572
B. Capuano et al.
1H, H3´´´. 13C NMR (CD2Cl2)
123.54, 124.6, 127.0, 127.8, 128.6, 129.4, 130.3, 131.0, 131.9, 132.9,
134.9, 136.9, 143.0, 143.4, 155.1, 164.0. ESI mass spectrum m/z 481.3.
δ
48.3, 53.8, 59.9, 121.2, 121.4, 123.48,
H2´´´; 6.87, d, J 8 Hz, 1H, H6; 6.91–6.97, m, 2H, H4´´´, H6´´´; 6.93, d,
J 2 Hz, 1H, H9; 7.02, ddd, J 8, 7.5, 1 Hz, 1H, H2; 7.06, dd, J 8, 1 Hz,
1H, H4; 7.22, app t, J 8 Hz, 1H, H5´´´; 7.29, dd, J 7.5, 1.5 Hz, 1H, H1;
7.33, ddd, J 7.5, 7, 2 Hz, 1H, H3. 13C NMR [(D6)acetone] δ 48.4, 53.8,
55.5, 63.5, 113.4, 115.4, 121.2, 121.4, 122.1, 123.45, 123.50, 124.7,
127.1, 128.6, 130.1, 131.0, 132.8, 141.1, 142.9, 143.5, 155.0, 160.9,
164.1. ESI mass spectrum m/z 433.4.
8-Chloro-11-(4-(3-fluorobenzyl)piperazino)-5H-dibenzo[b,e][1,4]-
diazepine (5d). Column chromatography (ethyl acetate/hexane; 1 : 2)
gave the title compound, which recrystallized from dichloro-
methane/hexane as bright yellow prisms (79%), m.p. 213.5–215°C
(Found: C, 68.6; H, 5.3; N, 13.2%. C24H22ClFN4 requires C, 68.5; H,
5.3; N, 13.3%). νmax 3292, 1604, 1562 cm–1. λmax (log10ε) 227 (4.38),
261 (4.21), 297 (4.00) nm. 1H NMR [(D6)acetone] δ 2.53, m, 4H, H3´,
H5´; 3.43, m, 4H, H2´, H6´; 3.57, s, 2H, H1´´; 6.50, s, 1H, H5; 6.80, dd,
J 8.5, 2.5 Hz, 1H, H7; 6.87, d, J 8.5 Hz, 1H, H6; 6.94, d, J 2.5 Hz, 1H,
H9; 6.97–7.10, m, 3H, H2, H4, H6´´´; 7.13–7.23, m, 2H, H2´´´, H4´´´;
7.27–7.41, m, 3H, H1, H3, H5´´´. 13C NMR [(D6)acetone] δ 48.3, 53.8,
62.9, 114.6 (J 22 Hz, CH), 116.3 (J 22 Hz, CH), 121.3, 121.4, 123.5,
123.6, 124.7, 125.6, 127.1, 128.7, 130.9 (d, J 8 Hz, CH), 131.0, 132.9,
142.7 (d, J 7 Hz, C), 143.0, 143.5, 155.1, 164.0 (d, J 244 Hz, CF), 164.1.
ESI mass spectrum m/z 421.3.
8-Chloro-11-(4-(3-trifluoromethylbenzyl)piperazino)-5H-dibenzo-
[b,e][1,4]diazepine (5i). Column chromatography (ethyl acetate/
hexane; 1 : 2) gave the title compound, which recrystallized from
dichloromethane/hexane as bright yellow prisms (78%), m.p.
202–204°C (Found: C, 64.0; H, 4.7; N, 11.9%. C25H22ClF3N4 requires
C, 63.8; H, 4.7; N, 11.9%). νmax 3284, 1602, 1558 cm–1. λmax (log10ε)
228 (4.48), 261 (4.29), 297 (4.09) nm. 1H NMR [(D6)acetone] δ 2.54,
m, 4H, H3´, H5´; 3.44, m, 4H, H2´, H6´; 3.65, s, 2H, H1´´; 6.50, s, 1H,
H5; 6.81, J 8.5, 2.5 Hz, 1H, H7; 6.88, d, J 8.5 Hz, 1H, H6; 6.95, d, J 2.5
Hz, 1H, H9; 7.01, app td, J 7.5, 1 Hz, 1H, H2; 7.06, br d, J 8 Hz, 1H,
H4; 7.26–7.37, m, 2H, H1, H3; 7.51–7.75, m, 4H, H2´´´, H4´´´, H5´´´,
H6´´´. 13C NMR [(D6)acetone] δ 48.3, 53.7, 62.8, 121.2, 121.4, 123.5,
123.6, 124.6, 124.7 (q, J 4 Hz, CH), 125.5 (q, J 271 Hz, CF), 126.3 (q,
J 4 Hz, CH), 127.1, 128.7, 130.0, 130.98 (q, J 32 Hz, C), 131.02, 132.9,
133.7 (m, CH), 141.2, 142.9, 143.4, 155.0, 164.0. ESI mass spectrum
m/z 471.3.
8-Chloro-11-(4-(3-chlorobenzyl)piperazino)-5H-dibenzo[b,e][1,4]-
diazepine (5e). Column chromatography (ethyl acetate/hexane; 1 : 2)
gave the title compound, which recrystallized from dichloro-
methane/hexane as bright yellow platelets (59%), m.p. 222–223°C
(Found: C, 66.0; H, 5.1; N, 13.1%. C24H22Cl2N4 requires C, 65.9; H, 5.1;
N, 12.8%).
(4.22), 297 (4.02) nm. 1H NMR [(D6)acetone]
3.44, m, 4H, H2´, H6´; 3.57, s, 2H, H1´´; 6.51, s, 1H, H5; 6.81, dd,
2.5 Hz, 1H, H7; 6.88, d, 8.5 Hz, 1H, H6; 6.93, d, 2.5 Hz, 1H, H9;
7.02, ddd, 8, 7.5, 1 Hz, 1H, H2; 7.07, dd, 8, 1 Hz, 1H, H4; 7.24–7.37,
m, 5H, H1, H3, H4´´´, H5´´´, H6´´´; 7.41, m, 1H, H2´´´. 13C NMR
[(D6)acetone] 48.3, 53.8, 62.8, 121.3, 121.4, 123.5, 123.6, 124.7,
ν
max 3292, 1604, 1562 cm–1.
λ
max (log10
2.54, m, 4H, H3´, H5´;
8.5,
ε
) 228 inf (4.42), 261
8-Chloro-11-(4-(4-fluorobenzyl)piperazino)-5H-dibenzo[b,e][1,4]-
diazepine (5j). Column chromatography (ethyl acetate/hexane; 1 : 1)
gave the title compound, which recrystallized from dichloromethane/
hexane as bright yellow prisms (66%), m.p. 201–202°C (Found: C,
68.2; H, 5.1; N, 13.2%. C24H22ClFN4 requires C, 68.5; H, 5.3; N,
13.3%). νmax 3292, 1603, 1560 cm–1. λmax (log10ε) 228 (4.39), 261
(4.21), 297 (4.01) nm. 1H NMR [(D6)acetone] δ 2.51, m, 4H, H3´, H5´;
3.42, m, 4H, H2´, H6´; 3.54, s, 2H, H1´´; 6.53, s, 1H, H5; 6.81, dd, J
8.5, 2.5 Hz, 1H, H7; 6.88, d, J 8.5 Hz, 1H, H6; 6.94, d, J 2.5 Hz, 1H,
H9; 6.98–7.12, m, 4H, H2, H4, H3´´´, H5´´´; 7.26–7.43, m, 4H, H1, H3,
H2´´´, H6´´´. 13C NMR [(D6)acetone] δ 48.3, 53.4, 62.7, 115.7 (d, J 21
Hz, CH), 121.2, 121.4, 123.4, 123.5, 124.7, 127.1, 128.7, 131.0, 131.6
(d, J 7.5 Hz, CH), 132.9, 135.6, 142.9, 143.5, 155.0, 163.0 (d, J 243 Hz,
CF), 164.6. FAB Mass spectrum m/z 421.4.
δ
J
J
J
J
J
δ
127.1, 128.0, 128.3, 128.6, 129.7, 130.8, 131.1, 132.9, 134.7, 142.3,
143.0, 143.5, 155.1, 164.1. ESI mass spectrum m/z 437.3.
8-Chloro-11-(4-(3-bromobenzyl)piperazino)-5H-dibenzo[b,e][1,4]-
diazepine (5f). Column chromatography (ethyl acetate/hexane; 1 : 2)
gave the title compound, which recrystallized from dichloro-
methane/hexane as bright yellow platelets (48%), m.p. 223–225°C
(Found: C, 60.1; H, 4.5; N, 11.5%. C24H22BrClN4 requires C, 59.8; H,
4.6; N, 11.6%).
261 (4.25), 297 (4.05) nm. 1H NMR [(D6)acetone]
H5´; 3.44, m, 4H, H2´, H6´; 3.57, s, 2H, H1´´; 6.50, s, 1H, H5; 6.81, dd,
8.5, 2.5 Hz, 1H, H7; 6.87, d, 8.5 Hz, 1H, H6; 6.93, d, 2.5 Hz, 1H,
H9; 7.02, ddd, 8, 7.5, 1 Hz, 1H, H2; 7.07, dd, 8, 1 Hz, 1H, H4;
7.23–7.46, m, 5H, H1, H3, H4´´´, H5´´´, H6´´´; 7.57, br s, 1H, H2´´´. 13
NMR [(D6)acetone] 48.3, 53.8, 62.8, 121.3, 121.4, 123.0, 123.5,
ν
max 3288, 1602, 1562 cm–1.
λ
max (log10
ε
) 225 inf (4.49),
8-Chloro-11-(4-(4-chlorobenzyl)piperazino)-5H-dibenzo[b,e][1,4]-
δ
2.54, m, 4H, H3´,
diazepine (5k). Column chromatography (ethyl acetate/hexane; 1 : 1)
gave the title compound, which recrystallized from dichloromethane/
hexane as bright yellow prisms (76%), m.p. 201–203°C (Found: C, 65.8;
H, 4.9; N, 12.7%. C24H22Cl2N4 requires C, 65.9; H, 5.1; N, 12.8%). νmax
J
J
J
J
J
C
3368, 1604, 1562 cm–1. λmax (log10
(3.98) nm. 1H NMR [(D6)acetone]
H2´, H6´; 3.54, s, 2H, H1´´; 6.50, s, 1H, H5; 6.80, dd,
H7; 6.87, d, 8.5 Hz, 1H, H6; 6.94, d, 2.5 Hz, 1H, H9; 7.01, app td,
8, 1 Hz, 1H, H2; 7.06, app d, 8 Hz, 1H, H4; 7.26–7.41, m, 6H, H1, H3,
H2´´´, H3´´´, H5´´´, H6´´´. 13C NMR [(D6)acetone]
48.3, 53.7, 62.6,
ε
) 232 inf (4.37), 261 (4.18), 298
2.52, m, 4H, H3´, H5´; 3.42, m, 4H,
8.5, 2.5 Hz, 1H,
δ
δ
123.6, 124.7, 127.1, 128.7, 128.8, 131.0, 131.07, 131.14, 132.7, 132.9,
142.6, 143.0, 143.5, 155.1, 164.1. ESI mass spectrum m/z 481.2.
J
J
J
J
J
8-Chloro-11-(4-(3-methylbenzyl)piperazino)-5H-dibenzo[b,e][1,4]-
δ
diazepine (5g). Column chromatography (ethyl acetate/hexane; 1 : 1)
gave the title compound, which recrystallized from dichloro-
methane/hexane as bright yellow prisms (72%), m.p. 202.5–204°C
(Found: C, 72.2; H, 6.1; N, 13.5%. C25H25ClN4 requires C, 72.0; H, 6.0;
121.2, 121.3, 123.4, 123.5, 124.6, 127.0, 128.6, 129.1, 131.0, 131.4,
132.8, 133.1, 138.5, 142.9, 143.4, 155.0, 164.0. ESI mass spectrum m/z
437.3.
N, 13.4%).
(4.22), 297 (4.02) nm. 1H NMR [(D6)acetone]
m, 4H, H3´, H5´; 3.42, m, 4H, H2´, H6´; 3.50, s, 2H, H1´´; 6.51, s, 1H,
H5; 6.80, dd, 8.5, 2.5 Hz, 1H, H7; 6.90, d, 8.5 Hz, 1H, H6; 6.94, d,
2.5 Hz, 1H, H9; 7.01, app td, 7.5, 1 Hz, 1H, H2; 7.04–7.09, m, 2H, H4,
H2´´´; 7.10–7.23, m, 3H, H4´´´, H5´´´, H6´´´; 7.25–7.36, m, 2H, H1, H3.
13C NMR [(D6)acetone]
21.5, 48.3, 53.8, 63.6, 121.2, 121.4, 123.45,
ν
max 3304, 1604, 1562 cm–1.
λ
max (log10
ε
) 228 inf (4.41), 261
8-Chloro-11-(4-(4-bromobenzyl)piperazino)-5H-dibenzo[b,e][1,4]-
δ
2.31, s, 3H, CH3; 2.51,
diazepine (5l). Column chromatography (ethyl acetate/hexane; 1 : 1)
gave the title compound, which recrystallized from dichloromethane/
hexane as bright yellow prisms (79%), m.p. 210–212°C (Found: C, 59.6;
H, 4.5; N, 11.5%. C24H22BrClN4 requires C, 59.8; H, 4.6; N, 11.6%).
J
J
J
J
ν
max 3368, 1612, 1564 cm–1.
(4.05) nm. 1H NMR [(D6)acetone]
H2´, H6´; 3.55, s, 2H, H1´´; 6.51, s, 1H, H5; 6.80, dd,
H7; 6.87, d, 8.5 Hz, 1H, H6; 6.93, d, 2.5 Hz, 1H, H9; 7.00, app td,
7.5, 1 Hz, 1H, H2; 7.06, app d, 8 Hz, 1H, H4; 7.25–7.37, m, 4H, H1,
H3, H2´´´, H6´´´; 7.49, d,
8.5 Hz, 2H, H3´´´, H5´´´. 13C NMR (CDCl3)
47.5, 53.2, 62.5, 120.2, 120.3, 121.2, 123.2, 123.3, 123.7, 127.0,
λ
max (log10
2.54, m, 4H, H3´, H5´; 3.44, m, 4H,
8.5, 2.5 Hz, 1H,
ε) 226 inf (4.55), 261 (4.24), 297
δ
δ
123.52, 124.7, 127.1 (2 × CH), 128.6, 129.0, 130.6, 131.0, 132.8, 133.9,
138.5, 139.4, 142.9, 143.5, 155.0, 164.1. ESI mass spectrum m/z 417.3.
J
J
J
J
J
8-Chloro-11-(4-(3-methoxybenzyl)piperazino)-5H-dibenzo[b,e]-
[1,4]diazepine (5h). Column chromatography (ethyl acetate/hexane;
1 : 2) gave the title compound, which recrystallized from dichloro-
methane/hexane as bright yellow prisms (81%), m.p. 156.5–158°C
(Found: C, 69.4; H, 5.8; N, 13.0%. C25H25ClN4O requires C, 69.4; H,
5.8; N, 12.9%). νmax 3276, 1602, 1562 cm–1. λmax (log10ε) 226 inf
J
δ
129.3, 130.5, 131.0, 131.6, 132.1, 137.3, 140.6, 142.1, 152.9, 163.0. ESI
mass spectrum m/z 481.2.
8-Chloro-11-(4-(4-methylbenzyl)piperazino)-5H-dibenzo[b,e][1,4]-
1
(4.49), 262 (4.19), 298 (3.99) nm. H NMR [(D6)acetone] δ 2.53, m,
diazepine (5m) Column chromatography (ethyl acetate/hexane; 1 : 2)
.
4H, H3´, H5´; 3.43, m, 4H, H2´, H6´; 3.53, s, 2H, H1´´; 3.78, s, 3H,
OCH3; 6.51, s, 1H, H5; 6.80, dd, J 8.5, 2.5 Hz, 1H, H7; 6.81, m, 1H,
gave the title compound, which recrystallized from dichloromethane/
hexane as bright yellow prisms (74%), m.p. 195–197°C (Found: C, 71.6;