Highly efficient preparation of 5-hydroxymethylfurfural from sucrose using ionic liquids and heteropolyacid catalysts in dimethyl sulfoxide–water mixed solvent

Article abstract of DOI:10.1016/j.cclet.2017.02.016

Several types of ILs and solid acids were used as catalysts in one-pot conversion of sucrose to 5-hydroxymethylfurfural (abbreviated as 5-HMF) in a dimethyl sulfoxide (DMSO)/water mixed solvent under hydrothermal conditions. A remarkable 5-HMF yield of 91.8% was achieved catalyzed by the cesium salt of dodecatungstophosphoric acid (Cs_2.3H_0.7PW₁₂O₄₀) within 3?h at 180?°C. The ionic liquid N-methylimidazolium hydrogen sulfate ([Hmim][HSO₄]) gave the 5-HMF in 82.0% yield from sucrose. To the best of our knowledge, it was almost the highest yield of HMF from sucrose by now. Various reaction parameters including reaction temperature and time and catalyst dosage were optimized. A possible mechanism for this catalytic process was proposed. Furthermore, fructose and glucose were also investigated, good yields of 5-HMF was obtained respectively. This increases the possibility of large-scale production of 5-HMF from carbohydrates.

Full text of DOI:10.1016/j.cclet.2017.02.016

G Model
CCLET 3989 No. of Pages 6
Chinese Chemical Letters xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
Original article
Highly efficient preparation of 5-hydroxymethylfurfural from sucrose
using ionic liquids and heteropolyacid catalysts in dimethyl sulfoxide–
water mixed solvent
*
Song-Bai Yu, Hong-Jun Zang , Xiao-Li Yang, Ming-Chuan Zhang, Rui-Rui Xie, Pei-Fei Yu
State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Department of Environmental and Chemical Engineering, Tianjin Polytechnic
University, Tianjin 300387, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Several types of ILs and solid acids were used as catalysts in one-pot conversion of sucrose to
5-hydroxymethylfurfural (abbreviated as 5-HMF) in a dimethyl sulfoxide (DMSO)/water mixed solvent
under hydrothermal conditions. A remarkable 5-HMF yield of 91.8% was achieved catalyzed by the
cesium salt of dodecatungstophosphoric acid (Cs2.3H0.7PW12O40) within 3 h at 180 ꢀC. The ionic liquid
N-methylimidazolium hydrogen sulfate ([Hmim][HSO4]) gave the 5-HMF in 82.0% yield from sucrose. To
the best of our knowledge, it was almost the highest yield of HMF from sucrose by now. Various reaction
parameters including reaction temperature and time and catalyst dosage were optimized. A possible
mechanism for this catalytic process was proposed. Furthermore, fructose and glucose were also
investigated, good yields of 5-HMF was obtained respectively. This increases the possibility of large-scale
production of 5-HMF from carbohydrates.
Received 4 November 2016
Received in revised form 20 February 2017
Accepted 28 February 2017
Available online xxx
Keywords:
5-Hydroxymethylfurfural
Sucrose
Hydrothermal conversion
Ionic liquid
Solid acid
© 2017 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
1. Introduction
and 2,5-furandicarboxylic acid), fuels (2,5-dimethylfuran), and
solvents such as levulinic acid (LA) can be obtained [6,7]. In
Owing to the shortage of resources and global warming,
sustainability is an emerging global issue of importance for
general, 5-HMF is produced from monosaccharides including
fructose and glucose, which are not economical substrates because
of their low availability and because their high costs limit their
further applications. Therefore, the ability to produce 5-HMF from
cellulose or other non-edible polysaccharides is desirable.
Unfortunately, the low 5-HMF yields and expensive and toxic
catalytic systems involved with using these polysaccharides as
substrates are problems that remain unsolved. Sucrose
humanity, and establishing
a renewable chemical industry
featuring renewable resources as the dominant feedstock rather
than fossil resources is very important for the future [1,2].
Nature produces 170 billion metric tons of biomass per year by
photosynthesis, 75% of which can be assigned to carbohydrates.
Surprisingly, only 3%–4% of these compounds are used by human
for consumption and other purposes [3,4]. Biomass is the most
(a-D
-glucopyranosyl-(1 !2)-b-D-fructofuranoside) is an inexpen-
abundant renewable available resource, and is
a
promising
sive chemical produced in sugar cane and sugar beet cultivation,
and consists of one fructose and one glucose moiety linked
together by a glycosidic bond. Compared to cellulose, its bond is
much more easily hydrolyzed and it produces higher 5-HMF yields
when used as a substrate [8]. Although high yields of 5-HMF have
been achieved with fructose [9,10], chemical and/or biochemical
transformations that convert sucrose to highly valuable synthetic
intermediates such as 5-HMF, bioethylene, 1,2-propylene glycol,
and LA are more commercially feasible [11,12]. There is no doubt
that the direct use of abundantly available sucrose for the large-
scale production of 5-HMF would be more ideal. However, it has
been observed in literature that less attention has been paid to the
conversion of sucrose to platform chemicals than to the
alternative as a sustainable supply of biofuel and related valuable
fine chemicals and is currently viewed as a feedstock for green
chemical processes for the future [5]. Among available biomass
resources, carbohydrates are regarded as some of the most
important raw materials for the production of 5-HMF, a very
versatile platform toward fuels and chemicals. Through selective
oxidation, reduction, and rehydration of HMF, other useful
intermediates, including bio-based polymers (2,5-diformylfuran
* Corresponding author.
E-mail address: zanghongjun@tjpu.edu.cn (H.-J. Zang).
http://dx.doi.org/10.1016/j.cclet.2017.02.016
1001-8417/© 2017 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: S.-B. Yu, et al., Highly efficient preparation of 5-hydroxymethylfurfural from sucrose using ionic liquids and
heteropolyacid catalysts in dimethyl sulfoxide–water mixed solvent, Chin. Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.02.016

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CCLET 3989 No. of Pages 6
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S.-B. Yu et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
Table 1
conversions of fructose and other sugars. Chun et al. achieved a 5-
HMF yield of 82.0 ꢁ 3.9 wt% using a reaction mixture containing 5 g
of [MOIM]Cl and 5 mL of a 20% sucrose solution with 0.5 mol/L HCl
and CrCl2 with a 30 min reaction time [13]. Jadhav et al. reported a
67.2% 5-HMF yield, which was achieved through dehydration of
sucrose at 120 ꢀC in 150 min using 2 equiv. of the ionic liquid
[TetraEG(mim)2][OMs]2 as a catalyst [14]. Jain et al. reported 5-
HMF synthesis from sucrose in a sealed reactor using zirconium
phosphate (ZrP) as a catalyst; 52% 5-HMF yield was obtained in
H2O–diglyme [6]. Jadhav et al. used 10 wt% acid-modified silver-
exchanged silicotungstic acid (AgSTA) as a catalyst, which resulted
in 92% conversion of sucrose with 62.5% 5-HMF yield with a
160 min reaction time at 120 ꢀC [5]. However, the strongly acidic of
hydrochloride, the harmfulness of chromium ion to environment,
the high cost of the catalyst such as AgSTA containing silver
elements, limit the further applications for conversion of sucrose
into 5-HMF. Therefore, it is strongly desired to use the catalyst
which is cheap, environmentally friendly, and obtained higher 5-
HMF yield from sucrose.
Ionic liquids (ILs) and heteropolyacids (HPAs) have been
attracting widespread interest in biomass conversion during the
past decades owing to their unique advantages [1,15,16]. ILs are
nonflammable and have negligible vapor pressure, high thermal
and chemical stability, and adjustable solvent power for organic
and inorganic substances [17,18]. They usually act as both solvents
and catalysts in the dehydration of biomass to chemical
intermediates. HPAs are protonic acids with strong Brønsted
acidity, and have also been widely applied as solid acids in the
conversion of biomass including monosaccharides and polysac-
charides to 5-HMF and LA [1,16,19]. In this study, several types of
ILs and solid acids were investigated as catalysts in the conversion
of sucrose to 5-HMF respectively; the IL N-methylimidazolium
hydrogen sulfate ([Hmim][HSO4]) and the cesium salt of dodec-
atungstophosphoric acid (Cs2.3H0.7PW12O40), showed excellent
catalytic activity, respectively. Various reaction parameters,
including reaction the temperature and time and the catalyst
dosage, were optimized. Moreover, the dehydrations of fructose
and glucose to 5-HMF in these reaction systems were studied
(Scheme 1).
Results for the conversion of sucrose into 5-HMF with different catalystsa.
Entry
Catalyst
5-HMF yield (mol%)
1
2
3
4
5
6
7
8
None
1.7
[Hmim][H2PO4] (5.843 mmol)
[Hmim][HSO4] (5.843 mmol)
[Hmim][NO3] (5.843 mmol)
[TM][HSO4] (5.843 mmol)
[TB][HSO4] (5.843 mmol)
[SO3H[TB] HSO4] (5.843 mmol)
Amberlyst-15 (0.5031 g)
H3PW12O40 (0.4524 g)
ChH2PW12O40 (0.4930 g)
Cs2.3H0.7PW12O40 (0.5071 g)
Cs2CO3 (0.0511 g)
36.0
82.2
39.8
46.4
52.6
54.6
76.6
82.0
19.9
91.8
Trace
9
10
11
12
a
Reaction condition: 100 mg sucrose; mixed solvent composed of DMSO (12 g)
and deionized water (8 g); reaction temperature, 180 ꢀC; reaction time, 3 h.
It was found that the imidazolium cation was more suitable for
promoting the conversion of sucrose to 5-HMF than the thiazolium
cation, and [Hmim][HSO4] showed the best catalytic performance
with an 82.2% 5-HMF yield (Table 1, entry 3). Meanwhile, with
[Hmim] as the cation, the catalytic activity in the dehydration of
sucrose in the presence of various anions decreased in the
following order: HSO4ꢂ > NO3ꢂ > H2PO4 (Table 1, entries 2–4).
ꢂ
HPAs have been attracting widespread interest in biomass
conversion owing to their unique advantages. In this study, we
used H3PW12O40, ChH2PW12O40, and Cs2.3H0.7PW12O40 as catalysts
for the conversion of sucrose to 5-HMF (Table 1, entries 9–10).
Interestingly, it was observed that Cs2.3H0.7PW12O40 and
H3PW12O40 showed much better catalytic activity than
ChH2PW12O40 although they have similar phosphotungstic acid
structures. Cs2.3H0.7PW12O40 showed better catalytic activity in the
conversion of sucrose to 5-HMF than H3PW12O40 did, which
suggests that the Cs+ cation is more suitable for this process.
However, no 5-HMF was obtained when Cs2CO3 (equimolar
amount of cesium) was used as the catalyst separately (Table 1,
entry 12), which indicated that Cs+ can only show good catalytic
performance in the conversion of sucrose to 5-HMF when
combined with phosphotungstic acid to form Cs2.3H0.7PW12O40
.
However, H3PW12O40 showed good catalytic activity despite being
used as a single catalyst (81.97% 5-HMF yield). In contrast, 5-HMF
has been obtained in low yield (<1%) from sucrose in ethanol-THF
using H3PW12O40 as the catalyst [16]. This shows that the solvent
also has a significant effect on the conversion of sucrose to 5-HMF.
Dimethylformamide (DMF), tetrahydrofuran (THF), n-butyl
alcohol (n-BuOH), DMSO, and acetonitrile (AN) are often used as
additives in water phase to suppress side reactions during
carbohydrate conversion reactions. The contributions of THF,
DMSO, AN, n-BuOH, and DMF to the conversion of sucrose to 5-
HMF were evaluated in the present study. As shown in Fig. 1, the
solvent that consisted of water (8 g) and DMSO as the co-solvent
(12 g) led to better performance in the conversion of sucrose to 5-
HMF compared to THF, AN, n-BuOH, and DMF. 5-HMF yields of
27.9% and 20.0% were obtained using Cs2.3H0.7PW12O40 and
[Hmim][HSO4] as catalysts, respectively, in pure water. With the
addition of a co-solvent such as DMSO, the 5-HMF yield improved
significantly. However, when the co-solvent was DMF, 5-HMF
generation was obviously suppressed (Fig. 1).
2. Results and discussion
2.1. Catalyst screening
We examined the effects of different catalysts on the conversion
of sucrose to 5-HMF, including several types of ILs and solid acids.
The results were shown in Table 1. We initially screened catalysts
by mixing 100 mg of sucrose with 20 g of a mixed solvent
composed of DMSO (12 g) and deionized water (8 g) for 3 h at
180 ꢀC, and a very low 5-HMF yield (1.7%) was obtained in the
absence of catalysts (Table 1, entry 1). Different ILs including
imidazolium-type and thiazolium-type ILs were used as catalysts.
2.2. Possible reaction pathway
Sucrose consists of one fructose and one glucose moiety linked
together by a glycosidic bond. A possible reaction pathway for the
dehydration of sucrose into 5-HMF is shown in Scheme 2. It is well
known that the conversion of sucrose to 5-HMF involves two steps.
First, sucrose rapidly hydrolyzes to monosaccharides glucose and
Scheme 1. Schematic illustration of the synthesis of 5-HMF from sucrose.
Please cite this article in press as: S.-B. Yu, et al., Highly efficient preparation of 5-hydroxymethylfurfural from sucrose using ionic liquids and
heteropolyacid catalysts in dimethyl sulfoxide–water mixed solvent, Chin. Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.02.016

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CCLET 3989 No. of Pages 6
S.-B. Yu et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
3
intramolecular hydride shift, the glucose with Cs+ or electron-
rich imidazolium cation complex gives a favorable transition via
the ene–diol intermediate, then loses its Cs+ or electron-rich
imidazolium cation and forms free fructose [8]. The mechanism of
5-HMF formation from fructose has been debated over the years;
both a pathway with cyclic intermediates and an open-chain
mechanism have been approved by most researchers. Finally,
5-HMF is obtained via acidic hydrolysis of 4-hydroxy-5-hydrox-
ymethyl-4,5-dihydrofuran-2-carbaldehyde, and the structure of
this intermediate was clearly confirmed by a combination of 1H
and 13C NMR data [21].
In this work, the conversions of d-fructose and glucose to 5-
HMF in these reaction systems were also studied. As shown in
Table 2, our results were consistent with previous results, where it
was also found that the 5-HMF yield from d-fructose was much
higher than that from glucose. Meanwhile, as the reaction time
increased, the 5-HMF yields from d-fructose increased up to 3 h
and then slowly decreased. In contrast, the 5-HMF yields from
glucose increased continuously as reaction time increased to 5 h.
This suggests that d-fructose generates 5-HMF more easily than
glucose does and requires shorter reaction times to achieve higher
5-HMF yields. Interestingly, it was observed that the 5-HMF yield
from d-fructose was dramatically lower than that from sucrose; we
speculate this result may be caused by follow reasons, on one hand,
when using sucrose as the substrate, fructose was constantly
replenished by sucrose hydrolysis, meanwhile, the isomerization
of glucose also production of fructose. And then fructose quickly
converted into the 5-HMF, fructose is less directly exposed in the
reaction system avoid more side-reaction, and obtained higher 5-
HMF yield. On the other hand, more by-products were obtained
when use D-fructose as substrate and were detected by HPLC.
Fig. 1. Results of the conversion of sucrose to 5-HMF with different co-solvents.
fructose, and then fructose and glucose dehydrate into 5-HMF
[7,18]. We speculated that the mechanism through which sucrose
is converted to 5-HMF in this reaction system is similar to those in
previous reports [8,20]. In the first step, new hydrogen bonds are
formed through coordination of HSO4ꢂ/H2PO4ꢂ/H2PW12O40ꢂ with
ꢂOH. Meanwhile, H+, Cs+, and electron-rich imidazolium cation
will weaken the glycosidic bond to facilitate hydrolysis. We
propose that glucose and fructose are produced in this way.
Moreover, in the presence of a catalyst, the active catalytic site has
the potential to initiate glucose isomerization via an
X
O
X
O
H
H
X
H
O
O
O
OH
O
O
O
O
O
H
X
O
OH
HO
HO
OH
M
M
O
O
H
X
H
X
X
H
X
H
Glucose
H
H / M
X
O
O
O
O
O
O
X
X
Hydrolysis
X
O
X
H
H
O
OH
H
X
H
H
O
X
H
H
H
O
O
O
H
O
O
H
O
OH
O
H
X
H
O
O
O
X
OH
H
OH
O
OH
O
OH
H
X
Sucrose
M
M
O
O
OH
Fructose
X
H
H
HO
O
OH
Tautomerization
X
HO
X
O
OH
HO
O
O
H
-
H X
OH
H
OH
H
OH
OH
OH
OH
OH
H
OH
OH
OH
OH
X
Fructose
HO
O
O
O
HO
O
O
HO
O
-H2O
M: Cs+, [Hmim]+; X: HSO4-, H2PO4-, NO3-, H2PW12O40
-
OH
-H2O
OH
5-HMF
OH
Scheme 2. Proposed mechanism for the transformation of sucrose into 5-HMF.
Please cite this article in press as: S.-B. Yu, et al., Highly efficient preparation of 5-hydroxymethylfurfural from sucrose using ionic liquids and
heteropolyacid catalysts in dimethyl sulfoxide–water mixed solvent, Chin. Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.02.016

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CCLET 3989 No. of Pages 6
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S.-B. Yu et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
Table 2
by-products such as LA were generated at higher temperatures.
Higher temperatures increased the rate of dehydration of sucrose
to 5-HMF, but also accelerated the decomposition of 5-HMF into
by-products. Hence, for the highest 5-HMF selectivity, the
optimum temperature was 180 ꢀC. It is well known that there is
a reciprocal relationship between the reaction temperature and
the time needed for proper conversion. Fig. 2b shows the effect of
reaction time on the conversion of sucrose to 5-HMF at 180 ꢀC.
There was an interesting phenomenon; the 5-HMF yield from
sucrose did not behave like that from fructose, which decreased
rapidly with the increase in reaction time (Table 2). This may be
because fructose was constantly replenished by sucrose hydrolysis
and because of glucose isomerization when using sucrose as the
substrate. Fructose is less directly exposed in the reaction system,
and thus, the amount of by-products generated is reduced
compared to when fructose is used as the substrate directly.
Therefore, the 5-HMF yield from sucrose decreases slowly as the
reaction time increases, as shown in Fig. 2b. Because the highest
5-HMF yield was obtained in 3 h and longer reaction times resulted
in the generation of more by-products, 3 h was the optimal
reaction time for 5-HMF production.
The introduction of DMSO as a co-solvent increased the 5-HMF
yield from sucrose when [Hmim][HSO4] was used as the catalyst.
Moreover, the effect of different DMSO/water mass ratios on the
conversion of sucrose to 5-HMF was also investigated. As shown in
Fig. 2c, the yield increased to a maximum of 82.2% at 12 g of added
DMSO in 20 g of mixed solvent. 5-HMF yields of 20.0% and 56.6%
were obtained when using water and DMSO as the solvent,
respectively. This suggests that DMSO as a co-solvent in this
reaction system played a key role in the conversion of sucrose to
5-HMF, and caused the dramatic breakage of the water-water
hydrogen bonds and associated with water molecules [23,24].
Meanwhile, water and DMSO can both push the reaction toward
5-HMF formation and inhibit undesired side reactions [25].
A 5-HMF yield of 1.7% was obtained when no catalyst was added
(Table 1, entry 1). As shown in Fig. 2d, 5-HMF yield increased
Comparison of 5-HMF production from different substrates under hydrothermal
conditionsa.
Substrate
Catalyst
Time (h)
Yield of 5-HMF(%)
D-fructose
[Hmim][HSO4] (11.11 mmol)
[Hmim][HSO4] (11.11 mmol)
[Hmim][HSO4] (11.11 mmol)
Cs2.3H0.7PW12O40 (0.4977 g)
[Hmim][HSO4] (11.11 mmol)
[Hmim][HSO4] (11.11 mmol)
[Hmim][HSO4] (11.11 mmol)
Cs2.3H0.7PW12O40 (0.5009 g)
[Hmim][HSO4] (5.843 mmol)
Cs2.3H0.7PW12O40 (0.5071 g)
1
3
5
3
1
3
5
3
3
3
52.6
73.2
57.7
81.1
0.5
12.6
22.1
0.7
Glucose
Sucrose
82.2
91.8
a
Reaction condition: 100 mg substrate; mixed solvent composed of DMSO (12 g)
and deionized water (8 g); reaction temperature, 180 ꢀC.
2.3. Effects of various reaction parameters on the conversion of sucrose
to 5-HMF
Various reaction parameters such as reaction temperature and
time, catalyst dosage, and co-solvent mixture have significant
effects on the dehydration of sucrose to 5-HMF. In this study, the
effects of the reaction parameters on the conversion of sucrose to
5-HMF were examined by using [Hmim][HSO4] as a model catalyst
for the optimization of reaction conditions owing to its unique
advantages and stronger solvent adaptability.
As shown in Fig. 2a, the effect of reaction temperature on the
conversion of sucrose to 5-HMF was investigated. Reactions were
conducted at 150, 160, 170, 180, 190, and 200 ꢀC. It was previously
reported that the activation energy is higher for 5-HMF formation
than for 5-HMF disappearance; thus, the maximum obtainable
concentration increases with increasing temperature [22]. In this
study, reaction temperature had a significant effect on the
conversion of sucrose to 5-HMF, and the optimal reaction
temperature was 180 ꢀC. When the temperature was increased
further (above 190 ꢀC), the 5-HMF yield decreased because more
90
(a)
85
(b)
80
70
60
50
40
30
20
80
75
70
65
60
55
150
160
170
180
190
200
2
3
4
5
6
7
8
℃
Time (h)
90
80
70
60
50
40
30
20
85
80
75
70
65
60
55
50
(c)
(d)
0
20
40
60
80
100
0.56mmol 1.46 mmol 2.92 mmol 4.38 mmol 5.84 mmol 7.30 mmol
Catalyst amount
The percentage of DMSO in solvent
Fig. 2. Effects of various reaction parameters on the conversion of sucrose (100 g) to 5-HMF. (a) temperature; (b) time; (c) mass ratios of DMSO/water; (d) catalyst amount.
Please cite this article in press as: S.-B. Yu, et al., Highly efficient preparation of 5-hydroxymethylfurfural from sucrose using ionic liquids and
heteropolyacid catalysts in dimethyl sulfoxide–water mixed solvent, Chin. Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.02.016

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S.-B. Yu et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
5
dramatically to 51.7% when 0.56 mmol of [Hmim][HSO4] was
added. This shows that [Hmim][HSO4] has excellent catalytic
activity in the conversion of sucrose to 5-HMF. When the catalyst
dosage was increased from 0.56 to 5.84 mmol, the 5-HMF yield
increased from 51.7% to 82.2%. However, when the amount of
catalyst was increased further, 5-HMF yield decreased. A possible
reason is that a high catalyst loading not only accelerated the
conversion of sucrose to 5-HMF, but also promoted other side
reactions [26].
similar procedures, 4,5-dimethylthiazole (or 2-isobutylthiazole)
was combined with sulfuric acid (50% w/w) in a 1:1 molar ratio and
refluxed for 12 h. 4,5-dimethyl-3-(4-sulfonic acid butyl)thiazolium
hydrosulfate ([SO3H[TB] HSO4]) was synthesized in our laboratory
and developed on the basis of a previous report [30]. All of the ionic
liquids were characterized by 1H NMR spectrum, moreover, the
ionic liquids which had not been reported previously were also
characterized by HPLC-MS (Supplementary material).
Cesium
salt
of
dodecatungstophosphoric
acid
It is obvious that the yield of 5-HMF is highly dependent on the
operation parameters such as the catalyst amount used. Therefore,
it is meaningful to normalize the apparent yields to the 5-HMF
formation rates with the unit of [mol(5-HMF)/mol(cat)], and make
a comparison among the values obtained in this study together
with those previously reported.
(Cs2.3H0.7PW12O40) was prepared by titration of an aqueous
solution of H3PW12O40 with an aqueous solution of Cs2CO3
according to the procedure reported elsewhere [19,31]. First,
Cs2CO3 was calcinated at 450 ꢀC for 2 h to remove the adsorbed
water before use. A series of acidic cesium salts, were prepared by a
titration method with cesium content ranging from 1 to 3. The
appropriate amounts of a 0.10 mol/L Cs2CO3 aqueous solution were
added dropwise with a constant rate to a 0.08 mol/L aqueous
solution of H3PW12O40 at room temperature with constant stirring.
The Cs content, x in CsxH3-xPW12O40, was adjusted by the amount
of Cs2CO3 solution added. After the resultant milky suspensions
were aged at room temperature overnight, the solutions were
slowly heated at 50 ꢀC to obtain white solid powers, the resulting
solid was ground into white powder. The ChxH3ꢂxPW12O40 was
combined with H3PW12O40 and choline chloride, the ChH2PW12O40
was synthesized on the basis of a previous report [1].
Catalyst recycling is an important goal in terms of green and
sustainable chemistry, the reusability of the catalyst [Hmim]
[HSO4] and Cs2.3H0.7PW12O40 were tried. After the reaction, most of
the 5-HMF in the aqueous solution was removed by ethyl acetate
extraction until no 5-HMF was detected in the ethyl acetate. The
water in the aqueous phase was completely removed through
vacuum evaporation. The remaining [Hmim][HSO4] and DMSO
were used directly in the next run by adding a fresh sucrose sample
and water under the same reaction conditions. However, the
unreacted sucrose is very difficult to remove completely from the
mixture of DMSO and ionic liquid. If we ignore the sucrose which
unreacted in the initial reaction, this processes was repeated 4
times, use [Hmim][HSO4] as catalyst obtaining 5-HMF yields of
90.7%, 88.4%, 86.9%, 80.4%, respectively. Therefore, it can be
concluded that the catalyst was stable in this system, although the
unreacted sucrose is not remove completely.
4.3. Conversion of sucrose to 5-HMF
A typical catalytic reaction for the hydrolysis of sucrose using
[Hmim][HSO4] or acidic cesium salt Cs2.3H0.7PW12O40 as a catalyst
was performed in a 50 mL stainless steel vessel with a Teflon lining
that was sealed with a screw cap. Into the reactor, 0.1 g of sucrose
and different catalysts were introduced, and then 20 g of a mixed
solvent composed of an organic reagent and deionized water was
added. Finally, the reactor was immersed in a preheated oil bath,
and the reaction mixture was stirred for a given time. Time zero
was recorded when the reactor was immersed in the preheated oil
bath. After the desired reaction time, the reactor was placed
immediately in an ice-water bath to quench the reaction. The
mixture was filtered to remove any insoluble solid residue and
1 mL of the filtrate was diluted with methanol up to a volume of
5.0 mL in a volumetric flask. The solution was sonicated for 1 min to
dissolve the sample and then injected into a glass tube after
3. Conclusion
Efficient conversion of sucrose to 5-HMF was investigated in a
DMSO/water mixed solvent, and [Hmim][HSO4]/Cs2.3H0.7PW12O40
showed excellent catalytic activity and selectivity. This one-pot
synthesis of 5-HMF from sucrose, which is an inexpensive
chemical produced in sugar cane and sugar beet cultivation,
instead of fructose increases the promising potential of large-scale
production of 5-HMF from carbohydrates.
4. Experimental
passage through
a 0.22 mm polytetrafluoroethylene filter to
4.1. Materials
remove the solid residue completely. The aqueous solution was
analyzed by high-performance liquid chromatography (HPLC). All
experiments were performed at least three times, and the
experimental error was ꢁ1%.
N-Methylimidazole was purchased from Nanjing Xiezun
Chemical Co., Ltd. (Nanjin, China). 5-HMF (purity > 97%) was
purchased from Heowns Biochem Technologies LLC (Tianjin,
China). Amberlyst-15 was purchased from purchased from Aladdin
Co. (Shanghai, China). H3PW12O40 and Cs2CO3 were purchased
from Tianjin Guangfu Fine Chemical Research Institute (Tianjin,
China). Methanol (HPLC grade) was purchased from Tianjin Kermel
Chemical Reagent Co., Ltd. Vitriolic acid, phosphoric acid, hydro-
chloric acid, and nitric acids were purchased from Tianjin Chemical
Reagent No. 5 Plant (Tianjin, China). All other chemicals were
supplied by local suppliers and used without further purification.
4.4. Determination of 5-HMF yield
Quantitative and qualitative analyses of 5-HMF were performed
by HPLC and gas chromatography and mass spectrometry (GC-MS).
The concentration of 5-HMF was quantified using the calibration
curve obtained with known concentrations of the standard
substance. Chromatographic analysis was performed using a HPLC
instrument (LC3000, Beijing Chuangxin Tongheng Science and
Technology Co., Ltd.) with a Kromasil C18 reversed phase column
4.2. Catalyst preparation
(5
m
m, 250 mm ꢃ 4.6 mm) and a UV detector. The mobile phase
consisted of methanol and water (23/77, v/v) with a flow rate of
0.5 mL/min. The column temperature was maintained at 30 ꢀC and
the detection wavelength set to 284 nm. The volume for each
Brønsted acidic [Hmim][HSO4], 1-methylimidazolium dihydric
phosphate ([Hmim][H2PO4]) and 1-methylimidazolium nitrate
([Hmim][NO3]) were synthesized in our laboratory via a neutrali-
zation reaction and developed on the basis of a previous report
[27–29]. 4,5-dimethylthiazole hydrosulfate ([TM][HSO4]) and 2-
isobutylthiazole hydrosulfate ([TB][HSO4]) were synthesized using
injection was 20 mL. The 5-HMF as staple and the peak in the HPLC
spectrogram appeared at 11.00 min. The 5-HMF yield was
determined by high performance liquid chromatography (HPLC)
Please cite this article in press as: S.-B. Yu, et al., Highly efficient preparation of 5-hydroxymethylfurfural from sucrose using ionic liquids and
heteropolyacid catalysts in dimethyl sulfoxide–water mixed solvent, Chin. Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.02.016

G Model
CCLET 3989 No. of Pages 6
6
S.-B. Yu et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
of these aqueous solutions, using a standard curve (Fig. S1 in
Supporting information) in order to quantify the amount.
The yields of 5-HMF (Y5-HMF) from sucrose/fructose/glucose
was calculated as follows:
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Y5-HMF (mol%) = Mole amount of 5-HMF/Mole amount of starting
substrate ꢃ 100%
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The qualitative analysis of 5-HMF (Fig. S2 in Supporting
information) was conducted by GC-MS using a Bruker SCIONSQ/
436-GC gas chromatograph from Agilent Technologies (USA)
equipped with a HP-5MS capillary column (30 m ꢃ 0.25 mm ꢃ 0.25
temperature was initially held at 50 ꢀC for 2 min, then programmed
to increase to 230 ꢀC at a rate of 15 ꢀC/min with a hold time of 6 min.
Helium was used as the carrier gas at a linear velocity of 1.0 mL/
min. Mass spectrometric measurements were performed using
electron impact ionization (EI) at 70 eV and a scan range of m/z 50-
500, at a rate of 1 scan/s.
m
m), as well as a MS single quadrupole detector. The column
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Acknowldgements
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(X = 1–3) heteropoly acid catalysts, Chem. Eng. Technol. 34 (2011) 482–486.
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d ꢂfructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at 150 ꢀC: an
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The authors would like to acknowledge the financial support
from National Natural Science Foundation of China (No.21406166)
and the Municipal Natural Science Foundation of Tianjin (No.
15JCQNJC13900).
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Please cite this article in press as: S.-B. Yu, et al., Highly efficient preparation of 5-hydroxymethylfurfural from sucrose using ionic liquids and
heteropolyacid catalysts in dimethyl sulfoxide–water mixed solvent, Chin. Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.02.016