中国药学杂志

砂茴香化学成分研究

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王光明 , 朝梁 , 宋亚伟 , 明慧 , 伊力奇 , 王青虎 ^*

中国药学杂志 | 论著 2024,59(23): 2216-2225

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中国药学杂志 | 论著 2024, 59(23): 2216-2225

砂茴香化学成分研究

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王光明, 朝梁, 宋亚伟, 明慧, 伊力奇, 王青虎^*

作者信息

内蒙古民族大学蒙医药学院, 内蒙古通辽 028000

王光明,男,硕士研究生研究方向:蒙药有效物质基础及其药理

通讯作者:

^* 王青虎,男,教授,博士生导师研究方向:蒙药有效物质基础及其药理研究 Tel:(0475)8314242

Chemical Constituents from Ferula bungeana Kitagawa

Guangming WANG, Liang CHAO, Yawei SONG, Hui MING, Liqi YI, Qinghu WANG^*

Affiliations

College of Traditional Mongolian Medicine, Inner Mongolia University for Nationalities, Tongliao 028000, China

出版时间: 2024-12-08 doi: 10.11669/cpj.2024.23.003

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摘要

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目的研究砂茴香化学成分。方法采用硅胶柱色谱、薄层色谱、半制备高效液相色谱、核磁共振波谱及高分辨质谱等方法,对砂茴香的化学成分进行了研究。结果从砂茴香中分离鉴定了33个化合物,分别为棕榈酸(1)、油酸(2)、亚油酸(3)、亚麻酸(4)、去氢镰叶芹醇(5)、镰叶芹醇(6)、β-谷甾醇(7)、2,6,11,15-四甲基-2,6,10,14-十六碳四烯(8)、arteordoyn A(9)、镰叶芹二醇(10)、去氢镰叶芹二醇(11)、伞形戊烯内酯(12)、圆锥茎阿魏酮(13)、金合欢阿魏酮 A(14)、托里阿魏酮(15)、多花素宁(16)、assafoetidnol B(17)、乙酰托里阿魏诺醇(18)、托里阿魏诺醇(19)、克乐利素(20)、圆锥茎阿魏醇(21)、多胶阿魏素(22)、金合欢基阿魏醇A(23)、托里阿魏素(24)、去乙酰基克乐利素(25)、assafoetidnol A(26)、卡拉阿魏醇(27)、14'-羟基-卡拉阿魏醇(28)、古蓬阿魏酸(29)、6,7-二甲氧基香豆素(30)、香草醛(31)、7-羟基香豆素(32)和6,7-二羟基香豆素(33)。。结论化合物 5~6、9~11为该属中首次分离得到,其他均为该植物中首次分离得到。

关键词

阿魏属 / 砂茴香 / 炔 / 倍半萜香豆素 / 化学成分

Abstract

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OBJECTIVE To investigate the chemical constituents from Ferula bungeana Kitagawa. METHODS The chemical constituents from Ferula bungeana Kitagawa were investigated by silica gel chromatography, TLC, preparative HPLC, NMR, and HR-MS. RESULTS Thirty-three compounds were isolated from Ferula bungeana Kitagawa and identified, namely palmitic acid(1), oleic acid(2), linoleic acid(3), linolenic acid(4), dehydrofalcarinol(5), falcarinol(6), β-itosterol(7), 2, 6, 11, 15-tetramethyl-2, 6, 10, 14-hexadecanetetraene(8), arteordoyn A(9), falcarindiol(10), dehydrofalcarindiol(11), umbelliprenin(12), conferone(13), farnesiferone A(14), ferukrinone(15), polyanthinin(16), assafoetidnol B(17), actylfekrynol(18), fekrynol(19), kellerin(20), mogoltacin(21), gummosin(22), farnesiferol A(23), ferukrin(24), deacetylkellerin(25), assafoetidnol A(26), karatavicinol (27), 14'-hydroxy-karatavicinol (28), galbanic acid(29), 6, 7-dimethoxycoumarin(30), vanillin(31), 7-hydroxycoumarin(32) and 6, 7-dihydroxycoumarin(33). CONCLUSION Compounds 5-6, 9-11 are isolated in this genus for the first time, and others are isolated from this plant for the time.

Key words

Ferula genus / Ferula bungeana Kitagawa / alkyne / sequiterpene coumarin / chemical constituent

引用本文

王光明, 朝梁, 宋亚伟, 明慧, 伊力奇, 王青虎. 砂茴香化学成分研究. 中国药学杂志, 2024 , 59 (23) : 2216 -2225 . DOI: 10.11669/cpj.2024.23.003

Guangming WANG, Liang CHAO, Yawei SONG, Hui MING, Liqi YI, Qinghu WANG. Chemical Constituents from Ferula bungeana Kitagawa[J]. Chinese Pharmaceutical Journal, 2024 , 59 (23) : 2216 -2225 . DOI: 10.11669/cpj.2024.23.003

正文

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阿魏属植物在中国约有26种,其中7种为中国特有种,13种具有药用价值,主要产于中国新疆和内蒙古^[1-2]。阿魏属植物中已分离得到化学成分有倍半萜-香豆素杂合化合物^[3-8]、倍半萜及其衍生物^[9-13]、苯丙素类^[14-17]和其他类^[18-19],然而砂茴香化学成分尚未见到研究报道。砂茴香(Ferula bungeana Kitagawa),又名硬阿魏,来源于伞形科阿魏属植物沙茴香,以根、种子、全草入药。其在内蒙古境内分布较广,资源丰富,是具有潜在开发利用价值的天然资源。民间相传砂茴香对结核病防治有显著效果,且未见毒副反应。为了摸清砂茴香的化学信息,本实验采用硅胶柱色谱、薄层色谱及半制备高效液相色谱法对砂茴香进行分离,并鉴定了33个化合物。

1 实验材料

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LC-20Ap半制备高效液相色谱仪, AUW220D 型电子天平(日本岛津公司);Bruker AVAIVCEⅢ-500型核磁共振波谱仪(布鲁克公司);KQ-600DB型超声波仪(昆山市超声仪器有限公司);XBridge ^® BEH C₁₈OBD^TM Prep Column C₁₈色谱柱(美国沃特斯公司);甲醇(色谱纯,美国飞世尔科学公司);LH-20葡聚糖凝胶(北京普瑞因生物色谱技术有限公司);硅胶(200~300目,青岛海洋化工厂);硅胶G-TLC薄层预制板(青岛海洋化工厂);其他试剂均为分析纯。砂茴香采集于内蒙古锡林浩特市,经药用植物学红艳副教授鉴定为伞形科阿魏属植物砂茴香(Ferula bungeana Kitagawa)的全草(编号:20220602)。样品保存于内蒙古民族大学蒙医药学院蒙药化学与分析实验室备用。

2 提取分离

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2.1 乙醇提取物的制备

砂茴香20.4 kg,用20倍量的体积分数95%乙醇回流提取2次,每次4 h,减压回收溶剂,得到体积分数95%乙醇提取物(3 806 g),其收率为18.7%。

2.2 不同溶剂萃取物的制备

取砂茴香体积分数95%乙醇提取物加水适量,搅拌成混悬液。混悬液依次用二氯甲烷、乙酸乙酯和正丁醇萃取,萃取至萃取液减压回收无产生固体为止,合并萃取物,自然晾干,即得3种溶剂萃取物,分别为713、50.6和105.6 g,其得率分别为18.7%、1.3%和2.8%。因从砂茴香乙酸乙酯和正丁醇萃取物中没分到化合物,故接下来实验中没报道其分离过程。

2.3 二氯甲烷萃取物的分离

称取砂茴香二氯甲烷萃取物700 g,加适量二氯甲烷湿润,再加少量硅胶,拌样均匀,自然晾干。用湿法拌样后的样品装入硅胶(200~300目)柱色谱,采用石油醚-丙酮(100∶1→5∶1)进行梯度洗脱,流份为500 mL,每个流份减压回收溶剂至干,加二氯甲烷10 mL,溶解,溶液经TLC检测合并相同部分,得到 10个流分(Fr.1~10)。

Fr.1 (18 g)经硅胶柱色谱(石油醚-丙酮=100∶1)洗脱,得到化合物1(2.7 g)。母液浓缩至5 mL,再用TLC(展开剂为石油醚-丙酮=25∶1)制备,得到化合物2(135 mg)。Fr.2 (2 g)经硅胶柱色谱(石油醚-丙酮=100∶1)洗脱,再用TLC(展开剂为石油醚-丙酮=20∶1)制备,得到化合物3(35 mg)和4(28 mg)。Fr.3 (23 g)经硅胶柱色谱(石油醚-丙酮=90∶1)洗脱,得到化合物7(1.2 g)。母液经TLC检测,分段为2份(Fr.3A和Fr.3B)。Fr.3A用TLC(展开剂为石油醚-丙酮=18∶1)制备,得到化合物5(23 mg)和6(87 mg);Fr.3B用TLC(展开剂为石油醚-丙酮=17∶1)制备,得到化合物8(69 mg)和9(24 mg)。Fr.4(5 g)经硅胶柱色谱(石油醚-丙酮=80∶1)洗脱,再用TLC(展开剂为石油醚-丙酮=17∶1)制备,得到化合物10(86 mg)和11(35 mg)。Fr.7 (65 g)经硅胶柱色谱(石油醚-丙酮=60∶1→40∶1)梯度洗脱,经TLC检测合并相同部分,得到2个流分(Fr.7A和 Fr.7B)。Fr.7A(36 g)经硅胶柱色谱(石油醚-丙酮=70∶1→50∶1)梯度洗脱,得化合物12(1.5 g)。母液经TLC检测,分段为2份(Fr.7A-1和Fr.7A-2)。Fr.7A-1和Fr.7A-2再经Sephadex LH-20葡聚糖凝胶柱色谱(三氯甲烷-甲醇=1∶3洗脱),洗脱液分别用半制备型高效液相色谱仪进行分离,流动相分别为甲醇-水(65∶35)和甲醇-水(61∶39),得到化合物13(76 mg)、14(55 mg)、15(47 mg)、16(52 mg)、17(39 mg)和18(81 mg)。Fr.7B(7 g)经Sephadex LH-20葡聚糖凝胶柱色谱(三氯甲烷-甲醇=1∶3洗脱),洗脱液用半制备型高效液相色谱仪(甲醇-水=57∶43)进行分离,得到化合物19(38 mg)和20(61 mg)。Fr.8 (74 g)经硅胶柱色谱(石油醚-丙酮=40∶1→20∶1)梯度洗脱,得化合物21(3.5 g)。母液经TLC检测,分段为2份(Fr.8A和Fr.7B)。Fr.8A经硅胶柱色谱(石油醚-丙酮=50∶1→30∶1)梯度洗脱3次,得化合物22(31 mg)和23(29 mg)。Fr.8B经硅胶柱色谱(石油醚-丙酮=30∶1→10∶1)梯度洗脱3次,得到化合物24(57 mg)和25(18 mg)。Fr.9 (46 g)经硅胶柱色谱(石油醚-丙酮=20∶1→10∶1)梯度洗脱,经TLC检测合并相同部分,得到 2个流分(Fr.9A和 Fr.9B)。Fr.9A和 Fr.9B分别再经Sephadex LH-20葡聚糖凝胶柱色谱洗脱,洗脱液分别用半制备型高效液相色谱仪进行分离,流动相分别为甲醇-水(49∶51)和甲醇-水(45∶55),得到化合物26(38 mg)、27(74 mg)、30(19 mg)和31(27 mg)。Fr.10 (27 g)加甲醇溶解,溶液用半制备型高效液相色谱仪进行分离,流动相为甲醇-水(41∶59),得到化合物28(25 mg)、29(73 mg)、32(20 mg)和33(17 mg)。

3 结构鉴定

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化合物1:白色蜡状固体,易溶于二氯甲烷、乙醚等有机溶剂。其¹H-NMR(500 MHz,CDCl₃)和¹³C-NMR(125 MHz,CDCl₃)数据与文献[20]对照,鉴定化合物1为棕榈酸。

化合物2:淡黄色油状物,易溶于二氯甲烷、乙醚等有机溶剂。其¹H-NMR(500 MHz,CDCl₃)和¹³C-NMR(125 MHz,CDCl₃)数据与文献[21]对照,鉴定化合物2为油酸。

化合物3:淡黄色油状物,易溶于二氯甲烷、乙醚等有机溶剂。其¹H-NMR(500 MHz,CDCl₃)和¹³C-NMR(125 MHz,CDCl₃)数据与文献[21]对照,鉴定化合物3为α-亚油酸。

化合物4:淡黄色油状物,易溶于二氯甲烷、乙醚等有机溶剂。其¹H-NMR(500 MHz,CDCl₃)和¹³C-NMR(125 MHz,CDCl₃)数据与文献[22]对照,鉴定化合物4为α-亚麻酸。

化合物5:淡黄色油状物,易溶于乙醚、二氯甲烷等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.33~1.36(6H, m, H-12, 13, 14), 1.98(2H, t, J=6.5 Hz, H-11), 2.03(2H, t, J=6.5 Hz, H-15), 3.11(2H, d, J=6.5 Hz, H-8), 4.90(1H, m, H-3), 4.96(1H, d, J=16.5 Hz, H-17a), 5.03(1H, dd, J=16.5, 2.0 Hz, H-17b), 5.19(1H, brd, J=10.0 Hz, H-1b), 5.29(1H, m, H-9), 5.41(1H, brd, J=12.0 Hz, H-1a), 5.55(1H, m, H-10), 5.78(1H, m, H-16), 5.89(1H, m, H-2)。¹³C-NMR(125 MHz, CDCl₃)δ:8.0(C-8), 28.0(C-11), 28.5(C-14), 29.0(C-13), 29.3(C-12), 34.0(C-15), 64.1(C-3), 65.0(C-6), 71.5(C-5), 75.0(C-4), 80.6(C-7), 115.1(C-17), 118.2(C-1), 122.3(C-9), 133.3(C-10), 135.8(C-2), 138.8(C-16)。与文献[23]对照, 鉴定化合物5为去氢镰叶芹醇。

化合物6:淡黄色油状物, 易溶于乙醚、二氯甲烷等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.90(3H, s, H-17), 1.28~1.30(8H, m, H-12, 13, 14, 15), 1.34(2H, m, H-16), 2.05(2H, m, H-11), 3.06(2H, d, J=7.0 Hz, H-8), 4.94(1H, brs, H-3), 5.27(1H, d, J=10.0 Hz, H-1a), 5.40(1H, m, H-9), 5.50(1H, d, J=10.0 Hz, H-1b), 5.56(1H, m, H-10), 5.97(1H, m, H-2)。¹³C-NMR(125 MHz, CDCl₃)δ:14.1(C-17), 17.7(C-8), 22.7(C-16), 27.2(C-11), 29.1(C-12), 29.2(C-13), 29.3(C-14), 31.8(C-15), 63.6(C-3), 64.0(C-6), 71.3(C-5), 74.2(C-4), 80.3(C-7), 117.1(C-1), 121.9(C-9), 133.1(C-10), 136.2(C-2)。与文献[24]对照, 鉴定化合物6为镰叶芹醇。

化合物7:无色针状结晶, 易溶于乙醚、二氯甲烷等有机溶剂。其¹H-NMR(500 MHz, CDCl₃)和¹³C-NMR(125 MHz, CDCl₃)数据与文献[25]对照, 鉴定化合物7为β-谷甾醇。

化合物8:白色固体粉末, 易溶于乙醚、二氯甲烷等有机溶剂。其¹H-NMR(500 MHz, CDCl₃)和¹³C-NMR(125 MHz, CDCl₃)数据与文献[26]对照, 鉴定化合物8为2, 6, 11, 15-四甲基-2, 6, 10, 14-十六碳四烯。

化合物9:淡黄色油状物, 易溶于乙醚、二氯甲烷等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.30~1.33(6H, m, H-11, 12, 13), 1.39(2H, m, H-14), 1.45(2H, m, H-10), 1.72(2H, m, H-9), 2.03(2H, m, H-15), 4.44(1H, m, H-8), 4.91(1H, m, H-17a), 4.95(1H, m, H-3), 5.01(1H, m, H-17b), 5.31(1H, brd, J=10.0 Hz, H-1a), 5.48(1H, brd, J=17.0 Hz, H-1b), 5.83(1H, m, H-16), 5.97(1H, m, H-2)。¹³C-NMR(125 MHz, CDCl₃)δ:25.0(C-10), 28.8(C-11), 28.9(C-14), 29.0(C-13), 29.4(C-12), 34.0(C-15), 37.3(C-9), 63.0(C-8), 64.0(C-3), 69.0(C-6), 70.5(C-5), 77.5(C-4), 81.3(C-7), 114.5(C-17), 117.8(C-1), 136.0(C-2), 138.9(C-16)。与文献[27]对照, 鉴定化合物9为arteordoyn A。

化合物10:淡黄色油状物, 易溶于乙醚、二氯甲烷等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.89(3H, t, J=7.0 Hz, H-17), 1.28~1.32(10H, m, H-12, 13, 14, 15, 16), 2.12(2H, m, H-11), 4.96(1H, m, H-3), 5.23(1H, d, J=8.5 Hz, H-8), 5.28(1H, brd, J=10.0 Hz, H-1a), 5.50(1H, brd, J=17.0 Hz, H-1b), 5.52(1H, m, H-9), 5.62(1H, m, H-10), 5.95(1H, m, H-2)。¹³C-NMR(125 MHz, CDCl₃)δ:14.1(C-17), 22.7(C-16), 27.7(C-11), 29.0(C-13), 29.1(C-12), 29.3(C-14), 31.8(C-15), 58.5(C-8), 63.4(C-3), 68.7(C-6), 70.3(C-5), 78.7(C-4), 79.8(C-7), 117.4(C-1), 127.6(C-9), 134.6(C-10), 135.8(C-2)。与文献[28]对照, 鉴定化合物10为镰叶芹二醇。

化合物11:淡黄色油状物, 易溶于乙醚、二氯甲烷等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.36~1.40(6H, m, H-12, 13, 14), 2.03(2H, brt, J=6.5 Hz, H-15), 2.11(2H, brt, J=6.5 Hz, H-11), 4.89(1H, m, H-3), 4.95(1H, dd, J=17.0, 8.0 Hz, H-17a), 5.00(1H, dd, J=17.0, 1.5 Hz, H-17b), 5.19(1H, brd, J=8.0 Hz, H-8), 5.30(1H, brd, J=10.0 Hz, H-1a), 5.50(1H, brd, J=17.0 Hz, H-1b), 5.53(1H, brd, J=7.5 Hz, H-9), 5.63(1H, m, H-10), 5.79(1H, m, H-16), 5.90(1H, m, H-2)。¹³C-NMR(125 MHz, CDCl₃)δ:27.5(C-11), 28.1(C-13), 28.3(C-14), 28.9(C-12), 34.0(C-15), 59.1(C-8), 63.3(C-3), 68.6(C-6), 70.7(C-5), 78.5(C-4), 80.3(C-7), 115.2(C-17), 118.1(C-1), 127.2(C-9), 134.1(C-10), 136.1(C-2), 138.9(C-16)。与文献[28]对照, 鉴定化合物11为去氢镰叶芹二醇。

化合物12:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.18(3H, s, H-13'), 1.60(3H, s, H-14'), 1.61(3H, s, H-15'), 1.78(3H, s, H-12'), 2.02(2H, m, H-1'), 2.07(2H, m, H-2'), 2.11(2H, m, H-7'), 2.12(2H, m, H-6'), 4.61(2H, d, J=6.5 Hz, H-11'), 5.07(1H, m, H-3'), 5.10(1H, m, H-5'), 5.48(1H, m, H-9'), 6.26(1H, d, J=9.5 Hz, H-3), 6.82(1H, d, J=2.5 Hz, H-8), 6.86(1H, dd, J=8.5, 2.5 Hz, H-6), 7.38(1H, d, J=8.5 Hz, H-5), 7.65(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:16.1(C-15'), 16.8(C-12'), 17.7(C-14'), 25.7(C-13'), 26.1(C-2'), 26.5(C-6'), 39.3(C-7'), 39.7(C-1'), 65.5(C-11'), 101.6(C-8), 112.4(C-9), 112.9(C-3), 113.2(C-6), 118.0(C-9'), 123.1(C-5'), 124.3(C-3'), 128.7(C-5), 131.7(C-4'), 135.6(C-10'), 142.4(C-8'), 143.5(C-4), 155.9(C-10), 161.3(C-2), 162.1(C-7)。与文献[29]对照, 鉴定化合物12为伞形戊烯内酯。

化合物13:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.11(3H, s, H-13'), 1.16(3H, s, H-14'), 1.17(3H, s, H-15'), 1.68(1H, m, H-1'a), 1.70(1H, m, H-5'), 1.76(3H, s, H-12'), 2.02(1H, m, H-6'a), 2.14(1H, m, H-6'b), 2.32(1H, m, H-1'b), 2.33(1H, m, H-9'), 2.34(2H, m, H-2'), 4.12(1H, dd, J=10.0, 5.0 Hz, H-11'a), 4.21(1H, dd, J=10.0, 4.0 Hz, H-11'b), 5.63(1H, m, H-7'), 6.29(1H, d, J=9.5 Hz, H-3), 6.84(1H, d, J=2.5 Hz, H-8), 6.88(1H, dd, J=8.5, 2.5 Hz, H-6), 7.40(1H, d, J=8.5 Hz, H-5), 7.67(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃ )δ:14.5(C-15'), 21.6(C-12'), 22.3(C-14'), 23.9(C-6'), 25.3(C-13'), 34.4(C-2'), 35.8(C-10'), 38.5(C-1'), 47.5(C-4'), 51.1(C-5'), 53.1(C-9'), 66.7(C-11'), 101.3(C-8), 112.9(C-9), 113.1(C-3), 113.2(C-6), 123.7(C-7'), 128.8(C-5), 132.4(C-8'), 143.3(C-4), 155.9(C-10), 161.1(C-2), 161.8(C-7), 216.1(C-3')。与文献[30]对照, 鉴定化合物13为圆锥茎阿魏酮。

化合物14:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.06(3H, s, H-13'), 1.15(3H, s, H-14'), 1.19(3H, s, H-15'), 1.57(2H, m, H-6'), 1.69(1H, brd, J=15.0 Hz, H-1'a), 1.78(1H, dd, J=10.0, 2.0 Hz, H-5'), 1.98(1H, m, H-1'b), 2.08(1H, m, H-7'a), 2.33(1H, m, H-7'b), 2.35(1H, m, H-9'), 2.38(1H, m, H-2'a), 2.81(1H, m, H-2'b), 4.02(1H, dd, J=10.0, 5.0 Hz, H-11'a), 4.25(1H, dd, J=10.0, 4.0 Hz, H-11'b), 4.61(1H, s, H-12'a), 4.90(1H, s, H-12'b), 6.23(1H, d, J=9.5 Hz, H-3), 6.77(1H, d, J=2.5 Hz, H-8), 6.79(1H, dd, J=8.5, 2.5 Hz, H-6), 7.33(1H, d, J=8.5 Hz, H-5), 7.61(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:20.3(C-15'), 21.2(C-14'), 23.8(C-6'), 25.6(C-13'), 32.8(C-2'), 35.0(C-7'), 36.1(C-1'), 37.5(C-10'), 47.5(C-5'), 47.9(C-4'), 56.1(C-9'), 68.0(C-11'), 101.6(C-8), 112.2(C-12'), 112.6(C-9), 112.8(C-6), 113.1(C-3), 128.6(C-5), 143.1(C-4), 146.1(C-8'), 155.8(C-10), 161.0(C-7), 161.5(C-2), 215.5(C-3')。与文献[31]对照, 鉴定化合物14为金合欢阿魏酮 A。

化合物15:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.06(3H, s, H-15'), 1.08(3H, s, H-14'), 1.14(3H, s, H-13'), 1.31(3H, s, H-12'), 1.48(1H, m, H-6'a), 1.57(1H, m, H-5'), 1.58(1H, m, H-7'a), 1.68(1H, m, H-6'b), 1.74(1H, m, H-1'a), 1.86(1H, m, H-9'), 1.98(1H, m, H-7'b), 2.03(1H, m, H-1'b), 2.47(1H, m, H-2'a), 2.56(1H, m, H-2'b), 4.20(1H, dd, J=10.0, 6.0 Hz, H-11'a), 4.38(1H, dd, J=10.0, 5.0 Hz, H-11'b), 6.26(1H, d, J=9.5 Hz, H-3), 6.86(1H, dd, J=8.5, 2.5 Hz, H-6), 6.90(1H, d, J=2.5 Hz, H-8), 7.35(1H, d, J=8.5 Hz, H-5), 7.65(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:15.5(C-15'), 21.3(C-14'), 21.4(C-6'), 24.0(C-12'), 26.1(C-13'), 33.8(C-2'), 37.3(C-10'), 38.5(C-1'), 43.1(C-7'), 47.5(C-4'), 54.5(C-5'), 58.0(C-9'), 66.5(C-11'), 72.3(C-8'), 101.6(C-8), 112.9(C-9), 113.1(C-6), 113.4(C-3), 128.8(C-5), 143.3(C-4), 155.9(C-10), 161.1(C-7), 161.5(C-2), 216.3(C-3')。与文献[32]对照, 鉴定化合物15为托里阿魏酮。

化合物16:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.89(3H, s, H-15'), 0.91(3H, s, H-13'), 0.94(3H, s, H-14'), 2.11(3H, s, COCH₃), 1.45(1H, m, H-6'a), 1.57(1H, m, H-6'b), 1.59(1H, m, H-1'a), 1.67(1H, m, H-5'), 1.73(1H, m, H-1'b), 1.76(1H, m, H-2'a), 1.93(1H, m, H-2'b), 2.17(1H, m, H-7'b), 2.36(1H, m, H-9'), 2.51(1H, m, H-7'a), 4.02(1H, m, H-11'a), 4.23(1H, dd, J=13.6, 6.5 Hz, H-11'b), 4.56(1H, brs, H-12'a), 4.71(1H, m, H-3'), 4.94(1H, brs, H-12'b), 6.27(1H, d, J=9.5 Hz, H-3), 6.85(1H, d, J=2.5 Hz, H-8), 6.86(1H, dd, J=8.5, 2.5 Hz, H-6), 7.39(1H, d, J=8.5 Hz, H-5), 7.66(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:15.3(C-15'), 21.3(COCH₃), 21.9(C-14'), 23.2(C-6'), 23.3(C-2'), 28.1(C-13'), 32.5(C-1'), 36.9(C-4'), 37.4(C-7'), 38.7(C-10'), 49.3(C-5'), 54.8(C-9'), 65.6(C-11'), 77.8(C-3'), 101.4(C-8), 107.8(C-12'), 112.5(C-9), 113.0(C-3), 113.1(C-6), 128.7(C-5), 143.4(C-4), 146.4(C-8'), 155.9(C-10), 161.2(C-2), 162.3(C-7), 170.5(COCH₃)。与文献[33]对照, 鉴定化合物16为多花素宁。

化合物17:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.01(3H, s, H-15'), 1.11(3H, s, H-14'), 1.22(3H, s, H-13'), 1.62(1H, m, H-1'a), 1.73(1H, m, H-1'b), 1.75(1H, m, H-2'a), 1.93(1H, m, H-2'b), 2.01(3H, s, COCH₃), 2.10(1H, J=12.0 Hz, H-5'), 2.34(1H, m, H-9'), 3.66(1H, dd, J=12.0, 10.0 Hz, H-6'), 4.03(1H, d, J=10.0 Hz, H-7'), 4.06(1H, dd, J=10.0, 6.0 Hz, H-11'a), 4.35(1H, dd, J=10.0, 5.0 Hz, H-11'b), 4.66(1H, brs, H-3'), 4.87(1H, brs, H-12'a), 5.17(1H, brs, H-12'b), 6.27(1H, d, J=9.5 Hz, H-3), 6.78(1H, d, J=2.5 Hz, H-8), 6.84(1H, dd, J=8.5, 2.5 Hz, H-6), 7.37(1H, d, J=8.5 Hz, H-5), 7.64(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:15.7(C-14'), 16.8(C-15'), 21.3(COCH₃), 23.0(C-2'), 28.7(C-13'), 30.2(C-1'), 37.5(C-10'), 37.7(C-4'), 45.2(C-5'), 56.6(C-9'), 68.3(C-11'), 74.8(C-6'), 77.5(C-7'), 79.9(C-3'), 101.4(C-8), 110.3(C-12'), 112.5(C-9), 113.0(C-3), 113.2(C-6), 128.8(C-5), 143.4(C-4), 145.7(C-8'), 155.9(C-10), 161.1(C-2), 161.9(C-7), 170.1(COCH₃)。与文献[34]对照, 鉴定化合物17为assafoetidnol B。

化合物18:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.92(3H, d, J=7.0 Hz, H-13'), 1.16(3H, s, H-12'), 1.20(2H, m, H-7'), 1.40(2H, m, H-2'), 1.44(3H, s, H-14'), 1.60(3H, s, H-15'), 1.69(1H, m, H-1'a), 1.73(1H, m, H-1'b), 1.86(1H, m, H-8'), 2.01(3H, s, COCH₃), 2.92(1H, m, H-10'), 2.50(2H, d, J=12.0 Hz, H-6'), 3.69(1H, d, J=8.0 Hz, H-11'a), 3.88(1H, d, J=8.0 Hz, H-11'b), 4.05(1H, brs, H-3'), 6.27(1H, d, J=9.5 Hz, H-3), 6.78(1H, d, J=2.5 Hz, H-8), 6.84(1H, dd, J=8.5, 2.5 Hz, H-6), 7.37(1H, d, J=8.5 Hz, H-5), 7.64(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:16.0(C-13'), 19.6(C-14'), 19.8(C-15'), 21.0(COCH₃), 22.5(C-12'), 23.4(C-1'), 24.4(C-6'), 26.8(C-2'), 31.7(C-7'), 35.0(C-8'), 40.8(C-9'), 43.0(C-10'), 65.0(C-3'), 71.7(C-11'), 101.1(C-8), 112.3(C-9), 112.6(C-3), 113.2(C-6), 124.6(C-4'), 128.5(C-5), 129.8(C-5'), 143.4(C-4), 155.9(C-10), 161.3(C-2), 162.6(C-7), 170.3(COCH₃)。与文献[35]对照, 鉴定化合物18为乙酰托里阿魏诺醇。

化合物19:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.89(3H, d, J=7.0 Hz, H-13'), 1.15(3H, s, H-12'), 1.23(2H, m, H-7'), 1.39(3H, s, H-14'), 1.43(2H, m, H-2'), 1.61(3H, s, H-15'), 1.71(1H, m, H-1'a), 1.75(1H, m, H-1'b), 1.88(1H, m, H-8'), 2.46(2H, d, J=12.0 Hz, H-6'), 2.91(1H, m, H-10'), 3.71(1H, d, J=8.0 Hz, H-11'a), 3.89(1H, d, J=8.0 Hz, H-11'b), 4.01(1H, brs, H-3'), 6.23(1H, d, J=9.5 Hz, H-3), 6.71(1H, d, J=2.5 Hz, H-8), 6.88(1H, dd, J=8.5, 2.5 Hz, H-6), 7.33(1H, d, J=8.5 Hz, H-5), 7.61(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:15.9(C-13'), 19.3(C-14'), 20.3(C-15'), 22.5(C-12'), 23.5(C-1'), 24.6(C-6'), 26.8(C-2'), 31.7(C-7'), 34.8(C-8'), 41.0(C-9'), 43.3(C-10'), 66.3(C-3'), 72.6(C-11'), 101.3(C-8), 112.1(C-9), 112.5(C-3), 113.2(C-6), 124.4(C-4'), 128.5(C-5), 129.6(C-5'), 143.5(C-4), 155.9(C-10), 161.1(C-2), 162.9(C-7)。与文献[36]对照, 鉴定化合物19为托里阿魏诺醇。

化合物20:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.03(3H, s, H-13'), 1.07(3H, s, H-15'), 1.09(3H, s, H-14'), 1.13(1H, m, H-1'a), 1.29(3H, s, H-12'), 1.45(1H, m, H-6'a), 1.56(1H, m, H-9'), 1.58(1H, m, H-2'a), 1.71(1H, m, H-6'b), 1.76(2H, m, H-7'), 1.80(1H, m, H-1'b), 2.01(3H, s, COCH₃), 2.06(1H, m, H-5'), 2.07(1H, m, H-2'b), 4.21(1H, dd, J=10.0, 5.0 Hz, H-11'a), 4.30(1H, dd, J=10.0, 3.0 Hz, H-11'b), 4.86(1H, t, J=3.0 Hz, H-3'), 6.26(1H, d, J=9.5 Hz, H-3), 6.89(1H, dd, J=8.5, 2.5 Hz, H-6), 6.93(1H, d, J=2.5 Hz, H-8), 7.46(1H, d, J=8.5 Hz, H-5), 7.76(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:16.8(C-15'), 19.8(COCH₃), 20.3(C-14'), 21.1(C-6'), 23.0(C-13'), 23.8(C-2'), 31.4(C-12'), 32.0(C-1'), 38.8(C-4'), 40.6(C-7'), 43.2(C-10'), 46.0(C-5'), 58.6(C-9'), 68.6(C-11'), 75.0(C-8'), 75.8(C-3'), 101.8(C-8), 113.2(C-3), 114.5(C-9), 115.0(C-6), 128.9(C-5), 144.1(C-4), 155.8(C-10), 161.3(C-2), 162.1(C-7), 171.1(COCH₃)。与文献[37]对照, 鉴定化合物20为克乐利素。

化合物21:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.94(3H, s, H-15'), 0.95(3H, s, H-14'), 0.99(3H, s, H-13'), 1.61(1H, m, H-1'a), 1.71(1H, m, H-6'a), 1.74(3H, s, H-12'), 1.76(1H, m, H-1'b), 1.78(1H, m, H-2'a), 1.80(1H, m, H-5'), 1.91(1H, m, H-2'b), 1.98(1H, m, H-6'b), 2.34(1H, m, H-9'), 3.50(1H, m, H-3'), 4.06(1H, dd, J=9.5, 1.0 Hz, H-11'a), 4.21(1H, dd, J=9.5, 3.0 Hz, H-11'b), 5.57(1H, m, H-7'), 6.27(1H, d, J=9.5 Hz, H-3), 6.84(1H, d, J=2.5 Hz, H-8), 6.86(1H, dd, J=8.5, 2.5 Hz, H-6), 7.39(1H, d, J=8.5 Hz, H-5), 7.66(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:14.8(C-15'), 21.8(C-12'), 22.4(C-14'), 23.2(C-2'), 25.1(C-6'), 28.1(C-13'), 31.8(C-1'), 35.6(C-10'), 37.2(C-4'), 43.4(C-5'), 53.5(C-9'), 67.1(C-11'), 75.8(C-3'), 101.3(C-8), 112.5(C-9), 113.0(C-3), 113.1(C-6), 123.8(C-7'), 128.7(C-5), 132.5(C-8'), 143.5(C-4), 155.9(C-10), 161.3(C-2), 162.1(C-7)。与文献[38]对照, 鉴定化合物21为圆锥茎阿魏醇。

化合物22:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.10(3H, s, H-13'), 1.20(3H, s, H-14'), 1.23(3H, s, H-15'), 1.55(2H, m, H-6'), 1.59(1H, brd, J=12.0 Hz, H-1'a), 1.69(1H, dd, J=10.0, 2.0 Hz, H-5'), 1.71(1H, m, H-2'a), 1.76(1H, m, H-2'b), 1.87(1H, m, H-1'b), 2.07(1H, m, H-7'a), 2.26(1H, m, H-7'b), 2.40(1H, m, H-9'), 3.68(1H, m, H-3'), 4.06(1H, dd, J=10.0, 5.0 Hz, H-11'a), 4.31(1H, dd, J=10.0, 4.0 Hz, H-11'b), 4.59(1H, s, H-12'a), 4.89(1H, s, H-12'b), 6.22(1H, d, J=9.5 Hz, H-3), 6.75(1H, d, J=2.5 Hz, H-8), 6.80(1H, dd, J=8.5, 2.5 Hz, H-6), 7.36(1H, d, J=8.5 Hz, H-5), 7.63(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:15.6(C-15'), 21.3(C-14'), 23.8(C-6'), 25.8(C-2'), 28.5(C-13'), 33.4(C-1'), 36.8(C-7'), 37.8(C-4'), 38.3(C-10'), 47.2(C-5'), 54.3(C-9'), 65.7(C-11'), 75.6(C-3'), 101.4(C-8), 107.3(C-12'), 112.4(C-9), 112.9(C-3), 113.2(C-6), 128.7(C-5), 143.3(C-4), 146.7(C-8'), 156.0(C-10), 161.2(C-7), 161.8(C-2)。与文献[39]对照, 鉴定化合物22为多胶阿魏素。

化合物23:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.96(3H, s, H-15'), 0.99(3H, s, H-13'), 1.33(1H, dd, J=14.0, 5.0 Hz, H-2'a), 1.36(3H, s, H-14'), 1.39(1H, d, J=10.0 Hz, H-5'), 1.55(2H, m, H-6'), 1.65(2H, m, H-1'), 1.68(1H, m, H-2'b), 2.10(1H, dd, J=6.0, 5.0 Hz, H-9'), 2.20(1H, dd, J=14.0, 13.0 Hz, H-7'a), 2.66(1H, dd, J=14.0, 5.0 Hz, H-7'b), 3.21(1H, dd, J=11.0, 5.0 Hz, H-3'), 4.05(1H, dd, J=10.0, 5.0 Hz, H-11'a), 4.27(1H, dd, J=10.0, 6.0 Hz, H-11'b), 4.75(1H, brs, H-12'a), 4.84(1H, bss, H-12'b), 6.22(1H, d, J=9.5 Hz, H-3), 6.77(1H, d, J=2.5 Hz, H-8), 6.80(1H, dd, J=8.5, 2.5 Hz, H-6), 7.31(1H, d, J=8.5 Hz, H-5), 7.64(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:15.9(C-15'), 23.2(C-14'), 24.1(C-6'), 27.1(C-1'), 31.2(C-13'), 35.3(C-2'), 38.3(C-10'), 39.2(C-4'), 43.6(C-7'), 47.3(C-5'), 56.0(C-9'), 67.5(C-11'), 78.8(C-3'), 101.4(C-8), 112.5(C-12'), 112.7(C-9), 112.8(C-3), 113.2(C-6), 128.7(C-5), 141.2(C-8'), 143.5(C-4), 155.7(C-10), 161.3(C-2), 161.9(C-7)。与文献[34]对照, 鉴定化合物23为金合欢基阿魏醇A。

化合物24:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.97(3H, s, H-15'), 1.01(3H, s, H-13'), 1.16(3H, s, H-14'), 1.28(3H, s, H-12'), 1.35(1H, dd, J=14.0, 5.0 Hz, H-2'a), 1.37(1H, d, J=10.0 Hz, H-5'), 1.55(2H, m, H-6'), 1.58(1H, m, H-9'), 1.67(2H, m, H-1'), 1.70(1H, m, H-2'b), 1.77(2H, m, H-7'), 3.22(1H, dd, J=11.0, 5.0 Hz, H-3'), 4.21(1H, dd, J=10.0, 3.0 Hz, H-11'a), 4.33(1H, dd, J=10.0, 2.0 Hz, H-11'b), 6.21(1H, d, J=9.5 Hz, H-3), 6.78(1H, d, J=2.5 Hz, H-8), 6.82(1H, dd, J=8.5, 2.5 Hz, H-6), 7.34(1H, d, J=8.5 Hz, H-5), 7.65(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:15.8(C-15'), 23.5(C-14'), 24.3(C-6'), 27.6(C-1'), 28.8(C-12'), 30.2(C-13'), 34.9(C-2'), 38.7(C-4'), 40.5(C-7'), 44.1(C-10'), 47.5(C-5'), 58.6(C-9'), 69.1(C-11'), 74.3(C-8'), 78.9(C-3'), 102.2(C-8), 113.2(C-3), 113.8(C-6), 114.1(C-9), 129.1(C-5), 145.3(C-4), 156.0(C-10), 162.1(C-2), 162.8(C-7)。与文献[40]对照, 鉴定化合物24为托里阿魏素。

化合物25:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.96(3H, s, H-13'), 1.13(1H, t, J=3.0 Hz, H-1'a), 1.16(3H, s, H-14'), 1.21(3H, s, H-15'), 1.29(3H, s, H-12'), 1.45(1H, m, H-6'a), 1.55(1H, m, H-9'), 1.57(1H, m, H-2'a), 1.73(1H, m, H-6'b), 1.76(2H, m, H-7'), 1.81(1H, d, J=12.0 Hz, H-1'b), 2.06(1H, m, H-2'b), 2.13(1H, m, H-5'), 3.34(1H, t, J=2.5 Hz, H-3'), 4.23(1H, dd, J=10.0, 3.0 Hz, H-11'a), 4.30(1H, dd, J=10.0, 2.0 Hz, H-11'b), 6.25(1H, d, J=9.5 Hz, H-3), 6.93(1H, dd, J=8.5, 2.5 Hz, H-6), 6.96(1H, d, J=2.5 Hz, H-8), 7.53(1H, d, J=8.5 Hz, H-5), 7.87(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:17.8(C-15'), 20.5(C-6'), 21.3(C-14'), 23.9(C-2'), 25.3(C-13'), 28.6(C-12'), 31.6(C-1'), 37.3(C-5'), 40.8(C-7'), 41.6(C-4'), 43.5(C-10'), 59.0(C-9'), 69.4(C-11'), 71.3(C-3'), 74.1(C-8'), 102.0(C-8), 113.2(C-3), 114.0(C-6), 114.2(C-9), 129.1(C-5), 145.3(C-4), 156.3(C-10), 162.1(C-2), 162.6(C-7)。与文献[40]对照, 鉴定化合物25为去乙酰基克乐利素。

化合物26:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.97(3H, s, H-15'), 1.01(3H, s, H-13'), 1.11(1H, t, J=3.0 Hz, H-1'a), 1.17(3H, s, H-14'), 1.40(1H, d, J=10.0 Hz, H-5'), 1.55(1H, m, H-2'a), 1.79(1H, d, J=12.0 Hz, H-1'b), 2.03(1H, m, H-2'b), 2.09(1H, dd, J=7.0, 5.0 Hz, H-9'), 2.20(1H, dd, J=14.0, 13.0 Hz, H-7'a), 2.60(1H, dd, J=14.0, 5.0 Hz, H-7'b), 3.36(1H, t, J=2.5 Hz, H-3'), 3.97(1H, m, H-6'), 4.05(1H, dd, J=10.0, 5.0 Hz, H-11'a), 4.26(1H, dd, J=10.0, 6.0 Hz, H-11'b), 4.71(1H, brs, H-12'a), 4.81(1H, bss, H-12'b), 6.24(1H, d, J=9.5 Hz, H-3), 6.76(1H, d, J=2.5 Hz, H-8), 6.81(1H, dd, J=8.5, 2.5 Hz, H-6), 7.35(1H, d, J=8.5 Hz, H-5), 7.66(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:17.9(C-15'), 21.9(C-14'), 24.1(C-2'), 25.6(C-13'), 31.8(C-1'), 38.7(C-10'), 41.8(C-4'), 43.1(C-7'), 50.9(C-5'), 55.9(C-9'), 67.8(C-11'), 70.5(C-6'), 73.1(C-3'), 102.5(C-8), 112.7(C-12'), 113.2(C-3), 114.1(C-6), 114.5(C-9), 129.1(C-5), 141.3(C-8'), 145.3(C-4), 156.1(C-10), 161.9(C-2), 162.6(C-7)。与文献[34]对照, 鉴定化合物26为assafoetidnol A。

化合物27:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.16(3H, s, H-14'), 1.19(3H, s, H-13'), 1.53(2H, m, H-2'), 1.60(3H, brs, H-12'), 1.73(3H, brs, H-15'), 2.23(2H, t, J=6.0 Hz, H-1'), 2.35(2H, t, J=6.0 Hz, H-7'), 2.43(1H, m, H-6'), 3.36(1H, dd, J=10.0, 2.5 Hz, H-3'), 4.53(2H, d, J=6.0 Hz, H-11'), 5.14(1H, brd, J=6.0 Hz, H-5'), 5.45(1H, t, J=6.0 Hz, H-9'), 6.21(1H, d, J=9.5 Hz, H-3), 6.75(1H, d, J=2.5 Hz, H-8), 6.80(1H, dd, J=8.5, 2.5 Hz, H-6), 7.30(1H, d, J=8.5 Hz, H-5), 7.62(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:16.3(C-15'), 17.0(C-13'), 23.7(C-14'), 26.1(C-12'), 26.2(C-2'), 30.2(C-6'), 36.8(C-7'), 39.2(C-1'), 65.3(C-11'), 73.2(C-4'), 78.0(C-3'), 101.5(C-8), 112.4(C-3), 113.0(C-6), 113.5(C-9), 118.2(C-9'), 124.0(C-5'), 128.9(C-5), 135.4(C-10'), 144.0(C-8'), 144.2(C-4), 156.0(C-10), 161.6(C-7), 162.0(C-2)。与文献[41]对照, 鉴定化合物27为卡拉阿魏醇。

化合物28:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:1.31(3H, s, H-13'), 1.58(3H, brs, H-12'), 1.46(2H, m, H-2'), 1.68(3H, brs, H-15'), 2.33(2H, t, J=6.0 Hz, H-7'), 2.37(1H, m, H-6'), 2.41(2H, t, J=6.0 Hz, H-1'), 3.67(1H, dd, J=10.0, 2.5 Hz, H-3'), 3.96(1H, d, J=12.0 Hz, H-14'a), 4.06(1H, d, J=12.0 Hz, H-14'b), 4.56(2H, d, J=6.0 Hz, H-11'), 5.15(1H, brd, J=6.0 Hz, H-5'), 5.50(1H, t, J=6.0 Hz, H-9'), 6.22(1H, d, J=9.5 Hz, H-3), 6.77(1H, d, J=2.5 Hz, H-8), 6.83(1H, dd, J=8.5, 2.5 Hz, H-6), 7.33(1H, d, J=8.5 Hz, H-5), 7.62(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:16.7(C-15'), 17.7(C-13'), 26.3(C-12'), 27.1(C-2'), 31.2(C-6'), 36.6(C-7'), 39.1(C-1'), 66.1(C-11'), 68.3(C-14'), 75.3(C-4'), 79.1(C-3'), 101.2(C-8), 112.9(C-3), 113.3(C-6), 113.5(C-9), 118.0(C-9'), 124.4(C-5'), 128.9(C-5), 135.3(C-10'), 144.1(C-8'), 144.3(C-4), 155.9(C-10), 161.8(C-7), 162.0(C-2)。与文献[41]对照, 鉴定化合物28为14'-羟基-卡拉阿魏醇。

化合物29:白色粉末, 易溶于乙醚、二氯甲烷、乙酸乙酯等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:0.93(3H, brs, H-15'), 1.14(3H, d, J=6.5 Hz, H-12'), 1.19(1H, m, H-7'a), 1.62(3H, s, H-13'), 1.70(2H, m, H-1'), 1.72(3H, s, H-14'), 1.75(1H, m, H-9'), 1.92(1H, m, H-7'b), 1.83(1H, m, H-8'), 2.37(2H, m, H-2'), 2.50(1H, m, H-6'), 3.97(1H, dd, J=10.0, 5.0 Hz, H-11'a), 4.02(1H, dd, J=10.0, 7.0 Hz, H-11'b), 5.13(1H, brd, J=10.0 Hz, H-5'), 6.24(1H, d, J=9.5 Hz, H-3), 6.77(1H, d, J=2.5 Hz, H-8), 6.82(1H, dd, J=8.5, 2.5 Hz, H-6), 7.35(1H, d, J=8.5 Hz, H-5), 7.63(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:18.1(C-13'), 20.7(C-12'), 21.0(C-15'), 26.3(C-14'), 29.1(C-2'), 33.2(C-1'), 36.1(C-8'), 40.1(C-7'), 47.0(C-9'), 49.3(C-6'), 53.1(C-10'), 69.3(C-11'), 101.2(C-8), 112.5(C-9), 112.6(C-6), 113.2(C-3), 125.3(C-5'), 128.7(C-5), 132.1(C-4'), 143.5(C-4), 156.0(C-10), 161.2(C-2), 162.1(C-7), 178.9(C-3')。与文献[32]对照, 鉴定化合物29为古蓬阿魏酸。

化合物30:白色针状结晶, 易溶于乙醚、二氯甲烷等有机溶剂。¹H-NMR(500 MHz, CDCl₃)δ:3.90(3H, s, 6-OCH₃), 3.92(3H, s, 7-OCH₃), 6.32(1H, d, J=9.5 Hz, H-3), 7.20(1H, s, H-8), 7.37(1H, s, H-5), 7.91(1H, d, J=9.5 Hz, H-4)。¹³C-NMR(125 MHz, CDCl₃)δ:56.5(6-OCH₃), 56.7(7-OCH₃), 103.1(C-8), 110.5(C-5), 112.8(C-9), 113.7(C-3), 143.1(C-4), 144.6(C-6), 146.5(C-7), 155.8(C-10), 161.1(C-2)。与文献[42]对照,鉴定化合物30为6,7-二甲氧基香豆素。

化合物31:白色针状结晶,易溶于乙醚、二氯甲烷等有机溶剂。其¹H-NMR(500 MHz,CDCl₃)和¹³C-NMR(125 MHz,CDCl₃)数据与文献[43]对照,鉴定化合物31为香草醛。

化合物32:白色针状结晶,在紫外灯下(365 nm)具有天蓝色荧光,易溶于乙醚、二氯甲烷等有机溶剂。其¹H-NMR(500 MHz,CDCl₃)和¹³C-NMR(125 MHz,CDCl₃)数据与文献[44]对照,鉴定化合物32为7-甲氧基香豆素。

化合物33:白色针状结晶,在紫外灯下(365 nm)具有天蓝色荧光,易溶于乙醚、二氯甲烷等有机溶剂。其¹H-NMR(500 MHz,CDCl₃)和¹³C-NMR(125 MHz,CDCl₃)数据与文献[44]对照,鉴定化合物33为6,7-二羟基香豆素。

4 讨论

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砂茴香是我国特有且具药用价值的阿魏属植物之一,在内蒙古境内分布较广,资源丰富,是具有潜在开发利用价值的天然资源。近几年,民间相传砂茴香对结核病防治有显著效果,且未见毒副反应。目前,对于砂茴香的化学成分方面研究尚未见到报道。本实验对砂茴香进行了系统的化学成分研究。

借助于现代色谱和波谱技术从砂茴香二氯甲烷萃取物中分离鉴定了33个化合物,其中倍半萜香豆素类18个、炔类5个、脂肪酸类4个、香豆素类3个和其他类3个。化合物5~6、9~11为该属中首次分离得到,其他化合物均为该植物中首次分离得到,为该植物后续研究打下了前期的实验基础。

基金

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蒙药研发国家地方联合工程研究中心开放基金项目(MDK2023040)
内蒙古自治区中蒙药重点实验室开放基金项目(MYX2022-K06)

参考文献

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文献

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2024年第59卷第23期

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doi: 10.11669/cpj.2024.23.003

接收时间：2024-05-13
首发时间：2025-11-13
出版时间：2024-12-08

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收稿日期：2024-05-13

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蒙药研发国家地方联合工程研究中心开放基金项目(MDK2023040)

内蒙古自治区中蒙药重点实验室开放基金项目(MYX2022-K06)

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内蒙古民族大学蒙医药学院, 内蒙古通辽 028000

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^* 王青虎,男,教授,博士生导师研究方向:蒙药有效物质基础及其药理研究 Tel:(0475)8314242

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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