Development of direct fluorination technology for application to materials for lithium battery

Article abstract of DOI:10.1016/S0022-1139(02)00317-2

Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride.

Full text of DOI:10.1016/S0022-1139(02)00317-2

Journal of Fluorine Chemistry 120 (2003) 105–110
Development of direct fluorination technology for
application to materials for lithium battery
Masafumi Kobayashi*, Tetsuya Inoguchi, Takashi Iida,
Takashi Tanioka, Hiroshi Kumase, Yasushi Fukai
New Materials Laboratory, New Products Development Division, Kanto Denka Kogyo Co. Ltd.,
1497 Shibukawa, Gunma 377-8513, Japan
Received 1 August 2002; received in revised form 7 October 2002; accepted 11 October 2002
Abstract
Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one,
which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental
fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl
fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of
perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Direct fluorination; Elemental fluorine; Lithium battery; 4-Fluoro-1,3-dioxolan-2-one; 4,5-Difluoro-13-dioxolan-2-one; 4,4-Difluoro-1,3-
dioxolan-2-one; Trifluoromethanesulfonyl fluoride; Difluoromethanesulfonyl fluoride; Fluoromethanesulfonyl fluoride
1. Introduction
transformed to three isomers of difluorinated 1,3-dioxolan-2-
ones by the same methodology [6].
4-Fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate)
has been expected as an attractive additive or solvent for
lithium ion secondary battery because of reducing the elec-
trolyte decomposition and substantially increasing the cell
efficiency [1]. Usually 4-fluoro-1,3-dioxolan-2-one is pre-
pared by the reaction of 4-chloro-1,3-dioxolan-2-one with
potassium fluoride, but this reaction requires severe reaction
conditions [2]. In recent years, electrochemical fluorination of
1,3-dioxolan-2-one (ethylene carbonate) without solvent has
been reported to give 4-fluoro-1,3-dioxolan-2-one in a reason-
able yield [3]. The use of elemental fluorine as a fluorine
source is profitable because the most fundamental method
for the introduction of fluorine atom into an organic
molecule is the direct substitution of hydrogen for fluorine.
Recently, direct fluorination of g-butyrolactone with elemen-
tal fluorine was reported to provide a mixture of fluorinated g-
butyrolactones [4]. We have new developed an efficient
method for preparing 4-fluoro-1,3-dioxolan-2-one by direct
fluorination of 1,3-dioxolan-2-one with elemental fluorine
[5]. 4-Fluoro-1,3-dioxolan-2-one has also been found to be
Another topic is the preparation of trifluoromethanesul-
fonyl fluoride by the reaction of methanesulfonyl fluoride
with elemental fluorine. Trifluoromethanesulfonyl fluoride
is one of the important intermediates of lithium salts used
as an electrolyte in lithium ion secondary battery. For
producing trifluoromethanesulfonyl fluoride is widely
employed the electrochemical fluorination of methanesul-
fonyl fluoride [7]. Gas phase direct fluorination of
dimethylsulfone gives bis(trifluoromethyl)sulfone as well
as trifluoromethanesulfonyl fluoride [8]. We have also
developed a new method for the preparation of trifluoro-
methanesulfonyl fluoride by the reaction of methanesulfo-
nyl fluoride with elemental fluorine [9].
2. Results and discussion
2.1. Direct fluorination of 1,3-dioxolan-2-one (1)
First, fluorination of 1,3-dioxolan-2-one (1) with elemen-
tal fluorine was carried out in various solvents and the results
are summarized in Table 1. The conversion of 1 (as well as
the selectivity of 4-fluoro-1,3-dioxolan-2-one (2) were
* Corresponding author. Tel.: þ81-279-22-3533; fax: þ81-279-22-3634.
E-mail address: mf-kbysh@kantodenka.co.jp (M. Kobayashi).
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 3 1 7 - 2

106
M. Kobayashi et al. / Journal of Fluorine Chemistry 120 (2003) 105–110
Table 1
Direct fluorination of 1,3-dioxolan-2-one (1)
a
F2 (eq)
Solvent
Ratio (wt/wt)
Reaction
Passing time
(ml/min)
Conversion (%)
Selectivityb
1:solvent
temperature (8C)
of 2 (%)
CHCl3
5:95
2:98
0
0
0.6
0.4
1.0
1.0
1.0
1.7
50
50
0
12
33
52
71
85
0
95
(CF3)2CFCF2CF2CF3
(CF3)2CFCF2CF2CF3
CClF2CCl2F
HF
2:98
50
50
10
50
50
79
10:90
17:83
100:0
50
68
50
350
93
86 (70)c
No solvent
a Fluorine, 30% mixture in nitrogen, was passed through the reaction mixture (50–350 ml/min).
b GC analysis.
c Isolated yield (in parentheses) based on 1.
strongly dependent on a choice of solvents. Fluorination of 1
in chloroform did not give 2 at all. This is presumably due to
preferential fluorination of chloroform. Peffluoro-2-methyl-
pentane and 1,1,2-trichloro-1,2,2-trifluoroethane are known
as effective solvents for the liquid phase direct fluorination
of organic compounds with elemental fluorine [10] because
of their inactive nature toward elemental fluorine at ambient
temperature. The use of perfluoro-2-methylpentane as the
solvent resulted in the formation of a significant amount of 2.
At 0 8C, the conversion of 1 was low and the reaction rate
was slow. It is considered that 1 would be less reactive
toward elemental fluorine at such low temperature as 0 8C.
On raising the reaction temperature, the reaction proceeded
faster but the selectivity of 2 did not increase. Polyfluori-
nated byproducts were formed together with 2. Fluorination
Scheme 2.
of 1 in 1,1,2-trichloro-1,2,2-trifluoroethane also gave similar
result. Hydrogen fluoride is known as effective solvent, and
the fluorination of 1 in hydrogen fluoride at 0 8C led to the
formation of 2 with good selectivity. However, the reaction
was very slow at this temperature. It is difficult to carry out
the fluorination in hydrogen fluoride at high temperature
such as 50 8C, because of the low boiling point of hydrogen
fluoride. Although the flow rate of fluorine at 0 8C was
increased, the reaction was not accelerated and a large
amount of unreacted fluorine remained. Finally we found
that the reaction of 1 with elemental fluorine proceeded
efficiently at 50 8C without solvent, giving 2 with good
selectivity (86%) and good isolated yield (70%).
and 5 was separated by distillation followed by recrystalli-
zation to obtain in 11, 59, and 5% yield, respectively.
1H NMR of 3 showed a doublet–doublet like signal
around d ¼ 6:23 ppm. But the splitting pattern was compli-
cated. 19F NMR of 3 also showed a doublet–doublet like
signal around d ¼ ꢀ148:1 ppm, whose splitting pattern was
complicated. Similarly, 1H and 19F NMR spectra of 4
showed doublet–doublet like signals around d ¼ 6:14 ppm
(1H NMR) and ꢀ134.8 ppm (19F NMR), respectively. Here
again both of the splitting patterns were complicated. The
1
shape of the H NMR signal of 3 was closed to that of 4.
Similarly, the shape of the 19F NMR signal of 3 was also
closed to that of 4. These NMR data strongly suggested that
3 and 4 were regarded as two vicinal difluoro compounds.
In order to determine the absolute structures of 3 and 4,
X-ray analysis was examined. Fortunately, 3 could be
Compound 2 was also fluorinated without solvent to give
three difluorinated compounds, cis-4,5-difluoro-1,3-dioxo-
lan-2-one (3), trans-4,5-difluoro-1,3-dioxolan-2-one (4) and
4,4-difluoro-1,3-dioxolan-2-one (5) (Schemes 1–3). The
ratio of 3:4:5 was about 2.5:6.5:1. Each compound 3, 4
Scheme 1.
Scheme 3.

M. Kobayashi et al. / Journal of Fluorine Chemistry 120 (2003) 105–110
107
Fig. 1. X-Ray ORTEP of cis-4,5-difluoro-1,3-dioxolan-2-one (3). Crystal system: orthorhombic, lattice parameters: a ¼ 0:7240 (nm), b ¼ 1:0807 (nm),
c ¼ 0:5513 (nm), space group: P212121, Z value: 4, residuals: R; Rw ¼ 0:029; 0.024.
crystalized readily and the X-ray analysis of 3 was success-
fully performed. The ORTEP structure of 3 obtained by X-ray
analysis is shown in Fig. 1. It was found that each fluorine
atom was attached to each carbon atom in cis position. So the
compound 3 has cis structure. Another isomer 4 was deter-
mined as the trans isomer.
1H NMR spectrum of 5 showed a triplet signal due to
methylene protons around d ¼ 4:68 ppm with a coupling
constant of 11.6 Hz. Similarly, 19F NMR spectrum of 5
showed a triplet signal due to difluoromelylene fluorine
atoms around d ¼ ꢀ72:8 ppm with a coupling constant of
11.6 Hz.
Table 2 summarizes some physical properties of the
fluorinated 1,3-dioxolan-2-ones, together with those of com-
mon carbonates. An introduction of fluorine atom(s) to 1,3-
dioxolan-2-one decreased the boiling point and melting
point, except cis-4,5-difluoro-1,3-dioxolan-2-one. Viscos-
ities of fluorinated 1,3-dioxolan-2-ones were increased
while dielectric constants and electric conductivities were
decreased.
6 (80%). It would be considered that solvent-free fluorina-
tion gave partially fluorinated compounds in preference of
perfluorinated compound. Presumably, a large excess of the
substrate against elemental fluorine in the reaction media
prevented perfluorination, so that the substrate should be
diluted with a solvent. The use of hydrogen fluoride as the
solvent resulted in a recovery of 6. A large amount of
unreacted fluorine gas was observed. Fluorination in formic
acid [13] afforded only carbon dioxide which would be
formed by a reaction of formic acid with elemental fluorine
followed by hydrolysis. The reaction in perfluoro-2-methyl-
pentane proceeded successfully to give 7 with good selec-
tivity (87.7%) and moderate isolated yield (64%) together
with 8 (2%), 9 (7%), and recovered 6 (22%).
The partially fluorinated byproducts 8 and 9 could be
regarded as intermediates of 7, so that the compounds 8 and
9 would be recycled and used as starting materials for the
preparation of 7. In fact, the fluorination of 9 gave 7 with
good selectivity (88.8% selectivity of 7). Similarly the
fluorination of 8 proceeded smoothly, affording 7 with
excellent selectivity (97.1% selectivity of 7).
2.2. Direct fluorination of methanesulfonyl fluoride (6)
Fluorination of methanesulfonyl fluoride (6) with ele-
mental fluorine in liquid phase was examined in several
solvents and the results are summarized in Table 3. Fluor-
ination of methanesulfonyl fluoride without solvent at 80 8C
did not give desired trifluoromethanesulfonyl fluoride (7) but
gave CF4, CO2, C2F6 and SO2F2, which would be formed by
a decomposition of 6. In contrast, fluorination of 6 without
solvent at 20 8C gave an appreciable amount of 7 but the
selectivity was poor. In this reaction, a trace of difluoro-
methanesulfonyl fluoride (8) and 12% of fluoromethanesul-
fonyl fluoride (9) were also obtained together with recovered
3. Experimental
3.1. General experimental procedures
1H and 13C NMR spectra were recorded on a Varian
Gemini 200 NMR spectrometer. Chemical shifts were
reported in ppm relative to internal tetramethylsilane, and
CDCl3, was used as the solvent. 19F NMR spectra were
recorded on a Varian Gemini 200 NMR spectrometer. Che-
mical shifts were reported in ppm relative to internal CFCl3,
and CDCl3 was used as the solvent. Low-resolution mass

108
M. Kobayashi et al. / Journal of Fluorine Chemistry 120 (2003) 105–110
Table 2
Physical properties of non-fluorinated and fluorinated carbonates
Compounds
bp (8C)
mp (8C)
Density d
(kg mꢀ3
Viscosity Z
Dielectric
Electric
conductivity k (S mꢀ1 a
Refb
[11]
)
(ꢁ10ꢀ3 Pa s)
constant e (ꢀ)
)
238
37
1321
1.9c
2.5d
90c
65d
1.31c
242
210
187
129
134
ꢀ49
17.3
56.6
7.8
1209
1497
1592
1508
1567
1.06d
1.04e
1.53f
0.95e
1.16e
[11]
4.1e
2.3f
2.5e
2.1e
78.4e
No data
37.1e
34e
Our data
Our data
Our data
Our data
3.2
91
3
1069
975
0.6g
0.7g
0.6g
2.8g
0.11g
0.06g
[12]
[12]
126
ꢀ43
a The electric conductivity was measured by a conductivity meter equipped with an H-type conductivity cell charged with organic liquid electrolyte
containing 1 M Et4NBF4.
b Physical properties are cited from ref. [11,12] except our data.
c At 40 8C.
d At 20 8C.
e At 23 8C.
f At 60 8C.
g At 25 8C.
Table 3
Direct fluorination of methanesulfonyl fluoride (6)a
Solvent
Temperature
Conversion
(%)
GC selectivityb
(8C)
7
8
CF4
CO2
C2F6
SO2F2
No solvent
No solventc
HFd
80
20
10
30
40
5
20
<1
<1
76
nd
nd
36.7
20.1
Trace
Trace
2.2
14.2
22.9
Trace
99.8
4.1
3.1
0.7
nd
46.0
25.8
Trace
0.2
30.5
Trace
nd
nd
HCOOH
(CF3)2CFCF2CF2CF3
nd
87.7 (64)e
nd
0.6
nd
0.1
4.2
a Fluorine, 30% mixture in nitrogen, was passed through the reaction mixture (50–200 ml/min).
b GC analysis of the gaseous products.
c 8 (Trace), 9 (12% GC yield), 6 (80% GC yield).
d Large amount of F2 was recovered.
e Isolated yield (in parentheses) based on 6.

M. Kobayashi et al. / Journal of Fluorine Chemistry 120 (2003) 105–110
109
spectra were obtained on a Shimazu GC–MS-QP5050A in
an electron impact mode. FT-IR spectra were recorded on a
JEOL JIR MICRO6000 reported in cmꢀ1. Boiling points
were determined during fractional distillation using a ther-
mometer, and are uncorrected. Melting points were recorded
on a Rigaku DSC8230L. All chemicals and solvents were
used without further purification.
(95) 29 (100). Anal Calcd. for C3H2F2O3: C, 29.05; H, 1.63.
Found: C, 29.03; H, 1.61.
3.3.2. trans-4,5-Difluoro-1,3-dioxolan-2-one (4)
1
Melting point 7.8 8C. bp 128.7 8C. HNMR (200 MHz,
CDCl3) d 6.14 (m, 2H). 13C NMR (50.28 MHz, CDCl3) d
150.2 (tt, C=O) 105.9 (dddd, 2C). 19F NMR (188 MHz,
CDCl3) d ꢀ134.8 (m, 2F). IR (neat): 3040, 1861, 1392, 1365,
1172, 1094. EIMS (probe) 70 eV, m/z (rel. int.) 124 [M]þ (5)
76 (80) 61 (20) 48 (48) 32 (95) 29 (100). Anal Calcd. for
C3H2F2O3: C, 29.05; H, 1.63. Found: C, 29.00; H, 1.55.
3.2. Synthesis of 4-fluoro-1,3-dioxolan-2-one (2)
The carbonate 1 (528 g, 6 mol) was charged into a 1 l PFA
vessel and stirred vigorously at 50 8C by passing N2 (200 ml/
min, 30 min). Fluorine gas, 30% mixture in nitrogen, was
passed at a constant flow rate (350 ml/min) through the
substrate. When 10.8 mol of fluorine was passed to the
reaction mixture, the gas line and the reactor were parged
with N2 (200 ml/min, 30 min). The reaction mixture was
washed with ice water (100 ml) and extracted with dichlor-
omethane (200 ml ꢁ 3). The combined organic layers were
dried over anhyd. MgSO4, followed by filtration and removal
of the solvents by a rotary evaporator. The organic residue was
purified by distillation to give 440 g (4.2 mol, 70%) of 2 as a
colorless liquid. mp 17.3 8C. bp 210 8C. 1H NMR (200 MHz,
CDCl3) d 6.29 (ddd, JHH ¼ 1:2, 4.1 Hz, JHF ¼ 64:0 Hz, 1H,
CHF) 4.60 (ddd, JHH ¼ 4:1, 11.0 Hz, JHF ¼ 32:9 Hz, 1H)
4.49 (ddd, JHH ¼ 1:2, 11.0 Hz, JHF ¼ 21:9 Hz, 1H). 13C
NMR (50.28 MHz, CDCl3) d 152.7 (s, 1C, C=O) 105.0 (d,
1C, CHF) 70.7 (d, 1C, CH2). 19F NMR (188 MHz, CDCl3) d
ꢀ121.7 (ddd, J ¼ 22:0, 32.7, 63.9 Hz, 1F). IR (neat): 3046,
1834, 1362, 1157, 1082, 909. EIMS (probe) 70 eV, m/z (rel.
int.) 106 [M]þ (20) 73 (10), 62 (100) 58 (40) 43 (70).
3.3.3. 4,4-Difluoro-1, 3-dioxolan-2-one (5)
Melting point 3.2 8C. bp 134 8C. 1H NMR (200 MHz,
CDCl3) d 4.68 (t, J ¼ 11:6 Hz, 2H). 13C NMR (50.28 MHz,
CDCl3) d 147.8 (t, C=O) 124.6 (tt, CF,) 70.6 (tt, CH2). 19F
NMR (188 MHz, CDCl3) d ꢀ72.8 (t, J ¼ 11:6 Hz, 2F). IR
(neat): 3054, 3003, 1866, 1467, 1403, 1313, 1264, 1204, 1167,
1084, 958. EIMS (probe) 70 eV, m/z (rel. int.) 124 [M]þ (3) 80
(95), 61 (15) 5 1 (30) 32 (95) 29 (100). Anal Calcd. for
C3H2F2O3: C, 29.05; H, 1.63. Found: C, 29.01; H, 1.50.
3.4. Synthesis of trifluoromethanesulfonyl fluoride (7)
The compound 6 (50 g, 0.61 mol) and perfluoro-2-
methylpenthane (500 g, 1.48 mol) were charged into a 1 l
PFA vessel and stirred vigorously at 40 8C by passing N2
(200 ml/min, 30 min). Fluorine gas, 30% mixture in nitro-
gen, was passed at a constant flow rate (200 ml/min, total
328 g (8.62 mol)) through a mixture of the substrate and
the solvent. The substrate 6 was continuously added with
a pump to the reaction mixture (total 250 g, 2.56 mol). The
gaseous product, which came out of the vessel, was washed
with water and trapped to a 500 ml SUS cylinder cooled
by liquid nitrogen. The gaseous product was purified to
give 303 g (1.99 mol, 64%) of 7. GCMS analysis of 7
showed peaks corresponding to the parent minus CF3,
and other prominent peaks corresponding to CF3þ, and
SOFþ. The 19F NMR spectra and the observed mass frag-
ment pattern were superimposed to those in the literature [8].
Boiling point (bp) ꢀ25 8C. 19F NMR d ꢀ113.8 (t, 1F, SO2F)
2.71 (d, J ¼ 17:9 Hz, 3F, CF3). EIMS (probe) 70 eV, m/z
(rel. int.) 83 [M-CF3]þ (3) 69 [CF3]þ (100) 67 [SOF]þ (13),
50 (3), 48 (4), 31 (3).
3.3. Synthesis of difluorinated 1-3-dioxolan-2-ones
The carbonate 2 (160 g, 1.5 mol) was charged into a
250 ml PFAvessel and stirred vigorously at 50 8C by passing
N2 (200 ml/min, 30 min). Fluorine gas, 30% mixture in
nitrogen, was passed at a constant flow rate (250 ml/min)
through the substrate. When 2.25 mol of fluorine (1.5
equivalent of 2) was passed to the reaction mixture, the
gas line and the reactor were parged with N2 (200 ml/min,
30 min). The reaction mixture was washed with ice water
(100 ml) and extracted with dichloromethane (250 ml ꢁ 6).
The combined organic layers were dried over anhyd.
MgSO4, followed by filtration and removal of the solvents
by a rotary evaporator. The crude products were purified by
distillation affording colorless crystals of 3 (21 g, 0.17 mol,
11%) colorless liquid of 4 (109 g, 0.88 mol, 59%) and
colorless liquid of 5 (10 g, 0.08 mol, 5%).
The upper layer (a mixture of 6, 8, and 9) of reaction
mixture was separated from perfluoro-2-methylpentane
(lower layer) and washed with water (50 ml). The organic
layer was dried over anhyd. MgSO4. The crude products
were purified by distillation affording colorless liquid of 8
(7 g, 0.05 mol, 2%), colorless liquid of 9 (24 g, 0.21 mol,
7%) and recovered 6 (65 g, 0.67 mol, 22%).
3.3.1. cis-4,5-Difluoro-1,3-dioxolan-2-one (3)
Melting point DCl3) d 6.23 (m, 2H). 13C NMR
(50.28 MHz, CDCl3) d 148.2 (m, 1C, C=O) 102.7 (dddd,
2C). 19F NMR (188 MHz, CDCl3) d ꢀ148.1 (m, 2F). IR
(neat): 3047, 1874, 1386, 13 18, 1095, 995. EIMS (probe)
70 eV, m/z (rel. int.) 124 [M]þ (2) 76 (45) 61 (15) 48 (40) 32
3.4.1. Difluoromethanesulfonyl fluoride (8)
1
Boiling point 52 8C. H NMR (200 MHz, CDCl3) d 6.53
(dt, J ¼ 3:5, 52.0 Hz, 1H). 13C NMR (50.28 MHz, CDCl3)
112.1 (ddt). 19F NMR (188 MHz, CDCl3) d 37.9 (dt,

110
M. Kobayashi et al. / Journal of Fluorine Chemistry 120 (2003) 105–110
JHF ¼ 3:5 Hz, JFF ¼ 3:3 Hz, 1F, SO2F) ꢀ119.3 (dd, JHF
¼
Acknowledgements
52:0 Hz, JFF ¼ 3:3 Hz, 2F, CHF2). IR (neat): 3050, 1560,
1229, 1126. EIMS (probe) 70 eV, m/z (rel. int.) 83 [M-
CHF2]þ (1) 67 [SOF]þ (10), 64 (5) 51 [CMF2]þ (100).
Anal Calcd. for CHF3O2S: C, 8.96; H, 0.75. Found: C,
8.78; H, 0.79.
The authors thank to professor Jun Nishimura and Dr.
Yosuke Nakamura in Gunma University for X-ray analysis.
The authors also acknowledge to Dr. Tomoya Kitazume in
Tokyo institute of Technology for elemental analysis.
3.4.2. Fluoromethanesulfonyl fluoride (9)
Boiling point 102 8C. 1H NMR (200 MHz, CDCl3) 6 5.49
(dd, J ¼ 7:0, 46.0 Hz, 2H). 13C NMR (50.28 MHz, CDCl3)
87.8 (ddt). 19F NMR (188 MHz, CDCl3) d 48.34 (td,
JHF ¼ 7:0 Hz, JFF ¼ 8:9 Hz, 1F, SO2F) ꢀ213.5 (td,
JHF ¼ 46:0 Hz, JFF ¼ 8:9 Hz, 1F, CH2F). IR (neat): 3032,
3031, 2968, 1456, 1211, 1090, 829. EIMS (probe) 70 eV m/z
(rel. int.) 83 [M-CH2F]þ (1) 67 [SOF]þ (26) 64 (10), 48 (10),
33 [CH2F]þ (100). Anal Calcd. for CH2F2O2S: C, 10.35; H,
1.74. Found: C, 10.08; H, 1.99.
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