An entirely new methodology for synthesizing perfluorinated compounds: Synthesis of perfluoroalkanesulfonyl fluorides from non-fluorinated compounds

Article abstract of DOI:10.1016/j.jfluchem.2004.09.024

A new synthetic procedure for the preparation of perfluoroalkanesulfonyl fluorides utilizing liquid-phase direct fluorination with elemental fluorine has been developed. Direct fluorination of a partially fluorinated ester, which has alkanesulfonyl fluoride in the end, was synthesized from non-fluorinated counterparts and perfluorinated acid fluoride according to the PERFECT process, gave the desired perfluorinated product in moderate yield as well as by-products arising from CS bond cleavage. The results of the direct fluorination of some model substrates suggest that the CS bond cleavage occurred due to radical formation at the α-position rather than the β-position.

Full text of DOI:10.1016/j.jfluchem.2004.09.024

Journal of Fluorine Chemistry 125 (2004) 1695–1701
www.elsevier.com/locate/fluor
An entirely new methodology for synthesizing
perfluorinated compounds:
synthesis of perfluoroalkanesulfonyl fluorides from
non-fluorinated compounds
*
Takashi Okazoe , Eisuke Murotani, Kunio Watanabe, Masahiro Itoh, Daisuke Shirakawa,
Kengo Kawahara, Isamu Kaneko, Shin Tatematsu
Research Center, Asahi Glass Co., Ltd., 1150 Hazawa-cho, Kanagawa-ku, Yokohama 221-8755, Japan
Available online 11 November 2004
Abstract
A new synthetic procedure for the preparation of perfluoroalkanesulfonyl fluorides utilizing liquid-phase direct fluorination with elemental
fluorine has been developed. Direct fluorination of a partially fluorinated ester, which has alkanesulfonyl fluoride in the end, was synthesized
from non-fluorinated counterparts and perfluorinated acid fluoride according to the PERFECT process, gave the desired perfluorinated
product in moderate yield as well as by-products arising from C–S bond cleavage. The results of the direct fluorination of some model
substrates suggest that the C–S bond cleavage occurred due to radical formation at the a-position rather than the b-position.
# 2004 Elsevier B.V. All rights reserved.
Keywords: Alkanesulfonyl fluorides; Acyl fluorides; Direct fluorination; Fluorine; Ion exchange; PERFECT process; Bond cleavage
1. Introduction
‘‘PERFECT’’ is the abbreviation of PERFluorination of
an Esterified Compound then Thermal elimination.
Liquid-phase direct fluorination is a powerful tool to
make perfluorinated compounds [1–5]. Especially, the
Exfluor-Lagow elemental fluorine process is effective under
mild conditions [6]. Lagow and co-workers reported direct
fluorination of non-fluorinated compounds with relatively
simple structure [6]. We have actually examined the reaction
with octyl octanoate in order to establish whether it can be
applied to the synthesis of useful perfluorinated monomers,
and found that it worked well. We have also examined the
direct fluorination of small molecules such as monomer
precursors. Unfortunately, we found that it was not easy.
In some cases, reaction in the vapor phase due to high
volatility of the substrate partly took place and led to an
explosion. In order to solve this problem, we have developed
the PERFECT method (Scheme 1) [7,8]. The name
In the PERFECT method, perfluorination is achieved by
direct fluorination of a partially fluorinated compound.
First, we prepare small hydrocarbon component with the
backbone structure of the desired compound in the alcohol
form 1, by conventional organic synthesis. Then, it is
coupled with a perfluorinated moiety, perfluoroacyl fluoride
2 in a typical case, to form a larger molecule, that is, partially
fluorinated ester 3. Perfluorination is achieved by liquid-
phase direct fluorination with elemental fluorine to give the
perfluorinated ester 4. In the direct fluorination process,
vapor-phase reaction is avoided since the substrate has low
vapor pressure and the solubility of the substrate in the
perfluorinated solvent significantly increases. It would be an
advantage that we can use various perfluorinated solvents,
especially the perfluoroacyl fluoride itself, instead of CFCs.
Final thermal elimination gives the starting perfluoroacyl
fluoride 2 and the desired perfluoroacyl fluoride 5. In the
situation where the acyl fluoride 2, which we start with, is
* Corresponding author. Tel.: +81 45 374 7103; fax: +81 45 374 8858.
E-mail address: takashi-okazoe@agc.co.jp (T. Okazoe).
0022-1139/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2004.09.024

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2. Results and discussion
2.1. Synthesis of FSO2CF2CF2OCF2COF (16)
Flemion, which has developed by Asahi Glass Co., is
used as the ion exchange membrane for chlor-alkali
production process. Nafion (Dupont) is also used for the
same purpose [12,13]. Our aim was the synthesis of a
precursor to perfluorinated alkanesulfonic acid for the ion
exchange membrane.
First, direct fluorination of alkanesulfonyl chloride 8
derived from isethionic acid sodium salt and perfluoroacyl
fluoride 6 was attempted according to the PERFECT
process. The synthetic route of the substrate is shown in
Scheme 2.
Liquid-phase direct fluorination of the partially fluori-
nated alkanesulfonyl chloride 8 did not afford the desired
perfluoroalkanesulfonyl fluoride 9 at all. Only compounds
with C–S bond cleavage were detected.
Scheme 1. The PERFECT cycle.
not the same as the desired acyl fluoride 5, the separation of
the mixture of acyl fluorides is achieved by distillation.
Then, we can use the desired perfluoroacyl fluoride 5 itself
as the starting perfluoroacyl fluoride 2 for the next
PERFECT cycle. Thus, the desired perfluoroacyl fluoride
can be multiplied by the cycle.
Next, the direct fluorination of the corresponding
partially fluorinated alkanesulfonyl fluoride 10, which could
be derived from the chloride 8, was attempted. However,
bond cleavage in the ester bond occurred instead of the
substitution of the chlorine atom with potassium fluoride.
The desired substrate for the next direct fluorination was not
obtained at all.
As such an example, we have reported the synthesis of
perfluorinated butenyl vinyl ether (BVE) which is the
monomer of transparent perfluorinated cyclic polymer,
CYTOP [9]. We have also reported the synthesis of the
carboxylic acid monomer for ion exchange membrane,
Flemion, using a hydrocarbon diol as the starting material
[10], and the synthesis of perfluoroketones using a
secondary alcohol as the starting material [11].
Then, we decided to adopt another synthetic strategy,
which entails formation of the fluorosulfonyl group before
the formation of the backbone structure.
Reaction of 2-chloroethanesulfonyl fluoride 11 [14],
which is a derivative of isethionic acid, with the sodium salt
of ethylene glycol gave the substrate 12 of the PERFECT
process as shown in Scheme 3. Esterification was carried out
as in the usual PERFECT methodology to give partially
fluorinated ester 13, although the yield was not satisfactory
Herein, we present a new application of the PERFECT
process to the preparation of perfluoroalkanesulfonyl
fluoride.
Scheme 2.
Scheme 3.

T. Okazoe et al. / Journal of Fluorine Chemistry 125 (2004) 1695–1701
1697
Scheme 4.
because the reaction of the sulfonyl fluoride group and the
hydroxyl group in the structure also took place intramole-
cularly.
cleavage mainly and gave perfluoroethane and sulfonyl
difluoride [16]. This suggests that the C–S bond cleavage
may be the result of b-elimination of the intermediate
radical species. In our case shown above, the desired
perfluorinated alkanesulfonyl fluoride was obtained in
moderate yield, however, the C–S bond cleavage was still
observed. In order to clarify the cause of the C–S bond
cleavage, liquid-phase direct fluorination reactions of the
substrates 17 and 19, respectively, were carried out
(Scheme 5).
Direct fluorination of this partially fluorinated sulfonyl
fluoride 13 was carried out with elemental fluorine as in the
usual PERFECT method. The desired perfluorinated ester 14
was obtained in moderate yield, although by-product arising
from C–S bond cleavage 15 was still detected even in the
PERFECT method. The ratio of the desired product 14 and
the by-product 15 was ca. 7:3, as determined by GC area.
Thermal elimination led to the desired product 16, a
precursor of a sulfonyl monomer for the ion exchange
membrane (Scheme 4).
If a radical at the b-position formed during direct
fluorination promotes the C–S bond cleavage, then the direct
fluorination of the substrate 17 would give by-products
arising from the C–S bond cleavage, because generation of a
radical during the direct fluorination takes place only at the
b-position. However, no C–S bond cleavage was observed
and the desired perfluorinated product 18 was obtained
almost quantitatively.
2.2. Examination of the effect of a- and b-fluorination
to a fluorosulfonyl group
The cleavage of C–S bonds during liquid-phase
direct fluorination has been reported previously [15,16].
For example, octanesulfonyl fluoride was perfluorinated
to give the corresponding perfluorooctanesulfonyl fluoride
as well as by-product perfluorooctane arising from C–S
bond cleavage, although yields are not described [15].
Kobayashi et al. reported direct fluorination of methane-
sulfonyl fluoride [17], but also reported that direct
fluorination of ethanesulfonyl fluoride led to C–S bond
If a radical at the a-position causes the C–S bond
cleavage, then direct fluorination of the substrate 19 would
give by-products arising from the C–S bond cleavage,
because generation of a radical takes place only at the
a-position. Actually, the direct fluorination gave the desired
perfluorinated product 20 in 77% yield along with the
formation of products with the C–S bond cleavage in around
20% yield.
Scheme 5.

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T. Okazoe et al. / Journal of Fluorine Chemistry 125 (2004) 1695–1701
From the above results, we concluded that the C–S bond
4.2. Typical procedure
cleavage occurred due to the radical formation at the
a-position rather than the b-position, although it cannot
explain the case of the direct fluorination of methanesulfonyl
fluoride [17].
4.2.1. Synthesis of FSO2CF2CF2OCF2COF (16)
Ethylene glycol (141 g) and a methanol solution of
sodium methoxide (28 wt.%, 96.4 g, 0.500 mol) were
charged and stirred, and heated under reduced pressure to
distill off methanol to afford a solution of sodium salt of
ethylene glycol. A solution of 11 [14] (50 g, 0.341 mol) in
THF (100 mL) was stirred under cooling with ice bath, and
the previously obtained solution of sodium salt of
ethyleneglycol was dropwise added thereto over a period
of 2.5 h, while maintaining the internal temperature to be at
10 8C. After completion of the dropwise addition, the
reaction mixture was stirred at room temperature for 2 h.
Then the reaction mixture was added to water (400 mL),
extracted with dichloromethane, and the combined organic
layer was dried over magnesium sulfate. Filtration and
evaporation gave a crude product 12 (47.1 g). The obtained
crude liquid was used for the next step without carrying out
purification.
3. Conclusions
The synthetic method for perfluoroalkanesulfonyl
fluorides utilizing liquid-phase direct fluorination with
elemental fluorine was investigated. Direct fluorination
of a partially fluorinated ester, which has alkanesulfonyl
chloride in the end 8 according to the PERFECT
process, did not give the desired perfluorinated alkane-
sulfonyl fluoride 9. Direct fluorination of a partially
fluorinated ester, which has alkanesulfonyl fluoride, gave
the desired perfluorinated products in moderate yield as
well as by-products arising from C–S bond cleavage. The
results of the direct fluorination of the substrates 17 and 19
suggest that the C–S bond cleavage occurred due to
the radical formation at the a- position rather than the
b-position.
1H NMR (300.4 MHz, CDCl3): d 3.63–3.71 (m, 4H),
3.74–3.79 (m, 2H), 3.99–4.05 (m, 2H) ppm.
19F NMR (282.7 MHz, CDCl3): d 58.4 (1F) ppm.
4. Experimental
The crude liquid 12 (47.1 g) and triethylamine (19.5 g,
0.193 mol) were put into a flask and stirred under cooling
with an ice bath. Perfluoro(2-propoxypropanoyl) fluoride 6
(64.1 g, 0.193 mol) was dropwise added over a period of
40 min, while maintaining the internal temperature at or
below 10 8C. After being stirred for 2 h at room temperature,
the reaction mixture was added to ice water (100 mL).
The organic layer was washed twice with water (100 mL)
and dried over magnesium sulfate, followed by filtration to
obtain a crude liquid. This liquid was purified by silica
gel column chromatography (dichloropentafluoropropane
(AK-225)) to obtain the product 13 (21.2 g, 43.8 mmol, 13%
from 11).
4.1. General
NMR spectra were obtained on a JEOL EX-400
(tetramethylsilane as internal standard for 1H, and
trichlorofluoromethane for 19F). High-resolution mass
spectra were obtained on JEOL SX-102A coupled to
HP-5890 with a 60-m capillary column J&W DB-1 or
DB-1301 [18]. Elemental fluorine was generated by
FluorodecTM 30, Fluoro Gas (UK) or obtained from Asahi
Glass Co. Elemental fluorine is highly toxic and corrosive
gas, and may cause explosion when it meets organics in
the vapor phase. Extreme care must be taken when
handling it! Both the liquid and vapor of hydrogen
fluoride (b.p. 19.5 8C) evolved during the reaction are also
highly corrosive and cause severe burns when in contact.
Care must be taken! Prior to use, all hydrocarbon greases
must be removed and the apparatus must be gradually
passivated with elemental fluorine. Although the use of
1,1,2-trichlorotrifluoroethane (R113) is regulated, we will
mention experimental examples with it for convenience,
because it is still much more cheaply available (Aldrich)
than the target molecule itself for use as solvent. Care
must be taken in order not to emit it to the environment by
using, for example, a rotary evaporator with PTFE
diaphragm type vacuum pump and cooling trap. Once
enough of the target molecule itself is obtained in the
cycle, it should be used instead of R113. Other reagents
were obtained from Kanto Chemicals (Japan) and used
without purification.
1H NMR (300.4 MHz, CDCl3): d 3.57–3.63 (m, 2H), 3.81
3
(t, J = 4.5 Hz, 2H), 3.95–4.00 (m, 2H), 4.48–4.60 (m, 2H)
ppm.
19F NMR (282.7 MHz, CDCl3): d 58.2 (1F, j), À79.8 (1F
of c), À81.3 (3F, a), À82.1 (3F, e), À86.6 (1F of c), À129.4
(2F, b), À131.5 (1F, d) ppm (Fig. 1).
Into a 500-mL autoclave made of nickel, R113 (313 g)
was charged, stirred and maintained at 25 8C. At the gas
outlet of the autoclave, a cooler maintained at 20 8C, a
packed layer of NaF pellets and a cooler maintained at
À10 8C were installed in series. Further, a liquid-returning
line was installed to return any condensed liquid from the
cooler maintained at À10 8C to the autoclave. After su-
pplying nitrogen gas for 1 h, 20% F2/N2 was supplied for
1 h at a flow rate of 7.78 L/h. Then, while supplying 20%
F2/N2 at the same flow rate, a solution of 13 (7.01 g,

T. Okazoe et al. / Journal of Fluorine Chemistry 125 (2004) 1695–1701
1699
Fig. 1. Structural formulae for NMR peak assignment.
14.5 mmol) in R113 (140 g) was supplied over a period of
5.5 h. Then, a solution of benzene in R113 (0.01 g/mL, 6 mL)
was supplied at 0.15 MPa intermittently, and this operation
was repeated four times. Nitrogen gas was supplied to remove
solvent and volatile materials to give the crude perfluorinated
product. The ratio of the desired perfluorinated ester 14 and
by-products arising from the C–S bond cleavage was ca. 7:3,
as determined by GC area. The structure of the desired pe-
rfluorinated ester 14 was confirmed by 19F NMR (376.0 MHz,
CDCl3): d 45.2 (1F, j), À79.9 (1F of c), À82.0 (3F, a), À82.2
(3F, e), À82.6 (2F, h), À87.0 (1F of c), À88.5 (2F, g), À92.3
(2F, f), À112.9 (2F, i), À130.2 (2F, b), À132.1 (1F, d) ppm
(Fig. 1).
Fig. 2. Structural formula for NMR peak assignment.
Into a mixture of the crude thioether (7.1 g, 13 mmol),
acetic acid (20 g), and water (1.6 g), nitrogen gas was passed
through and then chlorine gas (2.7 g, 38 mmol) was
gradually supplied with maintaining the internal tempera-
ture at around 10 8C. Nitrogen gas was supplied in order to
remove chlorine, and the reaction mixture was diluted by
AK-225, washed three times with water, washed with brine,
and dried over MgSO4. Evaporation gave the crude sulfonyl
chloride (6.3 g). The product was quantitatively analyzed by
19F NMR, and the yield was 60%.
Crude perfluorinated ester 14 (3.1 g) obtained, as
described above, was charged into a flask together with
NaF powder (0.02 g) and heated at 140 8C for 10 h in an oil
bath with vigorous stirring. At the upper portion of the flask,
a reflux condenser having the temperature adjusted at 20 8C
was installed. After cooling, the liquid sample (3.0 g) was
recovered. As a result of the analysis by GC–MS, starting
perfluoroacyl fluoride 6 and the desired product 16 were
confirmed to be the main products. The structure of the
desired product 16 was confirmed by 19F NMR [19] and the
yield determined by the 19F NMR was 71%.
2
1H NMR (300.4 MHz, CDCl3): d 6.45 (dt, JHF = 52.7 Hz,
3JHF = 5.0 Hz, 1H, CHF) ppm.
19F NMR (282.7 MHz, CDCl3): d À81.0 (3F, a), À83.5 to
À86.2 (2F, f), À109.6 to À110.1 (2F, h), À122.5 to À126.4
(8F, b, c, d, e), À140.8 (1F, g) ppm (Fig. 2).
4.2.2. Synthesis of n-C6F13OCF2CF2SO2F (18)
The crude sulfonyl chloride (6.3 g, 7.3 mmol) was added
dropwise to a mixture of KHF2 (2 g, 26 mmol), acetonitrile
(10 g), and water (8.5 g) at room temperature. After the
mixture was stirred for 2 days, diluted with AK-225, and
washed three times with water, sat. NaHCO3, and brine,
respectively, the organic layer was dried over MgSO4 and
evaporated to give the crude product (5.0 g). The residue was
distilled (b.p. 83 8C/3.2 kPa) to give the desired product 17
(2.5 g, 5.0 mmol, 68%).
Addition of benzyl mercaptan to perfluorovinyl ether was
carried out in a manner similar to the procedure described in
literature [20].
Into a solution of 48% aqueous potassium hydroxide
(3.1 g, 26 mmol) and dioxane (8.0 g), n-C6F13OCF=CF2
(7.1 g, 17 mmol) was added, then benzyl mercaptan (2.4 g,
19 mmol) was added dropwise at 10 8C, and the mixture was
stirred at room temperature for 4 h. The reaction mixture
was diluted with AK-225, washed three times with water,
and dried over MgSO4. Evaporation gave the crude thioether
(7.1 g, 13 mmol, 77%), which structure was confirmed and
quantitatively analyzed by 19F NMR. The purity was 99%.
2
1H NMR (300.4 MHz, CDCl3): d 6.38 (dt, JHF = 52.9 Hz,
3JHF = 5.1 Hz, 1H, CHF) ppm.
19F NMR (282.7 MHz, CDCl3): d 44.4 (1F, SO2F), À81.2
(3F, a), À83.7 to À86.7 (2F, f), À113.0 (2F, h), À122.7 to
À126.7 (8F, b, c, d, e), À142.5 (1F, g) ppm (Fig. 2).
High-resolution mass spectrum (CI+) 500.9444
([M + H]+, calculated for C8H2F17O3S: 500.9453).
1H NMR (300.4 MHz, CDCl3): d 4.1 (s, 2H, SCH2), 5.78–
2
3
5.99 (dt, JHF = 54.4 Hz, JHF = 3.9 Hz, 1H, CHF), 7.27
(m, 5H, C6H5) ppm.
19F NMR (282.7 MHz, CDCl3): d À81.2 (3F, a), À83.6 to
À86.2 (2F, f), À89.6 to À91.5 (2F, h), À122.7 to À126.7 (8F,
b, c, d, e), À139.6 (1F, g) ppm (Fig. 2).
The direct fluorination was carried out in a manner
similar to the procedure for the direct fluorination of 13,
where the flow rate of 20% F2/N2 was 2.97 L/h, and a
solution of 17 (2.5 g) in R113 (15.4 g) was supplied over a
period of 0.65 h. The structure of the desired product 18 was
Chlorination of benzyl thioether was carried out in a
manner similar to the procedure in literature [21].

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T. Okazoe et al. / Journal of Fluorine Chemistry 125 (2004) 1695–1701
Fig. 3. Structural formula for NMR peak assignment.
Fig. 5. Structural formula for NMR peak assignment.
confirmed by 19F NMR [22] and the yield determined by the
10 8C. Nitrogen gas was supplied in order to remove chl-
orine, and the reaction mixture was diluted by AK-225,
washed three times with water, washed with brine, and dried
over MgSO4. Evaporation gave the crude sulfonyl chloride
(9.3 g, purity = 96%, 23 mmol, 67% yield for two steps).
19F NMR was 96%.
4.2.3. Synthesis of n-C6F13SO2F (20)
Conversion from polyfluorinated alcohol to its triflate
was carried out in a manner similar to the procedure
described in literature [23].
1H NMR (300.4 MHz, CDCl3): d 4.4 (t, 3JHF = 15.0 Hz, 2H)
ppm.
To a solution of C5F11CH2OH (13 g, 43 mmol) in
AK-225 (12 g), trifluoromethanesulfonic anhydride (13 g,
46 mmol) was added, and the mixture was stirred at
60 8C for 1 day and further stirred at 80 8C for 1 day. The
reaction mixture was poured into water, and extracted with
AK-225. The organic layer was washed with water, satura-
ted aqueous NaHCO3, and brine, respectively. Evaporation
gave the crude triflate (15 g, purity = 96%, 35 mmol, 78%
yield).
19F NMR (282.7 MHz, CDCl3): d À81.1 (3F, a), À113.1 (2F,
e), À122.8 to À123.2 (4F, c, d), À126.6 (2F, b) ppm (Fig. 5).
The crude sulfonyl chloride (9.3 g, 23 mmol) was added
dropwise to a mixture of KHF2 (5.0 g, 64 mmol) and DMF
(8 g) at 0 8C. After the mixture was stirred for 2 h, diluted
with AK-225, and washed three times with water, sat.
NaHCO3, and brine, respectively, the organic layer was
dried over MgSO4 and evaporated. The residue was distilled
(b.p. 41–46 8C/2.4 kPa) to give a mixture of DMF and the
desired product. DMF was removed by washing three times
with water to give 19 with purity of 90% (0.91 g, 2.5 mmol,
10% yield). This crude product was used without further
purification for the next reaction.
1H NMR (300.4 MHz, CDCl3): d 4.8 (t, 3JHF = 12.3 Hz, 2H)
ppm.
19F NMR (282.7 MHz, CDCl3): d À74.4 (3F, g), À81.3 (3F,
a), À120.2 (2F, e), À122.5 to À124.2 (4F, c, d), À126.7 (2F,
b) ppm (Fig. 3).
1H NMR (300.4 MHz, CDCl3): d 4.2 (t, 3JHF = 15.1 Hz, 2H)
ppm.
19F NMR (282.7 MHz, CDCl3): d 66.7 (1F, SO2F), À81.2
(3F, a), À113.0 (2F, e), À122.8 (4F, c, d), À126.6 (2F, b)
ppm (Fig. 5).
The crude triflate (15 g, 35 mmol) was added dropwise to
a mixture of ethylxanthic acid potassium salt (6.1 g, 38 -
mmol) in acetone (30 g) at 0 8C with stirring. After the
mixture was stirred at room temperature for 12 h, AK-225
was added. The reaction mixture was washed five times with
water. The organic layer was dried over MgSO4 and eva-
porated to give the crude xanthate (10 g). The crude product
was used without further purification for the next reaction.
The direct fluorination was carried out in a manner si-
milar to the procedure for the direct fluorination of 13, where
the flow rate of 20% F2/N2 was 3.04 L/h, and a solution of 19
(0.91 g, 2.5 mmol) in R113 (13.7 g) was supplied over a
period of 0.6 h. Perfluorohexanesulfonyl fluoride was obt-
ained, and the yield was 77%, which was determined by
19F NMR.
3
1H NMR (300.4 MHz, CDCl3): d 1.4 (t, JHH = 7.2 Hz,
3
CH3), 4.0 (t, JHF = 17.4 Hz, 2H, SCH2), 4.7 (d,
3JHH = 7.2 Hz, 2H, OCH2) ppm.
19F NMR (282.7 MHz, CDCl3): d À81.3 (3F, a), À112.5 (2F,
e), À122.9 to À123.5 (4F, c, d), À126.9 (2F, b) ppm (Fig. 4).
Acknowledgement
Into a mixture of the crude xanthate (10 g), acetic acid
(20 g), and water (1.5 g), nitrogen gas was passed through
and then chlorine gas (4.2 g, 59 mmol) was gradually su-
pplied with maintaining the internal temperature at around
We would like to thank Prof. R.D. Chambers for helpful
discussions.
References
[1] S. Rosen, Reactions of fluorine in inert media, 4th ed. in: B.
Baasner, H. Hagemann, J.C. Tatlow (Eds.), Methoden Org. Chem.
(Houben-Weyl), vol. E10a, Georg Thieme Verlag, Stuttgart, 1999 ,
pp. 167–187.
Fig. 4.

T. Okazoe et al. / Journal of Fluorine Chemistry 125 (2004) 1695–1701
1701
[2] R.J. Lagow, Reactions of fluorine in the presence of solvents, 4th ed.
in: B. Baasner, H. Hagemann, J.C. Tatlow (Eds.), Methoden Org.
Chem. (Houben-Weyl), vol. E10a, Georg Thieme Verlag, Stuttgart,
1999, pp. 194–200.
[11] T. Okazoe, K. Watanabe, M. Itoh, D. Shirakawa, S. Tatematsu, K.
Kawahara, I. Kaneko, Abstract of the 16th Winter Fluorine Confer-
ence, vol. 96, 2003.
[12] M. Yamabe, H. Miyake, Fluorinated membranes, in: R.E. Banks, B.E.
Smart, J.C. Tatlow (Eds.), Organofluorine Chemistry: Principles and
Commercial Applications, Plenum Press, New York, 1994, pp. 403–
412.
[3] R.D. Chambers, Fluorine in Organic Chemistry, 2nd ed., Blackwell
Publishing, Oxford, 2004, p. 35.
[4] W.W. Schmiegel, Organic fluoropolymers, in: M. Hudlicky,
A.E. Pavlath (Eds.), Chemistry of Organic Fluorine Compounds
II, American Chemical Society, Washington, DC, 1995 , pp. 97–
112.
[13] T. Hiyama, Organofluorine Compounds, Springer, Berlin, 2000, pp.
228–230.
[14] J.J. Krutak, R.D. Burpitt, W.H. Moore, J.A. Hyatt, J. Org. Chem. 44
(1979) 3847–3858.
[5] J. Hutchinson, G. Sandford, Top. Curr. Chem. 193 (1997) 1–43.
[6] T.R. Bierschenk, T. Juhlke, H. Kawa, R.J. Lagow, US Patent 5,093,432
(1992).
[15] M.G. Costello, G.G. Moore, WO90/06296 (1990).
[16] M. Kobayashi, T. Tanioka, H. Kumase, Y. Fukai, Abstract of the 16th
Winter Fluorine Conference, no. 17, 2003.
[7] T. Okazoe, K. Watanabe, M. Itoh, D. Shirakawa, H. Murofushi,
H. Okamoto, S. Tatematsu, Adv. Synth. Catal. 343 (2001) 215–
219.
[17] M. Kobayashi, T. Inoguchi, T. Iida, T. Tanioka, H. Kumase, Y. Fukai, J.
Fluorine Chem. 120 (2003) 105–110.
[8] T. Okazoe, K. Watanabe, M. Itoh, D. Shirakawa, H. Murofushi,
H. Okamoto, S. Tatematsu, J. Fluorine Chem. 112 (2001) 109–
116.
[18] Details of the analytic method will be reported separately.
[19] D. Su, Q. Chen, R. Zhu, H. Hu, Acta Chim. Sin. 41 (1983) 946–959.
[20] I. Dlouha, J. Kvicala, O. Paleta, J. Fluorine Chem. 117 (2002) 149–
159.
[9] M. Iwaya, T. Okazoe, K. Watanabe, D. Shirakawa, K. Oharu, H.
Okamoto, M. Itoh, S. Tatematsu, Abstract of the 25th Fluorine
Conference of Japan, no. B04, 2001.
[21] A.E. Feiring, E.R. Wonchoba, S. Rozen, J. Fluorine Chem. 93 (1999)
93–101.
[10] T. Okazoe, K. Watanabe, S. Tatematsu, M. Itoh, D. Shirakawa, M.
Iwaya, H. Okamoto, Abstract of the 224th ACS National Meeting,
FLUO9, 2002.
[22] Acta Chim. Sin. 35 (1977) 209–219.
[23] C. Tonelli, A.D. Meo, S. Fontana, A. Russo, J. Fluorine Chem. 118
(2002) 107–121.