CN102532023A - Purification method of yunaconitine - Google Patents
Purification method of yunaconitine Download PDFInfo
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- CN102532023A CN102532023A CN2010106038659A CN201010603865A CN102532023A CN 102532023 A CN102532023 A CN 102532023A CN 2010106038659 A CN2010106038659 A CN 2010106038659A CN 201010603865 A CN201010603865 A CN 201010603865A CN 102532023 A CN102532023 A CN 102532023A
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- yunaconitine
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- purification process
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- methylene dichloride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention provides a purification method of yunaconitine, which includes the following steps: taking a vilmorrianine medicinal material as the raw material, smashing, adding alcohol, infiltrating for 1 to 2 hours, transferring to an extraction kettle, using supercritical carbon dioxide for extraction, collecting yunaconitine extract, dissolving with acid water, filtering, adding cation exchange resin for absorption, adding alkaline alcoholic solution for elution, enabling eluent to be decompressed and concentrated, adding methylene dichloride for extraction, enabling extract liquor to be concentrated, adding aluminum oxide and packing columns after drying, using petroleum ether methylene dichloride mixed solution for elution, detecting in thin layers, collecting yunaconitine flow content, enabling eluent to be concentrated and placed in small size for crystallization, drying crystals and obtaining the yunaconitine product. The purification method of yunaconitine causes little pollution, and is low in energy consumption, high in yield and suitable for industrial production.
Description
Technical field:
The present invention relates to a kind of purification process of Yunaconitine, particularly relate to a kind of application supercritical CO
2The method of purifying Yunaconitine is extracted in extraction.
Background technology:
Yunaconitine is isoaconitine, Vilmorrianine B again, is diterpene alkaloid, molecular formula C
35H
49O
11, molecular weight 659.77,142 ℃-143 ℃ of fusing points dissolve in methyl alcohol, ethanolic soln, are soluble in acetone, chloroform, methylene dichloride and sour water, are insoluble to sherwood oil and water.
Yunaconitine has anti-inflammatory, analgesia drawn game anaesthetic effect.But its toxicity is bigger, often carries out molecular structure alteration, reduces toxicity, as the Crassicauline A synthesis material.Patent " method for preparing Crassicauline A " and document " structure of modification of Yunaconitine " all are to be raw material with the Yunaconitine, carry out structure of modification, the less Crassicauline A of preparation toxicity.
The existing method of extracting Yunaconitine generally adopts sour water diacolation or organic reagent to extract, again extraction and column chromatography.Organic reagent and sour water large usage quantity because Yunaconitine content is lower in the general plant, about 1 ‰, all have multiple toxic alkaloid in the existing simultaneously rhizome of Chinese monkshood class medicinal material like this, and the personnel that cause easily poison.
Adopt supercritical CO
2Extraction is more satisfactory method, can avoid aconite alkaloid in extraction, to reduce, and having is a kind of pollution-free process for extracting.Like " the supercritical CO of Yadong rhizome of Chinese monkshood total alkaloids
2Extraction and assay ", this method has obtained good yield and effect, and the technology specificity is poor.
Summary of the invention:
The technical problem that the present invention will solve provides a kind of purification process of Yunaconitine, and this method adopts supercritical CO
2Extraction separates with resin column and to prepare Yunaconitine, pollute little, yield is high.
In order to solve the problems of the technologies described above, technical scheme of the present invention is following:
A kind of purification process of Yunaconitine is characterized in that may further comprise the steps: with yellow radix aconiti agrestis medicinal material is raw material, pulverizes, and adds alcohol and soaks into 1-2 hour, adds in the extraction kettle, adopts supercritical CO
2The Yunaconitine extract is collected in extraction, with the sour water dissolving, filters; Add cationic exchange resin adsorption, the alkaline alcohol solution wash-out, the elutriant concentrating under reduced pressure, extraction adds methylene chloride; Extraction liquid concentrates, and adorns post after adding the aluminum oxide drying, with sherwood oil-methylene dichloride mixing solutions wash-out, and the thin layer detection; Collect the Yunaconitine flow point, elutriant concentrates small volume and places crystallization, and crystallisate is drying to obtain the Yunaconitine product.
Described alcohol is 90-99% methyl alcohol or ethanol.
Said supercritical CO
2Extraction conditions is: extraction temperature is 40-50 ℃, and extracting pressure is 30-40MPa, CO
2Flow is 30-50L/h, and the extraction time is 2-3h, and the separation reactor I temperature is 50-60 ℃, and pressure is 8-10MPa, and separation reactor I I temperature is 30-45 ℃, and pressure is 5-6MPa.
Described sour water is 1-4% hydrochloric acid or aqueous sulfuric acid.
Described Zeo-karb is weakly acidic cation-exchange resin or strongly acidic cationic exchange resin.
Described alkaline alcohol is: the methyl alcohol of 60-80% or ethanolic soln, ammoniacal liquor is regulated pH9-11.
Described aluminum oxide is a neutral alumina, granularity 200-300 order.
Said sherwood oil methylene dichloride ratio 1: 2-4.
Positively effect of the present invention is: adopt supercritical CO
2Extraction is a kind of environment friendly and pollution-free method, and extraction time is short, and efficient is high, and energy consumption is lower, can continuous production; Adopt ion exchange resin, the alkaline alcohol wash-out is prone to reclaim reagent; The present invention also adopts alumina column, and sherwood oil methylene dichloride wash-out is simple to operate, and circulation ratio is high, amplifies easily and produces.
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 yellow radix aconiti agrestis medicinal material, pulverize 80 orders, get 1kg and add 500ml 90% methyl alcohol infiltration 2 hours, add in the extraction kettle; The opening device adjusting parameter: extraction temperature is 50 ℃, and extracting pressure is 35MPa, and the separation reactor I temperature is 60 ℃; Pressure is 10MPa, and separation reactor I I temperature is 40 ℃, and pressure is 6MPa.After reaching above-mentioned parameter,, collect and resolve extract, dissolving with hydrochloric acid extract with 4% with 30L/h flow extraction extraction 2h; Filter the absorption of adding 732 strongly acidic cationic exchange resins, get the methanol solution (ammoniacal liquor is regulated pH9) of 5BV80%, wash-out, the elutriant concentrating under reduced pressure does not have alcohol; Add the 2BV dichloromethane extraction 3 times, the collected organic layer extraction liquid concentrates, and adds 100g neutral alumina dry (200-300 order), the dress post; With sherwood oil-methylene dichloride (1: 2) mixing solutions wash-out, thin layer detects, and collects the Yunaconitine flow point, and elutriant concentrates small volume and places crystallization; Dry Yunaconitine product, content 98.5%, the yield 83.2% of getting of crystallisate.
Embodiment 2:
Get yellow radix aconiti agrestis medicinal material, pulverize 20 orders, get 1kg and add 500ml 95% ethanol infiltration 2 hours, add in the extraction kettle; The opening device adjusting parameter: extraction temperature is 50 ℃, and extracting pressure is 30MPa, and the separation reactor I temperature is 50 ℃; Pressure is 8MPa, and separation reactor I I temperature is 35 ℃, and pressure is 5MPa.After reaching above-mentioned parameter,, collect and resolve extract, dissolving with hydrochloric acid extract with 2% with 35L/h flow extraction extraction 2h; Filter the absorption of adding D151 weakly acidic cation-exchange resin, get the ethanolic soln (ammoniacal liquor is regulated pH11) of 6BV60%, wash-out, the elutriant concentrating under reduced pressure does not have alcohol; Add the 3BV dichloromethane extraction 2 times, the collected organic layer extraction liquid concentrates, and adds 80g neutral alumina dry (200-300 order), the dress post; With sherwood oil-methylene dichloride (1: 4) mixing solutions wash-out, thin layer detects, and collects the Yunaconitine flow point, and elutriant concentrates small volume and places crystallization; Dry Yunaconitine product, content 93.1%, the yield 86.3% of getting of crystallisate.
Embodiment 3:
Get yellow radix aconiti agrestis medicinal material, pulverize 60 orders, get 2kg and add 800ml 99% methyl alcohol infiltration 1 hour, add in the extraction kettle; The opening device adjusting parameter: extraction temperature is 45 ℃, and extracting pressure is 35MPa, and the separation reactor I temperature is 55 ℃; Pressure is 9MPa, and separation reactor I I temperature is 35 ℃, and pressure is 5MPa.After reaching above-mentioned parameter,, collect and resolve extract, dissolving with hydrochloric acid extract with 1% with 38L/h flow extraction extraction 2h; Filter the absorption of adding 001 * 3 strongly acidic cationic exchange resin, get the ethanolic soln (ammoniacal liquor is regulated pH10) of 5BV70%, wash-out, the elutriant concentrating under reduced pressure does not have alcohol; Add the 4BV dichloromethane extraction 2 times, the collected organic layer extraction liquid concentrates, and adds 180g neutral alumina dry (200-300 order), the dress post; With sherwood oil-methylene dichloride (1: 3) mixing solutions wash-out, thin layer detects, and collects the Yunaconitine flow point, and elutriant concentrates small volume and places crystallization; Crystallisate is drying to obtain the Yunaconitine product, content 95.4%, yield 88.2%.
Embodiment 4:
Get yellow radix aconiti agrestis medicinal material, pulverize 60 orders, get 5kg and add 2L 95% ethanol infiltration 2 hours, add in the extraction kettle; The opening device adjusting parameter: extraction temperature is 45 ℃, and extracting pressure is 35MPa, and the separation reactor I temperature is 55 ℃; Pressure is 8MPa, and separation reactor I I temperature is 35 ℃, and pressure is 5MPa.After reaching above-mentioned parameter,, collect and resolve extract, sulfuric acid dissolution extract with 2% with 40L/h flow extraction extraction 2h; Filtration adds the absorption of HZD-5 weakly acidic cation-exchange resin, gets the methanol solution (ammoniacal liquor is regulated pH11) of 5BV60%, wash-out, and the elutriant concentrating under reduced pressure does not have alcohol; Add the 3BV dichloromethane extraction 3 times, the collected organic layer extraction liquid concentrates, and adds 500g neutral alumina dry (200-300 order), the dress post; With sherwood oil-methylene dichloride (1: 4) mixing solutions wash-out, thin layer detects, and collects the Yunaconitine flow point, and elutriant concentrates small volume and places crystallization; Crystallisate is drying to obtain the Yunaconitine product, content 96.3%, yield 84.4%.
Claims (8)
1. the purification process of a Yunaconitine, it is characterized in that may further comprise the steps: with yellow radix aconiti agrestis medicinal material is raw material, pulverizes, and adds alcohol and soaks into 1-2 hour, adds in the extraction kettle, adopts supercritical CO
2The Yunaconitine extract is collected in extraction, with the sour water dissolving, filters; Add cationic exchange resin adsorption, the alkaline alcohol solution wash-out, the elutriant concentrating under reduced pressure, extraction adds methylene chloride; Extraction liquid concentrates, and adorns post after adding the aluminum oxide drying, with sherwood oil methylene dichloride mixing solutions wash-out, and the thin layer detection; Collect the Yunaconitine flow point, elutriant concentrates small volume and places crystallization, and crystallisate is drying to obtain the Yunaconitine product.
2. according to the purification process of the said Yunaconitine of claim 1, it is characterized in that described alcohol is 90-99% methyl alcohol or ethanol.
3. according to the purification process of the said Yunaconitine of claim 1, it is characterized in that said supercritical CO
2Extraction conditions is: extraction temperature is 40-50 ℃, and extracting pressure is 30-40MPa, CO
2Flow is 30-50L/h, and the extraction time is 2-3h, and the separation reactor I temperature is 50-60 ℃, and pressure is 8-10MPa, and separation reactor I I temperature is 30-45 ℃, and pressure is 5-6MPa.
4. according to the purification process of the said Yunaconitine of claim 1, it is characterized in that described sour water is 1-4% hydrochloric acid or aqueous sulfuric acid.
5. according to the purification process of the said Yunaconitine of claim 1, it is characterized in that described Zeo-karb is weakly acidic cation-exchange resin or strongly acidic cationic exchange resin.
6. according to the purification process of the said Yunaconitine of claim 1, it is characterized in that described alkaline alcohol is: the methyl alcohol of 60-80% or ethanolic soln, ammoniacal liquor is regulated pH9-11.
7. according to the purification process of the said Yunaconitine of claim 1, it is characterized in that described aluminum oxide is a neutral alumina, granularity 200-300 order.
8. according to the purification process of the said Yunaconitine of claim 1, it is characterized in that said sherwood oil-methylene dichloride ratio 1: 2-4.
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| CN2010106038659A CN102532023A (en) | 2010-12-24 | 2010-12-24 | Purification method of yunaconitine |
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| CN2010106038659A CN102532023A (en) | 2010-12-24 | 2010-12-24 | Purification method of yunaconitine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924376A (en) * | 2012-11-28 | 2013-02-13 | 云南省农业科学院药用植物研究所 | Method for preparing high-purity bulleyaconitine A |
| CN104678021A (en) * | 2015-03-09 | 2015-06-03 | 云南中医学院 | Method for measuring three diester diterpenoid alkaloid substances in Aconitum vilmorinianum Komarov medicinal material simultaneously |
| CN104678020A (en) * | 2015-03-09 | 2015-06-03 | 云南中医学院 | Method for measuring yunaconitine and 8-deacetylyunaconitine in prepared Aconitum vilmorinianum Komarov simultaneously |
| CN104739955A (en) * | 2015-02-04 | 2015-07-01 | 贵阳中医学院 | Preparation method of purified short-pedicel aconite root alkaloid by employing cation exchange resin method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1965814A (en) * | 2006-11-03 | 2007-05-23 | 昆明制药集团股份有限公司 | Cataplasma of bulleyaconitine A |
| CN101239947A (en) * | 2008-03-07 | 2008-08-13 | 中国科学院昆明植物研究所 | Method for preparing cryptotanshinone |
| CN101396492A (en) * | 2008-09-17 | 2009-04-01 | 云南植物药业有限公司 | Quality control method for toxin ingredient, yunaconitine in Yuannan Hongyao capsule |
-
2010
- 2010-12-24 CN CN2010106038659A patent/CN102532023A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1965814A (en) * | 2006-11-03 | 2007-05-23 | 昆明制药集团股份有限公司 | Cataplasma of bulleyaconitine A |
| CN101239947A (en) * | 2008-03-07 | 2008-08-13 | 中国科学院昆明植物研究所 | Method for preparing cryptotanshinone |
| CN101396492A (en) * | 2008-09-17 | 2009-04-01 | 云南植物药业有限公司 | Quality control method for toxin ingredient, yunaconitine in Yuannan Hongyao capsule |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924376A (en) * | 2012-11-28 | 2013-02-13 | 云南省农业科学院药用植物研究所 | Method for preparing high-purity bulleyaconitine A |
| CN102924376B (en) * | 2012-11-28 | 2014-10-29 | 云南省农业科学院药用植物研究所 | Method for preparing high-purity bulleyaconitine A |
| CN104739955A (en) * | 2015-02-04 | 2015-07-01 | 贵阳中医学院 | Preparation method of purified short-pedicel aconite root alkaloid by employing cation exchange resin method |
| CN104678021A (en) * | 2015-03-09 | 2015-06-03 | 云南中医学院 | Method for measuring three diester diterpenoid alkaloid substances in Aconitum vilmorinianum Komarov medicinal material simultaneously |
| CN104678020A (en) * | 2015-03-09 | 2015-06-03 | 云南中医学院 | Method for measuring yunaconitine and 8-deacetylyunaconitine in prepared Aconitum vilmorinianum Komarov simultaneously |
| CN104678021B (en) * | 2015-03-09 | 2016-06-29 | 云南中医学院 | A kind of method of 3 kinds of diester-type diterpene alkaloid class materials in yellow Radix Aconiti Kusnezoffii of mensuration simultaneously |
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Application publication date: 20120704 |