N. Vida, P. Beier / Journal of Fluorine Chemistry 143 (2012) 130–134
133
2
dropwise (over 2–8 min) to a solution of 1 or 2 (150 mg,
0.60 mmol) in THF or Et2O (7 mL) at À75 8C. After 2 min of stirring
at this temperature, powdered KMnO4 (158 mg, 1 mmol,
1.7 equiv.) followed by liquid NH3 (7 mL) were added. After
10 min of stirring solid NH4Cl (0.1 g) was carefully added and the
mixture was warmed to rt. Aqueous solution of oxalic acid was
added to decompose MnO2 and the crude product was extracted
into EtOAc (3 Â 15 mL). The combined organic phase was washed
with water (15 mL), aqueous NaHCO3 (15 mL) and brine (15 mL),
dried (MgSO4), and solvent was removed under reduced pressure.
Pure product was obtained by column chromatography using silica
gel 60 and hexane as an eluent.
NMR (376 MHz, CDCl3) dF 62.1 (d, 4F, JFF = 150.6 Hz), 80.4–82.0
(m, 1F); MS (EI) m/z (rel. int.) 263 (15) [M]+, 246 (100), 119 (57),
109 (30), 89 (54), 63 (30); HRMS (EI) m/z calcd for C7H6F5NO2S [M]+
263.0039, found 263.0034.
4.1.6. 2-Nitro-4-(pentafluorosulfanyl)-1-n-propylbenzene (5a)
An orange oil (58 mg, 33% yield); Rf 0.19 (hexane); 1H NMR
(600 MHz, CDCl3) dH 1.02 (t, 3H, JHH = 7.5 Hz), 1.71 (m, 2H), 2.92
3
3
3
(m, 2H), 7.49 (d, 1H, JHH = 8.5 Hz), 7.89 (dd, 1H, JHH = 8.5 Hz,
4JHH = 2.4 Hz), 8.29 (d, 1H, JHH = 2.4 Hz); 13C NMR (150.9 MHz,
4
3
CDCl3) dC 13.9, 23.7, 34.7, 122.8 (quin, JCF = 4.9 Hz), 129.7 (quin,
3JCF = 4.4 Hz), 132.4, 141.5, 148.7, 151.5 (quin, JCF = 19.8 Hz); 19F
2
2
NMR (376 MHz, CDCl3) dF 62.7 (d, 4F, JFF = 151.0 Hz), 80.5–82.2
4.1.1. 1-Nitro-4-(pentafluorosulfanyl)-2-n-propylbenzene (4a)
An orange oil (98 mg, 56% yield); Rf 0.13 (hexane); 1H NMR
(m, 1F); MS (EI) m/z (rel. int.) 291 (3) [M]+, 274 (100), 246 (20), 147
(98), 115 (38), 89 (37), 77 (22), 63 (24); HRMS (CI) m/z calcd for
C9H11F5NO2S [MH]+ 292.0431, found 292.0424.
3
(400 MHz, CDCl3) dH 1.02 (t, 3H, JHH = 7.4 Hz), 1.71 (m, 2H), 2.90
(m, 2H) 7.72–7.77 (m, 2H), 7.90–7.94 (m, 1H); 13C NMR (100 MHz,
3
CDCl3) dC 13.8, 23.8, 34.7, 124.8, 124.9 (quin, JCF = 4.7 Hz), 129.6
4.1.7. 4-Nitro-2-(pentafluorosulfanyl)-1-n-propylbenzene (6a)
A yellow oil (42 mg, 23% yield); Rf 0.26 (hexane:EtOAc, 97:3); 1H
3
2
(quin, JCF = 4.7 Hz), 138.4, 150.7, 155.8 (quin, JCF = 18.2 Hz); 19F
2
NMR (376 MHz, CDCl3) dF 62.0 (d, 4F, JFF = 150.6 Hz), 80.5–82.1
NMR (600 MHz, CDCl3) d
H 1.06 (t, 3H, 3JHH = 7.5 Hz), 1.66 (m, 2H),
(m, 1F); MS (EI) m/z (rel. int.) 291 (3) [M]+, 274 (87), 246 (24), 218
(19), 147 (100), 115 (34), 89 (37), 77 (22), 63 (28); HRMS (EI) m/z
calcd for C9H10F5NO2S [M]+ 291.0352, found 291.0349.
3.00 (m, 2H) 7.57 (d, 1H, 3JHH = 8.6 Hz), 8.27 (dd, 1H, 3JHH = 8.6 Hz,
4JHH = 2.3 Hz), 8.67 (d, 1H, JHH = 2.3 Hz); 13C NMR (150.9 MHz,
4
3
CDCl3) dC 14.3, 25.3, 36.8 (quin, JCF = 3.4 Hz), 123.9 (quin,
3JCF = 5.9 Hz), 125.6, 133.7, 145.5, 147.2, 153.0 (quin,
2JCF = 17.4 Hz); 19F NMR (376 MHz, CDCl3) dF 66.6 (d, 4F,
2JFF = 149.6 Hz), 82.5–84.2 (m, 1F); MS (EI) m/z (rel. int.) 291
(100) [M]+, 263 (17), 155 (52), 135 (30), 117 (33), 108 (53), 89 (86),
77 (22), 63 (24); HRMS (CI) m/z calcd for C9H11F5NO2S [MH]+
292.0431, found 292.0430.
4.1.2. 2-n-Butyl-1-nitro-4-(pentafluorosulfanyl)benzene (4b)
An orange oil (120 mg, 65% yield); Rf 0.15 (hexane); 1H NMR
(400 MHz, CDCl3)
1.58–1.70 (m, 2H), 2.89–2.95 (m, 2H) 7.73–7.77 (m, 2H), 7.89–7.93
(m, 1H); 13C NMR (100 MHz, CDCl3)
C 13.6, 22.5, 32.5, 32.6, 124.7–
d
H 0.96 (t, 3H, 3JHH = 7.3 Hz), 1.38–1.48 (m, 2H),
d
124.9 (m, 2C), 129.4–129.6 (m), 138.7, 150.6, 155.8 (quin,
2JCF = 18.6 Hz); 19F NMR (470 MHz, CDCl3) dF 62.1 (d, 4F,
2JFF = 150.4 Hz), 80.7–82.0 (m, 1F); MS (EI) m/z (rel. int.) 305 (4)
[M]+, 288 (100), 246 (74), 218 (20), 161 (57), 143 (23), 119 (24), 89
(32), 77 (20); HRMS (CI) m/z calcd for C10H13 F5NO2S [MH]+
306.0587, found 306.0581.
4.1.8. 1-n-Butyl-2-nitro-4-(pentafluorosulfanyl)benzene (5b)
An orange oil (62 mg, 34% yield); Rf 0.15 (hexane); 1H NMR
(400 MHz, CDCl3)
d
H 0.96 (t, 3H, 3JHH = 7.3 Hz), 1.38–1.48 (m, 2H),
3
1.60–1.69 (m, 2H), 2.92–2.97 (m, 2H) 7.49 (d, 1H, JHH = 8.5 Hz),
7.88 (dd, 1H, 3JHH = 8.5 Hz, 4JHH = 2.3 Hz), 8.29 (d, 1H,
4JHH = 2.3 Hz); 13C NMR (100 MHz, CDCl3) dC 13.7, 22.6, 32.5,
3
4.1.3. 2-Benzyl-1-nitro-4-(pentafluorosulfanyl)benzene (4c)
An orange oil (64 mg, 31% yield); Rf 0.28 (hexane:EtOAc, 97:3);
32.5, 122.6–122.9 (m), 129.6 (quin, JCF = 4.5 Hz), 132.4, 141.7,
148.7, 151.3–151.8 (m); 19F NMR (376 MHz, CDCl3)
dF 62.6 (d, 4F,
1H NMR (400 MHz, CDCl3)
7.28 (m, 1H), 7.29–7.35 (m, 2H), 7.69 (d, 1H, JHH = 2.4 Hz), 7.77
(dd, 1H, 3JHH = 8.9 Hz, 4JHH = 2.4 Hz), 7.96 (d, 1H, 3JHH = 8.9 Hz); 13
d
H 4.33 (s, 2H), 7.11–7.15 (m, 2H), 7.23–
2JFF = 150.9 Hz), 80.5–82.2 (m, 1F); MS (EI) m/z (rel. int.) 305 (3)
[M]+, 288 (100), 246 (62), 161 (51), 143 (25), 89 (33), 77 (19), 63
(19); HRMS (CI) m/z calcd for C10H13F5NO2S [MH]+ 306.0587, found
306.0576.
4
C
NMR (100 MHz, CDCl3) dC 38.3, 125.1, 125.3–125.5 (m), 127.2,
128.9 (2C), 128.9 (2C), 129.9–130.2 (m), 136.9, 137.1, 150.5, 155.5–
156.4 (m); 19F NMR (470 MHz, CDCl3) dF 62.0 (d, 4F,
2JFF = 150.7 Hz), 80.4–81.7 (m, 1F); MS (EI) m/z (rel. int.) 339
(12) [M]+, 338 (11), 305 (20), 195 (45), 183 (15), 165 (53), 105 (17),
77 (19); HRMS (CI) m/z calcd for C13H11F5NO2S [MH]+ 340.0431,
found 340.0425.
4.1.9. 1-n-Butyl-4-nitro-2-(pentafluorosulfanyl)benzene (6b)
A yellow oil (45 mg, 26% yield); Rf 0.26 (hexane:EtOAc, 97:3); 1H
NMR (500 MHz, CDCl3) d
H 0.98 (t, 3H, 3JHH = 7.3 Hz), 1.48 (m, 2H),
1.60 (m, 2H), 3.03 (m, 2H) 7.56 (d, 1H, 3JHH = 8.6 Hz), 8.27 (dd, 1H,
4
4
3JHH = 8.6 Hz, JHH = 2.3 Hz), 8.66 (d, 1H, JHH = 2.3 Hz); 13C NMR
3
(125.7 MHz, CDCl3) dC 13.7, 22.9, 34.2, 34.6 (quin, JCF = 3.6 Hz),
123.9 (quin, JCF = 6.0 Hz), 125.6, 133.8, 145.4, 147.5, 152.9 (quin,
3
4.1.4. 1-Nitro-4-(pentafluorosulfanyl)-2-isopropylbenzene (4d)
An orange oil (86 mg, 49% yield); Rf 0.32 (hexane:EtOAc, 97:3);
d
1H NMR (400 MHz, CDCl3) H 1.34 (d, 6H, 3JHH = 6.8 Hz), 3.42 (sept,
2JCF = 17.1 Hz); 19F NMR (470 MHz, CDCl3) dF 66.6 (d, 4F,
2JFF = 149.7 Hz), 82.5–84.2 (m, 1F); MS (EI) m/z (rel. int.) 305
(13) [M]+, 263 (43), 178 (15), 155 (70), 132 (51), 108 (30), 89 (30),
77 (15), 63 (15), 43 (100); HRMS (CI) m/z calcd for C10H13F5NO2S
[MH]+ 306.0587, found 306.0586.
1H, 3JHH = 6.8 Hz), 7.70–7.78 (m, 2H), 7.84–7.86 (m, 1H); 13C NMR
(125.7 MHz, CDCl3) dC 23.3 (2C), 29.0, 124.1, 124.7 (quin,
3JCF = 4.6 Hz), 125.8 (quin, 3JCF = 4.7 Hz), 143.5, 150.8, 156.1 (quin,
2JCF = 18.3 Hz); 19F NMR (376 MHz, CDCl3) dF 61.9 (d, 4F,
2JFF = 150.4 Hz), 80.7–82.3 (m, 1F); MS (EI) m/z (rel. int.) 291 (2)
[M]+, 276 (38), 247 (42), 231 (52), 147 (100), 130 (20), 115 (60), 102
(31), 89 (53), 77 (41); HRMS (CI) m/z calcd for C9H11F5NO2S [MH]+
292.0431, found 292.0426.
4.1.10. 2-Nitro-4-(pentafluorosulfanyl)-1-isopropylbenzene (5d)
An orange oil (31 mg, 18% yield); Rf 0.31 (hexane:EtOAc, 97:3);
1H NMR (500 MHz, CDCl3)
d
H 1.33 (d, 6H, 3JHH = 6.8 Hz), 3.46 (sept,
3
3
1H, JHH = 6.8 Hz), 7.61 (d, 1H, JHH = 8.7 Hz), 7.92 (dd, 1H,
4
3
3JHH = 8.7 Hz, JHH = 2.4 Hz), 8.12 (d, 1H, JHH = 2.4 Hz); 13C NMR
(125.7 MHz, CDCl3)
C 23.3, 28.8, 122.0 (quin, 3JCF = 4.9 Hz), 128.4,
129.6 (quin, 3JCF = 4.6 Hz), 146.5, 148.9, 151.3 (quin, 2JCF = 20.1 Hz);
4.1.5. 2-Methyl-1-nitro-4-(pentafluorosulfanyl)benzene (4f)
A yellow oil (103 mg, 64% yield); Rf 0.26 (hexane:EtOAc, 97:3);
d
1H NMR (400 MHz, CDCl3)
d
H 2.67 (s, 1H), 7.73–7.79 (m, 2H), 8.00-
19F NMR (376 MHz, CDCl3) F 62.6 (d, 4F, 2JFF = 151.1 Hz), 80.5–82.2
d
8.04 (m, 1H); 13C NMR (100 MHz, CDCl3)
d
C 20.2, 124.8–125.0 (m,
(m, 1F); MS (EI) m/z (rel. int.) 291 (2) [M]+, 274 (49), 256 (15), 247
3
2C), 130.4 (quin, JCF = 4.7 Hz), 134.5, 150.5, 155.5–156.3 (m); 19F
(37), 231 (47), 147 (100), 130 (20), 115 (68), 102 (29), 89 (52), 77