Selective oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by polymer-supported IBX amide

Article abstract of DOI:10.1055/s-0030-1259284

5-Hydroxymethyl-2-furfural (HMF) was selectively converted to 2,5-diformylfuran (DFF) under mild conditions by polymer-supported IBX amide reagent, thus providing a new platform for the production of highly valuable chemicals from biomass. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0030-1259284

LETTER
165
Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by
Polymer-Supported IBX Amide
Selective
O
xidatio
y
n
of Fructose
o
to 2,5-DFF
-
w
ith Het
J
erogeneou
i
s
IBX
n
Amide Yoon,a Jung-Woo Choi,a Hyung-Seok Jang,a Jin Ku Cho,b Jang-Woong Byun,c Woo-Jae Chung,a
Sang-Myung Lee,a Yoon-Sik Lee*a
a
School of Chemical and Biological Engineering, Seoul National University, Seoul 151-744, Korea
Fax +82(2)8769625; E-mail: yslee@snu.ac.kr
Green Process R&D Department, Korea Institute of Industrial Technology, Cheonan, 331-825, Korea
BeadTech Inc, Institute for Chemical Processes, Seoul National University, Seoul 151-744, Korea
b
c
Received 12 October 2010
pharmaceuticals and antifungal agents,8 and cross-linking
agent of poly(vinyl alcohol) for battery separations.9 Ad-
ditionally, there have been a number of reports describing
various oxidants and catalysts for the selective oxidation
of HMF to DFF (Scheme 2).10
Abstract: 5-Hydroxymethyl-2-furfural (HMF) was selectively
converted to 2,5-diformylfuran (DFF) under mild conditions by
polymer-supported IBX amide reagent, thus providing a new plat-
form for the production of highly valuable chemicals from biomass.
Key words: 2,5-diformylfuran (DFF), heterogeneous reagents,
oxidation, polymer-supported IBX
H
H
O
O
[O]
O
HO
O
O
Carbohydrates are currently focused as promising alterna-
tive feedstock for various commodity chemicals1 due to
their abundance and ability to remediate carbon dioxide.2
They can be transformed into valuable products such as
plastics, fine chemicals, and fuels.3 Among them, 5-
hydroxymethyl-2-furfural (HMF) is known as a platform
intermediate that affords a variety of fine chemicals and
fuels (Scheme 1).4
HMF
DFF
Scheme 2 Oxidation from HMF to DFF
However, most of these reports are accompanied by an
elaborate purification step and/or use of toxic metal cata-
lyst(s), which can be obstacles to mass production. Here,
we report a facile and practical synthetic method for the
selective oxidation of HMF using a heterogeneous oxi-
dant. Furthermore, direct conversion from carbohydrate
(fructose) to DFF is also described.
HO
OH
O
O
(H+)
H
OH
H
HO
O
OH
H
– 3H2O
HO
Hypervalent iodine reagent, IBX (o-iodobenzoic acid), is
a useful oxidizing agent due to its high efficiency, avail-
ability, mild reaction conditions, and stability in moisture
and air.11 We recently developed a polymer-supported
IBX ester and amide reagent and applied it to a wide range
of oxidative chemical transformations. The polymer-sup-
ported IBX amide reagent exhibited fast and efficient ox-
idative activities toward a series of alcohols under mild
conditions. The oxidation of the primary alcohol like ben-
zyl alcohol derivatives resulted in nearly complete con-
version after only 1 hour.12 Also, polymer-supported IBX
amide reagent can be readily separated from the reaction
mixture by simple filtration to yield the corresponding ox-
idative product in high purity and overcome solubility
problems of traditional IBX reagent. In addition, polymer-
supported IBX amide reagent can be practically reused af-
ter recovery and regeneration, which is an attractive point
for industrial applications.
5-hydroxymethylfurfural (HMF)
fructose
H
H
O
O
OH
O
HO
O
2,5-bis(hydroxymethyl)tetrahydrofuran
HO
2,5-furandicarbaldehyde
OH
O
O
O
2,5-furandicarboxylic acid
Scheme 1 Dehydration of fructose to HMF and variable products
In terms of application, 2,5-diformylfuran (DFF), ob-
tained by the selective oxidation of HMF, is a versatile
chemical that acts as a monomer in the synthesis of furan-
containing polymers,5 macrocyclic ligand,6 precursor for
organic metals,7 starting material for the synthesis of
SYNLETT 2011, No. 2, pp 0165–0168
x
x.
x
x.
2
0
1
1
Advanced online publication: 23.12.2010
DOI: 10.1055/s-0030-1259284; Art ID: U09010ST
Scheme 3 Preparation of polymer-supported IBX amide reagent14
© Georg Thieme Verlag Stuttgart · New York

166
H.-J. Yoon et al.
LETTER
In order to find the optimum conditions for the selective
oxidation of HMF to DFF, we initially screened various
solvents including dimethylformamide (DMF), dimethyl-
acetamide (DMA), dimethylsufoxide (DMSO), N-meth-
yl-2-pyrrolidone (NMP), acetone, acetonitile, chloroform,
dichloromethane, and 1,2-dichloroethane (1,2-DCE). In a
typical procedure, the reaction was carried out by adding
polymer-supported IBX amide (2 equiv) and HMF (0.1
mmol) to 1 mL of each solvent with shaking at room tem-
perature for 2 hours. The selectivity for DFF over HMF
was high for all solvents (over 98%), but interestingly sol-
vent polarity had a crucial effect on the conversion rate of
HMF. Nonpolar solvent such as chloroform showed the
highest oxidation performance (87% of conversion in 2
h), even though the solubility of HMF was very poor.
Meanwhile, HMF was slowly converted to DFF by polar
solvent at room temperature (Table 1).
Figure 1 Evaluation of minimal amounts of polymer-supported
IBX amide reagent for complete oxidation of HMF to DFF
Table 1 Investigation of Solvent Conditions for Selective Oxida-
tion of HMF to DFF by Polymer-Supported IBX Amidea
Entry
Solvent
DMA
Conversion (%)
Selectivity (%)
1
2
3
4
5
6
7
8
9
8
100
99
DMF
9
NMP
3
98
acetone
DMSO
MeCN
CHCl3
CH2Cl2
1,2-DCE
14
67
25
87
36
44
99
96
100
100
100
99
a Conversion and selectivity were determined by GC-MS analysis.
Figure 2 Time course for selective oxidation of HMF to DFF by po-
lymer-supported IBX amide
To minimize the amount of polymer-supported IBX
amide used in the oxidation, DFF yield was measured af-
ter the designated time (3 h) using the ratio of oxidant
(polymer-supported IBX amide)/substrate (HMF). The
results show that 2 equivalents of oxidant were sufficient
for the oxidation (Figure 1).
Next, the time course of the selective oxidation of HMF to
DFF by polymer-supported IBX amide was evaluated. A
mixture of HMF and polymer-supported IBX amide (2
equiv of HMF) in chloroform was stirred at room temper-
ature, after which an aliquot of sample was analyzed by
GC-MS at intervals. At the beginning of the reaction, ox-
idation occurred at a rapid rate but then lagged after 30
minutes as the concentration of HMF was decreased. Nev-
ertheless, HMF was completely oxidized to DFF within 3
hours (Figure 2).
A reuse test of polymer-supported IBX amide was also
performed. Regenerated polymer-supported IBX15 can be
reused at least five times without any loss in efficiency to
produce DFF without side products (Figure 3).
Figure 3 Yields of DFF produced by regenerated polymer-suppor-
ted IBX amide reagent
Synlett 2011, No. 2, 165–168 © Thieme Stuttgart · New York

LETTER
Selective Oxidation of Fructose to 2,5-DFF with Heterogeneous IBX Amide
167
Furthermore, direct conversion of fructose to DFF was highly-selective oxidation of HMF to DFF under mild
performed.16
conditions. Moreover, we showed that readily-prepared,
polymer-supported IBX amide reagent with solid-acid
catalyst was suitable for the direct conversion of fructose
to DFF. We expect that our efforts would be helpful for
the development of other processes related to biomass-
derived chemical production.
Acknowledgment
This work has been supported by the Seoul Fellowship and the
WCU (World Class University) program through the Korea Science
and Engineering Foundation funded by the Ministry of Education,
Science and Technology (grant number R32-2008-000-10213-0).
Scheme 4 Direct conversion of fructose to DFF under heterogene-
ous conditions in an one-pot reaction
Acid-catalyzed dehydration of fructose followed by sub-
sequent oxidation of HMF was performed in a one-pot
reaction. It is well known that HMF can be produced with
high yield in the presence of DMSO and Brønsted acid.
However, due to the high solubility of HMF and high boil-
ing point of DMSO, isolation of HMF still remains to be
addressed. Therefore, direct production of DFF from fruc-
tose without isolation of HMF would be helpful in devel-
oping an industrial process (Scheme 4).
References and Notes
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Figure 4 Conversion of fructose (substrate, diamond) along with
the production of HMF (circle), DFF (square) and unknown chemi-
cals (triangle) in a one-pot reaction in the presence of Amberlist 15®
resin and polymer-supported IBX amide reagent (DMSO, 100 °C)
Fructose was converted with approximately 95% yield to
HMF (60%) and DFF (27%) within 1 hour (Figure 4). As
the reaction proceeded, HMF was gradually consumed
while DFF was produced. After 3 hours, 36% of HMF re-
mained with the yield of DFF reaching 48%. However,
unknown chemicals including two main byproducts,
AMF (5-acetoxymethyl-2-furaldehyde) and OBMF {5,5¢-
[oxybis(methylene)-bis-2-furaldehyde]}, were also in-
creased in amount as reaction time was prolonged.17
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Synlett 2011, No. 2, 165–168 © Thieme Stuttgart · New York

168
H.-J. Yoon et al.
LETTER
(15) Reusability Test of Polymer-Supported IBX Amide
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Reagent
Upon completion of oxidation, DFF was extracted with
CH2Cl2 and the remaining polymer-supported IBA
(iodosobenzoic acid, reduced form of IBX) amide was
separated by simple filtration. The filtered polymer-
supported IBA was easily regenerated after treatment with
tetrabutylammonium oxone (5 equiv) and methanesulfonic
acid for 12 h as previously reported.12
(e) Varvoglis, A.; Meth-Cohn, O.; Kirschning, A.; Rees, C.
Hypervalent Iodine in Organic Synthesis; Academic Press:
London, 1996.
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(14) Synthesis of Polymer-Supported IBX Amide Reagent
Polymer-supported IBX amide reagent was prepared from
aminomethyl polystyrene resin (AM PS, 2.1 mmol of NH2/
g, Beadtech Inc.). After AM PS resin was pre-swollen with
DMF at r.t. for 1 h, 2-iodobenzoic acid was coupled to the
resin using DIPCDI/HOBt (3 equiv, each) at r.t. for 4 h to
produce 2-iodobenzamide resin (1, Scheme 3). The resin
was then oxidized by tetrabutylammonium oxone (5 equiv)
with methylsulfonic acid in CH2Cl2 for 12 h.13 The loading
level of polymer-supported oxidants was determined to be
1.02 mmol/g by methoxybenzyl alcohol oxidation method.12
(16) Direct Production of DFF from Fructose
In the one-pot reaction, Amberlist 15® resin (100 mg,
purchased from Aldrich) as a solid-acid catalyst along
with polymer-supported IBX amide reagent (100 mg) as an
oxidant reagent were reacted together with fructose
(1 mmol) under DMSO at 100 °C.
(17) Analysis of Products from Direct Conversion from
Fructose
Direct conversion of fructose to DFF was analyzed using
HPLC equipped with a refractive index detector. The
column oven temperature was 30 °C, and mobile phase was
a 25% MeCN aq solution applied at a flow rate of 1 mL/min.
The amounts of HMF and DFF in the reaction mixture were
also analyzed by HPLC with a UV detector, and the yields
were calculated by GC-MS analysis. From this experiment,
we identified two main byproducts as AMF (5-acetoxy-
methyl-2-furaldehyde, MS: m/z = 168.15) and OBMF {5,5¢-
[oxybis(methylene)-bis-2-furaldehyde], MS: m/z = 234.05}.
Synlett 2011, No. 2, 165–168 © Thieme Stuttgart · New York

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