K. M. Khan et al. / Bioorg. Med. Chem. 12 (2004) 1963–1968
1967
(td, 2H, J=7.9, J=1.6 Hz, H-6/60), 7.14 (td, 1H, J=8.4,
J=2.2 Hz, H-500), 6.17 (s, 1H, H-11); IR (KBr) nmax
1565.7, 1604.2, 1660, 2922.3, 3749 cmꢀ1; UV (DMSO)
lmax (log e) 307 (3.18) nm; MS (m/z) 446 (M+, 7), 446
(8), 410 (14), 325 (8), 249 (100), 162 (19), 120 (28), 92
(18), 62 (20). Anal. calcd for C25H15O6Cl C 67.20; H
3.38; Cl 7.93; Found: C 67.18; H 3.36; Cl 7.95.
(12), 281 (21), 265 (18), 249 (100), 162 (64), 120 (99), 92
(97), 63 (61). Anal. calcd for C26H18O7 C 70.58; H 4.10;
Found: C 70.61; H 4.13.
3.2.15.
3,30-(Dihydrocinnamylidene)-bis-(4-hydroxy-
coumarin) (15). Yield: 0.465 g (93%); mp 190 ꢁC;
Rf=0.58 (ethyl acetate); H1 NMR (400 MHz, DMSO-
d6); d 7.88 (d, 2H, J=8.0 Hz, H-5/50), 7.65 (td, 2H,
J=8.0, J=2.2 Hz, H-7/70), 7.33 (d, 2H, J=8.0 Hz, H-8/
80), 7.30 (td, 2H, J=8.0, J=2.4 Hz, H-6/60), 6.5–6.8 (m,
5H, Ar-H), 5.8 (t, 1H, J=6.8 Hz, H-11), 2.67 (m, 2H,-
CH2-CH2Ar), 1.89 (m, 3H, J=6.5 Hz, –CH2-CH2-Ar);
3.2.11. 3,30-(2-Bromobenzylidene)-bis-(4-hydroxycoumarin)
(11). Yield: 0.465 g (93%); mp 203 ꢁC; Rf=0.62 (ethyl
1
acetate); H NMR (400 MHz, DMSO-d6): 7.80 (d, 2H,
J=7.8 Hz, H-5/50), 7.78 (d, 2H, J=8.3 Hz, H-600), 7.51
(td, 2H, J=7.8, J=2.1 Hz, H-7/70), 7.31 (d, 1H, J=8.3
Hz, H-300), 7.28 (td, 1H, J=8.3, J=2.4 Hz, H-500), 7.25
(d, 2H, J=7.8 Hz, H-8/80), 7.21 (td, 2H, J=7.8, J=1.5
Hz, H-6/60), 7.01 (d, 1H, J=8.3 Hz, H-300), 5.98 (s, 1H,
H-11); IR (KBr) nmax 1530, 1616, 1650, 3010, 3672
cmꢀ1; UV (DMSO) lmax (log e) 308.1 (3.09) nm; MS
(m/z) 493 (M+, 4), 491 (5), 410 (11), 329 (2), 291 (12),
249 (100), 221 (17), 162 (53), 120 (64), 92 (66), 63 (56).
Anal. calcd for C25H15BrO6 C 61.12; H 3.08; Br 16.26;
Found: C 61.15; H 3.09; Br 16.30.
IR (KBr) nmax 1563.9, 1615, 1658.3, 3026, 3650 cmꢀ1
;
UV (DMSO) lmax (log e) 309.2 (3.27) nm; MS (m/z)
440, (M+, 4), 410 (17), 321 (12), 281 (21), 265 (18), 162
(64), 121 (100), 92 (97), 63 (61). Anal. calcd for
C27H20O6 C 73.63; H 4.58; Found: C 73.66; H 4.56.
3.2.16. 3,30-(3-Cinnamylidene)-bis-(4-hydroxycoumarin)
(16). Yield: 0.475 g (95%); mp 196 ꢁC; Rf=0.72 (ethyl
acetate); 1H NMR (300 MHz, DMSO-d6): d 7.89 (d, 2H,
J=8.0 Hz, H-5/50), 7.51 (td, 2H, J=8.0, J=1.7 Hz, H-
7/70), 7.29 (d, 2H, J=8.0 Hz, H-8/80), 7.25 (dd, 1H,
J=15.4, 3.5 Hz, –CH¼CH-Ar), 7.20 (td, 2H, J=8.0,
J=2.5 Hz, H-6/60), 7.15–7.18 (5H, m, Ar-H), 6.85 (d,
1H, J=15.4 Hz, –CH=CH-Ar), 4.9 (d, 1H, J=3.5 Hz,
H-11); IR (KBr) nmax 1560, 1637, 1680, 3050, 3648
cmꢀ1; UV (DMSO) lmax (log e) 305.9 (3.16) nm; MS
(m/z) 438, (M+, 6), 277 (84), 202 (3), 187 (5), 162 (64),
121 (100), 92 (86), 63 (59). Anal. calcd for C27H18O6 C
73.97; H 4.14; Found: C 73.92; H 4.10.
3.2.12.
3,30-(2-Methoxybenzylidene)-bis-(4-hydroxy-
coumarin) (12). Yield: 0.46 g (92%); mp 236 ꢁC; Rf=
1
0.46 (ethyl acetate); H NMR (400 MHz, DMSO-d6): d
7.78 (d, 2H, J=7.8 Hz, H-5/50), 7.65 (d, 2H, J=8.1 Hz,
H-600), 7.46 (td, 2H, J=7.8, J=2.3 Hz, H-7/70), 7.23 (d,
2H, J=7.8 Hz, H-8/80), 7.18 (td, 2H, J=7.8, J=2.5 Hz,
H-6/60), 6.44 (td, 1H, J=8.1, J=2.3 Hz, H-400), 6.38 (td,
1H, J=8.1, J=1.9 Hz, H-500), 6.35 (d, 1H, J=8.1 Hz,
H-300), 6.00 (1H, s, H-11), 2.9 (s, 3H, –OCH3); IR (KBr)
nmax 1556, 1610, 1645, 2945, 3746 cmꢀ1; UV (DMSO)
lmax (log e) 308.2 (3.11) nm; MS (m/z) 442, (M+, 34),
321 (2), 281 (2), 249 (100), 162 (30), 120 (45), 92 (25), 63
(17). Anal. calcd for C26H18O7 C 70.58; H 4.10; Found:
C 70.62; H 4.02.
3.2.17. 3,30-(2-Pyridyl-methylene-bis-(4-hydroxycoumarin)
(17). Yield: 0.485 g (97%); mp 278 ꢁC (decomposed);
1
Rf=0.63 (ethyl acetate); H NMR (300 MHz, DMSO-
d6): d 9.61 (s, 1H, H-200), 8.40 (d, 1H, J=8.7 Hz, H-400),
7.80 (d, 2H, J=8.0 Hz, H-5/50), 7.56 (td, 2H, J=8.0,
J=2.2 Hz, H-7/70), 7.35 (d, 2H, J=8.0 Hz, H-8/80), 7.30
(td, 2H, J=8.0, J=2.5 Hz, H-6/60), 6.93 (td, 1H, J=8.7,
J=2.3 Hz, H-500), 5.91 (1H, s, H-11); IR (KBr) max 1567,
1598, 1648, 3064, 3648 cmꢀ1; UV (DMSO) lmax (log e)
307.6 (3.35) nm; MS (m/z) 413, (M+, 27), 252 (44), 162
(64), 120 (100), 92 (93), 63 (73). Anal. calcd for
C24H15NO6 C 69.73; H 3.66; N 3.39; Found: C 69.70; H
3.60; N 3.41.
3.2.13.
3,30-(3-Methoxybenzylidene)-bis-(4-hydroxy-
coumarin) (13). Yield: 0.49 g (98%); mp 238 ꢁC;
1
Rf=0.61 (ethyl acetate); H NMR (400 MHz, DMSO-
d6): d 7.85 (d, 2H, J=7.9 Hz, H-5/50), 7.56 (td, 2H,
J=7.9, J=2.0 Hz, H-7/70), 7.39 (d, 1H, J=8.6 Hz, H-
600), 7.31 (d, 2H, J=7.9 Hz, H-8/80), 7.29 (s, 1H, H-200),
7.27 (td, 2H, J=7.9, J=2.1 Hz, H-6/60), 6.98 (td, 1H,
J=8.6, J=2.3 Hz, H-500), 6.58 (td, 1H, J=8.6 J=2.0
Hz, H-400), 6.11 (1H, s, H-11), 3.20 (3H, s, ꢀOCH3); IR
(KBr) nmax 1564, 1609, 1670, 2934, 3649 cmꢀ1; UV
(DMSO) lmax (log e) 308.6 (2.86) nm; MS (m/z) 442,
(M+, 40), 321 (17), 281 (52), 265 (53), 249 (100), 162
(83), 120 (99), 92 (86), 63 (67). Anal. calcd for C26H18O7
C 70.58; H 4.10; Found: C 70.60; H 4.01.
3.2.18. 3,30-(4-Nitrobenzylidene)-bis-(4-hydroxycoumarin)
(18). Yield: 0.465 g (93%); mp 219 ꢁC; Rf=0.59 (ethyl
acetate); 1H NMR (400 MHz, DMSO-d6): d 8.00 (d, 2H,
J=8.7 Hz, H-200/600), 7.86 (d, 2H, J=7.8 Hz, H-5/50),
7.78 (d, 2H, J=8.7 Hz, H-300/500), 7.57 (td, 2H, J=7.8,
J=2.0 Hz, H-7/70), 7.32 (d, 2H, J=7.8 Hz, H-8/80), 7.27
(td, 2H, J=7.8, J=2.4 Hz, H-6/60), 5.89 (s, 1H, H-11);
IR (KBr) nmax 1562, 1637, 1664, 3010, 3614 cmꢀ1; UV
(DMSO) lmax (log e) 307.1 (2.70) nm; MS (m/z) 457,
(M+, 32), 336 (7), 296 (10), 250 (16), 162 (42), 120 (85),
92 (100), 63 (30). Anal. calcd for C25H15NO8 C 65.65; H
3.31; N 3.06; Found: C 65.71; H 3.29; N 3.10.
3.2.14.
3,30-(4-Methoxybenzylidene)-bis-(4-hydroxy-
coumarin) (14). Yield: 0.49 g (98%); mp 242 ꢁC;
1
Rf=0.62 (ethyl acetate); H NMR (400 MHz, DMSO-
d6): d 7.86 (d, 2H, J=7.8 Hz, H-5/50), 7.57 (td, 2H,
J=7.8, J=1.9 Hz, H-7/70), 7.32 (d, 2H, J=7.8 Hz, H-8/
80), 7.27 (td, 2H, J=7.8, J=2.0 Hz, H-6/60), 7.01 (d, 2H,
J=8.3 Hz, H-300/500), 6.70 (d, 2H, J=8.3 Hz, H-200/600),
5.89 (s, 1H, H-11), 3.41 (s, 3H, ꢀOCH3); IR (KBr) nmax
1565, 1611, 1665, 2937, 3675 cmꢀ1; UV (DMSO) lmax
(log e) 288.6 (3.20) nm; MS (m/z) 442, (M+, 76), 321
3.2.19. 3,30-(2-Pyrolidene)-bis-(4-hydroxycoumarin) (19).
Yield: 0.475 g (95%); mp 160 ꢁC; Rf=0.42 (ethyl acetate);
H1 NMR (300 MHz, DMSO-d6): d 7.91 (d, 2H, J=7.9
Hz, H-5/50), 7.55 (td, 2H, J=7.9, J=1.7 Hz, H-7/70),