Electrochemical fluorination of unsaturated sulfides and sulfones

Article abstract of DOI:10.1023/A:1020708111882

Electrochemical fluorination of some unsaturated sulfides and sulfones and their reactions with anhydrous HF were studied.

Full text of DOI:10.1023/A:1020708111882

Russian Journal of Applied Chemistry, Vol. 75, No. 7, 2002, pp. 1095 1100. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 7,
2002, pp. 1112 1117.
Original Russian Text Copyright
2002 by Grigor’eva, Shainyan, Kaurova, Gracheva, Lesnevskaya, Barabanov.
APPLIED ELECTROCHEMISTRY
AND CORROSION PROTECTION OF METALS
Electrochemical Fluorination
of Unsaturated Sulfides and Sulfones
A. A. Grigor’eva, B. A. Shainyan, G. I. Kaurova, E. I. Gracheva,
N. B. Lesnevskaya, and V. G. Barabanov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Prikladnaya Khimiya Russian Scientific Center, St. Petersburg, Russia
Received May 25, 2001; in final form, January 2002
Abstract Electrochemical fluorination of some unsaturated sulfides and sulfones and their reactions with
anhydrous HF were studied.
Electrochemical fluorination (ECF) of organosulfur
compounds in anhydrous HF was studied with satu-
rated or aromatic sulfides, disulfides [1 3], thiols
[4 6], sulfoxides [1], and sulfones [7]. On the whole,
ECF of S(II) derivativres involves cleavage of one or
both S C bonds. The C S(O) C moiety in sulfoxides
is not preserved in ECF [1], whereas ECF of sulfones
yielded, along with perfluoroalkylsulfonyl fluorides
R SO F, also the corresponding sulfones R SO R [7].
quartet of triplets at 116 ppm corresponding to the
C F group. As judged from the boiling points, the
2 5
major products of ECF of I are dodecafluoropentane
C F (bp 29.3 C [10]) and pentafluoro(1,1,2,2,2-pen-
5 12
6
tafluoroethyl)- -sulfane C F SF (the boiling point
2 5
5
of the closest homolog, C F SF , is 43 C [6]). For-
mation of dodecafluoropentane was confirmed by the
fact that the intensity of F NMR signal at 84.2 ppm
3 7
5
19
(CF ) was equal to the sum of the intensities of the
f
2
f
2 f
3
3
2, 4
Virtually no data are available, except a single paper
[9], on ECF of unsaturated aliphatic or alkenylaromat-
ic sulfides and sulfones.
signals at 125.3 (C F ) and 128.9 ppm (C F ), by
2
2
its refractive index, which was close to the reference
value [10], and by the IR spectrum of the distilled
product, which coincided with the reference spectrum
[11]. The presence of pentafluoro(1,1,2,2,2-pentaflu-
In this work, we studied ECF of ethyl vinyl sulfide
C H SCH=CH (I), di(1-propenyl) sulfide (CH
2
5
2
3
6
oroethyl)- -sulfane is confirmed by the substantial
CH=CH) S (II), phenyl vinyl sulfide C H SCH=CH
2
6
5
5
2
2
(>6%) sulfur content in the liquid products and by the
(III), and phenyl vinyl sulfone C H SO CH=CH
6
2
19
presence in the F NMR spectrum of downfield sig-
(IV), and also reactions of anhydrous HF with III, IV,
and divinyl sulfide (CH =CH) S (V). We failed to
nals at
46.53 and 64.15 ppm with the intensity
F
2
2
ratio of 4 : 1 and J 143 Hz. According to [12], the
downfield signal belongs to the axial fluorine, and the
perform ECF of dichlorovinyl aryl sulfones ArSO
FF
2
CH=CCl (Ar = Ph, m-ClC H , m-NO C H ) because
2
6
4
2 6 4
upfield signal, to equatorial fluorine atoms of the SF
group. On the whole, ECF can be described by the
of their insolubility in HF. The compositions and
structures of liquid ECF products were determined by
GLC, GC MS, elemental analysis, IR spectroscopy,
5
equation
1
13
19
and H, C, and F NMR spectroscopy. Gaseous
ECF products were analyzed by IR spectroscopy and
gas chromatography (GC).
ECF
C2H5SCH=CH2
CnF2n + 2 (n = 1 5) + C2F5SF5
HF
Electrochemical fluorination of sulfide I yields
gaseous products among which we identified by GC
and IR spectroscopy CF , C F , C F , C F , SF ,
+ SF4 + SF6 + SO2F2 + F2O.
(1)
The gaseous products of ECF of sulfide II include
4
2 6
3 8
4 10
4
HF, CF , C F , CO, CO , F O, and SO F . CO,
SF , SO F , F O, and also liquid low-boiling prod-
4
2 6
2
2
2 2
6
2 2
2
CO , and SO F are formed by electrochemical fluo-
ucts (bp 30 35 C) exhibiting no IR absorption in the
2
2 2
1
range above 1350 cm , which indicates that these
rination of oxygen-containing organic impurities pres-
ent in the initial compound. Oxygen difluoride OF
is the product of electrochemical fluorination of water
13
products contain no C=C and C H bonds. The
C
2
NMR spectra of liquid ECF products of I contain a
1070-4272/02/7507-1095$27.00 2002 MAIK Nauka/Interperiodica

1096
GRIGOR’EVA et al.
present in small amounts in liquid HF and in the
substrate. The content of sulfur in liquid ECF prod-
ucts is about 2%, and that of hydrogen, about 0.5%
(at the level of the determination error); the absence of
ECF
HF
SO2 CH=CH2
F
+
F
CF3
VI
VII
5
4
1
absorption bands above 1350 cm indicates that C=C
1
2
3
+
6
CF2CF3 + C2F6 + CF4 + SO2F2
and C H bonds are absent. This means that ECF in-
volves substitution of all hydrogen atoms, addition of
fluorine to all double bonds, and noticeable removal
of sulfur. A GC MS analysis revealed formation of
four products, For all of them, the base peak is that of
7
8
VIII
(2)
+ SF4 + SF6.
Along with the compounds indicated in the scheme,
we identified in the gas phase HF, CO, CO , and F O.
The sulfur content in the liquid products is less than
3%, and the hydrogen content, less than 1%. A GC
MS analysis revealed three major products with the
fragmentation pattenrs similar to that given for II.
The F NMR spectrum of the products before distil-
lation contained downfield signals at
61.4 ppm, suggesting formation of R SF derivatives,
as in ECF of I and II. The low-boiling (48 C) fraction
from distillation of liquid ECF products of IV solidi-
+
the CF ion, and the other peaks (5 20%) are those
3
2
2
of C F ions (n = 1 6, m = 3 13, odd m). Since per-
b m
fluorocarbons typically give in the mass spectra the
[M F] ion and ions corresponding to successive
+
loss of CF up to formation of CF , our mass spectra
2
3
19
confirm formation of perfluorohexanes. Liquid prod-
ucts were fractionated at 50 86 C. The F NMR
19
65.8 and
F
spectra of all the fractions show signals at 75 to 85
(CF ), 110 to 130 (CF ), and 185 to 190 ppm
f
5
3
2
(CF). The presence of several CF signals suggests
3
19
formation of both linear (CF CF ,
80 to
70 to
fies; its F NMR spectrum contains a very broad
134 ppm. These data confirm formation
of perfluorocyclohexane VI (mp 51 C, bp 52 C [13];
3
2
CF
3
CF
85 ppm) and branched [(CF ) CF,
signal at
3 2
F
75 ppm] perfluoroalkanes; the presence of3branched
perfluoroalkanes is also confirmed by the CF signal at
185 to 190 ppm. As judged from the boiling points,
the major ECF products of II are linear and branched
perfluoroalkanes C C . The downfield region of the
133.25 ppm [14]). The large width of the signal is
F
due to mutual transformations of conformers of VI
[15]; the signal width varies by two orders of magni-
tude with temperature [13]. Perfluorocyclohexane VI
is formed by ECF of various aromatic compounds,
including thiophenol [16]. Formation of perfluoro-
alkylperfluorocyclohexanes VII and VIII is confirmed
by the presence of CF in the C NMR spectrum
(doublets of multiplets at 96 ppm for VII and at
88 ppm for VIII) and, in the case of VIII, of a quartet
of triplets at 116.6 ppm belonging to the CF gorup.
The presence of perfluoroethylperfluorocyclohexane
VIII was confirmed by GLC and by comparison of
the C and F NMR spectra with those of an authen-
6
7
19
F NMR spectrum of the fraction with bp 80 85 C
contains signals at 46.62 and 61.20 ppm (intensity
ratio 4 : 1, J 138.8 Hz) belonging, apparently, to
pentafluoro(1,1,2,2,3,3,3-heptafluoropropyl)- -sul-
fane C F SF . The F NMR spectrum of the fraction
with bp 100 C contains signals at
61 ppm (J 137.7 Hz), belonging, apparently, to
equatorial and axial fluorine atoms of the SF group
F
FF
13
6
19
3 7
5
42.82 and
F
3
FF
5
in C F SF . The signal at
= 28.09 ppm, character-
istic of the SF group [12], belongs, apparently, to
tetrafluoro[bis(1,1,2,2,3,3,3-heptafluoropropyl)]-
5 11
5
F
13
19
4
6
tic sample. The content of VIII in the product mixture
is 19.3%. The F NMR spectrum is a complex set of
-
19
sulfane (CF CF CF ) SF . These data indicate that
3
2
2 2
4
multiplets (see figure). Consideration of the chemical
shifts, multiplicities, and integral intensities of signals
ECF involved desulfuration with formation of linear
and branched C C perfluorocarbons, and also oxida-
6
8
19
and comparison with the F NMR spectrum of VII
tion of sulfur.
[17] lead to the following assignments, , ppm: CF
F
3
2
In the experiment on ECF of III, we analyzed only
the gaseous products by IR spectroscopy. Similar to
ECF of I and II, HF, CF , SF , SF , SOF , and
2
3
3
83.51 d.t.t, 3F, J 2.3, J 14.0, J 12.8 Hz; CF
3
4
118.13 t.t, 2F, J 15.8, J 21.5 Hz; CF 187.97 m,
3
4
8
2
4
4
6
2
1F, J 15.0 Hz; C F , C F
120.67 d.m, 2F, J
eq
eq
SO F are formed, i.e., the reaction involves oxidation
2 2
5
7
2
303.0 Hz; C F , C F
124.11 d.m, 2F, J 288.5 Hz;
of sulfur and cleavage of the C S bonds. Electrochem-
ical fluorination of IV occurs with complete saturation
and desulfuration and is accompanied by fragmenta-
tion, yielding perfluorocarbons of the cyclohexane
series:
eq
eq
6
2
3
4
C F
126.05 d.m, 1F, J 289.4, J 7.0 Hz; C F ,
ax
eq
ax
8
2
5
7
C F
131.78 d.m, 2F, J 303.0 Hz; C F , C F
ax
ax
2
6
141.7 d.m, 2F, J 288.5 Hz; C F
1F, J 289.4, J 7.0 Hz.
144.37 d.m,
ax
2
3
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 7 2002

ELECTROCHEMICAL FLUORINATION OF UNSATURATED SULFIDES AND SULFONES
1097
F, ppm
F NMR spectrum of perfluoroethylperfluorocyclohexane: (1) total, (2) CF , (3) CF , (4) C F , (5) C
19
6
4(8)
5(7)
F
, (6) C
F ,
eq
3
2
eq
eq
4(8)
5(7)
6
(7) C
F
, (8) C
F , (9) C F , and (10) CF.
ax ax
ax
The compounds studied in this work differ from
the previously studied alkanethiols, dialkyl sulfides,
and dialkyl sulfones in that, in ECF of unsaturated
sulfides and sulfones, the yield of sulfur-containing
organic compounds is extremely low. For example, in
ECF of vinyl sulfides, perfluoroalkyl derivatives of
sulfur hexafluoride R SF and R SF R , which are
typical products of ECF of saturated S(II) derivatives
[1 6], are formed in minor amounts. As for S(VI)
derivatives, it is noted in the literature that the S=O
bonds show very high stability in the process, which
opens up possibilities for commercial synthesis of
trifluoromethanesulfofluoride and, starting from this
compound, of the whole class of triflates. However,
this is true only for the lower representatives of this
series. The yield of perfluoroalkanesulfonyl fluorides
R SO F in ECF oof sulfonyl chlorides RSO Cl de-
f 2 2
creases in the order R = C C from 87 to 25% [18].
1
8
In unsaturated sulfones, as shown by the example of
IV, the ECF products contain virtually no organic
sulfonyl detivatives. An increased tendency of unsatu-
rated sulfides and sulfones to undergo desulfuration in
ECF is probably due to the fact that the C=C bond is
fluorinated more readily than the C H bond. In the
first stage of ECF of S(II) derivatives, S(II) is oxi-
dized to S(VI) [5]. Then, in the case of saturated
sulfides, an -centered radical is formed, and, in the
case of unsaturated sulfides, the fluorine atom can add
to the -C atom with subsequent -scission, which
increases the probability of formation of desulfuration
products. The general scheme of the process can be
represented as follows:
f
5
f
4 f
.
.
F
.
..
F
_
2
F
R S C
H
R SF4
C
R SF4 C
R SF4
C
RfSF4Rf,
HF
H
.
F
.
F
2
R S C= C
H
R SF4 C=C
H
R SF4 C C
F
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 7 2002

1098
GRIGOR’EVA et al.
.
.
.
-Scission
F
F
RSF4
RSF5
RfF + RfRf + SF6,
_
.
SF
.
F
4
R
RfF + RfRf.
(3)
To examine the possibility of fluorination of vinyl
sulfides and vinyl sulfones on dissolution in HF prior
to ECF, compounds III V were treated with anhy-
drous HF. We found that sulfone IV in which the
vinyl group shows a decreased reactivity toward elec-
trophilic agents due to the electron-withdrawing effect
of the sulfonyl group does not react with HF even
at 90 C (4 h). At the same time, sulfides III and V,
when brought in contact with anhydrous HF, undergo
transformations, probably due to the catalytic effect of
HF as acid. For example, divinyl sulfide, when kept
in HF at room temperature for several hours, polymer-
izes to give a light creamy powdered polymer contain-
ing 36% sulfur and 5% fluorine; prolonged heating
does not change the chemical composition of the
polymer, which indicates that the polymer contains
chemically bound fluorine rather than adsorbed HF.
The polymer is insoluble in organic solvents (benzene,
(1.0 3.5 ppm) protons, intensity ratio 5 : 4. Accord-
ing to elemental analysis, the product contains no
fluorine. These facts suggest oligomerization of the
+
initially formed [PhSCHCH ] ion with the formation
3
of oligomers of the composition close to (PhSC H ) .
2
4 n
We failed to isolate or identify any individual prod-
ucts.
EXPERIMENTAL
The IR spectra of the products in the liquid phase
were taken on an IKS-29 spectrometer in a thin film.
1
13
19
The H, C, and F NMR spectra were measured
on a Bruker DPX 400 spectrometer (400, 100, and
376 MHz, respectively) with neat samples, external
reference DMSO-d ; the chemical shifts are given
6
1
13
19
relative to TMS ( H, C) and CFCl ( F). The GC
3
MS analysis was performed with an LKB 2091 device
(EI, 70 eV), and GLC analysis, on a Tsvet-100 chro-
matograph [thermal conductivity detector, carrier gas
helium, 3000 3-mm columns, stationary phase 20%
, , -tris( -cyanoethyl)acetophenone on Silochrom-
80 (France)].
methanol, dichloroethane, CCl , DMSO, DMF) and
4
decomposes on heating above 290 C, which suggests
its cross-linked structure. We propose the following
structure of the polymers (n = 3 on the average):
]
CH2 CH
[
CH2 CH
S
The IR spectra of gaseous electrolysis products
were recorded on a Specord-20M spectrometer in a
10-cm Monel metal cell with AgCl windows. The GC
analysis was performed with an LKhM-80 chromato-
graph (thermal conductivity detector, carrier gas heli-
S
CH2 CH
CHF CH3
n
Under similar conditions, phenyl vinyl sulfide
gives products containing no vinyl group. After treat-
ment of the reaction mixture with chloroform, remov-
al of excess HF with NaF, distillation of the solvent,
and evacuation, we obtained a blue-green viscous oil,
from which we isolated by distillation thiophenol,
which is probably formed by addition of HF, followed
by protonation of sulfur and scission of the C S bond
with the release of volatile fluorocarbons:
um, 3000 3-mm columns, sorbent MgF -17, particle
2
diameter 0.25 0.5 mm).
Electrochemical fluorination was performed in a
3
150 cm cylindrical cell made from St.3 steel and
equipped with a reflux condenser and with stopcocks
for supplying HF and removing liquid fluorination
2
products; surface area of the nickel anode 54 cm . The
reflux condenser was kept at 35 C with HCFC 22 as
coolant.
HF
PhS CH CH2
[PhSCHF CH3]
Electrochemical fluorination of I IV was per-
formed as follows.
_
+
+
H
F
PhS CHF CH3
PhSH + [CH3CHF2].
Ethyl vinyl sulfide I. An electrochemical cell was
filled with 125 ml of anhydrous HF, and 10 g of di-
vinyl sulfide was added. Electrolysis was performed
at 14 16 C for 38 h (38 A h) at the anodic current
density of 2 A dm and cell voltage of 4.4 4.8 V.
Electrolysis gases from the reflux condenser were
H
1
The residue is a complex mixture; its H NMR
spectrum contains no signals from vinyl proton of the
initial compound but contains complex multiplets in
the range of aromatic (7.1 7.8 ppm) and aliphatic
2
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 7 2002

ELECTROCHEMICAL FLUORINATION OF UNSATURATED SULFIDES AND SULFONES
1099
sampled into an IR cell. IR spectrum of the gas,
,
at 14 16 C for 45 h (45 A h) at the anodic current
2
1
density of 2 A dm and cell voltage of 5.7 7.6 V. IR
cm : 3700 4000 (HF); 1502, 1269, 848, 885, 925
(O F ); 1300, 1290, 1250, 1120, 715 (C F ); 900,
1
spectrum of gaseous electrolysis products, , cm :
2 2
2 6
3700 4000 (HF); 1502, 1269, 848, 885, 925 (SO F );
830, 610 (SF , SF ); 828, 930 (F O). Gaseous sam-
2 2
4
6
2
1300, 1290, 1250, 1120, 715 (C F ); 828, 930 (F O);
ples for GC analysis were passed through aqueous KI.
2 6
2
900, 830, 610 (SF , SF ).
The following products were identified by GC: CF ,
4
6
4
C F , C F , C F , SO F , and SF . High-boiling
2 6
3 8
4 10
2 2
6
Phenyl vinyl sulfone IV. A 20-g portion of phenyl
vinyl sulfone was placed in an electrochemical cell,
and 125 ml of anhydrous HF was added. Electrolysis
was performed at 14 16 C for 64 h (64 A h) at the
fluorination products (1.6 g) were removed through
the stopcock on the electrolyzer bottom into a poly-
ethylene vessel filled with water. Found, %: C 19.46,
H 0.58, F 70.86, S 6.24. By distillaiton, we isolated
a fraction with bp 30 35 C, consisting mainly of
2
anodic current density of 2 A dm and cell voltage
of 5.5 6.6 V. IR spectrum of gaseous electrolysis
20
15
dodecafluoropentane, n
1.2805 (bp 29.3 C, n
1
D
D
products, , cm : 3700 400 (HF); 2320, 2350 (CO,
1.2411 [9]). The IR spectrum is in agreement with
CO ); 1502, 1269, 848, 885, 925 (SO F ); 1300,
19
2
2 2
2
published data [10]. F NMR spectrum, , ppm:
F
1290, 1250, 1120, 715 (C F ); 828, 930 (F O). CF ,
2 6
4
84.2 (CF ), 125.3 (CF CF CF ), 128.9 (CF CF ).
3
2
C
2
2
3
2
C F , CO , and SO F were identified by GC. The
13
1
2 6
2
2 2
C NMR spectrum,
, ppm: 116.2 q.t (CF CF ,
3 2
heavy fluorination products (8.74 g) were discharged
into a polyethylene vessel filled with water. Found,
%: C 17.2, H 0.80, F 66.41, S 2.92.
2
J
286.5, J 34.0 Hz), 109.4 m (CF CF CF ).
CF
CF
2
2
2
The fraction contains a minor amount of pentafluo-
ro(1,1,2,2,2-pentafluoroethyl)- -sulfane.
6
19
F NMR
The mixture was separated by fractional distilla-
tion. The fraction with bp 38 48 C solidifies on
cooling and mainly consists of perfluorocyclohexane
spectrum, , ppm: 83.54 [CF , J(CF SF ) 9 Hz],
F
2
3
3
4
4
100.1 [CF , J(CF F ) 13 Hz], 46.53 d (SF ), 64.15
2
eq
quintet [J(F F ) 143 Hz].
ax eq
19
VI. F NMR spectrum, , ppm: 134 br.s. The frac-
F
Di(propen-1-yl) sulfide II was treated similarly
to I. Electrolysis was performed with a 30-g portion
of II at 14 16 C for 122 h (122 A h) at the anodic
tion with bp 50 70 C contains perfluoromethylper-
fluorocyclohexane VII. F NMR spectrum, , ppm:
188.7 m (CF), J(CF CF) 14.7 Hz. The fraction
with bp 68 80 C mainly consists of perfluoroethylper-
19
F
3
2
2
current density of 2 A dm and cell voltage of 5.3
6.8 V. IR spectrum of gaseous electrolysis products,
13
fluorocyclohexane VIII. C NMR spectrum (DMSO-
1
, cm : 3700 4000 (HF); 1502, 1269, 848, 885, 925
1
2
d , , ppm: 116.26 q.t, CF , J 287.12, J 33.17 Hz;
6
C
3
(SO F ); 1300, 1290, 1250, 1120, 715 (C F ); 828,
2 2
2 6
4
2
3
103 112 m, CF ; 87.42 d.sept, J 218.93, J 25.8 Hz.
2
930 (F O); 900, 830, 610 (SF , SF ). CF , C F ,
2
4
6
2 6
CO , and SO F were identified by GC. Heavy fluo-
Reactions of III V with HF were performed as
follows.
2
2 2
rination products (7.35 g) were discharged into a poly-
ethylene vessel filled with water. Found, %: C 21.2,
3
Phenyl vinyl sulfide III. Into a 100 cm stainless
H 0.76, F 62.65, S 2.10. The mixture of liquid prod-
19
steel autoclave, 3 5 ml of HF was condensed, and
3.0 g of III was added. The autoclave was kept at
room temperature for 5 h. The mixture was diluted
with 50 ml of chloroform and purged with air, after
which NaF was added to pH 7.0. The solution was
filtered and evaporated. From the resulting green vis-
cous oil, 0.5 g of thiophenol was isolated by vacuum
ucts was fractionated. Fraction with bp 50 60 C.
F
NMR spectrum, , ppm (the most intense signals are
F
given): 74.96, 75.17 (iso-CF ), 83.80, 84.17
3
(n-CF ), 108.54, 127.64, 128.79 (CF ), 185.66,
3
2
19
188.70 (CF). Fraction with bp 84 86 C. F NMR
spectrum, , ppm: 46.62, 61.20 (SF ), 73.00,
74.86, 75.09 (iso-CF ), 83.85, 84.07, 84.15
F
5
3
1
distillation (bp 50 C/23 mm Hg). H NMR spectrum,
(n-CF ),
114.06,
114.90,
122.75,
124.97,
3
, ppm: 3.54 s (SH, 1H), 7.21 m (p-CH, 1H), 7.29 m
126.58, 128.39 (CF ), 184.87, 185.18, 187.46,
2
13
13
188.40 (CF). The C NMR spectra of all the frac-
(m-CH, 2H), 7.33 m (o-CH, 2H). C NMR spectrum,
tions contain doublets of multiplets in the range 90
92 ppm (CF), multiplets in the range 104 112 ppm
(CF ), and signals of two types of CF groups:
, ppm: 125.16 (C ), 128.99 (C ), 130.44 (C ). The
blue-green residue was analyzed by NMR. Found, %:
C 73.10, H 6.74, S 20.66.
C
p
o
1
2
3
1
2
118.11 q.d [CF CF, J 288.8, J 22.5 Hz] and
3
CF
CF
Phenyl vinyl sulfone IV. a. Similarly to the above
procedure, 1.1 g of IV was added to HF. The auto-
clave was heated at 90 C for 4 h. Then 50 ml of chlo-
roform was added, the mixture was purged with air,
1
2
116.61 q.t [CF CF ,
J
286.5,
J
34.4 Hz].
3
2
CF
CF
Phenyl vinyl sulfide III was treated similarly.
Electrolysis was performed with a 18-g portion of III
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 7 2002

1100
GRIGOR’EVA et al.
and NaF was added to pH 7.0. The solution was fil-
tered and evaporated to dryness, and the residue was
vacuum-dried (1 mm Hg). The initial sulfone IV
2. Dresdner, R.D. and Young, J.A., J. Am. Chem. Soc.,
1959, vol. 81, no. 3, pp. 574 577.
3. Drasdner, R.D., Reed, T.M., III, Taylor, T.E., and
Young, J.A., J. Org. Chem., 1960, vol. 25, no. 8,
pp. 1464 1466.
4. Abe, T., Nagase, S., and Baba, H., Bull. Chem. Soc.
Jpn., 1973, vol. 46, no. 12, pp. 3845 3848.
1
(0.8 g) was recovered; its melting point and the H
13
and C NMR spectra coincided with those of an
authentic sample.
b. Gaseous HF was passed for 1.5 h through a solu-
tion of 0.84 g of IV in 30 ml of dry benzene, cooled
with ice to 12 16 C. The mixture was purged with air
under stirring, and NaF was added to pH 7.0. The
solution was filtered and evaporated to dryness. The
initial sulfone IV (0.5 g) was recovered; its melting
5. Baba, H., Kodaira, K., Nagase, S., and Abe, T., Bull.
Chem. Soc. Jpn., 1977, vol. 50, no. 10, pp. 2809
2810.
6. Baba, H., Kodaira, K., Nagase, S., and Abe, T., Bull.
Chem. Soc. Jpn., 1978, vol. 51, no. 6, pp. 1891 1892.
7. Rozhkov, I.N., Bukhtiarov, A.V., and Knunyants, I.L.,
Izv. Akad. Nauk SSSR, Ser. Khim., 1969, no. 4,
pp. 945 947.
1
13
point and the H and C NMR spectra coincided with
those of an authentic sample.
8. Organicheskaya elektrokhimiya (Organic Electro-
chemistry), Petrosyan, V.A. and Feoktistov, L.G.,
Eds., Moscow: Khimiya, 1988.
9. Riyadh, S.M., Ishii, H., and Fuchigami, T., Tetrahed-
ron Lett., 2001, vol. 42, no. 16, pp. 3009 3011.
10. Maksimov, B.N., Barabanov, V.G., Serushkin, I.L.,
et al., Promyshlennye ftororganicheskie produkty
(Commercial Organofluorine Products), St. Peters-
burg: Khimiya, 1996.
Divinyl sulfide V. Into a stainless steel autoclave,
3 5 ml of HF was condensed, and 4.44 g of cooled
sulfide V was added. The mixture was kept at room
temperature for 24 h. A light creamy powdered poly-
mer (4.48 g) was obtained. Found, %: C 51.35, H
6.72, F 5.90, S 36.02. Found after heating at 50 C for
24 h, %: C 50.33, H 6.52, F 5.10, S 36.34.
CONCLUSIONS
11. Fluorine Chemistry, Simons, J.H., Ed., New York:
Academic, 1950, vol. 1.
12. Gmelin Handbook of Inorganic Chemistry, Berlin:
Springer, 1987, 8th ed.
13. Gutowsky, H.S. and Chen, F.-M., J. Phys. Chem.,
(1) Electrochemical fluorination of vinyl sulfides
and sulfones occurs with complete substitution of all
the hydrogen atoms by fluorine, addition of fluorine to
the double bonds and benzene ring, and considerable
desulfuration, yielding perfluorocarbons as major
products, and also perfluoroalkyl derivatives of sulfur
hexafluoride and fragmentation products.
1965, vol. 69, no. 9, pp. 3216 3219.
14. Gordon, A.J. and Ford, R.A., The Chemist’s Compan-
ion. A Handbook of Practical Data, Techniques, and
References, New York: Wiley, 1972.
(2) With no current applied, vinyl sulfones do not
react with anhydrous HF even on prolonged heating,
whereas vinyl sulfides take up HF (electrophilic addi-
tion to the double bond) with the subsequent scission
of the C S bond or polymerization.
15. Tiers, G.V.D., Proc. Chem. Soc., 1960, pp. 389 390.
16. Inoue, Y., Nagase, S., Kodaira, K., et al., Repts. Govt.
Ind. Res. Inst. Nagoya, 1973, vol. 22, no. 11, pp. 424
429.
17. Feeney, J. and Sutcliff, L.H., Trans. Faraday Soc.,
1960, vol. 56, no. 11, pp. 1559 1569.
18. Gramstad, T. and Haszeldine, R.N., J. Chem. Soc.,
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1957, no. 6, pp. 2640 2645.
1. Hoffmann, F.W., Simmons, T.C., Beck, R.B., et al.,
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3429.
19. Trofimov, B.A. and Amosova, S.V., Divinilsul’fid i
ego proizvodnye (Divinyl Sulfide and Its Derivatives),
Novosibirsk: Nauka, 1983.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 7 2002