916
N. Karal / European Journal of Medicinal Chemistry 37 (2002) 909ꢀ
/
918
ı
4.1.1.3. Spectral data of 3f. IR (KBr, cmꢁ1): 3303, 3169
96 (16), 95 (27), 93 (13), 91 (12), 87 (8), 85 (20), 84 (20),
83 (33), 82 (22), 81 (66), 73 (28), 71 (31), 70 (24), 69
(100), 68 (20), 67 (20), 60 (21), 57 (48), 56 (19).
1
S). H-
(NH), 1693 (CÄ
/
O), 1534, 1351 (NO2), 1151 (CÄ
/
NMR (DMSO-d6, d, ppm): 7.14 (d, J7,6: 8.7 Hz, 1H,
indole C7ÃH), 7.32 (d, J: 7.1 Hz, 1H, phenyl C4ÃH),
7.45 (t, J: 7.5 Hz, 1H, phenyl C3ÃH, C5ÃH), 7.60 (d, J:
7.9 Hz, 1H, phenyl C2ÃH, C6ÃH), 8.27, 8.29 (dd, J6,7
8.7 Hz, J6,4: 2.3 Hz, 1H, indole C6ÃH), 8.70 (d, J4,6: 2.4
Hz, 1H, indole C4ÃH), 11.04 (s, 1H, CSÃNH), 11.80
NH). EIMS (70
/
/
/
/
4.1.2.2. Spectral data of 4d. IR (KBr, cmꢁ1): 3314
/
/
:
1
S). H-
(NH), 1701 (CÄ
/
O), 1522, 1339 (NO2), 1160 (CÄ
/
/
NMR (DMSO-d6, d, ppm): 1.36 (br.s, 2H, piperidine
C4ÃH), 1.47 (br.s, 4H, piperidine C3ÃH, C5ÃH), 2.55
(br.s, 4H, piperidine C2ÃH, C6ÃH), 4.30 (t, J: 5.5 Hz,
2H, CH2ÃCHÄCH2), 4.57 (s, 2H, NÃCH2ÃN), 5.17,
5.23 (dd, J: 15.5, 10.1 Hz, 2H, CH2ÃCHÄCH2), 5.88ꢀ
6.04 (m, 1H, CH2ÃCH ÄCH2), 7.48 (d, J7,6: 8.6 Hz, 1H,
indole C7ÃH),8.32, 8.35 (dd, J6,7: 8.8 Hz, J6,4: 2.2 Hz,
1H, indole C6ÃH), 8.62 (d, J4,6: 2.2 Hz, 1H, indole C4Ã
H), 9.75 (br.s, 1H, CSÃ NH).
/
/
/
/
/
(br.s, 1H, indole NH), 12.57 (s, 1H, NÃ
/
eV): m/z (%) 341 ([Mꢂ], 12), 313 (37), 206 (38), 191 (6),
189 (10), 149 (12), 148 (4), 136 (14), 135 (60), 133 (12),
131 (13), 129 (13), 120 (19), 119 (18), 118 (18), 115 (16),
111 (11), 105 (17), 103 (10), 97 (20), 93 (100), 92 (18), 91
(23), 83 (23), 77 (56), 69 (30), 66 (34), 60 (15), 57 (45).
/
/
/
/
/
/
/
/
/
/
/
/
/
/
4.1.1.4. Spectral data of 3i. IR (KBr, cmꢁ1): 3312, 3161
/
NH), 12.33 (s, 1H, NÃ
/
EIMS (70 eV): m/z (%) 402 ([Mꢂ], 2), 305 (14), 277 (13),
206 (22), 192 (100), 178 (13), 163 (17), 162 (20), 149 (11),
133 (23), 117 (17), 115 (79), 114 (20), 105 (17), 103 (15),
101 (11), 99 (17), 85 (23), 84 (33), 83 (20), 81 (40), 78
(81), 73 (17), 71 (16), 70 (15), 69 (25), 63 (90), 61 (24), 60
(21), 57 (51), 56 (98).
1
S). H-
(NH), 1697 (CÄ
/
O), 1527, 1341 (NO2), 1153 (CÄ
/
NMR (DMSO-d6, d, ppm): 7.09 (d, J7,6: 8.9 Hz, 1H,
indole C7ÃH), 7.50, 7.66 (2d, J: 8.7 Hz, 4H, phenylÃH),
8.28, 8.29 (dd, J6,7: 8.7 Hz, J6,4: 2.2 Hz, 1H, indole C6Ã
H), 8.67 (d, J4,6: 2.4 Hz, 1H, indole C4ÃH), 11.05 (s, 1H,
CSÃ
/
/
/
/
/
NH), 11.80 (br.s, 1H, indole NH), 12.60 (s, 1H, NÃ
/
NH). EIMS (70 eV): m/z (%) 375 ([Mꢂ], 1), 341 [7 (343,
2)], 303 [8 (305, 3)], 206 (2), 191 (6), 150 [16 (152, 5)], 149
(16), 137 (34), 136 (23), 135 (15), 133 (6), 129 (10), 123
(21), 121 (20), 119 (8), 111 (15), 109 (20), 107 (15), 105
(7), 98 (15), 97 (25), 96 (16), 95 (32), 94 (11), 93 (19), 91
(8), 85 (15), 84 (17), 83 (30), 82 (23), 81 (69), 73 (15), 71
(26), 70 (22), 69 (100), 68 (24), 67 (21), 57 (40).
4.1.2.3. Spectral data of 4h. IR (KBr, cmꢁ1): 3195
1
S). H-
(NH), 1698 (CÄ
/
O), 1518, 1338 (NO2), 1164 (CÄ
/
NMR (DMSO-d6, d, ppm): 2.59 (s, 4H, morpholine C3Ã
H, C5ÃH), 3.54 (s, 4H, morpholine C2ÃH, C6ÃH), 4.60
(s, 2H, NÃCH2ÃN), 7.32 (d, J: 6.9 Hz, 1H, phenyl C4Ã
H), 7.44 (d, J: 7.5 Hz, 2H, phenyl C3ÃH, C5ÃH), 7.50 (s,
1H, indole C7ÃH), 7.58 (d, J: 8.2 Hz, 2H, phenyl C2ÃH,
C6ÃH), 8.35 (d, J6,7: 8.9 Hz, 1H, indole C6ÃH), 8.75 (s,
1H, indole C4ÃH), 11.15 (s, 1H, CSÃNH), 12.47 (s, 1H,
NÃNH). EIMS (70 eV): m/z (%) 206 (6), 190 (2), 159
/
/
/
/
/
/
/
/
/
/
/
4.1.2. Synthesis of 1-morpholino/piperidinomethyl-5-
/
/
nitroindole-2,3-dione-3-thiosemicarbazones (4aꢀm)
/
/
/
To a suspension of 3 (0.002 mol) in absolute EtOH
(20 mL), 37% formaldehyde solution (0.5 mL) and
morpholine or piperidine (0.002 mol) were added
dropwise with vigorous stirring. After combining all
reagents the reaction mixture was refluxed on a water
bath for 4 h. The product formed were filtered, washed
with petroleum ether.
/
(6), 149 (4), 148 (10), 146 (10), 136 (7), 135 (69), 133 (5),
119 (12), 118 (10), 115 (5), 105 (9), 103 (7), 93 (18), 92
(67), 91 (100), 87 (5), 86 (5), 77 (40), 71 (11), 70 (5), 69
(9), 65 (15), 64 (13), 63 (10), 60 (3), 57 (30), 56 (12).
4.1.2.4. Spectral data of 4j. IR (KBr, cmꢁ1): 3261 (NH),
4.1.2.1. Spectral data of 4c. IR (KBr, cmꢁ1): 3345, 3227
1705 (CÄ
/
O), 1519, 1335 (NO2), 1146 (CÄ
/
1
S). H-NMR
1
S). H-
(NH), 1699 (CÄ
/
O), 1526, 1343 (NO2), 1175 (CÄ
/
(DMSO-d6, d, ppm): 2.35 (s, 3H, CH3), 2.60 (t, J: 4.4
Hz, 4H, morpholine C3ÃH, C5ÃH), 3.56 (t, J: 4.4 Hz,
4H, morpholine C2ÃH, C4ÃH), 4.60 (s, 2H, NÃCH2Ã
N), 7.25 (d, J: 8.2 Hz, 2H, phenyl C3ÃH, C5ÃH), 7.46
(d, J: 8.2 Hz, 2H, phenyl C2ÃH, C6ÃH), 7.52 (d, J7,6: 8.8
Hz, 1H, indole C7ÃH), 8.33, 8.35 (dd, J6,7: 8.8 Hz, J6,4
2.4 Hz, 1H, indole C6ÃH), 8.75 (d, J4,6: 2.3 Hz, 1H,
indole C4ÃH), 11.05 (s, 1H, CSÃNH), 12.46 (br.s, 1H,
NÃNH). EIMS (70 eV): m/z (%) 224 (1), 191 (1), 149
NMR (DMSO-d6, d, ppm): 2.59 (t, J: 4.2 Hz, 4H,
/
/
morpholine C3Ã
morpholine C2Ã
CH2ÃCHÄ
(dd, J: 15.8, 9.0 Hz, 2H, CH2Ã
1H, CH2ÃCH ÄCH2), 7.50 (d, J7,6: 8.8 Hz, 1H, indole
C7ÃH), 8.31, 8.32 (dd, J6,7: 8.8 Hz, J6,4: 2.3 Hz, 1H,
indole C6ÃH), 8.62 (d, J4,6: 2.2 Hz, 1H, indole C4ÃH),
9.73 (br.s, 1H, CSÃ NH).
/
H, C5Ã
/
H), 3.55 (t, J: 4.2 Hz, 4H,
H), 4.29 (t, J: 4.6 Hz, 2H,
/
/
/
/
/
H, C6Ã
/
/
/
/
/
CH2), 4.58 (s, 2H, NÃ
/
CH2Ã
/
N), 5.16, 5.22
/
/
/
CHÄ
/
CH2), 5.85ꢀ
/6.04 (m,
/
:
/
/
/
/
/
/
/
/
/
/
NH), 12.35 (br.s, 1H, NÃ
/
(1), 119 (1), 115 (1), 105 (7), 103 (2), 91 (11), 87 (4), 86
(3), 77 (12), 71 (2), 70 (5), 69 (3), 65 (18), 64 (14), 63 (28),
62 (15), 60 (4), 57 (27), 56 (31), 54 (15), 53 (16), 52 (35),
51 (49), 50 (42), 49 (13), 46 (13), 45 (17), 44 (32), 43 (37),
42 (53), 41 (42), 40 (23), 39 (69), 38 (32), 37 (19), 35 (13),
32 (100), 31 (25), 30 (94).
EIMS (70 eV): m/z (%) 404 ([Mꢂ], 1), 368 (4), 341 (4),
256 (14), 205 (3), 192 (4), 191 (4), 171 (5), 167 (5), 161
(4), 157 (6), 152 (5), 149 (12), 141 (5), 137 (24), 136 (15),
135 (10), 133 (6), 129 (16), 123 (16), 121 (15), 119 (6), 117
(3), 111 (16), 109 (16), 107 (11), 105 (7), 98 (20), 97 (29),