CN116425817A - 一种从瑶药六方藤中提取多种单体化合物的方法 - Google Patents
一种从瑶药六方藤中提取多种单体化合物的方法 Download PDFInfo
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- CN116425817A CN116425817A CN202310144784.4A CN202310144784A CN116425817A CN 116425817 A CN116425817 A CN 116425817A CN 202310144784 A CN202310144784 A CN 202310144784A CN 116425817 A CN116425817 A CN 116425817A
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Abstract
本发明涉及中药提取分离技术领域,具体公开了一种从瑶药六方藤中提取多种单体化合物的方法。该方法包括将六方藤药材粉碎、经75%乙醇渗漉提取得到乙醇总提取物,将乙醇总提取物用水混悬,依次用石油醚、乙酸乙酯、正丁醇萃取,回收溶剂,得到石油醚部位浸膏、乙酸乙酯部位浸膏和正丁醇部位浸膏,以及石油醚部位和乙酸乙酯部位的分离纯化等步骤。采用本发明方法能从六方藤药材中提取分离得到β‑谷甾醇、白藜芦醇、没食子酸、岩白菜素、原儿茶酸、齐敦果酸等25个单体化合物,为更好的开发利用瑶药六方藤药材资源,发挥其药用价值,提供了物质基础。
Description
技术领域
本发明涉及中药提取分离技术领域,具体涉及一种从瑶药六方藤中提取多种单体化合物的方法。
背景技术
六方藤(Cissus hexangularisThorel ex Planch.)为葡萄科白粉藤属藤本植物,又名六方钻或抽筋藤、方茎宽茎藤、翅茎白粉藤等,分布于广西、福建、广东、海南等地,以藤入药,晒干或鲜用。味辛、微苦,性凉,归肝、肾经,具有祛风活络、散瘀活血功能。主治风湿关节痛,腰肌劳损,跌打损伤。六方藤是瑶族习用药材,为瑶药“虎牛钻风”中的六方钻。已被收录于2014版《广西壮族自治区瑶药材质量标准(第一卷)》,瑶药名:落帮准,瑶医多用于崩闭闷(风湿性关节痛),改闷(腰痛,腰肌劳损),播冲(跌打损伤)及眸名肿毒(痈疮肿毒)。
六方藤化学成分复杂,现有研究显示其含有黄酮类、皂苷类、糖类、酚类、蒽醌类、甾萜类、生物碱及挥发油等化学成分。在六方藤药材的化学成分研究方面,检索到相关的文献,如,题名为《翅茎白粉藤化学成分鉴别预试研究》的文献,作者:姚瑰玮、陈湛娟、杨斯斯,等,首次考察了翅茎白粉藤藤茎部分的化学成分,根据预试鉴别结果,可初步判断翅茎白粉藤中含有糖类、苷类、皂苷、鞣质、黄酮类、酚类、香豆素、强心苷、蒽醌类、甾萜类、生物碱及挥发油等化学成分,并初步判断翅茎白粉藤可能含有少量有机酸,且未检测到翅茎白粉藤中含有氨基酸、多肽及蛋白质。又如,题名为《不同产地六方藤挥发油成分比较研究》的文献,作者:梁爽,莫礼艳,陈诗曼,等,采用水蒸气蒸馏法提取六方藤的挥发油成分,用气相色谱-串联质谱技术进行测定,结合计算机检索技术对分离的化合物进行结构鉴定并用色谱峰面积归一化法获得各化合物的相对含量,并用因子分析对六方藤挥发油进行质量评价。
但目前关于六方藤药材的化学成分研究报道较少,对六方藤药材中化学成分的提取和研究还不充分。现代药理学研究表明白粉藤属植物具有多种潜在的抗菌、抗炎、抗氧化、抗过敏、抗肿瘤、拮抗内皮素和蛇毒、治疗糖尿病等多种生物活性。为进一步丰富六方藤药材的化学成分研究资料,寻找新的具有较好活性的抗氧化、抗过敏、抗肿瘤、拮抗内皮素、治疗糖尿病等先导化合物,更好的开发利用瑶药六方藤药材资源,发挥其药用价值,对六方藤药材中单体化合物的开发和分离是亟待需要的。
发明内容
本发明的目的是针对现有技术的不足而提供的一种从瑶药六方藤中提取多种单体化合物的方法。采用该方法能从六方藤药材中提取分离得到25个单体化合物,为进一步丰富六方藤药材的化学成分研究资料,更好的开发利用瑶药六方藤药材资源、发挥其药用价值提供物质基础。
为实现上述目的,本发明采用如下技术方案:
一种从瑶药六方藤中提取多种单体化合物的方法,包括以下步骤:
(1)将六方藤药材粉碎得粗粉,加入药材重量10倍量、体积浓度为75%的乙醇渗漉提取,渗漉流速为3ml/min•kg,合并提取液,减压浓缩,回收溶剂,得到六方藤药材乙醇总提取物;
(2)将乙醇总提取物用水混悬,依次用石油醚、乙酸乙酯、正丁醇萃取,回收溶剂,得石油醚部位浸膏、乙酸乙酯部位浸膏和正丁醇部位浸膏;
(3)石油醚部位分离:
取石油醚部位浸膏,用硅胶柱色谱分离,使用石油醚:乙酸乙酯体积比=100:0→0:1的混合溶剂梯度洗脱,TCL检识,合并相同组分,共获得4个组分,分别记作Fr1、Fr2、Fr3、Fr4;
Fr1组分使用硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,从第10馏分开始出现大量白色粉末,合并第10-21馏分,丙酮重结晶得到化合物1,经结构鉴定,化合物1为β-谷甾醇;
Fr2组分经硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,在第15-24流份得化合物2,经结构鉴定,化合物2为豆甾醇;
Fr3组分,经硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,从第9馏分开始出现白色粉末,TLC检识,合并第9-14馏分,记作Fr3(9-14);将Fr3(9-14)样品经硅胶柱层析分离,用石油醚:乙酸乙酯体积比=50:1→1:1的混合溶剂依次洗脱,得到化合物3,经结构鉴定,化合物3为二十四烷酸;
Fr4 组分得到白色粉末,经半制备液相色谱(Waters CSH Fluoro Phenyl OBDPrep Column,130A,5 μm,10 mm × 250 mm,1/pkg,石油醚-丙酮,3:1)分离纯化,得到化合物 4、5、6、7;经结构鉴定,化合物4为豆甾醇乙酸酯,化合物5为白藜芦醇,化合物6为没食子酸,化合物7为岩白菜素;
(4)乙酸乙酯部位分离:
取乙酸乙酯部位浸膏,经硅胶柱色谱分离,采用氯仿:丙酮体积比=100:0→5:1和氯仿-甲醇体积比30:1→0:1,梯度洗脱,收集流份,TCL检识,合并相同流份,共得到15个流份,即组分Fr5- Fr19;
Fr5 用硅胶柱色谱分离,以石油醚-丙酮,体积比15:1→1:1,洗脱,得到白色粉末,反复以硅胶柱色谱分离,经石油醚-丙酮,体积比3:1→1:1,梯度洗脱,得到化合物 8、9;经结构鉴定,化合物8为11-O-没食子酰岩白菜素,化合物9为原儿茶酸;
Fr7 用硅胶柱色谱分离,以石油醚-丙酮,体积比20:1→0:1,梯度洗脱,得到白色粉末,经硅胶柱色谱分离,石油醚-丙酮体积比30:1→0:1梯度洗脱,得到化合物 10和11;经结构鉴定,化合物10为蒲公英赛酮,化合物11为齐敦果酸;
Fr8 用硅胶柱色谱分离,以石油醚-丙酮体积比20:1→0:1梯度洗脱,在石油醚-丙酮,体积比10:1,洗脱部分得到白色细针状物,经氯仿-丙酮体积比1:1反复重结晶得到化合物 12;在石油醚-丙酮,体积比15:1,洗脱部分得到白色细针状物,经过 Sephadex LH-20柱色谱,三氯甲烷-甲醇=1:1,纯化,得到化合物 13、14、15;经结构鉴定,化合物13为高粱酚,化合物14为 β-胡萝卜苷,化合物15为熊果酸;
Fr10用 硅 胶 柱 色 谱 分 离 , 以 石 油 醚 - 丙 酮 ,体积比100:0→5:1,梯度洗脱,得到白色细针状物,经Sephadex LH-20柱色谱纯化得到化合物16、17、18、19;经结构鉴定,化合物16为芹菜素,化合物17为木犀草素,化合物18为牡荆素,化合物19为山奈酚;
Fr11用硅胶柱色谱分离,以氯仿-甲醇,体积比15:1→0:1,梯度洗脱,得到淡白色细针状物,经过 Sephadex LH-20 柱色谱,三氯甲烷-甲醇=1:1,纯化,得到化合物20、21;经结构鉴定,化合物20为槲皮素,化合物21为β-香树脂醇;
Fr13用硅胶柱色谱分离,以氯仿-甲醇,体积比15:1→1:1,梯度洗脱,得到白色细针状物,再经过硅胶柱色谱和Sephadex LH-20柱色谱纯化,得到化合物22;经结构鉴定,化合物22为白桦脂酸;
Fr16经硅胶柱色谱,氯仿-甲醇体积比10:1→1:1梯度洗脱和Sephadex LH-20柱色谱,氯仿:甲醇=1:1,分离,重结晶得到化合物23、24;经结构鉴定,化合物23为异绿原酸 A,化合物24为异绿原酸 B;
Fr19经硅胶柱色谱,氯仿-甲醇体积比10:1→1:1,梯度洗脱和Sephadex LH-20柱色谱分离,重结晶得到化合物25;经结构鉴定,化合物25为异绿原酸 C。
本发明的有益效果为:
本发明采用系统性提取分离方法,对六方藤药材展开化学成分研究,通过正相硅胶柱层析、Sephadex LH-20柱层析、制备型高效液相色谱仪等,从六方藤药材的乙醇提取物中分离得到25个单体化合物,经核磁共振光谱、高分辨质谱等技术鉴定出25个单体化合物。
本发明提供的一种从瑶药六方藤中提取多种单体化合物的方法,简单易行,采用本发明方法能从六方藤药材中提取分离得到β-谷甾醇、二十四烷酸、豆甾醇乙酸酯、白藜芦醇、没食子酸、岩白菜素、原儿茶酸、齐敦果酸等25个单体化合物,丰富了六方藤药材的化学成分研究资料,为进一步寻找新的具有较好活性的抗氧化、抗过敏、抗肿瘤、拮抗内皮素、治疗糖尿病等先导化合物,更好的开发利用瑶药六方藤药材资源,发挥其药用价值,提供了物质基础。
附图说明
图1本发明从瑶药六方藤中提取多种单体化合物的方法的提取分离纯化流程图。
具体实施方式
实施例1
一、实验材料与方法
1.实验材料
1.1实验仪器
100-200目层析硅胶、200-300目层析硅胶、300-400目层析硅胶(烟台江友硅胶开发有限公司);HSGF254硅胶薄层层析硅胶板(烟台江友硅胶开发有限公司)。
1.2实验试剂
石油醚、乙酸乙酯、二氯甲烷、甲醇、甲醇均为分析纯(国药试剂公司)色谱级甲醇、乙腈为赛默飞产品;氘代试剂为Cambridge Isotope Laboratories, Inc.产品。显色剂:10%硫酸-香兰素试剂。
六方钻(即六方藤)药材购买于玉林药材市场,经广西中医药大学韦松基教授鉴定为葡萄科白粉藤属植物翅茎白粉藤(Cissus hexangularisThorel ex Planch)的藤茎。
2.实验方法
2.1提取流程
将六方钻 (15 kg) 搅碎,经药材重量10倍量、75%乙醇渗漉,渗漉流速为3ml/min•kg,合并提取液,减压浓缩,得到六方钻药材提取浸膏1385.6 g。将浸膏用水混悬,依次用石油醚、乙酸乙酯、正丁醇萃取,回收溶剂得石油醚浸膏约189g,乙酸乙酯浸膏274g,正丁醇浸膏302g。
2.2分离纯化
2.2.1石油醚部位分离
取六方钻药材石油醚部位浸膏119 g,用硅胶柱色谱分离,使用石油醚:乙酸乙酯(100:0→0:1)梯度洗脱,TCL检识,合并相同组分,共获得4个组分(组分1-4)别记作Fr1、Fr2、Fr3、Fr4。
Fr1组分使用硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,从第10馏分开始出现大量白色粉末,合并第10-21馏分,丙酮重结晶得到化合物1(38.3 mg)。Fr2组分经硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,在第15-24流份得化合物2(42.6 mg)。Fr3组分(39-47,8.2 g),经硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,从第9馏分开始出现白色粉末,TLC检识,合并第9-14馏分,记作Fr3(9-14)。将Fr3(9-14)样品经硅胶柱层析分离,用石油醚:乙酸乙酯(50:1→1:1)依次洗脱,得到化合物3(20 mg)。 Fr4 组分得到白色粉末,经半制备液相色谱(Waters CSH Fluoro Phenyl OBD Prep Column,130A,5 μm,10 mm ×250 mm,1/pkg,石油醚-丙酮,3:1)分离纯化,得到化合物 4(15.0mg)、化合物 5(4.5mg)、化合物 6(3.0mg)和化合物7(5.0mg)。
2.2乙酸乙酯部位分离
取乙酸乙酯部位浸膏137 g,经硅胶柱色谱分离,氯仿-丙酮(100:0→5:1)和氯仿-甲醇(30:1→0:1)梯度洗脱,共收集 576 流份,TCL检识,合并相同流份,共得到15个流份(组分Fr5-19)。Fr5 用硅胶柱色谱分离,以石油醚-丙酮(15:1→1:1)洗脱,在 213-226 流份得到白色粉末,反复以硅胶柱色谱分离,经石油醚-丙酮(3:1→1:1)梯度洗脱,得到化合物 8(5.0mg)、9(11.0mg)。
Fr7 用硅胶柱色谱分离,以石油醚-丙酮(20:1→0:1)梯度洗脱,在 176-192 流份得到白色粉末,经硅胶柱色谱分离,石油醚-丙酮体积比30:1→0:1梯度洗脱,得到化合物10(8.0mg)和化合物 11(11.0 mg)。Fr8 用硅胶柱色谱分离,以石油醚-丙酮体积比20:1→0:1梯度洗脱,在石油醚-丙酮(10:1)洗脱部分得到白色细针状物,经氯仿-丙酮体积比1:1反复重结晶得到化合物 12(5.0mg);在石油醚-丙酮(15:1)洗脱部分得到白色细针状物,经过 Sephadex LH-20 柱色谱(三氯甲烷-甲醇=1:1)纯化,得到化合物 13(9.6mg)、14(11.8mg)、15(7.4mg)。Fr10用 硅 胶 柱 色 谱 分 离 , 以 石 油 醚 - 丙 酮 (体积比100:0→5:1)梯度洗脱,在 209-234流分得到白色细针状物,经Sephadex LH-20柱色谱纯化得到化合物16(10.5mg)、17(6.2mg)、18(3.8mg)、19(7.8mg)。Fr11用硅胶柱色谱分离,以氯仿-甲醇(15:1→0:1)梯度洗脱,在296-315流份得到淡白色细针状物,经过 Sephadex LH-20 柱色谱(三氯甲烷-甲醇=1:1)纯化,得到化合物 20(6.4mg)、21(7.0mg)。Fr13用硅胶柱色谱分离,以氯仿-甲醇(15:1→1:1)梯度洗脱,在368-486流份得到白色细针状物,再经过硅胶柱色谱和SephadexLH-20柱色谱纯化,得到化合物22(4.8mg)。Fr16经硅胶柱色谱,氯仿-甲醇体积比10:1→1:1,梯度洗脱和Sephadex LH-20柱色谱(氯仿:甲醇=1:1)分离,重结晶得到化合物23(5.6mg)、24(7.0mg)。Fr19经硅胶柱色谱氯仿-甲醇(体积比10:1→1:1)梯度洗脱和Sephadex LH-20柱色谱分离,重结晶得到化合物25(5.0mg)。
2.3分离纯化流程图见附图1。
二、实验结果(结构鉴定)
化合物1:β-谷甾醇(β-sitosterol)。白色针晶,Liebermann-Burchard 反应显紫红色后变墨绿色,难溶于水,甲醇,分子式:C29H50O。薄层检测,与 β-谷甾醇对照品Rf 值相同,且混合熔点不下降,故鉴定为β-谷甾醇。其化学结构式如下:
化合物2:豆甾醇(Stigmasterol)。白色针晶,10 %硫酸-乙醇显色为紫红色。1H-NMR (400 MHz,Chloroform-d) δ5.60(m,1H,H-23),5.33(m,1H,H-6), 5.16(m,1H,H-22),3.70(m,1H,H-3),2.30(m,1H,H-4),2.09(dd,J =6.4, 0.9 Hz,1H,H-20),1.96(m,1H, H-1),1.88(m,1H, H-7),1.76(m,3H, H-1,12,7),1.67(m, 4H, H-2,11,12,17),1.59(m, 5H,H-15,24,25),1.50(m,3H,H-11,16),1.41(m, 4H,H-16,12,15),1.24(m,1H,H-8),1.18(m,1H,H-9),1.00(m,3H,H-19), 0.93(dt,J =6.5,1.2 Hz,3H,H-21), 0.88(m, 9H, H-29,26,27), 0.77(s,3H, H-18).13C-NMR (100 MHz,Chloroform-d) δ37.26(C-1),31.51(C-2),71.44(C-3),42.10(C-4),141.02(C-5),121.51(C-6),31.94(C-7),32.59(C-8),50.34(C-9),36.51(C-10),21.17(C-11),38.92(C-12),43.58(C-13),56.19(C-14),25.14(C-15),27.32(C-16),55.93(C-17),13.03(C-18),19.31(C-19),40.15(C-20),20.34(C-21),137.15(C-22),130.71(C-23),50.51(C-24),32.51(C-25),20.16(C-26,27),25.35(C-28),11.80(C-29)。根据氢谱碳谱数据对比,与参考文献(张吕丽、吴云飞:《柄果海桐化学成分的研究》,《云南师范大学学报(自然科学版)》第2020年第20期)中一致,故鉴定为豆甾醇。其化学结构式如下:
化合物3:二十四烷酸(Tetracosanoic acid)。1H-NMR (400 MHz,Chloroform-d)δ 2.29(t,J =8.9 Hz,2H,H-2),1.58(m,2H,H-3),1.27(d,J =3.2 Hz,34H,H-4~22), 0.89(m,3H,H-24).13C-NMR (100 MHz,Chloroform-d) δ178.31(C-1),34.27(C-2),25.79(C-3),29.70(C-4),29.46(C-5),29.43(C-6),29.38(C-7),29.35(C-8),29.32(C-9),29.30(C-10),29.28(C-11),29.25(C-12),29.22(C-13~18),29.20(C-19),29.17(C-20),29.14(C-21),25.14(C-22),22.67(C-23),14.05(C-24).根据氢谱碳谱数据对比,与参考文献(徐锦:《两粤黄檀化学成分研究》,《广西中医药大学》2016年第44页)中一致,故鉴定为二十四烷酸。其化学结构式如下:
化合物4:豆甾醇乙酸酯(Stigmasteryl acetate)。白色针晶,mp138 ~ 140℃。易溶于氯仿、丙酮。1H-NMR (600 MHz,Chloroform-d) δ 5.58(m,1H, H-23), 5.35(m,1H, H-6), 5.15(dd,J =14.6, 8.1 Hz,1H, H-22), 4.66(s,1H,H-3),2.46(d,J =12.2 Hz,1H H-4),2.35(d,J =12.5 Hz,1H,H-20),2.07(d,J =13.8 Hz,1H, H-1),2.02 (s,3H, H-1'),1.92 (d,J =12.4 Hz,1H,H-7),1.85(m,1H,H-1),1.74(m,1H, H-12),1.70(d,J =14.4 Hz,1H,H-7),1.65(m,2H, H-2,11),1.60(s,2H, H-12,17),1.56(s,2H, H-15,24),1.51(m,2H,H-24,25),1.46(m,3H, H-16,12,15),1.37(m,3H, H-16,12,15),1.22 (d,J =12.9 Hz,1H,8),1.15(d,J =9.2 Hz,1H, H-9),1.01(s,3H), 0.96(d,J =15.8 Hz,1H,), 0.91(m,3H,H-21), 0.85(m, 9H, H-29,26,27), 0.75(s,3H, H-18)13C NMR (150 MHz,Chloroform-d)δ36.7(C-1),21.2(C-1'),170.4(C-1'),27.3(C-2),72.9(C-3),40.2(C-4),139.8(C-5),122.4(C-6), 32.0(C-7),32.6(C-8),50.2(C-9), 36.6(C-10),21.1(C-11),37.8(C-12),43.6(C-13),55.9(C-14),25.1(C-15),26.9(C-16),56.2(C-17), 13.0(C-18),19.3(C-19),38.9(C-20),20.3(C-21),137.2(C-22),130.7(C-23), 50.5(C-24), 32.5(C-25),20.2(C-26,27),25.4(C-28),11.8(C-29)。根据氢谱碳谱数据对比,与参考文献(DItoh,Kawano K, Nabeta K . Biosynthesis of chloroplastidic and extrachloroplastidicterpenoids in liverwort culturedcells: 13C serine as a probe of terpenebiosynthesis via mevalonate and non-mevalonate pathways. Journal of NaturalProducts,2003PP:332)中一致,故鉴定为豆甾醇乙酸酯。其化学结构式如下:
化合物5:白藜芦醇(Resveratrol)。淡黄色固体粉末,难溶于水,甲醇,易溶于乙醚,氯仿,丙酮。分子式:C14H12O3,1H-NMR (500 MHz, DMSO-d 6) δ 9.84(s,1H,OH-4'), 8.54(s,2H,OH-3,5), 7.43(d,J =0.8 Hz,1H,H-2'), 7.41(s,1H,H-6'), 7.03(d,J =0.8 Hz,1H, H-8), 6.99(d,J =0.9 Hz,1H,H-7), 6.84(s,1H,H-3'), 6.81(d,J =1.6 Hz,1H,H-5'), 6.79(d,J =1.6 Hz,2H,H-2,6), 6.44(s,1H,H-4).13C-NMR (125 MHz, DMSO-d 6) δ140.3(C-1),159.0(C-3,5),116.2(C-7),129.2(C-8),129.2(C-1')129.0(C-2'),,106.5(C-3'),157.4(C-4'),,102.4(C-5'),128.0(C-6')。根据氢谱碳谱数据对比,与参考文献(Ping W , Xu J , Qi W , et al. [Phenylpropanoids and diphenylethenecompoundsfrom roots and rhizomes of Smilax scobinicaulis].. China Journal ofChineseMateria Medica, 2013, PP:1531-1535)中一致,故鉴定为白藜芦醇。其化学结构式如下:
化合物6:没食子酸(gallic acid)。白色粉末,难溶于水,氯仿,易溶于甲醇,丙酮。分子式:C7H6O5, 1H-NMR (500 MHz, DMSO-d 6) δ12.75(s,1H, OH-7), 8.90(s,2H,H-3,5),8.39(s,1H,H-4), 6.96(s,2H,H-2,6).13C-NMR (125 MHz,Common NMR Solvents) δ122.0(C-1),145.4(C-3,5),138.6(C-4),109.6(C-2,6),169.3(C-7)。根据氢谱碳谱数据对比,与参考文献(王晓梅、张倩:《锁阳全草化学成分的研究》,《中草药》2011年第43卷)中一致,故鉴定为没食子酸。其化学结构式如下:
化合物7:岩白菜素(Bergenin)。白色粉末,难溶于水,易溶于甲醇,丙酮,三氯化铁反应显蓝色。分子式:C14H16O9,1H NMR (400 MHz,Chloroform-d) δ7.09(s,1H,H-6),5.06(dJ=6.6Hz,1H,OH-3',4.86(s,1H,OH-1'),4.76(m,1H,OH-4'),3.89(m,1H,H-3'),3.84(s,3H,OMe-3),3.71(m,2H,H-6'),3.58(m,1H,H-5'),3.49(m,1H,H-4').13C N,MR(100 MHz,Methanol-d 4) δ118.4(C-1),112.2(C-2),149.5(C-3),142.9(C-4),149.8(C-5),,109.6(C-6), 165.9(C-7),72.0(C-1'),74.8(C-2'),79.7(C-3'),71.6(C-4'),82.4(C-5'),62.5(C-6'),60.8(Me-4)。根据氢谱碳谱数据对比,与参考文献(谢一辉、邓鹏:《安痛钻化学成分研究》,《中药材》2009年第2期)中一致,故鉴定为岩白菜素。其化学结构式如下:
化合物8:11-O-没食子酰岩白菜素(11-O-galloyl bergenin)。白色粉末,不溶于氯仿,二氯甲醇,易溶于甲醇。1H-NMR (600 MHz, Methanol-d 4) δ 7.10(s,1H, H-6), 7.03(s,2H, H-9',13'), 5.41(d,J =6.4 Hz,1H, OH-3'), 4.92 (d,J =2.5 Hz,1H, OH-4'),4.89(m,1H, OH-10'), 4.69(d,J =6.1 Hz,1H, OH-1'), 4.19(dd,J =11.8, 4.7 Hz,1H,OH-4'),4.10(dd,J=11.8,4.7Hz,1H,H-3'),3.95(m,1H,OMe-3),3.93(m,1H,H-6'),3.85(s,3H,H-5'),3.54(m,1H,H-4').13C NMR (150 MHz, Methanol-d 4) δ118.43(C-1), 149.47(C-3),,142.92(C-4),149.78(C-5),109.62(C-6), 165.86(C-7),,73.05(C-1'),73.56(C-2'),77.49(C-3'),71.70(C-4'),77.50(C-5'),65.04(C-6'),167.47(C-7'),120.91(C-8'),109.75(C-9',13'),138.91(C-10',12'),123.16(C-11'),145.59(C-12'),60.77(Me-4)。根据氢谱碳谱数据对比,与参考文献(石晓丽、毛泽伟:《民族药岩白菜的化学成分研究》,《云南中医学院学报》2014年第1期)中一致,故鉴定为11-O-没食子酰岩白菜素。其化学结构式如下:
化合物9:原儿茶酸(Protocatechuic acid)。白色粉末(甲醇),mp:200~201 ℃,分子式:C7H6O4,ESI-MS:m/z 153[M-H]+。1H-NMR(CD3OD,500MHz)δ:7.51(1H, dd,J=8.0,1.5 Hz, H-6),7.43(1H,d, J=1.8 Hz,H-2),6.77(1H, d,J=8.4 Hz, 5-OH);13C-NMR(CD3OD,125 MHz)δ:123.9(C-1),117.5(C-2),147.1(C-3),152.5(C-4),117.1(C-5),124.3(C-6),169.6(C-7)。以上数据与文献(靳鑫、时圣明:《穿心莲化学成分的研究:Ⅱ》,《中草药》2014年第45期)基本一致,故鉴定该化合物为原儿茶酸。其化学结构式如下:
化合物10:蒲公英赛酮(Taraxerone)。白色针状晶体(甲醇),Libermann-Burchar反应显红色,10 %硫酸-乙醇加热显紫红色 (105 ℃)。1H-NMR (600 MHz, DMSO-d6)5.53(t,J =4.5 Hz,1H,H-15),2.50(m,1H,H-2a),2.44(m,1H,H-2b),1.90(m,1H,H-16a),1.87(m,1H,H-19a),1.75(m,1H,H-1a),1.74(m,1H,H-1b),1.71(t,J =1.8 Hz,1H,H-12a),1.70(m,2H,H-16b,7),1.60(m,2H,H-5),1.56(m,2H,H-11),1.53(s,1H,H-5),1.46(m,2H,H-6),1.39(m,2H,H-9,21a),1.36(m,2H,H-12b,19b),1.33(m,2H,H-22),1.31(m,1H,H-21b),1.07(s,3H,H-26),1.06(s,3H,H-25),1.03(d,J =6.9 Hz,1H,H-18), 0.99(s,3H,H-24), 0.96(s,3H,H-23), 0.94(s,3H,H-29), 0.92 (s,3H,H-30), 0.90(s,3H,H-27), 0.87(s,3H,H-28).13C-NMR (150 MHz, Methanol-d4) δ 37.5(C-1),33.9(C-2),217.4(C-3),47.4(C-4),54.6(C-5),19.7(C-6),37.5(C-7),39.1(C-8),50.1(C-9),37.8(C-10),17.8(C-11),37.2(C-12),37.7(C-13),158.3(C-14),117.5(C-15), 39.1(C-16), 35.4(C-17), 48.8(C-18),29.1(C-20), 40.1(C-20),35.6(C-21),34.6(C-22),22.2(C-23),25.0(C-24),15.9(C-25),25.3(C-26),24.3(C-27),28.4(C-28),28.6(C-29),29.9(C-30)。根据氢谱碳谱数据对比,与参考文献(韦建华、西庆男:《壮药青钻仔化学成分研究》,《广西师范大学学报(自然科学版)》2018年第36期)中一致,故鉴定为蒲公英赛酮。其化学结构式如下:
化合物11:齐敦果酸(oleanolic acid)。白色针状(丙酮);紫色斑点(10 %硫酸乙醇),1H NMR (600 MHz,Chloroform-d) δ 5.28(s,1H,H-12),3.28(d,J =10.8 Hz,1H,H-3),3.05(d,J =10.7 Hz,1H,H-18),2.80(dtd,J =6.2,2.1,1.0 Hz,1H,H-17),2.02 (d,J =1.0 Hz,1H,H-15),1.96(m,1H,H-16a),1.91(d,J =3.3 Hz,1H,H-16b),1.84(m,1H,H-11a),1.72 (m,1H,H-11b),1.65(m, 5H,H-19a,22a,1a,2a),1.49(m, 4H,H-6,7),1.36(m, 4H,H-2b,1b,22b,9),1.25(d,J =1.8 Hz,1H,H-19b),1.19(s,3H,H-27), 0.94(s,3H,H-30),0.93(s,3H,H-29), 0.92 (s,3H,H-26), 0.91(s,3H,H-25), 0.88(s,3H,H-24),0.87(s,3H,H-23).13C-NMR (150 MHz,Chloroform-d) δ38.26(C-1),27.13(C-2),78.49(C-3),38.58(C-4),54.80(C-5),18.22(C-6),32.57(C-7),39.71(C-8),47.47(C-9), 36.66(C-10),23.47(C-11),122.35(C-12), 144.46(C-13),42.02(C-14), 29.06(C-15),24.20(C-16),46.74(C-17),41.83(C-18), 46.34(C-19),30.87(C-20), 34.32(C-21),32.10(C-22),17.17(C-23),26.47(C-24),16.00(C-25),17.00(C-26),25.32(C-27),181.05(C-28),28.15(C-29),29.06(C-30)根据氢谱碳谱数据对比,与参考文献(韦建华、西庆男等:《壮药青钻仔化学成分研究》,《广西师范大学学报(自然科学版)》2018年第36期)中一致,故鉴定为齐敦果酸。其化学结构式如下:
化合物12:蒲公英赛醇(taraxerol) 。白色粉末,白色针状晶体(氯仿),Libermann-Burchard反应呈阳性,10%硫酸-乙醇加热显紫红色1H NMR (600 MHz,Chloroform-d) δ3.07(d,J =5.1 Hz,1H, H-3),1.81(m,1H,H-1a),1.64(m, 5H,H-7a,H-1b,2,21),1.56(m, 4H,H-12a,6,7b),1.51(m,2H,H-5,12b),1.37(m, 5H,H-16a,19,15),1.29(m, 4H,H-22,15),1.19(m,3H,H-18,14,16b),1.01(m,3H,H-30), 0.98(d,J =2.4 Hz,6H,H-29,25), 0.91(s,3H,H-28), 0.86(d,J =5.3 Hz, 6H,H-24,23), 0.82 (d,J =7.4Hz, 6H,H-27,26). 13C NMR (150 MHz,Chloroform-d) δ 39.8(C-1),28.4(C-2),79.9(C-3), 40.0(C-4),53.9(C-5),20.4(C-6),42.3(C-7),39.4(C-8),59.6(C-9),38.8(C-10),19.7(C-11),40.9(C-12),38.1(C-13), 59.7(C-14), 20.8(C-15), 40.2(C-16),34.8(C-17),51.3(C-18), 38.5(C-19),30.6(C-20), 37.7(C-21), 39.3(C-22),19.6(C-23),26.0(C-24),17.8(C-25),17.9(C-26),22.4(C-27),29.2(C-28),30.9(C-29),31.2(C-30).根据氢谱碳谱数据对比,与参考文献(赵保华、许琼明等:《瘤果紫玉盘地上部分化学成分研究》,《中草药》 2006年第37期)中一致,故鉴定为蒲公英赛醇。其化学结构式如下:
化合物13:高粱酚(sorghumol)。白色粉末,1H NMR (600 MHz, Methanol-d 4) δ5.37 (td,J= 3.8, 2.3 Hz, 1H), 4.01 (d,J= 10.7 Hz, 1H), 3.50 (dtd,J= 7.6, 2.9,1.5 Hz, 1H), 1.97 (m, 3H), 1.77 (m, 2H), 1.63 (m, 4H), 1.54 (m, 9H), 1.44 (m,2H), 1.36 (m,2H), 1.16 (s, 4H), 1.05 (t,J= 1.5 Hz, 3H), 1.00 (t,J= 1.5 Hz,3H), 0.88 (t,J= 1.5 Hz, 3H), 0.87 (t,J= 1.4 Hz, 3H), 0.85 (s, 3H), 0.80 (d,J=3.8 Hz, 6H).13C NMR (150 MHz, Methanol-d 4) δ 36. 1 ( C-1) ,28. 0 ( C- 2) ,79.2( C-3) ,39. 3( C-4) ,52. 3( C-5) ,21. 6( C-6) , 26. 6( C-7) ,41. 2( C-8) ,149.0( C-9) ,39. 8 ( C-10) , 114. 5( C-11) ,36. 1 ( C-12) ,38. 4 ( C-13) ,37.0 ( C- 14) ,29. 9( C-15) ,36. 2 ( C-16) ,43. 0 ( C-17) ,52. 6 ( C-18) ,20. 4( C-19 ) ,28. 4 ( C-20 ) ,59. 9( C-21 ) , 31. 0 ( C-22 ) ,28. 0 ( C-23 ) ,15.9 ( C-24 ) ,22. 3 ( C- 25) ,17. 3 ( C-26) ,15. 5( C-27) ,14. 2 ( C-28) ,23. 2( C-29) ,22. 4( C-30) 。根据氢谱碳谱数据对比,与参考文献(王义娜、蔡金艳:《滇越金线兰化学成分研究》,《中药材》2012年第35期)中一致,故鉴定为高粱酚。其化学结构式如下:
化合物14:白色粉末状结晶(甲醇),mp 291~ 293 ℃,Liebermann-Burchard反应呈阳性,Molish 反应呈阳性,经酸水解后用 PC 检测含有葡萄糖,证明为甾体苷类化合物。与 β-胡萝卜苷对照品薄层检识,在 3 种不同展开展开系统中 显色相同且Rf 值完全一致,与对照品混合熔点不下降,故鉴定化合物为 β-胡萝卜苷。其化学结构式如下:
化合物15:熊果酸(Ursolic acid)。难溶于水和石油醚,易溶于甲醇,丙酮,
1H-NMR (400 MHz, Methanol-d 4) δ 5.46(m,1H,H-12),3.14(m,1H,H-3),2.20(m,1H,H-18),2.00(m,2H,H-11a,15a),1.90(m,3H, H-16a,1a,22),1.75(m,3H,H-1b,2a,),1.67(m, 4H, H-11b,15b,16b),1.51(m,7H,H-19a,22a,1a,2a,6,7),1.38(m, 5H,H-2b,1b,22b,9b,19b),1.07(s,3H,H-27), 0.97(s,3H, H-30), 0.88(m,15H, H-24,23,25,26,29).13C-NMR (100 MHz, Methanol-d 4)δ38.65(C-1),27.31(C-2),78.57(C-3),38.67(C-4),55.18(C-5),20.47(C-6),33.11(C-7),39.27(C-8), 53.01(C-9),36.68(C-10),23.13(C-11),124.91(C-12),139.23(C-13),42.59(C-14),28.72(C-15), 24.42(C-16),48.35(C-17),39.32(C-18),47.58(C-19), 38.37(C-20),31.05(C-21), 36.10(C-22),17.74(C-23),25.49(C-24),16.64(C-25),17.04(C-26),23.78(C-27),180.53(C-28),18.34(C-29),20.64(C-30),根据氢谱碳谱数据对比,与参考文献(王晓梅、张倩:《锁阳全草化学成分的研究》,《中草药》 2011年第43卷)中一致,故鉴定为熊果酸。其化学结构式如下:
化合物16:芹菜素(Apigenin)。黄色粉末,盐酸镁粉反应呈阳性,三氯化铁反应呈阳性,三氯化铝反应呈阳性,Molish反应呈阴性。1H-NMR (600 MHz, Deuterium Oxide)δ12.96(s,1H,OH-5),10.85(s,1H, OH-7), 8.99(s,1H, OH-4'), 7.85(m,2H, H-2',6'),6.90(m,2H, H-3',5'), 6.74(s,1H,H-3), 6.52 (d,J =1.8 Hz,1H,H-8), 6.25(d,J =2.0Hz,1H,H-6).13C-NMR (150 MHz, Methanol-d 4)δ1104.49(C-3),183.81(C-4),161.82(C-5),99.49(C-6),164.98(C-7),94.84(C-8),159.15(C-9),105.06(C-10).22.47(C-1'),164.29(C-2),128.25(C-2',6'),161.07(C-4'),115.80(C-3',5'),根据氢谱碳谱数据对比,与参考文献(刘坤、 贾艳菊:《离舌橐吾干燥根中1个新的三萜皂苷》,《中草药》2018年第49卷)中一致,故鉴定为芹菜素。其化学结构式如下:
化合物17:木犀草素(Luteolin)。黄色粉末,能溶于二氯甲烷,甲醇,难溶于水。1H-NMR (600 MHz,Chloroform-d) δ12.94(s,1H,OH-5),11.02 (s,1H,OH-7), 7.44(m,2H,H-2',H-6'), 7.05(s,1H,OH-5'), 6.88(d,J =9.3 Hz,1H,H-4'), 6.57(s,1H,H-3), 6.48(d,J =1.8 Hz,1H,H-8), 6.20(d,J =1.8 Hz,1H,H-6).13C-NMR (150 MHz,Chloroform-d)δ164.05(C-2),105.76(C-3),182.58(C-4),162.45(C-5),99.64(C-6),94.77(C-8),158.67(C-9),104.59(C-10), 122.15(C-1'),119.57(C-2'),115.66(C-3'),149.07(C-4'),145.65(C-5'),113.74(C-6'),165.41(C-7')。根据氢谱碳谱数据对比,与参考文献(姚学军, 孟素蕊:《凤尾草抗糖尿病活性成分的研究》,《中成药》2014年第36期)中一致故鉴定为木犀草素。其化学结构式如下:
化合物18:牡荆素(Vitexin)。黄色粉末, 盐酸镁粉反应显阳性, 三氯化铝反应呈黄绿色荧光,1H-NMR (600 MHz, Methanol-d 4) δ 7.87(d,J =8.9 Hz,2H, H-2',6'), 6.90(d,J =8.9 Hz,2H,H-3',5'),6.69(s,1H,H-3), 6.29(s,1H,H-6), 4.88(d,J =5.7 Hz,1H,H-1''), 4.06(m,1H,H-2''),3.73(d,J =13.1 Hz,1H,H-3''),3.64(t,J =4.5 Hz,1H,H-6''a),3.59(m,1H, H-6''b),3.43(m,1H,,H-5''),3.39(m,1H,H-4'').13C-NMR (150 MHz,Methanol-d 4) δ163.22(C-2),104.08(C-3),182.20(C-4),161.40(C-5),98.11(C-6),164.35(C-7),103.57(C-8),158.16(C-9),104.34(C-10,121.88(C-1'),129.09(C-2',6'),115.85(C-3',5'),7 161.12(C-4'),74.69(C-1''),72.13(C-2''), 6.65(C-3''),70.76(C-4''),,81.31(C-5''),61.69(C-6''),根据氢谱碳谱数据对比,与参考文献(彭 晓, 于大永:《金花茶花化学成分的研究[》,《广西植物》2011年第31期)中一致,故鉴定为牡荆素。其化学结构式如下:
化合物19:山奈酚(Kaempferol)。黄色粉末,10%硫酸-乙醇溶液显黄色,不溶于氯仿,二氯甲烷,微溶于甲醇。1H-NMR (600 MHz, DMSO-d 6) δ12.41(s,1H,OH-5),10.72 (s,1H,OH-7), 9.86(s,1H,H-4'), 9.22 (s,1H,H-3), 7.82 (m,2H,H-2',6'), 6.76(m,2H,H-3',5'),6.19(d,J =1.8 Hz,1H,H-8), 6.09(d,J =1.8 Hz,1H,H-6).13C-NMR (150 MHz,DMSO-d 6) δ122.20(C-1),161.29(C-2),137.02(C-3),175.94(C-4),159.76(C-5),99.28(C-6),164.52(C-7),94.01(C-8),157.21(C-9),102.58(C-10)129.56(C-2',6'),115.90(C-3',5'),根据氢谱碳谱数据对比,与参考文献(彭晓, 于大永:《金花茶花化学成分的研究》,《广西植物》2011年第31期)中一致,故鉴定为山奈酚。其化学结构式如下:
化合物20:黄色粉末,盐酸镁粉反应显阳性,三氯化铝反应呈黄绿色荧光,证明为黄酮化合物。与对照品共薄层,在 3 种溶剂系统下Rf 值一致, 均为一个斑点,故鉴定其为槲皮素(quercetin)。
化合物21:β-香树脂醇(β-amyrin)。白色粉末状结晶(氯仿),mp 197~198 ℃,Libermann-Burchard反应呈阳性。1H-NMR (600 MHz,Chloroform-d) δ 5.22 (m,1H),3.28(s,1H),3.06(d,J =10.9 Hz,1H),1.94(m,1H),1.84(m,1H),1.80(d,J =11.6 Hz,1H),1.76(d,J =8.9 Hz,1H),1.74(s,1H),1.71(m,2H),1.69(d,J =2.8 Hz,1H),1.65(m,1H),1.54(d,J =21.0 Hz,1H),1.50(s,1H),1.48(d,J =6.6 Hz,2H),1.42 (d,J =6.8 Hz, 4H),1.39(m,1H),1.33(d,J =5.6 Hz,1H),1.27(m,2H),1.23(d,J =7.2 Hz,1H),1.17(s,3H), 0.97(d,J =1.7 Hz, 6H), 0.93(s,3H), 0.91(m, 6H), 0.88(s,3H), 0.86(s,3H).13C-NMR(150 MHz,Chloroform-d) δ38.6(C-1),27.5(C-2),78.7(C-3), 38.9(C-4),18.6(C-6),32.9(C-7),39.8(C-8),37.0(C-9),48.1(C-9),23.6(C-11),119.3(C-12),145.9(C-13),55.3(C-13), 42.3(C-14), 26.9(C-15),28.6(C-16),34.6(C-17),46.2(C-18),46.3(C-19), 31.4(C-20), 35.5(C-21),36.2(C-22),23.7(C-22,23),16.5(C-25),17.3(C-26),25.6(C-27),27.0(C-28),29.5(C-29,30)。根据氢谱碳谱数据对比,与参考文献(WeiJH ,ChenJ, Cai S F , et al. Chemical constituents in whole herb of Cardiospermumhalicacabum (Ⅰ)[J].Chinese Traditional and Herbal Drugs,2011,PP:1509-1511)中一致,故鉴定为β-香树脂醇。其化学结构式如下:
化合物22:白桦脂酸(Betulinic acid) 。无色粒状结晶(丙酮)1H-NMR (600 MHz,Chloroform-d) δ11.48(s,1H,OH-27), 4.83(d,J =1.4 Hz,1H,H-29a), 4.67(t,J =1.4Hz,1H,H-29b),3.28(m,1H,H-3),3.06(d,J=10.9 Hz,1H,H-19),2.08(ddd,J=12.2, 7.9,5.1 Hz,1H,H-16a),1.96(ddd,J=12.5, 8.0, 5.2 Hz,1H,H-16b),1.73(d,J=1.4 Hz,3H,H-21a,15b,2a),1.69(m,1H,H-7a),1.66(m,1H,H-6a),1.64(d,J=1.0 Hz,1H),1.63(m,1H,H-7b),1.58(d,J=1.2 Hz,1H,H-15a),1.58(s,1H,H-21b),1.56(s,1H,H-12),1.54(m,1H,H-6a),1.53(s,1H,H-2b),1.51(s,1H,H-6b),1.49(d,J =1.0 Hz,1H,H-21a),1.49(s,1H,H-11),1.48(m,1H,H-10),1.46(d,J =1.6 Hz,1H,H-7b),1.41(m,1H,H-1b),1.40(s,1H,H-5),1.30(m,1H,H-1a),1.22(m,1H,H-9),1.04(s,3H,H-26),1.01(s,3H,H-25), 0.97(d,J =1.5Hz,3H,H-23), 0.92 (d,J =1.5 Hz,3H,H-22), 0.83(s,3H,H-24).13C-NMR (150 MHz,Chloroform-d)δ37.0(C-1),27.2(C-2),78.3(C-3), 38.8(C-4),53.3(C-5),18.6(C-6),31.6(C-7),42.2(C-8),50.4(C-9),36.4(C-10),21.2(C-11),23.4(C-12),37.9(C-13),42.9(C-14),30.1(C-15,16),55.8(C-17),49.0(C-18),49.2(C-19),29.9(C-20),34.1(C-21), 17.3(C-22),25.6(C-23),16.3(C-24),16.2(C-25),14.9(C-26),179.8(C-27),149.7(C-28),110.3(C-29), 19.9(C-30).根据氢谱碳谱数据对比,与参考文献(孙琳、 李占林:《千斤拔化学成分研究[C]2010年中国药学大会暨第十届中国药师周论文集》 2010年)中一致,故鉴定为白桦脂酸。其化学结构式如下:
化合物23:异绿原酸 A( Isochlorogenic acid A)。白色粉末,易溶于甲醇、丙酮,微溶于二氯甲烷,氯仿。1H-NMR (600 MHz, Methanol-d 4) δ 7.54 (s, 1H, H-3), 7.51(s, 1H, H-3''),7.02 (d,J= 1.9 Hz, 2H,H-5'',5), 6.96 (d,J= 1.8 Hz, 1H,H-9''),6.94 (d,J= 1.8 Hz, 1H,H-9), 6.77 (s, 1H,H-8''), 6.76 (s, 1H,H-8), 6.15 (s,1H,H-2), 6.13 (s, 1H,H-2''), 5.31 (s, 1H,H-1'),5.06 (s, 1H,H-2'), 4.71 (d,J=6.4 Hz, 1H), 3.99 (t,J= 4.7 Hz, 1H, H-3'), 2.68 (s, 1H, H-2',H-6'a), 2.65 (s,1H,H-4'a), 2.31 (s, 1H,H-6'b), 2.29 (s, 1H,H-4'b)。13C-NMR (150 MHz, Methanol-d 4) δ 167.0(C-1,1'),70.7(C-1'),115.9(C-2'',2), 71.9(C-2'),146.4(C-3'',3),70.5(C-3'), 127.1(C-4'',4),37.2(C-4'),114.8(C-5'',5), 75.1(C-5'),146.6(C-6'',6), 37.1(C-6'),147.9(C-7'',7), 116.0(C-8'',8), 122.6(C-9'',9), 176.0(C-26)根据氢谱碳谱数据对比,与参考文献(Sun S W , Wang R R , Sun X Y , et al.Identification of Transient Receptor Potential Vanilloid 3 AntagonistsfromAchillea alpina L. and Separation by Liquid-Liquid-Refining Extraction andHigh-Speed Counter-Current Chromatography. 2020.PP:121-123)中一致,故鉴定为异绿原酸 A。其化学结构式如下:
化合物24:异绿原酸 B (Isochlorogenic acid B)。白色粉末,易溶于甲醇、丙酮,微溶于二氯甲烷,氯仿。与FeCl3-K3(CN)6反应呈阳性,1H-NMR (600 MHz, Methanol-d 4) δ7.56 (s, 1H,H-3), 7.53 (s, 1H,H-3''), 7.04 (d,J= 2.0 Hz, 2H,H-5'',5), 6.98(d,J= 1.9 Hz, 1H,H-9''),6.96 (d,J= 2.2 Hz, 1H,H-9), 6.79 (s, 1H,H-8''), 6.78(s, 1H,H-8), 6.33 (d,J= 16.0 Hz, 1H,H-2), 6.15 (d,J= 16.3 Hz, 1H,H-2''), 5.42(m, 1H,H-2'), 4.89 (dd,J= 7.1, 4.3 Hz, 1H,H-1'), 4.32 (m, 1H,H-3'), 2.56 (dd,J= 12.3, 4.5 Hz, 1H,H-6'a), 2.30 (dd,J= 12.5, 8.1 Hz, 1H,H-4'a), 2.23 (m,1H,,H-6'b), 2.22 (d,J= 1.5 Hz, 1H,H-4'b)。13C-NMR (150 MHz, Methanol-d 4) δ167.9(C-1), 167.4(C-1'),71.9(C-1'),115.2(C-2),74.8(C-2'), 116.1(C-2''),146.5(C-3), 67.8(C-3'),146.6(C-3''),127.1(C-4), 39.2(C-4'), 126.8(C-4''),114.8(C-5),75.6(C-5'),114.9(C-5''), 146.6(C-6),37.8(C-6'),146.7(C-6''), 148.0(C-7),148.0(C-7''),116.1(C-8),116.6(C-8''),122.6(C-9),122.7(C-9''),177.5(C-26)。根据氢谱碳谱数据对比,与参考文献(董俊丽、黄传奇:《绿萝花化学成分及其抗氧化活性》,《中成药》2019年第13期)中一致,故鉴定为异绿原酸B。其化学结构式如下:
化合物25:异绿原酸 C (Isochlorogenic acid C)。淡黄色粉末 ( 甲醇) ,与FeCl3-K3( CN )6 反 应 呈 阳 性。1H-NMR (600 MHz, Methanol-d 4) δ 7.56 (d,J= 1.1Hz, 1H, H-3), 7.53 (s, 1H,H-3''), 7.05 (s, 1H,H-5''), 7.04 (s, 1H,H-5),6.98(s, 1H,H-9''), 6.96 (d,J= 2.1 Hz, 1H,H-9), 6.79 (s, 1H,H-8''),6.78 (s, 1H,H-8), 6.33 (d,J= 16.0 Hz, 1H,H-2), 6.15 (d,J= 16.3 Hz, 1H,H-2''), 5.36 (m, 1H,H-2), 4.83 (dd,J= 7.0, 4.5 Hz, 1H,H-1'), 4.16 (dd,J= 5.3, 1.5 Hz, 1H,H-1'),2.50 (dd,J= 12.3, 4.5 Hz, 1H,H-5'a), 2.34 (dd,J= 12.5, 8.1 Hz, 1H,H-5'b),2.25 (m, 1H,H-3'a), 2.23 (d,J= 5.7 Hz, 1H,H-3'b)。13C-NMR (150 MHz, Methanol-d 4) δ 167.7(C-1),168.2(C-1'),75.0(C-1'),116.9(C-2),66.2(C-2'),115.5(C-2''),146.8(C-3),37.8(C-3'),146.8(C-3''), 127.0(C-4),75.9(C-4'),127.4(C-4''),116.3(C-5),37.2(C-5'),116.4(C-5''),148.2(C-6),70.0(C-6'),148.3(C-6''),146.9(C-7),177.7(C-7'),146.9(C-7''), 115.1(C-8),115.1(C-8''),122.9(C-9), 123.0(C-9'')。根据氢谱碳谱数据对比,与参考文献(董俊丽、黄传奇:《绿萝花化学成分及其抗氧化活性》,《中成药》2019年第13期)中一致,故鉴定为异绿原酸C。其化学结构式如下:
三、结论
通过现代天然产物化学研究手段,利用现代分离仪器和各种分离技术,从六方钻乙醇提取物的石油醚和乙酸乙酯层分离纯化得到共 25个单体化合物。分别为β-谷甾醇(β-sitosterol),豆甾醇(Stigmasterol),二十四烷酸(Tetracosanoic acid),豆甾醇乙酸酯,白藜芦醇(Resveratrol),没食子酸(gallic acid),岩白菜素(Bergenin),11-O-没食子酰岩白菜素(11-O-galloyl bergenin),原儿茶酸(Protocatechuic acid),蒲公英赛酮(Taraxerone),齐敦果酸(Oleanolicacid),蒲公英赛醇(Taraxerol),高粱酚(Sorghumol),β-胡萝卜苷(β- daucosterol),熊果酸(Ursolic acid),芹菜素(Apigenin),木犀草素(Luteolin),牡荆素(Vitexin),山奈酚(Kaempferol),槲皮素(quercetin),β-香树脂醇(β-amyrin),白桦脂酸(Betulinic acid),异绿原酸 A(Isochlorogenic acid A),异绿原酸 B(Isochlorogenicacid B),异绿原酸 C(Isochlorogenic acid C)。
Claims (2)
1.一种从瑶药六方藤中提取多种单体化合物的方法,其特征在于,包括以下步骤:
(1)将六方藤药材粉碎得粗粉,加入药材重量10倍量、体积浓度为75%的乙醇渗漉提取,渗漉流速为3ml/min•kg,合并提取液,减压浓缩,回收溶剂,得到六方藤药材乙醇总提取物;
(2)将乙醇总提取物用水混悬,依次用石油醚、乙酸乙酯、正丁醇萃取,回收溶剂,得石油醚部位浸膏、乙酸乙酯部位浸膏和正丁醇部位浸膏;
(3)石油醚部位分离:
取石油醚部位浸膏,用硅胶柱色谱分离,使用石油醚:乙酸乙酯体积比=100:0→0:1的混合溶剂梯度洗脱,TCL检识,合并相同组分,共获得4个组分,分别记作Fr1、Fr2、Fr3、Fr4;
Fr1组分使用硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,从第10馏分开始出现大量白色粉末,合并第10-21馏分,丙酮重结晶得到化合物1,经结构鉴定,化合物1为β-谷甾醇;
Fr2组分经硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,在第15-24流份得化合物2,经结构鉴定,化合物2为豆甾醇;
Fr3组分,经硅胶柱色谱分离,以石油醚-乙酸乙酯体积比=100:0→0:1梯度洗脱,回收溶剂,从第9馏分开始出现白色粉末,TLC检识,合并第9-14馏分,记作Fr3(9-14);将Fr3(9-14)样品经硅胶柱层析分离,用石油醚:乙酸乙酯体积比=50:1→1:1的混合溶剂依次洗脱,得到化合物3,经结构鉴定,化合物3为二十四烷酸;
Fr4 组分得到白色粉末,经半制备液相色谱分离纯化,得到化合物 4、5、6、7;经结构鉴定,化合物4为豆甾醇乙酸酯,化合物5为白藜芦醇,化合物6为没食子酸,化合物7为岩白菜素;
(4)乙酸乙酯部位分离:
取乙酸乙酯部位浸膏,经硅胶柱色谱分离,采用氯仿:丙酮体积比=100:0→5:1和氯仿-甲醇体积比30:1→0:1,梯度洗脱,收集流份,TCL检识,合并相同流份,共得到15个流份,即组分Fr5- Fr19;
Fr5 用硅胶柱色谱分离,以石油醚-丙酮,体积比15:1→1:1,洗脱,得到白色粉末,反复以硅胶柱色谱分离,经石油醚-丙酮,体积比3:1→1:1,梯度洗脱,得到化合物 8、9;经结构鉴定,化合物8为11-O-没食子酰岩白菜素,化合物9为原儿茶酸;
Fr7 用硅胶柱色谱分离,以石油醚-丙酮,体积比20:1→0:1,梯度洗脱,得到白色粉末,经硅胶柱色谱分离,石油醚-丙酮体积比30:1→0:1梯度洗脱,得到化合物 10和11;经结构鉴定,化合物10为蒲公英赛酮,化合物11为齐敦果酸;
Fr8 用硅胶柱色谱分离,以石油醚-丙酮体积比20:1→0:1梯度洗脱,在石油醚-丙酮,体积比10:1,洗脱部分得到白色细针状物,经氯仿-丙酮体积比1:1反复重结晶得到化合物12;在石油醚-丙酮,体积比15:1,洗脱部分得到白色细针状物,经过 Sephadex LH-20 柱色谱,三氯甲烷-甲醇=1:1,纯化,得到化合物 13、14、15;经结构鉴定,化合物13为高粱酚,化合物14为 β-胡萝卜苷,化合物15为熊果酸;
Fr10用 硅 胶 柱 色 谱 分 离 , 以 石 油 醚 - 丙 酮 ,体积比100:0→5:1,梯度洗脱,得到白色细针状物,经Sephadex LH-20柱色谱纯化得到化合物16、17、18、19;经结构鉴定,化合物16为芹菜素,化合物17为木犀草素,化合物18为牡荆素,化合物19为山奈酚;
Fr11用硅胶柱色谱分离,以氯仿-甲醇,体积比15:1→0:1,梯度洗脱,得到淡白色细针状物,经过 Sephadex LH-20 柱色谱,三氯甲烷-甲醇=1:1,纯化,得到化合物 20、21;经结构鉴定,化合物20为槲皮素,化合物21为β-香树脂醇;
Fr13用硅胶柱色谱分离,以氯仿-甲醇,体积比15:1→1:1,梯度洗脱,得到白色细针状物,再经过硅胶柱色谱和Sephadex LH-20柱色谱纯化,得到化合物22;经结构鉴定,化合物22为白桦脂酸;
Fr16经硅胶柱色谱,氯仿-甲醇体积比10:1→1:1梯度洗脱和Sephadex LH-20柱色谱,氯仿:甲醇=1:1,分离,重结晶得到化合物23、24;经结构鉴定,化合物23为异绿原酸 A,化合物24为异绿原酸 B;
Fr19经硅胶柱色谱,氯仿-甲醇体积比10:1→1:1,梯度洗脱和Sephadex LH-20柱色谱分离,重结晶得到化合物25;经结构鉴定,化合物25为异绿原酸 C。
2.根据权利要求1所述的从瑶药六方藤中提取多种单体化合物的方法,其特征在于,步骤(3)中Fr4 组分得到白色粉末,经半制备液相色谱分离纯化的色谱条件是: Waters CSHFluoro Phenyl OBD Prep Column,130A,5 μm,10 mm × 250 mm,1/pkg,石油醚-丙酮,3:1。
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