CN1680388A - Extraction of artemisine - Google Patents
Extraction of artemisine Download PDFInfo
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- CN1680388A CN1680388A CN 200510017340 CN200510017340A CN1680388A CN 1680388 A CN1680388 A CN 1680388A CN 200510017340 CN200510017340 CN 200510017340 CN 200510017340 A CN200510017340 A CN 200510017340A CN 1680388 A CN1680388 A CN 1680388A
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- artemisinin
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Abstract
An extraction of qinghaosu is carried out by: 1) immersing extracting the leaf of sweet wormwood with 60-70% alcohol as solvent, depositing, regulating pH of immersing extracting liquid to 7.5-8.0, depositing the impurities, filtering, and regulating pH of mother liquid to 6.5-7.0; 2) de-pressuring and concentrating the mother liquid to 8-15% of original volume, cooling, and removing impurities; 3)crystallizing, adding into isosteric 70% alcohol, heating, dissolving, laying aside, precipitating out coarse crystal; 4)re-crystallizing, dissolving the coarse crystal by hot mineral ether, laying aside, separating, and obtaining the refined products. Its advantages include low cost, good re-crystallizing effect, and high productivity.
Description
Technical field:
The present invention relates to a kind of traditional Chinese medicine extraction method, particularly from the feverfew sweet wormwood, extract the method for Artemisinin.
Background technology:
Artemisinin is the sesquiterpene lactones with novel texture that China scientist extracted from feverfew Herba Artemisiae annuae (Artemisiaannua Linn) first in 1971.Pure Artemisinin is a colourless acicular crystal, 150～153 ℃ of fusing points, specific rotatory power [α]
D 23+ 75 ° to+78 ° (dehydrated alcohol), bitter is soluble in benzene, chloroform, ethyl acetate, acetone and Glacial acetic acid, can be dissolved in ethanol, methyl alcohol, ether and hot sherwood oil.Artemisinin is owing to have peroxide bridge and ethylidene ether structure, and extremely unstable to highly basic to the soda acid instability, heat is to promptly decomposing rapidly more than the fusing point.It has very good antimalarial effect, comprises that those have chemical sproof falciparum infection to chloroquine.Artemisinin is again the unique Chinese medicine according to the research and development of Western medicine standard of China, is current generally acknowledged the most effective, the safest medicine of treatment malaria, is called " maximum of treatment malaria is wished " by the World Health Organization.
The extracting method of present Artemisinin such as " the volume gasoline method " of institute of materia medica, Yunnan, this method is terse, and technical process is short, and is easy to operate, but yield is undesirable, and lab scale only is 0.3%, and industrial production≤0.2%, and mass consumption gasoline are unsafe; " acetone-silica gel column chromatography " of institute of Chinese materia medica, Shandong (number of patent application 87101346A) and " the low spherical reaming filtered through silica gel of the gasoline-super short-thick type column chromatography that boils " (number of patent application 89103384), " rare pure method " of Traditional Chinese Medicine Research Institute, Sichuan Province and United States Patent (USP) (patent No. 4952603) " the fine analysis-silica gel column chromatography of hexane extraction-hexane/second ", these methods cut both ways, but industrial applicability all has very big difficulty; Discuss again in another invention " extracting method of Artemisinin " (number of patent application 93102934.1) of Yunnan Pharmaceutical Institute, use Diluted Alcohol to extract Artemisinin, gasoline extraction, activated carbon decolorizing, use ethyl alcohol recrystallization, this method is greatly improved on working foundation in the past, but this patent only adopts once immersion, fully stripping of Artemisinin; Use a large amount of gasoline extraction, operational danger is bigger; Use activated carbon decolorizing, the absorption portion Artemisinin has reduced yield inevitably, and gac price height; Use 50% ethyl alcohol recrystallization, the solvent temperature height, the destructible Artemisinin, effect is still undesirable.
Summary of the invention:
This law is bright to be intended to overcome above deficiency and a kind of method of extracting Artemisinin is provided, and this method technology is simple, product purity is high, have that operation is easily grasped, solvent consumption is few, cost is low, yield is high, safe, do not need large-scale and advantage such as specific installation.
For realizing that the technical solution used in the present invention is:
A kind of method of extracting Artemisinin comprises that the ethanol of employing 60～70% is solvent lixiviate raw material artemisia leaf, also comprises:
1) precipitation: regulate vat liquor pH value to 7.5～8.0, make most of contamination precipitation, filter and regulate mother liquor pH value 6.5～7.0;
2) concentrating under reduced pressure: mother liquor is concentrated into 8～15% of original volume, the cooling removal of impurities;
3) crystallization: add equivalent 70% ethanol and be heated to dissolving, leave standstill and separate out coarse crystallization;
4) recrystallization:, after the standing separation, obtain elaboration with hot petroleum ether dissolution coarse crystallization.
In order to improve product yield, when the ethanol of employing 60～70% was the solvent lixiviate, the lixiviate number of times was 3～5 times.
In precipitation process, in order to reduce cost and to remove impurity to greatest extent, the material of regulating the vat liquor pH value is a unslaked lime.
In precipitation process, in order to keep the stable of Artemisinin, the material of regulating the mother liquor pH value is an acetate.
In concentration process, for keeping Artemisinin stability, adopt 50 ℃～60 ℃ of thickening temperatures, concentrate pressure 0.047～0.053Mpa.
In crystallisation process, be to improve the total recovery of product, crystalline mother solution repeats 1 then with 60～70% alcohol dilutions of 3 times of amounts again), 2), 3) step, obtain coarse crystallization.
In recrystallization process, utilize Artemisinin big characteristic of dissolubility difference in cold and hot sherwood oil, obtain more products, and avoid Artemisinin to be destroyed, so adopt the hot sherwood oil of 30～60 ℃ of boiling ranges by high temperature.
Positively effect of the present invention is:
1, the present invention is through extracted many times, and the total recovery of the finished product can reach more than 0.48% with respect to the artemisia leaf meter.
2, the present invention adopts alcohol as extraction solvent, and without gasoline, greatly reduces the risk of operation.
3, the present invention adopts calcium lime powder (CaO) as precipitation agent, regulates pH value with the CaO powder, has both precipitated most of impurity, is easy to crystalline again and forms, and has reduced cost simultaneously.
4, the present invention adopts the recrystallization solvent of 30～60 ℃ of sherwood oil conducts of boiling range, and the recrystallization effect is better than alcohol.
5, lixiviate solvent for use of the present invention reclaims when concentrated, and whole process of production is to carry out under air-tight state, and solvent evaporates is few; After lixiviate is finished, the steam distilled method recovered alcohol of water, residue has so just reduced loss and operational risk as the mosquito-repellent incense raw material, has improved economic benefit.
Embodiment:
Embodiment one:
1, lixiviate: the 100kg artemisia leaf is placed the traditional Chinese medicine extraction jar, add 500kg70% ethanol, begin to stir, speed with 10～15rpm stirred 10 hours, stopped to stir, and made the size of material reach 60～70 orders, open the valve of extractor bottom, the automatic drop of vat liquor goes out, and obtains I immersion liquid 288kg, and is stand-by; Valve-off adds 300kg70% ethanol to extractor again, stirs 5 hours, obtains II immersion liquid 313kg, and is stand-by; Add 300kg70% ethanol at last, stirred 3 hours, form III immersion liquid 316kg, the III immersion liquid is used for following batch and applies mechanically.Residue after draining is delivered in the alcohol withdrawing can, adds purified water 300kg, adopts steam distillation will remain the ethanol recycling, obtains alcohol (folding 100%) 138kg, and residue is as the raw material of mosquito-repellent incense.
2, precipitation: merging I, II vat liquor 601kg, regulate pH value to 7.8 with calcium lime powder CaO, make most of contamination precipitation, and filter rapidly, obtain filtrate, filtrate is used acetate regulator solution pH value to 6.7.
3, concentrating under reduced pressure: filtrate is changed in the concentration tank, and in the control decompression process, temperature remains on 50 ℃～60 ℃, and pressure remains between 0.047～0.053MPa, is concentrated into 60kg in 2 hours.Place cooling, the supernatant liquor that inclines is removed water-soluble impurity, obtains concentrated solution 11kg.
4, crystallization: concentrated solution is changed in the crystallizer, add 11kg70% ethanol and be heated to 60 ℃ of dissolvings, left standstill 3～4 days, separate out and collect coarse crystallization I0.48kg.Mother liquor 63kg70% alcohol dilution precipitates according to 2,3,4 steps then, and filtrate decompression concentrates, and the concentrated solution crystallization is collected and obtained coarse crystallization II0.13kg.Merge twice coarse crystallization of I, II and obtain coarse crystallization III0.61kg.
5, recrystallization: adding 1.7kg boiling range is 30～60 ℃ hot petroleum ether dissolution coarse crystallization III, leaves standstill 24 hours, separates out acicular crystals, and through centrifugation, 50～60 ℃ of vacuum-dryings promptly obtain Artemisinin elaboration 482g, measure its content, contain C
15H
22O
599.3%.
Embodiment two:
1, lixiviate: the 100kg artemisia leaf is placed the traditional Chinese medicine extraction jar, add 500kg60% ethanol, begin to stir, speed with 10～15rpm stirred 10 hours, stopped to stir, and made the size of material reach 60～70 orders, open the valve of extractor bottom, the automatic drop of vat liquor goes out, and obtains I immersion liquid 285kg, and is stand-by; Valve-off adds 300kg60% ethanol to extractor again, stirs 5 hours, obtains II immersion liquid 314kg, and is stand-by; Add 300kg60% ethanol at last, stirred 3 hours, obtain III immersion liquid 306kg, the III immersion liquid is used for following batch and applies mechanically.Residue after draining is delivered in the alcohol withdrawing can, adds the 300kg purified water, adopts steam distillation will remain the ethanol recycling, obtains alcohol (folding 100%) 122kg, and residue is as the raw material of mosquito-repellent incense.
2, precipitation: merging I, II vat liquor 599kg, regulate pH value to 8.0 with calcium lime powder CaO, make most of contamination precipitation, and filter rapidly, obtain filtrate, filtrate is used acetate regulator solution pH value to 6.9.
3, concentrating under reduced pressure: filtrate is changed in the concentration tank, and in the control decompression process, temperature remains on 50 ℃～60 ℃, and pressure remains between 0.047～0.053MPa, is concentrated into 48kg in 2 hours.Place cooling, the supernatant liquor that inclines is removed water-soluble impurity, obtains concentrated solution 10.3kg.
4, crystallization: concentrated solution is changed in the crystallizer, add 10.3kg70% ethanol and be heated to 60 ℃ of dissolvings, left standstill 3～4 days, separate out and collect coarse crystallization I0.41kg.Mother liquor 60kg70% alcohol dilution precipitates according to 2,3,4 steps then, and filtrate decompression concentrates, and the concentrated solution crystallization is collected and obtained coarse crystallization II0.10kg.Merge twice coarse crystallization of I, II and obtain coarse crystallization III0.51kg.
5, recrystallization: adding 1.4kg boiling range is 30～60 ℃ hot petroleum ether dissolution coarse crystallization III, leaves standstill 24 hours, separates out acicular crystals, and through centrifugation, 50～60 ℃ of vacuum-dryings promptly obtain Artemisinin elaboration 489g, measure its content, contain C
15H
22O
599.2%.
Embodiment three:
1, lixiviate: the 100kg artemisia leaf is placed the traditional Chinese medicine extraction jar, add 500kg60% ethanol, begin to stir, speed with 10～15rpm stirred 10 hours, stopped to stir, and made the size of material reach 60～70 orders, open the valve of extractor bottom, the automatic drop of vat liquor goes out, and obtains I immersion liquid 283kg, and is stand-by; Valve-off adds 300kg60% ethanol to extractor again, stirs 5 hours, obtains II immersion liquid 316kg, and is stand-by; Add 300kg60% ethanol at last, stirred 3 hours, obtain III immersion liquid 305kg, the III immersion liquid is used for following batch and applies mechanically.Residue after draining is delivered in the alcohol withdrawing can, adds the 300kg purified water, adopts steam distillation will remain the ethanol recycling, obtains alcohol (folding 100%) 123kg, and residue is as the raw material of mosquito-repellent incense.
2, precipitation: merging I, II vat liquor 599kg, regulate pH value to 7.8 with calcium lime powder CaO, make most of contamination precipitation, and filter rapidly, obtain filtrate, filtrate is used acetate regulator solution pH value to 6.7.
3, concentrating under reduced pressure: filtrate is changed in the concentration tank, and in the control decompression process, temperature remains on 50 ℃～60 ℃, and pressure remains between 0.047～0.053MPa, is concentrated into 60kg in 2 hours.Place cooling, the supernatant liquor that inclines is removed water-soluble impurity, obtains concentrated solution 10kg.
4, crystallization: concentrated solution is changed in the crystallizer, add 10kg70% ethanol and be heated to 60 ℃ of dissolvings, left standstill 3～4 days, separate out and collect coarse crystallization I0.43kg.Mother liquor 58.5kg60% alcohol dilution precipitates according to 2,3,4 steps then, and filtrate decompression concentrates, and the concentrated solution crystallization is collected and obtained coarse crystallization II0.11kg.Merge twice coarse crystallization of I, II and obtain coarse crystallization III0.54kg.
5, recrystallization: adding 1.5kg boiling range is 30～60 ℃ hot petroleum ether dissolution coarse crystallization III, leaves standstill 24 hours, separates out acicular crystals, and through centrifugation, 50～60 ℃ of vacuum-dryings promptly obtain Artemisinin elaboration 483g, measure its content, contain C
15H
22O
599.9%.
Embodiment four:
1, lixiviate: the 100kg artemisia leaf is placed the traditional Chinese medicine extraction jar, add 500kg60% ethanol, begin to stir, speed with 10～15rpm stirred 10 hours, stopped to stir, and made the size of material reach 60～70 orders, open the valve of extractor bottom, the automatic drop of vat liquor goes out, and obtains I immersion liquid 284kg, and is stand-by; Valve-off adds 300kg60% ethanol to extractor again, stirs 5 hours, obtains II immersion liquid 317kg, and is stand-by; Add 300kg60% ethanol at last, stirred 3 hours, obtain III immersion liquid 304kg, the III immersion liquid is used for following batch and applies mechanically.Residue after draining is delivered in the alcohol withdrawing can, adds the 300kg purified water, adopts steam distillation will remain the ethanol recycling, obtains alcohol (folding 100%) 123kg, and residue is as the raw material of mosquito-repellent incense.
2, precipitation: merging I, II vat liquor 601kg, regulate pH value to 7.5 with calcium lime powder CaO, make most of contamination precipitation, and filter rapidly, obtain filtrate, filtrate is used acetate regulator solution pH value to 6.9.
3, concentrating under reduced pressure: filtrate is changed in the concentration tank, and in the control decompression process, temperature remains on 50 ℃～60 ℃, and pressure remains between 0.047～0.053MPa, is concentrated into 58kg in 2 hours.Place cooling, the supernatant liquor that inclines is removed water-soluble impurity, obtains concentrated solution 9.6kg.
4, crystallization: concentrated solution is changed in the crystallizer, add 9.6kg70% ethanol and be heated to 60 ℃ of dissolvings, left standstill 3～4 days, separate out and collect coarse crystallization I0.41kg.Mother liquor 56kg60% alcohol dilution precipitates according to 2,3,4 steps then, and filtrate decompression concentrates, and the concentrated solution crystallization is collected and obtained coarse crystallization II0.12kg.Merge twice coarse crystallization of I, II and obtain coarse crystallization III0.53kg.
5, recrystallization: adding 1.4kg boiling range is 30～60 ℃ hot petroleum ether dissolution coarse crystallization III, leaves standstill 24 hours, separates out acicular crystals, and through centrifugation, 50～60 ℃ of vacuum-dryings promptly obtain Artemisinin elaboration 485g, measure its content, contain C
15H
22O
599.5%.
Claims (7)
1, a kind of method of extracting Artemisinin comprises that the ethanol of employing 60～70% is solvent lixiviate raw material artemisia leaf, it is characterized in that also comprising:
1) precipitation: regulate vat liquor pH value to 7.5～8.0, make most of contamination precipitation, filter and regulate mother liquor pH value 6.5～7.0;
2) concentrating under reduced pressure: mother liquor is concentrated into 8～15% of original volume, the cooling removal of impurities;
3) crystallization: add equivalent 70% ethanol and be heated to dissolving, leave standstill and separate out coarse crystallization;
4) recrystallization:, after the standing separation, obtain elaboration with hot petroleum ether dissolution coarse crystallization.
2, the method for extraction Artemisinin as claimed in claim 1 is characterized in that: described lixiviate number of times is 3～5 times.
3, the method for extraction Artemisinin as claimed in claim 1 is characterized in that: the material of described adjusting vat liquor pH value is a unslaked lime.
4, as the method for claim 1 or 3 described extraction Artemisinins, it is characterized in that: the material of described adjusting mother liquor pH value is an acetate.
5, the method for extraction Artemisinin as claimed in claim 1 is characterized in that: described thickening temperature is 50 ℃～60 ℃, and pressure is 0.047～0.053MPa.
6, the method for extraction Artemisinin as claimed in claim 1 is characterized in that: described crystalline mother solution repeats 1 then with 60～70% alcohol dilutions of 3 times of amounts again), 2), 3) step, obtain coarse crystallization.
7, the method for extraction Artemisinin as claimed in claim 1 is characterized in that: described sherwood oil is the hot sherwood oil of 30～60 ℃ of boiling ranges.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510017340 CN1680388A (en) | 2005-01-25 | 2005-01-25 | Extraction of artemisine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510017340 CN1680388A (en) | 2005-01-25 | 2005-01-25 | Extraction of artemisine |
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|---|---|
| CN1680388A true CN1680388A (en) | 2005-10-12 |
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| CN 200510017340 Pending CN1680388A (en) | 2005-01-25 | 2005-01-25 | Extraction of artemisine |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445726C (en) * | 2006-08-09 | 2008-12-24 | 重庆医科大学 | Determining method of artemislnin content in artemisia apiacea |
| CN101130548B (en) * | 2006-08-25 | 2010-11-03 | 上海诺德生物实业有限公司 | Method for extracting and producing high content arteannuin |
| CN101975780A (en) * | 2010-04-28 | 2011-02-16 | 湖南农业大学 | Observation and density measurement method for glandular hairs on Artemisia annua leaf surfaces |
| CN102190665A (en) * | 2011-03-07 | 2011-09-21 | 中国药科大学 | Method for separating and purifying artemisinin by activated charcoal column chromatography employing nonaqueous system |
| CN102890087A (en) * | 2012-11-13 | 2013-01-23 | 宁夏医科大学 | Method for measuring artemisinin content in traditional Chinese medicinal materials such as Artemisia annua and samples containing artemisinin components |
| CN103087075A (en) * | 2013-01-24 | 2013-05-08 | 张家港威胜生物医药有限公司 | Simple and new technology for extracting and purifying arteannuin and artemisinic acid from southernwood through single process |
| CN103408566A (en) * | 2013-07-17 | 2013-11-27 | 张家港威胜生物医药有限公司 | New artemisinin extraction process |
| CN103641842A (en) * | 2013-12-02 | 2014-03-19 | 无锡合众信息科技有限公司 | Device for extracting artemisinin from artemisia annua |
-
2005
- 2005-01-25 CN CN 200510017340 patent/CN1680388A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445726C (en) * | 2006-08-09 | 2008-12-24 | 重庆医科大学 | Determining method of artemislnin content in artemisia apiacea |
| CN101130548B (en) * | 2006-08-25 | 2010-11-03 | 上海诺德生物实业有限公司 | Method for extracting and producing high content arteannuin |
| CN101975780A (en) * | 2010-04-28 | 2011-02-16 | 湖南农业大学 | Observation and density measurement method for glandular hairs on Artemisia annua leaf surfaces |
| CN101975780B (en) * | 2010-04-28 | 2012-01-11 | 湖南农业大学 | Observation and density measurement method for glandular hairs on Artemisia annua leaf surfaces |
| CN102190665A (en) * | 2011-03-07 | 2011-09-21 | 中国药科大学 | Method for separating and purifying artemisinin by activated charcoal column chromatography employing nonaqueous system |
| CN102890087A (en) * | 2012-11-13 | 2013-01-23 | 宁夏医科大学 | Method for measuring artemisinin content in traditional Chinese medicinal materials such as Artemisia annua and samples containing artemisinin components |
| CN103087075A (en) * | 2013-01-24 | 2013-05-08 | 张家港威胜生物医药有限公司 | Simple and new technology for extracting and purifying arteannuin and artemisinic acid from southernwood through single process |
| CN103408566A (en) * | 2013-07-17 | 2013-11-27 | 张家港威胜生物医药有限公司 | New artemisinin extraction process |
| CN103408566B (en) * | 2013-07-17 | 2016-04-20 | 张家港威胜生物医药有限公司 | A kind of extraction technology for artemisia annua element |
| CN103641842A (en) * | 2013-12-02 | 2014-03-19 | 无锡合众信息科技有限公司 | Device for extracting artemisinin from artemisia annua |
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