BREDIKHIN et al.
1556
refined in the riding model. The crystallographic data
were deposited in the Cambridge Crystallographic
Data Center.
1.794 g/cm3. 3595 indepen-dent reflections (θmax
28.7°), among them 2786 observed reflections. Final
refinement parameters R 0.0394, S 0.984 (CCDC
1405717).
Commercial reagents and solvents were used
without special purification. Fluorodichloromethane 6
was a technical product from a gas cylinder. Initial
polyfluoroarenethiols of 97–99% purity (GLC data)
were obtained by procedure [19], thiol 8 of 91% purity
contained an impurities of 1-chloro-2,3,5,6-tetrafluoro-
4-trifluoromethylbenzene (6%) and 1-chloro-2,3,4,5-
tetrafluoro-6-trifluoromethylbenzene (2%).
19F NMR spectra of obtained 1,2,4,5-tetrafluoro-
benzene 5a [20], pentafluorobenzene 5b [21], 3-
chloro-1,2,4,5-tetrafluorobenzene 5c [22], 1,2,4,5-tet-
rafluoro-3-trifluoromethylbenzene 5d [23] are consis-
tent with the published data.
Chloromethyl 2,3,5,6-tetrafluorophenyl sulfide
(3) [6] was identified in the reaction mixture. 1H NMR
spectrum, δ, ppm: 4.90 s (2H), 7.27 m (1Harom). 19F
NMR spectrum, δ, ppm: 24.6 m (2F3,5), 28.9 m (2F2,6).
GC-MS: M 230.
1-(Dichloromethyl)-2,3,5,6-tetrafluoro-4-[(2,3,5,6-
tetrafluorophenyl)sulfanyl]benzene (13). The reac-
tion mixture obtained from 0.21 g (1.15 mmol) of thiol
1a, 0.29 g (1.16 mmol) of benzyl chloride 11, and 0.17
g (1.23 mmol) of K2CO3 in 2.0 mL of DMF was stirred
for 5 h at 22°C and treated as described above. Yield
0.37 g (0.90 mmol) (78%). Colorless crystals, mp 40–
42°C (EtOH). Purity 97% (GC-MS). IR spectrum, ν,
cm–1: 3087, 1631, 1495, 1481, 1441, 1398, 1381, 1311,
1281, 1236, 1219, 1178, 1128, 1055, 968, 920, 893,
849, 775, 712, 602. UV spectrum, λmax, nm (log ε): 203
(4.19), 287 (3.79). 1H NMR spectrum, δ, ppm: 6.92 s (1H,
CHCl2), 7.14m (1H, Harom). 19F NMR spectrum, δ, ppm:
22.4 m (2F3,5), 25.2 m (2F3',5'), 29.3–29.5 m (4F2,2',6,6').
Mass spectrum, m/z (Irel, %): 414 (14) [M + 2]+, 412
(19) [M]+, 379 (35) [M + 2 – Cl]+, 378 (14) [M + 1 –
Cl]+, 377 (100) [M – Cl]+, 228 (10), 188 (8), 161 (8).
Found, %: C 37.58; H 0.41; Cl 16.96; F 37.08; S 7.75.
[M]+ 411.9117. C13H2Cl2F8S. Calculated, %: C 37.80;
H 0.49; Cl 17.16; F 36.79; S 7.76. [M]+ 411.9121.
Reactions of thiol (1а) with dichloromethane,
compounds (11 and 12), and of thiol (1b) with
compound (15). To a solution of the reagent in DMF
in the presence of potassium carbonate thiol 1a or 1b
was added. The reaction mixture that turned yellow-
green [7] was stirred with a magnetic stirrer at 20°C,
observing a gradual disappearance of the coloration.
On the completion of the reaction the mixture was
poured into a 5-fold greater volume of 5% HCl
solution. The organic product was separated and
purified by crystallization from EtOH (2, 13, and 16)
or by sublimation in a vacuum (14).
Bis(2,3,5,6-tetrafluorophenylsulfanyl)methane (2).
From 1.97 g (10.82 mmol) of thiol 1a, 0.46 g (5.41 mmol)
of dichloromethane, and 1.53 g (11.09 mmol) of K2CO3
in 10.0 mL of DMF after 7 days 1.90 g (5.05 mmol) of
compound 2 was obtained. Yield 93%. Colorless
crystals. Purity 99.8% (GLC), mp 62–64°C (EtOH). IR
spectrum, ν, cm–1: 3109, 3082, 1630, 1616, 1493,
1,2,4,5-Tetrafluoro-3-[(2,3,5,6-tetrafluorophe-
nyl)sulfanyl]-6-(trichloromethyl)benzene (14). A mix-
ture of 0.24 g (1.29 mmol) of thiol 1a, 0.38 g (1.30 mmol)
of compound 12, and 0.18 g (1.30 mmol) of K2CO3 in
2.0 mL of DMF was stirred for 5 h at 22°C and treated
as described above. Yield 0.47 g (1.05 mmol) (81%).
Light yellow liquid. IR spectrum, ν, cm–1: 3082, 1632,
1495, 1470, 1441, 1383, 1281, 1236, 1178, 1132,
1435, 1379, 1232, 1176, 918, 847, 710. UV spectrum,
1
1
λ
max, nm (log ε): 209 (4.20), 277 (4.02). H NMR
1045, 985, 922, 825, 783, 727, 714, 702. H NMR
spectrum, δ, ppm: 7.16 t.t (JH-F3',5' 9, JH-F2',6' 7 Hz). 19F
NMR spectrum, δ, ppm: 25.3 m (2F3',5'), 29.0 m (2F),
29.1 m (2F), 29.6 m (2F). Found [M]+ 445.8735.
C13HCl3F8S. Calculated [M]+ 445.8731.
spectrum, δ,ppm: 4.42 s (2H), 7.16 t.t (2Harom, JH-F3,5
9.5, JH–F2,6 7.2 Hz). 19F NMR spectrum, δ, ppm: 24.2 m
(4F3,3',5,5'), 28.5 m (4F2,2',6,6'). Mass spectrum, m/z (Irel,
%): 376 (8) [M]+, 195 (100) [M – HC6F4S]+, 181 (4)
[M – HC6F4SCH2]+, 163 (4) [M – C6HF4S2]+, 137 (6)
[M – C8H3F4S2]+. Found, %: C 41.45; H 1.06; F 40.60;
S 16.90. [M]+ 375.9621. C13H4F8S2. Calculated, %: C
41.49; H 1.07; F 40.39; S 17.04. [M]+ 375.9621.
2,3,4,5,6-Pentafluorobenzyl pentafluorophenyl
sulfide (16). A mixture of 1.01 g (5.05 mmol) of thiol
1b, 1.10 g (5.08 mmol) of compound 15, and 0.70 g
(5.07 mmol) of K2CO3 in 10 mL of DMF was stirred
for 4.5 h at 22°C and treated as described above. We
obtained 1.85 g of white precipitate containing accor-
ding to GC-MS data 94% of compound 16. Yield 90%.
XRD analysis. Monoclinic system, space group
P21/с. C13H4F8S2, M 376.28, a 14.8264(9), b 5.2109(3),
c 18.032(1) Å, β 90.736(2)°, V 1393.0(2) Å3, Z 4, dcalc
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 11 2015