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142.0, 146.9, 154.3, 160.2 ppm; MS (EI, 70 eV): m/z (%): 319 (16),
318 (99), 317 (18) [M+H]+, 316 (100) [M+], 290 (55), 288 (57), 181
(27) 153 (17), 152 (50), 151 (13), 126 (16), 119 (17), 76 (14), 71 (15),
69 (12), 57 (24), 55 (16); elemental analysis: calcd for C15H9BrO3:
C 56.81, H 2.86; found: C 56.86, H 2.90.
3-(3-Bromophenyl)-6-(cyclopentyloxy)coumarin (22): White solid;
yield 65%; mp: 228–2298C; 1H NMR (300 MHz; CDCl3): d=1.57–
1.99 (m, 8H; 2ꢅH2’’, 2ꢅH3’’, 2ꢅH4’’, 2ꢅH5’’), 4.77 (m, 1H; H1’’),
6.95 (d, J=3.0 Hz, 2H; H5), 7.05 (dd, J=8.8, J=2.7 Hz, 2H; H7, H8),
7.24–7.35 (m, 2H; H4’, H5’), 7.53 (m, 1H; H6’), 7.76 (s, 1H; H4),
7.84 ppm (t, J=2.0 Hz, 1H; H2’); 13C NMR (75 MHz; CDCl3): d=24.0,
32.7, 80.1, 111.9, 117.5, 119.7, 121.0, 122.5, 127.0, 127.3, 129.9,
131.4, 131.7, 136.8, 140.4, 147.8, 154.7, 160.4 ppm; MS (EI, 70 eV):
m/z (%): 387 (11), 386 (45), 385 (12) [M+H]+, 384 (45) [M+], 319
(19), 318 (100), 317 (22), 316 (100), 290 (27) 288 (27), 152 (11); ele-
mental analysis: calcd for C20H17BrO3: C 62.35, H 4.45; found:
C 62.30, H 4.39.
General procedure for the preparation of 6-(2-oxopropoxy)-3-
phenylcoumarins 18 and 21: Chloroacetone (0.25 mmol) was
added to a suspension of anhydrous K2CO3 (0.25 mmol) and the
corresponding hydroxycoumarin 16 or 17 (0.13 mmol) in anhy-
drous acetone (3 mL). The suspension was stirred, at reflux temper-
ature, for 16 h. The mixture was cooled and the precipitate was re-
covered by filtration and washed with anhydrous acetone (3ꢅ
40 mL). The solvent was evaporated under vacuum and the dry
residue was purified by FC (hexane/ethyl acetate, 85:15) to obtain
18 and 21, respectively.
Preparation of 2-[(3-phenylcoumarin-6-yl)oxy]acetyl chlorides 20
and 23: 2-Chloroacetyl chloride (0.25 mmol) was added to a sus-
pension of anhydrous K2CO3 (0.25 mmol) and the corresponding
6-hydroxycoumarin 16 or 17 (0.13 mmol) in anhydrous acetone
(3.0 mL). The suspension was stirred, at reflux temperature, for
24 h. The mixture was cooled and the precipitate was recovered
by filtration and washed with anhydrous acetone (3ꢅ40 mL). The
solvent was evaporated under vacuum, and the dry residue was
purified by FC (hexane/ethyl acetate, 8:2) to obtain 20 or 23, re-
spectively.
3-(4-Bromophenyl)-6-(2-oxopropoxy)coumarin (18): White solid;
1
yield 81%; mp: 157–1588C; H NMR (300 MHz; CDCl3): d=2.35 (s,
3H; CH3), 4.66 (s, 2H; CH2), 6.98 (d, J=2.9 Hz, 1H; H5), 7.20 (dd, J=
9.1, J=2.9 Hz, 1H; H7), 7.30 (d, J=9.1 Hz, 1H; H8), 7.55–7.67 (m,
4H; H2’, H3’, H5’, H6’), 7.79 ppm (s, 1H; H4); 13C NMR (75 MHz;
CDCl3): d=26.6, 73.5, 111.1, 117.9, 119.8, 119.9, 123.4, 127.9, 130.1,
131.7, 133.4, 139.4, 148.6, 154.3, 160.2, 204.6 ppm; MS (EI, 70 eV):
m/z (%): 376 (11), 375 (72), 374 (100), 373 (73) [M+H]+, 372 (99)
[M+], 332 (28), 331 (87), 330 (30), 329 (88), 302 (28), 301 (54), 245
(31), 164 (48), 163 (78), 152 (84), 151 (19), 126 (48); elemental anal-
ysis: calcd for C18H13BrO4: C 57.93, H 3.51; found: C 57.87, H 3.47.
2-[(3-(4-Bromophenyl)coumarin-6-yl)oxy]acetyl chloride (20):
1
White solid; yield 63%; mp: 118–1198C; H NMR (300 MHz; CDCl3):
d=5.52 (s, 2H; CH2), 7.07 (d, J=2.5 Hz, 1H; H5), 7.19 (d, J=8.3 Hz,
1H; H8), 7.26 (dd, J=8.8, J=2.4 Hz, 1H; H7), 7.60–7.72 (m, 4H; H2’,
H3’, H5’, H6’), 8.20 ppm (s, 1H; H4); 13C NMR (75 MHz; CDCl3): d=
89.0, 113.1, 117.2, 120.4, 122.3, 126.1, 131.0, 131.4, 131.6, 134.4,
141.3, 146.8, 154.3, 160.2, 169.0 ppm; MS (EI, 70 eV): m/z (%): 393
(10) [M+H]+, 392 (50) [M+], 319 (14), 318 (82), 317 (15), 316 (82),
297 (11) 295 (11), 290 (42), 288 (43), 216 (13), 214 (13), 181 (16),
172 (48), 171 (26), 170 (50), 169 (24), 152 (30), 126 (24), 118 (11), 90
(20), 89 (13); elemental analysis: calcd for C17H10BrClO4: C 51.87,
H 2.56; found: C 51.79, H 2.52.
3-(3-Bromophenyl)-6-(2-oxopropoxy)coumarin (21): White solid;
1
yield 83%; mp: 167–1688C; H NMR (300 MHz; CDCl3): d=2.30 (s,
3H; CH3), 4.61 (s, 3H; CH2), 6.94 (d, J=3.0 Hz, 1H; H5), 7.15 (dd, J=
9.1, J=2.0 Hz, 1H; H7), 7.33 (dd, J=8.1, J=2.4 Hz, 2H; H4’, H5’),
7.53 (d, J=9.1 Hz, 1H; H8), 7.66 (dd, J=8.2, J=2.3 Hz, 1H; H6’),
7.75 (t, J=2.5 Hz, 1H; H2’), 7.83 ppm (s, 1H; H4);13C NMR (75 MHz;
CDCl3): d=26.6, 73.5, 111.1, 117.9, 119.8, 119.9, 122.5, 127.2, 127.5,
130.0, 131.4, 132.0, 136.5, 139.9, 148.6, 154.3, 160.1, 204.5 ppm; MS
(EI, 70 eV): m/z (%): 375 (20), 374 (100), 373 (21) [M+H]+, 372 (100)
[M+], 331 (43), 329 (43), 301 (15) 273 (10), 164 (17), 163 (31), 152
(30), 126 (13); elemental analysis: calcd for C18H13BrO4: C 57.93, H
3.51; found: C 57.88, H 3.47.
2-[(3-(3-Bromophenyl)coumarin-6-yl)oxy]acetyl chloride (23):
1
White solid; yield 66%; mp: 157–1588C; H NMR (300 MHz; CDCl3):
d=5.04 (s, 2H; CH2), 7.05 (d, J=3.0 Hz, 1H; H5), 7.25 (dd, J=8.0,
J=3.5 Hz, 1H; H7), 7.40 (d, J=8.0 Hz, 1H; H8), 7.58–7.63 (m, 2H;
H4’, H5’), 7.72 (dd, J=7.6, J=1.2 Hz, 1H; H6’), 7.91 (d, J=1.3 Hz,
1H; H2’), 8.24 ppm (s, 1H; H4); 13C NMR (75 MHz; CDCl3): d=65.5,
112.6, 113.2, 117.3, 120.2, 120.6, 121.9, 125.7, 128.1, 130.8, 131.7,
137.6, 142.0, 146.9, 154.3, 160.2, 169.5 ppm; MS (EI, 70 eV): m/z (%):
393 (10) [M+H]+, 392 (50) [M+], 391 (17), 390 (86), 389 (17), 388
(86), 319 (16), 318 (99), 317 (29), 316 (100), 315 (13), 290 (53), 289
(19), 288 (54), 181 (21), 153 (17), 152 (60), 126 (23), 119 (16); ele-
mental analysis: calcd for C17H10BrClO4: C 51.87, H 2.56; found:
C 51.82, H 2.52.
Preparation of 6-(2-cyclopentyloxy)-3-phenylcoumarins 19 and
22: Cyclopentyl bromide (0.25 mmol) was added to a suspension
of anhydrous K2CO3 (0.25 mmol) and the corresponding 6-hydroxy-
coumarin 16 or 17 (0.13 mmol) in anhydrous acetone (3.0 mL). The
suspension was stirred, at reflux temperature, for 24 h. The mixture
was cooled and the precipitate was recovered by filtration and
washed with anhydrous acetone (3ꢅ40 mL). The solvent was
evaporated under vacuum, and the dry residue was purified by FC
(hexane/ethyl acetate, 9:1) to obtain 19 or 22, respectively.
Preparation of 2-[(3-phenylcoumarin-6-yl)oxy]acetic acids 24
and 25: Compounds 24 and 25 were obtained from the respective
acetyl chlorides 20 and 23 in contact with the atmosphere, due to
their instability.
3-(4-Bromophenyl)-6-(cyclopentyloxy)coumarin (19): White solid;
yield 63%; mp: 164–1658C; 1H NMR (300 MHz; CDCl3): d=1.27–
1.41 (m, 4H; 2ꢅH3’’, 2ꢅH4’’), 1.49–1.72 (m, 2H; 2ꢅH5’’), 1.77–2.29
(m, 2H; 2ꢅH2’’), 4.38 (m, 1H; H1’’), 6.96 (d, J=2.7 Hz, 1H; H5),
7.15 (dd, J=9.1, J=2.7 Hz, 2H; H7, H8), 7.2–7.38 (m, 2H; H2’, H6’)
7.44–7.67 (m, 2H; H3’, H5’), 7.76 ppm (s, 1H; H4); 13C NMR
(75 MHz; CDCl3): d=24.0, 32.8, 80.1, 111.9, 117.5, 119.8, 120.9,
123.0, 123.1, 127.3, 130.2, 131.6, 133.7, 139.9, 147.8, 154.7 ppm; MS
(EI, 70 eV): m/z (%): 387 (6), 386 (25), 385 (6) [M+H]+, 384 (25)
[M+], 319 (22), 318 (100), 317 (24), 316 (99), 290 (41) 288 (42), 181
(11), 152 (38); elemental analysis: calcd for C20H17BrO3: C 62.35, H
4.45; found: C 62.40, H 4.49.
2-[(3-(4-Bromophenyl)coumarin-6-yl)oxy]acetic acid (24): White
1
solid; yield 100%; mp: 118–1198C; H NMR (300 MHz; CDCl3): d=
4.60 (s, 2H; CH2), 7.08 (d, J=2.7 Hz, 1H; H5), 7.21 (d, J=8.3 Hz, 1H;
H8), 7.29 (dd, J=8.4, J=2.6 Hz, 1H; H7), 7.64–7.75 (m, 4H; H2’,
H3’, H5’, H6’), 8.22 (s, 1H; H4), 9.81 ppm (s, 1H; OH); 13C NMR
(75 MHz; CDCl3): d=66.0, 114.0, 117.3, 120.9, 122.4, 126.5, 131.3,
131.5, 132.0, 134.6, 141.5, 147.0, 154.5, 160.3, 171.8 ppm. MS (EI,
70 eV): m/z (%): 375 (10), 374 (32) [M+H]+, 373 (100) [M+], 319
(14), 181 (16), 171 (26), 126 (24), 118 (11), 90 (20), 89 (13); elemental
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