AMOSOVA et al.
404
added in small portions under stirring to a solution of
4.3 g (50 mmol) of divinyl sulfide in 150 ml of liquid
ammonia. The ammonia was evaporated, 70 ml of
DMF was added, and the resulting solution was added
dropwise to a solution of 47 g (200 mmol) of per-
fluorotoluene in 30 ml of DMF. The mixture was
stirred for 5 h, kept for 12 h at 25°C, diluted with
200 ml of water, and extracted with diethyl ether. The
extract was washed with water, dried over MgSO4, and
evaporated under reduced pressure. The residue was
subjected to fractional distillation under reduced pres-
sure to isolate 28 g of a fraction with bp 53–62°C
(3 mm); repeated fractionation gave 22.4 g (48%) of
2,3,5,6-tetrafluoro-4-trifluoromethylaniline (III) with
bp 50–52°C (3 mm) [10]. IR spectrum, ν, cm–1: 1655,
3428, 3525 (NH2); 1136, 1181, 1239, 1335 (CF3) [11].
Found, %: C 35.85; H 0.91; F 57.61; N 5.82. [M]+ 233.
C7H2F7N. Calculated, %: C 36.07; H 0.86; F 57.05;
N 6.01. M 233. The IR spectrum of 2,3,5,6-tetrafluoro-
4-trifluoromethyl-1-vinylsulfanylbenzene (IV) con-
tained an absorption band at 1592 cm–1 (SC=C).
1H NMR spectrum of IV, δ, ppm: 5.48 d (1H, HB),
10 ml of DMF was added. During the addition, the
mixture slightly warmed up, and it was cooled using
a cold water bath. The mixture was stirred for 5 h, kept
for 12 h at 25°C, diluted with water, and treated with
diethyl ether. The extract was washed with water, dried
over MgSO4, and evaporated under reduced pressure to
leave 3.3 g of a dark brown viscous material which
contained (according to the GC–MS data) 73.5% of
compound VIII and 13.4% of VI. By treatment with
hot hexane and ethanol we isolated 0.17 g (3%) of VI
and 2.4 g (42%) of VIII. IR spectrum, ν, cm–1: 1585
(SC=C); 3001, 3036, 3089 (=C–H); 1135, 1157, 1229,
1
1337 (CF3). H NMR spectrum, δ, ppm: 2.93 d [6H,
N(CH3)2], 5.04 d and 5.07 d (1H each, HB), 5.28 d and
5.31 d (1H each, HA), 6.23 d.d and 6.30 d.d (1H each,
3
3
HX); JBX = 8.4, JAX = 15.4 Hz. 13C NMR spectrum,
δC, ppm: 113.68 and 113.84 (Cβ), 131.24 and 132.01
(Cα). 19F NMR spectrum, δF, ppm: –52.74 d (CF3),
–94.45 d (6-F), –103.92 q.d (3-F). Found: [M]+ 341.
C13H12F5NS2. .Calculated: M 341.
3,6-Difluoro-4-trifluoromethyl-2,5-bis(vinyl-
sulfanyl)aniline (IX). Metallic sodium, 2.3 g
(100 mmol), was added in small portions under stirring
to a solution of 4.3 g (50 mmol) of divinyl sulfide in
100 ml of liquid ammonia. The ammonia was evapo-
rated, 40 ml of DMF was added to the residue, and
argon was bubbled through the mixture. A solution of
4.2 g (18 mmol) of 2,3,5,6-tetrafluoro-4-trifluoro-
methylaniline (III) in 25 ml of DMF was added drop-
wise, and the mixture was stirred for 5 h at 20–25°C,
kept for 12 h at 25°C, diluted with water, and treated
with diethyl ether. The extract was washed with water,
dried over MgSO4, and evaporated under reduced pres-
sure. The residue was 1.2 g of a dark brown liquid. It
was treated with hot hexane, and from the hexane
solution we isolated 1 g (18%) of compound IX. IR
spectrum, ν, cm–1: 1587 (SC=C); 3010, 3085 (=C–H);
3384, 3494 (NH2); 1124, 1162, 1229, 1368 (CF3).
1H NMR spectrum, δ, ppm: 5.04 d and 5.18 d (1H
each, HB), 5.27 d and 5.28 d (1H each, HA), 6.16 d.d
and 6.34 d.d (1H each, HX); 3JBX = 8.4, 3JAX = 15.4 Hz.
13C NMR spectrum, δC, ppm: 113.81 and 114.30 (Cβ),
3
5.51 d (1H, HA), 6.45 d.d (1H, HX), JBX = 8.4,
3JAX = 15.4 Hz. Found: [M]+ 276. C9H3F7S. Calculated:
M 276.
The still residue (4.85 g) was treated with hot
hexane, and the hexane solution was subjected to
column chromatography on aluminum oxide using
hexane as eluent. We isolated 0.5 g (3%) of 3,6-di-
fluoro-4-trifluoromethyl-1,2,5-tris(vinylsulfanyl)ben-
zene (VI) as a light brown liquid and 2 g (2%) of
compound V as a colorless crystalline substance [6].
IR spectrum of VI, ν, cm–1: 864, 876 sh, 982, 1590
(SC=C), 1142, 1179, 1299 (CF3). 1H NMR spectrum of
VI, δ, ppm: 5.23 d, 5.25 d, and 5.32 d (1H, HB); 5.35 d,
5.37 d, and 5.40 d (1H, HA); 6.35 d.d, 6.38 d.d, and
6.46 d.d (1H, HX); 3JBX = 8.4, 3JAX = 15.4 Hz. 13C NMR
spectrum of VI, δC, ppm: 116.48, 116.57, 117.40 (Cβ);
129.60, 129.90, 130.42 (Cα). 19F NMR spectrum of VI,
δF, ppm: –54.77 d (CF3), –94.65 d (6-F), –104.22 q.d
(3-F). Found: [M]+ 356. C13H9F5S3. Calculated: M 356.
Compound V: Found: [M]+ 449. C14HF14N. Calculated:
M 449.
3,6-Difluoro-N,N-dimethyl-4-trifluoromethyl-
2,5-bis(vinylsulfanyl)aniline (VIII). Metallic sodium,
2.3 g (100 mmol), was added in small portions under
stirring to a solution of 4.3 g (50 mmol) of divinyl
sulfide in 100 ml of liquid ammonia. The ammonia
was evaporated, 40 ml of DMF was added to the
residue, and argon was bubbled through the mixture.
A solution of 4 g (17 mmol) of perfluorotoluene in
19
127.52 and 129.88 (Cα). F NMR spectrum, δF, ppm:
4
–52.64 d [CF3, J(CF3,3-F) = 33.56 Hz], –106.67 q.d
4
5
[3-F, J(CF3, 3-F) = 33.56, J(3-F,6-F) = 13.48 Hz],
–124.95 d (6-F). Found, %: C 42.50; H 2.36; F 30.67;
N 4.19; S 20.07. [M]+ 313. C11H8F5NS2. Calculated, %:
C 42.17; H 2.57; F 30.32; N 4.47; S 20.47. M 313.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 02-03-32844).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005