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Green Chemistry
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ARTICLE
Journal Name
As the good MA yields were achieved from HMF over the V2O5 HMF to MA, up to 79% yield of MA was achieved over simple
DOI: 10.1039/C5GC01794G
catalysts, the direct synthesis of MA from more economic fructose vanadium oxide catalyst. The silica supported vanadium oxide
was therefore demonstrated (Scheme 2). Fructose dehydration catalyst showed comparable activity to the unsupported catalyst.
catalyzed by HCl in 2-propanol (IPA) was performed according to Both the supported and unsupported vanadium oxide catalysts
the previous report.[11b] IPA is a low boiling point green solvent and showed good recyclability. In the direct conversion of fructose to
therefore can be easily separated and recycled. After the maleic anhydride (MA), 50% overall yield of MA was achieved in
dehydration reaction, the IPA solvent was removed by evaporation one-pot two-step reactions. The mechanism study indicates that
to give the crude HMF product at 67% yield. Acetic acid solvent and HMF oxidation to MA is likely a free radical reaction.
the vanadium catalysts were then charged into the reactor for the
second step reaction. It turned out that 75% yield (50% overall) of
MA was achieved over V2O5 and 66% yield (44% overall) was
Acknowledgements
achieved over 5%V2O5/SiO2. The results indicate that the impurities
in the crude HMF sample did not affect HMF oxidation to MA. It is
noteworthy that the overall yields of MA directly from fructose in
this work are comparable to the MA yields from pure HMF in
homogeneous reactions.[8] It indicates great potential of the current
protocol in the practical synthesis MA from fructose.
This work was supported by the Institute of Bioengineering
and Nanotechnology (Biomedical Research Council, Agency
for Science, Technology and Research (A*STAR), Singapore),
Biomass-to-Chemicals Program (Science and Engineering
Research Council, A*STAR, Singapore).
Notes and references
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Scheme 2. The direct conversion of fructose to MA by the one-pot
two-step reactions. Fructose dehydration: fructose 0.36 g (2 mmol),
HCl 5 mol%, IPA 4 ml, 100 °C, 3 h. HMF oxidation using crude HMF
from Step 1: AcOH 10 ml; 5%V2O5/SiO2, 36 mg (0.5 mol% of V2O5);
or V2O5, 9 mg (2.5 mol%); O2 5 bar; 100 °C, 4 h. Yields include
maleic anhydride and maleic acid.
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The mechanism of HMF oxidation to MA is unclear yet. Yin et
al[8b] proposed that it might be a free radical reaction however no
evidence was provided. In fact, Xu et at[8a] indicated that it may not
be a free radical reaction in an earlier report. In order to have a
better understanding of the reaction mechanism, several control
experiments were conducted. Similar to previous reports[8], FDCA,
DFF, HFCA, and FFCA (2,5-formylfurancarboxylic acid) cannot be
converted to MA under our reaction conditions, indicating these
compounds could not be the possible intermediates for MA
formation over the current V2O5 catalyst (Fig. S6). When H2O2 was
added to the reaction system in the absence of V2O5 catalyst, MA
could be formed and the yield increased with increasing amount of
H2O2 input (Table S2). In contrast, when a free radical inhibitor 4-
tert-butylphenol was added into the reaction system in the
presence of V2O5 catalyst, both the HMF conversion and MA yield
gradually decreased (Table S2). Our results suggest that the free
radical reaction should be involved in this catalytic cycle. However,
more effort is required to reveal the actual reaction mechanism for
this reaction.
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Conclusions
We have demonstrated the heterogeneous catalytic conversion
of HMF to MA and moreover the direct conversion of fructose to
MA via the HMF intermediate. For the heterogeneous oxidation of
4 | J. Name., 2012, 00, 1-3
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