28
T.D. Petrova et al. / Journal of Fluorine Chemistry 98 (1999) 17±28
silica gel (eluent hexane) and then recrystallized from
petroleum ether (70±1008C).
(13, 22, 23) (2%, 10.5% and 84% according to GLC
data) was added. The mixture was re¯uxed for 6 h, then
0.04 g potassium permanganate was added and the
mixture was re¯uxed for a further 3 h. After reaction,
the mixture was poured into water and extracted with
ether. The ether layer was washed with water, dried over
CaCl2, the solvents distilled off and the residue (0.09 g)
was analysed by 19F NMR spectroscopy and GLC. The
residue contained (13), (22) and (23) in the ratio 6:4.7:1
according to 19F NMR data or 30%, 38% and 7%,
respectively, by GLC.
3.2. Hydrolysis of compounds (9, 17)
To a solution of 1.1 g of compound (9) in 20 ml dioxane,
35 ml of 10% HCl was added. A mixture was re¯uxed for
7 h. After reaction the mixture was extracted with ether, the
organic layer was washed with water and dried over CaCl2,
the solvents were distilled off. The solid residue was ®ltered,
washed with small amount of petroleum ether (70±1008C)
and 0.31 g of compound (21) was obtained which was
puri®ed by sublimation at 1108C/15 mm Hg.
The reaction with (19) was carried out by a procedure
similar to that for (9) (0.34 g of (19), 4 ml of dioxane and
6 ml of 10% HCl were used). 0.16 g of compound (18) was
obtained which was puri®ed by sublimation at 708C/
15 mm Hg.
2. Boiling of 0.04 g of (21) with 0.06 g of KMnO4 and
1.5 ml AcOH (3.5 h) gave 0.11 g of the reaction mixture
containing AcOH and disulphide (13).
3. To a suspension of chromium trioxide in acetic acid, a
dihalomethane was added. The mixture was refluxed,
then acetic acid distilled off, the residue was poured into
water and extracted with methylene chloride. The
organic layer was washed with water, dried over CaCl2,
the solvents distilled off, the residue analysed by
19F NMR spectroscopy, GC±MS, GLC and purified by
recrystallization. The conditions and results are shown in
Table 4.
3.3. Reactions with antimony fluorides ± see Table 2
Antimony tri¯uoride was dried at 210±2208C.
Method A. The reaction was carried out in a ¯ask con-
nected via a condenser to a trap immersed in a cooling bath.
Antimony halogenide was added to corresponding substrate.
The reaction mixture was further heated. Products did not
distil off during the reaction. After reaction, the mixture was
cooled to room temperature, extracted with methylene
chloride, the precipitate was ®ltered off. Then a solution
was washed with water, organic layer was dried over CaCl2,
the solvent distilled off and a residue analysed by 19F NMR
spectroscopy, GLC and GC±MS.
References
[1] T.I. Savchenko, I.V. Kolesnikova, T.D. Petrova, V.E. Platonov, J.
Fluorine Chem. 22 (1983) 439.
[2] T.D. Petrova, I.S. Popova, I.V. Kolesnikova, V.E. Platonov, Russ.
Chem. Bull. 43 (1994) 1027.
[3] T.D. Petrova, A.G. Ryabitchev, T.I. Savchenko, I.V. Kolesnikova,
V.E. Platonov, Zh. Org. Khim. 24 (1988) 1513.
[4] R.T. Wragg, Tetrahedron Lett. (1971) 2475.
[5] T.D. Petrova, V.E. Platonov, A.M. Maksimov, I.S. Popova, Russ.
Chem. Bull. 40 (1991) 1938.
Method B. The reaction was carried out by a procedure
similar to that for A, but in vacuo.
Method C. The reaction was carried out in the closed steel
vessel. After reaction, the mixture was worked up as in A.
[6] T.D. Petrova, V.E. Platonov, I.S. Popova, I.V. Kolesnikova, J.
Fluorine Chem. 54 (1991) 300.
[7] S. Oae, Chemistry of Organic Compounds of Sulphur, Khimiya,
Moscow, 1975, p. 20 (in Russian).
3.4. Reactions with caesium fluoride
[8] M.E. Peach, H.G. Spinney, Can. J. Chem. 49 (1971) 644.
[9] A.F. Feiring, E.R. Wonchoba, S.D. Arthur, J. Polym. Sci. A 28
(1990) 2809.
Caesium ¯uoride was dried at 2708C. The reactions were
carried out in the closed steel vessel or in the ¯ask. The
reaction conditions are indicated in Table 3.
[10] L.M. Yagupolsky, M.S. Marenec, Zh. Obshchei Khim. 24 (1954)
887.
A substrate was added to a caesium ¯uoride and the
mixture was heated. Work-up of the reaction mixture by a
procedure similar to that for Method A for antimony
¯uorides afforded a residue which was puri®ed by column
chromatography or sublimation and recrystallization.
[11] M. Hudlicky, Chemistry of Organic Compounds of Fluorine, GNTI,
Moscow, 1961, p. 137 (in Russian).
[12] R.N. Haszeldine, R.B. Rigby, A.E. Tipping, J. Chem. Soc., Perkin I
(1972) 2180.
[13] E. Laurent, B. Marquet, Ch. Roze, F. Ventalon, J. Fluorine Chem. 87
(1998) 215.
[14] T.D. Petrova, V.E. Platonov, L.N. Shchegoleva, A.M. Maksimov, A.
Haas, M. Schelvis, M. Lieb, J. Fluorine Chem. 79 (1996) 13.
[15] L.M. Yagupolskii, N.V. Kondratenko, V.P. Sambur, Synthesis (1975)
721.
3.5. Reaction with oxidants
1. To a suspension of 0.26 g potassium permanganate in
3 ml of acetic acid, 0.12 g of the mixture of compounds