Job/Unit: O20529
/KAP1
Date: 03-07-12 16:05:47
Pages: 9
Synthesis of Flavones and γ-Benzopyranones
2-p-Tolyl-4H-chromen-4-one (8d):[6f] Yellow solid. 1H NMR
(400 MHz, CDCl3): δ = 8.22 (dd, J = 7.6, 1.2 Hz, 1 H), 7.80 (d, J
= 8.0 Hz, 2 H), 7.67 (t, J = 8.8 Hz, 1 H), 7.54 (d, J = 8.0 Hz, 1 H),
8.8, 6.4 Hz, 1 H), 7.49–7.39 (m, 3 H), 7.25 (dd, J = 9.2, 2.4 Hz, 1
H), 7.15 (td, J = 8.4, 2.4 Hz, 1 H), 7.08 (ddd, J = 8.0, 2.8, 1.2 Hz,
1 H), 6.78 (s, 1 H), 3.89 (s, 3 H) ppm. 13C NMR (100 MHz,
7.40 (t, J = 7.6 Hz, 1 H), 7.30 (d, J = 8.0 Hz, 2 H), 6.78 (s, 1 H), CDCl3): δ = 177.7, 166.0 (J = 253.1 Hz), 163.7 (J = 1.5 Hz), 160.3,
2.42 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 178.4, 163.5, 157.4 (J = 12.9 Hz), 133.0, 130.4, 128.4 (J = 10.6 Hz), 121.1, 118.9,
156.1, 142.2, 133.6, 129.7, 128.8, 126.1, 125.6, 125.0, 123.9, 118.0,
117.5, 114.2 (J = 22.7 Hz), 111.9, 108.1, 105.1 (J = 25.0 Hz),
106.8, 21.5 ppm. LRMS (ESI): m/z = 237 [M + 1]+.
55.7 ppm. IR (KBr): ν = 3065, 1635, 1438 cm–1. LRMS (ESI): m/z
˜
= 293 [M + Na]+. HRMS (ESI): calcd. for C16H11FO3Na 293.0590;
found 293.0588.
2-(4-Fluorophenyl)-4H-chromen-4-one (8e):[6f] Yellow solid. 1H
NMR (400 MHz, CDCl3): δ = 8.23 (dd, J = 8.0, 1.6 Hz, 1 H), 7.94–
7.91 (m, 2 H), 7.70 (t, J = 8.4 Hz, 1 H), 7.55 (d, J = 8.4 Hz, 1 H),
7.42 (t, J = 8.0 Hz, 1 H), 7.23–7.19 (m, 2 H), 6.77 (s, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 178.3, 164.7 (J = 251.6 Hz),
162.4, 156.1, 133.8, 128.5 (J = 8.4 Hz), 127.9, 125.7, 125.3, 123.8,
118.0, 116.2 (J = 22.0 Hz), 107.3 ppm. LRMS (ESI): m/z = 241 [M
+ 1]+.
7-Chloro-2-phenyl-4H-chromen-4-one (8Јe):[20] White solid. 1H
NMR (400 MHz, CDCl3): δ = 8.15 (d, J = 8.4 Hz, 1 H), 7.89 (dd,
J = 8.0, 2.0 Hz, 2 H), 7.59 (d, J = 2.0 Hz, 1 H), 7.56–7.50 (m, 3
H), 7.38 (dd, J = 8.4, 2.0 Hz, 1 H), 6.80 (s, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 177.5, 163.6, 156.3, 139.8, 131.8, 131.3,
129.1, 127.1, 126.3, 126.1, 122.5, 118.2, 107.7 ppm. LRMS (ESI):
m/z = 257 [M + 1]+.
7-Bromo-2-phenyl-4H-chromen-4-one (8Јf):[20] Yellow solid. 1H
NMR (400 MHz, CDCl3): δ = 8.08 (d, J = 8.4 Hz, 1 H), 7.90–7.88
(m, 2 H), 7.77 (d, J = 0.8 Hz, 1 H), 7.55–7.50 (m, 4 H), 6.81 (s, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 177.6, 163.4, 156.2,
131.8, 131.3, 129.1, 128.8, 127.9, 127.1, 126.2, 122.8, 121.2,
107.7 ppm. LRMS (ESI): m/z = 301 [M + 1]+.
2-Cyclohexyl-4H-chromen-4-one (8f):[7c] Colorless oil. 1H NMR
(400 MHz, CDCl3): δ = 8.18 (dd, J = 8.0, 1.6 Hz, 1 H), 7.64 (td, J
= 8.8, 1.6 Hz, 1 H), 7.43 (d, J = 8.4 Hz, 1 H), 7.37 (td, J = 8.0,
1.2 Hz, 1 H), 6.18 (s, 1 H), 2.53 (tt, J = 11.6, 3.6 Hz, 1 H), 2.06–
2.03 (m, 2 H), 1.91–1.86 (m, 2 H), 1.80–1.75 (m, 1 H), 1.54–1.23
(m, 5 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 178.7, 173.4,
156.5, 133.4, 125.6, 124.8, 123.8, 117.8, 107.9, 42.8, 30.4, 25.7 ppm.
LRMS (ESI): m/z = 229 [M + 1]+.
Supporting Information (see footnote on the first page of this arti-
2-Butyl-4H-chromen-4-one (8g):[7c] Colorless oil. 1H NMR
(400 MHz, CDCl3): δ = 8.19 (dd, J = 8.0, 1.6 Hz, 1 H), 7.64 (td, J
= 8.8, 1.6 Hz, 1 H), 7.43 (d, J = 8.4 Hz, 1 H), 7.38 (td, J = 8.4,
1.2 Hz, 1 H), 6.18 (s, 1 H), 2.63 (t, J = 7.6 Hz, 2 H), 1.77–1.69 (m,
2 H), 1.49–1.39 (m, 2 H), 0.97 (t, J = 7.6 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 178.4, 169.8, 156.5, 133.4, 125.6, 124.8,
123.7, 117.8, 109.8, 34.0, 28.8, 22.1, 13.7 ppm. LRMS (ESI): m/z
= 203 [M + 1]+.
cle): Copies of NMR spectra.
Acknowledgments
This work was supported by grants from the National Science
Council, Taiwan (NSC 100-2325-B-039-005).
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2-tert-Butyl-4H-chromen-4-one (8h):[7c] Colorless oil. 1H NMR
(400 MHz, CDCl3): δ = 8.18 (dd, J = 8.0, 1.6 Hz, 1 H), 7.65 (td, J
= 8.8, 1.6 Hz, 1 H), 7.46 (d, J = 8.4 Hz, 1 H), 7.38 (td, J = 8.0,
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CDCl3): δ = 178.9, 176.0, 156.4, 133.4, 125.5, 124.8, 123.4, 117.8,
106.6, 36.4, 27.8 ppm. LRMS (ESI): m/z = 203 [M + 1]+.
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7-Methoxy-2-phenyl-4H-chromen-4-one (8Јa):[7c] Yellow solid. 1H
NMR (400 MHz, CDCl3): δ = 8.13 (d, J = 8.8 Hz, 1 H), 7.91–7.88
(m, 2 H), 7.54–7.49 (m, 3 H), 6.99–6.96 (m, 2 H), 6.76 (s, 1 H),
3.93 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 177.8, 164.1,
163.0, 157.9, 131.8, 131.4, 129.0, 127.0, 126.1, 117.8, 114.4, 107.5,
100.3, 55.8 ppm. LRMS (ESI): m/z = 253 [M + 1]+.
7-Methoxy-2-p-tolyl-4H-chromen-4-one (8Јb):[18] Brown solid. 1H
NMR (400 MHz, CDCl3): δ = 8.12 (d, J = 8.8 Hz, 1 H), 7.79 (d,
J = 8.4 Hz, 2 H), 7.30 (d, J = 8.4 Hz, 2 H), 6.98–6.95 (m, 2 H),
6.73 (s, 1 H), 3.93 (s, 3 H), 2.43 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 177.9, 164.1, 163.2, 157.9, 142.0, 129.7, 128.9, 127.0,
126.0, 117.8, 114.3, 106.8, 100.3, 55.8, 21.5 ppm. LRMS (ESI): m/z
= 267 [M + 1]+.
7-Fluoro-2-phenyl-4H-chromen-4-one (8Јc):[19] White solid. 1H
NMR (400 MHz, CDCl3): δ = 8.24 (dd, J = 8.8, 6.4 Hz, 1 H), 7.91–
7.88 (m, 2 H), 7.57–7.50 (m, 3 H), 7.25 (dd, J = 8.8, 2.0 Hz, 1 H),
7.14 (td, J = 8.8, 2.4 Hz, 1 H), 6.80 (s, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 177.4, 165.7 (J = 253.1 Hz), 163.6 (J =
1.5 Hz), 157.2 (J = 13.6 Hz), 131.7, 131.3, 129.0, 128.2 (J =
10.6 Hz), 126.2, 120.7 (J = 2.3 Hz), 114.0 (J = 22.7 Hz), 107.5,
104.7 (J = 25.8 Hz) ppm. LRMS (ESI): m/z = 241 [M + 1]+.
7-Fluoro-2-(3-methoxyphenyl)-4H-chromen-4-one (8Јd): White solid,
1
m.p. 169–170 °C. H NMR (400 MHz, CDCl3): δ = 8.24 (dd, J =
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