Molecules 2019, 24, 1249
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1-Fluoro-4-(((trifluoromethyl)sulfinyl)methyl)benzene 4g
[39]. Compound 3g was oxidized on a 0.05 g
scale. Product was purified by preparative TLC chromatography, eluent Et2O-petroleum ether, 1:9 (Rf
◦
◦
= 0.3). Pale yellow solid; yield 0.041 g (85%); m.p. 80 C (Lit. 81–82 C). IR (KBr): 2983, 2927, 1600, 1507,
1243, 1178, 1139, 1050, 1011, 842, 745 cm−1. H NMR (CDCl3, 300 MHz):
δ =
= 4.20 (AB syst., 2JH-H
1
13.2 Hz, 2H, CH2), 7.11 (t, 3JH-H = 3JH-F= 8.4 Hz, 2H, Ar-H), 7.35 (dd, 3JH-H = 8.4 Hz, 4JH-F = 5.3 Hz, 2H,
Ar-H). 19F NMR (CDCl3, 188 MHz): 112.25(m, 1F, Ar-F). 13C NMR (CDCl3,
73.11 (s, 3F, CF3),
75 MHz):
= 54.7 (q, 3JC-F = 3.1 Hz), 116.5 (d, 2JC-F = 21.9 Hz), 123.3 (d, 4JC-F = 3.3 Hz), 125.3 (q, 1JC-F
335.0 Hz, CF3), 132.3 (d, 3JC-F = 8.5 Hz), 163.4 (d, 1JC-F = 249.3 Hz, C-F).
δ
=
−
−
δ
=
1
((Difluoromethyl)sulfinyl)benzene 6a
[
40]. Colorless liquid; yield 1.2 g (70%); b.p. 130 ◦C (10 Torr). H
NMR (CDCl3, 400 MHz):
δ
= 6.02 (t, 2JH-F = 55.6 Hz, 1H, CHF2), 7.55-7.60 (m, 3H, Ar-H), 7.69–7.71 (m,
2H, Ar-H). 19F {H} NMR (CDCl3, 376.5 MHz):
δ
=
−
119.4 (d, 2JF-F = 260 Hz, 1F, CHF2), -120.2 (d, 2JF-F
δ
= 120.8 (dd, 1JC-F= 288 Hz, 287 Hz, CHF2), 125.4,
= 260 Hz, 1F, CHF2). 13C NMR (CDCl3, 100.6 MHz):
129.5, 132.8, 136.6 (t, 3JC-F = 4 Hz).
N-(4-((Difluoromethyl)sulfinyl)phenyl)acetamide 6b
166–167 C (Lit. 170–171 C). H NMR (DMSO-d6, 500 MHz):
[
30]. Pale yellow solid; yield 1.9 g (80%); m.p.
◦
◦
1
2
δ
= 2.09 (s, 3H, CH3), 6.89 (t, JH-F
= 54 Hz, 1H, CHF2), 7.70 (d, 3JH-H = 8 Hz, 2H, Ar-H), 7.85 (d, 3JH-H = 8 Hz, 2H, Ar-H), 10.34 (s, 1H,
NH). 19F NMR (DMSO-d6, 376.5 MHz): = -121.4 (dd, 2JF-F = 257 Hz, 2JH-F = 54 Hz, 1F, CHF2), -125.5
(dd, 2JF-F = 257 Hz, 2JH-F = 54 Hz, 1F, CHF2). 19F {H} NMR (CDCl3, 376.5 MHz): 121.5 (d, 2JF-F
= 257 Hz, 1F, CHF2), -123.3 (d, 2JF-F = 257 Hz, 1F, CHF2). 13C NMR (DMSO-d6, 125.7 MHz):
= 24.6,
119.8, 120.6 (t, 1JC-F = 292 Hz, CHF2), 120.9 (t, 1JC-F = 280 Hz, CHF2), 127.2, 127.3, 129.9, 143.8, 169.5.
δ
δ
=
−
δ
1-((Difluoromethyl)sulfinyl)-4-nitrobenzene 6c
30]. Pale yellow solid; yield 1.7 g (75%); m.p. 84–85 ◦C
(Lit. 81–83 ◦C). 1H NMR (DMSO-d6, 500 MHz): = 7.08 (t, 2JH-F = 56 Hz, 1H, CHF2), 8.04 (d, 3JH-H
6.5 Hz, 2H, Ar-H), 8.46 (d, 3JH-H = 6.5 Hz, 2H, Ar-H). 19F NMR (DMSO-d6, 376.5 MHz):
120.8 (dd,
2JF-F = 254 Hz, 2JH-F = 56 Hz, 1F, CHF2), -125.9 (dd, 2JF-F = 254 Hz, 2JH-F = 56 Hz, 1F, CHF2). 19F {H}
NMR (DMSO-d6, 376.5 MHz):
120.8 (d, 2JF-F = 254 Hz, 1F, CHF2), 125.9 (d, 2JF-F = 254 Hz, 1F,
CHF2). 13C NMR (DMSO-d6, 125.7 MHz): = 120.4 (t, 1JC-F = 284 Hz, CHF2), 120.6 (t, 1JC-F = 287 Hz,
CHF2), 124.7, 124.9, 127.4, 127.5, 133.9, 144.3, 150.4.
[
δ
=
δ
=
−
δ
=
−
−
δ
(1,1,2,2-Tetrafluoro-2-((1,2,4-triazol)-1-yl)-ethyl)-sulfinylbenzene 6d. Crude product was purified by
column chromatography, eluent CH2Cl2, then methyl-tert-butyl ether (Rf = 0.7). Pale yellow solid;
yield 2.7 g (92%); m.p. 77–78 ◦C. IR (KBr): 3105, 2872, 1819, 1688, 1582, 1512, 1477, 1453, 1403, 1378,
1
1294, 1262, 1221, 1191, 1140, 1111, 1070, 981, 903, 830, 756, 691, 667, 629, 591, 514, 482, 449 cm−1. H
NMR (CDCl3, 500 MHz):
(s, 1H, Het-H). 19F NMR (CDCl3, 376.5 MHz):
226 Hz, 1F, CF2),
112.5 (d, 2JF-F = 237 Hz, 1F, CF2), 124.3 (d, 2JF-F = 237 Hz, 1F, CF2). 13C NMR (CDCl3,
125.7 MHz):
δ
= 7.56–7.65 (m, 3H, Ar-H), 7.77 (d, 2H, Ar-H), 8.15 (s, 1H, Het-H), 8.59
δ
=
−
94.0 (d, 2JF-F = 226 Hz, 1F, CF2), 94.6 (d, 2JF-F
−
=
−
δ
= 113.0 (tt, 1JC-F = 271 Hz, 2JC-F = 31 Hz, CF2), 116.9 (ddt, 1JC-F = 318 Hz, 1JC-F = 308 Hz,
2JC-F 38 Hz, CF2), 126.7, 129.5, 133.8, 135.0, 143.4, 154.1. Anal. Calcd for C12H12F4N3OS: C, 44.72; H,
3.75; N, 13.04; S, 9.95. Found: C, 44.74; H, 3.76; N, 13.02; S, 9.98.
((Bromodifluoromethyl)sulfinyl)benzene 6e [41]. Compound 5e was oxidized only on a 50 mmol scale.
Crude product was purified by column chromatography, eluent petroleum ether-diethyl ether, 8:2 (Rf
1
= 0.6). Yellow oil; yield 8.1 g (91%). IR (KBr):1443, 1114, 1073, 1056, 854, 827, 742, 687 cm−1. H NMR
(CDCl3, 200 MHz):
δ
= 7.52 (m, 3H, ArH), 7.72 (m, 2H, ArH). 19F NMR (CDCl3, 188 MHz):
δ
= -53.49
and -55.56 (2F, CF2Br, syst. AB 2JC-F = 145 Hz). 13C NMR (CDCl3, 50 MHz):
355 Hz, 350.5Hz), 129.1, 133.4, 136.7 (dd, 3JC-F = 3 Hz, 1 Hz).
δ
= 126.2, 128.4 (dd, 1JC-F
=
((Dichlorofluoromethyl)sulfinyl)benzene 6f [42]. Compound 5f was oxidized only on a 50 mmol scale.
Crude product was purified by column chromatography, eluent petroleum ether-diethyl ether, 8:2 (Rf
1
= 0.5). Yellow oil; yield 10.6 g (69%). IR (KBr): 1445, 1104, 1061, 840, 792, 744, 684 cm−1. H NMR
(CDCl3, 200 MHz):
δ
= 7.61 (m, 3H, Ar-H), 7.82 (m, 2H, Ar-H). 19F NMR (CDCl3, 188 MHz):
δ
=
−
62.8