Dehydration of carbohydrates to 5-hydroxymethylfurfural in ionic liquids catalyzed by hexachlorotriphosphazene

Article abstract of DOI:10.1002/cjoc.201200691

Development of efficient catalysts for the dehydration of carbohydrates to produce 5-hydroxymethylfurfural (HMF) is a very attractive topic. In this work, dehydration of fructose catalyzed by three organic molecules, including hexachlorotriphosphazene (N₃P₃Cl₆), trichloromelamine (C₃N₆H₃Cl₃) and N-bromosuccinimide (NBS), was studied in ionic liquids. It was discovered that the three organic molecules had high activity in accelerating the dehydration of fructose and N₃P₃Cl₆ was the most efficient catalyst among them. The effects of amount of catalysts, temperature, solvents, reaction time, and substrate/solvent weight ratio on the reaction were investigated using N₃P₃Cl₆ as the catalyst and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) as the solvent. It was demonstrated that the N₃P₃Cl₆/[Bmim]Cl catalytic system was very effective for catalyzing the reaction. The yield of HMF could reach 92.8% in 20 min at the optimized conditions and the N ₃P₃Cl₆/[Bmim]Cl system could be reused. Further study indicated that the N₃P₃Cl₆/[Bmim]Cl system was also effective for the dehydration of sucrose and inulin and satisfactory yield could be obtained at suitable conditions.

Full text of DOI:10.1002/cjoc.201200691

FULL PAPER
DOI: 10.1002/cjoc.201200691
Dehydration of Carbohydrates to 5-Hydroxymethylfurfural in
Ionic Liquids Catalyzed by Hexachlorotriphosphazene†
Song, Jinliang(宋金良)
Zhang, Binbin(张斌斌)
Shi, Jinghua(史敬华)
Han, Buxing*(韩布兴)
Ma, Jun(马珺)
Yang, Guanying(杨冠英)
Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100190, China
Development of efficient catalysts for the dehydration of carbohydrates to produce 5-hydroxymethylfurfural
(HMF) is a very attractive topic. In this work, dehydration of fructose catalyzed by three organic molecules, includ-
ing hexachlorotriphosphazene (N3P3Cl6), trichloromelamine (C3N6H3Cl3) and N-bromosuccinimide (NBS), was
studied in ionic liquids. It was discovered that the three organic molecules had high activity in accelerating the de-
hydration of fructose and N3P3Cl6 was the most efficient catalyst among them. The effects of amount of catalysts,
temperature, solvents, reaction time, and substrate/solvent weight ratio on the reaction were investigated using
N3P3Cl6 as the catalyst and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) as the solvent. It was demonstrated
that the N3P3Cl6/[Bmim]Cl catalytic system was very effective for catalyzing the reaction. The yield of HMF could
reach 92.8% in 20 min at the optimized conditions and the N3P3Cl6/[Bmim]Cl system could be reused. Further
study indicated that the N3P3Cl6/[Bmim]Cl system was also effective for the dehydration of sucrose and inulin and
satisfactory yield could be obtained at suitable conditions.
Keywords carbohydrates, 5-hydroxymethylfurfural, dehydration, hexachlorotriphosphazene, ionic liquids
cles,[18] imidazolium salts,[19] and so on. In addition,
different reaction media, including water,[20] organic
solvents,[21] ILs,[22] and water/organic biphasic sys-
tems,[23] have been used in the dehydration reactions.
ILs are among promising media because they have some
unique properties, such as negligible vapor pressure,
nonflammability, high thermal and chemical stability,
and adjustable solvent power for organic and inorganic
substances.[24]
1,3,5-Triazo-2,4,6-triphosphorine-2,2,4,4,6,6-tetra-
chloride, commonly called as hexachlorotriphosphazene
(N3P3Cl6), has been widely used as the catalyst in or-
ganic reactions,[25] such as Beckmann rearrangement of
ketoximes to lactams,[26] oxidation of sulfides and de-
oxygenation of sulfoxides,[27] and N-alkylation of
amines with alcohols.[28]
Introduction
With growing concerns about global climate change
and energy security, the research for sustainable, alter-
native energy has attracted more and more attentions.[1]
Renewable and abundant biomass resources are prom-
ising alternatives for the sustainable supply of liquid
fuels and valuable intermediates,[2] and the biomass-
derived carbohydrates are potential chemical feed-
stocks.[3] However, efficient methods to transform car-
bohydrates into useful organic compounds need to be
developed. Dehydration of carbohydrates to produce
5-hydroxymethylfurfural (HMF) is one of the most
successful routes for biomass transformation because
HMF is considered to have the potential to be a sus-
tainable substitute for petroleum-based building
blocks.[4]
Exploration of highly efficient catalysts for the syn-
thesis of HMF from dehydration of carbohydrates under
mild reaction conditions is still highly desirable, al-
though many catalytic systems have been developed. In
this work, we conducted the dehydration reaction using
N3P3Cl6 as the catalyst in ILs under mild reaction condi-
tions. It was demonstrated that N3P3Cl6 could catalyze
the dehydration of carbohydrates very effectively. To
the best of our knowledge, this is the first application of
Catalysis is crucial for effective dehydration of car-
bohydrates to produce HMF. Up to now, many catalysts
have been developed, such as mineral acids,[5] lantha-
nide chlorides,[6] stannous chloride,[7] chromium chlo-
rides,[8] tungsten salts,[9] germanium chloride,[10] alu-
minium chloride,[11] boric acid,[12] heteropoly acids,[13]
strong acid cation exchange resins,[14] Tin-Beta Zeo-
lite,[15] acid-functionalized SBA-15,[16] sulfated zirco-
nia,[17] ionic liquid (IL) supported on silica nanoparti-
*
E-mail: hanbx@iccas.ac.cn; Tel.: 0086-010-62562821; Fax: 0086-010-62562821
Received July 8, 2012; accepted August 27, 2012.
Dedicated to the 80th Anniversary of Chinese Chemical Society.
†
Chin. J. Chem. 2012, 30, 2079—2084
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Song et al.
FULL PAPER
Results and Discussion
N3P3Cl6 to catalyze the dehydration of carbohydrates to
produce HMF.
Reaction with various catalysts
The activity of various catalysts for the dehydration
of fructose (Scheme 1) was tested at 80 ℃ in
1-butyl-3-methylimidazolium chloride ([Bmim]Cl), and
the results are summarized in Table 1. It can be seen
from Table 1 that nearly no product was produced
without catalyst (entry 1). It was shown that three types
of organic molecules (Scheme 2), N3P3Cl6, trichloro-
melamine (C3N6H3Cl3), and N-bromosuccinimide
(NBS), could catalyze the dehydration of fructose to
produce HMF effectively, and N3P3Cl6 had the best ac-
tivity among them. Therefore, N3P3Cl6 was used to
study the effects of various conditions on the reaction,
and the results are discussed in the following.
Experimental
Materials
Fructose, sucrose, inulin, glucose, hexachlorotri-
phosphazene (N3P3Cl6), trichloromelamine (C3N6H3Cl3),
and N-bromosuccinimide (NBS) were all A. R. grade
and were purchased from Alfa Aesar. Dimethylforma-
mide (DMF) and dimethylsulfoxide (DMSO) were A. R.
grade and were obtained from Beijing Chemical Re-
agent Company. The ILs 1-butyl-3-methylimidazolium
chloride ([Bmim]Cl), 1-butyl-3-methylimidazolium
tetrafluoroborate ([Bmim]BF4), and 1-butyl-3-methyl-
imidazolium hexafluorophosphoate ([Bmim]PF6) were
provided by Lanzhou Greenchem ILS, LICP, CAS,
China, and their purity was ＞99%. All chemicals were
used as received.
Scheme 1 Dehydration of fructose to produce HMF
OH
OH
O
O
Catalyst
80 oC, 20 min
OH
Analysis methods
O
OH
HO
OH
Fructose
The amount of HMF was analyzed by HPLC with
Supelcosil LC-18 5ìm column at 30 ℃, Shimadzu
LC-20AT pump, Sama UV-Vis LC-830 detector at
282.0 nm. Before analysis, the reaction mixture was
diluted to 1000 mL. Methanol/water solution (50/50 V/V)
was used as the mobile phase at 0.8 mL/min.
HMF
Table 1 Dehydration of fructose catalyzed by various catalysts
in IL [Bmim]Cl a
Entry
1
Catalyst
None
Yieldb/%
0.1
Catalytic reaction
2
N3P3Cl6
C3N6H3Cl3
NBS
92.8
90.1
82.3
90.3
89.5
88.8
87.5
Conversion of fructose into HMF In a typical
experiment, known amounts of fructose and N3P3Cl6
were dissolved in the solvent in a flask of 10 mL sealed
with a glass stopper. The mixture was stirred at a fixed
temperature for desired time. Then the mixture was
cooled to room temperature immediately. The samples
were analyzed by HPLC to obtain the yields. Each reac-
tion was repeated at least two times. In the experiments
to test the reusability, 1 mL of water was added into the
reaction system after the reaction. Then the mixture was
extracted 5 times with 50 mL of ether. After extraction,
the water in the N3P3Cl6/IL mixture was removed under
reduced pressure at 80 ℃. It was then used directly for
the next run by adding new fructose.
Conversion of sucrose, inulin and glucose in
[Bmim]Cl In an experiment, suitable amounts of re-
actant and N3P3Cl6 were dissolved in the IL (2 g) in a
flask of 10 mL sealed with a glass stopper. The mixture
was stirred at 80 ℃ for a desired time. Then the mix-
ture was cooled to room temperature immediately. The
sample was analyzed by HPLC to obtain the yields.
Each reaction was repeated at least two times.
3
4
5c
6d
7e
8f
N3P3Cl6
N3P3Cl6
N3P3Cl6
N3P3Cl6
a Reaction conditions: 0.1 g fructose, 5 mg catalyst, 2 g [Bmim]Cl,
reaction time 20 min, reaction temperature 80 ℃. b Yields were
determined by HPLC. c Recycled N3P3Cl6/IL from Entry 2. d Re-
e
cycled N3P3Cl6/IL from Entry 5. Recycled N3P3Cl6/IL from
Entry 6. f Recycled N3P3Cl6/IL from Entry 7.
Scheme 2 The structures of the three catalysts
NHCl
Cl Cl
P
Br
O
N
N
N
N
P
N
Cl
Cl
Cl
Cl
O
P
ClHN
N
NHCl
N
C3N6H3Cl3
N3P3Cl6
NBS
Effect of solvents
We studied the effect of different solvents on the re-
action and the results are shown in Figure 1. The reac-
tion did not occur when water was used as the solvent
due to the poor solubility of N3P3Cl6 in water. High
yields of HMF were obtained in dimethylformamide
Calculation of 5-HMF yield The yield of 5-HMF
was calculated by the following equation:
Moles of 5-HMF formed
5-HMF yield (mol%)＝
×100%
Moles of fructose used
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 2079—2084

Dehydration of Carbohydrates to 5-Hydroxymethylfurfural in Ionic Liquids
(DMF) and dimethylsulfoxide (DMSO), and the yields
were 65.5% and 80.7%, respectively. We also studied
the reaction catalyzed by N3P3Cl6 in other two ILs,
([Bmim]BF4) and ([Bmim]PF6). All the results are pre-
sented in Figure 1. It can be known from the figure that
an HMF yield of 92.8% was achieved in [Bmim]Cl. The
HMF yield in [BMim]PF6 was very low because of the
insoluble nature of fructose in the IL.
Figure 2 Effect of catalyst amount on the yield of HMF. Reac-
tion conditions: 0.1 g fructose, 2 g [Bmim]Cl, reaction tempera-
ture 80 ℃, reaction time 20 min.
100
80
60
40
20
0
Figure 1 Effect of different solvents on the yield of HMF. Re-
action conditions: 0.1 g fructose, 5 mg N3P3Cl6, 2 g solvents,
reaction temperature 80 ℃, reaction time 20 min.
Effect of catalyst amount
The results above indicate that N3P3Cl6/[Bmim]Cl
was the most efficient catalytic system studied in this
work. The influence of the amount of N3P3Cl6 in the
system on the dehydration of fructose to HMF was in-
vestigated at 80 ℃ with a reaction time of 20 min
(Figure 2). As shown in Figure 2, the yield of HMF in-
creased to a maximum of 92.8% with an increase in the
amount of N3P3Cl6 from 0 to 5 mg and then slowly de-
creased to 84.5% with further increase of the amount of
N3P3Cl6 from 5 to 20 mg. The results suggest that
smaller amount of the catalyst resulted in slower reac-
tion rate and excess catalyst could cause the side reac-
tions such as polymerization and rehydration of prod-
ucts. Therefore, 5 mg of the catalyst would be an ap-
propriate amount at the reaction conditions.
70
80
90
100
110
120
Temperature/oC
Figure 3 Influence of reaction temperature on the reaction.
Reaction conditions: 0.1 g fructose, 2 g [Bmim]Cl, 5 mg N3P3Cl6,
reaction time 20 min.
Effect of reaction time
The dependence of the yield of HMF on reaction
time is presented in Figure 4. The reaction was per-
formed in the presence of 5 mg N3P3Cl6 at 80 ℃ in
[Bmim]Cl. The yield increased dramatically at the be-
ginning, and reached the maximum at 20 min. Then the
yield decreased slightly with reaction time. The main
reason was that the conversion of fructose increased at
the beginning, and prolonged reaction time resulted in
rehydration of the HMF produced. Therefore, the
maximum yield occurred at 20 min.
Influence of reaction temperature
Figure 3 shows the effect of reaction temperature on
the dehydration of fructose to produce HMF in
[Bmim]Cl catalyzed by N3P3Cl6 in the temperature
range of 70 to 120 ℃, and the reaction time was 20 min.
The maximum yield occurred at 80 ℃. Increase of re-
action temperature affected the reaction in two opposite
ways. First, the dehydration reaction was accelerated by
increasing temperature, which was favorable to achiev-
ing high yield. At the same time, the side reactions were
also enhanced by rising temperatures. The competition
of the two opposite factors led to the largest yield at 80 ℃.
Influence of substrate/solvent weight ratio
The dependence of HMF yield on the fructose/
[Bmim]Cl weight ratio was also investigated and the
results are demonstrated in Figure 5. The yield of HMF
decreased continuously with the increasing substrate/
solvent weight ratio. This is easy to understand because
the amount of the catalyst was fixed in all the experi-
ments. However, the yield of HMF was still as high as
80.1% at the fructose/[Bmim]Cl weight ratio of
Chin. J. Chem. 2012, 30, 2079—2084
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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Song et al.
FULL PAPER
0.3∶1.
100
80
60
40
20
0
The reusability of catalyst system
The reusability of the N3P3Cl6/[Bmim]Cl catalytic
system was studied in this work. After the reaction, the
product was extracted by ether, and the catalytic system
was used directly for the next run after drying, as de-
scribed in the Experimental section. The results are also
listed in Table 1 (Entries 1, 5—8). It can be seen that the
decrease of the activity of the catalyst system was not
considerable after reused five times.
Reaction mechanism
0
10
20
30
40
50
60
Reaction time/min
As shown in Figure 1, solvents had important impact
on dehydration of fructose to HMF. Therefore, we
thought that the imidazolium ILs played an important
role in the catalyitc cycle. Imidazolium molecules may
take the role of activating the reactants and stabilizing
the products of each step through hydrogen-bonding
interactions, which had been reported previously.[22c,29]
N3P3Cl6 was easily nucleophilically attacked by O or
N in functional group to generate HCl.[25-28] Based on
the experimental results and discussions above, a plau-
sible reaction mechanism for the dehydration of fructose
catalyzed by N3P3Cl6 was proposed, which is shown in
Scheme 3. Firstly, the nucleophilic attack of fructose
and water on N3P3Cl6 leads to HCl, which is the catalyst
for the dehydration of fructose. Then, the HCl catalyzed
the dehydration reaction to produce HMF. In the cata-
lytic cycle, the IL may interact with fructose and the
intermediates through hydrogen bonding and nucleo-
philic effect to activate fructose and stabilize intermedi-
ates, which leads to the production of HMF with high
selectivity.[22c,29] Finally, HCl reacted with intermediates
a and b to regenerate the catalyst.
Figure 4 Effect of reaction time on the reaction. Reaction con-
ditions: 0.1 g fructose, 2 g [Bmim]Cl, 5 mg N3P3Cl6, reaction
temperature 80 ℃.
100
80
60
40
20
0
0.0
0.1
0.2
0.3
Substrate/[Bmim]Cl weight ratio
Figure 5 Influence of substrate/solvent weight ratio on the re-
action. Reaction conditions: reaction temperature 80 ℃, reaction
time 20 min.
Scheme 3 The plausible reaction mechanism for the dehydration of fructose catalyzed by N3P3Cl6
Cl
Cl
N
P
P
N
Cl
Cl
P
N
Cl Cl
HO
HO
O
OH
R
OH
N3P3Cl6
OH
OH
Cl
N
Cl
P
HCl
HO
HO
H2O
O
X
OH
OH
O
OH
2
O
OR
N
HO
P
OH
X
OH
2
a
N
HO
P
H2O
HCl
+
OH HCl
R
X
2
b
2082
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Chin. J. Chem. 2012, 30, 2079—2084

Dehydration of Carbohydrates to 5-Hydroxymethylfurfural in Ionic Liquids
Dehydration of other carbohydrates
tion in producing HMF by dehydration of the carbohy-
drates.
The N3P3Cl6/[Bmim]Cl catalytic system was also
used to catalyze the dehydration of other carbohydrates,
and the results are illustrated in Figure 6. As expected,
the sucrose (Scheme 4a) and inulin (Scheme 4b) with
fructose unit in the molecular structures gave moderate
HMF yields of 47.9% and 52.4%, respectively. Reaction
times for reaching the maximum HMF yield for sucrose
and inulin were 30 min and 60 min, respectively. How-
ever, the catalyst system had poor activity for the dehy-
dration of glucose (Scheme 4c) to produce HMF, and
the yield was only 1.3% after a reaction time of 120
min.
Acknowledgement
This work was supported by National Natural Sci-
ence Foundation of China (21003133, 21133009,
21021003).
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