Carbohydrate Research 350 (2012) 2024

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Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres

Conversion of fructose into 5-hydroxymethylfurfural (HMF) and its

derivatives promoted by inorganic salt in alcohol
Jitian Liu a,b, Yu Tang b,c,, Kaigui Wu a, Caifeng Bi a,, Qiu Cui b,
a

College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266101, China
Key Laboratory Of Energy Genetics, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China
c
Tianjin Key Laboratory for Modern Drug Delivery & High-Efciency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, China
b

a r t i c l e

i n f o

Article history:
Received 18 September 2011
Received in revised form 28 November 2011
Accepted 6 December 2011
Available online 5 January 2012

a b s t r a c t
The conversion of D-fructose to 5-hydroxymethylfurfural (HMF) on a 1 mmol scale was achieved in good
yield (68%) using NH4Cl as catalyst in isopropanol at 120 C. About 3% of 5-i-propoxymethylfurfural was
formed. The reaction in ethanol at 100 C on a 10 g scale gave a total yield of HMF and 5-ethoxymethylfurfural of 42%. No mineral acid such as H2SO4 and HCl are required.
2012 Elsevier Ltd. All rights reserved.

Keywords:
Fructose
HMF
EMF
Inorganic salt
Alcohol

1. Introduction
Fossil fuels such as coal, petroleum, and natural gas provide
more than three quarters of the worlds energy today. In addition
to producing most of the transportation fuel, petroleum is also
the feedstock used for the production of over 96% of the carboncontaining chemicals used in our society.1 But in less than two decades petroleum production is unlikely to meet the growing needs
of humanity and natural gas resources will be increasingly inaccessible.25 5-Hydroxymethylfurfural (HMF) (2) and its derivatives are
valuable biomass-derived intermediates for plastics, pharmaceuticals, ne chemicals, and liquid fuel.68 Many important scientic
studies have been reported recently on the synthesis and applications of these biomaterials.924 5-Ethoxymethylfurfural (EMF) (3a),
a liquid with a boiling point of 235 C, is already considered to be a
promising alternative fuel or fuel additive.2528 However, HMF and
EMF are not readily accessible, partly due to high production
costs.2931
The dehydration of fructose has long been an intriguing project
both from a mechanistic point of view and as a source of HMF (2)
and levulinic acid. Recent interest has grown quickly in developing
cheap, effective methods to produce HMF which are readily usable
for industrial scale-up. The newer methods described for HMF
production are also facing isolation problems from polar solvents
Corresponding authors. Tel.: +86 532 80662706; fax: +86 532 80662778.
E-mail addresses: tangyu114@gmail.com (Y. Tang), cuiqiu@qibebt.ac.cn (Q. Cui).
0008-6215/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2011.12.006

such as dimethylsulfoxide (DMSO), DMF, DMP, sulfolane.20,3234

To overcome this disadvantage, the use of organic and inorganic
salts in the synthesis of HMF in aqueous solution was the subject
of numerous works.3539 Recent reports illustrate that the use of
expensive ionic liquid (ILs) gave excellent yields in the conversion
of saccharides into HMF.4050 Along the same lines Dumesic and his
co-workers have developed a two-phase (aqueous/organic) system
for the separation and stablization of the HMF product.10,51 Microwave instead of oil-bath as the heating source was developed.5254
In this work, we developed an efcient and environmentfriendly process for the conversion of fructose into HMF and EMF
(Scheme 1), in which ethanol was used as the solvent and salts
as the promoter. In an optimized process, fructose was converted
into HMF and EMF in 46% isolated yield at 100 C for a reaction
time of 12 h. Levulinic acid ethyl ester (LAEE 6) was formed as
the only byproduct in less than 2% yield.
2. Results and discussion
Firstly, the inuence of addition of different inorganic salts on
the yield of EMF and HMF was surveyed, which is summarized in
Table 1. The stronger Lewis acids showed higher activity in the
conversion of fructose to HMF and EMF at 100 C. For example,
HMF and EMF yields ranging from 23% to 46% were achieved of
FeCl3, CrCl3, SnCl4, NH4Cl. The reaction mixtures were very clean.
The weaker Lewis acids, for example, CuCl2, FeCl2 are not efcient,
and LiCl, NaCl did not work. NH4Cl was found to be the optimal

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J. Liu et al. / Carbohydrate Research 350 (2012) 2024

HO

HO
HO

OH

EtOH

1 D-Fructose

H+

OEt
OH

HO

O +

HO

OH

HO
OH
4 Ethyl fructofuranoside

OH
OH

OEt

OH
OH
5 Ethyl fructopyranoside
O
O
+
O
EtO

EtO

6 LAEE O

3a EMF

2 HMF

Figure 1. Conversion of D-fructose (1) into HMF (2), EMF (3a), and 3b in variety
solvents.

Scheme 1. Conversion of D-fructose (1) into HMF (2) and EMF (3a).

inorganic salt and gave best overall yields of HMF and EMF. Control
experiment showed that the salt plays a key role in the dehydration of D-fructose. Some salts gave very low yields of HMF and
EMF with high D-fructose conversion. The major reason is that in
the rst step of D-fructose dehydration, ethyl fructofuranoside
(4), and ethyl D-fructopyranoside (5)55,56 (a:b = 4:1) were formed
as the major products but could not be dehydrated further when
weak Lewis acids such as NaCl was used as the catalyst. For instance, when the reaction was carried out at 100 C using NaCl
(50 mol %) as the catalyst, no HMF or EMF was formed after 12 h.
But after NH4Cl (50 mol %) was added, the reaction mixture was
stirred for another 12 h. 27% yield of HMF, and 4% yield of EMF
were obtained with 92% conversion of fructose. Effect of the anion
on the hydrolysis was investigated. Based on the low yield of HMF
and EMF in the presence of (NH4)2SO4 and NH4NO3, the nitrate and
sulfate are most likely unfavorable to the reaction. The yields of
HMF and EMF decreased by using bromide as the halide anion.
Furthermore, we tested the effect of solvent on the conversion
of D-fructose (Fig. 1). With 50 mol % NH4Cl at 100 C for 12 h, the
reaction proceeded smoothly in most common solvents. Acetone,
ethyl acetate, and Ethanol gave moderate to good yields of HMF
and EMF. Isopropanol is the best solvent to form HMF as it gave
the total yield of 61% (HMF (58%), 3b (3%)). MeOH gave very good
conversion of fructose, but no desired product was obtained.
Methyl fructofuranoside and methyl D-fructopyranoside were

obtained in 45% yield and 35% as the major products. H2O is an

inefcient solvent for dehydration of fructose to form HMF.
After choosing NH4Cl as the most promising catalyst for the
conversion of fructose to HMF and EMF, the reaction conditions
were further optimized (Table 2). Other factors, such as concentration of the catalyst, temperature, and reaction time were taken into
account. Entries 13 showed the effect on concentration of NH4Cl
on the yield. When the concentration of NH4Cl was controlled at
50 mol % (entry 2), the best overall yield was obtained.
Higher temperature was benecial for the formation of HMF
and EMF (entries 4 and 5), and the better yield and selectivity of
EMF was obtained after prolonging reaction time (entries 2, 79).
The highest yield and selectivity of HMF was obtained in isopropanol which only gave trace isoproxymethylfurfural (3b) (entry 11).
We tested the scalability of our optimized conditions for HMF
and EMF production by performing reactions on 10 g of fructose.
These conditions consistently provide HMF and EMF in total yield
of 42% (entry 13). Microwave irradiation in EtOH gave good yields
of HMF and EMF compared with oil-bath heating, and shortened
the reaction time from 12 h to 10 min (entry 14). But lower yield
of HMF was obtained when the reaction was carried out in isopropanol with mocrowave heating (entry 15). No humin was found in
the solution, as evidenced by the absence of insoluble material in
Table 2
HMF and its derivatives converted from fructose in the ethanol catalyzed by NH4Cla
Entry
c

Table 1
Effect of salts on the conversion of D-fructose to HMF and EMF in ethanola
Catalyst

Conversion (%)

4b (%)

5b (%)

EMFb (%)

HMFc (%)

LiCl
CuCl2
2H2O
NiCl2
6H2O
SnCl4
5H2O
NaCl
FeCl2
4H2O
FeCl3
CrCl3
6H2O
NH4Cl
(NH4)2SO4
NH4NO3
NH4Br
NaCl/NH4Cld

1
87
100
96
100
83
90
100
100
97
87
91
96
92

0
30
0
2
0
32
9
0
0
0
30
24
10

0
22
0
6
5
27
4
0
0
0
26
29
4

0
0
12
5
23
0
0
28
33
10
0
0
7
4

0
0
0
19
0
0
12
0
8
36
0
1
16
27

a
D-Fructose (1 mmol) was mixed with inorganic salts (0.5 mmol) at 100 C for
12 h in ethanol (2 mL).
b
Yield based on NMR analysis.
c
Yield based on NMR and HPLC analysis.
d
The reaction was carried out at 100 C using NaCl (50 mol %) as the catalyst for
12 h. then NH4Cl (50 mol %) was added, the reaction mixture was stirred for another
12 h.

1
2
3d
4
5
6
7
8
9
10e
11f
12g
13h
14i
15f,i

T (C)

Time (h)

Conversion (%)

Ratio (2/3)

Total yieldb (%)

100
100
100
78
120
100
100
100
120
100
120
100
100
120
120

12
12
12
12
12
24
6
18
24
24
12
12
12
10 min
10 min

92
97
97
94
99
99
93
97
100
100
100

98
99
92

100/0
79/21
86/14
92/8
78/22
66/34
94/6
71/29
41/59
94/6
96/4
85/15
81/19
86/14
100/0

8
45
41
14
47
57
16
51
54
61
71
26
42
65
37

a
Reaction were carried out with D-fructose 1 (1 mmol), NH4Cl (0.5 mmol), EtOH
(2 mL) in seal tube unless otherwise noted.
b
Yield was calculated by HPLC, 1H NMR and veried by isolation.
c
NH4Cl (0.1 mmol) was added.
d
NH4Cl (1 mmol) was added.
e
The reaction was run in air pressure.
f
Reaction was run in isopropanol.
g
Inulin as substrate.
h
Reaction were carried out with D-fructose 1 (55.6 mmol), NH4Cl (28 mmol),
EtOH (60 mL).
i
The reaction was carried out with D-fructose 1 (6 mmol), NH4Cl (3 mmol),
alcohol (12 mL) and microwave heating.

22

J. Liu et al. / Carbohydrate Research 350 (2012) 2024

one ethanol molecule. Under similar conditions, reaction of HMF

(2) was indeed converted into EMF (3a) as we postulated in
Scheme 2.

Table 3
Recycling of the catalyst system in the dehydration of D-fructose

Run Num.

Conversion (%)

HMF (%)

3ba (%)

1
2
3
4
5

100
100
99
99
90

65
61
55
52
38

6
4
6
4
0

3. Experimental
3.1. Materials

Yield calculated by HPLC, 1H NMR.

Fructose (extra pure, average particle size) was a commercial

product from Solarbio Company (Beijing, China); ethanol (AR,
>99.7%), ethyl acetate (AR, >99.5%) were purchased from Fuyu
Chemical Company (Tianjin, China); methanol (AR, >99.5%), isopropanol (AR, >99.7%), tert-Butanol (AR, >99.5%), acetone (AR, >99.5%)
were purchased from Jiangtian Chemical Company (Tianjin,
China); Deionized water was used for the preparation of aqueous
solutions. All other reagents and solvents were reagent grade and
were used without further purication.

the reaction vessel using ethanol as solvent. We also found that

after reaction most of the NH4Cl was dissolved in ethanol while
NH4Cl was almost insoluble in isopropanol. So recycling of the catalyst and solvent was possible.
The ability to recycle the catalyst is an important criterion for
practical biomass transformations. The catalyst remains active
after carefully removing the solvent and product. Experiments
were conducted at 120 C for a reaction time of 12 h in isopropanol.
After removal of the organic layer, isopropanol was added to wash
the residue three times after each reaction cycle. An equal amount
of fructose was added and used for next reaction cycle. As shown in
Table 3, the yield of HMF and EMF gradually decreased from 71% to
56% after four cycles, which might be due to the catalyst loss in the
recovering process. In the fth cycle, there was a dramatic decrease
of the yield, and we attributed this to humin formation, which precipitated on the surface of the catalyst that slows the further dehydration process down. It is worth noting that when NH4Cl was
predissolved in isopropanol under standard reaction conditions
without fructose for 12 h and the reaction mixture was ltered,
and the ltrate was then subjected into the reaction with fructose
under typical conditions resulted in 46% yield of HMF as well as 1%
of isoproxymethylfurfural (3b). The success of this experiment has
demonstrated the high degree of homogenous catalysis using
NH4Cl during this reaction as well as heterogenous fashion.
From the above experimental results, the dehydration of fructose to HMF catalyzed by salts is a very complex process. As shown
in Scheme 2, take Bronsted acid for example, intermediate 7 was
formed rst and then can be transformed into intermediate (8)
or ethyl fructoside. Intermediate (8) was treated with ethanol to
form ethyl D-fructopyranoside (5). HMF can be obtained from ethyl
fructofuranoside (4) through removal of two water molecules and

OH

HO

H
OH

HO

In a typical run, 0.18 g of fructose (1 mmol) and 27 mg of NH4Cl

(0.5 mmol) were loaded into a 25 mL glass tube (predried)
equipped with a magnetic stirring bar, then 2.0 mL ethanol was
added. The glass tube was sealed with a stopper and a screw cap
and then heated at 100 C in an oil-bath for a prescriptive time.
After reaction, the solution was transparent and there were no humins or insoluble solid visible.
3.3. Typical procedure for carbohydrate dehydration by
microwave heating
The synthesis was performed in the Anton Paar Synthos 3000,
using Rotor XF100 (80 mL quartz vessels, 80 bar) with immersed
T-probe. The vessel, equipped with a stirring bar, was charged with
1.08 g fructose (6 mmol), 162 mg of NH4Cl (3 mmol), and 12 mL
ethanol. Special openings in the rotor lid give access to the adequate bayonet adaptors on the vessel caps. This allows to prepare
and seal the vessel, place it in the rotor, close the rotor accordingly
and put it into the instrument. As a noteworthy safety measure,
there is no need to carry around pressurized reaction vessels. Finally, with a maximum of 600 W the mixtures were heated at 120 C
for a total time of 10 min.

OEt

HO

OH

3.2. Dehydration of fructose by oil-bath heating

OH
HO

4 OH

EtOH (-H )
LA
H
HO

OH
HO

OH

(-H+)

OH

O
OH
HO

OH

OH

O
OH

HO

OH

(-2H2O)

HO

OH
OH
8

O
O
2

OEt

EtOH (-H )

LA

OR
ROH (-H2O)

HO

O
O
3a (R = Et)
3b (R = i-Pr)

Scheme 2. Putative mechanism for the dehydration of D-fructose.

OH
OH

OH
5

(-H+)

HO

J. Liu et al. / Carbohydrate Research 350 (2012) 2024

23

3.4. Fructose analysis

Acknowledgments

The Fructose concentration after reaction was determined using

high performance ion chromatography (Dionex ICS3000) equipped
with electrochemical detector and CarboPac PA-20 column (column temperature was set at 303 K and ow rate at 0.5 mL/min).
Fructose retention time is 10.3 min.

This work was funded by grants KSCX2-YW-G-066 from The

Chinese Academy of Science, 30970050 from the National Natural
Science Foundation of China, 1102 from Fund Foundation of Tianjin
University. We thank Dr. Xiaobo Wan for prof-reading.
References

3.5. Analysis of EMF and LAEE

HMF was analyzed by HPLC(Waters) equipped with Waters
2489 UV/Visible Detector, Waters 1525 Binary Pump, C18 column
(SunFire C18 5 lm 250  4.6 mm). EMF and LAEE yields were obtained via 1H NMR using 25 lL of mesitylene as the standard.
EMF and LAEE yields were calculated by the integration of proton
peaks of EMF (4.52 ppm), LAEE (2.76 ppm) and mesitylene
(6.80 ppm). The yield of HMF is the average of three different types
of methods.
5-i-Propoxymethylfurfural (3b). Rf = 0.35 [20% EtOAchexane];
1
H NMR (400 MHz, CDCl3) d 1.21(d, 6H J = 6.0 Hz), 3.73 (sep, 1H,
J = 6.0 Hz), 4.54 (s, 2H), 6.51 (d, 1H, J = 3.6 Hz), 7.21 (d, 1H,
J = 3.6 Hz), 9.61 (s, 1H); 13C NMR (100 MHz, CDCl3) d 21.9, 62.5,
72.1, 110.7, 122.1, 152.5, 159.4, 177.6.
Ethyl fructofuranoside (4). Rf = 0.60 [CH2Cl2CH3OH = 7:1]; 1H
NMR (600 MHz, CD3OD, ppm) d 1.17 (t, 3H, J = 7.2 Hz), 3.56
3.67 (m, 4H), 3.69 (d, 1H, J = 12.0 Hz), 3.74 (dd, 1H, J = 2.8,
3.0 Hz), 3.823.90 (m, 2H), 4.04 (d, 1H, J = 4.8 Hz); 13C NMR
(150 MHz, CD3OD, ppm) d 16.1, 57.7, 61.5, 62.7, 78.6, 83.1, 84.1,
108.9.
Ethyl a-fructopyranoside (5). Rf = 0.42 [CH2Cl2CH3OH = 7:1];
1
H NMR (600 MHz, CD3OD, ppm) d 1.15 (t, 3H, J = 7.2 Hz), 3.51
3.61 (m, 3H), 3.643.79 (m, 4H), 3.94 (t, 1H, J = 7.8 Hz), 4.09 (d,
1H, J = 7.8 Hz); 13C NMR (150 MHz, CD3OD, ppm) d 16.1, 57.9,
61.9, 65.0, 77.3, 78.3, 83.4, 105.3; mass spectrum (ESI+ Na)+: m/e
(% relative intensity) 231.0 (100).
Ethyl b-fructopyranoside (5). Rf = 0.42 [CH2Cl2CH3OH = 7:1];
1
H NMR (600 MHz, CD3OD, ppm) d 1.18 (t, 3H, J = 7.2 Hz), 3.51
3.61 (m, 3H), 3.643.79 (m, 4H), 3.83 (t, 1H, J = 7.8 Hz), 3.90 (d,
1H, J = 9.6 Hz); 13C NMR (150 MHz, CD3OD, ppm) d 15.9, 57.3,
63.4, 65.2, 70.4, 71.1, 71.6, 101.8; mass spectrum (ESI+ Na)+: m/e
(% relative intensity) 231.0 (100).
Methyl fructofuranoside. Rf = 0.48 [CH2Cl2CH3OH = 7:1]; 1H
NMR (600 MHz, D2O, ppm) d 3.31 (s, 1H), 3.653.70 (m, 2H), 3.78
(d, 1H, J = 12.6 Hz), 3.80 (dd, 1H, J = 2.6, 2.8 Hz), 3.943.98 (m,
2H), 4.09 (d, 1H, J = 2.8 Hz); 13C NMR (150 MHz, D2O, ppm) d
48.1, 57.5, 61.2, 77.3, 79.9, 83.3, 108.2.
Methyl a-fructopyranoside. Rf = 0.32 [CH2Cl2CH3OH = 7:1]; 1H
NMR (600 MHz, D2O, ppm) d 3.31 (s, 1H), 3.633.66 (m, 2H), 3.71
(d, 1H, J = 12.6 Hz), 3.773.87 (m, 3H), 4.05 (t, 1H, J = 7.8 Hz),
4.16 (d, 1H, J = 8.4 Hz); 13C NMR (150 MHz, D2O, ppm) d 48.7,
59.5, 62.5, 74.8, 76.6, 81.1, 103.6.
Methyl b-fructopyranoside. Rf = 0.32 [CH2Cl2CH3OH = 7:1] 1H
NMR (600 MHz, D2O, ppm) d 3.28 (s, 3H), 3.633.66 (m, 2H), 3.71
(d, 1H, J = 12.6 Hz), 3.773.87 (m, 3H), 3.91 (d, 1H, J = 10.2 Hz),
3.97 (m, 1H); 13C NMR (150 MHz, D2O, ppm) d 48.3, 60.7, 63.7,
68.2, 69.0, 69.5, 100.3.
In conclusion, we have demonstrated that HMF and EMF can be
obtained in good yields through the NH4Cl promoted dehydration
of D-fructose either in ethanol or in isopropanol. Isopropanol
showed better selectivity toward HMF. No mineral acids such as
HCl or H2SO4 are required. Although challenges remain for
commercial application, this research opens a new environmentfriendly path for HMF and EMF production as biomass-derived
liquid transportation fuels.

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