Catalytic Synthesis of 2,5-Furandicarboxylic Acid from Concentrated 2,5-Diformylfuran Mediated by N-hydroxyimides under Mild Conditions

Article abstract of DOI:10.1002/asia.201901001

Producing polyester monomer 2,5-furandicarboxylic acid (FDCA) from biomass as an alternative to fossil-derived terephthalic acid has drawn much attention from both academy and industry. In this work, an efficient FDCA synthesis was proposed from 10.6 wt % 2,5-diformylfuran (DFF) in acetic acid using a combined catalytic system of Co/Mn acetate and N-hydroxyimides. The intermediate product of 5-formyl-2-furandicarboxylic acid (FFCA) possesses the least reactive formyl group. N-hydroxysuccinimide was found to be superior to N-hydroxyphthalimide in catalyzing the oxidation of the formyl group in FFCA intermediate, affording a near 95 % yield of FDCA under mild conditions of 100 °C. Trace maleic anhydride was detected as by-product, which mainly came from the oxidative cleavage of DFF via furfural, furoic acid and 5-acetoxyl-2(5H)-furanone as intermediates.

Full text of DOI:10.1002/asia.201901001

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Catalytic Aerobic Synthesis of 2,5-Furandicarboxylic Acid from
Concentrated 2,5-Diformylfuran Mediated by N-hydroxyimides
under Mild Conditions
Authors: Fei Xia, Jiping Ma, Xiuquan Jia, Meiling Guo, Xuebin Liu,
Hong Ma, Jin Gao, and Jie Xu
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10.1002/asia.201901001
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Catalytic Synthesis of 2,5-Furandicarboxylic Acid from
Concentrated 2,5-Diformylfuran Mediated by N-hydroxyimides
under Mild Conditions
Fei Xia,[a, b] Jiping Ma,*[b] Xiuquan Jia,[a] Meiling Guo,[c] Xuebin Liu,[c] Hong Ma,[a] Jin Gao,[a] Jie Xu*[a]
Abstract: Producing polyester monomer 2,5-furandicarboxylic acid
(FDCA) from biomass as an alternative to fossil-derived terephthalic
acid has drawn much attention from both academy and industry. In
this work, an efficient FDCA synthesis was proposed from 10.6 wt%
2,5-diformylfuran (DFF) in acetic acid using a combined catalytic
system of Co/Mn acetate and N-hydroxyimides. The intermediate
product of 5-formyl-2-furandicarboxylic acid (FFCA) possesses the
least reactive formyl group. NHSI (N-hydroxysuccinimide) was found
to be superior to NHPI (N-hydroxyphthalimide) in catalyzing the
oxidation of the formyl group in FFCA intermediate, affording a near
catalyst which is widely used in the p-xylene oxidation has been
reported for the oxidation of HMF in batch reactor.[3a,11] With the
promotion of acid or Zr additives, ca. 60% yield of FDCA were
obtained.[12] However, HMF oxidation in these cases were either
conducted in dilute solutions (usually lower than 2.1 wt.% in
noble metal catalysis system) or only moderate yield FDCA can
be obtained. This might be due to overactive hydroxymethyl and
formyl group in HMF which might result in side-reactions to
humins at high concentration during oxidation.
To solve the above-mentioned problems, reactive functional
group protection strategies have been applied to suppress
humins formation via etherification of hydroxymethyl[13] or
acetalization of aldehyde group,[14] during the oxidation. Inspired
by these work, 2,5-diformylfuran (DFF) could be used as
feedstock instead of HMF to produce FDCA. DFF can be
obtained via selective conversion of HMF or fructose.[15] It has
simplified functional groups, thus the formation of monoacid 5-
hydroxymethylfuran-2-carboxylic acid (HMFCA) and other
possible side-reactions can be avoided. Moreover, high purity
DFF production from HMF has been realized by our group in
kilogram scale.[15a,b] Unlike the Co/Mn/Br system which is
corrosive to equipment, organic free radical precursors such as
N-hydroxyphthalimide (NHPI) and its analogues were previously
used as an efficient alternative for the oxidation of
hydrocarbon.[16] Herein, based on our previous work, we
propose an efficient FDCA synthesis route through catalytic
aerobic oxidation of concentrated DFF in acetic acid. The
aldehyde groups both in DFF and the reaction intermediates
were efficiently oxidized to corresponding acids, and about 95%
yield of FDCA was obtained using the catalytic system of
Co/Mn/N-hydroxysuccinimide under mild conditions.
o
95% yield of FDCA under mild conditions of 100 C. Trace maleic
anhydride was detected as by-product, which mainly came from the
oxidative cleavage of DFF via furfural, furoic acid and 5-acetoxyl-
2(5H)-furanone as intermediates.
Introduction
Producing value-added chemicals from renewable biomass
resources has received increasing academic and industrial
attention.[1] 2,5-Furandicarboxylic acid (FDCA) has similar
conjugated and isoelectronic structures as purified terephthalic
acid (PTA), which makes it a promising alternative to PTA in the
production of poly(ethylene furanoate) (PEF) as
a furan
counterpart to poly(ethylene terephthalate) (PET).[2] In addition,
PEF were found to show superior properties to PET in barrier
performance for O2, H2O vapor and CO2 and thermal
properties,[3] which stoked an increased excitement in the
production of FDCA.
Currently, FDCA was mainly synthesized by the catalytic
oxidation of 5-hydroxymethylfurfural (HMF), a versatile platform
molecule obtained from fructose,[4] glucose,[5] or cellulose.[6]
Noble metal catalysts, such as supported Pt,[7] Au[8] and Pd[9]
have been widely applied for the catalytic oxidation of HMF to
FDCA.[10] Addition of stoichiometric base or a basic support is
usually essential to give high FDCA yields. The rarity of noble
metal and environmental concern caused by base additives
hindered their wide application. On the other hand, the MC
Results and Discussion
Comparison of oxidation of DFF and HMF
Controlled experiments were initially carried out under the
selected probe catalytic system of Co/Mn/NHPI using DFF and
HMF as substrate in different concentration, respectively (Figure
1). Despite that both DFF and HMF were nearly completely
converted at both 1.1 and 10.6 wt% concentration, moderate
yield of FDCA (61.3 and 63.2%) was obtained in the oxidation of
DFF and HMF at 1.1 wt% concentration. Besides, 26.0 and
12.1% yield of FFCA was detected respectively. However, when
DFF and HMF were treated at 10.6 wt% concentration, only
34.9% yield of FDCA was observed through the oxidation of
HMF, which is much lower than that obtained from DFF (90.6%).
In addition, only 52.6% carbon yield was obtained from HMF
oxidation at high concentration which is much lower than that
obtained from DFF oxidation (98.6% carbon yield), suggesting
that certain side-reaction occurs during the oxidation of
concentrated HMF. In short, poor FDCA yield and carbon
[a]
Fei Xia, Jiping Ma, Xiuquan Jia, Meiling Guo, Xuebin Liu, Hong Ma,
Jin Gao, Prof. Dr. Jie Xu
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Dalian 116023, China
E-mail: xujie@dicp.ac.cn
[b]
[c]
University of the Chinese Academy of Sciences
Beijing 100049, China
Energy Innovation Laboratory
BP Office (Dalian Institute of Chemical Physics)
Dalian 116023, China
Supporting information for this article is given via a link at the end of
the document.
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10.1002/asia.201901001
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balance were observed during concentrated HMF oxidation,
indicating that DFF was superior to HMF for the production of
FDCA.
Oxidation of DFF to FDCA with O2
DFF oxidation was studied under the probe catalytic system of
Co/Mn/NHPI at 80 oC to screen the promoters (Co, or Mn, or
Co/Mn) and N-hydroxyimides. It was found that DFF conversion
was inefficient and almost no FDCA was detected when
individually catalyzed by Co, Mn acetates and NHPI or by the
combination of Co and Mn acetates (Table 1, entries 1-4). When
NHPI was combined with Co or Mn acetates, DFF conversion
increased dramatically to about 70%, and more than 20% of
FDCA was obtained (Table 1, entries 5, 6). DFF conversion and
FDCA yield were further improved when combined these three
species. A 38.3% yield of FDCA with 30.7% yield of FFCA and
3.5% yield of MA were gained at the DFF conversion of 76.0%
using the combination catalytic system of Co/Mn/NHPI, and the
carbon balance was up to 98.2% (Table 1, entry 7). It is possible
that with the assistant of Co/Mn acetate, NHPI can be efficiently
transformed to phthalimide N-oxyl radical (PINO) to initiate the
conversion of DFF to FDCA. The interaction between Co/Mn
acetate and NHPI could be proposed as illustrated in the MC
Figure 1. Product distribution of DFF oxidation and HMF oxidation. Reaction
conditions: DFF or HMF (1 and 10 mmol), 5 mol% Co(OAc)2·4H2O, 5 mol%
Mn(OAc)2·4H2O, 20 mol% NHPI, 10 mL HOAc, 140 oC, 1.0 MPa O2, 110 min.
Table 1. Catalytic oxidation of DFF to FDCA with O2.[a]
Entry
Catalyst (mol%)
Conv. (C%)
Yield (C%)
Carbon
balance
(C%)
[b]
Co
5
Mn
-
NHPI
-
FDCA
-
FFCA
-
MA
-
CO2
1
13.8
12.7
28.3
12.1
68.4
74.2
76.0
> 99
> 99
-
86.2
90.5
83.5
87.9
75.2
72.6
98.2
98.6
> 99
2
-
5
-
-
3.2
9.9
-
-
-
3
-
-
20
-
-
1.3
-
0.6
-
4
5
5
-
5
5
-
20
20
20
20
30
22.2
27.5
38.3
90.6
98.7
18.1
15.7
30.7
0.4
0.9
2.2
2.4
3.5
5.1
0.3
1.1
1.2
1.7
2.5
0.1
6
-
5
7
5
5
8[c]
9[c]
5
5
15
15
[a] Reaction conditions: 10 mmol DFF, Co(OAc)2·4H2O, Mn(OAc)2·4H2O, NHPI, 10 mL HOAc, 0.6 MPa O2, 80 oC, 80 min. [b] The yield of CO2 was evaluated
according to the yield of MA. [c] Reaction conditions: 1.0 MPa O2, 140 oC, 110 min.
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Figure 2. The influence of the NHPI dosage on DFF oxidation. Reaction
conditions: 10 mmol DFF, 5 mol% Co(OAc)2·4H2O, 5 mol% Mn(OAc)2·4H2O,
NHPI, 10 mL HOAc, 140 oC, 1.0 MPa O2, 110 min.
Figure 3. Temperature effects on DFF oxidation. Reaction conditions: 1 mmol
DFF, 15 mol% Co(OAc)2·4H2O, 15 mol% Mn(OAc)2·4H2O, 30 mol% NHPI, 5
mL HOAc, 1.0 MPa air, 80 min.
catalysis system (Scheme S1).[12a,17] When the reaction
temperature increased to 140 oC, a 90.6% yield of FDCA was
obtained (Table 1, entry 8). Moreover, the influence of the NHPI
dosage on the catalytic performance was further investigated.
As seen in Figure 2, the conversion of DFF was positive
correlation to the amount of NHPI. And the FDCA yield
increased with the increase of the amount of NHPI. At the
As above-mentioned, 20-30 mol% NHPI relative to DFF was
necessary to gain better FDCA yield. The major reason is that
NHPI is unstable at higher reaction temperature. It would
degrade to phthalic anhydride and phthalic acid.[16a] In other
case, dimerization would occur when NHPI was converted to
PINO.[18] Considering the instability of NHPI at higher
temperature, the catalytic performance of NHPI at lower
temperature was then explored. DFF oxidation was carried out
at temperature range from 80 to 140 oC (Figure 3). When the
temperature decreased to 120 oC, the results were similar to that
of at 140 C. For the tested temperature from 120 to 80 C, the
temperature plays a great role on the product distribution. When
the temperature was decreased to 80 oC, the conversion of DFF
decreased to 83.6%, the yields of FDCA decreased remarkably
to 36.6%, and the major product was FFCA with a 43.9% yield.
This implied that the conversion of intermediate FFCA was
inefficient at lower temperature within 80 min.
o
temperature of 140 C, further modulation the molar ratio of Co,
Mn and NHPI resulted in 98.7% yield of FDCA (Table 1, entry 9).
These results demonstrated that the yield of FDCA should
mainly depend on the composition of catalysts and reaction
temperature. It is worth noting that trace amount of MA was
detected in the presence of NHPI (Table 1, entries 3, 5-9).
o
o
Air as oxidant instead of pure oxygen
In our reaction, using pure oxygen as the oxidant may cause
safety hazard. In order to decrease the experiments risk to a
minimum, air was used instead of pure oxygen. Under identical
oxygen partial pressure, the performance of air was comparable
to that of pure O2 (Table 2, entries 1-2). These results suggested
that air could be used as an alternative to O2 for our reaction.
Oxidation of DFF promoted by different N-hydroxyimides
Given that the catalytic performance of NHPI is inefficient at low
temperature and the instability of NHPI during the oxidation, it's
necessary to explore other organic free radical catalysts that
Effect of temperature on DFF aerobic oxidation over NHPI
Table 3. Oxidation of DFF promoted by different N-hydroxyimides.[a]
Table 2. Catalytic oxidation of DFF under the same partial pressure of O2.[a]
Entry
N-
Conv.
(C%)
Yield (C%)
FDCA
94.8
hydroxyimides
Entry
Pressure
(Oxidant)
(MPa)
Conv.
(C%)
Yield (C%)
FDCA
98.1
FFCA
1.8
MA
2.3
3.6
FFCA
0.1
MA
1.2
1.7
1
2
NHSI
NHPI
> 99
91.6
1
2
0.2 (O2)
1.0 (air)
> 99
> 99
51.9
31.4
97.1
0.4
[a] Reaction conditions: 1 mmol DFF, 15 mol% Co(OAc)2·4H2O, 15 mol%
Mn(OAc)2·4H2O, 30 mol% N-hydroxyimides, 5 mL HOAc, 1.0 MPa air, 80
min, 100 oC.
[a] Reaction conditions: 2 mmol DFF, 15 mol% Co(OAc)2·4H2O, 15 mol%
Mn(OAc)2·4H2O, 30 mol% NHPI, 5 mL HOAc, 140 oC, 110 min.
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Figure 4. Temperature effects on DFF oxidation over NHSI. Reaction
conditions: 1 mmol DFF, 15 mol% Co(OAc)2·4H2O, 15 mol% Mn(OAc)2·4H2O,
30 mol% NHSI, 5 mL HOAc, 1.0 MPa air, 80 min.
Figure 5. Time course of oxidation of DFF catalyzed by NHSI. Reaction
conditions: 1 mmol DFF, 15 mol% Co(OAc)2·4H2O, 15 mol% Mn(OAc)2·4H2O,
30 mol% NHSI, 5 mL HOAc, 1.0 MPa air, 100 oC.
could treat the oxidation at lower temperature with relatively
higher catalytic activity. N-hydroxysuccinimide (NHSI) is a novel
radical precursor that is synthesized from succinic anhydride.[19]
It has been reported that the N-hydroxyimides with larger O-H
bond dissociation energies (BDEs) showed higher H-atom
abstraction ability.[18c,20] Therefore, it would be expected that
NHPI analogues with larger O-H BDEs would be more efficient
for FDCA synthesis under mild conditions. According to the
calculation results of Chen et al.[20d] the BDEs of NHSI is higher
than that of NHPI (86.7 vs. 83.4 kcal/mol), In addition, the higher
solubility of NHSI in acetic acid compared with NHPI (Figure S1)
could contribute to better performance in catalytic reactions. The
DFF oxidation was conducted under the catalysis of NHSI and
NHPI respectively in the presence of Co/Mn at lower
temperature of 100 oC. And the detailed results were listed in
Table 3. As expected, DFF was fully converted in the presence
of NHSI, whereas 91.6% conversion of DFF was observed when
NHPI was used. The yield of FDCA follows the order as
NHSI>NHPI, while the trend of FFCA yield was contrary.
spending about 15 min, during which 98.0% of DFF was
converted. Full conversion of DFF reached at 25 min. Meanwhile,
the intermediate FFCA was gradually converted to FDCA
leading to the yield of FDCA increased rapidly to 90.8%. After
that the yield of FDCA was up to the peak in 45 min. Besides,
MA was detected at the beginning of the reaction, and its
variation was inconspicuous.
Formation route of MA
It's worth noting that the formation of MA was observed at the
beginning of the reaction. In order to explore the formation route
of the oxidative cleavage product MA, the oxidation of different
substrates including DFF, FFCA and FDCA were tested under
the selected probe catalytic system of NHPI (Table S1). A 2.8%
yield of MA was gained in the oxidation of DFF. Under the same
reaction conditions, the yields of MA were 1.0% and 0.6% for
oxidation of FFCA and FDCA, respectively. These results
implied that the formation of MA was a competing reaction and it
mainly came from DFF.
It was reported that MA can be obtained from the oxidative
cleavage of HMF,[21] and its formation route was proposed by
Yin et al..[21b,22] In order to understand how MA was occurred in
our reaction catalytic system, the possible intermediates were
detected by GC-MS at the initial period. Trace amount of furfural
(FFA) was detected at 10 min (Figure S2). In addition, CO2 was
detected by clear limewater and mass spectrometry (Figure S3
and S4). Thus it can be speculated that FFA was formed via
decarbonylation of DFF, during which CO was oxidized to CO2.
In addition, as illuminated in the MC process, CO2 could be
derived from the oxidation of solvent HOAc.[23] As the reaction
progress, trace amount of furoic acid (FA) was detected at 26
min (Figure S5). To identify whether FFA and FA were the
intermediates for the formation of MA, control experiments were
carried out using FFA and FA as the feedstocks, respectively.
MA, FA and 5-acetoxyl-2(5H)-furanone (AFO) were detected
during the oxidation of FFA at 10 min (Figure S6). In the case of
FA oxidation, MA and AFO were also detected at the initial
period (Figure S7). According to the above-mentioned results, a
Effect of temperature on DFF oxidation mediated by NHSI
Since NHSI shows higher activity than NHPI, it’s necessary to
study the catalytic performance of NHSI in detail. The
temperature effect of NHSI on aerobic oxidation of DFF was
studied from 50 to 140 oC (Figure 4). Remarkably, DFF was
almost completely converted at 60 oC affording FDCA in more
than 80% yield and FFCA as the intermediate product. The
further conversion of FFCA was observed with increasing the
temperature. At 100 oC, The FDCA yield was up to the peak and
the FFCA yield was 1.8%. When temperature was elevated
higher than 100 oC, there was no obvious change in the yield of
FDCA and FFCA. There was tiny change in MA yield during the
tested temperature range.
Time course of DFF oxidation over NHSI
To get more detailed information about the conversion of DFF
and intermediate FFCA catalyzed by NHSI at 100 oC, time
course was studied (Figure 5). Temperature reached 100 oC
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10.1002/asia.201901001
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proposed route for MA formation (pathway II and III) was put
forward in Scheme 1.
system is up to work for the efficient synthesis of FDCA from
DFF under mild conditions.
Reaction pathway
The proposed oxidation route of DFF under the tested catalytic
system of NHPI was showed in Scheme 1. As to the oxidation of
DFF to FDCA, the reaction may proceeds via pathway I, the
hydrogen atom of aldehyde group is abstracted by PINO to
generate the radical 1, which might be oxidized by oxygen to
give FFCA through peroxide radical and hydrogen peroxide
intermediates. Then FFCA is oxidized to FDCA via similar steps.
On the other hand, the radical 1 may undergo decarbonylation
and hydrogen atom transfer (HAT) to form FFA at the initial
period. According to the intermediate AFO detected in GC-MS,
AFO might form through 1,4-rearrangement of intermediate 2,[22]
which might generate from FFA via HAT, electron transfer (ET),
HOAc attack on furan ring, and decarbonylation as well as
reaction with H2O. After HAT and ET, and reaction with H2O, the
major side-product of MA was formed after release of HOAc via
pathway II. Besides, with the reaction proceeding, FA was
formed via FFA oxidation. Meanwhile, FA may proceed with
those similar steps such as HAT, ET, attacked by HOAc and
decarboxylation as well as H2O attack to generate intermediate
2 via pathway III. The following steps were similar as pathway II,
with both AFO and MA were detected.
Experimental Section
Co(OAc)2·4H2O, Mn(OAc)2·4H2O, furfural, glacial acetic acid were
purchased from Sinopharm. NHPI (98%), NHSI (98%), FFCA (98%),
FDCA (98%), furoic acid and maleic anhydride were supplied by Aladdin.
DFF was prepared according to the previous report.[15a] Reagents were of
analytical reagent grade and used without further purification unless
otherwise stated.
The oxidation of DFF was performed in a 45 mL teflon-lined stainless
steel autoclaves equipped with magnetic stirrer, pressure gauge and
automatic temperature control apparatus. The reactor was connected to
an oxygen/air cylinder for reaction pressure. In a typical experiment, DFF
(1 mmol), Co(OAc)2·4H2O (0.15 mmol), Mn(OAc)2·4H2O (0.15 mmol),
NHPI (0.30 mmol) and HOAc (5 mL) were loaded into the reactor. After
sealing and charging with oxygen or air, the autoclave was heated to the
desired temperature and kept for the desired reaction time under stirring.
After the reaction, the autoclave was cooled down to room temperature.
The residual gas was released carefully and collected for subsequent
analysis.
The products were identified by Agilent 6890N GC/5973 MS as well as
by comparison with the retention times to corresponding standards in gas
chromatography (GC) and high performance liquid chromatography
(HPLC) traces. The conversion of DFF and yield of MA were determined
using a GC (Agilent 7890A) equipped with a FID detector and HP-5
capillary column (30 m × 0.53 mm × 1.5 μm). Mesitylene was used as the
internal standard. After the GC sample was recovered, all the residuals
were diluted to 100 mL using deionized water. The yields of FDCA and
FFCA were analyzed with by HPLC (Waters e2695) with a column X
Bridge C18 (4.6 mm × 150 mm, 5 μm) with UV detector. Methanol and
0.1 wt% phosphoric acid aqueous solution were used as the mobile
phase, and the flow rate was 0.45 mL·min-1. Benzamide was used as the
internal standard.
Acknowledgements
The work was supported by the National Natural Science
Foundation of China (project 21790331), the Strategic Priority
Research Program of the Chinese Academy of Sciences (Nos.
XDB17020300 and XDA21030400), the Youth Innovation
Promotion Association, the Chinese Academy of Sciences
(2018219) and DICP ZZBS201811. We acknowledge Glenn
Sunley from BP International for the suggestions and
discussions.
Scheme 1. Proposed oxidation route of DFF
Conclusions
In summary, an efficient FDCA synthesis through catalytic
aerobic oxidation of concentrated DFF over Co/Mn acetate and
N-hydroxyimides was reported. The intermediate product of
FFCA was found to possess the less reactive formyl group in
comparison with DFF. N-hydroxysuccinimide was much more
active than N-hydroxyphthalimide in catalyzing the oxidation of
the formyl group in FFCA intermediate at low temperature.
About 95% yield of FDCA was obtained catalyzed by NHSI
under mild conditions of 100 oC. Trace by-product of maleic
anhydride was detected which mainly came from the oxidative
cleavage of DFF. This work revealed that non-noble catalytic
Keywords: Catalytic oxidation • Biomass • Aldehyde •
Carboxylic acid • N-Hydroxyimides
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10.1002/asia.201901001
Chemistry - An Asian Journal
FULL PAPER
Entry for the Table of Contents
FULL PAPER
Fei Xia, Jiping Ma,* Xiuquan Jia, Meiling
Guo, Xuebin Liu, Hong Ma, Jin Gao, Jie
Xu*
Page No. – Page No.
Catalytic Synthesis of 2,5-
Furandicarboxylic Acid from
Concentrated 2,5-Diformylfuran
Mediated by N-hydroxyimides under
Mild Conditions
An efficient 2,5-furandicarboxylic acid synthesis route from aerobic oxidation of
concentrated 2,5-diformylfuran mediated by N-hydroxyimides was described under
mild conditions.
This article is protected by copyright. All rights reserved.