中草药  2015, Vol. 46 Issue (10): 1426-1430
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引用本文doi: 10.7501/j.issn.0253-2670.2015.10.004
图斯库, 张树军, 李涛, 王金兰, 赵明. 臭椿树根化学成分研究[J]. 中草药, 2015, 46(10): 1426-1430.
TUSKUL Solovyev, ZHANG Shu-jun, LI Tao, WANG Jin-lan, ZHAO Ming. Chemical constituents from roots of Ailanthus altissima[J]. Chinese Traditional and Herbal Drugs, 2015, 46(10): 1426-1430.
臭椿树根化学成分研究
图斯库1, 张树军1, 李涛2, 王金兰1, 赵明1     
1. 齐齐哈尔大学化学与化学工程学院, 黑龙江 齐齐哈尔 161006;
2. 齐齐哈尔医学院, 黑龙江 齐齐哈尔 161042
收稿日期: 2014-11-17;
基金项目： 精细化工黑龙江省高校重点实验室开放基金项目(JX201209)
作者简介：图斯库(1989—),男,硕士研究生,研究方向为天然产物化学。E-mail:manutd24@mail.ru
摘要：目的 研究臭椿Ailanthus altissima根部的化学成分。方法 采用硅胶柱色谱和HPLC等分离方法, 对臭椿树根正己烷萃取物的化学成分进行分离, 并经波谱数据分析鉴定结构。结果 分离得到了14个化合物, 分别鉴定为20β-羟基达玛烷-24-烯-3-酮(1)、β-谷甾醇(2)、ocotillone(3)、5,6,7,8-四甲氧基香豆素(4)、尼洛替星(5)、isofouquierone peroxide(6)、20S,24S-二羟基达玛烷-25-烯-3-酮(7)、匹西狄醇A(8)、eichlerianic acid(9)、二氢尼洛替星(10)、12β,20β-二羟基达玛烷-24-烯-3-酮(11)、铁屎米-6-酮(12)、12β-hydroxy ocotillone(13)、20S,25-epoxy-24R-hydroxy-3-dammaranone(14)。结论 化合物3、4、6、9、10、13系首次从该植物中分离得到。
关键词： 臭椿     5,6,7,8-四甲氧基香豆素     匹西狄醇A     二氢尼洛替星     铁屎米-6-酮    
Chemical constituents from roots of Ailanthus altissima
TUSKUL Solovyev1, ZHANG Shu-jun1, LI Tao2, WANG Jin-lan1, ZHAO Ming1    
1. Institute of Chemistry and Chemistry Engineering, Qiqihar University, Qiqihar 161006, China;
2. Qiqihar Medical College, Qiqihar 161042, China
Abstract: Objective To study the chemical constituents from the roots of Ailanthus altissima. Methods Compounds were isolated and purified by silica gel column chromatography and HPLC, and their structures were identified by spectral analysis. Results Fourteen compounds were isolated and identified as 20-hydroxydammar-24-en-3-one (1), β-sitosterol (2), ocotillone (3), 5,6,7,8-tetramethoxycoumarin (4), niloticin (5), isofouquierone peroxide (6), 20S,24S-dihydroxydammar-25-en-3-one (7), piscidinol A (8), eichlerianic acid (9), dihydroniloticin (10), dammar-24-ene-12β,20β-diol-3-one (11), canthin-6-one (12), 12β-hydroxy ocotillone (13), and 20S,25-epoxy-24R-hydroxy-3-dammaranne (14). Conclusion Compounds 3, 4, 6, 9, 10, and 13 are isolated from this plant for the first time.
Key words: Ailanthus altissima (Mill.) Swingle     5,6,7,8-tetramethoxycoumarin     piscidinol A     dihydroniloticin     canthin-6-one    

臭椿Ailanthus altissima (Mill.) Swingle为苦木科（Simaroubaceae）臭椿属Ailanthus Desf. 落叶乔木，又名山椿、樗树、白椿等，是中国本土树种，除少数省区外，全国各地均有分布。臭椿皮也称樗白皮，臭椿根皮也称椿根皮，具有清热燥湿、收涩固肠、抗肿瘤、抗菌、抗病毒等作用，是我国民间常用的中草药[1]。此外，臭椿根部表现出极强的化感活性，根部周围土壤提取物能够明显抑制多种植物种子发芽和生根，树皮及根皮提取物具有较强的杀虫活性，也可做为除虫剂[2]。为进一步开发利用臭椿植物资源，在前期对臭椿树枝化学成分研究[3]的基础上，对臭椿树根甲醇浸出液正己烷萃取物的化学成分进行了研究，得到14个化合物，分别鉴定为20β-羟基达玛烷-24-烯-3-酮（20-hydroxydammar- 24-en-3-one，1）、β-谷甾醇（β-sitosterol，2 ）、ocotillone（3）、5,6,7,8-四甲氧基香豆素（5,6,7,8-tetramethoxy- coumarin，4）、尼洛替星（niloticin，5）、isofouquierone peroxide（6）、20S,24S-二羟基达玛烷-25-烯-3-酮（20S,24S-dihydroxydammar-25-en-3-one，7）、匹西狄醇A（piscidinol A，8）、eichlerianic acid（9）、二氢尼洛替星（10）、12β,20β-二羟基达玛烷-24-烯-3-酮（dammar-24-ene-12β,20β-diol-3-one，11）、铁屎 米-6-酮（canthin-6-one，12）、12β-hydroxy ocotillone (13)、20S,25-epoxy-24R-hydroxy-3-dammaranone（14）。其中，化合物3、4、6、9、10、13系首次从该植物中分离得到。

1 仪器与材料

X-6显微熔点测定仪（北京泰克仪器有限公司）；Bruker AM-400和Bruker-600 MHz型核磁共振仪（德国Bruker公司）；AUTOPOL V型旋光仪（美国鲁道夫公司）；高效液相色谱仪：HITACHI L-7100泵，HITACHI L-3350示差折光检测器，GL SCIRNCES Inc. Inertsil PREP-ODS（250 mm×10 mm，5 μm）不锈钢柱；柱色谱用硅胶为青岛海洋化工厂产品（200～300目）；薄层色谱硅胶板为烟台化工厂生产，实验用有机溶剂均为分析纯。

实验材料2012年5月3日采于辽宁省凌源市，经齐齐哈尔大学植物学教授沙伟鉴定为臭椿Ailanthus altissima (Mill.) Swingle的根，标本（Ams-201200503）保存于齐齐哈尔大学天然产物研究室。

2 提取与分离

干燥臭椿树根10 kg切碎，每次用35 L甲醇室温浸泡3 d后滤过，重复5次，合并浸出液，减压浓缩至2.5 L，加水1.9 L，依次用正己烷、醋酸乙酯、正丁醇萃取，浓缩萃取液得到正己烷萃取物84.1 g、醋酸乙酯萃取物88.7 g、正丁醇萃取物68.3 g。

取正己烷萃取物（59.0 g）用硅胶柱色谱分离，依次用正己烷-醋酸乙酯（9∶1、1∶1、0∶1）洗脱，TLC监测合并相同流分，得到10个部分F1～F10。

F6（16.7 g）用硅胶柱色谱分离，依次用正己烷-醋酸乙酯（90∶10、85∶15、80∶20、60∶40、1∶1）洗脱得到6个部分F6-1～6-6。F6-4（8.7 g）用硅胶柱色谱分离，依次用正己烷-醋酸乙酯（8∶2）、醋酸乙酯洗脱，得化合物1（416.1 mg）、3（433.0 mg）；F6-5（3.8 g）用硅胶柱色谱分离，依次用正己烷-醋酸乙酯（8∶2、1∶1）洗脱得化合物2（2.0 g）和其他5个部分F6-5-1～6-5-5；F6-5-4（650.1 mg）用半制备HPLC（正己烷-醋酸乙酯8∶2，体积流量4 mL/min）分离，得到化合物4（7.9 mg，tR=13.0 min）、5（127.1 mg，tR＝14.8 min）；F6-5-4（529.9 mg）用半制备HPLC（正己烷-醋酸乙酯9∶1，体积流量4 mL/min）分离，得化合物6（9.0 mg，tR＝28.2 min）、7（6.4 mg，tR＝32.2 min）、8（8.4 mg，tR＝36.7 min）。F7（15.6 g）经硅胶柱色谱分离，正己烷-醋酸乙酯（8∶2、7∶3）洗脱得化合物9（450.2 mg）和其他9个部分F7-1～7-9，F7-7（260.1 mg）用半制备HPLC（正己烷-醋酸乙酯9∶1，体积流量4 mL/min）分离，得化合物10（22.7 mg，tR＝25.4 min）；F7-8（4.6 g）用硅胶柱色谱分离，依次用正己烷-醋酸乙酯（8∶2、7∶3）洗脱，得化合物11（2.6 g）。F8（2.1 g）用醋酸乙酯重结晶得化合物12（70.0 mg）；母液用硅胶柱色谱分离，正己烷-醋酸乙酯（8.5∶1.5、6∶4）洗脱，得到6个部分（F8-1～8-6）。F8-5（280.1 mg）用半制备HPLC（正己烷-醋酸乙酯8∶2，体积流量4 mL/min）分离，得化合物1 3（130.0 mg，tR＝25.3 min）。F9（2.8 g）用硅胶柱色谱分离，正己烷-醋酸乙酯（1∶1、0∶1）洗脱，得到5个部分F9-1～9-5。F9-4（409.8 mg）用半制备HPLC（正己烷-醋酸乙酯7∶3，体积流量4 mL/min）分离，得化合物14（21.9 mg，tR＝28.0 min）。

3 结构鉴定

化合物1：白色针晶（醋酸乙酯），mp 171～172 ℃；+10° (c 0.5, MeOH)。1H-NMR (600 MHz, CDCl3) δ: 5.12 (1H, t, J = 7.2 Hz, H-23), 2.49 (1H, m, H-2), 2.43 (1H, m, H-2), 2.05 (2H, m, H-23), 1.92 (1H, m, H-1), 1.85 (1H, m, H-1), 1.75 (2H, t, J = 7.5 Hz, H-16), 1.69 (3H, s, H-26), 1.67 (1H, m, H-5), 1.63 (3H, s, H-27), 1.60～1.20 (15H, m, H-6, 7, 9, 11, 12, 13, 15, 17, 22), 1.15 (3H, s, H-21), 1.08 (3H, s, H-18), 1.04 (3H, s, H-28), 1.00 (3H, s, H-29), 0.94 (3H, s, H-19), 0.89 (3H, s, H-30)；13C-NMR (150 MHz, CDCl3) δ: 218.1 (C-3), 131.6 (C-25), 124.7 (C-24), 75.3 (C-20), 55.3 (C-5), 50.2 (C-14), 50.0 (C-9), 49.8 (C-17), 47.4 (C-4), 42.4 (C-13), 40.4 (C-22), 40.3 (C-8), 39.9 (C-1), 36.8 (C-10), 34.5 (C-7), 34.1 (C-2), 31.1 (C-15), 27.5 (C-28), 26.7 (C-16), 25.7 (C-26), 25.5 (C-12), 24.8 (C-21), 22.5 (C-23), 22.0 (C-29), 21.0 (C-11), 19.6 (C-6), 17.7 (C-27), 16.3 (C-30), 16. 0 (C-18), 15.2 (C-19)。以上数据与文献报道基本一致[4]，故鉴定化合物1为20β-羟基-达玛烷-24-烯-3-酮。

化合物2：无色针晶（醋酸乙酯），mp 135.1～136.2 ℃。1H-NMR (600 MHz, CDCl3) δ: 5.33 (1H, dd, J = 5.0, 2.0 Hz, H-6), 3.51 (1H, tt, J = 8.5, 4.5 Hz, H-3), 1.00 (3H, s, H-19), 0.92 (3H, d, J = 6.8 Hz, H-21), 0.83 (3H, t, J = 7.3 Hz, H-26), 0.82 (3H, d, J = 6.8 Hz, H-28), 0.80 (3H, d, J = 6.8 Hz, H-29), 0.67 (3H, s, H-18)。以上数据与文献报道基本一致[5]，故鉴定化合物2为β-谷甾醇。

化合物3：无色羽状晶体（氯仿），mp 186～187.5 ℃； −94° (c 0.5, MeOH)。1H-NMR (600 MHz, CDCl3) δ: 3.73 (1H, t, J = 7.2 Hz, H-24), 2.49 (1H, m, H-2), 2.43 (1H, m, H-2), 1.21 (3H, s, H-21), 1.14 (3H, s, H-26), 1.12 (3H, s, H-27), 1.08 (3H, s, H-19), 1.04 (3H, s, H-28), 0.99 (3H, s, H-29), 0.93 (3H, s, H-30), 0.88 (3H, s, H-18)；13C-NMR (150 MHz, CDCl3) δ: 218.0 (C-3), 86.3 (C-20), 83.3 (C-24), 71.4 (C-25), 55.3 (C-5), 50.1 (C-14), 50.0 (C-9), 49.5 (C-17), 47.4 (C-4), 43.8 (C-13), 40.3 (C-8), 39.9 (C-1), 36.9 (C-10), 35.7 (C-22), 34.6 (C-7), 34.1 (C-2), 31.4 (C-15), 27.5 (C-26), 27.4 (C-16), 26.7 (C-29), 26.1 (C-23), 25.7 (C-12), 24.3 (C-27), 23.6 (C-21), 22.1 (C-11), 21.0 (C-28), 19.7 (C-6), 16.4 (C-30), 16.0 (C-18), 15.1 (C-19)。以上数据与文献报道基本一致[4]，故鉴定化合物3为ocotillone。

化合物4：浅黄色无定形物（醋酸乙酯），mp 54～56 ℃。1H-NMR (600 MHz, CDCl3) δ: 7.94 (1H, d, J = 9.6 Hz, H-4), 6.29 (1H, d, J = 9.6 Hz, H-3), 4.04 (3H, s, 5-OCH3), 3.98 (3H, s, 7-OCH3), 3.97 (3H, s, 6-OCH3), 3.90 (3H, s, 8-OCH3)；13C-NMR (150 MHz, CDCl3) δ: 160.4 (C-2), 150.7 (C-7), 145.1 (C-6), 144.3 (C-5), 142.4 (C-8), 138.8 (C-4), 136.9 (C-9), 114.1 (C-3), 109.5 (C-10), 62.1 (5-OCH3), 61.9 (7-OCH3), 61.8 (6-OCH3), 61.5 (8-OCH3)。以上数据与文献报道基本一致[6]，故鉴定化合物4为5,6,7,8-四甲氧基香豆素。

化合物5：无色针晶（醋酸乙酯），mp 146.2～147.6 ℃。1H-NMR (600 MHz, CDCl3) δ: 5.32 (1H, brd, J = 3.0 Hz, H-7), 3.58 (1H, dt, J = 8.2, 6.4 Hz, H-23), 2.74 (1H, dt, J = 14.5, 5.6 Hz, H-2a), 2.64 (1H, d, J = 8.2 Hz, H-24), 2.27 (1H, m, H-2b), 2.23 (1H, dt, J = 14.0, 3.3 Hz, H-6a), 2.07 (2H, m, H-6b, 9), 2.03 (1H, m, H-1a), 1.98 (1H, m, H-1b), 1.80 (1H, m, H-5), 1.34 (3H, s, H-26), 1.32 (3H, s, H-27), 1.12 (3H, s, H-19), 1.05 (3H, s, H-28), 1.02 (3H, s, H-30), 1.01 (3H, s, H-29), 0.96 (1H, d, J = 6.1 Hz, H-21), 0.81 (3H, s, H-18)；13C-NMR (150 MHz, CDCl3) δ: 216.9 (C-3), 145.7 (C-8), 118.0 (C-7), 69.3 (C-23), 68.4 (C-24), 60.3 (C-25), 53.3 (C-17), 52.4 (C-5), 51.2 (C-14), 48.5 (C-9), 47.9 (C-4), 43.6 (C-13), 40.7 (C-22), 38.6 (C-1), 35.0 (C-10), 34.9 (C-2), 34.0 (C-15), 33.6 (C-12), 33.5 (C-20), 28.8 (C-16), 27.4 (C-30), 24.9 (C-28), 24.6 (C-27), 24.4 (C-6), 21.8 (C-29), 21.6 (C-26), 19.9 (C-21), 19.8 (C-19), 18.3 (C-11), 12.8 (C-18)。以上数据与文献报道基本一致[7]，故鉴定化合物5为尼洛替星& lt; /span>。

化合物6：无色针晶（醋酸乙酯），mp 80～81 ℃；+37° (c 0.3, CHCl3)。1H-NMR (600 MHz, CDCl3) δ: 5.79 (1H, dt, J = 15.8, 7.4 Hz, H-23), 5.62 (1H, d, J = 15.8 Hz, H-24), 2.53 (1H, m, H-2a), 2.43 (1H, m, H-2b), 2.20 (2H, m, H-22), 1.92 (1H, m, H-1), 1.86 (1H, m, H-1), 1.74 (2H, m, H-5, 16a), 1.68 (1H, m, H-16b), 1.60～1.40 (7H, m, H-6, 7, 12, 13, 17), 1.38 (1H, m, H-15), 1.36 (3H, s, H-26), 1.35 (3H, s, H-27), 1.35～1.20 (4H, m, H-9, 11, 15), 1.14 (3H, s, H-21), 1.11 (1H, m, H-12), 1.08 (3H, s, H-30), 1.04 (1H, m, H-29), 1.00 (3H, s, H-28), 0.94 (3H, s, H-19), 0.88 (3H, s, H-18)；13C-NMR (150 MHz, CDCl3) δ: 218.1 (C-3), 137.3 (C-24), 127.2 (C-23), 82.1 (C-25), 75.0 (C-20), 55.3 (C-5), 50.2 (C-14), 50.1 (C-9), 49.9 (C-17), 47.4 (C-4), 43.3 (C-13), 42.5 (C-22), 40.3 (C-8), 39.9 (C-1), 36.8 (C-10), 34.5 (C-7), 34.1 (C-2), 31.1 (C-15), 27.5 (C-27), 26.7 (C-26), 25.8 (C-12), 24.8 (C-16), 24.4 (C-28), 24.1 (C-21), 21.9 (C-11), 21.0 (C-29), 19.6 (C-6), 16.3 (C-30), 16.0 (C-18), 15.2 (C-19)。以上数据文献报道一致[8]，故鉴定化合物6为isofouquierone peroxide。

化合物7：无色针晶（醋酸乙酯），mp 92～93.5 ℃； +60° (c 1.25, MeOH)。1H-NMR (600 MHz, CDCl3) δ: 5.02 (2H, m, H-26), 4.29 (1H, t, J = 6.0 Hz, H-24), 2.51 (1H, dt, J = 14.0, 7.5 Hz, H-2a), 2.43 (1H, dt, J = 14.0, 4.5 Hz, H-2b), 1.92 (1H, m, H-1), 1.82 (1H, m, H-1), 1.76 (3H, s, H-27), 1.14 (3H, s, H-21), 1.08 (3H, s, H-18), 1.04 (3H, s, H-28), 0.99 (3H, s, H-29), 0.94 (3H, s, H-19), 0.88 (3H, s, H-30)；13C-NMR (150 MHz, CDCl3) δ: 218.1 (C-3), 143.6 (C-25), 114.2 (C-26), 76.4 (C-24), 75.1 (C-20), 55.7 (C-5), 50.6 (C-9), 50.5 (C-17), 50.4 (C-14), 47.6 (C-4), 42.8 (C-13), 40.6 (C-8), 40.2 (C-1), 37.1 (C-10), 37.0 (C-22), 34.8 (C-7), 34.3 (C-2), 31.4 (C-15), 29.4 (C-23), 27.7 (C-12), 26.9 (C-28), 25.1 (C-16), 25.0 (C-21), 22.3 (C-11), 21.1 (C-29), 19.9 (C-6), 17.6 (C-27), 16.5 (C-30), 16.1 (C-18), 15.3 (C-19)。以上数据与文献报道基本一致[9]，故鉴定化合物7为20S,24S-二羟基达玛烷-25-烯-3-酮。

化合物8：无色针晶（丙酮），mp 179～180 ℃； −176° (c 0.5, MeOH)。1H-NMR (400 MHz, CDCl3) δ: 5.31 (1H, t, J = 4.5 Hz, H-7), 4.12 (1H, dd, J = 4.4, 8.8 Hz, H-23), 3.17 (1H, s, H-24), 1.32 (3H, s, H-26), 1.31 (3H, s, H-27), 1.12 (3H, s, H-19), 1.05 (3H, s, H-29), 1.02 (3H, s, H-28), 1.01 (3H, s, H-30), 0.94 (3H, d, J = 6.4 Hz, H-21), 0.82 (3H, s, H-18)；13C-NMR (100 MHz, CDCl3) δ: 217.1 (C-3), 145.7 (C-8), 117.9 (C-7), 75.1 (C-24), 74.3 (C-25), 69.7 (C-23), 53.8 (C-17), 52.3 (C-5), 51.2 (C-14), 48.4 (C-9), 47.8 (C-13), 43.5 (C-4), 40.5 (C-22), 38.5 (C-1), 35.0 (C-10), 34.9 (C-2), 34.0 (C-12), 33.8 (C-15), 33.7 (C-20), 28.4 (C-16), 27.3 (C-27), 27.3 (C-30), 26.2 (C-26), 24.5 (C-28), 24.3 (C-6), 22.0 (C-18), 21.5 (C-29), 18.9 (C-21), 18.3 (C-11), 12.7 (C-19)。以上数据与文献报道基本一致[10]，故鉴定化合物8为匹西狄醇A。

化合物9：白色脂状物； +41° (c 0.96, CHCl3)。1H-NMR (600 MHz, CDCl3) δ: 4.85 (1H, s, H-28), 4.66 (1H, s, H-28), 3.74 (1H, t, J = 7.2 Hz, H-24), 2.38 (1H, m, H-2), 2.19 (1H, m, H-2), 1.97 (1H, brd, J = 10.7 Hz, H-5), 1.73 (3H, s, H-29), 1.20 (3H, s, H-27), 1.13 (3H, s, H-26), 1.12 (3H, s, H-21), 0.99 (3H, s, H-18), 0.89 (3H, s, H-30), 0.84 (3H, s, H-19)；13C-NMR (150 MHz, CDCl3) δ: 179.8 (C-3), 147.5 (C-4), 113.5 (C-28), 86.4 (C-20), 83.3 (C-24), 71.6 (C-25), 50.8 (C-17), 50.4 (C-14), 49.5 (C-9), 43.0 (C-13), 41.1 (C-5), 40.0 (C-8), 39.1 (C-10), 35.8 (C-22), 34.3 (C-2), 33.9 (C-7), 31.5 (C-6), 31.5 (C-15), 27.4 (C-27), 27.2 (C-16), 26.2 (C-23), 25.7 (C-12), 24.6 (C-1), 24.2 (C-26), 23.5 (C-21), 23.2 (C-29), 22.1 (C-11), 20.1 (C-19), 16.4 (C-30), 15.3 (C-18)。以上数据与文献报道基本一致[4]，故鉴定化合物9为eichlerianic acid。

化合物10：无色针晶（醋酸乙酯），mp 177.5～178.5 ℃。1H-NMR (600 MHz, CDCl3) δ: 5.27 (1H, dd, J = 6.4, 3.0 Hz, H-7), 3.58 (1H, dt, J = 8.2, 6.4 Hz, H-23), 3.24 (1H, dd, J = 11.6, 4.1 Hz, H-3), 2.67 (1H, d, J = 8.2 Hz, H-24), 2.19 (1H, m, H-6a), 2.14 (1H, m, H-6b), 2.03 (1H, m, H-9), 1.96 (1H, m, H-2a), 1.80 (1H, m, H-2b), 1.34 (3H, s, H-26), 1.32 (3H, s, H-27), 0.99 (3H, s, H-19), 0.98 (3H, s, H-30), 0.96 (1H, d, J = 6.1 Hz, H-21), 0.86 (3H, s, H-28), 0.82 (3H, s, H-29), 0.75 (3H, s, H-18)；13C-NMR (150 MHz, CDCl3) δ: 145.6 (C-8), 118.1 (C-7), 79.3 (C-3), 69.3 (C-23), 68.5 (C-24), 60.3 (C-25), 53.3 (C-17), 51.2 (C-14), 50.6 (C-5), 48.9 (C-9), 43.6 (C-13), 40.7 (C-22), 39.0 (C-4), 37.2 (C-1), 34.9 (C-10), 34.0 (C-12), 33.6 (C-15), 33.6 (C-20), 28.8 (C-2), 27.7 (C-16), 27.6 (C-28), 27.2 (C-30), 24.9 (C-27), 24.0 (C-6), 21.8 (C-18), 20.0 (C-21), 19.9 (C-26), 18.2 (C-11), 14.7 (C-29), 13.1 (C-19)。以上数据与文献报道一致[10]，故鉴定化合物10为二氢尼洛替星。

化合物11：白色针晶（醋酸乙酯），mp 188.9～191.0 ℃； +80° (c 0.5, MeOH)。1H-NMR (600 MHz, CDCl3) δ: 5.17 (1H, t, J = 7.2 Hz, H-24), 3.61 (1H, ddd, J = 10.4, 10.4, 5.2 Hz, H-12), 2.51 (1H, m, H-2), 2.43 (1H, m, H-2), 2.17 (1H, m, H-1), 2.05 (2H, m, H-22), 1.97 (1H, m, H-1), 1.85 (2H, m, H-11), 1.75 (1H, t, J = 10.6 Hz, H-5), 1.70 (3H, s, H-26), 1.64 (3H, s, H-27), 1.60～1.23 (13H, m, H-6, 7, 9, 13, 15, 16, 17, 22), 1.20 (3H, s, H-21), 1.08 (3H, s, H-18), 1.04 (3H, s, H-28), 1.02 (3H, s, H-29), 0.98 (3H, s, H-19), 0.89 (3H, s, H-30)；13C-NMR (150 MHz, CDCl3) δ: 217.8 (C-3), 132.0 (C-25), 124.8 (C-24), 74.6 (C-20), 70.6 (C-12), 55.3 (C-5), 53.3 (C-17), 51.6 (C-14), 49.3 (C-9), 48.0 (C-13), 47.4 (C-4), 39.7 (C-1), 39.7 (C-8), 36.8 (C-10), 34.1 (C-2), 34.2 (C-7), 34.3 (C-22), 31.5 (C-15), 30.9 (C-11), 27.0 (C-28), 26.7 (C-21), 26.4 (C-16), 25.7 (C-26), 22.3 (C-23), 21.0 (C-29), 19.6 (C-6), 17.7 (C-27), 16.7 (C-30), 15.9 (C-18), 15.4 (C-19)。以上数据与文献报道基本一致[3]，故鉴定化合物11为12β,20β-二羟基-达玛烷-24-烯- 3-酮。

化合物12：无色针晶（醋酸乙酯），mp 156～157 ℃。1H-NMR (600 MHz, CDCl3) δ: 8.81 (1H, d, J = 5.0 Hz, H-2), 8.64 (1H, d, J = 8.2 Hz, H-8), 8.18 (1H, d, J = 8.2 Hz, H-11), 8.01 (1H, d, J = 9.7 Hz, H-4), 7.92 (1H, d, J = 5.0 Hz, H-1), 7.69 (1H, t, J = 8.2 Hz, H-9), 7.52 (1H, t, J = 8.2 Hz, H-10), 6.98 (1H, d, J = 9.7 Hz, H-5)；13C-NMR (150 MHz, CDCl3) δ: 159.4 (C-6), 145.8 (C-2), 139.6 (C-4), 139.4 (C-3a), 136.2 (C-7a), 131.9 (C-11c), 130.8 (C-11b), 130.2 (C-5), 128.9 (C-11a), 125.6 (C-9), 124.3 (C-11), 122.6 (C-10), 117.2 (C-8), 116.3 (C-1)。以上数据与文献对照基本一致[3]，故鉴定化合物12为铁屎米-6-酮。

化合物13：针状透明晶体（醋酸乙酯），mp 172～173 ℃。1H-NMR (600 MHz, CDCl3) δ: 3.88 (1H, dd, J = 10.8, 5.4 Hz, H-24), 3.54 (1H, m, H-12), 2.51 (1H, m, H-2), 2.44 (1H, m, H-2), 1.28 (3H, s, H-26), 1.24 (3H, s, H-27), 1.11 (3H, s, H-21), 1.08 (3H, s, H-19), 1.05 (3H, s, H-28), 1.04 (3H, s, H-29), 0.97 (3H, s, H-30), 0.92 (3H, s, H-18)；13C-NMR (150 MHz, CDCl3) δ: 217.8 (C-3), 87.5 (C-24), 87.1 (C-20), 70.4 (C-12), 70.1 (C-25), 55.3 (C-5), 52.2 (C-14), 49.6 (C-9), 49.0 (C-13), 48.9 (C-17), 47.4 (C-4), 39.7 (C-1), 39.6 (C-8), 36.9 (C-10), 34.1 (C-7), 32.2 (C-2), 32.1 (C-11), 31.7 (C-15), 29.7 (C-22), 28.9 (C-27), 28.5 (C-23), 28.1 (C-21), 26.7 (C-28), 25.1 (C-16), 24.3 (C-26), 20.1 (C-29), 19.7 (C-6), 17.7 (C-18), 16.1 (C-30), 15.1 (C-19)。以上数据与文献报道基本一致[11]，故鉴定化合物13为12β-hydroxy ocotillone。

化合物14：针状透明晶体（醋酸乙酯），mp 175～176 ℃。1H-NMR (600 MHz, CDCl3) δ: 3.40 (1H, brd, J = 10.2 Hz, H-24), 2.50 (1H, m, H-2), 2.43 (1H, m, H-2), 1.92 (1H, m, H-1), 1.82 (1H, m, H-12), 1.77 (1H, m, H-17), 1.73 (1H, m, H-22), 1.67～1.25 (18H, m, H-1, 5, 6, 7, 9, 11, 12, 13, 15, 16, 22, 23), 1.23 (3H, s, H-27), 1.18 (3H, s, H-26), 1.16 (3H, s, H-21), 1.08 (3H, s, H-28), 1.04 (3H, s H-29), 1.00 (3H, s, H-18), 0.95 (3H, s, H-18), 0.89 (3H, s H-30)；13C-NMR (150 MHz, CDCl3) δ: 218.1 (C-3), 78.8 (C-24), 75.5 (C-20), 73.1 (C-25), 55.3 (C-5), 50.3 (C-14), 49.8 (C-17), 48.9 (C-9), 47.4 (C-4), 42.6 (C-13), 40.2 (C-8), 39.8 (C-1), 37.1 (C-22), 36.8 (C-10), 34.5 (C-7), 34.1 (C-2), 31.1 (C-15), 27.4 (C-12), 26.7 (C-28), 26.5 (C-27), 25.6 (C-16), 25.2 (C-21), 24.9 (C-23), 23.3 (C-26), 22.0 (C-29), 20.9 (C-11), 19.6 (C-6), 16.3 (C-30), 16.0 (C-19), 15.2 (C-18)。以上数据与文献报道一致[3]，故鉴定化合物14为20S,25-epoxy-24R-hydroxy-3-dammaranone。

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