CN102372725A - Purification method for high-content gambogic acid - Google Patents
Purification method for high-content gambogic acid Download PDFInfo
- Publication number
- CN102372725A CN102372725A CN2010102630534A CN201010263053A CN102372725A CN 102372725 A CN102372725 A CN 102372725A CN 2010102630534 A CN2010102630534 A CN 2010102630534A CN 201010263053 A CN201010263053 A CN 201010263053A CN 102372725 A CN102372725 A CN 102372725A
- Authority
- CN
- China
- Prior art keywords
- methanol
- methyl alcohol
- crystallization
- morellic acid
- macroporous resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a purification method for high-content gambogic acid. The method comprises the following steps: crushing the medicinal material of gamboge to 60 to 100 meshes, dissolving gamboge with the backflow of anhydrous methanol, removing insoluble substances through filtration, adding granular active carbon, recovering methanol, filling the active carbon in a column after drying, carrying out gradient elution by using an eluant, condensing fraction of active ingredients to a volume of 1/10 to 1/15, carrying out refrigeration and crystallization, filtering crystals, adding a proper amount of water to dissolve the crystals, adding aqueous ammonia with a pH value of 9 to 10, carrying out stirring to completely dissolve the crystals, adjusting the pH value of an obtained mixture to be 1 to 3, adding a macroporous resin column for adsorption, eluting impurities with methanol having a concentration of 30 to 50%, eluting gambogic acid with methanol having a concentration of 70 to 90%, recovering methanol, standing a resultant for crystallization, filtering a crystal for drying, dissolving the crystal with the backflow of a mixed solution of methanol and chloroform, refrigerating the crystal, and drying the crystal to obtain gambogic acid. When the method provided in the invention is used for production of gambogic acid, the advantages of a short production period, low cost, high content of an obtained product up to 99% are obtained. The invention is applicable to industrial production.
Description
Technical field:
The invention belongs to the Natural Medicine Chemistry field, especially relate to a kind of purification process of high-content morellic acid.
Background technology:
Morellic acid
Molecular formula: C
38H
44O
8
Molecular weight: 628.75.
Physico-chemical property: golden yellow powder, its pyridinium salt, orange needle crystal.
Morellic acid is natural to be present in the dry resin of guttiferae plant gamboge tree.Has stronger antitumour activity.Clinical study proves that mammary cancer, lymphoma, skin carcinoma, cancer of the stomach are all had certain curative effect.
Gamboge is the resin that guttiferae plant gamboge trunk oozes out.Nature and flavor are sour and astringent, and are poisonous.Be used for the desinsection detoxifcation.Be used for ulcer, swollen, the innominate toxic swelling of sore.Originate in ground such as India, Vietnam, the domestic place of production is in Yunnan, and be with in Hunan, Hubei one.Mainly contain effective constituents such as morellic acid and neogambogic acid.
Existing extraction separation morellic acid method:
Chinese patent (application number 200410014061) " a kind of production technique of morellic acid ", this technology disclosed method is that the raw material goa powder is broken into meal, with ETHYLE ACETATE or chloroform or saturated propyl carbinol refluxing extraction, suction filtration; United extraction liquid, concentrate the medicinal extract shape, with the basic soln extraction, obtain the buck layer again; Transfer with aqueous hydrochloric acid, and with ETHYLE ACETATE or chloroform or saturated n-butanol extraction acid liquid, obtain and merge organic solvent layer; Washing is to neutral, and normal pressure concentrates, and gets the morellic acid crude extract; The morellic acid crude extract continues with ether or acetone solution, and adding organic bases and petroleum ether and stirring are even, and half Sai Changwen places, and crystallization, suction filtration, precipitate are respectively with basic soln and distilled water wash, drying; Get above-mentioned dry thing and use ether dissolution, add sherwood oil water-bath crystallization, suction filtration, ether-sherwood oil mixing solutions washing is dry; Dry thing is used the ether dissolution crystallization, gets orange-yellow Powdered morellic acid.This method products obtained therefrom content is higher.
Chinese patent (application number 02148321) " salt of gambogic acid compounds, its preparation method and be the pharmaceutical composition of active ingredient with this salt ", this invention improves the morellic acid massfraction with metallic salt form.This method gained content is not high.
Chinese patent (application number 201010111243.4) " morellic acid in the supercritical extraction Chinese medicine gamboge and the method for neogambogic acid "; This patent disclosed method is that the gamboge feed particles is dropped in the extraction kettle; Input supercutical fluid, entrainment agent extract continuously; The high pressure fluid that will contain the dissolution extraction thing is depressured to below the subcritical pressure, gets into separating still and isolates the solute product.This method equipment cost is high, the follow-up purifying of also wanting.
" seven kinds of macroporous resins are to the preliminary study of neogambogic acid fractionation by adsorption " that Wang Ke etc. deliver, the document has adopted the AB-8 resin purification to obtain good effect.It is subject study resin purification effect.
As stated, existing technology exists high-load morellic acid technology less, and existing complex process is loaded down with trivial details.
Summary of the invention:
The present invention wants the technical solution problem to provide a kind of easy and simple to handle, morellic acid purification process that production cost is low.
For solving the problems of the technologies described above, technical scheme of the present invention is following:
A kind of purification process of high-content morellic acid is characterized in that comprising following steps:
1) activated carbon column purifying: get gamboge pulverizing medicinal materials 60-100 order, anhydrous methanol refluxes and dissolves the elimination insolubles; Add grain active carbon, reclaim methyl alcohol, activated carbon oven dry dress post; The eluent gradient elution, the effective constituent flow point is concentrated into the 1/10-1/15 volume, the refrigeration crystallization;
2) macroporous resin column purification: the filtering for crystallizing thing, add the suitable quantity of water dissolving, add the ammoniacal liquor of pH9-10; Stirring makes it to dissolve fully, and hydrochloric acid is regulated pH1-3, adds macroporous resin column absorption; 5-7 doubly measures 30-50% methanol-eluted fractions impurity; Get 5-8 again and doubly measure 70-90% methanol-eluted fractions morellic acid, reclaim methyl alcohol, place crystallization;
3) recrystallization: leach the crystallisate oven dry, methyl alcohol chloroform mixing solutions refluxes and dissolves the refrigeration crystallization, the dry morellic acid that gets of crystallisate.
The eluent gradient elution is doubly measured chloroform → 6-10 and is doubly measured eluent ethyl acetate for 8-15 successively doubly measures sherwood oil → 5-10 in the said step 1).
Said step 2) macroporous resin in is a NKA-II type macroporous resin.
Methyl alcohol chloroform blending ratio in the said step 3) is 1: 1-3.
The present invention adopts active pillars to separate morellic acid with macroporous resin column, compares with simple crystallization process, has to shorten production cycle and the advantage that reduces reagent volumes, also is prone to industriallization simultaneously.
To combine embodiment to further specify the present invention below, but the scope that the present invention requires to protect is not limited to following embodiment:
Embodiment:
Embodiment 1:
Get gamboge and pulverize 60 orders, get 500g, drop in the flask; Anhydrous methanol refluxes and dissolves, and the elimination insolubles adds grain active carbon 1kg; Behind the reclaim under reduced pressure methyl alcohol,, get 8L sherwood oil, 10L chloroform, 6L eluent ethyl acetate successively activated carbon oven dry dress post; The ETHYLE ACETATE flow point is concentrated into 600ml, the refrigeration crystallization; The filtering for crystallizing thing adds the suitable quantity of water dissolving, adds the ammoniacal liquor of pH9, stirs to make it to dissolve fully; Hydrochloric acid is regulated pH1, adds the absorption of 500mlNKA-II type macroporous resin column, earlier with 3.5L30% methanol-eluted fractions impurity, gets 2.5L90% methanol-eluted fractions morellic acid again; Reclaim methyl alcohol, place crystallization, leach the crystallisate oven dry, methyl alcohol chloroform (1: 1) mixing solutions refluxes and dissolves; Refrigeration crystallization, crystallisate leach the dry morellic acid 90g of getting, content 98%.
Embodiment 2:
Get gamboge and pulverize 100 orders, get 500g, drop in the flask; Anhydrous methanol refluxes and dissolves, and the elimination insolubles adds grain active carbon 1kg; Behind the reclaim under reduced pressure methyl alcohol,, get 15L sherwood oil, 5L chloroform, 10L eluent ethyl acetate successively activated carbon oven dry dress post; The ETHYLE ACETATE flow point is concentrated into 700ml, the refrigeration crystallization; The filtering for crystallizing thing adds the suitable quantity of water dissolving, adds the ammoniacal liquor of pH10, stirs to make it to dissolve fully; Hydrochloric acid is regulated pH3, adds the absorption of 500mlNKA-II type macroporous resin column, earlier with 25L50% methanol-eluted fractions impurity, gets 4L70% methanol-eluted fractions morellic acid again; Reclaim methyl alcohol, place crystallization, leach the crystallisate oven dry, methyl alcohol chloroform (1: 3) mixing solutions refluxes and dissolves; Refrigeration crystallization, crystallisate leach the dry morellic acid 85g of getting, content 99%.
Embodiment 3:
Get gamboge and pulverize 80 orders, get 500g, drop in the flask; Anhydrous methanol refluxes and dissolves, and the elimination insolubles adds grain active carbon 1kg; Behind the reclaim under reduced pressure methyl alcohol,, get 10L sherwood oil, 7L chloroform, 8L eluent ethyl acetate successively activated carbon oven dry dress post; The ETHYLE ACETATE flow point is concentrated into 600ml, the refrigeration crystallization; The filtering for crystallizing thing adds the suitable quantity of water dissolving, adds the ammoniacal liquor of pH10, stirs to make it to dissolve fully; Hydrochloric acid is regulated pH2, adds the absorption of 500mlNKA-II type macroporous resin column, earlier with 3L40% methanol-eluted fractions impurity, gets 3L80% methanol-eluted fractions morellic acid again; Reclaim methyl alcohol, place crystallization, leach the crystallisate oven dry, methyl alcohol chloroform (1: 2) mixing solutions refluxes and dissolves; Refrigeration crystallization, crystallisate leach the dry morellic acid 95g of getting, content 98.3%.
Embodiment 4:
Get gamboge and pulverize 80 orders, get 2kg, drop in the flask; Anhydrous methanol refluxes and dissolves, and the elimination insolubles adds grain active carbon 4kg; Behind the reclaim under reduced pressure methyl alcohol,, get 40L sherwood oil, 28L chloroform, 32L eluent ethyl acetate successively activated carbon oven dry dress post; The ETHYLE ACETATE flow point is concentrated into 2.4L, the refrigeration crystallization; The filtering for crystallizing thing adds the suitable quantity of water dissolving, adds the ammoniacal liquor of pH10, stirs to make it to dissolve fully; Hydrochloric acid is regulated pH2, adds the absorption of 2LNKA-II type macroporous resin column, earlier with 12L40% methanol-eluted fractions impurity, gets 12L80% methanol-eluted fractions morellic acid again; Reclaim methyl alcohol, place crystallization, leach the crystallisate oven dry, methyl alcohol chloroform (1: 2) mixing solutions refluxes and dissolves; Refrigeration crystallization, crystallisate leach the dry morellic acid 367g of getting, content 98.5%.
Embodiment 5:
Get gamboge and pulverize 80 orders, get 5kg, drop in the flask; Anhydrous methanol refluxes and dissolves, and the elimination insolubles adds grain active carbon 1kg; Behind the reclaim under reduced pressure methyl alcohol,, get 100L sherwood oil, 70L chloroform, 80L eluent ethyl acetate successively activated carbon oven dry dress post; The ETHYLE ACETATE flow point is concentrated into 6L, the refrigeration crystallization; The filtering for crystallizing thing adds the suitable quantity of water dissolving, adds the ammoniacal liquor of pH10, stirs to make it to dissolve fully; Hydrochloric acid is regulated pH2, adds the absorption of 5LNKA-II type macroporous resin column, earlier with 30L40% methanol-eluted fractions impurity, gets 30L80% methanol-eluted fractions morellic acid again; Reclaim methyl alcohol, place crystallization, leach the crystallisate oven dry, methyl alcohol chloroform (1: 2) mixing solutions refluxes and dissolves; Refrigeration crystallization, crystallisate leach the dry morellic acid 924g of getting, content 98%.
Claims (4)
1. the purification process of a high-content morellic acid is characterized in that comprising following steps:
1) activated carbon column purifying: get gamboge pulverizing medicinal materials 60-100 order, anhydrous methanol refluxes and dissolves the elimination insolubles; Add grain active carbon, reclaim methyl alcohol, activated carbon oven dry dress post; The eluent gradient elution, the effective constituent flow point is concentrated into the 1/10-1/15 volume, the refrigeration crystallization;
2) macroporous resin column purification: the filtering for crystallizing thing, add the suitable quantity of water dissolving, add the ammoniacal liquor of pH9-10; Stirring makes it to dissolve fully, and hydrochloric acid is regulated pH1-3, adds macroporous resin column absorption; 5-7 doubly measures 30-50% methanol-eluted fractions impurity; Get 5-8 again and doubly measure 70-90% methanol-eluted fractions morellic acid, reclaim methyl alcohol, place crystallization;
3) recrystallization: leach the crystallisate oven dry, methyl alcohol chloroform mixing solutions refluxes and dissolves the refrigeration crystallization, the dry morellic acid that gets of crystallisate.
2. the purification process of morellic acid according to claim 1 is characterized in that in the said step 1) that the eluent gradient elution doubly measures chloroform → 6-10 and doubly measure eluent ethyl acetate for 8-15 successively doubly measures sherwood oil → 5-10.
3. the purification process of morellic acid according to claim 1 is characterized in that said step 2) in macroporous resin be NKA-II type macroporous resin.
4. the purification process of morellic acid according to claim 1 is characterized in that the methyl alcohol chloroform blending ratio in the said step 3) is 1: 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102630534A CN102372725A (en) | 2010-08-26 | 2010-08-26 | Purification method for high-content gambogic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102630534A CN102372725A (en) | 2010-08-26 | 2010-08-26 | Purification method for high-content gambogic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102372725A true CN102372725A (en) | 2012-03-14 |
Family
ID=45792001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102630534A Pending CN102372725A (en) | 2010-08-26 | 2010-08-26 | Purification method for high-content gambogic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102372725A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688267A (en) * | 2012-06-18 | 2012-09-26 | 郭宏昌 | Preparation method for antineoplastic preparation of total gambogic acid |
| CN104817569A (en) * | 2015-03-07 | 2015-08-05 | 宝鸡文理学院 | Method for simultaneous separation of four gambogic acid components in Garcinia hanburyi |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1452960A (en) * | 2003-05-21 | 2003-11-05 | 戴建国 | Garcinolic acid injection and its prepn |
| CN1539443A (en) * | 2003-04-24 | 2004-10-27 | 北京中医药大学 | Process technique of preparing extract of Chinese traditional medicine for intravenous injection by using column chromatography of active carbon |
| CN1557816A (en) * | 2004-02-12 | 2004-12-29 | 江苏康缘药业股份有限公司 | Process for preparation of garcinia acid |
| US20090259054A1 (en) * | 2008-01-25 | 2009-10-15 | The Texas A&M University System | Methods and Compositions for the Treatment of Angiogenesis and Macular Degeneration |
| CN101607978A (en) * | 2008-06-20 | 2009-12-23 | 秦继红 | Two new compounds, its preparation method and pharmaceutical uses in the gamboge |
-
2010
- 2010-08-26 CN CN2010102630534A patent/CN102372725A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1539443A (en) * | 2003-04-24 | 2004-10-27 | 北京中医药大学 | Process technique of preparing extract of Chinese traditional medicine for intravenous injection by using column chromatography of active carbon |
| CN1452960A (en) * | 2003-05-21 | 2003-11-05 | 戴建国 | Garcinolic acid injection and its prepn |
| CN1557816A (en) * | 2004-02-12 | 2004-12-29 | 江苏康缘药业股份有限公司 | Process for preparation of garcinia acid |
| US20090259054A1 (en) * | 2008-01-25 | 2009-10-15 | The Texas A&M University System | Methods and Compositions for the Treatment of Angiogenesis and Macular Degeneration |
| CN101607978A (en) * | 2008-06-20 | 2009-12-23 | 秦继红 | Two new compounds, its preparation method and pharmaceutical uses in the gamboge |
Non-Patent Citations (6)
| Title |
|---|
| QUAN BIN HAN,等: "Preparative separation of gambogic acid and its C-2 epimer using recycling high-speed counter-current chromatography", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 刘修树，等: "新藤黄酸提取工艺的优化研究", 《安徽中医学院学报》 * |
| 吕归宝，等: "藤黄中新藤黄酸的分离及其结构", 《药学学报》 * |
| 杨虹，等: "药用藤黄化学成分的研究", 《中国药学杂志》 * |
| 王可，等: "七种大孔树脂对新藤黄酸吸附分离的初步研究", 《安徽化工》 * |
| 贾明美，等: "藤黄化学成分的研究", 《化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688267A (en) * | 2012-06-18 | 2012-09-26 | 郭宏昌 | Preparation method for antineoplastic preparation of total gambogic acid |
| CN104817569A (en) * | 2015-03-07 | 2015-08-05 | 宝鸡文理学院 | Method for simultaneous separation of four gambogic acid components in Garcinia hanburyi |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104513173B (en) | A kind of Maca extract, Its Preparation Method And Use | |
| CN111978158A (en) | Method for extracting purified hypocannabidiol from industrial cannabis sativa | |
| CN104415070A (en) | Method for separating and purifying total ginsenoside from ginseng | |
| CN101647828B (en) | Method for separating total alkaloid from sophora flavescens ait by using ion exchange resin | |
| CN103550285B (en) | Astragalus extractive grading preparation method | |
| CN101759543A (en) | Method for extracting chalcone from fresh angelica keiskei | |
| Wang et al. | Ultrasonic microwave-assisted micellar extraction and purification of flavonoids from licorice by metal complex and antisolvent recrystallization | |
| CN102372725A (en) | Purification method for high-content gambogic acid | |
| CN105859805A (en) | Preparation method and application of novel phenolic glycoside compound extracted from green peel of Juglans mandshurica Maxim | |
| CN104473825B (en) | Longan fruit stone polyphenol method for extraction and purification and its application in polyphenol skin-lightening cosmetic is prepared | |
| CN101735021B (en) | Method for separating and purifying magnolol and honokiol by HP-20 macroporous resin | |
| CN103664855A (en) | Preparation method of high-purity oligomer lotus seedpod procyanidin | |
| CN105153253A (en) | Purple sweet potato anthocyanin extraction process | |
| CN109053756B (en) | Phenylpropanoid ester type catechin and preparation method and application thereof | |
| CN111171106A (en) | Preparation method of 24-hydroxystearyl glycyrrhetinate | |
| CN104592322A (en) | Method for extracting and separating curculigoside from curculigo gaertn plants | |
| CN103980099A (en) | Method for extracting erianin from dendrobe | |
| CN104926823B (en) | The extracting method of alkaloid in a kind of Stephania tetrandra | |
| CN103585208A (en) | Preparation method of high-quality andrographolide component | |
| CN103768124B (en) | A kind of promoting blood circulation and stopping pain composition and capsules preparation technique and application | |
| CN105168328A (en) | Kudzuvine root extract, extracting method and dropping pill of kudzuvine root extract | |
| CN1064684C (en) | Effective components of wild opium poppy and extracting process and product thereof | |
| CN105061458B (en) | Preparation method of nontoxic high-purity ginkgo total lactones and monomers thereof | |
| CN113041280A (en) | Method for extracting licoflavone by using R19 | |
| CN102258625A (en) | Medicine for treating disease such as ulcerative colitis, colon cancer or rectal cancer and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice |
Addressee: Suzhou Baozetang Medical Technology Co.,Ltd. Document name: the First Notification of an Office Action |
|
| DD01 | Delivery of document by public notice |
Addressee: Han Shuyu Document name: Notification that Application Deemed to be Withdrawn |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120314 |