Imidazolium-2-Carboxylate as an Efficient, Expeditious and Eco-Friendly Organocatalyst
COMMUNICATIONS
Scheme 2. Synthesis of glycerol carbonate from crude glycerol coming from a biodiesel production plant.[17]
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need of industries. The application of this method in
the synthesis of other derivatives of glycerol and
higher alcohols is currently underway in our laborato-
ry and will be reported in due course. Further studies
regarding the mechanism of the reaction and specially
the identification of the reactive intermediates are in
progress.
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Experimental Section
General Procedure for the Synthesis of Glycerol
Carbonate
To a biphasic mixture of glycerol (2.66 g, 28.91 mmol) and
DMC (7.84 mL, 93.11 mmol) was added 1-n-butyl-3-methyl-
ACHTUNGTRENNUNG
imidazolium-2-carboxylate[12d] (0.053 g, 1 mol%) under an
inert atmosphere. The reaction was heated at 748C with stir-
ring for 80 min, rapidly becoming homogeneous. The vola-
tile organics were evaporated and dried under vacuum to
yield 99% pure product as determined by 1H NMR.
1H NMR (DMSO-d6, 300 MHz): d=3.52 (dd, 1H, J1 =3 Hz,
J2 =12 Hz, H-2), 3.68 (dd, 1H, J1 =3 Hz, J2 =12 Hz, H-2),
4.29 (m, 1H, H-4), 4.49 (t, 1H, J=7.5 Hz, H-4), 4.79 (m,
1H, H-3), 5.29 (bs, 1H, OH); 13C{1H} NMR (DMSO-d6,
75 MHz): d=60.5 (C-2), 65.8 (C-4), 77.0 (C-3), 155.2 (C-1);
IR (ATR, neat): n=3437, 2932, 1763, 1168 cmÀ1; IR (NaCl
windows, film): n=3386, 2931, 1790, 1181 cmÀ1.
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Acknowledgements
The authors thank CNRS, Universitꢀ de Bourgogne and
Region Bourgogne for support and for a postdoctoral fellow-
ship to PN. We also gratefully acknowledge Diester Industrie
for generously providing crude glycerol.
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ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1755