196
neutralized with 10% aqueous sodium bicarbonate solu-
tion and the precipitate formed was filtered out and dried.
(100%), 121 (14%), 91 (8%), 65 (27%); IR (KBr) cm–1:
3 244 (ν N–H), 1 648 (ν C=O), 1 598 (ν C = N), 1 290
and 1 260 (ν C–O). Anal. calcd. for C15H11BrN2O3: C,
51.89; H, 3.19; N, 8.07. Found: C, 51.83; H, 3.27; N,
8.15.
4.1.3.1. Benzylidene 3,4-methylenedioxy-
benzoylhydrazine 9a
The derivative 9a was obtained as a white solid by
condensation of 17 with benzaldehyde, (Rf acetone:tolu-
4.1.3.4. (4'-Methoxybenzylidene) 3,4-methylene-
dioxybenzoylhydrazine 9d
1
ene 30% = 0.50). H-NMR (200 MHz): δ 11.70 (s, 1H,
CONH-), 8.42 (s, 1H, -N=CH-), 7.70 (m, 2H, H2 and
H4'), 7.51 (d, 1H, H6, J = 8.1 Hz), 7.44 (m, 4H, H2' and
H3'), 7.05 (d, 1H, H5, J = 8.1 Hz), 6.17 (s, 2H, O–CH2–O)
ppm; 13C-NMR (50 MHz): δ 162.3 (C=O); 150.2 (C4),
148.1 (C3), 147.5 (N=CH), 134.4 (C1'), 130.0 (C4'), 128.8
(C2'), 127.2 (C1), 127.0 (C3'), 122.8 (C6), 108.0 (C2),
107.6 (C5), 101.8 (O–CH2–O) ppm; MS (70 eV) m/z
(relative abundance): 268 (5%), 165 (28%), 149 (100%),
121 (13%), 65 (15%); IR (KBr) cm–1: 3 448 (ν N–H),
1 636 (ν C=O), 1 601 (ν C=N), 1 300 and 1 261 (ν C–O).
Anal. calcd. for C15H12N2O3: C, 67.16; H, 4.51; N,
10.44. Found: C, 67.25; H, 4.67; N, 10.28.
The derivative 9d was obtained as a white solid by
condensation of 17 with 4-methoxybenzaldehyde (Rf
acetone:toluene 30% = 0.46). H-NMR (200 MHz): δ
1
11.39 (s, 1H, CONH-), 8.39 (s, 1H, -N=CH-), 7.66 (d,
1H, H5, J = 8.6 Hz), 7.50 (d, 1H, H6, J = 8.1 Hz), 7.44 (s,
1H, H2), 7.05 (d, 2H, H2', J = 6.5 Hz), 7.00 (d, 2H, H3',
J = 6.2 Hz), 6.15 (s, 2H, O–CH2–O), 3.81 (s, 3H, OCH3)
ppm; 13C-NMR (50 MHz): δ 162.1 (C=O), 160.8 (C4'),
150.1 (C4), 147.9 (C3), 147.3 (-N=CH-), 128.6 (C2'),
127.3 (C1), 126.9 (C1'), 122.7 (C6), 114.3 (C3'), 108.0
(C2), 107.6 (C5), 101.8 (O–CH2–O), 55.2 (OCH3) ppm;
MS (70 eV) m/z (relative abundance): 298 (8%), 165
(30%), 149 (100%), 121 (15%), 91 (12%), 77 (8%), 65
(27%); IR (KBr) cm–1: 3 262 (ν N–H), 1 647 (ν C=O),
1 605 (ν C=N), 1 254 and 1 288 (ν C–O), 1 437 (CH3).
Anal. calcd. for C16H14N2O4: C, 64.42; H, 4.73; N, 9.39.
Found: C, 64.37; H, 4.79; N, 9.46.
4.1.3.2. (4'-Fluorobenzylidene) 3,4-methylene-
dioxybenzoylhydrazine 9b
The derivative 9b was obtained as a white solid by
condensation of 17 with 4-fluorobenzaldehyde (Rf ac-
etone:toluene 30% = 0.52). 1H-NMR (200 MHz): δ 11.79
(s, 1H, CONH-), 8.48 (s, 1H, -N=CH-), 7.83 (d, 2H, H2',
J = 7.5 Hz), 7.59 (d, 1H, H6, J = 7.6 Hz), 7.52 (s, H2),
7.34 (d, 2H, H3', J = 7.5 Hz), 7.09 (d, 1H, H5, J = 7.5 Hz),
6.18 (s, 2H, O–CH2–O) ppm; 13C-NMR (50 MHz): δ
162.2 (C=O), 160.6 (C4'), 150.1 (C4), 147.4 (C3), 146.2
(-N=CH-), 131.0 (C1'), 129.2 (C2'), 127.0 (C1), 122.8
(C6), 115.6 (C3'), 108.0 (C2), 107.6 (C5), 101.8
(O–CH2–O) ppm; MS (70 eV) m/z (relative abundance):
286 (2%), 165 (24%), 149 (100%), 121 (18%), 91 (8%),
65 (2%); IR (KBr) cm–1: 3 383 (ν N-H), 1 647 (ν C=O),
1 604 (ν C=N), 1 309 (ν C–O). Anal. calcd. for
C15H11FN2O3: C, 62.94; H, 3.87; N, 9.79. Found: C,
63.03; H, 3.79; N, 9.81.
4.1.3.5. (4'-Nitrobenzylidene) 3,4-methylene-
dioxybenzoylhydrazine 9e
The derivative 9e was obtained as a yellow solid by
condensation of 17 with 4-nitrobenzaldehyde (Rf ac-
etone:toluene 30% = 0.52). 1H-NMR (300 MHz): δ 12.12
(s, 1H, CONH-), 8.63 (s, 1H, -N=CH-), 8.45 (d, 2H, H3',
J = 7.9 Hz), 8.10 (d, 2H, H2', J = 8.2 Hz), 7.67 (d, 1H, H5,
J = 7.9 Hz), 7.60 (s, 1H, H2), 7.20 (dd, 1H, H6, Jax = 8.1
Hz, Jbx = 1.2 Hz), 6.27 (s, 2H, O–CH2–O) ppm;
13C-NMR (75 MHz): δ 162.7 (C=O), 150.6 (C4), 147.9
(C4'), 147.6 (C3), 145.0 (-N=CH-), 140.9 (C1'), 128.1
(C2'), 126.9 (C1), 124.2 (C3'), 123.4 (C6), 108.3 (C2),
107.4 (C5), 102.1 (O–CH2–O) ppm; MS (70 eV) m/z
(relative abundance): 313 (6%), 165 (9%), 149 (100%),
121 (12%), 65 (11%); IR (KBr) cm–1: 3 220 (ν N–H),
1 648 (ν C=O), 1 607 (ν C=N), 1 293 (ν C–O), 1 509 (ν
NO2). Anal. calcd. for C15H11N3O5: C, 57.51; H, 3.54; N,
13.41. Found: C, 57.45; H, 3.61; N, 13.37.
4.1.3.3. (4'-Bromobenzylidene) 3,4-methylene-
dioxybenzoylhydrazine 9c
The derivative 9c was obtained as a white solid, by
condensation of 17 with 4-bromobenzaldehyde (Rf ac-
etone:toluene 30% = 0.56). 1H-NMR (200 MHz): δ 12.05
(s, 1H, CONH-), 8.72 (s, 1H, -N=CH-), 7.96 (m, 4H, H2'
and H3'), 7.83 (d, 1H, H6, J = 7.5 Hz), 7.75 (s, 1H, H2),
7.38 (d, 1H, H5, J = 7.5 Hz), 6.45 (s, 2H, O–CH2–O)
ppm; 13C-NMR (50 MHz); δ 162.5 (C=O), 150.5 (C4),
147.7 (C3), 146.4 (-N=CH-), 134.0 (C1'), 132.2 (C2'),
129.1 (C3'), 127.3 (C1), 123.5 (C4'), 123.2 (C6), 108.3
(C2), 107.9 (C5), 102.1 (O–CH2–O) ppm; MS (70 eV)
m/z (relative abundance): 346 (2%), 165 (27%), 149
4.1.3.6. (4'-N,N-Dimethylaminobenzylidene)
3,4-methylenedioxybenzoylhydrazine 9f
The derivative 9f was obtained as an orange solid by
condensation of 17 with 4-N,N-dimethylaminobenz-
aldehyde (Rf acetone:toluene 30% = 0.44). 1H-NMR (200
MHz): δ 11.40 (s, 1H, CONH-), 8.27 (s, 1H, -N=CH-),
7.52 (d, 2H, H2', J = 8.7 Hz), 7.49 (d, 1H, H6, J = 8.2 Hz),
7.42 (s, 1H, H2), 7.02 (d, 1H, H5, J = 8.2 Hz), 6.74 (d, 2H,