OXIDATION OF POLYFUNCTIONAL SULFIDES WITH CHLORINE DIOXIDE
129
1
orated, and the residue was subjected to column chro-
matography on silica gel using heptane–diethyl ether
as eluent to isolate 0.118 g (89%) of 3-benzylsulfinyl-
4,5-diphenyl-4H-1,2,4-triazole (VI). Colorless crystals,
mp 197–198°C. IR spectrum: ν 1038 cm–1 (S=O).
1H NMR spectrum, δ, ppm: 4.72 d and 5.05 d (1H
each, CH2, J = 12.46 Hz), 7.02–7.45 m (15H, C6H5).
13C NMR spectrum, δC, ppm: 58.82 (CH2), 125.64
(CiA), 127.55 (CoB), 128.61 (CmA), 128.68 (CmC), 128.76
(CpB), 128.97 (CoC), 129.91 (CoA), 130.39 (CpC), 130.49
(CpA), 130.88 (CmB), 132.90 (CiB, CiC), 138.31 (C3),
155.99 (C5). Found, %: C 70.12; H 4.85; N 11.60;
O 4.35; S 9.00. C21H17N3OS. Calculated, %: C 70.17;
H 4.77; N 11.69; O 4.45; S 8.92.
IR spectrum: ν 1050 cm–1 (S=O). H NMR spectrum,
δ, ppm: 4.36 d and 4.56 d (1H each, CH2, J = 13.2,
11.6 Hz), 7.07 m (2H, 5-H, 6-H), 7.26 m (2H, 4-H,
13
7-H), 7.16 m (5H, C6H5), 7.57 s (1H, NH). C NMR
spectrum, δC, ppm: 58.82 (CH2), 113.50 (C4), 115.51
(C7), 121.74 (C5), 123.44 (C6), 127.08 (Cm), 128.25
(Co, Cp), 130.06 (Ci), 138.87 (C3a, C7a), 152.01 (C2).
1-Butylsulfinyl-4-nitrobenzene (X). Yield 87–
94%. Colorless liquid. IR spectrum: ν 1044 cm–
1
1
(S=O). H NMR spectrum, δ, ppm: 0.94 t (3H, CH3,
J = 7.2 Hz), 1.46 m (2H, 3′-H), 1.80 m (2H, 2′-H),
2.84 m and 2.91 m (1H each, 1′-H), 7.83 d and 8.40 d
13
(2H each, C6H4, J = 8.4, 8.8 Hz). C NMR spectrum,
δC, ppm: 13.42 (C4′), 21.62 (C3′), 23.65 (C2′), 56.58
(C1′), 124.10 (C3, C5), 124.97 (C2, C6), 149.23 (C4),
151.53 (C1).
b. A mixture of air with chlorine dioxide (evolved
from an aqueous solution containing 0.5 mmol of
ClO2) was bubbled through a solution of 0.172 g
(0.5 mmol) of compound I in 25 ml of methylene
chloride over a period of 30 min at 20°C. The solvent
was distilled off, and the residue was subjected to
column chromatography on silica gel using heptane–
diethyl ether as eluent to isolate 0.163 g (87%) of
compound VI.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 10-03-00969).
REFERENCES
1. Minoru, U., Chem. Pharm. Bull., 1989, vol. 37, p. 210.
2. Holt, S. and Howden, C.W., Dig. Dis. Sci., 1991,
c. A solution of chlorine dioxide in methylene
chloride, 9 ml (0.42 mmol), was added over a period of
30 min to a solution of 0.144 g (0.42 mmol) of com-
pound I in 10 ml of methylene chloride under stirring
at 20°C. The mixture was evaporated, and the residue
was subjected to column chromatography on silica gel
using heptane–diethyl ether as eluent to isolate 0.135 g
(88%) of compound VI.
vol. 36, p. 385.
3. Shin, J.M., Cho, Y.M., and Sachs, G., J. Am. Chem. Soc.,
2004, vol. 126, p. 7800.
4. Kowalski, P., Mitka, K., Ossowska, K., and Kolar-
ska, Z., Tetrahedron, 2005, vol. 61, p. 1933.
5. Fernandez, I. and Khiar, N., Chem. Rev., 2003, vol. 103,
p. 3651.
6. Graber, D.R., Morge, R.A., and Sih, J.C., J. Org. Chem.,
5-Methylsulfinyl-1-phenyl-1H-tetrazole (VII)
[14]. Yield 92–97%. Colorless crystals, mp 79–80°C.
IR spectrum: ν 1044 cm–1 (S=O). 1H NMR spectrum,
δ, ppm: 2.41 s (3H, CH3), 7.55–7.72 m and 7.88–
7.95 m (5H, C6H5). 13C NMR spectrum, δC, ppm:
35.78 (CH3), 130.25 (Co), 132.36 (Cm, Cp), 133.87 (Ci),
142.46 (C5).
1987, vol. 52, p. 4620.
7. Masakazu, I. and Yasuhiro, T., Catal. Surv. Jpn., 2001,
vol. 1, p. 25.
8. Matsugi, M., Fukuda, N., Minamikawa, J.-i., and
Otsuka, S., Tetrahedron Lett., 1998, vol. 39, p. 5591.
9. Xu, L., Cheng, J., and Trudell, M.L., J. Org. Chem.,
2003, vol. 68, p. 5388.
10. Blaser, H.U., Spindler, F., and Studer, M., Appl.
Catal. A: General, 2001, vol. 221, p. 119.
11. Okabe, S., Satoh, M., Yamakawa, T., Nomura, Y., and
Hayashi, M., UK Patent Appl. no. 2163747, 1986.
12. Gol’tsberg, M.A. and Koldobskii, G.I., Russ. J. Org.
Chem., 1996, vol. 32, p. 1194.
2-Methylsulfinyl-1H-benzimidazole (VIII). Yield
85–89%. Colorless crystals, mp 139–140°C; published
data [23]: mp 200–206°C. IR spectrum: ν 1055 cm–1
1
(S=O). H NMR spectrum, δ, ppm: 3.23 s (3H, CH3),
13
7.38 m (4H, C6H4), 12.33 s (1H, NH). C NMR spec-
trum, δC, ppm: 41.54 (CH3), 113.30 (C3, C6), 121.04
(C4, C5), 124.0 (C2, C7), 153.64 (C1). Found, %:
C 53.02; H 4.29; N 15.61; O 8.95; S 17.85.
C11H12N2OS. Calculated, %: C 53.31; H 4.47; N 15.54;
O 8.88; S 17.79.
13. Egorov, N.E., Artamonova, T.V., and Koldobskii, G.I.,
Russ. J. Org. Chem., 2007, vol. 42, p. 475.
14. Hrabalek, A., Myznikov, L., Kunes, J., Vavrova, K., and
Koldobskii, G., Tetrahedron Lett., 2004, vol. 45,
p. 7955.
2-Benzylsulfinyl-1H-benzimidazole (IX) [24].
15. Galliani, G. and Rindone, B., J. Chem. Res., Synop.,
Yield 97–98%. Colorless crystals, mp 182.9–183.2°C.
1981, p. 74.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 1 2011