R.-Y. Tang et al. / Journal of Fluorine Chemistry 128 (2007) 636–640
639
(1C), 114.9 (2C), 129.6 (q, J = 306.0, 1C), 132.7 (1C), 138.3
(2C), 161.8 (1C). 19F NMR (220 MHz, CDCl3): d À44.1 (s, 3F,
SCF3). Anal. calcd for C8H7F3OS: C, 46.15%; H, 3.39%.
Found: C, 45.91%; H, 3.24%.
aromatic); 7.75 (d, J = 8.37, 2H, aromatic) 13C NMR (75 MHz,
CDCl3): d 55.7 (1C), 115.2 (2C), 124.1 (q, J = 333.6, 1C), 128.1
(2C), 130.8 (1C), 164.0 (1C). 19F NMR (220 MHz, CDCl3): d
À75.1 (s, 3F, OSCF3). Anal. calcd for C8H7F3O2S: C, 42.86%;
H, 3.15%. Found: C, 42.67%; H, 2.97%.
4.4. Typical procedure for the synthesis of compound 2 and
chlorinated compound 3
4.4.5. 2,6-Dichloro-5-aminophenyl trifluoromethylsulfide
(3e)
In a 25-mL flask was placed with 1a (0.112 g, 0.5 mmol),
ionic liquid [Bmim]BF4 (2 mL) and water (two drops). TCCA
(0.233 g, 1 mmol) was added. After stirring for 3.5 h, excessive
TCCA was destroyed by the slow addition of saturated solution
of NaHSO3. During this process, wet iodide-starch test paper
was used to periodically test for the presence of oxidizing
agents. The precipitate was removed by filtration and washed
with diethyl ether. Filtrate was extracted with diethylether (3Â
5 mL), ether phase was collected and washed with saturated
solution of NaCl (4 mL), and then was dried over MgSO4. After
removing the solvent, the crude product was purified by flash
column chromatography on silica gel using petroleum ether/
ethyl acetate (6:1) as eluent to give colorless solid (part ionic
liquid can be recovered).
Colorless solid; mp: 49–50 8C. IR (KBr) (cmÀ1): 3491,
3388, 1608, 1550, 1473, 1389, 1301, 1109, 875, 784, 719, 597.
1H NMR (300 MHz, CDCl3): d 4.80 (s, 2H, NH2); 7.49 (s, 2H,
aromatic). 13C NMR (75 MHz, CDCl3): d 111.3 (1C), 119.2
(2C), 129.2 (q, J = 306.8, 1C), 135.8 (2C), 142.7 (1C). 19F
NMR (220 MHz, CDCl3): d À43.9 (s, 3F, SCF3). Anal. calcd
for C7H4Cl2F3NS: C, 32.08%; H, 1.54%. Found: C, 31.91%; H,
1.32%.
4.4.6. 2,6-Dichloro-5-hydroxylphenyl
trifluoromethylsulfide (3f)
Yellow liquid. IR (KBr) (cmÀ1): 3611, 1602, 1548, 1475,
1
1377, 1217, 1103, 866, 773. H NMR (300 MHz, CDCl3): d
6.23 (s, 1H, OH); 7.60 (s, 2H, aromatic). 13C NMR (75 MHz,
CDCl3): d 116.2 (1C), 121.8 (2C), 129.3 (q, J = 306.7, 1C),
136.2 (2C), 150.5 (1C). 19F NMR (220 MHz, CDCl3): d À43.2
(s, 3F, SCF3). Anal. calcd for C7H3Cl2F3OS: C, 31.96%; H,
1.15%. Found: C, 31.75%; H, 0.97%.
4.4.1. 4-Nitrophenyl trifluoromethylsulfoxide (2a)
Colorless solid; mp: 55 8C. IR (KBr) (cmÀ1): 3110, 1608,
1533, 1345, 1207, 1138, 1086, 850, 804, 722, 682, 621. H
1
NMR (300 MHz, CDCl3): d 8.02 (dd, J = 8.80, J = 1.91, 2H,
aromatic); 8.49 (dd, J = 8.80, J = 1.91, 2H, aromatic). 13C
NMR (75 MHz, CDCl3): d 125.3 (q, J = 333.8, 1C), 125.5 (2C),
127.9 (2C), 143.5 (1C), 151.9 (1C). 19F NMR (220 MHz,
Acknowledgements
Project supported by the National Natural Science Founda-
tion of China (no. 20572079) and the National Natural Science
Foundation of Zhejiang Province (nos. M203001, Y205540 and
Y404039). Supported by the Postgraduate Innovation Founda-
tion of Wenzhou University (no. YCX0514).
CDCl3):
d
À73.18 (s, 3F, OSCF3). Anal. calcd for
C7H4F3NO3S: C, 35.15%; H, 1.69%. Found: C, 34.98%; H,
1.47%.
4.4.2. 4-Chlorophenyl trifluoromethylsulfoxide (2b)
Colorless liquid. IR (KBr) (cmÀ1): 3087, 1575, 1476, 1393,
1
1188, 1140, 1088, 826, 744. H NMR (300 MHz, CDCl3): d
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J = 333.2, 1C), 127.3 (2C), 130.0 (2C), 134.2 (1C), 140.3
(1C). 19F NMR (220 MHz, CDCl3): d À74.41 (s, 3F, OSCF3).
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1195, 1143, 1096, 688, 606. H NMR (300 MHz, CDCl3): d
7.55–8.06 (m, 5H, aromatic). 13C NMR (75 MHz, CDCl3): d
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133.9 (1C). 19F NMR (220 MHz, CDCl3): d À74.45 (s, 3F,
OSCF3). Anal. calcd for C7H5F3OS: C, 43.30%; H, 2.60%.
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