HETEROCYCLES, Vol. 81, No. 11, 2010
2597
+
+
1
92.95. HRMS (ESI): calcd for C14
H
13
O
5
, 261.0763 m/z (M+H) , found 261.0763 m/z (M+H) .
Synthesis of 1: A solution of 9 (0.26 g, 1.0 mmol) and pyridine (0.08 mL, 1.0 mmol) in anhydrous
CH Cl (15 mL) was stirred in an ice bath. Senecioyl chloride (0.12 mL) was added slowly and the
2
2
reaction was stirred for 3 h. The reaction produced crystalline precipitates and was extracted with CH
2 2
Cl .
The CH Cl extract was washed with water and brine, and then dried with MgSO . The volatiles were
2
2
4
removed under reduced pressure and the crude product was purified by silica gel column chromatography
using hexane and EtOAc to afford 1 as a white solid (0.33 g, 96.5%). Mp 139-140 °C. FT-IR (KBr):
–
1
+
1
747, 1708 cm . HRMS (ESI): calcd for C H NaO , 365.1001 m/z (M+Na) , found 365.1004 m/z
19 18 6
+
1
(
M+Na) . H-NMR (MeOH-d
4
), δ ppm: 1.39 (s, 3H), 1.57 (s, 3H), 2.00 (d, 3H, J = 1.2 Hz), 2.22 (d, 3H, J
=
1.2 Hz), 5.73 (s, 1H), 5.86 (br, 1H), 6.35 (d,1H, J = 9.6 Hz), 6.93 (s, 1H), 7.95 (d, 1H, J = 9.6 Hz), 8.10
1
3
(
s, 1H). C-NMR (MeOH-d ), δ ppm: 18.70, 19.42, 25.09, 26.38, 75.90, 82.77, 105.20, 114.32, 114.33,
4
1
14.36, 117.46, 127.80, 143.92, 159.69, 160.18, 160.31, 161.58, 164.93, 187.71. Comparison with natural
4
-1.
+
product : FT-IR: 2924, 1732, 1623cm HRMS (ESI): m/z 365.1013 ((M+Na) , calcd for 365.1001).
1
4
H-NMR (MeOH-d ), δ ppm: 1.39 (s, 3H), 1.58 (s, 3H), 1.97 (d, 3H, J = 1.2 Hz), 2.20 (d, 3H, J = 1.1 Hz),
5
.71 (s, 1H), 5.85 (br, 1H), 6.36 (d,1H, J = 9.6 Hz), 6.90 (s, 1H), 8.04 (d, 1H, J = 9.6 Hz), 8.11 (s, 1H).
1
3
C-NMR (MeOH-d
4
), δ ppm: 20.1, 20.5, 26.2, 27.5, 76.5, 83.6, 106.0, 115.1, 115.5, 115.6, 118.2, 128.7,
1
44.5, 159.9, 160.5, 160.6, 162.2, 165.23, 187.8.
ACKNOWLEDGMENT
This work was supported by a Korea Research Foundation grant funded by the Korean government
(MOEHRD; KRF-2005-041-E00499).
REFERENCES (AND NOTES)
1
.
.
S. Foster, Bus. Herbs, 1996, May/June, 14.
2
R. Awad, J. T. Arnason, V. Trudeau, C. Bergeron, J. W. Budzinski, B. C. Foster, and Z. Merali,
Phytomedicine, 2003, 10, 640.
3
4
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P. Wolfson and D. L. Hoffmann, Altern. Ther. Health Med., 2003, 9, 74.
J. Li, Y. Ding, X.-C. Li, D. Ferreira, S. Khan, T. Smillie, and I. A. Khan, J. Nat. Prod., 2009, 72,
9
83.
5.
K. Hata and K. Sano, Yakugaku Zasshi, 1969, 89, 549; K. Sano, I. Yosioka, and I. Kitagawa, Chem.
Pharm. Bull., 1973, 21, 2095; K.-S. Ahn, W.-S. Sim, and I.-H. Kim, Planta Med., 1996, 62, 7; K.-S.
Ahn, W-S. Sim, I.-K. Lee, Y.-B. Seu, and I.-H. Kim, Planta Med., 1997, 63, 360; For racemic
syntheses of 1 and related natural coumarins, see: W. Steck, Can. J. Chem., 1971, 49, 2297; R. D.