A new diterpene glycoside from the stem bark of acanthopanax trifoliatus

Journal of Chemistry, Vol. 42 (3), P. 384 - 387, 2004<br /> <br /> <br /> A New Phenylpropanoid Glycoside from the Stem<br /> Bark of Acanthopanax trifoliatus<br /> Received 19-8-2003<br /> Phan Van Kiem1, Chau Van Minh1, Nguyen Tien Dat2, Jung Joon Lee3 and<br /> Young Ho Kim2<br /> 1<br /> Institute of Natural Products Chemistry, VASC<br /> 2<br /> College of Pharmacy, Chungnam National University, Korea<br /> 3<br /> Korea Research Institute of Bioscience and Biotechnology, Korea<br /> <br /> SUMMARY<br /> A new phenylpropanoid glycoside 1-[ -D-glucopyranosyl-(1 6)- -D-glucopyranosyl]-2,6-<br /> dimethoxy-4-propenyl-benzene was isolated from the stem bark of Acanthopanax trifoliatus along<br /> with quecitrin. Their structures were established on the basis of spectral and chemical evidence.<br /> Key Words:Acanthopanax trifoliatus, Araliaceae, Acantrifoside F.<br /> <br /> <br /> I - INTRODUCTION II - MATERIALS AND METHODS<br /> <br /> Acanthopanax trifoliatus (L.) Merr., 1. General experimental procedures<br /> (Araliaceae) is distributed in Northern Vietnam Melting points were determined using a Kofler<br /> and used in the folk medicine of South–East micro-hotstage. IR spectra were obtained on a<br /> Asia (Chi, 1997; Loi, 2001) as a drug with Hitachi 270-30 type spectrometer from KBr discs.<br /> Optical rotations were determined on a JASCO<br /> ginseng-like activity. Lupane-triterpene<br /> DIP-1000 KUY polarimeter. EI-MS spectrum was<br /> carboxylic acids and a lupane-triterpene obtained on a Hewlett Packard 5989 B-MS. FAB-<br /> glycoside were reported from the leaves of A. MS spectrum was obtained using a JEOL JMS-DX<br /> trifoliatus (Ty et al., 1984, 1985; Lischewski et 300 spectrometer. 1H-NMR (300 MHz) and 13C-<br /> al., 1985; Yook et al., 1998). During the course NMR (75 MHz) were recorded on a Bruker<br /> of our continuing work on Acanthopanax DRX300 spectrometer, 1H-NMR (600 MHz) and<br /> 13<br /> species, we isolated and determined the C-NMR 150 MHz) spectra were recorded on a<br /> structure of a new phenylpropanoid glycoside Bruker AM600 FT-NMR spectrometer. Chemical<br /> named acantrifoside F (1) along with a known shifts are referenced to using TMS as an internal<br /> compound (2) from the stem bark of standard. Column chromatography (CC) was<br /> Acanthopanax trifoliatus. Based on performed on silica gel 60, YMC RP-18 resins or<br /> Dianion HP-20 resin.<br /> spectroscopic data the chemical structures of<br /> constituents were determined to be 1-[ -D- 2. Plant material<br /> glucopyranosyl-(1 6)- -D-glucopyranosyl]- A. trifoliatus was collected in Langson<br /> 2,6-dimethoxy-4-propenyl-benzene (1) and province, Vietnam in January 2001 and<br /> quercitrin (2). identified by Prof. Dr. Tran Minh Hoi, Institute<br /> 384<br /> of Ecology, Biological Resources, VASC of Mitsubishi Chem. Ind. Co. Ltd, Tokyo, Japan;<br /> Vietnam. Voucher pecimens (No 2539) are Column 70 mm × 800 mm) and eluted with<br /> deposited at the herbarium of the Institute of water containing increasing concentrations of<br /> Natural Products Chemistry, NCST, Vietnam, MeOH (100% H2O, 20% MeOH, 40% MeOH,<br /> and at the herbarium of the College of Pharmacy, 60% MeOH, 80% MeOH and 100% MeOH).<br /> Chungnam National University, Korea. The 40% MeOH fraction (12.0 g) was<br /> 3. Extraction and isolation chromatographed on a silica gel column ( 40<br /> mm × 800 mm) using CHCl3-MeOH-H2O (70 :<br /> The dried and powdered stem bark (2.0 kg) 30 : 4) as eluent and gave five fractions (Fr. A1<br /> was extracted three times with hot MeOH. The - A5). Fraction A1 (1.5 g) was purified on a<br /> combined solutions were evaporated under<br /> reduced pressure to give MeOH extract (120.0 YMC RP-18 column ( 20 mm × 600 mm)<br /> g), which was suspended in water and then using MeOH-H2O (8 : 2) as eluent yielded 1 (15<br /> partitioned with dichloromethane. The residue mg). Fraction A3 (2.7 g) was purified on a YMC<br /> of the water fraction (65.0 g) was adsorbed on RP-18 column ( 20 mm × 600 mm) using<br /> highly porous polymer resin (DIANION HP-20, MeOH-H2O (7 : 3) as eluent yielded 2 (20 mg).<br /> <br /> OCH3 OH<br /> 2 3 3'<br /> 7 4' OH<br /> 9<br /> 2 8<br /> R O 1 4 R1 HO 9 O 2<br /> 1'<br /> <br /> <br /> 5 7<br /> 6 10 3<br /> OCH3<br /> 4 O-rha<br /> R1 R2 O<br /> 1 6<br /> 1 H glc glc OH<br /> 1a OH glc 2<br /> <br /> Figure 1: Structures of 1 and 2<br /> <br /> 1-[ -D-glucopyranosyl-(1 6)- -D- NMR (75 MHz) (DMSO-d6) : 177.7 (C-4),<br /> glucopyranosyl]-2,6-dimethoxy-4-propenyl- 164.1 (C-7), 161.2 (C-5), 157.2 (C-9), 156.4 (C-<br /> benzene (acantrifoside F) (1) 2), 148.4 (C-4’), 145.2 (C-3’), 134.2 (C-3), 121.1<br /> (C-6’), 120.7 (C-1’), 115.6 (C-5’), 115.4 (C-2’),<br /> A white powder, m.p. 165 - 168oC, [ ]25D 104.1 (C-10), 101.8 (C-1-rha), 98.6 (C-6), 93.6<br /> –35.0o (c 0.5, MeOH); IR (KBr) max (cm-1): (C-8), 71.1 (C-4-rha), 70.5 (C-3-rha), 70.3 (C-2-<br /> 3420 (br, OH), 2985 (C-H), 1050 (C-O-C); rha), 70.0 (C-5-rha), 17.6 (C-6-rha).<br /> FAB-MS (positive) m/z: 519 [M+H]+, 341.1 [M-<br /> glc+H]+; 1H- and 13C-NMR, see table 1. III - RESULTS AND DISCUSSION<br /> Quercitrin (2)<br /> Compound 1 was obtained as white powder,<br /> Yellow powder, m.p. 178 - 180oC, [ ]25D gave absorption due to hydroxyl and C-O-C<br /> –147.0 o (c 0.5, MeOH); FAB-MS (positive) m/z: groups in the IR spectrum. Compound 1 showed<br /> 449 [M+H]+; 1H-NMR (300 MHz) (DMSO-d6) an [M+H]+ ion peak at m/z 519 as well as the<br /> : 7.99 (1H, d, J = 2.1, H-2’), 7.68 (1H, dd, J = following significant FAB-MS fragment peak<br /> 8.2, 2.1, H-6’), 7.28 (1H, d, J = 8.2, H-5’), 6.67 [M-glc+H]+ at m/z 341 in the positive FAB-MS,<br /> (1H, d, J = 2.1, H-6), 6.25 (1H, d, J = 7.8, H-1’’), corresponding to a molecular formula of<br /> 6.24 (1H, d, J = 2.1, H-8), 4.26-5.01 (4H, m, H- C23H34O13. The 1H-NMR spectrum of 1 (table 1,<br /> 2”, 3”, 4”, 5”), 1.44 (3H, d, J = 5.9, H-6’’); 13C- in DMSO) showed signals due to a methyl<br /> <br /> 385<br />  Table 1: 1H- and 13C-NMR spectral data of 1 6.65 (2H, s, H-3, 5), protons for two primary<br /> alcohol groups at 3.65 (1H, dd, J = 12.0, 5.4<br /> 1 Hz)/ 2.90 (1H, dd, J = 12.0, 2.5 Hz) and 3.82<br /> Pos. a,b a,c<br /> C H<br /> (1H, dd, 12.0, 2.5)/3.53 (1H, dd, 12.0, 5.4), and<br /> two anomeric protons at 4.87 (1H, d, J = 7.8<br /> 1 132.9<br /> Hz) and 4.05 (1H, d, 7.5). The 13C-NMR and<br /> 2 152.7 DEPT spectrums (table 1, in CD3OD-d4)<br /> revealed 23 carbon signals, including a methyl<br /> 3 103.5 6.65 (1H, s)<br /> group at 17.5, two methoxy groups at 57.8,<br /> 4 132.7 two anomeric carbons at 103.0 and 102.0.<br /> 5 103.5 6.65 (1H, s) The structure of 1 was determined by<br /> 6 152.7 comparison with the data of syringin (1a) [3, 6]<br /> and tracing the connectivities shown in the<br /> 7 130.2 6.32 (1H, d, 16.8) HMBC spectrum of 1. Cross peaks (Fig. 2) were<br /> 8 124.3 6.21 (1H, dq, 16.8, 6.4) observed between methoxy protons at 3.75<br /> 9 17.5 1.80 (3H, d, 6.4) and aromatic carbon at 152.7 (C-2, 6),<br /> between methyl protons at 1.80 (H-9) and<br /> 10 57.8 3.75 (6H, s) olefinic carbons at 130.2 (C-7)/124.3 (C-8),<br /> 1-O-glc between olefinic protons at 6.32 (H-7)/6.21<br /> 1’ 102.0 4.87 (1H, d, 7.8) (H-8) and methyl carbon at 17.5 (C-9), between<br /> anomeric proton at 4.87 (H-1’) and carbon at<br /> 2’ 75.9 3.30* 132.9 (C-1), and between anomeric proton at<br /> 3’ 78.6 3.20* 4.05 (H-1”) and carbon at 67.5 (C-6’) in the<br /> 4’ 71.7 3.43* HMBC spectrum of 1. This evidence confirmed<br /> that two methoxy groups were connected to C-2<br /> 5’ 75.7 3.20* and C-6, the methyl group was attached to C-8,<br /> 6’ 67.5 3.53 (1H, dd, 12.0, 5.4), one sugar (glc) was attached to C-1 of the<br /> 3.82 (1H, dd, 12.0, 2.5) arometic ring and another sugar (glc’) was<br /> Glc’ (1 6)-glc connected to glc at C-6 position. Based on above<br /> data and comparison with the data of syringin<br /> 1” 103.0 4.05 (1H, d, 7.5) (1a)[3, 6], compound 1 was determined to be 1-<br /> 2” 73.4 2.8 - 3.4 * [ -D-glucopyranosyl-(1 6)- -D-<br /> glucopyranosyl]-2,6-dimethoxy-4-propenyl-<br /> 3” 75.8 2.8 - 3.4* benzene, which we named acantrifoside F.<br /> 4” 68.9 2.8 - 3.4 * Compounds 2 was identified as quercitrin by<br /> 5” 75.5 2.8 - 3.4 * comparison of 1H-NMR (300 MHz), 13C-NMR<br /> 6” 64.8 3.65 (1H, dd, 12.0, 5.4), (75 MHz) and MS data reported in the literature<br /> 2.90 (1H, dd, 12.0, 2.5) (Choi et al., 1998).<br /> <br /> Glc, -D-glucopyranosyl, ain MeOD, b150MHz, Acknowledgements: This study was supported<br /> c<br /> 600MHz, din DMSO, *overlap signals. by a grant from the Korea-Vietnam<br /> group at 1.86 (3H, d, J = 6.4 Hz), two international cooperation project We are<br /> methoxy groups at 3.75 (6H, s), two olefinic grateful to the KBSI for measuring the NMR and<br /> protons at 6.21(1H, dq, J = 16.8, 6.4 Hz) and mass spectra, and we thank Prof. Dr. Tran Minh<br /> 6.32 (1H, d, J = 16.8 Hz) in trans- Hoi, Institute of Ecology, Biological Resources,<br /> configurations, protons of an aromatic ring at NCST for the plant identification.<br /> <br /> 386<br />  HOH2C<br /> OCH3<br /> HO O<br /> HO OH2C<br /> HO O<br /> OH HO O CH3<br /> <br /> OH<br /> <br /> H C HMBC<br /> OCH3<br /> <br /> Figure 2: The selected H-C long-range correlations in HMBC spectrum of 1<br /> <br /> REFERENCES and G. 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