北柴胡地上部分苯丙素及其抗細(xì)胞增殖活性

2022-12-02 14:39:12肖宗雨匡海學(xué)楊炳友

中成藥 2022年7期

劉艷，劉培，黃金，肖宗雨，潘娟，管偉，匡海學(xué)，楊炳友

(黑龍江中醫(yī)藥大學(xué)，教育部北藥基礎(chǔ)與應(yīng)用研究重點(diǎn)實(shí)驗(yàn)室，黑龍江哈爾濱 150040)

北柴胡為傘形科柴胡屬植物柴胡BupleurumchineseDC.的干燥地上部分，具有疏肝解郁、疏散退熱、升舉陽(yáng)氣的功效[1-2]，常用于治療寒熱往來(lái)、胸脅脹痛、月經(jīng)不調(diào)等癥。柴胡具有解熱鎮(zhèn)痛、鎮(zhèn)靜抗炎、保肝利膽等藥理作用，是治療少陽(yáng)證首選要藥[3-4]，而北柴胡與該植物具有相似藥理活性[5]，但目前對(duì)其地上部分的化學(xué)成分報(bào)道較少。課題組前期從北柴胡中分離鑒定出黃酮、生物堿等成分，發(fā)現(xiàn)一部分對(duì)癌細(xì)胞有抗增殖作用[6]；本實(shí)驗(yàn)對(duì)其地上部分化學(xué)成分作進(jìn)一步研究，共分離鑒定出35種苯丙素，并對(duì)其進(jìn)行抗細(xì)胞增殖活性研究。

1 材料

Bruker-400/600超導(dǎo)核磁共振光譜儀(美國(guó)布魯克公司)；Waters Q-TOF高分辨質(zhì)譜儀、Waters 2695-2996型分析HPLC色譜儀、Waters x-Bridge C18色譜柱(4.6 mm×150 mm，5 μm)(美國(guó)Waters公司)；LC-20AR型制備HPLC色譜儀(日本島津公司)；旋轉(zhuǎn)蒸發(fā)儀(日本EYELA公司)；Shim-pack GIST C18(20 mm×250 mm，5 μm，日本島津公司)；Sephadex LH-20(美國(guó)GE Healthcare公司)；柱色譜用硅膠(80～100、200～300目，青島海洋化工廠)；柱色譜用ODS(ODS-A-HG，50 μm，日本YMC公司)；薄層色譜硅膠板(Silicagel60 F254)、薄層色譜反相板(Rp-18)(德國(guó)默克公司)；恒溫CO2培養(yǎng)箱(美國(guó)Thermo公司)；Epoch 2型酶標(biāo)儀(美國(guó)Bio-Tek公司)；倒置相差顯微鏡(日本Olympus公司)；低溫高速離心機(jī)(上海安亭科學(xué)儀器廠)；超凈工作臺(tái)(北京王堂藍(lán)翼科技有限公司)。

柱色譜用分析純?cè)噭?天津富宇精細(xì)化工有限公司)；分析純甲醇(西隴化工股份有限公司)；色譜純甲醇(德國(guó)默克公司)。MGC-803細(xì)胞株(武漢大學(xué)細(xì)胞保藏中心)；Cell Counting Kit-8試劑盒(美國(guó)GlpBio公司)；DMEM培養(yǎng)基(美國(guó)Thermo公司)；Cellmax胎牛血清(北京賽貝生物技術(shù)有限公司)；0.25%胰蛋白酶、青霉素-鏈霉素、磷酸鹽緩沖液(上海碧云天生物技術(shù)有限公司)。

北柴胡采自黑龍江省大慶市林甸地區(qū)，經(jīng)黑龍江中醫(yī)藥大學(xué)藥學(xué)院藥用植物學(xué)教研室樊銳鋒副教授鑒定為傘形科植物北柴胡BupleurumchineseDC.的干燥地上部分，標(biāo)本(編號(hào)20170910)保存于黑龍江中醫(yī)藥大學(xué)中藥化學(xué)教研室。

2 提取與分離

柴胡干燥地上部分44.4 kg切成約2 cm的小塊，乙醇回流提取，提取物在45 ℃下真空濃縮，加水分散，依次用石油醚、正丁醇、乙酸乙酯萃取洗脫，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，采用硅膠柱層析，二氯甲烷-甲醇(1∶0～0∶1)進(jìn)行洗脫，得到Fr.2～Fr.10。Fr.2經(jīng)ODS反相柱，甲醇-水(1∶9～1∶0)洗脫，得Fr.2A～Fr.2E，F(xiàn)r.2A～Fr.2C經(jīng)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經(jīng)Sephadex LH-20、制備型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物17(4.7 mg，tR=11.8 min)。Fr.3經(jīng)ODS反相柱，甲醇-水(1∶9～1∶0)洗脫，得Fr.3A～Fr.3F，F(xiàn)r.3B、Fr.3C經(jīng)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經(jīng)Sephadex LH-20、制備型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物3(3.0 mg，tR=18.2 min)。Fr.4經(jīng)ODS反相柱，甲醇-水(1∶9～1∶0)洗脫，得Fr.4A～Fr.4D，F(xiàn)r.4B經(jīng)Sephadex LH-20、制備型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，采用硅膠柱層析，二氯甲烷-甲醇(1∶0～0∶1)進(jìn)行洗脫，得到Fr.1～Fr.11。Fr.2經(jīng)ODS反相柱，甲醇-水(1∶9～1∶0)洗脫，得Fr.2A～Fr.2E，F(xiàn)r.2B、Fr.2C、Fr.2D經(jīng)Sephadex LH-20，通過(guò)重結(jié)晶得化合物28(2.1 mg)、29(2.2 mg)、31(1.2 mg)、33(2.5 mg)。Fr.3經(jīng)ODS反相柱，甲醇-水(1∶9～1∶0)洗脫，得Fr.3A～Fr.3F，F(xiàn)r.3B、Fr.3C經(jīng)Sephadex LH-20，通過(guò)重結(jié)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經(jīng)Sephadex LH-20、制備型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物13(4.0 mg，tR=18.2 min)。Fr.5經(jīng)ODS反相柱，甲醇-水(1∶9～1∶0)洗脫，得Fr.5A～Fr.5D，F(xiàn)r.5A、Fr.5C經(jīng)Sephadex LH-20，通過(guò)重結(jié)晶得化合物15(2.3 mg)、16(1.2 mg)、24(2.3 mg)；Fr.5B經(jīng)Sephadex LH-20、制備型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經(jīng)ODS反相柱，甲醇-水(1∶9～1∶0)洗脫，得Fr.4A～Fr.4C、Fr.6A～Fr.6E、Fr.7A～Fr.7D，F(xiàn)r.6C、Fr.7C經(jīng)Sephadex LH-20，通過(guò)重結(jié)晶得化合物18(1.2 mg)、19(2.1 mg)、26(4.8 mg)、32(30.4 mg)；Fr.4A經(jīng)Sephadex LH-20、制備型HPLC(甲醇-水，55∶45，3 mL/min)，得化合物14(4.3 mg,tR=21.7 min)。

3 結(jié)構(gòu)鑒定

化合物1：無(wú)色片狀結(jié)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)。與文獻(xiàn)[7]報(bào)道一致，鑒定為阿魏酸。

化合物2：白色結(jié)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)。與文獻(xiàn)[2]報(bào)道一致，鑒定為咖啡酸。

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)。與文獻(xiàn)[8]報(bào)道一致，鑒定為對(duì)香豆酸。

化合物4：白色結(jié)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)。與文獻(xiàn)[9]報(bào)道一致，鑒定為異嗪皮啶-7-O-β-D-吡喃葡萄糖苷。

化合物5：白色固體，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)。與文獻(xiàn)[10]報(bào)道一致，鑒定為東莨菪苷。

化合物6：白色羽狀結(jié)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)。與文獻(xiàn)[11]報(bào)道一致，鑒定為莨菪亭。

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)。與文獻(xiàn)[12]報(bào)道一致，鑒定為異嗪皮啶。

化合物8：白色簇狀結(jié)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)。與文獻(xiàn)[13]報(bào)道一致，鑒定為8-甲氧基-6,7-亞甲二氧基香豆素。

化合物9：白色針狀結(jié)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)。與文獻(xiàn)[14]報(bào)道一致，鑒定為阿魏酸乙酯。

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)。與文獻(xiàn)[15]報(bào)道一致，鑒定為α-細(xì)辛醚。

化合物11：白色固體，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)。與文獻(xiàn)[16]報(bào)道一致，鑒定為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)。與文獻(xiàn)[17]報(bào)道一致，鑒定為紫丁香酚苷。

化合物13：白色固體，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)。與文獻(xiàn)[18]報(bào)道一致，鑒定為4-(β-D-Glucopyranosyloxy)-3,5-dimethoxy-phenylpropanone。

化合物14：無(wú)色油狀物，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)。與文獻(xiàn)[19]報(bào)道一致，鑒定為β-hydroxypropiovanillone-3-O-β-D-glucopyranside。

化合物15：白色固體，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)。與文獻(xiàn)[20]報(bào)道一致，鑒定為裂環(huán)異落葉松脂醇-9-O-β-D-吡喃葡萄糖苷。

化合物16：無(wú)色無(wú)定形固體，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)。與文獻(xiàn)[21]報(bào)道一致，鑒定為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)。與文獻(xiàn)[22]報(bào)道一致，鑒定為acutissimalignan B。

化合物18：白色固體，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)。與文獻(xiàn)[23]報(bào)道一致，鑒定為羅漢松脂素。

化合物19：白色固體，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)。與文獻(xiàn)[24]報(bào)道一致，鑒定為1-(4-hydroxy-3-methoxy)-phenyl-2-[4-(1,2,3-trihydroxypropyl)-2-methoxy]-phenoxy-1,3-propandiol。

化合物20：白色無(wú)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′)。與文獻(xiàn)[12]報(bào)道一致，鑒定為迷迭香酸。

化合物21：白色結(jié)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)。與文獻(xiàn)[25]報(bào)道一致，鑒定為升麻酸。

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)。與文獻(xiàn)[26]報(bào)道一致，鑒定為Dehydrodiconiferyl alcohol-4-O-β-D-glucopyranoside。

化合物23：淺黃色無(wú)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)。與文獻(xiàn)[27]報(bào)道一致，而且該化合物的CD光譜在284 nm (△ε+3.01) 處顯示正Cotton效應(yīng)，故鑒定為(7S,8R)-dehydrodiconiferyl-alcohol 9′-O-β-glucopyranoside。

化合物24：白色固體，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)。與文獻(xiàn)[28]報(bào)道一致，而且該化合物的CD光譜在272 nm (△ε+3.3) 、225 nm (△ε-2.02) 處顯示Cotton效應(yīng)，鑒定為(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)。與文獻(xiàn)[29]報(bào)道一致，鑒定為8-(3′,6′-二甲氧基)-4,5-環(huán)己二烯-(Δ11,12-二氧亞甲基)-稠二氫異香豆素。

化合物26：無(wú)色針晶，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)。與文獻(xiàn)[30]報(bào)道一致，鑒定為鵝掌楸堿。

化合物27：白色固體，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)。與文獻(xiàn)[31]報(bào)道一致，鑒定為(+)丁香脂素-4-O-β-D-吡喃葡萄糖苷。

化合物28：白色固體，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)。與文獻(xiàn)[20]報(bào)道一致，鑒定為(+)丁香脂素。

化合物29：白色固體，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)。與文獻(xiàn)[32]報(bào)道一致，鑒定為medioresinol。

化合物30：白色固體，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)。與文獻(xiàn)[33]報(bào)道一致，鑒定為松脂酚-4-O-β-D-吡喃葡萄糖苷。

化合物31：白色固體，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)。與文獻(xiàn)[31]報(bào)道一致，鑒定為(+)-松脂酚。

化合物32：白色固體，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)。與文獻(xiàn)[34]報(bào)道一致，鑒定為(+)-松脂酚-4, 4′-O-二吡喃葡萄糖苷。

化合物33：白色固體，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)。與文獻(xiàn)[35]報(bào)道一致，鑒定為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)。與文獻(xiàn)[36]報(bào)道一致，鑒定為herpetol B。

化合物35：黃色油狀物，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)。與文獻(xiàn)[37]報(bào)道一致，鑒定為pinnatifidanin A。

4 抗細(xì)胞增殖活性研究

采用Cell Counting Kit-8試劑盒評(píng)估MGC-803細(xì)胞的生存能力。將細(xì)胞置于DMEM培養(yǎng)基中，在5%CO2下培養(yǎng)，以1.5×105/孔密度接種在96孔板中培養(yǎng)4 h，加入不同濃度化合物1～35孵育24 h，避光下將10 μL CCK-8溶液(5 mg/mL)加到每孔中，再孵育1 h，采用酶標(biāo)儀檢測(cè)490 nm波長(zhǎng)處吸光度，通過(guò)SPSS 17.0中的Probit程序計(jì)算細(xì)胞毒性。結(jié)果見(jiàn)表1。

由此可知，化合物21、23、27、29對(duì)MGC-803細(xì)胞增殖有顯著抑制作用，化合物19、24、28、32有中等抑制作用，化合物2～3、6、9、11、16、26抑制作用較弱。

表1 各化合物對(duì)MGC-803細(xì)胞的細(xì)胞毒性

5 結(jié)論