Yu.P. Bandera et al. / Journal of Fluorine Chemistry 123 (2003) 197–205
203
1H NMR (exo): d 1.17–1.30 (1H, m, CH2); 1.66 (1H, tm,
CH2); 2.15–2.25 (1H, m, CH2); 2.48 (3H, s, CH3); 2.6 (1H,
tm, CH2); 3.54 (1H, m, CH); 3.72 (1H, m, CH); 6.06 (1H, dd,
Anal. Calcd. for 0:9C20H13F6NO5S2 þ 0:1C8H5NO2: C
46.30; H 2.50; N 2.87; S 11.82. Found: C 45.80; H 2.55; N
3.12; S 11.99.
2
3
CH¼CH); 6.08 (1H, tt, HCF2, JHF ¼ 52:7 Hz, JHF
5.9 Hz); 6.54 (1H, dd, CH¼CH); 7.38 (2H, d, Ar); 7.69
(2H, d, Ar). 1H NMR (endo): d 1.32–1.43 (2H, m, CH2); 1.58
(1H, tm, CH2); 1.93–2.03 (1H, m, CH2); 2.47 (3H, s, CH3);
3.66 (1H, m, CH); 3.83 (1H, m, CH); 6.21 (1H, tt, HCF2,
4.4. Synthesis of 5,6-dihydro-6-(p-tolylsulfonyl)-2H-thiins
(9, 10 and 11) from 5,6-dihydro-6-(2,2,3,3,4,4-
hexafluorobutyryl)-6-(p-tolylsulfonyl)-2H-thiins
(3a, 3b, 4 and 5): general procedure
3
2JHF ¼ 52:3 Hz, JHF ¼ 5:6 Hz) 7.34 (2H, d, Ar); 7.63
(2H, d, Ar). 19F NMR: dA –112.02, dB À113.18 AB (2F,
CF2, JAB ¼ 302 Hz); dA À130.13, dB À131.02 AB (2F,
Sodium hydroxide (0.36 g, 9 mmol) was added to a
solution of appropriate thiins 9, 10 and 11 (3 mmol) in
20 ml of dioxane–water mixture (5:1). The mixture was
stirred at room temperature for 72 h and filtered. Solvents
were removed in vacuum (20 mmHg) and residue was
treated with 20 ml of diethyl ether. Ether solution was
washed with 10 ml of water, dried over CaCl2 and evapo-
rated. Residue was extracted with hot hexane (10 Â 10 ml)
and hexane solution was concentrated up to 1/3 of volume
and cooled. The precipitated product was filtered and dried
in vacuum.
CF2, JAB ¼ 288:0 Hz); À138.20 (2F, dm, HCF2, JFH
¼
55:0 Hz). MS (70 eV) m/z (%) 458 (3) [Mþ], 303 (99)
[Mþ À SO2Tol].
Anal. Calcd. for C18H16F6O3S2: C 47.16; H 3.52; S 13.99.
Found: C 47.10; H 3.60; S 13.93.
4.2.3. 5,6-Dihydro-6-(2,2,3,3,4,4-hexafluorobutyryl)-2,
5-methylene-6-(p-tolylsulfonyl)-2H-thiin (5)
Mixture of isomers (endo:exo, 1:4). Yield 60%. Colorless
oil.
1H NMR: d 1.39 (1H, d, CH2, endo); 1.68 (1H, m, CH2,
exo, endo); 2.42 (1H, d, CH2, exo); 2.48 (3H, s, CH3, endo);
2.49 (3H, s, CH3, exo); 3.97 (1H, m, CH, exo); 4.24 (1H, m,
CH, exo, endo); 4.35 (1H, m, CH, endo); 5.79 (1H, m,
4.4.1. 5,6-Dihydro-3,4-dimethyl-6-(p-tolylsulfonyl)-
2H-thiin (9)
Yield 74%. Colorless crystals, mp 99–103 8C. 1H NMR: d
1.68 (3H, s, CH3); 1.72 (3H, s, CH3); 2.45 (3H, s, CH3); 2.7
(2H, m, CH2CH); 2.80 (1H, d, CH2S); 3.28 (1H, d,CH2S);
4.08 (1H, t, CHS); 7.34 (2Hþ, d, Ar); 7.82 (2H, d, Ar). MS
(70 eV) m/z (%) 282 (2) [M ], 127 (99) [Mþ À SO2Tol].
Anal. Calcd. for C14H18O2S2: C 59.54; H 6.42; S 22.71.
Found: C 60.25; H 6.86; S 22.34.
2
CH¼CH, exo, endo); 6.08 (1H, tt, HCF2, JHF ¼ 51:9 Hz,
exo); 6.56 (1H, m, CH¼CH, exo, endo); 7.37 (2H, d, Ar,
endo); 7.39 (2H, Ar, exo); 7.62 (2H, d, Ar, endo); 7.69 (2H,
Ar, exo). 19F NMR: dA À112.46, dB À114.42 AB (2F, CF2,
JAB ¼ 302:0 Hz); d À130.01, dA À131.30 AB (2F, CF2,
JAB ¼ 286:6 Hz); ÀA138.18 (2F, dm, HCF , JFH ¼ 55:0 Hz).
2
MS (70 eV) m/z (%) 444 (5) [Mþ], 289 (99) [Mþ À SO2Tol].
Anal. Calcd. for C17H14F6O3S2: C 45.95; H 3.18; S 14.43.
Found: C 46.10 H 3.24; S 14.51.
4.4.2. 5,6-Dihydro-2,5-ethylene-6-(p-tolylsulfonyl)-
2H-thiin (10)
Mixture of isomers (endo:exo, 1:2.5). Yield 75%. Colorless
crystals, mp 86–88 8C.
4.3. Synthesis of 3,3,4,4,5,5-hexafluoro-1-(p-tolylsulfonyl)-
1-phthalimidothiopentane-2-on (7b)
1H NMR: d 1.21 (1H, m, CH2); 1,71 (1H, dt, CH2); 2.27
(1H, m, CH2); 2.61 (1H, m, CH2); 3.47, 3.58 (1H, m, CH,
endo, exo); 4.12, 4.60 (1H, td, CH, exo, endo); 6.04, 6.35
(1H, t, CH¼CH, endo, exo); 6.46, 6.60 (1H, t, CH¼CH,
endo, exo); 7.34, 7.81 (2H, d, Ar, exo, endo). MS (70 eV) m/z
(%) 280 (3) [Mþ], 125 (99) [Mþ À SO2Tol].
Anal. Calcd. for C14H16O2S2: C 59.97; H 5.75; S 22.87.
Found: C 60.0; H 5.70; S 22.74.
Phtalimidosulfenyl chloride (7.0 g, 32.7 mmol) was
added to a solution of sulfone 6b (8.15 g, 23.4 mol) in
100 ml of dry chloroform and the mixture was stirred at
20 8C for 6 h. Some undissolved material was filtered off
and solvent was removed from mother liquor in vacuum
(20 mmHg). The residue was treated with 70 ml of diethyl
ether to give white crystalline product, which contained
10 mol% of phthalimide and was used for further trans-
formations without additional purification. Yield of crude
product was 80%, mp 135–140 8C (decomp.).
4.4.3. 5,6-Dihydro-2,5-methylene-6-(p-tolylsulfonyl)-
2H-thiin (11)
Mixture of isomers (endo:exo, 1:2.4). Yield 44%. Color-
1
less crystals, mp 40–50 8C. H NMR (exo): dA 1.6, dB 2.1
1H NMR: d 2.50 (3H, s, CH3); 5.24 (1H, s, CH); 6.15 (1H,
AB (2H, CH2, JAB ¼ 9:8 Hz), 2.45 (3H, s, CH3), 3.83 (1H, s,
CH), 3.97 (1H, s, CH), 4.16 (1H, s, CH), 5.98, 6.47 (2H, dd,
CH¼CH), 7.35, 7.83 (4H, d, Ar). 1H NMR (endo): dA 1.62,
dB 1.72 AB (2H, CH2, JAB ¼ 9:4 Hz), 2.45 (3H, s, CH3),
3.87 (1H, s, CH), 4.2 (1H, s, CH), 4.98 (1H, d, CH,
3JHH ¼ 3:5 Hz), 6.07, 6.49 (2H, dd, CH¼CH), 7.34, 7.77
(4H, d, Ar). MS (70 eV) m/z (%) 266 (4) [Mþ], 111 (100)
[Mþ À SO2Tol].
2
3
tt, HCF2, JHF ¼ 52:0 Hz, JHF ¼ 5:6 Hz); 7.55 (2H, d,
Ar); 7.82–7.85 (2H, m, Ar); 7.96–7.99 (2H, m, Ar); 8.07
(2H, d, Ar). 10 mol% admixture of phthalimide: 7.77,
7.86 (m, PhthN). 19F NMR: dA À119.73, dB À120.85 AB
2
(CF2, 2F, JAB ¼ 296:0 Hz); dA À130.87, dB À131.48 AB
2
(CF2,2F, JAB ¼ 291:0 Hz); À138.0 (HCF2, dm, 2F, JFH
52:0 Hz).
¼