536 JOURNAL OF CHEMICAL RESEARCH 2007
O
O
H
N
CHO
OH
O
O
O
O
ClSO3H
CH3CN, r.t.
2
+
OH
OH
CHO
N
H
O
O
4
5
Scheme 2
O
O
_
- Cl
O
O
O
CH3
:
N
C
CH3
+
C
OH2
HCl
- H2SO4
N
3
_
O
Ar
O
S
O
Ar
Cl
OH
6
S
O
HO
O
7
Scheme 3
N-[(2-Chlorophenyl)(4-hydroxy-2-oxo-2H-chromen-3-yl)
General procedure
methyl]acetamide (3d): White powder, m.p. 208–210°C, IR (KBr)
(νmax cm-1): 3225 (NH), 1662, 1625, (2 C=O). Analyses: Calcd. for
C18H14ClNO4: C, 62.89; H, 4.10; N, 4.07%. Found: C, 62.9; H, 4.2;
N, 4.2. MS (m/z, %): 343 (11). 1H NMR (500 MHz, d6-DMSO):
To a magnetically stirred solution of 4-hydroxycoumarin (3 mmol) and
aldehyde (3 mmol) in acetonitrile (15 ml) was added chlorosulfonic
acid (3.3 mmol) at room temperature. The reaction mixture was
then stirred for 1 h. The mixture was poured into 50 ml ice-water.
The solid product was filtered, washed with ice-water and recrystalised
from ethyl acetate/n-hexane to give the pure product.
N-[(4-Hydroxy-2-oxo-2H-chromen-3-yl)phenylmethyl]acetamide
(3a): White powder, m.p. 184–186°C, IR (KBr) (νmax cm-1): 3320
(NH), 1674, 1629, (2 C=O). Analyses: Calcd. for C18H15NO4:
C, 69.89; H, 4.89; N, 4.53%. Found: C, 69.9; H, 4.6; N, 4.6. MS (m/z,
3
δ 1.95 (3 H, s, CH3), 6.49 (1 H, d, JHH = 7 Hz, CH), 7.19–7.39
(6 H, m, 2 CH of coumarin moiety and 4 CH of C6H4Cl), 7.65 (1 H,
t, 3JHH = 8 Hz, CH of coumarin moiety), 8.03 (1 H, d, 3JHH = 8 Hz,
CH of coumarin moiety), 8.56 (1 H, d, 3JHH = 7 Hz, NH), 12.50 (1 H,
very broad, OH). 13C NMR (125.8 MHz, d6-DMSO): δ 23.22 (CH3),
47.40 (CH), 105.03, 116.82, 117.21, 124.54, 124.84, 132.56, 153.29,
162.09, and 170.17 (carbons of coumarin moiety), 127.09, 129.07,
129.92, 130.62, 133.36, and 138.90 (carbons of C6H4Cl), 162.80
(NC=O).
1
%): 309 (6). H NMR (500 MHz, d6-DMSO): δ 1.99 (3 H, s, CH3),
3
3
6.59 (1 H, d, JHH = 9 Hz, CH), 7.20 (1 H, t, JHH = 7 Hz, CH of
C6H5), 7.30 (4 H, m, 4 CH of C6H5), 7.40 (2 H, m, 2 CH of coumarin
moiety), 7.65 (1 H, t, 3JHH = 8 Hz, CH of coumarin moiety), 8.05
(1 H, d,3JHH = 8 Hz, CH of coumarin moiety), 8.49 (1 H, d,3JHH = 9 Hz,
NH), 12.49 (1 H, very broad, OH). 13C NMR (125.8 MHz, d6-DMSO):
δ 23.42 (CH3), 47.98 (CH), 106.69, 117.00, 117.15, 124.65, 124.87,
133.24, 153.24, 162.28, and 170.55 (carbons of coumarin moiety),
126.94, 127.37, 128.87, and 141.38 (carbons of C6H5), 162.60
(NC=O).
N-[(4-Chlorophenyl)(4-hydroxy-2-oxo-2H-chromen-3-yl)
methyl]acetamide (3b): White powder, m.p. 175–177°C, IR (KBr)
(νmax cm-1): 3325 (NH), 1677, 1637, (2 C=O). Analyses: Calcd.
for C18H14ClNO4: C, 62.89; H, 4.10; N, 4.07%. Found: C, 62.8; H,
N-[(3-nitrophenyl)(4-hydroxy-2-oxo-2H-chromen-3-yl)methyl]
acetamide (3e): White powder, m.p. 195–196°C, IR (KBr) (νmax
cm-1): 3315 (NH), 1676, 1634, (2 C=O). Analyses: Calcd. for
C18H14N2O6: C, 61.02; H, 3.98; N, 7.91%. Found: C, 60.9; H, 4.1;
N, 7.9. MS (m/z, %): 354 (10). 1H NMR (500 MHz, d6-DMSO):
3
δ 2.01 (3 H, s, CH3), 6.49 (1 H, d, JHH = 7 Hz, CH), 7.42 (2 H, m,
2 CH of coumarin moiety), 7.56 (1 H, t,3JHH = 8 Hz, CH of C6H4NO2),
7.65 (1 H, t, 3JHH = 8 Hz, CH of coumarin moiety), 7.78 (1 H, d,
3JHH = 8 Hz, CH of C6H4NO2), 8.03 (1 H, d, 3JHH = 8 Hz, CH of
coumarin moiety), 8.10 (1 H, d, 3JHH = 8 Hz, CH of C6H4NO2), 8.17
(1 H, s, CH of C6H4NO2), 8.69 (1 H, d, 3JHH = 7 Hz, NH). 13C NMR
(125.8 MHz, d6-DMSO): δ 22.91 (CH3), 47.13 (CH), 105.46, 116.45,
116.85, 124.37, 124.56, 133.09, 152.90, 162.01, and 170.29 (carbons
of coumarin moiety), 121.15, 122.04, 129.97, 133.43, 143.95, and
148.14 (carbons of C6H4NO2), 162.40 (NC=O).
1
4.2; N, 4.1. MS (m/z, %): 343 (5). H NMR (500 MHz, d6-DMSO):
δ 1.99 (3 H, s, CH3), 6.61 (1 H, d, JHH = 8 Hz, CH), 7.38 (6 H,
3
m, 2 CH of coumarin moiety and 4 CH of C6H4Cl), 7.65 (1 H, t,
3JHH = 8 Hz, CH of coumarin moiety), 8.04 (1 H, d, 3JHH = 8 Hz, CH
of coumarin moiety), 8.53 (1 H, d, 3JHH = 8 Hz, NH), 12.50 (1 H,
very broad, OH). 13C NMR (125.8 MHz, d6-DMSO): δ 22.96 (CH3),
46.97 (CH), 105.87, 116.53, 116.81, 124.30, 124.54, 132.98, 152.85,
162.05, and 170.14 (carbons of coumarin moiety), 128.37, 128.45
131.52, and 140.24 (carbons of C6H4Cl), 162.63 (NC=O).
N-[(4-nitrophenyl)(4-hydroxy-2-oxo-2H-chromen-3-
yl)methyl]acetamide (3f): White powder, m.p. 179–182°C, IR (KBr)
(νmax cm-1): 3350 (NH), 1691, 1636, (2 C=O). Analyses: Calcd. for
C18H14N2O6: C, 61.02; H, 3.98; N, 7.91%. Found: C, 61.0; H, 4.1; N,
7.9. MS (m/z, %): 354 (13). 1H NMR (500 MHz, d6-DMSO): δ 2.02
3
(3 H, s, CH3), 6.69 (1 H, d, JHH = 8 Hz, CH), 7.42 (2 H, m, 2 CH
of coumarin moiety), 7.52 (2 H, d, 3JHH = 8 Hz, 2 CH of C6H4NO2),
7.65 (1 H, t, 3JHH = 8 Hz, CH of coumarin moiety), 8.03 (1 H, d,
3JHH = 8 Hz, CH of coumarin moiety), 8.22 (2 H, d, 3JHH = 8 Hz,
2 CH of C6H4NO2), 8.62 (1 H, d, 3JHH = 8 Hz, NH). 13C NMR (125.8
MHz, d6-DMSO): δ 22.91 (CH3), 47.39 (CH), 105.47, 116.17,
116.43, 124.38, 124.64, 133.19, 152.97, 162.01, and 170.29 (carbons
of coumarin moiety), 123.63, 127.77, 133.19, and 149.54 (carbons of
C6H4NO2), 162.40 (NC=O).
N-[(4-Bromophenyl)(4-hydroxy-2-oxo-2H-chromen-3-yl)
methyl]acetamide (3c): White powder, m.p. 172–174°C, IR (KBr)
(νmax cm-1): 3235 (NH), 1668, 1625, (2 C=O). Analyses: Calcd. for
C18H14BrNO4: C, 55.69; H, 3.63; N, 3.61%. Found: C, 55.8; H, 3.6;
N, 3.5. MS (m/z, %): 387 (7). 1H NMR (500 MHz, d6-DMSO): δ 1.98
(3 H, s, CH3), 6.55 (1 H, d, 3JHH = 8 Hz, CH), 7.26 (2 H, d, 3JHH = 8 HZ,
2 CH of C6H4Br), 7.40 (2 H, m, 2 CH of coumarin moiety), 7.49
3
(2 H, d, JHH = 8 HZ, 2 CH of C6H4Br), 7.66 (1 H, t, 3JHH = 8 Hz,
CH of coumarin moiety), 8.04 (1 H, d, 3JHH = 8 Hz, CH of coumarin
moiety), 8.49 (1 H, d, 3JHH = 8 Hz, NH), 12.35 (1 H, very broad,
OH). 13C NMR (125.8 MHz, d6-DMSO): δ 23.35 (CH3), 47.40 (CH),
106.25, 116.89, 117.23, 124.69, 124.97, 133.42, 153.24, 162.40, and
170.52 (carbons of coumarin moiety), 120.37, 129.22 131.67, and
141.09 (carbons of C6H4Br), 162.44 (NC=O).
N-[(3-methoxyphenyl)(4-hydroxy-2-oxo-2H-chromen-3-yl)
methyl]acetamide (3g): White powder, m.p. 203–206°C, IR (KBr)
(νmax cm-1): 3300 (NH), 1677, 1631, (2 C=O). Analyses: Calcd. for
C19H17NO5: C, 67.25; H, 5.05; N, 4.13%. Found: C, 67.2; H, 5.2; N,
1
4.2. MS (m/z, %): 339 (7). H NMR (500 MHz, d6-DMSO): δ 2.00
(3 H, s, CH3), 3.72 (3 H, s, OCH3), 6.60 (1 H, d, 3JHH = 8 Hz, CH),
PAPER: 07/4749