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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
134
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.
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
Solvent
% Yield of 2-oxazolidinones
1
2
3
4
5
6
DMF
NMP
THF
DMAC
Toluene
Ethanol
80
25
63
29
37
83
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
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.
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.
138
References
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.
Considering above results, we extended the methodology to the
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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