After cooling to ambient temperature most of the ethanol was
removed in vacuo. The residue was extracted three times with
MTBE (50 mL each). The combined organic layers were dried
with MgSO4, filtered and all volatiles were removed in vacuo.
The residue was purified by column chromatography.
δ 7.02–6.90 (3H), 5.83 (ddt, 2H, J = 17.1, 10.0, 6.5), 5.10
(dddd, 2H, J = 17.1, 1.8, 1.4, 1.4), 5.04–4.97 (2H), 3.62 (d (br),
4H, J = 6.5), 2.29 (s, 6H); 13C NMR (75 MHz, CDCl3) δ 148.1
(0), 137.5 (0, 2C), 136.9 (1, 2C), 128.7 (1, 2C), 125.0 (1), 115.9
(2, 2C), 56.0 (2, 2C), 19.6 (3, 2C); IR: ν˜ = 3072 (w), 2919 (w),
2821 (w), 1684 (w), 1641 (w), 1473 (m), 1415 (m); HRMS (EI)
calcd for C14H19N [M]+: 201.1517, found: 201.1514; MS (EI)
m/z 201 (M+, 30), 144 (26), 132 (36), 117 (20), 77 (28),
41 (100), 29 (54).
N,N-Diallyl-4-chloroaniline (2a). Following the general proce-
dure, 2a was obtained from 1a (2.54 g, 20 mmol) as a colorless
1
liquid (3.60 g, 86%). H NMR (300 MHz, CDCl3) δ 7.11 (dd,
2H, J = 9.2, 0.8), 6.59 (d, 2H, J = 8.6), 5.89–5.74 (2H),
5.19–5.15 (2H), 5.15–5.09 (2H), 3.91–3.85 (4H); 13C NMR
(75 MHz, CDCl3) δ 147.3 (0), 133.6 (1, 2C), 128.8 (1, 2C),
121.2 (0), 116.2, (2, 2C), 113.6 (1, 2C), 53.0 (2, 2C); IR: ν˜ =
3082 (w), 3007 (w), 2980 (w), 2863 (w), 1596 (m), 1497 (s),
1387 (m), 1355 (m), 1233 (m); HRMS (EI) calcd for C12H14N
[35]Cl [M]+: 207.0815, found: 207.0827; MS (EI) m/z 207
(M+, 26), 180 (19), 138 (19), 130 (21), 111 (26), 75 (20),
41 (100), 39 (48).
N,N-Diallyl-3-fluoroaniline (2f). Following the general proce-
dure, 2f was obtained from 1f (2.22 g, 20 mmol) as a colorless
liquid (3.00 g, 79%). H NMR (300 MHz, CDCl3) δ 7.07 (m,
1
1H), 6.45–6.29 (3H), 5.80 (ddt, 2H, J = 17.7, 9.9, 4.8),
5.19–5.09 (4H), 3.87 (d (br), 4H, J = 4.7); 13C NMR (75 MHz,
3
CDCl3) δ 164.1 (0, d, 1J = 242.6), 150.5 (0, d, J = 10.7), 133.5
3
4
(1, 2C), 130.0 (1, d, J = 10.4), 116.2 (2, 2C), 107.9 (1, d, J =
2
2
2.0), 102.7 (1, d, J = 21.7), 99.3 (1, d, J = 26.1), 52.8 (2, 2C);
IR: ν˜ = 3083 (w), 2981 (w), 2864 (w), 1617 (s), 1577 (m), 1498
(s), 1388 (w), 1355 (w); HRMS (EI) calcd for C12H14NF [M]+:
191.1110, found: 191.1101; MS (EI) m/z 191 (M+, 100),
164 (46), 95 (32), 41 (44), 39 (38).
N,N-Diallylaniline (2b). Following the general procedure, 2b
was obtained from 1b (1.86 g, 20 mmol) as a colorless
1
liquid (3.11 g, 90%). H NMR (300 MHz, CDCl3) δ 7.21 (d,
1H, J = 7.2), 7.18 (d, 1H, J = 7.2), 6.74–6.63 (3H), 5.86 (ddt,
2H, J = 17.3, 10.0, 4.9), 5.18 (dddd, 2H, J = 17.2, 1.8, 1.8, 1.7),
5.15 (dddd, 2H, J = 9.9, 1.7, 1.7, 1.5), 3.92 (ddd, 4H, J = 4.8,
1.7, 1.5); 13C NMR (75 MHz, CDCl3) δ 148.7 (0), 134.1 (1,
2C), 129.0 (1, 2C), 116.4 (1), 115.9 (2, 2C), 112.5 (1, 2C), 52.8
(2, 2C); IR: ν˜ = 3062 (w), 2978 (w), 2908 (w), 1597 (s), 1503
(s), 1386 (m), 1351 (m); HRMS (EI) calcd for C12H15N [M]+:
173.1204, found: 173.1219; MS (EI) m/z 173 (M+, 30),
146 (65), 130 (42), 77 (28), 41 (63), 39 (50).
N,N-Diallyl-3-nitroaniline (2g) and N-allyl-3-nitroaniline (3g).
Following the general procedure, 2g was obtained from 1g
(2.76 g, 20 mmol) as a yellow liquid (2.66 g, 61%). 2g could be
separated from N-allyl-3-nitroaniline (3g), which was isolated as
an orange solid (1.21 g, 34%). Analytical data of N,N-diallyl-3-
nitroaniline (2g): 1H NMR (300 MHz, CDCl3) δ 7.50–7.44
(2H), 7.26 (dd, 1H, J = 8.5, 8.3), 6.93 (ddd, 1H, J = 8.7, 2.1,
1.3), 5.84 (ddt, 2H, J = 17.7, 9.9, 4.8), 5.20 (dddd, 2H, J = 9.2,
1.6, 1.5, 1.5), 5.17 (dddd, 2H, J = 17.0, 1.6, 1.4, 1.4), 3.98 (dt,
J = 4.7, 2.1); 13C NMR (75 MHz, CDCl3) δ 149.4 (0),
149.2 (0), 132.6 (1, 2C), 129.6 (1), 117.7 (1), 116.6 (2, 2C),
110.7 (1), 106.4 (1), 52.9 (2, 2C); IR: ν˜ = 3085 (w), 2981 (w),
2866 (w), 1616 (m), 1522 (s), 1494 (m), 1389 (m), 1342 (s),
1236 (m); HRMS (EI) calcd for C12H14N2O2 [M]+: 218.1055,
found: 218.1064; MS (EI) m/z 218 (M+, 30), 191 (32), 171 (20),
130 (28), 41 (100), 39 (27). Analytical data of N-allyl-3-nitro-
aniline (3g): Mp: 66–68 °C; 1H NMR (300 MHz, CDCl3) δ 7.54
(dd, 1H, J = 8.0, 1.2), 7.41 (dd, 1H, J = 2.1, 2.0), 7.28 (dd, 1H,
J = 8.2, 8.1), 6.90 (dd, 1H, J = 1.9, 1.9), 5.93 (ddt, 1H, J = 17.2,
10., 5.2), 5.32 (m, 1H), 5.23 (m, 1H), 4.26 (s (br), 1H), 3.85
(d (br), 2H, J = 5.2); 13C NMR (75 MHz, CDCl3) δ 149.4 (0),
148.7 (0), 134.0 (1), 129.6 (1), 118.8 (2), 116.9 (1), 111.9 (1),
106.5 (1), 46.1 (2).
N,N-Diallyl-3-chloro-2-methylaniline (2c). Following the
general procedure, 2c was obtained from 1c (2.82 g, 20 mmol)
as a colorless liquid (3.18 g, 72%). 1H NMR (300 MHz, CDCl3)
δ 7.08 (dd, 1H, J = 7.9, 1.7), 7.08 (dd, 1H, J = 7.9, 7.5), 6.91
(dd, 1H, J = 7.5, 1.7), 5.76 (ddt, 2H, J = 17.2, 10.3, 6.2),
5.20–5.07 (4H), 3.55 (d (br), 4H, J = 6.2), 2.37 (s, 3H); 13C
NMR (75 MHz, CDCl3) δ 151.5 (0), 135.6 (0), 134.8 (1, 2C),
132.4 (0), 126.1 (1), 124.2 (1), 120.6 (1), 117.3 (2, 2C), 55.9 (2,
2C), 15.4 (3); IR: ν˜ = 3076 (w), 2979 (w), 2922 (w), 2815 (w),
1644 (w), 1586 (m), 1565 (m), 1458 (s), 1363 (w); HRMS (EI)
calcd for C13H16N[35]Cl [M]+: 221.0971, found: 221.0962; (EI)
m/z 221 (M+, 17), 117 (20), 43 (20), 41 (100), 39 (47).
N,N-Diallyl-5-chloro-2-methoxyaniline (2d). Following the
general procedure, 2d was obtained from 1d (3.14 g, 20 mmol)
as a colorless liquid (4.40 g, 93%). 1H NMR (300 MHz, CDCl3)
δ 6.88 (dd, 1H, J = 8.5, 2.5), 6.84 (d, 1H, J = 2.4), 6.74 (d, 1H,
J = 8.5), 5.80 (ddt, 2H, J = 17.2, 10.2, 6.3), 5.24–5.13 (4H),
3.83 (s, 3H), 3.74 (d (br), 4H, J = 6.2); 13C NMR (75 MHz,
CDCl3) δ 151.3 (0), 140.9 (0), 134.8 (1, 2C), 125.6 (0), 121.4
(1), 120.9 (1), 117.4 (2, 2C), 112.6 (1), 55.8 (3), 54.2 (2, 2C);
IR: ν˜ = 3076 (w), 2936 (w), 2833 (w), 1588 (m), 1495 (s), 1458
(m), 1409 (m), 1239 (s), 1214 (s); HRMS (EI) calcd for
C13H16NO[35]Cl [M]+: 237.0920, found: 237.0936; MS (EI)
m/z 237 (M+, 20), 154 (20), 41 (100), 39 (55).
N-(3-(Diallylamino)phenyl)acetamide (2h). Following the
general procedure, 2h was obtained from 1h (3.00 g, 20.0 mmol)
as a colorless solid (3.39 g, 52%). Mp: 70–72 °C; 1H NMR
(300 MHz, CDCl3) δ 7.40 (s, (br), 1H), 7.12 (dd, 1H, J = 8.1,
8.1), 7.05 (m, 1H), 6.74 (d (br), 1H, J = 7.8), 6.46 (dd, 1H, J =
8.3, 2.0), 5.86 (ddt, 2H, J = 17.2, 10.0, 4.8), 5.23–5.13 (4H),
3.92 (d (br), 4H, J = 4.7), 2.15 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 168.2 (0), 149.4 (0), 138.9 (0), 133.8 (1, 2C), 129.4
(1), 116.1 (2, 2C), 108.6 (1), 108.0 (1), 104.1 (1), 52.8 (2, 2C),
24.6 (3); IR: ν˜ = 3301 (m), 3081 (w), 2979 (w), 2922 (w), 1663
(s), 1610 (s), 1583 (s), 1551 (s), 1496 (s), 1434 (m); HRMS (EI)
calcd for C14H18N2O [M]+: 230.1419, found: 230.1412; MS (EI)
m/z 230 (M+, 100), 215 (31), 161 (29), 145 (20).
N,N-Diallyl-2,6-dimethylaniline (2e). Following the general
procedure, 2e was obtained from 1e (2.42 g, 20 mmol) as a
colorless liquid (2.70 g, 67%). 1H NMR (300 MHz, CDCl3)
5124 | Org. Biomol. Chem., 2012, 10, 5119–5130
This journal is © The Royal Society of Chemistry 2012