Medicinal Chemistry Research
(
[
13), 90 (10), 70 (13); HRMS m/z calcd for C H N O
M + H] 319.1559, found 319.1612.
241 (100), 160 (8), 145 (10), 119 (23), 90 (10), 70 (15);
19
18
4
+
HRMS m/z calcd for C H N O [M + H]+ 349.1665,
2
0
20
4
2
found 349.1721.
(
[
S,E)-11-[2-(4-ethylphenyl-methylene)hydrazono]-pyrrolo
2,1-c][1,4]benzodiazepine (4b)
(S,E)-11-[2-(4-fluorophenylmethylene)hydrazono]-pyrrolo
2,1-c][1,4]benzodiazepine (4d)
[
Starting material benzaldehyde (1.34 mL, 10 mmol) was
used and the reaction mixture was stirred under nitrogen
gas overnight for 15 h. Evaporation of solvent mixture was
carried out under vacuum. Crystallization of the compound
was achieved with n-pentane to give a yellow solid rod-
shaped crystal of compound 4b. Yield 732 mg (70.4%);
Starting material 4-flurobenzaldehyde (1.07 mL, 10 mmol)
was used and the reaction mixture was stirred under nitro-
gen gas for 4 h. This is followed by quenching the mixture
with 20 mL distilled water to afford a white precipitate of
4d. Crystallization of the final product was accomplished in
hexane/acetone to yield greenish rod-shaped crystals. Yield
2
5
1
mp 168–170 °C; [α] = + 54° (c 0.5, CHCl ); H-NMR
D
3
2
5
(
400 MHz, CDCl ): 1.26 (t, J = 7.7 Hz, 3H), 1.99–2.15 (m,
740 mg (73.3%); mp 205–207 °C; [α] = + 30° (c 0.5,
3
D
1
3
3
5
1
7
1
2
1
1
3
H), 2.69 (q, J = 7.7 Hz, 2H), 2.98–2.99 (m, 1H),
.64–3.73 (m, 1H), 3.78–3.84 (m, 1H), 4.38 (d, J =
.5 Hz, 1H), 7.00 (d, J = 7.3 Hz, 1H), 7.17 (t, J = 8.1 Hz,
H), 7.26 (d, J = 8.6 Hz, 1H), 7.43 (t, J = 7.7 Hz, 1H),
.71 (d, J = 8.2 Hz, 2H), 7.97 (d, J = 9.5 Hz, 1H), 8.46 (s,
CHCl ); H-NMR (400 MHz, CDCl ): δ = 2.00–2.13 (m,
3
3
3H), 2.96–2.99 (m, 1H), 3.68–3.70 (m, 1H), 3.78–3.81 (m,
1H), 4.38 (d, J = 5.9 Hz, 1H, H-11a), 6.99 (d, J = 7.3 Hz,
1H), 7.12 (t, J = 8.8 Hz, 2H), 7.18 (t, J = 7.0 Hz, 1H), 7.43
(t, J = 6.6 Hz, 1H), 7.78 (t, J = 6.6 Hz, 2H), 7.96 (d, J =
1
3
13
H), 8.52(s,1H); C-NMR (100 MHz, CDCl ): δ = 15.5,
6.2 Hz, 1H), 8.45 (s, 1H, CH), 8.49 (s, 1H, NH); C-NMR
3
3.6, 26.2, 29.0, 47.4, 55.5 (C-11a), 120.7, 126.4, 128.3,
28.4, 131.5, 132.1, 132.5, 136.9, 147.6, 157.3, 157.7,
66.1 (C=O); UV λmax (MeOH): 224, 322; IR (neat):
733, 3598, 3343, 3261, 2966, 2873, 2360, 2341, 1625
(100 MHz, CDCl ): δ = 23.6, 26.1, 47.4, 55.5 (C-11a),
3
116.0, 116.2, 120.8, 123.9, 126.5, 130.1, 130.1, 131.5,
132.5, 136.7, 156.5, 157.7, 161.8, 166.0 (C=O); UV λmax
(MeOH): 222, 236, 313; IR (neat): 2348, 1710, 1625
(C=O), 1508, 1471, 1396, 1270, 1226, 1155, 833, 755,
700, 520; GC-MS (70 eV) m/z (%): 336 (44) [M+], 241
(100), 172 (9), 145 (19), 119 (19), 90 (10), 70 (13); HRMS
(
C=O), 1469, 1396, 1270, 1160, 970, 831, 752, 669; GC-
MS (70 eV) m/z (%): 403 (1) [M+], 346(32), 241 (100),
07 (9), 172 (8), 145 (14), 119 (12), 90 (8), 70 (11), 44 (4);
2
+
+
HRMS m/z calcd for C H N O [M + H] 347.1872,
m/z calcd for C H FN O [M + H] 337.1465, found
21
22
4
19 17
4
found 347.1930.
337.1521.
(
S,E)-11-[2-(4-methoxyphenylmethylene)hydrazono]-
(S,E)-11-[2-(4-pyridinemethylene)hydrazono]-pyrrolo[2,1-c]
[1,4]benzodiazepine (4e)
pyrrolo[2,1-c][1,4]benzodiazepine (4c)
Starting material 4-methoxybenzaldehyde (1.22 mL,
Starting material 4-pyridinecarboxaldehyde (0.94 mL,
10 mmol) was used and the reaction mixture was stirred
under nitrogen gas for 4 h. The reaction mixture was then
quenched with 20 mL of distilled water and filtered off.
Crystallization of the crude product was completed using
pentane to afford a yellow crystalline solid of compound 4e.
1
0 mmol) was used and the reaction mixture was stirred
under nitrogen gas for 6 h. The solution was filtered off and
washed with diethyl ether to afford a light yellow solid of
compound 4c. The final product was purified using crys-
tallization from isopropanol to yield colorless needle-
shaped crystals. Yield 711 mg (68%); mp 212–214 °C;
2
5
Yield 606 mg (63.3%) mp 242–244 °C; [α] = + 56°
D
2
5
D
1
1
[
α] = + 40° (c 0.5, CHCl3); H-NMR (400 MHz,
(c 0.5, CHCl3); H-NMR (400 MHz, CDCl ): δ =
3
CDCl ): δ = 1.88–2.13 (m, 3H), 2.99–3.00 (m, 1H),
1.88–2.13 (m, 3H), 2.97–2.98 (m, 1H), 3.67–3.71 (m, 1H),
3.79–3.84 (m, 1H), 4.38 (d, J = 5.8 Hz, 1H, H-11a), 7.02
(d, J = 8.0 Hz, 1H), 7.20 (t, J = 7.3 Hz, 1H), 7.45 (t, J =
8.1 Hz, 1H), 7.63 (d, J = 4.8 Hz, 2H, py), 7.97 (d, J =
3
3.44–3.71 (m, 1H), 3.77–3.80 (m, 1H), 3.84 (s, 3H, OCH3),
4.37 (d, J = 8.1 Hz, 1H, H-11a), 6.93 (d, J = 8.1 Hz, 2H),
6.98 (d, J = 7.7 Hz, 1H), 7.15 (t, J = 7.7 Hz, 1H), 7.42 (t,
J = 7.0 Hz, 1H), 7.73 (d, J = 8.8 Hz, 2H), 7.93 (d, J =
6
8.0 Hz, 1H), 8.44 (s, 1H, CH), 8.50 (s, 1H, NH), 8.68 (d,
.2 Hz, 1H), 8.42 (s, 1H, NH), 8.52 (s, 1H); 1 C-NMR
3
J = 4.8 Hz, 2H, py); C-NMR (100 MHz, CDCl ): δ =
13
3
(
100 MHz, CDCl ): δ = 23.6, 26.1, 47.4, 55.03 (C-11a,
23.6, 26.2, 47.43, 55.5 (C-11a), 120.9, 121.8, 124.3, 126.7,
131.5, 132.6, 136.3, 141.7, 150.5, 155.4, 158.9, 165.9
(C=O); UV λmax (MeOH): 223, 334; IR (neat): 3276, 2977,
2879, 2360, 2341, 1625 (C=O), 1585, 1400, 1220, 1097,
991, 755, 530; GC-MS (70 eV) m/z (%): 319 (14) [M+],
281(4), 241 (100), 207 (9), 172 (11), 145 (16), 119 (12),
3
CH ), 114.3, 120.7, 123.7, 126.3, 127.3, 129.8, 131.5,
1
3
32.5, 137.0, 157.0, 157.4, 161.8, 166.1 (CO); UV λmax
(
MeOH): 221, 325; IR (neat): 3259, 2958, 2854, 2350,
1
8
706, 1619 (C=O), 1517, 1469, 1394, 1224, 1120, 927,
27, 759, 700; GC-MS (70 eV) m/z (%): 348 (65) [M+],