68
H. V. Dang and W. Stadlbauer
Vol. 43
5
-Benzyl-4-phenylaminopyrido[3,2,1-jk]carbazol-6-one (3f).
after cooling to room temperature filtered, washed with cold
ethanol (10 mL) and dried. The yield was 0.9 g (51%) yellow
prisms, mp 130 °C (methanol); ir: 3400-2800 s, 1655 s, 1624 s,
This compound was obtained from 5-benzyl-4-hydroxypyrido-
carbazolone 1c (1.50 g, 4.6 mmol) and work up was as described
for 3b. The yield was 1.50 g (75%) yellow prisms, mp 176 °C
-
1 1
1
598 s, 1575 s cm ; H nmr (CDCl ): δ 1.34 (t, J = 7.3 Hz, Me),
3
3
.20 (q, J = 7.3 Hz, CH ), 7.32-7.36 (m, 9-H, 10-H), 7.47-7.55
-
1
1
2
(
hexane); ir: 3250 s, 1644 s, 1626 s, 1598 s cm ; H nmr
(
m, 2-H, 11-H), 8.03 (d, J = 7.8 Hz, 3-H), 8.12 (d, J = 7.8 Hz, 1-
H), 8.32 (d, J = 7.5 Hz, 8-H), 10.65 (s, NH).
Anal. Calcd. for C H NO: C, 80.69; H, 5.87; N, 6.27. Found:
(
CDCl ): δ 4.26 (s, CH ), 6.09 (s, NH), 6.92 (d, J = 7.7 Hz, 2-H
3
2
and 6-H of phenylamine), 7.04 (t, J = 7.4 Hz, 4-H of pheny-
lamine), 7.27 (t, J = 7.9 Hz, 3-H and 5-H of phenylamine), 7.30
1
5 13
C, 80.58; H, 5.88; N, 6.25.
(
7
t, J = 7.7 Hz, 2-H), 7.30-7.36 (m, 5 PhH), 7.46 and 7.47 (2 t, J =
.3 Hz, 9-H, 10-H), 7.58 and 8.06 (2 t, J = 7.3 Hz, 1-H, 3-H, 11-
H), 8.80 (d, J= 8.1 Hz, 8-H).
1-(9H-Carbazol-1-yl)-butan-1-one (5b).
This compound was obtained from 5-ethyl-4-hydroxypyrido-
carbazolone 1b (4.00 g, 15 mmol) at 220 °C after 18 hours
according to the procedure and work-up described for 5a. The
yield was 2.1 g (59%) yellow prisms, mp 110 °C (methanol); ir:
Anal. Calcd. for C28H20N O: C, 83.98; H, 5.03; N, 6.99.
2
Found: C, 83.65; H, 5.07; N, 6.80.
4
-Benzylamino-5-phenylpyrido[3,2,1-jk]carbazol-6-one (3g).
A solution of 4-hydroxy-5-phenylpyridocarbazolone 1d (1.50
-
1
1
3
400-2800 s, 1655 s, 1624 s, 1598 s, 1575 s cm ; H nmr
(
CDCl ): δ 1.11 (t, J = 7.3 Hz, Me), 1.89 (q, J = 7.3 Hz, CH ),
g, 4.8 mmol) in excess benzylamine (2a) (10 mL) was heated for
hours under reflux using an air condenser to remove the reac-
3 2
.15 (t, J = 7.3 Hz, CO-CH ), 7.26-7.32 (m, 9-H, 10-H), 7.48-
3
7
1
4
2
.55 (m, 2-H, 11-H), 8.03 (d, J = 7.8 Hz, 3-H), 8.12 (d, J = 7.8 Hz,
-H), 8.31 (d, J = 7.5 Hz, 8-H); 10.65 (s, NH).
tion water. The excess solvent (about 5 mL) was removed in
vacuo, then the reaction mixture was cooled to room temperature,
hexane (10 mL) and diethylether (5 mL) was added and the mix-
ture stirred for 1 hour; the resulting precipitate was filtered by
suction and washed with hexane (10 mL). The yield was 1.26 g
Anal. Calcd. for C H NO: C, 80.98; H, 6.37; N, 5.90. Found:
16 15
C, 80.67; H, 6.29; N, 5.83.
1
-(9H-Carbazol-1-yl)-3-phenylpropan-1-one (5c).
(
63%) yellow prisms, mp 173 °C (ethanol); ir: 3329 s, 1627 s,
-1
1
Method A: This compound was obtained from 5-benzyl-4-
1
606 s, 1522 s cm ; H nmr (CDCl ): δ 4.41 (s, CH ), 4.77 (s,
3 2
hydroxypyridocarbazolone 1c (2.50 g, 8 mmol) at 200 °C after 18
hours according to the procedure and work-up described for 5a.
The yield was 1.41 g (59%) yellow prisms, mp 136 °C
NH), 7.22-7.37 (m, 5 PhH of benzyl), 7.48 and 7.55 (2 t, J = 7.8
Hz, 2-H, 9-H, 10-H), 7.83, 8.06 and 8.15 (3 d, J = 7.6 Hz, 1-H, 3-
H, 11-H), 8.71 (d, J = 8.1 Hz, 8-H).
(
methanol).
Anal. Calcd. for C28H20N O: C, 83.98; H, 5.03; N, 6.99.
2
Method B: A solution of 5-benzyl-4-chloropyridocarbazolone
Found: C, 83.70; H, 4.90; N, 6.91.
4
c (2.74 g, 8 mmol) in excess piperidine (10 mL) was heated at
5
-Phenyl-4-phenylaminopyrido[3,2,1-jk]carbazol-6-one (3h).
A solution of 4-hydroxy-5-phenylpyridocarbazolone 1d (1.50
1
80 °C for 6 hours in a sealed tube (5 bar) and worked-up as
described for method A. The yield was 1.55 g (65 %), yellow
prisms, mp 136 °C (methanol); ir: 3400-2800 s, 1667 s, 1622 s,
g, 4.8 mmol) and aniline hydrochloride (0.50 g, 4 mmol) in
excess aniline (2b) (20 mL) was heated for 4 hours under reflux
using an air condenser to remove the reaction water. The excess
solvent (about 15 mL) was removed in vacuo, then the reaction
mixture was cooled to room temperature, hexane (20 mL) was
added and the mixture stirred for 1 hour; the resulting precipitate
was filtered by suction and washed with ethanol (10 mL). The
yield was 1.35 g (70%) yellow prisms, mp 203 °C (ethanol): ir:
-
1 1
1
3
5
586 s, 1575 s cm ; H nmr (CDCl ): δ 3.2 (t, J = 7.9 Hz, CH )
3 2
.52 (t, J = 8.0 Hz, CH ), 7.24-7.34 (m, 9-H, 10-H), 7.24-7.34 (m,
PhH), 7.47-7.56 (m, 2-H, 11-H), 8.01 (d, J = 7.2 Hz, 3-H), 8.13
2
(
d, J = 7.8 Hz, 1-H), 8.32 (d, J = 7.5 Hz, 8-H), 10.65 (s, NH); ms:
m/z (%) 300 (15, M+1), 299 (M, 100), 295 (33), 167 (7), 132
18), 104 (58).
Anal. Calcd. for C H NO: C, 84.25; H, 5.72; N, 4.68. Found:
(
21 17
-1
1
C, 84.64; H, 5.85; N, 4.66.
3
255 s, 1644 s, 1626 s, 1598 s cm ; H nmr (CDCl ): δ 6.06 (s,
3
NH), 7.05 (d, J = 7.8 Hz, 2-H and 6-H of phenylamine), 7.10 (t, J
7.4 Hz, 4-H of phenylamine); 7.28 (t, J = 7.9 Hz, 3-H and 5-H
of phenylamine), 7.30 (t, J = 7.7 Hz, 2-H), 7.42-7.45 (m, 5 PhH),
5
-Phenyl-4-piperidin-1-ylpyrido[3,2,1-jk]carbazol-6-one (6a).
=
A solution of 4-chloro-5-phenylpyridocarbazol-one 4d (3.30 g,
1
0 mmol) in excess piperidine (10 mL) was heated under reflux
7
7
.47 and 7.50 (2 t, J = 7.5 Hz, 9-H, 10-H), 7.56 and 8.06 (2 d, J =
.5 Hz, 1-H, 3-H, 11-H), 8.73 (d, J = 8.1 Hz, 8-H).
for 8 hours. The excess solvent was removed in vacuo, the mix-
ture cooled to room temperature, treated with a mixture of hexane
Anal. Calcd. for C27H18N O: C, 83.92; H, 4.69; N, 7.25.
2
(
10 mL) and diethylether (5 mL) and stirred for 1 hour. The
Found: C, 84.31; H, 4.50; N, 6.88.
resulting precipitate was filtered by suction, washed with hexane
4
-Chloropyrido[3,2,1-jk]carbazol-6-ones (4a-d).
(
10 mL) and dried. The yield was 2.25 g (59%) yellow prisms,
-
These compounds were obtained from 4-hydroxypyridocar-
bazolones 1a-d and phosphoryl chloride according to the method
described in ref [1].
mp 184 °C (ethanol); ir: 2800 - 3000 s, 1653 s, 1600 s, 1544 s cm
1
1
; H nmr (CDCl3): δ 1.67 (t, J = 5.7 Hz, 3 CH2 of piperidine),
2.93 (m, 2 N-CH2 of piperidine), 7.37-7.48 (m, 5 PhH), 7.48 and
.56 (2 t, J = 7.6 Hz, 2-H, 9-H, 10-H), 7.93, 8.08 and 8.12 (3 d, J
7.6 Hz, 1-H, 3-H, 11-H), 8.71 (d, J = 8.1 Hz, 8-H).
Anal. Calcd. for C26H22N O: C, 82.51; H, 5.86; N, 7.40.
7
=
1
-(9H-Carbazol-1-yl)-propan-1-one (5a).
A solution of 4-hydroxy-5-methylpyridocarbazolone 1a (2.03
2
g, 8 mmol) in excess piperidine (10 mL) was heated at 230 °C for
Found: C, 82.28; H, 5.74; N, 7.34.
8
hours in a sealed tube (8 bar). After cooling, the reaction mix-
4
-Morpholin-4-yl-5-phenylpyrido[3,2,1-jk]carbazol-6-one (6b).
ture was treated with a mixture of diethylether (20 mL) and
hexane (40 mL). The residue was triturated with hot ethanol and
This compound was obtained from 4-chloro-5-phenylpyrido-