Chemistry of Natural Compounds, Vol. 43, No. 3, 2007
COUMARINS FROM THE BARK OF Daphne marginata
Wei Zhang,1 YunHeng Shen,1 RunHui Liu,1
Chuan Zhang,1 HaiSheng Chen,1 Peng Fu,1
Lei Shan,1 and WeiDong Zhang1,2
UDC 547.972
Thegenus
(Thymelaeaceae), including 44 species, is widelydistributed in the southwest and northwest regions
Daphne
of China [1]. The roots or barks of most plants of this genus have been used to treat wound, bruises, and faucitis as a folk
medicine in China [2]. is an ornamental plant whose growth is restricted to the South of China. The barks
Daphne marginata
were collected in Dayu (Jiangxi province, China) in March 2005, and were authenticated byProf. Tan Ceming,
of
D. marginata
Jiangxi Plantation Research Institute, China. A voucher specimen is deposited in the Department of Pharmacognosy, Second
Military Medical University.
The air dried barks (7.5 kg) of
were extracted with 75% ethanol at room temperature. The EtOH extract
D. marginata
was partitioned with petroleum ether, CHCl , EtOAc, and -BuOH. Part of the EtOAc extract (50 g) was subjected to column
n
3
chromatography on silica gel with gradient elution by CHCl3–MeOH (100:1–1:1) to afford 1–9.
The compounds were identified using UV, IR, mass, and NMR spectra, and all these data were in good agreement with
the literature data [3–10]. All those compounds were isolated from
for the first time. The 13C NMR data of
D. marginata
compounds 1, 3, 4, 8, 9 are reported in this paper for the first time.
Umbelliferone (1) (7-hydroxycoumarin), C9H6O3, 162 [M]+, mp 226–228°C, UV (λmax, MeOH, nm): 325. IR (KBr,
cm–1): 3100, 1660, 1585, 1500, 1110, 820, 740. 13C NMR (125 MHz, DMSO-d6, δ, ppm): 102.1 (C-8), 111.2 (C-10), 111.3
(C-3), 113.1 (C-6), 129.6 (C-5), 144.4 (C-4), 155.5 (C-9), 160.4 (C-2), 161.2 (C-7) [3].
Herniarin (2) (7-methoxycoumarin), C10H8O3, 176 [M]+, mp 117–118°C, UV (λmax, MeOH, nm): 247, 320 [4].
Daphnetin (3) (7, 8-dihydroxycoumarin), C9H6O4, 178 [M]+, mp 225–227°C, UV (λmax, MeOH, nm): 261, 325. IR
(KBr, cm–1): 3500, 3050, 1680, 1570, 1490, 1320, 1290, 1000, 810. 13C NMR (125 MHz, DMSO-d6, δ, ppm): 111.1 (C-3),
112.0 (C-10), 112.4 (C-6), 118.8 (C-5), 132.1 (C-8), 143.7 (C-9), 145.0 (C-4), 149.7 (C-7), 160.3 (C-2) [5].
Hydrangetin (4) (7-hydroxy-8-methoxycoumarin), C10H8O4, 192 [M]+, mp 157–158°C, UV (λmax, MeOH, nm): 247,
256, 320. IR (KBr, cm–1): 3320, 1680, 1588, 1500, 835. 13C NMR (125 MHz, DMSO-d6, δ, ppm): 56.6 (-OCH3), 111.5 (C-3),
112.3 (C-10), 112.7 (C-6), 118.7 (C-5), 142.5 (C-9), 144.8 (C-4), 149.7 (C-7), 152.1 (C-8), 160.8 (C-2) [6].
Daphnoretin (5) (6-methoxy-7-hydroxy-3,7′-bicoumarin), C19H12O7, 352 [M]+, mp 244–245°C, UV (λmax, MeOH,
nm): 222, 265, 324, 345. IR (KBr, cm–1): 3400, 1680, 1590, 1480, 1250, 820. [3, 5].
Daphneticin (6) (6-demethoxy-5′′-methoxycleomiscosin B), C20H18O8, 386 [M]+, mp 235–238°C, UV (λmax, MeOH,
nm): 242, 260, 317. IR (KBr, cm–1): 3480, 3210, 1735, 1610, 1575, 1450, 1340, 1270, 835. [7].
Skimmin(7)(umbelliferone-7-O-β-D-glucoside), C15H16O8, 324[M]+, mp219–221°C. Acidhydrolysisof7produced
umbelliferone and D-glucose. IR (KBr, cm–1): 3420, 2910, 2850, 1720, 1700, 1620, 1500, 1400, 1350, 1280, 1240, 1200, 1170,
1120, 1080, 1020, 840. [8].
Daphnin (8) (daphnetin-7-O-β-D-glucoside), C15H16O9, 340 [M]+, mp 223–224°C, UV (λmax, MeOH, nm): 258, 311.
IR (KBr, cm–1): 3400, 2890, 1705, 1620, 1570, 1495, 1465. Acid hydrolysis of 8 produced daphnetin and D-glucose.
13CNMR(125MHz, DMSO-d6, δ, ppm): 60.7(glu:C-6), 69.7(glu:C-4), 73.2(glu:C-2), 75.7(glu:C-3), 77.3(glu:C-5),
101.8 (glu: C-1), 112.1 (C-6), 113.4 (C-3), 114.4 (C-10), 118.2 (C-5), 133.9 (C-8), 142.6 (C-9), 144.6 (C-4), 148.1 (C-7), 160.0
(C-2) [3, 9].
1) Department of Phytochemistry, School of Pharmacy, Second Military Medical University, Shanghai 200433, P. R.
China; fax +86 21 25070386, e-mail: wdzhangY@hotmail.com; 2) School of Pharmacy, Shanghai Jiao Tong University,
Shanghai 200030, P. R.China. Published in Khimiya Prirodnykh Soedinenii, No. 3, p. 264, May-June, 2007. Original article
submitted March 1, 2006.
0009-3130/07/4303-0317 ©2007 Springer Science+Business Media, Inc.
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