Transformation of glucose to 5-hydroxymethyl-2-furfural by SiO 2-MgCl2 composite

Article abstract of DOI:10.1246/bcsj.20100337

5-Hydroxymethyl-2-furfural (2a) was formed in a 70% yield by dehydration of glucose in MeCN at 140°C in an autoclave using a composite of MgCl ₂ with silica gel which served as an acid catalyst under dry conditions. 10% and 32% yields of 2a were obtained from mannose and galactose, respectively.

Full text of DOI:10.1246/bcsj.20100337

4
16
Bull. Chem. Soc. Jpn. Vol. 84, No. 4, 416–418 (2011)
Short Articles
Under dry conditions
Si OH
Transformation of Glucose to
-Hydroxymethyl-2-furfural
by SiO ­MgCl Composite
Si O
O
+ MCl2
O
Si O
M
+ 2 HCl
(1)
5
Si OH
2
2
(SiO2) M= Mg, Ca
In the presence of H O
2
Masahide Yasuda,* Yasuhisa Nakamura,
Jin Matsumoto, Haruhiko Yokoi, and
Tsutomu Shiragami
Si O
Si OH
Si OH
O
Si
M
+ 2H O
O
+ M(OH)2
(2)
2
O
Department of Applied Chemistry, Faculty of Engineering,
University of Miyazaki, 1-1 Gakuen-Kibanadai-Nishi,
Miyazaki 889-2192
Scheme 2.
have applied the water-dependant pH-change to develop an
SiO ­MgCl ­porphyrin composite acting as humidity indica-
tors of desiccants. Under dry conditions the protonated
porphyrin was formed and turned to free base porphyrins under
wet conditions, resulting in the color change from green to
2
2
11
Received December 1, 2010
E-mail: yasuda@cc.miyazaki-u.ac.jp
pink-orange. The acidity (pK ) of 3a was estimated to be 1.7
a
1
2
5
-Hydroxymethyl-2-furfural (2a) was formed in a 70%
under dry conditions. Thus, it was found that the pH of 3 can
be controlled by the presence of water. If 3 can catalyze the
dehydration of 1, it will provide an environmentally conscious
process without requiring strong acid and alkali.
yield by dehydration of glucose in MeCN at 140 °C in an
autoclave using a composite of MgCl2 with silica gel which
served as an acid catalyst under dry conditions. 10% and 32%
yields of 2a were obtained from mannose and galactose,
respectively.
SiO (1.0 g; 40 ¯mº; Fuji Silysia BW 300) was added to a
2
3
MeOH solution (40 cm ) of MgCl ¢6H O (68­806 mg). After
2
2
standing for 3 h at room temperature, the solvent was
evaporated and dried under reduced pressure at 50 °C for 24 h
to give 3a where the content of MgCl was 3­38 wt %/SiO .
Chemical transformation of biomass to organic chemicals
2
2
has been receiving much attention from the standpoint of
organic synthesis using a renewable carbon source. Saccha-
Also the SiO ­CaCl composite 3b with 12­31 wt %/SiO2
2 2
content of CaCl2 was prepared.
1
rides 1 are C5 and C6 carbon sources available from biomass.
Especially glucose (1a) is an abundant monosaccharide
obtained by the saccharification of cellulose and starch. A
typical transformation of 1 is the transformation from hexose
and pentose to 5-hydroxymethyl-2-furfural (2a) and 2-furfural
1a was soluble in highly polar solvents such as dimethyl
sulfoxide (DMSO) and N,N-dimethylformamide but the sepa-
ration of 2a from these solvents was troublesome in the follow-
1
3
up procedure. Also toluene where 1a was insoluble was poor
solvent for the formation of 2a. Therefore, 1a (0.5 g) and SiO
2
3
(
2b) which are versatile compounds for the transformation to
(1.0 g)­MCl 3 were suspended in MeCN (40 cm ) where 1a
2
a variety of chemicals (Scheme 1). The formation of 2 from
aldose proceeded via aldose­ketose (A­K) isomerization of 1
and the successive dehydration in the presence of acid
was slightly soluble and then heated under stirring in an
autoclave at various temperatures. After the reaction, 3 was
separated from the reactants by filtration and then the solvent
was evaporated to give crude 2a. The 2a was purified by
column chromatography. The yields are summarized in
Table 1. The yield of 2a was plotted against the content of
MCl in 3 (Figure 1). The optimized content of MgCl was
2
catalysts. Instead of mineral acid such as the H SO , H PO ,
2
4
3
4
or HI used in earlier studies,3 a variety of heterogeneous
­5
6
catalysts involving solid acid (H-form zeolite, ion-exchange
7
8
9
resins, and metal oxide ) and protic ionic liquids have been
used in the transformation of 1 to 2 for convenience of
separation and recycling.
2
2
32 wt %/SiO . The reaction of 1a using SiO without the MCl
2
2
2
2
did not provide 2a at all (Run 5). Moreover, the SiO ­CaCl
2
Recently we have studied the application of a composite
composite 3b was ineffective for the formation of 2a (Run 6).
(
3; SiO ­MCl ) of MCl (M = Mg and Ca) with silica gel
Here, the formed H O was removed from the solvent by
2
2
2
2
which can generate protons under dry conditions (eq 1 in
adsorption with SiO to maintain the acidic condition of 3. The
2
1
0
Scheme 2). In the presence of H O, 3a (M = Mg) readily
maximum yield of 2a from 1a was 70% which was obtained
from the reaction at 140 °C for 24 h using 3a with 32 wt %/
SiO2 of the content of MgCl2 (Run 2 in Table 1). This
2
turned neutral without the addition of other alkali (eq 2). We
R
2
14
exceeded the maximum yields (53% and 58% ) reported for
the heterogeneous catalytic formation of 2a from 1a so far. In
homogeneous catalytic reaction, 90% yield was reported for
O
O
O
OH
CHO
R
R
HO
HO
OH
OH − 3 H2O
OH
(aldose)
HO
OH
formation of 2a from 1a using CrCl in ionic liquid under
3
2
a; R= CH OH
2b; R= H
15
2
microwave irradiation.
1
1 (ketose)
Time-conversion plots for the transformation from 1a to 2a
are shown in Figure 2. The yield of 2a reached its maximum at
Scheme 1.
Published on the web March 30, 2011; doi:10.1246/bcsj.20100337

M. Yasuda et al.
Bull. Chem. Soc. Jpn. Vol. 84, No. 4 (2011)
417
Table 1. Formation of Furfural Derivatives 2 from Saccha-
rides 1 Using SiO2­MCl2 Composite 3
90
a)
8
0
Run
1
3 (MCl2/wt %)b)
Temp/°Cc)
2 (Yield/%)
1
2
3
4
5
6
7
8
9
1a
1a
1a
1a
1a
1a
SiO2­MgCl2 (32)
SiO2­MgCl2 (32)
SiO2­MgCl2 (32)
SiO2­MgCl2 (32)
SiO2
160
140
120
100
140
140
140
140
140
140
140
140
180
2a (72)
2a (70)
2a (1)
2a (0)
2a (0)
2a (19)
2a (10) [9]
2a (32) [11]
2a (82)
2a (32)
70
6
5
4
3
0
0
0
0
SiO2­CaCl2 (25)
d)
1b SiO2­MgCl2 (32)
1c SiO2­MgCl2 (32)
1d SiO2­MgCl2 (32)
1e
1f
d)
10
SiO2­MgCl2 (32)
SiO2­MgCl2 (32)
SiO2­MgCl2 (32)
20
10
0
1
1
2a (10)
2a (31)
2b (17)
1
1
2
3
1g
e)
1h SiO2­MgCl2 (23)
3
a) Reaction was performed for MeCN (40 cm ) containing 1
0.5 g) and SiO2 (1.0 g)­MCl2 3 at a given temperature for
4 h in autoclave. b) The values in parenthesis were the content
0
5
10
15
20
25
(
2
Reaction time/h
of MCl2 (wt %) in SiO2. c) Reaction temperature. d) In
3
Figure 2. Time-conversion plots of the yields of 2a in the
reaction of glucose (1a; ), mannose (1b; ), galactose
MeCN­DMSO (9:1, 40 cm ) at 140 °C for 24 h. e) Reaction
3
was performed for MeCN (40 cm ) containing 1 (2.5 g) and
(
1c; ), fructose (1d; ), and sorbose (1e; ) under 140 °C
SiO2 (1.0 g)­MgCl2 (0.23 g) at 180 °C for 1.5 h.
using the SiO2­MgCl2 (32 wt %).
8
6
4
2
0
0
0
0
0
1
2
CHO
OH
CHO
H
H
HO
H
6
5
1
HO
HO
H
HO
OH
3
O
H
OH
H
2
4
5
HO
OH
OH
4
3
H
OH
H
OH
OH
6
CH2OH
CH2OH
Glucose (1a)
Fructose (1d)
Mannose (1b)
CHO
CH2OH
O
CHO
H
HO
HO
H
OH
H
H
HO
H
OH
H
H
HO
H
OH
H
H
OH
0
5
10 15 20 25 30 35 40
OH
OH
CH OH
CH OH
CH2OH
2
MCl /wt%
2
2
Galactose (1c)
Sorbose (1e)
Xylose (1h)
Figure 1. Plots of yield of 5-hydroxymethyl-2-furfural (2a)
against the contents of MgCl2 ( ) and CaCl2 ( ) in SiO2­
MCl2 composites 3 in the reaction of 1a at 140 °C for 24 h.
HO
HO
HO
O
O
O
O
HO
HO
OH
OH
OH
O
O
HO
1
8 h. The dehydration reaction of 1a was compared with that of
OH
OH
OH
OH
other aldoses such as mannose (1b) and galactose (1c) and
ketoses such as fructose (1d) and sorbose (1e) (Scheme 3). The
conversions of 1b and 1c were slow. The conversion of 1d was
similar to the case of 1a. Although A­K isomerization of both
HO
Sucrose (1g)
HO
OH Cellobiose (1f)
Scheme 3. Monosaccharides 1a­1c, 1e, and 1h shown by
Fisher projection form and fructose (1d) and disaccharides
1f and 1g written by furanose and pyranose forms.
1
a and 1b gave the same 1d, the conversion of 1b was very
slow compared with that of 1a. Ketohexoses are known to
produce 2a more efficiently than aldohexoses.1 Therefore, it
was suggested that the A­K isomerization was the rate-
determining step in the case of 1b. Ebitani et al. have promoted
A­K isomerization of 1 using a combination of basic hydro-
6
ketoses is preferable since the conversion of 1c and 1e was
slower than that of 1a and 1d. It has been reported that DMSO
performs effectively as base for dehydration. In the present
cases, however, the reaction of 1c in MeCN­DMSO (v/v 9:1)
could not enhance the yield of 2a (Runs 7 and 8).
1
7
µ 14
talcite and acidic Amberlyst-15 . Moreover, it was suggested
that cis-elimination of H O from the C-4 and C-5 positions of
2

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Bull. Chem. Soc. Jpn. Vol. 84, No. 4 (2011)
© 2011 The Chemical Society of Japan
The 2a was obtained in 10% and 31% yields from
(s, 1H); 13C NMR: ¤ 57.02, 110.06, 124.11, 151.96, 161.44,
disaccharides such as cellobiose (1f) and sucrose (1g),
respectively (Table 1, Runs 11 and 12). The bond-fission of
the ¢-1,4-bond in 1f showed the possibility of the formation of
173.05.
1
2-Furfural (2b): Oil. H NMR: ¤ 6.63 (dd, J = 3.6, 1.6 Hz,
1H), 7.29 (d, J = 3.6 Hz, 1H), 7.72 (brt, J = 1.6 Hz, 1H), 9.67
(s, 1H); C NMR: ¤ 112.42, 121.63, 148.08, 152.64, 177.59.
1
3
2
a from cellulose. However, 2-furfural (2b) was formed from
xylose (1h) in only a 17% yield under the optimized reaction
conditions at 180 °C for 1.5 h using 3a where the content of
MgCl was 23 wt %/SiO (Run 13). These show that 3a is a
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2