Fluorinated epoxides: 5. Highly selective synthesis of diepoxides from α,ω-diiodoperfluoroalkanes. Regioselectivity of nucleophilic epoxide-ring opening and new amphiphilic compounds and monomers

Article abstract of DOI:10.1016/S0022-1139(99)00301-2

An improved procedure for the radical addition of α,ω-diiodoperfluoroalkanes I-(CF₂CF₂)_n-I (n=2, 3) to allyl acetate that afford the corresponding bis-adducts AcOCH₂CHICH₂(CF₂CF₂) _nCH₂CHI-CH₂OAc (2a-2b) has been developed. The primary bis-adducts 2a-2b suffered a subsequent rearrangement in the addition mixture to afford semi-rearranged adducts AcOCH₂CHICH₂-(CF₂CF₂) _n-CH₂CH-(OAc)CH₂I (3a-3b) in an amount of ca. 15% rel. at reaction temperatures. Both adducts 2a-2b and rearranged adducts 3a-3b were converted to diepoxides CH₂(-O-)CHCH₂(CF₂CF₂) _nCH₂CH-(-O-)CH₂ (4a-4b) with high chemoselectivity in two ways: the selectivity of the direct epoxidation of 2a-2b and/or 3a-3b with potassium hydroxide was extremely dependent on the solvent; the second method included hydrolysis of 2a-2b and/or 3a-3b to bis-iodohydrins 5a-5b and 6a-6b that were easily transformed to the diepoxides 4a-4b. Ring-opening reactions of bis-epoxides 4a-4b with hydroxy compounds in the presence of boron trifluoride etherate took place at the terminal carbon atom of both epoxide rings with complete regioselectivity. A convenient transformation of the diepoxides to the corresponding amphiphilic tetrols (14a-14b) via dioxolane intermediates was accomplished with overall yields of 57-65% . Base-catalyzed ring-opening by methacrylic acid was not completely regioselective (89% terminal attack on both oxirane rings) and afforded a mixture of regioisomeric bis-methacrylates (16a-16b and 17a-17b) bearing two hydroxyl groups. In contrast, epoxide ring-opening with morpholine was completely regioselective in both diepoxides 4a and 4b.

Full text of DOI:10.1016/S0022-1139(99)00301-2

Journal of Fluorine Chemistry 102 (2000) 349±361
Fluorinated epoxides
5. Highly selective synthesis of diepoxides from
a,o-diiodoper¯uoroalkanes. Regioselectivity of nucleophilic
epoxide-ring opening and new amphiphilic compounds and monomers$
1
*
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Vladimõr Cõrkva, Manuel Gaboyard , Oldrich Paleta
Department of Organic Chemistry, Prague Institute of Chemical Technology, Technicka 5, 16628 Prague 6, Czech Republic
Received 15 August 1999; received in revised form 26 August 1999; accepted 27 September 1999
Dedicated to Professor Paul Tarrant on the occasion of his 85th birthday
Abstract
An improved procedure for the radical addition of a,o-diiodoper¯uoroalkanes I±(CF2CF2)n±I (n ˆ 2, 3) to allyl acetate that afford the
corresponding bis-adducts AcOCH2CHICH2(CF2CF2)nCH2CHI±CH2OAc (2a±2b) has been developed. The primary bis-adducts 2a±2b
suffered a subsequent rearrangement in the addition mixture to afford semi-rearranged adducts AcOCH2CHICH2±(CF2CF2)n±CH2CH±
(OAc)CH2I (3a±3b) in an amount of ca. 15% rel. at reaction temperatures. Both adducts 2a±2b and rearranged adducts 3a±3b were
converted to diepoxides CH2(±O±)CHCH2(CF2CF2)nCH2CH±(±O±)CH2 (4a±4b) with high chemoselectivity in two ways: the selectivity of
the direct epoxidation of 2a±2b and/or 3a±3b with potassium hydroxide was extremely dependent on the solvent; the second method
included hydrolysis of 2a±2b and/or 3a±3b to bis-iodohydrins 5a±5b and 6a±6b that were easily transformed to the diepoxides 4a±4b.
Ring-opening reactions of bis-epoxides 4a±4b with hydroxy compounds in the presence of boron tri¯uoride etherate took place at the
terminal carbon atom of both epoxide rings with complete regioselectivity. A convenient transformation of the diepoxides to the
corresponding amphiphilic tetrols (14a±14b) via dioxolane intermediates was accomplished with overall yields of 57±65% . Base-catalyzed
ring-opening by methacrylic acid was not completely regioselective (89% terminal attack on both oxirane rings) and afforded a mixture of
regioisomeric bis-methacrylates (16a±16b and 17a±17b) bearing two hydroxyl groups. In contrast, epoxide ring-opening with morpholine
was completely regioselective in both diepoxides 4a and 4b. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Radical addition of a,o-diiodoper¯uoroalkanes; Rearrangement of a-iodoacetates; Bis-iodohydrins; Epoxidation; Nucleophilic rearrangement of
¯uoroalkyloxiranes; Diepoxy¯uoroalkanes; Nucleophilic oxirane ring opening; Amphiphilic compounds; a,o-Bis(2,2-dimethyl-1,3-dioxolan-4-yl)¯uoroalk-
anes; Fluoroalkanetetrols; Dihydroxy¯uoroalkane-a,o-diyl bis-methacrylates; a,o-Bis(morpholin-4-yl)¯uoroalkanediols
1. Introduction
applications. Unfortunately, this review has not included a
series of recent papers [5±13] from the Journal of Fluorine
Chemistry which correct some previous results [5,10],
improve procedures to some important synthetic intermedi-
ates [6±11,13] and extend variety of useful products for
potential practical applications prepared on the basis of the
radical additions [9,12,14,15]. A careful spectral analysis of
the reaction mixture in additions of per¯uoroalkyl iodides to
allyl acetate, that were originally carried out previously
[4,16±18], led to the discovery of a novel rearrangement
[5,8]. The new and improved knowledge presented in the
recent papers [5,8±12] were employed with advantage in this
paper.
Some years ago, P. Tarrant had emphasized in a review [3]
that ¯uorocarbon iodides have been useful reagents for the
preparation of a variety compounds by several fundamental
reactions including radical additions. Recently, N.O. Brace
summarized in a recent review [4] free radical chemistry of
per¯uoroalkyl iodides in the synthesis of organic substances
of a large variety of structures with emphasis on practical
$ Part 1, [1]. Part 2, [2]. Part 3, [11]. Part 4, [12].
* Corresponding author. Fax: ‡42-2-2431-1082.
E-mail address: oldrich.paleta@vscht.cz (O. Paleta).
1
Analogously to the chemistry of per¯uoroalkyl iodides
[3,4], the chemistry of diiodoper¯uoroalkanes can lead to a
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Present address: Ecole Nationale Superieure de Chimie de Montpellier,
34296 Montpellier Cedex 5, France.
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 3 0 1 - 2

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
350
variety of mono- and bifunctional compounds, e.g. special
amphiphilic compounds, substituted diols for polyesters or
polyurethanes [14,15,19±21], bifunctional monomers and
curing and crosslinking agents for polymers including coat-
ings [22]. While the chemistry of per¯uoroalkyl iodides has
been extensively studied [4,8 and references therein], the
reports on the chemistry of a,o-diiodoper¯uoroalkanes are
relatively scarce. Among radical additions of the reagents to
ole®ns, e.g. the additions to ethylene and propene [7,23], b-
bromostyrene [24], vinyl acetate [25] or allyl-substituted
steroide compound [26] have been published. In addition,
several papers have reported additions of diiodoper¯uor-
oalkanes to allyl acetate: the addition reaction of some a,o-
diiodoper¯uoro-alkanes [16,17,25] has been described pre-
viously, but the structures of products were assigned, as
usual in that time, only on the basis of elemental analyses
and refractive indexes and/or boiling points; in a more
recent study [7], the addition products were not puri®ed
and characterized; recently, the additions with diiodoper-
¯uoroalkanes were described [8] in details and main and by-
products were characterized. The last reaction afforded
mixtures of mono- and bis-adducts. In this paper, a proce-
dure has been developed affording almost pure bis-adducts.
Diepoxides, in which the oxirane rings are connected by a
¯uorinated or per¯uorinated alkane-a,o-diyl, i.e.
±
(CH2)n(CF2)m(CH2)n± (n ˆ 0, 1; m ˆ 4, 6, 8), are quite
rarely reported in the literature: the ®rst type (n ˆ 0,
m ˆ 4) was obtained by a several-step synthesis from per-
¯uorodicarboxylate [27], while the second type (n ˆ 1,
m ˆ 4) was obtained by a direct epoxidation of the bis-
adduct to allyl acetate [16]. Concerning reactions of these
diepoxides, we have not found any characterized compound
prepared from the diepoxides.
Scheme 1. Products of radical addition of diiodoperfluoroalkanes to allyl
acetate.
initially and subsequently react with the second molecule of
allyl acetate to form bis-adducts 2a±2b (Scheme 1) [8]. The
relative amount of mono- and bis-adducts can be strongly
in¯uenced by a solvent: the reaction in butyronitrile leads to
almost exclusive formation of bis-adducts, while without
solvent the end reaction mixture contained 25±33% of
mono-adducts 1a±1b (Table 1). In contrast to previous
report [8], no 2 : 1 telomers were detected in the mixture
probably owing to a lower reaction temperature and lower
reactivity of relatively bigger molecules 2a±2b. The primary
adducts 1a±1b and 2a±2b undergo a subsequent rearrange-
ment [5,8]. The amount of rearranged products is dependent
on reaction temperature, but after some time an equilibrium
is established [5]. In this study the content of semi-rear-
2. Results and discussion
2.1. Radical additions of a,o-diiodoperfluoroalkanes to
allyl acetate
The reactions of diiodides I±(CF2)n±I (n ˆ 4, 6) were
initiated with dibenzoyl peroxide [7,8,16]. They are step-
wise processes in which mono-adducts 1a±1b are formed
Table 1
Composition of mono- and bis-adducts obtained in the radical addition of diiodoperfluoroalkanes to allyl acetate
Starting
diiodide
Solvent
Conversion
(%)
Composition of adducts (%)b
Ratio of
bis-adducts
Mono-adduct
Bis-adducts
2/3 (% rel.)
1
2
3
a
I±(CF2CF2)2±I
I±(CF2CF2)3±I
±
98
98
98
98
1a
1a
1b
1b
33
4
2a
2a
2b
2b
67
0
Butyronitrile
a
±
82.5
75
3a
3b
13.5
0
86/14
84/16
25
2
Butyronitrile
82.5
15.5
a [8].
b Calculated from 19F NMR spectra.

Table 2
Selectivity of the formation of epoxides 4a±4b from diacetates 2a±2b (AcOCH2CHICH2±QF±CH2CHI±CH2OAc), 3a±3b or diiodohydrins 5a±5b, 6a±6b by potassium hydroxide in solvents
Starting compound
QF
Solventa
Time (h)
Conversion (%)
Reaction mixture compositionb (% rel.)
Diepoxide yield (%)
Purity
Diepoxide
Unsaturated
Unsaturated
4a±4b
ester 11a±11b
alcohol 9a±9b
2a
2a
2a
2a
2a
2b
2b
2b
5a
5a
5b
5b
C4F8
C4F8
C4F8
C4F8
C4F8
C6F12
C6F12
C6F12
C4F8
C4F8
C6F12
C6F12
100
100
100
100
86c
100
100
84d
100
86f
Hexane
5
0
98
98
99
99
98
99
99
98
98
98
98
±
±
±
4a
4a
4a
4a
4a
4b
4b
4b
4a
4a
4b
4b
0
Et2O
5
25
62
86
88
25
86
87
95
94
95
94
51
25
9
24
13
5
15
50
71h
72
10
72h
72
73h
74
76h
76
Hexane/Et2O (1 : 1)
Hexane/Et2O (4 : 1)
Hexane/Et2O (4 : 1)
Hexane
5
5
5
8
4
5
50e
9e
8e
±
25e
5e
5e
5
Hexane/Et2O (4 : 1)
Hexane/Et2O (4 : 1)
Et2O
5
5
0.5
0.5
0.5
0.5
Et2O
Et2O
±
6
100
84g
±
5e
6e
Et2O
±
a Mixing at room temperature.
b GC analyses with calibration.
c Isomer 3a, 14% rel.
d Isomer 3b,16% rel.
e The structures of 9b and 11b were not confirmed.
f Isomer 6a, 14% rel.
g Isomer 6b, 16% rel.
h Purity 99%.

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
352
Table 3
of by-product. No by-products have been reported in pre-
vious papers using pentane or hexane [9,16].
Optimization of the solvent mixture for epoxidation of diiododiacetates
2a±2b and 3a±3b
We employed our experience [11] in the optimization of a
solvent system for the preparation of diepoxides 4a±4b
using powdered potassium hydroxide (Tables 2 and 3,
Scheme 2) that appeared to be a better base than sodium
hydroxide in the epoxidations [11]. However, solvent-che-
moselectivity relation appeared to be rather different from
that observed in the preparation of per¯uoroalkylated oxi-
ranes on the basis of additions of per¯uoroalkyl iodides
[11]: diethyl ether again caused the formation of about 75%
rel. of by-products 9a and 11a in the epoxidation, but
epoxidation in hexane, the best solvent for the preparation
of monoepoxides from the iodoacetates [11] gave surpris-
ingly no product or low yield (Table 2). Therefore, a mixed
solvent containing diethyl ether was optimized (Table 3).
Petroleum ether and hexane as the main component
appeared to be the best among other hydrocarbons, but
the latter gave better chemoselectivity (Tables 2 and 3).
By this methodology, the amount of the by-products 9 and
11 was reduced to about 13% rel. (Table 2), which is a more
worse result than that for the preparation of monoepoxides
where the relative amount of by-products was suppressed to
about 2% rel. [11]. Both initial bis-adducts 2a±2b and
rearranged bis-adducts 3a±3b were converted to the diep-
oxides 4a±4b which is an analogous observation to that for
the formation of monoepoxides [11].
Solvent mixture
Vol. : Vol.
Reaction mixture composition (%)
Diepoxide 4a
Diacetates 2a, 3a
Petroleum ether/diethyl ether
4 : 1
5 : 1
6 : 1
7 : 1
8 : 1
82
84
80
74
66
0
0
<1
ca. 2
14
Hexane/diethyl ether
1 : 1
2 : 1
3 : 1
4 : 1
5 : 1
6 : 1
62
60
74
86
67
69
0
5
0
0
0
0
ranged compounds 3a±3b was relatively low (14 and 16%
rel.) owing to a lower reaction temperature and short reac-
tion time. When the reaction was carried out below 1008C
no rearranged product was observed during 1 h reaction
time (Section 3.2).
2.2. Preparation of diepoxides 4a±4b and formation of
by-products 9 and 11
2.2.1. From diiodoalkanediyl diacetates 2a±2b and 3a±3b
We have reported in our recent paper [11] that the
chemoselectivity of the transformation of per¯uoroalkyl
iodide adducts onto allyl acetate to the corresponding
epoxides is extremely dependent on the solvent used. The
amount of by-products formed in diethyl ether, that was
found as the least convenient solvent [11], was up to 75%
rel. The previous papers using this procedure [18,25] have
not mentioned the formation of any amount of by-products.
We have also found [11] that the chemoselectivity of
epoxidation is the best in hexane giving only ca. 2% rel.
2.2.2. From diiododiols 5a±5b and 6a±6b
To avoid the formation of by-products and to obtain pure
diepoxides, a two step synthesis of the diepoxides was
accomplished. The mixtures of products 2 and 3 were ®rst
converted to the corresponding iodohydrins 5 and 6
(Scheme 2) in 84±86% preparative yields by reesteri®cation
with acidic methanol. The iodohydrins 5 and 6 (Scheme 2)
were subsequently epoxidized in 64±74% preparative yields
using powdered potassium hydroxide in diethyl ether, i.e. by
analogous procedure previously reported [25] for the pre-
paration of monoepoxides. By using iodohydrins 5 and 6 as
Scheme 2. Preparation of diepoxides 4a±4b from bis-adducts 2a±2b and rearranged bis-adducts 3a±3b.

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
353
Scheme 3. Probable reaction sequence in the formation of by-products in the epoxidation of adducts 2a±2b and 3a±3b.
substrates instead of iodoacetates 2 and 3, the relative
amount of by-products 9 was suppressed to 5±6% rel.
(Table 2) and unsaturated esters 11 were not detected
in the reaction mixture at all. No unsaturated by-products
were reported in the previous paper [25] for an analogous
reaction.
bis-iodohydrins 5 are used as substrates and short reaction
time applied (Table 2). Thus, unsaturated by-products gen-
erally accompany diepoxides 4 prepared by the above
reactions in higher relative amount than in structurally
analogous monoepoxides [11]. As the formation of the
by-products was studied in our preceding paper [11], we
veri®ed the by-products only for one of the bis-adducts, i.e.
2a (Scheme 3).
2.2.3. Formation of by-products 9 and 11
The amount of by-products 9 and 11 is strongly depen-
dent on the substrate and solvent used (Table 3): in diethyl
ether or hexane the by-products strongly dominate when
diiododiacetates are used as substrates (Table 2), which is a
sharp contrast to the preparation of monoepoxides from
iodoacetates reported recently [11]. The amounts of by-
products are strongly reduced when bis-iodohydrins 5 are
employed in diethyl ether. The reason of the formation of
by-products 9 and 11 (Scheme 3) is the acidity of the a-bond
C±H relatively to the per¯uorinated chain (for a discussion
on the reactions by which the by-products are formed see the
preceding paper [11]).This bond can be attacked directly in
the iodoacetate 2 (as well as in rearranged adduct 3 [11]) to
afford unsaturated epoxyacetate 11 that subsequently
affords allylic epoxyalkenol 9 by hydrolysis. The a-bond
C±H is also attacked by hydroxyl anion in the diepoxides
4 to start a rearrangement leading to epoxyalkenol 9
(Scheme 3). This subsequent side transformation of diep-
oxides 4 to the corresponding epoxyalkenols 9 is much
slower than the formation of the diepoxides 4, but cannot be
completely suppressed in the reaction system even when
2.3. Nucleophilic ring-opening reactions in diepoxides
4a±4b
It has been shown in our preceding paper ([12] and
references therein) that the regioselectivity of the epox-
ide-ring opening in 2-[(per¯uoroalkyl)methyl]oxiranes is
dependent on the type of a catalyst applied. Both mechan-
isms for acid-catalyzed (boron tri¯uoride etherate, magne-
sium perchlorate) and triethylamine-catalyzed reactions
were discussed to explain different regioselectivity. As
diepoxides 4a±4b are two-fold analogues of 2-[(per¯uor-
oalkyl)methyl]oxiranes, a similar reactivity toward nucleo-
philes and similar regioselectivity [12] of reactions can be
expected.
2.3.1. Acid-catalyzed ring opening, reaction with alkanols
The reported Lewis-acid catalyzed reactions of per¯uor-
oalkylated epoxides with hydroxy compounds have pro-
ceeded with complete regioselectivity [12,28±30].
The same result has been observed for the reactions of

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
354
Scheme 4. Nucleophilic reactions of diepoxides 4a±4b.
diepoxides 4a±4b with methanol in the presence of boron
tri¯uoride etherate (Scheme 4): the oxygen of hydroxy
groups attacked both terminal carbon atoms at the epoxide
rings with complete regioselectivity to afford dihydroxy bis-
ethers 12a±12b; no regioisomers were found in the reaction
mixtures by 19F NMR (the sensitivity of the method is about
1% rel. [31,32]. a,o-Dialkoxydiols 12a±12b can further be
transformed to bifunctional monomers as bis-(meth)-acry-
lates [9,12,14] or used directly for poly(urethanes), bis-
(meth)acrylates etc. As the ring opening in the diepoxides
4a±4b can be performed with monohydroxy compounds of
different structure ([12] and references therein), e.g. oli-
goethylene glycol monoalkyl ethers or hydroxyalkyl
(meth)acrylates [12], the synthesis that starts from a,o-
diiodoper¯uoroakanes can afford a number of interesting
compounds for various practical applications including
hydrophilic biocompatible polymers.
yields and subsequently re-acetalized with methanol and
hydrochloric acid to tetrols 14a±14b in 63±70% preparative
yields. The tetrols 14a±14b can be applied for the prepara-
tion of new dendrimeric compounds, or as crosslinking
agents for polymers. Heating of bis-dioxolanyl derivative
13a in wet ethyl acetate caused partial hydrolysis to dioxo-
lanyldiol 15a.
2.3.3. Ring opening in the presence of a base and with
morpholine, preparation of amphiphilic bis-methacrylates
16 and 17
It has been known [12] that the nucleophilicity of hydro-
xylic oxygen in (meth)acrylic acids is low to cause a ring
opening in per¯uoroalkyl epoxides under acid catalysis. A
similar reactivity was observed for non-¯uorinated epox-
ides, where tertiary amines were used as catalysts [39±41].
In the case of ¯uoroalkyl epoxides, the ring opening was
performed in the presence of potassium methacrylate
[42,43], triphenylphosphane [42,43] or triethylamine
[12,44]. Before base-catalyzed ring opening the reaction
was not regioselective with 10±17% rel. of the inner carbon
attack [12,42±44]. According to the previous experience, we
used triethyl amine as a catalyst for the ring opening. As
previously observed for monoepoxides [12,42±44], the ring
opening in the diepoxides 4a±4b was also not completely
regioselective (Scheme 4): the attack of the terminal carbons
occurred from 89% rel. to afford major regioisomers
2.3.2. Transformation to tetrols 14a±14b
We have recently developed a novel method for the
transformation of ¯uoroalkylated epoxides to the corre-
sponding vicinal diols [12,14,15], because the yields of
the direct acid-catalyzed reaction or were not very satisfac-
tory [28,33,34], or required special conditions [35±38]. In
this method, the epoxides 4a±4b were ®rst transformed to
the corresponding bis-1,3-dioxolanyl derivatives 13a±13b
by acid-catalyzed reaction with acetone [12] in 90±92%

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
355
16a±16b. The attack at the inner carbon atom (11% rel.,
products 17a±17b) has been previously explained in the
terms of the HSAB concept [12]. Thus, base-catalyzed ring
opening of ¯uoroalkylated epoxides [12] or diepoxides
prepared by the addition to allyl acetate or allylic alcohol
afford mixture of the corresponding amphiphilic methacry-
lates [12] or bis-methacrylates with the regioisomers formed
by the terminal attack highly prevailing (83±90% rel.).
Amphiphilic bis-methacrylates as mixtures of 16a±16b
and 17a±17b can be used as special crosslinking agents
including hydrophilic biocompatible copolymers.
In contrast to (meth)acrylate quasi-oxyanions acting in
the above epoxide ring-opening reactions [12], morpholine
possessing a strongly nucleophilic nitrogen reacted with
complete regioselectivity: the nucleophilic attack occurred
at the both terminal carbon atoms in diepoxides 4a±4b to
afford dihydroxylated bis-morpholinyl 18a±18b (Scheme
4). The same regioselectivity has been reported [9] for the
analogous reaction of morpholine with 2-[(per¯uoroalkyl)-
methyl]oxiranes. The different regioselectivity in ring-
opening reactions of oxyanions and secondary amines
can be caused by different hardness of these two nucleo-
philic centers, nitrogen being a softer nucleophile, as dis-
cussed in our preceding paper [12].
ether was dried with sodium and distilled over sodium;
hexane (Fluka) and morpholine (Lachema) was distilled
prior to use and stored over molecular sieves; methacrylic
acid (Aldrich); petroleum ether, chloroform, methanol,
acetone and toluene were puri®ed according to standard
procedures [45].
3.2. General procedure for the radical addition of
diiodoperfluoroalkanes to allyl acetate
The reactions were carried out in a two-necked round-
bottom ¯ask (250 ml) equipped with a long re¯ux condenser
and magnetic spinbar on a oil bath.
Method A: The ¯ask was charged with a mixture of
diiodoper¯uoroalkane, allyl acetate and butyronitrile that
was heated up to ca. 1158C. Then, dibenzoyl peroxide was
added portionwise to the mixture through the neck and
heating was stopped. A slight foam at the mixture surface
appeared indicating start of the reaction, by which the
temperature in ¯ask increased up to 1258C. The amber
solution became clear after 5 min reaction indicating almost
completion of the reaction. The mixture was stirred for
30 min until the temperature fell down to 908C. Volatile
components were distilled off in vacuum by oil pump
(0.5 mm Hg, 1308C bath temperature) to afford crude
product consisting of compounds 1, 2 and 3 (Table 1).
For analytical purposes and further transformations, the
mono-adducts 1 and di-adducts 2 and 3 were separated
by simple column chromatography (silica gel; hexane,
chloroform).
3. Experimental details
3.1. General comments
Boiling points were not corrected. GC analyses were
performed on Micromat HRGC 412 (Nordion Analytical;
25 m glass capillary column, SE-30) and a Chrom 5 instru-
Method B: The same reactants as in Method A, but
without butyronitrile as a solvent, were used and the reac-
tion was carried out according to [8]. The mixture was
warmed up to ca. 908C and the peroxide was added in
several portions to keep reaction temperature below 1008C
during 1 h reaction time. After removing volatile compo-
nents as above, the crude product contained compounds 1
and 2 (Table 1), which were easily separated by simple
column chromatography (see Method A).
Â
Â
ment (Laboratornõ pùõstroje, Prague; FID, 380 cm  0.3 cm
column packed with silicon elastomer E-301 on Chromaton
N-AW-DMCS (Lachema, Brno); nitrogen was used as
carrier gas, detector/injector temperatures were 260/
2558C); the GC apparatus was connected to a Hewlett±
Packard integrator (model 3390). NMR spectra were
recorded on a Bruker 400 AM (FT, 19F at 376.5 MHz)
and a Bruker WP 80 SY (FT, 19F at 75 MHz) instruments
using TMS and CFCl3 as the internal standards. Chemical
shifts are quoted in ppm (s: singlet, bs: broad singlet, d:
doublet, t: triplet, q: quadruplet, m: multiplet), coupling
constants J in Hz, solvent CDCl3.
3.2.1. From 1,4-diiodoperfluorobutane
Method A: 1,4-Diiodoper¯uorobutane (68.1 g, 0.15 mol),
allyl acetate (30 g, 0.3 mol), dibenzoyl peroxide (1.81 g,
7.5 mmol), butyronitrile (31.1 g, 0.45 mol). On the conver-
sion of 98%, the crude product consisted of a mixture
of mono-adduct 1a (4%) and diadducts 2a and 3a (96%,
Table 1), yield 94.7 g (95%).
The chemicals used were as follows: silica gel L40/100
(Merck); potassium hydroxide pellets were ground to pow-
der before use; boron tri¯uoride etherate (Lachema) was
distilled before use; 1,4- and 1,6-diiodoper¯uoroalkanes
were obtained from Asahi Glass Co., Japan, and were
worked-up with alkaline thiosulphate solution; dibenzoyl
peroxide (Fluka) was precipitated from its chloroform
solution by methanol and dried in vacuo; 2,2-diphenyl-1-
picrylhydrazyl (Aldrich); allyl acetate (Aldrich), butyroni-
trile (Aldrich) and were used without puri®cation; triethyl-
amine (Aldrich) was distilled before use (88±898C); diethyl
2,7-Diiodo-4,4,5,5,6,6,7,7-octa¯uoroheptyl acetate (1a):
1
for H and 19F NMR and MS spectra see [8].
(2,9-Diiodo-4,4,5,5,6,6,7,7-octa¯uorodecane-1,10-diyl)
1
diacetate (2a, ca. 86% rel.): for H and 19F NMR and MS
spectra see [8].
(2,10-Diiodo-4,4,5,5,6,6,7,7-octa¯uorodecane-1,9-diyl)
diacetate (3a, ca. 14% rel.) [CH3COOCH2CHICH2(CF2)4-
1
CH2CH(OCOCH3)CH2I]: H NMR (CDCl3) d: 2.07, 2.10
(2s, 6H, CH3); 2.40±2.60 (m, 2H, CH2CF2); 3.25±3.45 (m,

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
356
2H, CH2I); 4.20±4.35 (m, 2H, CH2O); 4.35±4.50 (m, 1H,
CHI); 5.12 (m, 1H, CHO) ppm.
19F NMR (CDCl3): The same spectrum as for 2a.
3.3.2. From mixtures of diacetates 2a±2b and rearranged
diacetates 3a±3b (14 and 16% rel.) by reaction with
potassium hydroxide in solvents
Preparative reactions: The reactions were performed in
the same manner as in Section 3.3.1. For results see Table 2.
Optimization of the solvent mixture for epoxidations: A
round-bottom ¯ask (50 ml) was charged with a mixture of
diacetates 2a and 2b (1.31 g, 2 mmol), powdered potassium
hydroxide (0.6 g, 10 mmol) and solvent (25 ml). The het-
erogenous mixture was re¯uxed while stirring by mechanic
stirrer with spirals from stainless wire for 5 h. Then, the
mixture was ®ltered, solvents were evaporated on rotary
evaporator and the residue was analyzed by GC (for results
see Table 3).1,2;9,10-Diepoxy-4,4,5,5,6,6,7,7-octa¯uorode-
cane (4a) [(CH2(O)CHCH2CF2CF2)2]: Analysis Ð Found:
C, 38.0; H, 3.30; F, 48.8%. C10H10F8O2, requires: C, 38.23;
H, 3.21; F, 48.38%; M, 314.2.
3.2.2. From 1,6-diiodoperfluorohexane
Method A: 1,6-Diiodoper¯uorohexane (68.1 g, 0.12 mol),
allyl acetate (30 g, 0.3 mol), dibenzoyl peroxide (1.81 g,
7.5 mmol), butyronitrile (31.1 g, 0.45 mol). On the conver-
sion of 98%, the crude product consisted of a mixture
of mono-adduct 1b (2%) and diadducts 2b and 3b (98%,
Table 1), yield 88.4 g (92%).
2,9-Diiodo-4,4,5,5,6,6,7,7,8,8,9, 9-dodeca¯uorononyl
1
acetate (1b): for H and 19F NMR and MS spectra see
[8].
(2,11-Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorodode-
F
cane-1,12-diyl) diacetate (2b, ca. 84% rel.): for 1H and 19
NMR and MS spectra see [8].
(2,12-Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorodode-
cane-1,11-diyl) diacetate (3b, ca. 16%) [CH3COOCH2-
CHICH2(CF2)6CH2CH(OCOCH3)CH2I]: 1H NMR (CDCl3)
d: 2.07, 2.10 (2s, 6H, CH3); 2.60±3.00 (m, 2H, CH2CF2);
1H NMR (CDCl3) d: 2.1±2.45 (m, 2H, CH2CF2); 2.55 (dd,
HA, CH2O, 2JHH ˆ 5, 3JHH ˆ 2); 2.83 (t, HB, CH2O, 2JHH
ˆ
3JHH ˆ 4); 3.17±3.21 (m, 1H,CHO) ppm.
13C NMR (CDCl3) d: 35.19 (t, CH2CF2,2JCF ˆ 22); 44.82
2
4.20±4.35 (m, 2H, CH2O); 4.35±4.50 (m, 1H, CHI) ppm. 19
F
(t, CHCH2CF2, JCF ˆ 5); 45.75 (s, CH2O) ppm.19F NMR
NMR (CDCl3) d: 113.75 (m, 4F, CF2CH2); 122.07 (m,
4F, CH2C2F4CF2); 123.93 (m, 4F, CH2CF2CF2) ppm.
(CDCl3) d: 112.99 (m, 4F, CF2CH2); 123.89 (m, 4F,
CH2CF2CF2) ppm. 1,2;11,12-Diepoxy-4,4,5,5,6,6,7,7,8,8,-
9,9-dodeca¯uorododecane (4b) [(CH2(O)CHCH2CF2CF2-
CF2)2]: Analysis Ð Found: C, 34.4; H, 2.52; F, 55.3%.
C12H10F12O2, requires: C, 34.80; H, 2.43; F, 55.04%; M,
414.2.
3.3. Preparation of diepoxides 4a±4b from diacetates 2a±
2band 3a±3b
1H NMR (CDCl3) d: 2.10±2.45 (m, 2H, CH2CF2); 2.52
3.3.1. From individual non-rearranged diacetates 2a±2b
by reaction with potassium hydroxide in solvents (Table 2)
A round-bottom ¯ask (500 ml) was charged with diace-
tate 2a or 2b (13.1 or 15.1 g, respectively; 0.02 mol),
powdered potassium hydroxide (5.6 g, 0.10 mol), hexane
(200 ml) and diethyl ether (50 ml). The heterogenous mix-
ture was re¯uxed while stirring by mechanic stirrer with
spirals from stainless wire for 5 h (conversion 99%). Then,
the mixture was ®ltered, solvents were evaporated on rotary
evaporator, and yield of pure diepoxides (or, respectively)
were obtained by distillation on oil pump: 4a, 5.4 g (86%),
purity 99%. bp 90±928C/0.5 mm Hg (lit. value [16]: 110±
1128C/5 mm Hg); 4b: 7.1 g (85%), bp 104±1068C/0.5 mm
Hg, purity 99%. The distillation residue also contained
unsaturated by-products. In the reaction of the starting
diacetate 2a the following by-products were isolated and
identi®ed as mixtures of cis and trans isomers: epoxy-
acetate 11a (0.6 g, 9% rel., bp 81±838C/0.1 mm Hg, purity
98%) and epoxy-alcohol 9a (0.3 g, 5% rel., bp 75±788C/
0.2 mm Hg, purity 98%). In the case of diacetate 2b the by-
products epoxy-alcohol 9b (11,12-epoxy-4,4,5,5,6,6,7,7,-
8,8,9,9-dodeca¯uorododec-2-en-1-ol) and epoxy-acetate
11b [(11,12-epoxy-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorodo-
dec-2-ene-1-yl) acetate] were not isolated and their struc-
tures were approximately assigned on the basis of NMR
spectra of reaction mixture (and their similarity with 9a,
11a) and similarity of gas chromatograms with the mixture
of products in the reaction of 2a.
2
3
(dd, HA, CH2O, JHH ˆ 5, JHH ˆ 2); 2.81 (t, HB, CH2O,
2JHH ˆ 3JHH ˆ 4); 3.13±3.21 (m, 1H, CHO) ppm.
19F NMR (CDCl3) d: 113.83 (m, 4F, CF2CH2); 122.12
(m, 4F, CH2C2F4CF2); 124.04 (m, 4F, CH2CF2CF2) ppm.
9,10-Epoxy-4,4,5,5,6,6,7,7-octa¯uorodec-2-en-1-ol (9a)
[CH2(O)CHCH2CF2CF2-CF2CF2CH=CHCH2OH]: Analy-
sis Ð Found: C, 38.1; H, 3.2; F, 48.5%. C10H10F8O2,
requires: C, 38.23; H, 3.21; F, 48.38%; M, 314.18.
trans isomer (89% rel.): 1H NMR (CDCl3) d: 2.02 (s, 3H,
CH3); 2.10±2.40 (m, 2H, CH2CF2); 2.52 (q, 2H, CH2O);
2.79 (s, 1H,OH); 3.15 (m, 1H, CHO); 4.21 (m, 2H, CH2OH);
6.30±6.38 (m, HA, CH=CH); 6.38±6.45 (m, HB, CH=CH)
2
ppm. 13C NMR (CDCl3) d: 35.09 (t, CH2CF2, JCF ˆ 22);
3
44.80 (t, CHO, JCF ˆ 5); 45.60 (s, CH2O); 60.88 (s,
2
CH2OH); 141.09 (t, CHCF2, JCF ˆ 22 Hz); 170.16 (s,
C=O) ppm. 19F NMR (CDCl3) d: 108.25 (m, 1F, CF2CH);
112.20 (m, 1F, CF2CH); 112.90 (m, 2F, CF2CH2);
113.15 (m, 2F, CF2CH2); 123.86 (m, 4F, CH2CF2CF2)
ppm.
1
cis isomer (11% rel.): H NMR (CDCl3) d: 2.02 (s, 3H,
CH3); 2.10±2.40 (m, 2H, CH2CF2); 2.52 (q, 2H, CH2O);
2.79 (s, 1H, OH); 3.15 (m, 1H, CHO); 4.35 (m, 2H,
CH2OH); 6.49 (m, 2H, CH=CH) ppm. 13C NMR (CDCl3)
d: 20.21 (s, CH3); 35.09 (t, CH2CF2,2JCF ˆ 22); 44.80 (t,
CHO,3JCF ˆ 5); 45.60 (s, CH2O); 61.92 (s, CH2OAc);
2
144.50 (t, CHCF2, JCF ˆ 22 H); 170.16 (s, C=O) ppm.
19F NMR (CDCl3): the same as for the trans isomer.

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
357
(9,10-Epoxy-4,4,5,5,6,6,7,7-octa¯uorodec-2-ene-1-yl)
acetate (11a) [CH2(O)CHCH2CF2CF2CF2CF2CH=CH-
CH2OCOCH3]: Analysis Ð Found: C, 40.4; H, 3.43; F,
43.0%. C12H12F8O3, requires: C, 40.46; H, 3.40; F, 42.67%;
M, 356.2.
CH2CF2); 3.31 (dd, HA, CH2I, 2JHH ˆ 10 Hz, 3JHH ˆ 6 Hz);
2
3
3.42 (dd, HB, CH2I, JHH ˆ 10 Hz, JHH ˆ 4 Hz); 3.80 (m,
2H, CH2O); 4.00±4.10 (m, 1H, CHO); 4.40 (m, 1H, CHI)
ppm. 19F NMR (CDCl3) d: the same as for 5a.
trans isomer (81% rel): 1H NMR (CDCl3) d: 2.05 (s, 3H,
CH3); 2.10±2.40 (m, 2H, CH2CF2); 2.79 (q, 2H, CH2O);
3.15 (m, 1H, CHO); 4.65 (m, 2H, CH2OAc); 5.70±6.00 (m,
2H, CH=CH) ppm. 13C NMR (CDCl3) d: 20.21 (s, CH3);
3.4.1.2. Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorodo-
decanediols (5b and 6b). The same procedure as in Section
3.4.1.1 was used; a mixture of diiododiacetates 2b (84%
rel.) and 3b (15.1 g, 20 mmol) was reacted. The mixture of
products 5b and 6b (purity ca. 96%) was obtained in an yield
of 10.2 g (85%). For analytical purposes the mixture of
products was purified by column chromatography (silica
gel, toluene/methylene chloride).
2
3
35.09 (t, CH2CF2, JCF ˆ 22); 44.80 (t, CHO, JCF ˆ 5);
45.60 (s, CH2O); 61.92 (s, CH2OAc); 135.46 (t, CHCF2,
2JCF ˆ 22); 170.16 (s, C=O) ppm. 19F NMR (CDCl3) d:
108.90 (m, 1F, CF2CH); 112.90 (m, 1F, CF2CH2);
113.15 (m, 2F, CF2 CH2); 123.86 (m, 4F, CH2CF2CF2)
ppm.
Analysis (5b and 6b) Ð Found: C, 21.8.1; H, 1.83; F,
34.7; I, 38.0%. C12H12F12I2O2, requires: C, 21.51; H, 1.80;
F, 34.0; I, 37.9%; M, 670.0.2,11-Diiodo-4,4,5,5,6,6,7,7,8,-
8,9,9-dodeca¯uorododecane-1,12-diol (84% rel., 5b) [(HO-
CH2CHICH2CF2CF2CF2)2]: 13C NMR (CDCl3) d: 22.68 (s,
1
cis isomer (19% rel.): H NMR (CDCl3) d: 2.05 (s, 3H,
CH3); 2.10±2.40 (m, 2H, CH2CF2); 2.79 (q, 2H, CH2O);
3.15 (m, 1H, CHO); 4.80 (m, 2H, CH2OAc); 6.05±6.20 (m,
2H, CH=CH) ppm. 13C NMR (CDCl3) d: 20.21 (s, CH3);
2
CHI); 38.30 (t, CH2QF, JCF ˆ 21 Hz); 68.64 (s, CH2O)
35.09 (t, CH2CF2, JCF ˆ 22); 44.80 (t, CHO, JCF ˆ 5 );
45.60 (s, CH2O); 61.92 (s, CH2OAc); 138.58 (t, CHCF2,
2JCF ˆ 22); 170.16 (s, C=O) ppm. 19F NMR (CDCl3): the
same as for the trans isomer.
ppm. 1H NMR (CDCl3) d: 2.15 (s, 1H, OH); 2.69±2.84 (m,
1H, CH2CF2); 2.93±3.08 (m, 1H, CH2CF2); 3.78 (dd, HA,
2
3
2
3
CH2O, JHH ˆ 12 Hz, JHH ˆ 5 Hz); 3.83 (dd, HB, CH2O,
3
2JHH ˆ 12 Hz, JHH ˆ 5 Hz); 4.44 (kv, 1H, CHI) ppm. 19F
NMR (CDCl3) d: 113.83 (m, 4F, CF2CH2); 122.12 (m,
4F, CH2C2F4CF2); 124.04 (m, 4F, CH2CF2CF2) ppm.1,12-
Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorododecane-2,11-
diol (16% rel., 6b) (HOCH2CHICH2(CF2)6CH2CHOH-
CH2I): 13C NMR (CDCl3) d: 14.76 (s, CH2I); 38.30 (t,
3.4. Preparation of diepoxides 4a±4b from diiodohydrins
5a±5b and 6a±6b (Table 2)
3.4.1. Preparation of diiodohydrins 5a±5b and 6a±6b from
mixtures of diacetates 2a±2b and rearranged diacetates
3a±3b (14 and 16% rel.) by acid reesterification with
methanol
2
CH2QF, JCF ˆ 21 Hz); 65.45 (s, CHO); 68.64 (s, CH2O)
ppm. 1H NMR (CDCl3) d: 2.15 (s, 1H, OH); 2.30±2.50 (m,
2H, CH2CF2); 3.32±3.40 (m, 1H, CH2I); 4.05±4.12 (m, 1H,
CHO); 4.44 (q, 1H, CHI) ppm. 19F NMR (CDCl3) d: the
same as for 5b
3.4.1.1. Diiodo-4,4,5,5,6,6,7,7-octafluorodecanediols (5a
and 6a). A mixture of diiododiacetates 2a and 3a (86
and 14% rel. 13.1 g, 20 mmol), methanol (39.5 g,
1.2 mol) and concentrated hydrochloric acid (4 drops)
was refluxed for 6 h when the conversion was ca. 98%
(checked by GC). Then, volatile components were distilled
off in vacuum (0.5 mm Hg) on a distillation apparatus with
oil pump to give almost pure mixture (ca. 97%) of 5a and 6a
in an yield of 9.25 g (86%) was obtained. For analytical
purposes the mixture of products was purified by column
chromatography (silica gel, toluene/methylene chloride).
Analysis (5a and 6a) Ð Found: C, 21.2.1; H, 2.24; I,
44.1%. C10H12F8I2O2, requires: C, 21.07; H, 12.08; I,
44.51%; M, 570.0.
2,9-Diiodo-4,4,5,5,6,6, 7,7-octa¯uorodecane-1,10-diol
(86% rel., 5a) [(HOCH2CHICH2±CF2CF2)2]: 1H NMR
(CDCl3) d: 2.57 (s, 1H, OH); 2.60±2.87 (m, 1H, CH2CF2);
2.87±3.10 (m, 1H, CH2CF2); 3.80 (m, 2H, CH2O); 4.40 (m,
1H, CHI) ppm. 19F NMR (CDCl3) d: 113.54 (m, 4F,
CF2CH2); 123.89 (m, 4F, CH2CF2CF2) ppm.
3.4.2. Preparation of diiodohydrins 5a±5b from diacetates
2a±2b by acid reesterification with methanol (Table 2)
3.4.2.1. 2,9-Diiodo-4,4,5,5,6,6,7,7-octafluorodecane-1,10-
diol (5a). The same procedure as in Section 3.4.1.1 was
applied; a mixture of diiododiacetate 2a (4.6 g, 7 mmol),
methanol (13.2 g, 0.4 mol) and concentrated hydrochloric
acid (2 drops) was refluxed for 6 h when the conversion was
ca. 98% (checked by GC). After removing volatile
components, almost pure mixture (ca. 95%) of 5a in an
yield of 3.05 g (83%) was obtained. For analytical purposes
the product was purified by column chromatography (silica
gel, toluene/methylene chloride).
3.4.2.2. 1,12-Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodecafluor-
ododecane-2,11-diol (5b). The same procedure as in
Section 3.4.2.1 was applied; a mixture of diiododiacetate
2b (5.1 g, 6.8 mmol), methanol (13.2 g, 0.4 mol) and
concentrated hydrochloric acid (2 drops) was refluxed for
6 h when the conversion was ca. 98% (checked by GC).
After removing volatile components, almost pure mixture
(ca. 95%) of 5b in an yield of 3.25 g (82%) was obtained.
2,10-Diiodo-4,4,5,5,6,6,7, 7-octa¯uorodecane-1,9-diol
(14% rel., 6a) (HOCH2CHICH2±(CF2)4CH2CHOHCH2I):
1H NMR (CDCl3) d: 2.30±2.60 (2m, 2H, CH2CF2); 2.57 (s,
1H, OH); 2.60±2.87 (m, 1H, CH2CF2); 2.87±3.10 (m, 1H,

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
358
For analytical purposes the product was purified by column
chromatography (silica gel, toluene/methylene chloride).
3.5.2. 1,12-Dimethoxy-4,4,5,5,6,6,7,7,8,8,9,9-dode-
cafluorododecane-2,11-diol (12b)
The same procedure as in Section 3.5.1 was applied;
diepoxide 4b (0.434 g, 1.05 mmol), boron tri¯uoride ethe-
rate (4 drops). With the complete conversion of the starting
diepoxide and after precipitation from toluene solution the
product 12b was obtained in an yield of 0.40 g (80%), mp
90±928C. Analysis Ð Found: C, 34.8; H, 3.70; F, 48.0%.
3.4.3. Preparation of diepoxides 4a±4b from diiodohydrins
5a±5b and 6a±6b by reaction with potassium hydroxide
(Table 2)
3.4.3.1. 1,2;9,10-diepoxy-4,4,5,5,6,6,7,7-octafluorodecane
(4a). In a round-bottom flask equipped with a reflux
condenser with a drying tube, a mixture of diiodohydrins
5a (86% rel.) and 6a (2.2 g, 4 mmol), powdered potassium
hydroxide (1.2 g, 0.02 mol) and diethyl ether (20 ml) was
refluxed while stirring intensively with magnetic spinbar for
30 min when the conversion was ca. 98% (checked by GC).
After filtration, the ether was removed from the filtrate
under reduced pressure and the residue was distilled in
vacuum to afford diepoxide 4a in an yield of 0.95 g
(74%), bp 88±908C/0.5 mm Hg, which contained
unsaturated alcohol 11a (ca. 6%, GC and 19F NMR).
C14H18F12O4, requires: C, 35.15; H, 3.79; F, 47.65%; M,
478.3. 13C NMR (CDCl3) d: 35.43 (t, CH2CF2, JCF
2
ˆ
21 Hz); 59.84 (s, CH3O); 64.92 (s, CHO); 76.53 (s,
CH2O) ppm. 1H NMR (CDCl3) d: 2.20±2.40 (2m, 2H,
CH2CF2); 2.47 (s, 1H, OH); 3.40 (dd, HA, CH2O,
3
2JHH ˆ 9.5 Hz, JHH ˆ 6 Hz); 3.42 (s, 3H, CH3); 3.50
2
3
(dd, HB, CH2O, JHH ˆ 9.5 Hz, JHH ˆ 4 Hz); 4.29 (m,
1H, CHO) ppm. 19F NMR (CDCl3) d: 113.22 (m, 4F,
CF2CH2); 122.12 (m, 4F, CH2C2F4CF2); 124.18 (m, 4F,
CH2CF2CF2) ppm.
3.6. Transformation of diepoxides 4a and 4b to bis-
dioxolanyl derivatives (products 13a±13b)
3.4.3.2. 1,2;11,12-Diepoxy-4,4,5,5,6,6,7,7,8,8,9,9-dode-
cafluorododecane (4b). The same procedure as above
[diiodohydrins 5b (84% rel.) and 6b (2.92 g, 4 mmol)]
was applied to obtain diepoxide 4b in an yield of 1.16 g
(66%), bp 103±1058C/0.5 mm Hg, which contained
unsaturated alcohol 11b (ca. 6%, GC and 19F NMR).
3.6.1. Reaction of 1,2;9,10-diepoxy-4,4,5,5,6,6,7,7-
octafluorodecane (4a) with acetone (product 13a)
In a round-bottom ¯ask equipped with a re¯ux condenser
with a drying tube (MgSO4), a mixture of diepoxide 4a
(0.347 g, 1.10 mmol), acetone (10 ml), and boron tri¯uoride
etherate (4 drops) was re¯uxed while stirring intensively
with magnetic spinbar for 1 h when the conversion was ca.
98% (checked by GC). Then, acetone and volatile compo-
nents were removed on rotary evaporator and crude product
13a as a white solid was obtained (0.45 g, 94%). Recrys-
tallization of this product was unsuccessful. For analytical
purposes, 13a was puri®ed by simple column chromato-
graphy (silica gel; hexane, chloroform), mp 62±658C.
An attempt of recrystallization in boiling ethyl acetate led
to the formation of dioxolanyldiol 15a, mp 95±978C. The
partial hydrolysis of the starting 13a was caused by traces of
water and acetic acid in ethyl acetate.
3.4.4. Preparation of diepoxides 4a±4b from diiodohydrins
5a±5b by reaction with potassium hydroxide (Table 2)
The same procedures and same amounts of reactants were
employed as in Section 3.4.3. For results see Table 2.
3.5. Ring opening of diepoxides 4a and 4b with methanol
(products 12a and 12b)
3.5.1. 1,10-dimethoxy-4,4,5,5,6,6,7,7-octafluorodecane-
2,9-diol (12a)
In a round-bottom ¯ask equipped with a re¯ux condenser
with a drying tube (MgSO4), a mixture of diepoxide 4a
(0.325 g, 1.03 mmol), methanol (7.9 g, 0.25 mol) and boron
tri¯uoride etherate (2 drops) was re¯uxed while stirring
intensively with magnetic spinbar for 4 h when the conver-
sion was complete (checked by GC). After evaporation of
methanol on rotary evaporation, crude 12a as a white solid
was obtained that was dissolved in boiling toluene and
precipitated with petroleum ether to afford pure dimethox-
ydiol 12a in an yield of 0.21 g (54%), mp 87±898C. Analysis
Ð Found: C, 37.8; H, 4.70; F, 39.7%. C12H18F8O4, requires:
C, 38.10; H, 4.80; F, 40.16%; M, 378.25. 13C NMR (CDCl3)
d: 35.42 (t, CH2CF2, 2JCF ˆ 21 Hz); 59.75 (s, CH3O); 64.68
(s, CHO); 76.64 (s, CH2O) ppm. 1H NMR (CDCl3) d: 2.20±
2.40 (2m, 2H, CH2CF2); 2.76 (s, 1H, OH); 3.37 (dd, HA,
1,6-Bis(2,2-dimethyl-1,3-dioxolan-4-yl)-2,2,3,3,4,4,5,5-
octa¯uorohexane (13a): Analysis Ð Found: C, 40.2; H,
5.37; F, 36.1%. C16H22F8O4, requires: C, 40.65; H, 5.15; F,
35.30%; M, 430.3. 13C NMR (DMSO) d: 25.52, 26.55 (2s,
2
CH3); 34.31 (t, CH2QF, JCF ˆ 21 Hz); 68.48 (s, CH2O);
1
68.67 (s, CHO); 108.72 (s, C) ppm. H NMR (DMSO) d:
1.29, 1.34 (2s, 6H, CH3); 2.30±2.60 (m, 2H, CH2CF2); 3.63
2
3
(dd, HA, CH2O, JHH ˆ 8 Hz, JHH ˆ 7 Hz); 4.09 (dd, HB,
2
3
CH2O, JHH ˆ 8 Hz, JHH ˆ 6 Hz); 4.37 (kv, 1H, CHO)
ppm. 19F NMR (DMSO) d: 112.01 (m, 4F, CF2CH2);
123.00 (m, 4F, CH2CF2CF2) ppm
8-(2,2-Dimethyl-1,3-dioxolan-4-yl)-4,4,5,5,6,6,7,7-octa-
¯uorooctane-1,2-diol (15a). Analysis Ð Found: C, 39.6; H,
4.37; F, 39.4%. C13H18F8O4, requires: C, 40.00; H, 4.65; F,
38.93%; M, 390.3. 13C NMR (DMSO) d: 25.58, 26.60 (2s,
2
3
CH2O, JHH ˆ 10 Hz, JHH ˆ 6.5 Hz); 3.41 (s, 3H, CH3);
3.48 (dd, HB, CH2O, 2JHH ˆ 10 Hz, 3JHH ˆ 4 Hz); 4.26 (m,
1H, CHO) ppm. 19F NMR (CDCl3) d: 113.33 (m, 4F,
CF2CH2); 124.06 (m, 4F, CH2CF2CF2) ppm.
2
CH3); 34.34 (t, CH2QF, JCF ˆ 21 Hz); 65.05 (s, CHO);
65.26 (s, CH2O); 68.54 (s, CH2O); 68.73 (s, CHO); 108.80

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
359
(s, C) ppm. 1H NMR (DMSO) d: 1.29, 1.34 (2s, 6H, CH3);
2.00±2.20 (m, 1H, CH2CF2); 2.30±2.50 (m, 1H, CH2CF2);
3.24 (dd, HA, CH2O, 2JHH ˆ 11 Hz, 3JHH ˆ 7 Hz); 3.39 (dd,
HB, CH2O, 2JHH ˆ 11 Hz, 3JHH ˆ 5 Hz); 3.62 (t, HA, CH2O,
2JHH ˆ 3JHH ˆ 7.5 Hz); 3.85 (m, 1H, CHO); 4.09 (t, HB,
ppm. 19F NMR (DMSO) d: 113.20 (m, 4F, CF2CH2);
123.79 (m, 4F, CH2CF2CF2) ppm.
3.7.2. 4,4,5,5,6,6,7,7,8,8,9,9-Dodecafluorododecane-
1,2,11,12-tetrol (14b)
2
CH2O, JHH ˆ 3JHH ˆ 7.5 Hz); 4.37 (m, 1H, CHO) ppm.
The same procedure as in Section 3.7.1 was applied to
crude bis-dioxolane (13b) (0.53 g, 1 mmol). After removing
acetone and volatile components and precipitation, pure
crude 14b as a white solid (0.30 g, 67%) was obtained, mp
103±1058C. Analysis Ð Found: C, 31.7; H, 2.9; F, 51.1%.
19F NMR (DMSO) d: 113.01 (m, 4F, CF2CH2); 123.70
(m, 4F, CH2CF2CF2) ppm.
3.6.2. Reaction of1,2;11,12-diepoxy-4,4,5,5,6,6,7,7,8,8,9,9-
dodecafluorododecane (4b) with acetone(1,8-bis(2,2-
dimethyl-1,3-dioxolan-4-yl)-2,2,3,3,4,4,5,5,6,6,7,7-
dodecafluorooctane, 13b)
C12H14F12O4, requires: C, 32.01; H, 3.13; F, 50.61%; M,
2
450.2. 13C NMR (DMSO) d: 34.08 (t, CH2QF, JCF
ˆ
1
21 Hz); 65.01 (s, CHO); 65.18 (s, CH2O) ppm. H NMR
(DMSO) d: 2.00±2.20 (m, 1H, CH2CF2); 2.30±2.50 (m, 1H,
CH2CF2); 3.24 (dd, HA, CH2O, 2JHH ˆ 11 Hz,
The same procedure as in Section 3.7.1 was applied;
diepoxide 4b (0.425 g, 1.02 mmol). After removing acetone
and volatile components, crude 13b as a white solid (0.52 g,
95%) was obtained. For analytical purposes, 13b was
puri®ed by simple column chromatography (silica gel;
hexane, chloroform), mp 72±758C. An attempt of recrys-
tallization of the crude product in boiling ethyl acetate led to
the total hydrolysis of the dioxolane rings to tetrol 14b (see
Section 3.7.2). Analysis Ð Found: C, 40.1; H, 4.01; F,
43.5%. C18HF12O4, requires: C, 40.76; H, 4.18; F, 42.97%;
M, 530.5. C18H22O4F12 M ˆ 530.35) calculated/found
40.76/37.47 %C, 4.18/3.85 %H, 42.97/43.65 %F. 13C
NMR (DMSO) d: 25.51, 26.52 (2s, CH3); 34.17 (t, CH2QF,
2JCF ˆ 21 Hz); 68.43 (s, CH2O); 68.59 (s, CHO); 108.81 (s,
2
3
3JHH ˆ 7 Hz); 3.40 (dd, HB, CH2O, JHH ˆ 11 Hz, JHH
ˆ
5 Hz); 3.85 (m, 1H, CHO); 4.45 (2s, 2H, OH) ppm. 19F
NMR (DMSO) d: 112.98 (m, 4F, CF2CH2); 121.69 (m,
4F, CH2C2F4CF2); 123.75 (m, 4F, CH2CF2CF2) ppm.
3.8. Base catalyzed ring opening of diepoxides 4a and 4b
with methacrylic acid (products 16a±16b, and 17a±17b)
3.8.1. Reaction of 1,2;9,10-diepoxy-4,4,5,5,6,6,7,7-
octafluorodecane (4a) (products 16a and 17a)
In a round-bottom ¯ask equipped with a re¯ux condenser
with a drying tube (MgSO4), a mixture of diepoxide 4a
(0.317 g, 1.01 mmol), methacrylic acid (1.70 g,
19.7 mmol), triethylamine (5 drops) and diphenyl picryl
hydrazyl (15 mg) was heated to 1008C while stirring inten-
sively with magnetic spinbar for 2 h when the conversion
was ca. 98% (checked by GC). Then, the excess of
methacrylic acid was distilled off in vacuum in a distillation
apparatus with oil pump (0.5 mm Hg, 1008C bath tempera-
ture) to afford crude product (16a and 17a) as a brown solid.
Pure mixture of regioisomeric products was obtained 16a
and 17a (89 and 11% rel.) by their precipitation from boiling
toluene solution using petroleum ether, the yield was
0.205 g (41%), mp 75±788C. Analysis (16a and 17a) Ð
Found: C, 43.8; H, 4.47; F, 31.7%. C18H22F8O6, requires: C,
43.45; H, 4.56; F, 31.24%; M, 486.4.
1
C) ppm. H NMR (DMSO) d: 1.29, 1.34 (2s, 6H, CH3);
2.20±2.70 (m, 2H, CH2CF2); 3.63 (t, HA, CH2O,
2
2JHH ˆ 3JHH ˆ 7 Hz); 4.09 (t, HB, CH2O, JHH ˆ 8 Hz,
3JHH ˆ 6 Hz); 4.37 (m, 1H, CHO) ppm. 19F NMR (DMSO)
d:
CH2C2F4CF2); 123.50 (m, 4F, CH2CF2CF2) ppm.
112.00 (m, 4F, CF2CH2);
121.00 (m, 4F,
3.7. Alcoholysis of bis-dioxolanylderivatives 13a and
13b
3.7.1. 4,4,5,5,6,6,7,7-Octafluorodecane-1,2,9,10-tetrol
(14a)
In a round-bottom ¯ask equipped with a re¯ux condenser,
a mixture of crude bis-dioxolanyl derivatives 13a (0.45 g,
1.05 mmol), methanol (10 ml) and concentrated hydrochlo-
ric acid (4 drops) was re¯uxed while stirring for 1 h when
the conversion was ca. 98% (checked by GC). Volatile
components were removed under reduced pressure on rotary
evaporator to obtain crude 14a as a white solid. This solid
was dissolved in boiling ethyl acetate and precipitated with
petroleum ether to obtain pure 14a in an yield of 0.28 g
(74%), mp 101±1038C. Analysis Ð Found: C, 33.9; H, 3.9;
F, 43.1%. C10H14F8O4, requires: C, 34.29; H, 4.03; F,
43.38%; M, 350.2. 13C NMR (DMSO) d: 34.27 (t, CH2QF,
2JCF ˆ 21 Hz); 65.29 (s, CHO); 65.29 (s, CH2O) ppm.1H
NMR (DMSO) d: 2.00±2.20 (m, 1H, CH2CF2); 2.30±2.50
(2, 9-Dihydroxy-4, 4,5, 5, 6,6,7, 7-octa¯uorodecan-1,10-
diyl) dimethacrylate (16a, 89% rel.) [(CH2=C(CH3)COO-
CH2CHOHCH2CF2CF2)2]: 13C NMR (CDCl3) d: 18.83 (s,
2
CH3); 35.69 (t, CH2CF2, JCF ˆ 21 Hz); 64.75 (s, CHO);
68.50 (s, CH2OMA); 127.19 (s, CH2=); 136.38 (s, C=);
1
167.98 (s, C=O) ppm. H NMR (CDCl3) d: 1.97 (s, 3H,
CH3); 2.20±2.50 (m, 2H, CH2CF2); 2.65 (s, 1H, OH); 4.19
(dd, HA, CH2OMA, 2JHH ˆ 12 Hz, 3JHH ˆ 6 Hz); 4.27 (dd,
2
3
HB, CH2OMA, JHH ˆ 12 Hz, JHH ˆ 4 Hz); 4.42 (m, 1H,
CHO); 5.64 (s, Hcis, CH2=); 6.16 (s, Htrans, CH2=) ppm. 19
F
NMR (CDCl3) d: 112.85 (m, 4F, CF2CH2); 123.86 (m,
4F, CH2CF2CF2) ppm.
(2,10-Dihydroxy-4, 4,5,5,6, 6, 7, 7-octa¯uorodecan-1,9-
diyl) dimethacrylate (17a, 11% rel.) (CH2C(CH3)COOCH2-
CHOHCH2(CF2)4CH2CH(OCOC(CH3)CH2)CH2OH): 13C
2
(m, 1H, CH2CF2); 3.24 (dd, HA, CH2O, JHH ˆ 11 Hz,
2
3JHH ˆ 7 Hz); 3.39 (dd, HB, CH2O, JHH ˆ 11 Hz,
3JHH ˆ 5 Hz); 3.86 (m, 1H, CHO); 4.92 (2s, 2H, OH)

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361
360
NMR (CDCl3) d: 18.83 (s, CH3); 32.65 (t, CH2CF2,
5.75%. C18H28F8N2O4, requires: C, 44.26; H, 5.78; F, 31.10;
N, 5.73%; M, 488.4. 13C NMR (CDCl3) d: 36.77 (t, CH2QF,
2JCF ˆ 21 Hz); 54.14 (s, CH2N); 60.89 (s, CHO); 64.88 (s,
2
2JCF ˆ 21 Hz); 35.69 (t, CH2CF2, JCF ˆ 21 Hz); 46.41
(s, CH2O); 64.75 (s, CHO); 69.17 (s, CHOMA); 68.50 (s,
CH2OMA); 127.19 (s, CH2=); 136.38 (s, C=); 167.98 (s,
1
CH2N); 67.54 (s, CH2O) ppm. H NMR (CDCl3) d: 2.00±
1
C=O) ppm. H NMR (CDCl3) d: 1.97 (s, 3H, CH3); 2.20±
2.20 (m, 1H, CH2CF2); 2.20±2.37 (m, 1H, CH2CF2); 2.32±
2.50 (m, 4H, CH2N); 2.67 (m, 2H, CH2N); 3.64 (s, 1H, OH);
3.72 (m, 4H, CH2O); 4.14 (m, 1H, CHO) ppm. 19F NMR
(CDCl3) d: 112.82 (m, 4F, CF2CH2); 124.06 (m, 4F,
CH2CF2CF2) ppm.
2.50 (m, 2H, CH2CF2); 2.50±2.60 (m, 2H, CH2CF2); 2.65 (s,
1H, OH); 3.76 (dd, HA, CH2O, 2JHH ˆ 12 Hz, 3JHH ˆ 5 Hz);
3.82 (dd, HB, CH2O, 2JHH ˆ 12 Hz, 3JHH ˆ 4 Hz); 4.19 (dd,
3
HA, CH2OMA, 2JHH ˆ 12 Hz, JHH ˆ 6 Hz); 4.27 (dd, HB,
2
3
CH2OMA, JHH ˆ 12 Hz, JHH ˆ 4 Hz); 4.42 (m, 1H,
CHO); 5.37 (m, 1H, CHOMA); 5.64 (s, Hcis, CH2=);
6.16 (s, Htrans, CH2=) ppm. 19F NMR (CDCl3) d: the same
as for 16a.
3.9.2. 1,12-Bis(morpholin-4-yl)-4,4,5,5,6,6,7,7,8,8,9,9-
dodecafluorododecane-2,11-diol (18b)
The same procedure as in Section 3.9.1 was applied;
diepoxide 4b (0.453 g, 1.09 mmol), 90 min reaction. The
crude 18b as a yellow solid (0.52 g, 95%) was obtained.
Pure product 18b was obtained by its precipitation from
boiling toluene solution using petroleum ether, the yield was
0.48 g (75%), mp 102±1058C. Analysis Ð Found: C, 40.3;
H, 4.69; F, 39.2; N, 4.74%. C20H28F12N2O4, requires: C,
40.82; H, 4.78; F, 38.73; N, 4.76%; M, 588.4. 13C NMR
3.8.2. Reaction of 1,2;11,12-diepoxy-4,4,5,5,6,6,7,-
7,8,8,9,9-dodecafluorododecane (4b) (products 16b and
17b)
The same procedure as in Section 3.8.1 was applied;
diepoxide 4b (0.459 g, 1.11 mmol), methacrylic acid (2.0 g,
23.2 mmol), 3 h reaction at 1008C. With ca. 97% conversion
of the starting diepoxide and after repeated crystallization
(toluene/petroleum ether) the product (16b and 17b, ca.
90% rel.) was obtained in an yield of 0.26 g (40%), mp 80±
828C. Analysis (16b and 17b) Ð Found: F, 38.2%.
C20H22F12O6, requires: F, 38.86%; M, 586.4. (2,11-Dihy-
droxy-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorododecan-1,12-
diyl) dimethacrylate (16b, ca. 90% rel.) [(CH2=
2
(CDCl3) d: 36.84 (t, CH2QF, JCF ˆ 21 Hz); 54.22 (s,
CH2N); 60.89 (s, CHO); 64.94 (s, CH2N); 67.59 (s,
CH2O) ppm. 1H NMR (CDCl3) d: 2.00±2.20 (m, 1H,
CH2CF2); 2.20±2.37 (m, 1H, CH2CF2); 2.32±2,55 (m,
4H, CH2N); 2.69 (m, 2H, CH2N); 3.64 (s, 1H, OH); 3.72
(m, 4H, CH2O); 4.15 (m, 1H, CHO) ppm. 19F NMR (CDCl3)
d: 112.70 (m, 4F, CF2CH2); 122.10 (m, 4F, CH2C2F4-
CF2); 124.10 (m, 4F, CH2CF2CF2) ppm.
C(CH3)COOCH2CHOHCH2CF2CF2CF2)2]: 13C NMR
2
(CDCl3) d: 18.95 (s, CH3); 35.64 (t, CH2CF2, JCF
21 Hz); 64.77 (s, CHO); 68.49 (s, CH2OMA); 127.26 (s,
ˆ
1
CH2=); 136.34 (s, C=); 167.96 (s, C=O) ppm. H NMR
Acknowledgements
(CDCl3) d: 1.97 (s, 3H, CH3); 2.20±2.50 (m, 2H, CH2CF2);
2
2.45 (s, 1H, OH); 4.19 (dd, HA, CH2OMA, JHH ˆ 12 Hz,
The authors thank heartily the Asahi Glass Company,
Japan for the kind gift of diiodoper¯uoroalkanes. The
research was supported by the Grant Agency of the Czech
Republic (Grant No. 203/98/1174 and 106/001296) and the
grant of the Ministry of Education of the Czech Republic
(Project LB98233). Elemental analyses and measurements
of some NMR spectra were carried out in the Central
Laboratories of the Prague Institute of Chemical Technol-
ogy; the authors thank their staff members for the kind
assistance.
2
3JHH ˆ 6 Hz); 4.29 (dd, HB, CH2OMA, JHH ˆ 12 Hz,
3JHH ˆ 4 Hz); 4.42 (m, 1H, CHO); 5.65 (s, Hcis, CH2=);
6.15 (s, Htrans, CH2=) ppm. 19F NMR (DMSO) d: 113.00
(m, 4F, CF2CH2); 121.80 (m, 4F, CH2C2F4CF2); 124.00
(m, 4F, CH2CF2CF2) ppm.
3.9. Ring opening of diepoxides 4a and 4b with
morpholine
3.9.1. 1,10-Bis(morpholin-4-yl)-4,4,5,5,6,6,7,7-
octafluorodecane-2,9-diol (18a)
References
In a round-bottom ¯ask equipped with a re¯ux condenser
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(0.453 g, 1.44 mmol) and anhydrous morpholine (7.1 g,
81.5 mmol) was heated to 1008C while stirring intensively
with magnetic spinbar for 1 h when the conversion was ca.
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product (18a) as a brown solid. Pure product 18a was
obtained by its precipitation from boiling toluene solution
using petroleum ether, the yield was 0.43 g (61%), mp 95±
978C. Analysis Ð Found: C, 43.9; H, 5.69; F, 31.6; N,
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