PLANT COUMARINS: XVII. SYNTHESIS AND TRANSFORMATIONS
1523
7.2 Hz), 6.25 d (1H, 4-H, J = 9.4 Hz), 6.79 s (1H,
8-H), 7.58 d (1H, 3-H, J = 9.4 Hz), 7.64 s (1H, 5-H),
8.35 d (1H, NH, J = 6.5 Hz). 13C NMR spectrum, δC,
ppm: 18.21 (CH3), 48.41 (OCH3), 52.90 (CH), 105.42
(C8), 111.40 (C4a), 111.67 (C6), 113.89 (C3), 126.38
(C5), 142.82 (C4), 158.02 (C8a), 160.18 (C2), 164.70
(C=O), 168.35 (C7), 173.43 (COOMe). Found, %:
C 57.89; H 4.60; N 4.73. C14H13NO6. Calculated, %:
C 57.73; H 4.50; N 4.81.
0.057 g (55%, method c), yellow oil, [α]D28.5 = +7.12°
(c = 1.00). IR spectrum, ν, cm–1: 3369, 3062, 3029,
2919, 2850, 1743, 1648, 1619, 1600, 1571, 1540,
1388, 1217, 1147, 1101, 823, 700. UV spectrum
(EtOH), λmax, nm (logε): 201 (4.57), 205 (4.32), 225
1
(4.67), 243 (4.21), 327 (4.18), 375 (3.84). H NMR
spectrum, δ, ppm: 3.01–3.24 m (2H, CH2), 3.71 s (3H,
OCH3), 4.95 m (1H, CH), 6.13 d (1H, 3-H, J =
9.4 Hz), 6.72 s (1H, 8-H), 7.15–7.24 m (3H, o-H, p-H),
7.32–7.40 m (2H, m-H), 7.42 s (1H, 5-H), 7.43 d (1H,
4-H, J = 9.4 Hz). 13C NMR spectrum, δC, ppm: 37.57
(CH2), 52.64 (OCH3), 53.37 (CH), 105.32 (C8), 111.32
(C4a), 111.72 (C6), 113.72 (C3), 126.35 (C4), 127.32
(Cp), 128.65 (Co), 129.13 (Cm), 135.29 (Ci), 142.77
(C5), 157.96 (C8a), 160.05 (C2), 164.51 (C=O), 168.11
(COOMe), 171.77 (C7). Mass spectrum: m/z 367.1053
[M]+. Found, %: C 65.68; H 4.73; N 3.75. C20H17NO6.
Calculated, %: C 65.39; H 4.66; N 3.81. M 367.1050.
Methyl 2-(7-hydroxy-2-oxo-2H-chromene-6-
carboxamido)-3-methylbutanoate (18). Yield 0.06 g
(40%, method c), mp 168°C, [α]D28.5 = +3.18° (c =
1.05). IR spectrum, ν, cm–1: 3344, 3066, 2952, 2919,
1743, 1620, 1600, 1565, 1538, 1496, 1388, 1307,
1282, 1147, 1103, 987, 825. UV spectrum (CHCl3),
λ
max, nm (logε): 247 (4.78), 307 (4.24), 330 (4.52), 343
1
(4.44). H NMR spectrum, δ, ppm: 0.85 d (6H, CH3,
J = 7.0 Hz), 3.50 m (1H, 3′-H), 3.68 s (3H, OCH3),
5.09 d.d (1H, 2′-H, J = 7.0, 6.4 Hz), 6.26 d (1H, 3-H,
J = 9.4 Hz), 6.86 s (1H, 8-H), 7.59 d (1H, 4-H, J =
9.4 Hz), 8.00 s (1H, 5-H), 8.67 d (1H, NH, J = 6.4 Hz),
11.17 s (1H, OH). 13C NMR spectrum, δC, ppm: 22.60
(CH3), 23.42 (CH3), 29.68 (C3′), 52.76 (OCH3), 60.02
(C2′), 104.81 (C8), 109.96 (C4a), 111.13 (C6), 111.91
(C3), 126.99 (C4), 142.97 (C5), 158.87 (C8a), 160.43
(C2), 161.83 (C=O), 164.23 (C7), 169.43 (COOMe).
Found, %: C 60.80; H 5.94; N 4.40. C16H17NO6.
Calculated, %: C 60.18; H 5.37; N 4.39.
Methyl 3-(7-hydroxy-2-oxo-2H-chromene-6-
carboxamido)-3-phenylpropanoate (21). Yield
0.095 g (53%, method c), mp 94°C (decomp., from
Et2O). IR spectrum, ν, cm–1: 3435, 3336, 3060, 3033,
2951, 2850, 1737, 1621, 1600, 1533, 1436, 1390,
1296, 1238, 1213, 1168, 1116, 910, 700. UV spectrum
(EtOH), λmax, nm (logε): 206 (4.75), 223 (4.45), 328
1
(4.29), 372 (4.03). H NMR spectrum, δ, ppm: 2.65 m
and 2.97 m (1H each, CH2), 3.61 s (3H, OCH3), 5.58 m
(1H, CH), 6.18 d (1H, 4-H, J = 9.4 Hz), 6.75 s (1H,
8-H), 7.22–7.30 m (3H, o-H, p-H), 7.41–7.48 m (2H,
m-H), 7.61 d (1H, 3-H, J = 9.4 Hz), 7.89 s (1H, 5-H).
13C NMR spectrum, δC, ppm: 39.76 (CH2), 49.79 (CH),
51.99 (OCH3), 104.76 (C8), 111.23 (C4a), 112.93 (C6),
113.38 (C3), 126.13 (Co), 128.12 (C4), 128.17 (Cp),
128.72 (Cm), 143.61 (C5), 147.22 (Ci), 157.50 (C8a),
160.89 (C2), 163.92 (C=O), 167.21 (C7), 171.93
(COOMe). Found, %: C 65.48; H 4.73; N 3.77.
C20H17NO6. Calculated, %: C 65.39; H 4.66; N 3.81.
Methyl 2-(7-hydroxy-2-oxo-2H-chromene-6-
carboxamido)-4-(methylsulfanyl)butanoate (19).
Yield 0.104 g (60%, method c), yellow oil, [α]D28.5
=
+13.34° (c = 1.00). IR spectrum, ν, cm–1: 3344, 3062,
2952, 2920, 2850, 1739, 1648, 1600, 1568, 1548,
1439, 1388, 1307, 1230, 1147, 1103, 912, 825, 752.
UV spectrum (EtOH), λmax, nm (logε): 247 (4.84), 306
1
(4.27), 330 (4.14). H NMR spectrum, δ, ppm: 2.08 s
(3H, SCH3), 2.14 m (2H, CHCH2), 2.58 t (2H, SCH2,
J = 8.4 Hz), 3.79 s (3H, OCH3), 4.90 t (1H, CH),
6.19 d (1H, 3-H, J = 9.5 Hz), 6.71 s (1H, 8-H), 7.56 d
(1H, 4-H, J = 9.5 Hz), 7.77 s (1H, 5-H). 13C NMR
spectrum, δC, ppm: 15.47 (SCH3), 30.21 (SCH2), 30.73
(CHCH2), 51.86 (OCH3), 52.90 (CH), 105.23 (C8),
111.37 (C4a), 111.71 (C6), 113.69 (C3), 126.90 (C4),
143.03 (C5), 157.92 (C8a), 160.25 (C2), 164.49 (C=O),
168.61 (C7), 172.49 (COOMe). Mass spectrum:
m/z 351.0772 [M]+. Found, %: C 54.86; H 4.94;
N 3.87; S 9.02. C16H17NO6S. Calculated, %: C 54.69;
H 4.88; N 3.99; S 9.12. M 351.0771.
Methyl 8-(7-hydroxy-2-oxo-2H-chromene-6-
carboxamido)octanoate (22). Yield 0.132 g (75%,
method c), viscous oily material. IR spectrum, ν, cm–1:
3409, 3380, 3055, 2925, 2854, 1736, 1708, 1653,
1622, 1570, 1437, 1390, 1311, 1246, 1145, 916, 854,
837, 825. UV spectrum (EtOH), λmax, nm (logε): 245
1
(3.72), 307 (3.34), 331 (3.20). H NMR spectrum, δ,
ppm: 1.33 m (6H, CH2), 1.59 m (4H, CH2), 2.28 t (2H,
COCH2), 3.43 t (2H, NHCH2), 3.64 s (3H, OCH3),
6.22 d (1H, 3-H, J = 9.4 Hz), 6.83 s (1H, 8-H), 7.59 d
(1H, 4-H, J = 9.4 Hz), 7.65 s (1H, 5-H). 13C NMR
spectrum, δC, ppm: 24.63 (C6′), 26.57 (C3′), 28.73 (C5′),
28.87 (C4′), 29.22 (C2′), 33.93 (C7′), 39.82 (C1′), 51.53
Methyl 2-(7-hydroxy-2-oxo-2H-chromene-6-
carboxamido)-3-phenylpropanoate (20). Yield
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019