CN102372757B - Method for preparing chenodeoxycholic acid in pig bile by esterification method - Google Patents
Method for preparing chenodeoxycholic acid in pig bile by esterification method Download PDFInfo
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Abstract
The invention discloses a method for preparing chenodeoxycholic acid in pig bile by an esterification method, which comprises the following steps that: methanol, concentrated sulfuric acid and sodium hydroxide are used for esterification; acetic anhydride is used for acidylation; sherwood oil is used for extraction; the primary crystallization and the secondary crystallization are realized through ethanol and the sherwood oil; the sodium hydroxide is used for hydrolytic acidification; ethyl acetate and active carbon are used for crystallization; and the chenodeoxycholic acid is obtained through drying. The chenodeoxycholic acid is prepared by the method disclosed by the invention, the preparation method is simple, safety and environment protection are realized, the method can be used for large-scale industrial production, the content of the extracted chenodeoxycholic acid is higher or equal to 98 percent, the extraction rate is high, and the purity requirement on products in markets can be met.
Description
Technical field
The present invention relates to a kind of preparation method of Chenodiol, relate in particular to the method for preparing chenodeoxycholic acid in pig bile by esterification method.
Background technology
Chenodiol (being called for short CDCA) is a kind of important biochemical substances that is present in the animal bile, also is one of effective constituent of animal bile.Have treatment cholesterol type calculus, antibiotic, anti-inflammatory, antianaphylaxis, analgesic, the pharmacological action such as reduce phlegm, relieving asthma, or the synthetic expensive main raw material of ursodesoxycholic acid.
The at present acquisition of CDCA mainly is the method for being synthesized take cholic acid (CA) as raw material and the method two large classes that (bird gall and Fel Sus domestica) extracts in bile, complex steps when 1, utilizing synthetic method to obtain CDCA, reaction conditions requires harsh, is unfavorable for industrialized mass production; When 2, utilizing extracting method to obtain CDCA, mainly be to utilize barium salt and calcium salt precipitation method, the physical environment that utilizes barium salt directly the mankind to be depended on for existence brings serious threat, utilize calcium salt then to use a large amount of water, great waste water resource, and two kinds of extracting method products obtained therefrom content are lower, generally all are lower than 90%.
And that current suitability for industrialized production is badly in need of is a kind of simple to operate, and safety and environmental protection extract CDCA content more than or equal to the method for 98% Chenodiol, but this kind method has no report at present.
Summary of the invention
The purpose of this invention is to provide the method with preparing chenodeoxycholic acid in pig bile by esterification method, the method can drop into suitability for industrialized production, simple to operate, safety and environmental protection.
For achieving the above object, the present invention adopts method as follows:
One, esterification: will extract the mother liquor rotary evaporation of bilirubin and Hyodeoxycholic Acid to paste, and add the methyl alcohol that 3-5 doubly measures, 4% the vitriol oil, make it to dissolve fully, after normal temperature left standstill 10-12h, hydro-oxidation sodium was transferred pH to 6.0-7.0, leaves standstill 1-2h, suction filtration, filtrate decompression is concentrated, pressure 0.05-0.07MPa is set, set temperature 40-45 ℃, reclaim methyl alcohol, obtain the esterification paste;
Two, acidylate: add the diacetyl oxide that 1.0-1.5 doubly measures in step 1 gained esterification paste, heated and stirred backflow 1-3h leaves standstill, and concentrating under reduced pressure arranges pressure 0.08-0.1Mpa, and set temperature 90-95 ℃, reclaim diacetyl oxide, obtain the acidylate paste;
Three, petroleum ether extraction: add the water that sherwood oil that 2-4 doubly measures and 1-2 doubly measure in the step 2 gained acidylate paste, heated and stirred backflow 1.0h leaves standstill, discard lower water layer, petroleum ether layer is washed to the pH value and is 5-7,50 ℃ of insulation 4h, 30 ℃ of insulation 2h, filter, filtrate decompression is concentrated, pressure 0.06-0.08Mpa is set, set temperature 70-80 ℃, reclaim sherwood oil, be extracted paste;
Four, primary crystallization: extract the ethanol of the 90%-95% that adding 2-3 doubly measures in the paste to the step 3 gained, leave standstill crystallization 24h, suction filtration, crystal 6 vacuum-drying below 0 ℃ obtains the primary crystallization body;
Five, secondary crystal: add the sherwood oil that 1-2 doubly measures in above-mentioned primary crystallization body, heating makes it to dissolve fully, leaves standstill crystallisation by cooling 2-5h, suction filtration, and crystal is dry;
Six, acidication: take by weighing dried crystal and add the sodium hydroxide that 1-2 doubly measures, the purified water that 8-10 doubly measures is more than the heating saponification 12h, be cooled to the room temperature standing demix, take off layer and add a small amount of purified water and make it dissolving, hcl acidifying is transferred pH to 4-5, both filters to get the crude product Chenodiol;
Seven, crystallization: in above-mentioned crude product Chenodiol, add ethyl acetate and the 5%-10% gac that 10-12 doubly measures, reflux 30min-60min filters, and is washed to neutrality, filtrate decompression is concentrated, pressure 0.040.06MPa is set, set temperature 45-50 ℃, reclaims ethyl acetate, volume is to the 1/8-1/4 of original volume after reclaiming, be cooled to room temperature, leave standstill crystallization, filter and both get elaboration;
Eight, drying: above-mentioned crystal is put into the vacuum drying oven drying, temperature 60 C in the loft drier is set, both got the elaboration Chenodiol.
Usefulness of the present invention is: utilize the inventive method to prepare Chenodiol, the preparation method is simple, and safety and environmental protection utilizes large-scale industrial production; This method is extracted the CDCA acid content more than or equal to 98%, extracts ratio high, and the energy satisfying the market is to the purity requirement of this product.
Embodiment
Embodiment 1
The method of preparing chenodeoxycholic acid in pig bile by esterification method, step is as follows:
The laboratory lab scale, one, esterification: get the paste 0.1kg that carried bilirubin and Hyodeoxycholic Acid and put into experimental ware, add the methyl alcohol of 3 times of amounts, the vitriol oil of 4ml makes it to dissolve fully, after normal temperature leaves standstill 10h, hydro-oxidation sodium is transferred pH to 7.0, leave standstill 1h, suction filtration is put into Rotary Evaporators with filtrate, set Rotary Evaporators vacuum tightness 0.05Mpa, 45 ℃ of design temperatures, circulating water reclaims methyl alcohol, obtains the esterification paste;
Two, acidylate: step 1 gained esterification paste is taken out, the vessel of packing into, the diacetyl oxide that adds 1.0 times of amounts, heated and stirred backflow 1h leaves standstill, and liquid is put into Rotary Evaporators, set Rotary Evaporators vacuum tightness 0.08Mpa, 95 ℃ of design temperatures, circulating water reclaims diacetyl oxide, obtains the acidylate paste;
Three, petroleum ether extraction: step 2 gained acidylate paste is taken out, and the vessel of packing into add the sherwood oil of 2 times of amounts and the water of 1 times of amount, heated and stirred backflow 1.0h leaves standstill, and discards water layer, it is 5,50 ℃ of insulation 4h that petroleum ether layer is washed to the pH value, 30 ℃ of insulation 2h, filter-cloth filtering, filtrate is put into Rotary Evaporators, set Rotary Evaporators vacuum tightness 0.06Mpa, 80 ℃ of design temperatures, circulating water reclaims sherwood oil, is extracted paste;
Four, primary crystallization: step 3 gained extraction paste is taken out, and the vessel of packing into add 90% ethanol of 2 times of amounts, leave standstill crystallization 24h, suction filtration, crystal are put the vacuum drying oven drying, setting vacuum drying oven vacuum tightness is 0.08Mpa, and 60 ℃ of dryings of design temperature obtain the primary crystallization body;
Five, secondary crystal: above-mentioned primary crystallization body is taken out, pack in the vessel, the sherwood oil that adds 1 times of amount, heating makes it to dissolve fully, leaves standstill crystallisation by cooling 4h, suction filtration, crystal is put the vacuum drying oven drying, if it is 0.08Mpa that vacuum drying oven is decided vacuum tightness, 60 ℃ of dryings of design temperature obtain the secondary crystal body;
Six, acidication: above-mentioned secondary crystal body is taken out, pack in the vessel, the sodium hydroxide that adds 1 times of amount, the purified water of 8 times of amounts more than the heating saponification 12h, is cooled to the room temperature standing demix, take off the layer add a small amount of purified water make it the dissolving, hcl acidifying is transferred pH to 4, and filter-cloth filtering had both got the crude product Chenodiol;
Seven, crystallization: take out above-mentioned crude product Chenodiol, in the vessel of packing into, add ethyl acetate and 5% gac of 10 times of amounts, reflux 30min, filter-cloth filtering is washed to neutrality, filtrate is put into Rotary Evaporators, set Rotary Evaporators vacuum tightness 0.06MPa, 50 ℃ of design temperatures, circulating water reclaim ethyl acetate to 1/8 of original volume, be cooled to room temperature, leave standstill crystallization, filter-cloth filtering had both got the elaboration Chenodiol;
Eight, drying: the elaboration Chenodiol is put into drying, and setting vacuum drying oven vacuum tightness is 0.08Mpa, and 60 ℃ of dryings of design temperature had both got the elaboration Chenodiol.
Use HPLC to detect, adopt marker method calculation result, the CDCA acid content reaches 99.5%.
Embodiment 2
During pilot scale, one, esterification: get the paste 10kg that carried bilirubin and Hyodeoxycholic Acid and put into experimental ware, add the methyl alcohol of 4 times of amounts, the vitriol oil of 400ml makes it to dissolve fully, after normal temperature leaves standstill 12h, hydro-oxidation sodium is transferred pH to 6.5, leave standstill 1-2h, suction filtration is put into Rotary Evaporators with filtrate, set Rotary Evaporators vacuum tightness 0.06Mpa, 45 ℃ of design temperatures, circulating water reclaims methyl alcohol, obtains the esterification paste;
Two, acidylate: step 1 gained esterification paste is taken out, the vessel of packing into, the diacetyl oxide that adds 1.3 times of amounts, heated and stirred backflow 2h leaves standstill, and liquid is put into Rotary Evaporators, set Rotary Evaporators vacuum tightness 0.09Mpa, 95 ℃ of design temperatures, circulating water reclaims diacetyl oxide, obtains the acidylate paste;
Three, petroleum ether extraction: step 2 gained acidylate paste is taken out, and the vessel of packing into add the sherwood oil of 3 times of amounts and the water of 2 times of amounts, heated and stirred backflow 1.0h leaves standstill, and discards water layer, it is 6,50 ℃ of insulation 4h that petroleum ether layer is washed to the pH value, 30 ℃ of insulation 2h, filter-cloth filtering, filtrate is put into Rotary Evaporators, set Rotary Evaporators vacuum tightness 0.07Mpa, 80 ℃ of design temperatures, circulating water reclaims sherwood oil, is extracted paste;
Four, primary crystallization: step 3 gained extraction paste is taken out, and the vessel of packing into add 93% ethanol of 3 times of amounts, leave standstill crystallization 24h, suction filtration, crystal are put the vacuum drying oven drying, setting vacuum drying oven vacuum tightness is 0.07Mpa, and 60 ℃ of dryings of design temperature obtain the primary crystallization body;
Five, secondary crystal: above-mentioned primary crystallization body is taken out, pack in the vessel, the sherwood oil that adds 2 times of amounts, heating makes it to dissolve fully, leaves standstill crystallisation by cooling 4h, suction filtration, crystal is put the vacuum drying oven drying, setting vacuum drying oven vacuum tightness is 0.07Mpa, and 60 ℃ of dryings of design temperature obtain the secondary crystal body;
Six, acidication: above-mentioned secondary crystal body is taken out, pack in the vessel, take by weighing the sodium hydroxide that dried crystal adds 2 times of amounts, the purified water of 10 times of amounts more than the heating saponification 12h, is cooled to the room temperature standing demix, take off the layer add a small amount of purified water make it the dissolving, hcl acidifying is transferred pH to 5, and filter-cloth filtering had both got the crude product Chenodiol;
Seven, crystallization: take out above-mentioned crude product Chenodiol, in the vessel of packing into, in the vessel that the crude product Chenodiol is housed, add ethyl acetate and 8% gac of 12 times of amounts, reflux 45min, filter-cloth filtering is washed to neutrality, filtrate is put into Rotary Evaporators, set Rotary Evaporators vacuum tightness 0.05MPa, 45 ℃ of design temperatures, circulating water reclaims ethyl acetate, to 1/6 of original volume, be cooled to room temperature, leave standstill crystallization, filter-cloth filtering had both got the elaboration Chenodiol;
Eight, drying: the elaboration Chenodiol is put into drying, put into the vacuum drying oven drying, setting vacuum drying oven vacuum tightness is 0.07Mpa, and 60 ℃ of dryings of design temperature had both got the elaboration Chenodiol.
Use HPLC to detect, adopt marker method calculation result, the CDCA acid content reaches 98.9%.
Embodiment 3
In the production process, one, esterification: get the paste 100kg that carried bilirubin and Hyodeoxycholic Acid and put into container, add the methyl alcohol of 5 times of amounts, the vitriol oil of 4000ml makes it to dissolve fully, after normal temperature leaves standstill 12h, hydro-oxidation sodium is transferred pH to 6.0, leave standstill 2h, filter-cloth filtering is put into spherical concentrator with filtrate, set spherical concentrator vacuum tightness 0.07Mpa, 45 ℃ of design temperatures, circulating water reclaims methyl alcohol, obtains the esterification paste;
Two, acidylate: step 1 gained esterification paste is taken out, the vessel of packing into, the diacetyl oxide that adds 1.5 times of amounts, heated and stirred backflow 3h leaves standstill, and liquid is put into spherical concentrator, set spherical concentrator vacuum tightness 0.1Mpa, 95 ℃ of design temperatures, circulating water reclaims diacetyl oxide, obtains the acidylate paste;
Three, petroleum ether extraction: step 2 gained acidylate paste is taken out, and the vessel of packing into add the sherwood oil of 4 times of amounts and the water of 2 times of amounts, heated and stirred backflow 1.0h leaves standstill, and discards water layer, it is 5,50 ℃ of insulation 4h that petroleum ether layer is washed to the pH value, 30 ℃ of insulation 2h, filter-cloth filtering, filtrate is put into spherical concentrator, set spherical concentrator vacuum tightness 0.08Mpa, 80 ℃ of design temperatures, circulating water reclaims sherwood oil, is extracted paste;
Four, primary crystallization: step 3 gained extraction paste is taken out, the vessel of packing into, the ethanol that adds the 90%-95% of 3 times of amounts, leave standstill crystallization 24h, it is dry that suction filtration, crystal are put large vacuum drying oven, and setting large vacuum drying oven vacuum tightness is 0.06-0.08Mpa, 60 ℃ of dryings of design temperature obtain the primary crystallization body;
Five, secondary crystal: above-mentioned primary crystallization body is taken out, pack in the vessel, the sherwood oil that adds 2 times of amounts, heating makes it to dissolve fully, leaves standstill crystallisation by cooling 4h, suction filtration, it is dry that crystal is put large vacuum drying oven, setting large vacuum drying oven vacuum tightness is 0.08Mpa, and 60 ℃ of dryings of design temperature obtain the secondary crystal body;
Six, acidication: above-mentioned secondary crystal body is taken out, pack in the vessel, the sodium hydroxide that adds 2 times of amounts, the purified water of 10 times of amounts more than the heating saponification 12h, is cooled to the room temperature standing demix, take off the layer add a small amount of purified water make it the dissolving, hcl acidifying is transferred pH to 5, and filter-cloth filtering had both got the crude product Chenodiol;
Seven, crystallization: take out above-mentioned crude product Chenodiol, in the vessel of packing into, add ethyl acetate and 10% gac of 12 times of amounts, reflux 60min, filter-cloth filtering is washed to neutrality, filtrate is put into spherical concentrator, set spherical concentrator vacuum tightness 0.06MPa, 50 ℃ of design temperatures, circulating water reclaims ethyl acetate, to 1/4 of original volume, be cooled to room temperature, leave standstill crystallization, filter-cloth filtering had both got the elaboration Chenodiol;
Eight, drying: the elaboration Chenodiol is put into drying, put into the vacuum drying oven drying, set vacuum drying oven vacuum tightness 0.08Mpa, 60 ℃ of dryings of design temperature had both got the elaboration Chenodiol.
Use HPLC to detect, adopt marker method calculation result, the CDCA acid content reaches 98.5%.
Claims (1)
1. the method for preparing chenodeoxycholic acid in pig bile by esterification method comprises that step is as follows:
One, esterification: will extract the mother liquor rotary evaporation of bilirubin and Hyodeoxycholic Acid to paste, and add the methyl alcohol that 3-5 doubly measures, 4% the vitriol oil, make it to dissolve fully, after normal temperature left standstill 10-12h, hydro-oxidation sodium was transferred pH to 6.0-7.0, leaves standstill 1-2h, suction filtration, filtrate decompression is concentrated, pressure 0.05-0.07MPa is set, set temperature 40-45 ℃, reclaim methyl alcohol, obtain the esterification paste;
Two, acidylate: add the diacetyl oxide that 1.0-1.5 doubly measures in step 1 gained esterification paste, heated and stirred backflow 1-3h leaves standstill, and concentrating under reduced pressure arranges pressure 0.08-0.1Mpa, and set temperature 90-95 ℃, reclaim diacetyl oxide, obtain the acidylate paste;
Three, petroleum ether extraction: add the water that sherwood oil that 2-4 doubly measures and 1-2 doubly measure in the step 2 gained acidylate paste, heated and stirred backflow 1.0h leaves standstill, discard lower water layer, petroleum ether layer is washed to the pH value and is 5-7,50 ℃ of insulation 4h, 30 ℃ of insulation 2h, filter, filtrate decompression is concentrated, pressure 0.06-0.08Mpa is set, set temperature 70-80 ℃, reclaim sherwood oil, be extracted paste;
Four, primary crystallization: extract the ethanol of the 90%-95% that adding 2-3 doubly measures in the paste to the step 3 gained, leave standstill crystallization 24h, suction filtration, crystal 6 vacuum-drying below 0 ℃ obtains the primary crystallization body;
Five, secondary crystal: add the sherwood oil that 1-2 doubly measures in above-mentioned primary crystallization body, heating makes it to dissolve fully, leaves standstill crystallisation by cooling 2-5h, suction filtration, and crystal is dry;
Six, acidication: take by weighing dried crystal and add the sodium hydroxide that 1-2 doubly measures, the purified water that 8-10 doubly measures is more than the heating saponification 12h, be cooled to the room temperature standing demix, take off layer and add a small amount of purified water and make it dissolving, hcl acidifying is transferred pH to 4-5, both filters to get the crude product Chenodiol;
Seven, crystallization: in above-mentioned crude product Chenodiol, add ethyl acetate and the 5%-10% gac that 10-12 doubly measures, reflux 30min-60min filters, and is washed to neutrality, filtrate decompression is concentrated, pressure 0.04-0.06MPa is set, set temperature 45-50 ℃, reclaims ethyl acetate, volume is to the 1/8-1/4 of original volume after reclaiming, be cooled to room temperature, leave standstill crystallization, filter and namely get elaboration;
Eight, drying: above-mentioned crystal is put into the vacuum drying oven drying, temperature 60 C in the loft drier is set, both got the elaboration Chenodiol.
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Families Citing this family (6)
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| US9238673B2 (en) | 2012-06-19 | 2016-01-19 | Intercept Pharmaceuticals, Inc. | Preparation and uses of obeticholic acid |
| US9982008B2 (en) | 2012-06-19 | 2018-05-29 | Intercept Pharmaceuticals, Inc. | Preparation and uses of obeticholic acid |
| CN105418716B (en) * | 2015-12-25 | 2017-11-17 | 成都市新功生物科技有限公司 | A kind of method of the duck cholic acid synthesis chenodeoxycholic acid extracted in the bile with duck |
| CN110790805B (en) * | 2019-11-14 | 2022-08-30 | 湖南九典制药股份有限公司 | Method for extracting chenodeoxycholic acid from pig bile paste |
| CN112010920A (en) * | 2020-09-22 | 2020-12-01 | 安徽科宝生物工程有限公司 | Method for preparing chenodeoxycholic acid by extraction complexation method |
| CN111961105A (en) * | 2020-09-23 | 2020-11-20 | 安徽科宝生物工程有限公司 | Method for separating hyodeoxycholic acid from pig bile paste by extraction method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1869043A (en) * | 2006-06-09 | 2006-11-29 | 沈阳化工学院 | Synthesis method of chenodeoxycholic acid |
| CN101351470A (en) * | 2005-12-12 | 2009-01-21 | 株式会社大熊制药 | Purification process for chenodeoxycholic acid |
| CN101830956A (en) * | 2008-11-19 | 2010-09-15 | 毕小升 | Preparation method for separating and purifying chenodeoxycholic acid in porcine bile paste or leftovers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101351470A (en) * | 2005-12-12 | 2009-01-21 | 株式会社大熊制药 | Purification process for chenodeoxycholic acid |
| CN1869043A (en) * | 2006-06-09 | 2006-11-29 | 沈阳化工学院 | Synthesis method of chenodeoxycholic acid |
| CN101830956A (en) * | 2008-11-19 | 2010-09-15 | 毕小升 | Preparation method for separating and purifying chenodeoxycholic acid in porcine bile paste or leftovers |
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