B. Gabriele, L. Veltri, R. Mancuso, G. Salerno, M. Costa
FULL PAPER
and evaporation of the solvent, the products were purified by col-
umn chromatography on silica gel using 9:1 hexane/AcOEt as the
eluent.
65 (21). C19H21N (263.38): C 86.65, H 8.04, N 5.32; found C 86.64,
H 8.06, N 5.30.
N-Benzyl-4-chloro-2-(phenylethynyl)aniline (1e): Yield: 2.07 g, start-
N-Benzyl-2-(phenylethynyl)aniline (1a): Yield: 1.99 g, starting from
ing from 2.19 g of 4-chloro-2-(phenylethynyl)aniline (68%). Yellow
1.86 g of 2-(phenylethynyl)aniline (73%). Colorless solid, m.p. 56–
solid, m.p. 83–86 °C. IR (KBr): ν = 3398 (m), 2205 (vw), 1591 (w),
˜
57 °C. IR (KBr): ν = 3410 (m), 2208 (w), 1581 (m), 1575 (m), 1510 1566 (w), 1488 (s), 1468 (m), 1412 (m), 1384 (m), 1321 (m), 1262
˜
(s), 1430 (m), 1384 (m), 1326 (m), 1265 (m), 1162 (w), 1024 (w),
749 (s), 692 (m) cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.53–7.44
(m, 2 H, aromatic), 7.43–7.24 (m, 9 H, 8 H aromatic + 3-H), 7.19–
7.10 (m, 1 H, 5-H), 6.66 (td, J = 7.5, 1.0 Hz, 1 H, 4-H), 6.57 (dis-
torted d, br., J = 8.5, 0.8 Hz, 1 H, 6-H), 5.13 (br. s, 1 H, NH), 4.42
(m), 1150 (w), 1121 (w), 1067 (w), 879 (m), 803 (m), 754 (s), 689
(s) cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.50–7.44 (m, 2 H,
aromatic), 7.37–7.25 (m, 9 H, 8 H aromatic + 3-H), 7.08 (dd, J =
8.9, 2.4 Hz, 1 H, 5-H), 6.47 (d, J = 8.9 Hz, 1 H, 6-H), 5.12 (t, br.,
J = 5.7 Hz, 1 H, NH), 4.43 (d, J = 5.7 Hz, 2 H, CH2Ph) ppm. 13C
(d, J = 4.9 Hz, 2 H, CH2Ph) ppm. 13C NMR (75 MHz, CDCl3): δ NMR (75 MHz, CDCl3): δ = 147.3, 138.7, 131.5, 131.4, 129.8,
= 148.7, 139.2, 132.2, 131.4, 130.0, 128.7, 128.37, 128.18, 127.2,
127.1, 123.3, 116.7, 110.0, 107.6, 95.3, 86.1, 47.7 ppm. GC–MS:
128.8, 128.5, 128.4, 127.4, 127.0, 122.8, 121.0, 111.1, 109.0, 96.2,
84.7, 47.8 ppm. GC–MS: m/z (%) = 319 (9) [M + 2]+, 317 (26)
m/z (%) = 283 (20) [M+], 207 (17), 206 (100), 204 (11), 178 (7), 165 [M+], 316 (11), 242 (32), 240 (100), 204 (10), 191 (10), 190 (8), 176
(12), 128 (4), 91 (22), 65 (9). C21H17N (283.37): C 89.01, H 6.05,
N 4.94; found C 89.01, H 6.07, N 4.92.
(5), 164 (9), 163 (9), 91 (34), 65 (11). C21H16ClN (317.81): C 79.36,
H 5.07, Cl 11.16, N 4.41; found C 79.40, H 5.06, Cl 11.14, N 4.40.
N-Benzyl-2-(4-bromophenylethynyl)aniline (1b): Yield: 2.60 g, start-
N-Benzyl-4-methyl-2-(phenylethynyl)aniline (1f): Yield: 2.21 g, start-
ing from 2.62 g of 2-(4-bromophenylethynyl)aniline (75%). Yellow
ing from 1.99 g of 4-methyl-2-(phenylethynyl)aniline (77%). Yellow
solid, m.p. 67–68 °C. IR (KBr): ν = 3409 (m), 2210 (w), 1600 (m), solid, m.p. 36–37 °C. IR (KBr): ν = 3483 (m), 2196 (w), 1614 (w),
˜
˜
1571 (m), 1511 (s), 1384 (m), 1327 (m), 1266 (m), 1163 (w), 1067 1511 (s), 1489 (w), 1451 (w), 1401 (m), 1384 (m), 1317 (m), 1273
(w), 1008 (m), 827 (m), 750 (s) cm–1. 1H NMR (300 MHz, CDCl3): (w), 1157 (w), 1068 (w), 1024 (w), 792 (m), 731 (m), 685 (m) cm–1.
δ = 7.49–7.43 (m, 2 H, aromatic), 7.42–7.27 (m, 8 H, 7 H aromatic
+ 3-H), 7.21–7.13 (m, 1 H, 5-H), 6.67 (td, J = 7.7, 0.8 Hz, 1 H, 4-
1H NMR (300 MHz, CDCl3): δ = 7.50–7.44 (m, 2 H, aromatic),
7.40–7.19 (m, 9 H, 8 H aromatic + 3-H), 6.96 (dd, J = 8.5, 1.8 Hz,
H), 6.58 (br. d, J = 8.5 Hz, 1 H, 6-H), 5.08 (br. s, 1 H, NH), 4.46 1 H, 5-H), 6.48 (d, J = 8.5 Hz, 1 H, 6-H), 4.99 (t, br., J = 5.7 Hz,
(d, J = 5.3 Hz, 2 H, CH2Ph) ppm. 13C NMR (75 MHz, CDCl3): δ 1 H, NH), 4.42 (d, J = 5.7 Hz, 2 H, CH2Ph), 2.21 (s, 3 H, Me)
= 148.8, 139.0, 132.8, 132.2, 131.6, 130.3, 128.7, 127.3, 127.0, 122.4,
ppm. 13C NMR (75 MHz, CDCl3): δ = 146.6, 139.4, 132.4, 131.4,
122.2, 116.7, 110.0, 107.2, 94.2, 87.2, 47.7 ppm. GC–MS: m/z (%) 130.7, 128.6, 128.4, 128.1, 127.1, 127.0, 125.7, 123.3, 110.1, 107.5,
= 363 (27) [M + 2]+, 361 (27) [M+], 286 (95), 284 (100), 206 (55), 95.0, 86.2, 47.9, 20.2 ppm. GC–MS: m/z (%) = 297 (28) [M+], 296
204 (30), 191 (18), 190 (17), 176 (9), 164 (20), 163 (18), 91 (57), 65
(17). C21H16BrN (362.26): C 69.62, H 4.45, Br 22.06, N 3.87; found
C 69.54, H 4.46, Br 22.12, N 3.88.
(12), 221 (19), 220 (100), 204 (11), 191 (10), 178 (15), 152 (5), 91
(34), 65 (11). C22H19N (297.39): C 88.85, H 6.44, N 4.71; found C
88.82, H 6.46, N 4.72.
N-Benzyl-2-(p-tolylethynyl)aniline (1c): Yield: 2.07 g, starting from
1.99 g of 2-(2-p-tolylethynyl)aniline (72%). Colorless solid, m.p.
N-Benzyl-2-(phenylethynyl)-5-(trifluoromethyl)aniline (1g): Yield:
2.75 g, starting from 2.51 g of 5-(trifluoromethyl)-2-(phenylethyn-
73–75 °C. IR (KBr): ν = 3410 (m), 2207 (vw), 1600 (m), 1572 (m), yl)aniline (82%). Colorless solid, m.p. 54–56 °C. IR (KBr): ν =
˜
˜
1512 (s), 1448 (m), 1384 (w), 1362 (m), 1326 (m), 1266 (m), 1180 3436 (m), 2204 (vw), 1612 (m), 1577 (m), 1521 (w), 1434 (m), 1335
(w), 1163 (w), 1061 (w), 1017 (w), 989 (w), 930 (w), 818 (s), 749 (s), (s), 1274 (m), 1163 (s), 1120 (s), 1081 (w), 1021 (w), 913 (w), 850
728 (s), 695 (m) cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.40–7.20
(m, 8 H, 7 H aromatic + 3-H), 7.15–7.06 (m, 3 H, 2 H aromatic +
5-H), 6.63 (td, J = 7.7, 0.8 Hz, 1 H, 4-H), 6.54 (d, J = 8.1 Hz, 1
H, 6-H), 5.13 (t, br., J = 4.8 Hz, 1 H, NH), 4.39 (d, J = 4.8 Hz, 2
(w), 814 (m), 755 (m), 689 (m) cm–1. 1H NMR (300 MHz, CDCl3):
δ = 7.49–7.42 (m, 2 H, aromatic), 7.40–7.25 (m, 9 H, 8 H aromatic
+ 3-H), 6.90 (br. d, J = 8.1 Hz, 1 H, 4-H), 6.80 (br. s, 1 H, 6-H),
5.24 (t, br., J = 5.7 Hz, 1 H, NH), 4.45 (d, J = 5.7 Hz, 2 H, CH2Ph)
H, CH2Ph), 2.31 (s, 3 H, Me) ppm. 13C NMR (75 MHz, CDCl3): ppm. 13C NMR (75 MHz, CDCl3): δ = 148.7, 138.3, 132.3, 131.60
δ = 148.6, 139.1, 138.3, 132.0, 131.3, 129.8, 129.1, 128.6, 127.1,
127.0, 120.2, 116.6, 109.9, 107.8, 95.4, 85.3, 47.6, 21.4 ppm. GC–
(q, J = 32.0 Hz), 131.56, 128.9, 128.7, 128.5, 127.6, 127.2, 124.2 (q,
J = 272.6 Hz), 122.6, 113.1 (q, J = 4.0 Hz), 111.0, 106.2 (q, J =
MS: m/z (%) = 297 (29) [M+], 296 (18), 221 (19), 220 (100), 206 4.0 Hz), 97.1, 84.7, 47.7 ppm. 19F NMR (471 MHz, CDCl3): δ =
(24), 204 (13), 191 (6), 179 (8), 178 (12), 165 (2), 152 (3), 128 (4), –63.0 (s, 3 F, CF3) ppm. GC–MS: m/z (%) = 351 (19) [M+], 275
115 (2), 91 (13). C22H19N (297.39): C 88.85, H 6.44, N 4.71; found (19), 274 (100), 233 (8), 204 (7), 190 (7), 163 (4), 91 (76), 65 (24).
C 88.84, H 6.46, N 4.70.
C22H16F3N (351.36): C 75.20, H 4.59, F 16.22, N 3.99; found C
75.16, H 4.57, F 16.27, N 4.00.
N-Benzyl-2-(hex-1-ynyl)aniline (1d): Yield: 1.74 g, starting from
1.66 g of 2-(hex-1-ynyl)aniline (69%). Yellow oil. IR (film): ν =
N-Benzyl-5-methyl-2-(phenylethynyl)aniline (1h): Yield: 1.75 g,
˜
3400 (m, br.), 2930 (m), 2860 (m), 2221 (vw), 1600 (m), 1577 (m),
1508 (s), 1458 (m), 1323 (m), 1282 (s), 1161 (w), 1028 (w), 745 (s),
starting from 1.99 g of 5-methyl-2-(phenylethynyl)aniline (61%).
Yellow solid, m.p. 101–102 °C. IR (KBr): ν = 3308 (m, br.), 2230
˜
698 (m) cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.36–7.18 (m, 6 (w), 1664 (m), 1537 (m), 1490 (w), 1385 (w), 1315 (m), 1280 (m),
H, 5 H aromatic + 3-H), 7.09–7.02 (m, 1 H, 5-H), 6.58 (td, J =
7.5, 1.2 Hz, 1 H, 4-H), 6.50 (br. d, J = 8.1 Hz, 1 H, 6-H), 4.99 (br.
1258 (m), 1158 (m), 1112 (m), 1009 (m), 856 (w), 756 (m), 692 (m)
cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.48–7.42 (m, 2 H, aro-
s, 1 H, NH), 4.33 (br. s, 2 H, CH2Ph), 2.41 (t, J = 6.9 Hz, 2 H, matic), 7.41–7.23 (m, 9 H, 8 H aromatic + 3-H), 6.49 (dd, J = 7.7,
CH2CH2CH2CH3), 1.59–1.33 (m, 4 H, CH2CH2CH3), 0.86 (t, J = 0.8 Hz, 1 H, 4-H), 6.41 (br. s, 1 H, 6-H), 5.05 (br. s, 1 H, NH), 4.42
7.3 Hz, 3 H, Me) ppm. 13C NMR (75 MHz, CDCl3): δ = 148.6, (br. s, 2 H, CH2Ph), 2.40 (s, 3 H, Me) ppm. 13C NMR (75 MHz,
139.2, 131.9, 129.0, 128.6, 127.2, 127.1, 116.4, 109.6, 108.6, 96.2,
77.1, 47.8, 30.9, 22.0, 19.3, 13.6 ppm. GC–MS: m/z (%) = 263 (100)
[M+], 234 (7), 220 (21), 218 (18), 206 (87), 186 (88), 172 (4), 156
CDCl3): δ = 148.7, 140.3, 139.2, 131.9, 131.3, 128.7, 128.3, 127.9,
127.2, 127.1, 123.5, 117.7, 110.6, 104.8, 94.7, 86.2, 47.7, 22.1 ppm.
GC–MS: m/z (%) = 297 (100) [M+], 220 (6), 206 (28), 191 (5), 179
(6), 144 (12), 143 (15), 130 (21), 115 (19), 103 (7), 91 (81), 77 (12), (19), 178 (12), 152 (2), 128 (2), 115 (1), 102 (2), 91 (70), 77 (9),
2554
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Eur. J. Org. Chem. 2012, 2549–2559