1
014
KOSHCHEEV et al.
1
19
1
The H and F NMR spectra were recorded on
4 Hz), 108.8 m, 119.9 d.d.t (CHF , J = 292, 284,
2
CF
4
1
a Bruker AV-300 spectrometer at 300 and 282.4 MHz,
respectively, using carbon tetrachloride containing
some CDCl as solvent; the chemical shifts were
measured relative to hexafluorobenzene ( F) or hexa-
methyldisiloxane ( H, δ 0.04 ppm downfield from
J
≈ 4 Hz), 140.2 d.m (CF, J = 253 Hz), 143.4 t.t
( J ≈ 11, J ≈ 4 Hz), 146.2 d.d.d.d (CF, J = 255,
JCF = 13, J ≈ 8, J ≈ 4 Hz). F NMR spectrum,
δ , ppm: 7.1 m (2F, 3-F, 5-F), 23.3 m (2F, 2-F, 6-F),
F
CF CF
2
3
1
CF
CF
CF
2
3
4
19
3
CF CF
1
9
1
2
2
5
43.4 d.t (CHF , J = 268, J = 56, J ≈ 4 Hz),
2 FF FH FF
1
3
2
2
5
TMS). The C NMR spectra were recorded on the
46.5 d.t (CHF , J = 268, J = 55, J = 5 Hz).
2 FF FH FF
same instrument at 100.6 MHz using CDCl as solvent
Found, %: C 34.25; H 1.56; F 41.21; S 11.25.
3
+
and tetramethylsilane as internal standard. The IR
spectra were measured on a Bruker Vector 22 IR in-
strument. The UV spectra were recorded on a Hewlett
Packard 8453 UV spectrophotometer. The molecular
weights and elemental compositions were determined
from the mass spectra (electron impact, 70 eV) which
were obtained on a Thermo Electron Corporation DFS
instrument. Gas chromatographic–mass spectrometric
analysis was performed using an HP 5890 gas chro-
matograph coupled with an HP 5971 mass-selective
detector (electron impact, 70 eV; HP-5 column,
m/z 277.9832 [M] . C H F O S. Calculated, %:
8
4
6
2
C 34.54; H 1.45; F 40.98; S 11.53. M 277.9831.
1-Difluoromethanesulfinyl)-2,3,5,6-tetrafluoro-
-phenoxybenzene (3). A ~0.6 M solution of sodium
(
4
phenoxide in water, 12.7 mL (7.87 mmol), was added
dropwise with stirring to a mixture of 2.01 g
(
7.48 mmol) of sulfoxide 1 and 40 mL of water, heated
to 42°C. Water, 10 mL, was then added, and the mix-
ture was stirred for 24 h at 42–50°C (oil bath). The
mixture was cooled to room temperature, and the pre-
cipitate was filtered off, washed with water, and dried
in air. Yield 2.41 g (94%), white solid, mp 74–76°C.
UV spectrum (CHCl ), λ , nm (logε): 267 (3.96),
3
0 m×0.25 mm, film thickness 0.25 μm; carrier gas
helium, flow rate 1 mL/min; oven temperature prog-
ramming from 50 to 280°C; ion source temperature
3
max
–
1
2
1
1
72 (3.96). IR spectrum (KBr), ν, cm : 2985, 1637,
1
73°C). Gas chromatographic analyses were obtained
591, 1493, 1483, 1458, 1392, 1296, 1211, 1165, 1130,
with an HP 5890 chromatograph equipped with a ther-
mal conductivity detector (HP-5 column, 30 m×
095, 1076, 1024, 982, 760, 729, 711, 688, 660, 507,
1
4
78, 440. H NMR spectrum, δ, ppm: 6.83 d.d (CHF ,
2
2
13
0
.52 mm, film thickness 2.6 μm; oven temperature
programming from 40 to 280°C, detector temperature
80°C; carrier gas helium, flow rate 5 mL/min). The
melting points were determined on a Kofler hot stage.
-(Difluoromethanesulfinyl)-2,3,5,6-tetrafluoro-
-methoxybenzene (2). A ~0.36 M solution of sodium
JHF = 56, 55 Hz), 7.16 m (5H, Harom). C NMR
spectrum, δ , ppm: 112.2 m, 115.9 s (CH), 119.9 d.d.t
C
1
4
2
(
CHF , J = 293, 285, J ≈ 4 Hz), 124.6 s (CH),
2 CF CF
2
3
129.9 s (CH), 139.1 t.t ( J ≈ 12, J ≈ 4 Hz),
41.5 d.d.d (CF, J = 258, J ≈ 12, J ≈ 5 Hz),
46.1 d.d.d.d (CF, J = 257, J = 12, J ≈ 7,
CF CF
JCF ≈ 4 Hz), 156.3 s. F NMR spectrum, δ , ppm:
CF
CF
1
2
3
1
1
CF CF CF
1
2
3
1
4
CF
19
4
methoxide in methanol, 15.5 mL (5.58 mmol), was
added with stirring over a period of 2 min at 24–30°C
to a solution of 1.50 g (5.58 mmol) of sulfoxide 1 in
F
1
1.8 m (2F, 3-F, 5-F), 24.2 m (2F, 2-F, 6-F), 43.4 d.t
2
2
5
(CHF , J = 269, J = 56, J = 3 Hz), 47.4 d.t
2 FF FH FF
2
2
5
(CHF , J = 269, J = 55, J = 4 Hz). Found, %:
7
mL of methanol. The mixture was stirred for 3 h, the
2
FF
FH
FF
+
C 45.82; H 1.83; F 33.63; S 9.14. m/z 339.9988 [M] .
C H F O S. Calculated, %: C 45.89; H 1.78; F 33.50;
solvent was distilled off, and the residue was washed
with methylene chloride (2×5 mL). The undissolved
material was separated, and the solvent was distilled
off. Yield 1.34 g (78%), purity 90% (GLC). The crude
product was distilled under reduced pressure (2 mm),
gradually raising the oil bath temperature to ~140°C.
Three fractions were isolated: first fraction, 0.23 g,
bp 122–131°C, purity 95%; second fraction, 0.53 g,
bp 132–137°C, purity 98%; third fraction, 0.06 g,
bp 137–139°C, purity 98% (GLC). Colorless liquid.
13
6
6
2
S 9.42. M 339.9987.
Pentafluorobenzene (4). A solution of 1.47 g
(36.75 mmol) of sodium hydroxide in 5 mL of water
was added at 20–23°C to a solution of 1.91 g
(7.00 mmol) of sulfoxide 1 in 18 mL of acetonitrile.
The mixture was stirred for 3 h and poured into
200 mL of water (two layers were formed). The bottom
layer was separated and dried over CaCl . Yield 0.70 g
2
1
UV spectrum (EtOH): λ
spectrum (film), ν, cm : 2966, 1635, 1504, 1487,
226 nm (logε 3.97). IR
(57%). H NMR spectrum: δ 6.86 ppm, m (6-H) [12].
max
1
–
13
2
C NMR spectrum, δ , ppm: 100.6 t.d (CH, J = 23,
C CF
1
5
2
4 1
1
7
439, 1396, 1286, 1269, 1196, 1119, 1076, 993, 947,
JCF = 3 Hz), 137.6 d.d.d.d.d (C , C or C , C , J
251, J = 18, 13, 5, 1 Hz), 141.8 d.t.t (C , J = 254,
JCF = 13, J = 5 Hz), 146.2 d.t.t (C , C or C , C ,
JCF = 249, JCF ≈ 12, JCF ≈ 4 Hz). F NMR spectrum,
=
CF
1
3 1
91, 509, 449. H NMR spectrum, δ, ppm: 4.21 t
CF
CF
5
2
2
1
3
2
4
1
5
(
OCH , J = 2 Hz), 6.80 d.d (CHF , J = 56, 55 Hz).
3
HF
2
CF
1
3
4
19
C NMR spectrum, δ , ppm: 62.0 t (OCH , J ≈
C
3
CF
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 7 2017