Reactivity study of 1,1,2,4,4,5,7,7,8,8,9,9,-tridecafluoro-5- trifluoromethyl-3,6-dioxanon-1-ene in nucleophilic reactions: Fluorination properties of secondary amine adducts

Article abstract of DOI:10.1016/S0022-1139(02)00159-8

A series of nucleophiles was reacted with (1) as a representative of perfluoro(alkyl vinyl ethers). All reactions were completely regioselective with the nucleophilic attack at the terminal carbon atom. Reactions of hydroxy compounds, thiols and sec-amines afforded addition products, but butyllithium, tributylphosphane or complex hydrides caused displacement of vinylic fluorine: butyllithium afforded cis-derivative, while reactions with hydrides and the phosphane led to mixtures of cis- and trans-derivatives. Diethylamine and piperidine adducts displayed the property to substitute hydroxyl for fluorine in hexadecan-1-ol. Molecular properties of hexafluoropropene and perfluoro(methyl vinyl ether) were calculated by ab initio method at the MP2/6-311G(d,p) level of theory and their impact on relative reactivity was estimated.

Full text of DOI:10.1016/S0022-1139(02)00159-8

Journal of Fluorine Chemistry 117 (2002) 149–159
Reactivity study of 1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-
trifluoromethyl-3,6-dioxanon-1-ene in nucleophilic reactions:
fluorination properties of secondary amine adducts
*
Ivona Dlouh a´ , Jaroslav Kvi cˇ ala, Old ˇr ich Paleta
Department of Organic Chemistry, Prague Institute of Chemical Technology, Technick a´ 5,
1
6628 Prague 6, Czech Republic
Received 20 April 2002; received in revised form 18 May 2002; accepted 20 May 2002
Dedicated to Professor Lev M. Yagupolskii on the occasion of his 80th birthday.
Abstract
A series of nucleophiles was reacted with 1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-trifluoromethyl-3,6-dioxanon-1-ene (1) as a represen-
tative of perfluoro(alkyl vinyl ethers). All reactions were completely regioselective with the nucleophilic attack at the terminal carbon atom.
Reactions of hydroxy compounds, thiols and sec-amines afforded addition products, but butyllithium, tributylphosphane or complex hydrides
caused displacement of vinylic fluorine: butyllithium afforded cis-derivative, while reactions with hydrides and the phosphane led to mixtures
of cis- and trans-derivatives. Diethylamine and piperidine adducts displayed the property to substitute hydroxyl for fluorine in hexadecan-1-
ol. Molecular properties of hexafluoropropene and perfluoro(methyl vinyl ether) were calculated by ab initio method at the MP2/6-311G(d,p)
level of theory and their impact on relative reactivity was estimated.
#
2002 Elsevier Science B.V. All rights reserved.
Keywords: Perfluoro vinyl ether; 1,1,2,4,4,5,7,7,8,8,9,9,9-Tridecafluoro-5-trifluoromethyl-3,6-dioxanon-1-ene; Nucleophilic addition; Fluorination agent;
Vinylic fluorine displacement; Ab initio calculation; Molecular properties; LUMO energy; Electrostatic potential-derived charge; Merz–Kollman–Singh
scheme
1
. Introduction
ether) with phenyllithium [13] and nucleophilic addition of
pyridin-3-ol [14] and phenols [15] to perfluorinated vinyl
ethers. Nucleophilic addition of alkanol to (trifluoroviny-
l)oxy group of a bifunctional monomer was also employed
in the synthesis of polyether polymers [16]. Recently, we
published [17] preliminary results on reactions of a variety
of nucleophiles with 1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-
5-trifluoromethyl-3,6-dioxanon-1-ene (1) and found fluor-
inating properties of secondary amine adducts. Later on,
papers on additions of alcohols [18] and secondary or
tertiary amines [19] to olefin 1 were published in the
Russion journal. The papers [18,19] were combined and
published subsequently as a new publication [20] in this
journal. At present time, the synthesis of sugar derivatives of
the olefin 1 (Scheme 1), which display very good hemo-
compatibility and co-emulsifying properties when mixed
with perfluorocarbon—Pluronic F-68 emulsion, has been
reported [21].
Nucleophilic reactions of terminal perfluoroolefins have
been the subject of a broad academic research for tens of
years [1–7]. On the other hand, the reports on the chemistry
of perfluorinated vinyl ethers including olefins bearing
perfluorinated polyether part have appeared relatively
recently. Recent studies of radical additions to perfluoro
vinyl ethers showed their high reactivity toward nucleo-
philic radicals [8–10]. The reactions were applied in a
convenient synthesis of fluoroalkylated diols and the corre-
sponding bis-methacrylates as special crosslinking agents
[
10]. Original papers on the reactivity of perfluoro vinyl
ethers in nucleophilic reactions started to appear in the
sixties of the last century: short communication on the
reactions of perfluoro(methyl vinyl ether) with methanol
or diethylamine [11] or with azide ion in trapping the inter-
mediate carbanion [12]; reaction of perfluoro(propyl vinyl
In this work, we would like to report our completed results
that were preliminary reported as original in [17]: we carried
out reactions of olefin 1 with a range of nucleophilic
*
Corresponding author. Fax: þ420-2-2431-1082.
E-mail address: oldrich.paleta@vscht.cz (O. Paleta).
0022-1139/02/$ – see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 2 ) 0 0 1 5 9 - 8

150
I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
hexafluoropropene and perfluoro(methyl vinyl ether) at their
equilibrium geometries. Moreover, as both above-mentioned
charges assignments are somewhat arbitrary, we calculated
charges fit to the electrostatic potential at points selected
according to the Merz–Singh–Kollman scheme [25], which
should better correspond to reality. For both fluoroalkenes,
electrostatic potentials calculated at total electron density of
0.001 surface (darker areas indicate places of higher positive
electrostatic potential) are depicted in Fig. 1 together with
values of all three calculated charges.
Calculations confirmed that both Mullikan and Lowdin
charges are not satisfactory for the description of electronic
properties of fluoroalkenes, as seen from high differences
between them. Higher positive charge calculated by MSK
scheme on difluoromethylene group for hexafluoropropene
reflects higher electron-acceptor power of trifluoromethyl
group compared with trifluoromethoxy group.
Scheme 1. D-Glucose and D-galactose hemocompatible derivatives of
perfluorolefin 1.
reagents under comparable conditions to get an overview
on the reactivity abilities of the olefin 1. In the case that in
the meantime some compounds have been reported [20], we
present novel procedures. We also present quantum chemi-
cal calculations of perfluoro(methyl vinyl ether) and hexa-
fluoropropene as model compounds to compare the impact
of substitution of fluoroalkene by perfluoroalkyl or perfluoro-
alkoxy group on its reactivity.
As the attack of the nucleophilic reagents to fluoroalkenes
should be provided by a flow of electrons from HOMO
Ã
orbital of the nucleophile to p antibonding orbital (LUMO)
Ã
of the fluoroalkenes, we also calculated p orbital energies
for both model fluoroalkenes, which are depicted together
with the corresponding orbitals in Fig. 2.
Ã
Lower energy of p antibonding orbital of hexafluoro-
propene compared with perfluoro(methyl vinyl ether) again
implies higher reactivity of perfluoroalkenes compared with
perfluoro(alkyl vinyl ethers) towards nucleophilic reagents.
The shape of p orbital of hexafluoropropene is distorted by
electron-acceptor trifluoromethyl group, whereas oxygen
2
. Results and discussion
Ã
2.1. General observation in the reaction of 1 with
nucleophiles
atom in perfluoro(methyl vinyl ether) separates efficiently
Ã
The experiments were carried under nitrogen. All the
reactions took place with the complete regioselectivity and
exclusive nucleophilic attack at the terminal CF -group in
this influence at the corresponding p orbital.
2.3. Additions of O- and S-nucleophiles to olefin 1
2
olefin 1. No by-products were formed in the reactions as
verified by checking the reaction mixtures by 19F NMR or
following the reactions by 19F NMR. An overview of the
addition reactions is given in Table 1 together with the
structures of the products 2–12. In the additions, the second
stereogenic center is formed at original vinyl ether carbon (the
C-2). Thus, mixtures of diastereoisomers were formed in
approximate ratio 1:1 as verified in some cases by 19F NMR.
The reactions of hydroxy compounds were characterized
by the fact that no unsaturated products were formed by
replacement of vinylic fluorine in 1 or by a subsequent
elimination of hydrogen fluoride from the primary addition
products (check by 19F NMR). This observation correlates
with the calculated molecular properties (see Section 2.2 and
Fig. 1). The reaction conditions for hydroxy compounds
were optimized on the addition of 1-naphthol (Table 2).
Sodium or lithium 1-naphthoxides were used as catalysts,
but the best isolated yield was obtained with equimolar
amount of the lithium salt in tetrahydrofuran (Table 2). This
methodology was applied to other hydroxy compounds, viz.
hexan-1-ol, hexadecan-1-ol, 4-(trifluoromethylsulfanyl)phe-
nol, while disodium salt of benzene-1,2-diol was reacted in
N,N-dimethylformamide (Table 2). Addition product of
hexan-1-ol to olefin 1, the product 2, appeared to be unstable
on heating during distillation or column chromatography on
silica gel and underwent hydrolysis of the a-bonds C–F in
grouping –CH –O–CF – to afford the corresponding ester 3
2.2. Electronic structure of perfluoro(methyl vinyl ether)
and perfluoropropene
Fluoroalkenes react with nucleophilic reagents by either
addition or addition–elimination mechanism depending on
basicity of reagent and molecular properties of fluoroalkene.
The attack proceeds with high regioselectivity on the terminal
difluoromethylene group due to its higher positive charge and
stabilization of intermediate carbanion by negative hypercon-
jugation [22]. To compare an impact of substitution of
fluoroalkene by perfluoroalkyl or perfluoroalkoxy group, we
calculated related molecular properties, i.e. Mullikan [23]
and Lowdin [24] charges at both vinylic carbons, and
orbital energies, of two corresponding model compounds,
2
2
bearing grouping –CH –O–CO–. Such hydrolysis is
2
reported in literature by means of strong mineral acids
[26] or on heating with silica gel [26]. On the other hand,

I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
151
Table 1
Results of addition reactions of some nucleophiles Nu–H to perfluoro vinyl ether 1
Nucleophilic reagent
Conditions
Product(s)
Yield (%)
CH
3
2
(CH )
4
CH
2
–OH
BuLi, THF, À75 8C to RT; 5 days at RT
38
Distillation
9
CH
3
2
(CH )
14CH
2
–OH
BuLi, THF, À75 8C to RT; 5 days at RT
BuLi, THF, À75 8C to RT; 5 days at RT
41
30
Na, THF, RT; 5 days at RT
5
Na, THF, DMF, RT; 5 days at RT
25
BuLi, THF, À75 8C to RT; 5 days at RT
54–61
Na, DMF, 0 8C to RT; over night
41
BuLi, THF, À75 8C to RT; 5 days at RT
55
Na, THF, 0 8C to RT; 5 days at RT
THF, RT; 3 days at RT
52
10
Et
2
NH
3 days at RT
27
Column chromatography
5
days at RT
79
Column chromatography

152
I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
Fig. 1. Electrostatic potential fitted to total electron density surface and Mullikan, Lowdin and Merz–Singh–Kollman charges at vinylic carbons for
hexafluoropropene and perfluoro(methyl vinyl ether).
Ã
Fig. 2. p LUMO orbitals and their eigenvalues for hexafluoropropene and perfluoro(methyl vinyl ether).

I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
153
Table 2
Yields of the addition of 1-naphthol to perfluoro vinyl ether 1
Molar ratio
R-OH:1:alkoxide)
Alkoxide
Solvent
Yield (%)
(
a
1
1
1
1
1
:1:0.2
:1:0.2
Na
Na
THF
THF/DMF
THF
5
25
54
55
61
b
:1.07:0.2
:1.07:0.3
:0.95:1
Li
Li
Li
THF
THF
a
Generated by Na.
b
Generated by butyllithium.
the product of the nucleophilic addition of hexadecan-1-ol to 1,
the ether 4, appeared to be stable on column chromatography.
Phenolic compounds, 4-(trifluoromethylsulfanyl)phenol
or 1-naphthol afforded the corresponding addition products
5
or 6 that were stable on column chromatography. Dis-
Scheme 2. Fluorination properties of amine adducts 9 and 11.
odium salt of benzene-1,2-diol in N,N-dimethylformamide
afforded the bis-addition product 7, which is a sharp contrast
to the reaction of benzene-1,2-diol with perfluoro(2-methyl-
prop-1-ene) where 2-[1,1,1,3,3,3-hexafluoropropane-2,2-
diyl]-1,3-benzo[b]dioxole was formed [27].
The reaction of perfluoro vinyl ether 1 with S-nucleo-
philes have not been reported so far. Therefore, we carried
out an examination of reaction conditions using benze-
nethiol. The results are given in Table 3. Benzenethiol
afforded small amount of the addition product 8 (10% yield)
even at the absence of a catalyst. The highest yields were
obtained with lithium thiolate (Table 3) and the sulfide 8 was
stable on aluminum oxide chromatography.
and piperidine to olefin 1 without a solvent with respect to a
further use of the reaction mixture as a reagent. The addition
products 9 and 11 were characterized by their 19F NMR
spectra (Table 1) and displayed high sensitivity to moisture.
On column chromatography, the adducts 9 and 11 were
completely hydrolyzed to the corresponding amides 10 and
12 (Table 1).
Fluorination properties of the amine adducts 9 and 11
were verified in the following arrangement (Scheme 2): a
solution of hexadecan-1-ol in dichloromethane was added to
the reaction mixture containing crude amine adduct. The
reaction with the adduct 9 was carried by refluxing the
mixture to afford 1-fluorohexane in 49% isolated yield.
When the fluorination of hexadecan-1-ol with the amine
adduct 11 was performed at RT, the isolated yield was only
29%. The second products of fluorinations, the correspond-
ing amides 10 and 12 were characterized as quarternary
ammonium fluorides (Scheme 2).
2.4. Additions of N-nucleophiles to olefin 1, fluorination
properties of the adducts
One of the aims of our first report [17] on the reaction of
olefin 1 with secondary amines had been to verify, whether
the adducts display fluorination ability similar to that of
Yarovenko–Raksha [28] or Ishikawa reagents [29,30] or
dimethylamine adduct to tetrafluoroethene [31]. In the
meantime, two papers have appeared [19,20] where the
reactions were carried out [19,20] in tetrahydrofuran and
crude products were hydrolyzed in water to give the corre-
sponding amines. The products were not tested for fluorina-
tion properties. We carried out the additions of diethylamine
2.5. Replacement of vinylic fluorine: reactions of
butyllithium, hydride ion and phosphane nucleophiles
with olefin 1
The previous reaction between perfluoro(propyl vinyl
ether) and phenyllithium [13] at RT yielded mono-, di- or
trisubstituted products in dependence on the stoichiometry
of the reactants. In the 1:1 stoichiometry [13], (Z)-substitu-
tion product was obtained in a relative yield of 92%. In our
reaction of olefin 1 with butyllithium (Scheme 3), only the
product 15, formed by the substitution of terminal fluorine,
having (Z)-configuration was obtained in low yield at
À78 8C. Thus, the reaction appeared to be completely regio-
and stereoselective. At higher temperatures, a rich mixture
of compounds was obtained.
Table 3
Yields of the addition of benzenethiol to perfluoro vinyl ether 1
Thiolate
Molar ratio (PhSH:1:thiolate)
Yield (%)
–
1:1:0
1:0.94:0.46
10
45
52
55
55
a
Na
Na
Li
Li
1:1.05:1.27
b
1:1.10:0.97
1:1.07:0.57
Tributylphosphane was found [32,33] to displace fluorine
at the terminal carbon of the double bond in perfluoroolefins
to form the corresponding phosphonium fluorides, which by
a
Generated by Na.
b
Generated by butyllithium.

154
I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
protonic acids to afford saturated products even when alkali
salts of hydroxy compounds or benzenethiol were used.
Butyllithium, tributylphosphane or complex hydrides
reacted by replacement of vinylic fluorine: butyllithium
afforded (Z)-substituted product (14) and tributylphosphane
gave after hydrolysis (E)-hydrogenated product 16 exclu-
sively, while complex hydrides reacted with the formation of
a 1:1 (E)–(Z) mixture of 16. Diethylamine and piperidine
adducts (9 and 11) possessing very reactive a-bonds C–F
were found to substitute hydroxyl for fluorine in hexadecan-
Scheme 3. Reaction of alkene 1 with butyllithium.
1-ol. Quantum chemical calculations of perfluoro(methyl
vinyl ether) and hexafluoropropene as model compounds to
compare the impact of substitution of fluorine by perfluoro-
alkyl or perfluoroalkoxy group on the reactivity of fluoro-
alkene revealed a better reactivity for hexafluoropropene
toward nucleophilic attack than for perfluoro vinyl ether 1.
4. Experimental
4.1. General experimental procedures
The temperature data were not corrected. Column chro-
matography: CC1 (d ¼ 2:0 cm); CC2 (d ¼ 3:0 cm); CC3
Scheme 4. Reduction of perfluorvinyl ether 1.
(
d ¼ 5:0 cm). GC analyses were performed on a Chrom 5
hydrolysis afforded 1H-derivatives of the starting perfluoroo-
lefins with (E)-configuration. The reactions of phosphanes
with perfluoro vinyl ethers have not been reported in the
literature. The reaction of perfluoro vinyl ether 1 with tribu-
tylphosphane (Scheme 4) we carried out at À78 8C; the
hydrolysis of the reaction mixture at À78 8C afforded the
(Laboratorn ´ı p rˇ ´ı stroje, Prague; FID, 350 cm ꢀ 0:3 cm
packed column, silicone elastomer E-301 on Chromaton
N-AW-DMCS (Lachema, Brno), nitrogen) and a Chrom 3
(Laboratorn ´ı p rˇ ´ı stroje, Prague; FID, 350 cm ꢀ 0:5 cm
packed column, silicone elastomer E-301 on Chromaton
N-AW-DMCS (Lachema, Brno), nitrogen) instruments.
NMR spectra were recorded on a Bruker 400 AM (FT,
(
E)-1H-perfluoro(5-methyl-3,6-dioxanon-1-ene) (16) as the
1
9
F at 376.5 MHz, H at 400.1 MHz, 13C at 100.6 MHz),
1
exclusive product, no isomers were observed in NMR spectra.
The intermediate phosphonium salt 15 was not analyzed.
There is a number of papers reporting the reactions of
perfluoroolefins with complex hydrides, e.g. lithium alumi-
num hydride or sodium borohydride [34,35]. The reactions
of (per)fluoroalk-1-enes afforded mixtures of regioisomers
and configurational isomers. We have not found any report
on the reactions of perfluoro vinyl ethers in the literature. We
carried the reactions of fluoroolefin 1 with complex hydrides
at À78 8C (Scheme 4) and obtained the product 16 as a
mixture of (E)–(Z) configurational isomers in a 1:1 ratio.
The results under various conditions are summarized in
Table 3. We have not found any product of a two-fold
reduction of the starting compound 1 even after 6 h reduc-
tion (check by 19F NMR). Both complex hydrides used gave
approximately the same yields of the product 16 (Table 3).
1
Varian Gemini 300 HC (FT, H at 300 MHz) and a Bruker
WP 80 SY (FT, 19F at 75.4 MHz) instruments: TMS and
CFCl
singlet; d, doublet; t, triplet; q, quadruplet; m, multiplet),
coupling constants J in Hz, solvent CDCl . MS spectra were
as the internal standards, chemical shifts in ppm (s,
3
3
scanned on a Hewlett-Packard MSD 5971A instrument
(1989, EI 70 eV).
Ab initio calculations were performed using the PC
GAMESS version [36] of the GAMESS (US) QC package
[37]. The energy minima were determined by complete
optimization of the geometrical parameters by gradient
methods using 6–311G(d,p) basis set with d polarization
functions on C, O, F, and p polarization function on H at the
MP2 levels of theory. Vibrational frequencies were calcu-
lated for both structures to characterize them as minima.
Calculated charges at carbon atoms were based on Mulliken
[23] and Lowdin [24] population analyses. Electrostatic
3
. Conclusions
potential-derived charges were calculated according to the
Merz–Kollman–Singh scheme [25] using Gaussian 98W
program suite [38]. Visualization were performed with
MOLEKEL molecular graphics package [39].
Chemical used were as follows: 1,1,2,4,4,5,7,7,8,8,9,9,9-
tridecafluoro-5-trifluoro-methyl-3,6-dioxanon-1-ene (1) was
All the reactions of perfluoro vinyl ether 1 with nucleo-
philes carried out were completely regioselective with
nucleophilic attack at the terminal carbon. Alcohols, phe-
nols, benzenethiol or secondary amines used added to 1 as

I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
155
3
prepared according to the literature [8,40]; 1-naphth-ol, ben-
zene-1,2-diol, hexan-1-ol and hexadecan-1-ol (Lachema);
3JHH ¼ 7:1 Hz); 4.54 (t, 2H, CH , J ¼ 6:6 Hz); 6.07
2
HH
19
2
(d, 1H, CHF, J ¼ 54:9 Hz) ppm. For F NMR spectra
HF
13
4-(trifluoromethylsulfanyl)phenol (Baeyer), benzenethiol
(75.4 MHz, CDCl ) see Table 4. C NMR (100.61 MHz,
3
(
Aldrich); chloroform, heptane, acetone, petroleum ether
CDCl ): d 23.1; 25.9; 28.9; 31.9; 68.1 (CH ); 14.5 (CH );
3
2
À1
3
2
(bp 40–65 8C), tetrahydrofuran were dried and purified
162.4 (d, CO, JCF ¼ 30:2 Hz) ppm. IR (cm ): 2933, 2861,
according to standard laboratory procedures; diethylamine
and piperidine were distilled before use. Butyllithium solution
1775, 1249, 1309, 1159, 1051. Anal. calcd. for C H F O :
1
4 14 14 4
C, 32.8; H, 2.7. Found: C, 33.0; H, 2.9%.
(hexane, 2.4 or 1.8N; Aldrich), lithium aluminum hydride
(
1
Merck), sodium borohydride (Lachema, Brno), silica gel (60–
00 mm, Merck), tributylphosphane 85% (Aldrich).
4.2.3. Addition of hexadecan-1-ol: 1,1,1,2,2,3,3,5,6,6,8,9,9-
Tridekafluoro-5-trifluoromethyl-4,7,10-trioxahexacosane (4)
A mixture of hexadecan-1-ol (0.44 g, 1.83 mmol), per-
fluoro vinyl ether 1 (0.83 g, 1.92 mmol), butylithium
(1.8 mmol, 1.8 M in n-hexane) was stirred for 5 days.
Column chromatography CC1 (Al O , 35 g, heptane-acet-
4
.2. Addition of alcohols to 1,1,2,4,4,5,7,7,8,8,9,9,9-
tridecafluoro-5-trifluoromethyl-3,6-dioxanon-1-ene (1)
products 2–7)
(
2
3
one 4:1, check by TLC). Yield of 4: 0.50 g (41%).
1
4
.2.1. General procedure
The reactions were carried out in a sealed (with septum)
H NMR (300.07 MHz, CDCl ): d 0.88 (t, 3H, CH ,
3
3
3
3
JHH ¼ 6:9 Hz); 1.26 (s, 26H, CH ); 1.64 (t, 2H, CH ,
2
2
round-bottomed flask (magnetic spinbar) under inert
atmosphere. To a solution of alcohol in dry tetrahydro-
furan (3 ml) cooled to À70 8C (dry-ice–ethanol bath), a
solution of butyllithium in hexane was added while stir-
ring. After 10 min reaction, the mixture was rapidly with-
drawn with a pre-cooled syringe, and added to cooled
JHH ¼ 6:6 Hz); 3.95 (t, 2H, CH ); 5.83 (dt, 1H, CHF,
3 19
HF
2
2JHF ¼ 53:8 Hz, J ¼ 2:9 Hz) ppm. For F NMR spectra
(75.4 MHz, CDCl ) see Table 4. Anal. calcd. for
3
C H F O : C, 42.7; H, 5.1; F, 45.1. Found: C, 42.3; H,
2
4 34 16 3
4.7; F, 45.1%.
(
À70 8C) solution of perfluoro vinyl ether in tetrahydro-
4.2.4. Addition of 4-(trifluoromethylsulfanyl)phenol:
1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-trifluoromethyl-1-
[4-(trifluoromethylsulfanyl)-1-phenyloxy]-3,6-dioxanonane
(5)
furan (1 ml). The reaction mixture was stirred for 1 h at
À70 8C, then allowed to warm to RTand continued until no
apparent change occurred (check by TLC). The reaction
was quenched by the addition of trifluoroacetic acid,
volatile components were removed on rotary evaporator
and the residue was chromatographed or distilled to get a
product.
A mixture of 4-(trifluoromethylsulfanyl)phenol (0.23 g,
1.14 mmol), perfluoro vinyl ether 1 (0.64 g, 1.47 mmol),
butyllithium (1.12 mmol, 1.8 M in n-hexane) was stirred for
5 days. Column chromatography CC1 (Al O , 10 g, hep-
2
3
tane–acetone 4:1, check by TLC). Yield of 5: 0.21 g 30%.
1
4
.2.2. Addition of 1-hexanol: 1,1,2,4,4,5,7,7,8,8,9,9,9-
Tridecafluoro-5-trifluoromethyl-3,6,10-trioxahexadecane
2) and hexyl 2,4,4,5,7,7,8,8,9,9,9-undecafluoro-5-
H NMR (300.07 MHz, CDCl ): d 7.24 (d, 2H, CH,
3
3JHH ¼ 8:2 Hz); 7.69 (dt, 2H, CH, J ¼ 2:2 Hz); 6.07
4
HF
2
3
19
(
(dt, 1H, CHF, J ¼ 53:2 Hz, J ¼ 2:7 Hz) ppm.
F
HF
HF
trifluoromethyl-3,6-dioxanonanoate (3)
NMR (75.4 MHz, CDCl ): d À43.4 (s, 1F, CF S). For the
3
3
1
9
A mixture of hexan-1-ol (0.67 g, 6.56 mmol), perfluoro
vinyl ether 1 (3.25 g, 7.53 mmol), and butyllithium(3.28 m-
mol, 2.47 M in n-hexane) was stirred for 5 days. Tetrahy-
drofuran was removed by distillation. Fractional distillation
of the residue afforded two fractions: first, bp 111–113 8C/
main part of the F NMR spectra (75.4 MHz, CDCl ) see
3
Table 4. MS (M ¼ 626), m/z (% relative intensity): EI: 538/
r
2 (M À CF –F), 507/2, 438/2, 338/8, 372/7, 335/10, 290/6,
r
3
275/20, 243/10, 193/20, 177/40, 169/50, 108/25, 69/100,
50/15.
1
20 mmHg (0.915 g, 63% of 2, 6% of 3, check by GC);
second, bp 113 8C/120 mmHg (0.981 g, 76% of 2, 10% of
). Samples for analyses were purified by preparative GC,
yields: 2, 1.32 g (38%); 3, 0.34 g (9%).
4.2.5. Addition of 1-naphthol: 1-
(2,2,3,5,5,6,8,8,9,9,10,10,10-tridecafluoro-5-
trifluoromethyl-1,4,7-trioxadecyl)naphthalene (6)
3
1
2
: H NMR (300.07 MHz, CDCl ): d 0.88 (t, 3H, CH ,
Procedure A: The reactions were carried out in a sealed
(with septum) round-bottomed flask (magnetic spinbar)
under inert atmosphere. To a solution of 1-naphthol
(0.20 g, 1.38 mmol) in dry tetrahydrofuran (2 ml) and
N,N-dimethylformamide, pieces of sodium (0.01 g,
0.26 mmol) were added while stirring. Then, perfluoro vinyl
ether 1 (0.81 g, 1.41 mmol) was added dropwise to the
mixture at RT. After 5-day reaction, solvents were removed
in vacuum by rotary evaporator. The residue was then
chromatographed. Column chromatography CC1 (Al O ,
3
3
3
3
JHH ¼ 6:5 Hz); 1.30 (m, 6H, CH ); 1.64 (p, 2H, CH ,
2
2
3
JHH ¼ 7:1 Hz); 3.95 (t, 2H, CH , JHH ¼ 6:5 Hz); 5.83
2
2
19
(
d, 1H, CHF, JHF ¼ 53:3 Hz) ppm. For F NMR spectra
13
3
(
376.6 MHz, CDCl ) see Table 4. C NMR (100.61 MHz,
CDCl ): d 22.9; 25.7; 29.4; 31.8; 65.3 (CH ); 13.9 (CH );
3
2
3
1
2
9
Anal. calcd. for C H F O : C, 31.5; H, 2.6. Found: C,
8.8 (m, CHF, JCF ¼ 244:1 Hz, JCF ¼ 43:3 Hz) ppm.
1
4 14 16 3
3
0.5; H, 2.8%.
1
3
: H NMR (300.07 MHz, CDCl ): d 0.88 (t, 3H, CH ,
3
3
2 3
3
JHH ¼ 6:6 Hz); 1.31 (m, 6H, CH ); 1.68 (p, 2H, CH ,
10 g, heptane–acetone 4:1, check) to afford product 6,
2
2

156
I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
Table 4
19F NMR spectra of compounds 2–12, 14 and 16
a
b
c
d
e
f
g
h
CF
2
CHF
CF
2
CF
CF
3
CF
2
CF
2
CF
3
2
3
F
A
À90.5,
ds1,2 À145.1,
ds3,4 À145.2,
ds1,2
F
A
À84.2,
À145.4 t,
À80.6 m
F
A
À82.3,
À82.7,
À130.1 s
À81.9 s
3
F
B
À90.9,
F
B
À86.4,
JFdFf ¼ 20:3
F
B
2
3
2
2
JFF ¼ 146:1
JFF ¼ 7:4
JFF ¼ 141:1,
JFF ¼ 142:3
ds3,4
F
A
À84.5,
2
F
B
À86.8, JFF ¼ 140:4
ds1,2 À135.9,
ds3,4 À136.0,
À84.6 to À85.5 m
À145.2 t,
À80.5 m
À82.1 m
À130.0 s
À81.8 s
3
JFdFf ¼ 19:9
3
JFF ¼ 7:3
4
5
6
À90.1 m
À87.1 m
À145.2 m
ds1,2 À84.5, ds3,4 À85.5 m
À84.2 to (À86.0) m
À145.2 m
À145.1 m
À145.4 t,
À80.6 m
À80.5 m
À80.4 m
À81.9 m
À82.1 m
À130.1 s
À130.1 s
À130.0 s
À81.7 s
À81.8 s
À82.9 s
À145.5 m
F
A
À85.7,
À87.0,
ds1,2 À144.0,
ds3,4 À144.6,
ds1,2
F
A
À83.9,
F
A
À81.9,
À82.3,
2
3
F
B
F
B
À85.7, JFF ¼ 144:2,
JFdFf ¼ 21:0
F
B
2
3
2
JFF ¼ 146:1
JFF ¼ 8:3
J
FF ¼ 5.6, ds3,4
À84.1,
JFF ¼ 145:3
F
A
2
F
B
À86.0, JFF ¼ 141:5
7
89.8 m
À144.8 m
À82.5 to (À90.0)
À145.4 t,
À80.7 m
À82.5 to
(À90.0) m
À81.9 m
À81.5
À130.2 s
À81.9 s
3
JFdFf ¼ 18:6
8
9
À90.5 m
À84.7 m
À140.2 m
À144.9 m
À84.2 to (À85.7) m
À85.7 to (À86.7) m
À145.4 m
À145.4 t,
À80.5 m
À80.5 m
À130.0 s
À130.2 s
À81.8 s
À81.9 s
3
JFdFf ¼ 18:6
to (À82.3) m
À82.1 m
1
0
1
À87.1 m
À145.5 m
À84.2 to (86.0) m
À145.1 m
À145.4 m
À80.5 m
À80.4 s
À130.1 s
À130.0 s
À81.8 s
À81.7 s
1
ds1,2 À128.9,
ds3,4 À129.1,
ds1,2
F
A
À84.5,
F
A
À81.8,
À82.3,
2
F
B
À85.9, JFF ¼ 142:7,
F
B
2
2
JFF ¼ 55:8
ds3,4
F
A
À84.4,
JFF ¼ 144:9
2
F
B
À85.9, JFF ¼ 141:9
1
2
ds1,2 À129.0,
ds3,4 À129.1,
ds1,2
F
A
À84.6,
À80.5 m
F
A
À81.8,
À82.5,
À130.2 s
À81.9 s
2
F
B
À85.9, JFF ¼ 140:7,
À145.1 t,
F
B
4
2
JFF ¼ 11:9
ds3,4
2
F
A
À84.6, F
B
À86.1,
3
JFF ¼ 144:7
JFdFf ¼ 19:9
JFF ¼ 143:7
CF=
=CF–
1
4
6
À149.9 m
109.4 m,
3
85.2 m
À145.3 m
À145.5 m
À82.4 m
À80.3 m
À81.8 s
À129.4 s
À130.0 s
À81.8 s
À81.8 s
JFF ¼ 23:6
1
À145.5 m
À135.3 d,
À84.2 to À86.1 m
À82.0 m
3
JFF ¼ 49:9
1
2
yield 0.19 g (25%). For another reaction conditions see
Table 4.
JCF ¼ 269:4 Hz; JCF ¼ 37:9 Hz); 107.5 (sextet t, CF ,
2
1
2
J
CF
¼ 268:9 Hz,
J
¼ 39:0 Hz); 116.4 (dtt, CF ,
CF
2
Procedure B:
.71 mmol), butylithium (0.72 mmol, 2.47 M in n-hexane),
A
mixture of 1-naphthol (0.10 g,
1J ¼ 288:6 Hz, 2J ¼ 29:0 Hz, J ¼ 4:3 Hz); 117.4
CF
CF CF
2
1
0
(dt, CF ,
2
J
¼ 297:5 Hz,
J
CF
¼ 29:3 Hz); 118.1 (dt,
CF
1
2
alkene 1 (0.39 g, 0.67 mmol, molar ratio 1-naphthole:
alkene 1: BuLi 1:0.95:1.01) was stirred for 5 days. Column
chromatography CC1 (Al O , 10 g, heptane–acetone 4:1,
CF , JCF ¼ 286:0 Hz, JCF ¼ 28:7 Hz); 118.0 (tq, CF ,
2
3
1
1
2
JCF ¼ 287:1 Hz,
JCF ¼ 32:8 Hz); 118.6 (dq, CF ,
3
2
JCF ¼ 223:8 Hz, JCF ¼ 31:0 Hz) ppm. Anal. calcd. for
2
3
check by TLC). Yield of 6: 0.238 g (61%). For another
reaction conditions see Table 2.
C H F O : C, 37.5; H, 1.4; F, 52.7. Found: C, 37.8; H,
18 8 16 3
1.5; F, 52.6%.
1
H NMR (300.07 MHz, CDCl ): d 7.35–7.54 (m, 4H,
3
3
4
CH); 8.07 (dd, 1H, CH, J ¼ 8:7 Hz, J ¼ 1:5 Hz);
4.2.6. Addition of benzene-1,2-diol: 1,2-bis-
(1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-trifluoromethyl-
3,6-dioxanonan-1-yloxy)-benzene (7)
Sodium (5.4 mg, 2.35 mmol) was added to a solution of
benzene-1,2-diol (0.13 g, 1.18 mmol) in dry dimethylfor-
mamide (2 ml) in round-bottomed flask (magnetic spinbar),
The reaction mixture was stirred overnight. To the solution
of alkoxide, perfluoro vinyl ether 1 (0.728 g, 1.68 mmol,
HH
HH
7
.82 (dd, 1H, CH); 7.71 (dd, 1H, CH); 6.21 (dt, 1H, CHF,
2
JHF ¼ 53:4 Hz, JHF ¼ 2:5 Hz) ppm. For 19F NMR spectra
3
13
(
376.6 MHz, CDCl ) see Table 4. C NMR (100.61 MHz,
3
CDCl ): d 145.6 (C); 128.4 (C); 135.7 (C); 118.1 (CH);
3
1
25.9 (CH); 122.3 (CH); 128.5 (CH); 127.5 (CH); 127.6
1
(
CH); 118.2 (CH); 99.2 (ttd, CHF, JCF ¼ 245:0 Hz,
JCF ¼ 41:8 Hz, JCF ¼ 4:8 Hz); 103.6 (sextet d, CF,
2

I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
157
1
43 mol%) was added under ice-cooling the reaction flask
4.4. Addition of amines to 1,1,2,4,4,5,7,7,8,8,9,9,9-
tridecafluoro-5-trifluoromethyl-3,6-dioxanon-1-ene (1)
(products 9–12)
and the mixture was stirred overnight at RT. The mixture was
poured into water (5 ml) and extracted with diethyl ether
(
MgSO and volatile components were removed in vacuum
3 ꢀ 5 ml). Combined ethereal extracts were dried over
4.4.1. General procedure
4
(
by column chromatography (CC1, Al O , 15 g, petroleum
rotary evaporator). The residue–crude product was purified
Perfluoro vinyl ether 1 was dropwise added to amine in a
round-bottomed flask under cooling (ice bath). The mixture
stirred at room temperature, a sample of reaction mixture
was rapidly withdrawn by syringe, the H NMR and 19F
NMR spectra were taken. Amine was removed under
reduced pressure (rotary evaporator). The residue was puri-
fied by column chromatography.
2
3
ether–aceton 4:1, check by TLC) to afford product 7, yield
.34 g (41%).
1
0
1
H NMR (300.07 MHz, CDCl ): d 7.28–7.40 (m, 4H,
3
2
19
CH); 6.05 (d, 2H, CHF, JHF ¼ 53:8 Hz) ppm. For F NMR
spectra (75.4 MHz, CDCl ) see Table 4. Anal. calcd. for
3
C H F O : C, 27.1; H, 0.6; F, 62.4. Found: C, 27.4; H, 0.8;
22 6 32 6
F, 62.5%.
4.4.2. Addition of diethyl amine: N,N-diethyl-
1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-trifluoromethyl-
3,6-dioxanonan-1-amine (9) and N,N-diethyl-
2,4,4,5,7,7,8,8,9,9,9-undecafluoro-5-trifluoromethyl-3,6-
dioxanonanamide (10)
4
1
3
.3. Addition of benzenethiol: 1-phenylsulfanyl-
,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-trifluoromethyl-
,6-dioxanonane (8)
A mixture of diethyl amine (0.38 g, 5.29 mmol), perfluoro
vinyl ether 1 (1.69 g, 3.91 mmol) was stirred for 3 days.
Amine 9 was identified in crude reaction mixture and
spontaneously hydrolyzed to amide 10 on the air moisture.
Procedure A: A mixture of perfluoro vinyl ether 1 (0.35 g,
.82 mmol) and benzenethiol (0.09 g, 0.83 mmol) in dry
tetrahydrofurane (3 ml) was stirred for 3 days at RT. The
solvent was then removed in vacuum (rotary evaporator) and
the crude product was purified by column chromatography
0
Column chromatography CC2 (SiO , 35 g, heptane–acetone
2
4:1, check by TLC). Yield of 10: 1.02 g (54%) (literature
[10]: yield 74%, bp 57–58 8C/0.2 mmHg).
(CC1, Al O , 10 g, petroleum ether–acetone 4:1, check by
2 3
TLC) to afford pure 8, yield 0.04 g (10%).
Procedure B: Sodium (0.6 g, 2.35 mmol) was added to a
solution of benzenethiol (0.20 g, 1.81 mmol) in dry tetra-
hydrofurane (2 ml) in round-bottomed flask (magnetic spin-
bar). To the thiolate solution, perfluoro vinyl ether 1 (0.84 g,
1
9: H NMR (300.07 MHz, CDCl ): d 1.08 (t, 6H, CH ,
3
3
3J ¼ 7:1 Hz); 2.9 (q, 4H, CH ); ds 5.96, ds3,4 6.02 (1H,
HH
2
1,2
CHF, J ¼ 54:4 Hz, J ¼ 53:3 Hz) ppm. For 19F NMR
2
2
HF
HF
spectra (75.4 MHz, CDCl ) see Table 4.
3
1
10: H NMR (300.07 MHz, CDCl ): d 1.18 (t, 6H, CH ,
3
3
3
1
.95 mmol) was added under ice-cooling the reaction flask
JHH ¼ 7:3 Hz); 3.35 (q, 4H, CH ); 6.24 (d, 1H, CHF) ppm.
19 13
3
2
and the mixture was stirred for 5 days at RT. Tetrahydrofuran
was removed in vacuum (rotary evaporator) and the residue
was chromatografted (CC1, Al O , 30 g, petroleum ether–
For F NMR spectra (470.5 MHz, CDCl ) see Table 4.
C
NMR (125.75 MHz, CDCl ): d 12.1 (CH ); 14.0 (CH ); 40.8
3
3
3
1
2
(CH ); 117.9 (tq, CF , J ¼ 270:4 Hz, J ¼ 27:6 Hz);
2
3
2
3
CF
CF
1
2
acetone 4:1, check by TLC) to obtain pure 8, yield 0.65 g
(
117.7 (dq, CF , J ¼ 272:8 Hz, J ¼ 31:3 Hz); 106.6
1 2
2 2
CF CF
3
CF
CF
52%). For another reaction conditions see Table 3.
Procedure C: A solution of buthyllithium (2.04 mmol,
(qt, CF , J ¼ 269:5 Hz, J ¼ 37:9 Hz); 115.4 (tt, CF ,
1
2
1
JCF ¼ 287:5 Hz, JCF ¼ 29:9 Hz); 118.3 (dt, CF , JCF ¼
2
2
1
2.47 M in n-hexane) was added to a solution of benzenethiol
0.23 g, 2.1 mmol) in dry tetrahydrofuran (2 ml) in a flask
296:5 Hz, JCF ¼ 28:9 Hz); 101.4 (dq, CF, JCF ¼ 269:1 Hz,
2
1
(
JCF ¼ 38:3 Hz); 101.3 (d, CHF, JCF ¼ 250:5 Hz); 160.5 (d,
2
À1
cooled to À70 8C under nitrogen atmosphere while stirring.
After 10 min reaction, the mixture was rapidly withdrawn by
a pre-cooled syringe and put in cooled (À70 8C) solution of
perfluoro vinyl ether (1.0 g, 2.32 mmol) in tetrahydrofuran
CO, JCF ¼ 24:5 Hz) ppm. IR (cm ) 3025 (CH , CH ); 1667
3
2
(C=O); 1245 (–O–); 1306, 1159 (CF). Anal. calcd. for
C H F NO : C, 29.8; H, 2.3; F, 55.0. Found: C, 30.4; H,
2.5; F, 55.2%.
12
11 14
3
(
1 ml). The reaction was stirred at À75 8C for 2 h and than at
room temperature for 5 days. The mixture was quenched
with trifluoroacetic acid and volatile components were
removed in vacuum (rotary evaporator). The residue was
purified by column chromatography (CC1, Al O , 30 g,
4.4.3. Addition of piperidine: 1,1,2,4,4,5,7,7,8,8,9,9,9-
tridecafluoro-1-(piperidin-1-yl)-5-trifluoromethyl-3,6-
dioxanonane (11) and 1-(2,4,4,5,7,7,8,8,9,9,9-
undecafluoro-5-trifluoromethyl-3,6-
2
3
petroleum ether–acetone 4:1) to afford product 8, yield
.45 g (55%). For another reaction conditions see Table 3.
dioxanonanoyl)piperidine (12)
0
A mixture of piperidine (1.64 g, 19.21 mmol), perfluoro
vinyl ether 1 (2.95 g, 6.38 mmol) was stirred for 5 days.
Amine 11 was identified in crude reaction mixture and
spontaneously hydrolyzed to amide 12 on the air moisture.
1
H NMR (300.07 MHz, CDCl ): d 7.20–7.65 (m, 5H,
3
2
3
CH); 5.92 (dt, 1H, CHF, J ¼ 54:9 Hz, J ¼ 3:9 Hz)
HF
HF
ppm. For 19F NMR spectra (75.4 MHz, CDCl ) see Table 4.
3
þ
MS (Mr ¼ 542) m/z (% relative intensity): EI: 542/20 (M ),
Column chromatography CC3 (SiO , 70 g, petroleum ether–
2
4
1
73/2 (M À CF ), 423/2, 357/2, 355/2, 304/3, 206/2, 191/4,
acetone 6:1, check by TLC). Yield of 12: 2.64 g (78%)
(literature [10] yield 70%, bp 92–93 8C/0.4 mmHg).
3
59/100, 119/5, 109/65, 77/32, 69/55.

158
I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
1
1
1
1: H NMR (300.07 MHz, CDCl ): d 1.55 (m, 6H, CH );
(t, CH F, J ¼ 164:7 Hz) ppm. Anal. calcd. for C H F:
3
2
2
CF
16 33
3
.45 (m, 4H, CH ); ds
2
6.00, ds
3
6.03 (1H, CHF,
3
C, 78.6; H, 13.6; F, 7.9. Found: C, 78.9; H, 13.6; F, 8.2%.
2
1,2
3,4
2
JHF ¼ 53:8 Hz, JHF ¼ 52:9 Hz, JHH ¼ 3:2 Hz, JHH ¼
2
:4 Hz) ppm. For 19F NMR spectra (75.4 MHz, CDCl )
see Table 4.
4.5. Reaction of fluoroolefin 1 with butyllithium: (Z)-
5,6,8,8,9,11,11,12,12,13,13,13-dodecafluoro-9-
trifluoromethyl-7,10-dioxatridec-5-ene (14)
3
1
1
2: H NMR (300.07 MHz, CDCl ): d 1.55 (m, 6H, CH ,
3
2
3
2
JHH ¼ 7:3 Hz); 3.45 (m, 4H, CH ); 6.23 (d, 1H, CHF, J
2
HF
19
¼
56.0 Hz) ppm. For F NMR spectra (470.5 MHz, CDCl )
3
A solution of butyllithium (3.0 ml, 5.4 mmol, 1.8 M in n-
hexane) was added dropwise to a solution of perfluoro vinyl
ether 1 (2.25 g, 5.2 mmol) in dry diethyl ether (2.5 ml) in a
round-bottomed flask under inert atmosphere while cooling
(À70 8C) and stirring (magnetic spinbar). The mixture was
stirred for 2 h at À70 8C, allowed to warm to RT, then
quenched with trifluoroacetic acid and neutralized with a
solution of potassium carbonate. Solvents were removed by
distillation and subsequent distillation of the residue
afforded not pure 14 (0.419 g, purity ca. 42%, calcd. from
GC), bp 120–140 8C, calculated yield ca. 8%. Sample for
analysis was purified by preparative GC.
1
3
see Table 4. C NMR (125.75 MHz, CDCl ): d 24.7 (CH );
3
2
1
2
2
5.9 (CH ); 44.5 (CH ); 118.1 (tq, CF , J ¼ 287:9 Hz,
2
2
3
CF
1
2
JCF ¼ 31:3 Hz); 118.3 (dq, CF , JCF ¼ 274:3 Hz, JCF ¼
3
1
2
3
1
1:2 Hz); 107.1 (qt, CF , JCF ¼ 268:6 Hz, JCF ¼ 37:3 Hz);
2
1
2
16.0 (dt, CF , JCF ¼ 292:7 Hz, JCF ¼ 31:4 Hz); 119.8 (dt,
2
1
2
CF , JCF ¼ 295:2 Hz, JCF ¼ 28:6 Hz); 103.3 (dq, CF,
2
1
1
2
JCF ¼ 270:0 Hz,
JCF ¼ 37:0 Hz); 102.1 (d, CHF,
2
J
¼ 250:4 Hz); 160.0 (d, CO, J ¼ 24:5 Hz) ppm. IR
CF
À1
CF
(
1
2
cm ) 3020, 2928, 2882 (CH ); 1685 (C=O); 1244 (–O–);
2
305, 1158 (CF). Anal. calcd. for C H F NO : C, 31.5; H,
13 11 14 3
.2; F, 53.7. Found: C, 31.9; H, 2.4; F, 51.2%.
1
H NMR (300.07 MHz, CDCl ): d 0.92 (t, 3H, CH ,
3
3
3
3
4.4.4. Fluorination properties of amine adducts 9
and 11: 1-fluorohexadecane (13)
JHH ¼ 7:4 Hz); 2.22 (dtd, 2H, CH , JHF ¼ 22:7 Hz);
2
3
1.53 (p, 2H, CH , J ¼ 7.4 Hz); 1.35 (sextet, 2H, CH )
2
HH
2
ppm. For 19F NMR spectra (75.4 MHz, CDCl ) see Table 4.
Anal. calcd. for C H F O : C, 30.6, H, 1.9, F, 60.6. Found:
C, 30.9, H, 1.5, F, 60.3%.
3
4.4.4.1. Fluorination with the adduct 9. Under nitrogen,
perfluoro vinyl ether 1 (2.14 g, 4.96 mmol) was dropwise
added through septum by syringe to diethylamine (0.430 g,
1
2 9 15 2
5
(
.88 mmol) in a round-bottomed flask (10 ml) while cooling
ice bath) and stirring (magnetic spinbar) for 1 h. After that,
4.6. Reaction of fluoroolefin 1 with tributylphosphane:
1,2,4,4,5,7,7,8,8,9,9,9-dodecafluoro-5-trifluoromethyl-3,6-
dioxanon-1-ene (16)
the mixture was stirred for 24 h at RT, then the flask
immersed in ice bath and a solution of hexadecan-1-ol
(
0.601 g, 2.48 mmol) in dichloromethane (7 ml) was
Tributylphosphane (85%, 1.94 g, 8.15 mmol) was added
dropwise through septum to a stirred solution of alkene 1
(3.74 g, 8.66 mmol) in dry diethyl ether (3 ml) at À75 8C
under nitrogen. The mixture was stirred for 2 h at À75 8C,
then water (0.5 ml) was added and the mixture dried over
molecular sieves (A4). Distillation afforded not completely
pure 15 (1.72 g, purity ca. 85%, GC, calculated yield ca.
41%), fraction 65–100 8C. Sample for analysis was purified
by preparative GC.
added through septum. After 1 h, the mixture was slowly
heated to 50 8C and gently refluxed for 12 h. Then, the
mixture was washed in a dropping funnel with potassium
solution (10%, 2 ꢀ 5 ml) and water (2 ꢀ 5 ml) and dried
over MgSO . Volatile components were then removed on
4
rotary evaporator (30 8C, ca. 30 mmHg) and the residue
(
0.924 g) was purified by chromatography (CC1, SiO , 30 g,
2
petroleum ether) to afford product 13, yield 0.293 g (48%)
and amide 10 as an ammonium salt.
1
2
H NMR (300.07 MHz, CDCl ): d 5.68 (dd, JHF ¼
3
3
19
57:7 Hz,
JHF ¼ 4:4 Hz). For
F
NMR spectra
4.4.4.2. Fluorination with the adduct 11. By the protocol
according to Section 4.4.4.1, perfluoro vinyl ether 1 (2.32 g,
5
1
(75.4 MHz, CDCl ) see Table 4. MS (Mr ¼ 414) m/z (%
3
þ
relative intensity): EI: 414/2 (M ), 383/3, 335/7, 285/2, 169/
75, 149/5, 119/15, 100/18, 83/100, 69/95, 51/15, 33/20.
.37 mmol), piperidine (0.50 g, 5.87 mmol) and hexadecan-
-ol (0.575 g, 2.37 mmol) were reacted and the end reaction
mixture treated as above. After evaporation of volatile
components, the residue (1.58 g) was chromatographed
4.7. Reaction of fluoroolefin 1 with lithium aluminum
hydride or sodium borohydride: product 16
(
yield 0.156 g (27%) and amide 12 as an ammonium salt.
CC2, SiO , 45 g, petroleum ether) to afford product 13,
2
The suspension of a hydride in dry tetrahydrofurane in
a round-bottomed flask under nitrogen was cooled to
À75 8C. Perfluoro vinyl ether 1 was slowly added to the
flask through septum while stirring. In intervals 1 and 6.5 h
after the addition of the olefin 1, a sample of reaction
mixture was rapidly withdrawn by pre-cooled syringe, put
in cooled water, organic layer separated and the 19F NMR
spectrum was taken. The contents of the starting alkene 1
1
1
3: H NMR (300.07 MHz, CDCl ): d 0.88 (t, 3H, CH ,
3
3
3
3
JHH ¼ 6:9 Hz); 1.26 (s, 26H, CH ); 1.69 (pd, 2H, CH ,
2
2
3
JHH ¼ 6:4 Hz,
J
¼ 24:7 Hz); 4.44 (td, 2H, CH F,
HF
2
19
2JHF ¼ 47:2 Hz) ppm. F NMR (75.4 MHz, CDCl ): d
3
1
3
À211.4 (tt) ppm. C NMR (100.61 MHz, CDCl ): d 24.7
3
(
(
CH ); 25.1 (CH ); 25.2 (CH ); 29.3 (CH ); 29.4 (CH ); 29.5
2 2 2 2 2
CH ); 29.6 (CH ); 30.3 (CH ); 30.6 (CH ); 31.9 (CH ); 84.2
2
2
2
2
2

I. Dlouh a´ et al. / Journal of Fluorine Chemistry 117 (2002) 149–159
159
Table 5
[19] G.G. Furin, I.A. Salmanov, V.G. Kiriyanov, Zh. Prikl. Khim. 72
(1999) 1345.
Reduction of perfluoro vinyl ether 1 by complex hydrides
[
[
[
20] G.G. Furin, L.S. Pressman, L.M. Pokrovsky, A.P. Krysin, K.-W. Chi,
J. Fluorine Chem. 106 (2000) 13.
Hydride
Molar ratio
1: hydride)
Time (h)
Reaction mixture composi-
a
tion (% relative intensity )
(
21] O. Paleta, I. Dlouh a´ , R. Kapl a´ nek, K. Kefurt, M. Kod ´ı e` ek,
Carbohydr. Res., in press.
1
16
22] L.G. Sprague, K.B. Baucom, S.F. Sellers, R.A. DuBoisson, in: M.
Hudlick y´ , A.E. Pavlath (Eds.), Chemistry of Organic Fluorine
Compounds, vol. II, American Chemical Society, Washington, DC,
1995, p. 729.
NaBH
LiAlH
NaBH
4
1:0.49
1:0.83
1:0.49
1:0.73
0.75
1
80
70
50
50
20
30
50
50
4
4
6.5
6.5
LiAlH
4
[23] R.S. Mulliken, J. Chem. Phys. 23 (1955) 1833.
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New York, 1982, p. 152.
a
19F NMR.
[
25] B.H. Besler, K.M. Merz Jr., P.A. Kollman, J. Comp. Chem. 11 (1990)
31;
4
and product 16 under various conditions are given in
Table 5.
U.C. Singh, P.A. Kollman, J. Comp. Chem. 5 (1984) 129.
26] E.R. Larsen, J. Org. Chem. 28 (1963) 1133.
[
[
27] H. Harada, S. Mituzaki, S. Hayashi, N. Ishikawa, J. Fluorine Chem.
1
2 (1978) 211.
Acknowledgements
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N.N. Yarovenko, M.S. Raksha, J. Gen. Chem. USSR (Engl. Transl.)
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The research has been supported by the Grant Agency of
the Czech Republic (Grant No. 203/01/1311) and the Min-
istry of Education of the Czech Republic (Grant No. MSM
[
[
(
30] S. Bohm, Methods of organic chemistry, in: B. Baasner, H.
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