Chinese Journal of Natural Chinese Journal of Natural Medicines 2012, 10(5): 0358−0362 Medicines

doi: 10.3724/SP.J.1009.2012.00358

A new 1, 10-secoguaianolide from the aerial parts of Artemisia anomala

ZAN Ke1, CHEN Xiao-Qing2, TU Peng-Fei1*

1State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University Health Science Center, Beijing 100191, China; 2School of Traditional Chinese Medicine, Capital Medical University, Beijing 100069, China Available online Sep. 2012

[ABSTRACT] AIM: To study chemical constituents of the aerial parts of Artemisia anomala (). METHODS: The constituents were isolated with silica gel, ODS column chromatography and semi-preparative HPLC, and their structures were elucidated on the basis of physical characteristics and spectral data. RESULTS: Eight compounds were obtained, and their structures were identified as 3β-ethoxytanapartholide (1), (4S*, 5S*)-dihydro-5-[(1R*, 2S*)-2-hydroxy-2-methyl-5-oxo-3-cyclopenten-1-yl]-3-methylene-4-(3-oxobutyl)- 2(3H)-furanone (2), ligucyperonol (3), cyperusol C (4), santamarin (5), 1α, 2α, 3α, 4α, 10α -pentahydroxyguaia-11(13)-ene-12, 6α-olide (6), balanophonin (7), methyl 3-(2’-hydroxy-4’-methoxyphenyl) propanoate (8). CONCLUSION: Compound 1 was a new artifact, 4 and 8 were isolated from the genus Artemisia for the first time, and compounds 2–3, 5–7 were isolated from this for the first time. [KEY WORDS] Artemisia anomala; Chemical constituents; 1, 10-secoguaianolides; structure elucidation [CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2012)05-0358-05

1 Introduction 2 Experimental

Artemisia anomala S. Moore (Chinese name ‘Nan-Liu- 2.1 Apparatus and reagents Ji-Nu’), a perennial belonging to the As- Optical rotations were recorded on a Perkin-Elmer 243B teraceae family, has been commonly used in traditional Chi- digital polarimeter. NMR spectra were recorded on an Inova nese medicines as an analgesic, antibiotic, and as a wounds 500 spectrometer, operating at 500 MHz for 1H NMR and 13 healing agent [1]. Previous phytochemical investigations led 125 MHz for C NMR. The chemical shifts were given in δ to the isolation of flavonoids, coumarins, sesquiterpene lac- with TMS as internal standard. ESI-MS were measured on an tones and prostaglandin-like fatty acid derivatives from A. Agilent 6320 ion trap MS spectrometer. Semi-preparative anomala [2-13]. Compounds with antitumor and anti-inflam- HPLC was carried on a Waters 600 instrument with ODS matory activities were obtained from this plant by this labo- column (Agilent Technologies 250 mm × 9.4 mm, i.d., 5 μm) [6] ratory . As a continuation of this work, a systematically and C18 guard column with a 2996 photodiode array detector. phytochemical investigation on A. anomala has been carried Column chromatography was performed with silica gel (200–300 out. Herein, the isolation and structural elucidation of eight mesh, Qingdao Haiyang Chemical Works) and ODS (Merck). compounds from the aerial parts of A. anomala are reported. 2.2 Plant material The aerial parts of A. anomala were collected in Hang- zhou, Zhejiang Province, China in July, 2008. The plant ma-

[Received on] 10-Oct.-2011 terial was authenticated by Prof. TU Peng-Fei. A voucher [Research funding] This project was supported by the National specimen (No. CM20071215) was deposited at the Herbar- Natural Science Foundation of China (No. 30973629), China Post- ium of the Peking University Modern Research Center for doctoral Science Foundation (No. 20110490251), Foundation of State Key Laboratory of Natural and Biomimetic Drugs in Peking Traditional Chinese Medicine. University (No. K20120213) and Capital TCM & Nursing Foun- 2.3 Extraction and isolation dation ( No.11ZYH08). Dried aerial parts (300 kg) of A. anomala were chopped [*Corresponding author] TU Peng-Fei: Prof., Tel: 86-10-82802750; and extracted three times with 95% EtOH. After evaporation E-mail: [email protected] of the solvent under reduced pressure, the residue was sus- These authors have no any conflict of interest to declare. pended in water and extracted with petroleum ether and chlo-

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roform, successively. The residue of the CHCl3 layer (1 000 g) 1.24 (3H, t, J = 7.0 Hz) were displayed, which was confirmed was fractionated by silica gel column chromatography using by the 1H-1H COSY spectrum of 1. 1 a step-wise gradient of CHCl3 and MeOH to give 72 fractions. Apart from an ethoxyl, H NMR spectrum of 1 showed

Fractions 25–29 (15 g) were subjected to ODS open column two methyl signals at δH 2.14 (s), 2.15 (s), a pair of olefinic chromatography (MeOH–H2O, 50 : 50 to 80 : 20) to afford protons at δH 6.34 (1H, d, J = 3.0 Hz), and 5.67 (1H, d, J = sub-fractions 1–5. Sub-fraction 2 was subjected to semi- 3.0 Hz) and a downfield signal of an O-substituted methine preparative HPLC eluted with MeOH–H2O(40 : 60) respec- proton at δH 4.98 (1H, d, J = 5.0 Hz). Complete analysis of tively, followed by repeated semi-preparative HPLC the 1H, 13C, and 1H-1H COSY spectra of 1 revealed the pres-

(MeCN–H2O, 35 : 65) to yield 1 (10 mg) and 2 (5 mg). ence of a 2-oxo-butyl moiety in 1. The spectroscopic charac- Sub-fraction 3 was separated by semi-preparative HPLC teristics mention- ed above suggested that 1 might be a 1 13 (MeOH–H2O, 45 : 55) to give 3 (20 mg), 4 (9 mg) and 5 (18 secoguaianolide. Comparison of its H and C NMR data mg). Sub-fraction 4 was finally isolated by semi-preparative with those of the known compound 3-O-methyl-iso-seco- [14] HPLC (MeCN–H2O, 30 : 70) to afford 6 (9 mg). Sub-fraction tanapartholide revealed that they possessed a similar 5 was further purified by silica gel column chromatography skeleton, and that the difference between them was that the (CC) eluted with petroleum ether–acetone (3 : 1), repeatedly signal of the methoxyl group in the known compound disap- and finally affording 7 (15 mg) and 8 (30 mg). peared, replaced by an ethoxyl in 1. All of the protons and carbons were unambiguously assigned by analysis of 1H, 13C, 3 Results and Discussion 1H-1H COSY, HSQC spectra and confirmed by the HMBC Compound 1 was obtained as a colorless gum. The mo- spectrum (Fig. 2). The relative stereochemistry of 1 was es- lecular formula of C17H22O5 with seven degrees of unsatura- tablished by the NOESY spectrum. The relative configuration tion was deduced on the basis of HR-ESI-MS (m/z 329.137 0 of H-6 was assigned to be β, the same as the known com- + 13 13 [14] ([M + Na] ; (Calcd. for 329.136 5, C17H22O5Na). C NMR pound by detailed comparison of the C NMR data . In spectrum of 1 indicated 17 carbons including three carbonyl the NOESY spectrum, a weak effect was observed between carbons at δc 207.1, 202.6 and 169.9, four olefinic carbons at H-7 and H-3, whereas no NOEs could be discerned between δc 171.2, 138.4, 137.2 and 122.4, and two oxygen-bearing H-6 and H-7. These observations indicated that H-3 was carbons at δc 76.3 and 77.4. The 1H NMR revealed the pres- α-oriented. Thus, the structure of 1 was established and the ence of an ethoxy group at δH3.63 (2H, q, J = 7.0 Hz) and isolate named as 3β-ethoxytanapartholide.

Fig. 1 Structures of compounds 1-8

Fig. 2 Significant 1H-1H COSY ( ), HMBC ( ) correlations for compound 1

4 Identification

22 Compound 1 Colorless gum. [α]D −38.5 (c 0.1, Fig. 3 Key NOESY ( ) of compound 1

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MeOH); IR (KBr)νmax: 3 449, 2 925, 1 764, 1 711, 1 649, 1 2.52 (1H, m, H-7), 2.40 (1H, ddd, J = 3.5, 5.0, 17.0 Hz, 435, 1 346, 1 252, 1 203, 1 170, 1 113, 1 024, 818, 699 cm−1. H-2α), 2.35 (1H, d, J = 10.0 Hz, H-5), 2.09 (1H, m, H-8α), 1 13 H NMR spectral data (500 MHz, CDCl3) and C NMR 2.04 (1H, m, H-9β), 1.96 (1H, ddd, J = 3.5, 10.0, 17.0 Hz, spectral data (125 MHz, CDCl3), see Table 1; ESI-MS m/z H-2β), 1.83 (3H, s, H-15), 1.68 (1H, m, H-8β), 1.33 (1H, m, + + 13 329 [M + Na] ; HR-ESI-MS m/z: 329.137 0 [M + Na] H-9α), 0.88 (3H, s, H-14); C NMR (125 MHz, CDCl3) δ:

(Calcd. for C17H22O5 Na, 329.136 5). 75.2 (C-1), 32.7 (C-2), 121.3 (C-3), 133.4 (C-4), 51.2 (C-5), Compound 2 Colorless gum (MeOH); positive ESI- 81.6 (C-6), 51.1 (C-7), 21.4 (C-8), 34.2 (C-9), 40.9 (C-10), + 22 1 MS m/z 301 [M + Na] . [α]D + 53° (c 0.2, CHCl3). H NMR 138.9 (C-11), 171.2 (C-12), 116.8 (C-13), 11.1 (C-14), 23.5

(500 MHz, CDCl3) δ: 7.44 (1H, d, J = 5.0 Hz, H-3), 6.31 (1H, (C-15). Compound 5 was identified as santamarin by compa- d, J = 2.5 Hz, H-13a), 6.10 (1H, d, J = 5.0 Hz, H-2), 5.61 (1H, rison of the physical and spectral data with the literature [18]. d, J = 2.5 Hz, H-13b), 4.46 (1H, d, J = 6.5 Hz, H-6), 3.56 (1H, Compound 6 Colorless gum (MeOH); positive + 22 1 m, H-7), 2.64 (1H, s, H-5), 2.61 (2H, t, J = 5.0 Hz, H-9), 2.18 ESI-MS m/z 337 [M + Na] . [α]D + 35° (c 0.1, CHCl3). H 13 (3H, s, H-14), 1.94 (2H, m, H-8), 1.61 (3H, s, H-15); C NMR (500 MHz, CDCl3) δ: 6.25 (1H, d, J = 3.0 Hz, H-13a),

NMR (125 MHz, CDCl3) δ: 203.4 (C-1), 132.4 (C-2), 166.2 5.51 (1H, d, J = 3.0 Hz, H-13b), 4.94 (1H, dd, J = 3.5, 10.0 (C-3), 78.4 (C-4), 59.8 (C-5), 78.7 (C-6), 41.5 (C-7), 26.2 Hz, H-6), 4.09 (1H, d, J = 3.0 Hz, H-3), 4.03 (1H, d, J = 3.0 (C-8), 39.9 (C-9), 208.0 (C-10), 138.3 (C-11), 169.8 (C-12), Hz, H-2), 2.72 (1H, m, H-7), 2.42 (1H, d, J = 3.5 Hz, H-5), 122.3 (C-13), 30.2 (C-14), 24.5 (C-15). Compound 2 was 2.01 (2H, m, H-9), 1.95 (2H, m, H-8), 1.77 (3H, s, H-15), 13 identified as ((4S*, 5S*)-dihydro-5-[(1R*, 2S*)-2-hydroxy 1.18 (3H, s, H-14); C-NMR (125 MHz, CDCl3) δ: 87.0 -2-methyl-5-oxo-3-cyclopenten-1-yl]-3-methylene-4-(3-oxob (C-1), 77.5 (C-2), 64.5 (C-3), 74.2 (C-4), 59.1 (C-5), 79.8 utyl)-2(3H)-furanone by comparison of the physical and (C-6), 48.6 (C-7), 22.4 (C-8), 37.4 (C-9), 72.1 (C-10), 138.7 spectral data with the literature [15]. (C-11), 169.9 (C-12), 119.9 (C-13), 27.8 (C-14), 24.5 (C-15). Compound 3 Colorless needles. Positive ESI-MS m/z Compound 6 was identified as 1α, 2α, 3α, 4α, 10α-pentahy- + 22 1 257 [M + Na] . [α]D +85° (c 0.1, CHCl3). H NMR (500 droxyguaia-11(13)-ene-12, 6α-olide by comparison of the [19] MHz, CDCl3) δ: 4.79 (2H, s, H-13), 3.83 (1H, dd, J = 7.0, physical and spectral data with the literature . 22 11.0 Hz, H-1), 2.71 (1H, dd, J = 7.0, 18.0 Hz, H-2), 2.50 (1H, Compound 7 Yellow powder (MeOH), [α]D −115° (c + 1 dd, J = 11.0, 18.0 Hz, H-2’), 1.78 (3H, s, H-15), 1.77 (3H, s, 0.2, CHCl3). ESI-MS m/z 379 [M + Na] . H NMR (CDCl3, 13 H-12), 1.18 (3H, s, H-14); C NMR (125 MHz, CDCl3) δ: 500 MHz) δ: 9.66 (1H, d, J = 7.5 Hz, 9’-H), 7.41 (1H, d, J = 74.4 (C-1), 42.4 (C-2),197.2 (C-3), 129.4 (C-4), 161.7 (C-5), 15.5 Hz, 7’-H), 3.66(1H, q, J = 6.0 Hz, H-8), 3.95-4.01(2H, 37.7 (C-6), 45.2 (C-7), 26.5 (C-8), 32.9 (C-9), 41.3 (C-10), m, H-9), 7.13 (1H, s, H-6’), 7.04 (1H, d, J =1.0 Hz, H-2’), 148.9 (C-11), 20.6 (C-12), 109.3 (C-13), 11.1 (C-14), 16.2 6.96(1H, d, J =8.0 Hz, H-6), 6.93 (1H, d, J = 8.0 Hz, H-5), (C-15). Compound 3 was identified as ligucyperonol by compa- 6.90(1H, s, H-2), 6.61 (1H, dd, J = 7.5, 15.5 Hz, 8’-H), 5.62 rison of the physical and spectral data with the literature [16]. (1H, d, J = 7.0 Hz, H-7), 3.93 (3H, s, OMe), 3.89 (3H, s, 13 Compound 4 Colorless gum (MeOH). positive ESI- OMe); C NMR (CDCl3, 125MHz) δ: 132.1 (C-1), 111.4 + 22 1 MS m/z 261 [M + Na] . [α]D + 53° (c 0.2, CHCl3). H NMR (C-2), 146.7 (C-3), 143.9 (C-4), 114.5 (C-5), 121.1 (C-6),

(500 MHz, CDCl3) δ: 4.73 (1H, m, H-13a), 4.72 (1H, m, 88.9 (C-7), 53.0 (C-8), 63.9 (C-9), 128.2 (C-1’), 112.2 (C-2’), H-13b), 3.32 (1H, dd, J = 5.0, 12.0 Hz, H-1), 1.96 (1H, m, 144.8 (C-3’), 151.5 (C-4’), 132.2 (C-5’), 118.1 (C-6’), 153.0 H-7), 1.90 (1H, ddd, J = 3.5, 3.5, 13.0 Hz, H-9β), 1.83 (1H,m, (C-7’), 126.5 (C-8’), 193.5(C-9’), 56.0 (OMe), 56.1(OMe). H-6α), 1.78 (1H, ddd, J = 3.5, 12.0, 13.0 Hz, H-3β), 1.75 (1H, Compound 7 was identified as balanophonin by comparison s, H-15), 1.70 (1H, m, H-2β), 1.63 (1H, m, H-2α), 1.60 (1H, of the physical and spectral data with the literature [20]. m, H-8α), 1.50 (1H, ddd, J = 3.5, 12.0, 13.5 Hz, H-3α), 1.38 Compound 8 Colorless gum (MeOH), positive ESI- + 1 (1H, ddd, J = 3.5, 12.0, 13.0 Hz, H-8β), 1.27 (1H, m, H-6β), MS m/z 233 [M + Na] . H NMR (500 MHz, CDCl3) δ: 6.96 1.13 (1H,m, H-9α), 1.10 (3H, s, H-14), 0.88 (3H, s, H-12); (1H, d, J = 8.5 Hz, H-5), 6.46 (1H, d, J = 2.5 Hz, H-3), 6.44 13 C NMR (125 MHz, CDCl3) δ: 79.2 (C-1), 28.5 (C-2), 40.7 (1H, dd, J = 2.5, 8.0 Hz, H-5), 3.75 (3H, s, COOMe), 3.69 (C-3), 71.6 (C-4), 52.7 (C-5), 25.6 (C-6), 45.5 (C-7), 26.4 (3H, s, OMe), 2.84(2H, t, J = 6.0Hz, H-7 ), 2.69 (2H, t, J = 13 (C-8), 40.6 (C-9), 38.9 (C-10), 150.2 (C-11), 21.0 (C-12), 6.0Hz, H-8 ); C NMR (125 MHz, CDCl3) δ: 176.4 (C-9), 108.2 (C-13), 13.1 (C-14), 22.5 (C-15). Compound 4 was 159.6 (C-4), 155.3 (C-2), 131.0 (C-6), 119.4 (C-1), 106.9 identified as cyperusol C by comparison of the physical and (C-5), 102.8 (C-3), 55.2 (OMe), 52.3 (COOMe), 35.3 (C-8), spectral data with the literature [17]. 23.9 (C-7). Compound 8 was identified as methyl 3-(2’- Compound 5 Colorless gum (MeOH). positive ESI- hydroxy-4’-methoxyphenyl) propanoate by comparison of + 22 1 [21] MS m/z 271 [M + Na] . [α]D + 13° (c 0.1, CHCl3); H NMR the physical and spectral data with the literature . (500 MHz, CDCl ) δ: 6.08 (1H, d, J = 3.0 Hz, H-13a), 5.41 3 4 Discussion (1H, d, J = 3.0 Hz, H-13b), 5.33 (1H, t, J = 3.0 Hz, H-3), 3.94 (1H, t, J = 10.0 Hz, H-6), 3.70 (1H, dd, J = 5.0, 10.0 Hz, H-1), HPLC-MS was employed to establish that compound 1

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ZAN Ke, et al. /Chinese Journal of Natural Medicines 2012, 10(5): 358−362 was an artificial compound during the separation process. anomala [J]. Phytochemistry, 1987, 26(10): 2777-2779. Powdered dried aerial parts of A. anomala (5.0 g) were [5] Tian FR, Zhang L, Tian JK, et al. Chemical constituents of placed into a 500 mL flask containing 100 mL of methanol, Artemisia anomala S. Moore [J]. Chin J Med Chem, 2008, 18 then the mixture was extracted in ultrasonic bath (Eima Ul- (5): 362-365. trasonic Corp., Germany) at room temperature for 0.5 h. The [6] Wen J, Shi HM, Xu ZR, et al. Dimeric guaianolides and ses- methanol solution was filtered through a 0.22 μm membrane, quiterpenoids from Artemisia anomala [J]. J Nat Prod, 2010, and then an aliquot of 10 μL of the filtrate was injected into 73(1): 67-70. the HPLC-MS system for analysis. Meanwhile, compound 1 [7] Zan K, Chen XQ, Fu Q, et al. Chemical ingredients isolated was dissolved in methanol as reference solution. from the aerial parts of Artemisia anomala [J]. J Chin Pharm The HPLC-DAD analysis was carried out on an Agilent Sci, 2010, 19(2): 95-99. 1200 Series liquid chromatograph system (Agilent Techno- [8] Zhang L, Li BG, Tian FR, et al. Flavonoids of Artemisia logies, USA), equipped with a binary pump, an auto sampler, anomala S. Moore [J]. Chin Pharm J, 2010, 45(2): 104-107. a photo-diode array detector and a column temperature con- [9] Zan K, Chen XQ, Fu Q, et al. 1, 10-Secoguaianolides from troller. The analytical column was an Agilent-Zorbax Eclipse Artemisia anomala (Asteraceae) [J]. Biochem Syst Ecol, 2010,

Plus C18 (5 μm, 250 mm × 4.6 mm, i.d.) with the oven tem- 38(3): 431-434. perature maintained at 25 °C. 0.1% formic acid aqueous so- [10] Zan K, Zhou, SX, Chen XQ, et al. Prostaglandin-like fatty acid lution (V/V, solvent A) and acetonitrile (solvent B) were used derivatives from Artemisia anomala [J]. J Asian Nat Prod Res, as mobile phase for the LC separation. The elution conditions 2010, 12(6): 492-497. applied with a linear gradient of as follows: 0–60 min, [11] Zan K, Shi SP, Fu Q, et al. New sesquiterpenoids from Arte- 5%–25% B; 60–120 min, 25%–50% B; 120–150 min, misia anomala [J]. Helv Chim Acta, 2010, 93(10): 2000-2006. 50%–100% B. The flow rate was at 1.0 mL/min and peaks [12] Wen, J, Shi, HM, Liu, YF, et al. Flavonoids from Artemisia were detected at 210 nm. For ESI-MS analysis, a 6320 Ion anomala [J]. China J Chin Mater Med, 2010, 35(14): 1827-1830. Trap Mass spectrometer (Santa Clara, CA, USA) was con- [13] Wen J, Shi HM, Zan K, et al. Chemical constituents in Arte- nected on the same Agilent 1200 HPLC instrument via an misia anomala [J]. Chin Tradit Herb Med, 2010, 41(6): 870- electrospray ionization (ESI) interface. The HPLC effluent 873. was introduced into the ESI source in a post-column splitting [14] Marco JA, Sanz-Cervera JF, Manglano E, et al. Sesquiterpene ratio of 1 : 4. The ESI-MS was performed in positive ioni- lactones from Iranian Artemisia species [J]. Phytochemistry, 1993, 34(6): 1561-1564. zation mode with source settings as follows: nebulizer gas [15] Kazuyoshi K, Yoshiko T, Norasyikin A, et al. Sesquiterpenoids pressure of 30.00 psi; dry gas flow rate of 12.00 L·min−1; from Artemisia gilvescens and an anti-MRSA compound [J]. J electrospray voltage of the ion source of 3 500 V; capillary Nat Prod, 2003, 66(4): 538-539. temperature of 350 °C; scan range of m/z 100–800; Nitrogen [16] Xu FM, Morikawa T, Matsuda H, et al. Sesquiterpenes from (> 99.99%) and He (> 99.99%) were used as sheath and the rhizomes of Ligularia dentata Hara [J]. Bull Chem Soc Ja- damping gas, respectively. The results showed that com- pan, 1990, 63(8): 2239-2245. pound 1 was an artifact during the isolation process because [17] Xu FM, Morikawa T, Matsuda H, et al. Structures of new it was not observed in the methanol extract of A. anomala. desquiterpenes and hepatoprotective constituents from the References Egyptian herbal medicine Cyperus longus [J]. J Nat Prod, 2004, 67(4): 569-576. [1] Jiangsu New Medical College. Dictionary of Traditional Chi- [18] Glasl S, Kastner U, Baumann A, et al. Eudesmanolides from nese Materia Medica [M]. Shanghai Science and Technology pratensis [J]. Phytochemistry, 1995, 38(1): 159-161. Press, 1977: 1167. [19] Tan RX, Jia ZJ, Jakupovic J, et al. Sesquiterpene lactones from [2] Xiao YQ, Tu YY. Isolation and identification of the lipophilic Artemisia rutifolia [J], Phytochemistry 1991, 30(9): 3033-3035. constituents from Artemisia anomala S. Moore [J]. Acta Pharm [20] Haruna M, Koube T, Ito K, et al. Balanophonin , a new neo- Sin, 1984, 19(12): 909-913. lignan from Balanophora japonica Makino [J]. Chem Pharm [3] Xiao YQ, Tu YY. Chemical constituents of Artemisia anomala Bull, 1982, 30(4): 1525-1527. S. Moore [J]. Acta Bot Sin, 1986, 28(3): 307-310. [21] Bourke DG, Collins DJ. Conversion of 7-methoxy-3, 4-dihydro- [4] Jakupovic J, Chen ZL, Bohlmann F. Artanomaloide, a dimeric 2H-1-benzopyran-2-one into the corresponding dimethyl ortho guaianolide and phenylalanine derivatives from Artemisia ester [J]. Tetrahedron, 1997, 53(11): 3863-3878.

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ZAN Ke, et al. /Chinese Journal of Natural Medicines 2012, 10(5): 358−362

南刘寄奴中的一个新 1, 10-裂环愈创木烷型倍半萜

昝 珂 1, 陈筱清 2, 屠鹏飞 1*

1 北京大学药学院 天然药物及仿生药物国家重点实验室, 北京 100191 2 首都医科大学中医药学院, 北京 100069

【摘 要】 目的：研究南刘寄奴中化学成分。方法：采用硅胶和 ODS 等柱层析分离手段以及半制备高效液相, 运用 NMR、 MS 以及理化性质鉴定化合物的结构。结果：从南刘寄奴中分离得到 8 个化合物, 其结构鉴定为 3β-ethoxytanapartholide (1), ((4S*, 5S*)-dihydro-5-[(1R*, 2S*)-2-hydroxy-2-methyl-5-oxo-3-cyclopenten-1-yl]-3-methylene-4-(3-oxobutyl)-2(3H)-furanone) (2), ligucy- peronol (3), cyperusol C (4), santamarin (5), 1α, 2α, 3α, 4α, 10α-pentahydroxyguaia-11(13)-ene-12, 6α-olide (6), balanophonin (7), methyl 3-(2’-hydroxy-4’-methoxyphenyl) propanoate (8)。结论：化合物 1 是新人工产物, 化合物 4和8 为首次从蒿属中分离得到, 化 合物 2–3, 5–7 为首次从该植物中分离得到。 【关键词】 南刘寄奴; 蒿属; 化学成分; 1, 10-裂环愈创木烷型倍半萜

【基金项目】 国家自然科学基金(No. 30973629)、中国博士后科学基金(No. 20110490251)、北京大学天然药物及仿生药物国家重点实 验室开放基金(No. K20120312)、首都中医药护理专项(No. 11ZYH08)资助

362 Chin J Nat Med Sep. 2012 Vol. 10 No. 5 2012 年 9 月 第 10 卷 第 5 期