1206
Chem. Pharm. Bull.
Vol. 64, No. 8 (2016)
6.94 (1H, d, J=8.3Hz, H-5′), 6.90 (1H, dd, J=8.3, 1.9Hz, that previously reported.20)
H-6′), 6.87 (1H, d, J=1.9Hz, H-2′), 5.40 (2H, d, J=2.9Hz, (3E)-2,3-Dihydro-7-hydroxy-3-[(4-methoxyphenyl)-
H-2), 3.94 (3H, s, OMe), 3.92 (3H, s, OMe). 13C-NMR (CDCl3, methylene]-4H-1-benzopyran-4-one (14)
100 MHz) δ: 182.1, 160.9, 150.3, 148.9, 137.5, 135.7, 129.1,
Yield 84%. Yellow crystal. mp 223°C (lit. 206–208°C20)).
127.9, 127.2, 123.6, 122.0, 121.8, 117.8, 113.2, 111.0, 67.8, 56.0. 1H-NMR (DMSO-d6, 400MHz) δ: 7.72 (1H, d, J=8.7Hz, H-5),
MS (EI) m/z: 296 [M]+. Anal. Calcd for C18H16O4: C, 72.96; H, 7.64 (1H, brs, CH), 7.40 (2H, d, J=8.8Hz, H-2′ and H-6′), 7.05
5.44. Found: C, 72.73; H, 5.28.
(3E)-2,3-Dihydro-3-[(4-dimethylaminophenyl)methylene]- H-6), 6.30 (1H, d, J=2.2Hz, H-8), 5.35 (2H, d, J=1.9Hz, H-2),
4H-1-benzopyran-4-one (8)
3.82 (3H, s, OMe). MS (EI) m/z: 282 [M]+. The 1H-NMR
Yield 51%. Yellow crystal. mp 149–151°C (lit. 150–153°C17)). spectrum was similar to that previously reported.20)
1H-NMR (CDCl3, 400MHz) δ: 8.02 (1H, dd, J=8.0, 1.7Hz,
(3E)-2,3-Dihydro-3-[(4-dimethylaminophenyl)methylene]-7-
H-5), 7.83 (1H, brs, CH), 7.46 (1H, ddd, J=8.3, 7.1, 1.7Hz, hydroxy-4H-1-benzopyran-4-one (15)
(2H, d, J=8.8Hz, H-3′ and H-5′), 6.54 (1H, dd, J=8.7, 2.2Hz,
H-7), 7.27 (2H, d, J=8.9Hz, H-2′ and H-6′), 7.05 (1H, ddd,
Yield 78%. Yellow crystal. mp 266°C (lit. 264–266°C20)).
J=8.0, 7.1 1.0Hz, H-6), 6.95 (1H, dd, J=8.3, 1.0Hz, H-8), 6.73 1H-NMR (DMSO-d6, 400MHz) δ: 7.72 (1H, d, J=8.8Hz, H-5),
(2H, d, J=8.9Hz, H-3′ and H-5′), 5.44 (2H, d, J=2.0Hz, H-2), 7.59 (1H, brs, CH), 7.30 (2H, d, J=8.9Hz, H-2′ and H-6′), 6.78
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3.05 (6H, s, NMe2). MS (EI) m/z: 279 [M]+. The H-NMR (2H, d, J=8.9Hz, H-3′ and H-5′), 6.53 (1H, dd, J=8.8, 2.3Hz,
spectrum was similar to that previously reported.17)
H-6), 6.31 (1H, d, J=2.3Hz, H-8), 5.38 (2H, d, J=1.7Hz, H-2),
(3E)-2,3-Dihydro-3-[(4-fluorophenyl)methylene]-4H-1- 3.00 (6H, s, NMe2). MS (EI) m/z: 295 [M]+. The H-NMR
1
benzopyran-4-one (9)
spectrum was similar to that previously reported.20)
(3E)-2,3-Dihydro-7-methoxy-3-(phenylmethylene)-4H-1-
Yield 36%. White crystal. mp 150°C. 1H-NMR (CDCl3,
400MHz) δ: 8.03 (1H, dd, J=8.0, 1.7Hz, H-5), 7.83 (1H, brs, benzopyran-4-one (16)
CH), 7.50 (1H, ddd, J=8.3, 7.1, 1.7Hz, H-7), 7.33–7.29 (2H, m,
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Yield 62%. Yellow solid. mp 69°C (lit. 94°C29)). H-NMR
H-2′ and H-6′), 7.18–7.12 (2H, m, H-3′ and H-5′), 7.09 (1H, (CDCl3, 400MHz) δ: 7.97 (1H, d, J=8.8Hz, H-5), 7.85 (1H,
ddd, J=8.0, 7.1, 0.9Hz, H-6), 6.98 (1H, dd, J=8.3, 0.9Hz, brs, CH), 7.46–7.38 (3H, m, H-3′, H-4′ and H-5′), 7.32–7.28
H-8), 5.33 (2H, d, J=1.7Hz, H-2). MS (EI) m/z: 254 [M]+. The (2H, m, H-2′ and H-6′), 6.63 (1H, dd, J=8.8, 2.3Hz, H-6),
1H-NMR spectrum was similar to that previously reported.28)
6.40 (1H, d, J=2.3Hz, H-8), 5.33 (2H, d, J=2.0Hz, H-2), 3.84
(3E)-3-[(4-Chlorophenyl)methylene]-2,3-dihydro-4H-1- (3H, s, OMe). 13C-NMR (CDCl3, 100MHz) δ: 181.0, 166.0,
benzopyran-4-one (10)
163.1, 136.8, 134.5, 130.8, 129.9, 129.7, 129.2, 128.7, 115.7,
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Yield 70%. White crystal. mp 172°C (lit. 170–173°C27)). 110.5, 100.7, 67.8, 55.6. MS (EI) m/z: 266 [M]+. The H-NMR
1H-NMR (CDCl3, 400MHz) δ: 8.02 (1H, dd, J=7.7, 1.7Hz, spectrum was similar to that previously reported.29)
H-5), 7.81 (1H, brs, CH), 7.50 (1H, ddd, J=8.3, 7.1, 1.7Hz,
H-7), 7.43 (2H, d, J=8.6Hz, H-2′ and H-6′), 7.25 (2H, d, methoxy-4H-1-benzopyran-4-one (17)
J=8.6Hz, H-3′ and H-5′), 7.09 (1H, ddd, J=7.7, 7.1, 0.9Hz, Yield 74%. Yellow crystal. mp 226°C. H-NMR (DMSO-d6,
(3E)-2,3-Dihydro-3-[(4-hydroxyphenyl)methylene]-7-
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H-6), 6.98 (1H, dd, J=8.3, 0.9Hz, H-8), 5.32 (2H, d, J=2.0Hz, 400MHz) δ: 7.80 (1H, d, J=8.9Hz, H-5), 7.63 (1H, brs, CH),
1
H-2). MS (EI) m/z: 270 [M]+. The H-NMR spectrum was 7.32 (2H, d, J=8.8Hz, H-2′ and H-6′), 6.87 (2H, d, J=8.8Hz,
similar to that previously reported.27)
H-3′ and H-5′), 6.69 (1H, dd, J=8.9, 2.3Hz, H-6), 6.56 (1H,
(3E)-2,3-Dihydro-7-hydroxy-3-(phenylmethylene)-4H-1- d, J=2.3Hz, H-8), 5.41 (2H, dd, J=1.8Hz, H-2), 3.83 (3H, s,
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benzopyran-4-one (11)
OMe). MS (EI) m/z: 282 [M]+. The H-NMR spectrum was
Yield 98%. Colorless crystal. mp 192–194°C. 1H-NMR similar to that previously reported.30)
(DMSO-d6, 400MHz) δ: 7.90 (1H, d, J=8.6Hz, H-5), 7.83 (1H,
(3E)-2,3-Dihydro-3-[(3,4-dihydroxyphenyl)methylene]-7-
brs, CH), 7.66–7.55 (5H, m, Ph), 6.70 (1H, dd, J=8.6, 2.3Hz, methoxy-4H-1-benzopyran-4-one (18)
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H-6), 6.46 (1H, d, J=2.3Hz, H-8), 5.49 (2H, d, J=2.0Hz,
Yield 81%. Yellow solid. mp 204°C. H-NMR (DMSO-d6,
H-2). MS (EI) m/z: 252 [M]+. The H-NMR spectrum was 400MHz) δ: 9.72 (1H, brs, OH), 9.32 (1H, brs, OH), 8.86 (1H,
similar to that previously reported.19)
d, J=8.9Hz, H-5), 7.61 (1H, brs, CH), 6.92–6.81 (3H, m, H-2′,
(3E)-2,3-Dihydro-7-hydroxy-3-[(4-hydroxyphenyl)- H-5′ and H-6′), 6.75 (1H, dd, J=8.9, 2.3Hz, H-6), 6.62 (1H,
1
methylene]-4H-1-benzopyran-4-one (12)
d, J=2.3Hz, H-8), 5.46 (2H, d, J=1.8Hz, H-2), 3.89 (3H, s,
Yield 69%. Yellow crystal. mp 263°C (lit. 220–222°C20)). OMe). 13C-NMR (DMSO-d6, 100MHz) δ: 179.7, 165.5, 162.4,
1H-NMR (DMSO-d6, 400MHz) δ: 7.73 (1H, d, J=8.6Hz, 147.6, 145.4, 136.5, 128.9, 127.4, 125.4, 123.3, 117.7, 115.9,
H-5), 7.60 (1H, brs, CH), 7.30 (2H, d, J=8.6Hz, H-2′ and 115.3, 110.3, 100.9, 67.8, 55.8. [M]+. HR-MS m/z: Calcd for
H-6′), 6.87 (2H, d, J=8.6Hz, H-3′ and H-5′), 6.54 (1H, dd, C17H14O5 (M+): 298.0843; Found: 298.0841. Anal. Calcd for
J=8.6, 2.2Hz, H-6), 6.31 (1H, d, J=2.2Hz, H-8), 5.35 (2H, d, C17H14O5: C, 68.45; H, 4.73. Found: C, 68.05; H, 4.59.
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J=1.7Hz, H-2). MS (EI) m/z: 268 [M]+. The H-NMR spec-
trum was similar to that previously reported.20)
(3E)-2,3-Dihydro-3-[(3,4-dihydroxyphenyl)methylene]-7-
hydroxy-4H-1-benzopyran-4-one (13)
(3E)-2,3-Dihydro-7-methoxy-3-[(4-methoxyphenyl)-
methylene]-4H-1-benzopyran-4-one (19)
Yield 68%. Pale yellow crystal. mp 124–126°C (lit.
130–132°C20)). 1H-NMR (CDCl3, 400MHz) δ: 7.96 (1H, d,
Yield 36%. Yellow crystal. mp 239°C (lit. 220–222°C20)). J=8.8Hz, H-5), 7.81 (1H, brs, CH), 7.28 (2H, d, J=8.9Hz,
1H-NMR (DMSO-d6, 400MHz) δ: 7.72 (1H, d, J=8.9Hz, H-5), H-2′ and H-6′), 6.97 (2H, d, J=8.9Hz, H-3′ and H-5′), 6.63
7.52 (1H, brs, CH), 6.85–6.81 (2H, m, H-2′ and H-5′), 6.76 (1H, dd, J=8.8, 2.3Hz, H-6), 6.40 (1H, d, J=2.3Hz, H-8), 5.37
(1H, dd, J=8.3, 2.0Hz, H-6′), 6.54 (1H, dd, J=8.8, 2.3Hz, (2H, d, J=2.0Hz, H-2), 3.86 (3H, s, OMe), 3.85 (3H, s, OMe).
H-5), 6.31 (1H, d, J=2.3Hz, H-8), 5.35 (2H, d, J=1.4Hz, H-2). MS (EI) m/z: 296 [M]+. The H-NMR spectrum was similar to
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MS (EI) m/z: 284 [M]+. The H-NMR spectrum was similar to that previously reported.20)
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