2 × 4-Hα), 7.12–7.19 (2H, m, 2 × Bz-H), 7.26–7.30 (2H, m,
2 × Bz-H), 7.38–7.43 (4H, d, 2 × 9-H, 2 × Bz-H), 7.46–7.54
(8H, m, 2 × 3Ј-H, 2 × 5Ј-H, 2 × 8-H, 2 × 7-H), 7.61–7.75 (8H,
m, 2 × 2H-2Ј, 6Ј-H, 4 × Bz-H), 8.13–8.16 (2H, d, 2 × 6-H);
δC (75 MHz, CDCl3) 20.88 (2 × C-10), 23.73 (2 × C-4), 39.29
(2 × C-10a), 40.21 (2 × C-3a), 114.9 (2 × C-6), 115.39 (2 × Cq),
118.03 (2 × C-9), 118.38 (2 × C-8), 123.20 (2 × Cq), 123.60
(2 × C-7), 126.71 (2 × C-3Ј, 2 × C-5Ј), 127.67 (2 × 2 × Ct-Bz),
128.23 (2 × Cq), 128.38 (2 × 2 × Ct-Bz), 129.58 (2 × C-2Ј,
2 × C-6Ј), 133.05 (2 × Ct-Bz), 133.40 (2 × Cq), 134.86 (2 × Cq),
135.31 (2 × Cq), 136.87 (2 × Cq), 164.05 (2 × Cq), 168.91
N1,N4-Bis[4-(5-acetyl-1,3-dioxo-1,2,3,3a,4,5,10,10a-octahydro-
pyrrolo[3,4-b]carbazol-2-yl)phenyl]succinamide 5j
This compound was obtained from in situ generated N-
acetylindole-2,3-quinodimethane
3
from N-acetyl-2,3-bis-
(bromomethyl)indole 2 1000 mg (2.89 mmol) as starting
material and bismaleimide 4 660 mg (1.44 mmol). The crude
product was purified by flash column chromatography using
gradient light petroleum and ethyl acetate as eluent (ratio
1 : 2). Yield 50%, mp 180–185 ЊC (from ethanol); C48H40N6O8;
δH (300 MHz, DMSO) 2.73 (4H, s, 2 × CH2), 2.85 (6H, s,
2 × CH3), 3.09–3.30 (2H, m, 2 × 10-Hβ), 3.36–3.42 (4H, m,
2 × 10-Hα, 2 × 4-Hβ), 3.55–3.70 (4H, m, 2 × 10a-H, 2 × 3a-H),
3.89–3.93 (2H, d, 2 × 4-Hα), 7.02–7.10 (4H, d, 2 × 3Ј-H, 2 ×
5Ј-H), 7.22–7.34 (4H, m, 2 × 2Ј-H, 2 × 6Ј-H), 7.39–7.50 (2H, m,
2 × 9-H), 7.52–7.64 (4H, m, 2 × 7-H, 2 × 8-H), 8.09–8.12 (2H,
m, 2 × 6-H), 8.90 (2H, s, 2 × N-H); δC (75 MHz, DMSO) 19.96
(2 × C-10), 22.99 (2 × C-4), 26.40 (2 × CH3), 31.70 (2 × CH2),
39.77 (2 × C-10a), 42.90 (2 × C-3a), 109.69 (2 × Cq), 115.20
(2 × C-6), 117.15 (2 × C-9), 122.99 (2 × Ct), 124.79 (2 × C-8),
126.90 (2 × C-7), 127.89 (2 × 2 × Ct), 128.86 (2 × Cq), 131.85
(2 × Cq), 132.31 (2 × Ct), 134.10 (2 × Cq), 135.95 (2 × Cq),
(2 × C᎐O, Bz), 177.50 (2 × C-1), 178.07 (2 × C-3); m/z (FD)
᎐
906.7 (M+, 100%).
Bis[4-(5-benzoyl-1,3-dioxo-1,2,3,3a,4,5,10,10a-octahydro-
pyrrolo[3,4-b]carbazol-2-yl)phenoxyphenyl]bis(trifluoromethyl)-
methane 5h
This compound was obtained from in-situ generated N-benz-
oylindole-2,3-quinodimethane
3
from N-benzoyl-2,3-bis-
(bromomethyl)indole 2 630 mg (1.54 mmol) as starting material
and bismaleimide 4 525 mg (0.77 mmol). The crude product
was purified by flash column chromatography using gradient
light petroleum and ethyl acetate as eluent (ratio 1 : 2). Yield
50%, mp 130–133 ЊC (from ethanol); C69H46F6N4O8; δH (300
MHz, CDCl3) 3.03–3.14 (4H, m, 2 × 10-Hα, 2 × 10-Hβ), 3.33–
3.42 (4H, dd, J 8.8, J 2.8, 2 × 10a-H, 2 × 3a-H), 3.44–3.57 (4H,
m, 2 × 4-Hβ, 2 × 4-Hα), 6.95–6.98 (4H, d, J 6.9, 2 × 2ЈЈ-H,
2 × 6ЈЈ-H), 6.99–7.04 (4H, d, J 15.9, 2 × 3Ј-H, 2 × 5Ј-H), 7.06–
7.16 (6H, m, 2 × 3ЈЈ-H, 2 × 5ЈЈ-H, 2 × 9-H), 7.21–7.27 (4H, m,
2 × Bz-H, 2 × 2Ј-H), 7.30–7.35 (4H, m, 2 × Bz-H, 2 × 6Ј-H),
7.49–7.53 (6H, m, 2 × Bz-H, 2 × 8-H, 2 × 7-H), 7.68–7.70 (2H,
d, J 8.7, 2 × Bz-H), 7.68–7.70 (4H, d, J 7.2, 2 × Bz-H, 2 × 6-H);
δC (75 MHz, CDCl3) 14.9 (CF3), 15.6 (CF3), 20.9 (2 × CH2,
C-10), 23.8 (2 × CH2, C-4), 39.2 (2 × CH, C-10a), 40.1
(2 × CH, C-3a), 65.6 (Cq), 114.9 (2 × CH, C-6), 115.4 (2 × Cq),
118.0 (2 × CH, C-9), 118.1 (2 × 2CH), 119.8 (2 × 2CH),
123.2 (2 × CH, C-8), 124.1 (2 × CH, C-7), 127.4 (2 × Cq),
127.9 (6 × CH, 2 × C-3Ј, 2 × C-5Ј, 2 × CH), 128.2 (2 × Cq),
128.4 (2 × Cq), 128.9 (2 × 2 × CH, Bz), 129.5 (2 × 2 × CH,
Bz), 131.8 (2 × CH, C-2Ј), 133.0 (2 × CH, C-6Ј), 133.4
(2 × Cq), 135.3 (2 × Cq), 136.8 (2 × Cq), 156.1 (2 × Cq),
138.27 (2 × C ), 168.86 (2 × C᎐O), 169.73 (2 × C᎐O, C-Ac),
᎐
᎐
q
178.65 (2 × C-1), 179.36 (2 × C-3); m/z (FD) 828.6 (M+, 100%).
Bis[4-(5-acetyl-1,3-dioxo-1,2,3,3a,4,5,10,10a-octahydropyrrolo-
[3,4-b]carbazol-2-yl)phenyl]piperazine 8a
This compound was obtained from furocarbazole 6 500 mg
(1.76 mmol) as starting material and piperazinoaniline 7a 236
mg (0.90 mmol). The crude product was purified by flash
column chromatography using gradient light petroleum and
ethyl acetate as eluent (ratio 1 : 2). Yield 37%, mp 173–178 ЊC
(from ethyl acetate–hexane); C48H42N6O6; δH (300 MHz,
DMSO) 2.86 (6H, s, 2 × CH3), 2.94 (8H, s, 4 × NCH2), 3.19–
3.36 (6H, m, 2 × 10-Hα, 2 × 10-Hβ, 2 × 4-Hβ), 3.41–3.76
(6H, m, 2 × 3a-H, 2 × 10a-H, 2 × 4-Hα), 6.97–7.04 (4H, m,
H-aromatic), 7.20–7.35 (4H, d, H-aromatic), 7.46–7.49 (4H, m,
H-aromatic), 7.92–7.95 (2H, m, H-aromatic), 7.98–8.01 (2H, m,
H-aromatic); δC (75 MHz, DMSO) 21.54 (2 × C-10), 23.32
(2 × C-4), 25.92 (2 × CH3), 38.84 (2 × C-10a), 41.67 (2 × C-3a),
45.74 (4 × NCH2), 115.23 (2 × C-aromatic), 115.97 (2 × Cq),
118.35 (2 × C-aromatic), 124.13 (2 × C-aromatic), 126.89
(2 × C-aromatic), 128.17 (4 × C-aromatic), 129.87 (2 × Cq),
133.09 (2 × C-aromatic), 134.48 (2 × Cq), 135.80 (2 × Cq),
157.4 (2 × C ), 168.9 (2 × C᎐O, Bz), 177.9 (2 × C-1), 178.5
᎐
q
(2 × C-3).
136.07 (2 × C ), 136.41 (2 × C ), 168.80 (2 × C᎐O, Ac), 169.24
᎐
q
q
(2 × C᎐O), 177.90 (2 × C-1), 178.23 (2 × C-3); m/z (FD) 798.8
᎐
Bis[4-(5-benzoyl-1,3-dioxo-1,2,3,3a,4,5,10,10a-octahydropyr-
rolo[3,4-b]carbazol-2-yl)benzoyl]piperazine 5i
(M+, 100%).
This compound was obtained from in-situ generated N-benz-
1,4-Bis{N-[4-(5-acetyl-1,3-dioxo-1,2,3,3a,4,5,10,10a-octahydro-
pyrrolo[3,4-b]carbazol-2-yl)phenyl]piperazinylmethyl}benzene
oylindole-2,3-quinodimethane
3
from N-benzoyl-2,3-bis-
(bromomethyl)indole 2 1000 mg (2.45 mmol) as starting
material and bismaleimide 4 593 mg (1.22 mmol). The crude
product was purified by flash column chromatography using
gradient light petroleum and ethyl acetate as eluent (ratio
1 : 2). Yield 47%, mp 170–185 ЊC (from ethanol); C60H46N6O8;
δH (300 MHz, pyridine) 3.12–3.20 (6H, m, 2 × 10-Hα, 2 × 10-
Hβ, 2 × 10a-H), 3.55–3.68 (6H, m, 2 × 3a-H, 2 × 4-Hβ, 2 × 4-
Hα), 3.69–3.70 (8H, s, 4 × NCH2), 7.15–7.20 (2H, m, 2 × 8-H),
7.23–7.30 (2H, m, 2 × 7-H), 7.40–7.45 (8H, m, 2 × 3Ј-H, 2 ×
5Ј-H, 2 × 2H Bz-H), 7.51–7.57 (8H, m, 2 × 2Ј-H, 2 × 6Ј-H,
2 × 6-H, 2 × 9-H), 7.61–7.68 (2H, d, 2 × Bz-H), 7.72–7.75 (4H,
d, 2 × 2H-Bz-H,); δC (75 MHz, pyridine) 20.94 (2 × C-10),
24.22 (2 × C-4), 39.84 (2 × C-10a), 40.74 (2 × C-3a), 49.74
(4 × NCH2), 115.23 (2 × C-6), 115.97 (2 × Cq), 118.35 (2 ×
C-9), 124.13 (2 × 2 × Ct), 126.99 (2 × 2 × Ct), 128.16 (2 × C-3Ј,
2 × C-5Ј), 129.07 (2 × Cq), 129.16 (2 × 2 × Ct-Bz), 129.68
(2 × 2 × Ct-Bz), 133.02 (2 × Ct), 134.04 (2 × Cq), 134.28
(2 × Cq), 135.90 (2 × Cq), 136.17 (2 × Cq), 137.21 (2 × Cq),
8b
This compound was obtained from furocarbazole 6 500 mg
(1.76 mmol) as starting material and piperazinoaniline 7b 401
mg (0.88 mmol). The crude product was purified by flash
column chromatography using gradient light petroleum and
ethyl acetate as eluent (ratio 1 : 2). Yield 30%, mp 137–144 ЊC
(from ethyl acetate–hexane); C60H58N8O6; δH (300 MHz,
DMSO) 2.78 (4H, s, 2 × CH2), 2.85 (6H, s, 2 × CH3), 2.93 (16H,
s, 8 × NCH2), 3.15–3.22 (6H, m, 2 × 10-Hα, 2 × 10-Hβ, 2 ×
4-Hβ), 3.65–3.86 (6H, m, 2 × 3a-H, 2 × 10a-H, 2 × 4-Hα),
6.96–7.03 (4H, m, H-aromatic), 7.19–7.34 (4H, m, H-aromatic),
7.45–7.48 (2H, m, H-aromatic), 7.91–7.94 (4H, m, H-aromatic),
7.98–8.0 (2H, m, H-aromatic), 8.04 (4H, s, H-aromatic); δC (75
MHz, DMSO) 18.25 (2 × CH2), 25.59 (2 × CH3), 27.46 (2 ×
C-10a), 29.66 (2 × CH2), 31.51 (2 × CH2), 33.44 (4 × NCH2),
36.57 (2 × C-3a), 47.48 (4 × NCH2), 96.75 (2 × Cq), 115.07
(2 × C-6), 116.88 (2 × Ct), 117.67 (2 × Cq), 118.47 (2 × C-9),
123.23 (2 × Ct), 123.63 (2 × Ct), 124.33 (2 × 2 × Ct), 124.53
(2 × Ct), 128.09 (2 × 2 × Ct), 129.61 (2 × Cq), 134.43 (2 × Cq),
168.92 (2 × C᎐O, Bz), 169.24 (2 × C᎐O), 178.50 (2 × C-1),
᎐
᎐
178.90 (2 × C-3); m/z (FD) 978.8 (M+, 100%).
J. Chem. Soc., Perkin Trans. 1, 2001, 1406–1412
1411