Kinetic analyses of intramolecular dehydration of hexitols in high-temperature water

Article abstract of DOI:10.1016/j.carres.2019.107880

Intramolecular dehydration of the biomass-derived hexitols D-sorbitol, D-mannitol, and galactitol was investigated. These reactions were performed in high-temperature water at 523–573 K without added acid catalyst. The rate constants for the dehydration steps in the reaction networks were determined at various reaction temperatures, and the activation energies and pre-exponential factors were calculated from Arrhenius plots. The yield of each product was estimated as a function of reaction time and temperature using the calculated rate constants and activation energies. The maximum yield of each product from the dehydration reactions was predicted over a range of reaction time and temperature, allowing the selective production of these important platform chemicals.

Full text of DOI:10.1016/j.carres.2019.107880

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Kinetic analyses of intramolecular dehydration of hexitols in high-temperature water
Aritomo Yamaguchi, Naoki Mimura, Masayuki Shirai, Osamu Sato
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S0008-6215(19)30544-0
DOI:
https://doi.org/10.1016/j.carres.2019.107880
CAR 107880
Reference:
To appear in: Carbohydrate Research
Received Date: 11 September 2019
Revised Date: 30 October 2019
Accepted Date: 19 November 2019
Please cite this article as: A. Yamaguchi, N. Mimura, M. Shirai, O. Sato, Kinetic analyses of
intramolecular dehydration of hexitols in high-temperature water, Carbohydrate Research (2019), doi:
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Kinetic analyses of intramolecular dehydration of hexitols in high-temperature
water
Aritomo Yamaguchi, Naoki Mimura, Masayuki Shirai, and Osamu Sato
Highlights


The intramolecular dehydration of biomass-derived hexitols was performed.
The rate constants for the dehydration steps in the reaction networks were
determined.


The yield of each product was estimated as a function of reaction time and
temperature.
Products can be selected by choosing the appropriate reaction time and temperature.
1

Kinetic analyses of intramolecular dehydration of hexitols in
high-temperature water
a,
a
a,b
a
Aritomo Yamaguchi, * Naoki Mimura, Masayuki Shirai, and Osamu Sato
a
Research Institute for Chemical Process Technology
National Institute of Advanced Industrial Science and Technology (AIST)
4
-2-1 Nigatake, Miyagino, Sendai 983-8551, Japan
b
Chemistry Course, Faculty of Science and Engineering
Iwate University
Ueda 4-3-5, Morioka, Iwate 020-8551, Japan
*
Corresponding author
E-mail: a.yamaguchi@aist.go.jp
Fax: +81-22-237-5224
1

Abstract
Intramolecular dehydration of the biomass-derived hexitols D-sorbitol,
D-mannitol, and galactitol was investigated. These reactions were performed in
high-temperature water at 523–573 K without added acid catalyst. The rate constants
for the dehydration steps in the reaction networks were determined at various reaction
temperatures, and the activation energies and pre-exponential factors were calculated
from Arrhenius plots. The yield of each product was estimated as a function of reaction
time and temperature using the calculated rate constants and activation energies. The
maximum yield of each product from the dehydration reactions was predicted over a
range of reaction time and temperature, allowing the selective production of these
important platform chemicals.
Keywords
Dehydration; Sugar alcohol; High-temperature water; Isosorbide; Isomannide
2

Highlights


The intramolecular dehydration of biomass-derived hexitols was performed.
The rate constants for the dehydration steps in the reaction networks were
determined.


The yield of each product was estimated as a function of reaction time and
temperature.
Products can be selected by choosing the appropriate reaction time and
temperature.
3

1
. Introduction
The production of chemicals from renewable lignocellulosic biomass has
attracted much attention because of possible improvements in environmental
sustainability relative to other sources for production [1–3]. Cellulose and
hemicellulose are major polysaccharide components of lignocellulosic biomass; they
can be hydrolyzed into sugars such as glucose and xylose and then hydrogenated into
sugar alcohols [4–6]. The sugar alcohols sorbitol and xylitol are on the DOE list of the
top 12 platform chemicals [5] (that is, chemicals that can be used as building blocks
and converted to a wide range of materials), and also on the new list produced by
Bozell and Petersen of the top 10 chemicals derived from biomass [2]. Fukuoka et al.
reported the use of supported metal catalysts and hydrogen to convert cellulose directly
into sorbitol [7–10]. The conversion of cellulose into sorbitol has been further
developed by other research groups [10–15]. Hemicellulose has also been directly
converted into sugar alcohols through hydrolysis and hydrogenation reactions over
supported metal catalysts under hydrogen [16]. In previous studies we have reported
that cellulose and hemicellulose in lignocellulosic biomass could be directly converted
to sugar alcohols such as sorbitol, mannitol, and xylitol without delignification of the
biomass [17–19].
4

The dehydration of hexitols has attracted attention as a means to provide
valuable chemicals from biomass-derived sugar alcohols [20–23]. Isosorbide and
isomannide, which can be obtained from the dehydration of sorbitol and mannitol,
have a rigid structure with two hydroxyl groups; thus, they are promising monomers
for the preparation of polyesters and polycarbonates, and provide enhanced heat
resistance when compared with monomer ethylene glycol [24]. Anhydrohexitol is also
a key material for the production of fatty acid esters, which are naturally derived
surfactants and nontoxic food additives [25, 26].
Some researchers have reported the dehydration of sorbitol with inorganic
acid catalysts such as sulfuric acid and hydrochloric acid at 377–408 K [27, 28] or with
zeolite catalysts [23, 29]. High-temperature water has also attracted much attention as a
promising reaction medium for acid-catalyzed reactions [30–32]. In our previous work,
we have reported the dehydration of hexitols such as sorbitol, mannitol, and galactitol,
in high-temperature water without the addition of any acid catalysts [20, 21, 33]. We
have also reported the rate constants and activation energies of each step in the reaction
networks of these hexitol dehydrations.
The prediction of products from dehydration reactions by using functions of
reaction time and temperature is important, as it allows valuable products to be
5

obtained efficiently from biomass. In this manuscript, we compare the intramolecular
dehydration of biomass-derived hexitols D-sorbitol, D-mannitol, and galactitol in
high-temperature water without the addition of any hazardous acid catalyst;
furthermore, we calculate the products as functions of reaction time and temperature
with the rate constants and activation energies of these hexitol dehydrations. The
reaction time and temperature required for the maximum yield of each product from
the dehydration reactions can be determined, allowing selective production.
2
. Experimental
D-sorbitol, D-mannitol, and galactitol were purchased from Wako Pure
Chemical Industries, Ltd. and used without further purification.
The dehydration of hexitols was performed in a batch reactor (inner volume: 6
3
cm ) made of a stainless steel 316 tube [20, 21, 33]. An aqueous solution of sorbitol or
3
−3
mannitol (3 cm , 0.5 mol dm ) was loaded into the reactor and then purged with argon
3
−3
gas to remove the air. For the dehydration of galactitol, 3 cm of 0.1 mol dm was
used because of its low solubility in water. The reactor was submerged into a
molten-salt bath at the desired reaction temperature for a given reaction time and then
submerged into a water bath to cool quickly to ambient temperature after the reaction.
6

A mixture of the reactant and products was rinsed out of the reactor with distilled water,
and the solids were separated by filtration.
The quantitative analysis of the unreacted reactant and the liquid products was
conducted using high-performance liquid chromatography (HPLC, Shimadzu)
equipped with a SUGAR SC1211 column (Shodex) with a refractive index detector
(
Shimadzu, RID-10A) and a UV–Vis detector (Shimadzu, SPD-20AV). The products
were identified by comparing the retention times with those of standard materials:
,4-anhydro-D-sorbitol and 2,5-anhydro-D-sorbitol (Toronto Research Chemicals,
Inc.); isosorbide (Alfa Aesar); 1,5-anhydro-D-sorbitol, 1,4-anhydro-D-mannitol,
,5-anhydro-D-mannitol, and 2,5-anhydro-D-mannitol (Carbosynth, Ltd.); and
1
1
isomannide (Tokyo Chemical Industries Co., Ltd.). The HPLC peaks that could not be
identified by comparison with the standard materials were identified by collecting the
appropriate fractions with a fraction collector, removing the solvent with a rotary
1
13
evaporator, and performing H and C nuclear magnetic resonance (NMR)
spectroscopy (Bruker AVANCE III HD 400 MHz). The products and rate constant for
each step are shown in Scheme 1.
3
. Results and discussion
7

3
.1. Dehydration of hexitols
We have previously reported reaction mechanism of the intramolecular
dehydration of polyalcohols from the results of (2R,5R)-(–)-2,5-hexanediol
dehydration into 2,5-dimethyltetrahydrofuran (2,5-DMTHF) [32]. The high cis
selectivity of 2,5-DMTHF in the products indicated that the polyalcohol dehydration
proceeded mainly via an S 2 substitution process as follows. At first, hydroxyl groups
N
connected with C-2 or C-5 position was protonated, and then oxygen atom in
unprotonated hydroxyl group attacked carbon atom connected with protonated
hydroxyl group and simultaneous elimination of water occurred (S 2 mechanism). The
N
dehydration reactions of hexitols such as D-sorbitol, D-mannitol, and galactitol in
high-temperature water have been described in previous papers [20, 21, 33]. The
reaction schemes are shown in Scheme 1, and yields of products from D-sorbitol,
D-mannitol, and galactitol dehydration at 523 K and 573 K are shown in Fig. 1. In the
case of hexitol dehydration, the hydroxyl group at the C-x position is protonated, and
then the oxygen atom at the C-y position attacks the C-x carbon and a water molecule
is eliminated simultaneously, resulting in the production of a cyclic ether, which is
represented as x-y-AHzz in this paper where zz represents the following two letter
codes SO = sorbitol, MA = mannitol, GL = galactitol (the abbreviations of
8

anhydrohexitols are shown in Scheme 1). Briefly, 1-4-AHSO and 1-4-AHGL were the
main products from the monomolecular dehydration of D-sorbitol and galactitol,
respectively, in high-temperature water at 523 K and 573 K; both 1-4-AHMA and
2
-5-AHMA were comparably produced from the monomolecular dehydration of
D-mannitol. Isosorbide and isomannide were produced by the further dehydration of
-4-AHSO and 1-4-AHMA, respectively (Scheme 1). The yield of isosorbide was
1
higher than that of isomannide because D-sorbitol was dehydrated to 1-4-AHSO with a
high yield. Dehydration of 1-4-AHGL did not proceed in high-temperature water even
at 573 K. The dehydration rates of D-sorbitol, D-mannitol, and galactitol increased
with increasing reaction temperature (Fig. 1).
The hydroxyl groups at the C-3 and C-6 positions are located on the same side
of the tetrahydrofuran ring in the molecular structure of 1-4-AHSO and 1-4-AHMA
(Scheme 1), allowing the further dehydration of these anhydrohexitols between the
hydroxyl groups at the C-3 and C-6 positions via an S 2 substitution process.
N
Conversely, the hydroxyl groups at the C-3 and C-6 positions are located on different
sides across the tetrahydrofuran ring in the molecular structure of 1-4-AHGL (Scheme
1
(c)) [33–35] because the oxygen atom at the C-3 (C-6) position cannot attack the C-6
(C-3) carbon.
9

Previously, we showed that the dehydration reactions of hexitols have a
first-order dependence on their concentrations [20]. To understand the kinetics of the
hexitol dehydration, the rate constants (Scheme 1) were estimated from linear
regression analyses by minimizing the residuals of the data (Table 1) with the
following equations in the cases of D-sorbitol and D-mannitol (equations for galactitol
have been presented in the Supporting Information of our previous paper [33]).
(1)
(2)
(3)
(4)
(5)
(
6)
7)
(
10

(8)
In the equations, A represents D-sorbitol or D-mannitol, and [A] represents
i
the initial concentration of A. The rate constants for the dehydration reactions at 523 K
and 573 K are summarized in Table 1, and the activation energy and pre-exponential
factor were evaluated from Arrhenius plots using the kinetic data at 523 K, 548 K, 560
K, and 573 K (Table 1). The fitting results (calculated yields from the equations and
the parameters in Table 1) are shown in Figure 1. In all cases, the correlation
2
coefficients (R ) are more than 0.97, indicating that the fitting results are reasonable.
3
.2. Product yields from hexitol dehydration as functions of reaction temperature and
time
The rate constant as a function of reaction temperature can be estimated from
the activation energy and pre-exponential factor for the corresponding step in the
dehydration network (Table 1). The yield of each product from the hexitol dehydration
as a function of reaction time can be calculated from the rate constants and rate
11

equations (eqs. (5)–(8)). Therefore, the yield of each product can be estimated as a
function of reaction time and temperature (Fig. 2).
In the case of sorbitol dehydration, the 1-4-AHSO yield is predicted to
increase with decreasing reaction temperature. The maximum yield of 1-4-AHSO
within the reaction time of 10 h is estimated to be 64.6% at 525 K for 10 h; the
maximum yield of isosorbide from the dehydration of sorbitol is estimated to be 57.6%
at 590 K for 1 h (Fig. 2 (a)).
We predict that the individual products from sorbitol dehydration can be
produced selectively by controlling the reaction time and temperature. In the case of
mannitol dehydration, the yield of 2-5-AHMA is calculated to be always higher than
that of 1-4-AHMA in the temperature range of 500–600 K (Fig. 2 (b)). The maximum
yields of 1-4-AHMA and 2-5-AHMA are predicted to be 23.5% (at 540 K for 10 h)
and 40.5% (at 550 K for 10 h), respectively. Isomannide can be obtained after the peak
of 1-4-AHMA and the maximum yield of isomannide is estimated to be 25.3% at 585
K for 10 h, indicating that selective production of isomannide is difficult from
mannitol dehydration in water. However, isomannide can be produced from mannitol
dehydration by using the solid acid catalyst Hβ zeolite (yield 63%) [36]. For the
12

galactitol dehydration, 1-4-AHGL is the main product and the predicted maximum
yield of 1-4-AHGL is 62.4% at 550 K for 10 h (Fig. 2 (c)).
4
. Conclusions
The intramolecular dehydration of biomass-derived sugar alcohols D-sorbitol,
D-mannitol, and galactitol was carried out in high-temperature water at 523 K – 573 K
without any added acid catalyst. The kinetic parameters of the dehydration reactions
were estimated. The yield of each product from the dehydration reaction was
calculated as a function of reaction time and temperature. The maximum yield of
1
-4-AHSO within the reaction time of 10 h is predicted to be 64.6% (at 525 K for 10 h),
and of isosorbide to be 57.6% (at 590 K for 1 h) from the sorbitol dehydration. By
controlling the reaction time and temperature, it is predicted that individual products
can be produced selectively.
Acknowledgements
This study was supported by JSPS KAKENHI Grant Number JP17H00803.
References
13

[
[
[
1] G.W. Huber, S. Iborra, A. Corma, Chem. Rev., 106 (2006) 4044-4098.
2] J.J. Bozell, G.R. Petersen, Green Chem., 12 (2010) 539-554.
3] C.O. Tuck, E. Pérez, I.T. Horváth, R.A. Sheldon, M. Poliakoff, Science, 337 (2012)
6
95-699.
[
[
4] R.D. Cortright, R.R. Davda, J.A. Dumesic, Nature, 418 (2002) 964-967.
5] PNNL, in, Pacific Northwest National Laboratory (PNNL) and National Renewable
Energy Laboratory (NREL), 2004.
[
6] N. Yan, C. Zhao, C. Luo, P.J. Dyson, H. Liu, Y. Kou, J. Am. Chem. Soc., 128
(2006) 8714-8715.
[
[
[
[
7] A. Fukuoka, P.L. Dhepe, Angew. Chem. Int. Ed., 45 (2006) 5161-5163.
8] P.L. Dhepe, A. Fukuoka, Catal. Surveys Asia, 11 (2007) 186-191.
9] P.L. Dhepe, A. Fukuoka, ChemSusChem, 1 (2008) 969-975.
10] H. Kobayashi, Y. Ito, T. Komanoya, Y. Hosaka, P.L. Dhepe, K. Kasai, K. Hara, A.
Fukuoka, Green Chem., 13 (2011) 326-333.
[
[
11] C. Luo, S. Wang, H. Liu, Angew. Chem. Int. Ed., 46 (2007) 7636-7639.
12] L.-N. Ding, A.-Q. Wang, M.-Y. Zheng, T. Zhang, ChemSusChem, 3 (2010)
8
18-821.
14

[
13] S. Van de Vyver, J. Geboers, M. Dusselier, H. Schepers, T. Vosch, L. Zhang, G.
Van Tendeloo, P.A. Jacobs, B.F. Sels, ChemSusChem, 3 (2010) 698-701.
[
[
14] A.M. Liu, K. Hidajat, S. Kawi, D.Y. Zhao, Chem. Commun., (2000) 1145-1146.
15] S. Van de Vyver, J. Geboers, W. Schutyser, M. Dusselier, P. Eloy, E. Dornez, J.W.
Seo, C.M. Courtin, E.M. Gaigneaux, P.A. Jacobs, B.F. Sels, ChemSusChem, 5
(2012) 1549-1558.
[
[
[
[
16] S.K. Guha, H. Kobayashi, K. Hara, H. Kikuchi, T. Aritsuka, A. Fukuoka, Catal.
Commun., 12 (2011) 980-983.
17] A. Yamaguchi, O. Sato, N. Mimura, Y. Hirosaki, H. Kobayashi, A. Fukuoka, M.
Shirai, Catal. Commun., 54 (2014) 22-26.
18] A. Yamaguchi, O. Sato, N. Mimura, M. Shirai, Catal. Today, 265 (2016)
1
99–202.
19] A. Yamaguchi, N. Mimura, M. Shirai, O. Sato, ACS Sustainable Chem. Eng., 7
2019) 10445-10451.
(
[
[
[
20] A. Yamaguchi, N. Hiyoshi, O. Sato, M. Shirai, Green Chem., 13 (2011) 873-881.
21] A. Yamaguchi, O. Sato, N. Mimura, M. Shirai, RSC Adv., 4 (2014) 45575-45578.
22] Y. Morita, S. Furusato, A. Takagaki, S. Hayashi, R. Kikuchi, S.T. Oyama,
ChemSusChem, 7 (2014) 748-752.
15

[
[
23] H. Kobayashi, H. Yokoyama, B. Feng, A. Fukuoka, Green Chem., 17 (2015)
732-2735.
2
24] F. Fenouillot, A. Rousseau, G. Colomines, R. Saint-Loup, J.-P. Pascault, Progress
Polym. Sci., 35 (2010) 578-622.
[
[
25] H. Kobayashi, A. Fukuoka, Green Chem., 15 (2013) 1740-1763.
26] M. Yabushita, H. Kobayashi, A. Shrotri, K. Hara, S. Ito, A. Fukuoka, Bull. Chem.
Soc. Jpn., 88 (2015) 996-1002.
[
27] K. Bock, C. Pedersen, H. Thogersen, Acta Chemica Scandinavica B, 35 (1981)
4
41-449.
[
[
[
[
28] G. Fleche, M. Huchette, Starch, 38 (1986) 26-30.
29] R. Otomo, T. Yokoi, T. Tatsumi, Appl. Catal. A, 505 (2015) 28-35.
30] P.E. Savage, Chem. Rev., 99 (1999) 603-622.
31] A. Yamaguchi, N. Hiyoshi, O. Sato, K.K. Bando, M. Shirai, Green Chem., 11
(2009) 48-52.
[
[
32] A. Yamaguchi, N. Hiyoshi, O. Sato, M. Shirai, ACS Catal., 1 (2011) 67-69.
33] A. Yamaguchi, N. Muramatsu, N. Mimura, M. Shirai, O. Sato, Phys. Chem. Chem.
Phys., 19 (2017) 2714-2722.
16

[
[
[
34] A. Wisniewski, E. Skorupowa, J. Sokolowski, J. Carbohydr. Chem., 10 (1991)
7-90.
7
35] M. Kurszewska, E. Skorupowa, J. Madaj, A. Konitz, W. Wojnowski, A.
Wiśniewski, Carbohydr. Res., 337 (2002) 1261-1268.
36] H. Yokoyama, H. Kobayashi, J. Hasegawa, A. Fukuoka, ACS Catal., 7 (2017)
4
828-4834.
17

(a)
(b)
18

(c)
Scheme 1 The reaction pathways for the dehydration of (a) D-sorbitol, (b) D-mannitol,
and (c) galactitol.
19

Table 1 Kinetic parameters for the dehydration reactions of D-sorbitol, D-mannitol,
and galactitol
Rate
Activation
energy
Pre-exponential
factor
Reaction temperature (K)
constant
−
1
523
573
−1
−1
(
h )
(kJ mol )
(h )
1
1
1
1
1
1
1
1
1
1
1
1
4
7
1
3
3
1
3
7
3
4
k1S
0.13
0.84
0.32
0.78
0.11
0.44
0.60
0.065
0.17
0.51
0.84
0.14
0.062
0.24
127
166
195
136
148
153
135
151
196
144
133
–
8.4 × 10
3.1 × 10
5.8 × 10
5.9 × 10
1.6 × 10
5.3 × 10
1.5 × 10
1.1 × 10
3.7 × 10
1.2 × 10
1.1 × 10
–
k2S
0.013
0.016
0.0083
0.023
0.028
0.0044
0.0093
0.0097
0.049
0.0056
–
k4S
k5S
k1M
k2M
k3M
k4M
k6M
k1G
k2G
k5G
k6G
11
0.017
163
3.0 × 10
k = k = k = k = 0
3
S
6S
5M
3G
20

21

Fig. 1 Dehydration yields in high-temperature water as a function of elapsed time.
Sorbitol dehydration at (a) 523 K and (b) 573 K: 1-4-AHSO (■), 2-5-AHSO (▲),
isosorbide (●), and unreacted sorbitol (▼). Mannitol dehydration at (c) 523 K and (d)
5
73 K: 1-4-AHMA (■), 2-5-AHMA (▲), isomannide (●), and unreacted mannitol
(
▼). Galactitol dehydration at (e) 523 K and (f) 573 K: 1-4-AHGL (■), 2-5-AHGL
▲), and unreacted galactitol (▼). The lines show the fitting results of the obtained
(
data to the equations (5) – (8) with the kinetic parameters in Table 1.
22

(
a)
isosorbide
-4-AHSO
-5-AHSO
1
2
80
isosorbide
1
-4-AHSO
40
2
-5-AHSO
560
(
b)
isomannide
1
2
-4-AHMA
-5-AHMA
80
2
-5-AHMA
1
-4-AHMA
40
isomannide
560
23

(
c)
1
-4-AHGL
-5-AHGL
2
80
1
-4-AHGL
40
2
-5-AHGL
560
Fig. 2 Predicted dehydration yields in high-temperature water as functions of reaction
time and temperature. (a) Yields of 1-4-AHSO, 2-5-AHSO, and isosorbide from
sorbitol dehydration; (b) yields of 1-4-AHMA, 2-5-AHMA, and isomannide from
mannitol dehydration; and (c) yields of 1-4-AHGL and 2-5-AHGL from galactitol
dehydration.
24

OH OH
HO
OH
OH
H
H
OH OH
D-Sorbitol
O
O
HO
Isosorbide
Sorbitol dehydration

Prof. Kan Ding,
Editor of Carbohydrate Research
Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, China
October 30, 2019
Manuscript ID: CAR_2019_419
Title: Kinetic analyses of intramolecular dehydration of hexitols in high-temperature water
Dear Prof. Kan Ding,
All the authors declare no conflicts of interest associated with this manuscript.
Very sincerely yours,
Aritomo Yamaguchi, Dr.
Research Institute for Chemical Process Technology
National Institute of Advanced Industrial Science and Technology (AIST)
4-2-1 Nigatake, Miyagino, Sendai 983-8551, Japan
e-mail: a.yamaguchi@aist.go.jp
Fax: +81-22-237-5224