CN104610273B - Method of extracting gambogic acid and neogambogic acid from gamboge - Google Patents

Method of extracting gambogic acid and neogambogic acid from gamboge Download PDF

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CN104610273B
CN104610273B CN201510077377.1A CN201510077377A CN104610273B CN 104610273 B CN104610273 B CN 104610273B CN 201510077377 A CN201510077377 A CN 201510077377A CN 104610273 B CN104610273 B CN 104610273B
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acid
gamboge
gambogicacid
neo
ethanol
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CN104610273A (en
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梁玉强
白易
高瑞
赵永强
张成亮
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INNER MONGOLIA CHANGHUI BIOLOGICAL TECHNOLOGY Co.,Ltd.
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Inner Mongolia Changhui Biotechnology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D493/00Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/20Spiro-condensed systems

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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Medicines Containing Plant Substances (AREA)

Abstract

The invention aims at providing a method of efficiently extracting and separating gambogic acid and neogambogic acid from gamboge, serving as a traditional Chinese medicine. The method comprises the following steps: crushing the gamboge, carrying out microwave extraction, and concentrating to obtain an extract A; leaching with petroleum ether, dissolving and filtering with ethanol, and carrying out chromatographic separation by virtue of a simulated moving bed to obtain a component B rich in the gambogic acid and a component C containing the gambogic acid and the neogambogic acid; and recovering a solvent, drying to obtain products, including the gambogic acid with the purity to be above 95 percent and a mixture of 10-20 percent of the gambogic acid and 30-50 percent of the neogambogic acid, in two specifications. The method of extracting the effective components of the gamboge, serving as the traditional Chinese medicine, is simple in step and high in product purity and is capable of simultaneously obtaining the products, including the gambogic acid and the neogambogic acid, in two specifications, fully extracting and separating the effective components from the raw materials and improving the production efficiency while saving the raw material resources.

Description

A kind of method extracting gambogicacid and Neo-garcinolic acid in gamboge
Technical field
The present invention relates to a kind of method extracting gambogicacid and Neo-garcinolic acid in Chinese medicine gamboge.
Background technology
Gamboge be Garcinia maingayii gamboge (garcinia hanburyi hook f.) trunk hurt after flow out glue Shape resin, is in the cylindric or irregular block of yellowish-brown after being dried, and matter is crisp frangible, original Southeast Asia, and China some areas are such as There is introducing and planting on the ground such as Yunnan, Guangxi, Guangdong.Gambogicacid (gambogic acid), Neo-garcinolic acid is contained in gamboge The Multiple components such as (neomogenic acid), allogambogic acid (allogambogic acid).In clinical practice of Chinese medicine, rattan Huang is mainly used in treating the illnesss such as swollen ulcer drug, ulcer, wet sore, tumour, stubborn dermatitis.Modern pharmacological research shows, gambogicacid is to many Plant tumour cell and there is stronger inhibitory action, and toxic and side effect is less in effective dosage ranges, the suppression to tumour cell There is higher selectivity, and intact animal hemopoietic system and immunologic function are not affected.There are some researches show Neo-garcinolic acid Antitumor activity is about 2 times of gambogicacid, and being expected to exploitation is new type antineoplastic medicine.
In prior art, disclose one kind in cn101781309a using gambogicacid in supercritical fluid extraction Chinese medicine gamboge Method with Neo-garcinolic acid.But the method need to strictly regulate and control pressure in kettle, it is difficult to adapt to the demand of industrialized production. Cn101921283a disclose a kind of by pulverize after gamboge mix with one of silica gel, diatomite, silica flour or polyacrylamide Load column chromatography, afford the gambogicacid extracting method of gambogicacid primary extract through methyl alcohol, ethyl acetate equal solvent.Lin Qinghua etc. Combine to prepare Neo-garcinolic acid with preparative liquid chromatography using silica gel column chromatography, there is organic solvent and use less, avoid instead The high cost of cladding analysis and the advantage extremely adsorbing the production loss causing, product purity can reach chemical reference substance quality requirement (traditional Chinese medicine journal, Neo-garcinolic acid prepares liquid phase separation method, Lin Qinghua, Zhang Jian, Li Guanglei etc., vol.42, no.3, Jun.2014, p71-72).But above two method is all to be suitable only for isolating gambogicacid or a kind of active ingredient of Neo-garcinolic acid, Remaining active component is caused waste.
Microwave Extraction is the difference absorbing microwave ability using the material of different structure in microwave field, makes in material Some components in some regions or extraction system are selectively heated, so that extract separates from material or system, Enter that dielectric constant is less, in microwave absorption capacity relative mistake extractant.The advantage of this method is that extract is had relatively High selectivity, recovery rate is high, extraction rate is fast, solvent load is few, safety, energy-conservation, equipment are simple.
Content of the invention
The present invention is intended to provide a kind of efficiently can extract the side separating gambogicacid and Neo-garcinolic acid from Chinese medicine gamboge Method.
The method extracting gambogicacid and Neo-garcinolic acid from gamboge of the present invention, comprises the following steps:
(1) gamboge being dried is pulverized, cross 40~80 mesh sieves, be placed in microwave synthesis abstraction instrument and extracted, add second Alcohol reflux extracts;
(2) filter out extract, after reduced pressure concentration recycling design, obtain medicinal extract a;
(3) add petroleum ether drip washing in medicinal extract a, dissolved with ethanol afterwards, filter, filtrate enters simulation and moves Bed chromatogram carries out separating, and obtains component b rich in gambogicacid and component c containing gambogicacid, Neo-garcinolic acid;
(4) recycling design, drying under reduced pressure obtain the gambogicacid of the gambogicacid of purity more than 95% and purity 10%~20% with The product of two kinds of specifications of Neo-garcinolic acid mixture of purity 30%~50%.
In step (1) of the present invention, during extraction, microwave power 200w~400w, 30 DEG C~70 DEG C of microwave heating temperature, Microwave Extraction time 60s~300s, the alcohol solvent of addition and raw material solid-to-liquid ratio are 10:1~20:1.
In step (3) of the present invention, the adsorbent of SMBC filling is low pole macroporous absorbent resin, Water wash zone is purified water, and strippant is 20~50% ethanol, and its consumption is 1~3 times of resin volume;Resin adsorption regenerated solvent For 95% ethanol or 2~4% sodium hydrate aqueous solutions;Adsorption zone flow velocity 1~2bv/h;Water wash zone flow velocity 1~3bv/h;Desorption zone is flowed Fast 1~3bv/h;Renewing zone flow velocity 2~3bv/h;Switching time is 600~900s;Temperature control is at 40 DEG C~60 DEG C;Pressure control System is in 0.2mpa~0.6mpa.
Further, in step (1) of the present invention, 50 DEG C~70 DEG C of microwave heating temperature, Microwave Extraction time 100s ~200s, the alcohol solvent of addition and the liquid-solid ratio of raw material are 15:1~20:1.
Further, in step (3) of the present invention, the switching time preferably 700~800s of SMBC;Mould The adsorbent intending mobile bed chromatic filling is ab-8 or dm130;Strippant consumption is preferably 3 times of resin volume.
Although simulated moving bed technology can apply to natural products or the separating-purifying of medicine has had altogether in the art Know, but because Simulation moving bed big be structurally characterized in that by chemical industry continuous, countercurrently, rectifying, the key element such as backflow all concentrate into System, it is a multiple degrees of freedom, dynamic, be mutually related nonlinear system.Therefore, for its prediction, optimize and control It is more complicated problem, in particular for a certain natural products kind, the prediction of separation parameter is a sufficiently complex problem. Reported microwave radiation exaraction is mainly used in extraction alkaloids, Anthraquinones, flavonoids, saponins, polysaccharide, volatilization The traditional Chinese medicine ingredients such as oil, pigment.But the extraction specific to active ingredient in gamboge, whether microwave radiation exaraction adapts to, and its phase The determination closing technological parameter is still a complicated process.
Chinese medicine gamboge extraction process of effective component of the present invention, using microwave radiation exaraction and SMBC , it is determined that related process parameters, simply, product purity is higher, can obtain two simultaneously for step for the technique that method separating-purifying combines Plant gambogicacid and the Neo-garcinolic acid product of specification, the active ingredient in raw material is fully extracted and separates, saved raw material resources Also improve production efficiency simultaneously.
Specific embodiment
Embodiment 1
The Gamboge (gamboge acid content 31.28%, Neo-garcinolic acid content 12.34%) that 200g is dried crosses 40 mesh after pulverizing Sieve, adds Extraction solvent absolute ethyl alcohol, Microwave Extraction 2min under the conditions of power 250w, temperature 50 C with solid-to-liquid ratio 1:20.Cross Leach extract, after reduced pressure concentration recycling design, obtain medicinal extract a;Add appropriate petroleum ether drip washing in medicinal extract a, add 95% Ethanol is dissolved, and filters, and filtrate enters SMBC and carries out separating.Adsorbent is ab-8 macroporous absorbent resin, solution Vapor is 25% ethanol water, and its consumption is 3 times of resin volume, and water wash zone is purified water, and resin adsorption regenerated solvent is 95% ethanol, adsorption zone flow velocity 2bv/h, desorption zone flow velocity 3bv/h, water wash zone flow velocity 3bv/h, renewing zone flow velocity 3bv/h, switching Time is 700s, temperature 50 C, pressure 0.5mpa.Separate component b obtaining rich in gambogicacid and contain gambogicacid, Neo-garcinolic acid Component c.Component b and c are separately recovered solvent, drying under reduced pressure, respectively obtain gamboge acid content 96.1% product 33.3g and Gamboge acid content 13.4%, the product 15.9g of Neo-garcinolic acid content 48.2%.
Embodiment 2
The Gamboge (gamboge acid content 31.28%, Neo-garcinolic acid content 12.34%) that 500g is dried crosses 80 mesh after pulverizing Sieve, adds Extraction solvent absolute ethyl alcohol, Microwave Extraction 2.5min under the conditions of power 300w, temperature 70 C with solid-to-liquid ratio 1:15. Filter out extract, after reduced pressure concentration recycling design, obtain medicinal extract a;Add appropriate petroleum ether drip washing in medicinal extract a, add 95% ethanol is dissolved, and filters, and filtrate enters SMBC and carries out separating.Adsorbent is dm130 macroporous absorption tree Fat, strippant is 30% ethanol water, and its consumption is 3 times of resin volume, and water wash zone is purified water, and resin adsorption regeneration is molten Agent is 95% ethanol, adsorption zone flow velocity 2bv/h, desorption zone flow velocity 3bv/h, water wash zone flow velocity 3bv/h, renewing zone flow velocity 3bv/h, Switching time is 750s, temperature 50 C, pressure 0.5mpa.Separate component b obtaining rich in gambogicacid and contain gambogicacid, new rattan Component c of yellow acid.Component b and c are separately recovered solvent, drying under reduced pressure, respectively obtain the product of gamboge acid content 95.8% The 82.9g and product 44.3g of gamboge acid content 11.2%, Neo-garcinolic acid content 44.6%.
Embodiment 3
The Gamboge (gamboge acid content 31.28%, Neo-garcinolic acid content 12.34%) that 600g is dried crosses 60 mesh after pulverizing Sieve, adds Extraction solvent absolute ethyl alcohol, Microwave Extraction 3min under the conditions of power 250w, temperature 70 C with solid-to-liquid ratio 1:20.Cross Leach extract, after reduced pressure concentration recycling design, obtain medicinal extract a;Add appropriate petroleum ether drip washing in medicinal extract a, add 95% Ethanol is dissolved, and filters, and filtrate enters SMBC and carries out separating.Adsorbent is ab-8 macroporous absorbent resin, solution Vapor is 30% ethanol water, and its consumption is 3 times of resin volume, and water wash zone is purified water, and resin adsorption regenerated solvent is 95% ethanol, adsorption zone flow velocity 2bv/h, desorption zone flow velocity 3bv/h, water wash zone flow velocity 3bv/h, renewing zone flow velocity 3bv/h, switching Time is 750s, temperature 50 C, pressure 0.5mpa.Separate component b obtaining rich in gambogicacid and contain gambogicacid, Neo-garcinolic acid Component c.Component b and c are separately recovered solvent, drying under reduced pressure, respectively obtain gamboge acid content 96.4% product 98.3g and Gamboge acid content 12.6%, the product 52.1g of Neo-garcinolic acid content 45.2%.

Claims (1)

1. a kind of method of extraction gambogicacid and Neo-garcinolic acid from gamboge is it is characterised in that comprise the following steps:
(1) gamboge being dried is pulverized, cross 40~80 mesh sieves, be placed in microwave synthesis abstraction instrument and extracted, add ethanol to return Stream extracts;During extraction, microwave power 200w~400w, 50 DEG C~70 DEG C of microwave heating temperature, Microwave Extraction time 100s~ 200s, the alcohol solvent of addition and raw material solid-to-liquid ratio are 15:1~20:1;
(2) filter out extract, after reduced pressure concentration recycling design, obtain medicinal extract a;
(3) add petroleum ether drip washing in medicinal extract a, dissolved with ethanol afterwards, filter, filtrate enters SMBC Carry out separating, obtain component b rich in gambogicacid and component c containing gambogicacid, Neo-garcinolic acid;SMBC is filled Adsorbent be low pole macroporous absorbent resin ab-8 or dm130, water wash zone be purified water, strippant be 20~50% ethanol, Its consumption is 1~3 times of resin volume;Resin adsorption regenerated solvent is 95% ethanol or 2~4% sodium hydrate aqueous solutions, uses Measure 3 times for resin volume;Adsorption zone flow velocity 1~2bv/h;Water wash zone flow velocity 1~3bv/h;Desorption zone flow velocity 1~3bv/h;Again Raw area flow velocity 2~3bv/h;Switching time is 700~800s;Temperature control is at 40 DEG C~60 DEG C;Stress control 0.2mpa~ 0.6mpa;
(4) recycling design, drying under reduced pressure obtain the gambogicacid of purity more than 95% and the gambogicacid of purity 10%~20% with pure The product of two kinds of specifications of Neo-garcinolic acid mixture of degree 30%~50%.
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CN107137392A (en) * 2017-06-02 2017-09-08 南方医科大学 Neo-garcinolic acid is preparing the application in suppressing hepatoma cell proliferation, migration and liver cancer apoptosis reducing medicine
CN110229169A (en) * 2019-06-27 2019-09-13 济宁医学院 A kind of method Neo-garcinolic acid separation and its prepare the new gamboge amide of N- aryl

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CN101781309B (en) * 2010-02-09 2013-04-24 夏伦祝 Method for extracting gambogic acid and neo-gambogic acid in traditional Chinese medicine gamboge by using supercritical fluid
CN102617590A (en) * 2012-03-07 2012-08-01 广州牌牌生物科技有限公司 Preparation process for neogambogic acid

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