Development of New Pyrrolocoumarin Derivatives
8.55 (d, J = 9.6 Hz, 1 H), 7.95 (d, J = 8.7 Hz, 2 H), 7.81 (d, J = 7-(4-Methoxyphenyl)-2,3-dimethylpyrano[2,3-f]indol-6(1H)-one (7):
8.4 Hz, 2 H), 7.53 (s, 1 H), 6.45 (d, J = 9.6 Hz, 1 H), 2.41 (s, 3 H),
Bright yellow solid (42 mg, 77%). Column chromatography mobile
2.40 (s, 3 H) ppm. 13C NMR ([D6]DMSO, 100 MHz): δ = 159.7, phase: CH2Cl2/petroleum ether = 2:1–3:1. M.p. 280–282 °C. IR
146.1, 142.1, 141.6, 136.8, 131.9, 131.2, 130.3, 123.4, 119.4, 118.7,
115.3, 113.4, 110.5, 109.5, 106.6, 11.1, 10.9 ppm. HRMS: calcd. for
C20H15N2O2 [M + H]+ 315.1128; found 315.1132.
(KBr): ν = 3248, 1665, 1610, 1517, 1294, 1264, 1244, 1176, 1036,
˜
832 cm–1. 1H NMR ([D6]DMSO, 300 MHz): δ = 11.13 (s, 1 H),
8.24 (s, 1 H), 7.69 (d, J = 8.4 Hz, 2 H), 7.60 (s, 1 H), 7.32 (s, 1 H),
7.00 (d, J = 9.0 Hz, 2 H), 3.79 (s, 3 H), 2.36 (s, 3 H), 2.18 (s, 3 H)
ppm. 13C NMR ([D6]DMSO, 100 MHz): δ = 161.2, 159.5, 147.2,
141.5, 138.2, 132.9, 132.0, 130.0, 128.2, 122.5, 114.1, 114.0, 109.2,
106.5, 102.6, 55.6, 12.0, 8.67 ppm. MS (ESI): m/z = 320 [M +
H]+. C20H17NO3 (319.35): calcd. C 75.22, H 5.37, N 4.39; found C
75.22, H 5.64, N 4.46.
9-(4-Methoxyphenyl)-2,3-dimethylpyrano[2,3-f]indol-6(1H)-one (20):
Yellow solid (114 mg, 87 %). Column chromatography mobile
phase: CH2Cl2/petroleum ether = 1:1–10:1. M.p. Ͼ300 °C. IR
(KBr): ν = 3249, 1692, 1625, 1604, 1554, 1513, 1493, 1247, 1171,
˜
1145, 1035, 835 cm–1. 1H NMR ([D6]DMSO, 300 MHz): δ = 10.58
(s, 1 H), 7.64 (d, J = 9.9 Hz, 1 H), 7.36 (d, J = 8.7 Hz, 2 H), 7.33
(s, 1 H), 7.14 (d, J = 8.1 Hz, 2 H), 6.16 (d, J = 9.9 Hz, 1 H), 3.86
4-(2,3-Dimethyl-6-oxo-1,6-dihydropyrano[2,3-f]indol-7-yl)benzoni-
(s, 3 H), 2.31 (s, 3 H), 2.19 (s, 3 H) ppm. 13C NMR ([D6]- trile (8): Dark yellow solid (55 mg, 62%). Column chromatography
DMSO, 100 MHz): δ = 161.2, 159.6, 148.4, 143.4, 139.4, 132.0,
131.5, 126.6, 122.5, 114.8, 112.0, 111.1, 106.9, 102.4, 55.6, 11.9,
8.59 ppm. MS (ESI): m/z = 320 [M + H]+. C20H17NO3 (319.35):
calcd. C 75.22, H 5.37, N 4.39; found C 75.14, H 5.59, N 4.34.
mobile phase: CH2Cl2/petroleum ether = 1:1–10:1. M.p. Ͼ300 °C.
IR (KBr): ν = 3241, 2223, 1678, 1633, 1595, 1548, 1315, 1181, 1138,
˜
1
1037, 846 cm–1. H NMR ([D6]DMSO, 300 MHz): δ = 11.21 (s, 1
H), 8.47 (s, 1 H), 7.96 (d, J = 8.4 Hz, 2 H), 7.89 (d, J = 9.0 Hz, 2
H), 7.63 (s, 1 H), 7.33 (s, 1 H), 2.37 (s, 3 H), 2.18 (s, 3 H) ppm.
13C NMR ([D6]DMSO, 75 MHz): δ = 160.2, 147.2, 144.2, 140.3,
138.9, 132.5, 132.5, 132.0, 128.9, 120.3, 118.9, 113.2, 110.0, 109.6,
106.4, 102.3, 11.7, 8.21 ppm. HRMS: calcd. for C20H15N2O2 [M +
H]+ 315.1128; found 315.1123.
9-(2-Methoxyphenyl)-2,3-dimethylpyrano[2,3-f]indol-6(1H)-one (21):
Yellow solid (123 mg, 74 %). Column chromatography mobile
phase: CH2Cl2/petroleum ether = 1:1–10:1. M.p. 260–261 °C. IR
(KBr): ν = 3269, 1691, 1552, 1503, 1309, 1243, 1135, 1030,
˜
815 cm–1. 1H NMR ([D6]DMSO, 300 MHz): δ = 10.53 (s, 1 H),
7.57–7.51 (m, 1 H), 7.42 (d, J = 9.6 Hz, 1 H), 7.34 (s, 1 H), 7.24 8-[4-(Dimethylamino)phenyl]-1,2-dimethylpyrano[3,2-e]indol-7(3H)-
(d, J = 7.8 Hz, 1 H), 7.14 (t, J = 7.8 Hz, 1 H), 6.15 (d, J = 9.9 Hz, one (30): Bright yellow solid (111 mg, 85%). Column chromatog-
1 H), 3.67 (s, 3 H), 2.30 (s, 3 H), 2.19 (s, 3 H) ppm. 13C NMR ([D6]- raphy mobile phase: CH2Cl2/petroleum ether = 1:1–5:1. M.p. 250–
DMSO, 100 MHz): δ = 160.9, 157.2, 147.7, 143.3, 138.6, 131.9,
131.6, 131.2, 130.1, 122.4, 120.6, 118.9, 111.8, 111.5, 111.0, 106.1,
102.0, 55.3, 11.4, 8.18 ppm. MS (ESI): m/z = 320 [M + H]+.
252 °C. IR (KBr): ν = 3233, 2919, 1677, 1610, 1590, 1522, 1361,
˜
1
1202, 1133, 995, 948, 814 cm–1. H NMR (CDCl3, 300 MHz): δ =
11.21 (s, 1 H), 8.39 (s, 1 H), 7.67 (d, J = 8.7 Hz, 2 H), 7.44 (d, J =
8.4 Hz, 1 H), 7.01 (d, J = 8.7 Hz, 1 H), 6.78 (d, J = 9.0 Hz, 2 H),
2.94 (s, 6 H), 2.43 (s, 3 H), 2.36 (s, 3 H) ppm. 13C NMR ([D6]-
DMSO, 100 MHz): δ = 161.1, 150.9, 149.0, 135.6, 135.4, 132.1,
129.6, 124.6, 123.6, 123.5, 114.7, 112.5, 112.2, 108.7, 107.4,
11.9 ppm. MS (ESI): m/z = 333 [M + H]+. C21H20N2O2 (332.40):
calcd. C 75.88, H 6.06, N 8.43; found C 75.60, H 5.95, N 8.30.
C
20H17NO3 (319.35): calcd. C 75.22, H 5.37, N 4.39; found C
75.41, H 5.39, N 4.31.
4-(2,3-Dimethyl-6-oxo-1,6-dihydropyrano[2,3-f]indol-9-yl)benzoni-
trile (22): Yellow solid (90 mg, 84%). Column chromatography mo-
bile phase: CH2Cl2/petroleum ether = 1:1–5:1. M.p. Ͼ300 °C. IR
(KBr): ν = 3255, 2229, 1686, 1603, 1554, 1506, 1491, 1384, 1309,
˜
1195, 1145, 842 cm–1. 1H NMR ([D6]DMSO, 300 MHz): δ = 10.70 8-(2-Methoxyphenyl)-1,2-dimethylpyrano[3,2-e]indol-7(3H)-one
(s, 1 H), 8.06 (d, J = 8.1 Hz, 2 H), 7.66 (d, J = 8.4 Hz, 2 H), 7.58
(d, J = 9.6 Hz, 1 H), 7.43 (s, 1 H), 6.21 (d, J = 9.9 Hz, 1 H), 2.31
(31): Yellow solid (117 mg, 81%). Column chromatography mobile
phase: CH2Cl2/petroleum ether = 1:1–5:1. M.p. 265–266 °C. IR
(s, 3 H), 2.20 (s, 3 H) ppm. 13C NMR ([D6]DMSO, 100 MHz): δ = (KBr): ν = 3373, 1703, 1596, 1494, 1441, 1363, 1254, 1235, 1137,
˜
1
160.6, 147.8, 142.3, 139.4, 139.3, 132.7, 131.8, 131.6, 130.6, 120.3,
118.8, 112.4, 111.0, 110.3, 106.6, 103.2, 11.4, 8.13 ppm. HRMS:
calcd. for C20H15N2O2 [M + H]+ 315.1128; found 315.1123.
1012, 962 cm–1. H NMR ([D6]DMSO, 300 MHz): δ = 11.26 (s, 1
H), 8.42 (s, 1 H), 7.52–7.37 (m, 3 H), 7.12 (d, J = 8.1 Hz, 1 H),
7.06–7.01 (m, 2 H), 3.79 (s, 3 H), 2.36 (s, 6 H) ppm. MS (ESI): m/z
= 320 [M + H]+. C20H17NO3 (319.35): calcd. C 75.22, H 5.37, N
4.39; found C 75.29, H 5.17, N 4.19.
8-(4-Methoxyphenyl)-2,3-dimethylpyrano[2,3-f]indol-6(1H)-one (16):
Yellow solid (46 mg, 78%). Column chromatography mobile phase:
CH Cl /MeOH = 100:1. M.p. 294 °C. IR (KBr): ν = 3195, 1677, 8-(2-Fluorophenyl)-1,2-dimethylpyrano[3,2-e]indol-7(3H)-one (32):
˜
2
2
1635, 1607, 1512, 1381, 1243, 1174, 1136, 1022, 968, 830 cm–1. H
NMR ([D6]DMSO, 300 MHz): δ = 10.93 (s, 1 H), 7.45 (d, J =
8.4 Hz, 2 H), 7.32 (s, 1 H), 7.24 (s, 1 H), 7.07 (d, J = 8.4 Hz, 2 H),
6.06 (s, 1 H), 3.79 (s, 3 H), 2.27 (s, 3 H), 2.11 (s, 3 H) ppm. MS
(ESI): m/z = 320 [M + H]+. C20H17NO3 (319.35): calcd. C 75.22,
H 5.37, N 4.39; found C 75.18, H 5.60, N 4.24.
Bright yellow solid (124 mg, 90%). Column chromatography mo-
bile phase: CH2Cl2/petroleum ether = 1:1–5:1. M.p. 298 °C. IR
1
(KBr): ν = 3269, 1682, 1598, 1494, 1434, 1398, 1361, 1335, 1211,
˜
1
1101, 1046, 995, 972, 751 cm–1. H NMR ([D6]DMSO, 400 MHz):
δ = 11.31 (s, 1 H), 8.50 (s, 1 H), 7.67 (dt, J = 5.7, 1.2 Hz, 1 H),
7.54 (d, J = 6.6 Hz, 1 H), 7.50–7.44 (m, 1 H), 7.33–7.28 (m, 2 H),
7.07 (d, J = 6.6 Hz, 1 H), 2.38 (s, 3 H), 2.37 (s, 3 H) ppm. 19F
NMR ([D6]DMSO, 282 MHz): δ = 114.37 (m) ppm. 13C NMR
([D6]DMSO, 100 MHz): δ = 160.2 (d, J = 245.6 Hz), 159.9, 159.0,
149.9, 141.1, 136.2, 132.1 (d, J = 9.7 Hz), 130.9 (d, J = 8.2 Hz),
124.9, 124.1 (d, J = 14.2 Hz), 123.7, 119.9, 116.2 (d, J = 22.4 Hz),
116.0, 111.0, 108.7, 107.3, 11.8, 11.6 ppm. MS (ESI): m/z = 308 [M
+ H]+. C19H14FNO2·0.045CH2Cl2 (307.32): calcd. C 73.51, H 4.56,
N 4.50; found C 73.49, H 4.53, N 4.53.
4-(2,3-Dimethyl-6-oxo-1,6-dihydropyrano[2,3-f]indol-8-yl)benzoni-
trile (17): Yellow solid (46 mg, 86%). Column chromatography mo-
bile phase: CH Cl /MeOH = 100:1. M.p. Ͼ300 °C. IR (KBr): ν =
˜
2
2
2231, 1686, 1637, 1542, 1378, 1358, 1242, 1138, 1037, 970 cm–1. 1H
NMR ([D6]DMSO, 300 MHz): δ = 10.99 (s, 1 H), 8.06 (d, J =
6.6 Hz, 2 H), 7.78 (d, J = 6.9 Hz, 2 H), 7.43 (s, 1 H), 7.08 (s, 1 H),
6.24 (s, 1 H), 2.34 (s, 3 H), 2.18 (s, 3 H) ppm. 13C NMR ([D6]-
DMSO, 100 MHz): δ = 160.4, 154.6, 147.3, 140.6, 138.5, 132.7,
132.3, 132.1, 129.6, 118.4, 112.1, 111.6, 111.6, 107.0, 106.0, 103.5,
11.6, 8.19 ppm. HRMS: calcd. for C20H15N2O2 [M + H]+ 315.1128;
found 315.1125.
Methyl 1,2-Dimethyl-7-oxo-3,7-dihydropyrano[3,2-e]indole-8-car-
boxylate (33): Dark yellow solid (54 mg, 83%). Column chromatog-
raphy mobile phase: CH2Cl2/petroleum ether = 1:1–10:1. M.p.
Eur. J. Org. Chem. 2008, 6175–6182
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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