Synthesis of glucose esters from cellulose in ionic liquids

Igor A. Ignatyev,a Charlie Van Doorslaer,a Pascal G.N. Mertens,a Koen Binnemans,b and Dirk E.
de Vos*a
* E-mail: dirk.devos@biw.kuleuven.be (D.E. De Vos), Fax: +32 16321998; Tel: + 32 16321610
a

Centre for Surface Chemistry and Catalysis, K.U.Leuven, Kasteelpark Arenberg 23 box 2461,

B-3001, Heverlee, Belgium

b

Department of Chemistry, Molecular Design and Synthesis, K.U.Leuven, Celestijnenlaan 200F

box 2404, B-3001, Heverlee, Belgium

Abstract
The transformation of cellulose into the glucose ester -D-glucose pentaacetate (GPAc) was
carried out in the ionic liquid 1-butyl-3-methylimidazolium chloride under mild reaction
conditions. The reaction comprises two steps: the first involves a hydrolysis reaction, yielding D-glucose and glucose oligomers; only after some time, the acetylating reagent acetic anhydride

is added. Under optimized conditions and with the acidic resin Amberlyst 15DRY as a
hydrolysis catalyst, a 70% yield of GPAc was obtained. This product could be quantitatively
isolated by simple liquid-liquid extraction, which allowed easy recycling of the ionic liquid and
catalyst.
Keywords: acetylation; acid catalysis; cellulose; ionic liquids; heterogeneous catalysis

Introduction
As a major constituent of wood, straw, grass and crop residues (Soltes and Elder 1981) cellulose
is the most abundant biopolymer on the planet (Ragauskas et al. 2006). Transformation of this
renewable resource into commodity chemicals and high-value products may be a profitable
process for the chemical industry (Chheda et al. 2007; Himmel et al. 2007; Romn-Leshkov et
al. 2007). Its very rigid structure and consequently its difficult dissolution and chemical
processing remain however a scientific and technological challenge (Krssig 1993; Jarvis 2003).
1

In contrast with classical organic solvents, which need often extreme conditions to solubilize
cellulose, some ionic liquids display a high cellulose solubility even at moderate temperatures
(Swatloski et al. 2003). In general, the interaction between wood (and wood components) and
ionic liquids belongs to an essential research field in the context of biorefinery (Honglu and
Tiejung 2006; Stasiewicz et al. 2008; Liebner et al. 2010; Jia et al. 2010; Nakamura et al. 2010;
Viell and Marquardt 2011). In particular, chloride- or acetate-based ionic liquids efficiently
dissolve cellulose due to their ability to disrupt the three-dimensional hydrogen bond network of
cellulose (Swatloski et al. 2002; Swatloski et al. 2003; Zhang et al. 2005; Zhu et al. 2006; Fort et
al. 2007; Fukaya et al. 2008; Vitz et al. 2009; Stark 2011). For example, 1-butyl-3methylimidazolium chloride ([BMIm][Cl]) and 1-ethyl-3-methylimidazolium acetate
([EMIm][AcO]) can dissolve up to respectively 25 (Swatloski et al. 2002) and 12 (Vitz et al.
2009) wt.% of cellulose. As could be expected, these two ionic liquids are currently the most
effective solvents for the (chemical) processing of this biopolymer (Swatloski et al. 2002; Kosan
et al. 2008; Rinaldi and Schth 2009; Vitz et al. 2009; Stark 2011).
Various cellulose transformation processes in ILs have been reported (Venkataramanan et al.
2007; Zhang et al. 2007; Rinaldi et al. 2008; Sun et al. 2008; Li et al. 2009; Rinaldi and Schth
2009; Vanoye et al. 2009; Ignatyev et al. 2010; Ignatyev et al. 2010; Peng et al. 2010; Villandier
and Corma 2010; Kim et al. 2011), e.g., acid-catalyzed dehydration into 5hydroxymethylfurfural (Zhang et al. 2011), conversion into levulinic acid (Peng et al. 2010),
production of magnetically active cellulose fibers (Sun et al. 2008), and transformation of
cellulose into alkylglucosides in [BMIm][Cl] in the presence of Amberlyst 15DRY (Ignatyev et
al. 2010; Villandier and Corma 2010). Also derivatisation reactions of cellulose have been
reported before (Wu et al. 2004; Abbott et al. 2005; Heinze et al. 2005; Barthel and Heinze 2006;
Khler et al. 2007; Khler et al. 2008; Cao et al. 2009; Crpy et al. 2009; Gericke et al. 2009;
Khler et al. 2009; Li et al. 2009; Mormann and Wezstein 2009), such as acetylation, which
leads to formation of the valuable product cellulose acetate (Wu et al. 2004; Abbott et al. 2005;
2

Heinze et al. 2005; Barthel and Heinze 2006; Khler et al. 2007; Cao et al. 2009). Synthesis of
monomeric acetylated species from cellulose can also be of high practical interest. Cellulose
hydrolysis was successfully performed in [BMIm][Cl] with glucose as the major product in the
presence of Amberlyst 15DRY and other acidic catalysts (Rinaldi et al. 2008; Vanoye et al.
2009; Rinaldi et al. 2010). Glucose acetylation in ILs, applying acetic anhydride as the
acetylating reagent, has also been reported (Abbott et al. 2005). This prompted us to consider an
alternative cellulose transformation pathway, namely the direct one-pot conversion into -Dglucose pentaacetate (GPAc). GPAc is a valuable compound with multiple applications, such as
the activation of percompounds, like H2O2 and sodium percarbonate (Coxon 1987), which are
applied in bleaching (Nakagawa et al. 1976), disinfection and cold-sterilization processes
(Cavinato et al. 2009). GPAc is also known to promote insulin synthesis and release (Usac et al.
2000). Moreover, this glucose ester can be easily separated from the reaction mixture by liquid
liquid extraction (Gholap et al. 2003). This is a big advantage since the isolation of classical
cellulose hydrolysis products such as glucose and sorbitol from the ionic liquid, is often
problematic due to their higher polarity (Ignatyev et al. 2010; Ignatyev et al. 2010; Villandier
and Corma 2010).
In this paper, the feasibility of the mild transformation of cellulose into -D-glucose pentaacetate
will be demonstrated in [BMIm][Cl], with Amberlyst 15DRY as acidic catalyst.

Materias and methods

1-Butyl-3-methylimidazolium chloride [BMIm][Cl] (99%) was obtained from Ionic Liquids
Technologies GmbH (IoLiTec). 1-Butyl-3-methylimidazolium acetate (95%), -D-glucose
pentaacetate, -D-glucose pentaacetate, cellulose (Avicel PH 101; DP 215240), Nafion SAC-13
and Amberlyst 15DRY were purchased from Sigma-Aldrich. Smopex-101 was purchased from
Alfa Aesar GmbH & Co KG. HNbMoO6 and was prepared in-house based on a literature recipe
(Tagusagawa et al. 2008): LiNbMoO6 was prepared by calcination of a stoichiometric mixture of
Li2CO3, Nb2O5, and MoO3 at 580C. After 12 h of calcination a grinding was performed; then
3

calcination was restarted for another 12 h. Then a proton-exchange reaction towards HNbMoO6
was carried out by shaking LiNbMoO6 in 1 M HNO3 at room temperature for 1 week.
Afterwards the product was washed with distilled water and dried in air at 343 K. Other
chemicals were obtained from commercial suppliers and were used as received.
Typical reaction procedure
Reactions were performed in sealed glass vials (10 ml) with continuous stirring. In a typical
reaction, 0.05 g cellulose was hydrolyzed in 1 g [BMIm][Cl] for 4 h at 110C in the presence of
Amberlyst 15DRY (0.005 g) and 20 L water. Next, Amberlyst 15DRY particles were removed
from a fraction of the reaction mixture (0.1 ml), and the resulting mixture was acetylated with
0.17 ml acetic anhydride at 100C for 16 h.
Separation of reaction product and IL/catalyst recycling
Amberlyst 15DRY particles were removed from the IL and regenerated by washing with 95-97%
sulfuric acid according to a procedure described elsewhere (Rinaldi et al. 2010). The IL phase
was stirred with n-Bu2O in a 1:5 volume ratio at 80C for 1 h. In this way the product was nearly
quantitatively extracted into the ether phase. The remaining 1 ml IL and the regenerated catalyst
were then reused for a second transformation of cellulose into GPAc under the conditions
described in paragraph 2.2.
Analysis
Prior to GC and GC-MS analysis glucose and similar compounds with free hydroxyl groups
were silylated with N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA). Typically, a fourfold excess of MSTFA with respect to the hydroxyl groups was added to 0.1 ml of reaction
mixture. This was mixed with 0.3 ml of pyridine, and stirred for 3 h at 80C. The silylated
compounds were then extracted into 0.5 ml of dibutylether. The extraction procedure was
optimized and confirmed to be quantitative by means of known amounts of reference compounds
such as glucose, -D-glucose pentaacetate, -D-glucose pentaacetate, levoglucosan,
hydroxymethylfurfural, and cellobiose. Quantitative and qualitative GC analyses were performed
4

on a 30 m HP-1 column in a GC (HP 5890) or a GC-MS (Agilent 6890 GC and 5973 MS)
instrument.
The depolymerization of cellulose was followed by gel-permeation chromatography (GPC) of
the tricarbanilate derivatives of the cellulose samples. Dried isolated cellulose (0.005 g) was
derivatized with phenylisocyanate (0.1 ml) in DMSO (1 ml) at 70C, resulting in cellulose
tricarbanilates, which are readily soluble in THF (Evans et al. 1989). The GPC analysis was
carried out at 35C with a Shimadzu HPLC LC10 instrument. For the detection of the derivates a
UV-Vis detector at 236 nm was used. The system was calibrated with polystyrene standards.
The water content of the ILs was determined with a coulometric Karl-Fischer titrator (Mettler
Toledo DL39). The level of water contamination of [BMIm][Cl] and 1-butyl-3methylimidazolium acetate was found to be ca. 0.1 wt.%.
The concentration of H+-cations, released from Amberlyst 15DRY beads, was detected by
titration with 0.0001 M NaOH with a Metrohm 848 Titrino Plus autotitrator.

Results and discussion

Peracetylation of glucose in IL
In order to tackle the transformation of cellulose into the glucose ester -D-glucose pentaacetate
(GPAc), the acetylation of glucose was investigated first. As cellulose hydrolysis was
successfully performed before in [BMIm][Cl] (Rinaldi et al. 2008; Vanoye et al. 2009; Rinaldi et
al. 2010), this ionic liquid was selected for the valorization of cellulose into glucose esters.
Based on the good results in literature acetic anhydride (Ac2O) was chosen as acetylating agent
(Wu et al. 2004; Abbott et al. 2005; Heinze et al. 2005; Barthel and Heinze 2006).
In a first experiment 3.110-4 mol glucose was dissolved in 1 g of [BMIm][Cl], together with
varying amounts of Ac2O. The acetylation of the hydroxyl groups of cellulose does not require a
catalyst (Forsyth et al. 2002; Gholap et al. 2003; Wu et al. 2004; Abbott et al. 2005). Figure 1
shows that if 1.710-3 mol of Ac2O (a close-to-stoichiometric amount with respect to the
hydroxyl groups of glucose) was employed the conversion of glucose increased till 100%.
5

However, apart from the desired product GPAc (60% yield), also a significant fraction of the
glucose diacetate (GDAc, 7% yield) and triacetate (GTAc 33% yield) were obtained. The
presence of incompletely acetylated glucose molecules in case of a close-to-stoichiometric ratio
of hydroxyl groups of glucose/acetic anhydride was reported before (Coxon 1987). Increasing
the amount of Ac2O further to 3.410-3 mol resulted in a 100% yield of GPAc. In practice, this
amounts to an acetic anhydride to glucose ratio of at least 11 which is needed to attain nearly full
acetylation of the glucose molecule.
Synthesis of GPAc from cellobiose
With the glucose acetylation explored, the transformation of cellobiose into GPAc was studied.
A series of acidic catalysts were chosen and tested in the hydrolysis of cellobiose in the ionic
liquid medium. The sulfonated resin Amberlyst 15DRY possesses strong acidic properties and
has been reported as catalyst for efficient cellulose hydrolysis (Rinaldi et al. 2008). Silicasupported Nafion SAC-13 was selected in view of its high recyclability in a similar process
(Hegner et al. 2010). Smopex-101, a fiber based on polyethylene grafted with styrene and
sulfonated with chlorosulfonic acid, has been claimed to be a more effective catalyst than
Amberlyst 15DRY due to the presence of stronger Brnsted acid sites (Peters et al. 2006; Heravi
and Sadjadi 2009). HNbMoO6 is an exfoliated nanosheet material with strong acid properties,
which has been relatively recently reported as a promising solid acid catalyst for saccharide
hydrolysis (Takagaki et al. 2008). In Figure 2, it can be seen that in the catalyst-free reaction
system the glucose yield is near to zero. Introducing 0.01 g of Nafion SAC-13 into the reaction
mixture did not improve the glucose yield much (5%). The activities of HNbMoO 6 and Smopex101 were significantly higher with glucose yields of 20% and 60%, respectively. However, the
highest yield of glucose was observed in the presence of Amberlyst 15DRY. The low activity of
Nafion SAC-13 as an acid catalyst can be ascribed to its relatively low content of acid sites:
Amberlyst 15DRY has an acid amount of 4.7 meq H+g-1 vs. 0.12 meq H+g-1 for Nafion SAC-13
(data provided by the supplier). HNbMoO6 has a layered structure (Takagaki et al. 2008);
6

possibly, in the relatively viscous ionic liquid medium the intercalation of molecules between the
sheets proceeds less well than e.g. in water, and this may decrease the access of the cellobiose
reactants to the active sites.
As Amberlyst 15DRY showed the highest activity, it was used for production of GPAc from
cellobiose. After the hydrolysis Amberlyst 15DRY particles were removed from the reaction
mixture. For the subsequent acetylation a fraction of this mixture (0.1 ml), containing about
3.110-5 mol of glucosidic units, was mixed with 1.710-3 mol of Ac2O. Note that a large excess
of Ac2O was added, as this gave the best results in the acetylation of glucose. Despite the large
excess of acetylating agent, after 4 h at 100C only 12% yield of GPAc was obtained. It was
hypothesized that this low yield was caused by the degradation of GPAc under strong acidic
conditions, as such a degradation has been reported before (Rinaldi et al. 2008). Leaching of
protons from the Amberlyst 15DRY particles has been proposed before (Rinaldi et al. 2010),
thus some protons may remain in the solution even after removal of the polymeric catalyst
particles. To investigate this influence of the acid on the GPAc instability, the hydrolysis of
cellobiose was performed under the same reaction conditions but with a lowered amount of
Amberlyst 15DRY (0.005 g). Although this led to a slightly lower glucose yield of 85% after the
hydrolysis step, a 95% yield of GPAc was obtained after the second step. The lower amount of
catalyst probably leads to less proton leaching, resulting in an environment in which GPAc is
more stable. This will be examined in more detail with cellulose as the substrate.
Synthesis of GPAc from cellulose
Evaluation of decomposition of GPAc
Next, the hydrolysis and acetylation of the principal substrate, i.e. cellulose, were investigated. In
a first experiment, 0.05 g cellulose in 1 g of [BMIm][Cl] was reacted with 20 L H2O in the
presence of 0.01 g Amberlyst 15DRY. As shown in Table 1 (# 1), after 4 h at 110C, a 40%
yield of glucose was attained. Subsequent acetylation of a 0.1 ml fraction with a large excess of
Ac2O (1.710-3 mol) did only yield 2% GPAc after 7 h (# 2). This yield is based on the amount of
7

glucose monomers initially present in the cellulose substrate. This low yield is in line with the
low yields of GPAc obtained from cellobiose with the same amount of catalyst and may be due
to fast degradation of GPAc under the applied acidic reaction conditions. The presence of typical
degradation products such as 5-hydroxymethylfurfural and levoglucosan in the product pool
supports this hypothesis (Carlson et al. 2010). In order to check whether acetic acid, which could
be formed from Ac2O, contributes to the GPAc decomposition side reaction, n-BuOAc was used
as an acetylating agent under the same conditions (# 3). Indeed, n-BuOAc would only release
butanol as a by-product of the acylation instead of a carboxylic acid. However this ester turns out
to be insufficiently reactive to perform a transacylation, and no GPAc was obtained.
To confirm the hypothesis of GPAc degradation, two control experiments were conducted. In a
first experiment, 310-4 mol of GPAc was dissolved in 1 g of [BMIm][Cl] and reacted at 100C
in the presence of 0.01 g Amberlyst 15DRY and 20 L H2O. Figure 3 illustrates the fast
degradation of GPAc under the employed conditions, with only 15% of the GPAc remaining
after 2 h. After 7 h no GPAc can be detected anymore. Note that the GPAc decomposition does
not necessarily proceed via glucose as an intermediate, but rather involves direct formation of
anhydride compounds via elimination of acetyl groups, which results in the formation of acetic
anhydride and acetic acid (Moldoveanu 2010). The combined yield of GPAc and
hydroxymethylfurfural and levoglucosan is well below 100%, which is probably due to the
formation of light degradation products that were not quantified in the GC analysis (Carlson et
al. 2010). Secondly, an experiment with glucose was carried out under identical conditions. The
evolution of glucose in time when reacted at 100C is also presented in Figure 3. It seems that
glucose is substantially more stable than GPAc, even if it eventually also forms degradation
products like levoglucosan or hydroxymethylfurfural.
In order to prove that the degradation is acid-catalyzed, control experiments were also conducted
in absence of the acidic catalyst. Figure 4 illustrates that the concentration of both GPAc and

glucose remained almost unchanged after 6 h. Only minor amounts of levoglucosan (3% after
GPAc degradation and 1% after glucose degradation) were detected in both cases.
Influence of amount of Amberlyst 15DRY
As the acid catalyst causes degradation of GPAc, it was important to optimize the amount of this
catalyst in order to prevent excessive product degradation, but without affecting the hydrolysis
yield too much. Therefore, three hydrolysis experiments were performed with lower amounts of
Amberlyst 15DRY. In Table 2, the results of these experiments are compared with the ones for
0.01 g of catalyst. In absence of a catalyst (Table 2, # 1) only a minor amount of glucose was
detected after cellulose hydrolysis. Lowering the amount of catalyst from 0.01 g till 0.005 g did
not affect the product distribution after hydrolysis much, with respectively 40% and 36% glucose
yields (# 2 - 3). Further reducing the amount of Amberlyst 15DRY, however, led to a significant
decrease in glucose yield (# 4).
In a second step, Amberlyst 15DRY particles were removed and 0.1 ml of the reaction mixtures
(ca. 3.0910-5 mol of glucosidic units), was acetylated with an excess of Ac 2O under the same
conditions as in the preliminary experiment with 0.01 g (Table 1, # 2). While in the case of 0.01
g of catalyst, the GPAc yield was only 10%, a yield of 70% was reached with 0.005 g after 16 h
of acetylation. The difference in GPAc yield can be explained by the higher concentration of
leached protons for the reaction solution with 0.01 g of catalyst compared to the one starting with
only 0.005 g of catalyst, which makes it more acidic and thus more active for the degradation of
GPAc and glucose. It has been observed before that the amount of leached protons in the
reaction solution is proportional with the amount of catalyst (Rinaldi et al. 2010). The result with
0.003 g catalyst confirmed this hypothesis. Although the hydrolysis was far from optimal with
this amount, still a larger amount of GPAc was formed than with 0.01 g Amberlyst 15DRY.
Probably decomposition of GPAc and glucose hardly takes place at this low catalyst
concentration.
Screening of acidic catalysts
9

After optimizing the catalyst amount, the performance of some alternative acid catalysts, which
were also evaluated in the cellobiose hydrolysis, was assessed: Nafion SAC-13, Smopex-101 and
HNbMoO6 (Table 3). The optimized reaction conditions for Amberlyst 15DRY were employed:
0.05 g (3.110-4 mol glucosidic units) cellulose, 0.005 g acid catalyst, 1 g [BMIm][Cl], 110C, 4
h. Application of these three catalysts gave no satisfactory results compared to Amberlyst
15DRY. While a 70% GPAc yield was attained in the presence of Amberlyst 15DRY (# 4), only
1% of GPAc and 3% of glucose were reached with Nafion SAC-13 (# 1). In the presence of the
other catalysts even no acetylated glucose was formed at all (Entries 2-3).
The poor results obtained for the cellulose transformation into GPAc with these three other
acidic catalysts are in line with the observations for cellobiose. Again, the low acidity and
potentially hindered diffusion due to the polymeric structure of cellulose explain the lack in
activity for respectively Nafion SAC-13 and HNbMoO6 (Peters et al. 2006; Takagaki et al.
2008). Smopex, on the other hand, probably has a too high acidity compared to Amberlyst
15DRY (Peters et al. 2006). Moreover, it is practically impossible to separate the catalytic fibers
of Smopex-101 from the ionic liquid based product mixture. Thus, while the hydrolysis of
cellulose is efficiently catalyzed in the presence of Smopex-101 (see the relatively good
hydrolysis results with cellobiose), the too strong acidity and the problematic removal from the
reaction mixture likely contribute to the decomposition of GPAc.
Evolution of GPAc yield in time
To find an optimal duration of the acetylation, the reaction course was followed as a function of
time in optimal conditions. In these experiments 0.1 ml of mixture A, containing ca. 3.0910-5
mol of glucosidic units, was acetylated with 1.710-3 mol of Ac2O at 100C. Mixture A is the
product mixture, obtained after hydrolysis of 0.05 g of cellulose in 1 g of [BMIm][Cl] in
presence of 0.005 g of Amberlyst 15DRY at 110C for 4 h. Catalytic beads were removed prior
to acetylation. Figure 5 illustrates that a maximum yield of GPAc is attained after 16 h reaction

10

time. Upon prolonging the reaction time, the GPAc yield started to decrease again. More insight
in this reaction course will be provided below.
Influence of other reaction parameters
As demonstrated above, the amount of Ac2O has a significant influence on the yield of GPAc. In
the following, the influence of the amount of acetylating agent was also investigated for the
cellulose transformation into glucose esters. One can conclude from Table 4, that a too small
amount of Ac2O decreased the acetylation degree of the glucose derivatives (Table 4, entries 1
and 2). Apart from GPAc also glucose triacetate and diacetate were detected, as was the case for
the glucose acetylation. 1.710-3 mol seems to be the optimal amount of acetylation agent (Table
4, # 3). In contrast with glucose acetylation, also a too high excess of Ac 2O decreased the GPAc
yields (Table 4, # 4 - 5). This has been previously reported by Zhang et al. (2005) for a similar
ionic liquid, 1-allyl-3-methylimidazolium chloride. This effect can be explained by the fact that
at the moment of the Ac2O addition, the depolymerization of the cellulose is not yet complete, as
is evidenced by the detection of dimeric compounds after the first stage. If a too large excess of
Ac2O is added after the first stage, it could compromise the solubility of the remaining cellulose
fragments and glucose oligomers in the IL.
After optimizing the amount of Ac2O, an acetylation experiment was performed with propanoic
anhydride (Table 4, # 6); a 65% yield of -D-glucose pentapropanoate was obtained after mixing
0.1 ml of mixture A with 1.710-3 mol of propanoic anhydride at 100C for 16 h.
Separation of reaction products and IL/catalyst recycling
To demonstrate the recycling of the [BMIm][Cl] and the catalyst, the GPAc formed in the first
reaction run needed to be removed first. Control experiments with purchased GPAc showed that
dibutylether was suited for the isolation of the product by simple extraction. In these experiments
a known amount of GPAc was dissolved in the IL phase, which was then stirred with n-Bu2O in
a 1:5 volume ratio at 80C for 1 h. In this way, the GPAc was nearly quantitatively extracted into
the ether phase. Thus, after performing the cellulose hydrolysis and acetylation under optimal
11

conditions, the GPAc was isolated with dibutylether. The remaining 1 ml IL was then reused for
a second transformation of cellulose into GPAc under identical conditions. Note that the catalyst
particles should be washed with H2SO4 solution before reuse, due to the release of its H3O+
content (Rinaldi et al. 2010). Titrating the ionic liquid phase after removal of Amberlyst 15DRY
particles revealed that after 4 h of stirring at 110C 80% of H +-cations is released into
[BMIm][Cl]. Because of this, we added only 0.001 g (20% of the standard amount of 0.005 g) of
Amberlyst 15DRY into the recycled IL. Only a small decrease in GPAc yield was observed after
the first recycle. While after the first reaction cycle a 70% GPAc yield was attained, 65% yield
could be obtained with the recycled Amberlyst 15DRY/[BMIm][Cl] system.
Mechanism of the formation of glucose esters from cellulose
Finally, the mechanism of glucose ester formation starting from cellulose will be discussed. This
reaction typically consists out of two steps: 1) hydrolysis of the cellulose with formation of
glucose and oligomeric species 2) acetylation of the hydrolysis products. The rate determining
step hereby is the first step, as the acetylation of the hydroxyl groups proceeds relatively fast
(Forsyth et al. 2002). Hydrolysis of the (14) links in the cellulose molecules occurs more
slowly as was proven by GPC. With this technique, the extent of cellulose depolymerization
degree was evaluated at different time intervals of the hydrolysis reaction. The chromatograms
are presented in Figure 6. After 1 h of hydrolysis only a small fraction of the cellulose is
converted into oligomeric species. Although a small peak appeared after 1 h, a large peak,
representing a compound with a degree of polymerization (DP) close to that of the original
substrate (DP 215240), was still present. This large peak nearly disappeared after 2.5 h, but a
distinct group of peaks with lower MW (oligomeric species) could be observed. After 4 h, the
peaks of oligomeric species were still visible, which means that hydrolysis was incomplete after
the first step (hydrolysis).
As GPAc is the only end product of the optimized cellulose transformation, it can be concluded
that the depolymerization still continues during the second step. In the course of the acetylation
12

step, the (14) links in acetylated oligomeric molecules are probably being directly cleaved by
AcOH rather than by water. To confirm this hypothesis, the direct acetylation of cellobiose has
been investigated. No hydrolysis conditions were applied first. This acetylation of 1.5510-4 mol
of cellobiose, with 1.710-2 mol Ac2O in 1 g [BMIm][Cl] was performed at 100C. After 16 h a
GPAc yield of 23% was reached. Detection of a significant amount of GPAc upon cellobiose
acetylation in the absence of extra added water confirms our hypothesis.
The reaction proceeds stereoselectively as the -anomer is much more stable than the -anomer
due to the anomeric effect (Ternay 1979). Thus, the -anomer is almost exclusively formed
(Scheme 1, Table 2, # 3). This is in good agreement with the data previously reported in
literature (Ternay 1979; Streitwieser 1985). The stereoconfiguration was confirmed by GC and
GC-MS using commercial samples of -D-glucose pentaacetate and -D-glucose pentaacetate.

Conclusions
In this work an efficient transformation of cellulose into glucose esters in the ionic liquid
medium of [BMIm][Cl] was demonstrated. A 70% yield of -D-glucose pentaacetate (GPAc)
could be reached in the presence of an acidic catalyst. By keeping the concentration of this
catalyst low, degradation of the glucose ester could be minimized. This cellulose transformation
typically involves two steps: after hydrolysis of the polymer a consecutive reaction with acetic
anhydride takes place, in which glucose is acetylated and oligomers are being directly cleaved by
AcOH/Ac2O. This results in selective formation of GPAc, which can be easily isolated by
extraction. Both IL and catalyst could be recycled after reaction.

Acknowledgements
IAI thanks the Leuven Arenberg Doctoral School for a PhD fellowship (DBOF). This work is
supported by the IAP project Functional Supramolecular Systems (Belgian Science Policy) and
by the CASAS Methusalem Grant. This work is also supported by IoLiTec (Denzlingen,
Germany).

13

Table 1. Cellulose transformation into GPAc.

Reaction parameters
#

Step

(C)

Reactant

(h)

Product yields (%)

[a]

110

20 l H2O

4 levoglucosan
40 glucose
7 other C6 sugars
1 dimers of C6 sugars

2[b]

100

1.710-3
mol Ac2O

5 hydroxymethylfurfural
2 GPAc

[b]

100

1.710
mol n-BuOAc

2 levoglucosan
15 glucose

-3

[a] Hydrolysis conditions: 0.05 g cellulose (3.110-4 mol glucosidic units), 1

g [BMIm][Cl], 0.01 g Amberlyst 15DRY
[b] Acetylation: 0.1 ml of the reaction mixture of # 1 was taken, and
catalyst particles were removed prior to the acetylation reaction.

14

Table 2. Cellulose hydrolysis/acetylation in the presence of various amounts of Amberlyst

15DRY as catalyst. GPAc: -D-glucose pentaacetate

Amount of
Amberlyst
15DRY (g)

Yield of products (%)

After step 1

[a]

3 glucose

After step 2
-

0.01

4 levoglucosan
40 glucose
7 other C6 sugars
1 dimers of C6 sugars

10 GPAc

0.005

1 levoglucosan
36 glucose
2 other C6 sugars
8 dimers of C6 sugars

GPAc 70

0.003

19 glucose
12 dimers of C6 sugars

GPAc 15

[b]

[a] Hydrolysis conditions: 0.05 g (3.110-4 mol glucosidic units)

cellulose, 20 H2O, 1 g [BMIm][Cl], 110C, 4 h.
[b] Acetylation conditions: 0.1 ml (one tenth) reaction mixture after
hydrolysis (with catalyst particles removed), 1.710-3 mol (0.17 ml)
Ac2O, 100C, 16 h.

15

Table 3. Screening of acidic catalysts for transformation of cellulose to -D-glucose pentaacetate

(GPAc) [a,b]
#

Catalyst

Product yields
(%)

0.005 g Nafion SAC-13

3 glucose
1 GPAc

0.005 g Smopex-101

11 HMF

0.005 g HNbMoO6

2 glucose

0.005 g Amberlyst 15DRY

70 GPAc

[a] Hydrolysis conditions: 0.05 g (3.110-4 mol

glucosidic units) cellulose, 1 g [BMIm][Cl], 20
H2O, 110C, 4 h.
[b] Acetylation conditions: 0.1 ml (one tenth)
reaction mixture after hydrolysis (with as many as
-3
possible catalyst particles removed), 1.710 mol
(0.17 ml) Ac2O, 100C, 16 h.
[c] HMF: hydroxymethylfurfural

16

Table 4. Influence of the acetylation agent. [a]

#

Acetylating agent

4.910 mol Ac2O

9.810 mol Ac2O

1.710 mol Ac2O

Yield (%)
17 GPAc
8 glucose triacetate
5 glucose diacetate

-4

35 GPAc
5 glucose triacetate

-4

-3

70 GPAc

-3

40 GPAc

-2

31 GPAc

310 mol Ac2O

110 mol Ac2O

1.710 mol
propanoic anhydride

-3

65 glucose
pentapropanoate

[a] Reaction conditions: 0.1 ml mixture A (hydrolysis

mixture; see paragraph Evolution of GPAc yield in time),
100C, 16 h.

17

Figure 1. Influence of amount of Ac2O on the glucose acetylation (Reaction conditions: 3.110-4
mol (0.056 g) glucose, 1 g [BMIm][Cl], 100C, 4 h).

18

Figure 2. Influence of acidic catalyst on the cellobiose hydrolysis (Reaction conditions: 1.55104

mol (0.053 g) cellobiose, 0.01 g catalyst, 1 g [BMIm][Cl], 20 H 2O, 110C, 4 h).

19

Figure 3. Decomposition of GPAc [a] and glucose [b] (Reaction condition: 3.110-4 mol GPAc
[a] or glucose [b], 0.01g Amberlyst 15DRY, 1 g [BMIm][Cl], 20 H 2O, 100C, 4 h).

20

Figure 4. Decomposition of GPAc [a] and glucose [b] under acid-free conditions (Reaction
condition: 3.110-4 mol GPAc [a] or glucose [b], 1 g [BMIm][Cl], 20 H 2O, 100C, 6 h).

21

Figure 5. Progress of the acetylation yield after the hydrolysis step (Reaction conditions: 0.1 ml
mixture A, 1.710-3 mol Ac2O, 100C).

22

Figure 6. Gel-permeation chromatograms of cellulose hydrolysis (Reaction conditions: 0.05 g

cellulose, 1 g [BMIm][Cl], 0.001 g Amberlyst 15DRY, numbers on top of the figure (360,000,
270,000 etc.) indicate Mw).

23

Scheme 1. Cellulose hydrolysis (1) and subsequent formation of GPAc via acetylation of
glucose (2) or direct cleavage of the glucose oligomers (3).

24

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