R.W. Winter et al. / Journal of Fluorine Chemistry 126 (2005) 1202–1214
1209
GC–MS (m/z, ion, rel. %): 446, 444, 442 (M)+ (7, 13, 7);
319, 317, 315 (M–SF5)+ (4, 10, 5); 238, 236 (M–SF5–Br)+
(95, 100); 89 (SF3)+ (12).
added to a 30 ml Carius tube. The mixture was irradiated for
20 h at 0 8C. The product was isolated by silica gel
chromatography; 0.209 g, 0.482 mmol, yield was 22%; low
yield due to volatility of product.
3.3. 4-Bromo-1-(2-pentafluorosulfanyl-1-
bromotrifluoroethyl)benzene (2)
IR spectrum (cmÀ1): C–H, 3124, 3088, 2932 (vw); C–F,
1328 (vs), 1204 (m), 1195 (m), 1176 (m), 1141 (m); S–F, 921
(m-s), 912 (m), 881 (vs), 865 (s), 597 (m-s).
Following the general procedure given above, p-
CF2 CFC6H4Br (1.49 g, 6.28 mmol) dissolved in 3 ml
pentane, 5 ml CH2Cl2, and 2.52 g (12.2 mmol) SF5Br were
added to a 30 ml Carius tube. The mixture was irradiated for
25 h at 0 8C. The product was isolated by silica gel
chromatography; 1.49 g, 3.34 mmol, yield was 53%.
IR spectrum (cmÀ1): C–H, 3101 (vw); C–F, 1230 (w-m),
1199, 1189 (m); S–F, 917 (s), 877 (vs), 855 (m-s); 596 (s).
GC–MS (m/z, ion, rel. %): 446, 444, 442 (M)+ (2, 4, 2);
319, 317, 315 (M–SF5)+ (4, 8, 4); 238, 236 (M–SF5–Br)+
(98, 100); 89 (SF3)+ (8).
GC–MS (m/z, ion, rel. %): 434, 432 (M)+ (0.1, 0.1); 353
(M–Br)+ (31); 307, 305 (M–SF5)+ (10, 11); 226 (M–SF5–
Br)+ (100); 195 (C8H4F5)+ (93); 89 (SF3)+ (6).
3.7. 4-Nitro-1-(2-pentafluorosulfanyl-1-
bromotrifluoroethyl)benzene (6)
Following the general procedure given above, p-
CF2 CFC6H4NO2 (4.30 g, 21.17 mmol) dissolved in
3 ml pentane, 5 ml CH2Cl2, and 8.7 g (42.0 mmol) SF5Br
were added to a 30 ml Carius tube. The mixture was
irradiated for 51 h at 0 8C. The product was isolated by
silica gel chromatography; 6.95 g, 16.94 mmol, yield was
80%.
IR spectrum (cmÀ1): C–H, 3122, 3087 (w), 3061, 2867
(vw); C–F, 1352 (s), 1212 (m), 1199 (s), 1188 (m-s); S–F,
920, 879, 870 (vs), 853 (s), 597 (s).
3.4. 4-Chloro-1-(2-pentafluorosulfanyl-1-
bromotrifluoroethyl)benzene (3)
Following the general procedure given above, p-
CF2 CFC6H4Cl (1.08 g, 5.61 mmol) dissolved in 3 ml
pentane, 5 ml CH2Cl2, and 1.20 g (5.80 mmol) SF5Br were
added to a 30 ml Carius tube. The mixture was irradiated for
20 h at 0 8C. The product was isolated by silica gel
chromatography; 1.17 g, 2.92 mmol, yield was 52%.
IR spectrum (cmÀ1): C–H, 2975, 2941 (w); C–F, 1201,
1188, 1102 (s); S–F, 919 (vs), 907 (s), 881 (vs), 858 (s), 597
(s).
GC–MS (m/z, ion, rel. %): 395, 393 (M)+ (0.4, 0.4); 330
(M–Br)+ (33); 282, 284 (M–SF5)+ (8, 8); 203 (M–SF5–Br)+
(100); 89 (SF3)+ (31).
3.8. 2-Fluoro-1-(2-pentafluorosulfanyl-1-
bromotrifluoroethyl)benzene (7)
GC–MS (m/z, ion, rel. %): 400, 398 (M)+ (2, 2); 273, 271
(M–SF5)+ (7, 5); 192 (M–SF5–Br)+ (100); 89 (SF3)+ (4).
Following the general procedure given above, o-
CF2 CFC6H4F (1.0 g, 10.10 mmol) dissolved in 3 ml
pentane, 5 ml CH2Cl2, and 1.40 g (6.76 mmol) SF5Br
were added to a 30 ml Carius tube. The mixture was
irradiated for 17 h at 0 8C. The product was isolated by
silica gel chromatography; 1.78 g, 4.65 mmol, yield was
82%.
IR spectrum (cmÀ1): C–H, 3095, 2969 (vw); C–F, 1285
(w-m), 1251 (m-s), 1193 (s); S–F, 921 (s), 907 (s), 876 (vs),
849 (s), 597 (s).
GC–MS (m/z, ion, rel. %): 384, 382 (M)+ (0.3, 0.4); 257,
255 (M–SF5)+ (7, 7); 176 (M–SF5–Br)+ (100); 89 (SF3)+ (6).
3.5. 4-Methyl-1-(2-pentafluorosulfanyl-1-
bromotrifluoroethyl)benzene (4)
Following the general procedure given above, p-
CF2 CFC6H4CH3 (1.00 g, 5.81 mmol) dissolved in 3 ml
pentane, 5 ml CH2Cl2, and 1.80 g (8.70 mmol) SF5Br were
added to a 30 ml Carius tube. The mixture was irradiated for
48 h at 0 8C. The product was isolated by silica gel
chromatography; 0.910 g, 2.40 mmol, yield was 41%.
IR spectrum (cmÀ1): C–H, 3042, 2929 (w); C–F, 1204 (s),
1191 (vs), 1159 (w-m); S–F, 921 (vs), 905 (s), 879 (vs), 857
(s), 596 (s).
3.9. 2-Trifluoromethyl-1-(2-pentafluorosulfanyl-1-
bromotrifluoroethyl)benzene (8)
GC–MS (m/z, ion, rel. %): 380, 378 (M)+ (1, 1); 299 M–
Br+ (47); 253 251 (M–SF5)+ (5, 5); 172 (M–SF5–Br)+ (100);
89 (SF3)+ (4).
Following the general procedure given above, o-
CF2 CFC6H4CF3 (1.55 g, 6.85 mmol) dissolved in 3 ml
pentane, 5 ml CH2Cl2, and 1.22 g (5.89 mmol) SF5Br were
added to a 30 ml Carius tube. The mixture was irradiated for
18 h at 0 8C. The product was isolated by silica gel
chromatography; 1.55 g, 3.58 mmol, yield was 74%.
IR spectrum (cmÀ1): C–H, 3064, 2923 (vw); C–F, 1309
(m), 1294, 1283, 1198, 1177 (m), 1156 (m-s); S–F, 915 (m),
876 (vs), 849 (m), 598 (m-s).
3.6. 4-Trifluoromethyl-1-(2-pentafluorosulfanyl-1-
bromotrifluoroethyl)benzene (5)
Following the general procedure given above, p-
CF2 CFC6H4CF3 (0.50 g, 2.21 mmol) dissolved in 3 ml
pentane, 5 ml CH2Cl2, and 1.22 g (5.89 mmol) SF5Br were