Efficient Dehydration of Glucose, Sucrose, and Fructose to 5-Hydroxymethylfurfural Using Tri-cationic Ionic Liquids

Article abstract of DOI:10.1007/s10562-019-02667-0

Abstract: Imidazolium predicated room temperature tri-cationic ionic liquid (RTILs) shows highly efficient and selective dehydration of fructose, sucrose, and glucose into 5-hydroxymethylfurfural (5-HMF). The formation of 5-HMF has been investigated using different reaction parameters, such as catalyst weight, reaction time and temperature. Among different reaction parameters, 93% yield of 5-HMF was obtained from fructose in [GLY(mim)₃][OMs]₃ at 120?°C within 2?h, while 72% and 51% yield of 5-HMF were achieved from dehydration of sucrose, and glucose respectively at 120–140?°C in 3?h to 5?h. In addition, the effect of reaction time, molar ratio, and temperature with CC-SO₃H co-catalyst have been discussed. In which, 97%, 77%, and 58% yield of 5-HMF were obtained from fructose, sucrose, and glucose, respectively, in the presence of [GLY(mim)₃][Cl]₃ and CC-SO₃H catalyst at 130–140?°C within 3–5?h. Both catalytic systems showed excellent recyclability for carbohydrates to 5- HMF conversion without any loss in its catalytic activity. Graphical Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-019-02667-0

Catalysis Letters
https://doi.org/10.1007/s10562-019-02667-0
Efficient Dehydration of Glucose, Sucrose, and Fructose
to 5-Hydroxymethylfurfural Using Tri-cationic Ionic Liquids
Pramod V. Rathod1 · Rajendra B. Mujmule1 · Wook‑Jin Chung1 · Amol R. Jadhav1 · Hern Kim1
Received: 4 December 2018 / Accepted: 12 January 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
Imidazolium predicated room temperature tri-cationic ionic liquid (RTILs) shows highly efficient and selective dehydration of
fructose, sucrose, and glucose into 5-hydroxymethylfurfural (5-HMF). The formation of 5-HMF has been investigated using
different reaction parameters, such as catalyst weight, reaction time and temperature. Among different reaction parameters,
93% yield of 5-HMF was obtained from fructose in [GLY(mim)3][OMs]3 at 120 °C within 2 h, while 72% and 51% yield of
5-HMF were achieved from dehydration of sucrose, and glucose respectively at 120–140 °C in 3 h to 5 h. In addition, the
effect of reaction time, molar ratio, and temperature with CC-SO3H co-catalyst have been discussed. In which, 97%, 77%, and
58% yield of 5-HMF were obtained from fructose, sucrose, and glucose, respectively, in the presence of [GLY(mim)3][Cl]3
and CC-SO3H catalyst at 130–140 °C within 3–5 h. Both catalytic systems showed excellent recyclability for carbohydrates
to 5- HMF conversion without any loss in its catalytic activity.
Graphical Abstract
Keywords Biomass · Ionic liquid · 5-Hydroxymethylfurfural
Electronic supplementary material The online version of this
1 Introduction
article (https://doi.org/10.1007/s10562-019-02667-0) contains
supplementary material, which is available to authorized users.
The synthesis of value-added chemicals from renewable
* Hern Kim
sources has gained much attention over the last decade
hernkim@mju.ac.kr
[1–3]. Renewable energy is one of the most effective option
Extended author information available on the last page of the article
Vol.:(0123456789)
1 3

P. V. Rathod et al.
to achieve sustainable development. The nineteenth century
chemistry discoveries led to use of biomass as a raw mate-
rial for the production of various value-added chemicals.
Furan based compounds are the very substantial precursors
for various value-added chemicals, and such furan-based
compound can be precisely obtained from dehydration of
biomass-based carbohydrates. 5-hydroxymethylfurfural
(5-HMF) is one of the furan derivatives obtained from C6
carbohydrates, which is an important bio-refinery building
block [4, 5]. This compound is useful for the development
of various chemical intermediates as well as liquid fuels
such as 2,5-diformylfuran [6], 2,5-furan dicarboxylic acid
(FDCA) [7], 2,5-dimethylfuran (DMF) [8], and levulinic
acid (LA) [9], such FDCA chemical further can be polym-
erized into polyethylene furanoate (PEF), which is useful for
bottle, films, and fibers production. 5-HMF has been listed
as the top 10 value-integrated bio-predicated chemicals by
the US Department of Energy.
dehydration of sugar into 5-HMF using [C4C1im] Cl(ILs)
combined with various metal salts, in which they got 70%
yield of 5-HMF at 120 °C within 3 h. For the dehydra-
tion of fructose into 5-HMF, metal salt systems plus ionic
liquids are reported, but the production cost of 5-HMF by
these catalytic systems is very high. Besides, the reported
catalytic system gives a separation problem that leads to
lower 5-HMF yield [28]. The objective of the present work
is to develop a new protocol for dehydration of biomass
to 5-HMF using Tri-cationic room temperature ionic liq-
uid catalysts. Tri-cationic room temperature ionic liquids
(RTILs) is an environmentally friendly catalyst, relatively
cheap, stable in air and easy to handle.
In this work, we have introduced Imidazolium predicated
room temperature tri-cationic ionic liquids (RTILs) as cata-
lysts for highly selective dehydration of fructose, sucrose,
and glucose into 5-HMF. The present catalytic system is
eco-friendly and low cost, and it can be useful for large-scale
industrial production of 5-HMF.
So far, various acid catalysts has been reported for the
conversion of carbohydrates into 5-HMF. In which metal
chlorides, mineral acids, and HPAs give extraordinary
5-HMF yields but they lead to concerns with recycling and
eco-friendliness [10]. Various homogeneous catalysts are
also used to hydrolyse biomass to 5-HMF during the last
century, which includes benzenesulfonic acid, HCl in water
[11], H3PO4, or H2SO4 [12]. Unfortunately, such homoge-
neous acids suffer from drawback like corrosion, difficul-
ties during isolation of 5-HMF, catalyst recovery, environ-
mental pollution, etc. Several heterogeneous catalysts are
also established for biomass to 5-HMF conversions, such
as Sn-beta [13], HY zeolite [14, 15], Amberlyst-15 [16],
phosphoric-acid-treated metal oxide, sulfonic acid-contain-
ing ionic liquids and sulfonic acid-functionalized carbon
materials. However, SO3H modified carbon derived from
biomass and sulfuric acid or oleum is not a green option,
since sulfuric acid is highly corrosive and oleum is danger-
ous especially at massive quantity which causes environ-
mental problems.
2 Experimental Section
2.1 Materials
The chemicals were purchased from Sigma Aldrich and
used without any purification. 3-methylimidazole, tri-
methylamine, glycerol, potassium bromide, sodium sulfate
,bis(trifluoromethane-sulfonyl)imide lithium salt, methane
sulfonyl chloride, potassium hexafluorophosphate, fructose,
sucrose, glucose, and p-toluenesulfonic acid.
2.2 Preparation of Trimesylate Precursors
As-reported synthesis procedure was followed for the
preparation of trimesylate precursors for the preparation of
glycerol-derived ionic liquids [29, 30]. Glycerol (1.0 mmol)
and triethylamine (3.0 mmol) were used as raw materials
and mixed with dichloromethane (DCM) in a round bottom
flask under the vigorous stirring condition to make a homo-
geneous mixture. The solution temperature was maintained
at 0 °C using an ice bath, and methane sulfonyl chloride
(3.5 mmol) was added dropwise to the above solution. The
solution was allowed for 12 h at 0 °C to room temperature.
After completion of the reaction, the reaction mixture was
extracted by DCM, and for confirmation of the product,
it was further examined by TLC. To remove its impurity,
the crude product was washed several times by DI water
and dried using Na2SO4. Finally, the organic solvent was
removed using rota-evaporator at high vacuum. The obtained
orange-coloured solid trimesylate precursor yield was 89%.
Recently, the room temperature ionic liquids (RTILs)
also employed in the dehydration of carbohydrates into
5-HMF [17–19]. RTILs are essential salt composed by
cations and anions which show extraordinary character-
istics such as non-flammable nature, non-volatile, chemi-
cally and thermally stable, dissolve many chemicals,
and recyclable [20–22]. In particular, the RTILs can be
established with a specific task through the selection or
functionalization of the cation or anion and therefore,
have been widely utilized in many chemical reactions,
and variety of research fields [23–25]. Biomass conver-
sion industries economic rapidly increased, since the ILs
dissolves lignin, wood, and other biomass [26, 27]. So
far, several research groups reported the use of ILs in
biomass conversion. In 2007, Zhang et al. reported the
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Efficient Dehydration of Glucose, Sucrose, and Fructose to 5-Hydroxymethylfurfural Using…
2.2.1 Synthesis of Glycerol-tri (3-methylimidazolium)
Trimesylate
added to diluted reaction mixture and 5-HMF was extracted.
A high vacuum pump was used to evaporate reaction mixture
to get crude 5-HMF. The crude 5-HMF product was con-
1
A trimesylate precursor (1.0 mmol) and 3-methylimida-
zolium (3.0 mmol) were used to synthesize glycerol-tri
(3-methylimidazolium) trimesylate, with acetonitrile as a
solvent in reflux condition for 28 h. After completion of
the reaction, the reaction mixture was allowed to cool at a
normal temperature. Further, it was evaporated by a high
vacuum pump and to remove unreacted starting materials
the residue was washed several times by ethyl acetate. The
crude oil was denoted by glycerol tri(3-methylimidazolium)
trimesylate (RTILs) (yield 92.5%).
firmed by H NMR, 13C NMR, GC-Mass Spectra, HPLC,
and FTIR-Spectra.
2.5 5‑HMF Analysis
1
The crude 5-HMF product analyzed by H and 13C NMR
spectra and were confirm using previously reported NMR
data. GC–mass was recorded on Agilent Technologies
5977A (EI) (Fig. S2, Supporting Information). Additionally,
Crude 5-HMF was analyzed by HPLC (Agilent Technolo-
gies 1200 series), using a C18 column and a UV detector
at 25 °C. Aqueous H2SO4 (5 mM) and methanol (9:1) were
used as the mobile phase at a flow rate of 1.0 mL/min (Fig.
S1, Supporting Information).
2.3 Procedures of Anion Exchanges [GLY(mim)3]
[PF6]3, [GLY(mim)3][Br]3 and [GLY(mim)3][Cl]3
Ionic Liquids
Glycerol-tri (3-methylimidazolium) trimesylate (0.17 mol)
and potassium hexafluorophosphate (0.52 mol) were dis-
solved in acetone respectively for the synthesis of glycerol-tri
(3-methylimidazolium) hexafluorophosphate [GLY(mim)3]
[PF6]3. The reaction mixture was further stirred for 28 h
at room temperature followed by evaporation using a high
vacuum pump, to get resultant crude [GLY(mim)3][PF6]3
product (yield 90.6%). A similar synthesis procedure was
used to prepare [GLY(mim)3][Br]3 and [GLY(mim)3][Cl]3
(RTILs) by replacing potassium hexafluorophosphate with
potassium bromide (0.52 mol) and potassium chloride
(0.52 mol). Finally, [GLY(mim)3][Br]3, [GLY(mim)3][Cl]3
(RTILs) were obtained by filtration and Acetone was evapo-
rated using a high vacuum pump, and the obtained yield
were 93.7% and 90.3% respectively.
3 Results and Discussion
3.1 Catalyst Preparation and Characterization
In the first step synthesis of the trimesylate precursor, glyc-
erol hydroxyl groups selectively protected using methanesul-
fonyl chloride. To the next step, using trimesylate glycerol
and 3-methylimidazoles to tricationic methylimidazolium
(RTILs) were prepared (Scheme 1). Ionic liquids (RTILs)
with different anions were obtained by reacting N-meth-
ylimidazolium (RTILs) with various anionic salts such
as –PF6, –Cl and –Br. (Scheme 2). N-Methylimidazolium
based (RTILs) were selected because of its compatibility
with acids, wide availability, and low cost. The synthetic
process has been described in detailed experimental sec-
tions. The tri-cationic RTILs shows a competent acidity
for the production of 5-HMF from fructose, sucrose, and
glucose. Prepared tri-cationic (RTILs) shows Lewis acidic
nature [29]. Prepared RTILs are highly efficient and selective
for conversion of fructose, sucrose, and glucose to 5-HMF
mainly because of the strong hydrogen bond is produced in
the sugar and mesylate (CH3SO3–) anions [17]. The hydro-
gen bond forming mesylate anions, nitrogen-containing tri
(imidazolium) cations are beneficial to the sugar dissolution
2.4 Typical Reaction Procedure for 5‑HMF Synthesis
Ionic liquid was dried under vacuum before to use. Fructose
(0.2 g)/sucrose (0.2 g), or glucose (0.2 g), and [GLY(mim)3]
[OMs]3 (RTIL) were added in a 50 mL RBF and stirred for
2–5 h at 120–140 °C. Then, the reaction was monitored by
TLC, after completion of the reaction the reaction mixture
was allowed to cool at room temperature. 5 mL DI water was
used to dilute the reaction mixture, then ethyl acetate was
Scheme 1 The synthesis of the tri-cationic RTIL [GLY(mim)3][OMs]3 from glycerol
1 3

P. V. Rathod et al.
Scheme 2 The synthesis of three different tri-cationic RTILs, metathesis of glycerol-tri (3-methylimidazolium trimesylate) RTILs
in the synthesized RTILs. Their ability to build hydrogen
bonds is believed to be the main functioning of dissolving
sugar [31].
For the synthesis of catalysts, d-glucose biomass com-
ponent was selected as a carbon precursor, because of their
wide availability. The CC-SO3H catalyst was prepared by
taking glucose and p-TSA in a clean, dry, round bottom
flask, which was then stirred at 180 °C for 24 h in a nitro-
gen atmosphere. The temperature controlled carbonization
of glucose in the presence of p-TSA has favored the struc-
ture to undergo decomposition, hydrolysis, dehydration
and molecular conversion of glucose to produce a polycy-
clic aromatic structure integrated with active sulfonic acid,
carboxylic acid, and hydroxyl groups [32]. The various
characterization techniques like Fourier transform infrared
(FTIR), X-ray diffraction (XRD), field emission scanning
electron microscopy (FE-SEM), Energy-dispersive X-ray
spectroscopy (EDX), Brunauer–Emmett–Teller (BET)
surface area and X-ray photoelectron spectroscopy (XPS)
were used to analyses as-prepared CC-SO3H catalyst. Fig-
ure 1 shows the FT-IR spectrum of the CC-SO3H. The
vibration bands at 1008 cm−1 and 1032 cm−1 are related
to –SO3H groups which are attributed to O–S–O stretching
vibrations and band peak at 1240 cm−1 is related to SO3H
Fig. 1 FT-IR of the synthesized CC-SO3H Catalysts
stretching. This indicates that the sulfonic acid groups
were subsequently incorporated into the catalyst surface.
The vibration band peaks at 1615 cm−1 were allocated to
the C=C aromatic carbons, the band peak at 1695 cm−1
attributed is C=O stretching vibration –COOH group.
Bands at 2990–2875 cm−1 and 3450 cm−1 are attributed
for C–H and O–H stretching, respectively.
1 3

Efficient Dehydration of Glucose, Sucrose, and Fructose to 5-Hydroxymethylfurfural Using…
The XRD patterns of the CC-SO3H catalyst (Fig. 2)
shows the characteristic broad diffraction peak at 2θ angles
of 10°–30° can be assigned to C (002) planes and a small
peak at 2θ angles of 35°–46° that are assigned to typical
amorphous carbon [33]. The results of Field emission-
scanning electron microscopy (FE-SEM) analysis for pre-
pared CC-SO3H catalyst samples are shown in (Fig. 3a–c)
the rough particle morphologies observed in the images
(Fig. 3b). In general, the investigated CC-SO3H catalyst
have larger particle sizes. Furthermore, FE-SEM equipped
with energy dispersive X-ray analysis (EDX) utilized to
check the elemental composition of CC-SO3H catalysts
surface. The EDX spectra (Fig. 3d) shows the presence
of carbon, oxygen, and sulfur elements (C = 69.7%,
O = 23.8%, S = 6.5%). Thus showing the presence of
–SO3H, –COOH, and –OH on the catalyst surface. The
acid-base titration method was used to calculate the total
acid density of the catalyst [34], which was observed at
1.2 mmol/g. Brunauer–Emmett–Teller (BET) surface
areas and mean pore diameter was calculated using the
standard BET equation and was found to be 2.81 m2/g and
125.6 nm.
X-ray photoelectron spectroscopy (XPS) was further
used to check the chemical state of elements. The full XPS
survey spectra (Fig. 4a) shows the presence of C, O, S ele-
ments on the prepared composites. The peak for K and Br
were observed because the sample for XPS was prepared
in the form of KBr pellets. Figure 4b shows the S 2p XPS
spectra of CC-SO3H, the peak at binding energy 167 eV
shows the presence of SO3H group [35]. In high-resolu-
tion C 1s spectra (Fig. 4c), the peak at binding energy
283.5 eV, 284.5 eV, and 287.53 corresponds to C=C, C–C,
and C=O functionality respectively [36]. Figure 4d shows
the O 1s core level spectrum, which confirms the presence
of C=O bonds.
Fig. 2 X-ray diffraction (XRD) patterns of the synthesized CC-SO3H
Catalysts
Fig. 3 FE-SEM (a–c) and EDX
(d) of the CC-SO3H Catalysts
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P. V. Rathod et al.
Fig. 4 Representative XPS
spectra, CC-SO3H catalysts: a
full survey, b S 2p, c C 2s, d
O 2s
solvents system (Table 1). The reactions were conducted at
100 °C for 3 h using 1.1 mmol of fructose in the presence
of [GLY(mim)3][OMs]3 (RTIL). It was observed that in sol-
vents THF and IPA the yield of 5-HMF were around 7 and
14%, respectively (entry 1 and 2). However, in solvent water,
the corresponding 5-HMF yield is slightly higher 21% (entry
3). Meanwhile, the biphasic solvent gave a higher yield of
5-HMF in comparison with pure organic solvent suggest-
ing that water is crucial for dehydration of fructose, due to
3.2 Dehydration of Fructose, Sucrose, and Glucose
to 5‑HMF
3.2.1 Dehydration of Fructose, Sucrose, and Glucose
to 5-HMF in the Presence of Tri-cationic Ionic Liquids
(Scheme 3)
Initially, the tri-cationic ionic liquids activity has been
evaluated for converting fructose to 5-HMF in various
Scheme 3 The synthesis of fructose, sucrose, and glucose to 5-hydroxymethylfurfural
1 3

Efficient Dehydration of Glucose, Sucrose, and Fructose to 5-Hydroxymethylfurfural Using…
Table 1 Study of fructose, sucrose, and glucose to 5-HMF in differ-
ent solvents
Entry
Substrate
Solvent
Ionic liquids
(ILs)
Yield
(%)
HMFa
1
2
3
4
5
6
7
8
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
Sucrose
Glucose
THF
IPA
H2O
H2O/THF
H2O/IPA
Neat
Neat
Neat
Neat
Neat
Neat
Neat
[GLY(mim)3][OMs]3
[GLY(mim)3][OMs]3
[GLY(mim)3][OMs]3
[GLY(mim)3][OMs]3
[GLY(mim)3][OMs]3
[GLY(mim)3][OMs]3
Without ionic liquid
[GLY(mim)3][PF6]3
[GLY(mim)3][Cl]3
7
14
21
26
31
72
–
19
37
26
57
16
9
10
11
12
[GLY(mim)3][Br]3
[GLY(mim)3][OMs]3
[GLY(mim)3][OMs]3
Reaction conditions: fructose (0.2 g)/sucrose (0.2 g)/glucose (0.2),
ILs (0.5 g), 100 °C, 3 h, N2 atmosphere
Fig. 5 Study of fructose, sucrose, and glucose to 5-HMF using
[GLY(mim)3][OMs]3 RTIL in various temp. Reaction conditions:
fructose (0.2 g)/sucrose (0.2 g)/glucose (0.2), [GLY(mim)3][OMs]3
IL (0.5 g), temp, N2 atmosphere
aIsolated yield
less solubility of fructose in a most organic solvent. Upon
analysis of the result in Table 1, it can be seen that THF/
H2O and IPA/H2O was the most effective response medium,
According to our response scenario with 26% and 31% yield
of 5-HMF respectively.
This observation confirms the ionic liquids plays a sig-
nificant role through a dehydration process. As ionic liquids
have the ability to tune their chemical and physical proper-
ties to provide the best medium for a specific transformation.
The presence of an acidic proton in [GLY(mim)3][OMs]3
(RTIL) possibly enhance the dehydration reaction rate,
thereby in the presence of Ionic liquid 5-HMF yield is high.
As in the absence of ionic liquid, such acidic proton is una-
vailable for this transformation, resulting in no 5-HMF for-
mation, the same kind of results were also reported by Emi-
nov and co-worker. They reported a yield of 5-HMF 96%, in
the presence of [C4C1im]{HSO4} ionic liquid catalyst [39].
The mildly acidic [GLY(mim)3][OMs]3 Ionic liquid acts as
a catalyst as well as a green solvent in the reaction medium.
The effect of the reaction temperature on the yield of
5-HMF was also studied at different reaction temperature
using 1.1 mmol fructose, and [GLY(mim)3][OMs]3 (RTIL).
As shown in Fig. 5, the reaction temperature shows adverse
effects on the conversion of fructose to 5-HMF, when the
reaction was done at 80, 100, 120 and 140 °C. Increasing
the temperature from 60 to 100 °C, resulting in the increase
in yield of 5-HMF from 47 to 72% (isolated). When the
reaction temperature was further increased to 120 °C, the
yield of 5-HMF increased to 93% in 2 h. The results show
that, due to the increased reaction temperature, the maxi-
mum 5-HMF production is not increased, but the reaction
time required to reach the maximum yield of 5-HMF was
reduced. But the reaction time required to reach the maxi-
mum yield of 5-HMF was reduced. But when we increase
Further, we studied neat (without solvent) system in
which we observed that without any solvents the correspond-
ing 5-HMF yield is very high, as the fructose to 5-HMF
yield (isolated) was 72% reached (Table 1, entry 6). But
with the same reaction but in the absence of [GLY(mim)3]
[OMs]3 (RTIL) there was no 5-HMF formation observed.
Further, we studied the effect of the different anion of ionic
liquids on the fructose dehydration reaction. In which, we
observed that the dehydration of fructose with [GLY(mim)3]
[PF6]3, [GLY(mim)3][Cl]3 and [GLY(mim)3][Br]3 (RTILs)
gives 5-HMF yield of 19, 37 and 26% respectively, using a
similar reaction condition. This observation confirms the
[GLY(mim)3][OMs]3 (RTIL) plays a significant role through
a dehydration process. And also we have studied sucrose and
glucose dehydration to 5-HMF, in which 57% and 16% yield
of 5-HMF was observed in [GLY(mim)3][OMs]3 (RTIL), at
100 °C within 3 h, for sucrose dehydration, it can be initially
hydrolysed to one molecule of glucose and one molecule of
fructose, and then the glucose and fructose are dehydrated to
produce 5-HMF [37]. Isomerization of glucose into fructose
is an important step in the Lewis acid site, glucose isomeri-
zation into fructose need high Lewis acid site and high tem-
perature [38]. During these dehydration process, 5-HMF is
the only product in the presence of an acid catalyst or the
[GLY(mim)3][OMs]3 (RTIL).
1 3

P. V. Rathod et al.
the reaction temperature to 140 °C, It did not show any
appreciable increase in the 5-HMF yield.
(RTIL) has increased the 5-HMF yield up to a 54, 38% and
21% (isolated) from fructose, sucrose, and glucose, respec-
tively. And further increased of catalyst loading from 0.3 to
0.5 g, made the generation of 5-HMF gradually increased.
The highest yield of 5-HMF from fructose, sucrose, and glu-
cose was 93%, 72%, and 44% (isolated) respectively, using
the 0.5 g [GLY(mim)3][OMs]3 catalysts. However, in the
case of fructose and sucrose dehydration, when the amount
of ionic liquids loading was more than 0.5 g, the yield of
5-HMF was reduced to 92 and 70% (isolated) Meanwhile,
we observed in glucose case, even with 0.6 g and 0.8 g of
ionic liquid, we have achieved an increased in 5-HMF yield
from 45 to 51% (isolated). glucose isomerization into fruc-
tose need high Lewis acid site and high temperature, and
then the fructose will be dehydrated to produce 5-HMF [38].
It’s important to know that fructose, sucrose, and glucose
dehydration reaction with catalyst loading above 0.5 g and
0.9 g will not give a higher yield of 5-HMF; the decrease in
the activity is possibly due to the decrease of the area and
the surface acidity on the catalyst because of the increase of
[GLY(mim)3][OMs]3 (RTIL) [41]. Additionally, the reaction
time effect on sugar dehydration to 5-HMF was studied at
different reaction times. As shown in Fig. 7, with increasing
reaction time from 1 to 2 h, 5-HMF performance increased
from 64 to 93% at 120 °C in [GLY(mim)3][OMs]3 (RTIL)
catalyzed fructose dehydration reaction. However, further
increasing the reaction time up to 5 h did not help improve
the 5-HMF yield. Dehydration of fructose to 5-HMF at
120 °C in 2 h, the maximum 93% yield (isolated) of 5-HMF
Same results were observed in sucrose and glucose
dehydration reaction. When the reaction was done at 60
and 120 °C increasing the temperature observed Increase
in yield of 5-HMF from 33 to 72% and 5 to 23% (isolated).
Further, we have done in 140 °C for Sucrose dehydration,
which gives a lower yield of 5-HMF, but glucose case we
noted at 140 °C increasing the temperature increase in yield
of 5-HMF from 43%(isolated). But, when we increased reac-
tion temperature up to 160 °C, the yield of 5-HMF slightly
decreases. Furthermore, in various reaction temperature,
5-HMF production first always grows in growth reaction
temperature. When the yield of 5-HMF has reached its peak
value, any further increase reaction temperature resulted in
a lower yield of 5-HMF, which can lead to a higher density
in the 5-HMF sub-products [40]. So finally, the sucrose and
glucose reaction temperature of 120 °C and 140 °C is con-
sidered to be the most suitable for sugar conversion, with the
higher productivity of 5-HMF.
Figure 6 shows the of catalyst loading effects for the yield
of 5-HMF from fructose, sucrose, and glucose. In the case of
fructose, sucrose, and glucose dehydration in the absence of
[GLY(mim)3][OMs]3 (RTIL), there was no reaction proceeds
even up to 24 h. But upon addition of 0.1 g of [GLY(mim)3]
[OMs]3 for dehydration of fructose, sucrose, and glucose at
a reaction temperature of 120–140 °C and reaction time of
2–3 h, product formation takes place yielding 35%, 21%, and
13% of 5-HMF. Moreover, 0.2 g of [GLY(mim)3][OMs]3
Fig. 6 Study of ionic liquid loading effect on the conversion of fruc-
tose, sucrose, and glucose to 5-HMF. Reaction conditions: fruc-
tose (0.2 g)/sucrose (0.2 g)/glucose (0.2), [GLY(mim)3][OMs]3(IL),
120 °C, N2 atmosphere
Fig. 7 Study of reaction time for dehydration of fructose, sucrose,
and glucose to 5-HMF using [GLY(mim)3][OMs]3 (RTIL). Reaction
conditions: fructose (0.2 g)/sucrose (0.2 g)/glucose (0.2), IL (0.5 g),
120–140 °C, N2 atmosphere
1 3

Efficient Dehydration of Glucose, Sucrose, and Fructose to 5-Hydroxymethylfurfural Using…
was obtained with 100% fructose conversion. The same per-
formance of 5-HMF yield was also seen for the dehydration
of sucrose and glucose in the same reaction condition, with
increased reaction time (Fig. 7). The increasing reaction time
from 1 to 2 h, the 5-HMF yield improved 29 to 51% and 13
to 21% from sucrose and glucose. Subsequently, a similar
trend were observed in the sucrose and glucose decomposi-
tion with an increase in 5-HMF yield up to 72% and 51%
over 3 h and 5 h. In our results, the colour of the reaction
mixture rapidly changed from light yellow to dark brown
after dehydrations of fructose and sucrose for 2–3 h, and
glucose dehydration for 5 h are the optimal reaction time
for 5-HMF production.
molecule of glucose and one molecule of fructose, and
isomerization of glucose into fructose is an important
step in the Lewis acid site, where glucose isomerization
into fructose will need high Lewis acid site and high tem-
perature, then the fructose will be dehydrated to produce
5-HMF. In general, the efficiency in the sugar dehydration
is closely related to the acidity of the catalyst as well as
the strong hydrogen bond is produced in the sugar and
mesylate (CH3SO3–) anions [42]. The mesylate anions
forming hydrogen bond and nitrogen-containing tri (imi-
dazolium) cations are beneficial to the fructose, sucrose,
and glucose dissolution in the synthesized RTILs. Their
ability to construct hydrogen bonds is believed to be a
major function (mechanism) for solubilizing biomass and
5-HMF. The tri-cationic RTILs synthesized in this study
has a Lewis acidic character. Lewis acid ILs are reported
to be more effective than Brønsted acid ILs in terms of
sugar conversion and 5-HMF yield [43].
The dehydration of fructose, sucrose, and glucose to
5-HMF catalyses by the acidic (RTILs) is a very complex
process (as shown in Scheme 4). As mentioned above,
the sucrose dehydration can be firstly hydrolysed to one
Scheme 4 Possible reaction transformation for the formation of 5-HMF from sucrose with ionic liquid
1 3

P. V. Rathod et al.
3.2.2 Catalytic Study of CC-SO3H for Fructose, Sucrose,
and Glucose to 5-HMF Conversion in the Presence
of Tri-cationic Ionic Liquids
and 130 °C, with increasing the reaction temperature the
5-HMF yield increase from 24%, 61%, and 77% respectively.
But when we have done above reaction at 150 °C, we got a
decrease in 5-HMF yield. The decrease in 5-HMF yield is
possible because the 5-HMF is unstable at high temperature
as it could be transformed into levulinic acid by alcoho-
lysis thus leading to a low yield of 5-HMF as illustrated
[40]. Table 2 shows the influence of reaction temperature on
the yield of 5-HMF yield from glucose. It is clear from the
Table 2 that the increase of temperature from 120 to 140 °C
had a significant effect on 5-HMF yield from glucose. The
yield of 5-HMF increased from 36 to 58%. Increasing reac-
tion temperature upto160 °C slightly decreases 5-HMF yield
may be due to the instability of 5-HMF at high temperatures.
Therefore, 140 °C was considered to be the optimum reac-
tion temperature for this system.
Above results show a conversion of fructose, sucrose, and
glucose to 5-HMF with 93%, 72%, and 51% yield, respec-
tively obtained in [GLY(mim)3][OMs]3 RTIL at 120–140 °C,
showing used catalytic system is highly efficient for sugar to
5-HMF conversion. The effect of the different anion (ionic
liquids) with metal-free co-catalyst used for dehydration
reaction of fructose, sucrose, and glucose. For comparison
purposes, we studied a neat system for the same reaction.
In which we observed that without solvent the correspond-
ing 5-HMF yield is very high; such that the fructose to
5-HMF selectivity increase resulted in 100% conversion
and the corresponding isolated reached 93% 5-HMF yield.
However, under the same reaction but in the absence of
[GLY(mim)3][OMs]3 ionic liquid, no 5-HMF product forma-
tion took place. Moreover, we observed that in presence of
[GLY(mim)3][Cl]3, [GLY(mim)3][PF6]3 and [GLY(mim)3]
[Br]3 the dehydration of sugar to 5-HMF reaction rate is low
as the isolated 5-HMF yield was very low as compared to
[GLY(mim)3][OMs]3 (RTIL).
Table 3 shows the effect of CC-SO3H catalyst loading on
the fructose to 5-HMF conversion. In which we observed
that when the catalysts amount was increased from 0.025,
0.050 and 0.100 g the yield of 5-HMF improved from 78, 85
and 97% (isolated). But further increasing catalysts loading
above 0.100 g doesn’t give a higher yield of 5-HMF. The
decrease in activity possibly because of the area and the
surface acidity on the catalyst decreases due to the increase
of CC-SO3H concentration [44]. We have also studied the
But when we combined the above mentioned ionic liquids
(RTILs) and CC-SO3H co-catalyst, we observed the corre-
sponding 5-HMF yield is high. We observed the dehydration
of fructose with [GLY(mim)3][PF6]3, [GLY(mim)3][Cl]3 and
[GLY(mim)3][Br]3 (RTILs) with co-catalyst CC-SO3H at
100 °C gives 5-HMF yield of 56%, 71% and 61% (isolated)
respectively, using a similar reaction condition. In the pres-
ence of [GLY(mim)3][Cl]3 ionic liquid, we got a high yield
of 5-HMF as compared with other ionic liquids. Further,
we investigated different reaction parameter effect on dehy-
dration of fructose, sucrose, and glucose to 5-HMF in the
presence of [GLY(mim)3][Cl]3 (RTIL). Initially, we chose
fructose as the substrate. As expected, as the temperature
increases, the conversion of fructose increases with increas-
ing temperature. More importantly, the yield of 5-HMF not
only increases, but also the reaction time decreases with
increasing temperature. As we observed after the 24 h at the
low temperature of 80 °C, the obtained 5-HMF yield was
32%. However, by increasing the reaction temperature to
100 °C, just within 8 h the 5-HMF yield increased signifi-
cantly to 71%, indicating that higher temperatures improve
reaction rate resulting in an increase in 5-HMF yield in a
shorter time. When further reaction temperature increased
up to 130 °C, the yield of 5-HMF increased to 97% within
3 h. But, when we increased reaction temperature up to
150 °C, the yield of 5-HMF slightly decreases. So finally,
the reaction temperature of 130 °C is considered to be the
most suitable for the higher productivity of 5- HMF.
Table 2 Study of fructose, sucrose, and glucose to 5-HMF using CC-
SO3H Catalyst in various temperature
Entry Substrate Ionic liquid
(IL)
Temp Time (h) Yield (%)HMFa
oC
1
2
3
4
5
6
7
8
9
10
Fructose [GLY(mim)3]
[Cl]3
80
24
12
3
32.6
71.4
97.0
92.1
24
Fructose [GLY(mim)3] 100
[Cl]3
Fructose [GLY(mim)3] 130
[Cl]3
Fructose [GLY(mim)3] 150
3
[Cl]3
Sucrose [GLY(mim)3]
[Cl]3
80
24
15
3
Sucrose [GLY(mim)3] 100
61
[Cl]3
Sucrose [GLY(mim)3] 130
[Cl]3
77
Glucose [GLY(mim)3] 120
5
36
[Cl]3
Glucose [GLY(mim)3] 140
[Cl]3
5
58
Glucose [GLY(mim)3] 160
5
54
[Cl]3
Reaction conditions: fructose (0.2 g) / Sucrose (0.2 g) / glucose (0.2),
[GLY(mim)3][Cl]3 IL (0.5 g), CC-SO3H catalyst (0.1 g), without sol-
vent, N2 atmosphere
Similar results were observed for sucrose to 5-HMF con-
version reaction. When the reaction was done at 80, 100
aIsolated yield
1 3

Efficient Dehydration of Glucose, Sucrose, and Fructose to 5-Hydroxymethylfurfural Using…
Table 3 Study of fructose,
Entry
Substrate
Catalyst loading
mg
Ionic liquid
(IL)
Temp
°C
Time (h)
Yield
(%)
sucrose, and glucose to 5-HMF
using loading effect CC-SO3H
catalyst
HMFa
1
2
3
4
5
7
8
9
Fructose
Fructose
Fructose
Fructose
Fructose
Sucrose
Sucrose
Sucrose
Glucose
Glucose
Glucose
–
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
130
130
130
130
130
130
130
130
140
140
140
24
5
4
4
3
8
5
3
5
5
5
–
0.025
0.050
0.100
0.150
0.025
0.050
0.100
0.050
0.100
0.150
78
85
96
94
15
51
77
22
58
55
10
11
12
Reaction conditions: fructose (0.2 g)/sucrose (0.2 g)/glucose (0.2), CC-SO3H catalyst, [GLY(mim)3][Cl]3
IL(0.5 g), N2 atmosphere
aIsolated yield
CC-SO3H catalysts loading effect on sucrose dehydration to
5-HMF using a different ratio of the catalyst. The 5-HMF
yield was 15, 51, and 77%, when the amount of CC-SO3H
was 0.025, 0.050, and 0.100 g respectively. And we have
also observed CC-SO3H catalyst uses different proportions
of catalyst to load glucose to dehydrate into 5-HMF. When
CC-SO3H catalysts loading were 0.050, 0.100, 0.150 g
respectively, the yield found of 22%, 58%, and 55% (iso-
lated) respectively. From the results as mentioned earlier, the
ionic liquid plus CC-SO3H catalyst system is highly efficient
for fructose, sucrose, and glucose conversion to 5-HMF with
97%, 77%, and 58% yield respectively.
[Cl−]. They used this combination for sugar conversion.
Their previous work with fructose showed that [BMIM+]
−
[HSO4 ] could be a suitable co-catalyst to produce 5-HMF,
due to the anion being mildly acidic and abundant in the
medium [39]. This low acidity prevents the over-dehydra-
tion usually observed with stronger acids. However, the low
−
yields obtained from glucose with [BMIM+][HSO4 ] sug-
−
gested that [HSO4 ] prevents the isomerization of glucose
to fructose, which tends to be base catalyzed. A probable
explanation is that, in the presence of CrCl3, [Cl−] leads to
−
the formation of [CrCl4 ], which catalyzes glucose-fructose
−
isomerization. On the other hand [HSO4 ], appears to form
In fructose, sucrose, and glucose dehydration reaction
both [GLY(mim)3][Cl]3 (RTIL) and CC-SO3H catalyst play
an important role. As, in acid catalyzed reaction the strength
of an acid is an important factor of the action of the cata-
lyst, for sugar hydrolysis. Practical aspects of the reaction,
concerning the homogeneous nature of the catalysis in spite
of using a CC-SO3H catalyst. Scheme 5 shows the reaction
mechanism for this reaction. As shown in the mechanism,
the adding CC-SO3H catalyst into [GLY(mim)3][Cl]3 ionic
liquid starts an ion-exchange process, resulting in H+ ions
release [45]. So, the number of the concentration of the H+
ions in the reaction mixture depends on the loading of the
catalyst. And as expected the effect of the CC-SO3H catalyst
loading shows the effect on the reaction performance. As
shown in the mechanism, the homogeneous nature of the
catalysis in spite of using a solid acid indicates that the slow
release of H+ species governs the initial rate of the dehy-
dration of sugar using CC-SO3H. The overall dehydration
reaction rate depends on the total number of H + as well as
the reaction temperature [46].
a non-active complex with CrCl3, which is preferred over
−
[CrCl4 ] (Table 4).
3.2.3 Catalyst Recyclability
A catalyst is considered effective only if it can be recy-
cled and reused. For the practical large-scale production of
5-HMF from sugar, the reusability of catalysts and ionic liq-
uids are a very important consideration. The reusable cata-
lytic system significantly reduces production costs. In this
work, for both systems, the recyclability of catalysts and the
ionic liquids was tested to study their stability and activity.
After completion of one cycle of the fructose dehydration
reaction. The product was extracted by using ethyl acetate
four times and in the remaining reaction mixture, 15 mL of
acetonitrile was added and the resulting solution was stirred
vigorously at room temperature for 20 min. Separation of
acetonitrile layer containing RTILs done by decantation, and
were dried using Na2SO4. Finally, the RTILs were obtained
by removing organic solvent using rota-evaporator at high
vacuum. This ionic liquid was reused for a minimum of four
runs and showed no significant decrease yields of 5-HMF
Eminov et al. used CrCl3⋅6H2O as catalyst in the presence
−
of Brønsted IL [BMIM+][HSO4 ] and Lewis IL [BMIM+]
1 3

P. V. Rathod et al.
+
+
Scheme 5 An ion-exchange process involving [GLY(mim)3] and H species possible reaction transformation for the formation of 5-HMF
from sucrose
(as shown in Fig. 8). The ionic liquids were found to be
sufficiently stable and reactive even after four runs. The fur-
ther ionic liquid was analysed using 1H NMR which clearly
indicated that ionic liquid was stable after reuse (Fig. S5
Supporting Information).
was separated from the reaction mixture using a simple fil-
tration method followed by washing with 5 mL of DI water
and ethanol for a couple of times and dried at 100 °C. In
the filtrate, ethyl acetate was added in DI water and 5-HMF
was extracted. A high vacuum pump was used to evaporate
ethyl acetate to get crude 5-HMF. The spent catalysts were
analyzed using XRD (Fig. S3, support information), which
Also, we have done recyclability test for CC-SO3H co-
catalyst system. After completion of the reaction, the catalyst
1 3

Efficient Dehydration of Glucose, Sucrose, and Fructose to 5-Hydroxymethylfurfural Using…
Table 4 Reported catalysts comparison with [GLY(mim)3][OMs]3 for fructose, sucrose, and glucose to 5-HMF conversion
Sr. No
Substrates
Catalysts
Solvent
Time (h)
Temp of oC
5-HMF yield References
(%)
1
2
3
4
5
6
7
8
Glucose
Glucose
Glucose
Fructose
Fructose
Fructose
Sucrose
Glucose
Fructose
Glucose
Glucose
Glucose
Fructose
Sucrose
Glucose
Fructose
Sucrose
Glucose
CrCl3
CrCl3
CrCl3
CrCl3.6H2O
WO3/SnO2
ZrP
[C4C1im]Cl
BmimHSO4
BmimCl
[C4C1im]{HSO4}
DMSO
H2O–diglyme
H2O–diglyme
–
DMSO
DMSO
NaCl aq. phase/MIBK
EMIMBr
Neat
0.1
0.1
2
3
2
1
2
3
0.5
3
0.5
3
2
3
5
3
3
5
140
70
43
12
65.5
96
93
80
53
60
96.7
49
42
58.3
93
72
51
96
77
58
[47]
[48]
[49]
[39]
[41]
[50]
[50]
[51]
[52]
[53]
[54]
[55]
This work
This work
This work
This work
This work
This work
125
100
100
150
180
100
140
180
195
120
120
120
140
130
130
140
ZrP
Nb2O5 /TiO2
HCP-x, eSO3H
LaOCl/Nb2O5
H-ZSM-5
9
10
11
12
13
14
15
16
17
18
SnPO
[GLY(mim)3][OMs]3
[GLY(mim)3][OMs]3
[GLY(mim)3][OMs]3
CC-SO3H/
CC-SO3H/
CC-SO3H/
Neat
Neat
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
[GLY(mim)3][Cl]3
1
in its H NMR spectra (Fig. S4, Supporting Information).
The dried catalyst and ionic liquid were used directly for the
next reaction by adding an equal amount of fructose under
the same condition. The catalyst and ionic liquid retained
its activity up to 4 successive cycles with 94.2% yield of
5-HMF (as shown in Fig. 8). It is important that the cata-
lyst exhibited reusability without any pre-treatment. This
represents the high stability as well as the activity of the
CC-SO3H catalyst with ionic liquids for the fructose dehy-
dration reaction.
4 Conclusion
In this study, a new catalytic system has developed for
the efficient conversion of fructose, sucrose, and glucose
to 5-HMF first-time using tri-cationic ionic liquids. The
strong hydrogen bond is produced in the sugar and mesylate
(CH3SO3–) anions are beneficial for dehydration reaction.
The [GLY(mim)3][OMs]3 (RTIL) showed fructose, sucrose,
and glucose decompositions with 93%, 72% and 51% yield
(isolated) of 5-HMF at 120–140 °C for only 2–5 h respec-
tively. And co-catalyst system, the excellent 5-HMF yield of
97%, 77% and 58% (isolated) was obtained from fructose,
sucrose, and glucose in the presence of [GLY(mim)3][Cl]3,
and CC-SO3H catalyst at 130–140 °C for only 2–5 h. For
fructose, sucrose, and glucose to 5-HMF conversion, both
Ionic liquid and solid acid catalysts play a significant role
through H+ source. The present catalytic system is shown
Fig. 8 Catalyst recycling study. (a) IL system. Reaction conditions:
fructose (0.2 g), [GLY(mim)3][OMs]3 IL (0.5 g), 120 °C for 2 h, N2
atmosphere. (b) IL + CC-SO3H catalyst system. Reaction conditions:
fructose (0.2 g) CC-SO3H catalyst (0.1 g), [GLY(mim)3][Cl]3 IL
(0.5 g), 120 °C for 3 h, N2 atmosphere
confirms the catalyst was stable after reuse. And the same
procedure was followed for extraction of [GLY(mim)3][Cl]3
(RTIL). The extracted ionic liquid from the reaction mix-
ture was also characterized using 1H NMR, and results show
ionic liquid was stable after reuse, as no changes appeared
1 3

P. V. Rathod et al.
Ind Eng Chem Res 46:7703–7710. https://doi.org/10.1021/ie061
673e
recyclability up to 4 successive cycles. The developed
catalytic system is highly economical and environmentally
friendly gives high 5-HMF yield. Importantly, the present
catalytic system is scalable and could be useful for industrial
level 5-HMF production.
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Acknowledgements This work was supported by Basic Science
Research Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education (2018R1D1A1B07048146)
and by the Korea Institute of Energy Technology Evaluation and Plan-
ning (KETEP)—Grants funded by the Ministry of Trade, Industry &
Energy (MOTIE) (No. 20174010201160).
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Compliance with Ethical Standards
Conflict of interest The authors declare no conflicts of interest.
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P. V. Rathod et al.
Affiliations
Pramod V. Rathod1 · Rajendra B. Mujmule1 · Wook‑Jin Chung1 · Amol R. Jadhav1 · Hern Kim1
1
Department of Energy Science and Technology, Smart
Living Innovation Technology Center, Myongji University,
Yongin, Gyeonggi-do 17058, Republic of Korea
1 3