PAPER
2-(1-Vinyl-1H-pyrrol-2-yl)-1H-benzimidazoles
3607
117.3 (4 C, Ar), 116.6 (1 C, C-5¢), 108.8 (1 C, C-4¢), 107.0 (1 C, C-
3¢), 95.9 (1 C, Cb).
N-[(5-Phenyl-1-vinyl-1H-pyrrol-2-yl)methylene]benzene-1,2-
diamine (2f)
Yield: 0.56 g (97%) from 0.39 g (2 mmol) of 1f.
Anal. Calcd for C13H13N3 (211.27): C, 73.91; H, 6.20; N, 19.89.
Found: C, 73.52; H, 6.22; N, 19.32.
Yellow crystals; mp 102–104 °C.
IR (KBr): 3456, 3360, 3025, 2990, 1711, 1635, 1607, 1589, 1566,
1541, 1508, 1488, 1462, 1454, 1420, 1407, 1381, 1337, 1322, 1310,
1267, 1230, 1215, 1188, 1153, 1134, 1077, 1045, 1026, 1011, 966,
938, 918, 878, 834, 782, 765, 755, 744, 712, 697, 659, 645, 631,
608, 578, 560, 537, 501, 488, 464, 419 cm–1.
N-(4,5,6,7-Tetrahydro-1H-indol-2-ylmethylene)benzene-1,2-di-
amine (2c)
Yield: 0.26 g (91%; conversion: 58%) from 0.30 g (2 mmol) of 1c.
Orange crystals; mp 117–119 °C.
IR (KBr): 3411, 3027, 2968, 2926, 2869, 2837, 2725, 1639, 1602,
1552, 1541, 1497, 1480, 1452, 1438, 1416, 1377, 1337, 1296, 1260,
1209, 1193, 1162, 1134, 1119, 1099, 1050, 1009, 970, 935, 912,
870, 836, 813, 785, 759, 736, 706, 669, 652, 602, 474 cm–1.
1H NMR (400 MHz, CDCl3): d = 9.54 (br s, 1 H, NH), 8.45 (s, 1 H,
CH=N), 7.31 (m, 1 H, Ar), 6.99 (m, 2 H, Ar), 6.89 (m, 1 H, Ar), 6.67
(s, 1 H, H-3¢), 4.99 (br s, 2 H, NH2), 2.64 (m, 2 H, H-7¢), 2.50 (m, 2
H, H-5¢), 1.85 (m, 2 H, H-6¢), 1.76 (m, 2 H, H-4¢).
1H NMR (400 MHz, CDCl3): d = 8.45 (s, 1 H, CH=N), 7.44 (m, 5
3
3
H, Ar), 7.37 (dd, JA–X = 8.7 Hz, JB–X = 15.7 Hz, 1 H, HX), 7.35,
7.31 (m, 2 H, Ar), 6.93 (d, 3J3¢–4¢ = 3.9 Hz, 1 H, H-3¢), 6.74 (m, 2 H,
3
3
Ar), 6.36 (d, J3¢–4¢ = 3.9 Hz, 1 H, H-4¢), 5.13 (d, JA–X = 8.7 Hz, 1
H, HA), 4.92 (d, 3JB–X = 15.7 Hz, 1 H, HB), 4.16 (br s, 2 H, NH2).
13C NMR (100 MHz, CDCl3): d = 146.6 (1 C, C=N), 143.1, 142.1,
131.5, 130.3 (5 C, Ar), 129.3 (1 C, Ca), 128.6 (1 C, C-5¢), 128.1,
126.3 (3 C, Ar), 125.6 (1 C, C-2¢), 124.4, 122.7, 120.0, 115.3 (4 C,
Ar), 105.9 (1 C, Cb), 104.4 (1 C, C-4¢), 104.1 (1 C, C-3¢).
Anal. Calcd for C15H17N3 (239.32): C, 75.28; H, 7.16; N, 17.56.
Found: C, 75.72; H, 7.22; N, 17.12.
Anal. Calcd for C19H17N3 (287.36): C, 79.41; H, 5.96; N, 14.62.
Found: C, 79.65; H, 6.00; N, 14.88.
N-[(1-Vinyl-4,5,6,7-tetrahydro-1H-indol-2-yl)methylene]ben-
zene-1,2-diamine (2d)
Yield: 0.52 g (98%) from 0.35 g (2 mmol) of 1d.
N-{[5-(4-Methoxyphenyl)-1-vinyl-1H-pyrrol-2-yl]methyl-
ene}benzene-1,2-diamine (2g)
Yield: 0.61 g (96%) from 0.45 g (2 mmol) of 1g.
Orange viscous oil.
Orange crystals; mp 123–125 °C.
IR (KBr): 3479, 3379, 1640, 1615, 1597, 1575, 1566, 1503, 1495,
1478, 1458, 1447, 1410, 1389, 1355, 1331, 1317, 1305, 1292, 1266,
1218, 1193, 1155, 1132, 1086, 1054, 1034, 951, 893, 875, 856, 843,
818, 805, 761, 747, 711, 684, 648, 614, 587, 486, 433 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.31 (s, 1 H, CH=N), 7.68 (dd,
3JA–X = 8.8 Hz, 3JB–X = 15.9 Hz, 1 H, HX), 6.94, 6.74 (m, 2 H, Ar),
6.71 (m, 2 H, Ar), 6.56 (s, 1 H, H-3¢), 5.07 (d, 3JB–X = 15.9 Hz, 1 H,
HB), 5.03 (d, 3JA–X = 8.8 Hz, 1 H, HA), 4.20 (br s, 2 H, NH2), 2.70
(m, 2 H, H-7¢), 2.54 (m, 2 H, H-4¢), 1.82 (m, 2 H, H-6¢), 1.75 (m, 2
H, H-5¢).
13C NMR (100 MHz, CDCl3): d = 148.3 (1 C, C=N), 142.5, 142.1
(2 C, Ar), 135.4 (1 C, C-7a¢), 132.7 (1 C, Ca), 129.8 (1 C, C-2¢),
126.5 (1 C, Ar), 121.0 (1 C, C-3a¢), 118.6 (1 C, Ar), 118.0 (1 C, C-
3¢), 116.7, 115.0 (2 C, Ar), 105.9 (1 C, Cb), 24.7, 23.4, 23.1, 23.0 (4
C, C-4¢, C-5¢, C-6¢, C-7¢).
IR (KBr): 3476, 3377, 3013, 2894, 2800, 1643, 1621, 1588, 1575,
1555, 1513, 1484, 1471, 1451, 1438, 1401, 1398, 1344, 1331, 1320,
1303, 1288, 1259, 1227, 1200, 1155, 1129, 1091, 1047, 1037, 955,
888, 869, 853, 848, 818, 800, 773, 744, 716, 694, 649, 632, 572,
545, 524, 497, 465 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.44 (s, 1 H, CH=N), 7.36 (m, 4
H, Ar), 6.96 (dd, 3JA–X = 8.7 Hz, 3JB–X = 15.9 Hz, 1 H, HX), 6.90 (d,
3Jo–m = 8.64 Hz, 2 H, Ho), 6.75 (d, 3Jo–m = 8.64 Hz, 2 H, Hm), 6.72
(d, 3J3¢–4¢ = 3.9 Hz, 1 H, H-3¢), 6.30 (d, 3J3¢–4¢ = 3.9 Hz, 1 H, H-4¢),
5.12 (d, 3JA–X = 8.7 Hz, 1 H, HA), 4.92 (d, 3JB–X = 15.9 Hz, 1 H, HB),
4.17 (br s, 2 H, NH2), 3.82 (s, 3 H, OMe).
13C NMR (100 MHz, CDCl3): d = 157.1 (1 C, COMe), 148.5 (1 C,
C=N), 143.2, 142.4, 131.0 (4 C, Ar), 129.7 (1 C, Ca), 128.5 (1 C, C-
5¢), 125.1 (1 C, C-2¢), 124.6, 124.3, 122.9, 120.8, 115.8, 114.5 (7 C,
Ar), 105.7 (1 C, Cb), 104.2 (1 C, C-3¢), 103.5 (1 C, C-4¢), 56.0 (1 C,
OCH3).
Anal. Calcd for C17H19N3 (265.36): C, 76.95; H, 7.22; N, 15.84.
Found: C, 76.54; H, 7.18; N, 15.80.
Anal. Calcd for C20H19N3O (317.38): C, 75.69; H, 6.03; N, 13.24.
Found: C, 75.65; H, 6.11; N, 13.68.
N-[(5-Phenyl-1H-pyrrol-2-yl)methylene]benzene-1,2-diamine
(2e)
Yield: 0.48 g (92%) from 0.34 g (2 mmol) of 1e.
N-{[5-(Naphthalen-2-yl)-1-vinyl-1H-pyrrol-2-yl]methyl-
ene}benzene-1,2-diamine (2h)
Yield: 0.64 g (95%) from 0.49 g (2 mmol) of 1h.
Yellow crystals; mp 159–162 °C.
IR (KBr): 3397, 3044, 3000, 2968, 2926, 2725, 1602, 1552, 1541,
1497, 1480, 1452, 1438, 1416, 1377, 1337, 1296, 1260, 1209, 1193,
1162, 1134, 1119, 1099, 1050, 1009, 970, 935, 912, 870, 836, 785,
759, 736, 706, 669, 652, 602, 474 cm–1.
1H NMR (400 MHz, CDCl3): d = 9.49 (br s, 1 H, NH), 8.28 (s, 1 H,
CH=N), 7.52 (m, 2 H, Ar), 7.38 (m, 2 H, Ar), 7.25 (m, 1 H, Ar), 6.99
(m, 2 H, Ar), 6.74 (m, 2 H, Ar), 6.69 (d, 3J3¢–4¢ = 3.9 Hz, 1 H, H-3¢),
6.58 (d, 3J3¢–4¢ = 3.9 Hz, 1 H, H-4¢), 4.18 (br s, 2 H, NH2).
13C NMR (100 MHz, CDCl3): d = 150.6 (1 C, C=N), 142.4, 139.1,
131.0 (3 C, Ar), 130.8 (1 C, C-5¢), 129.1 (2 C, Ar), 128.0 (1 C, C-
2¢), 126.4, 125.5, 124.0, 122.3, 120.2, 115.5 (7 C, Ar), 113.0 (1 C,
C-3¢), 109.4 (1 C, C-4¢).
Yellow crystals; mp 177–180 °C.
IR (KBr): 3460, 3365, 3101, 3050, 2860, 1643, 1616, 1595, 1571,
1497, 1482, 1453, 1440, 1417, 1383, 1369, 1350, 1327, 1321, 1304,
1290, 1271, 1263, 1248, 1216, 1195, 1186, 1154, 1131, 1048, 1036,
1014, 975, 962, 931, 896, 860, 841, 822, 791, 771, 746, 712, 694,
677, 640, 629, 599, 557, 481, 472, 427, 398 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.48 (s, 1 H, CH=N), 7.93 (s, 1 H,
Ar), 7.83 (m, 4 H, Ar), 7.54 (m, 3 H, Ar), 7.50 (dd, 3JA–X = 8.6 Hz,
3JB–X = 15.7 Hz, 1 H, HX), 7.10 (m, 1 H, Ar), 6.99 (d, 3J3¢–4¢ = 4.1 Hz,
3
1 H, H-3¢), 6.73 (m, 2 H, Ar), 6.47 (d, J3¢–4¢ = 4.1 Hz, 1 H, H-4¢),
5.13 (d, 3JA–X = 8.6 Hz, 1 H, HA), 4.92 (d, 3JB–X = 15.7 Hz, 1 H, HB),
4.18 (br s, 2 H, NH2).
Anal. Calcd for C17H15N3 (261.33): C, 78.13; H, 5.79; N, 16.08.
Found: C, 78.58; H, 5.28; N, 15.89.
13C NMR (100 MHz, CDCl3): d = 148.9 (1 C, C=N), 143.3, 142.5,
139.4, 138.0, 135.0, 133.2, 131.1 (7 C, Ar), 129.9 (1 C, Ca), 129.2
(1 C, Ar), 128.0 (1 C, C-5¢), 127.6, 126.7 (2 C, Ar), 125.4 (1 C, C-
Synthesis 2009, No. 21, 3603–3610 © Thieme Stuttgart · New York