CN101899055A

CN101899055A - Method for rapidly extracting artemisinin

Info

Publication number: CN101899055A
Application number: CN 201010250672
Authority: CN
Inventors: 刘硕谦; 刘仲华; 田娜; 黄建安
Original assignee: Hunan Agricultural University
Current assignee: Hunan Agricultural University
Priority date: 2010-08-12
Filing date: 2010-08-12
Publication date: 2010-12-01
Anticipated expiration: 2030-08-12
Also published as: CN101899055B

Abstract

The invention provides a method for rapidly extracting artemisinin, comprising the following steps: taking fresh and non-dry artemisia annua as an extraction raw material; extracting the artemisinin from the raw material using analytically pure ethyl acetate or chloroform or dichloromethane under the condition of normal temperature and normal pressure; filtering, collecting extracting solution, decolorizing by active carbon, concentrating and then recovering an extraction solvent to obtain a crude artemisinin product; and crystallizing and purifying the crude artemisinin product by edible ethanol or petroleum ether or n-hexane to finally obtain the artemisinin product with high purity up to over 95% and high recovery rate up to over 86%. The method has the advantages of being efficient and fast, low cost and applicability to industrial application.

Description

The method of rapidly extracting artemisinin

Technical field

The present invention relates to the Separation of Natural Products field of engineering technology, relate to a kind of method of quick, efficient extracting artemisinin from fresh non-exsiccant Herba Artemisiae annuae at normal temperatures and pressures particularly.

Background technology

Artemisinin is to separate a kind of sesquiterpene lactones superoxide that obtains from Herba Artemisiae annuae, is the specifics of treatment malaria.Because plasmodium has produced resistance to quinoline, Artemisinin becomes the choice drug of treatment malaria, thereby the demand of Artemisinin sharply rises.Further pharmacological research proves that Artemisinin and derivative thereof have the effect of killing multiple cancer cells, and very little to normal cell injury, and does not have crossing drug resistant with traditional chemotherapeutic.Therefore, with Artemisinin and derivative thereof be developed to efficiently, low toxicity, inexpensive, the wide PTS of spectrum, be with a wide range of applications.

Present commercial Artemisinin product all is to extract from sweet wormwood plant, and the extracting method of Artemisinin mainly contains four classes, is respectively traditional organic solvent reflux extraction, microwave extraction method, ultrasonic extraction and supercritical extraction method.These a few class extraction processes all exist some defectives on industrial application: the organic solvent reflux extraction is the Artemisinin extractive technique of generally using at present, exist the energy, raw materials consumption amount excessive, solvent load is excessive, extraction efficiency is low excessively, process time is long, defectives such as the industrial pollution quantity discharged is big, the rate of recovery is low, production cost height; The heat collapse of microwave extraction method is bigger, and the heat effect of microwave can cause some heat-sensitive component decomposition in the plant in leaching process, and particularly Artemisinin has thermolability, thereby causes extract biological activity and extraction yield to descend; There is complex operation in ultrasonic extraction, inefficient shortcoming; Though have the extraction yield height, pollute few advantage, there is the high problem of cost in the supercritical extraction method, can't realize suitability for industrialized production at present.

This shows, set up low cost, low consumption, safety and fast Artemisinin extraction separation purification technique be still the major issue of Artemisinin production industry urgent need solution.

Summary of the invention

Technical problem to be solved by this invention is: at above-mentioned the deficiencies in the prior art, a kind of method of rapidly extracting artemisinin is proposed, it is the novel method of from sweet wormwood plant, extracting artemisinin purifying, rapid extraction Artemisinin at normal temperatures and pressures, and adopt simple crystallization purifying just can obtain highly purified Artemisinin, thereby provide one efficient, quick, low-cost, but the technical matters of the extraction separation high purity Artemisinin of industrial applications.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of method of rapidly extracting artemisinin, this method comprises the steps:

A, fresh Herba Artemisiae annuae is carried out lixiviate with extracting solvent, extracting solvent once adds, total input amount of fresh Herba Artemisiae annuae is extracted the ratio that solvent adds the fresh Herba Artemisiae annuae of 250-1500g in 1L, divide 1-10 equivalent input, extraction and filtration, each normal temperature and pressure lixiviate 2-8min, the raw material that drops into next time is to utilize the last raw material filtrate filtered that drops into of extraction to carry out lixiviate, collects extracting solution;

The said extracted solvent is ethyl acetate, chloroform or methylene dichloride, is all analytical pure;

B, add the ratio of 2-8g activated carbon in every 100ml extracting solution, add decolorizing with activated carbon in said extracted liquid, the elimination gac in 30-50 ℃ of vacuum concentration, reclaims and extracts solvent, the Artemisinin crude product;

C, add the ratio of 4-9ml solvating agent in 1g Artemisinin crude product, add solvating agent in above-mentioned Artemisinin crude product, be heated to boiling, stirring and dissolving is filtered, and crystallizing at room temperature gets needle-like crystal, with solvating agent crystal is carried out recrystallization again, promptly gets the Artemisinin elaboration;

Above-mentioned solvating agent is edible ethanol or the analytical pure sherwood oil or the analytical pure normal hexane of 60-90% volumetric concentration.

Optimizing technology parameters is in the inventive method: extract solvent and be preferably the analytical pure ethyl acetate; Fresh Herba Artemisiae annuae is divided the equivalent input 3-5 time, and total input amount is every liter and extracts solvent throwing 400-900g raw material; The add-on of activated carbon is that every 100ml extracting solution adds the 4-6g activated carbon; Solvating agent is preferably the edible ethanol of 65-80% volumetric concentration.

The most critical part of the inventive method is to adopt fresh Herba Artemisiae annuae for extracting raw material.Adopt fresh but not the exsiccant Herba Artemisiae annuae, the drying-free process has shortened the production time on the one hand; The more important thing is because chrysanthemum mugwort or the glandular hairs (synthetic with the tissue that stores Artemisinin) of spending the surface are when vegetable material is fresh, form is the fullest, the surface-area maximum, thereby the easiest with extract solvent and contact, the contact area maximum, and this moment, glandular hairs cell walls and cytolemma were loose active condition, helped Artemisinin molecule breakthrough cytolemma and wall and entered in the organic solvent.In addition, Artemisinin still is present in the glandular hairs with the state of solution in the fresh material, therefore very easily is dissolved in the organic solvent.In contrast, if behind the raw material drying, glandular hairs are shrivelled, and it is fine and close that cell walls and film become, and Artemisinin exists in the plant stem cell with the solid form, thereby cause Artemisinin to extract increasing considerably of difficulty.

The present invention uses fresh vegetable material, but material dehydration the or wilting result is not had influence.

Advantage of the present invention is: use fresh Herba Artemisiae annuae for extracting material, do not need at first material to be carried out drying, shortened the production time; In leaching process, adopt normal temperature and pressure to extract, can avoid the thermolysis of Artemisinin in leaching process, also can reduce energy consumption significantly; Adopt analytical pure ethyl acetate or chloroform or methylene dichloride for extracting solvent, increased substantially extraction efficiency, and shortened extraction time significantly and reduced the solvent usage quantity; The Artemisinin purity of obtaining through refining is more than 95%, and the Artemisinin rate of recovery reaches more than 86%.

Embodiment:

Below, the present invention will be described further with embodiment, but the present invention is not limited to any or the similar example of these embodiment.

Embodiment 1:

In extractor, add 10 liters of ethyl acetate (analytical pure), in extractor, drop into the fresh Herba Artemisiae annuae (weight in wet base of 2500g then, down together), lixiviate 8min under the normal temperature and pressure, filter, collect extracting solution, in extracting solution, add 200g decolorizing with activated carbon, elimination gac, 35 ℃ of vacuum concentration, reclaim ethyl acetate solvent, obtain the thick product of 16.12g, add 120mL normal hexane (analytical pure) again and be heated to boiling, dissolving, filter, room temperature is placed 2h and is got needle-like crystal, with the edible ethanol recrystallization acquisition 3.71g Artemisinin elaboration of 80% volumetric concentration; Utilize gas chromatographic detection, Artemisinin purity is 98.7%, and the Artemisinin rate of recovery is 87.1%.

Embodiment 2:

10 liters of ethyl acetate of disposable adding (analytical pure) in extractor drop into fresh Herba Artemisiae annuae raw material then in extractor, the raw material total amount is 4500g, divide 3 inputs, extractions, also filter, and each the input extracted 1500g, at every turn lixiviate 5min under the normal temperature and pressure; Collect extracting solution, in extracting solution, add 400g decolorizing with activated carbon, elimination gac, 40 ℃ of vacuum concentration, reclaim ethyl acetate, obtain the thick product of 39.01g, add the edible ethanol of 200mL80% volumetric concentration again, be heated to boiling, dissolving, filter, room temperature is placed 3h and is got needle-like crystal, with the edible ethanol recrystallization acquisition 6.65g Artemisinin elaboration of 65% volumetric concentration; Utilize gas chromatographic detection, Artemisinin purity is 99.6%, and the Artemisinin rate of recovery is 88.6%.

Embodiment 3:

10 liters of ethyl acetate of disposable adding in extractor drop into fresh Herba Artemisiae annuae raw material then in extractor, the raw material total amount is 9000g, divide 5 inputs, extractions, also filter, and each the input extracted 1800g, at every turn normal temperature and pressure lixiviate 4min; Collect extracting solution, in extracting solution, add 550g decolorizing with activated carbon, elimination gac, 50 ℃ of vacuum concentration, reclaim ethyl acetate, obtain the thick product of 69.11g, add the edible ethanol of 400mL70% volumetric concentration again, be heated to boiling, dissolving, filter, room temperature is placed 5h and is got needle-like crystal, obtains 13.57g Artemisinin elaboration with sherwood oil (analytical pure) recrystallization; Utilize gas chromatographic detection, Artemisinin purity is 99.8%, and the Artemisinin rate of recovery is 89.5%.

Embodiment 4:

10 liters of chloroforms of disposable adding (analytical pure) drop into fresh Herba Artemisiae annuae raw material then in extractor in extractor, the raw material total amount is 15kg, divide 10 inputs, extractions, also filter, and each the input extracted 1500g, at every turn normal temperature and pressure lixiviate 2min; Collect extracting solution, in extracting solution, add the 800g decolorizing with activated carbon, the elimination gac, 40 ℃ of vacuum concentration reclaim chloroform, obtain the thick product of 97.86g, add 880mL analytical pure sherwood oil again, be heated to the boiling dissolving, filter, room temperature is placed 2h and is got needle-like crystal, obtains 22.65g Artemisinin elaboration with analytical pure normal hexane recrystallization; Utilize gas chromatographic detection, Artemisinin purity is 96.7%, the Artemisinin rate of recovery 86.3%.

Embodiment 5:

10 liters of methylene dichloride of disposable adding (analytical pure) drop into fresh Herba Artemisiae annuae raw material then in extractor in extractor, the raw material total amount is 6000g, divide 3 inputs, extractions, also filter, and each the input extracted 2000g, at every turn normal temperature and pressure lixiviate 6min; Collect extracting solution, in extracting solution, add the 600g decolorizing with activated carbon, the elimination gac, 30 ℃ of vacuum concentration reclaim methylene dichloride, obtain the thick product of 39.50g, add 350mL analytical pure normal hexane again and be heated to boiling, dissolving is filtered, room temperature is placed 3h and is got needle-like crystal, with the edible ethanol recrystallization acquisition 9.00g Artemisinin elaboration of 90% volumetric concentration; Utilize gas chromatographic detection, Artemisinin purity is 97.6%, and the Artemisinin rate of recovery is 87.1%.

Claims

1. the method for a rapidly extracting artemisinin, it is characterized in that: this method comprises the steps:

A, fresh Herba Artemisiae annuae is carried out lixiviate with extracting solvent, the extraction solvent once adds, total input amount of fresh Herba Artemisiae annuae is extracted the ratio that solvent adds the fresh Herba Artemisiae annuae of 250-1500g in 1L, and fresh Herba Artemisiae annuae is divided 1-10 equivalent input, extraction and filtration, each normal temperature and pressure lixiviate 2-8min collects extracting solution;

C, add the ratio of 4-9ml solvating agent in 1g Artemisinin crude product, add solvating agent in above-mentioned Artemisinin crude product, be heated to boiling, dissolving is filtered, and crystallizing at room temperature gets needle-like crystal, with solvating agent crystal is carried out recrystallization again, promptly gets the Artemisinin elaboration;

2. the method for rapidly extracting artemisinin as claimed in claim 1, it is characterized in that: described extraction solvent is the analytical pure ethyl acetate.

3. the method for rapidly extracting artemisinin as claimed in claim 1 is characterized in that: the total input amount of described fresh Herba Artemisiae annuae raw material is every liter to be extracted solvent and adds the 450-900g raw material, divides the equivalent input 3-5 time.

4. the method for rapidly extracting artemisinin as claimed in claim 1, it is characterized in that: the add-on of described activated carbon is that every 100ml extracting solution adds the 4-6g activated carbon.

5. the method for rapidly extracting artemisinin as claimed in claim 1, it is characterized in that: described solvating agent is the edible ethanol of 65-80% volumetric concentration.