NEW PROCEDURE FOR NUCLEOPHILIC SULFONATION
1169
7.60–7.80 m (3H), 8.08 d (2H, 3J 5.6 Hz), 8.27 s (1H),
8.37 s(H), 8.38 s (H).
Found, %: C 37.49; H 2.31; K 10.63; N 3.83; S 16.41.
C12H8KNO7S2.Calculated, %: C 37.79; H 2.11; K 10.25;
N 3.67; S 16.81.
Methyl 2-(4-nitrophenylsulfanyl)acetate (IId).
Yield 85%, mp 51–52°C (from MeOH) (50.9– 52.4°C
[7]). 1H NMR spectrum, δ, ppm: 3.66 s (3H), 4.15 s (2H),
7.52 d (2H, 3J 5.8 Hz), 8.15 d (2H, 3J 5.8 Hz).
Potassium 4-nitrophenylsulfonate (IVd). Yield
1
55%, mp > 360°C (from EtOH) (328°C [9]). H NMR
spectrum, δ, ppm: 8.21 d (2H, 3J 6.1 Hz), 7.86 d (2H,
3J 6.1 Hz). Found, %: C 30.08; H 1.71; K 16.38; N 5.64;
S 13.31. C6H4KNO5S. Calculated, %: C 29.87; H 1.67;
K 16.21; N 5.81; S 13.29.
Potassium sulfonates. General procedure. A mix-
ture of 1 g of sulfide IIa–IId and 5 ml of 70% nitric acid
was slowly heated at stirring to boiling and boiled at
reflux for 3 h; therewith nitrogen oxides liberated. The
reaction mixture was evaporated in a vacuum to dryness,
the residue was dissolved in EtOH, and to the cooled
solution was added at stirring a solution of KOH in
ethanol in an amount equivalent to compound II. The
separated precipitate was filtered off and dried in air.
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant OFI-
a no. 05-03-08164).
REFERENCES
Potassium 3,5-dinitrophenylsulfonate (IVa) [8].
Yield 80%, mp 332–334°C (from water). H NMR
spectrum, δ, ppm: 8.63 d (2H, 4J 1.9 Hz), 8.79 t (1H,
4J 1.9 Hz). Found, %: C 25.27; H 1.08; K 13.73; N 9.36;
S 10.92. C6H3KN2O7S. Calculated, %: C 25.17; H 1.06;
K 13.66; N 9.79; S 11.20.
1. Gorelik, M.V. and Efros, L.S., Osnovy khimii i tekhnologii
aromaticheskikh soedinenii (Fundamentals of Chemistry
and Technology of Aromatic Compounds), Moscow:
Khimiya, 1992, p. 388.
2. Bannet, J., Gisler, M., and Zollinger, H., Helv. Chim. Acta,
1982, vol. 65, p. 63.
1
3. Serushkina, O.V., Dutov, M.D., and Shevelev, S.A., Izv.
Akad. Nauk, Ser. Khim., 2001, p. 252. (Russ. Chem. Bull.,
Int. Ed., 2001, vol. 50, p. 261).
4. Walker, D. and Leib, J., Can. J. Chem., 1962, vol. 40, p. 1242.
5. Walker, D. and Leib, J., J. Org. Chem., 1962, vol. 27, p. 4455.
6. Walker, D. and Leib, J., J. Org. Chem., 1963, vol. 28, p. 3077.
7. Langler, R.F. and Steeves, J. L., Aust. J. Chem., 1994,
vol. 47, p. 1641.
Potassium 2-methyl-3,5-dinitrophenylsulfonate
(IVb). Yield 66%, mp > 360°C (from EtOH). 1H NMR
spectrum, δ, ppm: 2.71 s (3H), 8.63 d (1H, 4J 2.1 Hz),
8.78 d (1H, 4J 2.1 Hz). Found, %: C 28.35; H 1.70; N 9.36;
S 10.20; K 13.45. C7H5KN2O7S. Calculated, %: C 28.00;
H 1.68; K 13.02; N 9.33; S 10.68.
Potassium 3-nitro-5-(phenylsulfonyl)phenyl-
sulfonate (IVc). Yield 52%, mp > 360°C (from EtOH).
1H NMR spectrum, δ, ppm: 7.60–7.85 m (3H), 8.08 d
(2H, 3J 5.6 Hz), 8.38 s (1H), 8.50 s (1H), 8.60 s (1H),
8. Griffith, R.H., J. Chem. Soc., 1924, vol. 125, p. 1401.
9. Vainshtein, F.M., Kukhtenko, I.I., Tomilenko, E.I., and
Shilov, E.A., Zh. Org. Khim, 1967, vol. 3, p. 1654.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007