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N-(2-Chloro-3,5-diuorophenyl)-4-methylbenzenamine (Table 7,
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MHz, CDCl3) d 7.42–7.40 (m, 1H), 7.37–7.34 (m, 1H), 7.08 (dt, J ¼
7.6, 1.6 Hz, 1H), 6.44 (m, 2H), 6.33 (br, 1H); 13C NMR (100 MHz,
CDCl3) d 161.6 (dd, J ¼ 243.7, 14.1 Hz), 159.0 (d, J ¼ 246.5 Hz),
159.0 (dd, J ¼ 247.3, 15.7 Hz), 142.6 (dd, J ¼ 13.1, 4.0 Hz), 134.4
(d, J ¼ 3.4 Hz), 124.4 (d, J ¼ 8.4 Hz), 120.6 (d, J ¼ 25.2 Hz), 118.5
(d, J ¼ 9.8 Hz), 115.5 (d, J ¼ 22.2 Hz), 103.7 (dd, J ¼ 18.5, 4.0 Hz),
96.8 (dd, J ¼ 27.7, 3.1 Hz), 95.8 (dd, J ¼ 27.2, 25.4 Hz); HRMS
(ESI): m/z [M ꢁ H]ꢁ calc. for C12H5BrClF3N 333.9246, found
333.9241.
entry 1). White solid (205 mg, 81%); 1H NMR (400 MHz, CDCl3) d
7.21 (d, J ¼ 8.0 Hz, 2H), 7.10 (d, J ¼ 7.6 Hz, 2H), 6.59 (dd, J ¼ 10.0,
2.4 Hz, 1H), 6.36 (dt, J ¼ 8.6, 2.4 Hz, 1H), 6.23 (br, 1H), 2.38 (s, 3H);
13C NMR (100 MHz, CDCl3): d 161.7 (dd, J ¼ 242.0, 14.9 Hz), 158.9
(dd, J ¼ 245.0, 15.7 Hz), 143.8 (dd, J ¼ 12.5, 4.2 Hz), 136.9, 134.6,
130.2, 123.0, 102.3 (dd, J ¼ 19.0, 6.0 Hz), 96.0 (dd, J ¼ 27.0, 3.9 Hz),
94.3 (dd, J ¼ 27.4, 25.5 Hz), 20.9; HRMS (ESI): m/z [M ꢁ H]ꢁ calc. for
C13H9ClF2N 252.0392, found 252.0390.
2-Chloro-3,5-diuoro-N-phenylbenzenamine (Table 7, entry
8). White solid (208 mg, 87%). 1H NMR (400 MHz, CDCl3) d 7.39
(t, J ¼ 7.6 Hz, 2H), 7.21–7.15 (m, 3H), 6.68 (d, J ¼ 10.8 Hz, 1H),
6.39 (tt, J ¼ 10.4, 2.4 Hz, 1H), 6.29 (br, 1H); 13C NMR (100 MHz,
CDCl3) d 161.7 (dd, J ¼ 244.3, 15.8 Hz), 159.1 (dd, J ¼ 245.6, 15.6
Hz), 143.2 (dd, J ¼ 13.1, 4.1 Hz), 139.7, 129.7, 124.5, 122.3, 102.9
(dd, J ¼ 20.4, 3.8 Hz), 96.5 (dd, J ¼ 27.8, 3.0 Hz), 94.9 (dd, J ¼
27.5, 25.5 Hz). HRMS (ESI): m/z [M ꢁ H]ꢁ calc. for C12H7ClF2N
238.0230, found 238.0239.
4-Chloro-N-(2-chloro-3,5-diuorophenyl)benzeneamine (Table
7, entry 2). White solid (238 mg, 87%); 1H NMR (400 MHz, CDCl3) d
7.35 (m, 2H), 7.13 (m, 2H), 6.61 (dt, J ¼ 10.8, 2.4 Hz, 1H), 6.41 (tt, J
¼ 8.8, 2.8 Hz, 1H), 6.23 (br, 1H); 13C NMR (100 MHz, CDCl3): d
161.7 (dd, J ¼ 250.1, 17.6 Hz), 159.0 (dd, J ¼ 246.3, 15.5 Hz), 142.8
(dd, J ¼ 13.0, 4.2 Hz), 138.3, 129.8, 129.6, 123.4, 103.2 (dd, J ¼ 20.0,
4.0 Hz), 96.7 (dd, J ¼ 27.7, 3.0 Hz), 95.3 (dd, J ¼ 27.0, 25.4 Hz);
HRMS (ESI): m/z [M ꢁ H]ꢁ calc. for C12H6Cl2F2N 271.9845, found
271.9841.
4-Bromo-N-(2-chloro-3,5-diuorophenyl)benzeneamine (Table 7,
entry 3). White solid (284 g, 89%); 1H NMR (400 MHz, CDCl3) d 7.47
(m, 2H), 7.08 (m, 2H), 6.63 (dt, J ¼ 10.8, 2.0 Hz, 1H), 6.41 (tt, J ¼ 8.8,
2.8 Hz, 1H), 6.23 (br, 1H); 13C NMR (100 MHz, CDCl3) d 161.6 (dd, J
¼ 242.6, 13.3 Hz), 159.0 (dd, J ¼ 246.2, 15.7 Hz), 142.5 (dd, J ¼ 13.0,
4.2 Hz), 138.8, 132.7, 123.5, 117.0, 103.3 (dd, J ¼ 20.3, 4.4 Hz), 96.8
(dd, J ¼ 27.7, 3.1 Hz), 95.4 (dd, J ¼ 27.3, 25.4 Hz). HRMS (ESI): m/z [M
ꢁ H]ꢁ calc. for C12H6BrClF2N 315.9340, found 315.9356.
General procedure of amination of 1,2,4,5-tetrauorobenzene
In a typical run, a 4 mL vial was charged with t-BuOK (1 mmol)
in glove box, and the capped vial was move out of glove box.
Aniline (1 mmol), 1,2,4,5-tetrauorobenzene (1 mmol), and
toluene (1 mL) were injected into the vial respectively. The
mixture was stirred at room temperature for 3 h. The reaction
mixture was concentrated under reduced pressure, and the
product was puried by ash column chromatography on silica
gel (PE/EtOAc ¼ 100 : 1).
2-Chloro-N-(2-chloro-3,5-diuorophenyl)benzeneamine (Table 7,
1
entry 4). White solid (233 mg, 85%). H NMR (400 MHz, CDCl3) d
7.47–7.39 (m, 2H), 7.30–7.28 (m, 1H), 7.06 (t, J ¼ 7.6 Hz, 1H), 6.72 (d,
J ¼ 10.4 Hz, 1H), 6.55 (br, 1H), 6.47 (tt, J ¼ 8.8, 2.0 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d 161.6 (dd, J ¼ 244.0, 14.3 Hz), 159.0 (dd, J ¼
246.0, 15.3 Hz), 141.9 (dd, J ¼ 13.0, 2.0 Hz), 136.9, 130.3, 127.6, 125.9,
124.4, 121.1, 104.5 (dd, J ¼ 21.0, 4.0 Hz), 97.7 (dd, J ¼ 27.5, 3.2 Hz),
96.2 (dd, J ¼ 27.1, 25.4 Hz); HRMS (ESI): m/z [M ꢁ H]ꢁ calc. for
C12H6Cl2F2N 271.9848, found 271.9840.
m-Tolyl-(2,4,5-triuoro-phenyl)-amine (Table 8, entry 1).
Yellow solid (192 mg, 81%); mp: 50.2–52.4 ꢀC; 1H NMR (400
MHz, CDCl3) d 7.21 (m, 1H), 7.09 (dt, J ¼ 12.0, 8.0 Hz, 1H), 6.96
(td, J ¼ 10.4, 7.2 Hz, 1H), 6.90–6.84 (m, 3H), 5.62 (s, 1H), 2.34 (s,
3H); 13C NMR (100 MHz, CDCl3) d 141.1, 139.6, 129.4, 123.6,
119.8, 116.2, 105.6–105.3 (m), 105.2–104.9 (m), 100.0, 21.5; 19F
NMR (376 MHz, CDCl3) ꢁ145.9 (d, J ¼ 22.2 Hz), ꢁ141.7 (dd, J ¼
22.2, 12.8 Hz), ꢁ134.9 (d, J ¼ 12.8 Hz); HRMS (ESI): m/z [M ꢁ
H]ꢁ calc. for C13H9F3N 236.0687, found: 236.0684.
(4-Chloro-phenyl)-(2,4,5-triuoro-phenyl)-amine (Table 8,
entry 2). Yellow solid (175 mg, 68%); mp: 63.5–65.2 ꢀC; 1H NMR
(400 MHz, CDCl3) d 7.30–7.26 (m, 2H), 7.05 (dd, J ¼ 9.8, 6.0 Hz,
1H), 7.04–6.99 (m, 2H), 6.97 (dd, J ¼ 8.6, 5.6 Hz, 1H), 5.63 (br,
1H); 13C NMR (100 MHz, CDCl3) d 139.9, 129.6, 127.5, 120.1,
105.7 (m), 105.4 (m); 19F NMR (376 MHz, CDCl3) ꢁ144.6 (d, J ¼
22.2 Hz), ꢁ141.2 (dd, J ¼ 22.2, 13.5 Hz), ꢁ133.9 (d, J ¼ 13.5 Hz);
HRMS (ESI): m/z [M ꢁ H]ꢁ calc. for C12H6ClF3N 256.0141,
found: 256.0143.
(2-Bromo-4-methyl-phenyl)-(2,4,5-triuoro-phenyl)-amine (Table
8, entry 3). Yellow solid (228 mg, 72%); 1H NMR (400 MHz, CDCl3) d
7.41 (d, J ¼ 1.0 Hz, 1H), 7.11–6.96 (m, 4H), 5.84 (br, 1H), 2.30 (s, 3H);
13C NMR (100 MHz, CDCl3) d 136.8, 133.6, 133.4, 129.0,
118.4, 114.6, 106.5–106.3 (m), 105.6–105.9 (m), 20.4; 19F NMR (376
MHz, CDCl3) ꢁ144.0 (m), ꢁ141.4 (m), ꢁ132.8 (m); HRMS (ESI): m/z
[M ꢁ H]ꢁ calc. for C13H8BrF3N 313.9798, found 317.9792.
(4-Fluoro-phenyl)-(2,4,5-triuoro-phenyl)-amine (Table 8,
entry 4). Orange solid (193 mg, 80%); mp: 53.4–55.2 ꢀC; 1H NMR
(400 MHz, CDCl3) d 7.11–7.03 (m, 4H), 7.03–6.97 (m, 1H),
3-Chloro-N-(2-chloro-3,5-diuorophenyl)benzeneamine (Table 7,
1
entry 5). White solid (211 mg, 77%). H NMR (400 MHz, CDCl3) d
7.32–7.28 (m, 1H), 7.12–7.06 (m, 2H), 6.71 (d, J ¼ 10.4 Hz, 1H), 6.44
(tt, J ¼ 8.8, 2.0 Hz, 1H), 6.27 (br, 1H); 13C NMR (100 MHz, CDCl3) d
161.6 (dd, J ¼ 258.0 Hz, 14.2 Hz), 159.2 (dd, J ¼ 245.0 Hz, 15.2 Hz),
142.3 (dd, J ¼ 13.0, 4.0 Hz), 141.2, 135.3, 130.7, 124.3, 121.5, 119.6,
103.9 (dd, J ¼ 20.0, 5.0 Hz), 97.3 (dd, J ¼ 27.0, 3.0 Hz), 95.9 (dd, J ¼
27.7, 25.4 Hz); HRMS (ESI): m/z [M ꢁ H]ꢁ calc. for C12H6Cl2F2N
271.9848, found 271.9837.
2-Bromo-N-(2-chloro-3,5-diuorophenyl)-4-methylbenze-
namine (Table 7, entry 6). White solid (289 mg, 87%). 1H
NMR (400 MHz, CDCl3) d 7.47 (s, 1H), 7.27 (d, J ¼ 8.0 Hz,
1H), 7.13 (d, J ¼ 8.0 Hz, 1H), 6.55 (d, J ¼ 10.8 Hz, 1H), 6.41
(m, 2H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3) d 161.5 (dd,
J ¼ 243.0, 14.1 Hz), 159.0 (dd, J ¼ 244.0, 16.1 Hz), 142.7 (dd, J
¼ 13.0, 4.2 Hz), 135.7, 135.3, 133.8, 129.1, 122.7, 117.5,
103.6 (dd, J ¼ 20.0, 5.0 Hz), 96.8 (dd, J ¼ 27.8, 3.0 Hz), 95.4
(dd, J ¼ 27.4, 25.4 Hz), 20.6; HRMS (ESI): m/z [M ꢁ H]ꢁ calc.
for C13H8BrClF2N 329.9497, found 329.9487.
2-Bromo-N-(2-chloro-3,5-diuorophenyl)-4-uorobenzenam-
ine (Table 7, entry 7). White solid (303 mg, 90%). 1H NMR (400
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RSC Adv., 2015, 5, 7035–7048 | 7045