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Green Chemistry
Page 6 of 7
DOI: 10.1039/C5GC01336D
Journal Name
ARTICLE
reported in Fig. 6, it clearly appears that the highest yield of to DFF in the presence of a bifunctional acid/redox catalyst i.e.
DFF was always obtained in the presence of DMSO suggesting, HPMoV catalyst. Notably, yield of DFF as high as 84% were
in a first approximation, that DMSO does not have the only obtained from fructose. The process is also applicable to inulin
role of co-solvent. When a mixture of [TBMA]Cl/DMSO was from which DFF was produced with 40% yield. In addition,
used, the solubility of the oxygen was lower than in the reaction can be conducted under air without affecting the
presence of ChCl/DMSO and neat DMSO (Fig. 3). This lack in selectivity of the reaction which is of huge interest with
oxygen solubility can be responsible of the decrease of the DFF respect of process safety. Although clarification of the reaction
yield. For the other solvents, the solubility of oxygen is not definitely deserve deeper investigation, one may draw few
correlated to the oxidation of HMF to DFF as shown by Fig. 3. conclusions at this stage (1) ChCl has a beneficial effect on the
This low DFF yield in the presence of these solvents can be due in situ production of HMF, (2) ChCl helps to solubilize O2
to secondary reactions that can occur between the solvent and leading to an increase in the oxidation rate reaction.
HMF preventing its oxidation by producing ethers for example
as reported in the literature.26
Acknowledgements
To get more insight on the reaction mechanism, the oxygen
flow exiting the reactor was analyzed by means of a mass
spectrometer. Interestingly, formation of Me2S was clearly
evidenced under standard conditions suggesting a partial
reduction of DMSO (Fig. S13). When the catalytic reaction was
carried out under helium instead of air, Me2S was still
observed but DFF was produced in a very low yield (7%). In this
case, HMF was the major product (63% yield, Fig. S14)
suggesting that O2 was required to promote the oxidation of
HMF to DFF. In addition, without catalyst, no Me2S was
observed indicating that reduction of DMSO to Me2S might be
catalyzed by HPMoV. Although deeper analyses would be
required to fully assess the reaction mechanism with accuracy,
one may propose at this stage a plausible reaction mechanism.
First of all, ChCl helps to produce HMF from fructose in the
presence of HPMoV, secondly DMSO was reduced to Me2S
while the catalyst oxidizes HMF to DFF. ChCl plays also the role
to enhance the solubility of O2.
The authors would like to thanks the Erasmus Al Idrissi grant
for the fellowship of Wahiba Ghezali.
Notes and references
‡ Footnotes relating to the main text should appear here. These
might include comments relevant to but not central to the
matter under discussion, limited experimental and spectral data,
and crystallographic data.
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Next, inulin and glucose were tested as two other
carbohydrate feed. One can note that from glucose, the
reaction is more challenging and our attempts to produce DFF
from glucose failed even by combining HPMoV with 1.25 wt%
of AlCl3, 6H2O to promote the isomerization of glucose to
fructose, a critical step on the route to HMF under the same
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of HMF (Table 2, entry 6) from inulin. Hence in these
conditions, the amount of ChCl was too high to achieve a total
conversion of HMF to DFF. Hence the ChCl/DMSO was
modified to a 50/50 mixture and we were pleased to see that,
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from inulin after 14 h of reaction suggesting that HPMoV is
capable of hydrolyzing inulin to fructose, dehydrating fructose
to HMF and then oxidizing HMF to DFF in a single reactor
(Table 2, entry 6). As observed from fructose, the temperature
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reaction rate since at this temperature DFF was produced in
only 22% yield along with 27% yield of HMF (Table 2, entry 7).
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5
,
Herein, we report that mixtures of ChCl and DMSO are
attractive media to promote the direct conversion of fructose
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