Substituted Pyrrolo[3,4-a]carbazoles
1805
(CO), 1597, 1499, 1479 (ar C–C), 1351, 1163 (SO2), 1114, 1090 (C–O–C) cmꢂ1
;
1H NMR
(300 MHz): ꢂ ¼ 1.73 (ddd, J4A=5 ¼ 0.7 Hz, J4A=3a ¼ 8.5 Hz, J4A=4B ¼ 14.7 Hz, 4-HA), 2.71 (ddd,
J4B=3a ¼ 1 Hz, J4B=5 ¼ 4.4 Hz, J4B=4A ¼ 14.9Hz, 4-HB), 2.35 (s, Me), 3.14 (s, MeO), 3.22 (ddd,
J3a=4B ¼ 1 Hz, J3a=4A ¼ 8.5 Hz, J3a=10b ¼ 10.0Hz, 3a-H), 3.45 (dd, J5a=5 ¼ 6.1 Hz, J5a=10a ¼ 11Hz, 5a-
H), 3.74 (dd, J10b=3a ¼ 10.0 Hz, J10b=10a ¼ 7.8 Hz, 10b-H), 3.90 (dd, J5=5a ¼ 5.1 Hz, J5=4B ¼ 5.1 Hz, 5-
H), 4.68 (dd, J10a=10b ¼ 7.8 Hz, J10a=5a ¼ 11 Hz, 10a-H), 6.91–7.67 (m, 13 ar H) ppm.
5-Methoxy-2-methyl-10-tosyl-4,5,5a,10,10a,10b-hexahydro-3aH-pyrrolo[3,4-a]carbazole-
1,3-dione (4b, C23H24N2O5S)
From 3b (1.0g, 2.3 mmol) as described for 4a. Yield 720 mg (72%); colorless crystals; mp 240ꢁC;
IR: ꢃꢀ¼ 2851 (Me), 1701 (CO), 1597 (ar C–C), 1346, 1163 (SO2), 1111, 1090 (C–O–C), 835,
1
815 (ar) cmꢂ1; H NMR (300MHz): ꢂ ¼ 1.67 (dd, J4A=3a ¼ 7.8 Hz, J4A=4B ¼ 14.2Hz, 4-HA), 2.38
(s, Me), 2.66 (dd, J4B=5 ¼ 4.6 Hz, J4B=4A ¼ 14.2Hz, 4-HB), 2.82 (s, NMe), 3.08 (s, MeO), 3.06–3.12 (m,
3a-H), 3.42 (dd, J5a=5 ¼ 6.1 Hz, J5a=10a ¼ 11Hz, 5a-H), 3.60 (dd, J10b=3a ¼ 9.7 Hz, J10b=10a ¼ 7.8 Hz,
10b-H), 3.85 (dd, J5=5a ¼ 5.1 Hz, J5=4B ¼ 5.1 Hz, 5-H), 4.62 (dd, J10a=10b ¼ 7.8 Hz, J10a=5a ¼ 11Hz,
10a-H), 6.89 (d, J6=7 ¼ 7.3 Hz, 6-H), 7.01 (ddd, J7=9 ¼ 1 Hz, J7=6 ¼ 7.5 Hz, J7=8 ¼ 7.5Hz, 7-H), 7.21
(d, J ¼ 8.1 Hz, 2 ar H), 7.26 (dd, J8=9 ¼ 7.6 Hz, J8=7 ¼ 7.2 Hz, 8-H), 7.66 (d, J ¼ 8.3 Hz, 2 ar H),
7.71 (d, J9=8 ¼ 8.1 Hz, 9-H) ppm.
5-Methoxy-2-ethyl-10-tosyl-4,5,5a,10,10a,10b-hexahydro-3aH-pyrrolo[3,4-a]carbazole-
1,3-dione (4c, C24H26N2O5S)
From 3c (1.0g, 2.2 mmol) as described for 4a. Yield 650 mg (65%); colorless crystals; mp 221–223ꢁC;
IR: ꢃꢀ¼ 1697 (CO), 1599 (ar C–C), 1352, 1167 (SO2), 1090 (C–O–C), 837, 815 (ar) cmꢂ1; 1H NMR
(300 MHz): ꢂ ¼ 1.0 (t, J ¼ 7.1 Hz, Me), 1.61 (ddd, J4A=10a ¼ 0.9 Hz, J4A=3a ¼ 8.3 Hz, J4A=4B ¼ 14.7Hz,
4-HA), 2.33 (s, Me), 2.59 (ddd, J4B=3a ¼ 1.3 Hz, J4B=5 ¼ 4.7 Hz, J4B=4A ¼ 14.7Hz, 4-HB), 3.00 (ddd,
J3a=4B ¼ 1.3 Hz, J3a=4A ¼ 9 Hz, J3a=10b ¼ 9 Hz, 3a-H), 3.05 (s, MeO), 3.34 (dq, J ¼ 1.8 Hz, J ¼ 7.1 Hz,
CH2), 3.37 (m, 5a-H), 3.52 (dd, J10b=3a ¼ 9.8 Hz, J10b=10a ¼ 8.1 Hz, 10b-H), 3.80 (dd, J5=5a
¼
4.9 Hz, J5=4B ¼ 4.8 Hz, 5-H), 4.57 (dd, J10a=5a ¼ 10.9Hz, J10a=10b ¼ 7.9 Hz, 10a-H), 6.85 (d,
J6=7 ¼ 7.5Hz, 6-H), 6.96 (ddd, J7=9 ¼ 1.1 Hz, J7=6 ¼ 7.5 Hz, J7=8 ¼ 7.5Hz, 7-H), 7.16 (dd, J ¼ 0.6 Hz,
J ¼ 8.6 Hz, 2 ar H), 7.20 (dd, J8=7 ¼ 7.5 Hz, J8=9 ¼ 7.5 Hz, 8-H), 7.60 (d, J ¼ 8.4 Hz, 2 ar H), 7.66
(d, J9=8 ¼ 8.1 Hz, 9-H) ppm.
5-Hydroxy-2-phenyl-10-tosyl-4,10,10a,10b-tetrahydro-3aH-pyrrolo[3,4-a]carbazole-
1,3-dione (5a, C27H22N2O5S)
Compound 3a (500mg, 1 mmol) was suspended in a mixture of 20 cm3 dil. H2SO4 (98 g ꢆ dmꢂ3) and
10cm3 conc. H2SO4, the mixture was refluxed until the reaction was completed (TCL control), and
after cooling to room temperature the precipitate was separated and washed with H2O until H2O
1
reacted neutral. Yield 3–5 mg; H NMR (300MHz): ꢂ ¼ 2.31 (s, Me), 2.62 (dd, J4A=4B ¼ 15.8Hz,
J4A=3a ¼ 7.7 Hz, 4-HA), 2.88 (d, J4B=4A ¼ 15.8 Hz, 4-HB), 3.42 (dd, J3a=10b ¼ 7.1 Hz, J3a=4A ¼ 7.1 Hz,
3a-H), 3.92 (dd, J10b=10a ¼ 6.8 Hz, J10b=3a ¼ 8.7 Hz, 10b-H), 4.85 (dd, J10a=4A ¼ 1.5 Hz, J10a=10b
6.8 Hz, 10a-H), 6.9–8.0 (m, 13 ar H), 9.8 (bs, H–O) ppm.
¼
5-Hydroxy-2-methyl-10-tosyl-4,10,10a,10b-tetrahydro-3aH-pyrrolo[3,4-a]carbazole-
1,3-dione (5b, C22H20N2O5S)
From 3b (400 mg, 0.9 mmol) as described for 5a. Yield 140 mg (40%); colorless crystals; mp 245ꢁC;
IR: ꢃꢀ¼ 3432 (OH), 1777, 1702 (CO), 1595 (ar C–C), 1361, 1166 (SO2) cmꢂ1; 1H NMR (300MHz):
ꢂ ¼ 2.32 (s, Me), 2.53 (ddd, J4A=10a ¼ 2 Hz, J4A=3a ¼ 7.3 Hz, J4A=4B ¼ 15.6Hz, 4-HA), 2.72 (s, NMe),
2.95 (dd, J4B=3a ¼ 1.5 Hz, J4B=4A ¼ 15.8Hz, 4-HB), 3.27 (ddd, J3a=4B ¼ 1.5 Hz, J3a=4A ¼ 7.6 Hz,
J3a=10b ¼ 7.8 Hz, 3a-H), 3.88 (dd, J10b=3a ¼ 8.8 Hz, J10b=10a ¼ 6.6 Hz, 10b-H), 4.78 (dd, J10a=4A ¼ 2 Hz,
J10a=10b ¼ 6.6 Hz, 10a-H), 6.89 (ddd, J7=9 ¼ 1 Hz, J7=6 ¼ 7.6 Hz, J7=8 ¼ 7.6Hz, 7-H), 7.03 (ddd,