CN103755630B - 野生葫芦巴碱的新型提取方法 - Google Patents
野生葫芦巴碱的新型提取方法 Download PDFInfo
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- CN103755630B CN103755630B CN201310706466.9A CN201310706466A CN103755630B CN 103755630 B CN103755630 B CN 103755630B CN 201310706466 A CN201310706466 A CN 201310706466A CN 103755630 B CN103755630 B CN 103755630B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
本发明属于天然有机化学领域,采用超高压提取,具有加热均匀、过程易于控制,无需干燥等预处理,简化了工艺,减少了投资,大大提高了萃取效率;利用大孔树脂吸附一柱层析技术分离纯化葫芦巴碱,对葫芦巴碱的吸附选择性良好,吸附快、解析也快,吸附容量较大,提取方便快捷,生产成本低廉,分离效果明显,提取纯度高,可以通过物理吸附从溶液中有选择地吸附葫芦巴碱,得到含量40%以上的葫芦巴碱半成品和含量90%以上的葫芦巴碱终产品,克服了常规提取率相对较低、提取纯度低的缺点。
Description
技术领域:
本发明属于天然药物提取领域,涉及一种葫芦巴碱的纯化方法,特别是涉及一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法。
背景技术:
胡芦巴,又名:芸香草《盛京通志》,香草、苦草、苦朵菜、香苜蓿。一年生草本,高40~50厘米。茎丛生,几光滑或被稀疏柔毛。3出复叶,小叶卵状长卵圆形或宽披针形,长1.2~3厘米,宽1~1.5厘米,近先端有锯齿,两面均有稀疏柔毛,小叶柄长1~2毫米,总柄长6~12毫米;托叶与叶柄连合,狭卵形,先端急尖。花无梗,1~2朵腋生:萼筒状,萼齿5,披针形,比花冠短一半,外被长柔毛;花冠蝶形,初为白色,后渐变淡黄色,基部微带紫晕,旗瓣长圆形,先端具缺刻,基部尖楔形,龙骨瓣偏匙形,长仅旗瓣的1/3,翼瓣耳形,雄蕊10,2体;子房无柄,柱头顶生。荚果细长圆筒状,长6~11厘米,宽0.5厘米左右,被柔毛,并具网脉,先端有长尖。种子棕色,长约4毫米。花期4~6月。果期7~8月。我国黑龙江、吉林、辽宁、河北、河南、安徽、浙江、湖北、四川、贵州、云南、陕西、甘肃以及新疆等地有栽培。种子含龙胆宁碱、番木瓜碱、胆碱、胡芦巴碱等生物碱,皂甙元主要是薯蓣皂甙元、雅姆皂甙元和少量芰脱皂甙元、痕量替告皂甙元。尚分离出牡荆素、牡荆素-7-葡萄糖甙、荭草素或异荭草素的***糖甙、黄酮的葡萄糖鼠李糖二糖甙,槲皮素、木犀草素等黄酮类。种子的一般组成为:水分10.30%、灰分3.15%、脂肪7.61%、总蛋白16.97%、总糖3.68%、纤维素6.4%、半纤维素11.98%。脂肪油中固体脂肪酸92.9%、挥发性脂肪酸1.5%、不皂化成分0.9%;卵磷脂6.25%、植物甾醇0.5露。脂肪酸中主要是亚油酸和棕榈酸,并有少量油酸及亚麻酸。蛋白质中核蛋白55%。总糖中主要是半乳糖配甘露聚糖,还含维生素B1-320微克%
葫芦巴碱具有温肾,祛寒,止痛等功效,已引起国际社会的普遍关注。近年来,人们发现天然植物葫芦巴中含有大量的葫芦巴碱,从中提取葫芦巴碱并且取得了可喜进展,原料葫芦巴来源较广。
发明内容:本发明的目的在于克服常规技术提取率相对较低、提取纯度低等缺点,提供一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法。
为实现上述目的,本发明采用的技术方案是:
一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法,其步骤如下:
(1)将干葫芦巴粉碎,加入乙酸乙酯,浸泡1小时后放入耐压袋中,在20℃条件下处理,超高压压力在400—500MPA之间,时间在3—5min,回收乙酸乙酯,在60℃~70℃真空干燥得葫芦巴碱粗提物;
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附,吸附为静态吸附或动态吸附;
(3)用50%~90%不同浓度的乙醇对大孔吸附树脂进行洗脱,用薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液;
(4)将葫芦巴碱各阶段洗脱液浓缩,回收乙醇,得葫芦巴碱半成品,其含量在40%以上;
(5)将所得葫芦巴碱半成品粉末溶于石油醚中,加适量硅胶搅拌,烘干过60—80目筛,干法上样,上工业级柱200—300目硅胶柱层析;
(6)以丙酮、石油醚在1~7∶1条件下进行梯度洗脱,薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液,减压浓缩,回收溶剂;
(7)所得浓缩液在60℃~80℃下进行真空干燥;
(8)将干燥后的产品用75%-90%无水乙醇溶解,浓缩到原体积的十分之一,放置过夜得晶体;分离晶体将剩余物用50%-60%乙醇溶解,再次浓缩,重结晶,如此反复两次,得到精制的葫芦巴碱,其含量在90%以上。
所述的步骤(1)中,干葫芦巴粉碎后过80~100目筛。
所述的步骤(2)中,所用的大孔吸附树脂为NKA-9、D3520、D4006、H103、D4020、AB-8H和NKA-II型树脂中的一种,吸附为静态吸附或动态吸附。
本发明应用超高压技术和大孔吸附技术分离纯化葫芦巴碱,对葫芦巴碱的提取速度快,节省时间,提取率高,利用大孔树脂分离纯化分离效果明显,提取纯度高,可以得到含量40%以上的葫芦巴碱半成品和含量90%以上的葫芦巴碱终产品,克服了常规提取率相对较低、提取纯度低的缺点。
本发明选用理化性质稳定、表面积较大、交换速度较快、机械强度高、抗污染能力强、热稳定性好的大孔吸附树脂,不容于酸、碱及有机媒,对有机物选择性较好,不受无机盐类及强离子低分子化合物存在的影响,可以通过物理吸附从溶液中有选择地吸附葫芦巴碱,吸附快、解析也快,吸附容量较大。
具体实施方式:
实施例1:一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法其步骤如下:
(1)将1000g干葫芦巴粉碎后过80目筛,加入12倍体积的乙酸乙酯,浸泡1小时后放入耐压袋中,在20℃条件下处理,超高压压力400MPA,时间3min,回收乙酸乙酯,在60℃真空干燥得葫芦巴碱粗提物;
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附,所用的大孔树脂为D4006型树脂,吸附为静态吸附或动态吸附;
(3)用50%、60%、70%、80%、90%不同浓度的乙醇对大孔吸附树脂进行洗脱,用薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液;
(4)将葫芦巴碱各阶段洗脱液浓缩,回收乙醇,得葫芦巴碱半成品,其含量在41.4%;
(5)将所得葫芦巴碱半成品粉末溶于石油醚,加适量硅胶搅拌,烘干过60目筛,干法上样,上工业级柱200目硅胶柱层析;
(6)以丙酮、石油醚在1∶1、2∶1、3∶1、4∶1、5∶1、6∶1、7∶1条件下进行梯度洗脱,薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液,减压浓缩,回收溶剂;
(7)所得浓缩液在60℃下进行真空干燥;
(8)将干燥后的产品用8倍体积的75%无水乙醇溶解,浓缩到原体积的十分之一,放置过夜得晶体;分离晶体将剩余物用50%无水乙醇溶解,再次浓缩,重结晶,如此反复两次,得到精制的葫芦巴碱3.2g,其含量在91.2%。
实施案例2:一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法其步骤如下:
(1)将1000g干葫芦巴粉碎后过90目筛,加入14倍体积的乙酸乙酯,浸泡1小时后放入耐压袋中,在20℃条件下处理,超高压压力450MPA,时间4min,回收乙酸乙酯,在60℃真空干燥得葫芦巴碱粗提物;
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附,所用的大孔树脂为AB-8H型树脂,吸附为静态吸附或动态吸附;
(3)用50%、60%、70%、80%、90%不同浓度的乙醇对大孔吸附树脂进行洗脱,用薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液;
(4)将葫芦巴碱各阶段洗脱液浓缩,回收乙醇,得葫芦巴碱半成品,其含量在40.3%;
(5)将所得葫芦巴碱半成品粉末溶于石油醚,加适量硅胶搅拌,烘干过60目筛,干法上样,上工业级柱200目硅胶柱层析;
(6)以丙酮、石油醚在1∶1、2∶1、3∶1、4∶1、5∶1、6∶1、7∶1条件下进行梯度洗脱,薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液,减压浓缩,回收溶剂;
(7)所得浓缩液在60℃下进行真空干燥;
(8)将干燥后的产品用10倍体积的80%无水乙醇溶解,浓缩到原体积的十分之一,放置过夜得晶体;分离晶体将剩余物用60%无水乙醇溶解,再次浓缩,重结晶,如此反复两次,得到精制的葫芦巴碱4.0g,其含量在92.7%。
实施案例3:一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法其步骤如下:
(1)将1000g干葫芦巴粉碎后过100目筛,加入16倍体积的乙酸乙酯,浸泡1小时后放入耐压袋中,在20℃条件下处理,超高压压力500MPA,时间5min,回收乙酸乙酯,在60℃真空干燥得葫芦巴碱粗提物;
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附,所用的大孔树脂为D3520型树脂,吸附为静态吸附或动态吸附;
(3)用50%、60%、70%、80%、90%不同浓度的乙醇对大孔吸附树脂进行洗脱,用薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液;
(4)将葫芦巴碱各阶段洗脱液浓缩,回收乙醇,得葫芦巴碱半成品,其含量在42.1%;
(5)将所得葫芦巴碱半成品粉末溶于石油醚,加适量硅胶搅拌,烘干过60目筛,干法上样,上工业级柱200目硅胶柱层析;
(6)以丙酮、石油醚在1∶1、2∶1、3∶1、4∶1、5∶1、6∶1、7∶1条件下进行梯度洗脱,薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液,减压浓缩,回收溶剂;
(7)所得浓缩液在60℃下进行真空干燥;
(8)将干燥后的产品用10倍体积的90%无水乙醇溶解,浓缩到原体积的十分之一,放置过夜得晶体;分离晶体将剩余物用60%无水乙醇溶解,再次浓缩,重结晶,如此反复两次,得到精制的葫芦巴碱3.6g,其含量为91.9%。
Claims (2)
1.一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法,其步骤如下:
(1)将干葫芦巴粉碎,加入乙酸乙酯,加入乙酸乙酯的体积为物料粉碎体积的12-16倍,浸泡1小时后放入耐压袋中,在20℃条件下处理,超高压压力在400-500MPA之间,时间在3-5min,回收乙酸乙酯,在60℃~70℃真空干燥得葫芦巴碱粗提物;
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附,吸附为静态吸附或动态吸附;
(3)用50%~90%不同浓度的乙醇对大孔吸附树脂进行洗脱,用薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液;
(4)将葫芦巴碱各阶段洗脱液浓缩,回收乙醇,得葫芦巴碱半成品,其含量在40%以上;
(5)将所得葫芦巴碱半成品粉末溶于石油醚中,加适量硅胶搅拌,烘干过60-80目筛,干法上样,上工业级柱200-300目硅胶柱层析;
(6)以丙酮、石油醚在1~7:1条件下进行梯度洗脱,薄层色谱法跟踪检测,收集葫芦巴碱各阶段洗脱液,减压浓缩,回收溶剂;
(7)所得浓缩液在60℃~80℃下进行真空干燥;
(8)将干燥后的产品用75%-90%无水乙醇溶解,浓缩到原体积的十分之一,放置过夜得晶体;分离晶体将剩余物用50%-60%乙醇溶解,再次浓缩,重结晶,如此反复两次,得到精制的葫芦巴碱,其含量在90%以上;
所述的步骤(1)中,干葫芦巴粉碎后过80~100目筛;
所述的步骤(2)中,所用的大孔吸附树脂为NKA-9、D3520、D4006、H103、D4020、AB-8H和NKA-II型树脂中的一种,吸附为静态吸附或动态吸附。
2.根据权利要求1所述的利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法,其特征是:所述步骤(8)中,加入无水乙醇的体积为干燥后产品的8-10倍。
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