北柴胡地上部分苯丙素及其抗细胞增殖活性

刘 艳， 刘 培， 黄 金， 肖宗雨， 潘 娟， 管 伟， 匡海学， 杨炳友

(黑龙江中医药大学，教育部北药基础与应用研究重点实验室，黑龙江 哈尔滨 150040)

北柴胡为伞形科柴胡属植物柴胡BupleurumchineseDC.的干燥地上部分，具有疏肝解郁、疏散退热、升举阳气的功效[1-2]，常用于治疗寒热往来、胸胁胀痛、月经不调等症。柴胡具有解热镇痛、镇静抗炎、保肝利胆等药理作用，是治疗少阳证首选要药[3-4]，而北柴胡与该植物具有相似药理活性[5]，但目前对其地上部分的化学成分报道较少。课题组前期从北柴胡中分离鉴定出黄酮、生物碱等成分，发现一部分对癌细胞有抗增殖作用[6]；本实验对其地上部分化学成分作进一步研究，共分离鉴定出35种苯丙素，并对其进行抗细胞增殖活性研究。

1 材料

Bruker-400/600超导核磁共振光谱仪(美国布鲁克公司)；Waters Q-TOF高分辨质谱仪、Waters 2695-2996型分析HPLC色谱仪、Waters x-Bridge C18色谱柱(4.6 mm×150 mm，5 μm)(美国Waters公司)；LC-20AR型制备HPLC色谱仪(日本岛津公司)；旋转蒸发仪(日本EYELA公司)；Shim-pack GIST C18(20 mm×250 mm，5 μm，日本岛津公司)；Sephadex LH-20(美国GE Healthcare公司)；柱色谱用硅胶(80～100、200～300目，青岛海洋化工厂)；柱色谱用ODS(ODS-A-HG，50 μm，日本YMC公司)；薄层色谱硅胶板(Silicagel60 F254)、薄层色谱反相板(Rp-18)(德国默克公司)；恒温CO2培养箱(美国Thermo公司)；Epoch 2型酶标仪(美国Bio-Tek公司)；倒置相差显微镜(日本Olympus公司)；低温高速离心机(上海安亭科学仪器厂)；超净工作台(北京王堂蓝翼科技有限公司)。

柱色谱用分析纯试剂(天津富宇精细化工有限公司)；分析纯甲醇(西陇化工股份有限公司)；色谱纯甲醇(德国默克公司)。MGC-803细胞株(武汉大学细胞保藏中心)；Cell Counting Kit-8试剂盒(美国GlpBio公司)；DMEM培养基(美国Thermo公司)；Cellmax胎牛血清(北京赛贝生物技术有限公司)；0.25%胰蛋白酶、青霉素-链霉素、磷酸盐缓冲液(上海碧云天生物技术有限公司)。

北柴胡采自黑龙江省大庆市林甸地区，经黑龙江中医药大学药学院药用植物学教研室樊锐锋副教授鉴定为伞形科植物北柴胡BupleurumchineseDC.的干燥地上部分，标本(编号20170910)保存于黑龙江中医药大学中药化学教研室。

2 提取与分离

柴胡干燥地上部分44.4 kg切成约2 cm的小块，乙醇回流提取，提取物在45 ℃下真空浓缩，加水分散，依次用石油醚、正丁醇、乙酸乙酯萃取洗脱，得741 g乙酸乙酯部位、606 g正丁醇部位。

取400 g乙酸乙酯部位，采用硅胶柱层析，二氯甲烷-甲醇(1∶0～0∶1)进行洗脱，得到Fr.2～Fr.10。Fr.2经ODS反相柱，甲醇-水(1∶9～1∶0)洗脱，得Fr.2A～Fr.2E，Fr.2A～Fr.2C经Sephadex LH-20，得化合物1(32.4 mg)、6(3.8 mg)、8(3.3 mg)、10(2.2 mg)、20(3.0 mg)、25(1.2 mg)；Fr.2B经Sephadex LH-20、制备型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物17(4.7 mg，tR=11.8 min)。Fr.3经ODS反相柱，甲醇-水(1∶9～1∶0)洗脱，得Fr.3A～Fr.3F，Fr.3B、Fr.3C经Sephadex LH-20，得化合物2(13.6 mg)、7(2.0 mg)、9(2.2 mg)、12(4.3 mg)、21(4.2 mg)；Fr.3B经Sephadex LH-20、制备型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物3(3.0 mg，tR=18.2 min)。Fr.4经ODS反相柱，甲醇-水(1∶9～1∶0)洗脱，得Fr.4A～Fr.4D，Fr.4B经Sephadex LH-20、制备型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物34(1.8 mg，tR=19.8 min)、35(4.7 mg，tR=18.9 min)。

取300 g正丁醇萃取部位，采用硅胶柱层析，二氯甲烷-甲醇(1∶0～0∶1)进行洗脱，得到Fr.1～Fr.11。Fr.2经ODS反相柱，甲醇-水(1∶9～1∶0)洗脱，得Fr.2A～Fr.2E，Fr.2B、Fr.2C、Fr.2D经Sephadex LH-20，通过重结晶得化合物28(2.1 mg)、29(2.2 mg)、31(1.2 mg)、33(2.5 mg)。Fr.3经ODS反相柱，甲醇-水(1∶9～1∶0)洗脱，得Fr.3A～Fr.3F，Fr.3B、Fr.3C经Sephadex LH-20，通过重结晶得化合物4(1.0 mg)、5(1.2 mg)、11(3.2 mg)、27(2.3 mg)、30(11.3 mg)；Fr.3B经Sephadex LH-20、制备型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物13(4.0 mg，tR=18.2 min)。Fr.5经ODS反相柱，甲醇-水(1∶9～1∶0)洗脱，得Fr.5A～Fr.5D，Fr.5A、Fr.5C经Sephadex LH-20，通过重结晶得化合物15(2.3 mg)、16(1.2 mg)、24(2.3 mg)；Fr.5B经Sephadex LH-20、制备型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物23(2.0 mg，tR=19.6 min)、22(3.6 mg，tR=17.9 min)。Fr.4、Fr.6、Fr.7经ODS反相柱，甲醇-水(1∶9～1∶0)洗脱，得Fr.4A～Fr.4C、Fr.6A～Fr.6E、Fr.7A～Fr.7D，Fr.6C、Fr.7C经Sephadex LH-20，通过重结晶得化合物18(1.2 mg)、19(2.1 mg)、26(4.8 mg)、32(30.4 mg)；Fr.4A经Sephadex LH-20、制备型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物14(4.3 mg,tR=21.7 min)。

3 结构鉴定

化合物1：无色片状结晶，分子式C10H10O4；HR-ESI-MSm/z：195.065 4 [M+H]+。1H-NMR (CD3OD, 400 MHz)δ: 7.58 (1H, d,J=15.9 Hz, H-8), 7.16 (1H, d,J=1.9 Hz, H-2), 7.04 (1H, dd,J=8.2, 1.9 Hz, H-6), 6.80 (1H, d,J=8.2 Hz, H-5), 6.30 (1H, d,J=15.9 Hz, H-7), 3.87 (3H, s, 3-OCH3);13C-NMR (CD3OD, 100 MHz)δ: 127.8 (C-1), 111.7 (C-2), 149.4 (C-3), 150.5 (C-4), 115.9 (C-5), 124.0 (C-6), 146.9 (C-7), 116.5 (C-8), 171.0 (C-9), 56.5 (3-OCH3)。与文献[7]报道一致，鉴定为阿魏酸。

化合物2：白色结晶，分子式C9H8O4；HR-ESI-MSm/z：181.049 4 [M+H]+。1H-NMR (Pyridine-d5, 400 MHz)δ: 8.10 (1H, d,J=15.9 Hz, H-8), 7.64 (1H, brs, H-2), 7.21 (1H, overlapped, H-6), 7.20 (1H, d,J=7.3 Hz, H-5), 6.82 (1H, d,J=15.9 Hz, H-7);13C-NMR (Pyridine-d5, 100 MHz)δ: 127.4 (C-1), 115.8 (C-2), 145.3 (C-3), 149.6 (C-4), 116.9 (C-5), 121.9 (C-6), 147.8 (C-7), 116.8 (C-8), 169.8 (C-9)。与文献[2]报道一致，鉴定为咖啡酸。

化合物3：白色粉末，分子式C9H8O3；HR-ESI-MSm/z：165.054 7 [M+H]+。1H-NMR (Pyridine-d5, 600 MHz)δ: 8.11 (1H, d,J=15.8 Hz, H-7), 7.63 (1H×2, d,J=8.4 Hz, H-3, 5), 7.18 (1H×2, d,J=8.4 Hz, H-2, 6), 6.84 (1H, d,J=15.8 Hz, H-8);13C-NMR (Pyridine-d5, 150 MHz)δ: 126.5 (C-1), 130.5 (C-2, 6), 117.0 (C-3, 5), 161.2 (C-4), 144.6 (C-7), 116.8 (C-8), 169.6 (C-9)。与文献[8]报道一致，鉴定为对香豆酸。

化合物4：白色结晶，分子式C17H20O10；HR-ESI-MSm/z：385.113 5 [M+H]+。1H-NMR (CD3OD, 400 MHz)δ: 7.89 (1H, d,J=9.5 Hz, H-4), 7.02 (1H, s, H-5), 6.36 (1H, d,J=9.5 Hz, H-3), 5.21 (1H, d,J=7.8 Hz, glc-H-1′), 4.02 (3H, s, 8-OCH3), 3.90 (3H, s, 6-OCH3), 3.77 (1H, dd,J=12.0, 2.3 Hz, glc-H-6a′), 3.63 (1H, dd,J=12.0, 5.4 Hz, glc-H-6b′), 3.51～3.23 (1H×4, m, glc-H-2′, 3′, 4′, 5′);13C-NMR (CD3OD, 100 MHz)δ: 162.6 (C-2), 115.8 (C-3), 144.1 (C-4), 106.2 (C-5), 151.5 (C-6), 143.5 (C-7), 142.4 (C-8), 145.9 (C-9), 116.7 (C-10), 104.2 (glc-C-1′), 75.7 (glc-C-2′), 77.9 (glc-C-3′), 71.4 (glc-C-4′), 78.6 (glc-C-5′), 62.6 (glc-C-6′), 57.1 (6-OCH3), 62.5 (8-OCH3)。与文献[9]报道一致，鉴定为异嗪皮啶-7-O-β-D-吡喃葡萄糖苷。

化合物5：白色固体，分子式C16H18O9；HR-ESI-MSm/z：355.102 9 [M+H]+。1H-NMR (Pyridine-d5, 600 MHz)δ: 7.64 (1H, d,J=9.5 Hz, H-4), 7.52 (1H, s, H-8), 7.03 (1H, s, H-5), 6.34 (1H, d,J=9.5 Hz, H-3), 5.73 (1H, d,J= 7.0 Hz, glc-H-1′), 4.55 (1H, dd,J=12.0, 1.9 Hz, glc-H-6a′), 4.42～4.34 (1H×4, overlapped, glc-H-3′, 4′, 5′, 6b′), 4.19 (1H, m, glc-H-2′), 3.72 (3H, s, 6-OCH3);13C-NMR (Pyridine-d5, 150 MHz)δ: 161.0 (C-2), 114.0 (C-3), 143.5 (C-4), 109.7 (C-5), 146.9 (C-6), 150.2 (C-7), 104.1 (C-8), 151.2 (C-9), 112.8 (C-10), 101.8 (glc-C-1′), 74.6 (glc-C-2′), 78.5 (glc-C-3′), 71.0 (glc-C-4′), 79.1 (glc-C-5′), 62.2 (glc-C-6′), 56.1 (6-OCH3)。与文献[10]报道一致，鉴定为东莨菪苷。

化合物6：白色羽状结晶，分子式C10H8O4；HR-ESI-MSm/z：193.049 3 [M+H]+。1H-NMR (CD3OD, 400 MHz)δ: 7.84 (1H, d,J=9.4 Hz, H-4), 7.10 (1H, s, H-5), 6.76 (1H, s, H-8), 6.19 (1H, d,J=9.4 Hz, H-3), 3.90 (3H, s, 6-OCH3);13C-NMR (CD3OD, 100 MHz)δ: 164.0 (C-2), 112.6 (C-3, 10), 146.1 (C-4), 110.0 (C-5), 147.1 (C-6), 152.9 (C-7), 104.0 (C-8), 151.4 (C-9), 56.8 (6-OCH3)。与文献[11]报道一致，鉴定为莨菪亭。

化合物7：白色粉末，分子式C11H10O5；HR-ESI-MSm/z：223.060 4 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.85 (1H, d,J=9.5 Hz, H-4), 6.90 (1H, s, H-5), 6.23 (1H, d,J=9.5 Hz, H-3), 3.95 (3H, s, 8-OCH3), 3.88 (3H, s, 6-OCH3);13C-NMR (CD3OD, 150 MHz)δ: 163.4 (C-2), 112.9 (C-3), 146.5 (C-4), 105.1 (C-5), 147.4 (C-6), 144.7 (C-7), 136.2 (C-8), 145.7 (C-9), 112.2 (C-10), 56.9 (6-OCH3), 61.6 (8-OCH3)。与文献[12]报道一致，鉴定为异嗪皮啶。

化合物8：白色簇状结晶，分子式C11H8O5；HR-ESI-MSm/z：221.044 7 [M+H]+。1H-NMR (Pyridine-d5, 400 MHz)δ: 7.65 (1H, d,J=9.6 Hz, H-4), 6.75 (1H, s, H-5), 6.34 (1H, d,J=9.6 Hz, H-3), 6.17 (2H, s, H-11), 3.77 (3H, s, 8-OCH3);13C-NMR (Pyridine-d5, 100 MHz)δ: 160.3 (C-2), 114.7 (C-3), 144.7 (C-4), 106.6 (C-5), 141.9 (C-6), 136.5 (C-7), 134.8 (C-8), 140.8 (C-9), 115.4 (C-10), 104.5 (C-11), 57.2 (8-OCH3)。与文献[13]报道一致，鉴定为8-甲氧基-6,7-亚甲二氧基香豆素。

化合物9：白色针状结晶，分子式C12H14O4；HR-ESI-MSm/z：223.096 2 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.60 (1H, d,J=15.9 Hz, H-7), 7.18 (1H, d,J=1.9 Hz, H-2), 7.07 (1H, dd,J=8.2, 1.9 Hz, H-6), 6.80 (1H, d,J=8.2 Hz, H-5), 6.35 (1H, d,J=15.9 Hz, H-8), 4.22 (2H, q,J=7.1 Hz, H-10), 3.89 (3H, s, 3-OCH3), 1.31 (3H, t,J=7.1 Hz, H-11);13C-NMR (CD3OD, 150 MHz)δ: 127.8 (C-1), 115.6 (C-2), 149.4 (C-3), 150.6 (C-4), 116.5 (C-5), 124.0 (C-6), 146.6 (C-7), 111.7 (C-8), 169.3 (C-9), 61.4 (C-10), 14.6 (C-11), 56.4 (3-OCH3)。与文献[14]报道一致，鉴定为阿魏酸乙酯。

化合物10：白色粉末，分子式C12H16O3；HR-ESI-MSm/z：209.117 0 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.90 (1H, s, H-6), 6.61 (1H, dq,J=15.4, 1.5 Hz, H-7), 6.42 (1H, s, H-3), 6.05 (1H, dd,J=15.4, 6.8 Hz, H-8), 3.83 (3H, s, 5-OCH3), 3.80 (3H, s, 2-OCH3), 3.72 (3H, s, 4-OCH3), 1.89 (3H, dd,J=6.8, 1.5 Hz, H-9);13C-NMR (CD3OD, 150 MHz)δ: 120.5 (C-1), 152.5 (C-2), 99.6 (C-3), 150.5 (C-4), 144.7 (C-5), 112.0 (C-6), 126.4 (C-7), 124.6 (C-8), 18.9 (C-9), 56.7 (2-OCH3), 57.0 (4-OCH3), 57.4 (5-OCH3)。与文献[15]报道一致，鉴定为α-细辛醚。

化合物11：白色固体，分子式C16H22O7；HR-ESI-MSm/z：327.146 6 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.07 (1H, d,J=8.2 Hz, H-5), 6.82 (1H, d,J=1.8 Hz, H-2), 6.72 (1H, dd,J=8.2, 1.8 Hz, H-6), 5.94 (1H, ddt,J=17.0, 10.1, 6.6 Hz, H-8), 5.04 (1H, dd,J=17.0, 1.9 Hz, H-9a), 5.01 (1H, dd,J=10.1, 1.9 Hz, H-9b), 4.84 (1H, overlapped, glc-H-1′), 3.86 (1H, dd,J=12.0, 2.4 Hz, glc-H-6a′), 3.84 (3H, s, 3-OCH3), 3.68 (1H, dd,J=12.0, 4.9 Hz, glc-H-6b′), 3.49～3.45 (1H×2, overlapped, glc-H-2′, 3′), 3.39～3.37 (1H×2, overlapped, glc-H-4′, 5′), 3.32 (2H, overlapped, H-7);13C-NMR (CD3OD, 150 MHz)δ: 136.5 (C-1), 114.1 (C-2), 150.8 (C-3), 146.3 (C-4), 122.1 (C-5), 118.3 (C-6), 40.8 (C-7), 139.0 (C-8), 115.8 (C-9), 103.1 (glc-C-1′), 74.9 (glc-C-2′), 77.8 (glc-C-3′), 71.4 (glc-C-4′), 78.2 (glc-C-5′), 62.5 (glc-C-6′), 56.7 (3-OCH3)。与文献[16]报道一致，鉴定为Citrusin C。

化合物12：白色粉末，分子式C17H24O9；HR-ESI-MSm/z：373.148 9 [M+H]+。1H-NMR (Pyridine-d5, 600 MHz)δ: 6.88 (1H×2, s, H-2, 6), 6.88 (1H, d,J=15.8 Hz, H-7), 6.62 (1H, dt,J=15.8, 5.2 Hz, H-8), 5.80 (1H, d,J=6.8 Hz, glc-H-1′), 4.59 (2H, dd,J=5.2, 1.3 Hz, H-9), 4.40 (1H, dd,J=11.6, 2.5 Hz, glc-H-6b′), 4.34～4.31 (1H×4, m, glc-H-2′, 3′, 4′, 6a′), 3.94 (1H, m, glc-H-5′), 3.75 (3H×2, s, 3, 5-OCH3);13C-NMR (Pyridine-d5, 150 MHz)δ: 133.9 (C-1), 105.2 (C-2, 6), 153.8 (C-3, 5), 135.7 (C-4), 131.1 (C-7), 129.3 (C-8), 62.7 (C-9), 104.9 (glc-C-1′), 76.0 (glc-C-2′), 78.7 (glc-C-3′), 71.6 (glc-C-4′), 78.4 (glc-C-5′), 62.6 (glc-C-6′), 56.5 (3, 5-OCH3)。与文献[17]报道一致，鉴定为紫丁香酚苷。

化合物13：白色固体，分子式C17H24O9；HR-ESI-MSm/z：373.149 9 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.32 (1H×2, s, H-2, 6), 5.09 (1H, d,J=7.6 Hz, glc-H-1′), 3.90 (3H×2, s, 3, 5-OCH3), 3.76 (1H, dd,J=11.9, 5.3 Hz, glc-H-6a′), 3.64 (1H, dd,J=12.0, 5.2 Hz, glc-H-6b′), 3.49 (1H, m, glc-H-2′), 3.44～3.38 (1H×2, overlapped, glc-H-4′, 5′), 3.22 (1H, m, glc-H-3′), 3.04 (2H, q,J=7.2 Hz, H-8), 1.17 (3H, t,J=7.2 Hz, H-9);13C-NMR (CD3OD, 150 MHz)δ: 134.2 (C-1), 107.2 (C-2, 6), 154.3 (C-3, 5), 140.4 (C-4), 201.9 (C-7), 32.5 (C-8), 8.7 (C-9), 104.4 (glc-C-1′), 75.7 (glc-C-2′), 78.5 (glc-C-3′), 71.4 (glc-C-4′), 77.9 (glc-C-5′), 62.5 (glc-C-6′), 57.1 (3, 5-OCH3)。与文献[18]报道一致，鉴定为4-(β-D-Glucopyranosyloxy)-3,5-dimethoxy-phenylpropanone。

化合物14：无色油状物，分子式C16H22O9；HR-ESI-MSm/z：359.134 2 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.60 (1H, dd,J=8.3, 1.8 Hz, H-6), 7.55 (1H, d,J=1.8 Hz, H-2), 6.86 (1H, d,J=8.3 Hz, H-5), 4.32 (1H, d,J=7.8 Hz, glc-H-1′), 4.25 (1H, dt,J=12.7, 6.4 Hz, H-9a), 3.99 (1H, dt,J=12.7, 6.4 Hz, H-9b), 3.90 (3H, s, 3-OCH3), 3.85 (1H, overlapped, glc-H-6a′), 3.65 (1H, dd,J=11.9, 5.0 Hz, glc-H-6b′), 3.43～3.26 (2H, overlapped, H-8), 3.43～3.26 (1H×3, overlapped, glc-H-3′, 4′, 5′), 3.15 (1H, m, glc-H-2′);13C-NMR (CD3OD, 150 MHz)δ: 130.5 (C-1), 112.0 (C-2), 153.5 (C-3), 149.1 (C-4), 115.8 (C-5), 124.9 (C-6), 199.4 (C-7), 39.4 (C-8), 66.5 (C-9), 104.7 (glc-C-1′), 75.0 (glc-C-2′), 78.0 (glc-C-3′), 71.6 (glc-C-4′), 78.0 (glc-C-5′), 62.7 (glc-C-6′), 56.4 (3-OCH3)。与文献[19]报道一致，鉴定为β-hydroxypropiovanillone-3-O-β-D-glucopyranside。

化合物15：白色固体，分子式C26H36O11；HR-ESI-MSm/z：525.233 6 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.66 (1H, d,J=3.0 Hz, H-2), 6.64 (1H, d,J=3.0 Hz, H-2′), 6.63 (1H, d,J=1.8 Hz, H-5), 6.61 (1H, d,J=1.8 Hz, H-5′), 6.58 (1H, dd,J=4.5, 1.9 Hz, H-6), 6.56 (1H, dd,J=4.5, 1.9 Hz, H-6′), 4.19 (1H, d,J=7.8 Hz, glc-H-1″), 3.88 (1H, dd,J=8.3, 3.9 Hz, H-9a), 3.86 (1H, dd,J=10.3, 1.3 Hz, glc-H-6a″), 3.74 (3H×2, s, 3, 3′-OCH3), 3.66 (1H, d,J=5.3 Hz, glc-H-6b″), 3.64 (1H, overlapped, H-9a′), 3.56 (1H, dd,J=5.7, 1.5 Hz, H-9b′), 3.54 (1H, d,J=6.0 Hz, H-9b), 3.36～3.25 (1H×3, overlapped, glc-H-3″, 4″, 5″), 3.19 (1H, m, glc-H-2″), 2.70 (1H, dd,J=13.4, 8.0 Hz, H-7a), 2.61 (2H, overlapped, H-7′), 2.59 (1H, dd,J=11.6, 5.0 Hz, H-7b), 2.07 (1H, m, H-8), 2.00 (1H, m, H-8′);13C-NMR (CD3OD, 150 MHz)δ: 134.0 (C-1, 1′), 113.6 (C-2), 148.8 (C-3, 3′), 145.5 (C-4), 115.8 (C-5, 5′), 122.8 (C-6), 35.6 (C-7), 41.6 (C-8), 70.4 (C-9), 113.4 (C-2′), 145.4 (C-4′), 122.7 (C-6′), 35.5 (C-7′), 44.0 (C-8′), 62.8 (C-9′), 104.7 (glc-C-1″), 78.2 (glc-C-2″), 78.0 (glc-C-3″), 71.7 (glc-C-4″), 75.2 (glc-C-5″), 62.8 (glc-C-6″), 56.3 (3, 3′-OCH3)。与文献[20]报道一致，鉴定为裂环异落叶松脂醇-9-O-β-D-吡喃葡萄糖苷。

化合物16：无色无定形固体，分子式C26H36O11；HR-ESI-MSm/z：525.233 6 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.01 (1H, d,J=8.2 Hz, H-1), 6.68 (1H, d,J=1.8 Hz, H-4), 6.65 (1H, d,J=8.0 Hz, H-5′), 6.64 (1H, dd,J=8.2, 1.8 Hz, H-10), 6.59 (1H, d,J=1.8 Hz, H-2′), 6.53 (1H, dd,J=8.0, 1.8 Hz, H-6′), 4.83 (1H, d,J=7.6 Hz, glc-H-1″), 3.75 (3H, s, 4′-OCH3), 3.74 (3H, s, 3′-OCH3), 3.69 (1H×2, m, H-6a′, 7a′), 3.68 (1H, overlapped, glc-H-6a″), 3.59 (1H×2, m, H-6a, 7a), 2.67 (2H, m, H-8), 2.55 (2H, m, H-5), 1.90 (1H×2, m, H-6, 7);13C-NMR (CD3OD, 150 MHz)δ: 117.7 (C-1), 146.1 (C-2), 145.5 (C-3), 114.2 (C-4), 36.1 (C-5), 44.2 (C-6), 62.1 (C-6a), 44.0 (C-7), 62.0 (C-7a), 36.0 (C-8), 137.4 (C-9), 122.8 (C-10), 133.8 (C-1′), 113.4 (C-2′), 150.4 (C-3′), 148.8 (C-4′), 115.8 (C-5′), 122.7 (C-6′), 103.0 (glc-C-1″), 74.9 (glc-C-2″), 77.8 (glc-C-3″), 71.4 (glc-C-4″), 78.1 (glc-C-5″), 62.5 (glc-C-6″), 56.5 (3′-OCH3), 56.3 (4′-OCH3)。与文献[21]报道一致，鉴定为Sargentodoside D。

化合物17：白色粉末，分子式C20H20O6；HR-ESI-MSm/z：379.115 0[M+Na]+。1H-NMR (CD3OD, 600 MHz)δ: 7.60 (1H, d,J=2.0 Hz, H-6), 7.28 (1H, dd,J=8.4, 2.0 Hz, H-6′), 7.07 (1H, d,J=2.0 Hz, H-2′), 7.04 (1H, d,J=8.4 Hz, H-5′), 6.89 (1H, d,J=8.2 Hz, H-5″), 6.75 (1H, dd,J=8.2, 1.9 Hz, H-6″), 6.68 (1H, d,J=1.9 Hz, H-2″), 4.35 (1H, dd,J=8.9, 7.0 Hz, H-4a), 4.32 (1H, dd,J=8.9, 1.9 Hz, H-4b), 3.91 (3H, s, 3′-OCH3), 3.83 (3H, s, 3″-OCH3), 3.87 (1H, m, H-3), 3.03 (1H, dd,J=14.2, 4.4 Hz, H-5a), 2.71 (1H, dd,J=14.2, 9.1 Hz, H-5b);13C-NMR (CD3OD, 150 MHz)δ: 175.4 (C-1), 126.5 (C-2), 40.5 (C-3), 71.6 (C-4), 38.0 (C-5), 139.0 (C-6), 127.2 (C-1′), 114.5 (C-2′), 149.3 (C-3′), 150.4 (C-4′), 116.8 (C-5′), 126.0 (C-6′), 130.9 (C-1″), 113.9 (C-2″), 149.0 (C-3″), 146.5 (C-4″), 116.4 (C-5″), 122.7 (C-6″), 56.6 (3′-OCH3), 56.4 (3″-OCH3)。与文献[22]报道一致，鉴定为acutissimalignan B。

化合物18：白色固体，分子式C20H22O6；HR-ESI-MSm/z：359.149 5 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.70 (1H, d,J=8.0 Hz, H-5′), 6.68 (1H, d,J=8.0 Hz, H-5), 6.66 (1H, d,J=1.6 Hz, H-2′), 6.55 (1H, d,J=1.4 Hz, H-2), 6.58 (1H, dd,J=8.0, 1.6 Hz, H-6′), 6.51 (1H, dd,J=8.0, 1.4 Hz, H-6), 4.14 (1H, dd,J=8.5, 7.5 Hz, H-9a), 3.90 (1H, dd,J=8.5, 7.5 Hz, H-9b), 3.78 (3H, s, 3-OCH3), 3.77 (3H, s, 3′-OCH3), 2.88 (1H, dd,J=14.0, 5.4 Hz, H-7a′), 2.81 (1H, dd,J=14.0, 7.1 Hz, H-7b′), 2.64 (1H, m, H-8′), 2.52 (2H, m, H-7), 2.47 (1H, m, H-8);13C-NMR (CD3OD, 150 MHz)δ: 130.8 (C-1), 113.3 (C-2), 149.0 (C-3), 146.2 (C-4), 116.2 (C-5), 122.2 (C-6), 38.9 (C-7), 42.5 (C-8), 72.9 (C-9), 131.4 (C-1′), 113.9 (C-2′), 149.0 (C-3′), 146.4 (C-4′), 116.1 (C-5′), 123.0 (C-6′), 35.4 (C-7′), 47.7 (C-8′), 181.6 (C-9′), 56.3 (3, 3′-OCH3)。与文献[23]报道一致，鉴定为罗汉松脂素。

化合物19：白色固体，分子式C20H26O9；HR-ESI-MSm/z：411.165 5 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.05 (1H, d,J=1.8 Hz, H-2′), 7.01 (1H, d,J=1.0 Hz, H-2), 7.00 (1H, d,J=8.3 Hz, H-5′), 6.87 (1H, dd,J=8.3, 1.8 Hz, H-6′), 6.86 (1H, dd,J=8.0, 1.0 Hz, H-6), 6.73 (1H, d,J=8.0 Hz, H-5), 4.88 (1H, d,J=7.4 Hz, H-7), 4.56 (1H, d,J=5.9 Hz, H-7′), 4.26 (1H, d,J=4.4 Hz, H-8), 3.87 (3H, s, 3-OCH3), 3.81 (3H, s, 3′-OCH3), 3.78 (1H, dd,J=12.0, 4.4 Hz, H-9a), 3.65 (1H, m, H-8′), 3.50 (1H, dd,J=11.8, 2.0 Hz, H-9a′), 3.42 (1H, dd,J=12.0, 6.0 Hz, H-9b), 3.35 (1H, dd,J=11.8, 5.0 Hz, H-9b′);13C-NMR (CD3OD, 150 MHz)δ: 133.8 (C-1), 111.7 (C-2), 148.9 (C-3), 147.2 (C-4), 115.8 (C-5), 120.7 (C-6), 74.0 (C-7), 77.5 (C-8), 61.9 (C-9), 137.9 (C-1′), 112.2 (C-2′), 151.5 (C-3′), 148.8 (C-4′), 118.6 (C-5′), 120.6 (C-6′), 75.1 (C-7′), 87.2 (C-8′), 64.2 (C-9′), 56.5 (3-OCH3), 56.4 (3′-OCH3)。与文献[24]报道一致，鉴定为1-(4-hydroxy-3-methoxy)-phenyl-2-[4-(1,2,3-trihydroxypropyl)-2-methoxy]-phenoxy-1,3-propandiol。

化合物20：白色无定形粉末，分子式C18H16O8；HR-ESI-MSm/z：361.091 2 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.52 (1H, d,J=15.7 Hz, H-7), 7.02 (1H, d,J=2.1 Hz, H-2′), 6.91 (1H, dd,J=8.2, 2.0 Hz, H-6), 6.74 (1H, d,J=8.2 Hz, H-5), 6.72 (1H, d,J=2.0 Hz, H-2), 6.66 (1H, d,J=8.0 Hz, H-5′), 6.60 (1H, dd,J=8.0, 2.1 Hz, H-6′), 6.24 (1H, d,J=15.7 Hz, H-8), 5.15 (1H, dd,J=8.3, 4.2 Hz, H-8′), 3.07 (1H, dd,J=14.5, 4.2 Hz, H-7a′), 2.98 (1H, dd,J=14.5, 8.3 Hz, H-7b′);13C-NMR (CD3OD, 150 MHz)δ: 127.7 (C-1), 114.4 (C-2), 146.8 (C-3), 149.8 (C-4), 116.5 (C-5), 123.1 (C-6), 147.7 (C-7), 115.2 (C-8), 168.4 (C-9), 129.3 (C-1′), 117.6 (C-2′), 146.2 (C-3′), 145.3 (C-4′), 116.3 (C-5′), 121.8 (C-6′), 37.9 (C-7′), 74.6 (C-8′), 173.4 (C-9′)。与文献[12]报道一致，鉴定为迷迭香酸。

化合物21：白色结晶，分子式C20H20O7；HR-ESI-MSm/z：373.138 0 [M+H]+。1H-NMR (Pyridine-d5, 600 MHz)δ: 7.48 (1H, brs, H-6′), 7.32 (1H, br.s, H-6), 7.29 (1H, brs, H-2′), 7.23 (1H×2, brs, H-2, 4), 6.89 (1H, d,J=15.8 Hz, H-8′), 6.14 (1H, d,J=6.9 Hz, H-7), 5.12 (1H, d,J=15.8 Hz, H-7′), 4.26 (2H, m, H-9), 3.99 (1H, m, H-8), 3.84 (3H, s, 3′-OCH3), 3.66 (3H, s, 3-OCH3);13C-NMR (Pyridine-d5, 150 MHz)δ: 133.1 (C-1), 119.8 (C-2), 148.4 (C-3), 116.6 (C-4), 148.8 (C-5), 110.8 (C-6), 89.3 (C-7), 54.3 (C-8), 63.9 (C-9), 129.1 (C-1′), 113.0 (C-2′), 145.0 (C-3′), 151.3 (C-4′), 131.0 (C-5′), 118.3 (C-6′), 144.9 (C-7′), 117.7 (C-8′), 169.6 (C-9′), 55.8 (3-OCH3), 56.1 (3′-OCH3)。与文献[25]报道一致，鉴定为升麻酸。

化合物22：白色粉末，分子式C26H32O11；HR-ESI-MSm/z：521.202 3 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.14 (1H, d,J=8.3 Hz, H-5), 7.02 (1H, d,J=1.7 Hz, H-2), 6.95 (1H×2, d,J=2.0 Hz, H-2′, 6′), 6.93 (1H, dd,J=8.3, 1.7 Hz, H-6), 6.53 (1H, d,J=15.8 Hz, H-7′), 6.22 (1H, dt,J=15.8, 5.9 Hz, H-8′), 5.58 (1H, d,J=5.9 Hz, H-7), 4.88 (1H, d,J=7.6 Hz, glc-H-1″), 4.19 (2H, brd,J=5.1 Hz, H-9′),3.88 (3H, s, 3-OCH3), 3.82 (3H, s, 3′-OCH3), 3.78 (1H, m, H-9b), 3.86～3.84 (1H, overlapped, H-9a), 3.86～3.84 (1H, overlapped, glc-H-6a″), 3.67 (1H, m, glc-H-6b″), 3.50～3.38 (1H, overlapped, H-8), 3.50～3.38 (1H×4, overlapped, glc-H-2″, 3″, 4″, 5″);13C-NMR (CD3OD, 150 MHz)δ: 138.1 (C-1), 111.2 (C-2), 151.0 (C-3), 147.7 (C-4), 118.0 (C-5), 119.4 (C-6), 88.8 (C-7), 55.4 (C-8), 64.9 (C-9), 132.7 (C-1′), 112.1 (C-2′), 145.5 (C-3′), 149.2 (C-4′), 130.0 (C-5′), 116.5 (C-6′), 131.9 (C-7′), 127.6 (C-8′), 63.8 (C-9′), 102.7 (glc-C-1″), 74.9 (glc-C-2″), 78.2 (glc-C-3″), 71.3 (glc-C-4″), 77.8 (glc-C-5″), 62.5 (glc-C-6″), 56.8 (3-OCH3), 56.7 (3′-OCH3)。与文献[26]报道一致，鉴定为Dehydrodiconiferyl alcohol-4-O-β-D-glucopyranoside。

化合物23：浅黄色无定形粉末，分子式C26H32O11；HR-ESI-MSm/z：521.202 3 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.97 (1H, brs, H-6′), 6.95 (1H, d,J=1.9 Hz, H-2), 6.94 (1H, brs, H-2′), 6.82 (1H, dd,J=8.2, 1.9 Hz, H-6), 6.76 (1H, d,J=8.2 Hz, H-5), 6.57 (1H, d,J=15.7 Hz, H-7′), 6.23 (1H, dt,J=15.7, 5.5 Hz, H-8′), 5.52 (1H, d,J=6.2 Hz, H-7), 4.49 (1H, dd,J=12.7, 5.5 Hz, H-9a′), 4.36 (1H, d,J=7.8 Hz, glc-H-1″), 4.30 (1H, dd,J=12.7, 6.8 Hz, H-9b′), 3.89～3.21 (2H, overlapped, H-9), 3.89～3.21 (1H, overlapped, H-8), 3.89～3.21 (1H×6, overlapped, glc-H-2″, 3″, 4″, 5″, 6a″, 6b″), 3.87 (3H, s, 3′-OCH3), 3.81 (3H, s, 3-OCH3);13C-NMR (CD3OD, 150 MHz)δ: 134.5 (C-1), 110.6 (C-2), 149.1 (C-3), 147.6 (C-4), 116.2 (C-5), 119.8 (C-6), 89.4 (C-7), 55.2 (C-8), 64.9 (C-9), 132.3 (C-1′), 112.2 (C-2′), 145.5 (C-3′), 149.4 (C-4′), 130.4 (C-5′), 116.7 (C-6′), 134.2 (C-7′), 124.2 (C-8′), 71.0 (C-9′), 103.2 (glc-C-1″), 75.2 (glc-C-2″), 78.0 (glc-C-3″), 71.7 (glc-C-4″), 78.2 (glc-C-5″), 62.8 (glc-C-6″), 56.8 (3-OCH3), 56.4 (3′-OCH3)。与文献[27]报道一致，而且该化合物的CD光谱在284 nm (△ε+3.01) 处显示正Cotton效应，故鉴定为(7S,8R)-dehydrodiconiferyl-alcohol 9′-O-β-glucopyranoside。

化合物24：白色固体，分子式C27H34O12；HR-ESI-MSm/z：551.212 8[M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.96 (1H×2, d,J=2.8 Hz, H-2′, 6′), 6.73 (1H×2, s, H-2, 6), 6.54 (1H, d,J=15.8 Hz, H-7′), 6.23 (1H, dt,J=15.8, 5.9 Hz, H-8′), 5.59 (1H, d,J=5.8 Hz, H-7), 4.87 (1H, overlapped, glc-H-1″), 4.19 (2H, dd,J=5.9, 1.0 Hz, H-9′), 3.90 (3H, s, 3′-OCH3), 3.88 (1H, overlapped, H-9a), 3.82 (3H×2, s, 3, 5-OCH3), 3.79 (1H, overlapped, H-9b), 3.77 (1H, m, glc-H-6a″), 3.65 (1H, dt,J=11.9, 5.0 Hz, glc-H-6b″), 3.48～3.39 (1H, overlapped, H-8), 3.48～3.39 (1H×3, overlapped, glc-H-2″, 3″, 4″), 3.19 (1H, m, glc-H-5″);13C-NMR (CD3OD, 150 MHz)δ: 135.8 (C-1), 104.5 (C-2, 6), 154.4 (C-3, 5), 140.0 (C-4), 88.8 (C-7), 55.5 (C-8), 65.0 (C-9), 132.8 (C-1′), 112.2 (C-2′), 145.6 (C-3′), 149.1 (C-4′), 129.9 (C-5′), 116.5 (C-6′), 131.9 (C-7′), 127.7 (C-8′), 63.8 (C-9′), 105.2 (glc-C-1″), 75.7 (glc-C-2″), 78.3 (glc-C-3″), 71.3 (glc-C-4″), 77.8 (glc-C-5″), 62.6 (glc-C-6″), 57.0 (3, 5-OCH3), 56.8 (3′-OCH3)。与文献[28]报道一致，而且该化合物的CD光谱在272 nm (△ε+3.3) 、225 nm (△ε-2.02) 处显示Cotton效应，鉴定为(7S,8R)-5-methoxydehydrodiconiferyl alcohol 4-O-β-D-glucopyanoside。

化合物25：白色粉末，分子式C21H18O6；HR-ESI-MSm/z：389.098 9[M+Na]+。1H-NMR (Pyridine-d5, 400 MHz)δ: 6.98 (1H, d,J=2.0 Hz, H-5′), 6.80 (1H, overlapped, H-6), 6.77 (1H, d,J=8.1 Hz, H-7), 6.70 (1H, d,J=8.2 Hz, H-2′), 6.58 (1H, dd,J=8.2, 2.0 Hz, H-4′), 5.90 (1H, d,J=1.4 Hz, H-14a), 5.88 (1H, d,J=1.4 Hz, H-14b), 5.04 (1H, brs, H-4), 4.89 (1H, brd,J=17.0 Hz, H-3a), 4.80 (1H, dd,J=17.0, 2.0 Hz, H-3b), 3.89 (1H, dd,J=22.0, 3.5 Hz, H-13b), 3.84 (3H, s, 5′-OCH3), 3.81 (3H, s, 2′-OCH3), 3.67 (1H, dd,J=22.0, 2.7 Hz, H-13a);13C-NMR (Pyridine-d5, 100 MHz)δ: 172.4 (C-1), 71.4 (C-3), 37.7 (C-4), 120.4 (C-5), 107.8 (C-6), 148.9 (C-7), 159.5 (C-8), 121.8 (C-9), 127.3 (C-10), 134.9 (C-11), 113.5 (C-12), 146.1 (C-13), 125.9 (C-14), 112.5 (C-1′), 120.4 (C-2′), 120.5 (C-3′), 146.6 (C-4′), 28.4 (C-5′), 101.7 (C-6′), 55.8 (2′, 5′-OCH3)。与文献[29]报道一致，鉴定为8-(3′,6′-二甲氧基)-4,5-环己二烯-(Δ11,12-二氧亚甲基)-稠二氢异香豆素。

化合物26：无色针晶，分子式C34H46O18；HR-ESI-MSm/z：743.276 2[M+H]+。1H-NMR (Pyridine-d5, 400 MHz)δ: 6.93 (1H×4, s, H-2, 2′, 6, 6′), 5.81 (1H×2, d,J=7.0 Hz, glc-H-1″, 1‴), 4.94 (1H×2, d,J=3.6 Hz, H-7, 7′), 4.40～4.28 (1H×2, overlapped, H-9a, 9a′), 4.04 (1H×2, m, H-9b, 9b′), 3.78 (3H×4, s, 3, 3′, 5, 5′-OCH3), 3.14 (1H×2, m, H-8, 8′);13C-NMR (Pyridine-d5, 100 MHz)δ: 135.5 (C-1, 1′), 105.3 (C-2, 2′), 154.4 (C-3, 3′), 138.7 (C-4, 4′), 154.4 (C-5, 5′), 105.3 (C-6, 6′), 86.6 (C-7, 7′), 55.2 (C-8, 8′), 72.7 (C-9, 9′), 105.4 (glc-C-1″, 1‴), 76.5 (glc-C-2″, 2‴), 78.8 (glc-C-3″, 3‴), 72.1 (glc-C-4″, 4‴), 79.2 (glc-C-5″, 5‴), 63.1 (glc-C-6″, 6‴), 57.2 (3, 3′, 5, 5′-OCH3)。与文献[30]报道一致，鉴定为鹅掌楸碱。

化合物27：白色固体，分子式C28H36O13；HR-ESI-MSm/z：581.223 4 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.74 (1H×2, s, H-2, 6), 6.67 (1H×2, s, H-2′, 6′), 4.88 (1H, overlapped, glc-H-1″), 4.79 (1H, d,J=3.4 Hz, H-7), 4.74 (1H, d,J=4.0 Hz, H-7′), 4.29 (1H×2, m, H-9a, 9a′), 3.93 (1H×2, m, H-9b, 9b′), 3.88 (3H×2, s, 3, 5-OCH3), 3.86 (3H×2, s, 3′, 5′-OCH3), 3.79 (1H, dd,J=12.0, 2.3 Hz, glc-H-6a″), 3.68 (1H, dd,J=12.0, 5.2 Hz, glc-H-6b″), 3.50 (1H, m, glc-H-2″), 3.21 (1H, m, glc-H-3″), 3.45～3.41 (1H×2, overlapped, glc-H-4″, 5″), 3.15 (1H×2, m, H-8, 8′);13C-NMR (CD3OD, 150 MHz)δ: 139.5 (C-1), 104.5 (C-2, 6), 154.4 (C-3, 5), 135.6 (C-4), 87.2 (C-7), 55.7 (C-8), 72.9 (C-9), 133.1 (C-1′), 104.8 (C-2′, 6′), 149.4 (C-3′, 5′), 136.2 (C-4′), 87.6 (C-7′), 55.5 (C-8′), 73.0 (C-9′), 105.3 (glc-C-1″), 75.7 (glc-C-2″), 78.3 (glc-C-3″), 71.3 (glc-C-4″), 77.8 (glc-C-5″), 62.6 (glc-C-6″), 57.1 (3, 5-OCH3), 56.8 (3′, 5′-OCH3)。与文献[31]报道一致，鉴定为(+)丁香脂素-4-O-β-D-吡喃葡萄糖苷。

化合物28：白色固体，分子式C22H26O8；HR-ESI-MSm/z：419.170 6 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.65 (1H×4, s, H-2, 6, 2′, 6′), 4.71 (1H×2, d,J=4.3 Hz, H-7, 7′), 4.26 (1H×2, dd,J=9.1, 6.8 Hz, H-9a, 9a′), 3.88 (1H×2, dd,J=9.1, 3.5 Hz, H-9b, 9b′), 3.84 (3H×4, s, 3, 3′, 5, 5′-OCH3), 3.13 (1H×2, dd,J=6.8, 4.3 Hz, H-8, 8′);13C-NMR (CD3OD, 150 MHz)δ: 133.1 (C-1, 1′), 104.5 (C-2, 6, 2′, 6′), 149.3 (C-3, 5, 3′, 5′), 136.2 (C-4, 4′), 87.6 (C-7, 7′), 55.5 (C-8, 8′), 72.8 (C-9, 9′), 56.8 (3, 3′, 5, 5′-OCH3)。与文献[20]报道一致，鉴定为(+)丁香脂素。

化合物29：白色固体，分子式C21H24O7；HR-ESI-MSm/z：389.160 0 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.95 (1H, d,J=1.8 Hz, H-2), 6.81 (1H, dd,J=8.2, 1.8 Hz, H-6), 6.76 (1H, d,J=8.2 Hz, H-5), 6.65 (1H×2, s, H-2′, 6′), 4.71 (1H×2, d,J=4.3 Hz, H-7, 7′), 4.25 (1H×2, m, H-9a, 9a′), 3.86 (1H×2, overlapped, H-9b, 9b′), 3.85 (3H, s, 3-OCH3), 3.84 (3H×2, s, 3′, 5′-OCH3), 3.14 (1H×2, m, H-8, 8′);13C-NMR (CD3OD, 150 MHz)δ: 133.8 (C-1), 111.0 (C-2), 149.1 (C-3), 147.3 (C-4), 116.1 (C-5), 120.1 (C-6), 87.5 (C-7), 55.3 (C-8), 72.6 (C-9), 133.1 (C-1′), 104.5 (C-2′, 6′), 149.4 (C-3′, 5′), 136.2 (C-4′), 87.7 (C-7′), 55.6 (C-8′), 72.7 (C-9′), 56.4 (3-OCH3), 56.8 (3′, 5′-OCH3)。与文献[32]报道一致，鉴定为medioresinol。

化合物30：白色固体，分子式C26H32O11；HR-ESI-MSm/z：521.202 3[M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.13 (1H, d,J=8.3 Hz, H-5), 7.01 (1H, d,J=1.6 Hz, H-2), 6.93 (1H, d,J=1.7 Hz, H-2′), 6.90 (1H, dd,J=8.3, 1.6 Hz, H-6), 6.80 (1H, dd,J=8.1, 1.7 Hz, H-6′), 6.76 (1H, d,J=8.1 Hz, H-5′), 4.87 (1H, d,J=7.4 Hz, glc-H-1″), 4.74 (1H, d,J=4.0 Hz, H-7), 4.69 (1H, d,J=4.4 Hz, H-7′), 4.22 (1H×2, m, H-9a, 9a′), 3.85 (1H×2, overlapped, H-9b, 9b′), 3.85 (3H, s, 3-OCH3), 3.84 (3H, s, 3′-OCH3), 3.69～3.39 (1H×5, overlapped, glc-H-2″, 3″, 4″, 5″, 6″), 3.10 (1H×2, m, H-8, 8′);13C-NMR (CD3OD, 150 MHz)δ: 137.4 (C-1), 111.6 (C-2), 150.9 (C-3), 147.3 (C-4), 118.0 (C-5), 119.8 (C-6), 87.0 (C-7), 55.3 (C-8), 72.6 (C-9), 133.7 (C-1′), 111.0 (C-2′), 147.4 (C-3′), 149.1 (C-4′), 116.1 (C-5′), 120.0 (C-6′), 87.4 (C-7′), 55.5 (C-8′), 72.7 (C-9′), 102.8 (glc-C-1″), 74.9 (glc-C-2″), 77.8 (glc-C-3″), 71.3 (glc-C-4″), 78.2 (glc-C-5″), 62.5 (glc-C-6″), 56.4 (3-OCH3), 56.7 (3′-OCH3)。与文献[33]报道一致，鉴定为松脂酚-4-O-β-D-吡喃葡萄糖苷。

化合物31：白色固体，分子式C20H22O6；HR-ESI-MSm/z：359.149 5 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.94 (1H×2, d,J=1.6 Hz, H-2, 2′), 6.80 (1H×2, dd,J=8.2, 1.6 Hz, H-6, 6′), 6.76 (1H×2, d,J=8.2 Hz, H-5, 5′), 4.69 (1H×2, d,J=4.1 Hz, H-7, 7′), 4.21 (1H×2, dd,J=8.9, 6.7 Hz, H-9a, 9a′), 3.84 (3H×2, s, 3, 3′-OCH3), 3.82 (1H×2, dd,J=8.9, 3.2 Hz, H-9b, 9b′), 3.13 (1H×2, m, H-8, 8′);13C-NMR (CD3OD, 150 MHz)δ: 133.8 (C-1, 1′), 111.0 (C-2, 2′), 149.1 (C-3, 3′), 147.3 (C-4, 4′), 116.1 (C-5, 5′), 120.0 (C-6, 6′), 87.5 (C-7, 7′), 55.3 (C-8, 8′), 72.6 (C-9, 9′), 56.4 (3, 3′-OCH3)。与文献[31]报道一致，鉴定为(+)-松脂酚。

化合物32：白色固体，分子式C32H42O16；HR-ESI-MSm/z：683.255 1 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 7.14 (1H×2, d,J=8.3 Hz, H-5, 5′), 7.02 (1H×2, d,J=1.7 Hz, H-2, 2′), 6.91 (1H×2, dd,J=8.3, 1.7 Hz, H-6, 6′), 4.87 (1H×2, d,J=7.4 Hz, glc-H-1″, 1‴), 4.74 (1H×2, d,J=3.8 Hz, H-7, 7′), 4.24 (1H×2, dd,J=8.9, 6.8 Hz, H-9a, 9a′), 3.88 (1H×2, overlapped, H-9b, 9b′), 3.87 (3H×2, s, 3, 3′-OCH3), 3.85 (1H×2, overlapped, glc-H-6a″, 6a‴), 3.68 (1H×2, dd,J=11.0, 3.7 Hz, glc-H-6b″, 6b‴), 3.50～3.38 (1H×8, overlapped, glc-H-2″, 2‴, 3″, 3‴, 4″, 4‴, 5″, 5‴), 3.11 (1H×2, m, H-8, 8′);13C-NMR (CD3OD, 150 MHz)δ: 137.4 (C-1, 1′), 111.6 (C-2, 2′), 151.0 (C-3, 3′), 147.5 (C-4, 4′), 118.0 (C-5, 5′), 119.8 (C-6, 6′), 87.0 (C-7, 7′), 55.5 (C-8, 8′), 72.8 (C-9, 9′), 102.8 (glc-C-1″, 1‴), 74.9 (glc-C-2″, 2‴), 77.8 (glc-C-3″, 3‴), 71.3 (glc-C-4″, 4‴), 78.2 (glc-C-5″, 5‴), 62.5 (glc-C-6″, 6‴), 56.8 (3, 3′-OCH3)。与文献[34]报道一致，鉴定为(+)-松脂酚-4, 4′-O-二吡喃葡萄糖苷。

化合物33：白色固体，分子式C20H20O7；HR-ESI-MSm/z：373.128 7 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.96 (1H, d,J=1.8 Hz, H-2′), 6.93 (1H, d,J=1.4 Hz, H-2), 6.83 (1H, dd,J=8.1, 1.8 Hz, H-6′), 6.82 (1H, dd,J=8.0, 1.4 Hz, H-6), 6.80 (1H, d,J=8.0 Hz, H-5), 6.78 (1H, d,J=8.1 Hz, H-5′), 5.38 (1H, d,J=3.9 Hz, H-7), 5.22 (1H, d,J=3.8 Hz, H-7′), 4.28 (1H, dd,J=9.4, 7.0 Hz, H-9a), 4.01 (1H, dd,J=9.4, 4.4 Hz, H-9b), 3.86 (3H, s, 3′-OCH3), 3.85 (3H, s, 3-OCH3), 3.65 (1H, dd,J=9.4, 3.8 Hz, H-8′), 3.30 (1H, overlapped, H-8);13C-NMR (CD3OD, 150 MHz)δ: 132.4 (C-1), 110.7 (C-2), 149.3 (C-3), 148.2 (C-4), 116.2 (C-5), 119.8 (C-6), 87.2 (C-7), 51.0 (C-8), 73.8 (C-9), 133.2 (C-1′), 110.6 (C-2′), 149.1 (C-3′), 147.4 (C-4′), 116.4 (C-5′), 119.5 (C-6′), 85.0 (C-7′), 54.4 (C-8′), 179.7 (C-9′), 56.5 (3-OCH3), 56.4 (3′-OCH3)。与文献[35]报道一致，鉴定为tetrahydro-4,6-bis(4-hydroxy-3-methoxyphenyl)-1H,3H-furo[3,4-c]-furan-1-one。

化合物34：白色粉末，分子式C21H22O7；HR-ESI-MSm/z:387.150 2 [M+H]+。1H-NMR (Pyridine-d5, 600 MHz)δ: 7.34 (1H, d,J=1.9 Hz, H-6′), 7.17 (1H×2, s, H-2, 6), 7.06 (1H, brd,J=14.5 Hz, H-7′), 6.78 (1H, d,J=1.9 Hz, H-2′), 6.68 (1H, dt,J=14.5, 5.3 Hz, H-8′), 5.29 (2H, s, H-9), 4.43 (2H, dd,J=5.3, 1.2 Hz, H-9′), 3.94 (3H, s, 3′-OCH3), 3.85 (3H×2, s, 3, 5-OCH3);13C-NMR (Pyridine-d5, 150 MHz)δ: 121.0 (C-1), 106.0 (C-2, 6), 149.4 (C-3, 5), 139.0 (C-4), 155.2 (C-7), 115.9 (C-8), 54.8 (C-9), 134.0 (C-1′), 105.4 (C-2′), 145.7 (C-3′), 143.0 (C-4′), 134.0 (C-5′), 110.8 (C-6′), 132.7 (C-7′), 130.2 (C-8′), 63.0 (C-9′), 56.3 (3, 5-OCH3), 55.8 (3′-OCH3)。与文献[36]报道一致，鉴定为herpetol B。

化合物35：黄色油状物，分子式C32H38O11；HR-ESI-MSm/z:599.245 6 [M+H]+。1H-NMR (CD3OD, 600 MHz)δ: 6.97 (1H×2, brs, H-2′, 6′), 6.96 (1H, brs, H-2″), 6.77 (1H, d,J=8.1 Hz, H-5″), 6.72 (1H, dd,J=8.1, 1.0 Hz, H-6″), 6.67 (1H×2, brs, H-2, 6), 6.57 (1H, brd,J=15.8 Hz, H-7′), 6.18 (1H, dd,J=15.8, 5.9 Hz, H-8′), 5.58 (1H, dd,J=5.9, 3.8 Hz, H-7), 4.89 (1H, d,J=5.2 Hz, H-7″), 4.25 (1H, m, H-8″), 4.05 (2H, d,J=6.2 Hz, H-9′), 3.90 (1H, overlapped, H-9a″), 3.87 (1H, m, H-9a), 3.85 (1H, m, H-9b), 3.81 (3H, s, 3″-OCH3), 3.80 (3H, s, 3′-OCH3), 3.79 (3H×2, s, 3, 5-OCH3), 3.58 (1H, dd,J=12.0, 3.3 Hz, H-9b″), 3.48 (1H, m, H-8), 3.36 (3H, s, 9′-OCH3);13C-NMR (CD3OD, 150 MHz)δ: 136.4 (C-1), 103.9 (C-2, 6), 154.6 (C-3, 5), 134.2 (C-4), 88.9 (C-7), 55.4 (C-8), 64.9 (C-9), 132.5 (C-1′), 111.4 (C-2′), 145.6 (C-3′), 149.4 (C-4′), 130.0 (C-5′), 116.7 (C-6′), 132.5 (C-7′), 124.4 (C-8′), 74.3 (C-9′), 133.8 (C-1″), 112.3 (C-2″), 148.6 (C-3″), 146.8 (C-4″), 115.7 (C-5″), 120.7 (C-6″), 74.1 (C-7″), 87.3 (C-8″), 61.7 (C-9″), 56.6 (3, 5-OCH3), 56.4 (3′-OCH3), 56.8 (3″-OCH3), 58.0 (9′-OCH3)。与文献[37]报道一致，鉴定为pinnatifidanin A。

4 抗细胞增殖活性研究

采用Cell Counting Kit-8试剂盒评估MGC-803细胞的生存能力。将细胞置于DMEM培养基中，在5%CO2下培养，以1.5×105/孔密度接种在96孔板中培养4 h，加入不同浓度化合物1～35孵育24 h，避光下将10 μL CCK-8溶液(5 mg/mL)加到每孔中，再孵育1 h，采用酶标仪检测490 nm波长处吸光度，通过SPSS 17.0中的Probit程序计算细胞毒性。结果见表1。

由此可知，化合物21、23、27、29对MGC-803细胞增殖有显著抑制作用，化合物19、24、28、32有中等抑制作用，化合物2～3、6、9、11、16、26抑制作用较弱。

表1 各化合物对MGC-803细胞的细胞毒性

5 结论

本实验对北柴胡地上部分化学成分进行研究，共得到35种苯丙素，其中化合物8～9、11、13～16、18～19、21、23～24、32～35为首次从伞形科植物中分离得到，化合物4、7、10、12、20、27为首次从柴胡属植物中分离得到，化合物1、3、6、22、29、31为首次从该植物中分离得到。化合物21、23、27、29对MGC-803胃癌细胞增殖有显著抑制作用，化合物19、24、28、32对MGC-803细胞增殖有中等抑制作用。