Chemistry of [(perfluoroalkyl)methyl] oxiranes. Regioselectivity of ring opening with O-nucleophiles and the preparation of amphiphilic monomers

Article abstract of DOI:10.1016/S0022-1139(97)00032-8

The reactions of oxiranes R_FCH₂CH(-O-)CH₂ (R_F≡C₄F₉, C₆F₁₃, C₈F₁₇; 4a-4c) with a series of alkanols in the presence of a Lewis acid took place at the terminal carbon atom with complete regioselectivity. 2-Hydroxyethyl methacrylate and acrylate reacted similarly. The reaction with alkane diols was controlled to proceed with one or two molecules of the oxiranes chemoselectively. Non-regioselective, base-catalysed ring opening by methacrylic acid (83% terminal attack) was discussed on the basis of the hard and soft acids and bases (HSAB) concept. A convenient transformation of the oxiranes to the corresponding diols 13a-13c via dioxolane intermediates, and their conversion to bis-methacrylates, was accomplished with overall yields of 75%-79%. Thiourea converted the oxiranes into the corresponding thiiranes (15a-15c). The reactions afforded products generally in yields of 82%-98%.

Full text of DOI:10.1016/S0022-1139(97)00032-8

Journal of Fluorine Chemistry 84 (1997) 53–61
Chemistry of [(perfluoroalkyl)methyl] oxiranes. Regioselectivity of ring
opening with O-nucleophiles and the preparation of amphiphilic
monomers
Vladim´ır C´ırkva a, Bruno Ame´duri b, Bernard Boutevin b, Oldrˇich Paleta a,
a Department of Organic Chemistry, Prague Institute of Chemical Technology, 16628 Prague 6, Czech Republic
b ESA (CNRS) 5076, Ecole Nationale Supe´rieure de Chimie de Montpellier, 8, rue de l’Ecole Normale, 34296 Montpellier Ce´dex 5, France
Received 27 November 1996; accepted 2 March 1997
Abstract
The reactions of oxiranes RFCH2CH(–O–)CH2 (RF C4F9, C6F13, C8F17; 4a–4c) with a series of alkanols in the presence of a Lewis acid
took place at the terminal carbon atom with complete regioselectivity. 2-Hydroxyethyl methacrylate and acrylate reacted similarly. The
reaction with alkane diols was controlled to proceed with one or two molecules of the oxiranes chemoselectively. Non-regioselective, base-
catalysed ring opening by methacrylic acid (83% terminal attack) was discussed on the basis of the hard and soft acids and bases (HSAB)
concept. A convenient transformation of the oxiranes to the corresponding diols 13a–13c via dioxolane intermediates, and their conversion
to bis-methacrylates, was accomplished with overall yields of 75%–79%. Thiourea converted the oxiranes into the corresponding thiiranes
(15a–15c). The reactions afforded products generally in yields of 82%–98%. q 1997 Elsevier Science S.A.
Keywords: Amphiphilic fluoroalkyl (meth)acrylates; Fluoroalkane-1,2-diols; Fluoroalkane-1,2-diyl-bis-methacrylates; 4-Fluoroalkyl-2,2-dimethyl-1,3-
dioxolanes; Fluoroalkyl thiiranes; Nucleophilic oxirane ring opening
1. Introduction
Chemical transformations of fluoroalkyl oxiranes provide
good possibilities for the preparation of interesting interme-
diates and products of practical importance. Therefore the
applied chemistry of fluoroalkyl oxiranes 1 has been the sub-
ject of much industrial interest as it may yield a series of
advanced technical applications. Epoxides have been
employed as polymers for special purposes and as surfactants
with the general structures 2 and 3 (Scheme 1). In the pol-
ymer area, oxiranes 1 are used in the preparation of amphi-
philic monomethacrylates of perfluoroalkyl diols (2a)[1,2],
materials for optical fibres (2a and 3a) [3–5], polymers for
Scheme 1. General structures of (meth)acrylate monomers and hydroxyl-
contact lenses with improved oxygen transport (3b) [5],
hydrophobic coatings and surface property modifiers for pol-
ymers (2a and 3a) [6,7], oleophobic copolymers (2d and
3a) [7,8] and polyacrylates containing perfluoro pendant
chains which display very low surface tensions (2a) [9].
The epoxides 1 can be transformed to 1,2-diols, which are
then used for new polyurethane resins for different purposes
[4,10]. In the area of surface-active compounds, new non-
containing surfactants.
ionogenic (2b) and ionogenic (2c) surfactants have been
prepared [11–14], together with oil dispersants (2d) [15].
Fluoroalkyl oxiranes 1 are versatile intermediates which
can be transformed into various products [1–15]; the first
reactions in syntheses and preparations involve nucleophilic
ring opening. Several reactions of perfluoroalkylated oxira-
nes 1 with O- and S-nucleophiles have been reported in the
literature. The nucleophilic reagents reported in the reactions
Corresponding author.
0022-1139/97/$17.00 q 1997 Elsevier Science S.A. All rights reserved
PII S0022-1139(97)00032-8

54
V. C´ırkva et al. / Journal of Fluorine Chemistry 84 (1997) 53–61
Scheme 2. Two-step preparation of perfluoroalkyl epoxides from perfluo-
roalkyl iodides.
of oxiranes 1 include water [16–18], alkali metal hydroxides
[19], acrylic or methacrylic acid [2,20], monoethers of
poly(ethylene glycols) [20,21], monomethacrylates of
poly(ethylene glycols) [6,7] and thiourea [19]. Reactions
of perfluoroalkylated oxirane with potassium hydroxide[19]
lead to an unsaturated product.
Scheme 3. Mechanisms of nucleophilic oxirane ring opening under acid
catalysis.
be explained by the destabilizing effect of b-perfluoroalkyl
on the potentially formed intermediate carbocation.
Previously [22,23], we have developed a convenient two-
step preparation of perfluoroalkyl oxiranes 4a–4c, based on
the radical addition of perfluoroalkyl iodides onto allyl ace-
tate (Scheme 2), with overall yields of 85%–87%. In this
paper, we present the ring-opening reactions of these epoxi-
des with a series of O-nucleophiles and thiourea. The purpose
has been to obtain basic and comparative information about
the reactivity of the epoxides and about the regioselectivity
of the ring opening with alkanols, as models for reactions of
more complicated hydroxy compounds; in addition, the aim
has been to develop a preparative method for amphiphilic
(meth)acrylate monomers and perfluoroalkylated ethane-
1,2-diol bis-methacrylates.
2.2. Acid-catalysed reactions with alkanols, a,v-alkane
diols and hydroxyalkyl (meth)acrylates
The reactions of alkanols with the epoxide 4b were carried
out in the presence of magnesium perchlorate (Scheme 4,
5a–5g). We did not observe the formation of the epoxide 4b
oligomers. The results in Table 2 also reveal no apparent
decrease in yield with branching of the alkanol chain, as
demonstrated for the series of 1- and 2-propanol (products
5c and 5d) and primary, secondary and tertiarybutylalcohols
(products 5e–5g); however, the reaction times were longer
for branched alkanols to achieve complete conversion of the
epoxides (Table 2). On this basis, the reactions of polyhy-
droxy compounds with the epoxides 4a–4c were successfully
carried out during the synthesis of potential biosurfactants as
reported previously [12]. All reactions with alkanols took
place with 100% regioselectivity of ring opening and no
regioisomers were found in the reaction mixtures.
2. Results and discussion
2.1. Regioselectivity of the acid-catalysed ring-opening
reactions
All previously reported reactionsofepoxideswithhydroxy
compounds, carried out under acid catalysis [6,7,16–21],
have proceeded with complete regioselectivity. We testedthe
reactivity of epoxides 4a–4c with a series of hydroxy com-
pounds (Schemes 4 and 5) in the presence of Lewis acid
catalysts (boron trifluoride etherate, magnesium perchlo-
rate). All the reactions took place with complete regioselec-
tivity independent of the structure and branching of the
alkanols (see below). Non-fluorinated alkyloxiranesareusu-
ally cleaved at the C2 carbon atom of the oxirane ring [24]
(Scheme 3); the reason for this regioselectivity is the for-
mation of an intermediate carbocation-like reactant which is
stabilized by the attached alkyl. In the case of the fluoroal-
kylated epoxides 4a–4c, our observations have confirmed
complete nucleophilic attack at C1, as depicted in Scheme 3
and Scheme 4. The reversed regioselectivity in this case can
Scheme 4. Reaction of epoxide (4b) with alcohols and diols.

V. C´ırkva et al. / Journal of Fluorine Chemistry 84 (1997) 53–61
55
The reactions of the epoxide 4b with aliphatic diols were
carried out in the presence of boron trifluoride etherate
(Scheme 4). We have developed reaction conditions under
which only one hydroxyl group reacts with the epoxide to
afford monofluoroalkylated products 6a–6d. These com-
pounds can be converted subsequently to the bis-fluoroalky-
lated diols (7a and 7d), which can also be obtained directly
from the diols with an excess of the epoxide.
As a continuation of the study of oxirane 4b ring-opening
reactions, we carried out reactions of the epoxides 4a–4c with
2-hydroxyethyl acrylate or methacrylate (Scheme 5). The
reactions afforded the corresponding amphiphilic acrylate 8
and methacrylates 9a–9c in 92% yield (Table 2). Thesecom-
pounds have been obtained previously [20] by the direct
reaction of iodohydrins with potassium (meth)acrylate in
octafluoropentanol in yields of approximately 9.2%. An anal-
ogous ring opening of epoxides 4a–4c with methacrylic acid
in the presence or absence of boron trifluoride etherate or
magnesium perchlorate did not take place, probably due to
the low nucleophilicity of the acid hydroxylic oxygen; the
polymerization of the starting epoxides was observed as the
only reaction.
2.3. Regioselectivity of base-catalysed reactions with
methacrylic acid
Tertiary amines have been used as catalysts for the ring
opening of non-fluorinated epoxides [25–28] with methac-
rylic acid, whereas the reaction of fluoroalkyl epoxide 4b was
accomplished in the presence of potassium methacrylate [2]
or triphenylphosphine [2]. We carried out the reaction of
epoxides 4a–4c in the presence of triethylamine to gen-
Scheme 5. Reaction of epoxides 4a–4c with nucleophiles.
centre at the oxirane ring, i.e. at the carbon, which is closer
to the perfluoroalkyl group having strong electron-withdraw-
ing properties (17). The smaller yield of the product of this
erate
a quasi-methacrylate anion (CH2_C(CH3)CO–
O(y)HEt3N(q)) as a stronger nucleophile of the free acid
(Scheme 5). The reaction took place readily, but the nucleo-
philic attack was not regioselective as previously reported
[29]: the main attack of quasi-methacrylate anion took place
at C1 (83% terminal attack) in oxiranes 4a–4c; the regio-
isomeric products 10 and 11 were not separated and theminor
products were identified by nuclear magnetic resonance
(NMR) spectroscopy. The regioselectivity results are listed
in Table 1. A very similar regioselectivity of ring opening
was reported previously [2].
Table 1
Regioselectivity of oxirane ring opening in 4a–4c with methacrylic acid in
the presence of NEt3
Epoxide RF
Regioisomeric productsa (% rel.)
RFCH2CH(OH)CH2OMA RFCH2CH(OMA)CH2OH
4a
4b
4b
4c
C4F9 10a
83
11a
11b
11b
11c
17
C6F13 10b
C6F13 10b
C8F17 10c
85–90b
83
10–15b
17
The regioselectivity of base-catalysed ring opening in per-
fluoroalkyl epoxides 4a–4c is surprising whencomparedwith
non-fluorinated alkyloxiranes in which ring opening with
alkoxides is completely regioselective [24]. On the other
hand, the opening reaction of epoxides 4a–4c is similar to the
partly selective acid-catalysed ring opening of non-fluori-
nated epoxides [24]. The unexpected result can be explained
using the hard and soft acids and bases (HSAB) concept
[30–32] as depicted in Scheme 6: under acid catalysis, the
complex of oxirane and the acid (16) is attacked by a softer
nucleophile at a softer (delocalized) centre; the reaction of
the charged nucleophile, which is a harder agent than oxygen
in the hydroxyl group [30–32], can take place at a harder
83
17
aThe formation of regioisomers has also been mentioned in the presence of
Me4NCl as the catalyst [1].
bIn the presence of potassium methacrylate or triphenylphosphine [2].
Scheme 6. Hard and soft attack in oxirane ring opening.

56
V. C´ırkva et al. / Journal of Fluorine Chemistry 84 (1997) 53–61
attack (11) than expected may be caused by a repulsive
interaction between the perfluoroalkyl group and the charged
nucleophile in this SN2 reaction.
3. Conclusions
The regioselectivity of the ring opening of the fluoroalkyl
oxiranes 4a–4c with different O-nucleophiles and thiourea
was studied: the ring opening with alkanols and 2-hydroxy-
ethyl acrylate or methacrylate in the presence of a Lewis acid
catalyst took place at the terminal carbon atom with complete
regioselectivity. Branching of the alkyl chain of the alkanols
prolonged the reaction times, but did not influence the com-
plete epoxide conversion. The reaction of the epoxides with
hydroxyalkyl (meth)acrylates afforded new amphiphilic
fluoroalkyl (meth)acrylates in 81%–92% yield; contrary to
this selective reaction, the oxirane ring opening with meth-
acrylic acid in the presence of triethylamine was not com-
pletely selective (terminal attack of 83%).
2.4. Preparation of perfluoroalkylated 1,2-diols;
(meth)acrylate monomers
The transformation of fluoroalkyl epoxides to the corre-
sponding 1,2-diols under acid catalysis has been described
previously [16,17,33,34]. The yields were not very satisfac-
tory [16,17] or required special conditions[33,34]. Wehave
developed a procedure in which the epoxides 4a–4c are first
converted into the dioxolanes 12a–12c (Scheme 5) in yields
of approximately 95%, and then easily hydrolysed to the
corresponding diols13a–13cinaqueousmethanolinthepres-
ence of hydrochloric acid in mean yields of 96% (Table 2).
We assume that the attack of epoxides 4a–4c proceeds by the
enol form of acetone (Scheme 5).
The epoxides were easily converted to the corresponding
diols in a two-step synthesis via 1,3-dioxolane intermediates
with overall yields of approximately 91%. The reaction of
the epoxides with thiourea afforded the corresponding
thiiranes in 86%–89% yield.
The diols 13a–13c can be converted to the bis-methacry-
lates 14a–14c, which are examples of bifunctionalmonomers
that can be used to modifythe propertiesofhighlyhydrophilic
and water-soluble poly(methacrylates). The mono-fluoroal-
kylated (13a–13c) and bis-fluoroalkylated (7a and 7d) diols
are potential intermediates for well-defined structured poly-
mers, such as polyurethanes or polyesters, and for
poly(meth)acrylate compositions as cross-linking agents.
Acrylate 8 and methacrylates 9 and 10 represent types of
amphiphilic monomer which can be used as biocompatible
materials, enabling better oxygen transport [35].
4. Experimental details
4.1. General comments
The temperature data were uncorrected. Distillations of
high boiling compounds were carried out on a Vacuubrand
RC5 high vacuum oil pump. Gaschromatography(GC)anal-
yses were performed on a Chrom 5 instrument (Laboratorn´ı
prˇ´ıstroje, Prague; FID, 380 cm 0.3 cm packed column, sil-
icone elastomer E-301 on Chromaton N-AW-DMCS (Lach-
ema, Brno), nitrogen) and on a Delsi apparatus (model 330,
equipped with SE30 column, 100 cm 1/8 in (i.d.), nitro-
gen, temperature programme in the range 50–250 8C); the
GC apparatus was connected to a Hewlett-Packard integrator
(model 33990). NMR spectra were recorded on Bruker 400
AM (FT, 19F at 376.5 MHz) and Bruker WP 80 SY (FT,
19F at 75 MHz) instruments; tetramethylsilane (TMS) and
CFCl3 were used as internal standards and the chemical shifts
are given in parts per million (s, singlet; bs, broad singlet; d,
doublet; t, triplet; q, quadruplet; qi, quintuplet; sex, sextuplet;
sep, septuplet; m, multiplet); the coupling constants J are
given in hertz and the solvents used were CDCl3, acetone-d6
and dimethylsulphoxide-d6 (DMSO-d6).
The chemicals used were as follows: fluoroalkyloxiranes
4a–4c were prepared according to the procedure described in
Ref. [22]; iodoperfluoroalkanes were obtained from Elf Ato-
chem and were distilled before use; silica gel L40/100
(Merck); magnesium perchlorate (Aldrich); boron trifluor-
ide etherate (Aldrich); triethylamine (Aldrich) was distilled
before use (88–89 8C); thiourea (Aldrich); methacrylic acid
(Aldrich); 2-hydroxyethyl acrylate (Aldrich); 2-hydroxy-
ethyl methacrylate (Aldrich); 1-propanol, 2-propanol, 1-
butanol, 2-butanol, tert-butyl alcohol (all Fluka) and acetone
were dried and purified according to standard procedures
2.5. Reaction with thiourea
According to the previously described procedure [19], we
carried out the reaction of the epoxides 4a–4c with thiourea
in a non-catalysed reaction. The nucleophilicity of the thiol
form of thiourea, as depicted in Scheme 5, was sufficient to
attack the oxirane ring of fluoroalkyl epoxides to afford thiir-
anes (Table 2) in much higher yields(86%–89%) thanthose
reported previously [19] for a branched perfluoroalkyl oxi-
rane 1 (yield below 20%).
The structures of the compounds prepared were elucidated
13
on the basis of elemental analyses and 1
spectra. A detailed study of the
,
and 19 NMR
H
C F
13C
NMR spectra of the
epoxide 4b and similar compounds has been published pre-
viously [36]. In a preceding paper [37], we reported the
1
13
and
NMR spectra of the individual epoxides 4a–4c.
C
H
The chemical shifts of the corresponding individual atoms
and groups in the 19 NMR spectra of the reaction products
F
appear to be similar to those in the starting epoxides 4a–4c
and therefore are presented briefly (see Section 4).
Compounds 5a–5g, 6a–6d, 7a, 7d, 8, 9a–9c, 10a, 11a,
11c, 12a–12c, 14a–14c and 15a–15c are new.

V. C´ırkva et al. / Journal of Fluorine Chemistry 84 (1997) 53–61
57
Table 2
Yields, physical properties and elemental analyses of compounds 5–15
Starting
Time Product Yield
Purity B.p. (m.p.)
Formula
M.W.
Analysis: found/calculated (%)
compound (h)
(%)
(8C/mmHg; 8C)
(g)
(%)
C
H
F or (S)
4b
4b
4b
4b
4b
4b
4b
4b
4b
4b
4b
6a
6d
4b
4a
4b
4c
4a
4b
4c
4a
4b
4c
3
4
4
4
4
4
5
1
1
1
1
1
1
2
2
2
2
2
2
2
0.5
0.5
0.5
5a
5b
5c
5d
5e
5f
5g
6a
6b
6c
6d
7a
7d
8
9a
9b
9c
3.91
4.03
4.10
4.12
4.33
4.30
4.28
23.1
24.2
25.2
26.6
6.68
7.30
12.0
18.7
23.3
27.9
35.5
44.4
52.9
6.35
8.25
10.2
96
95
94
94
96
96
95
88
89
90
92
82
85
81
92
92
92
98
96
94
95
95
95
99
98
98
98
99
99
98
98
98
99
99
96
96
98
98
98
98
98
98
98
98
98
98
58–59/1.5
66–68/1.5
72–73/1.5
67–69/1.5
78–79/1.5
77–78/1.5
78–79/1.5
88–89/0.025
105–107/0.03
113–115/0.04
122–124/0.03
105–107/0.015
131–133/0.012
95–98/0.005
100–102/0.08
100–103/0.02
102–104/0.003
73–75/0.8
77–79/0.08b
93–95/0.01c
70–72/15
C10H9F13O2
408.2
422.2
436.2
436.2
450.2
450.2
450.2
438.2
452.2
466.2
482.2
814.3
858.4
492.2
29.4/29.4
31.2/31.3
32.9/33.0
32.7/33.0
34.3/34.7
34.8/34.7
34.4/34.7
30.65/30.15
32.3/31.9
33.7/33.5
33.16/32.4
29.7/29.5
30.2/30.8
34.25/34.2
2.33/2.22 59.9/60.5
2.73/2.63 57.0/58.5
3.03/3.00 57.1/56.6
3.04/3.00 56.1/56.6
3.39/3.36 55.9/54.9
3.64/3.36 54.9/54.9
3.50/3.36 54.4/54.9
2.71/2.53 55.3/56.4
3.11/2.90 55.3/54.6
3.39/3.24 51.89/53.0
3.51/3.14 50.6/51.2
1.91/1.98 59.9/60.7
2.71/2.35 56.8/57.5
2.79/2.66 50.5/50.2
3.46/3.72 41.8/42.1
3.35/2.99 47.7/48.7
2.62/2.49 53.0/53.3
2.89/3.06 46.9/47.2
2.65/2.40 54.2/53.4
1.93/1.97 57.35/57.45
3.33/3.32 51.4/51.2
2.62/2.55 57.2/56.9
1.99/2.08 60.0/60.5
C
C
11H11F13O2
12H13F13O2
C12H13F13O2
13H15F13O2
C13H15F13O2
C
C
C
13H15F13O2
11H11F13O3
C12H13F13O3
C
C
13H15F13O3
13H15F13O4
C20H16F26O4
C
C
22H20F26O5
14H13F13O4
C13H15F9O4
15H15F13O4
406.25 38.1/38.4
C
506.2
606.3
362.2
462.2
562.2
334.2
434.2
534.2
35.9/35.6
33.3/33.7
36.3/36.5
33.3/33.8
32.2/32.05
35.7/35.9
32.9/33.2
30.5/31.5
C17H15F17O4
C11H11F9O3
C13H11F13O3
C15H11F17O3
10aa
10ba
10ca
12a
12b
12c
C
C
10H11F9O2
12H11F13O2
77–79/5
81–83/1
C14H11F17O2
(32–33)
12a
12b
2
2
13a
13b
2.82
3.78
96
96
99
99
104–106/5
108–109/1
(62–63)
C7H7F9O2
C9H7F13O2
294.1
394.1
28.8/28.6
27.1/27.4
2.51/2.40 57.8/58.1
1.80/1.79 63.4/62.7
12c
2
13c
4.74
96
99
125–129/0.8
(114–115)
84–85/0.12
90–91/0.06
95–97/0.005
(31–32)
71–73/50
73–75/20
85–87/10
C11H7F17O2
494.15 26.9/26.7
1.55/1.43 65.7/65.4
13a
13b
13c
2
2
2
14a
14b
14c
1.74
2.20
2.71
81
83
86
98
98
98
C
15H15F13O4
C17H15F13O4
19H15F17O4
430.3
530.3
630.3
42.0/41.9
38.7/38.5
36.2/36.2
3.59/3.51 39.9/39.7
2.98/2.85 46.7/46.6
2.55/2.40 51.3/51.2
C
4a
4b
4c
4
4
4
15a
15b
15c
2.51
3.41
4.38
86
87
89
98
98
98
C7H5F9S
C9H5F13S
C11H5F17S
292.2
392.2
492.2
28.1/28.8
27.3/27.6
26.6/26.8
1.91/1.72 (10.4/11.0)d
1.44/1.29 (8.25/8.17)d
1.06/1.02 (6.40/6.51)d
(33–34)
aContent of 17% of the corresponding regioisomer 11a, 11b or 11c.
bLiterature value [20]: 108–112 8C/1.0–1.2 mmHg.
cLiterature value [20]: 127–130 8C/2.5–2.8 mmHg.
dSulphur content; the fluorine content could not be determined in the presence of sulphur.
[38]; ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol and
diethylene glycol (all Aldrich) were dried with sodium and
further purified by distillation or according to standard pro-
cedures [38].
CF2 and CF3) ppm. 19F NMR (CDCl3) d: 81.35–82.77 (t,
3F, CF3, JFFs10), 113.02–114.22 (m, 2F, CF2CH2),
122.15–125.63 (m, 2–10F, 1–5CF2), 126.34–127.67 (m, 2F,
CF2CF3) ppm.
3
4.2. Reactions of epoxide 4b with hydroxy compounds
4.2.1. Reactions with alkanols (products 5a–5g)
In a round-bottomed flask (25 ml), equipped with a Dim-
roth reflux condenser connected to the atmosphere through a
drying tube (potassium hydroxide) and a magnetic spinbar,
a mixture of alkanol (0.1 mol), epoxide 4b (3.76 g, 0.01
mol) and magnesium perchlorate (1.12 g, 5 mmol) was
heated at 70 8C for 3–5 h (complete conversion of 4b) with
stirring. After cooling to room temperature, water (25 ml)
was added to the mixture and the lower oily yellow-coloured
The summarized NMR spectra of 4a–4c [23] are as fol-
lows. 1H NMR (CDCl3) d: 2.18, 2.29 (2 dm, 2H, CH2CF2,
2JHHs12), 2.45 (dd, 1H(a), CH2, 2JHHs4, 3JHHs6), 2.75
2
3
(t, 1H(b), CH2, JHHs JHHs4), 3.12 (dq, 1H, CH,
3JHHs6(q) and 4) ppm. 13C NMR (CDCl3) d: 34.74–34.89
2
(t, 1C, CH2CF2, JCFs21), 44.11–44.19 (t, 1C, CHO,
3JCFs5), 44.94–45.08 (s, 1C, CH2O), 109–119 (m, 4–8C,

58
V. C´ırkva et al. / Journal of Fluorine Chemistry 84 (1997) 53–61
layer was separated, diluted with diethyl ether (10 ml) and
dried with magnesium sulphate. After filtering off the drier,
the solvent was evaporated and the residue was distilled in
vacuo (oil pump) (for boiling points (b.p.), yields, purity
of products 5a–5g and elemental analyses, see Table 2; 5a,
6,6,7,7,8,8,9,9,10,10,11,11,11-tridecafluoro-2-oxaundecan-
4-ol; 5b, 7,7,8,8,9,9,10,10,11,11,12,12,12,-tridecafluoro-3-
oxadodecan-5-ol; 5c, 8,8,9,9,10,10,11,11,12,12,13,13,13-
tridecafluoro-4-oxatridecan-6-ol; 5d, 7,7,8,8,9,9,10,10,-
11,11,12,12,12-tridecafluoro-2-methyl-3-oxadodecan-5-ol;
5e, 9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluoro-5-
oxatetradecan-7-ol; 5f, 8,8,9,9,10,10,11,11,12,12,13,13,13-
tridecafluoro-3-methyl-4-oxatridecan-6-ol; 5g, 7,7,8,8,-
9,9,10,10,11,11,12,12,12-tridecafluoro-2,2-dimethyl-3-oxa-
dodecan-5-ol).
a mixture of a,v-diol (1.2 mol), epoxide 4b (22.6 g, 60
mmol) and boron trifluoride etherate (0.21 g, 1.5 mmol) was
heated at 90 8C for 1 h with stirring (complete conversion of
4b, the mixture becomes clear). The unreacted diol was dis-
tilled off in vacuo (oil pump) and the distillation was contin-
ued to obtain products 6a–6d (for b.p., yields, purity of
products and elemental analyses, see Table 2; 6a, 7,7,-
8,8,9,9,10,10,11,11,12,12,12-tridecafluoro-3-oxadodecan-
1,5-diol; 6b, 8,8,9,9,10,10,11,11,12,12,13,13,13-trideca-
fluoro-4-oxatridecan-1,6-diol;
6c,
9,9,10,10,11,11,-
12,12,13,13,14,14,14-tridecafluoro-5-oxatetradecan-1,7-
diol; 6d, 9,9,10,10,11,11,12,12,13,13,14,14,14-trideca-
fluoro-3,5-dioxatetradecan-1,7-diol).
1H NMR (CDCl3) d, common signals of 6a–6d: 2.18, 2.28
2
(2 dm, 2H, CH2CF2, JHHs19), 3.38 and 3.45 (2 dd,
1H NMR (CDCl3) d, common signals of 5a–5g: 2.20, 2.32
2H, CH2O, 2JHHs10, 3JHHs5), 3.72–4.78 (bs, 2H, 2OH),
4.18–4.26 (m, 1H, CHOH) ppm.
2
(2 dm, 2H, CH2CF2, JHHs19), 3.31 and 3.45 (2 dd,
2
3
2H, CH2O, JHHs9.5, JHHs5), 3.15–3.50 (bs, 1H, OH),
4.20–4.23 (m, 1H, CHOH) ppm.
1H NMR (CDCl3) d, individual signals of 6a–6d: 6a: 3.55
and 3.70 (2 m, 4H, 2CH2O) ppm; 6b: 1.84 (qi, 2H,
1H NMR (CDCl3) d, individual signals of 5a–5g: 5a: 3.37
(s, 3H, CH3O) ppm; 5b: 1.14 (t, 3H, CH3, 3JHHs7), 3.48
CH2CH2OH, JHHs6), 3.66 and 3.68 (2 dt, 2H, CH2O,
3
2JHHs4, 3JHHs6), 3.76 (t, 2H, CH2OH, 3JHHs6) ppm; 6c:
1.60 (m, 4H, (CH2)2CH2O), 3.46 (m, 2H, CH2O), 3.56 (t,
2H, CH2OH, 3JHHs6) ppm;6d:3.44–3.55(m, 6H, 3CH2O),
3.57 (m, 2H, CH2OH) ppm.
3
(q, 2H, CH2CH3, JHHs7) ppm; 5c: 0.90 (t, 3H, CH3,
3
3JHHs7), 1.59 (sex, 2H, CH2CH3, JHHs7), 3.42 (t, 2H,
3
3
CH2O, JHHs7) ppm; 5d: 1.15 (d, 6H, 2CH3, JHHs6),
3.60 (sep, 1H, CHO, 3JHHs6) ppm; 5e: 0.90 (t, 3H, CH3,
3JHHs7), 1.35 (sex, 2H, CH2CH3, 3JHHs7), 1.55 (qi, 2H,
CH2CH2O, 3JHHs7), 3.46 (t, 2H, CH2O, 3JHHs7) ppm; 5f,
2 diastereoisomers, A (50% rel.), B (50% rel.): 0.91 (t, 3H,
CH3CH2, 3JHHs7.4), 1.14, 1.15 (2 d, 3H(A, B), CH3CH,
3JHHs6.2), 1.44, 1.48 (2 dqi, 2H(A), CH2CH3, 2JHHs14,
3JHHs7), 1.55, 1.59 (2 dqi, 2H(B), CH2CH3, 2JHHs14,
3JHHs7), 3.58 (m, 1H, CHO) ppm; 5g: 1.15 (s, 9H, 3CH3)
ppm.
13C NMR (CDCl3) d, common signals of 6a–6d: 34.02–
2
34.30 (t, 1C, CH2CF2,
s21), 63.67–63.93 (s, 1C,
JCF
CHOH), 74.07–74.67 (s, 1C, CH2O), 110–120 (m, 6C, CF2
and CF3) ppm.
13
NMR (CDCl ) d, individual signals of 6a–6d: 6a:
C
3
61.01 (s, 1C, CH2OH), 72.17 (s, 1C, CH2O) ppm; 6b: 32.54
(s, 1C, CH2), 61.30 (s, 1C, CH2OH), 70.27 (s, 1C, CH2O)
ppm; 6c: 25.88 and 29.11 (2 s, 2C, 2CH2), 61.84 (s, 1C,
CH2OH), 71.10 (s, 1C, CH2O) ppm; 6d: 60.91 (s, 1C,
CH2OH), 69.84 (s, 1C, CH2CH2OH), 70.13 (s, 1C,
CH2CH2O), 72.27 (s, 1C, CH2O) ppm.
13C NMR (CDCl3) d, common signals of 5a–5g: 34.27–
2
34.39 (t, 1C, CH2CF2, JCFs21), 63.87–64.29 (s, 1C,
19F NMR (CDCl3) of 6a–6d: the same as for 4a–4c.
CHOH), 72.26–75.81 (s, 1C, CH2O), 110–120 (m, 6C, CF2
and CF3) ppm.
13C NMR (CDCl3) d, individual signals of 5a–5g: 5a:
58.60 (s, 1C, CH3O) ppm; 5b: 14.07 (s, 1C, CH3), 66.46
(s, 1C, CH2CH3) ppm; 5c: 9.83 (s, 1C, CH3), 22.39 (s, 1C,
CH2CH3), 72.97 (s, 1C, OCH2CH2) ppm; 5d: 21.50 and
21.61 (2 s, 2C, 2CH3), 71.23 (s, 1C, CHO) ppm; 5e: 13.19
(s, 1C, CH3), 18.87 (s, 1C, CH2CH3), 31.29 (s, 1C,
CH2CH2O), 71.11 (s, 1C, CH2O) ppm; 5f: 10.30 (s, 1C,
CH3CH2), 19.63, 19.78 (2 s, 1C(A, B), CH3CH), 29.76,
29.78 (2 s, 1C(A, B), CH2), 78.28, 78.40 (2 s, 1C(A,
B), CHO) ppm; 5g: 26.78 (s, 3C, 3CH3), 64.97 (s, 1C, C)
ppm.
4.2.2.2. Bis-perfluoroalkylated diols 7a and 7d
In the same equipment as above (flask, 25 ml), a mixture
of diol 6a or 6d (20 mmol), epoxide 4b (3.76 g, 10 mmol)
and boron trifluoride etherate (85 mg, 0.6 mmol) was heated
at 90 8C for 1 h with stirring (complete conversion of 4b).
The products 7a and 7d were obtained as above (for b.p.,
yields, purity of products 7a and 7d and elemental analyses,
see Table 2; 7a, 1,1,1,2,2,3,3,4,4,5,5,6,6,18,18,19,19,20,-
20,21,21,22,22,23,23,23-hexacosafluoro-10,13-dioxadocos-
ane-8,16-diol; 7d, 1,1,1,2,2,3,3,4,4,5,5,6,6,20,20,21,21,22,-
22,23,23,24,24,25,25,25-hexacosafluoro-10,13,16-trioxa-
19F NMR (CDCl3) of 5a–5g: the same as for 4a–4c.
pentacosane-8,18-diol).
1
NMR (CDCl ) d, common signals of 7a and 7d: 2.25–
H
4.2.2. Reactions with diols
3
2.35 (m, 4H, 2CH2CF2), 3.50 (m, 4H, 2CH2O), 3.61–3.65
(m, 4 or 8H, 2 or 4CH2CH2O), 4.43–4.86 (bs, 2H, 2OH),
4.19– 4.22 (m, 2H, 2CHO) ppm.
4.2.2.1. Monoperfluoroalkylated diols 6a–6d
In a round-bottomed flask (100 ml), equipped with a Dim-
roth reflux condenser connected to the atmosphere through a
drying tube (potassium hydroxide) and a magnetic spinbar,
13C
NMR (CDCl3) d, common signals of 7a and 7d:
2
34.00–35.55 (t, 2C, 2CH2CF2,
s21), 63.70–65.04 (s,
JCF

V. C´ırkva et al. / Journal of Fluorine Chemistry 84 (1997) 53–61
59
2C, 2CHO), 70.00–71.75 (1 or 2 s, 2 or 4C, CH2CH2O),
74.90–75.90 (s, 2C, 2CH2O), 110–120 (m, 12C, CF2 and
CF3) ppm.
1H NMR (CDCl3) d, common signals of 9a–9c: 1.90–1.95
(t, 3H, CH3, 4JHHs2), 2.28 and 2.38 (2 dm, 2H, CH2CF2,
2JHHs19), 2.80–2.98 (bs, 1H, OH), 3.51 and 3.62 (2 dd,
2
3
19F NMR (CDCl3) of 7a and 7d: the same as for 4a–4c.
2H, CH2O, JHHs9.5, JHHs4), 3.77 and 3.78 (2 t, 2H,
OCH2CH2, 3JHHs4), 4.27 (m, 1H, CHO), 4.28–4.33 (t, 2H,
3
CH2OCO, JHHs4), 5.54–5.60 (q, 1H(E), CH2_,
4.3. Reactions of epoxides 4a–4c with 2-hydroxyethyl
(meth)acrylates (products 8 and 9a–9c)
4JHHs2), 6.08–6.27 (s, 1H(Z), CH2_) ppm.
13C NMR (CDCl3) d, common signals of 9a–9c: 17.52–
17.73 (s, 1C, CH3), 34.12–34.24 (t, 1C, CH2CF2, 2JCFs21),
63.21–63.27 (s, 1C, CH2OCO), 63.81–63.94 (s, 1C, CHO),
69.03–69.11 (s, 1C, OCH2CH2), 74.24–74.25 (s, 1C,
CH2O), 110–120 (m, 4–8C, CF2 and CF3), 125.36–126.52
(s, 1C, CH2_), 135.80–135.84 (s, 1C, C_), 167.13–167.23
(s, 1C, CO2) ppm.
4.3.1. Reaction of 4b with 2-hydroxyethyl acrylate (HEA)
(product 8)
In the same equipment as described in Section 4.2.1
(flask, 50 ml), a mixture of HEA (13.9 g, 120 mmol), epox-
ide 4b (11.3 g, 30 mmol), boron trifluoride etherate (0.11 g,
0.76 mmol) and a stabilizer (di-tert-octylpyrocatechol; 33.5
mg, 0.1 mmol) was heated at 80 8C for 2 h with stirring
(complete conversion of the epoxide). The mixture was then
distilled in vacuo: the catalyst was first distilled off on a water
pump, followed by unreacted HEA (oil pump) and finally
product 8 as the last fraction (high vacuum pump) (for b.p.,
yields, purity of the product and elemental analyses, see
Table 2; 8, 7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluoro-5-
hydroxy-3-oxadodecyl acrylate).
19F NMR (CDCl3) of 9a–9c: the same as for 4a–4c.
4.4. Reactions of epoxides 4a–4c with methacrylic acid
(products 10a–10c and 11a–11c)
In the same equipment as described in Section 4.2.1
(flask, 100 ml), a mixture of methacrylic acid (17.22 g, 200
mmol), epoxide 4a–4c (100 mmol), triethylamine (2.02 g,
20 mmol) and a stabilizer (di-tert-octylpyrocatechol(67mg,
0.2 mmol) or hydroquinol (44 mg, 0.4 mmol)) was heated
at 100 8C for 2 h with stirring (complete conversion of the
epoxides). The mixture was then distilled in vacuo: triethy-
lamine was first distilled off on a water pump, followed by
unreacted methacrylic acid (oil pump) and finally products
10a–10c (high vacuum pump) (contained approximately
17% (rel.) of the corresponding regioisomers 11a–11c) (for
b.p., yields, purity of products and elemental analyses, see
Table 2; 10a, 4,4,5,5,6,6,7,7,7- nonafluoro-2-hydroxyhep-
tan-1-yl methacrylate; 10b, 4,4,5,5,6,6,7,7,8,8,9,9,9-trideca-
fluoro-2-hydroxynonan-1-yl methacrylate; 10c, 4,4,5,5,6,6,-
7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-hydroxytri-
decan-1-yl methacrylate; 11a, 4,4,5,5,6,6,7,7,7-nonafluoro-
1-hydroxyheptan-2-yl methacrylate; 11b, 4,4,5,5,6,6,7,7,-
8,8,9,9,9-tridecafluoro-1-hydroxynonan-2-yl methacrylate;
11c, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-
1-hydroxytridecan-2-yl methacrylate).
1H NMR (CDCl3) d: 2.29 and 2.37 (2 dm, 2H, CH2CF2,
2JHHs17), 2.81 (bs, 1H, OH), 3.50 (dd, 1H(a), CH2O,
2JHHs9.6, 3JHHs6.2), 3.61 (dd, 1H(b), CH2O, 2JHHs9.6,
3JHHs3.8), 3.77 and 3.78 (2 t, 2H, OCH2CH2, 3JHHs4),
4.28 (m, 1H, CHO), 4.34 (t, 2H, CH2OCO, 3JHHs4), 5.86
(dd, 1H(cis), CH2_, 2JHHs1.3, 3JHHs10.4), 6.15 (dd, 1H,
3
–CH_, JHHs17.3(trans) and 10.4(cis)), 6.44 (dd,
1H(trans), CH2_, 2JHHs1.3, 3JHHs17.3) ppm.
13C NMR (CDCl3) d: 35.28 (t, 1C, CH2CF2, 2JCFs21),
63.95 (s, 1C, CH2OCO), 64.94 (s, 1C, CHO), 70.11 (s, 1C,
OCH2CH2), 75.14 (s, 1C, CH2O), 110–120 (m, 6C, CF2
and CF3), 128.74 (s, 1C, –CH_), 131.88 (s, 1C, CH2_),
166.80 (s, 1C, CO2) ppm.
19F NMR (CDCl3): the same as for 4a–4c.
4.3.2. Reactions with 2-hydroxyethyl methacrylate (HEMA)
(products 9a–9c)
1H NMR (CDCl3) d, common signals of 10a–10c: 1.92
(d, 3H, CH3, 4JHHs2), 2.29 and 2.40 (2 dm, 2H, CH2CF2,
2JHHs19), 3.22–3.58 (bs, 1H, OH), 4.18 and 4.20 (2 dd,
In the same equipment as described in Section 4.2.1
(flask, 100 ml), a mixture of HEMA (66.1 g, 0.5 mol),
epoxide 4a–4c (50 mmol), boron trifluoride etherate (0.18
g, 1.27 mmol) and a stabilizer (di-tert-octylpyrocatechol(67
mg, 0.2 mmol) or hydroquinol (44 mg, 0.4 mmol)) was
heated at 80 8C for 2 h with stirring (complete conversion of
the epoxides). The mixture was then distilled in vacuo: the
catalyst was first distilled off on a water pump, followed by
unreacted HEMA (oil pump) and finally products 9a–9c as
the last fraction on a high vacuum pump (for b.p., yields,
purity of products and elemental analyses, see Table 2;
9a, 7,7,8,8,9,9,10,10,10-nonafluoro-5-hydroxy-3-oxadecyl
methacrylate; 9b, 7,7,8,8,9,9,10,10,11,11,12,12,12-trideca-
fluoro-5-hydroxy-3-oxadodecyl methacrylate; 9c, 7,7,8,8,-
9,9,10,10,11,11,12,12,13,13,14,14,14-heptadecafluoro-5-
hydroxy-3-oxatetradecyl methacrylate).
2
3
2H, CH2O, JHHs9, JHHs5), 4.32–4.39 (m, 1H, CHO),
4
5.54–5.60 (q, 1H(E), CH2_, JHHs2), 6.07–6.13 (s,
1H(Z), CH2_) ppm.
13C NMR (CDCl3) d, common signals of 10a–10c: 17.75–
17.91 (s, 1C, CH3), 34.51–34.68 (t, 1C, CH2CF2, 2JCFs21),
63.28–63.70 (s, 1C, CHO), 67.54–67.67 (s, 1C, CH2O),
110–120 (m, 4–8C, CF2 and CF3), 126.16–126.34 (s, 1C,
CH2_), 135.51–135.69 (s, 1C, C_), 167.22–167.39 (s, 1C,
CO2) ppm.
19
NMR (CDCl ) of 10a–10c: the same as for 4a–4c.
F
3
1
NMR (CDCl ) d, common signals of 11a–11c: 1.92
H
3
(d, 3H, CH3, 4 s2), 2.48 and 2.58 (2 dm, 2H, CH2CF2,
JHH
2
s19), 3.22–3.58 (bs, 1H, OH), 3.73 (dm, 2H, CH2O,
JHH

60
V. C´ırkva et al. / Journal of Fluorine Chemistry 84 (1997) 53–61
3JHHs5), 5.36 (m, 1H, CHO), 5.54–5.60 (q, 1H(E), CH2_,
4JHHs2), 6.07–6.13 (s, 1H(Z), CH2_) ppm.
1H NMR (DMSO-d6) d, common signals of 13a–13c:
2.13, 2.43 (2 m, 2H, CH2CF2), 3.25, 3.40 (2 dd, 2H(a,
2
3
13C NMR (CDCl3) d, common signals of 11a–11c: 17.65–
17.83 (s, 1C, CH3), 31.62–31.77 (t, 1C, CH2CF2, 2JCFs21),
63.10–63.56 (s, 1C, CH2OH), 68.01–68.24 (s, 1C, CHO),
110–120 (m, 4–8C, CF2 and CF3), 126.25–126.47 (s, 1C,
CH2_), 135.51–135.69 (s, 1C, C_), 166.48–166.71 (s, 1C,
CO2) ppm.
b), CH2O, JHHs10.7, JHHs6.7 or 5.1), 3.86 (m, 1H,
CHO), 4.86 (bs, 1H, CH2OH), 5.06 (d, 1H, CHOH,
3JHHs5) ppm.
13C NMR (DMSO-d6) d, common signals of 13a–13c:
2
33.87 (t, 1C, CH2CF2, JCFs21), 64.97 (s, 1C, CHOH),
65.17 (s, 1C, CH2OH), 110–120 (m, 4–8C, CF2 and CF3)
ppm.
19F NMR (CDCl3) of 11a–11c: the same as for 4a–4c.
19F NMR (DMSO-d6) of 13a–13c: the same as for 4a–4c.
4.5. Preparation of dioxolanes 12a–12c and their
transformation to polyfluoroalkan-1,2-diyl bis-
methacrylates 14a–14c
4.5.3. Bis-methacrylates 14a–14c
In the same equipment as described in Section 4.2.1
(flask, 50 ml), a mixture of methacryloyl chloride (3.14 g,
30 mmol), diol 13a–13c (5 mmol), triethylamine (3.54 g,
35 mmol), diethyl ether (30 ml) and a stabilizer (di-tert-
octylpyrocatechol; 33.5 mg, 0.1 mmol) was stirred at room
temperature for2 h (complete conversionofthediols).Meth-
anol (0.64 g, 20 mmol) was then added and the mixture was
stirred for an additional hour. Water (2 50 ml) was then
added slowly to the mixture in a separation funnel, the ether
layer was separated, the water layer was extracted with ether
(20 ml), the ether solutions were combined and were dried
with magnesium sulphate. After evaporation of diethyl ether,
triethylamine and methyl methacrylate were removed (water
pump) and the residue was distilled on a high vacuum pump
(for b.p., yields, purity of products 14a–14c and elemental
analyses, see Table 2; 14a, 4,4,5,5,6,6,7,7,7-nonafluorohep-
tane-1,2-diyl bis-methacrylate; 14b, 4,4,5,5,6,6,7,7,8,8,9,-
9,9-tridecafluorononane-1,2-diyl bis-methacrylate;14c, 4,4,-
5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorounde-
cane-1,2-diyl bis-methacrylate).
4.5.1. Reactions of epoxides 4a–4c with acetone (products
12a–12c)
In the same equipment as described in Section 4.2.1
(flask, 25 ml), a mixture of epoxide 4a–4c (20 mmol),
acetone (5.81 g, 100 mmol) and boron trifluoride etherate
(28 mg, 0.2 mmol) was refluxed for 0.5 h with stirring(com-
plete conversion of the epoxides). After evaporation of ace-
tone, the residue was distilled in vacuo (oil pump) and the
products 12a–12c were distilled as the final fractions (for
b.p., yields, purity of products and elemental analyses, see
Table 2; 12a, 4-(2,2,3,3,4,4,5,5,5-nonafluoropentan-1-yl)-
2,2-dimethyl-1,3-dioxolane; 12b, 4-(2,2,3,3,4,4,5,5,6,6,-
7,7,7-tridecafluoroheptan-1-yl)-2,2-dimethyl-1,3-dioxo-
lane; 12c, 4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadeca-
fluoroundecan-1-yl)-2,2-dimethyl-1,3-dioxolane).
1H NMR (CDCl3) d, common signals of 12a–12c: 1.38,
1.43 (2 s, 6H, 2CH3), 2.28, 2.55 (2 m, 2H, CH2CF2),
3.67, 4.19 (2 dd, 2H(a, b), CH2O, 2JHHs8, 3JHHs7 or 6),
4.45 (dq, 1H, CHO, 3JHHs7 and 6(q)) ppm.
1H NMR (CDCl3) d, common signals of 14a–14c: 1.94,
1.95 (2 s, 6H, 2CH3), 2.48 and 2.58 (2 dm, 2H, CH2CF2,
13C NMR (CDCl3) d, common signals of 12a–12c: 26.19,
27.41 (2 s, 2C, 2CH3), 36.06 (t, 1C, CH2CF2, 2JCFs21),
69.88 (s, 1C, CHO), 70.23 (s, 1C, CH2O), 110.10 (s, 1C,
C), 110–120 (m, 4–8C, CF2 and CF3) ppm.
2JHHs19), 4.27–4.32 (dd, 1H(a), CH2O, JHHs12,
2
3JHHs5), 4.43–4.48 (dd, 1H(b), CH2O, JHHs12,
2
3JHHs4), 5.58–5.62 (s, 2H(E), 2CH2_), 5.63–5.65 (m,
19F NMR (CDCl3) of 12a–12c: the same as for 4a–4c.
1H, CHO), 6.12, 6.13 (2 m, 2H(Z), 2CH2_) ppm.
13
NMR (CDCl ) d, common signals of 14a–14c: 18.54,
C
3
4.5.2. Methanolysis of 4-(polyfluoroalkyl)-1,3-dioxolanes to
diols 13a–13c
18.62 (2 s, 2C, 2CH3), 32.77–32.90 (t, 1C, CH2CF2,
2
s21), 65.19–65.25 (s, 1C, CH2O), 65.74–65.87 (s, 1C,
JCF
In the same equipment as described in Section 4.2.1
(flask, 25 ml), a mixture of dioxolane 12a–12c (10 mmol),
methanol (6.4 g, 0.200 mol) and concentrated hydrochloric
acid (0.5 g) was refluxed for 2 h with stirring (complete
conversion of the dioxolanes). After evaporation of metha-
nol, the residual water, together with hydrogen chloride, was
removed by azeotropic fractional distillation with toluene
which was distilled off. The residue was then distilled in
vacuo (oil pump) and the products 13a–13c were distilled
as the final fractions (for b.p., melting points (m.p.), yields,
purity of products and elemental analyses, see Table 2; 13a,
4,4,5,5,6,6,7,7,7-nonafluoroheptane-1,2-diol; 13b, 4,4,5,5,-
6,6,7,7,8,8,9,9,9-tridecafluorononane-1,2-diol; 13c, 4,4,5,5,-
6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecane-
1,2-diol).
CHO), 110–120 (m, 4–8C, CF2 and CF3), 126.84, 127.03
(2 s, 2C, 2CH2_), 136.31, 136.36 (2 s, 2C, 2C_),
166.53, 167.21 (2 s, 2C, 2CO2) ppm.
19
NMR (CDCl ) of 14a–14c: the same as for 4a–4c.
F
3
4.6. Preparation of thiiranes 15a–15c
In the equipment described in Section 4.2.1, a mixture of
epoxide 4a–4c (10 mmol), thiourea (1.52 g, 20 mmol) and
methanol (15 ml) was refluxed for 4 h with stirring (com-
plete conversion of the epoxides). After cooling to room
temperature, water (30 ml) was added to the mixture and the
lower oily layer was diluted with diethyl ether (50 ml),

V. C´ırkva et al. / Journal of Fluorine Chemistry 84 (1997) 53–61
61
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1992; Chem. Abs. 118 (1993) 73866.
[11] S. Szo¨nyi, A. Cambon, Fr. Patent 2530623, 1984; Chem. Abs. 100
(1984) 176906.
washed with water (3 30 ml) and dried with magnesium
sulphate. After filtering the drier off, the solvent was evapo-
rated and the residue was distilled in vacuo (water pump) to
yield products 15a–15c (for b.p., yields, purity of products
and elemental analyses, see Table 2; 15a, 1-
(2,2,3,3,4,4,5,5,5-nonafluoropentan-1-yl) thiirane; 15b, 1-
(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptan-1-yl)thiirane;
15c, 1-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoroun-
decan-1-yl) thiirane).
[12] O. Paleta, V. C´ırkva, R. Pola´k, K. Kefurt, J. Moravcova´, M. Kod´ıcˇek,
S. Forman, M. Baresˇ, Abstracts of Papers of 3e´me Colloque
Francophone sur la Chimie Organique du Fluor, P10, Reims, 1996.
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01,246,237, 1989; Chem. Abs. 112 (1990) 141794.
[16] J.D. Park, F.E. Rogers, J.R. Lacher, J. Org. Chem. 26 (1961) 2089.
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125942.
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37.
[19] H. Plenkiewicz, W. Dmowski, J. Fluor. Chem. 51 (1991) 43.
[20] Daikin Kogyo Co., Ltd., Fr. Pat. 1,535,485, 1968; Chem. Abs. 71
(1969) 12585.
1H NMR (CDCl3) d, common signals of 15a–15c: 2.23
2
3
and 2.61 (2 dq, 2H, CH2CF2, JHHs16, JHHs8 or 6,
2
3JHFs16), 2.23 and 2.60 (2 dd, 2H, CH2S, JHHs6,
3JHHs2), 3.03 (ddt, 1H, CHS, 3JHHs8, 6 and 2(t)) ppm.
13C NMR (CDCl3) d, common signals of 15a–15c: 23.91
(s, 1C, CH2S), 24.36 (t, 1C, CHS, 3JCFs5), 38.29 (t, 1C,
CH2CF2, 2JCFs21), 110–120 (m, 4–8C, CF2 and CF3) ppm.
19F NMR (CDCl3) of 15a–15c: the same as for 4a–4c.
[21] H. Matsuo, K. Oharu, Jpn. Kokai Tokkyo Koho JP 01,50,844, 1989;
Chem. Abs. 111 (1989) 134917.
Acknowledgements
[22] V. C´ırkva, B. Ame´duri, B. Boutevin, J. Kv´ıcˇala, O. Paleta, J. Fluor.
Chem. 74 (1995) 97.
[23] V. C´ırkva, B. Ame´duri, B. Boutevin, O. Paleta, J. Fluor. Chem.,(1997)
in press.
[24] J. March, Advanced Organic Chemistry, 4th ed., Wiley-Interscience,
New York, 1992, p. 368.
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The authors thank the Tempus Programme JEP 2139 for
the opportunity for V. C´ırkva to visit Ecole Nationale Supe´-
rieure de Chimie, Montpellier for part of his PhD study and
Elf Atochem S.A. for the gift of perfluoroalkyl iodides. Ele-
mental analyseswereperformedattheAnalyticalDepartment
of the Institute of Chemical Technology, Prague (Dr L.
Helesˇic, Head). This research was mainly supported by grant
no. 203/95/1146 from the Grant Agency of the Czech
Republic.
[28] P.J. Madec, E. Mare´chal, Makromol. Chem. 184 (1983) 323, 335,
343, 357.
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Fluorinated Monomers and Polymers, P33, Prague, July, 1993.
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Hutchinson and Ross, Stroudsburg, 1973.
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