Jan-Feb 2006
Synthesis of Novel Substituted Flavonoids
63
Table 2 (continued)
1
-1
Compound
H-NMR (δ ppm)
IR (ν cm KBr)
17
(deuteriochloroform): δ 3.87, 3.89 (s, 9H,
1660 (C=O),
1613 (C=C Ar),
1592 (C=C),
1133 (C-O) cm .
1656 (C=O),
-CH O), 8.01-8.02 (d, J=2.4 Hz, 1H, Ar), 7.67-
3
7.68 (d, J=2.4 Hz, 1H, Ar), 6.74 (s, 1H, O=C-
CH=), 7.14 (s, 2H, Ar)
-1
18
19
20
(deuteriochloroform): δ 3.93, 3.94 (s, 9H,
-CH O), 8.27-8.28 (d, J=2.2 Hz, 1H, Ar), 8.02-
1610 (C=C Ar),
1591 (C=C),
3
8.03 (d, J=2.2 Hz, 1H, Ar), 6.80 (s, 1H, O=C-
CH=), 7.23 (s, 2H, Ar)
-1
1134 (C-O) cm .
(deuteriochloroform): δ 3.87, 3.91 (s, 9H,
1654 (C=O),
1618 (C=C Ar),
1583 (C=C),
-CH O), 8.24 (s, 1H, Ar), 8.19-8.20 (d, J=2.1 Hz,
3
1H, Ar), 6.79 (s, 1H, O=C-CH=), 7.23 (s, 2H, Ar),
-1
2.49 (s, 3H, -CH )
1126 (C-O) cm .
3
(deuteriochloroform): δ 3.95, 3.96 (s, 6H,
1654 (C=O),
1561 (C=C Ar),
1519 (C=C),
-CH O), 8.07-8.06 (d, J=2.3 Hz, 1H, Ar), 7.70-
3
7.71 (d, J=2.6 Hz, 1H, Ar), 6.77 (s, 1H, O=C-
CH=), 6.97-6.99 (d, J=8.4 Hz, 1H, Ar) 7.44-7.45
(d, J=2.0 Hz, 1H, Ar), (td, J=2.3, 8.7 Hz, 1H, Ar)
(deuteriochloroform): δ 3.92, 3.93 (s, 6H,
-1
1278 (C-O) cm .
21
22
1677 (C=O),
1650 (C=C Ar),
1599 (C=C),
-CH O), 8.26-8.27 (d, J=2.4 Hz, 1H, Ar), 7.99-
3
8.00 (d, J=2.2 Hz, 1H, Ar), 6.82 (s, 1H, O=C-
CH=), 7.74-7.77 (dd, J=1.9 Hz, 6.4 Hz, 1H, Ar),
7.57-7.58 (d, J=1.6 Hz, 1H, Ar), 6.88-6.91 (d,
J=8.5 Hz, 1H, Ar)
-1
1235 (C-O) cm .
(deuteriochloroform): δ 3.96, 4.00 (s, 6H,
1647 (C=O),
1615 (C=C Ar),
1531 (C=C),
-CH O), 8.30 (s, 1H, Ar), 8.22-8.23 (d, J=2.0 Hz,
3
1H, Ar), 6.84 (s, 1H, O=C-CH=), 6.97-7.00 (d,
J=8.9 Hz, 1H, Ar), 7.82-8.00 (dd, J=1.8 Hz, 50.3,
1H, Ar), 7.58-7.59 (d, J=2.0 Hz, 1H, Ar), 2.54 (s,
-1
1256 (C-O) cm .
3H, -CH )
3
REFERENCES AND NOTES
Synthesis of Flavones 17-22 [20, 25-26].
Compounds 3 (Scheme 4) were mixed with 1.7 times excess
of 3,4,5-trimethoxy benzoyl chloride or 3,4-dimethoxy ben-
zoyl chloride, 4, correspondingly, in pyridine. The reaction
mixture was heated at 70 °C for 4 h, and then poured onto ice
containing 5 N HCl. The precipitate that formed was collected
by vacuum filtration and air dried. The crude product was dis-
solved in pyridine in the presence of 10 times excess of KOH.
The reaction was carried out for 4 h at 65 °C, and then the
mixture poured onto an ice-5 N HCl bath. A yellow precipi-
tate was formed, which was collected by filtration and air
dried. The crude product was dissolved in acetic acid contain-
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ing 1 mL concentrated H SO , heated at 60 °C for 4 h and left
2
4
stirring overnight at room temperature. After 24 h, the reac-
tion mixture was poured onto an ice-NaHCO mixture, the
3
product collected by filtration and recrystallized from ethanol.
The pure flavone was obtained by purification on
Chromatotrone with CH Cl :MeOH 8:1 as eluent. The yields
2
2
were 30-50%.
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This research was supported by the National Institutes of Health,
the National Institute of General Medical Sciences, MBRS
Program, Grant Number GM 08111 and the National Center of
Research Resources, Research Center for Minority Institutions
(RCMI), Grant Number 03020. We are also grateful to Dr.
Thomas Gedris, Florida State University, Department of
Chemistry, NMR Unit, for recording all NMR spectra of the com-
pounds published in this paper.