Solvent-free thermal dehydration of pentitols on zeolites

Article abstract of DOI:10.1081/CAR-200030003

Dehydration of D-arabinitol, ribitol, and xylitol at high temperature in the presence of molecular sieves without solvent in an argon atmosphere is described. Products arising after the dehydration-cyclization (cyclodehydration) reaction with retention or inversion of the configuration of asymmetric carbon atoms, were observed. Complete analytical separations of exhaustively O-acetylated reaction products were achieved by means of GC. The chemical structures of the compounds obtained were assigned using co-injection with standards. Copyright

Full text of DOI:10.1081/CAR-200030003

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Solvent‐Free Thermal Dehydration of
Pentitols on Zeolites
Maria Kurszewska a , Eugenia Skorupowa a , Janusz Madaj a &
Andrzej Wiśniewski a
a Department of Chemistry , University of Gdańsk , Sobieskiego 18,
PL‐80‐952, Gdańsk, Poland
Published online: 17 Aug 2006.
To cite this article: Maria Kurszewska , Eugenia Skorupowa , Janusz Madaj & Andrzej Wiśniewski
(2004) Solvent‐Free Thermal Dehydration of Pentitols on Zeolites, Journal of Carbohydrate Chemistry,
23:4, 169-177, DOI: 10.1081/CAR-200030003
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JOURNAL OF CARBOHYDRATE CHEMISTRY
Vol. 23, No. 4, pp. 169–177, 2004
Solvent-Free Thermal Dehydration of Pentitols
on Zeolites#
Maria Kurszewska, Eugenia Skorupowa, Janusz Madaj,
*
´
and Andrzej Wisniewski
´ ´
Department of Chemistry, University of Gdansk, Gdansk, Poland
CONTENTS
ABSTRACT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
II. RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . . . . . . . . 170
III. EXPERIMENTAL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
A. General Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
B. General Procedure for Dehydration Reaction . . . . . . . . . . . . . 175
1. Dehydration of D-Arabinitol . . . . . . . . . . . . . . . . . . . . 175
2. Dehydration of Xylitol . . . . . . . . . . . . . . . . . . . . . . . 176
3. Dehydration of Ribitol . . . . . . . . . . . . . . . . . . . . . . . 176
ACKNOWLEDGMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
#
´
Dedicated to Professor Gerard Descotes on the occasion of the jubilee of his scientific career.
*
´ ´
Correspondence: Andrzej Wisniewski, Department of Chemistry, University of Gdansk, Sobies-
´
kiego 18, PL-80-952, Gdansk, Poland; E-mail: andrzejw@chemik.chem.univ.gda.pl.
169
DOI: 10.1081/CAR-200030003
0732-8303 (Print); 1532-2327 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

170
Kurszewska et al.
ABSTRACT
Dehydration of D-arabinitol, ribitol, and xylitol at high temperature in the presence of
molecular sieves without solvent in an argon atmosphere is described. Products arising
after the dehydration–cyclization (cyclodehydration) reaction with retention or inver-
sion of the configuration of asymmetric carbon atoms, were observed. Complete
analytical separations of exhaustively O-acetylated reaction products were achieved
by means of GC. The chemical structures of the compounds obtained were assigned
using co-injection with standards.
Key Words: D-Arabinitol; Ribitol; Xylitol; Dehydration–cyclization.
INTRODUCTION
Alditols undergo dehydration under different conditions. Most of them require treat-
ment with strong acidic aqueous solutions (sulfuric acid,[1–3] and hydrochloric acid[4,5]) or
hydrogen fluoride with a catalytic amount of formic or acetic acid,[6] or ion-exchange
resins.[3,7] We previously described the solvent-free thermal dehydration of tetritols[8]
and hexitols[9] in an argon atmosphere in the presence of a zeolite catalyst. We now
report the behaviour of pentitols under the same conditions.
RESULTS AND DISCUSSION
˚
Heating of pentitols in an argon atmosphere in the presence of 3 A zeolites led to
a mixture of monoanhydropentitols. The major compounds formed by dehydration of
D-arabinitol (1) are presented in Sch. 1.
Scheme 1. Monoanhydropentitols formed by dehydration of D-arabinitol (1).

Thermal Dehydration of Pentitols on Zeolites
171
The 1,4- and 2,5-cyclizations of xylitol (2) and ribitol (3) led to pairs of enantiomers
(racemic mixtures), because of substrates symmetry (Schs. 2 and 3).
TLC and GC analyses of the mixtures obtained after dehydration of pentitols in the
[10,11]
˚
presence of 3 A zeolites, as well as in the presence of mineral acids,
indicate that
only monoanhydropentitols were formed due to an intramolecular dehydration. There
were no traces of dianhydropentitols or products obtained by intermolecular dehydration.
The monoanhydropentitols obtained were mostly five-membered ring products with
retention of configuration of carbon atoms. Five-membered ring products with inverted
configuration at C-2 or C-4 were formed in yields from traces to 14.9 % (see Table 2).
The dehydration reaction of D-arabinitol (1), xylitol (2), and ribitol (3) in the conditions
studied also provides anhydro-products with inverted configuration of C-3, but five-
membered and particularly six-membered cyclic products were formed in low yield. Three
1,5-anhydropentitols (6, 9, 10) and four 1,4-anhydropentitols (4, 5, 7, 8) were formed and
could be separated by GC. Six of them were identified as per-O-acetylated derivatives by
co-injection with authentic samples. The per-O-acetylated derivative of 7 (or of its enantio-
mer 70, both give a single peak) was identified based on its mass spectrum (GC-MS).
Hudson and Barker[10] concluded from their results on the dehydration of pentitols in
the presence of mineral acids that ribitol undergoes dehydration fastest, and D-arabinitol
(;D-lyxitol) is the least reactive. Our investigations suggested an alternative sequence
of reactivity: Ribitol . D-Arabinitol . Xylitol which is in accordance with Baddiley’s
results.[12] Ribitol heated for 2 hr at 2908C in an argon atmosphere underwent dehydration
without catalyst yielding mostly 1,4-anhydro-D,L-ribitol isolated in 45% yield as pure
˚
crystals. D-Arabinitol treated in the same conditions as ribitol but in the presence of 3 A
Scheme 2. Major products formed by dehydration of xylitol (2, symbol prime refers to
enantiomer).

172
Kurszewska et al.
Scheme 3. Simultaneous SN1 and SN2 mechanisms proposed for ribitol dehydration.

Thermal Dehydration of Pentitols on Zeolites
173
zeolites underwent dehydration in 95% yield. Xylitol underwent dehydration only in 42%
in the same conditions as D-arabinitol. Longer reaction time 4 hr at 2908C improve the
dehydration rate to 60% but further elongation of reaction time cased visible progression
of decomposition. Additional amounts of zeolites strongly increased this process (Table 1).
Two major products of D-arabinitol dehydration, i.e., 1,4-anhydro-D-arabinitol (4)
and 1,4-anhydro-L-xylitol (5) could not be separated by GC due to identical retention
times and were identified by the Bock et al. procedure[3] (chemical shifts of carbon
atoms were identical with those given in the literature[13]).
The composition of the mixtures after dehydration of the pentitols in the presence of
3 A zeolites suggested that these reactions follow simultaneously SN1 and SN2 mechan-
isms as shown in Sch. 3 (for ribitol as an example).
˚
Protonation of the primary hydroxyl groups at C-1 or C-5 in the ribitol molecule and
intramolecular substitution by the hydroxyl groups at C-4 or C-2 give 1,4-anhydro-D,L-
ribitol as the main product. Substitution of the protonated secondary hydroxyl group at
C-2 or C-4 by an appropriate hydroxymethyl group yields 2,5-anhydro-D,L-arabinitol
(7 and 70). 1,5-Anhydroribitol (10) is formed as a result of the substitution of a protonated
primary hydroxyl group by the other primary hydroxyl group of the molecule. The total con-
centration of the 1,4-anhydropentitols and the relative concentration of 1,4-anhydro-D,L-
ribitol to 2,5-anhydro-D,L-arabinitol (5 : 1), strongly confirm that substitution at the
primary carbon atom (with retention of configuration) by SN2 mechanism is preferred.
The presence of arabinitol (inversion of C-2 or C-4) and xylitol (inversion of C-3) and
their dehydration products in the post-reaction mixture indicate the formation of secondary
carbocations. These cations undergo intramolecular substitution faster than intermolecular
substitution or elimination what can explain the lack of intermolecular dehydration
products[8] or enols in the reaction mixture. The formation of some of the dehydration
products of D-arabinitol or xylitol (Table 2) can be explained in the same manner. 1,4-Anhy-
dropentitols obtained under the conditions used do not undergo further dehydration, also
Table 1. Composition of exhaustively O-acetylated mixture formed by
˚
dehydration of xylitol for 2 hr at 2908C with various amounts of 3 A
zeolites (xylitol : zeolites, w/w).
Concentration (%) of productsa
Compound
(1 : 0.4)
(1 : 1)
9ab
6a
4a
5a
8a
7a
3a
1a
2a
3.2
Trace
13.7
22.7
Trace
Trace
—
5.6
1.1
35.0
54.2
Trace
Trace
Trace
Trace
3.2
—
58.0
aConcentrations were calculated from GC peak areas.
bLetter “a” refers to per-O-acetylated derivatives.

174
Kurszewska et al.

Thermal Dehydration of Pentitols on Zeolites
175
heating of 1,4-anhydro-D,L-ribitol (8 and 80) and 2,5-anhydro-D,L-arabinitol (7 and 70) for
8 hr at 2908C left the unchanged substrates. Increasing of the zeolites amounts in relation to
those of the alditol used accelerate the process of dehydration in all our experiments.
EXPERIMENTAL
General Methods
1H and 13C NMR spectra were recorded at 258C with a Varian Mercury spectrometer at
400 and 100 MHz, respectively, with Me4Si as internal standard. Assignments were based on
homonuclear decoupling experiments, and homo- and heteronuclear correlation. Optical
rotations were measured with a JASCO J-20 polarimeter. Elemental analyses were made
with Carlo Erba apparatus. Commercial D-arabinitol, ribitol and xylitol (Aldrich Chemical
˚
Co.) and molecular sieves type 3 A (Polish Chemical Co., Gliwice) were used. All reactions
were conducted under normal pressure of dry argon. Wood’s alloy as a heating medium was
˚
used. Molecular sieves type 3 A before use were desiccated at 2508C for 5 hr. Evaporation
was performed under reduced pressure. All reactions were monitored by thin-layer chromato-
graphy (TLC) on Kieselgel 60 F254 silica gel plates (E. Merck, 0.20mm thickness). The spots
were detected by spraying with 5% ethanolic H2SO4 and charring. Column chromatography
was carried out with Kieselgel 60 silica gel (E. Merck, smaller than 200 mesh). GC separation
of per-O-acetylated derivatives of all compounds was carried out by a VEGA 6180 (Carlo
Erba) Gas Chromatograph equipped with DB 23 fused silica capillary column
(60 m ꢀ 0.258 mm I.D.) and flame ionization detector (FID). Hydrogen was used as a
carrier gas. The running conditions were: initial temperature 1408C, increase 48C/min to
1608C, 68C/min to 2008C, 88C/min to 2408C, final hold 10min, detector temperature 2608C.
The standard compounds 1,4-anhydro-D-arabinitol,[10] 1,4-anhydro-D,L-xylitol,[14]
1,4-anhydro-D-ribitol,[15] 1,5-anhydroxylitol,[16] 1,5-anhydro-D-arabinitol[17] and 1,5-
anhydroribitol[18] were conventionally acetylated by using acetic anhydride–sodium
acetate prior to GC.
General Procedure for Dehydration Reaction
˚
Pentitol and 3 A molecular sieves were placed in a quartz apparatus, which was purged
with argon for 30min. Then the reaction mixture was heated in an argon atmosphere at
various temperature for various time. After cooling to room temperature the crude post-
reaction mixtures were dissolved in hot MeOH, and TLC analyses were made in a
solvent mixture of 3 : 2 : 1 Et2O–CHCl3–MeOH. A small portion of each product
mixture was concentrated to a thick syrup under a nitrogen stream and exhaustively
O-acetylated with Ac2O in the presence of catalytic amounts of anhydrous NaOAc over
1 hr at 1008C, after which the per-O-acetylated products were analysed by GC.
Dehydration of D-Arabinitol
˚
D-Arabinitol (1, 0.5 g) and 3 A molecular sieves (0.5 g) were placed in a quartz
apparatus. Then the reaction mixture was heated at 2808C or 2908C for 2 hr.

176
Kurszewska et al.
Dehydration of Xylitol
˚
Xylitol (2, 0.6 g) and 3 A molecular sieves (0.6 g) were placed in a quartz apparatus.
Then the reaction mixture was heated at 2908C for 2, 3, or 4 hr.
Dehydration of Ribitol
˚
Ribitol (3, 0.6 g) and 3 A molecular sieves (0.6 g) were placed in a quartz apparatus.
Then the reaction mixture was heated at 2608C, 2708C, or 2808C for 2 hr and at 2908C for
1 or 4 hr.
1,4-Anhydro-D,L-ribitol (8). Ribitol (3, 0.38 g) was placed in a quartz apparatus,
which was purged with argon for 30 min. Then the reaction mixture was heated in an
argon atmosphere at 2908C for 2 hr. After cooling to room temperature the crude post-
reaction mixtures was dissolved in hot isopropyl alcohol. The solution was cooled and
the precipitate was filtered to give 1,4-anhydro-D,L-ribitol (0.15 g, 45% yield) [m.p.
1
0
74–758C, [a]D 08 (c 0.97, H2O); H NMR (D2O): d 3.66 (1H, dd, J1,2 5.2 Hz, J1,1
0
0
10.3 Hz, H-1), d 3.81 (dd, 1H, J5,5 10.4 Hz, J4,5 2.6 Hz, H-5), d 3.82 (dd, 1H, J1 ,2
0
2.8 Hz, H-10), d 3.88 (m, 1H, J2,3 7.2 Hz, H-2), d 4.08 (dd, 1H, J4,5 4.2 Hz, H-50), d
4.11 (dd, 1H, J3,4 5.0 Hz, H-3), d 4.30 (m, 1H, H-4); 13C NMR (D2O): d 62.46 (C-5), d
72.11 (C-2), d 73.69 (C-3), d 73.28 (C-1), d 82.65 (C-4)].
ACKNOWLEDGMENTS
This work was supported by a research grant DS/8361-4-0134-1 from the Polish State
Committee for Scientific Research (KBN).
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Received March 3, 2003
Accepted August 12, 2003