E. M. Beccalli et al. / Tetrahedron 61 (2005) 61–68
67
120.5 (d), 122.8 (d), 123.5 (d), 124.5 (d), 125.0 (s), 125.9
(d), 132.8 (d), 133.1 (d), 135.8 (s), 143.5 (s), 151.0 (s), 168.9
(s). Anal. Calcd for C14H12N2O: C, 74.98; H, 5.39; N, 12.49.
Found: C, 75.03; H, 5.52; N, 12.57.
dec. (cream crystals from CH2Cl2–hexane); IR (nujol): n
1619, 3310 cmK1; 1H NMR (CDCl3): dZ3.55 (3H, s), 5.36
(1H, br s, absent after deuteriation), 6.78 (1H, dd, JZ4.4,
8.7 Hz), 6.93 (1H, dd, JZ1.5, 7.5 Hz), 7.03 (1H, ddd, JZ
3.0, 8.4, 9.0 Hz), 7.09 (1H, ddd, JZ1.4, 7.3, 7.3 Hz), 7.13
(1H, ddd, JZ1.4, 7.3, 7.3 Hz), 7.21 (1H, dd, JZ1.5,
7.2 Hz), 7.59 (1H, dd, JZ3.0, 9.0 Hz); 13C NMR (CDCl3):
3.7.3. 10-(2-Dimethylamino-ethyl)-5,10-dihydro-di-
benzo[b,e][1,4]diazepin-11-one (7ab).2 76% Yield; mp
113–115 8C (cream crystals from Et2O); IR (nujol): n 1644,
dZ38.6 (q), 119.1 (dd, JC–FZ23.9 Hz), 120.0 (dd, JC–F
Z
1
3373 cmK1; H NMR (CDCl3): dZ2.25 (6H, s), 2.72 (2H,
23.1 Hz), 120.3 (dd, JC–FZ7.2 Hz), 120.7 (d), 123.7 (d),
124.8 (d), 126.4 (d), 135.8 (s), 143.8 (s), 143.9 (s), 147.3 (s),
158.7 (d, JC–FZ239.5 Hz), 167.9 (s). Anal. Calcd for
C14H11FN2O: C, 69.41; H, 4.58; N, 11.56. Found: C, 69.24;
H, 4.77; N, 11.65.
overlapping), 3.28 (1H, m), 4.60 (1H, m), 5.20 (1H, br s,
absent after deuteriation), 6.84 (1H, ddd, JZ1.5, 7.7,
7.7 Hz), 7.09 (1H, ddd, JZ1.5, 7.7, 7.7 Hz), 7.27–7.35 (2H,
overlapping), 7.43 (1H, ddd, JZ1.1, 7.3, 8.1 Hz), 7.57 (1H,
dd, JZ1.1, 7.7 Hz), 7.76 (1H, dd, JZ1.1, 8.1 Hz), 7.95 (1H,
d, JZ7.7 Hz); 13C NMR (CDCl3): dZ41.3 (t), 45.8 (q), 55.5
(t), 115.7 (d), 122.2 (d), 123.3 (d), 124.3 (d), 124.5 (d),
124.8 (d), 125.4 (s), 131.6 (d), 132.8 (d), 137.5 (s), 142.6 (s),
151.3 (s), 163.6 (s). Anal. Calcd for C17H19N3O: C, 72.57;
H, 6.81; N, 14.93. Found: C, 72.59; H, 6.73; N, 15.08.
3.7.8. 2-Fluoro-7-chloro-10-methyl-5,10-dihydro-di-
benzo[b,e][1,4]diazepin-11-one (7ea). 75% Yield; mp
205–208 8C (cream crystals from CH2Cl2–hexane); IR
1
(nujol): n 1621, 3304 cmK1; H NMR (CDCl3): dZ3.53
(3H, s), 5.42 (1H, br s, absent after deuteriation), 6.75 (1H,
dd, JZ4.4, 8.8 Hz), 6.93 (1H, d, JZ1.8 Hz), 7.04 (1H,
ddd, JZ3.0, 8.5, 9.0 Hz), 7.08–7.12 (2H, overlapping), 7.58
(1H, dd, JZ3.0, 9.2 Hz); 13C NMR (CDCl3): dZ38.7 (q),
119.2 (dd, JC–FZ24.0 Hz), 120.2 (dd, JC–FZ24.0 Hz),
120.4 (dd, JC–FZ7.8 Hz), 120.7 (d), 124.7 (d), 124.8 (d),
126.4 (s), 131.3 (s), 134.5 (s), 144.7 (s), 146.4 (s), 158.9 (d,
JC–FZ240.5 Hz), 167.5 (s). Anal. Calcd for C14H10ClFN2O:
C, 60.77; H, 3.64; N, 10.12. Found: C, 60.73; H, 3.81; N,
9.97.
3.7.4. 7-Chloro-10-ethyl-5,10-dihydro-dibenzo[b,e][1,4]-
diazepin-11-one (7bc). 84% Yield; mp 180 8C dec. (cream
1
crystals from Et2O); IR (nujol): n 1598, 3360 cmK1; H
NMR (CDCl3): dZ1.31 (3H, t, JZ6.9 Hz), 4.09 (2H, q, JZ
6.9 Hz), 5.45 (1H, br s, absent after deuteriation), 6.80 (1H,
d, JZ7.4 Hz), 6.98 (1H, s), 7.03–7.14 (2H, overlapping),
7.18 (1H, d, JZ8.0 Hz), 7.29 (1H, d, JZ7.4 Hz), 7.84 (1H,
d, JZ6.5 Hz); 13C NMR (CDCl3): dZ14.2 (q), 45.8 (t),
118.9 (d), 120.9 (d), 123.5 (d), 124.6 (d), 125.4 (d) 125.9 (s),
131.2 (s), 132.8 (d), 133.1 (d), 139.3 (s), 146.2 (s), 150.4 (s),
166.4 (s). Anal. Calcd for C15H13ClN2O: C, 66.06; H, 4.80;
N, 10.27. Found: C, 65.91; H, 4.89; N, 10.31.
3.8. Synthesis of compounds 11 and 15
The reaction was performed as described for compound 7,
using t-BuOK (2 mmol) as base and heating at reflux for
48 h.
3.7.5. 2-Chloro-10-methyl-5,10-dihydro-dibenzo[b,e]-
[1,4]diazepin-11-one (7ca). 77% Yield; mp 205–206 8C
(cream crystals from Et2O); IR (nujol): n 1617, 3290 cmK1
;
1H NMR (CDCl3): dZ3.55 (3H, s), 5.51 (1H, br s, absent
after deuteriation), 6.77 (1H, d, JZ8.4 Hz), 6.93 (1H, dd,
JZ1.3, 7.3 Hz), 7.09 (1H, ddd, JZ1.3, 7.3, 7.9 Hz), 7.13
(1H, ddd, JZ1.3, 7.3, 7.3 Hz), 7.19 (1H, dd, JZ1.3,
7.9 Hz), 7.25 (1H, dd, JZ2.4, 8.4 Hz), 7.86 (1H, d, JZ
2.4 Hz); 13C NMR (CDCl3): dZ38.6 (q), 120.3 (d), 120.7
(d), 123.8 (d), 125.0 (d), 126.3 (d), 128.2 (s), 132.7 (d),
132.8 (d), 135.6 (s), 135.7 (s), 143.2 (s), 149.6 (s), 167.8 (s).
Anal. Calcd for C14H11ClN2O: C, 65.00; H, 4.29; N, 10.83.
Found: C, 65.11; H, 4.21; N, 10.62.
3.8.1.
5-Methyl-5,11-dihydro-benzo[e]pyrido[3,2-
b][1,4]diazepin-6-one (11).17 55% Yield; mp 208–210 8C
dec. (pale yellow crystals from CH2Cl2–hexane); IR (nujol):
n 1620, 3289 cmK1; H NMR (CDCl3): dZ3.51 (3H, s),
1
6.75 (1H, br s, absent after deuteriation), 6.87 (1H, d, JZ
8.0 Hz), 7.02–7.08 (2H, overlapping), 7.33 (1H, dd, JZ7.5,
7.5 Hz), 7.46 (1H, d, JZ7.8 Hz), 7.92 (1H, d, JZ7.8 Hz),
8.02 (1H, d, JZ4.4 Hz);13C NMR (CDCl3): dZ38.5 (q),
119.5 (d), 119.9 (d), 123.1 (d), 124.1 (s), 130.1 (s), 131.4
(d), 133.3 (d), 133.4 (d), 144.0 (d), 148.1 (s), 154.9 (s),
168.5 (s). Anal. Calcd for C13H11N3O: C, 69.32; H, 4.92; N,
18.65. Found: C, 69.43; H, 5.07; N, 18.65.
3.7.6. 2-Chloro-10-ethyl-5,10-dihydro-dibenzo[b,e][1,4]-
diazepin-11-one (7cc). 98% Yield; mp 225–228 8C (cream
crystals from CH2Cl2–hexane); IR (nujol): n 1613,
3275 cmK1 1H NMR (CDCl3): dZ1.31 (3H, t, JZ
;
3.8.2.
6-Methyl-6,11-dihydro-benzo[b]pyrido[2,3-
6.9 Hz), 4.10 (2H, q, JZ6.9 Hz), 5.48 (1H, br s, absent
after deuteriation), 6.72 (1H, d, JZ8.8 Hz), 6.81 (1H, s),
6.91 (1H, d, JZ8.2 Hz), 6.96–7.14 (2H, overlapping), 7.19
(1H, d, JZ8.2 Hz), 7.83 (1H, dd, JZ7.4, 8.8 Hz); 13C NMR
(CDCl3): dZ14.2 (q), 45.8 (t), 120.2 (d), 121.0 (d), 124.4
(d), 124.9 (d), 126.5 (d), 132.3 (d), 132.6 (d), 132.9 (s),
133.7 (s), 143.4 (s), 144.8 (s), 149.7 (s), 167.4 (s). Anal.
Calcd for C15H13ClN2O: C, 66.06; H, 4.80; N, 10.27.
Found: C, 65.98; H, 4.97; N, 10.19.
e][1,4]diazepin-5-one (15).10d 42% Yield; mp 167–169 8C
(cream crystals from CH2Cl2–hexane); IR (nujol): n 1661,
3046 cmK1; H NMR (CDCl3): dZ3.74 (3H, s), 4.60 (1H,
1
br s, absent after deuteriation), 7.01 (1H, dd, JZ5.2,
7.1 Hz), 7.29–7.45 (3H, overlapping), 7.84 (1H, d, JZ
7.9 Hz), 7.94 (1H, d, JZ7.1 Hz), 8.31 (1H, d, JZ3.3 Hz);
13C NMR (CDCl3): dZ29.0 (q), 109.9 (d), 115.7 (s), 116.8
(d), 120.0 (d), 122.6 (d), 123.1 (d), 134.4 (s), 136.4 (s),
141.9 (d), 143.1 (s), 149.0 (d), 161.3 (s). Anal. Calcd for
C13H11N3O: C, 69.32; H, 4.92; N, 18.65. Found: C, 69.26;
H, 5.04; N, 18.45.
3.7.7. 2-Fluoro-10-methyl-5,10-dihydro-dibenzo[b,e]-
[1,4]diazepin-11-one (7da). 63% Yield; mp 175–177 8C