Green Chemistry
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We tested the recyclability of both excess glycerol and catalyst
for the synthesis of one of our target product i.e. mephenesin (3c).
The products after each run were extracted from the crude
mixture with toluene and analyzed by NMR. After the first run
(conditions as reported in Table 2) and likewise after the second
run, 1 equivalent of cresol (2c), 1.4 equivalents of glycerol and
1.4 equivalents of DEC were added to the residue recovered after
the extraction and the resulting mixture was reacted for 28 h at
105-110 °C. As shown in Fig. 3, the reaction gave very good
3
4
V. Cadierno, Chem. Commun., 2011, 47, 6208; (b) Y. Gu, and F.
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(ChemSpider ID); (c) Chlorphenesin, 7411 (ChemSpider ID); (d)
Tara E. Gottschalck and John E. Bailey (editors) International
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10 yields (76-80%), which means that the catalyst kept its efficiency.
More details are given in the supplementary information.
5
6
100
90
80
70
60
50
40
30
20
10
0
3
1
2
number of run
Fig. 3 Yield of mephenesin (3c) after the recycle of glycerol and K2CO3
(runs 2 and 3).
7
15 Conclusions
We believe that although linear and cyclic carbonate reactions
were deeply investigated, little study was done on competitive
reactions. Our protocol allows the use of more available
hydroxy derivatives and DEC instead of cyclic carbonates as
20 reagents. This method represents a green and easy access to
aryloxyproapanediols 3 which, beside their own importance,
are also in fact used as intermediates in biological products
and in polymer chemistry. The great advatage of this synthetic
protocol comes from the use of largely available and benign
25 glycerol instead of epoxides or chlorinated derivatives and the
synthesis does not involve toxic intermediates. The base
potassium carbonate, is readily available and cheap and can be
recycled as well as the excess of glycerol. No solvent is
required for reaction.
8
9
(a) R. De Sousa, C. Thurier, C. Len, Y. Pouilloux, J. Barrault and F.
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10 US Pat., 0288230A1, 2011 claims also about the preparation of
polyurethans from glycerol, diamines and DMC. No experimental
details are reported.
11 A. B. Shivarkar, S. P. Gupte and R. V. Chaudhari, Ind. Eng, Chem.
Res, 2008, 47, 2484.
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Chem., 2005, 7, 529; (b) G. Rokicki, Prog . Polym. Sci., 2000, 25,
259; (c) W.W. Carlson, and L. H. Cretcher, J. Am. Chem Soc, 1947,
69, 1952; (d) G. Rokicki, J. Pawlicki, and W. Kuran, J. Prakt. Chem.,
1985, 327, 718.
13 In this case it was not necessary an excess of starting diol because the
final products contain only one hydroxyl group and further reactions
could not occur.
30 Notes and references
a
Department of Chemistry, Materials and Chemical Engineering "Giulio
Natta", Politecnico di Milano, Piazza Leonardo da Vinci, 32 - 20133
Milano, Italy. Fax: +39(02)23993180; Tel: +39(02)23993038; E-mail:
b
35
Università Carlo Cattaneo - LIUC, Corso Matteotti, 22 - 21053
Castellanza (VA), Italy. E-mail: sergio.auricchio@polimi.it
† Electronic Supplementary Information (ESI) available: Experimental
procedures and copies of 1H NMR and 13C NMR spectra. See
40 DOI: 10.1039/b000000x/
1
2
M. Pagliaro and M. Rossi, The Future of Glycerol, RSC Publishing,
Cambridge, UK, 2nd edn., 2008.
(a) I. M. Atadashi, M. K. Aroua and A. Abdul Aziz, Renew. Sust.
Energ. Rev., 2010, 14, 1999 and (b) Renew. Energy, 2011, 36, 437;
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