Glucose to value-added chemicals: Anhydroglucose formation by selective dehydration over solid acid catalysts

Article abstract of DOI:10.1246/cl.2009.650

Selective dehydration of glucose to anhydroglucoses, 1,6-anhydro-β-D- glucopyranose (levoglucosan) and 1,6-anhydro-β-D-glucofuranose, which are highly value-added intermediates for drugs, polymers, and surfactants was performed. Solid acids with sulfonic acid groups like Amberlyst-15 were found to effectively produce anhydroglucoses in polar aprotic solvents. Copyright

Full text of DOI:10.1246/cl.2009.650

6
50
Chemistry Letters Vol.38, No.7 (2009)
Glucose to Value-added Chemicals: Anhydroglucose Formation
by Selective Dehydration over Solid Acid Catalysts
ꢀ
Atsushi Takagaki and Kohki Ebitani
School of Materials Science, Japan Advanced Institute of Science and Technology,
1-1 Asahidai, Nomi 923-1292
(Received March 9, 2009; CL-090239; E-mail: ebitani@jaist.ac.jp)
Selective dehydration of glucose to anhydroglucoses, 1,6-
anhydro-ꢀ-D-glucopyranose (levoglucosan) and 1,6-anhydro-
-D-glucofuranose, which are highly value-added intermediates
for drugs, polymers, and surfactants was performed. Solid acids
with sulfonic acid groups like Amberlyst-15 were found to effec-
tively produce anhydroglucoses in polar aprotic solvents.
tive dehydration of glucose over solid acid catalysts under mild
conditions. Solid acid catalysts offer the opportunity to reduce
environmental impact because of easy separation from product,
nontoxicity, and reusability.
ꢀ
A general reaction scheme for glucose transformation ac-
9
cording to the literature is shown in Figure 1. 1,6-Anhydro-ꢀ-
D-glucopyranose (AGP, levoglucosan) and 1,6-anhydro-ꢀ-D-
glucofuranose (AGF) were formed by intramolecular dehydra-
tion of glucopyranose and glucofuranose, respectively, where
pyranose and furanose forms are under tautomeric equilibrium.
The reaction was performed using 0.1 g of solid acid cata-
lyst, 0.1 g of glucose and 3 mL of solvent at 373–393 K.10 The
typical results of dehydration of glucose in N,N-dimethylform-
amide (DMF) over several solid acid catalysts at 373 K for 3 h
are listed in Table 1. Ion-exchange resins, metal oxides, clay,
and H-type zeolites were used as solid acid catalysts.
Production of chemicals such as solvents, surfactants, poly-
mers, cosmetics, and pharmaceuticals deeply rely on petroleum
resources. They should be however, synthesized from renewable
resources from the viewpoint of severe global warming. The
concept of carbon-neutral allows us to utilize biomass as a
1
nonpetroleum candidate to overcome this problem. Among
biomass utilization, cellulose conversion from wood including
gasification and hydrolysis has attracted considerable attention
2
–4
because of the nonfood nature and universal availability.
Amberlyst-15 which is a styrene–divinylbenzene sulfonated
ion-exchange resin was found to produce anhydroglucoses, AGP
and AGF; high conversion and selectivity were achieved at
393 K. Nafion NR50, a perfluorinated resin sulfonic acid also ex-
hibits moderate activity for selective dehydration of glucose with
high selectivity. Other conventional solid acids such as niobic
acid, SO4/ZrO2, H-montmorillonite, and H-type zeolites
(HZSM-5 and HY) were inactive for the reaction. Under the
above conditions, fructose by isomerization and HMF by elimi-
nation of three water molecules were not obtained in any case.
This selective dehydration also proceeded in other polar aprotic
solvents which can dissolve glucose such as dimethyl sulfoxide,
1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, and sul-
Glucose, which is produced by hydrolysis of cellulose, is further
transformed into ethanol as biofuel by fermentation, 5-(hydroxy-
methyl)furfural and sorbitol as chemical intermediates by cata-
lytic processes.
Dehydration of glucose gives two products, 5-(hydroxy-
methyl)furfural and anhydroglucose as shown in Figure 1; the
former is obtained by removal of three water molecules and
the latter is by one water. Little has been reported about the for-
mation of anhydroglucose, though anhydroglucose is a highly
5
value-added chemical for drugs, surfactants, and polymers,
e.g., ring-opening polymerization of anhydrosugars results in
the formation of hyperbranched polysaccharides with spherical
6
10
macromolecular structure.
Anhydroglucose has been obtained by tosylation of glucose
folane at comparable yields to that in DMF.
7
and successive neutralization by sodium hydroxide, pyrolysis
8
Table 1. Anhydroglucose formation from D-glucose over solid
a
of starch or cellulosic biomass, and noncatalytic dehydration
9
acids
from glucose at high temperatures, typically above 573 K. Here
we demonstrate efficient production of anhydroglucose by selec-
Conversion
Yield/% (Selectivity/%)
AGPb AGFc AGP þ AGF
Catalyst
/%
Amberlyst-15
69
88
34
7
15
33
12
0
0
0
0
0
0
0
17
30
14
0
0
0
0
0
0
0
32 (47)
63 (71)
26 (77)
OH
O
d
d
d
d
O
O
Dehydration
- H
OH
OH
OH
OH
OH
Isomerization
HO
OH
2
O
Nafion NR50
e
O
HO
OH
OH
SO /ZrO
4
2
0
0
0
0
0
0
0
OH
Glucopyarnose
1,6-anhydro-β-D-glucopyarnose
OH
(AGP, levoglucosan)
Nb O nH O
2
.
12
2
6
2
4
5
2
Fructose
Dehydration
Tautomeric
equilibrium
TiO
H-Mont
2
Dehydration - 3H
2
O
-
2
3H O
f
HZSM-5
g
HO
CH
2
OH
HO
O
HO
O
O
Dehydration
O
HY
Blank
OH
O
OH
OH
-
2
H O
2
OH
OH
5
-(hydroxymethyl)furfural
HMF)
Glucofuranose
Glucose
1,6-anhydro-β-D-glucofuranose
a
Reaction conditions: glucose (0.1 g), catalyst (0.1 g), DMF
3 mL), 373 K, 3 h. 1,6-Anhydro-ꢀ-D-glucopyranose. 1,6-
d e
(
(AGF)
b
c
(
Anhydro-ꢀ-D-glucofuranose. 393 K. From Wako Pure
Chemicals. JRC-Z5-90H. JRC-Z-HY5.5.
f
g
Figure 1. A reaction scheme for glucose transformation.
Copyright Ó 2009 The Chemical Society of Japan

Chemistry Letters Vol.38, No.7 (2009)
651
Table 2. Anhydroglucose formation from D-glucose over solid
a
(A) 373 K
80
(B) 393 K
80
and liquid sulfonic acids
7
0
70
60
50
40
30
20
10
0
Reaction Conv. Yield/% (Selectivity/%)
Conv.
b
60
Catalyst
5
4
0
0
AGP + AGF
AGP
temp/K /% AGP AGF AGP þ AGF
Conv.
Amberlyst-15
Nafion NR50
Nafion SAC13
373
93
373
93
373
93
28
66
36
58
25
71
60
57
14
25
13
15
12
13
15
13
14
22
14
17
11
17
16
15
28 (>99)
46 (70)
26 (75)
32 (56)
24 (96)
30 (43)
31 (52)
29 (51)
30
AGP + AGF
2
1
0
0
0
3
AGF
AGP AGF
3
0
2
4
6
8
0
2
4
6
8
Reaction time /h
Reaction time /h
3
Figure 2. Time courses of glucose dehydration into anhydro-
glucoses over Amberlyst-15 at (A) 373 and (B) 393 K. glucose
conversion ( ), yields of anhydroglucoses (AGP þ AGF) ( ),
yield of AGP ( ), and AGF (ꢃ). Reaction conditions: Glucose
(0.432 mmol), Amberlyst-15 (30 mg, acid amount; 0.144 mmol),
and DMF (36 mmol).
p-TsOH
H2SO4
373
373
a
Reaction conditions: mole ratio of acid amount of catalyst:glu-
cose:DMF = 1:3:250. 3 h. Acid amounts of samples tested are
b
ꢁ1
4.8, 0.9, 0.15, 5.3, and 20.4 mmol g for Amberlyst-15, Nafion
NR50, Nafion SAC13, p-TsOH, and H2SO4, respectively.
formed under mild conditions. Amberlyst-15 was found to ex-
hibit remarkably higher selectivity of anhydroglucoses at high
conversions than Nafion and sulfuric acid due to relatively weak
acidity.
Table 2 shows anhydroglucose formation over sulfonated
solid acids, p-toluenesulfonic acid and concentrated sulfuric acid
under a molar ratio of acid catalyst (SO3H groups), glucose, and
DMF of 1:3:250. At 373 K, yields of anhydroglucoses were al-
most the same among solid and liquid acids tested. It should
be noted that Amberlyst-15 and Nafion SAC13, which is a highly
dispersed Nafion on amorphous silica, exhibit excellent selectiv-
ity of anhydroglucoses (above 95%), whereas the selectivity for
p-TsOH and H2SO4 was about 50%. At 393 K, yields of an-
hydroglucoses increased for Amberlyst-15 with high selectivity
This work was supported by a Grant-in-Aid for Young Sci-
entists (Start-up) (No. 20860038) of the Ministry of Education,
Culture, Sports, Science and Technology (MEXT), Japan.
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1
1
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1
2
of Amberlyst-15 (H0 ¼ ꢁ2:2) affords high selectivity whereas
1
3
strong acidity of Nafion (H0 ꢂ ꢁ12) causes undesired oligo-
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5
6
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Time courses of glucose dehydration over Amberlyst-15 at
3
73 and 393 K are shown in Figure 2. At 373 K, considerably
high selectivity of anhydroglucoses (>99%) was obtained over
–3 h. At 393 K, significant increase of yields as well as conver-
7
8
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9
1
1
1
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water inhibits the dehydration because this reaction did not pro-
ceed in water.10 Further investigation is therefore necessary to
improve the reaction system such as flow reactor system to re-
move water continuously and develop solid acids with a high
density of SO3H groups in order to obtain anhydroglucoses with
high yield and selectivity.
0
1
2
D. F a˘ rca sꢀ iu, A. Ghenciu, G. Marino, K. D. Rose, J. Am. Chem. Soc.
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13 G. A. Olah, P. S. Iyer, G. K. S. Prakash, Synthesis 1986, 513.
In summary, selective dehydration of glucose into anhydro-
glucoses over solid acids with sulfonic acid groups was per-
Published on the web (Advance View) May 30, 2009; doi:10.1246/cl.2009.650