1464
SHAINYAN et al.
Bond lengths (d) and bond angles ( ) in the molecule of
methyl 3,3,6,6-tetrafluoro-1,4-cyclohexadienyl sulfone (IV)
2-Fluorophenyl methyl sulfone (IIa). 13C NMR
spectrum, C, ppm: 43.68 d (CH3, JC, F = 2.6 Hz),
4
2
4
117.02 d (C3, JC, F = 21.1 Hz), 124.71 d (C5, JC, F
=
3.9 Hz), 128.84 d (C1, JC, F = 29.2 Hz), 130.10 d (C6,
Bond
d,
Bond
d,
2
3JC, F = 9.9 Hz), 136.12 d (C4, JC, F = 8.2 Hz),
3
S O1
S O2
S C1
S C7
F1 C2
F2 C2
F3 C5
1.428(2)
1.422(2)
1.789(2)
1.750(2)
1.364(2)
1.360(2)
1.371(3)
F4 C5
C1 C6
C1 C2
C2 C3
C3 C4
C4 C5
C5 C6
1.368(3)
1.320(3)
1.498(3)
1.483(3)
1.306(3)
1.472(3)
1.490(3)
1
159.25 d (C2, JC, F = 254.8 Hz). 19F NMR spectrum:
107.60 ppm, m. Mass spectrum, m/z (Irel, %): 174
F
(31) [M]+ , 159 (20) [M CH3]+, 112 (39) [M
CH2 S O]+ , 95 (100) [C6H4F]+ .
3-Fluorophenyl methylsulfone (IIb). 13C NMR
spectrum, C, ppm: 44.06 s (CH3), 114.50 d (C2,
2
2JC, F = 24.6 Hz), 120.80 d (C4, JC, F = 21.1 Hz),
4
3
123.04 d (C6, JC, F = 3.4 Hz), 131.28 d (C5, JC, F
=
Angle
, deg
Angle
, deg
7.8 Hz), 142.42 d (C1, JC, F = 6.5 Hz), 162.25 d
(C3, JC, F = 252.2 Hz). 19F NMR spectrum:
3
O2S1O1
O2SC7
O1SC7
O2SC1
O1SC1
C7SC1
C6C1C2
C6C1S
C2C1S
F2C2F1
F2C2C3
F1C2C3
117.7(1)
109.7(1)
109.1(1)
107.2(1)
106.5(1)
105.9(1)
121.9(2)
117.6(1)
120.4(1)
104.2(2)
108.8(2)
108.5(2)
F2C2C1
F1C2C1
C3C2C1
C4C3C2
C3C4C5
F4C5F3
F4C5C4
F3C5C4
F4C5C6
F3C5C6
C4C5C6
C1C6C5
110.5(2)
109.2(2)
115.1(2)
122.8(2)
122.3(2)
104.1(2)
110.1(2)
109.0(2)
108.8(2)
108.1(2)
116.1(2)
121.7(2)
1
F
106.82 ppm, m. Mass spectrum, m/z (Irel, %): 174
(38) [M]+ , 159 (41) [M CH3]+, 112 (62) [M
CH2 S O]+ , 95 (100) [C6H4F]+ .
Methyl 3,3,6,6-tetrafluoro-1,4-cyclohexadienyl
1
sulfone (IV). mp 81 82 C. H NMR spectrum,
,
ppm: 3.11 s (3H, CH3), 6.34 m (2H, 4-H, 5-H),
7.23 m (1H, 2-H). 13C NMR spectrum, C, ppm:
43.96 (CH3), 109.19 t (C3, 1JC, F = 232.6 Hz), 109.35 t
1
2
(C6, JC, F = 231.9 Hz), 128.51 t.t (C5, JC, F = 29.3,
3JC, F = 9.1 Hz), 129.50 t.t (C4, JC, F = 30.0, JC, F
=
2
3
9.1 Hz), 136.68 t.t (C2, JC, F = 32.8, JC, F = 5.6 Hz),
2
3
141.67 t.t (C1, JC, F = 28.8, 3JC, F = 8.9 Hz). 19F NMR
2
Electrochemical fluorination of methyl phenyl
sulfone (I). The reaction was carried out in a steel
(St-3) 130-cm3 electrolyzer equipped with nickel
anodes (overall area 63 cm2), tubes with stop-cocks
for supplying HF and discharging fluorination prod-
ucts, and reflux condenser filled with a 1:1 mixture
of acetone and diethyl ether (which was cooled to
20 C with liquid nitrogen). The electrolytic cell was
cooled and charged with 120 g of anhydrous HF, and
2 g of KF and 10 g of methyl phenyl sulfone (I) were
added. The time of electrolysis was 14 h (13.8 A h),
anode current density 1.6 A/dm2, cell voltage 5.8
6.4 V, temperature 5 C. The reaction mixture was
poured into an ice water mixture, NaF was added to
adsorb HF, the mixture was extracted with diethyl
ether, and the extract was dried over CaCl2 and kept
over NaF. The solvent was removed, and the residue
was distilled under reduced pressure, bp 80 90 C
(1 mm). The distillate and the still residue were
passed through a column packed with 25 g of silica
gel (Merck 60s). The column was eluted in succession
with hexane chloroform (1 : 1), chloroform, and
hexane acetone (1:1) to isolate pure sulfone IV and
a mixture of unreacted sulfone I with fluorinated
products II and III.
spectrum, , ppm: 93.49 m (3-F), 93.11 m (5-F).
Found, %: C 36.51; H 2.90; F 32.78; S 14.04.
C7H6F4O2S. Calculated, %: C 36.53; H 2.63; F 33.01;
S 13.93.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002