significant decrease of yield, thus showing the environmental and
economical advantage of this route.
role in agriculture, they also have numerous other applications,
such as their use as linkers in organic synthesis, pharmaceutical
ingredients, vulcanisation accelerators, among others. For more
details, please see the introduction of ref. 6.
4 (a) J. Zhang, V. A. Fitsanakis, G. Gu, D. Jing, M. Ao, V. Amarnath
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Because of the important industrial applications of DTCGs,
we then scaled up the process. Using our strategy, we successfully
produced 1 kg of DTCG from glycerol, diethyl carbonate, CS2
and diethylamine, thus showing the viability of this process. Note
that at the kilogram scale, the ethyl acetate used for the selective
extraction of the DTCG from the glycerol/NaOH phase was
recycled for use in further extractions, in order to minimize as
much as possible the environmental and economical impact of
the process. A schematic representation of the process is given
in Scheme S1†.
Conclusions
We report here that glycerol carbonate can be considered as
a highly valuable intermediate for the direct and regioselective
functionalization of glycerol by a dithiocarbamate moiety. From
the viewpoint of green chemistry, this procedure has many
advantages, such as: (i) utilization of glycerol as a renewable
raw material; (ii) 100% sulfur and nitrogen efficiency, (iii) CO2
and ethanol as only waste; (iv) the possibility of recycling NaOH
and the excess of glycerol used as solvent; and (v) the possible
scale-up of the process. The biological activities of these DTCGs
are currently being tested in an open field over sunflower, wheat
and soy crops – the results of these tests will be published in a
more specialized journal. This procedure opens an avenue for
the synthesis of safer fungicides, but also provides new synthetic
tools for the selective conversion of glycerol to higher-value
chemicals. Generalization of this method to other nucleophiles
and other natural polyols is now a topic of current investigation.
6 For a recent example, see: N. Azizi, F. Aryanasab and M. R. Saidi,
Org. Lett., 2006, 8, 5275.
7 D. Chaturvedi and S. Ray, Tetrahedron Lett., 2006, 47,
1307.
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ChemSusChem, 2008, 1, 586; (b) C.-H. Zhou, J. N. Beltramini, Y. X.
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10 The attack on the carbonyl group is normally kinetically favored over
the nucleophilic attack on the methylene position. However, attack
on the carbonyl group is reversible, whereas this is not the case for
attack on the methylene position due to a rapid decarboxylation. For
more details, see: G. Rokicki, P. Rakoczy, P. Parzuchowski and M.
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Acknowledgements
11 M. Ghandi, A. Mostashari, M. Karegar and M. Barzegar, J. Am. Oil
Chem. Soc., 2007, 84, 681.
Authors are grateful to the CNRS and the French Ministry
of Research for their financial support. The authors also
acknowledge the Agence National de la Recherche (CP2D
action) for their financial support. RDS and CT also thanks the
Agence National de la Recherche for their PhD and postdoctoral
grants, respectively.
12 (a) J. W. Yoo and Z. Mouloungui, Stud. Surf. Sci. Catal., 2003, 146,
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15 Note that some groups are currently investigating the synthesis
of carbonate from CO2 and alcohols. Such studies may offer a
way for reconverting CO2 and ethanol to diethyl carbonate. For a
comprehensive review, see: M. Shi and Y.-M. Shen, Curr. Org. Chem.,
2003, 7, 737.
Notes and references
2 For a recent review, see: B. Cvek and Z. Dvorak, Curr. Pharm. Des.,
2007, 13, 3155.
3 For a selected review, see: A. K. Malik and W. Faubel, Pestic. Sci.,
1999, 55, 965. Note that although dithiocarbamates play a pivotal
1132 | Green Chem., 2011, 13, 1129–1132
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