Converting wastes into added value products: From glycerol to glycerol carbonate, glycidol and epichlorohydrin using environmentally friendly synthetic routes

Article abstract of DOI:10.1016/j.tet.2010.11.070

Glycerol carbonate, synthesised via a non-phosgene route using glycerol and CO₂ or urea in presence of a heterogeneous catalyst, was efficiently converted into a series of derivatives through the functionalization of the -OH moiety, using high yield, high selectivity synthetic routes not affecting the carbonate functionality. So, for example, glycerol carbonate was converted into epichlorohydrin, a product that has a large industrial application, under very mild conditions, using a two-step reaction with a 98% yield and 100% selectivity. The high yield and mild reaction conditions (very often close to the ambient conditions) make the environmentally friendly synthetic approach described in this work of potential applicative interest. All compounds prepared were fully characterized.

Full text of DOI:10.1016/j.tet.2010.11.070

Tetrahedron 67 (2011) 1308e1313
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Converting wastes into added value products: from glycerol to glycerol carbonate,
glycidol and epichlorohydrin using environmentally friendly synthetic routes
*
Angela Dibenedetto , Antonella Angelini, Michele Aresta, Jayashree Ethiraj,
Carlo Fragale, Francesco Nocito
Department of Chemistry and CIRCC, University of Bari, Campus Universitario, 70126, Bari (BA), Italy
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 21 July 2010
Received in revised form 29 October 2010
Accepted 23 November 2010
Available online 27 November 2010
Glycerol carbonate, synthesised via a non-phosgene route using glycerol and CO2 or urea in presence of
a heterogeneous catalyst, was efficiently converted into a series of derivatives through the functionali-
zation of the eOH moiety, using high yield, high selectivity synthetic routes not affecting the carbonate
functionality. So, for example, glycerol carbonate was converted into epichlorohydrin, a product that has
a large industrial application, under very mild conditions, using a two-step reaction with a 98% yield and
100% selectivity. The high yield and mild reaction conditions (very often close to the ambient conditions)
make the environmentally friendly synthetic approach described in this work of potential applicative
interest. All compounds prepared were fully characterized.
Keywords:
Glycerol valorization
Glycerol carbonate
Epichlorohydrin
Eterogeneous catalyst
Ó 2010 Elsevier Ltd. All rights reserved.
1. Introduction
O
The production of glycerol is increasing worldwide because of
the boost of the production of biofuels from lipids. There is, thus,
a need for finding new uses of the polyol in order to prevent its
accumulations as a waste. Several routes are under screening and
the conversion into the relevant carbonate is one of the possible
options as large volumes of the latter can be utilized either directly
or indirectly. In fact, besides the direct use of the carbonate itself, it
is possible to search for new ways of expanding its application as
starting material for new and old compounds.
, B,
cat.
Cl
Cl
A
C
D
- 2 BH+ -Cl
CO2 , cat. 1
- H2O
O
H
H
H
H
H
OH
OH
OH
O
O
Glycerol carbonate (1 Scheme 1) is a bifunctional compound
employed as solvent1 or surfactant2 or else in the synthesis of
polyurethanes3 and polycarbonates.4
CO(NH3)2 , cat. 2
1
-
2 NH3
CH2OH
Due to its low toxicity, vapour pressure and flammability, good
biodegradability and moisturizing ability, glycerol carbonate also
possesses the right characteristics of a wetting agent for cosmetic
clays or a carrier for drugs. The actual synthetic routes to glycerol
carbonate (Scheme 1) are based on:
O
O
O
, SC-CO2, cat.
B
H
H
(i) the reaction of glycerol with phosgene5 (route A)
H
H
OH
OH
(ii) the transesterification with other carbonates6 (route B)
-
Scheme 1. Different synthetic routes to glycerol carbonate, 1.
7
Recently, the direct carboxylation with CO2 (route C, in which
two wastes are converted into an added value product) and the
glycerolysis of urea8 (route D, in which urea is used as an activated
* Corresponding author. Tel/fax: 0039 080 544 3606; e-mail address: a.dibene-
detto@chimica.uniba.it (A. Dibenedetto).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.11.070

A. Dibenedetto et al. / Tetrahedron 67 (2011) 1308e1313
1309
form of CO2) have been described as new clean routes that may find
industrial exploitation.
the carboxylation of glycerol in the absence of phosgene and other
organic carbonates.
The hydroxyl functionality of glycerol carbonate allows its de-
rivatization in many different ways to afford either known or new
compounds. For example, the eOH moiety has been reacted with
either anhydrides9,10 to form ester linkages, or with isocyanates to
form urethanes.11,12
In this paper we describe: (i) the utilization of some newcatalysts
active in the direct carboxylation of glycerol and in the reaction with
urea; (ii) the functionalization reactions of the hydroxymethyl
group of glycerol carbonate for the production of halogenated- and
thionyl chloride-derivatives that can either give origin to new
products or afford known compounds through alternative routes,
which are cleaner and safer than those on stream. A reaction of in-
terest is, for example, the production of glycidol and epichlorohy-
drin under controlled and safe conditions.
Avoiding the use of phosgene, a highly toxic agent banned in
several countries, brings a good deal of safety to the chemical in-
dustry. Concerning the organic carbonates, it must be emphasized
that they are prepared from phosgene (acyclic carbonates) or from
epoxides (cyclic carbonates). The availability of the latter is linked
to the market of hydrogen peroxide (all other routes being strongly
polluting).14b
Glycerol carbonate obtained in such phosgene-free and organic-
carbonate-free routes has been cleanly converted into a few
derivatives, as reported below. Scheme 2 shows the compounds
obtained in this work through the functionalization of the
hydroxymethyl moiety eCH2OH of 1. Of particular interest is the
synthesis of epichlorohydrin, that is, carried out under mild and
very selective conditions.
O
O
2. Results and discussion
O
O
In our previous studies7a,8a we have developed new synthetic
routes to glycerol carbonate based on either the direct carboxylation
of glycerol with CO2 or the use of urea. The former route (route C in
Scheme 1) converts two wastes into added value products, and the
latter (route D in Scheme 1) results to be an indirect use of CO2 again,
considered that urea, when reacted with glycerol, releases NH3, that
is, recovered and can be converted back to urea by reactionwith CO2.
We describe in this paper new synthetic approaches to glycerol
carbonate and its conversion into useful chemicals, usually prepared
through more harsh synthetic procedures that are not very selective.
Both the use of two wastes, such as glycerol and CO2 and particularly
the mild and safe working conditions, coupled to the high yield and
selectivity of the processes carried out in presence of heterogeneous
catalysts, when necessary, attach environmental value to the syn-
thetic procedures described in this paper.
O
2
O
3
CH2OS(O)Cl
CH2Cl
4-oxothionyl-chloromethyl-
1,3-dioxolan-2-one
4-chloromethyl-1,3-dioxolan-2-one
O
O
O
4
O
1
CH2Cl
2-chloro,ethyl-oxirane
CH2OH
4-hydroxymethyl-1,3-dioxolan-2-one
CeO2 loaded with either Al2O3 [CeO2/Al2O3] or Nb2O5 [CeO2/
Nb2O5] were used as catalysts for the direct carboxylation of glyc-
erol in a biphasic system, while TS1 was used in the reaction of
glycerol with urea. All the heterogeneous catalysts can be easily
recovered and re-used.
O
O
O
The CeO2-based catalysts, that we have found to be active in the
carboxylation of methanol and ethanol13,14 afforded a good per-
formance also in the direct carboxylation of glycerol in a biphasic
system using tetra(ethylenglycol)dimethylether-TEGDME as sol-
vent under 5 MPa of CO2. The conversion yield is much better than
that found when nBu2Sn(OMe)2 was used as catalyst.7a We have
also used the same conditions described in a report in the liter-
ature7b saying that glycerol in the presence of methanol is car-
boxylated to a 32% conversion at 353 K using the catalyst described
in our work.7a Indeed, using such conditions with either the tin
catalyst7 or using the CeO2-based catalysts described here, neither
glycerol nor methanol were carboxylated in a detectable amount.
As a matter of fact, if glycerol is heated at 353 K under a CO2
pressure of 1.8 MPa, glycerol carbonate is not observed at all:
a much higher temperature is needed for its conversion, that is,
observed only above 453 K.
6
CH2OC(O)R
4-methylester-1,3-dioxolan-2-one
Scheme 2. Products of functionalization of glycerol carbonate.
4-Oxothionylchloromethyl-1,3-dioxolan-2-one (2, Scheme 2) is
a newcompound, neverdescribed in the literature. It is a paleyellow,
irritating liquid. This compound, differently from the starting car-
bonate, does not form hydrogen bonds. Its decomposition temper-
ature (at 0.1 MPa) is 383 K. The surface tension (71.8 dyn/cm3) and
the density (1.73 g/cm3) are higher than those of glycerol carbonate
(44.1 dyn/cm3 and 1.42 g/cm3, respectively). Compound 2 was
synthesised through a direct thio-chlorination of glycerol carbonate
(Scheme 3) with >98% yield.
The use of urea as carbonylating agent instead of CO2 improves the
thermodynamics of the reaction, as urea can be considered an acti-
O
O
vated form (
D
G¼ꢀ334 kJ/mol) of CO2 ( G¼ꢀ395 kJ/mol). TS1 is quite
D
O
active in catalysing such reaction to afford 1 very selectively with a ca.
60% conversion of glycerol. The catalyst shows a good recoverability
under the reaction conditions at least for a few cycles. After fourefive
cycles the catalyst starts to be slowly micro-pulverized because of
mechanical stresses, that may cause a slight loss of TS1.
O
O
+
SOCl2
O
+
HCl
1
2
CH2OH
CH2OS(O)Cl
99%
Such routes of conversion of glycerol represent an extension of
our previous findings and add new opportunities to the tool-box for
Scheme 3. Thio-chlorination of glycerol carbonate.

1310
A. Dibenedetto et al. / Tetrahedron 67 (2011) 1308e1313
O
The reaction needs to be carried out very carefully at 315 K and
O
under a nitrogen flow so as to avoid the formation of 4-chloromethyl-
1,3-dioxolan-2-one and to assist the elimination of the hydrogen
chlorideformed.Compound2wasisolatedand characterizedbymass
spectrometry (see Experimental section) and 13C NMR (Fig. 1). A
signal at 154.5 ppm is attributed to the carbonylic-C and the signals at
73.2, 66.6 and 63.3 ppm are due to C4, C6 and C5, respectively.
Compound 2 is moisture sensitive and after exposure to moist
air its 13C NMR and FTIR spectra, show (Fig. 2) that it cleanly and
quantitatively back-converts into 1.
O
O
18-crown-6 traces
+
KCl traces
+
SO2 (g)
99%
O
O
3
2
CH2Cl
CH2OS(O)Cl
Scheme 5. Reaction of desulfurization of 2 to afford 3.
Fig. 1. {1H}e13C NMR (100 MHz, CD3Cl) spectrum of 2.
Fig. 2. {1H}e13C NMR (100 MHz, CD3Cl) spectrum of 2 after exposure to air: 2 is converted back to 1.
O
O
Compound 2 can be advantageously used for the synthesis of
compounds, such as 4-chloromethyl-1,3-dioxolan-2-one 3, that is,
a good intermediate for organic syntheses.15
O
O
The synthesis of the latter is presently mainly based on the
cycloaddition of carbon dioxide to epichlorohydrin 4 (Scheme 4),16
that requires the preliminary synthesis of 4, obtained by high
temperature oxo-chlorination of propene followed by further
work-up with Ca(OH)2 at 373 K17
O
+
PCl3
3
3
O
+
H3PO3
3
1
CH2OH
CH2Cl
92%
Scheme 6. Direct chlorination of glycerol carbonate to afford 3.
In order to avoid complex synthetic procedures that are not
selective, we synthesised 3 by desulfurization of 2 (Scheme 5) or by
direct chlorination of 1 (Scheme 6).
O
Both reactions proceed with a >92% yield. In particular, the de-
sulfurization of 2 was carried out with a >99% yield and in milder
conditions than those used for the carboxylation of the epichloro-
hydrin. The catalytic use of KCl and crown-ether (<1%) make the
desulfurization reaction very clean and fast also under mild con-
ditions (298 K and 0.1 MPa). The formed SO2 can directly be re-
moved from the reaction medium with a nitrogen flow and
condensed at low temperature (and eventually re-used).
O
cat.
O
+
CO2
O
CH2Cl
3
4
CH2Cl
Scheme 4. Carboxylation of epichlorhydrin.

A. Dibenedetto et al. / Tetrahedron 67 (2011) 1308e1313
1311
If the direct chlorination of 1 is made using PCl3, 3 can be sep-
arated from the formed phosphoric acid by using toluene that se-
lectively extracts 3.
anhydrides under very mild conditions and often with an almost
quantitative conversion.
The results reported in the Experimental section demonstrate
that, will the nucleophile being the same in all reactions, the steric
and electronic factors of the reagents play a prominent role, but the
conversion yield is always >92%. The acyl chlorides show a higher
activity compared to aroyl chlorides, which is what one expects
considering the electronic factors. In the alkylic series, this factor
was overturned from 6c to 6d because of the steric hindrance of the
dimethyl moiety in 6d. All the isolated ester species, were fully
characterized and stable in the air.
Interestingly, starting from 3 we easily obtained 4 by distillation
under vacuum at 353 K with an almost quantitative yield. The
overall conversion yield of glycerol into epichlorohydrin is close to
70%. This route based on glycerol, that is, converted into the car-
bonate using urea (Scheme 7), represents an interesting alternative
synthetic methodology for epichlorohydrin, that is, a colourless
highly reactive compound used in the production of plastics, elas-
tomers and epoxy resins.18
O
3. Conclusions
H
H
H
H
OH
OH
OH
urea, cat
- 2 NH3
New catalysts active in the carboxylation of glycerol to glycerol
carbonate are described using heterogeneous catalysts. The car-
bonate obtained with the exclusion of the use of phosgene or other
organic carbonates (often prepared from phosgene or using epox-
ides that require hydrogen peroxide for their synthesis) have been
converted into known or new compounds. In this way, molecules,
such as epichlorohydrin, which may have a large application, were
obtained by using simple and safe synthetic routes. All the reactions
described in this paper require very simple manipulations and are
characterized by a very high yield (often almost quantitative) and
100% selectivity. These processes open the way to new synthetic
methodologies, which do not require either phosgene or epoxides
and use two wastes, such as the abundant glycerol and carbon
dioxide as starting material for the synthesis of several chemicals.
O
O
1
2 H2O
H
O
- HCl
CH2OH
O
- HCl
SOCl2
CH2Cl
O
distill
O
O
KCl, CE
- SO2
O
O
2
3
CH2Cl
CH2OS(O)Cl
4. Experimental section
4.1. Chemical reagents
Scheme 7. Reaction-chain for the synthesis of epichlorohydrin from glycerol.
Interesting classes of compounds obtained from glycerol car-
bonate are ethers19,20 and esters21e23 that find application as in-
termediates for pharmaceuticals.19
Compound 3 can be easily converted into the relevant phenoxyl
ether (Scheme 8) with a 54% yield of conversion that represents an
improvement of the routes reported in the patent and scientific
literature19,20 that are based on the reaction of CO2 and epoxides. In
the latter processes the catalyst always contaminates the product.
All reagents and solvents were RP grade purchased by Aldrich.
Starting glycerol carbonate was prepared as reported in Ref. 1. The
infrared spectra were obtained using a SHIMADZU IR Prestige 21
spectrometer placing the sample between KBr disks, neat or dis-
persed in Nujol. The reaction liquid and/or gas products were an-
alyzed using a gas chromatograph HP 6850 series equipped with
a capillary column ZB-WAX (30 mꢁ0.25 mm) and with a flame
ionization detector. The gas-mass analyses were conducted with
a GCeMS Shimadzu QP5050 equipped with the same column as the
gas chromatograph. The 1H NMR and 13C NMR spectra were
recorded using a Bruker spectrometer operating at 600 MHz with
deuterated toluene (C7D8), deuterated chloroform (CDCl3) or deu-
terated methylene chloride (CD2Cl2) as solvent and tetramethylsi-
lane (TMS) as the internal reference at 298 K. TS1 was a gift of
ENI-IT.
O
O
O
K2CO3
O
+
PhOH
O
+
HCl
O
3
5
CH2Cl
Scheme 8. Etherification of 4-chloro glycerol carbonate.
CH2OPh 54%
Surface characterization was carried out using Pulse Chemisorb
Micrometrics 2750 Instrument. The acid and basic sites of the
catalysts were determined by TPD of NH3 and CO2, respectively. BET
The esters of cyclic carbonates find application in demolding
thermoplastic polycarbonates21 or in urethane coatings.22 The main
synthetic approach for esters is based on the reaction of CO2 with
substituted epoxides23 or on the reaction of the eOH moiety of the
carbonate with Ac2O.22 We have performed the esterification of
glycerol carbonate with different acyl chlorides (Scheme 9) or
surface analyses were performed using
mixture.
a 30%N2/70%He gas
4.2. Synthesis of CeO2/Al2O3 and CeO2/Nb2O5
These mixed oxides were synthesised as reported in Refs. 13a,b.
Below we report the acid/base properties and the BET surface of the
calcinated catalysts (2 h at 823 K).
O
O
O
O
13a
Catalyst: Al2O3/CeO2
RC(O)Cl
O
O
+
+ HCl (g)
BET: 81 m2/g
R= alkyl, aryl
6
Acid/basic sites ratio: 0.53
13b
Catalysts: Nb2O5/CeO2
CH2OC(O)R
Scheme 9. Esterification of glycerol carbonate.
>90%
CH2OH
BET: 36 m2/g
Acid/basic sites ratio: 1.09

1312
A. Dibenedetto et al. / Tetrahedron 67 (2011) 1308e1313
4.3. Direct carboxylation of glycerol in TEGDME using
modified-ceria catalysts
15.65. MS: m/z 87 (loss of CH2Cl), 57 (loss of Cl and CO2), 49
(CH2Clþ), 43 (loss of CO2 from fragment 87), 29 (CHOþ derived
from fragment 57).
Glycerol (4 g, 43 mmol) were transferred into a conditioned
reactor together with tetra(ethylene glycol)dimethyl ether-
TEGDME (10 mL) and mixed oxide (ca. 20 mg) in order to have
a catalyst/glycerol ratio equal to 0.3% in mol. The reactor was placed
in a stainless steel autoclave charged with 5 MPa of CO2. The re-
action was carried out for 15 h at 453 K under stirring.
At the end of the reaction, the organic phase was analyzed with
a gas chromatograph using biphenyl ether as internal standard. The
catalyst was recovered by filtration, washed with methanol, dried
at 423 K for 15 min and used again in a new reaction cycle. The
same catalyst was recycled at least three times without any loss of
activity. The conversion of glycerol into glycerol carbonate was
equal to 2.5% with an apparent TON of 8 in each of the three con-
secutive cycles of reaction. After a few cycles a total conversion of
10% glycerol was observed. This value is higher than that obtained
using heterogenized Sn-catalysts.7a
4.6. Synthesis of 4-chloromethyl-1,3-dioxolan-2-one,
3 by desulfurization of 2
To liquid 4-oxothionylchloromethyl-1,3-dioxolan-2-one (1.84 g,
11.75 mmol), toluene (solvent, 3 mL), crown-ether 18-crown-6
(152.20 mg, 0.576 mmol) and KCl (49.40 mg, 0.576 mmol) were
added. The suspension was heated for 3 h at 60 ꢂC in a system that
allowed the removal of the formed SO2. The conversion of the
sulfonyl chloride into the chloromethyl derivative was >99%.
The liquid phase was separated from KCl and CE by filtration.
The final liquid was evaporated in vacuum at 20 ꢂC so to remove
toluene. The residual liquid was analyzed by gas chromatography,
mass spectrometry and 13C NMR and shown to be pure 3.
13C NMR (C7D8, 100 MHz):
d
¼155, 75, 67, 44.8 ppm attributes to
C2, C4, C6 and C5, respectively. Anal. Calcd for C4H5ClO3: C, 35.19; H,
3.67; Cl, 25.95; O, 35.19. Found: C, 35.06; H, 3.60; Cl, 25.75%. MS: m/
z 87 (loss of CH2Cl), 57(loss of C1 and CO2), 49 (CH2Clþ), 43 (loss of
CO2 by fragment 87), 29 (CHOþ derived by the fragment 57).
The addition of methanol7b did not improve the conversion of
glycerol also at 453 K. Lower yields were observed at lower tem-
perature. No reaction was observed at all below 400 K, in presence
or absence of methanol. This is in line with the fact that the direct
synthesis of dimethylcarbonate from methanol and CO2 is observed
only at 413 K.
4.7. Synthesis of 4-chloromethyl-1,3-dioxolan-2-one,
3 by direct chlorination of 1
4.4. Reaction of glycerol with urea using TS1 as catalyst
To a solution of 4-hydroxymethyl-1,3-dioxolan-2-one (2.10 g,
17.78 mmol) in CH2Cl2 (5 mL), the stoichiometric amount of PCl3
according to Scheme 6 (0.81 g, 5.93 mmol) was added dropwise and
the reaction was allowed to proceed at 40 ꢂC for 3 h. At the end of
the reaction the product was extracted with toluene (3ꢁ3 mL),
toluene was evaporated in vacuum at 20 ꢂC and the remaining
liquid (2.23 g, 92% of 4-chloromethyl-1,3-dioxolan-2-one) was an-
alyzed by gas chromatography, mass spectrometry and 13C NMR
and shown to be pure 3.
Anal. Calcd for C4H5ClO3: C, 35.20; H, 3.66; Cl, 25.97; O, 35.17.
Found: C, 35.1; H, 3.60; Cl, 25.90. The GCeMS and NMR data
obtained were the same as for the compound obtained in the
previous reaction.
The catalyst TS1 was preliminarily calcinated for 3 h at 773 K.
Glycerol (5.1087 g, 55 mmol), powdered urea (1.6521 g, 27.5 mmol)
and the catalyst (0.0318 g) were placed in the reactor. A vacuum
system (20 Pa) for the removal and capture of ammonia during the
reaction was connected to the head of the reactor. The reaction was
allowed to proceed for 3 h at 418 K under stirring after which the
reactor was cooled to room temperature. Glycerol carbonate was
extracted using CH3CN in which neither glycerol nor urea was
soluble and analyses were performed by gas chromatography, FTIR
and NMR on the extracts. The conversion of glycerol into glycerol
carbonate was equal to 58%. This reaction was also performed using
a 1/1 glycerol/urea molar ratios, with a 3% w/w catalyst. The glyc-
erol conversion yield was 36%. In order to optimize the glycerol use,
a glyecrol/urea molar ratio as close as possible to 1 was used by
adopting a technique in which starting with a 2:1 glycerol/urea
molar ratio, urea was slowly added over 3 h until a 1/1 M ratio was
reached.
4.8. Synthesis of 2-chloromethyloxirane, 4 by
decarboxylation of 2
4-Chloromethyl-1,3-dioxolan-2-one obtained as described in
the reactions above was subjected to a vacuum distillation at 80 ꢂC.
The distilled fraction was analyzed by infrared spectroscopy, mass
spectrometry and nuclear magnetic resonance. The conversion of
2 into 4 was >99%.
The glycerol conversion yield was monitored to be close to 60%
with 100% selectivity.
4.5. Synthesis of 4-oxothionylchloromethyl-1,3-dioxolan-2-
one, 2
IR: nmax/cmꢀ1 3063m, 3004s, 2963m, 2926m, 1519w, 1480m,
1448m, 1433s, 1398s, 1277s, 1267s, 1266s, 1209w, 1137w, 1092w,
962s, 927s, 906m, 854s, 844s, 836s, 761s, 738s, 723s, 696m, 444m.
13C NMR (CDCl3, 100 MHz) 51.3, 46.9, 45.5. MS: m/z 94 (mol. ionþ2),
92 (mol. ion), 57 (CH2(O)CHCHþ2 ), 51 (CH2Clþ), 49 (CH2Clþ), 64
(eCO), 28 (COþ).
Thionyl chloride (3 mL, 41.20 mmol) were placed in a three-
necked flask equipped with a condenser under a nitrogen flow and
4-hydroxymethyl-1,3-dioxolan-2-one (1 mL, 11.86 mmol) was
added dropwise with stirring. A trap of triethylamine for the neu-
tralization of hydrogen chloride formed during the reaction was
placed on the top of the condenser. The addition of carbonate was
carried out at room temperature and the reaction was allowed to
proceed for 1 h after the addition was completed. The excess of
thionyl chloride was eliminated under vacuum at 40 ꢂC and
recovered and the final liquid was analyzed by gas chromatography,
mass spectrometry and 13C NMR and shown to be pure 2 (2.36 g,
99.1%).
4.9. Synthesis of 4-phenoxymethyl-1,3-dioxolan-2-one, 5
4-Chloromethyl-1,3-dioxolan-2-one (1.1223 g, 7.38 mmol) in
CH2Cl2 (4 mL), phenol (0.6948 g, 7.38 mmol) and an excess of K2CO3
were placed in a flask under a nitrogen flow. The reaction was
carried out for 3 h under reflux. At the end of the reaction the excess
of the potassium carbonate was removed by filtration and the
obtained solution was analyzed by 13C NMR. The solvent was
eliminated under vacuum and elemental analyses were performed
on the residual liquid (0.77 g, 54%).
13C NMR (C7D8, 100 MHz):
tributed as in Fig. 1. Anal. Calcd for C4H5ClO5S: C, 23.94; H, 2.59;
Cl, 17.68; O, 39.90; S, 15.99. Found: C, 23.88; H, 2.65; Cl, 17.61; S,
d
¼154.5, 73.2, 65.6, 63.3 ppm at-

A. Dibenedetto et al. / Tetrahedron 67 (2011) 1308e1313
1313
13C NMR (CDCl3, 100 MHz):
d
¼162.7 (C1 Ph), 155.4 (eCO), 129.3
4.82, 4.36 and 4.19 (H, glycerol carbonate moiety); 13C NMR (CDCl3,
100 MHz):
C6H8O5: C, 45.0; H, 5.0; O, 55.0. Found: C, 45.1; H, 5.0.
(C3 Ph), 124.1 (C4 Ph), 118.2 (C2 Ph), 74.2 (C4 glycerol carbonate
moiety), 66.6 (C6 glycerol carbonate moiety), 63.7 (C5 glycerol
carbonate moiety). Anal. Calcd for C10H10O4: C, 61.85; H, 5.15; O,
32.99. Found: C, 61.06; H, 5.04.
d
¼171.0, 155.4, 74.5, 67.0, 63.7, 21.1. Anal. Calcd for
4.13. Synthesis of 4-dimethylacetate-1,3-dioxolan-2-one, 6d
4.10. Synthesis of 4-methylbenzoate-1,3-dioxolan-2-one, 6a
4-Dimethylacetate-1,3-dioxolan-2-one was synthesised in the
same way as reported in 4.10 from 1 and isobutyryl chloride with
84% isolated yield (>98% GC-conversion and 100% selectivity).
4-Hydroxymethyl-1,3-dioxolan-2-one (1.1613 g, 9.83 mmol) in
CH2Cl2 (4 mL) were placed in a flask under a dinitrogen flow.
Benzoyl chloride (1.38 g, 9.83 mmol) were added and the reaction
allowed to proceed for 3 h under reflux while the formed HCl was
stripped away and trapped in a KOH water solution (1.90 g, 87%).
The final pure product (100% selectivity and 99% chromato-
graphic yield) was isolated by column chromatography (the column
was packed with silica and chloroform/toluene¼1/1 was used as
eluent) with a 92% yield.
13C NMR (CD2Cl2, 100 MHz):
d
¼174.0, 151.5, 74.5, 66.0, 63.7, 35.5,
18.2. Anal. Calcd for C8H12O5: C, 51.06; H, 6.38; O, 42.56. Found: C,
51.0; H, 6.25.
Acknowledgements
Theresearchleadingtotheseresultshasreceivedfundingfromthe
European Union Seventh Framework Programme (FP7/2007e2013)
under grant agreement no 241718 EuroBioRef. One of us (F.N.) thanks
the University of Bari, MiUR-PRIN08 and the Apulia Region for a Ph.D.
grant.
The collected fractions were concentrated under vacuum and
a white powder was obtained, which was characterized by ele-
mental analyses, FTIR, 1H and 13C NMR.
IR: nmax/cmꢀ1 (in the range 1800e700): 1790s, 1705s, 1597m,
1475m,1463m,1452m,1400m,1319m,1270m,1252m,1180s,1175m,
1081s, 1025m, 1033m; 984m, 866m, 808w, 767m, 702s; 1H NMR
References and notes
1. Behr, A.; Bahke, P.; Klinger, B.; Becker, M. J. Mol. Catal. A: Chem. 2007, 267,
149e156.
2. Weuthen, M.; Hees, U. DE Patent 4335947, 1995.
(CDCl3, 600 MHz):
d
¼8.01, 7.55, 7.66 (5H, Ph), 4.61, 4.36 (2H, CH2),
4.79, 4.28, 4.23 (3H, cyclic carbonate); 13C NMR (CDCl3, 100 MHz):
d
¼166.4 (CO ester),155.3 (CO carbonate),134.3 (C4 Ph),132.8 (C1 Ph),
3. Randall, D.; De Vos, R. EP Patent 419114, 1991.
4. Plasman, V.; Caulier, T.; Boulos, N. Plast. Addit. Compd. 2005, 7, 30e33.
5. Encyclopedia of Chemical Processing and Design; McKetta, J. J., Cunningham, W.
A., Eds.; Marcel Decker: New York, NY, 1984; Vol. 20; p 177.
6. Vieville, C.; Yoo, J. W.; Pelet, S.; Mouloungui, Z. Catal. Lett. 1998, 56, 245e247.
7. (a) Aresta, M.; Dibenedetto, A.; Nocito, F.; Pastore, C. J. Mol. Catal. A: Chem. 2006,
257, 149e153; (b) George, J.; Patel, Y.; Muthukumaru Pillai, S.; Munshi, P. J. Mol.
Catal. A: Chem. 2009, 304, 1e7.
130.0 (C2 Ph), 128.7 (C3 Ph), 74.2, 66.6, 63.7 (C4, C6 and C5 of glycerol
carbonate moiety, respectively). Anal. Calcd for C11H10O5: C, 59.46;
H, 4.50; O, 36.04. Found: C, 59.2; H, 4.50.
4.11. Synthesis of 4-phenylacetate-1,3-dioxolan-2-one, 6b
8. (a) Aresta, M.; Dibenedetto, A.; Nocito, F.; Ferragina, C. J. Catal. 2009, 268,
106e114; (b) Li, Q.; Zhang, W.; Zhao, N.; Wei, W.; Sun, Y. Catal. Today 2006, 115,
111e116; (c) Okutsu, M.; Kitsuki, T. JP Patent 039347, 2007; (d) Sylvain, C.;
Muloungui, Z.; Yoo, J.W.; Gaset A. EP Patent 0955298 B1, 2001; (e) Okutsu, M.;
Kitsuki, T. EP Patent 1156042 A1, 2001.
9. D’Alelio, G.; Huemmer, T. J. Poly. Sci. A. 1967, 5, 307e321.
10. Moeller, T.; Kinzelmann, H. G. EP Patent 0328150, 1989.
11. Gillis, H.R.; Stanssens, D.; De Vos, R.; Postema, A. R.; Randall, D. U.S. Patent
5,703,136, 1997.
Following the same procedure reported in Section 4.10, 4-phe-
nylacetate-1,3-dioxolan-2-one was synthesised from 1 and phe-
nylacetyl chloride with a 92% isolated yield (99% GC-conversion,
100% selectivity).
13C NMR (CDCl3, 100 MHz):
d¼172.2 (CO ester), 155.3 (CO car-
bonate), 136.1 (C1 Ph), 130.4 (C2 Ph), 129.4 (C3 Ph), 127.6 (C4 Ph),
74.2, 66.6, 63.7 (C4, C6 and C5 of the glycerol carbonate moiety,
respectively), 39.7 ppm (CH2 benzyl). Anal. Calcd for C11H12O5: C,
61.02; H, 5.08; O, 33.90. Found: C, 60.95; H, 5.05.
12. Whelan, J.M.Jr; Hill, M.; Cotter, R.J. U.S. Patent 3,072,613, 1963.
13. (a) Aresta, M.; Dibenedetto, A.; Pastore, C.; Angelini, A.; Aresta, B.; Papai, I.
ꢀ
J. Catal. 2010, 269, 44e52; (b) Aresta, M.; Dibenedetto, A.; Angelini, A.; Ethiraj, J.;
Aresta, B. submitted for publication.
14. (a) Aresta, M.; Dibenedetto, A.; Pastore, C.; Cuocci, C.; Aresta, B.; Cometa, S.; De
Giglio, E. Catal. Today 2008, 137, 125e131; (b) Dibenedetto, A.; Aresta, M.;
Fragale, C.; Distaso, M.; Pastore, C.; Venezia, A. M.; Liu, C. J.; Zhang, M. Catal.
Today 2008, 137, 44e51.
15. U.S. Patent 4,849,529, 1984; Rokicki, G.; Kuran, W. J. Prakt. Chem. 2004, 327,
718e722.
16. Palanichamy, M.; Meenakshisundaram, S. U.S. Patent 0,242,903, 2004; Jia-Li, J.;
Feixue, G.; Ruimao, H.; Xianqing, Q. J. Org. Chem. 2005, 70, 381e383.
17. Nagato, N.; Mori, H.; Maki, K.; Ishioka, R. U.S. Patent 4,634,784, 1987.
18. Chemical Economics Handbook Report Epichlorohydrin; SRI Consulting: Sep-
tember 2004.
19. North, M. WO Patent, 132474, 2008.
20. Zhou, Y.; Hu, S.; Ma, X.; Liang, S.; Jiang, T.; Han, B. J. Mol. Catal. A: Chem. 2008,
284, 52e57.
21. Kaufmann, R.; Ebert, W.; Loewer, H.; Kadelka, J.; Wulff, C. DE Patent, 19545330,
1997.
22. Grahe, G.; Lachowicz, A. DE Patent 3804820, 1989.
23. Jin, L.; Chang, T.; Jing, H. J. Catal. 2007, 28, 287e289.
4.12. Synthesis of 4-methylacetate-1,3-dioxolan-2-one, 6c
4-Hydroxymethyl-1,3-dioxolan-2-one (1.2233 g, 10.35 mmol) in
CH2Cl2 (4 mL) were placed in a flask under a dinitrogen flow. Acetyl
chloride (0.81 g, 10.35 mmol) were added and the reaction allowed
to proceed for 1.5 h under reflux with HCl trapping, as described
above (1.62 g, 98%). The solvent was eliminated under vacuum and
a pale yellow liquid was obtained, which was characterized by
elemental analyses, FTIR and 13C NMR as pure ester (100%
GC-conversion, 100% selectivity; 98% isolated yield).
IR: nmax/cmꢀ1 (in the range 1800e700): 1792s, 1714s, 1481w,
1398s,1294s,1280w,1180s,1087s,1053s, 935m, 856w, 775m, 717m.
1H NMR (CDCl3, 600 MHz):
d¼2.04 (3H, CH3), 4.61, 4.33 (2H, CH2),