May 2009
An Efficient Synthesis of Indeno[1,2-b]pyridine and
Benzo[h]quinoline Derivatives Under Solvent-Free Conditions
467
2836, 2219, 1637, 1616, 1560, 1517, 1485, 1458, 1418, 1356,
1294, 1258, 1234, 1179, 1159, 1031, 835, 767, 731, 648; 1H
NMR (400 MHz, DMSO-d6) (d, ppm): 3.72 (2H, s, CH2), 3.87
(3H, s, OCH3), 7.14 (2H, t, J ¼ 8.8 Hz, ArH), 7.52 (2H, t,
J ¼ 3.6 Hz, ArH), 7.66 (1H, m, ArH), 7.89 (2H, d, J ¼ 8.8
Hz, ArH), 8.17 (1H, br, ArH), 13.59 (1H, s, NH). Anal. Calcd.
For C20H14N2O2: C 76.42, H 4.49, N 8.91. Found C 76.60, H
4.47, N 8.87.
4-(4-Fluorophenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]quino-
line-3-carbonitrile (4h). This compound was obtained as yel-
low crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3131, 3069,
2931, 2220, 1634, 1606, 1555, 1533, 1510, 1499, 1458, 1403,
1345, 1298, 1250, 1218, 1160, 1141, 1098, 894, 843, 824,
Figure 2. The structure of compound 4j.
1
794, 772, 736; H NMR (400 MHz, DMSO-d6) (d, ppm): 2.33
4-(4-Chlorophenyl)-2-oxo-2,5-dihydro-1H-indeno[1,2-b]
pyridine-3-carbonitrile (4c). This compound was obtained as
yellow crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3296, 3045,
2696, 2219, 1637, 1596, 1560, 1487, 1459, 1396, 1356, 1298,
1265, 1233, 1203, 1159, 1134, 1086, 1014, 955, 899, 835,
(2H, br, CH2), 2.74 (2H, t, J ¼ 7.2 Hz, CH2), 7.35 (1H, d, J ¼
6.4 Hz, ArH), 7.39–7.46 (4H, m, ArH), 7.52 (2H, dd, J ¼
5.2 Hz, J ¼ 5.6 Hz, ArH), 8.07 (1H, br, ArH), 12.77 (1H, s,
NH). Anal. Calcd. For C20H13FN2O: C 75.94, H 4.14, N 6.01.
Found C 75.81, H 4.12, N 6.04.
1
772, 734, 684, 634; H NMR (400 MHz, DMSO-d6) (d, ppm):
4-(4-Bromophenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]quino-
line-3-carbonitrile (4i). This compound was obtained as yel-
low crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3124, 3032,
2939, 2221, 1638, 1606, 1552, 1497, 1458, 1389, 1344, 1298,
1250, 1215, 1160, 1103, 1071, 1010, 908, 833, 811, 773, 738,
666; 1H NMR (400 MHz, DMSO-d6) (d, ppm): 2.36 (2H, t,
J ¼ 6.0 Hz, CH2), 2.76 (2H, t, J ¼ 6.8 Hz, CH2), 7.35 (1H, d,
J ¼ 6.8 Hz, ArH), 7.43 (4H, dd, J ¼ 8.4 Hz, J ¼ 8.4 Hz,
ArH), 7.78 (2H, d, J ¼ 8.8 Hz, ArH), 8.07 (1H, d, J ¼ 7.6
Hz, ArH), 12.62 (1H, s, NH). Anal. Calcd. For C20H13BrN2O:
C 63.68, H 3.47, N 7.43. Found C 63.50, H 3.49, N 7.46.
4-(4-Chlorophenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]qui-
noline-3-carbonitrile (4j). This compound was obtained as
yellow crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3130, 3031,
2931, 2223, 1637, 1553, 1535, 1498, 1460, 1425, 1340, 1346,
1297, 1251, 1217, 1198, 1176, 1142, 1086, 1014, 909, 836,
813, 774, 739, 707, 658; 1H NMR (400 MHz, DMSO-d6) (d,
ppm): 2.37 (2H, br, CH2), 2.76 (2H, t, J ¼ 6.8 Hz, CH2), 7.35
(1H, d, J ¼ 7.2 Hz, ArH), 7.43 (2H, dd, J ¼ 7.2 Hz, J ¼
7.2 Hz, ArH), 7.49 (2H, d, J ¼ 8.0 Hz, ArH), 7.64 (2H, d,
J ¼ 8.4 Hz, ArH), 8.07 (1H, d, J ¼ 7.6 Hz, ArH), 12.62 (1H,
s, NH). Anal. Calcd. For C20H13ClN2O: C 72.18, H 3.94, N
8.42. Found C 72.38, H 3.91, N 8.46.
3.68 (2H, s, CH2), 7.53 (2H, t, J ¼ 5.6 Hz, ArH), 7.64 (1H, d,
J ¼ 5.6 Hz, ArH), 7.70 (4H, dd, J ¼ 8.4 Hz, 8.4 Hz, ArH),
8.19 (1H, d, J ¼ 5.6 Hz, ArH), 13.68 (1H, s, NH). Anal.
Calcd. For C19H11ClN2O: C 71.59, H 3.48, N 8.79. Found C
71.41, H 3.50, N 8.84.
4-(2-Chlorophenyl)-2-oxo-2,5-dihydro-1H-indeno[1,2-b]
pyridine-3-carbonitrile (4d). This compound was obtained as
yellow crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3337, 3066,
2222, 1698,1612, 1474, 1465, 1442, 1396, 1316, 1281, 1244,
1210, 1179, 1156, 1099, 1034, 1011, 918, 780, 758, 702, 667,
1
628; H NMR (400 MHz, DMSO-d6) (d, ppm): 3.50 (2H, dd,
J ¼ 22.4 Hz, J ¼ 22.4 Hz, CH2), 7.54 (2H, t, J ¼ 3.6 Hz,
ArH), 7.58 (2H, br, ArH), 7.62 (2H, t, J ¼ 4.0 Hz, ArH), 7.72
(1H, d, J ¼ 7.2 Hz, ArH), 8.20 (1H, d, J ¼ 4.0 Hz, ArH),
13.68 (1H, s, NH). Anal. Calcd. For C19H11ClN2O: C 71.59, H
3.48, N 8.79. Found C 71.40, H 3.45, N 8.82.
4-(2,4-Dichlorophenyl)-2-oxo-2,5-dihydro-1H-indeno[1,2-b]
pyridine-3-carbonitrile (4e). This compound was obtained as
yellow crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3291, 3067,
2781, 2223, 1635, 1594, 1561, 1482, 1458, 1419, 1399, 1375,
1351, 1315, 1298, 1272, 1255, 1202, 1190, 1155, 1135, 1010,
1056, 940, 900, 859, 838, 771, 735, 678, 652, 637; 1H NMR
(400 MHz, DMSO-d6) (d, ppm): 4.13 (2H, s, CH2), 7.50–7.54
(1H, m, ArH), 7.52 (2H, t, J ¼ 6.4 Hz, ArH), 7.84 (2H, t, J ¼
6.4 Hz, ArH), 7.89 (1H, d J ¼ 6.8 Hz, ArH), 8.00 (1H, s,
ArH), 13.85 (1H, s, NH). Anal. Calcd. For C19H10Cl2N2O: C
64.61, H 2.85, N 7.93. Found C 64.88, H 2.84, N 7.89.
4-(3,4-Dichlorophenyl)-2-oxo-2,5-dihydro-1H-indeno[1,2-b]
pyridine-3-carbonitrile (4f). This compound was obtained as
yellow crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3339, 3072,
2744, 2219, 1658, 1616, 1558, 1507, 1488, 1481, 1458, 1419,
1398, 1375, 1355, 1299, 1268, 1229, 1203, 1191, 1139, 1122,
1032, 865, 824, 767, 728, 680, 669; 1H NMR (400 MHz,
DMSO-d6) (d, ppm): 3.71 (2H, s, CH2), 7.54 (2H, q, J ¼
60 Hz, J ¼ 7.2 Hz, ArH), 7.66 (1H, d, J ¼ 7.2 Hz, ArH), 7.69
(1H, d, J ¼ 8.4 Hz, ArH), 7.89 (1H, d J ¼ 8.0 Hz, ArH), 8.04
(1H, d, J ¼ 7.6 Hz, ArH), 8.19–8.21 (1H, br, ArH), 13.76
(1H, s, NH). Anal. Calcd. For C19H10Cl2N2O: C 64.61, H
2.85, N 7.93. Found C 64.50, H 2.87, N 7.90.
4-(2-Chlorophenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]qui-
noline-3-carbonitrile (4k). This compound was obtained as
yellow crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3130, 3031,
2931, 2223, 1637, 1553, 1535, 1498, 1460, 1425, 1340, 1346,
1297, 1251, 1217, 1198, 1176, 1142, 1086, 1014, 909, 836, 813,
1
774, 739, 707, 658; H NMR (400 MHz, DMSO-d6) (d, ppm):
2.37 (2H, br, CH2), 2.76 (2H, t, J ¼ 6.8 Hz, CH2), 7.35 (1H, d,
J ¼ 7.2 Hz, ArH), 7.44 (4H, dd, J ¼ 8.0 Hz, J ¼ 8.0 Hz, ArH),
7.78 (2H, d, J ¼ 8.4 Hz, ArH), 8.07 (1H, d, J ¼ 7.6 Hz, ArH),
12.66 (1H, s, NH). Anal. Calcd. For C20H13ClN2O: C 72.18, H
3.94, N 8.42. Found C 72.32, H 3.91, N 8.46.
4-(3,4-Dichlorophenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]-
quinoline-3-carbonitrile (4l). This compound was obtained
as yellow crystals, mp 287–289ꢀC; IR (KBr, m, cmꢁ1): 3123,
3023, 2940, 2218, 1635, 1557, 1497, 1474, 1455, 1397, 1374,
1341, 1297, 1247, 1212, 1194, 1129, 1031, 952, 896, 821,
1
773, 737, 664; H NMR (400 MHz, DMSO-d6) (d, ppm): 2.28
4-(4-Methoxyphenyl)-2-oxo-2,5-dihydro-1H-indeno[1,2-b]
pyridine-3-carbonitrile (4g). This compound was obtained as
yellow crystals, mp >300ꢀC; IR (KBr, m, cmꢁ1): 3292, 3059,
(1H, t, J ¼ 7.2 Hz, CH2), 2.38 (1H, t, J ¼ 6.8 Hz, CH2), 2.75
(2H, q, J ¼ 6.8 Hz, J ¼ 8.0 Hz, CH2), 7.23–7.30 (1H, m,
ArH), 7.35–7.48 (3H, m, ArH), 7.69–7.85 (2H, m, ArH), 8.03–
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet