May-Jun 2001
Synthesis and Spectral Properties
667
24-48 hours. The reaction mixture was cooled and washed with
water (3 x 15 ml). The organic phase was dried over sodium
sulphate, filtered and evaporated in vacuo to yield a solid. The
residual solid was purified by crystallization from dichloro-
methane-hexane to yield the compounds VI, 1-12 in 50-84%
yield.
7.32 (AA'BB', 4H, J = 8.7 Hz, phenyl protons of "D" ring), 7.00
(d, 1H, J = 2.1 Hz, 6-H), 7.20 (d, 1H, J = 8.7 Hz, 9-H), 7.31 (dt,
1H, J = 2.0, 7.5 Hz, 5'-H), 7.33 (dd, 1H J = 2.4, 8.7 Hz, 8-H),
7.34 (dd, 1H, J = 2.0, 7.2 Hz, 3'-H), 7.35 (dt, 1H, J = 2.0, 7.2 Hz,
4'-H), 7.43 (dd, 1H, J = 3.0, 7.5 Hz, 6'-H), 8.91 (bs, 1H, N-H,
+
+
deuterium oxide exchangeable); ms: m/z 409 (M) , 411 [M+2] ;
+
413 [M+4] .
2-(o-Chloroaminophenyl)-3H-5-(o-chlorophenyl)-7-chloro-1,4-
benzodiazepine (1).
Anal. Calcd. for: C
H Cl N O: C, 64.40; H, 4.18; N, 10.24.
22 17 2 3
Found: C, 64.32; H, 4.27; N, 10.30.
This compound was obtained as white needles in 76% yield,
2-(o-Chloroaminophenyl)-3H-5-(p-chlorophenyl)-7-chloro-1,4-
benzodiazepine (5).
mp 204°; ir (chloroform): υ N-H 3419, C=N 1636, C-N 1346
-1
1
and 1308 cm ; H nmr (deuteriochloroform): δ 4.24 (bs, 2H,
3-H), 7.00 (dt, 1H, J = 1.5, 7.5 Hz, 4"-H), 7.04 (d, 1H, J = 2.4
Hz, 6-H), 7.26 (d, 1H, J = 8.7 Hz, 9-H), 7.27 (dt, 1H, J = 1.5, 8.1
Hz, 5"-H), 7.34 (dt, 1H, J = 2.0, 7.5 Hz, 5'-H), 7.35 (dd, 1H,
J = 1.2, 7.8 Hz, 3"-H), 7.36 (dd, 1H, J = 2.0, 7.5 Hz, 3'-H), 7.37
(dt, 1H, J = 2.0, 7.5 Hz, 4'-H), 7.38 (dd, 1H, J = 2.4, 8.7 Hz,
8-H), 7.46 (dd, 1H, J = 3.0, 7.5 Hz, 6'-H), 8.67 (dd, 1H, J = 1.2,
8.1 Hz, 6"-H), 870 (bs, 1H, N-H, deuterium oxide exchange-
This compound was obtained as yellowish needles in 57%
yield, mp 148°; ir (chloroform): υ N-H 3417, C=N 1634, C-N
-1
1
1348 and 1306 cm ; H nmr (deuteriochloroform): δ 3.65 and
4.74 (bs, 2H, 3-H), 7.00 (dt, 1H, J = 1.5, 7.8 Hz, 4"-H), 7.25 (d,
1H, J = 2.1 Hz, 6-H), 7.25 (dt, 1H, J = 1.5, 7.5 Hz, 5"-H), 7.28
(d, 1H, J = 8.7 Hz, 9-H), 7.35 (dd, 1H, J = 1.5, 7.8 Hz, 3"-H),
7.37 and 7.50 (AA'BB', 4H, J = 8.7 Hz, phenyl protons of "C"
ring), 7.43 (dd, 1H J = 2.4, 8.7 Hz, 8-H), 8.10 (dd, 1H, J = 1.8,
8.1 Hz, 6"-H), 8.71 (bs, 1H, N-H, deuterium oxide exchange-
+
+
+
+
able); ms: m/z 413 (M) , 415 [M+2] ; 417 [M+4] ; 419[M+6] .
Anal. Calcd. for: C Cl N : C, 60.82; H, 3.40; N, 10.14.
H
21 14
3 3
+
+
+
+
Found: C, 60.91; H, 3.33; N, 10.21.
able); ms: m/z 413 (M) , 415 [M+2] ; 417 [M+4] ; 419 [M+6] .
Anal. Calcd. for: C Cl N : C, 60.82; H, 3.40; N, 10.14.
H
21 14
3 3
2-(p-Chloroaminophenyl)-3H-5-(o-chlorophenyl)-7-chloro-1,4-
benzodiazepine (2).
Found: C, 60.89; H, 3.34; N, 10.21.
2-(p-Chloroaminophenyl)-3H-5-(p-chlorophenyl)-7-chloro-1,4-
benzodiazepine (6).
This compound was obtained as yellowish needles in 80%
yield, mp 240°; ir (chloroform): υ N-H 3286, C=N 1630, C-N
-1
1
1360 and 1312 cm ; H nmr (deuteriochloroform and deuterio-
dimethyl sulfoxide): δ 4.26 (bs, 2H, 3-H), 6.93 (d, 1H, J = 2.7
Hz, 6-H), 7.19 (d, 1H, J = 8.7 Hz, 9-H), 7.23 and 7.83 (AA'BB',
4H, J = 8.7 Hz, phenyl protons of "D" ring), 7.35 (dd, 1H,
J = 2.4, 8.7 Hz, 8-H), 7.37 (dt, 1H, J = 2.0, 7.5 Hz, 5'-H), 7.38
(dd, 1H, J = 2.0, 7.5 Hz, 3'-H), 7.39 (dt, 1H, J = 2.0, 7.5 Hz,
4'-H), 7.49 (dd, 1H, J = 3.0, 7.5 Hz, 6'-H), 9.69 (bs, 1H, N-H,
This compound was obtained as brown needles in 50% yield,
mp 197°; ir (chloroform): υ N-H 3439, C=N 1630, C-N 1348
-1
1
and 1304 cm ; H nmr (deuteriochloroform): δ 3.60 and 4.80
(bs, 2H, 3-H), 7.17 and 7.41 (AA'BB', 4H, J = 8.4 Hz, phenyl
protons of "D" ring), 7.24 (d, 1H, J = 2.7 Hz, 6-H), 7.27 (d, 1H,
J = 8.7 Hz, 9-H), 7.43 (dd, 1H J = 2.4, 8.7 Hz, 8-H), 7.37 and
7.50 (AA'BB', 4H, J = 8.7 Hz, phenyl protons of "C" ring), 9.10
(bs, 1H, N-H, deuterium oxide exchangeable); ms: m/z 413
+
+
deuterium oxide exchangeable); ms: m/z 413 (M) , 415 [M+2] ,
+
+
+
+
+
+
417 [M+4] ; 419 [M+6] .
Anal. Calcd. for: C
(M) , 415 [M+2] ; 417 [M+4] ; 419 [M+6] .
Anal. Calcd. for: C Cl N : C, 60.82; H, 3.40; N, 10.14.
H
Cl N : C, 60.82; H, 3.40; N, 10.14.
H
21 14
3
3
21 14
3 3
Found: C, 60.74; H, 3.48; N, 10.05.
Found: C, 60.92; H, 3.31; N, 10.06.
2-(o-Methoxyaminophenyl)-3H-5-(o-chlorophenyl)-7-chloro-
1,4-benzodiazepine (3).
2-(o-Chloroaminophenyl)-3H-5-(o-fluorophenyl)-7-chloro-1,4-
benzodiazepine (7).
This compound was obtained as brownish needles in 80%
This compound was obtained as white needles in 70% yield,
yield, mp 155°; ir (chloroform): υ N-H 3422, C=N 1636, C-N
mp 178°; ir (chloroform): υ N-H 3423, C=N 1636, C-N 1356
-1
1
-1
1
1356 and 1306 cm ; H nmr (deuteriochloroform): δ 4.24 (bs,
and 1292, C-O 1247 and 1030 cm ; H nmr (deuteriochloro-
2H, 3-H), 7.01 (dt, 1H, J = 1.5, 7.8 Hz, 4"-H), 7.08 (dd, 1H,
form): δ 3.87 (s, 3H, C2"-OCH ), 4.23 (bs, 2H, 3-H), 6.86 (dd,
3
1
J
= 1.2, J
= 8.4, J
= 9.6 Hz, 3'-H), 7.22 (dt, 1H, J
=
1H, J = 2.4, 7.8 Hz, 3"-H), 6.96 (dt, 1H, J = 2.4, 7.8 Hz, 5"-H),
6.99 (dt, 1H, J = 2.4, 7.5 Hz, 4"-H), 7.02 (d, 1H, J = 2.7 Hz, 6-
H), 7.29 (d, 1H, J = 8.7 Hz, 9-H), 7.31 (dt, 1H, J = 2.0, 7.5 Hz,
5'-H), 7.34 (dd, 1H, J = 2.0, 7.2 Hz, 3'-H), 7.35 (dt, 1H, J = 2.0,
7.2 Hz, 4'-H), 7.38 (dd, 1H, J = 2.4, 8.7 Hz, 8-H), 7.43 (dd, 1H, J
= 3.0, 7.5 Hz, 6'-H), 8.71 (dd, 1H, J = 1.5, 7.8 Hz, 6"-H), 8.71
(bs, 1H, N-H, deuterium oxide exchangeable); ms: m/z 409
H-H
H-H
H-F
H-H
1.2, J
= 7.5 Hz, 5'-H), 7.25 (d, 1H, J = 3.0 Hz, 6-H), 7.27 (dt,
H-H
1H, J = 1.5, 7.8 Hz, 5"-H), 7.29 (d, 1H, J = 9.0 Hz, 9-H), 7.36
(dd, 1H, J = 1.5, 8.1 Hz, 3"-H), 7.42 (dd, 1H, J = 2.4, 8.7 Hz, 8-
2
H), 7.45 (dt, 1H, J
= 1.2, J
= 8.4, J
= 5.5 Hz, 4'-H),
H-H
H-H
H-F
2
7.52 (dd, 1H, J
= 1.8, J
= 7.5, J
= 7.3 Hz, 6'-H), 8.70
H-H
H-H
H-F
(d, 1H, J = 6.0 Hz, 6"-H), 8.70 (bs, 1H, N-H, deuterium oxide
+
+
+
+
+
+
exchangeable); ms: m/z 397 (M) ; 399 [M+2] ; 401 [M+4] .
Anal. Calcd. for: C Cl FN : C, 63.33; H, 3.54; N, 10.55.
(M) , 411 [M+2] ; 413 [M+4] .
Anal. Calcd. for: C Cl N O: C, 64.40; H, 4.18; N, 10.24.
H
H
21 14
2
3
22 17
2 3
Found: C, 63.44; H, 3.59; N, 10.61.
Found: C, 64.49; H, 4.10; N, 10.33.
2-(p-Chloroaminophenyl)-3H-5-(o-fluorophenyl)-7-chloro-1,4-
benzodiazepine (8).
2-(p-Methoxyaminophenyl)-3H-5-(o-chlorophenyl)-7-chloro-
1,4-benzodiazepine (4).
This compound was obtained as greenish needles in 73%
This compound was obtained as brownish needles in 82%
yield, mp 172°; ir (chloroform): υ N-H 3441, C=N 1626, C-N
yield, mp 220°; ir (chloroform): υ N-H 3286, C=N 1612, C-N
-1
1
-1 1
1346 and 1298, C-O 1245 and 1036 cm ; H nmr (deuteriochlo-
1360 and 1306 cm ; H nmr (deuteriochloroform and deuterio-
and
roform): δ 3.75 (s, 3H, C4"-OCH ), 4.19 (bs, 2H, 3-H), 6.77
dimethyl sulfoxide): δ 4.25 (bs, 2H, 3-H), 7.07 (dd, 1H,
3