544
B. S. Kirkiacharian and M. Brillard
Synthesis of Compounds 10a, 10b, 2, and 1
3-(7-Coumarinyloxy)-4-hydroxy-7-methoxycoumarin 10a (4-hydroxy-O-
methyledge-worin, C19H12O7). In a dry, round-bottom flask equipped with
an argon bubbler and a Vigreux distillation column, a mixture of O-methyl-
resorcine (2.48 g, 2.0 mmol), diethyl coumarinyl-7-oxy)malonate[19] (7.44 g,
2.2 mmol), and diphenylether (5.0 mL) is heated at 2508C for 5 h (the
progress of the reaction is monitored by TLC). The reaction mixture is evap-
orated under reduced pressure on a rotary evaporator. The cooled mixture is
then triturated with diethylether (5 mL), giving a white solid, which is
filtered and washed with a small portion of diethylether (5.0 mL). The solid
is crystallized in acetic acid and in an ethanol–THF–water mixture (7/2/1),
Yield 4.55 g (65%); mp 3258C.
IR (cm21): 3078, 1688, 1610, 1236, 1129, 1076, 834. 1H NMR (DMSO-
d6): 3.88 (s, 3H, OCH3), 6.33 (d, J ¼ 9.4 Hz, 1H), 7.0–7.06 (m, 4H), 7.66
(d, J ¼ 9.4 Hz, 1H), 7.82 (d, J ¼ 9.6 Hz, 1H), 8.02 (d, J ¼ 9.6 Hz, 1H).
Anal. calcd. for C19H12O7: C, 64.78; H, 3.43. Found: C, 64.43; H, 3.36.
Acetate (C21H14O8): mp: 2838C. IR (cm21): 3422, 1719, 1612, 1274,
1
1256, 1123, 849. H NMR (DMSO-d6): 2.36 (s, 3H, CH3), 3.91 (s, 3H,
OCH3), 6.30 (d, J ¼ 9.4 Hz, 1H), 6.93–7.00 (m, 4H), 7.39–7.48 (m, 2H),
7.64 (d, J ¼ 9.8 Hz, 1H).
Tosylate (C26H18O9S): mp: 2388C. IR (cm21): 3087, 1722, 1614, 1392,
1371, 1254, 1132, 1058, 731. H NMR (DMSO-d6): 2.39 (s, 3H, CH3), 3.91
1
(s, 3H, OCH3), 6.30 (d, J ¼ 9.4 Hz, 1H), 6.85 (dd, J ¼ 8.6 Hz and 2.6 Hz, 1H),
6.96 (d, J ¼ 2.2 Hz, 1H), 7.07 (d, J ¼ 2.2 Hz, 1H), 7.10 (dd, J ¼ 8.8 Hz and
2.2 Hz, 1H), 7.19 (d, J ¼ 2.2 Hz, 1H), 7.42 (d, J ¼ 8.2 Hz, 2H), 7.51 (d, J ¼
8.8 Hz, 1H), 7.59 (d, 8.6 Hz, 1H), 7.85 (d, 8.4 Hz, 1H), 8.00 (d, J ¼ 9.6 Hz, 1H).
3-(7-Coumarinyloxy)-4-bromo-7-methoxycoumarin 10b (4-bromo-O-
methyledgeworin, C19H11BrO6). In a dry, 100 mL, double-necked, round-
bottom flask fitted with a magnetic stirring bar and a reflux condenser
protected with a CaCl2 drying tube, 1.0 g (2.8 mmol) of 4-hydroxy-O-methyl-
edgeworin 10, 0.9 g (31 mmol) of phosphorus oxybromide, and 1,2-dichloro-
benzene (40 mL) are introduced. The mixture is heated under reflux for 8 h
(the progress of the reaction is monitored by TLC). The solvent is concen-
trated to 10 mL under reduced pressure, and the crude mixture is purified by
column chromatography over silica gel (solvent: CHCl3) to give 0.767 g
(yield: 66%) of pure product. Mp: 2308C. IR (cm21): 3074, 2918, 2850,
1
1714, 1611, 1249, 1120, 835. H NMR (DMSO-d6): 3.91 (s, 3H, OCH3),
6.37 (d, J ¼ 9.6 Hz, 1H), 7.08–7.21 (m, 3H), 7.29 (d, J ¼ 2.4 Hz, 1H), 7.71
(d, J ¼ 8.6 Hz, 1H), 7.76 (d, J ¼ 8.6 Hz, 1H), 8.02 (dd, J ¼ 9.4 Hz, 1H).
Anal. calcd. for C19H11BrO6: C, 54.96; H, 2.67. Found: C, 54.43; H, 2.46.
3-(7-Coumarinyloxy)-7-methoxycoumarin2 (O-methyledgeworin C19H12O6).
In a 200 mL, double-necked, round-bottom flask fitted with a magnetic stirring