毛药藤枝叶的化学成分研究

2021-12-06邵磊孙彪王晓雯徐杰叶文才张晓琦

暨南大学学报（自然科学与医学版） 2021年1期

邵磊，孙彪，王晓雯，徐杰，叶文才，张晓琦*

(1.青岛市食品药品检验研究院, 山东青岛 266071； 2.暨南大学药学院∥广东省现代中药工程技术研究中心, 广东广州 510632)

毛药藤(Sindechiteshenryi)为夹竹桃科(Apocynaceae)毛药藤属植物，又名土牛党七、黄经树等，生于海拔600～1 300 m的山地疏林、山腰路旁阳处灌木丛中或山谷密林中水沟旁，主要分布在云南、广西等地[1].具有健脾补虚、清热解毒之功效，主要用于消化不良、血虚乳少、口舌生疮、牙痛等的治疗；在广西民间常用其作为补药，但孕妇忌用[1-2].国内外未见有关毛药藤化学成分的研究报道，为了阐明其药理活性的物质基础，本文对毛药藤的化学成分进行了研究，从毛药藤的地上部分共分离鉴定了16个化合物，分别为：1-羟基-8-甲氧基蒽(1-hydroxy-8-methoxyanthraquinone,1)、大黄素(emodin,2)、大黄素甲醚(physcion,3)、曲霉酮8-O-β-D-吡喃葡糖糖苷 (torachrysone 8-O-β-D-glucopyranoside,4)、黄杞苷(engeletin,5)、槲皮素3-O-α-L-鼠李糖苷 (quercetin-3-O-α-L-rhamnopyranoside,6)、阿魏糖苷(kaempferol-3-O-α-L-rhamnoside,7)、山奈酚-3-葡萄糖苷(kaempferol-3-glucoside,8)、扁蓄甙(avicularin,9)、槲皮素3-O-β-D-吡喃木糖苷(quercetin 3-O-β-D-xylopyranoside,10)、落新妇苷(astilbin,11)、番石榴苷(guaijaverin,12)、槲皮素(quercetin,13)、乔松酮(pinostrobin,14)、bistortaside A (15)、stigmast-4-en-6β-ol-3-one (16).以上化合物均为首次从该植物中分离得到.

1 材料与方法

1.1 实验仪器与材料

Jasco UV-550紫外/可见光谱仪(日本Jasco公司)；Jasco FT/IR-480 Plus Fourier Transform红外光谱仪(KBr压片,日本Jasco公司)；Chirascan分光仪(英国应用光物理公司)；Jasco P-1020旋光仪(日本Jasco公司)；Agilent 6210 ESI/TOF质谱仪(美国安捷伦公司)；Bruker AV-400/AV-600型核磁共振仪(德国布鲁克公司)；Agilent 1260分析及制备型高效液相色谱仪(美国安捷伦公司)；柱层析硅胶(80～100目、20～300目)为青岛海洋化工公司生产；碳十八烷基反相键合硅胶(ODS, 50 μm)柱层析填料为美国Merck公司生产；Sephadex LH-20柱层析所用材料为瑞典Pharmacia Biotech AB公司生产；TLC硅胶GF254预制板为烟台化学工业研究所生产；分析及制备色谱柱为美国Phenomenex公司的普通C18分析柱(柱长250 mm，粒度5 μm)和制备柱(柱长250 mm，粒度5 μm)；氘代试剂为美国CIL公司生产；所用试剂均为分析纯或色谱纯(天津大茂化学试剂厂).

实验用药材毛药藤于2016年5月采于云南省昆明市，经暨南大学药学院张英副教授鉴定为毛药藤(Sindechiteshenryi).植物标本(No.CP2016051002)保存于暨南大学中药及天然药物研究所.

1.2 提取和分离

毛药藤干燥枝叶20.3 kg，由体积分数95%乙醇渗漉提取，减压浓缩得总浸膏1.6 kg.加水混悬均匀后，依次用石油醚、乙酸乙酯、正丁醇萃取，减压浓缩得石油醚部位 (212.2 g)、乙酸乙酯部位(105.1 g)、正丁醇部位(65.8 g).乙酸乙酯部位(105.1 g)通过硅胶柱层析，氯仿-甲醇(100∶0-0∶100)梯度洗脱，经分析合并得到14个馏分.馏分K经凝胶柱(V氯仿∶V甲醇=1∶1)洗脱后过ODS得到子馏分K1-K9，其中馏分K4 (350.1 mg)过凝胶柱经甲醇洗脱，经Pre-HPLC制备(V甲醇∶V水=40∶60)得到化合物5(15.6 mg)，8(8.0 mg)，9(11.7 mg)，馏分K6 (153.2 mg)经甲醇凝胶柱洗脱，以及Pre-HPLC制备(V甲醇∶V水=50∶50)得到化合物7(13.3 mg)，馏分K7 (68.5 mg)经Pre-HPLC制备(V甲醇∶V水=50∶50)得到化合物13(8.3 mg).馏分L经凝胶柱(V氯仿∶V甲醇=1∶1)洗脱后，过ODS得到馏分L1-L11，其中馏分L6经Pre-HPLC制备(V甲醇∶V水=40∶60)得到化合物6(9.2 mg)，馏分L8经甲醇凝胶柱洗脱后经Pre-HPLC制备(V甲醇∶V水=40∶60)得到化合物10(21.2 mg)、14(14.7 mg)，馏分L10经Pre-HPLC制备(V甲醇∶V水=40∶60)得到化合物11(7.5 mg)、12(9.0 mg).石油醚部位 (212.2 g)通过硅胶柱层析，石油醚-乙酸乙酯(100∶0-0∶100)梯度洗脱，经分析合并得到馏分P1-P11.馏分P8经凝胶柱(V氯仿∶V甲醇=1∶1)洗脱后得到9个子馏分，其中馏分P8-9经Pre-HPLC制备(V甲醇∶V水=80∶20)得到化合物1(8.1 mg)、2(10.2 mg)、3(7.8 mg)；馏分P9析出化合物16(13.7 mg)，过滤后经凝胶柱(V氯仿∶V甲醇=1∶1)洗脱再经甲醇凝胶柱洗脱后，经Pre-HPLC制备(V甲醇∶V水=75∶25)得到化合物4(9.3 mg)、15(11.4 mg).

2 实验结果

2.1 结构鉴定

(1) 化合物1无定型粉末(氯仿)；HR-ESI-MSm/z255.062 5 [M+H]+; UV (CH3OH)λmax(logε) 219 (3.53), 253 (3.26), 411 (2.79) nm; IR (KBr)vmaxIR (KBr) 3 437, 1 668, 1 636, 1 583, 1 479, 1 453, 1 359, 1 293, 1 237, 1 019 cm-1;1H-NMR (600 MHz, DMSO-d6)δH: 12.95 (1H, s, OH), 7.97 (1H, d,J=7.9 Hz, H-2), 7.77 (1H, t,J=8.4 Hz, H-6), 7.75 (1H, d,J=7.9 Hz, H-4), 7.62 (1H, t,J=7.9 Hz,H-3), 7.37 (1H, d,J=8.4 Hz, H-5), 7.29 (1H, d,J=8.3 Hz, H-7), 4.08 (3H, s, 8-OCH3);13C-NMR (150 MHz, DMSO-d6)δC: 189.0 (C-9), 182.9 (C-10), 162.7 (C-1), 161.1 (C-8), 136.1 (C-11), 136.0 (C-6), 135.9 (C-3), 133.0 (C-14), 124.9 (C-2), 121.1 (C-12), 120.4 (C-5), 119.0 (C-7), 118.4 (C-4), 117.3 (C-13), 56.8 (-OCH3).以上化合物数据与文献报道的数据一致[3]，故鉴定化合物1为1-羟基-8-甲氧基蒽醌(1-hydroxy-8-methoxyanthraquinone).

(2) 化合物2无定型粉末(氯仿)；HR-ESI-MSm/z271.0605 [M+H]+; UV (CH3OH)λmax(logε)207 (3.54), 254 (2.75), 288 (2.76) nm; IR (KBr)vmax3 418, 2 738, 2 650, 2 252, 1 676, 1 630, 1 609, 1 563, 1 476, 1 397, 1 368, 1 290, 1 258, 1 167, 1 033 cm-1;1H-NMR (600 MHz, DMSO-d6)δH: 7.45 (1H,s, H-2), 7.12 (1H, s, H-7), 7.04 (1H, s, H-4), 6.48 (1H, s,H-5), 2.39 (3H, s, H-15);13C-NMR (150 MHz, DMSO-d6)δC: 188.6 (C-9), 181.7 (C-10), 167.5 (C-6), 164.7 (C-8), 161.4 (C-1), 147.9 (C-3), 135.0 (C-11), 132.8 (C-14), 124.0 (C-2), 120.3 (C-4), 113.5 (C-13), 110.0 (C-5), 108.0 (C-12), 107.9 (C-7), 21.5 (C-15).以上化合物数据与文献报道一致[4]，故鉴定化合物2为大黄素(emodin).

(3) 化合物3无定型粉末(氯仿)；HR-ESI-MSm/z308.065 1 [M+Na]+; UV (CH3OH)λmax(logε)207 (3.48), 287 (2.75); IR (KBr)vmax3 421, 1 630, 1 388, 1 362, 1 290, 1 261, 1 213, 1 173, 1 022, 1 001 cm-1;1H-NMR (600 MHz, DMSO-d6)δH: 12.07 (1H, s, 8-OH), 12.06 (1H, s, 1-OH), 7.39 (1H, s, H-5), 7.07 (1H, s, H-4), 7.01 (1H, s, H-7), 6.47 (1H, s, H-2), 3.26 (3H, s, 3-OCH3), 2.36 (3H, s, H-15);13C-NMR (150 MHz, DMSO-d6)δC: 188.9 (C-9), 181.51 (C-10), 167.2 (C-3), 164.6 (C-8), 161.3 (C-1), 147.8 (C-6), 134.9 (C-11), 132.7 (C-14), 124.0 (C-7), 120.2 (C-5), 113.4 (C-13), 109.7 (C-12), 108.1 (C-4), 107.8 (C-2), 48.6 (-OCH3), 21.4 (C-15).以上化合物数据与文献报道一致[5]，故鉴定化合物3为大黄素甲醚(physcion).

(4) 化合物4黄色油状物(甲醇)；HR-ESI-MSm/z431.131 7 [M+Na]+; UV (CH3OH)λmax(logε) 232 (3.50), 263 (3.25); IR (KBr)vmax3 400, 2 927, 2 884, 1 679, 1 624, 1 592, 1 447,1 398,1 303,1 257,1 200,1 165,1 071 cm-1;1H-NMR (400 MHz, CD3OD)δH: 7.01 (1H, s, H-4), 6.99 (1H, s, H-5), 6.81 (1H, s, H-7), 5.08 (1H, d,J=7.6 Hz, H-1′), 3.92 (1H, dd,J=12.1, 2.2 Hz, H-6′α), 3.84 (3H, s, 6-OCH3), 3.72 (1H, dd,J=12.1, 5.7 Hz, H-6′β), 3.53 (1H, m, H-5′), 3.43 (1H, m, H-4′), 3.35 (1H, m, H-3′), 3.34 (1H, m, H-2′), 2.58 (3H, s, H-12), 2.26 (3H, s, H-13);13C-NMR (100 MHz, CD3OD)δC: 208.2 (C-11), 160.4 (C-6), 157.2 (C-8), 153.7 (C-1), 139.2 (C-3), 135.5 (C-2), 123.9 (C-9), 120.3 (C-4), 110.3 (C-10), 104.4 (C-5), 104.3 (C-7), 102.4 (C-1′), 78.8 (C-3′), 78.1 (C-5′), 74.9 (C-2′), 71.3 (C-4′), 62.4 (C-6′), 56.0 (-OCH3), 32.7 (C-12), 20.2 (C-13).以上化合物数据与文献报道一致[6]，故鉴定化合物4为曲霉酮8-O-β-D-吡喃葡萄糖苷 (torachrysone 8-O-β-D-glucopyranoside).

(5) 化合物5无定型粉末(甲醇)；HR-ESI-MSm/z457.111 0 [M+Na]+; UV (CH3OH)λmax(logε) 212 (3.49), 292 (3.28); IR (KBr)vmax3 370, 2 933, 1 644, 1 597, 1 518, 1 469, 1 381, 1 290, 1 170, 1 115, 1 061, 1 033 cm-1;1H-NMR (400 MHz, CD3OD)δH: 7.34 (2H, d,J=8.1 Hz, H-2′, H-6′), 6.83 (2H, d,J=8.1 Hz, H-3′, H-5′), 5.91 (1H, d,J=2.0 Hz, H-8), 5.88 (1H, d,J=2.0 Hz, H-6), 5.12 (1H, d,J=10.9 Hz, H-2), 4.60 (1H, d,J=10.9 Hz, H-3), 4.24 (1H, dt,J=12.3, 6.2 Hz, H-5″), 3.99 (1H, s, H-1″), 3.65 (1H, dd,J=9.6, 3.3 Hz, H-3″), 3.49 (1H, d,J=3.2 Hz, H-2″), 3.30 (1H, m, H-4″), 1.17 (3H, d,J=6.2 Hz, H-6″);13C-NMR (100 MHz, CD3OD)δC: 196.0 (C-4), 168.6 (C-7), 165.5 (C-9), 164.1 (C-5), 159.4 (C-4′), 130.0 (C-2′), 130.0 (C-6′), 128.6 (C-1′), 116.4 (C-3′), 116.4 (C-5′), 102.5 (C-1″), 102.2 (C-10), 97.4 (C-8), 96.3 (C-6), 83.8 (C-2), 78.7 (C-3), 73.8 (C-4″), 72.1 (C-3″), 71.8 (C-2″), 70.5 (C-5″), 17.8 (C-6″).以上化合物数据与文献报道一致[7]，故鉴定化合物5为黄杞苷(engeletin).

(6) 化合物6无定型粉末(甲醇)；HR-ESI-MSm/z471.089 8 [M+Na]+; UV (CH3OH)λmax(logε) 204 (3.50), 257 (3.25), 349 (3.14); IR (KBr)vmax3 304, 2 956, 1 655, 1 572, 1 501, 1 358,1 301,1 269,1 201,1 167,1 141,1 058 cm-1;1H-NMR (600 MHz, CD3OD)δH: 7.32 (1H, d,J=2.1 Hz, H-2′), 7.28 (1H, dd,J=8.3, 2.1 Hz, H-6′), 6.89 (1H, d,J=8.3 Hz, H-5′), 6.33 (1H, d,J=2.1 Hz, H-8), 6.17 (1H, d,J=2.0 Hz, H-6), 5.33 (1H, d,J=1.5 Hz, H-1″), 4.21 (1H, dd,J=3.4, 1.7 Hz, H-5″), 3.74 (1H, dd,J=9.5, 3.3 Hz, H-3″), 3.40 (1H, dq,J=9.7, 6.1 Hz, H-2″), 3.33 (1H, d,J=3.5 Hz, H-4″), 0.93 (3H, d,J=6.2 Hz, H-6″);13C-NMR (150 MHz, CD3OD)δC: 179.6 (C-4), 165.8 (C-7), 163.1 (C-9), 159.3 (C-5), 158.4 (C-2), 149.7 (C-4′), 146.3 (C-3′), 136.2 (C-3), 122.9 (C-1′), 122.9 (C-6′), 116.9 (C-5′), 116.3 (C-2′), 105.9 (C-10), 103.5 (C-1″), 99.8 (C-6), 94.7 (C-8), 73.2 (C-4″), 72.1 (C-3″), 72.0 (C-5″), 71.9 (C-2″), 17.6 (C-6″).以上化合物数据与文献报道一致[8]，故鉴定化合物6为槲皮素3-O-α-L-鼠李糖苷 (quercetin-3-O-α-L-rhamnopyranoside).

(7) 化合物7无定型粉末(甲醇)；HR-ESI-MSm/z433.112 3 [M+H]+; UV (CH3OH)λmax(logε) 204 (3.43), 265 (3.25), 349 (3.14); IR (KBr)vmax3 403, 2 944, 1 655, 1 606, 1 501, 1 364, 1 269, 1 176, 1 138, 1 084, 1 061 cm-1;1H-NMR (400 MHz, CD3OD)δH: 7.78 (1H, s, H-2′), 7.77 (1H, s, H-6′), 6.95 (1H, s, H-3′), 6.94 (1H, s, H-5′), 6.39 (1H, s, H-8), 6.21 (1H, s, H-6), 5.39 (1H, s, H-1″), 4.23 (1H, d,J=3.1 Hz, H-2″), 3.72 (1H, s, H-3″), 3.36 (1H, s, H-5″), 3.34 (1H, s, H-4″), 0.93 (3H, d,J=4.7 Hz, H-6″);13C-NMR (100 MHz, CD3OD)δC: 179.6 (C-4), 165.9 (C-7), 163.2 (C-5), 161.6 (C-4′), 159.3 (C-2), 158.6 (C-9), 136.2 (C-3), 131.9 (C-2′), 131.9 (C-6′), 122.6 (C-1′), 116.5 (C-3′), 116.5 (C-5′), 105.9 (C-10), 103.5 (C-1″), 99.8 (C-6), 94.8 (C-8), 73.2 (C-4″), 72.1 (C-3″), 72.0 (C-2″), 71.9 (C-5″), 17.6 (C-6″).以上化合物数据与文献报道一致[9]，故鉴定化合物7为阿魏糖苷(kaempferol 3-O-α-L-rhamnoside).

(8) 化合物8无定型粉末(甲醇)；HR-ESI-MSm/z449.108 2 [M+H]+; UV (CH3OH)λmax(logε) 204 (3.36), 265 (3.14), 348 (3.09); IR (KBr)vmax3 377, 2 887, 1 655, 1 603, 1 507, 1 455,1 358,1 278,1 210,1 181,1 064,1 010 cm-1;1H-NMR (600 MHz, CD3OD)δH: 8.00 (1H, s, H-2′), 7.99 (1H, s, H-6′), 6.83 (1H, s, H-5′), 6.82 (1H, s, H-3′), 6.33 (1H, s, H-8), 6.13 (1H, d,J=1.9 Hz, H-6), 5.20 (1H, d,J=7.3 Hz, H-1″), 3.64 (1H, dd,J=11.9, 2.3 Hz, H-6″a), 3.48 (1H, dd,J=11.9, 5.5 Hz, H-6″b), 3.43 (1H, m, H-3″), 3.42 (1H, m, H-2″), 3.29 (1H, s, H-4″), 3.15 (1H, ddd,J=9.8, 5.5, 2.3 Hz, H-5″);13C-NMR (150 MHz, CD3OD)δC: 179.4 (C-4), 166.4 (C-5), 166.3 (C-7), 161.6 (C-4′), 159.0 (C-9), 158.5 (C-2), 135.4 (C-3), 132.3 (C-2′), 132.3 (C-6′), 122.8 (C-1′), 116.1 (C-3′), 116.1 (C-5′), 105.7 (C-10), 104.1 (C-1″), 100.0 (C-6), 94.8 (C-8), 78.4 (C-3″), 78.0 (C-5″), 75.7 (C-2″), 71.3 (C-4″), 62.6 (C-6″).以上化合物数据与文献报道的kaempferol-3-glucoside数据一致[10]，故鉴定化合物8为山奈酚-3-葡萄糖苷(kaempferol-3-glucoside).

(9) 化合物9无定型粉末(甲醇)；HR-ESI-MSm/z457.074 2 [M+Na]+; UV (CH3OH)λmax(logε) 204 (3.49), 258 (3.23), 356 (3.10); IR (KBr)vmax3 386, 2 886, 1 647, 1 595, 1 521, 1 472,1 453,1 363,1 300,1 271,1 197,1 111 cm-1;1H-NMR (400 MHz, CD3OD)δH: 7.52 (1H, d,J=2.1 Hz, H-2′), 7.49 (1H, dd,J=8.4, 2.1 Hz, H-6′), 6.90 (1H, d,J=8.4 Hz, H-5′), 6.39 (1H, d,J=1.8 Hz, H-8), 6.20 (1H, d,J=1.9 Hz, H-6), 5.46 (1H, s, H-1″), 4.33 (1H, d,J=2.8 Hz, H-2″), 3.91 (1H, dd,J=5.2, 2.9 Hz, H-3″), 3.87 (1H, q,J=4.5 Hz, H-4″), 3.52 (1H, d,J=8.5 Hz, H-5″b), 3.35 (1H, s, H-5″a);13C-NMR (100 MHz, CD3OD)δC: 180.0 (C-4), 166.2 (C-7), 163.1 (C-5), 159.3 (C-2), 158.6 (C-9), 149.9 (C-4′), 146.4 (C-3′), 134.9 (C-3), 123.1 (C-6′), 123.0 (C-1′), 116.8 (C-5′), 116.4 (C-2′), 109.5 (C-1″), 105.6 (C-10), 99.9 (C-6), 94.8 (C-8), 88.0 (C-4″), 83.3 (C-2″), 78.7 (C-3″), 62.5 (C-5″).以上化合物数据与文献报道的avicularin数据一致[11]，故鉴定化合物9为扁蓄甙(avicularin).

(10) 化合物10无定型粉末(甲醇)；HR-ESI-MSm/z457.074 3 [M+Na]+; UV (CH3OH)λmax(logε) 204 (3.25), 257 (2.98), 354 (2.90); IR (KBr)vmax3 371, 1 653, 1 601, 1 570, 1 507, 1 360, 1 300, 1 203, 1 168, 1 053, 1 024 cm-1;1H-NMR (400 MHz, CD3OD)δH: 7.57 (1H, d,J=2.1 Hz, H-2′), 7.55 (1H, dd,J=8.4, 2.2 Hz, H-6′), 6.81 (1H, d,J=8.4 Hz, H-5′), 6.35 (1H, d,J=2.1 Hz, H-8), 6.16 (1H, d,J=2.1 Hz, H-6), 5.14 (1H, d,J=7.2 Hz, H-1″), 3.73 (1H, dd,J=11.6, 5.2 Hz, H-2″), 3.50 (1H, m, H-3″),3.45 (1H, m, H-4″), 3.35 (1H, t,J=8.7 Hz, H-5″b), 3.05 (1H, dd,J=11.6, 9.5 Hz, H-5″a);13C-NMR (100 MHz, CD3OD)δC: 179.4 (C-4), 166.1 (C-7), 163.1 (C-9), 158.9 (C-5), 158.4 (C-2), 149.9 (C-4′), 146.1 (C-3′), 135.4 (C-3), 123.3 (C-6′), 123.0 (C-1′), 117.2 (C-5′), 116.0 (C-2′), 105.6 (C-10), 104.6 (C-1″), 99.9 (C-6), 94.7 (C-8), 77.5 (C-3″), 75.3 (C-2″), 71.0 (C-4″), 67.2 (C-5″).以上化合物数据与文献报道一致[12]，故鉴定化合物10为槲皮素3-O-β-D-吡喃木糖苷(quercetin 3-O-β-D-xylopyranoside).

(11) 化合物11无定型粉末(甲醇)；HR-ESI-MSm/z473.105 2 [M+Na]+; UV (CH3OH)λmax(logε) 202 (3.36), 291 (3.00); IR (KBr)vmax3 400, 2 892, 1 642, 1 524, 1 472, 1 386, 1 289, 1 260, 1 171, 1 151, 1 114, 1 094, 1 062, 1 033 cm-1;1H-NMR (400 MHz, CD3OD)δH: 6.96 (1H, d,J=1.9 Hz, H-2′), 6.84 (1H, dd,J=8.2, 2.0 Hz, H-6′), 6.81 (1H, d,J=8.1 Hz, H-5′), 5.90 (1H, s, H-8), 5.07 (1H, d,J=10.7 Hz, H-2), 4.58 (1H, d,J=10.7 Hz, H-3), 4.25 (1H, m, H-5″), 4.05 (1H, d,J=1.6 Hz, H-1″), 3.67 (1H, dd,J=9.6, 3.3 Hz, H-3″), 3.54 (1H, dd,J=3.3, 1.6 Hz, H-2″), 3.32 (1H, d,J=6.2 Hz, H-4″), 1.19 (3H, d,J=6.2 Hz, H-6″);13C-NMR (100 MHz, CD3OD)δC: 196.0 (C-4), 168.6 (C-7), 165.4 (C-5), 164.1 (C-9), 147.4 (C-4′), 146.5 (C-3′), 129.2 (C-1′), 120.5 (C-6′), 116.3 (C-2′), 115.5 (C-5′), 102.5 (C-1″), 102.1 (C-10), 97.4 (C-6), 96.3 (C-8), 83.9 (C-2), 78.6 (C-3), 73.8 (C-4″), 72.1 (C-3″), 71.8 (C-2″), 70.5 (C-5″), 17.8 (C-6″).以上化合物数据与文献报道一致[13]，故鉴定化合物11为落新妇苷(astilbin).

(12) 化合物12无定型粉末(甲醇)；HR-ESI-MSm/z457.074 1 [M+Na]+; UV (CH3OH)λmax(logε) 203 (3.32), 257 (3.06), 357 (2.93); IR (KBr)vmax3 414, 2 924, 1 650, 1 604, 1 559, 1 509, 1 489, 1 472, 1 455, 1 363, 1 292, 1 200, 1 120, 1 068, 1 013 cm-1;1H-NMR (600 MHz, CD3OD)δH: 7.70 (1H, d,J=2.2 Hz, H-2′), 7.53 (1H, dd,J=8.5, 2.2 Hz, H-6′), 6.83 (1H, d,J=8.5 Hz, H-5′), 6.36 (1H, d,J=2.1 Hz, H-8), 6.16 (1H, d,J=2.0 Hz, H-6), 5.12 (1H, d,J=6.6 Hz, H-1″), 3.85 (1H, dd,J=8.5, 6.6 Hz, H-2″), 3.79 (1H, d,J=3.7 Hz, H-4″), 3.77 (1H, s, H-5″α), 3.60 (1H, dd,J=8.5, 3.0 Hz, H-3″), 3.40 (1H, m, H-5″β);13C-NMR (150 MHz, CD3OD)δC: 179.5 (C-4), 166.1 (C-7), 163.1 (C-5), 158.8 (C-2), 158.5 (C-9), 149.9 (C-4′), 146.0 (C-3′), 135.7 (C-3), 123.1 (C-1′), 123.0 (C-6′), 117.5 (C-2′), 116.2 (C-5′), 105.7 (C-10), 104.7 (C-1″), 99.9 (C-6), 94.7 (C-8), 74.1 (C-3″), 72.9 (C-2″), 69.0 (C-4″), 66.8 (C-5″).以上化合物数据与文献报道一致[14]，故鉴定化合物12为番石榴苷(guaijaverin).

(13) 化合物13无定型粉末(甲醇)；HR-ESI-MSm/z303.049 7 [M+H]+; UV (CH3OH)λmax(logε) 203 (3.58), 255 (3.25), 296 (2.97), 370 (3.23); IR (KBr)vmax3 389, 3 292, 1 655, 1 615, 1 512, 1 364, 1 316, 1 239, 1 210, 1 164, 1 109 cm-1;1H-NMR (600 MHz, CD3OD)δH: 7.73 (1H, d,J=2.1 Hz, H-2′), 7.63 (1H, dd,J=8.5, 2.2 Hz, H-6′), 6.88 (1H, d,J=8.5 Hz, H-5′), 6.38 (1H, d,J=2.0 Hz, H-8), 6.18 (1H, d,J=2.0 Hz, H-6);13C-NMR (150 MHz, CD3OD)δC: 177.3 (C-4), 165.5 (C-7), 162.5 (C-5), 158.2 (C-9), 148.7 (C-2), 148.0 (C-4′), 146.2 (C-3′), 137.2 (C-3), 124.1 (C-1′), 121.7 (C-6′), 116.2 (C-5′), 116.0 (C-2′), 104.5 (C-10), 99.2 (C-6), 94.4 (C-8).以上化合物数据与文献报道一致[15]，故鉴定化合物13为槲皮素(quercetin).

(14) 化合物14无定型粉末(甲醇)；HR-ESI-MSm/z271.096 4 [M+H]+; UV (CH3OH)λmax(logε) 209 (3.42), 287 (3.53); IR (KBr)vmax3 434, 3 059, 3 037, 2 968, 2 932, 1 768, 1 642, 1 588, 1 520, 1 445, 1 380, 1 349, 1 380, 1 346, 1 302, 1 209 cm-1;1H-NMR (400 MHz, CD3OD)δH: 12.02 (1H, s, OH), 7.46 (1H, m, H-3′), 7.46 (1H, m, H-5′), 7.43 (1H, m, H-2′), 7.43 (1H, m, H-6′), 7.40 (1H, m, H-4′), 6.07 (2H, m, H-6, H-8), 5.43 (1H, dd,J=13.0, 3.0 Hz, H-2), 3.81 (3H, s, 7-OCH3), 3.09 (1H, dd,J=17.2, 13.0 Hz, H-3α), 2.83 (1H, dd,J=17.2, 3.0 Hz, H-3β),13C-NMR (100 MHz, CD3OD)δC: 195.9 (C-4), 168.1 (C-7), 164.3 (C-5), 162.9 (C-9), 138.5 (C-1′), 129.0 (C-3′), 129.0 (C-4′), 129.0 (C-5′), 126.3 (C-2′), 126.3 (C-6′), 103.3 (C-10), 95.3 (C-6), 94.4 (C-8), 79.4 (C-2), 55.9 (-OCH3), 43.6 (C-3).以上化合物数据与文献报道一致[16]，故鉴定化合物14为乔松酮(pinostrobin).

(15) 化合物15无定型粉末(甲醇)；HR-ESI-MSm/z533.126 5 [M+Na]+; UV (CH3OH)λmax(logε) 205 (3.41), 282 (1.99); IR (KBr)vmax3 418, 2 258, 1 682, 1 668, 1 647, 1 051, 1 024, 998 cm-1;1H-NMR (600 MHz, DMSO-d6)δH: 7.46 (1H, d,J=1.9 Hz, H-2′), 7.33 (1H, dd,J=8.4, 1.9 Hz, H-6′), 7.19 (1H, s, H-2″), 7.19 (1H, s, H-6″), 7.17 (1H, d,J=8.6 Hz, H-5′), 5.14 (1H, m, H-2), 4.63 (1H, d,J=10.1 Hz, H-6α), 4.16 (1H, dd,J=11.8, 7.6 Hz, H-6β), 3.80 (3H, s, 3′-OCH3), 3.77 (6H, s, OCH3);13C-NMR (150 MHz, DMSO-d6)δC: 166.9 (C-7′), 165.4 (C-7″), 150.0 (C-3′), 148.4 (C-4′), 147.6 (C-3″), 147.6 (C-5″), 141.0 (C-4″), 124.2 (C-6′), 122.5 (C-1′), 119.2 (C-1″), 114.0 (C-5′), 112.7 (C-2′), 107.1 (C-2″), 107.1 (C-6″), 99.1 (C-1), 76.6 (C-3), 74.1 (C-5), 73.0 (C-2), 70.1 (C-4), 64.2 (C-6), 56.1 (-OCH3), 55.6 (-OCH3x2).以上化合物数据与文献报道一致[17]，故鉴定化合物15为bistortaside A.

(16) 化合物16无定型粉末(甲醇)；HR-ESI-MSm/z429.372 5 [M+H]+; UV (CH3OH)λmax(logε) 237 (3.50); IR (KBr)vmax3 443, 2 956, 2 866, 1 762, 1 685, 1 653, 1 455, 1 380, 1 082 cm-1;1H-NMR (400 MHz, CDCl3)δH: 5.81 (1H, s, H-4), 4.34 (1H, d,J=3.0 Hz, H-6), 1.66 (1H, m，H-11α)，1.51 (1H, m, H-28β), 1.37 (3H, s, H-21), 1.25 (1H, m, H-28α), 0.86 (3H, s, H-27), 0.84 (3H, s, H-26), 0.82(3H, s, H-29), 0.74 (3H, s, H-18);13C-NMR (100 MHz, CDCl3)δC: 200.6 (C-3), 168.7 (C-5), 126.5 (C-4), 73.4 (C-6), 56.2 (C-17), 56.0 (C-14), 53.8 (C-9), 46.0 (C-24), 42.6 (C-13), 39.7 (C-7), 38.7 (C-12), 38.1 (C-10), 37.2 (C-1), 36.3 (C-20), 34.4 (C-2), 34.0 (C-22), 29.9 (C-25), 29.3 (C-8), 28.3 (C-16), 26.2 (C-23), 24.3 (C-15), 23.2 (C-28), 21.1 (C-11), 20.0 (C-26), 19.7 (C-19), 19.2 (C-27), 18.9 (C-21), 12.2 (C-18), 12.1 (C-29).以上化合物数据与文献报道一致[18]，故鉴定化合物16为stigmast-4-en-6β-ol-3-one.