656 JOURNAL OF CHEMICAL RESEARCH 2007
2H, C2-H2), 2.45 (s, 3H, C6-CH3), 2.29–2.22 (m, 2H, C3-H2). MS:
m/z (%) 241 (12, M+), 225 (10), 199 (100), 198 (30), 168 (11), 157
(22), 143 (95), 115 (30). Anal. Calcd. for C14H15N3O: C, 69.69; H,
6.26; N, 17.41. Found: C, 69.45; H, 6.14; N, 17.09%.
1H, N9-H), 7.57–7.53 (d, 1H, C5-H, J = 8.2 Hz), 7.19 (s,1H, C8-H),
6.94–6.90 (d, 1H, C6-H, J = 8.2 Hz), 6.80–6.74 (m, 2H, CSNH2),
2.95–2.90 (m, 2H, C4-H2), 2.62 (s, 3H, C7-CH3), 2.55–2.50 (m, 2H,
C2-H2), 2.19–2.11 (m, 2H, C3-H2). MS: m/z (%) 257 (8, M+), 256
(20), 200 (15), 199 (100), 185 (20), 171 (16), 170 (40), 143 (78).
Anal. Calcd. for C14H15N3S: C, 65.34; H, 5.87; N, 16.33. Found: C,
65.71; H, 5.77; N, 15.91%.
1-Carbimido-7-methyl-2,3,4,9-tetrahydro-1H-carbazole
(8b):
brown powder (0.154 g, 64%), m.p. 178–180°C. IR: νmax 3269, 2926,
1
2858, 1636, 1539, 1470, 1323 cm-1. H NMR (CDCl3): d 8.66 (b s,
1-Thiocarbimido-8-methyl-2,3,4,9-tetrahydro-1H-carbazole (9c):
brown powder (0.175 g, 68%), m.p. 142–144°C. IR: νmax 3234, 2924,
2854, 1641, 1618, 1545, 1327 cm-1. 1H NMR (CDCl3): d 11.57 (br s,
1H, N9-H), 7.50–7.48 (d, 1H, C5-H, J = 7.8 Hz), 7.21–6.98 (m, 2H,
C6, C7-H), 6.81–6.69 (m, 2H, CSNH2), 3.05–2.96 (m, 2H, C4-H2),
2.61–2.54 (m, 2H, C2-H2), 2.51 (s, 3H, C8-CH3), 2.20–2.12 (m, 2H,
C3-H2). MS: m/z (%) 257 (4, M+), 256 (16), 200 (20), 199 (100), 198
(35), 170 (36), 157 (28), 143 (92). Anal. Calcd. for C14H15N3S: C,
65.34; H, 5.87; N, 16.33. Found: C, 65.09; H, 5.67; N, 15.95%.
6-Chloro-1-thiocarbimido-2,3,4,9-tetrahydro-1H-carbazole (9d):
brown powder, (0.19 g, 69%), m.p. 151–153°C. IR: νmax 3269, 2933,
2858, 1641, 1535, 1468, 1319 cm-1. 1H NMR (CDCl3): d 11.79 (b s,
1H, N9-H), 7.76 (s, 1H, C5-H), 7.40–7.37 (d, 1H, C8-H, J = 8.2 Hz),
7.32–7.29 (d, 1H, C7-H, J = 8.2 Hz), 6.59–6.50 (m, 2H, CSNH2),
3.05–2.88 (m, 2H, C4-H2), 2.64–2.50 (m, 2H, C2-H2), 2.22–2.09 (m,
2H, C3-H2). MS: m/z (%) 277 (10, M+), 220 (16), 220 (20), 219 (100),
191 (22), 190 (18), 177 (16), 163 (75). Anal. Calcd. for C13H12ClN3S:
C, 56.21; H, 4.35; N, 15.13. Found: C, 56.00; H, 4.23; N, 15.98%.
1-Thiocarbimido-2,3,4,9-tetrahydro-1H-carbazole (9e): brown
powder (0.15 g, 62%), m.p. 137–139°C. IR: νmax 3275, 2930, 2860,
1H, N9-H), 7.56–7.49 (d, 1H, C5-H, J = 8.3 Hz), 7.16 (s,1H, C8-H),
7.00–6.94 (d, 1H, C6-H, J = 8.3 Hz), 6.15–6.03 (m, 2H, CONH2),
3.02–2.94 (m, 2H, C4-H2), 2.66–2.59 (m, 2H, C2-H2), 2.47 (s, 3H,
C7-CH3), 2.30–2.21 (m, 2H, C3-H2). MS: m/z (%) 241 (15, M+),
226 (16), 225 (11), 199 (100), 198 (25), 157 (32), 143 (90), 115 (38).
Anal. Calcd. for C14H15N3O: C, 69.69; H, 6.26; N, 17.41. Found: C,
69.33; H, 6.12; N, 17.22%.
1-Carbimido-8-methyl-2,3,4,9-tetrahydro-1H-carbazole
(8c):
brown powder (0.15 g, 63%), m.p. 194–196°C. IR: νmax 3292, 2924,
1
2856, 1616, 1549, 1475, 1327 cm-1. H NMR (CDCl3): d 8.82 (b s,
1H, N9-H), 7.68–7.65 (d, 1H, C5-H, J = 8.0 Hz), 7.31–7.00 (m, 2H,
C6, C7-H), 6.34–6.27 (m, 2H, CONH2), 3.05–2.97 (m, 2H, C4-H2),
2.70–2.64 (m, 2H, C2-H2), 2.49 (s, 3H, C8-CH3), 2.31–2.22 (m, 2H,
C3-H2). MS: m/z (%) 241(10, M+), 225 (16), 199 (100), 198 (20), 168
(16), 157 (36), 131 (10), 115 (32). Anal. Calcd. for C14H15N3O: C,
69.69; H, 6.26; N, 17.41. Found: C, 69.42; H, 6.20; N, 17.16%.
1-Carbimido-6-chloro-2,3,4,9-tetrahydro-1H-carbazole
(8d):
brown powder (0.17 g, 64%), m.p. 210–212°C. IR: νmax 3273, 2924,
1
2858, 1641, 1541, 1481, 1325 cm-1. H NMR (CDCl3): d 9.29 (b s,
1H, N9-H), 7.62 (s,1H, C5-H), 7.43–7.29 (m, 2H, C7- C8-H), 6.26–
6.12 (m, 2H, C1-NCONH2), 3.04–2.93 (m, 2H, C4-H2), 2.73–2.63 (m,
2H, C2-H2), 2.34–2.22 (m, 2H, C3-H2); MS: m/z (%) 261(20, M+),
246 (10), 245 (16), 219 (100), 188 (14), 177 (24), 151 (16), 149 (10).
Anal. Calcd. for C13H12ClN3O: C, 59.66; H, 4.62; N, 16.06. Found:
C, 59.72; H, 4.54; N, 15.86%.
1
1645, 1539, 1472, 1331 cm-1. H NMR (CDCl3): d 11.57 (b s, 1H,
N9-H), 7.70–7.62 (d, 1H, C5-H, J = 7.8 Hz), 7.42–7.39 (d, 1H, C8-H,
J = 8.3 Hz), 7.34–7.28 (m, 1H, C7-H), 7.13–7.05 (m, 1H, C6-H),
6.58–6.44 (m, 2H, CSNH2), 3.02–2.93 (m, 2H, C4-H2), 2.62-2.55 (m,
2H, C2-H2), 2.23-2.13 (m, 2H, C3-H2). MS: m/z (%) 243 (14, M+),
242 (16), 185 (100), 183 (22), 171 (18), 156 (24), 143 (32), 129 (83).
Anal. Calcd. for C13H13N3S: C, 64.17; H, 5.38; N, 17.27. Found: C,
64.54; H, 5.22; N, 17.06%.
1-Carbimido-2,3,4,9-tetrahydro-1H-carbazole
(8e):
brown
powder (0.14 g, 62%), m.p. 187–189°C. IR: νmax 3269, 2930, 2858,
1
1645, 1575, 1539, 1473, 1331 cm-1. H NMR (CDCl3): d 9.08 (b s,
1H, N9-H), 7.69–7.62 (d, 1H, C5-H, J = 8.0 Hz), 7.46–7.41 (d, 1H,
C8-H, J = 8.2 Hz), 7.40–7.33 (m, 1H, C6-H), 7.19–7.11 (m, 1H,
C7-H), 6.21–6.11 (m, 2H, CONH2), 3.05–2.97 (m, 2H, C4-H2), 2.71–
2.62 (m, 2H, C2-H2), 2.32–2.22 (m, 2H, C3-H2). MS: m/z (%) 227
(16, M+), 211 (16), 185 (100), 183 (16), 143 (16), 117 (20), 115 (32).
Anal. Calcd. for C13H13N3O: C, 68.70; H, 5.77; N, 18.49. Found: C,
68.33; H, 5.65; N, 18.16%.
The authors are grateful to the ISO Quality Assurance Cell,
IICT, Hyderabad and the NMR Research Centre, IISc,
bangalore for providing mass spectral data and NMR spectra
respectively.
Received 18 July 2007; accepted 7 November 2007
Paper07/4754 doi: 10.3184/030823407X266324
Reaction of methyl 2-(1-oxo-2,3,4,9-tetrahydro-1H-carbazol-2-yl)
oxoacetates (1a–e) with thiourea
The respective methyl 2-(1-oxo-2,3,4,9-tetrahydro-1H-carbazol-2-
yl)oxoacetate (1, 1 mmol) in alcoholic KOH (5 g in 20 ml EtOH) was
refluxed with thiourea (1 mmol) for 8 h. The reaction was monitored
by TLC. After completion of the reaction the solvent was evaporated,
cooled, poured into crushed ice, washed with water, filtered, dried
and recrystallised from ethanol.
References
1
2
N. Haider and E. Sotelo, Chem. Pharm. Bull., 2002, 50, 1479.
b.H. Long, W.C. Rose, D.M. Vyas, J.A. Matson and S. Forenza, Curr.
Med. Chem. Anticancer Agents, 2002, 2, 255.
3
C. Guillonneau, A. Pierre, Y. Charton, N. Guilbaud, L.K. berthier,
S. Leonce, A. Michel, E. besagni and G. Atassi, J. Med. Chem., 1999,
42, 2191.
1-Thiocarbimido-6-methyl-2,3,4,9-tetrahydro-1H-carbazole (9a):
brown powder (0.16 g, 62%), m.p. 146–148°C. IR: νmax 3273,
4
5
A.E. Martin and K.J. Rajendra Prasad, Acta. Pharm., 2006, 56, 79.
K. Hirata, C. Ito, H. Furukawa, M. Itogiawa, L.M. Cosentino and
K.H. Lee, Bioorg. Med. Chem. Lett., 1999, 9, 119.
1
2922, 2862, 1641, 1537, 1481, 1440, 1321 cm-1. H NMR (CDCl3):
d 11.44 (br s, 1H, N9-H), 7.44 (s,1H, C5-H), 7.32–7.27 (d, 1H, C8-H,
J = 8.4 Hz), 7.18–7.12 (d, 1H, C7-H, J = 8.4 Hz), 6.54–6.46 (m, 2H,
CSNH2), 2.95–2.90 (m, 2H, C4-H2), 2.59–2.52 (m, 2H, C2-H2), 2.39
(s, 3H, C6-CH3), 2.19–2.11 (m, 2H, C3-H2). MS: m/z (%) 257 (10,
M+), 256 (15), 200 (20), 199 (100), 185 (13), 170 (32), 157 (20), 143
(85). Anal. Calcd. for C14H15N3S: C, 65.34; H, 5.87; N, 16.33. Found:
C, 65.11; H, 5.73; N, 15.98%.
1-Thiocarbimido-7-methyl-2,3,4,9-tetrahydro-1H-carbazole (9b):
brown powder (0.162 g, 63%), m.p. 135–137°C. IR: νmax 3261, 2932,
2860, 1636, 1537, 1470, 1327 cm-1. 1H NMR (CDCl3): d 11.42 (b s,
6
J. Wang, Y. Zheng, T. Efferth, R. Wang, Y. Shen and X. Hao,
Phytochemistry, 2005, 66, 697.
G.H. Kirsch, Curr. Org. Chem., 2001, 5, 507.
H.J. Knolker and K.R. Reddy, Chem. Rev., 2002, 102, 4303.
A.E. Martin and K.J. Rajendra Prasad, J. Chem. Res., 2006, 473.
7
8
9
10 M. Sekar, S. Vanitha and K.J. Rajendra Prasad, Z. Naturforsch., 1994,
49b, 687.
11 D. Sowmithran and K.J. Rajendra Prasad, Heterocycles, 1986, 24, 2195.
12 V. Sangeetha, Ph.D thesis, bharathiar University, Coimbatore, 2004;
V. Sangeetha and K.J. Rajendra Prasad, Indian J. Chem., 2007, 46B, 135.
13 D. Sowmithran and K.J. Rajendra Prasad, Heterocycles, 1986, 24, 711.
PAPER: 07/4754