Novel perfluoroalkylated derivatives of D-galactopyranose and xylitol for biomedical uses. Hemocompatibility and effect on perfluorocarbon emulsions

Article abstract of DOI:10.1016/j.carres.2004.06.019

6-O-(4,4,5,5,6,6,7,7,7-Nonafluoro-2-hydroxyheptyl)-, 6-O-(4,4,5,5,6,6,7,7, 8,8,9,9,9-tridecafluoro-2-hydroxynonyl)-, and 6-O-(4,4,5,5,6,6,7,7,8,8,9,9,10, 10,11,11,11-heptadecafluoro-2-hydroxyundecyl)-d-galactopyranose (9, 10, and 11, resp.) were prepared by a two-step synthesis including the reaction of 1,2:3,4-di-O-isopropylidene-α-D-galactopyranose with 2-[(perfluoroalkyl) methyl]oxiranes under catalysis with BF₃·Et₂O. Similarly, 1-O-(4,4,5,5,6,6,7,7,7-nonafluoro-2-hydroxyheptyl)-, 1-O-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-2-hydroxynonyl)-, 1-O-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-hydroxyundecyl) -dl-xylitol (18, 19, and 20, resp.) were prepared by a two-step synthesis from the corresponding 1,2:3,4-di-O-isopropylidene-dl-xylitol. Most of the both types of fluoroalkylated carbohydrate derivatives 9-11 and 18-20 generally displayed very low level of hemolytic activity and excellent co-emulsifying properties on testing on perfluorodecalin-Pluronic F-68 microemulsions.

Full text of DOI:10.1016/j.carres.2004.06.019

Carbohydrate
RESEARCH
Carbohydrate Research 339 (2004) 2177–2185
Novel perfluoroalkylated derivatives of D-galactopyranose and
xylitol for biomedical uses. Hemocompatibility and effect on
perfluorocarbon emulsions
a
Vladimır C rıkva, Radek Polak, Oldrich Paleta, Karel Kefurt, Jitka Moravcova,
a
a,
b
b
*
´
´
´
´ˇ
Milan Kodıcek and Stanislav Forman
ˇ
´
c
c
a
´
Department of Organic Chemistry, Institute of Chemical Technology Prague, Technicka 5, 166 28 Prague, Czech Republic
Department of Chemistry of Natural Compounds, Institute of Chemical Technology Prague, Technicka 5, 166 28 Prague,
b
´
Czech Republic
Department of Biochemistry and Microbiology, Institute of Chemical Technology Prague, Technicka 5, 166 28 Prague, Czech Republic
c
´
Received 4 March 2004; received in revised form 8 June 2004; accepted 26 June 2004
Available online 29 July 2004
Abstract—6-O-(4,4,5,5,6,6,7,7,7-Nonafluoro-2-hydroxyheptyl)-, 6-O-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-2-hydroxynonyl)-, and
6-O-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-hydroxyundecyl)-D-galactopyranose (9, 10, and 11, resp.) were
prepared by a two-step synthesis including the reaction of 1,2:3,4-di-O-isopropylidene-a-D-galactopyranose with 2-[(perflu-
oroalkyl)methyl]oxiranes under catalysis with BF3ÆEt2O. Similarly, 1-O-(4,4,5,5,6,6,7,7,7-nonafluoro-2-hydroxyheptyl)-, 1-O-
(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-2-hydroxynonyl)-, 1-O-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-hydroxyun-
decyl)-DL-xylitol (18, 19, and 20, resp.) were prepared by a two-step synthesis from the corresponding 1,2:3,4-di-O-isopropylid-
ene-DL-xylitol. Most of the both types of fluoroalkylated carbohydrate derivatives 9–11 and 18–20 generally displayed very low
level of hemolytic activity and excellent co-emulsifying properties on testing on perfluorodecalin-Pluronic F-68 microemulsions.
ꢀ 2004 Elsevier Ltd. All rights reserved.
Keywords: Perfluoroalkyl epoxides; Fluorinated surfactants; 6-O-(Fluoroalkyl)-D-galactopyranoses; 1-O-(Fluoroalkyl)-DL-xylitol; Hemocompati-
bility; Microemulsion, stability
1. Introduction
Perfluoroalkylated biocompatible surfactants can be ap-
plied as oxygen carriers (including blood substitutes),5,6
oxygen transporting gels for surgery, medium for cell
cultures,7 contrast agent for diagnosis by ultrasound
imaging,6 and drug delivery systems.6
Recently, perfluoroalkylated derivatives of D-galac-
tose and DL-xylitol possessing an unsaturated spacer be-
tween the hydrophilic saccharide and hydrophobic
perfluoroalkyls by a several-step synthesis have been
reported.1,2 Additionally, fluoroalkylated derivatives of
D-glucose and D-galactose were synthesized by the
one-step nucleophilic addition of protected carbohy-
drates to perfluorinated vinyl oligoether,8 but their co-
emulsifying properties were limited. In recent papers,
we have published a convenient method for fluoroalky-
lation of hydroxy compounds9,10 by their reaction with
The synthesis of amphiphilic molecules has been re-
ported,1,2 the molecular structures of which involve
polyfluoroalkylated chains, spacers of various chain
lengths, junction units (ether, or ester groups), and
hydrophilic heads derived from polyethylene glycol,
polyols (alditols), or saccharides. They have been pro-
posed as biocompatible surfactants in the medical
area1,2 displaying unique properties for the formulation
of colloidal systems including perfluorocarbon (PFC)
emulsions, fluorinated vesicles, and other highly fluori-
nated self-assemblies with supramolecular structures.3,4
*
Corresponding author. Tel.: +420-22435-4284; fax: +420-22431-
1082; e-mail: oldrich.paleta@vscht.cz
0008-6215/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2004.06.019

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V. Cırkva et al. / Carbohydrate Research 339 (2004) 2177–2185
2178
catalyst
(CF2)nCF3
CH2
(CF2)nCF3
CH2
+
R
OH
R
O
O
OH
Scheme 1. Completely regioselective10 reaction of hydroxy compounds with fluoroalkylated oxiranes.
perfluoroalkylated epoxides11–13 according to a general
scheme (Scheme 1).
2.2. Fluoroalkylations of 1,2:3,4-di-O-isopropylidene-a-D-
galactopyranose
The reaction was applied to the preparation of sets of
amphiphilic perfluoroalkylated triols,9,14 tetritols,11 and
saccharides.15,16
This paper deals with a novel one-step synthesis of
fluoroalkylated derivatives of D-galactopyranose and
DL-xylitol as surfactants possessing the –CH2–CHOH–
CH2– spacer between the hydrophilic saccharide and
hydrophobic perfluoroalkyl. The new surfactants were
subjected to preliminary tests for hemocompatibility
and co-emulsifying properties.
The practicality of acid-catalyzed reactions of perflu-
oroalkylated epoxides 2–4 with alkane-a,x-diols,10,15
protected triols,9 and partially protected tetritols16 has
opened a preparative pathway to the biosurfactants
from pentitols and aldohexoses. As both primary and
secondary hydroxy groups have appeared9 to react with
the epoxides 2–4, it is necessary to let unprotected only
one hydroxy group.
Protected galactose, that is 1,2:3,4-di-O-isopropylid-
ene-a-D-galactopyranose17 (5) was reacted with racemic
2-[(perfluoroalkyl)-methyl]oxiranes (2–4) in the presence
of boron trifluoride diethyl etherate in diisopropyl ether
as a solvent to afford monofluoroalkylated products 6–8
(Scheme 3) in good isolated yields of 70–73%. The at-
tack of the oxirane ring in epoxides 2–4 by O-nucleo-
phile 5 took place at the terminal carbon atom with
the complete regioselectivity as observed previously.10
For the deprotection of fluoroalkylated compounds
6–8 to obtain the target fluoroalkylated D-galactopyra-
2. Results and discussion
2.1. Improved synthesis of 2-[(tridecafluorohexyl)-
methyl]oxirane
Fluoroalkylated oxiranes 2–4 were used as fluorinated
building blocks in this paper. A highly selective synthesis
of the oxiranes from iodoacetate 1 has recently been
developed (Scheme 2).12 The last step, the epoxide for-
mation, has to be carried out very carefully, but still
small amounts of byproducts are formed. As an
improvement, we have developed a completely selective
synthesis of the most frequently used epoxide 3 by using
potassium hydroxide anchored on silica gel surface
(Table 1). No unsaturated byproducts12 have been de-
tected in the reaction mixture.
noses 9–11,
a variety of O-deisopropylidenation
methods are available, for example, deprotection by io-
dine in methanol,18 on an acidic ion-exchange resins19,20
or using aluminum iodide.21 The convenient deprotec-
tion method for fluoroalkylated triols,9 that is transace-
talization by methanol in the presence of hydrochloric
acid cannot be applied to aldohexoses due to methoxy-
lation at the anomeric position.22 This effect can be
attributed to the rather hydrophobic character conferred
on molecule by the fluoroalkyl chain.23 The best depro-
tection method for fluoroalkylated compounds 6–8 was
using aqueous trifluoroacetic acid to afford the fluoro-
alkylated D-galactopyranoses 9–11 (Scheme 3) in high
isolated yields of 85–90%.
O
KOH/SiO2
C6F13
CH2
O
C6F13
O
hexane,reflux
3
1
I
Scheme 2. Improved synthesis of 2-[(tridecafluorohexyl)methyl]oxi-
rane 3.
2.3. Fluoroalkylations of 1,2:3,4-di-O-isopropylidene-DL-
xylitol
Table 1. Conditions of the improved synthesis of epoxide 3
The protected xylitol, that is 1,2:3,4-di-O-isopropylid-
ene-DL-xylitol17,18 (13) was reacted with racemic 2-[(per-
fluoroalkyl)methyl]oxiranes (2–4) in the presence of
boron trifluoride diethyl etherate in diisopropyl ether
to afford monofluoroalkylated products 15–17 (Scheme
4) in good yields of 75–81%.
Due to marked difference in the reactivity of the pri-
mary and secondary hydroxy groups with the epoxide
3, as reported for diols,9 the product of the reaction of
Reagenta
KOH/Silica
gel (w/w)
Yield of
3 (%)
Time
(min)
KOH
––
1:5
73.7
85.1
91.8
93.2
34.5
360
120
80
KOH/Silica gel
KOH/Silica gel
KOH/Silica gel
1:7.5
1:10
––
60
600
b
K2CO3
a Molar ratio iodoacetate 1/KOH was 1/2.2.
b Molar ratio iodoacetate 1/K2CO3 was 1/2.2.

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V. Cırkva et al. / Carbohydrate Research 339 (2004) 2177–2185
2179
OH
O
O
O
HO
HO
CF2(CF2) nCF3
OH
CF2(CF2) nCF3
O
O
O
O
OH
O
O
O
O
5
HO
O
a
b
OH
+
O
6-8
9-11
CF2(CF2) CF3
n
O
2-4
n = 2, 4, 6
Scheme 3. Preparation of perfluoroalkylated derivatives of D-galactopyranose. Reagents and conditions: (a) BF3ÆEt2O, i-Pr2O, reflux, 5h;
(b) CF3CO2H/H2O (9:1), rt, 30min.
amounts up to 10% relatively to the main emulsifier,
for example, Pluronic F-68, and in positive case stabilize
microemulsions. Preliminary testing was carried out
using a reference microemulsion of perfluorodecalin
emulsified with Pluronic F-68. Two kinds of testing were
applied; the effects on microemulsion stability and
hemolytic stability of erythrocytes in microemulsion
media. In the standard microemulsion, Pluronic was
gradually substituted with the sugar amphiphile tested
and the state of the new emulsion under testing condi-
tions visually evaluated. The xylitol derivative 21 was
tested together with the compounds 9–11 and 18–20 as
a standard23 to verify reliability of the results with re-
spect to the quality of hemoglobin used.
O
O
OH
OH
OH
O
a
+
HO
HO
O
O
O
OH
OH
O
O
(6:1)
14
12
13
2 - 4
6 h
b
OH
OH
CF2(CF2) CF3
n
O
O
O
OH
CF2(CF2) CF3
n
c
O
HO
O
O
OH
OH
15-17
18-20
The results summarized in Table 2 show that the effect
of the co-emulsifier on microemulsion stability is
strongly dependent on both the saccharide moiety and
the length of the perfluoroalkyl chain. Generally, the
derivatives 9–11 of the cyclic D-galactopyranose showed
lower co-emulsifying effect than the derivatives 18–20
containing the open-chained xylitol (Table 2). Com-
pounds 9 and 18 possessing the shortest perfluoroalkyl
displayed the lowest and insufficient co-emulsification
and therefore they were not further tested. The best re-
sults were obtained with D-galactopyranose derivatives
9–11 bearing medium–long perfluoroalkyl (C6F13)
chains, while longer perfluoroalkyl in 11 caused collapse
of the microemulsion. This is in contrast to the xylitol
derivatives 19 and 20 where the microemulsion was sta-
ble up to 80% of the substitution of Pluronic for the
both co-emulsifiers (Table 2). The long-term stability
of the microemulsions was tested for 6weeks at room
temperature mimicking a long-term storage. The results
(Table 3) generally show better co-emulsifying effect for
the derivatives of D-galactose than that of xylitol. As
shown in Table 4, all compounds and concentrations
tested showed that addition of erythrocytes does not
cause coalescence of the microemulsions or hemolysis
of the erythrocytes (Table 5). Amphiphiles bearing per-
fluorohexyl or perfluorooctyl (10, 11, 19, and 20) moiety
displayed no hemolysis up to 80% substitution of Plu-
ronic. Among them, perfluorohexyl derivative of xylitol
O
OH
CF2(CF2) CF3
n
HO
OH
OH
21
n = 2, 4, 6
Scheme 4. Preparation of perfluoroalkylated xylitols. Reagents and
conditions: (a) acetone, H+; (b) BF3ÆEt2O, i-Pr2O, reflux, 10h; (c)
CF3CO2H/H2O (9:1), rt, 30min.
the minor protected xylitol isomer 14 was not detected
in the reaction mixture by proton NMR spectrum. A
pattern signals appear after ca. 30h reaction in the ex-
cess of the epoxide 3.
The deprotection of fluoroalkylated compounds 15–
17 was carried out by using aqueous trifluoroacetic
acid23 to afford the fluoroalkylated xylitols 18–20
(Scheme 4) in yields of 75–90%.
2.4. Testing of co-emulsifying properties and hemocom-
patibility
The novel sugar amphiphiles 9–11 and 18–20 were tested
as co-surfactants for potential oxygen carriers. Co-surf-
actants for microemulsions are usually used3,24–27 in

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V. Cırkva et al. / Carbohydrate Research 339 (2004) 2177–2185
2180
Table 2. Stability of the emulsions after centrifugation
Emulsifier
Substitution of Pluronic F-68 by tested emulsifiers (% w/v PF-68)
20%
40%
60%
Stability of the emulsion
80%
100%
9
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2CF2CF2CF3
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)2CF3
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)3CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2CF2CF22CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)2CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)3CF3
[Xylitol-1-O-yl]-CH2–CH2–CH2–CF2CF2CF2CF2CF2CF3
+
+
À
+
+
+
+
À
+
À
À
+
+
+
nt
+
À
À
+
+
+
nt
nt
nf
nf
nt
À
10
11
18
19
20
21
+
À
nt
+
+
+
nf
À
Plus value means no apparent change of emulsion; minus value means colaps of the emulsion; nt––not tested; nf––the emulsion was not formed.
Table 3. Long-term stability of the emulsions for 6weeks at rt
Emulsifier
Substitution of Pluronic F-68 by tested emulsifiers (% w/v PF-68)
20%
40%
60%
Stability of the emulsion
80%
100%
10
11
19
20
21
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)2CF3
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)3CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)2CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)3CF3
[Xylitol-1-O-yl]-CH2–CH2–CH2–CF2CF2CF2CF2CF2CF3
+
+
+
+
+
+
+
+
+
+
+
+
À
+
+
+
nf
nf
À
nf
À
+
À
+
+
Plus value means no apparent change of emulsion; minus value means colaps of the emulsion; nf––the emulsion was not formed.
Table 4. Stability of the emulsions for 6h after mixing with erythrocytes at 37ꢁC
Emulsifier
Substitution of Pluronic F-68 by tested emulsifiers (% w/v PF-68)
20%
40%
60%
Stability of the emulsion
80%
100%
10
11
19
20
21
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)2CF3
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)3CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)2CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)3CF3
[Xylitol-1-O-yl]-CH2–CH2–CH2–CF2CF2CF2CF2CF2CF3
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
nf
nf
À
nf
+
+
+
+
+
Plus value means no apparent change of emulsion; minus value means colaps of the emulsion; nf––the emulsion was not formed.
Table 5. Hemocompatibility (range of hemolysis, %) of the new amphiphilic compounds
Emulsifier
Substitution of Pluronic F-68 by tested emulsifiers (% w/v PF-68)
20%
40%
60%
Range of hemolysis (%)
80%
100%
9
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2CF2CF2CF3
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)2CF3
[D-Galactose-6-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)3CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)2CF3
[Xylitol-1-O-yl]-CH2–CHOH–CH2–CF2(CF2CF2)3CF3
[Xylitol-1-O-yl]-CH2–CH2–CH2–CF2CF2CF2CF2CF2CF3
9
0
0
1
0
0
27
1
nt
0
nt
nt
nf
nf
0
10
11
19
20
21
0
0
0
0
1
0
0
0
0
nt
0
nt
0
0
0
19, which is a mixture of two diastereoisomers with a
stereogenic center CH(OH) in fluoroalkyl chain showed
no hemolysis at 100% substitution of Pluronic, that is
equally as racemic analogue 21. Thus, the stereoisomers
of both compounds 19 and 21 must be nonhemolytic
under the conditions tested. It can be concluded that
compound 19, which is much easier accessible than its
nonhydroxylated analogue 21, can also be used as
hemolytic standard.
In conclusion, we reported herein a novel standard
compound 19 for an assessment hemocompatibility
and the co-emulsifying properties.

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V. Cırkva et al. / Carbohydrate Research 339 (2004) 2177–2185
2181
3. Experimental
3.1. General methods
3.2.2. Hemocompatibility testing23,27,28
.
Human eryth-
rocytes (from a healthy donor, stored in a refrigerator
not longer than 1week) were washed by isotonic Tris–
HCl buffer. Packed erythrocytes (0.5mL) were added
to the emulsion of perfluorodecalin (see above), the mix-
ture was then gently stirred at 37ꢁCfor 6h and after that
shortly centrifuged. The amount of the extracellular he-
moglobin in the water phase was determined spectro-
photometrically and used as a measure of hemolytic
activity of the co-emulsifier tested.
The temperature data were not corrected. Distillations
of high boiling compounds were carried out on a Vacu-
umbrand RC5 high vacuum oil pump. GC analyses were
performed on Micromat HRGC412 (Nordion Analyti-
cal; 25m glass capilary column, SE-30); nitrogen was
used as carrier gas. NMR spectra were recorded on a
Bruker 400 AM (FT, 19F at 376.5MHz) and Bruker
WP 80 SY (FT, 19F at 75MHz) instruments using Me4Si
and CFCl3 as the internal standards. Chemical shifts are
quoted in ppm (d-scale; s singlet, br s broad singlet; d
doublet, t triplet, m multiplet), coupling constants J in
Hz.
3.2.3. Improved preparation of 2-(2,2,3,3,4,4,5,5,6,6,
7,7,7-tridecafluoroheptyl)oxirane (3). Modified KOH
was prepared as follows: Saturated water solution of
KOH was mixed with silica gel (L60/100), then toluene
was added and the mixture was evaporated on rotary
evaporator. The water residue was removed under vac-
uum (130–150ꢁC/53Pa) for 10h.
The reactions were carried out in a double-neck
round-bottomed flask equipped with a Dimroth con-
denser that was connected with atmosphere by a drying
tube. The apparatus was flushed with argon then
charged with KOH/silica gel, iodoacetate 1 (1.03g;
1.9mmol), and hexane (10mL) (for the ratio of reagents
see Table 1). The mixture was gently refluxed while stir-
ring. The advance of the reaction was periodically
checked by GCand 19F NMR. Then the reaction flask
was equipped with a jacketed short packed column (Ber-
le saddles, column 4cm) and a fraction receiver (a head)
and the reaction mixture was fractionally distilled.
For yields, see Table 1. The analysis of the product 3
(GC, NMR) confirmed the absence of unsaturated by-
products.
Chemicals used were as follows: fluoroalkyl epoxides
2–4 were prepared according to our procedure;12
1,2:3,4-di-O-isopropylidene-a-D-galactopyranose
(5)
and 1,2:3,4-di-O-isopropylidene-DL-xylitol (13) were
prepared according to Refs. 17,23,27; diisopropyl ether
was dried with sodium and further purified by distilla-
tion; boron trifluoride diethyl etherate (Lachema) was
distilled before use; acetone, petroleum ether, tetra-
hydrofuran, chloroform, MeOH (all Aldrich) were dried
before use; trifluoroacetic acid (Aldrich); silica gel (60–
100lm, Merck).
3.2. Preparation of emulsions
Perfluorodecalin (0.125mL) was mixed with isotonic
Tris–HCl buffer of pH7.4 and Pluronic F-68 (block
co-polymer of polyoxypropylene and polyoxyethylene,
5% w/v) as a standard emulsifier and the mixture was so-
nicated for 15s to afford 0.5mL of an emulsion. (For a
more detailed description of the testing procedures see
Ref. 28.)
3.3. Fluoroalkylated derivatives of D-galactopyranose
(compounds 6–8 and 9–11)
3.3.1. General procedure for the reaction of 1,2:3,4-di-O-
isopropylidene-a-D-galactopyranose (5) with 2-[(perflu-
oroalkyl)methyl]oxiranes 2–4 (products 6–8). A mixture
of 1,2:3,4-di-O-isopropylidene-D-galactopyranose (5)
(5.21g, 20mmol), epoxide 2–4 (20mmol), diisopropyl
ether (40g, 0.39mol), and boron trifluoride etherate
(43mg, 0.3mmol) was heated at reflux for 5h while stir-
ring (complete conversion of epoxide). The mixture was
filtered, solvent was evaporated, and crude yellowish oil
product was purified on a silica gel column (5g, elution
with petroleum ether/acetone 4:1). Slightly yellow vis-
cous products 6–8 were obtained in 99% purity (check
by 19F NMR).
3.2.1. Testing of co-emulsifying properties. In the prep-
aration of an emulsion (see above), Pluronic F-68 was
partially or completely substituted by the tested co-
emulsifier; if any apparent phase separation of water
and perfluorodecalin phases did not appear immediately
after finishing the test, the emulsion was considered to
be stable. Stable emulsions in the test are indicated as
ꢀ+ꢁ, unstable emulsion are denoted marked by the sign
ꢀÀꢁ. Stabilities of the mixtures were tested under three
different conditions: (1) stability during centrifugation:
the emulsion was centrifuged for 5min at 400g; (2)
long-term stability at room temperature: the emulsion
was gently stirred (magnetic spinbar) for 6weeks; (3) sta-
bility of the emulsion in the presence of erythrocytes: the
emulsion was mixed with erythrocytes and gently stirred
(magnetic spinbar) at 37ꢁCfor 6h.
3.3.2. 1,2:3,4-Di-O-isopropylidene-6-O-(4,4,5,5,6,6,7,7,7-
nonafluoro-2-hydroxyheptyl)-a-D-galactopyranose (6).
Yield 7.8g (73%); bp 141–143ꢁC/0.67Pa; 1H NMR
(CDCl3): d, 2 diastereoisomers, A (53% rel.), B (47%
rel.): 1.34, 1.35, 1.45, 1.51 (4·s, 12H, 4·CH3), 2.26,

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V. Cırkva et al. / Carbohydrate Research 339 (2004) 2177–2185
2182
2.36 (2·m, 2H, CH2CF2), 3.36, 3.37 (2·br s, 1H, OH),
3.48, 3.55 (2·dd, 1H(H(a), A, B), 2J 10.5, 3J 6.6,
(CDCl3): d, 2 diastereoisomers, A (53% rel.), B (47%
rel.): 1.34, 1.37, 1.47, 1.52 (4·s, 12H, 4·CH3), 2.29,
2.33 (2·m, 2H, CH2CF2), 3.31, 3.42 (2·br s, 1H,
2
3
CH2O), 3.60, 3.67 (2·dd, 1H(H(b), B, A), J 10.5, J
2
3
2
3
4, CH2O), 3.69, 3.73 (2·dd, 1H(H(a), B, A), J 6, J5,6
OH), 3.48, 3.55 (2·dd, 1H(H(a), A, B), J 10.5, J 6.6,
3
3
2 3
3.5, H-6), 3.71, 3.72 (2·ddd, 1H(A, B), J5,6 6, J5,6
CH2O), 3.62, 3.68 (2·dd, 1H(H(b), B, A), J 10.5, J
2 3
3
2
3.5, J4,5 2, H-5), 4.00, 4.01 (2·t, 1H(H(b), A, B), J
4, CH2O), 3.71, 3.75 (2·dd, 1H(H(a), B, A), J 6, J5,6
3
3
3 3
6, J5,6 6, H-6), 4.25, 4.27 (2·dd, 1H(B, A), J3,4 8,
3.5, H-6), 3.71, 3.73 (2·ddd, 1H(A, B), J5,6 6, J5,6
3 2
3J4,5 2, H-4), 4.26 (m, 1H, CH), 4.34, 4.35 (2·dd,
3.5, J4,5 2, H-5), 4.05, 4.08 (2·t, 1H(H(b), A, B), J
3
3
3
3
1H(B, A), J1,2 5, J2,3 2.5, H-2), 4.63, 4.64 (2·dd,
6, J5,6 6, H-6), 4.28, 4.31 (2·dd, 1H(B, A), J3,4 8,
3
3
1H(A, B), J3,4 8, J2,3 2.5, H-3), 5.54, 5.55 (2·d,
3J4,5 2, H-4), 4.33 (m, 1H, CH), 4.35, 4.37 (2·dd,
1H(B, A), J1,2 5, H-1); 13CNMR (CDCl 3): d 24.47,
1H(B, A), J1,2 5, J2,3 2.5, H-2), 4.66, 4.68 (2·dd,
3
3
3
3 3
24.94, 25.98, 26.00 (4·s, 4·CH3), 34.55, 34.71 (2·t,
1H(A, B), J3,4 8, J2,3 2.5, H-3), 5.56, 5.58 (2·d,
2
3
C-A, C-B, JCF 21, C2CF2), 64.12, 64.47 (2·s, C-B, C-
1H(B, A), J1,2 5, H-1); 13C NMR (CDCl3): d 24.47,
A, CH), 66.80, 67.21 (2·s, C-B, C-A, C-5), 70.06,
70.70 (2·s, C-A, C-B, C-6), 70.58, 70.65 (2·s, C-B, C-
A, C-4), 70.81 (s, C-3), 71.30 (s, C-2), 74.95, 75.21
(2·s, C-B, C-A, CH2O), 96.43 (s, C-1), 108.85, 109.62
(2·s, 2Cq), 105.03–125.06 (m, CF2 and CF3); 19F
24.95, 25.96, 26.04 (4·s, 4·CH3), 34.56, 34.72 (2·t,
2
C-A, C-B, JCF 21, C2CF2), 64.15, 64.47 (2·s, C-B, C-
A, CH), 66.82, 67.24 (2·s, C-B, C-A, C-5), 70.06,
70.65 (2·s, C-A, C-B, C-6), 70.53, 70.70 (2·s, C-B, C-
A, C-4), 70.81 (s, C-3), 71.33 (s, C-2), 74.94, 75.25
(2·s, C-B, C-A, CH2O), 96.45 (s, C-1), 108.82, 109.65
(2·s, 2Cq), 105–125 (m, CF2 and CF3); 19F NMR
3
NMR (CDCl3): d À81.34 (t, 3F, JFF 10, CF3),
À113.12 (m, 2F, CF2CH2), À122.21 (m, 2F, CF2),
À126.43 (m, 2F, CF2CF3); Anal. Calcd for
C19H25F9O7: C, 42.55; H, 4.70; F, 31.88. Found: C,
42.61; H, 4.64; F, 32.08.
3
(CDCl3): d À81.58 (t, 3F, JFF 10, CF3), À113.47 (m,
2F, CF2CH2), À122.34 (m, 2F, CF2), À124.82 (m, 6F,
3·CF2), À125.02 (m, 2F, CF2), À126.51 (m, 2F,
CF2CF3); Anal. Calcd for C23H25F17O7: C, 37.51; H,
3.42; F, 43.86. Found: C, 37.42; H, 3.48; F, 44.03.
3.3.3. 1,2:3,4-Di-O-isopropylidene-6-O-(4,4,5,5,6,6,7,7,8,
8,9,9,9-tridecafluoro-2-hydroxynonyl)-a-D-galactopyra-
nose (7). Yield 9.2g (72%); 1H NMR (CDCl3): d, 2 dia-
stereoisomers, A (54% rel.), B (46% rel.): 1.33, 1.36, 1.46,
1.51 (4·s, 12H, 4·CH3), 2.28, 2.34 (2·m, 2H,
CH2CF2), 3.33, 3.38 (2·br s, 1H, OH), 3.47, 3.54
3.3.5. General procedure for the deprotection of 1,2:3,
4-di-O-isopropylidene-6-O-(fluoroalkyl)-a-D-galactopyr-
anoses 6–8 (products 9–11). A mixture of fluoroalkylat-
ed 1,2:3,4-di-O-isopropylidene-D-galactopyranose 6–8
(10mmol) in 10% aqueous TFA (30mL) was stirred
for 30min at rt when the conversion was complete.
The reaction mixture was concentrated to dryness,
petroleum ether (25mL) added, and evaporated (·2).
The crude product crystallized from a mixture THF–
chloroform (1:3) as a white foam to afford after recrys-
tallization pure product (9–11) in 99% purity (check by
19F NMR).
2
3
(2·dd, 1H(H(a), A, B), J 10.5, J 6.6, CH2O), 3.61,
3.66 (2·dd, 1H(H(b), B, A), 2J 10.5, 3J 4, CH2O),
2
3
3.70, 3.74 (2·dd, 1H(H(a), B, A), J 6, J5,6 3.5, H-6),
3
3
3
3.70, 3.72 (2·ddd, 1H(A, B), J5,6 6, J5,6 3.5, J4,5 2,
2
3
H-5), 4.02, 4.03 (2·t, 1H(H(b), A, B), J 6, J5,6 6, H-
3
3
6), 4.26, 4.28 (2·dd, 1H(B, A), J3,4 8, J4,5 2, H-4),
3
4.29 (m, 1H, CH), 4.33, 4.34 (2·dd, 1H(B, A), J1,2 5,
3
3J2,3 2.5, H-2), 4.65, 4.67 (2·dd, 1H(A, B), J3,4 8,
3
3J2,3 2.5, H-3), 5.55, 5.57 (2·d, 1H(B, A), J1,2 5, H-
1); 13CNMR (CDCl 3): d 24.45, 24.92, 25.95, 26.02
3.3.6. 6-O-(4,4,5,5,6,6,7,7,7-Nonafluoro-2-hydroxyhept-
yl)-D-galactose (9). Yield 3.9g (85%); mp 157–
2
(4·s, 4·CH3), 34.57, 34.73 (2·t, C-A, C-B, JCF 21,
1
C2CF2), 64.14, 64.45 (2·s, C-B, C-A, CH), 66.81,
67.22 (2·s, C-B, C-A, C-5), 70.08, 70.68 (2·s, C-A,
C-B, C-6), 70.55, 70.72 (2·s, C-B, C-A, C-4), 70.83 (s,
C-3), 71.32 (s, C-2), 74.93, 75.22 (2·s, C-B, C-A,
CH2O), 96.44 (s, C-1), 108.81, 109.64 (2·s, 2Cq), 105–
125 (m, CF2 and CF3); 19F NMR (CDCl3): d À81.46
159ꢁC; H NMR (D2O/THF-d8): d, 2 diastereoisomers,
A (53% rel.), B (47% rel.), 2.18–2.45 (m, 2H, CH2CF2),
3.32–3.45 (m, 1H, OH), 3.72–3.84 (m, 4H, CH2O and H-
6), 3.85–4.65 (m, 5H, H-1, H-2, H-3, H-4, H-5), 4.33–
4.44 (m, 1H, CH), 4.85–5.02 (m, 4H, OH); 13CNMR
2
(D2O/THF-d8): d 34.5, 34.8 (2·t, C-A, C-B, JCF 21,
3
(t, 3F, JFF 10, CF3), À113.29 (m, 2F, CF2CH2),
C2CF2), 62.1, 62.5 (2·s, CH), 68.3, 68.9, 69.4, 69.8,
70.4, 70.7, 72.1, 72.4, 75.1, 75.6 (10·s, 5·D-galactose
ring carbons C-2, C-3, C-4, C-5, C-6), 74.1, 74.3 (2·s,
CH2O), 94.5, 98.9 (2·s, C-1), 105–125 (m, CF2 and
À122.25 (m, 2F, CF2), À124.42 (m, 4F, 2·CF2),
À126.51 (m, 2F, CF2CF3); Anal. Calcd for
C21H25F13O7: C, 39.63; H, 3.96; F, 38.81. Found: C,
39.72; H, 3.93; F, 38.92.
3
CF3); 19F NMR (D2O/THF-d8): d À81.3 (t, 3F, JFF
10, CF3), À113.1 (m, 2F, CF2CH2), À122.2 (m, 2F,
CF2), À126.4 (m, 2F, CF2CF3); Anal. Calcd for
C13H17F9O7: C, 34.22; H, 3.76; F, 37.48. Found: C,
34.20; H, 3.61; F, 37.61.
3.3.4. 1,2:3,4-Di-O-isopropylidene-6-O-(4,4,5,5,6,6,7,7,8,
8,9,9,10,10,11,11,11-heptadecafluoro-2-hydroxyundecyl)-
1
a-D-galactopyranose (8). Yield 10.3g (70%); H NMR

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V. Cırkva et al. / Carbohydrate Research 339 (2004) 2177–2185
2183
3.3.7. 6-O-(4,4,5,5,6,6,7,7,8,8,9,9,9-Tridecafluoro-2-hy-
droxynonyl)-D-galactose (10). Yield 4.9g (88%); mp
171–173ꢁC; H NMR (D2O/THF-d8): d, 2 diastereoiso-
3.4.2. 2,3:4,5-Di-O-isopropylidene-1-O-(4,4,5,5,6,6,7,7,7-
nonafluoro-2-hydroxyheptyl)-DL-xylitol (15). Yield
1
1
3.8g (75%); H NMR (CDCl3): d, 2 diastereoisomers,
A (52% rel.), B (48% rel.): 1.16, 1.18, 1.37, 1.43 (4·s,
12H, 4·CH3), 2.02–2.48 (m, 2H, CH2CF2), 2.72 (s,
1H, OH), 3.30–4.60 (m, 10H, CH2O, CH, 2·H-1, H-2,
H-3, H-4, 2·H-5); 13CNMR (CDCl 3): d 21.73, 21.84
mers, A (54% rel.), B (46% rel.), 2.20–2.50 (m, 2H,
CH2CF2), 3.31–3.44 (m, 1H, OH), 3.75–3.88 (m, 4H,
CH2O and H-6), 3.87–4.66 (m, 5H, H-1, H-2, H-3, H-
4, H-5), 4.32–4.43 (m, 1H, CH), 4.83–5.05 (m, 4H,
OH); 13CNMR (D O/THF-d8): d 34.6, 34.9 (2·t, C-
(2·s, 4·CH3), 34.69 (t, JCF 21, C2CF2), 64.42 (s,
2
2
2
A, C-B, JCF 21, C2CF2), 62.2, 62.6 (2·s, CH), 68.4,
CH), 66.73, 68.20 (2·s, C-1), 69.03 (s, C-2), 69.21
(s, C-5), 71.39 (s, CH2O), 72.43 (s, C-3, C-4), 109.39
(s, 2·Cq), 104–122 (m, CF2 and CF3); 19F NMR (C DC3l):
d À81.39 (t, 3F, 3J 8.7, CF3), À114.07 (m, 2F, CF2CH2),
À122.23 (m, 2F, CF2), À126.61 (m, 2F, CF2CF3); Anal.
Calcd for C18H25F9O6: C, 42.53; H, 4.96; F, 33.63.
Found: C, 42.56; H, 4.99; F, 33.72.
68.8, 69.4, 69.9, 70.4, 70.8, 72.1, 72.5, 75.2, 75.7 (10·s,
5·D-galactose ring carbons C-2, C-3, C-4, C-5, C-6),
74.4, 74.8 (2·s, CH2O), 94.8, 99.5 (2·s, C-1), 105–125
(m, CF2 and CF3); 19F NMR (D2O/THF-d8): d À81.5
3
(t, 3F, JFF 10, CF3), À113.3 (m, 2F, CF2CH2),
À122.5 (m, 2F, CF2), À124.8 (m, 4F, CF2), À126.5
(m, 2F, CF2CF3); Anal. Calcd for C15H17F13O7: C ,
32.39; H, 3.08; F, 44.40. Found: C, 32.33; H, 3.19; F,
44.52.
3.4.3. 2,3:4,5-Di-O-isopropylidene-1-O-(4,4,5,5,6,6,7,7,8,
8,9,9,9-tridecafluoro-2-hydroxynonyl)-DL-xylitol (16). Yield
4.6g (76%); 1H NMR (CDCl3): d, 2 diastereoisomers, A
(53% rel.), B (47% rel.): 1.17, 1.19, 1.36, 1.42 (4·s, 12H,
4·CH3), 2.10–2.45 (m, 2H, CH2CF2), 2.68 (s, 1H, OH),
3.27–4.59 (m, 10H, CH2O, CH, 2·H-1, H-2, H-3, H-4,
2·H-5); 13C NMR (CDCl3): d 21.75, 21.81 (2·s,
3.3.8. 6-O-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Hepta-
decafluoro-2-hydroxyundecyl)-D-galactose (11). Yield
1
5.9g (90%); mp 176–178ꢁC; H NMR (D2O/THF-d8):
d, 2 diastereoisomers, A (53% rel.), B (47% rel.), 2.15–
2.55 (m, 2H, CH2CF2), 3.31–3.47 (m, 1H, OH), 3.73–
3.83 (m, 4H, CH2O and H-6), 3.81–4.64 (m, 5H, H-1,
H-2, H-3, H-4, H-5), 4.35–4.48 (m, 1H, CH), 4.83–5.01
2
4·CH3), 34.62 (t, JCF 21, C2CF2), 64.45 (s, CH),
66.71, 68.22 (2·s, C-1), 69.12 (s, C-2), 69.28 (s, C-5),
71.35 (s, CH2O), 72.48 (s, C-3, C-4), 109.33 (s, 2·Cq),
102–125 (m, CF2 and CF3); 19F NMR (CDCl3): d
(m, 4H, OH); 13CNMR (D O/THF-d8): d 34.4, 34.7
2
3
2
À81.41 (t, 3F, J 8.7, CF3), À114.54 (m, 2F, CF2CH2),
(2·t, C-A, C-B, JCF 21, C2CF2), 62.0, 62.6 (2·s,
À122.34 (m, 2F, CF2), À123.31 (m, 2F, CF2), À124.11
(m, 2F, CF2), À126.61 (m, 2F, CF2CF3); Anal. Calcd
for C20H25F13O6: C, 39.48; H, 4.14; F, 40.60. Found:
C, 39.52; H, 4.23; F, 40.75.
CH), 68.4, 68.8, 69.6, 69.9, 70.3, 70.7, 72.2, 72.4, 75.2,
75.9 (10·s, 5·D-galactose ring carbons C-2, C-3, C-4,
C-5, C-6), 74.5, 74.9 (2·s, CH2O), 94.1, 98.5 (2·s, C-
1), 105–125 (m, CF2 and CF3); 19F NMR (D2O/THF-
3
d8): d À81.6 (t, 3F, JFF 10, CF3), À113.5 (m, 2F,
CF2CH2), À122.5 (m, 2F, CF2), À124.6 (m, 6F, CF2),
À125.4 (m, 2F, CF2), À126.6 (m, 2F, CF2CF3); Anal.
Calcd for C17H17F17O7: C, 31.11; H, 2.61; F, 49.21.
Found: C, 31.10; H, 2.72; F, 49.34.
3.4.4. 2,3:4,5-Di-O-isopropylidene-1-O-(4,4,5,5,6,6,7,7,8,
8,9,9,10,10,11,11,11-heptadecafluoro-2-hydroxyundecyl)-
1
DL-xylitol (17). Yield 5.7g (81%); H NMR (CDCl3):
d, 2 diastereoisomers, A (53% rel.), B (47% rel.): 1.16,
1.18, 1.35, 1.41 (4·s, 12H, 4·CH3), 2.15–2.40 (m, 2H,
CH2CF2), 2.69 (s, 1H, OH), 3.25–4.66 (m, 10H,
CH2O, CH, 2·H-1, H-2, H-3, H-4, 2·H-5); 13C
NMR (CDCl3): d 21.71, 21.79 (2·s, 4·CH3), 34.65 (t,
2JCF 21, C2CF2), 64.44 (s, CH), 66.75, 68.24 (2·s, C-
1), 69.13 (s, C-2), 69.29 (s, C-5), 71.32 (s, CH2O),
72.47 (s, C-3, C-4), 109.35 (s, 2·Cq), 102–125 (m, CF2
3.4. Fluoroalkylated derivatives of DL-xylitol (compounds
15–17 and 18–20)
3.4.1. General procedure for the reaction of 1,2:3,4-di-O-
isopropylidene-dl-xylitol (13) with 2-[(perfluoroalkyl)-
methyl]oxiranes 2–4 (products 15–17). A mixture of
3
and CF3); 19F NMR (CDCl3): d À81.48 (t, 3F, J 8.7,
1,2:3,4-di-O-isopropylidene-DL-xylitol
(13)
(2.32g,
CF3), À114.68 (m, 2F, CF2CH2), À122.31 (m, 2F,
CF2), À123.44 (m, 6F, 3·CF2), À124.15 (m, 2F, CF2),
À126.69 (m, 2F, CF2CF3); Anal. Calcd for
C22H25F17O6: C, 37.30; H, 3.56; F, 45.59. Found: C,
37.35; H, 3.69; F, 45.68.
10mmol), epoxide 2–4 (10mmol), diisopropyl ether
(20g, 0.2mol) and boron trifluoride etherate (22mg,
0.15mmol) was heated at reflux for 10h while stirring
(complete conversion of epoxide, TLCcheck, petroleum
ether/acetone 4:1). The solids were removed, solvent was
evaporated, and crude yellow oil product was purified
on a silica gel column (50g, elution with petroleum
ether/acetone 4:1). The viscous product (15–17) was ob-
tained in 99% purity (check by 19F NMR).
3.4.5. General procedure for the deprotection of 2,3:
4,5-di-O-isopropylidene-1-O-(fluoroalkyl)xylitols 15–17
(products 18–20).
A
mixture of fluoroalkylated

´
V. Cırkva et al. / Carbohydrate Research 339 (2004) 2177–2185
2184
1,2:3,4-di-O-isopropylidenexylitol 15–17 (5mmol) in
water solution of trifluoroacetic acid (15mL, 1:9) was
stirred for 30min at rt when the conversion was com-
plete. Reaction mixture was concentrated to dryness
and a crude viscous product of brown color was dis-
solved in MeOH (15mL) and treated with carbon black
(2g) at 50ꢁCfor 0.5h. After filtration, the solvent was
evaporated and the viscous oil was heated to 60ꢁC/
266Pa for 12h to afford the waxy product (18–20) in
99% purity (check by 19F NMR).
(m, 2F, CF2), À122.58 (m, 6F, 3·CF2), À123.32 (m,
2F, CF2), À125.74 (m, 2F, CF2CF3); Anal. Calcd for
C16H17F17O6: C, 30.59; H, 2.73; F, 51.41. Found: C,
30.72; H, 2.85; F, 51.56.
Acknowledgements
The authors thank the Atofina S.A. (former Elf Ato-
chem S.A.) for the gift of perfluoroalkyl iodides. The re-
search was supported by the Grant Agency of the Czech
Republic (grant no 203/01/1131) and partly by the Min-
istry of Education of the Czech Republic (Project MSM
223100001). Elemental analyses and measurements of
some NMR spectra were carried out in the Central Lab-
oratories of the Institute of Chemical Technology, Pra-
gue; the authors thank their staff members for the kind
assistance.
3.4.6. 1-O-(4,4,5,5,6,6,7,7,7-Nonafluoro-2-hydroxyhept-
yl)-DL-xylitol (18). Yield 1.61g (75%); 1H NMR
(CD3OD): d, 2 diastereoisomers, A (52% rel.), B (48%
rel.), 2.10–2.60 (m, 2H, CH2CF2), 3.40–4.35 (m, 10H,
H-1, H-2, H-3, H-4, H-5, CH2O, CH), 4.85 (m, 5H,
OH); 13CNMR (DC
2
3OD): d 35.57 (t, JCF 20,
C2CF2), 64.31 (s, C-1), 65.14 (s, CH), 72.04 (s, C-2),
72.20, 72.34 (2·s, C-3), 73.77, 73.92 (2·s, C-4), 74.03
(s, C-5), 76.19 (s, CH2O), 105–124 (m, CF2 and CF3);
19F NMR (CD3OD): d À80.96 (t, 3F, 3J 9, CF3),
À112.36 (m, 2F, CF2CH2), À121.50 (m, 2F, CF2),
À125.97 (m, 2F, CF2CF3); Anal. Calcd for
C12H17F9O6: C, 33.66; H, 4.00; F, 39.93. Found: C,
33.72; H, 4.12; F, 40.05.
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droxynonyl)-DL-xylitol (19). Yield 2.17g (82%); 1H
NMR (CD3OD): d, 2 diastereoisomers, A (53% rel.), B
(47% rel.), 2.11–2.58 (m, 2H, CH2CF2), 3.45–4.40 (m,
10H, H-1, H-2, H-3, H-4, H-5, CH2O, CH), 4.77 (m,
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´
´ˇ
9. Cırkva, V.; Kaplanek, R.; Paleta, O.; Kodıcek, M. Collect.
Czech. Chem. Commun. 2002, 67, 1436–1448.
´
´
10. Cırkva, V.; Ameduri, B.; Boutevin, B.; Paleta, O. J.
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2
5H, OH); 13CNMR (CD 3OD): d 35.59 (t, JCF 20,
CH2CF2), 64.30 (s, C-1), 65.15 (s, CH), 72.01 (s, C-2),
72.18, 72.32 (2·s, C-3), 73.78, 73.91 (2·s, C-4), 74.02
(s, C-5), 76.17 (s, CH2O), 105–124 (m, CF2 and CF3);
19F NMR (CD3OD): d À81.14 (t, 3F, 3J 9, CF3),
À113.02 (m, 2F, CF2CH2), À121.48 (m, 2F, CF2),
À122.59 (m, 2F, CF2), À123.28 (m, 2F, CF2), À125.93
(m, 2F, CF2CF3); Anal. Calcd for C14H17F13O6: C ,
31.83; H, 3.24; F, 46.75. Found: C, 31.75; H, 3.33; F,
46.62.
11. C´ırkva, V.; Gaboyard, M.; Paleta, O. J. Fluorine Chem.
2000, 102, 349–361.
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12. Cırkva, V.; Ameduri, B.; Boutevin, B.; Paleta, O. J.
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13. Cırkva, V.; Duchek, J.; Paleta, O. J. Fluorine Chem. 2003,
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2002, 113, 195–200.
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15. Cırkva, V. Dissertation. Institute of Chemical Technol-
ogy, Prague, 1998.
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16. Kefurt, K.; Moravcova, J.; Bambasova, S.; Buchalova, K.;
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Vymetalıkova, B.; Kefurtova, Z.; Stanık, J.; Paleta, O.
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decafluoro-2-hydroxyundecyl)-DL-xylitol
(20). Yield
2.83g (90%); 1H NMR (CD3OD): d, 2 diastereoisomers,
A (53% rel.), B (47% rel.), 2.12–2.55 (m, 2H, CH2CF2),
3.44–4.42 (m, 10H, H-1, H-2, H-3, H-4, H-5, CH2O,
CH), 4.75 (m, 5H, OH); 13CNMR (CD 3OD): d 35.57
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2
(t, JCF 20, CH2CF2), 64.35 (s, C-1), 65.22 (s, CH),
72.05 (s, C-2), 72.19, 72.33 (2·s, C-3), 73.79, 73.92
(2·s, C-4), 74.03 (s, C-5), 76.19 (s, CH2O), 105–124
(m, CF2 and CF3); 19F NMR (CD3OD): d À81.05 (t,
3F, 3J 9, CF3), À112.95 (m, 2F, CF2CH2), À121.44

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