Applied Catalysis A: General 341 (2008) 133138

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Heterogeneous base catalyzed synthesis of 2-oxazolidinones/

2-imidiazolidinones via transesterication of ethylene carbonate
with b-aminoalcohols/1,2-diamines
Sachin R. Jagtap a, Yogesh P. Patil a, Shin-Ichiro Fujita b, Masahiko Arai b, Bhalchandra M. Bhanage a,*
a
b

Department of Chemistry, Institute of Chemical Technology (Autonomous), University of Mumbai, Matunga, Mumbai 400019, India
Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 5 November 2007
Received in revised form 19 February 2008
Accepted 20 February 2008
Available online 26 February 2008

Several heterogeneous basic metal oxide catalysts were screened for the synthesis of 2-oxazolidinones
and 2-imidiazolidinones via transesterication of ethylene carbonate with different b-aminoalcohols or
1,2-diamines. Among the several catalysts screened, MgO was found to be the best catalyst, as it has
excellent recyclability. Various reaction parameters were studied in detail. Excellent yields of the
products were obtained using MgO as catalysts at 80 8C within 6 h in ethanol. Basic properties of the
metal oxide catalysts were compared using temperature programmed desorption (TPD) studies with CO2.
The relationship between the catalyst performance and the basic property of each catalyst has been
discussed.
2008 Elsevier B.V. All rights reserved.

Keywords:
Oxazolidinones
Imidiazolidinones
Ethylene carbonate
Heterogeneous catalysis
Basic metal oxide

1. Introduction
Carbon dioxide is one of the greenhouse gases and its
utilization as a building block has gained considerable attention
in recent years [15]. The search for the molecules that can be
effectively used for carbon dioxide xation is an important task
from the environmental viewpoint. Epoxides [68], dienes [9,10],
alkynes [11], formic acid synthesis [12] and dimethylformamide
synthesis [13] have all been well studied in this regard. 1,2Diamines and b-aminoalcohols are also worth investigating as an
effective agent for carbon dioxide xation into valuable chemicals. 2-Imidiazolidinones can nd extensive applications as an
intermediate for the synthesis of medicines [1416], chemothetaputic agents [17], dislignication reagents [18] and cosmetics
[19]. 2-Oxazolidinones nd similar useful applications [20].
Conventionally 2-imidiazolidinones and 2-oxazolidinones can
be synthesized by reactions of 1,2-diamines and b-aminoalcohols
with several reagents like phosgene [21], urea [2224], dialkyl
carbonates [14,2527], or the mixture of carbon monoxide and
oxygen via oxidative carbonylation [20,28]. The synthesis using

* Corresponding author. Tel.: +91 22 24145616; fax: +91 22 24145614.

E-mail addresses: bhalchandra_bhanage@yahoo.com, bmb@udct.org
(B.M. Bhanage).
0926-860X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2008.02.035

urea has a major drawback of formation of large quantities of

polyurea along with the requirement of high temperature [29].
Syntheses using dialkyl carbonates and oxidative carbonylations
are not eco-friendly due to the risk associated with explosion
hazards using CO/O2 mixtures or the necessity of poisonous
phosgene or carbon monoxide involved in the synthesis. It should
be noted that synthesis of dialkyl carbonates also requires such
hazardous routes [3033]. 2-Oxazolidinones can be produced
from aziridines and carbon dioxide; however, this route also
requires high temperatures or has drawbacks of polymer
formation [34]. In this view, direct addition of carbon dioxide
with alkylene diamines and aminoalcohols to produce 2imidiazolidinones and 2-oxazolidinones is the most desired
route. However, the synthesis is often associated with the use
of high pressure and high temperature [35,36].
Alternatively, 2-imidiazolidinones/2-oxazolidinones can be
synthesized using reactions of ethylene carbonate (EC) with 1,2diamines/b-aminoalcohols in the presence of base catalyst [37].
The reaction can be considered as a carbon dioxide xation
reaction, since EC is synthesized via reaction of ethylene oxide and
carbon dioxide [3842]. Recently, there is a report about the
syntheses of 2-imidiazolidinones/2-oxazolidinones from EC with
1,2-diamines/b-aminoalcohols in the presence of homogenous
base catalyst [39]. However, such reaction suffers from drawbacks
of catalystproduct separation and regeneration. Solid base

S.R. Jagtap et al. / Applied Catalysis A: General 341 (2008) 133138

134

Scheme 1. Synthesis of 2-oxazolidinones/2-imidiazolidinones from cyclic carbonates and b-aminoalcohols/1,2-diamines.

catalysts are inexpensive and are more easily separable and

recyclable than the homogeneous catalysts. Hence the use of solid
base catalyst is desirable from the viewpoints of economy and of
green chemistry. Herein, we report heterogeneous base catalyzed-syntheses of 2-oxazolidinones and 2-imidiazolidinones
from EC and b-aminoalcohols/1,2-diamines for the rst time
(Scheme 1).
2. Experimental
2.1. General

3. Results and discussion

3.1. Screening of various solid base catalysts
The reactions of EC with ethanolamine were carried out in
the presence of various heterogeneous solid base catalysts. The
inuences of various reaction parameters like solvent, temperature, type of catalyst and catalyst loading were studied in detail.
Several commercially available metal oxides, such as MgO, CaO,
ZnO, CeO2, La2O3, and ZrO2, were used without any pretreatment. The BET surface areas of the metal oxides used were 14,

All chemicals and catalysts were procured from rms of repute

and were used without further purication/pretreatment, as
received. The conversions and yields were calculated based on
GC analysis (Chemito 1000) using external the standard method.
All products were also characterized by GCMS analysis (Shimadzu
QP-2010).
2.2. Transesterication reactions
For each reaction cyclic carbonate (10 mmol), b-aminoalcohol
or 1,2-diamines (10 mmol) in ethanol (5 ml) and MgO 15 wt%
(w.r.t. EC) were charged into a 25 ml round bottom ask
equipped with a magnetic stirrer at 80 8C for 6 h. The progress
of the reaction was monitored using a gas chromatograph
(Chemito 1000). After completion of the reaction the reaction
mixture was ltered to separate the catalyst from the reaction
mixture and the resulting products were analyzed by using GC
and GCMS (Shimadzu QP-2010).
2.3. Measurement of basic properties of metal oxides
The basic properties of the catalysts were examined by
temperature programmed desorption (TPD) of adsorbed CO2 using
a conventional ow reactor. After a stream of 10% CO2He mixture
was passed over the catalyst at room temperature for 20 min, gases
in the reactor were ushed with a helium stream. Then the
temperature was ramped at a heating rate of 10 8C/min up to
800 8C. The efuent from the reactor was analyzed by gas
chromatography. Fig. 1 depicts the TPD proles of CO2 absorbed
on MgO, CaO, ZnO, CeO2, La2O3 and ZrO2.

Fig. 1. TPD spectra of absorbed CO2 over (a) CeO2; (b) La2O3; (c) CaO; (d) MgO; (e)
ZrO2; (f) ZnO. Numbers above the peaks indicates amount of CO2 desorbed ml/g of
catalysts.

S.R. Jagtap et al. / Applied Catalysis A: General 341 (2008) 133138

Fig. 2. Effects of various basic metal oxides on the synthesis of 2-oxazolidinones.

Reaction conditions: EC, 10 mmol; ethanolamine, 10 mmol; ethanol, 5 ml; catalyst,
15 wt%; temperature, 80 8C, time, 6 h. Yields are based on GC analysis.

25, 17, 30, 19 and 40 m2/g for MgO, CaO, ZnO, CeO2, La2O3, and
ZrO2, respectively. The quantitative data indicating CO2 desorption (in ml/g) is indicated in Fig. 1. CeO2 shows a CO2
desorption peak at 100 8C, while in higher temperature region above
200 8C, a desorption peak was observed at 300 and 480 8C. Two peaks
were observed at 300 and 620 8C for La2O3. A desorption peak at
80 8C was seen for CaO and in the higher temperature region
desorption peaks at 320 and 580 8C were observed. For MgO a
desorption peak at 150 8C was observed; this peak is accompanied
by a shoulder peak at 250 8C. ZrO2 shows three desorption peaks at:
90, 250 and 350 8C. For ZnO a desorption peak at 260 and 350 8C was
observed. The peak observed at 100 8C for CeO2 and the peaks at 150
and 250 8C for MgO are broad. These results strongly suggest that
moderately basic sites exist on CeO2 and that stronger basic sites
exist on MgO in the low temperature regions (below 200 8C).
However, CaO and La2O3 showed weak basic sites at lower
temperature, while at higher temperatures CaO and La2O3 show a
broad peak at 580 and 620 8C, respectively. This observation
indicates that CaO and La2O3 both have strong basic sites at higher
temperature.
As shown in Fig. 2 MgO, CaO and CeO2 are highly active for the
reaction of ethanolamine and EC. It can be seen that CaO has
maximum number of basic sites and most of them occurs at high
temperature region (550600 8C). Whereas, MgO and CeO2 have
major basic sites at a low temperature region (<150 8C, i.e. reaction
temperature range). Hence, MgO and CeO2 showed better
performance rather than CaO. It can be seen from Fig. 1, activity
of the catalyst is proportional to number of basic sites occurs at low
temperature region (<150 8C). Fig. 2 also shows the results
obtained using these metal oxides. It can be seen that, among
the various catalysts screened, only MgO gives excellent yield of 2oxazolidinones (83%) after 6 h. CaO, CeO2 and La2O3 were also
found to give good yields of 2-oxazolidinones: 68, 72, and 60%,
respectively. A catalyst like ZrO2 that has both acidic and basic
properties gives only 32% yield. It has been observed that ZnO or
ZrO2 gives a very poor yield and are not effective catalysts for this
transformation.
3.2. Inuence of reaction time
In order to optimize the reaction time we carried out the
reaction at various reaction time periods. The results obtained
were shown in Fig. 3.
It was observed that the yield of the oxazolidinones increases
with increase in the reaction time from 2 to 6 h and that the higher
yield of oxazolidinones (83%) was obtained after 6 h. Further
increases in the reaction time have no signicant effect on the yield
of the reaction.

135

Fig. 3. Inuence of reaction time on the synthesis of 2-oxazolidinones. Reaction

conditions: EC, 10 mmol; ethanolamine, 10 mmol; ethanol, 5 ml; MgO, 15 wt%;
temperature, 80 8C. Yields are based on GC analysis.

Fig. 4. Inuence of temperature on the synthesis of 2-oxazolidinones. Reaction

conditions: EC, 10 mmol; ethanolamine, 10 mmol; ethanol, 5 ml; MgO, 15 wt%;
time, 6 h. Yields are based on GC analysis.

3.3. Inuence of temperature

Fig. 4 shows the inuence of the reaction temperature on the
synthesis 2-oxazolidinones, when the reaction temperature
increases from 60 to 80 8C; the yield of oxazolidinones also
increases from 26 to 83%. However, further increase in the
temperature does not cause any signicant increases in the yield of
oxazolidinones.
Table 1
Inuence of solvents on the synthesis of 2-oxazolidinons
Entry

Solvent

% Yield of 2-oxazolidinones

1
2
3
4
5
6

DMF
NMP
THF
DMAC
Toluene
Ethanol

80
25
63
29
37
83

Reaction conditions: EC, 10 mmol; ethanolamine, 10 mmol; MgO, 15 wt%;

temperature, 80 8C, time, 6 h. Yields are based on GC analysis.
Table 2
Inuence of MgO loading on the synthesis of 2-oxazolidinones
Entry

MgO (wt%)

% Yield of 2-oxazolidinones

1
2
3
4
5
6

2.5
5.0
7.5
10.0
15.0
20.0

57
65
70
76
83
84

Reaction conditions: EC, 10 mmol; ethanolamine, 10 mmol; ethanol, 5 ml;

temperature, 80 8C; time, 6 h. Yields are based on GC analysis.

S.R. Jagtap et al. / Applied Catalysis A: General 341 (2008) 133138

136

Table 3
Synthesis of 2-oxazolidinones from b-aminoalcohols and cyclic carbonates
Entry

Cyclic carbonates

Aminoalcohols

2-Oxazolidinones

Yield (%)

83

80

81

78

75

77

70

80

No reaction

10

No reaction

11

80

12

72

Reaction conditions: cyclic carbonate, 10 mmol; aminoalcohol, 10 mmol; ethanol, 5 ml; temperature, 80 8C; time, 6 h; MgO, 15 wt%. Yields are based on GC analysis. GCMS
m/z (entries-17) 87 (M+), 59, 42 (entry-11) m/z 101 (M+), 84, 71, 56, 44 (entry-12) m/z 140 (M+), 100, 56, 42 (entry-8) m/z 115 (M+), 100, 72, 56, 42.

S.R. Jagtap et al. / Applied Catalysis A: General 341 (2008) 133138

137

Table 4
Synthesis of 2-imidiazolidinones from 1,2-diamines and cyclic carbonates
Entry

Cyclic carbonates

Diamines

2-imidiazolidinones

Yield (%)

85

81

83

80

79

75

76

No reaction

82

Reaction conditions: cyclic carbonate, 10 mmol; 1,2-diamine, 10 mmol; ethanol, 5 ml; temperature, 80 8C; time, 6 h; MgO 15 wt%. Yields are based on GC analysis. GCMS
(entries-17) m/z 86 (M+), 58, 42 (entry-9) m/z 100 (M+), 71, 56, 40.

3.4. Inuence of solvents

It has been observed that a solvent plays a crucial role in
the activity and the selectivity performance; thus, choice of a
proper solvent is necessary. The reaction was carried out in
various solvents; the higher yield of 83% was obtained in
ethanol. Table 1 represents the inuence of solvent on the
yield of 2-oxazolidinones. It can be seen that dimethylformamide (DMF) and ethanol gives an optimum yield of 2oxazolidinones, however considering additional advantage of
isolation of the product ethanol was selected as the best solvent

over DMF. Further optimization studies were carried out using

ethanol.
3.5. Inuence of catalyst loading
The effect of catalyst loading on the yield of 2-oxazolidinones
has been shown in Table 2. With increases in the amount of the
catalyst from 2.5 to 15 wt%, some increases in the yield of the 2oxazolidinone was observed; however, further increases in the
catalyst amount do not show any signicant increase in the yield of
the oxazolidinones.

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S.R. Jagtap et al. / Applied Catalysis A: General 341 (2008) 133138

in nature and so it allows easy catalyst/product separation and it

can be recycled efciently.
Acknowledgements
The authors are thankful for nancial support for this work from
a Technical Education Quality Improvement Program (TEQIP) grant
of Indian government. We are thankful to Prof. G.D. Yadav, Head,
Chemical Engineering Division, UICT, for extending us TPD
measurement facilities.

References

Fig. 5. Recyclibility study of MgO for the synthesis of 2-oxazolidinones. Reaction

conditions: EC, 10 mmol; ethanolamine, 10 mmol; ethanol, 5 ml; MgO, 15 wt%;
temperature, 80 8C; time, 6 h. Yields are based on GC analysis.

3.6. Recyclibility
Recycling use of MgO was examined for the synthesis of 2oxazolidinones (Fig. 5). After the completion of the reaction, the
catalyst was separated from the reaction mixture by ltration.
Thus, the catalyst recovered was washed with ethanol, dried under
vacuum and reused for a subsequent reaction without any
signicant loss in the catalytic activity.
Using these optimized reaction parameters, we carried out the
reactions of various cyclic carbonates with different aminoalcohols; results obtained are shown in Table 3. It can be seen that
current method has applications for a wide range of substrate
variations for the synthesis of variety of 2-oxazolidinones from
their corresponding aminoalcohols and cyclic carbonates. It can be
seen that aliphatic aminoalcohols show high reactivity and give
excellent yields, while aromatic aminoalcohols such as 2aminophenol and 2-aminobenzyl alcohol are found to be inactive.
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synthesis of 2-imidiazolidinones from EC and 1,2-diamines. By using
the above-optimized parameters we carried out reactions of various
cyclic carbonates with various 1,2-diamines; the results obtained
are listed in Table 4. It was observed that aliphatic 1,2-diamines
showed high reactivity and gives excellent yields, while aromatic
diamines such as o-phenylenediamine were found to be inactive.
4. Conclusion
In conclusion, basic metal oxide shows the high activity for the
synthesis of 2-oxazolidinones and 2-imidiazolidinones from
ethylene carbonate and b-aminoalcohols/1,2-diamines. Among
the catalyst examined, MgO is the most active catalyst for the
reaction. This method of synthesis of 2-oxazolidinones and 2imidiazolidinones is very simple, convenient and eco-friendly
process. The solvent used (ethanol) can be easily separated by
evaporation to obtain products. The catalyst used is heterogeneous

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