M. Ishikura et al. / Tetrahedron 56 (2000) 193–207
203
169.2. MS m/z: 306 (Mϩ), 291, 263, 249, 235. Anal. Calcd
for C20H22N2Oϩ1/10H2O: C, 77.88; H, 7.28; N, 9.06.
Found: C, 77.94 H, 7.25; N, 9.09.
13C NMR (CDCl3) d: 22.1, 29.9, 32.1, 32.5, 44.5, 44.7, 51.6,
52.2, 99.7, 109.3, 115.2, 115.6, 119.6, 120.2, 121.2, 121.7,
124.6, 125.2, 127.9, 129.2, 137.0, 137.6, 140.7, 141.1,
141.4, 151.3, 153.5. High-resolution MS m/z: Calcd for
C24H24N2O2: 372.1836. Found: 372.1818.
Phenyl 5,6,11-trimethyl-1,2,3,4-tetrahydropyrido[4,3-b]-
carbazole-2-carboxylate (12f). Mp 171–172ЊC (recryst.
from ethyl acetate). IR (CHCl3): 1706 cmϪ1
.
1H NMR
Phenylmethyl 3-methylene-4-[(1-methylindol-2-yl)ethyl-
(CDCl3) d: 2.71 (s, 3H), 2.76 (s, 3H), 3.00–3.10 (m, 2H),
3.80–4.00 (m, 2H), 4.05 (s, 3H), 4.86 (s, 1H), 4.97 (s, 1H),
7.13–7.25 (m, 4H), 7.33–7.40 (m, 3H), 7.45 (t, 1H,
J7.8 Hz), 8.21 (d, 1H, J7.8 Hz). 13C NMR (CDCl3) d:
14.9, 15.4, 27.2, 27.5, 33.6, 41.6, 42.2, 44.5, 45.0, 108.5,
115.6, 115.9, 118.9, 121.2, 121.8, 122.6, 123.0, 123.4,
125.0, 125.2, 125.3, 127.0, 127.3, 129.2, 131.4, 131.5,
139.6, 142.9, 151.5, 153.8, 153.9. MS m/z: 384 (Mϩ), 291.
Anal. Calcd for C25H24N2O2: C, 78.10; H, 6.29; N, 7.29.
Found: C, 77.97; H, 6.47; N, 7.28.
idene]piperidine-1-carboxylate
(13c).
IR
(neat):
1706 cmϪ1. H NMR (CDCl3) d: 2.13 (s, 3H), 2.15–2.25
(m, 2H), 3.40–3.50 (m, 2H), 3.58 (s, 3H), 4.12 (s, 2H),
5.05–5.20 (m, 3H), 5.25–5.50 (m, 1H), 6.27 (s, 1H), 7.10
(t, 1H, J7.8 Hz), 7.20 (t, 1H, J7.8 Hz), 7.27–7.45
(m, 6H), 7.57 (d, 1H, J7.8 Hz). 13C NMR (CDCl3) d:
22.0, 29.9, 32.3, 44.2, 51.6, 67.1, 99.6, 109.3, 115.1,
119.6, 120.2, 121.1, 124.2, 127.8, 127.9, 128.4, 136.7,
137.0, 137.9, 141.2, 141.5, 155.1. High-resolution MS
m/z: Calcd for C25H26N2O2: 386.1993. Found: 386.2024.
1
Phenylmethyl 5,6,11-trimethyl-1,2,3,4-tetrahydropyr-
tert-Butyl 3-methylene-4-[(1-methylindol-2-yl)ethylidene]-
ido[4,3-b]carbazole-2-carboxylate (12g). Mp 130–132ЊC
piperidine-1-carboxylate (13d). IR (neat): 1680 cmϪ1
.
1
(recryst. from ethyl acetate). IR (CHCl3): 1688 cmϪ1. H
1H-NMR (CDCl3) d: 1.45 (s, 9H), 2.05–2.20 (m, 2H),
2.13 (s, 3H), 3.20–3.33 (m, 2H), 3.59 (s, 3H), 3.95–4.10
(m, 2H), 5.08 (s, 1H), 5.25–5.40 (m, 1H), 7.10 (dt, 1H, J1,
6.8 Hz), 7.20 (dt, 1H, J1, 6.8 Hz), 7.31 (d, 1H, J7.8 Hz),
7.58 (d, 1H, J7.8 Hz). 13C NMR d: 22.0, 28.5, 29.9, 32.6,
44.1, 51.2, 79.7, 99.7, 109.3, 114.8, 119.6, 120.2, 121.1,
123.9, 128.1, 137.1, 138.4, 141.7, 154.7. High-resolution
MS m/z: Calcd for C22H28N2O2: 352.2194. Found:
352.2154.
NMR (CDCl3) d: 2.70 (s, 3H), 2.60–2.75 (m, 3H), 2.90–
3.00 (m, 2H), 4.07 (s, 3H), 4.81 (s, 2H), 5.21 (s, 2H), 7.21 (t,
1H, J7.8 Hz), 7.30–7.50 (m, 7H), 8.21 (d, 1H, J7.8 Hz).
13C NMR (CDCl3) d: 14.8, 15.3, 27.3, 27.5, 33.6, 41.5, 44.4,
67.1, 108.5, 118.8, 121.1, 122.6, 123.5, 124.9, 127.8, 128.5,
136.9, 139.5, 142.9, 155.5. MS m/z: 398 (Mϩ), 307, 263.
Anal. Calcd for C26H26N2O2: C, 78.36; H, 6.58; N, 7.03.
Found: C, 78.12; H, 6.69; N, 7.01.
tert-Butyl 5,6,11-trimethyl-1,2,3,4-tetrahydropyrido[4,3-
b]carbazole-2-carboxylate (12h). Mp 148–149ЊC (recryst.
1-Acetyl-3-ethylidene-4-[(1-methylindol-2-yl)ethylidene]-
1
piperidine (13e). IR (neat): 1626 cmϪ1. H NMR (CDCl3)
from ethyl acetate). IR (CHCl3): 1680 cmϪ1
.
1H-NMR
d: 1.87 (d, 3H, J6.8 Hz), 2.04 (s, 3H), 2.09 (s, 3H), 2.10–
2.23 (m, 2H), 3.38 (q, 1H, J6 Hz), 3.50–3.60 (m, 1H),
3.57 and 3.58 (two s, 3H), 4.12 and 4.30 (two s, 2H), 5.65
(q, 1H, J6.8 Hz), 6.26 and 6.27 (two s, 1H), 7.10 (t, 1H,
J6.8 Hz), 7.19 (t, 1H, J6.8 Hz), 7.30 (d, 1H, J7.8 Hz),
7.57 (d, 1H, J7.8 Hz). 13C NMR (CDCl3) d: 13.4, 21.4,
21.6, 22.0, 22.1, 29.8, 32.0, 32.6, 42.3, 43.0, 46.3, 47.1,
99.4, 99.5, 109.2, 119.5, 120.1, 121.0, 123.4, 124.0, 125.3,
127.9, 128.0, 132.9, 133.3, 137.0, 139.0, 139.3, 141.9,
168.8, 168.9. High-resolution MS m/z: Calcd for
C20H24N2O: 308.1878. Found: 304.1894.
(CDCl3) d: 1.51 (s, 9H), 2.68 (s, 3H), 2.74 (s, 3H), 2.89–
2.98 (m, 2H), 3.65–3.74 (m, 2H), 4.05 (s, 3H), 4.73 (s, 2H),
7.20 (t, 1H, J7.8 Hz), 7.36 (d, 1H, J7.8 Hz), 7.44 (t, 1H,
J7.3 Hz), 8.20 (d, 1H, J7.8 Hz). 13C NMR (CDCl3) d:
14.7, 14.9, 27.5, 28.2, 28.5, 33.0, 33.4, 79.6, 108.4, 108.5,
115.6, 118.7, 121.0, 122.6, 123.5, 124.7, 124.8, 124.9,
131.8, 139.4, 142.9, 154.9. MS m/z: 364 (Mϩ), 307, 263.
Anal. Calcd for C23H28N2O2: C, 75.79; H, 7.74; N, 7.69.
Found: C, 75.81; H, 7.68; N, 7.52.
1-Acetyl-3-methylene-4-[(1-methylindol-2-yl)ethylidene]-
1
piperidine (13a). IR (neat): 1638 cmϪ1. H NMR (CDCl3)
2-Acetyl-5,10-dimethylspiro[2,3,4,6,7-pentahydrocyclo-
penta[1,2-c]pyridine-6,20-indoline] (14a). Mp 124–125ЊC
(recryst. from hexane–ethyl acetate). IR (CHCl3):
d: 2.03 and 2.08 (two s, 3H), 2.14 (s, 3H), 2.00–2.30 (m,
2H), 3.38 (t, 1H, J6 Hz), 3.50–3.60 (m, 1H), 3.59 and 3.60
(s, 3H), 4.05 (s, 1H), 4.23 (s, 1H), 5.13 (d, 1H, J1 Hz),
5.34 and 5.41 (two s, 1H), 6.28 and 6.29 (two s, 1H), 7.11
(dt, 1H, J1.3, 7 Hz), 7.21 (dt, 1H, J1.3, 7.8 Hz), 7.31 (d,
1H, J8.3 Hz), 7.58 (dd, 1H, J1.3, 7.8 Hz). 13C NMR
(CDCl3) d: 22.0, 22.1, 29.9, 32.1, 32.6, 42.0, 46.1, 49.4,
54.1, 99.6, 99.7, 109.3, 114.9, 115.7, 119.6, 120.2, 121.2,
124.7, 127.9, 137.0, 137.4, 137.5, 140.7, 141.3, 141.4,
168.8, 168.9. High-resolution MS m/z: Calcd for
C19H22N2O: 294.1731. Found: 294.1709.
1
1630 cmϪ1. H NMR (CDCl3) d: 1.60 (s, 3H), 2.17 and
2.19 (two s, 3H), 2.53 (s, 3H), 2.45–2.60 (m, 3H), 2.78
and 2.80 (two dd, 1H, J1.5, 16 Hz), 2.86 and 2.87 (two
d, 1H, J16 Hz), 3.15 and 3.17 (two d, 1H, J16 Hz),
3.60–3.90 (m, 2H), 6.20–6.30 (m, 1H), 6.61 and 6.59
(two t, 1H, J1.5, 7.8 Hz), 6.93–7.13 (m, 2H). 13C NMR
(CDCl3) d: 10.3, 21.7, 22.0, 22.9, 23.5, 28.3, 36.2, 39.4,
40.7, 43.9, 80.9, 105.1, 114.4, 115.3, 116.8, 123.8, 127.4,
127.5, 127.6, 127.9, 132.6, 133.3, 137.2, 137.7, 151.8,
167.2, 167.9. MS m/z: 308 (Mϩ), 293, 251, 188. Anal.
Calcd for C19H22N2Oϩ1/5H2O: C, 76.57; H, 7.57; N,
9.40. Found: C, 76.74; H, 7.63; N, 9.47.
Phenyl 3-methylene-4-[(1-methylindol-2-yl)ethylidene]-
1
piperidine-1-carboxylate (13b). IR (neat): 1714 cmϪ1. H
NMR (CDCl3) d: 2.17 (s, 3H), 2.22–2.33 (m, 2H), 3.45–
3.65 (m, 2H), 3.62 (s, 3H), 4.15–4.35 (m, 2H), 5.16 (s, 1H),
5.42 (s, 1H), 6.30 (s, 1H), 7.11 (t, 1H, J7.8 Hz), 7.21 (t,
1H, J7.8 Hz), 7.28–7.40 (m, 6H), 7.59 (d, 1H, J7.8 Hz).
Phenyl 5,10-dimethylspiro[2,3,4,6,7-pentahydrocyclo-
penta[1,2-c]pyridine-6,20-indoline]-2-carboxylate (14b).
1
IR (neat): 1710 cmϪ1. H NMR (CDCl3) d: 1.61 (s, 3H),