300
LOSKUTOV, SHELKOVNIKOV
1
chloroform-ethanol). IR spectrum, n, cm : 1657 (C=O),
5CH ), 3.97 t (2H, OCH , J 6.4 Hz), 4.57 c (2H, BrCH ),
2
2
2
37
1
1
026 (S=O). H NMR spectrum, d, ppm: 4.57 s (2H,
7.02 d, 7.65 d (4H, C H , J 9.0 Hz), 7.94 m (5H, H ),
6 4
3
1,8 19
CH ), 7.44 d.d (1H, H , J 8.0 and 1.5 Hz), 7.85 m (2H,
8.59 m (2H, H ). F NMR spectrum, d, ppm: 89.9 d
(JFP 713.4 Hz). Found, %: C 51.30; H 4.26; Br 12.20;
F 17.82; S 4.86. C H BrO S·PF . Calculated, %:
2
,7
6
4,5
1,8
H ), 8.14 m (2H, H ), 8.35 m (2H, H ). Found, %:
+
C 52.23; H 3.23; Br 24.95; S 10.15. [M] 319.9509.
C H BrO S. Calculated, %: C 52.34; H 2.80; Br 24.92;
2
7
28
2
6
C 50.55; H 4.37; Br 12.48; F 17.78; S 4.99.
1
4
9
2
S 9.97. M 319.9507.
Hexafluorophosphate of 2,4-diethyl-9-oxo-10-(4-
2
,4-Diethyl-9H-thioxanthen-9-one 10-oxide
heptoxyphenyl)-9H-thioxanthenium (IVc). Yield
1
1
66%, mp 125128°C. IR spectrum, n, cm : 2932, 2871
(
2
1
IIIc). Yield 96%, mp 9499°C. IR spectrum, n, cm :
966, 2935, 2872 (CH), 1656 (C=O), 1021 (S=O).
H NMR spectrum, d, ppm: 1.27 t, 1.41 t, 2.75 q, 3.24 m
10H, 2Et, J 7.4 Hz), 7.45 d (1H, H , J 1.4 Hz), 7.71 t.d,
.79 t.d (2H, H , J 7.4 and 1.8 Hz), 8.03 d.d (1H, H ,
J 7.4 and 1.8 Hz), 8.10 d (1H, H , J 1.4 Hz), 8.35 d.d
1H, H , J 7.4 and 1.8 Hz). Found, %: S 11.56. [M]
84.0870. C H O S. Calculated, %: S 11.27.
1
(
CH), 1675 (C=O), 845 (PF). H NMR spectrum, d,
ppm: 0.84 m (3H, CH ), 1.28 m, 1.72 m (10H, 5CH ),
3
2
3
1.35 t, 2.90 m, 3.18 m (10H, 2Et, J 7.6 Hz), 3.94 t (2H,
(
7
6
,7
5
OCH , J 6.7 Hz), 6.98 d, 7.64 d (4H, C H , J 9.0 Hz),
2
6
4
3
6,7
1
7.63 d (1H, H , J 2.3 Hz), 7.90 m (2H, H ), 8.32 m,
8.50 m (2H, H ), 8.35 d (1H, H , J 2.3 Hz). F NMR
spectrum, d, ppm: 89.7 d (J713.2 Hz). Found, %: C 60.05;
5
,8
1
19
8
+
(
2
17 16 2
H 5.79; F 18.94; S 5.35. C H O S·PF . Calculated, %:
M 284.0871.
30 35
2
6
C 59.60; H 5.79; F 18.87; S 5.30.
4
-Propoxy-1-chloro-9H-thioxanthen-9-one 10-
Hexafluorophosphate of 4-propoxy-1-chloro-9-
oxide (IIId). Yield 87%, mp 168172°C (from ethanol).
oxo-10-(4-heptoxyphenyl)-9H-thioxanthenium
Reaction of thioxanthenones IIIaIIId S-oxides
with heptyl phenyl ether. At stirring 0.8 g of P O was
dissolved in 4 ml of freshly distilled methanesulfonic acid.
To the mixture obtained was added 2 mmol of heptyl
phenyl ether and 2 mmol of S-oxide III, the mixture was
stirred for 2-3 h, a solution of 3 mmol of KPF in 10 ml
of water was added, and the mixture was stirred for
0 min. The tarry precipitate was separated, dissolved in
dichloromethane, the organic layer was washed with
water, dried over Na SO , evaporated to a small volume,
1
(
2
IVd). Yield 53%, mp 171173°C. IR spectrum, n, cm :
2
5
1
932, 2858 (CH), 1681 (C=O), 845 (PF). H NMR
spectrum, d, ppm: 0.83 m (3H, CH ), 0.99 t (3H, CH ,
3
3
J 7.6 Hz), 1.26 m, 1.72 m, 1.90 m (12H, 6CH ), 3.94 t,
2
4
.20 t (4H, 2OCH , J 6.4 and 7.0 Hz), 7.98 d, 7.58 d (4H,
2
6
2
C H , J 9.1 Hz), 7.45 d (1H, H , J 9.0 Hz), 7.90 m (3H,
H
6
4
,6,7
3
5,8
), 8.15 d.d, 8.39 d.d (2H, H , J 6.5 and 3.5 Hz).
3
Found, %: C 54.27; H 5.32; Cl 5.50; F 18.42; S 5.20.
C H ClO S PF6. Calculated, %: C 54.37; H 4.99;
·
2
9
32
3
2
4
Cl 5.54; F 17.80; S 4.99.
and ethyl ether was added thereto. The separated salt
IV was isolated and once more reprecipitated with ether
from dichloromethane.
IR spectra were recorded on a Vector 22 instrument
1
19
from KBr pellets; H and F NMR spectra were
registered on a spectrometer Bruker AC-200 in CDCl3
Hexafluorophosphate of 2-methyl-9-oxo-10-(4-
heptoxyphenyl)-9H-thioxanthenium (IVa). Yield
4%, mp 128.5131°C. IR spectrum, n, cm : 2953, 2930,
869 (CH), 1672 (C=O), 843 (PF). H NMR spectrum,
d, ppm: 0.83 m (3H, CH ), 1.24 m, 1.70 m (10H, 5CH ),
.56 s (3H, CH ), 3.95 t (2H, OCH , J 6.4 Hz), 6.99 d,
3 2
.62 d (4H, C H , J 9.2 Hz), 7.73 d.d (1H, H , J 9.0 and
.5 Hz), 7.87 d (1H, H , J 9.0 Hz), 7.96 m (3H, H ),
(
internal references the residual proton signal in the
solvent and C F respectively), mass spectra were
1
6 6
5
2
measured on a mass spectrometer Finnigan MAT-8200
the molecular mass and composition of compounds was
1
(
3
2
established from the precise mass of the molecular ion).
The reaction progress was monitored and the purity of
compounds was checked by TLC on Silufol UV-254 plates
2
7
1
8
3
6
4
4
57
(
eluent benzene or chloroform).
1
8
19
.39 m (1H, H ), 8.58 m (1H, H ). F NMR spectrum,
The study was carried out under the financial support
d, ppm: 89.75 d (JFP 713.2 Hz). Found, %: C 58.40;
H 4.78; F 20.08; S 5.80. C H O S·PF . Calculated, %:
of the Presidium of the Russian Academy of Sciences
projects 52, 83) and Siberian Division of the Russian
2
7
29
2
6
(
C 57.65; H 5.16; F 20.28; S 5.69.
Academy of Sciences (integration project 84).
Hexafluorophosphate of 2-bromomethyl-9-oxo-
1
0-(4-heptoxyphenyl)-9H-thioxanthenium (IVb).
REFERENCES
1
Yield 42%, mp 147151°C. IR spectrum, n, cm : 2928,
2
d, ppm: 0.84 m (3H, CH ), 1.24 m, 1.71 m (10H,
1
856 (CH), 1670 (C=O), 843 (PF). H NMR spectrum,
1. Akhtar, S.R., Crivello, J.V., Lee, J.L., and Smitt, M.L., Chem.
Mater., 1990, vol. 2, p. 732.
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 2 2006