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1-(4-aminobenzoyl)-7-Chloro-5-methoxy-2,3,4,5-tetra-
hydro-1H-1-benzazepine (25a). Using the same pro-
cedure as 3a, 25a (0.85 g, 93%) was obtained from 24a
7-Chloro-1-(2-methoxy-4-nitrobenzoyl)-5-oxo-2,3,4,5-
tetrahydro-1H-1-benzazepine (27d). Using the same pro-
cedure as 10a, 27d (11.6 g, 92%) was obtained as yellow
powder from 9a (6.6 g, 33.8 mmol) and 26d20 (10 g,
51 mmol). Pyridine (80 mL) was used as a solvent
instead of Et3N and CH2Cl2: 1H NMR (CDCl3) d 1.69±
2.48 (2H, m), 2.68±2.99 (2H, m), 3.03±5.20 (4H, m), 6.75
(1H, d, J=8.4 Hz), 7.15 (1H, dd, J=8.4, 2.6 Hz), 7.30±
7.93 (4H, m).
1
(1 g, 2.8 mmol) as white powder: H NMR (CDCl3) d
1.37±2.47 (4H,m), 2.62±3.03 (1H, m), 3.27±3.96 (5H, m),
4.14±4.87 (2H, m), 6.28±6.98 (2H, m), 6.52±6.70 (1H,
m), 6.87±7.58 (4H, m).
5-Allyloxy-1-(4-aminobenzoyl)-7-chloro-2,3,4,5-tetra-
hydro-1H-1-benzazepine (25b). Using the same pro-
cedure as 3a, 25b (0.65 g, 78%) was obtained from 24b
(0.9 g, 2.3 mmol) as yellow powder: 1H NMR (CDCl3) d
1.36±3.03 (5H, m), 3.68±4.85 (6H, m), 5.05±5.44 (2H,
m), 5.77±6.13 (1H, m), 6.32±6.48 (2H, m), 6.52±6.72
(1H, m), 6.88±7.68 (4H, m).
7-Chloro-1-(3-methoxy-4-nitrobenzoyl)-5-oxo-2,3,4,5-
tetrahydro-1H-1-benzazepine (27e). Using the same pro-
cedure as 10a, 27e (3.5 g, 31%) was obtained as yellow
powder from 9a (6 g, 30.7 mmol) and 26e21 (6.7 g,
34 mmol): 1H NMR (CDCl3) d 1.91±2.37 (2H, m), 2.77±
2.93 (2H, m), 3.17±5.07 (2H, m), 3.81 (3H, s), 6.62±6.87
(2H, m), 6.90±6.97 (1H, m), 7.26 (1H, dd, J=8.3,
2.5 Hz), 7.65 (1H, d, J=8.3 Hz), 7.77 (1H, d, J=2.5 Hz).
7-Chloro-5-methoxy-1-[4-[(2-methylbenzoyl)amino]benz-
oyl]-2,3,4,5-tetrahydro-1H-1-benzazepine (21). Using the
same procedure as 12a, 21 (0.29 g, 72%) was obtained
from 25a (0.3 g, 0.91 mmol) as white powder: mp.
1-(4-Amino-2-chlorobenzoyl)-7-chloro-5-oxo-2,3,4,5-tetra-
hydro-1H-1-benzazepine (28a). Using the same pro-
cedure as 3a, 28a (13.5 g, 95%) was obtained as yellow
powder from 27a (15.4 g, 40.6mmol): mp. 188±191.5ꢀC;
1H NMR (CDCl3) d 1.78±2.33 (2H, m), 2.73±3.01 (2H, m),
3.34±4.67 (4H, m), 6.20±7.42 (5H, m), 7.64±7.87 (1H, m).
196.5±198.5ꢀC; H NMR (CDCl3) d 1.45±3.03 (5H, m),
1
2.48 (3H, s), 3.31±3.62 (3H, m), 4.22±5.18 (2H, m),
6.50±6.67 (1H, m), 6.88±7.05 (1H, m), 7.12±7.58 (10H,
m); MS (ES) m/z 448 [M]+. Anal. calcd for C26H25
ClN2O3: C, 69.56; H, 5.61; N, 6.24; found C, 69.49; H,
5.44; N, 6.09.
(4-Amino-3-chlorobenzoyl)-7-chloro-5-oxo-1-2,3,4,5-tetra-
hydro-1H-1-benzazepine (28b). Using the same pro-
cedure as 3a, 28b (5.75 g, 86%) was obtained as yellow
powder from 27b (7.25 g, 19.1 mmol): 1H NMR (CDCl3)
d 2.01±2.27 (2H, m), 2.82±2.96 (2H, m), 3.65±4.67 (4H,
m), 6.46 (1H, d, J=8.4 Hz), 6.72 (1H, d, J=8.5 Hz),
6.77 (1H, dd, J=8.4, 2.0 Hz), 7.22 (1H, dd, J=8.5,
2.5 Hz), 7.40 (1H, d, J=2.0 Hz), 7.84 (1H, d, J=2.5 Hz).
5-Allyloxy-7-chloro-1-[4-[(2-methylbenzoyl)amino]benz-
oyl]-2,3,4,5-tetrahydro-1H-1-benzazepine (22). Using the
same procedure as 12a, 22 (0.19 g, 72%) was obtained
from 25a (0.2 g, 0.56 mmol) as white powder: mp.
129.5±131.5ꢀC; H NMR (CDCl3) d 1.48±3.04 (5H, m),
1
2.48 (3H, s), 3.97±4.86 (4H, m), 5.06±5.47 (2H, m),
5.83±6.13 (1H, m), 6.52±6.63 (1H, m), 6.90±7.04 (1H,
m), 7.13±7.62 (10H, m); MS (ES) m/z 474 [M]+. Anal.
calcd for C28H27ClN2O3: C, 70.80; H, 5.73; N, 5.90;
found C, 70.87; H, 5.53; N, 5.98.
1-(4-Amino-2-methylbenzoyl)-7-chloro-5-oxo-2,3,4,5-tetra-
hydro-1H-1-benzazepine (28c). Using the same pro-
cedure as 3a, 28c (2.92 g, 39%) was obtained as white
powder from 27c (8.13 g, 22.7 mmol): mp. 190±191ꢀC;
1H NMR (CDCl3) d 1.22±2.43 (2H, m), 2.34 (3H, s),
2.73±3.00 (2H, m), 3.32±4.43 (4H, m), 6.12±6.30 (1H,
m), 6.44 (1H, d, J=2.1 Hz), 6.53±6.36 (2H, m), 7.20
(1H, dd, J=8.5, 2.5 Hz), 7.77 (1H, d, J=2.5 Hz). Anal.
calcd for C18H17ClN2O2: C, 65.40; H, 5.24; N, 8.47;
found C, 65.27; H, 5.03; N, 8.38.
7-Chloro-1-(2-chloro-4-nitrobenzoyl)-5-oxo-2,3,4,5-tetra-
hydro-1H-1-benzazepine (27a). Using the same pro-
cedure as 10a, 27a (16.6 g, 57%) was obtained as yellow
powder from 9a (15 g, 76.7 mmol) and 26a (18.6 g,
84.5 mmol): mp. 125±126.5ꢀC; 1H NMR (CDCl3) d
1.87±2.45 (2H, m), 2.75±2.99 (2H, m), 3.13±5.33 (2H, m),
6.81±6.98 (1H, m), 7.07±7.44 (2H, m), 7.71 (1H, d, J=
2.5 Hz), 7.87±8.18 (2H, m); MS (ES) m/z 348 [M±H]+.
1-(4-Amino-2-methoxybenzoyl)-7-chloro-5-oxo-2,3,4,5-
tetrahydro-1H-1-benzazepine (28d). Using the same pro-
cedure as 3a, 28d (7.4 g, 89%) was obtained as white
7-Chloro-1-(3-chloro-4-nitrobenzoyl)-5-oxo-2,3,4,5-tetra-
hydro-1H-1-benzazepine (27b). Using the same pro-
cedure as 10a, 27b (7.25 g, 89%) was obtained as yellow
powder from 9a (4.2 g, 21.5 mmol) and 26b18 (4.5 g,
22.3 mmol): 1H NMR (CDCl3) d 1.97±2.43 (2H, m), 2.78±
2.97 (2H, m), 3.13±5.37 (2H, m), 6.51±6.76 (1H, m), 6.95±
7.10 (1H, m), 7.22±7.35 (1H, m), 7.58 (1H, d, J=1.7 Hz),
7.66 (1H, d, J=8.3 Hz), 7.83 (1H, d, J= 2.5 Hz).
1
powder from 27d (9 g, 24 mmol): H NMR (CDCl3) d
1.82±2.33 (2H, m), 2.53±4.96 (6H, m), 3.36 (3H, s),
5.76±5.88 (1H, m), 6.23 (1H, dd, J=8.2, 2.0 Hz), 6.62±
6.83 (1H, m), 7.11 (1H, dd, J=8.5, 2.5 Hz), 7.18±7.32
(1H, m), 7.79 (1H, d, J=2.5 Hz).
1-(4-Amino-3-methoxybenzoyl)-7-chloro-5-oxo-2,3,4,5-
tetrahydro-1H-1-benzazepine (28e). Using the same pro-
cedure as 11a, 28e (2.3 g, 83%) was obtained as yellow
7-Chloro-1-(2-methyl-4-nitrobenzoyl)-5-oxo-2,3,4,5-tetra-
hydro-1H-1-benzazepine (27c). Using the same pro-
cedure as 10a, 27c (8.13 g, 32%) was obtained as white
powder from 9a (14 g, 71.6 mmol) and 26c19 (16.9 g,
93 mmol): H NMR (CDCl3) d 1.75±2.66 (2H, m), 2.48
(3H, s), 2.72±3.04 (2H, m), 3.32±5.07 (2H, m), 6.66 (1H,
d, J=8.4 Hz), 6.95 (1H, d, J=8.4Hz), 7.08±8.35 (4H, m).
1
oil from 27e (3 g, 8 mmol): H NMR (CDCl3) d 2.03±
2.24 (2H, m), 2.81±2.95 (2H, m), 3.57±4.38 (4H, m), 3.69
(3H, s), 6.41 (1H, d, J=8.2 Hz), 6.64 (1H, dd, J=8.2,
1.8 Hz), 6.71 (1H, d, J=8.5 Hz), 6.80 (1H, d, J=1.8 Hz),
7.19 (1H, dd, J=8.5, 2.5 Hz), 7.81 (1H, d, J=2.5 Hz).
1