CN100465176C - Method for extracting cantharidin - Google Patents
Method for extracting cantharidin Download PDFInfo
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- CN100465176C CN100465176C CNB2006100409911A CN200610040991A CN100465176C CN 100465176 C CN100465176 C CN 100465176C CN B2006100409911 A CNB2006100409911 A CN B2006100409911A CN 200610040991 A CN200610040991 A CN 200610040991A CN 100465176 C CN100465176 C CN 100465176C
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- cantharidin
- suction filtration
- cold soaking
- acetone
- ethanol
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Abstract
The invention discloses a method for extracting cantharidin, including extraction and recrystallization process. The said extraction process includes: (1) cold maceration process: drying and meshing mylabris worms into 40-60 meshes, adding maceration solvents and stirring for 5-10 h, and vacuum-filtering at a mylabris worms/hydrochloric acid/acetone weight ratio of 1:0.01-0.05:3-9; (2) concentration and standing process: concentrating and distilling the filtrate at 40-60degreeC until no liquid flows out, cooling to room temperature, and placing for 5-9 hours; and (3) washing process: vacuum-filtering the concentrated liquid, and washing with the mixed solution of ethanol and petroleum ether for several times until the liquid clears up. Compared with the existing technology, this invention has the advantages of simplified process, short production cycles, simple operation, and high yield (increase by 50% compared with the existing technology).
Description
Technical field:
The invention belongs to the method for from animals and plants, extracting compound, belong to the method for from the Chinese blister beetle polypide, extracting Cantharidin especially.
Background technology:
Chinese blister beetle is the medicine that is found antitumous effect in China's Chinese medicine the earliest, and its activeconstituents is Cantharidin (Cantharidin, C
10H
12O
4), it has stronger inhibition and destruction to multiple cancer cells.Chinese patent " preparation technology of disodium cantharidinate " (publication number: disclose CN1374310) disodium cantharidinate the preparation method, it comprises the extraction of Cantharidin, recrystallization, step such as preparation disodium cantharidinate etc.In the leaching process of its Cantharidin, this patent at first with hydrochloric acid with cantharis powder acidifying 24 hours, used the acetone cold soaking then 72 hours, extraction time reaches 96 hours, simultaneously the yield according to the prepared Cantharidin that goes out of its two steps of front is 0.6%, yield is on the low side.
Summary of the invention:
It is simple that technical problem to be solved by this invention provides a kind of technology, the method for the extraction Cantharidin that yield is high.
The technical scheme of technical solution problem of the present invention is a kind of method of extracting Cantharidin, comprises the extraction of Cantharidin, recrystallization process, and the leaching process of described Cantharidin is:
The cool treating processes of soaking: the cantharis soma is ground into 40-60 orders after dry, add the cold soaking solvent, described cold soaking solvent is the hydrochloric acid of weight concentration 30-36% and the mixed solvent of acetone, intermittently slowly stir after 5-10 hours, suction filtration, the weight ratio of Chinese blister beetle polypide and hydrochloric acid, acetone are 1:0.01-0.05:3-9;
Concentrate and to leave standstill process: the filtrate behind the suction filtration is distilled concentrated under 60-65 ℃, till being distilled to absence of liquid and flowing out, be cooled to room temperature, placed 5-9 hours steaming good concentrated solution;
Wash assorted process: the concentrated solution suction filtration that will leave standstill, repeatedly wash with the mixed solvent of ethanol, sherwood oil, until washings become clear till.
Also resulting filter residue in the cold soaking treating processes can be handled according to the technology of cold soaking treating processes again, resulting filtrate is as the cold soaking solvent, thereby fully extracts Cantharidin, increases its yield.
Stir to stir within 1 hour 10-15 minutes described intermittence, and rotating speed is 10-30 rev/mins.
In the cold soaking treating processes, the weight ratio of preferred Chinese blister beetle polypide and hydrochloric acid, acetone is 1:0.02-0.04:4-6.
In washing assorted process, preferred alcoholic acid weight concentration is 90-99%, and the boiling range of sherwood oil is 30-60 ℃, and the volume ratio of ethanol and sherwood oil is 1:1.5-2.5.
The present invention is merged into a procedure with hcl acidifying in the background technology and cold soaking technology, shortened life cycle of the product, and because the time of cold soaking is short, the impurity that produces reduces in a large number, improved the purity of product, reduce the loss of washing the product that assorted process brings, thereby improved the yield of product.
In washing assorted process, because cold soaking technology of the present invention unlike the prior art, thereby the character that extracts impurity contained in the Cantharidin is also different, lipid impurity and resene impurity volume ratio are about 1:1 in the Cantharidin impurity of prior art, and lipid impurity and resene impurity volume ratio are 1:1.5-2.5 in the Cantharidin impurity of the present invention, thereby the present invention is used, and to wash assorted solvent be ethanol and sherwood oil, its volume ratio=1:1.5-2.5.
The present invention compared with prior art has and simplifies working process, and is with short production cycle, simple to operate, and yield has improved characteristics such as 50% than prior art.
Embodiment:
The purity of Cantharidin detects with gas-chromatography according to external standard method.
Embodiment 1:
Leaching process: with 100 kilograms of Chinese blister beetle polypides, crushed after being dried becomes 40-60 orders, add 1 kilogram of hydrochloric acid and 300 kilograms of (CP level) acetone, after intermittently slowly stirring 5 hours under the normal temperature reward normal pressure, suction filtration, the filtrate behind the suction filtration is distilled under 60 ℃ concentrated, till being distilled to absence of liquid and flowing out, be cooled to room temperature with steaming good concentrated solution, placed 5 hours; With the concentrated solution suction filtration that leaves standstill, with 90% weight concentration ethanol: (30 ℃-60 ℃) sherwood oil=1:1.5 (volume ratio) repeatedly washs, until washings become clear till.
Recrystallization process: the product after the washing, fully drain, (AR level) acetone that adds 40 times of volumes refluxed filtered while hot, natural cooling crystallization 20 minutes, carry out suction filtration after the crystallization again, use 95% weight concentration ethanol again: (30 ℃-60 ℃) sherwood oil=1:1.5 (volume ratio) washing, drain oven dry below 60 ℃, obtain Cantharidin finished product 900 grams, its purity is 99.3%.
Embodiment 2:
Leaching process: with 100 kilograms of Chinese blister beetle polypides, crushed after being dried becomes 40-60 orders, add 2 kilograms of hydrochloric acid and 400 kilograms of (CP level) acetone, after intermittently slowly stirring 6 hours under the normal temperature reward normal pressure, suction filtration, the filtrate behind the suction filtration is distilled under 61 ℃ concentrated, till being distilled to absence of liquid and flowing out, be cooled to room temperature with steaming good concentrated solution, placed 6 hours; With the concentrated solution suction filtration that leaves standstill, with 96% weight concentration ethanol: (30 ℃-60 ℃) sherwood oil=1:2 (volume ratio) repeatedly washs, until washings become clear till.
Recrystallization process is identical with embodiment 1.
Present embodiment obtains Cantharidin finished product 950 grams, and its purity is 99.6%.
Embodiment 3:
Leaching process: with 100 kilograms of Chinese blister beetle polypides, crushed after being dried becomes 40-60 orders, add 4 kilograms of hydrochloric acid and 600 kilograms of (CP level) acetone, after intermittently slowly stirring 8 hours under the normal temperature reward normal pressure, suction filtration, the filtrate behind the suction filtration is distilled under 62 ℃ concentrated, till being distilled to absence of liquid and flowing out, be cooled to room temperature with steaming good concentrated solution, placed 6 hours; With the concentrated solution suction filtration that leaves standstill, with 95% weight concentration ethanol: (30 ℃-60 ℃) sherwood oil=1:1.5 (volume ratio) repeatedly washs, until washings become clear till.
Recrystallization process is identical with embodiment 1.
Present embodiment obtains Cantharidin finished product 960 grams, and its purity is 99.8%.
Embodiment 4:
Leaching process: with 100 kilograms of Chinese blister beetle polypides, crushed after being dried becomes 40-60 orders, add 5 kilograms of hydrochloric acid and 900 kilograms of (CP level) acetone, after intermittently slowly stirring 10 hours under the normal temperature reward normal pressure, suction filtration, the filtrate behind the suction filtration is distilled under 65 ℃ concentrated, till being distilled to absence of liquid and flowing out, be cooled to room temperature with steaming good concentrated solution, placed 6 hours; With the concentrated solution suction filtration that leaves standstill, with 99% weight concentration ethanol: (30 ℃-60 ℃) sherwood oil=1:2.5 (volume ratio) repeatedly washs, until washings become clear till.
Recrystallization process is identical with embodiment 1.
Present embodiment obtains Cantharidin finished product 920 grams, and its purity is 99.2%.
Embodiment 5:
Except that the cold soaking solvent, all the other are identical with embodiment 3.
Cold soaking solvent preparation process: with 100 kilograms of Chinese blister beetle polypides, crushed after being dried becomes 40-60 orders, add 4 kilograms of hydrochloric acid and 600 kilograms of (CP level) acetone, after intermittently slowly stirring 8 hours under the normal temperature reward normal pressure, suction filtration, obtain filter residue, filter residue adds hydrochloric acid and acetone by said ratio, after intermittently slowly stirring 8 hours under the normal temperature reward normal pressure, and suction filtration, obtain filtrate, with resulting filtrate as the cold soaking solvent.
Present embodiment obtains Cantharidin finished product 970 grams, and its purity is 99.8%.
Embodiment 6:
Leaching process: with 100 kilograms of Chinese blister beetle polypides, crushed after being dried becomes 40-60 orders, and (publication number: the leaching process CN1374310) extracts by Chinese patent " preparation technology of disodium cantharidinate "
Recrystallization process is identical with embodiment 1.
Present embodiment obtains Cantharidin finished product 600 grams, and its purity is 99.2%.
Embodiment 7:
Except that washing assorted solvent is 95% weight concentration ethanol: (30 ℃-60 ℃) sherwood oil=1:1, all the other are identical with embodiment 3.
Present embodiment obtains Cantharidin finished product 980 grams, and its purity is 98%.
Claims (4)
1, a kind of method of extracting Cantharidin comprises the extraction of Cantharidin, and recrystallization process is characterized in that: the leaching process of described Cantharidin is:
The cool treating processes of soaking: the cantharis soma is ground into 40-60 orders after dry, add the cold soaking solvent, described cold soaking solvent is the hydrochloric acid of weight concentration 30-36% and the mixed solvent of acetone, intermittently slowly stir after 5-10 hours, suction filtration, the weight ratio of Chinese blister beetle polypide and hydrochloric acid, acetone are 1:0.01-0.05:3-9;
Concentrate and to leave standstill process: the filtrate behind the suction filtration is distilled concentrated under 60-65 ℃, till being distilled to absence of liquid and flowing out, be cooled to room temperature, placed 5-9 hours steaming good concentrated solution;
Wash assorted process: the concentrated solution suction filtration that will leave standstill, repeatedly wash with the mixed solvent of ethanol, sherwood oil, until washings become clear till;
Described recrystallization process: the product after will washing, fully drain, the AR grade acetone that adds 40 times of volumes refluxed filtered while hot, natural cooling crystallization 20 minutes, carry out suction filtration after the crystallization again, be 30 ℃-60 ℃ petroleum ether again with 95% weight concentration ethanol, boiling range, 95% weight concentration ethanol and boiling range are the volume ratio=1:1.5 of 30 ℃-60 ℃ sherwood oil, drain, oven dry gets final product below 60 ℃.
2, a kind of method of extracting Cantharidin according to claim 1 is characterized in that: also resulting filter residue in the cold soaking treating processes can be handled according to the technology of cold soaking treating processes again, resulting filtrate is as the cold soaking solvent.
3, a kind of method of extracting Cantharidin according to claim 1 is characterized in that: in the cold soaking treating processes, the weight ratio of Chinese blister beetle polypide and hydrochloric acid, acetone is 1:0.02-0.04:4-6.
4, a kind of method of extracting Cantharidin according to claim 1 is characterized in that: in washing assorted process, the alcoholic acid weight concentration is 90-99%, and the boiling range of sherwood oil is 30-60 ℃, and the volume ratio of ethanol and sherwood oil is 1:1.5-2.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100409911A CN100465176C (en) | 2006-08-18 | 2006-08-18 | Method for extracting cantharidin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100409911A CN100465176C (en) | 2006-08-18 | 2006-08-18 | Method for extracting cantharidin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1966508A CN1966508A (en) | 2007-05-23 |
| CN100465176C true CN100465176C (en) | 2009-03-04 |
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| CNB2006100409911A Expired - Fee Related CN100465176C (en) | 2006-08-18 | 2006-08-18 | Method for extracting cantharidin |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108853B (en) * | 2007-07-27 | 2010-05-26 | 贵州大学 | Separation purification process of cantharidin |
| CN101108854B (en) * | 2007-07-27 | 2010-05-26 | 贵州大学 | Separation purification process of cantharidin |
| CN102268006B (en) * | 2011-06-15 | 2013-08-14 | 北京联合大学生物化学工程学院 | Method for extracting cantharidin from compound enzyme |
| AU2014308690B2 (en) | 2013-08-21 | 2019-07-18 | Verrica Pharmaceuticals, Inc. | Compositions, methods and systems for the treatment of cutaneous disorders |
| CN114106013A (en) | 2014-12-17 | 2022-03-01 | 维里卡制药有限公司 | Commercially viable synthesis of cantharidin and biologically active cantharidin derivatives |
| US11168091B2 (en) | 2015-01-20 | 2021-11-09 | Verrica Pharmaceuticals Inc. | Quantification and preparation of pharmaceutical grade cantharidin |
| CN106674247A (en) * | 2016-12-06 | 2017-05-17 | 广西壮族自治区兽医研究所 | Method for extracting cantharidin by using supercritical carbon dioxide |
| CA3065151A1 (en) | 2017-06-06 | 2018-12-13 | Verrica Pharmaceuticals Inc. | Treatment of cutaneous disorders |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593400A (en) * | 2004-07-05 | 2005-03-16 | 俞锋 | Anticancer methylcantharidinimide tablet and its preparation method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593400A (en) * | 2004-07-05 | 2005-03-16 | 俞锋 | Anticancer methylcantharidinimide tablet and its preparation method |
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Address after: 241000 No. 6, venture Road, Yijiang hi tech Development Zone, Yijiang District, Anhui, Wuhu Patentee after: Wuhu Tianyuan Biological Technology Co., Ltd. Address before: 241009 No. 6, pioneering Road, hi tech Development Zone, Anhui, Wuhu Patentee before: Wuhu Tianyuan Science and Technology Development Co., Ltd. |
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