Highly efficient catalytic activity of lanthanide(III) ions for conversion of saccharides to 5-hydroxymethyl-2-furfural in organic solvents

Article abstract of DOI:10.1246/cl.2000.22

All lanthanide(III) ions were found to catalyze dehydration of saccharides to 5-hydroxymethyl-2-furfural (HMF) in DMSO at 100 - 120 °C. Particularly, D-fructose was almost quantitatively converted to HMF without generating any byproducts. The results of the reaction with di- and trisaccharides indicated that the D-fructose moiety in the substrates was selectively converted to HMF.

Full text of DOI:10.1246/cl.2000.22

2
2
Chemistry Letters 2000
Highly Efficient Catalytic Activity of Lanthanide(III) Ions for Conversion of Saccharides
to 5-Hydroxymethyl-2-furfural in Organic Solvents
†
, †
Kei-ichi Seri, Yoshihisa Inoue, and Hitoshi Ishida*
Interior Design Research Institute, Fukuoka Industrial Technology Center, Ohkawa, Fukuoka 831-0031
†
Inoue Photochirogenesis Project, ERATO, JST, 4-6-3 Kamishinden, Toyonaka, Osaka 560-0085
(Received September 22, 1999; CL-990812)
All lanthanide(III) ions were found to catalyze dehydration
of saccharides to 5-hydroxymethyl-2-furfural (HMF) in DMSO
at 100 - 120 °C. Particularly, D-fructose was almost quantita-
tively converted to HMF without generating any byproducts.
The results of the reaction with di- and trisaccharides indicated
that the D-fructose moiety in the substrates was selectively con-
verted to HMF.
Utilization of saccharides, the most abundant biomass, as a
carbon resource has been strenuously explored. In particular,
the conversion of hexose into HMF (eq. 1) has been investigat-
ed as an industrial utilization of saccharides.1-4 This reaction
has been catalyzed by Brønsted acids such as hydrogen chlo-
ride and sulfuric acid in aqueous solutions. Under such condi-
tions, however, the product HMF tends to decompose to lev-
ulinic acid by the acid catalysts and the yield remains moder-
ate; e.g., the reported HMF yield was 26% in an aqueous solu-
3
tion of D-fructose (0.5 M) and HCl (0.5 M) at 95 °C. We have
sulfolane, the reaction did not further proceed after the HMF
yield attained to ca. 50%. In 1,4-dioxane and 1-butanol, HMF
was generated much more slowly than in the other solvents,
and the ultimate HMF yields were ca. 25%.
found that lanthanide(III) ions can catalyze the dehydration of
D-glucose into HMF, however, the yield was quite low; the
maximum yield was 8% with ErCl catalyst in water at 140 °C
3
5
in an autoclave. Moreover, the catalytic activity toward the
Next, the catalytic activities of the other lanthanide ions
other saccharides has never been reported. We report herein
that the conversion of saccharides to HMF efficiently proceeds
in the presence of lanthanide(III) ion catalysts. We will also
describe that fructose was almost quantitatively converted to
HMF in DMSO and only the fructose moiety was selectively
dehydrated in di- or trisaccharides substrates.
than LaCl were examined. The yields of HMF from D-fructose
3
in DMSO at 100 °C for 12 h were 90.5, 91.8, 93.0, 94.8% for
NdCl , EuCl , DyCl , and LuCl catalysts, respectively. Thus,
3
3
3
3
all of the lanthanide ions examined were satisfactorily good
catalysts for the reaction, and the yields were almost independ-
ent of the lanthanide(III) ion employed.
The reaction was carried out by heating an organic solu-
tion (50 cm ) containing a saccharide (0.20 M) and a lan-
Lanthanide(III) ions have been used as Lewis acid cata-
lyst. It is also reported that lanthanide(III) ions are strongly
3
6
thanide(III) ion (5.0 - 10.0 mM) under an N atmosphere at 100
hydrated and therefore the reaction could be inhibited or influ-
enced by the existence of water, which is generated during the
2
7
-
120 °C. Quantitative analysis of HMF was performed by gas
chromatography on a polyethylene glycol 20M column
reaction. Hence we examined the effects of water on the con-
version of saccharides to HMF. The reaction of D-fructose by
(Shimadzu GC-9A (FID)).
In representative experiments, dehydration of D-fructose
LaCl in 10%-water/DMSO at 100 °C proceeded slower than in
3
catalyzed by LaCl was examined in six solvent systems at 100
DMSO, but the yield of HMF, 90.4% after 24 h in 10%-
water/DMSO, is virtually the same as that in DMSO, 95.2%
after 4 h. The results clearly indicate that the presence of water
up to 10% do not affect the HMF yields.
3
°
C (Figure 1). The reaction efficiently proceeded in DMSO,
DMF, and DMA. The yields of HMF attained to more than
0% after 4 h. Neither byproducts nor levulinic acid, which
9
would be generated as a decomposition product of HMF, was
observed. Among these solvents, DMSO gave the best yields
up to 95.2%. The turnover number for the reaction was 38, evi-
dently indicating that the reaction proceeded catalytically. In
The reactions of various saccharides catalyzed by LaCl in
3
DMSO were examined (Table 1). Although aldoses such as D-
glucose, D-galactose, D-mannose in mono-saccharides scarcely
produced HMF (yields < 10%), the yields of HMF for ketoses
Copyright © 2000 The Chemical Society of Japan

Chemistry Letters 2000
23
(
e.g. D-fructose and L-sorbose) were considerably high. In par-
Also, the hydroxyl groups at 1 and 3 positions of D-fructose
was suggested to be involved in the dehydration reaction. The
interaction between a lanthanide(III) ion and a saccharide on a
molecular level is currently under investigation.
ticular, D-fructose almost quantitatively produced HMF. More
interestingly, the yield (61.4%) of HMF from L-sorbose, which
possesses different C3 and C4 hydroxyl configuration, was
smaller than that for D-fructose. A similar tendency is observed
in the results for disaccharides. Although the disaccharides
consisting of only aldoses scarcely yielded HMF (data not
shown), the HMF yields from the disaccharides containing D-
fructose were relatively high. Specifically, sucrose, in which D-
fructose connects with D-glucose (aldose) at 2 position, did
The present work was supported by a Grant-in-Aid for
Scientific Research on Priority Areas “New Development of
Rare Earth Complexes” (No. 08220256) from the Ministry of
Education, Science, Sports, and Culture.
8
produce HMF in 93.0% yield. By considering the results that
References and Notes
aldose scarcely yielded HMF and an equimolar HMF was gen-
erated from sucrose, we conclude that the D-fructose moiety
was selectively converted to HMF. In contrast, palatinose and
turanose, in which D-fructose binds with D-glucose at 1 and 3
positions, gave relatively fewer amounts of HMF in 35.8 and
1
2
C. J. Moye, Aust. J. Chem. 19, 2317 (1966).
D. W. Harris and M. S. Feather, J. Org. Chem., 39, 724
(1974).
B. F. M. Kuster and H. S. Van der Baan, Carbohydr. Res.,
54, 165 (1977).
H. H. Szmant and D. D. Chundury, J. Chem. Tech.
Biotechnol., 31, 135 (1981).
H. Ishida and K. Seri, J. Mol. Catal. A: Chem., 112, L163
(1996).
3
4
5
2
4.8% yields, respectively. The similar propensity was also
observed in the results for trisaccharides: raffinose (D-fructose
connects at 2 position) gave the higher HMF yield (64.8%)
than melezitose (D-fructose connects at 2 and 3 positions;
2
3.8% yield).
6
7
S. Kobayashi, Synlett, 689 (1994).
K. Araki, T. Kajikawa, and S. Kawaguchi, Chem. Lett.,
1996, 295.
D-Glucose (170.3 mM, 85.2% yield) was also detected
from the same solution by an HPLC analysis.
In summary, it was found that lanthanide(III) ions effi-
ciently catalyze dehydration of saccharides, particularly D-fruc-
tose, in organic solvents such as DMSO. D-Fructose in di- and
trisaccharides was found to be selectively converted to HMF.
8