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1 药学学报 Acta Pharmaceutica Sinica 2014, 49 (11): 中药益智正丁醇萃取部位的化学成分研究谢彬彬, 侯蕾, 郭宝林, 黄文华 *, 余竞光 ( 中国医学科学院北京协和医学院药用植物研究所, 北京 ) 摘要 : 采用 MDS 树脂正相硅胶反相 ODS 等柱色谱和制备 HPLC 等多种色谱方法, 从中药益智 95% 乙醇提取物的正丁醇萃取部位中分离得到 9 个化合物, 根据理化性质和波谱数据分别鉴定为 : (1R, 4R, 10R)-1β, 4α-dihydroxy-11, 12, 13-trinor-5, 6-eudesmen-7-one ( 1) 1β, 4β-dihydroxy-11, 12, 13-trinor-8, 9-eudesmen-7-one ( 2) oxyphyllenone A (3) oxyphyllenone B (4) 3, 5, 4'- 三羟基 -7- 甲氧基黄酮 (rhamnocitrin, 5) staphylionoside D (6) 苄基-β-D- 吡喃葡萄糖苷 (benzyl-1-o-β-d-glucopyranoside, 7) 2-O-β-D-glucopyranosyl-(1S)-phenylethylene glycol (8) 和 (S)-1-phenylethyl-β-D-glucopyranoside (9) 其中化合物 1 是一个新的倍半萜类化合物, 命名为 oxyphyllenone C, 化合物 8 9 为新天然产物, 化合物 2 6 为首次从山姜属中分离得到, 化合物 7 为首次从益智中分离得到关键词 : 益智 ; 化学成分 ; 倍半萜 ; 糖苷中图分类号 : R284 文献标识码 : A 文章编号 : (2014) The compounds from n-butanol fraction of Alpinia oxyphylla XIE Bin-bin, HOU Lei, GUO Bao-lin, HUANG Wen-hua *, YU Jing-guang (Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing , China) Abstract: Nine compounds were isolated from the n-butanol fraction of 95% ethanol extract of the fruit of Alpinia oxyphylla Miq. with a combination of various chromatographic approaches, including MDS resin, silica gel, reverse phase C 18 and preparative HPLC. On the basis of spectroscopic data analysis, they were elucidated as (1R, 4R, 10R)-1β, 4α-dihydroxy-11, 12, 13-trinor-5, 6-eudesmen-7-one (1), 1β, 4β-dihydroxy-11, 12, 13-trinor-8, 9-eudesmen-7-one (2), oxyphyllenone A (3), oxyphyllenone B (4), rhamnocitrin (5), staphylionoside D (6), benzyl-1-o-β-d-glucopyranoside (7), 2-O-β-D-glucopyranosyl-(1S)-phenylethylene glycol (8), and (S)-1-phenylethyl-β-D-glucopyranoside (9). Among them, compound 1 is a new sesquiterpene, named as oxyphyllenone C; compounds 8 and 9 are new natural products; compounds 2 and 6 were isolated from the genus Alpinia for the first time, and compound 7 was isolated from A. oxyphylla for the first time. Key words: Alpinia oxyphylla; chemical constituent; sesquiterpene; glycoside 中药益智是姜科 (Zingberaceae) 山姜属植物益智 (Alpinia oxyphylla Miq.) 的干燥成熟果实, 别名益智仁, 益智子, 主产于海南广东广西福建等收稿日期 : ; 修回日期 : 基金项目 : 国家重大新药创制科技重大专项 (2012ZX ); 重大新药创制科技重大专项公共资源平台课题 (2011ZX ); 药用植物研究所创新团队发展计划资助. * 通讯作者 Tel / Fax: , whhuang69@163.com 地, 为海南道地药材, 也是我国四大南药之一, 具有温脾止泻摄唾涎暖肾固精缩尿的功效 [1] 现代药理学研究表明 : 益智主要具有抗炎神经保护抗氧化强心舒张血管提高免疫力等作用, 是一种安全性高的药食两用植物资源目前, 从益智中分到的化合物主要为萜类黄酮类二苯庚烷类酚类甾醇类等成分, 其中倍半萜类化合物能抑制脂多糖和 IFN-γ 诱导的鼠巨噬细胞产生 NO [2, 3] 本课题组前

2 1570 药学学报 Acta Pharmaceutica Sinica 2014, 49 (11): 期已对益智 95% 乙醇提取物的乙酸乙酯萃取部位进行化学成分研究 [4], 为了进一步阐明其药效物质基础, 本文对益智 95% 乙醇提取物的正丁醇萃取部位进行研究, 分离并鉴定了 9 个单体化合物 ( 图 1), 包括 4 个桉叶烷型倍半萜 ( 化合物 ) 1 个黄酮 ( 化合物 5) 4 个糖苷 ( 化合物 ) 其中化合物 1 为新倍半萜类化合物, 化合物 8 9 为新天然产物, 化合物 2 6 为首次从山姜属中分得, 化合物 7 为首次从益智中分得此前, An 等 [5] [6] Ly 等从高良姜中分离到一些 β-d- 吡喃葡萄糖苷类化合物, 而本文分离到的 4 个糖苷类化合物也均为 β-d- 吡喃葡萄糖苷类化合物 1 无色油状物磷钼酸显蓝绿色 HR-ESI-MS (+): m/z [M+Na] + (calcd. for C 12 H 18 O 3 Na, ), 并结合 NMR 数据, 确定其分子式为 C 12 H 18 O 3, 不饱和度为 4 13 C NMR (CDCl 3, 150 MHz) 给出 12 个碳信号 : 其中 1 个羰基碳 (C=O) 和 1 个碳碳双键 (C=C) 构成的 α, β- 不饱和酮结构 [δ C (C-6) (C-5) (C-7)]; 此外还有 2 个甲基碳 (δ C 17.7 和 28.4) 4 个亚甲基碳 (δ C ) 1 个季碳 (δ C 41.4) 以及 1 个连氧的叔碳 (δ C 78.3) 和 1 个连氧的季碳 (δ C 70.8) 同时, 1 H NMR (CDCl 3, 600 MHz) 显示化合物 1 有 1 个烯氢 [δ H 6.05 (1H, s)] 2 个分别取代在季碳上的甲基氢 [δ H 1.32 (3H, s) 1.34 (3H, s)] 由化合物 1 的 NMR 数据, 结合其不饱和度 4, 推断结构中含有 2 个环根据 HSQC 图谱数据将对应的碳氢信号进行了归属 ( 表 1) 甲基羟基以及 α, β- 不饱和酮在双环结构上的取代位置进一步通过 HMBC 确定, 如图 2a 所示在 HMBC 谱图显示 : H-14 (δ H 1.34) 与 C-10 C-9 C-1 有多键相关, 推断 CH 3-14 取代在双环 C-10 位上 ; H-1 (δ H 3.40) 与 C-2 C-10 C-9 C-14 有多键相关, 推断 -OH 取代在双环 C-1 位上 ; H-8α H-8β (δ H 2.42, 2.53) 分别与 C-9 C-7 C-10, H-9α H-9β (δ H 1.81, 2.21) 分别与 C-8 C-7 C-10 C-14 有多键相关, 推断羰基取代在双环 C-7 位上 ; H-15 (δ H 1.32) 与 C-4 Table 1 NMR spectral data of compound 1 in CDCl 3 (600 MHz for 1 H and 150 MHz for 13 C) Position δ C δ H (J in Hz) NOESY (1H, dd, J = 4.0, 12.0) H-2α, 3α, 9α (1H, H-2α, ddd, J = 4.0, 8.0, 12.0) 2.12 (1H, H-2β, ddd, J = 3.8, 12.0, 12.0) (1H, H-3α, ddd, J = 4.0, 8.0, 14.0) 1.95 (1H, H-3β, dd, J = 3.8, 14.0) (1H, s) (1H, H-8α, dd, J = 4.4, 18.0) 2.53 (1H, H-8β, ddd, J = 5.0, 16.0, 18.0) (1H, H-9α, ddd, J = 4.4, 12.0, 16.0) 2.21 (1H, H-9β, dd, J = 5.0, 12.0) (3H, s) H-9β, 8β, 2β (3H, s) H-3β Figure 1 The structures of compounds 1 9

3 谢彬彬等 : 中药益智正丁醇萃取部位的化学成分研究 1571 Figure 2 Key HMBC correlations (a) and NOESY correlations (b) of compound 1 C-3 有多键相关, 推断 CH 3-15 与 -OH 共取代在双环 C-4 位上 ; 此外 H-15 与 C-5 C-6, H-6 (δ H 6.05) 与 C-5 C-4 C-10 C-8 有多键相关, 推断碳碳双键形成于双环 C-5 6 位, 与羰基共轭形成 α, β- 不饱和酮结构综上, 确定化合物 1 的平面结构为 1, 4- 二羟基 -11, 12, 13- 降碳桉叶烷型倍半萜 NOESY 谱图显示, 如图 2b 所示 : H-3α (δ H 1.56) 与 H-1, H-3β (δ H 1.95) 与 H-15 有 NOESY 相关, 确定 CH 3-15 与 OH-1 均处于 β 位, 而 4-OH 处于 α 位 ; H-9α (δ H 1.81) 与 H-1, H-9β (δ H 2.21) 与 H-14 有 NOESY 相关, 确定 CH 3-14 处于 β 位, 综上, 确定化合物 1 的相对构型为 1β, 4α- 二羟基 -11, 12, 13- 降碳桉叶烷型 [7] 倍半萜以上结果与文献报道的 Calamusin Ⅰ 具有相同的平面结构和相对构型但化合物 1 的 [α] 20 D= 28.2 (c 0.02, MeOH), 符号与 Calamusin Ⅰ 相反, 推断化合物 1 与 Calamusin Ⅰ 的绝对构型存在差异化合物 1 的 CD 谱 ( 图 3) 证实以上推测 : 在 345 nm (Δε 0.16) 处出现由 α, β- 不饱和环己酮 n π * 电子跃迁引起的负的 Cotton 效应, 而 Calamusin I 在 340 nm (Δε +0.23) 处出现由 α, β- 不饱和环己酮 n π * 电子跃迁引起的正的 Cotton 效应 [7] 综上, 确定该化合物的绝对构型为 1R, 4R, 10R 为 Calamusin Ⅰ 的对映体综上所述, 化合物 1 的结构为 (1R, 4R, 10R)-1β, 4α-dihydroxy-11, 12, 13-trinor-5, 6-eudesmen-7-one 实验部分 1 仪器与试剂 LTQ-Obitrap XL 液质联用仪, Bruker Avance DRX-600 型超导核磁共振仪 ( 美国 Bruker 公司, TMS 为内标 ), Jasco J-815 圆二色谱仪 ( 日本 Jasco 公司 ), Fihser-Johns 熔点仪 ( 温度未校正 ), Agela CHEETAH TM 中压制备液相 ( 天津博纳艾杰尔科技有限公司 ), MDS GEL ( 北京麦迪生新技术开发中心 ), 薄层色谱用硅胶 GF254 柱色谱用硅胶 H ( 青岛海洋化工厂 ), YMC-ODS 制备型 HPLC 色谱柱 (10 mm 250 mm, 5 μm) 中压柱 ODS 填料 (YMC-ODS, 50 μm, 北京绿百草科技发展有限公司 ), 所用试剂为色谱纯和分析纯中药益智药材购于河北安国药材市场, 经中国医学科学院药用植物研究所郭宝林研究员鉴定为姜科植物益智 (Alpinia oxyphylla Miq.) 的干燥成熟果实, 凭证样品存放于本所天然药物研究中心 2 提取与分离益智干燥果实 89 kg, 粉碎后用 95% 乙醇渗漉, 减压浓缩得醇浸膏 kg, 用水混悬后, 依次用正己烷 (n-hexane) 乙酸乙酯 (EtOAc) 正丁醇 (n-buoh) 萃取, n-buoh 萃取液回收溶剂得正丁醇萃取部位 0.5 kg 取 200 g 用 MDS 中压柱分离, 甲醇水 (0 10~ 10 0) 梯度洗脱, 得 9 个流分其中, MDS-20% 甲醇部分 ( g) 经中压 ODS 柱分离, 甲醇水 (2 8~1 1) 梯度洗脱, 合并相似洗脱部分, 得到 9 个流分 (Fr.A~I) Fr.A (7.947 g), 经中压硅胶柱色谱, 氯仿甲醇 (99 1~86 14) 梯度洗脱, 得 70 个流分 (Fr.A-1~ 70) Fr. A-(13~18) (616 mg), 依次经中压 ODS 柱色谱制备 HPLC (C 18 ) 分离制备 TLC 纯化, 得化合物 1 (10 mg) 2 (2 mg) 3 (31 mg) 4 (20 mg) 5 (7 mg); Figure 3 CD spectrum of compound 1 (MeOH) (a); diagram of n π * transition rule of α, β-unsaturated cyclic ketone applied in compound 1 (b)

4 1572 药学学报 Acta Pharmaceutica Sinica 2014, 49 (11): Fr.A-25 (402 mg) 依次经中压 ODS 柱色谱制备 HPLC (C 18 ) 分离制备 TLC 纯化, 得化合物 7 (5 mg); Fr.A-(38~40) (360 mg), 依次经中压 ODS 柱色谱制备 HPLC (C 18 ) 分离, 得化合物 8 (6 mg); Fr.A-44 (97 mg) 经制备 HPLC (C 18 ) 分离得化合物 6 (5 mg) Fr.B (3.873 g), 经中压硅胶柱色谱, 氯仿甲醇 (99 1~86 14) 梯度洗脱, 得 58 个流份 (Fr.B1~58) Fr.B-20 (91 mg) 经制备 HPLC (C 18 ) 分离制备 TLC 纯化, 得化合物 9 (16 mg) 3 结构鉴定化合物 1 无色油状物 ( 甲醇 ), [α] 20 D = 28.2 (c 0.02, MeOH); IR (KBr) ν max : 3 397, 2 948, 2 961, 1661, 1 456, 1 374, cm 1 MeOH ; UV l max (nm) (logε): 237 (3.94); CD (MeOH) λ max (Δε) ( 0.16), (+0.03), 291 ( 0.07), 246 (+0.83), ( 1.41); HR-ESI-MS (+): m/z [M+Na] + (calcd. for C 12 H 18 O 3 Na, ), 分子式 C 12 H 18 O 3, 1 H NMR (600 MHz, CDCl 3 ) 和 13 C NMR (150 MHz, MeOD) 见表 1 化合物 2 无色油状物 HR-ESI-MS (+): m/z [M+Na] + (calcd. for C 12 H 18 O 3 Na, ), 分子式 C 12 H 18 O 3 1 H NMR (600 MHz, CD 3 OD) δ: 7.32 (1H, d, J = 10.0 Hz, H-9), 5.81 (1H, d, J = 10.0 Hz, H-8), 3.42 (1H, dd, J = 4.4, 12.0 Hz, H-1), 2.67 (1H, dd, J = 14.2, 18.0 Hz, H-6α), 2.47 (1H, dd, J = 3.8, 18.0 Hz, H-6β), 2.01 (1H, m, H-2α), 1.80 (1H, dd, J = 3.8, 14.2 Hz, H-5), 1.75 (1H, ddd, J = 3.2, 4.4, 13.2 Hz, H-3β), 1.65 (1H, m, H-2β), 1.57 (1H, dd, J = 4.4, 13.2 Hz, H-3α), 1.23 (3H, s, H-14), 1.15 (3H, s, H-15) 13 C NMR (150 MHz, CD 3 OD) δ: (C-7), (C-9), (C-8), 75.1 (C-1), 71.3 (C-4), 49.5 (C-5), 43.6 (C-10), 40.2 (C-3), 35.5 (C-6), 29.2 (C-15), 27.8 (C-2), 13.8 [8] (C-14) 以上数据与文献报道一致, 故鉴定为 1β, 4β- dihydroxy-11, 12, 13-trinor-8, 9-eudesmen-7-one 化合物 3 白色蜡状固体, mp 185~186 HR-ESI-MS (+): m/z [M+Na] + (calcd. for C 12 H 18 O 3 Na, ), 分子式 C 12 H 18 O 3 1 H NMR (600 MHz, CD 3 OD) δ: 6.01 (1H, br s, H-6), 3.69 (1H, dd, J = 2.8, 3.0 Hz, H-3), 2.63 (1H, ddd, J = 5.0, 13.6, 18.0 Hz, H-8β), 2.41 (1H, dddd, J = 2.8, 4.0, 12.0, 13.6 Hz, H-2β), 2.32 (1H, br d, J = 18.0 Hz, H-8α), 1.92 (1H, ddd, J = 4.4, 13.6, 14.0 Hz, H-9α), 1.82 (1H, ddd, J = 4.2, 14.0, 13.6 Hz, H-1α), 1.73 (1H, ddd, J = 2.4, 5.0, 14.0 Hz, H-9β), 1.56 (1H, ddd, J = 3.0, 4.2, 12.0 Hz, H-2α), 1.46 (3H, s, H 3-14), 1.43 (1H, ddd, J = 3.2, 4.0, 14.0 Hz, H-1β), 1.41 (3H, s, H 3-15) 13 C NMR (150 MHz, CD 3 OD) δ: (C-7), (C-5), (C-6), 76.4 (C-3), 74.1 (C-4), 41.2 (C-9), 36.8 (C-10), 35.5 (C-1), 35.1 (C-8), 25.6 (C-15), 25.7 (C-2), 25.5 (C-14) 以上 [9] 数据与文献报道一致, 故鉴定为 oxyphyllenone A 化合物 4 无色油状物 HR-ESI-MS (+): m/z [M+Na] + (calcd. for C 12 H 18 O 3 Na, ), 分子式 C 12 H 18 O 3 1 H NMR (600 MHz, CDCl 3 ) δ: 6.28 (1H, s, H-6), 3.55 (1H, dd, J = 4.4, 12.0 Hz, H-3), 2.43 (1H, ddd, J = 4.0, 15.0, 18.0 Hz, H-8β), 2.29 (1H, ddd, J = 2.2, 3.4, 18.0 Hz, H-8α), 1.82 (1H, dddd, J = 4.0, 12.0, 14.0, 15.0 Hz, H-2β), 1.79 (1H, ddd, J = 3.4, 15.0, 13.6 Hz, H-9α), 1.72 (1H, ddd, J = 2.2, 4.0, 13.6 Hz, H-9β), 1.68 (1H, dddd, J = 3.6, 4.0, 4.4, 15.0 Hz, H-2α), 1.60 (1H, ddd, J = 3.6, 4.0, 13.8 Hz, H-1β), 1.37 (1H, ddd, J = 4.0, 14.0, 13.8 Hz, H-1α), 1.30 (3H, s, H 3-15), 1.24 (3H, s, H 3-14) 13 C NMR (150 MHz, MeOD) δ: (C-7), (C-5), (C-6), 77.3 (C-3), 76.5 (C-4), 40.8 (C-9), 37.9 (C-1), 36.1 (C-10), 33.7 (C-8), [9] 26.7 (C-2), 24.8 (C-14), 22.9 (C-15) 以上数据与文献报道一致, 故鉴定为 oxyphyllenone B 化合物 5 黄色针晶, mp 226~228 HR-ESI- MS (+): m/z [M+H] + (calcd. for C 16 H 13 O 6, ), 分子式 C 16 H 12 O 6 1 H NMR (600 MHz, DMSO-d 6 ) δ: (1H, s, 5-OH), (1H, s, 4'-OH), 9.51 (1H, s, 3-OH), 8.08 (2H, td, H-2', 6'), 6.93 (2H, td, H-3', 5'), 6.75 (1H, d, H-8), 6.35 (1H, d, H-6), 3.90 (3H, s, 7-OCH 3 ) 13 C NMR (150 MHz, DMSO-d 6 ) δ: (C-4), (C-7), (C-5), (C-4'), (C-9), (C-2), (C-3), (C-2', 6'), (C-1'), (C-3, 5'), (C-10), 97.4 (C-6), 92.0 [10] (C-8), 56.0 (C-11) 以上数据与文献报道一致, 故鉴定为 3, 5, 4'- 三羟基 -7- 甲氧基黄酮 (rhamnocitrin) 化合物 6 无定形粉末 HR-ESI-MS (+): m/z [M+Na] + (calcd. for C 19 H 30 O 8 Na, ), 分子式 C 19 H 30 O 8 ; 1 H NMR (600 MHz, CD 3 OD) δ: 5.85 (1H, s, H-8); 4.46 (1H, d, J = 8.0 Hz, H-1'), 4.35 (1H, m, H-3), 3.88 (1H, dd, J = 2.0, 12.0 Hz, H-6'b), 3.69 (1H, dd, J = 5.0, 12.0 Hz, H-6'a), 3.16 (1H, dd, J = 8.0, 9.0 Hz, H-2'), 2.38 (1H, ddd, J = 2.0, 4.0, 13.0 Hz, H-4eq), 2.10 (1H, ddd, J = 2.0, 4.0, 13.0 Hz, H-2eq), 2.19 (3H, s, H 3-10), 1.47 (1H, m, H-2ax), 1.46 (1H, m, H-4ax), 1.39 (3H, s, H-13), 1.38 (3H, s, H-11), 1.16 (3H, s, H-12); 13 C NMR (150 MHz, CD 3 OD) δ: (C-9), (C-7), (C-6), (C-1'), (C-8), 78.4 (C-3'), 78.1 (C-5'), 75.3 (C-2'), 72.8 (C-3), 72.6 (C-5), 71.9 (C-4'), 62.9 (C-6'), 48.3 (C-4), 46.8 (C-2), 37.2 (C-1), 32.5 (C-12), 31.0 (C-13), 29.6 (C-11), [11] 26.7 (C-10) 以上数据与文献报道一致, 故鉴定为 staphylionoside D 化合物 7 白色针晶状 ( 甲醇 ), mp 212~213

5 谢彬彬等 : 中药益智正丁醇萃取部位的化学成分研究 1573 HR-ESI-MS (+): m/z [M+Na] + (calcd. for C 13 H 18 O 6 Na, ), 分子式 C 13 H 18 O 6 ; 1 H NMR (600 MHz, CD 3 OD) δ: 7.42 (2H, d, J = 7.4 Hz, H-2', 6'), 7.33 (2H, t, J = 7.4 Hz, H-3', 5'), 7.28 (1H, t, J = 7.4 Hz, H-4'), 4.93 (1H, d, J = 11.8 Hz, H-1a), 4.67 (1H, d, J = 11.8 Hz, H-1b), 4.36 (1H, d, J = 7.8 Hz, H-1''), 3.89 (1H, dd, J = 2.0, 12.0 Hz, H-6''b), 3.69 (1H, dd, J = 6.0, 12.0 Hz, H-6''a); 13 C NMR (150 MHz, CD 3 OD) δ: (C-1'), (C-2', 6'), (C-3', 5'), (C-4'), (C-1''), 78.2 (C-3''), 78.1 (C-5''), 75.3 (C-2''), 71.9 (C-1), 71.8 (C-4''), 62.9 (C-6'') 以上数据 [12, 13] 与文献报道一致, 故鉴定为 benzyl-1-o-β-d- glucopyranoside 化合物 8 无定形粉末, mp 68~70 HR-ESI- MS (+): m/z [M+Na] + (calcd. for C 14 H 20 O 7 Na, ), 分子式 C 14 H 20 O 7 1 H NMR (600 MHz, CD 3 OD) δ: 7.40 (2H, d, J = 7.2 Hz, H-2', 6'), 7.34 (2H, t, J = 7.2 Hz, H-3', 5'), 7.27 (1H, t, J = 7.2 Hz, H-4'), 4.89 (1H, dd, J = 3.0, 9.0 Hz, H-1), 4.34 (1H, d, J = 7.8 Hz, H-1''), 4.02 (1H, dd, J = 3.0, 10.0 Hz, H-2a), 3.86 (1H, dd, J = 2.0, 12.0 Hz, H-6''b), 3.66 (1H, dd, J = 5.0, 12.0 Hz, H-6''a), 3.56 (1H, dd, J = 9.0, 10.0 Hz, H-2b), 3.38 (1H, t, J = 7.8 Hz, H-2'') 13 C NMR (150 MHz, CD 3 OD) δ: (C-1'), (C-3', 5'), (C-4'), (C-2', 6'), (C-1''), 78.2 (C-3''), 78.1 (C-5''), 76.8 (C-2), 75.5 (C-2''), 74.6 (C-1), 71.8 (C-4''), 62.9 [14] (C-6'') 以上数据与文献报道一致, 故鉴定为 2-O-β- D-glucopyranosyl-(1S)-phenylethylene glycol 化合物 9 无色透明状固体 HR-ESI-MS (+): m/z [M+Na] + (calcd. for C 14 H 20 O 6 Na, ), 分子式 C 14 H 20 O 6 ; 1 H NMR (600 MHz, CD 3 OD) δ: 7.42 (2H, d, J = 7.4 Hz, H-2', 6'), 7.32 (2H, t, J = 7.4 Hz, H-3', 5'), 7.26 (1H, t, J = 7.4 Hz, H-4'), 5.05 (1H, q, J = 6.6 Hz, H-1), 4.08 (1H, d, J = 7.8 Hz, H-1''), 3.88 (1H, dd, J = 1.8, 12.0 Hz, H-6'b), 3.68 (1H, dd, J = 6.0, 12.0 Hz, H-6'a), 3.31~3.33 (4H, m, H-2'', 3'', 4'', 5''), 1.46 (3H, d, J = 6.6 Hz, H-2) 13 C NMR (150 MHz, CD 3 OD) δ: (C-1'), (C-3', 5'), (C-4'), (C-2', 6'), (C-1''), 76.2 (C-1), 78.2 (C-3''), 78.1 (C-5''), 75.4 (C-2''), 71.9 (C-4''), 63.0 (C-6''), 24.8 [15] (C-2) 以上数据与文献报道一致, 故鉴定为 (S)-1- phenylethyl β-d-glucopyranoside References [1] Chinese Pharmacopoeia Commission. Pharmacopoeia of the People s Republic of China ( 中华人民共和国药典 ) [S]. I. Beijing: China Medical Science Press, 2010: Vol [2] Xu JJ, Ji CJ, Zhang YM, et al. Inhibitory activity of eudesmane sesquiterpenes from Alpina oxyphylla on production of nitric oxide [J]. Bioorg Med Chem Lett, 2012, 22: [3] Luo JG, Lv XQ, Wang XB, et al. Sesquiterpenoids from the fruits of Alpina oxyphylla and inhibition of nitric oxide production in lipopolysaccharide-activated macrophages [J]. Phytochem Lett, 2012, 5: [4] Hou L, Lv XX, Xie BB, et al. Studies on the chemical constituents in Alpinia oxyphylla [J]. Nat Prod Res Dev ( 天然产物研究与开发 ), 2013, 25: [5] An N, Lin J, Yang SL, et al. A new glycoside from Alpinia officinarum [J]. Acta Pharm Sin ( 药学学报 ), 2006, 41: [6] Ly YN, Shimoyamada M, Kato M. Isolation and characterization of some antioxidative compounds from the Rhizomes of smaller Galanga (Alpinia officinarum Hance) [J]. J Agric Food Chem, 2003, 51: [7] Hao ZY, Liang D, Luo H, et al. Bioactive sesquiterpenoids from the rhizomes of Acorus calamus [J]. J Nat Prod, 2012, 75: [8] Henchiri H, Bodo B, Deville A, et al. Sesquiterpenoids from Teucrium ramosissimum [J]. Phytochemistry, 2009, 70: [9] Muraoka O, Fujimoto M, Tanabe G, et al. Absolute stereostructures of novel norcadinane- and trinoreudesmanetype sesquiterpenes with nitric oxide production inhibitory activity from Alpinia oxyphylla [J]. Bioorg Med Chem Lett, 2001, 11: [10] Tu YC, Lian TW, Yen JH, et al. Antiatherogenic effects of kaempferol and rhamnocitrin [J]. Agric Food Chem, 2007, 55: [11] Qian YU, Katsuyoshi M, Hideaki O, et al. Staphylionosides A K: megastigmane glucosides from the leaves of Staphylea bumalda DC [J]. Chem Pharm Bull, 2005, 53: [12] Wen Q, Lin X, Liu Y, et al. Phenolic and lignan glycosides from the butanol extract of Averrhoa carambola L. root [J]. Molecules, 2012, 17: [13] Zeng Q, Chang RJ, Qin JJ, et al. New glycosides from Dracocephalum tanguticum Maxim [J]. Arch Pharm Res, 2011, 34: [14] Ooi Y, Mitsuo N, Satoh T. Enzymic synthesis of glycosides of racemic alcohols using β-galactosidase and separation of the diastereomers by high-performance liquid chromatography using a conventional column [J]. Chem Pharm Bull, 1985, 33: [15] Shimoda K, Katsuragi H. Enzymatic resolution of (RS)-1- phenylalkyl β-d-glucosides to (R)-1-phenylalkyl β-primeverosides and (S)-1-phenylalkyl β-d-glucosides via plant xylosyltransferase [J]. Tetrahedron: Asymmetry, 2010, 21:

Microsoft Word - Supporting Information clear

Microsoft Word - Supporting Information clear Supporting Information Galanthamine, Plicamine, and Secoplicamine Alkaloids from Zephyranthes candida and Their Anti-acetylcholinesterase and Anti-inflammatory Activities Guanqun Zhan, Junfei Zhou, Rong