A strategy of ketalization for the catalytic selective dehydration of biomass-based polyols over H-beta zeolite

Article abstract of DOI:10.1039/c7gc03248j

Biomass contains plentiful hydroxyl groups that lead to an oxygen-rich structure compared to petroleum-based chemicals. Dehydration is the most energy-efficient technique to remove oxygen; however, multiple similar vicinal hydroxyl groups in sugar alcohols impose significant challenges for their selective dehydration. Here, we present a novel strategy to control the etherification site in sugar alcohols by the ketalization of the vicinal-diol group for the highly selective formation of tetrahydrofuran derivatives. A ketone firstly reacts with terminal vicinal hydroxyl groups to form the 1,3-dioxolane structure. This structure of the constrained 1,3-dioxolane ring would improve the accessibility of reactive groups to facilitate intramolecular etherification. As a better leaving group than water, the ketone can also promote intramolecular etherification. Consequently, a range of tetrahydrofuran derivatives are produced in excellent yields with the H-beta zeolite catalyst under mild reaction conditions. This strategy opens up new opportunities for the efficient upgrading of biomass via the modification or protection of hydroxyl groups.

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A strategy of ketalization for catalytic selective dehydration of
biomass-based polyols over H-beta zeolite†
Penghua Che,a Fang Lu,*a Xiaoqin Si,ab Hong Ma,a Xin Niea and Jie Xu*a
Received 00th January 20xx,
Accepted 00th January 20xx
Biomass contains plentiful hydroxyl groups that cause oxygen-rich structure compared with petroleum-based chemicals.
Dehydration is the most energy-efficient technique to remove oxygen, however multiple similar vicinal hydroxyl groups in
sugar alcohols impose significant challenges for their selective dehydration. Here we present a novel strategy to control
the etherification site in sugar alcohols by ketalization of vicinal-diol group for highly selective formation of
tetrahydrofuran derivatives. Ketone firstly reacts with terminal vicinal hydroxyl groups to form 1,3-dioxolane structure.
This structure of the constrained 1,3-dioxolane ring would improve the accessibility of reactive groups to facilitate
intramolecular etherification. As a better leaving group than water, ketone can also promote the intramolecular
etherification. Consequently, a range of tetrahydrofuran derivatives are produced in excellent yields with H-beta zeolite
catalyst under mild reaction conditions. This strategy opens up new opportunities for efficient upgrading of biomass via
modification or protection of hydroxyl groups.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Nowadays, current method for isosorbide from sorbitol
undergoes an acid-catalyzed double dehydration pathway (Fig.
1, blue frame).22 At the first dehydration step, etherification
Introduction
The growing demand for sustainability has urged research into
utilization of lignocellulosic biomass for the production of
renewable chemicals and biofuels.1-4 Sugar alcohols are
considered as important biomass-based platform molecules
that are directly accessible from carbohydrates, like glucose
and cellulose.5-8 However, the challenge remains for the
valorization of sugar alcohols due to inherent oxygen-rich
structure compared with petroleum-based chemicals.9,10
Among the reported deoxygenation methods, dehydration has
provided a key technique for removal of hydroxyl groups from
biomass-derived polyols to build up a wide range of valuable
derivatives.11-14
sites could be the carbon hydroxyl groups at 1, 2, 4 or 5
positions of sorbitol which lead to 1,4-sorbitan intermediate
and other dead-end sorbitan isomers like 2,5-sorbitan and 1,5-
sorbitan. In addition, plentiful hydroxyl groups of sorbitol or
dehydrated sorbitol products also easily form polymeric
humins in acidic conditions.23,24 Therefore, reported selectivity
to isosorbide was normally around 60−87% using acid catalysts,
generally requiring high temperature and vacuum
conditions.21,25-29
It has been reported that dimethyl carbonate (DMC) can
enhance the selectivity to tetrahydrofuran derivatives such as
isosorbide.30,31 In this approach, DMC was used as
carboxymethylating agent, which reacted with terminal
hydroxyl groups in polyols, and constituted the leaving group
in cyclization reaction in the presence of strong soluble base.
However, the carboxymethylation is still proceeding between
DMC and hydroxyl groups in isosorbide after double cyclization,
leading to byproducts of carboxymethyl derivatives. Moreover,
isosorbide is formed at the expense of DMC, being converted
into methanol and CO2 byproducts. Therefore, the substantial
challenge remains for selective modification of the hydroxyl
groups in sugar alcohol for high yield production of
tetrahydrofuran derivatives.
Cyclic ether products derived from the dehydration of
sugar alcohols could be utilized in the synthesis of high-boiling
green solvents, plasticizers, surfactants, pharmaceuticals and
polymers.15-19 More importantly, isosorbide, which is
synthesized by double dehydration of sorbitol, could be used
as an alternative to bisphenol A for the production of biomass-
based and harmless baby bottles and plastic drinking bottles.20
Nevertheless, low selectivity to isosorbide caused by the
similar chemical environment of six vicinal hydroxyl groups in
sorbitol molecule during the dehydration process is the
bottleneck for promoting isosorbide widely as a feedstock.21
Herein, we report a novel strategy for controlling the
etherification site in sugar alcohols by ketalization of vicinal-
diol group to achieve remarkably high yields of
tetrahydrofuran derivatives (Fig. 1, red frame). Ketone
(particularly methyl isobutyl ketone and diethyl ketone) was
used as modification agent of vicinal-diol group to enhance the
a.State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy,
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian,
116023, PR China. E-mail: xujie@dicp.ac.cn; lufang@dicp.ac.cn.
b.University of Chinese Academy of Sciences, Beijing, 100049, PR China.
† Electronic Supplementary Information (ESI) available: Experimental procedures;
additional figures and tables; and NMR as well as GC-MS spectra (PDF). See
DOI: 10.1039/x0xx00000x
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Table 1 Comparison of different solvents for sorbitol
conversion to isosorbide over H-beta(20)a
Selectivity (%)
Conv.
Entry
Solvent
Neat
Sorbitan
2
Othersb
(%)
3
4
1
2
3
100
9.7
68.8 c
8.9
22.3
18.3
15.7
13.6
68.1
24.6 11.2
73.1
4
59.3 17.1
72.8
10.1
5
6
95.8 46.4
41.9
11.7
28.9
21.1
5.9
Fig. 1 Current and proposed methods for the synthesis of
isosorbide from sorbitol. Blue: current method by acid-
catalyzed double dehydration; red: proposed high-
efficiency method by ketalization of the terminal vicinal-
diol group with ketone to control the etherification site of
sorbitol.
100
100
100
100
54.0 c 17.1
67.3 c 11.6
7
8
91.4 c
93.0 c
2.7
2.3
3.7
9
4.7
99.8 85.9 c
100
81.6 c
10.4
selectivity of tetrahydrofuran derivatives catalyzed by
commercial H-beta zeolite under mild conditions. Ketone
10
agent can construct
a 1,3-dioxolane structure with the
11
3.5
14.9
terminal vicinal hydroxyl groups in sugar alcohol to facilitate
subsequent intramolecular etherification.
a Reaction conditions: sorbitol (2 mmol), H-beta(20) (0.037
b
g), solvent (4.5 mL), 170 oC, 2 h. Mainly unknown
humins. c Undetected by 13C NMR spectroscopy.
Results and discussion
Comparison of different solvents for the conversion of sorbitol to
isosorbide
reactivities were exhibited with the sorbitol conversions of
100% (entries 6 and 7). However, low selectivity to isosorbide
was also found, and the selectivity towards 2,5-sorbitan was
between 11.6% and 17.1% (further demonstrated by Fig. S2
and S3, ESI†).
Conversion of sorbitol to isosorbide was initially examined
using various commonly used solvents over H-beta at 170 oC
for 2 h (Table 1). In the present catalytic system, sorbitol
converted leading to isosorbide and 1,4-sorbitan as the
major products together with minor amount of 2,5-sorbitan
Negligible amount of 1,5-sorbitan and some non-identified
1 was
2
3
To our interest, ketone agent, like diethyl ketone (DEK) and
methyl isobutyl ketone (MIBK), demonstrated high efficiency
in improving the isosorbide selectivity and sorbitol conversion
(entries 8 and 9). The isosorbide selectivity was between 91%
and 93% at complete conversions of sorbitol. In particular, the
use of MIBK provided the highest selectivity of 93.0%
isosorbide at 100% conversion, and the lowest selectivities of
4.7% unidentified byproducts and 2.3% 2,5-sorbitan (further
determined by Fig. S4, ESI†). More generally, enhanced
selectivity for isosorbide from sorbitol can also be achieved
using other MIBK isomers. Isosorbide selectivities over 81%
were obtained with around 100% sorbitol conversion using
methyl n-butyl ketone and methyl sec-butyl ketone,
respectively (entries 10 and 11). Such slight decrease of
isosorbide selectivity compared to that in MIBK suggests that
different ketone agent could influence the selective formation
of isosorbide in the conversion of sorbitol. Therefore, the use
of ketone agent is highly efficient for the production of
4
.
5
substances were all termed here as "others". First, solvent-free
dehydration of sorbitol was conducted as a control experiment
(entry 1). The solvent-free medium afforded about 69%
isosorbide selectivity with
a
full sorbitol conversion.
Nevertheless, 2,5-sorbitan selectivity reached 9% without
detection of 1,4-sorbitan as revealed by 13C NMR spectroscopy
(Fig. S1, ESI†). Also, significant carbon loss to unidentified
byproducts was noticed, most of which might be attributed to
humin formation as indicated by the brownish reaction
mixture. By contrast, the sorbitol conversion was 9.7%, 24.6%,
59.3% and 95.8%, when using methanol, n-butanol, sulfolane
and 1,4-dioxane (entries 2−5), respectively. The isosorbide
selectivity was quite low, ranging from 11.2% to 46.4%.
However, the selectivity for unidentified byproducts using
these solvents was decreased when compared with solvent-
free system. When the reaction was performed in ester media
like γ-valerolactone and dimethyl carbonate, the enhanced
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isosorbide and effective for suppression of byproducts like and (
humins and 2,5-sorbitan.
Comparison of various acid catalysts for the sorbitol conversion to products
±
)-1,2,4-butanetriol
9
. The examined polyols all reacted
smoothly to afford the corresponding desired tetrahydrofuran
and 10 13 in good to excellent yields at high
conversions (Table 2, entries 1 5). Notably, 1,4-sorbitan was
2
−
isosorbide
−
almost quantitatively converted into isosorbide with high
yields between 95.1% and 97.5% in ketone like DEK and MIBK,
which was superior to other media (Table S2, ESI†). This
prominent result indicates that the presence of ketone can
promote the selective conversion of 1,4-sorbitan to isosorbide.
Thus, our strategy using ketone agent is applicable for the
selective intramolecular etherification of polyols to desired
tetrahydrofuran derivatives.
The behavior of acid catalysts in ketone is studied to identify
the optimal catalyst for this catalytic process. To this end,
various acid catalysts were evaluated for the conversion of
sorbitol to isosorbide, see Table S1 (ESI†). The control
experiment was also performed in the absence of catalyst
under same conditions and sorbitol conversion was only 10.3%
mainly leading to sorbitol ketals with trace of isosorbide.
Among all tested acid catalysts, H-beta zeolites demonstrated
excellent performances (entries 5 and 6). Similar phenomena
have been reported by previous methods using H-beta zeolites
Reaction pathway for polyol conversion to tetrahydrofuran
derivatives via ketone
with high Si/Al ratios.32,33 Particularly, H-beta with the Si/Al To gain insights into the unusual selectivity to isosorbide and
ratio of 20 (H-beta(20)) achieved the highest selectivity for reaction pathways, the reaction progress profiles of the
isosorbide up to 93% at a 100% sorbitol conversion in MIBK.
Selective conversion of other sugar-derived polyols to
tetrahydrofuran derivatives
sorbitol conversion as a model reaction over H-beta(20) was
studied (Fig. 2a). Sorbitol conversion reached up to 68.8% in
just 1 min, and then gradually increased to 100% with
prolonging reaction time to 120 min. The selectivity to sorbitan
mainly including 1,4-sorbitan displayed a volcano trend with a
maximum value at 10 min. This result indicates that 1,4-
sorbitan is the intermediate product as reported in literature22.
Besides 1,4-sorbitan, some non-identified products also
appeared during the reaction. The selectivity of non-identified
Encouraged by the results described above, we next explore
the generality of this approach by extending the same strategy
o
to a series of sugar-derived polyols over H-beta(20) at 170 C.
Polyols bearing an additional hydroxyl group at the
relative to the terminal vicinal-diol group were chosen
including 1,4-sorbitan , mannitol , xylitol , meso-erythritol 8
β-position
3
6
7
a)
Table 2 Conversion of different polyols to tetrahydrofuran
derivatives over H-beta(20)a
O
HO
OH OH
HO
Conv.
(%)
Yield
(%)b
Entry
1
Polyol
Product
100
97.5
3
2
2
99.4
100
75.2
71.4
b)
6
10
OH
HO
OH
3
OH OH
7
11
12
4c
100
100
90.1
90.4
8
9
5
13
a
Reaction conditions: polyol (2 mmol), methyl isobutyl
o
ketone (4.5 mL), H-beta(20) (0.037 g), 170 C, 1 h, except
entry 2 (2 h). b Determined by GC yields, except entry 3 (by
Fig. 2 Time course for the conversion of (a) sorbitol and (b)
1,4-sorbitan to isosorbide over H-beta(20). Sorbitan: 1,4-
sorbitan and minor amount of 2,5-sorbitan. Reaction
conditions: sorbitol or 1,4-sorbitan (2 mmol), H-beta(20)
(0.037 g), diethyl ketone (4.5 mL), 170 oC.
c
HPLC). After the reaction, a solution of the residual in
o
THF:4M HCl (1:1 v/v, 4 mL) was heated at 60 C for 3 h to
obtain 12
.
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a)
b)
c)
Fig. 3 13C NMR spectra confirming the formation of terminal 1,3-dioxolane ketal intermediates. (a) Stack of 13C NMR spectra
as a function of time for the conversion of 1,4-sorbitan in DEK catalyzed by H-beta(20) (DEK layer), under conditions in Fig.
2b. (b) Partial 13C NMR spectrum of the reaction mixture for the reaction of ( )-1,2,4-butanetriol with DEK. (c) Partial 13C
±
NMR spectrum of the reaction mixture for the reaction of meso-erythritol with DEK. Reaction conditions for (b) and (c):
polyol (2 mmol), H-beta(20) (0.012 g), DEK (4.5 mL), 170 oC for 1 min. DEK: diethyl ketone.
products decreased with prolonged time, accompanying an the un-identified intermediate. Pure 5,6-O-3-pentylidene-1,4-
increase in the isosorbide selectivity. This reaction pattern, sorbitan 14 (5,6-O-ketal) (Fig. 3a) was successfully isolated and
typical of a consecutive reaction, suggests that the non- confirmed with a five-membered 1,3-dioxolane ring by 1D (1H,
identified products are also mainly the reactive intermediates, 13C), 2D (H-H COSY, HSQC) NMR and HRMS analyses.
which can undergo further conversion to isosorbide.
Subsequently, the reaction of 1,4-sorbitan to isosorbide in DEK
To further understand the reaction pathway, we also was monitored by 13C NMR spectroscopy to follow the
performed the conversion of 1,4-sorbitan intermediate by changing trend of 5,6-O-ketal 14 (Fig. 3a and S5, ESI†). The 13C
following the same procedure as that for sorbitol conversion NMR spectra in Fig. 3a confirmed the formation of 5,6-O-ketal
(Fig. 2b). 1,4-Sorbitan conversion rapidly reached 72.1% within 14 with the peaks at 7.0, 7.2, 28.7, 29.2, 67.1, 73.3, 73.4, 76.3,
1 min, and then smoothly increased to 100% with increasing 77.1, 81.3 and 111.3 ppm, and the 5,6-O-ketal peaks
reaction time to 60 min. Like the sorbitol conversion process, dominated the spectrum recorded at the initial 1 min. With
un-identified products were dominant in the beginning. With prolonging reaction time, the peaks characteristic of 5,6-O-
prolonged reaction time, a decrease in the selectivity to un- ketal gradually decreased accompanying an increase in the
identified products was accompanied by an increase in the isosorbide peaks. After 60 min, the 5,6-O-ketal peaks
isosorbide selectivity. This reaction pattern is in line with that completely disappeared while the isosorbide peaks dominated
in Fig. 2a, and suggests that the un-identified products the spectrum. The selective formation of 5,6-O-ketal 14 could
principally appear as intermediate.
be attributed to high stability of 1,3-dioxolane ring.34,35 Also,
Based on the importance of un-identified products, further we noticed that ketone did not react with the internal vicinal
isolation experiment after conversion of 1,4-sorbitan in DEK hydroxyl groups in trans-configuration of 1,4-sorbitan due to
o
over H-beta(20) at 170 C for 1 min was conducted to confirm the high stress of the potential five-membered ketal ring. The
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aforementioned observations indicate that five-membered
5,6-O-ketal is an intermediate formed by ketalization of the
terminal vicinal-diol group of 1,4-sorbitan with the carbonyl
group of DEK.
Considering the common feature of sorbitol and 1,4-
sorbitan, we speculate that sorbitol conversion in ketone
follows a similar pathway as described for 1,4-sorbitan. To
verify this hypothesis, the sorbitol conversion to isosorbide in
DEK was also monitored by 13C NMR analysis (Fig. S6 and S7,
ESI†). The peaks in the ranges of 111.3
ESI†) are consistent with the chemical shift for the ketal
carbon (111.3 ppm) of 5,6-O-ketal 14 suggesting the
−112.4 pm (Fig. S6a,
,
Scheme 1 Reaction pathway for isosorbide formation from
sorbitol in ketone media over H-beta zeolite. Terminal 1,3-
formation of 5,6-O-ketal and multiple five-membered sorbitol
ketals as expected. Cleary, the characteristic 13C NMR peaks
between 67 and 82 ppm for 1,4-sorbtian moiety of 14
achieved the maximum in intensity at 10 min, and then
declined on a longer time scale (Fig. S6b, ESI†). It further
demonstrates that five-membered 5,6-O-ketal 14 is a key
intermediate. Although direct recognition of five-membered
sorbitol ketals is rather difficult due to the complexity of
sorbitol with six similar vicinal hydroxyl groups, it is still desired
to determine the preferential ketalization positions of hydroxyl
groups within sorbitol molecule.
dioxolane ring and secondary hydroxyl group at the
β-
position are highlighted in blue color and green ball,
respectively.
sorbitol via ketone occurs with complete retention of
configuration. This retention of configuration at C3 and C4
supports that ketalization of the terminal vicinal-diol group is
followed by intramolecular nucleophilic attack of the
Thus simple polyols including (±)-1,2,4-butanetriol and
secondary hydroxyl group at the β-position on the methylene
meso-erythritol were chosen as probe molecules, and the
initial reaction with DEK was performed at 170 oC for 1 min
over H-beta(20). The corresponding cyclic ketal intermediates
group of the terminal 1,3-dioxolane ring with elimination of
ketone under acidic catalysis. A similar mechanism has been
proposed by Tomczyk et al.36 Consequently, the highly
selective formation of isosorbide from sorbitol in ketone
reveals that our strategy enables selective intramolecular
etherification via 1,4 and 3,6-elimination. In our strategy,
ketone is firstly used for the construction of the terminal five-
membered 1,3-dioxolane (ketal) structure, by ketalization of
terminal vicinal-diol groups of sorbitol with the carbonyl group
on ketone. The 1,3-dioxolane core is a constrained ring which
would improve the accessibility of reactive groups to facilitate
intramolecular etherification towards 1,4-sorbitan and
isosorbide. As a better leaving group than water, ketone can
also promote the intramolecular etherification. On the other
hand, ketalization of the terminal vicinal-diol group in sorbitol
enables selective deactivation of terminal vicinal hydroxyl
groups to reduce the number of etherification active sites, and
therefore effectively preventing the formation of byproducts
like 2,5-sorbitan and humins. Thus, the construction of the
terminal 1,3-dioxolane structure can control the etherification
site of sorbitol for high yield production of isosorbide by
ketalization of the terminal vicinal-diol group with ketone.
Recyclability of Catalyst
15
tetrahydrofurans 13 and 18 in the initial 1 min (Fig. 3b and 3c).
With ( )-1,2,4-butanetriol as substrate containing both 1,2-diol
−17 were formed together with corresponding
±
and 1,3-diol groups, the reaction with DEK afforded only one
ketal intermediate 15, with a 1,3-dioxolane ring, determined
by the chemical shift for ketal carbon at 111.2 ppm (Fig. 3b and
S8, ESI†). Hence, the ketalization can exclusively occur on the
terminal 1,2-diol moiety of (±)-1,2,4-butanetriol. When using
meso-erythritol as substrate bearing terminal and internal
vicinal-diol groups, the reaction with DEK principally gave two
terminal ketal intermediates including monoketal 16 and
diketal 17. By using 13C NMR spectroscopy, we ascertained
that both erythritol ketals were present as the 1,3-dioxolane
ring structure due to the chemical shift for ketal carbon at
111.9 and 112.3 ppm, respectively (Fig. 3c and S9, ESI†). The
selective formation of the terminal five-membered ketals 16
and 17 further demonstrates that the terminal vicinal-diol
group preferentially reacts with ketone to form the terminal
five-membered ketal intermediate. Thus, we believe that the
terminal vicinal hydroxyl groups within sorbitol molecule can
be preferentially modified with ketone.
Reuse experiments of H-beta(20) were performed to evaluate
the recyclability for the conversion of sorbitol to isosorbide at
170 oC for 2 h (Fig. S10, ESI†). The spent catalyst was recovered
by simple centrifugation and regenerated by calcination at 550
oC. The sorbitol conversion was kept unchanged at 100% after
three consecutive cycles. This result demonstrates that the
catalyst could be used at least three times without significant
loss of reactivity.
Based on the above results, we propose that the general
pathway for isosorbide production from sorbitol in ketone
should consist of double ketalizations and double
intramolecular etherifications, in which cyclic ketals with the
terminal 1,3-dioxolane structure acted as key intermediates
including sorbitol ketals and 5,6-O-ketal of 1,4-sorbitan
(Scheme 1). In this pathway, ketone functions simultaneously
as ketalization agent, leaving group and reaction media.
Moreover, we noticed that the formation of isosorbide from
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9
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In conclusion, we have established a novel strategy to control
the etherification site in sugar alcohols via ketalization of
vicinal-diol group for selective formation of tetrahydrofuran
derivatives. The use of ketone, especially diethyl ketone and
methyl isobutyl ketone, as modification agent of terminal
vicinal hydroxyl groups can substantially improve the
selectivity to tetrahydrofuran products catalyzed by
commercial H-beta zeolite under simple and mild reaction
conditions. Key to the success of the reaction is the
construction of the terminal 1,3-dioxolane structure, which
can facilitate subsequent intramolecular etherification and
effectively prevent side-reactions. With this method, a range
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5
of tetrahydrofuran derivatives from C4−C6 sugar-derived
polyols were attained in good to excellent yields. Especially,
highly selective isosorbide formation from sorbitol has been
demonstrated in 93% yield by using methyl isobutyl ketone
over H-beta(20) catalyst, which could be used at least three
consecutive times. It is the first time that ketone was used
simultaneously as ketalization agent, leaving group and
reaction media, which represents an innovative concept for
the synthesis of cyclic ethers. It also provides feasible access
for selective conversion of complex polyhydroxyl molecules
into valuable molecules with less oxygen content.
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Green Chemistry
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DOI: 10.1039/C7GC03248J
Table of contents entry
A strategy is presented to control etherification site in sugar alcohols via ketalization
of terminal vicinal-diol group with ketone.