A gram scale selective oxidation of 5-hydroxymethylfurfural to diformylfuran in the presence of oxone and catalyzed by 2-iodobenzenesulfonic acid

Article abstract of DOI:10.1039/d0nj01653e

In the present work, an alternative system of 5-hydroxymethylfurfural (HMF) oxidation was studied, in an attempt to avoid the use of expensive metal catalysts, polluting systems and high pressures. In this context, the partial oxidation of the hydroxyl gr

Full text of DOI:10.1039/d0nj01653e

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A gram scale selective oxidation of 5-hydroxymethylfurfural to
diformylfuran in the presence of Oxone and catalyzed by 2-
iodobenzenesulfonic acid
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
a
a
Nadim Ayoub , Carla Bergère , Joumana Toufaily , Erwann Guénin , Gérald Enderlin*
DOI: 10.1039/x0xx00000x
In the present work, an alternative system of 5-hydroxymethylfurfural (HMF) oxidation was studied, in an attempt to avoid
the use of expensive metal catalysts, polluting systems and high pressures. In this context, the partial oxidation of the
hydroxyl group on the HMF molecule leads to the formation of the corresponding aldehyde, 2,5-diformylfuran (DFF). This
reaction was catalyzed by 2-iodobenzenesulfonic acid in the presence of Oxone. Under optimized experimental conditions,
the HMF conversion was found to be 100%, while the DFF yield and selectivity were almost 90%.
oxidant. The old methods with conventional oxidants can also
be very effective, for example, the use of barium manganate
gives 93% yield of DFF, however these methods suffer from the
Introduction
Biomass, as a source of chemicals, represents a sustainable
alternative to fossil fuel. It is composed of 75% of
carbohydrates, which are the main carbon source in
biorefineries. However, carbohydrates are highly oxygenated
molecules Cn(H2O)n and must be deoxygenated to regain
similar properties to those of petroleum compounds. The
dehydration of C5 and C6 carbohydrates leads to the formation
use of dangerous compounds and the generation of significant
2
2,23,24,25
amounts of waste.
These reactions are also often
carried out in very dilute media making these methods difficult
to exploit with the aim of changing the production scale from
milligrams to kilos.
2
6,27
Hypervalent iodine derivatives such as 2-iodoxybenzoic acid
2
8
(
IBX) or Dess-Martin reagent (DMP) are well known for
1
,2,3
of furan derivatives such as furaldehyde
and 5-
effective and selective oxidation of primary alcohols to
aldehydes (Scheme 1).
4
,5,6
hydroxymethylfurfural
(HMF). The latter compounds are
therefore platform molecules and represent a major interest in
the context of sustainable development. These molecules are
already used and valued in many ways, mainly by reduction or
oxidation. Numerous applications, towards bio-based solvents,
lubricants, bio-based polymers or fine chemicals, are being
These compounds offer an interesting alternative to the use of
metal catalysts, which can make the processes more
sustainable and less expensive, without the need of extraction,
purification and recycling or treatment of metals that are often
rare and/or toxic. This strategy has already been used to oxidize
HMF into DFF. Lee et al. reported the use of a polymer bearing
group similar to IBX, leading under optimal conditions to
7
,8,9,10,11
developed nowadays.
Transformations by selective
oxidation of furfural and HMF are particularly studied because
they lead to bifunctionalized molecules of interest like maleic
2
9
quantitative yields of DFF. However to use this strategy in a
viable process, major constraints need to be overcome. Indeed,
the polymer contains only a low concentration of oxidant 1.02
1
2
anhydride or diacids such as succinic acid, levulinic acid,
furanedicarboxylic acid (FDCA) or diformylfuran (DFF).1
3,14
Numerous oxidation methods of HMF to DFF have been
reported in the literature, mainly in heterogeneous phase using
noble or heavy metals in the presence of oxygen or other
-1
mmol.g , and it must be prepared in its oxidative form with a
large excess of tetrabutylammonium oxone (5 equiv.) in the
presence of methanesulfonic acid in dichloromethane for 12
hours followed by filtration before use.
oxidants.1
5,16,17,18,19,20,21
Very often, these methods however
require the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl
(TEMPO) or its derivatives as an oxidation mediator. These
methods are sometimes very effective but may require the
preparation of a complex catalyst or multi-component mixture,
long reaction times, high boiling solvents and a large excess of
HO
OAc
HO
AcO
O
O
I
I
I
OAc
O
O
O
S
O
O
O
O
IBX
DMP
IBS
a. Université de technologie de Compiègne, ESCOM, TIMR (Integrated
Scheme 1. Hypervalent Iodine derivatives used to oxidize selectively primary alcohols to
Transformations of Renewable Matter), Centre de recherche Royallieu - CS 60 319
aldehydes.
-
60 203 Compiègne Cedex
b.
Laboratoire de Matériaux, Catalyse, Environnement et Méthodes analytiques
MCEMA-CHAMSI), EDST, Université Libanaise, Campus Rafic Hariri, Hadath,
Beyrouth, Liban.
(
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O
OH
I
O
View Article Online
I
Oxone
DOI: 10.1039/D0NJ01653E
Table 1. Comparison of the effectiveness of IBX and IBS formed in situ for the selective
oxidation of HMF to DFF
R OH
R
HO
O
O
O
R=CO, SO2
R=CO (IBX)
Oxone
O
O
SO (IBS)
2
Catalyst
Scheme 2. One step preparation of hypervalent iodine compounds from 2-iodobenzoic
acid or 2-iodosulfonic acid and Oxone, leading to highly selective oxidant species of
primary alcohol, IBX and IBS.
0
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DFF Yield
81%
Catalyst
I
Other teams have prepared IBX supported on polymer which
prove to be very effective for the oxidation of alcohols (not
HMF), nevertheless, the same usage constraints are
encountered, in particular the numerous stages of preparation
of the catalyst, the very low molar fraction of iodine hypervalent
on the polymer and generally its activation in the organic phase
IBX
CO H
2
I
IBS
89%
SO3Na
Reaction conditions: 200 mg (1.6 mmol) of HMF, 1.17 g Oxone, equivalent to
KHSO /HMF mol ratio = 1.2, 30 mg of catalyst in 6 mL of nitromethane, 70°C, 4h.
30,31,32,33
5
by tetrabutylammonium oxone.
Among the iodine derivatives used for catalytic oxidation,
Ishihara et al have demonstrated that 2-iodoxybenzenesulfonic
acid (IBS, scheme 1) is a particularly selective and effective
With these very encouraging results, we decided to explore the
reaction conditions of the transformation with IBS.
Polar aprotic solvents often show good properties for the
oxidation of HMF to DFF, DMSO, for example, has frequently
been reported as the best solvent for this type of
34
catalyst for this type of oxidation. Furthermore, it has been
demonstrated that it is possible to generate the catalytic
species of hypervalent iodine in situ from 2-iodobenzene
carboxylic or sulfonic acids in the presence of Oxone® (2KHSO5,
KHSO4, K2SO4) as co-oxidant (Scheme 2). This makes it possible
to avoid the preparation of the hypervalent iodine species in
stoichiometric proportions and to handle these compounds
reported to be shock-sensitive.
reported for the selective oxidation of primary alcohols by
Vinod et al., Giannis et al. and Ishihara et al.
Compared to oxygen and hydrogen peroxide, which are well
responding oxidants to the principle of atom economy, Oxone®
provides an inert and useless mass for oxidation. However the
processes using oxygen or hydrogen peroxide require special
precautions related to the management of gas pressure or the
risk of concentration and rapid decomposition of hydrogen
peroxide. Oxone® has, moreover, many advantages, it is a
solid oxidant which can be easily transported and handled, it
has a non-toxic nature and doesn’t produce polluting by-
product, and it is rather economical. Considering some of
these criteria, it can be classified among green oxidants.
In this work, we report the metal free oxidation of HMF into DFF
in the presence of Oxone® as a co-oxidant and 2-
iodobenzenesulfonic acid as a catalyst.
1
3,41
transformation.
However, exposure to DMSO sets problems
of toxicity because of its ability to easily dissolve the chemical
substances that can be absorbed through the skin, moreover it
has a very high boiling point (191 °C), which complicates its
separation or recycling in the processes. To this purpose, we
carried out a solvent screening for this transformation in order
to find an alternative to DMSO. (Table 2)
The same procedure was used with all solvents (same
conditions of concentration, agitation speed and temperature),
by mixing the Oxone® previously ground using a mortar with the
hydroxymethylfurfural and the 2-iodoxybenzensulfonic acid as
catalyst. The set temperature is 70 °C. The solvents having a
boiling point below this temperature (chloroform, DCM, THF
and acetone) were heated under reflux (entries 10, 11, 13, 3,
table 2).
35,36
This strategy has been
34,37,38
39
Results are presented in table 2. For most of the solvents, the
conversions are high and no trends can be drawn between the
nature of the solvent and the HMF conversion. Among these
solvents, the best selectivity of HMF to DFF is obtained using
nitromethane, acetonitrile, ethyl acetate and acetone. This can
be interpreted by 64% and 89% of DFF yield and selectivity
using, respectively, acetonitrile and nitromethane that appear
to be the most effectives (entries 1 and 8). Furthermore, a
50/50 mixture of acetonitrile and nitromethane leads to a DFF
yield equivalent to that carried out in pure nitromethane (data
not shown). One should note that DMSO in our case is
inefficient. When using solvents that completely dissolve the
reactant and catalyst (DMA and water), a complex mixture of
40
37
Results and discussion
During our preliminary tests, we evaluated the efficiency of the
hypervalent iodine derivatives formed "in situ" during the
transformation of HMF into DFF, and compared the two
catalysts,
2-iodobenzenecarboxylic
acid
and
2-
iodobenzenesulfonic acid. As we can see in table 1, the two products without DFF is detected, and only some of them could be
catalysts lead to the formation of DFF selectively but IBS is identified, which are mainly diacids such as maleic acid, fumaric acid
particularly more effective. In addition, Ishihara et al. have and dicarboxylic furan. With acidic solvents (entries 6 and 7) the
proved that IBS is a selective and effective catalyst for this type reaction medium rapidly turned dark brown which
34
of oxidation and more active than IBX.
2
| J. Name., 2012, 00, 1-3
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Table 2. Catalytic oxidation of HMF into DFF using different solvents.a
View Article Online
Dielectric constant (20D°CO) I: 10.B10o3ili9n/gDp0oNiJn0t 1(°6C5)3E
Entry
solvent
CH NO
AcOEt
Conversion (%)
Selectivity (%)
Yield (%)
1
2
3
4
5
6
7
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9
3
2
100
87
89
62
84
39
0
89
54
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38
0
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6
101
77
Acetone
MIBK
49
21
13
37
58
6
56
95
116
164
101
118
82
DMA
100
100
100
100
91
0
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Formic Acid
Acetic Acid
0
0
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64
0
11
64
0
CH
DMSO
CHCl
DCM
3
CN
38
47
5
190
61
1
0
3
87
23
36
0
20
36
0
11
100
97
9
40
1
1
1
1
2
3
4
5
2
H O
80
7
100
66
THF
Cyclohexane
Tert-butanol
-
53
0
0
100
100
97
10
0
10
0
2
81
12
-
83
16
23
22
-
a
Reaction conditions: 200 mg (1.6 mmol) of HMF, 1.17 g of Oxone® (KHSO
5
/HMF mol ratio = 1.2), 30 mg of sodium 2-iodobenzenesulfonate (0.36 wt%), 6 mL solvent,
7
0°C with reflux for solvents having boiling point below this temperature, 4h.
O
signifies the formation of humin and degradation of HMF.
However, acetic acid, which is less dissociating and less acid (εr
O
O
OH
HO
I
HMF
O
O
Oxone
OH
=
6.2 and pKa = 4.7 at 20 ° C), allows to obtain a small proportion
S
O
of DFF. These results corroborate the observations already
reported that an excessively acidic environment is not favorable
and can lead to the degradation of furan derivatives or its
H2O
I
O
Oxone
I
O
S
SO3Na
O
42,43
O
polymerization into humin.
Compared with the work of
O
Sodium 2-
iodobenzen
sulfonate
O
O
O
I
Yoon Sik Lee et al. which reports the best oxidation results in
29
S
chloroform , when using chlorinated solvents (entries 10 and
O
O
O
O
O
1
3
1) only low yields of DFF were obtained. However, with DCM,
5% yield of DFF was obtained which relatively remarkable in
DFF
Scheme3. Different iodine derivatives and supposed catalytic cycle during the selective
view of the relatively low working temperature 40 °C, compared
to the other solvents. Regarding the reaction without solvent,
which was carried out under the same conditions, almost total
HMF conversion is obtained but with a 22% yield of DFF, even
though the homogenization of the reaction mixture was difficult
to be achieved. This result should be compared with similar
ones obtained with non-polar solvents, justifying the hypothesis
of complete insolubility of the catalytic oxidizing species of
hypervalent iodine in these solvents.
In conclusion, the best solvent for this selective oxidation of
HMF to DFF turns out to be nitromethane. The great diversity of
results obtained demonstrates the difficulty of being able to
predict the efficiency of a solvent according to its physical
properties; we can simply note that for this transformation,
aprotic polar solvents tend to be more selective towards DFF in
the oxidation of HMF. On the base of the proposed mechanism
oxidation of HMF to DFF
oxidation is a necessary but not sufficient condition for the
selective oxidation of DFF. Note that, the oxidation depends in
particular on the dissociation of the pairs of ions and the
solubility of Oxone® in different solvents. Another important
aspect of this reaction is that oxidation takes place under partial
acid conditions in all cases (Oxone® is a salt of persulfate and
hydrogen sulfate pKa = 1.9) and that acidic conditions could lead
to the formation of humins.
In view of the good results obtained in nitromethane and their
potential optimization, we studied, in this solvent, the effects of
the various reaction parameters of the transformation. First, we
evaluate the influence of the temperature over a 4 h reaction
Figure 1). The conversion of HMF is larger than 90% at 40°C;
however, this value is 100% at temperatures above or equal to
70°C.
(
44
by Santagostino (Scheme3), we can assume that partial
solubilization of the different species produced during the
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0
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Figure 1. Effect of temperature on HMF conversion, selectivity and yield of DFF. 1.6 mmol of HMF, 1.17g Oxone (KHSO
nitromethane, 4h.
5
/HMF mol ratio=1.2), 30mg of catalyst (0.36 wt%), 6 mL
Despite the fact that there were no traces of DFF formation at The catalyst’s stability was also verified by preheating it at 90°C
room temperature (21 °C) after 4 hours of reaction, it was for one hour then introducing it into the reactor for 4 hours of
interesting to note that around 50% of HMF have been oxidation at 70°C. Despite this, a DFF yield of 90% was still
converted to unknown products (probably intermediate obtained.
species) that could not be identified by our GC method. DFF Nevertheless, these results also demonstrate once again the
yield and selectivity varied similarly with the reaction instability of the formed DFF towards temperature. Thus, the
temperature reaching a maximum for 70°C. Furthermore, best results are obtained for a moderate heating at 70°C over
above 70 °C, the conversion rate of HMF is total, but the yield 4h. This is in accordance with the known instability of DFF
of DFF gradually drops, demonstrating its instability at high (storage at low temperature is recommended to avoid its
temperatures. At 101 °C, the boiling point of nitromethane, only degradation). In conclusion, increasing the temperature
18% of the DFF can be measured in GC after 4 hours of reaction. increases the reaction rate of DFF formation and its
The degradation products have been identified as being mainly degradation.
maleic acid and furan dicarboxylic acid (NMR analysis, SI).
In order to verify the hypothesis of DFF degradation at reaction with the increase of the catalyst quantity, we
temperatures above 70 °C, we performed reaction monitoring investigated the effect of its concentration (Figure 3). It is
For the purpose of verifying a potential acceleration of the
at 70°C, 80°C and 90°C (Figure 2).
observed that in the absence of catalyst, the HMF conversion
These experiments show that high yield of DFF could be reached reaches only 60% without leading to the formation of DFF. The
rapidly at higher temperature, 80% at 90°C in half an hour obtained brownish yellow mixture signifies the
(Figure 2). This also indicates that the catalyst presents a good decomposition of furan derivatives into humins due to
stability at higher temperature and could play its full role the acid characteristics of Oxone. With increasing the
without inconvenience.
amount of catalyst at 70 °C in 4 hours, the conversion reaches
100 % and the yield of DFF attain a maximum using 0.36 wt% of
the catalyst before decreasing to values around 50 to 40%. In
order to further investigate these results, we compared the
formation of DFF with time at 0.36 and 0.73 wt% of catalyst
(Figure 4). Even though an acceleration of the DFF formation is
observed during the two first hours using more catalyst it
quickly appears that during time the DFF degradation becomes
preponderant. Therefore, it could reasonably be hypothesized
that increasing the quantity of catalyst is detrimental to DFF
stability and formation, probably due to the acidic nature of the
catalyst leading to DFF degradation. To conclude, the best
compromise is a reasonable 70°C heating over 4h with 0.36 wt%
of catalyst.
In order to maximize the production of DFF by limiting the
production of wastes, we studied the effect of the amount of
co-oxidant Oxone® and the HMF concentration on the yield of
DFF. We know that these factors can have a significant impact
on the transformation.
Figure 2. Effect of temperature as a function of time on the conversion of HMF at 70°C
and the yield of DFF at 70 °C, 80 °C and 90 °C. HMF 1.6 mmol, Oxone® 1.17 g (KHSO
mol ratio=1.2), catalyst 30 mg (0.098mmol, 0.36 wt%), 6 mL nitromethane.
5
/HMF
4
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Figure 3. Effect of the catalyst weight sodium 2-iodobenzenesulfonate (wt%) on HMF
conversion and DFF selectivity. HMF 1.6 mmol, Oxone 1.17g, sodium 2-
iodobenzenesulfonate 0 to 1.44 wt%, 6 mL nitromethane, 70°C.
Figure 5. Effect of the amount of HMF (from 100 mg to 400 mg) on the yield of DFF with
various oxone to HMF ratio and catalyst to HMF ratio, 6 mL of nitromethane, 70°C, 4h.
(□): The mass of Oxone is kept constant to 1,17 g and catalyst to 30 mg, Oxone/HMF
ratio= 2.4 (100 mg of HMF), 1.2 (200 mg of HMF), 0.8 (300 mg of HMF) and 0.6 (400 mg
of HMF), (Δ): Oxone/HMF ratio = 1.2, catalyst/HMF ratio = 0.12 (100 mg of HMF), 0.06
(200 mg of HMF), 0.04 (300 mg of HMF) and 0.03 (400 mg of HMF), (◊): Solvent volume
is invariable i.e. 6 mL, the ratio Oxone/HMF = 1.2 and catalyst/HMF ratio = 0.06, (○): HMF
conversion as a function of HMF mass.
Finally, during a final series of experiments, the volume of
solvent is kept as the only constant parameter, i.e. 6 mL. The
Oxone/HMF ratio is maintained at 1.2 and the Catalyst/HMF
ratio at 0.06.
In this case, it is interesting to note that the yield obtained in
DFF remains very high, close to the maximum yield under
optimal conditions. Thus, with 1.3wt%, 3.4wt% and 4.2 wt% of
HMF corresponding to a mass of 100 mg, 300 mg and 400 mg,
the corresponding DFF yields are 85%, 86 % and 84% (Figure 5
(
◊), yellow curve). These last results are very important because
they confirm the possibility of working at higher HMF
Figure 4. Effect of the amount of catalyst on DFF yield as a function of time. HMF 1.6
mmol, Oxone® 1.17g, sodium 2-iodobenzenesulfonate 0.36wt% (red) and 0.73wt% concentrations without significantly affecting the production of
(green), 6 mL of nitromethane, 70°C.
DFF.
For effective industrial utilizations of heterogeneous catalysts,
We carried out a first series of experiments by keeping the the lifetime, stability and reusability is an important parameter.
quantities of catalyst and Oxone® constant and varying only the Hence, the recyclability test of 2-iodobenzenesulfonic acid was
HMF mass. This, therefore, implies a variable Oxone/HMF ratio investigated on the oxidation of HMF to DFF under the
ranging from 2.4 corresponding to 100 mg to 0.6 corresponding optimized experimental conditions. After the catalytic test, the
to 400 mg of HMF introduced (Figure 5, red line (□)). We catalyst was recovered by simple filtration and extensively
observe that the Oxone® used in excess, corresponding to 2.4 washed with ethyl acetate. After being dried under vacuum, 14
eq, leads to a loss of selectivity and yield of DFF (Figure 5 (□), mg of catalyst precipitates were obtained (around 50% of initial
point at 100 mg). While it is used as a limiting reagent, we mass). This exact amount was reused for the next reaction,
observe a quantitative yield compared to the Oxone® which is instead of 30 mg, and a DFF yield of 50% was obtained.
totally consumed to oxidize the HMF to DFF (Figure 5 (□), points Note that, at the end of the reaction, the catalyst is present in
at 300 and 400 mg of HMF). Furthermore, in the latter two different forms with different oxidation degrees (+I, +III and +V)
cases, the remaining expected HMF is no longer visible, more or less soluble in the washing solvent. This could explain
demonstrating its transformation along unknown reaction path. the loss of around 50% of the catalyst.
During a second series of experiments, we maintained the Thus, the catalyst recovery is a feature to improve, but it
Oxone/HMF ratio at 1.2, keeping the other parameters constant appears that the recovered catalyst is still active and permit to
(Figure 5 (Δ), Green curve). In this case, the constant amount of perform the reaction as efficiently.
catalyst (30 mg) mainly affects the yield of DFF, there is a slight At the end of this work, we wanted to verify that this method
decrease in the yield at low HMF concentration (point at 100 could be adapted to the preparation of DFF on the scale of
mg), and a loss of activity when the HMF concentration several grams. By multiplying by ten the quantities of materials
increases with respect to the amount of catalyst.
we obtained 1.78 g (87%) of DFF with the same grade of purity
This journal is © The Royal Society of Chemistry 20xx
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yields. The method is particularly simple, because only filtration
View Article Online
O
O
6
mol% catalyst
DOI: 10.1039/D0NJ01653E
or extraction of the sulfate salts and the catalyst at the end of
1.2 equiv. oxone
6 mL nitromethane
70 °C, 4h
the reaction are required to obtain the DFF with a high grade of
purity. The active oxidizing species obtained "in situ" eliminate
the risks associated with the use of iodine derivatives in
stoichiometric proportions and reduce the costs of the catalyst.
We optimized the reaction conditions by considering the
product stability and competitive reactions. The best
compromise was obtained for a 4 hours of reaction at 70 °C,
using nitromethane. In these conditions, 89% of DFF is obtained
as the only product after extraction and filtration. In addition,
very good results are also observed over much shorter times, in
2
.0 g
87% isolated yield
Scheme 4. Synthesis of DFF by selective oxidation of HMF in gram scale.
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(NMR analysis, SI), confirming the possibility of extending our
method to this first stage of scale-up. Finally, a gram scale
synthesis was performed in the optimized conditions. Starting
with 2 g of HMF, a 87% isolated yield of DFF was achieved
(Scheme 4), which further highlighted the interest of this
catalyst in this oxidation reaction.
In order to highlight the simplicity and the inherent advantages
of our process, we have extracted some of the best recent
methods of DFF synthesis described in the literature. Although
we can see that the yields of DFF can be higher, almost all these
methods require the preparation of complex metallic catalyst,
the presence of co-catalyst of TEMPO type and/or very dilute
reaction media. By comparing these various methodologies, it
appears that our process is competitive and could be suitable
for the production of DFF (Table 3).
3
0 min at 90 °C, where 80% of DFF is obtained. On the contrary
to what was described in literature this method involves no
metallic catalyst, uses reasonable concentration of HMF, and
we have demonstrated the possibility of extending the method
to a gram-scale production of DFF. Therefore, we believe that
these results lay the foundation for the development of a larger
scale process.
Conflicts of interest
There are no conflicts to declare.
Conclusion
Acknowledgement
With this work, we demonstrated the possibility of using
hypervalent iodine derivatives in the presence of Oxone®, an We gratefully acknowledge the funding received from Région
economical and non-toxic oxidant with non-toxic byproducts, to Hauts-de-France and the Lebanese municipality of Chehabie,
carry out the oxidation of HMF to DFF with great selectivity and towards the PhD of M. Ayoub.
Table 3. Examples of recent studies about DFF synthesis
HMF
wt%
[HMF]
mol.dm
Mole ratio,
Oxidant/HMF
Product(s)
(%)
Catalyst wt%
Solvent
AcOH
Oxidant
Temp. (°C)
50
Time (h)
5
Ref.
-3
Flow O
1bar
2
a
ECS-IL-Al(NO
3
)
3
3,75%
DFF 98%
FDCA 1%
5
,4
0,5
-
1
5
TEMPO 0,37%
O
2
b
HKUST-1 0,09% TEMPO
0
,045
0,004
DMSO
AcN
3,4 bar
35
-
120
39
3
4
DFF 96%
DFF 99%
1
1
7
6
0
,09%
c
MnO2-NRs 0,13%
UV Light 375nm
TEMPO like nitroxided
,28%,
Collidine 0,3%, NaHCO
,6%
Sodium 2-
iodobenzenesulfonate
,36%
0,008
3,2
0,0005
0,4
Air
0
4
5
DCM/H
2
O
Iodine
2
22
1
DFF 93%
3
6
70
90
4
DFF 89%
DFF 80%
0
,26
2,44
4,2
0,5
0
This
CH
3
NO
2
Oxone®
1,2
work
Sodium 2-
iodobenzenesulfonate
0,53
70
4
DFF 84%
0
,62%
a
; b HKUST-1: Cu based metal organics frameworks, Cu and 1,3,5
ECS-IL-Al(NO
3
)
3
: Expanded corn starch covalently bonded to a ionic liquid with Al(NO )
3 3
c
d
benzenetricarboxylic acid; Manganese Oxide nanorods; TEMPO like: 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl.
6
| J. Name., 2012, 00, 1-3
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M. Mülbaier and A. Giannis, Angew. Chem. VIinewt.AErtdic.leEOnnglinl.e,
DOI: 10.1039/D0NJ01653E
M. Uyanik, M. Akakura and K. Ishihara, J. Am. Chem. Soc.,
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001, 40, 4393–4394.
References
1
2
3
4
K. J. Zeitsch, Ed., The chemistry and technology of furfural
and its many by-products, Elsevier, 2000.
2009, 131, 251–262.
35
D. J. Plumb, J. B.; Harper, Chem. Eng. News, 1990, 68, 3.
M. Frigerio, M. Santagostino and S. Sputore, J. Org. Chem.,
1999, 64, 4537–4538.
A. P. Thottumkara, M. S. Bowsher and T. K. Vinod, Org.
Lett., 2005, 7, 2933–2936.
A. Schulze and A. Giannis, Synthesis (Stuttg)., 2006, 257–
260.
C. W. Jones and J. H. Clark, Applications of Hydrogen
Peroxide and Derivatives, RSC Clean Technology Monographs,
1999.
B. R. Travis, M. Sivakumar, G. O. Hollist and B. Borhan, Org.
Lett., 2003, 5, 1031–1034.
Q. Girka, B. Estrine, N. Hoffmann, J. Le Bras, S. Marinković
and J. Muzart, React. Chem. Eng., 2016, 1, 176–182.
X. Gao, L. Peng, H. Li and K. Chen, BioResources, 2015, 10,
6548–6564.
S. K. R. Patil, J. Heltzel and C. R. F. Lund, Energy and Fuels,
2012, 26, 5281–5293.
S. De Munari, M. Frigerio and M. Santagostino, J. Org.
Chem., 1996, 61, 9272–9279.
C. M. Cai, T. Zhang, R. Kumar and C. E. Wyman, J. Chem. 36
Technol. Biotechnol., 2014, 89, 2–10.
R. Mariscal, P. Maireles-Torres, M. Ojeda, I. Sádaba and M. 37
López Granados, Energy Environ. Sci., 2016, 9, 1144–1189.
S. P. Teong, G. Yi and Y. Zhang, Green Chem., 2014, 16, 38
2015–2026.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
6
J. Lewkowski, Arkivoc, 2001, 2001, 17–54.
L. Hu, L. Lin, Z. Wu, S. Zhou and S. Liu, Renew. Sustain.
Energy Rev., 2017, 74, 230–257.
39
7
R. J. Van Putten, J. C. Van Der Waal, E. De Jong, C. B. 40
Rasrendra, H. J. Heeres and J. G. De Vries, Chem. Rev., 2013,
113, 1499–1597.
41
8
9
D. Liu and E. Y. X. Chen, Green Chem., 2014, 16, 964–981.
W. Fan, C. Verrier, Y. Queneau and F. Popowycz, Curr. Org. 42
Synth., 2019, 16, 583–614.
1
0
K. Kohli, R. Prajapati and B. K. Sharma, Energies, , 43
DOI:10.3390/en12020233.
11
R. Šivec, M. Grilc, M. Huš and B. Likozar, Ind. Eng. Chem. 44
Res., 2019, 58, 16018–16032.
1
1
2
3
Y. Lou, S. Marinkovic, B. Estrine, W. Qiang and G. Enderlin, 45
ACS Omega, 2020, 5, 2561–2568.
P. Pal and S. Saravanamurugan, ChemSusChem, 2019, 12,
145–163.
V. P. Kashparova, V. A. Klushin, I. Y. Zhukova, I. S.
Kashparov, D. V. Chernysheva, I. B. Il’chibaeva, N. V. Smirnova,
E. S. Kagan and V. M. Chernyshev, Tetrahedron Lett., 2017, 58,
3517–3521.
14
Z. Zhang and G. W. Huber, Chem. Soc. Rev., 2018, 47,
1
351–1390.
1
1
5
6
M. Hong, S. Wu, J. Li, J. Wang, L. Wei and K. Li, Catal.
Commun., , DOI:10.1016/j.catcom.2019.105909.
D. A. Giannakoudakis, V. Nair, A. Khan, E. A. Deliyanni, J.
C. Colmenares and K. S. Triantafyllidis, Appl. Catal. B Environ.,
2019, 256, 1–10.
1
1
7
8
J. Y. Lin, M. H. Yuan, K. Y. A. Lin and C. H. Lin, J. Taiwan Inst.
Chem. Eng., 2019, 102, 242–249.
N. Mittal, G. M. Nisola, J. G. Seo, S. P. Lee and W. J. Chung,
J. Mol. Catal. A Chem., 2015, 404–405, 106–114.
W. Partenheimer and V. V Grushin, Adv- Synth. Catal.,
2001, 343, 102–111.
19
2
2
0
1
B. Karimi, H. M. Mirzaei and E. Farhangi, ChemCatChem,
2
2
014, 6, 758–762.
Z. Yang, W. Qi, R. Su and Z. He, ACS Sustain. Chem. Eng.,
017, 5, 4179–4187.
L. Cottier, G. Descotes, J. Lewkowski and R. Skowroñski,
Org. Prep. Proced. Int., 1995, 27, 564–566.
22
2
2
3
4
T. El-Hajj, J. Martin and G. Descotes, 1983, 233–235.
J. W. Van Reijendam, G. J. Heeres and M. J. Janssen,
Tetrahedron, 1970, 26, 1291–1301.
N. Mittal, G. M. Nisola, L. B. Malihan, J. G. Seo, S. P. Lee
and W. J. Chung, Korean J. Chem. Eng., 2014, 31, 1362–1367.
C. Hartmann and V. Meyer, Chem. Ber., 1893, 26, 1727–
2
5
26
1
732.
2
2
7
8
M. Frigerio and M. Santagostino, Tetrahedron Lett., 1994,
3
5, 8019–8022.
D. B. Dess and J. C. Martin, J. Org. Chem., 1983, 48, 4155–
4156.
29
H. J. Yoon, J. W. Choi, H. S. Jang, J. K. Cho, J. W. Byun, W.
J. Chung, S. M. Lee and Y. S. Lee, Synlett, 2011, 165–168.
Z. Lei, C. Denecker, S. Jegasothy, D. C. Sherrington, N. K. H.
Slater and A. J. Sutherland, Tetrahedron Lett., 2003, 44, 1635–
637.
U. Carbamates, G. Sorg, A. Mengel, G. Jung and J.
3
0
1
31
Rademann, Angew. Chem. Int. Ed. Engl., 2001, 40, 4395–4397.
N. N. Reed, M. Delgado, K. Hereford, B. Clapham and K. D.
Janda, Bioorganic Med. Chem. Lett., 2002, 12, 2047–2049.
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