3 (96%) and Al2O3/BaO mixture (78:22) were
evaluated for PC synthesis in the same conditions. However, all data
gave low activity with PG conversion below 3%. In some cases, PC
and PGB have been detected. Other catalysts such as CeO2 (99.5%)
and CeO2/ZrO2 mixture (58:42) did not increase the conversion.
These results are coherent with those observed in the presence of
Ce-catalysts in acetonitrile [30]. For all cases, we noted that the reac-
tion occurred to be very slow in heterogeneous mixture.
3.4. Other parameters
3.2. Nitrile solvents screening
The best result was obtained with a 1:1 ratio of Benzonitrile/PG.
Decreasing 5 times the concentration of PG with respect to benzonitrile
and CO2, the values of PG conversion and PC yield remained
unchanged. That implied that increasing CO2 molar fraction into
alcohol/benzonitrile mixture did not affect the activity of the reaction
inducing limitation process. Moreover, the maximum PG conversion
was obtained when the pressure value was 10 MPa under supercritical
conditions. Increasing the CO2 pressure up to 15 MPa at 448 K, the PG
value dropped until 24% showing a heterogeneous solution after cooling
down at room temperature. Decreasing pressure until 6 MPa, PG con-
version was similar to that obtained with a much higher pressure.
Indeed under non-supercritical conditions (gaseous/liquid phase), the
reactivity is lower than supercritical conditions where all substances
are soluble giving a homogeneous solution. The supercritical medium
considerably accelerated the rate of PC formation.
Other nitrile solvents have been studied in order to evaluate the effi-
ciency of the dehydrating agent. Data are summarized in Table 2.
Mononitrile solvents such as acetonitrile, cyanamide and isobutyronitrile
were used. Acetonitrile is a common solvent and widely tested for PC
synthesis from PG and CO2 with PC. In terms of efficiency, benzonitrile
presented better conversion and PC yield than acetonitrile (Table 2, en-
tries 1–2). Cyanamide and isobutyronitrile did not perform the reaction
at all. Benzonitrile presents a better choice compared to acetonitrile in
terms of solubility. Indeed, high-pressure vapor–liquid equilibria for
CO2+benzonitrile at high temperature and pressure have been studied
by Whalter and Maurer showing good compatibility and miscibility be-
tween them [31]. Using benzamide as co-solvent, only 8% of PG con-
version occurred with a yield of 2% and 4% for PC and PGB,
respectively. Benzamide is less dehydrating than benzonitrile.
Dicyanated solvents were also tested such as adiponitrile,
glutaronitrile and succinonitrile in order to raise the dehydrating ef-
fect by introducing two cyano groups. Two of them bearing short
alkyl chains (entries 4–5) generated polymers which are difficult to
characterize by GC. In the case of adiponitrile (entry 3), PG conver-
sion was similar to that with benzonitrile but showed a better selec-
tivity for PC with 27% of yield. The high selectivity can be explained
by the fact that water molecules were trapped faster than with
monocyanated solvents. Byproducts correspond to adiponitrile hy-
dration and ester derivatives with a global yield of 17%.
3.5. Mechanism proposal
Up to now, the real challenge was to convert totally PG to PC. Un-
fortunately, complete conversion of PG into desired final compound
could be limited either by the stability of desired product or the for-
mation of byproducts. Indeed, we synthesized a mixture of PGB in a
70/30 ratio (PG-2-B and PG-1-B respectively) and the carbonatation
of this mixture was performed in the presence of K2CO3 and CO2 at
10 MPa and 448 K. We observed the formation of PG with a PGB con-
version of 2% as shown in Scheme 4. In this case, the formation of PC
was not detected and PGB appeared not to be an intermediate. In par-
allel, benzoic acid was detected by GC technique as hydration ester
product. Applying optimal conditions, pure propylene carbonate
was converted to PG with 1% inducing a high stability of alkylene car-
bonate in supercritical conditions. Indeed, the formation of PGB ap-
pears to be the main limitation of the reaction.
It is worth to mention that propylene carbonate and ester deriva-
tives have a good stability in supercritical carbon dioxide. If the starting
compounds were not dried, we observed an increasing value of conver-
sion up to 10 and 20%. In this paper, the value of 44% of PG conversion is
the highest we have observed. Of course, it would be interesting to focus
on the selectivity of the reaction in favor of alkylene carbonate. Thermo-
dynamic studies are on going to provide insights on the mechanism of
hydration and esterification processes but this is another work which
will be done in due course.
3.3. Alcohol screening
The efficiency of the reaction has been extrapolated to other glycols
like propylene-1,3-glycol (PG1,3), ethylene glycol (EG) and octane-1,2-
diol (OG) for formation of alkylene carbonate. For PG1,3 and EG, only
traces of corresponding carbonate have been observed with a glycol
conversion below 3% inducing the difficult implement for cyclic
carbonatation having hydroxyl groups in terminal position. For OG
compound with long alkyl chain, less polar and less hydroscopic than
PG, the synthesis of octylene carbonate has been performed under
standard conditions giving OC yield of 10%. The OC yield was lower
Table 2
Effect of nitrile solvents on PC synthesis.
Ent.
Solvent
PGconv
(%)
YPC
(%)
Ybyproduct
(%)
TON
4. Conclusion
1
2
3
4
5
6
7
Benzonitrile
Acetonitrile
Adiponitrile
Glutaronitrile
Succinonitrile
Cyanamide
44
34
44
20
12
27
24
22
17
4
2.4
5.4
The reaction of PG+CO2 +Benzonitrile showed relatively good
conversion in supercritical media but suffered of limitations due to
the presence of intermediate ester derivatives and side reactions col-
lapsing the yield of PC. Benzonitrile plays the role of dehydrating
agent and co-solvent and seems to be the best solvent for this trans-
formation. Basic alkali carbonates like potassium and cesium give the
best result for PC synthesis. Under optimal reaction conditions, the
Polymerization
Dark polymer: degradation
1
5
–
trace
2
–
Isobutyronitrile
1
0.2
Reaction conditions: PG (100 mmol), Benzonitrile (Bn, 100 mmol), 5% mol K2CO3, CO2
10 MPa, temperature 448 K, time 18 h.

62
E. Da Silva et al. / Catalysis Communications 29 (2012) 58–62
Scheme 4. Hydrolysis of esters and propylene carbonate under optimal reaction conditions.
[12] K. Kohno, J.-C. Choi, Y. Ohshima, A. Yili, H. Yasuda, T. Sakakura, Journal of Organ-
ometallic Chemistry 693 (2008) 1389–1392.
[13] J.-C. Choi, L.-N. He, H. Yasuda, T. Sakakura, Green Chemistry 4 (2002) 230–234.
[14] J. Kizlink, I. Pastucha, Collection of Czechoslovak Chemical Communications 60
(1995) 687–692.
production of PC is limited by the reaction equilibrium. The future
challenge is to find an alternative process to remove water molecules
from the system while limiting formation of side products.
[15] D. Ballivet-Tkatchenko, T. Jerphagnon, R. Ligabue, L. Plasseraud, D. Poinsot, Applied
Catalysis A: General 255 (2003) 93–99.
[16] D. Ballivet-Tkatchenko, R. Burgat, S. Chambrey, L. Plasseraud, P. Richard, Journal
of Organometallic Chemistry 691 (2006) 1498–1504.
[17] D. Ballivet-Tkatchenko, S. Chambrey, R. Keiski, R. Ligabue, L. Plasseraud, P. Richard, H.
Turunen, Catalysis Today 115 (2006) 80–87.
[18] D. Ballivet-Tkatchenko, O. Douteau, S. Stutzmann, Organometallics 19 (2000)
4563–4567.
[19] Y. Du, D.-L. Kong, H.-Y. Wang, F. Cai, J.-S. Tian, J.-Q. Wang, L.-N. He, Journal of
Molecular Catalysis A: Chemical 241 (2005) 233–237.
[20] Y. Du, L.-N. He, D.-L. Kong, Catalysis Communications 9 (2008) 1754–1758.
[21] K. Tomishige, H. Yasuda, Y. yoshida, M. Nurunnabi, B. Li, K. Kunimori, Catalysis
Letters 95 (2004) 45–49.
Acknowledgment
E.D.S. and W.D. acknowledge SOFIPROTEOL industry for financial
support. We thank F. Albrieux, C. Duchamp and N. Henriques from
the Centre de Spectrométrie de Masse (ICBMS UMR-5246), for the
assistance and access to the Mass Spectrometry facilities. We thank
E. Rohart from Rhodia Electronics and Catalysis (La Rochelle, France)
for lanthanum catalysts.
References
[22] K. Tomishige, H. Yasuda, Y. Yoshida, M. Nurunnabi, B. Li, K. Kunimori, Green
Chemistry 6 (2004) 206–214.
[1] T. Sakakura, K. Kohno, Chemical Communications (2009) 1312–1330.
[2] M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi, C. Della Pina, Angewandte Chemie
International Edition 46 (2007) 4434–4440.
[3] C.-H. Zhou, J.N. Beltramini, Y.-X. Fan, G.Q. Lu, Chemical Society Reviews 37 (2008)
527–549.
[4] C. Vriet, 2005, Généralisation de la carbonatation aux substrats polyhydroxylés.
Synthèse de carbonates cycliques, linéaires et mixtes, à partir d'érythritol, de xylitol
et de sorbitol. Thesis (PhD), Université de Toulouse.
[23] S. Huang, S. Liu, J. Li, N. Zhao, W. Wei, Y. Sun, Catalysis Letters 112 (2006)
187–191.
[24] S. Huang, S. Liu, J. Li, N. Zhao, W. Wei, Y. Sun, Catalysis Letters 118 (2007)
290–294.
[25] X. Zhao, N. Sun, S. Wang, F. Li, Y. Wang, Industrial and Engineering Chemistry
Research 47 (2008) 1365–1369.
[26] S. Huang, J. Ma, J. Li, N. Zhao, W. Wei, Y. Sun, Catalysis Communications 9 (2008)
276–280.
[5] B. Schäffner, F. Schäffner, S.P. Verevkin, A. Börner, Chemical Reviews 110 (2010)
4554–4581.
[27] I.-H. Lin, C.-S. Tan, Journal of Chemical and Engineering Data 53 (2008)
1886–1891.
[6] I. Vauthey, F. Valot, C. Gozzi, F. Fache, M. Lemaire, Tetrahedron Letters 41 (2000)
6347–6350.
[28] J.A. Campbell, G. McDougald, H. McNab, L.V.C. Rees, R.G. Tyas, Synthesis 20 (2007)
3179–3184.
[7] M. Aresta, A. Dibenedetto, F. Nocito, C. Pastore, Journal of Molecular Catalysis A:
Chemical 257 (2006) 149–153.
[8] J. George, Y. Patel, S. Muthukumaru Pillai, P. Munshi, Journal of Molecular Catalysis A:
Chemical 304 (2009) 1–7.
[9] T. Sakakura, J.-C. Choi, Y. Saito, T. Masuda, T. Sako, T. Oriyama, The Journal of
Organic Chemistry 64 (1999) 4506–4508.
[10] T. Sakakura, Y. Saito, M. Okano, J.-C. Choi, T. Sako, The Journal of Organic Chemis-
try 63 (1998) 7095–7096.
[29] H. Sharghi, M.H. Sarvari, Tetrahedron 59 (2003) 3627–3633.
[30] M. Honda, S. Kuno, N. Begum, K.-I. Fujimoto, K. Suzuki, Y. Nakagawa, K.
Tomishige, Applied Catalysis A: General 384 (2010) 165–170.
[31] D. Walther, G. Maurer, Journal of Chemical and Engineering Data 38 (1993)
247–249.
[32] M. Honda, S. Kuno, S. Sonehara, K.-I. Fujimoto, K. Suzuki, Y. Nakagawa, K.
Tomishige, ChemCatChem 3 (2011) 365–370.
[33] K. Suzuki, K. Fujimoto, K. Tomishige, Jpn. Kokai Tokkyo Koho JP 2010077113.
[11] T. Sakakura, J.-C. Choi, Y. Saito, T. Sako, Polyhedron 19 (2000) 573–576.