CN1257182C - The preparation method of glycyrrhetinic acid - Google Patents
The preparation method of glycyrrhetinic acid Download PDFInfo
- Publication number
- CN1257182C CN1257182C CN 200410018838 CN200410018838A CN1257182C CN 1257182 C CN1257182 C CN 1257182C CN 200410018838 CN200410018838 CN 200410018838 CN 200410018838 A CN200410018838 A CN 200410018838A CN 1257182 C CN1257182 C CN 1257182C
- Authority
- CN
- China
- Prior art keywords
- glycyrrhetinic acid
- acid
- water
- glycyrrhetinic
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- MPDGHEJMBKOTSU-YKLVYJNSSA-N 18beta-glycyrrhetic acid Chemical compound C([C@H]1C2=CC(=O)[C@H]34)[C@@](C)(C(O)=O)CC[C@]1(C)CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H](O)C1(C)C MPDGHEJMBKOTSU-YKLVYJNSSA-N 0.000 title claims description 93
- MPDGHEJMBKOTSU-UHFFFAOYSA-N Glycyrrhetinsaeure Natural products C12C(=O)C=C3C4CC(C)(C(O)=O)CCC4(C)CCC3(C)C1(C)CCC1C2(C)CCC(O)C1(C)C MPDGHEJMBKOTSU-UHFFFAOYSA-N 0.000 title claims description 48
- 229960003720 enoxolone Drugs 0.000 title claims description 48
- 238000002360 preparation method Methods 0.000 title claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- -1 glycyrrhetinic acid sodium salt Chemical class 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000287 crude extract Substances 0.000 claims description 2
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 229960004949 glycyrrhizic acid Drugs 0.000 description 6
- 235000019410 glycyrrhizin Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 244000303040 Glycyrrhiza glabra Species 0.000 description 3
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 description 3
- ILRKKHJEINIICQ-OOFFSTKBSA-N Monoammonium glycyrrhizinate Chemical compound N.O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@H]1CC[C@]2(C)[C@H]3C(=O)C=C4[C@@H]5C[C@](C)(CC[C@@]5(CC[C@@]4(C)[C@]3(C)CC[C@H]2C1(C)C)C)C(O)=O)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O ILRKKHJEINIICQ-OOFFSTKBSA-N 0.000 description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 235000011477 liquorice Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VTAJIXDZFCRWBR-UHFFFAOYSA-N Licoricesaponin B2 Natural products C1C(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2)C(O)=O)C)(C)CC2)(C)C2C(C)(C)CC1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O VTAJIXDZFCRWBR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000003110 anti-inflammatory effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- LPLVUJXQOOQHMX-UHFFFAOYSA-N glycyrrhetinic acid glycoside Natural products C1CC(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2=O)C(O)=O)C)(C)CC2)(C)C2C(C)(C)C1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O LPLVUJXQOOQHMX-UHFFFAOYSA-N 0.000 description 2
- UYRUBYNTXSDKQT-UHFFFAOYSA-N glycyrrhizic acid Natural products CC1(C)C(CCC2(C)C1CCC3(C)C2C(=O)C=C4C5CC(C)(CCC5(C)CCC34C)C(=O)O)OC6OC(C(O)C(O)C6OC7OC(O)C(O)C(O)C7C(=O)O)C(=O)O UYRUBYNTXSDKQT-UHFFFAOYSA-N 0.000 description 2
- 239000001685 glycyrrhizic acid Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000053187 Glucuronidase Human genes 0.000 description 1
- 108010060309 Glucuronidase Proteins 0.000 description 1
- 206010019799 Hepatitis viral Diseases 0.000 description 1
- 208000031226 Hyperlipidaemia Diseases 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 102400000336 Thyrotropin-releasing hormone Human genes 0.000 description 1
- 101800004623 Thyrotropin-releasing hormone Proteins 0.000 description 1
- 238000005377 adsorption chromatography Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000003699 antiulcer agent Substances 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 210000004051 gastric juice Anatomy 0.000 description 1
- 125000004395 glucoside group Chemical group 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- XNSAINXGIQZQOO-SRVKXCTJSA-N protirelin Chemical compound NC(=O)[C@@H]1CCCN1C(=O)[C@@H](NC(=O)[C@H]1NC(=O)CC1)CC1=CN=CN1 XNSAINXGIQZQOO-SRVKXCTJSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 201000001862 viral hepatitis Diseases 0.000 description 1
Images
Landscapes
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
- Steroid Compounds (AREA)
Abstract
The present invention discloses a method for preparing glycyrrhetinic acid. The crude product of glycyrrhizic acid is adopted as a raw material, and processed through extraction by using ethanol, pH value regulation by using ammonia water, concentration, ethyl alcohol recovery, dissolution by adding water, and impurity removal by using ADS-10 macroporous adsorption resin, glycyrrhizic acid in effluent of resin columns is purified and processed through acid hydrolysis to obtain the crude product of glycyrrhetinic acid, and the crude product of glycyrrhetinic acid is further purified so as to obtain glycyrrhetinic acid with high purity. The present invention has the advantages that glycyrrhizic acids with different purity can be used to prepare glycyrrhetinic acid, the purification of glycyrrhetinic acid does not need column chromatography, a method of carrying out respective extraction by using organic solvent twice is adopted, and the present invention has good effects of separation and purification, and product purity of higher than 98%.
Description
Technical field
The present invention relates to a kind of preparation method of glycyrrhetinic acid.
Background technology
Radix Glycyrrhizae is a conventional Chinese medicine, is widely used in fields such as medicine, tobacco, food.It mainly contains the effective constituent Potenlini and has the effect of thyroliberin sample, can be used for detoxifcation, anti-inflammatory, antibechic, antitumor etc.The glucoside unit of Potenlini is a glycyrrhetinic acid, Potenlini through the hydrochloric acid in gastric juice hydrolysis or in liver GRD beta-glucuronidase be decomposed to form glycyrrhetinic acid, the pharmacological action of Potenlini comes down to the effectiveness of glycyrrhetinic acid; In recent years pharmacological research finds, the effect such as have anti-inflammatory, antiulcer agent, antianaphylaxis, antiviral, reducing blood-fat, antibechic, relieving asthma and eliminate the phlegm of Potenlini and glycyrrhetinic acid class medicine also can be used for preventing and treating diseases such as viral hepatitis, hyperlipidemia and cancer.China is the leading exporter of Radix Glycyrrhizae, carries out deep processing and the comprehensive utilization of Radix Glycyrrhizae, and is significant.
The method that in the past prepared glycyrrhetinic acid is a raw material with Glycyrrhizinic acid monopotassium salt or ammonium salt normally, through adding sulphuric acid hydrolysis, filters, and the glycyrrhetinic acid purity that obtains like this is very poor, and is difficult to purify with common recrystallization method; When Glycyrrhizinic acid monopotassium salt or ammonium salt hydrolysis prepare glycyrrhetinic acid,, be easy to take place isomerization reaction if hydrolysising condition control is bad.For example, detected 18 β-H, 18 α-H glycyrrhetinic acid after the bibliographical information hydrolysis, 18 β-H glycyrrhetinic acid methyl esters, glycyrrhetinic acid dewatered product and methyl esters thereof etc.This not only makes the glycyrrhetinic acid yield reduce, and separation difficulty.
People adopt chloroform to dissolve thick glycyrrhetinic acid more, through equipment and higher aluminum oxide or the polymeric amide adsorption chromatography column chromatography for separation of technical requirements, just can make pure glycyrrhetinic acid, the Technology complexity, and turnout also is restricted.
Developed enzymatic hydrolysis process afterwards, Potenlini can obtain pure glycyrrhetinic acid through enzymic hydrolysis.In addition, also available chemical process purifying liquorice hypo acid.After the Potenlini hydrolysis, first acetylize forms the acetylize glycyrrhetinic acid, and then hydrolysis deacetylate and prepare pure glycyrrhetinic acid, or allows it generate glycyrrhetinic acid methyl esters earlier, thereby and then obtains pure glycyrrhetinic acid through basic hydrolysis, acidifying.Though enzyme hydrolysis method and chemical purification method can obtain pure glycyrrhetinic acid, preparation condition and Technology are difficult for realizing industrialization.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation and separation and purification method of high-purity liquorice hypo acid.The molecular formula of glycyrrhetinic acid is: C
30H
16O
1, molecular weight is 470, is prepared by the Potenlini hydrolysis, that is:
Potenlini (Glycyrrhizinic acid) glycyrrhetinic acid (Glycyrrtinic acid)
C
42H
62O
16 FW822.92 C
30H
46O
4 FW470.67
The present invention solves this technical problem the technical scheme that is adopted:
Present method is divided into two steps: the first step is removed impurity composition with the ADS-10 absorption with macroporous adsorbent resin and is come the thick Potenlini of purifying, its preparation technology is: with the ethanol heat of solution of Radix Glycyrrhizae crude extract, add ammoniacal liquor and transfer pH8-9, after concentrating recovery ethanol, residuum is dissolved in water, with the impurity composition in this solution usefulness ADS-10 macroporous adsorptive resins adsorbent solution, and water-soluble ammonium glycyrrhizunate is not by resin absorption, to adsorb effluent liquid and transfer pH1-2 with hydrochloric acid, heating hydrolysis, after the solution cooling, the solids of separating out obtains thick glycyrrhetinic acid after filtering; Second step was the preparation of glycyrrhetinic acid and purifying, and its preparation technology is: with thick glycyrrhetinic acid organic solvent dissolution, leaching insoluble impurities, is the glycyrrhetinic acid sodium salt with buck with the glycyrrhetinic acid alkalization, makes it to separate with non-water-soluble impurity; Make it become the glycyrrhetinic acid that is dissolved in organic solvent with acidifying then, separate with water-soluble impurity, after twice such separation, the purity of glycyrrhetinic acid improves greatly.Behind twice recrystallization, can obtain purity again and be higher than 98% product.
The first step is taked different treatment processs respectively according to the Potenlini raw material of different purity.If adopt the lower glycyrrhizic acid inclusion compound of purity, just remove impurity with the ADS-10 absorption with macroporous adsorbent resin, make water-soluble Monoammonium glycyrrhizinate be able to purifying, promptly carry out acid hydrolysis without concentrating then, because glycyrrhetinic acid is water-soluble very poor, can in water, separate out, filter and obtain the glycyrrhetinic acid crude product.If adopt glycyrrhizic acid content high product such as monoammonium glycyrrhizinate or monopotassium salt, can take direct alcohol-water dissolution, the method for acid hydrolysis obtains thick glycyrrhetinic acid.
The invention has the beneficial effects as follows and can select for use the Potenlini of different purity to prepare glycyrrhetinic acid, the purifying of glycyrrhetinic acid adopts twice difference of organic solvent method of extraction not by column chromatography, and it is good to separate refining effect, and product purity can reach more than 98%.
Description of drawings
Fig. 1 is preparation technology's schematic flow sheet of glycyrrhetinic acid
Embodiment
Embodiment 1
Extracting liquorice acid crude (content about 40%) 40g, with 400ml alcohol heating for dissolving 4 hours, leach insoluble impurities, filtrate is transferred pH7-8 with strong aqua, recovery of alcohol distillation, residuum 300ml water dissolution is crossed ADS-10 macroporous adsorptive resins (50,50,50ml) three posts series connection absorption with this aqueous solution, use the water wash resin column, merge effluent liquid and water lotion, adding concentrated hydrochloric acid to the acid concentration of solution is 3%, and 200ml alcohol, reflux 6 hours, cold putting filtered the solids of separating out, water washing, dry, obtain the glycyrrhetinic acid crude product.Adsorb saturated resin column with ammoniacal liquor-ethanolic soln regeneration, wash the back resin column and can be used for next circulation absorption.
The glycyrrhetinic acid crude product is further purified, and recrystallization can obtain pure glycyrrhetinic acid product 4.2g, purity 95% (HPLC method).
Embodiment 2
10g monoammonium glycyrrhizinate (content about 70%) adds water 100ml heating for dissolving, drips the 20ml concentrated hydrochloric acid, adds 70ml ethanol, stirring and refluxing reaction 6 hours, and cold putting filtered the solids of separating out, water washing, solids dries, and obtains the glycyrrhetinic acid crude product.Be further purified, and recrystallization can obtain pure glycyrrhetinic acid product 2.3g.Purity 96% (HPLC method).
Embodiment 3
100g Glycyrrhizinic acid monopotassium salt (content about 80%) after 500ml water heating for dissolving, adds 300ml alcohol, stir and drip 100ml concentrated hydrochloric acid, back flow reaction 6 hours, cold putting down, the solids that filtration is separated out, water washing, solids dissolves with the 400ml chloroform, and insoluble solids leaches, NaOH aqueous solution extraction secondary with 1mol/L, merge water, be neutralized to pH2-3, use chloroform extraction water secondary again with hydrochloric acid.Chloroform is washed mutually, concentrates, and the excess ethyl alcohol recrystallization obtains glycyrrhetinic acid product 22.3g purity 96%, behind the secondary recrystallization, obtains the 18.2g product.Purity 〉=98%.
Claims (1)
1. the preparation method of a glycyrrhetinic acid, this method is divided into two steps: the first step: with the ethanol heat of solution of Radix Glycyrrhizae crude extract, add ammoniacal liquor and transfer pH8-9, behind the concentrated recovery ethanol, residuum is dissolved in water, with the impurity composition in this solution usefulness ADS-10 macroporous adsorptive resins adsorbent solution, and water-soluble ammonium glycyrrhizunate will adsorb effluent liquid to transfer pH1-2 with hydrochloric acid not by resin absorption, heating hydrolysis, after the solution cooling, the solids of separating out obtains thick glycyrrhetinic acid after filtering; Second step: thick glycyrrhetinic acid being dissolved with chloroform, leach insoluble impurities, is the glycyrrhetinic acid sodium salt with aqueous sodium hydroxide solution with the glycyrrhetinic acid alkalization, makes it to separate with non-water-soluble impurity; Make it become the glycyrrhetinic acid that is dissolved in organic solvent with hcl acidifying then, separate with water-soluble impurity again, by twice such separation, again behind twice ethyl alcohol recrystallization promptly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410018838 CN1257182C (en) | 2004-04-06 | 2004-04-06 | The preparation method of glycyrrhetinic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410018838 CN1257182C (en) | 2004-04-06 | 2004-04-06 | The preparation method of glycyrrhetinic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1563073A CN1563073A (en) | 2005-01-12 |
| CN1257182C true CN1257182C (en) | 2006-05-24 |
Family
ID=34479554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410018838 Expired - Fee Related CN1257182C (en) | 2004-04-06 | 2004-04-06 | The preparation method of glycyrrhetinic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1257182C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565817A (en) * | 2016-11-09 | 2017-04-19 | 深圳市新阳唯康科技有限公司 | Amorphous glycyrrhetinic acid and preparation method thereof |
| CN111171106A (en) * | 2020-02-19 | 2020-05-19 | 洛阳蓝斯利科技有限公司 | Preparation method of 24-hydroxystearyl glycyrrhetinate |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100488979C (en) | 2005-10-14 | 2009-05-20 | 天津药物研究院 | Glycyrrhetinic acid-30-acylamide derivatives and its use |
| CN100415766C (en) * | 2006-06-06 | 2008-09-03 | 南京工业大学 | A method for purifying glycyrrhetin |
| CN101817867B (en) * | 2010-05-27 | 2012-12-05 | 高颖 | Method for preparing glycyrrhetinic acid |
| CN101838303A (en) * | 2010-06-07 | 2010-09-22 | 昆明理工大学 | Preparation method of glycyrrhetinic acid |
| CN102653550A (en) * | 2011-03-01 | 2012-09-05 | 广西壮族自治区药用植物园 | Preparation and application of glycyrrhetinic acid |
| CN102786574A (en) * | 2011-05-17 | 2012-11-21 | 中国医学科学院药物研究所 | Glycyrrhetinic acid crystal A substance, its preparation method, and its applications in medicines and healthcare products |
| CN102786573B (en) * | 2011-05-17 | 2016-01-13 | 中国医学科学院药物研究所 | Glycyrrhetinic acid crystal B-type material and preparation method and apply in medicine and healthcare products |
| CN103588849A (en) * | 2012-08-14 | 2014-02-19 | 江苏汉邦科技有限公司 | Preparation method for glycyrrhetinic acid |
| CN103788167B (en) * | 2012-10-31 | 2015-06-03 | 江苏汉邦科技有限公司 | Preparation method for glycyrrhetinic acid monoglucuronide (GAMG) |
| CN104829681A (en) * | 2015-05-08 | 2015-08-12 | 江苏天晟药业有限公司 | Method for purifying glycyrrhetinic acid |
| CN107531745B (en) * | 2015-05-19 | 2019-11-29 | 正大天晴药业集团股份有限公司 | A kind of new 18 α-Enoxolone derivative and its medical usage |
| CN105693813A (en) * | 2016-03-15 | 2016-06-22 | 合肥华方医药科技有限公司 | Preparation and medical application of glycyrrhizic acid berberine coupling compound |
| CN107412319A (en) * | 2017-06-02 | 2017-12-01 | 新疆全泰兴药业科技有限公司 | A kind of efficiency reduces the method for glycyrrhizic acid and enoxolone in liquorice flavonoids compound |
| CN110283225B (en) * | 2019-07-29 | 2021-02-02 | 洛阳蓝斯利科技有限公司 | Preparation method of 24-hydroxy-glycyrrhetinic acid |
| CN114196723A (en) * | 2021-12-30 | 2022-03-18 | 淮安兄弟生物科技有限公司 | Preparation method of glycyrrhetinic acid |
-
2004
- 2004-04-06 CN CN 200410018838 patent/CN1257182C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565817A (en) * | 2016-11-09 | 2017-04-19 | 深圳市新阳唯康科技有限公司 | Amorphous glycyrrhetinic acid and preparation method thereof |
| CN111171106A (en) * | 2020-02-19 | 2020-05-19 | 洛阳蓝斯利科技有限公司 | Preparation method of 24-hydroxystearyl glycyrrhetinate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1563073A (en) | 2005-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1257182C (en) | The preparation method of glycyrrhetinic acid | |
| CN101838200B (en) | Method for extracting and separating chlorogenic acid from honeysuckle | |
| CN1291028C (en) | Process for extracting tea polyphenol, caffeine as a byproduct thereof and tea polysaccharide from tea | |
| CN101671294B (en) | Method for continuously extracting and separating 1-Deoxynojirimycin (DNJ) and flavone from mulberry leaves | |
| CN101020649A (en) | Process of separating and purifying natural theanine | |
| CN101891781A (en) | A method for preparing high-purity geniposide | |
| CN101613390A (en) | A method for separating and purifying high-purity cordycepin | |
| CN106146278B (en) | A kind of technique for extracting separation Co-Q10 from bacteria residue | |
| CN103204800B (en) | A kind of extracting method of 1 DNJ | |
| CN103012544B (en) | A kind of method extracting saponin and polysaccharide from tea seed grouts | |
| CN102351926B (en) | A kind of preparation method of arctinin | |
| EP4215538A1 (en) | Method for purifying sucralose | |
| CN102286058A (en) | Method for preparing glycyrrhizic acid with high purity | |
| CN104119229A (en) | Technology for producing pure chlorogenic acid | |
| CN108117571B (en) | Preparation method of gentiopicroside monomer | |
| CN108689849B (en) | Method for simultaneous separation of flavonoids and chlorogenic acids from crude extracts of hawthorn leaves | |
| CN101941908A (en) | Method for preparing and partially-synthesizing chlorogenic acid from processing residual liquid of aqua lonicerae foliae | |
| CN111056941B (en) | Method for preparing high-purity shikimic acid by utilizing ginkgo leaf extract chromatography waste liquid | |
| CN106279197B (en) | The purifying of isobide reaction solution and crystallization processes | |
| CN104311616A (en) | Method for extracting high-purity esculine and fraxin from Cortex Fraxini | |
| CN104418852A (en) | Extracting method and application of high-purity coptisine | |
| CN105111144A (en) | Method of extracting nuciferine from lotus leaves | |
| CN102229540A (en) | Method for producing lysine acetate for injection | |
| CN1546461A (en) | A kind of extraction process of theanine | |
| CN100341845C (en) | Chlorogenic acid extracting and purifying process from sunflower seed dregs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060524 |