CN110960577A - Preparation method of tertiary amine alkali component in rhizoma corydalis - Google Patents
Preparation method of tertiary amine alkali component in rhizoma corydalis Download PDFInfo
- Publication number
- CN110960577A CN110960577A CN201811144625.XA CN201811144625A CN110960577A CN 110960577 A CN110960577 A CN 110960577A CN 201811144625 A CN201811144625 A CN 201811144625A CN 110960577 A CN110960577 A CN 110960577A
- Authority
- CN
- China
- Prior art keywords
- acid
- tertiary amine
- preparation
- stirring
- rhizoma corydalis
- 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.)
- Pending
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/4353—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom ortho- or peri-condensed with heterocyclic ring systems
- A61K31/4375—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom ortho- or peri-condensed with heterocyclic ring systems the heterocyclic ring system containing a six-membered ring having nitrogen as a ring heteroatom, e.g. quinolizines, naphthyridines, berberine, vincamine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/66—Papaveraceae (Poppy family), e.g. bloodroot
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/30—Extraction of the material
- A61K2236/33—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/50—Methods involving additional extraction steps
- A61K2236/51—Concentration or drying of the extract, e.g. Lyophilisation, freeze-drying or spray-drying
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/50—Methods involving additional extraction steps
- A61K2236/53—Liquid-solid separation, e.g. centrifugation, sedimentation or crystallization
Landscapes
- Health & Medical Sciences (AREA)
- Natural Medicines & Medicinal Plants (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical & Material Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pain & Pain Management (AREA)
- Engineering & Computer Science (AREA)
- Rheumatology (AREA)
- Organic Chemistry (AREA)
- Alternative & Traditional Medicine (AREA)
- Medical Informatics (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides a preparation method of a tertiary amine alkali component in rhizoma corydalis. The preparation method of the class components provided by the invention reduces berberine quaternary ammonium bases in the corydalis tuber extract into protoberberine tertiary amine bases, wherein two kinds of quaternary ammonium bases with the highest content in corydalis tuber, namely palmatine and dehydrocorydaline, are respectively reduced into tetrahydropalmatine and corydaline. Adjusting the pH of the reaction supernatant to be neutral, evaporating to dryness, desalting, and drying to obtain the tertiary amine alkali component, wherein the total alkali content is more than 50%. The preparation method has the advantages of simple process, high efficiency, high recovery rate and low production cost, and provides a good technical scheme for developing safe, effective and controllable rhizoma corydalis alkaloid component preparations.
Description
Technical Field
The invention relates to the field of drug synthesis, and in particular relates to a preparation method of a tertiary amine base component in rhizoma corydalis.
Background
Rhizoma Corydalis (rhizoma Corydalis) is tuber of Corydalis yanhusuo W.T. Wang of Papaveraceae, and has effects of promoting blood circulation, removing blood stasis, regulating qi-flowing and relieving pain. Modern pharmaceutical chemistry and pharmacological experiments show that the main active ingredients in the corydalis tuber are tertiary amine and quaternary ammonium alkaloid, wherein the content of tertiary amine alkali is about 0.65%, and the content of quaternary ammonium alkali is about 0.3%. (Haokai, Gaojiali, Zhao Guang Tree. corydalis yanhusuo chemical component, pharmacological action and quality control research progress, Chinese herbal medicine 2007, 38(12): 1909-. The two components are not only structurally different, but also have great difference in solubility and pharmacological action. Tertiary amine alkaloids represented by corydaline, tetrahydropalmatine, and tetrahydropalmatine are hardly soluble in water, often have good analgesic and sedative effects, and are the main active ingredients of rhizoma corydalis for traditional analgesic treatment (Zhao emerald Zhao, Xiaoqin, Liyong and Vinegar processed rhizoma corydalis B content and analgesic effect comparative study, Xinjiang traditional Chinese medicine, 2007, 25(2): 34-36); the significant effect of corydalis tuber in resisting myocardial ischemia, reducing myocardial oxygen consumption and the like is mainly due to the quaternary ammonium base with better water solubility (Cheng xing Ye, the basic research of corydalis tuber anti-myocardial ischemia active site substance, the Chinese Shuo scholar paper of the university of medicine, 2008). It is clear that the quaternary ammonium base in corydalis tuber is not the material basis for its analgesic activity. If the berberine quaternary ammonium base with higher content in the corydalis tuber can be directly converted into the protoberberine tertiary amine base with good analgesic activity, the analgesic effect of the berberine quaternary ammonium base is more targeted and the quality of the berberine quaternary ammonium base is easier to control. At present, no relevant patent is reported. Therefore, through intensive research, a method for directly converting berberine quaternary ammonium base in the corydalis tuber extract into protoberberine tertiary amine base is found, the content of the protoberberine tertiary amine active compound in the corydalis tuber extract can be greatly increased, and berberine quaternary ammonium base is removed.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to directly convert berberine quaternary ammonium base in the rhizoma corydalis extract into protoberberine tertiary amine base so as to improve the content of protoberberine tertiary amine base with analgesic activity in the rhizoma corydalis extract, so that the acting mode and the curative effect of the rhizoma corydalis extract have higher pertinence.
The technical scheme of the invention is as follows: a preparation method of tertiary amine alkali components in rhizoma corydalis comprises the following steps:
(1) dispersing dry powder of rhizoma corydalis extract into 5-100 times of alcohol solvent system, and stirring;
(2) adding 0.1-2 times of alkali, and stirring for 10-60 min;
(3) dropwise adding 0.01-2.0 equivalent of NaBH4 (NaBH 4 dissolved in NaOH solution) within 30min, and stirring at room temperature for 0.5-3 h;
(4) after the reaction is completed, filtering, and concentrating the filtrate;
(5) adjusting pH of the concentrated solution to 6.5-8.0, removing solvent under reduced pressure, and desalting to obtain yellow solid product.
Further, the corydalis tuber extract comprises a crude extract obtained by using one or more of water, acid water, methanol or ethanol as a solvent and adopting an extraction mode of percolation, decoction, reflux, ultrasound or microwave assistance and the like, or a total alkali extract obtained by purifying the crude extract in a mode of acid-extraction-base precipitation, solvent distribution or resin column chromatography and the like.
Preferably, the method of step (1) is: dispersing dry powder of rhizoma corydalis extract into 10-100 times of methanol or ethanol, and stirring at room temperature.
Preferably, the method of step (2) is: adding 0.1-2 times of K2CO3, NaOH or KOH, and stirring at room temperature for 10-30 min.
Preferably, the method of step (3) is: 0.01-2.0 equivalent of NaBH4 (NaBH 4 dissolved in 2-10 ml of 5% NaOH solution) is added dropwise, the addition is completed within 30min, and the mixture is stirred for 0.5-3h at room temperature.
Further, the specific method of the step (4) is as follows: after completion of the reaction as detected by HPLC or dot plate, the solid was removed by filtration, washed with a large amount of the reaction solvent, and the filtrate was concentrated under reduced pressure.
Further, the specific method of the step (5) is as follows: adjusting pH of the concentrated solution to 6.5-8.0 with organic or inorganic acid, removing solvent under reduced pressure, and desalting to obtain white or yellow solid product; the tertiary amine base content was >50% by qualitative quantitative analysis by HPLC.
Further, the organic or inorganic acid is dilute hydrochloric acid, dilute sulfuric acid, citric acid, formic acid.
Furthermore, the obtained tertiary amine base has poor water solubility and poor bioavailability, and one or more than two acids compatible with biological systems such as acetic acid, nitric acid, hydrochloric acid, sulfuric acid and the like can be added in the subsequent desalting step to react with the alkaloid to form physiologically acceptable salt so as to improve the solubility and the bioavailability.
The reaction is carried out at normal temperature and normal pressure, the reaction condition is mild, and the operation is easy; the reaction conversion efficiency is high, and under the condition of slight excess NaBH4, the quaternary ammonium base in the extract can be converted into corresponding tertiary amine base almost 100%; the alcohol solvent, the reducing agent and the acid and the alkali are all bulk raw materials commonly used in the pharmaceutical industry, are low in price and easy to obtain, and are suitable for industrial production.
The high performance liquid chromatography qualitative and quantitative method of the tertiary amine alkali component obtained by the method comprises the following steps: a Waters Alliance high performance liquid chromatography system, gradient elution on a Unit C18 column (4.6X 150 mm, 5 μm) with acetonitrile (A) and water (0.1% phosphoric acid, 0.2% triethylamine, pH 6.0) as mobile phases, the elution conditions being: 23 percent of A in 0-20 min,23 percent of A in 20-30 min, 23-55 percent of A in 30-45 min, 55 percent of A in 45-46 min, 55-23 percent of A in 46-60 min, and 23 percent of A in 30-45 min. The flow rate was 1 mL/min, PDA detector, column temperature 30 ℃. For the tertiary amine alkali component, an external standard working curve is prepared by taking tetrahydropalmatine as a reference substance, the obtained regression equation is y =2E +07x-16050, R2=0.9999, the detection wavelength is 280 nm, and the linear range is 0.008-1.6 mg/mL. The content of 10 main peaks in the tertiary amine alkali component obtained by the method is more than 50 percent based on tetrahydropalmatine (figure 1, peak 5).
Based on the technical method, the high-content tertiary amine alkali component can be prepared from the corydalis tuber extract through simple chemical reaction, and a good foundation is laid for the development of a targeted pharmaceutical preparation.
Drawings
FIG. 1 chromatogram of corydalis tuber extract and UV spectrum of 9 main peaks of tertiary amine base in example 1;
FIG. 2 chromatogram of tertiary amine base component and UV spectrum of 10 main peaks;
FIG. 3 is a comparative spectrum of the sample solution before and after the reaction in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting in any way.
A method for preparing tertiary amine alkali component in corydalis ambigua is carried out by the following examples.
Example 1
Adding rhizoma corydalis extract 2.0 g (containing tertiary amine alkali 0.5% by tetrahydropalmatine, figure 1) into 250ml reaction flask, adding methanol 100 ml, stirring for 0.5 hr, adding K2CO33.0 g, stirred for 10 min, and 0.12 g of NaBH added dropwise42.4 ml of 5 percent sodium hydroxide solution, stirring for 2 min after dropwise addition, filtering, concentrating the filtrate to remove methanol, adding 30 ml of water, adjusting the pH to 7-8 by using 1N hydrochloric acid, adding 30 ml of dichloromethane for extraction for three times, combining, washing once by using saturated sodium chloride, drying by using anhydrous sodium sulfate, concentrating to obtain 0.05 g of yellow solid, analyzing by HPLC, wherein the content of the tertiary amine alkali is 50.2 percent calculated by tetrahydropalmatine, and referring to fig. 2, the comparative spectrogram of sample solution before and after reaction is shown in fig. 3, peaks of two main quaternary ammonium bases, namely palmatine and dehydrocorydaline in the extract disappear in the reaction solution, peaks of tetrahydropalmatine and methyl ethyl amine A are obviously increased, and the quaternary ammonium base in the extract is almost 100 percent converted into the corresponding tertiary amine base.
Example 2
Adding corydalis tuber extract 2.0 g into a 250ml reaction bottle, adding ethanol 100 ml, stirring for 0.5 h, adding K2CO33.0 g, stirring for 10 min, dropwise adding 0.12 g of NaBH4 into 2.4 ml of 5% sodium hydroxide solution, stirring for 2 min after dropwise adding, filtering, concentrating the filtrate to remove ethanol, adding 30 ml of water, adjusting the pH to 7-8 by using 1N hydrochloric acid, adding 30 ml of ethyl acetate for extraction for three times, combining, washing once by using saturated sodium chloride, drying by using anhydrous sodium sulfate, concentrating to obtain yellow solid 0.04 g, and analyzing by HPLC, wherein the content of tertiary amine alkali is 55.6% in terms of tetrahydropalmatine.
Example 3
Adding corydalis tuber extract 2.0 g into a 250ml reaction bottle, adding ethanol 50ml, stirring for 0.5 h, adding K2CO33.0 g, stirring for 10 min, dropwise adding 0.1 g NaBH4 into 2.0 ml5% sodium hydroxide solution, stirring for 2 h after 2 min is completed, filtering, concentrating the filtrate to remove ethanol, adding 30 ml water, adjusting the pH to 7-8 with 1N sulfuric acid, adding 30 ml ethyl acetate for extraction for three times, combining, washing once with saturated sodium chloride, drying with anhydrous sodium sulfate, concentrating to obtain yellow solid 0.03 g, and analyzing by HPLC, wherein the tertiary amine alkali content is 60.5% calculated by tetrahydropalmatine.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (9)
1. A preparation method of tertiary amine alkali components in rhizoma corydalis is characterized by comprising the following steps:
(1) dispersing dry powder of rhizoma corydalis extract into 5-100 times of alcohol solvent system, and stirring;
(2) adding 0.1-2 times of alkali, and stirring for 10-60 min;
(3) dropwise adding 0.01-2.0 equivalent of NaBH4 (NaBH 4 dissolved in NaOH solution) within 30min, and stirring at room temperature for 0.5-3 h;
(4) after the reaction is completed, filtering, and concentrating the filtrate;
(5) adjusting pH of the concentrated solution to 6.5-8.0, removing solvent under reduced pressure, and desalting to obtain yellow solid product.
2. The method according to claim 1, wherein the corydalis tuber extract in step (1) comprises a crude extract obtained by percolating, decocting, refluxing, ultrasonic extracting or microwave-assisted extracting with one or more of water, acid water, methanol or ethanol as solvent, or a total alkali extract obtained by purifying the crude extract by acid-extraction-base precipitation, solvent distribution or resin column chromatography.
3. The method according to claim 1, wherein the method of step (1) is: dispersing dry powder of rhizoma corydalis extract into 5-100 times of methanol or ethanol, and stirring at room temperature.
4. The method according to claim 1, wherein the method of step (2) is: adding 0.1-2 times of K2CO3, NaOH or KOH, and stirring at room temperature for 10-60 min.
5. The method according to claim 1, wherein the method of step (3) is: 0.01-2.0 equivalent of NaBH4 (NaBH 4 dissolved in 2-10 ml of 5% NaOH solution) is added dropwise, the addition is completed within 30min, and the mixture is stirred for 0.5-3h at room temperature.
6. The preparation method according to claim 1, wherein the specific method of step (4) is as follows: after completion of the reaction as detected by HPLC or dot plate, the solid was removed by filtration, washed with a large amount of the reaction solvent, and the filtrate was concentrated under reduced pressure.
7. The preparation method according to claim 1, wherein the specific method of step (5) is: adjusting pH of the concentrated solution to 6.5-8.0 with organic or inorganic acid, removing solvent under reduced pressure, and desalting to obtain white or yellow solid product; the tertiary amine base content was >50% by qualitative quantitative analysis by HPLC.
8. The method according to claim 7, wherein the organic or inorganic acid is dilute hydrochloric acid, dilute sulfuric acid, citric acid, or formic acid.
9. The method according to claim 1, wherein one or more of acetic acid, nitric acid, hydrochloric acid and sulfuric acid is added in the desalting step of step 7.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811144625.XA CN110960577A (en) | 2018-09-29 | 2018-09-29 | Preparation method of tertiary amine alkali component in rhizoma corydalis |
| PCT/CN2018/118603 WO2020062545A1 (en) | 2018-09-29 | 2018-11-30 | Method for preparing tertiary amine basic components in rhizoma corydalis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811144625.XA CN110960577A (en) | 2018-09-29 | 2018-09-29 | Preparation method of tertiary amine alkali component in rhizoma corydalis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110960577A true CN110960577A (en) | 2020-04-07 |
Family
ID=69950899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811144625.XA Pending CN110960577A (en) | 2018-09-29 | 2018-09-29 | Preparation method of tertiary amine alkali component in rhizoma corydalis |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110960577A (en) |
| WO (1) | WO2020062545A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021212535A1 (en) * | 2020-04-25 | 2021-10-28 | 江苏天士力帝益药业有限公司 | Method for refining benzhexol hydrochloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816152A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院大连化学物理研究所 | Application and preparation method of berberine compound |
| CN104415573A (en) * | 2013-09-10 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for classifying and preparing tertiary amine alkaloid and quaternary ammonium alkaloid from corydalis extract |
| CN106117197A (en) * | 2016-06-16 | 2016-11-16 | 长春工业大学 | A kind of method being prepared 2,3,9,10 4 butoxy protoberberines by Rhizoma Coptidis mixed biologic alkali |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104510781A (en) * | 2015-01-25 | 2015-04-15 | 王小华 | Application of rhizoma corydalis to resistance to tumor pain |
| CN104547055A (en) * | 2015-01-25 | 2015-04-29 | 王小华 | Application of rhizoma corydalis in inhibiting advanced tumor pain |
| CN104547054A (en) * | 2015-01-25 | 2015-04-29 | 汪甬娜 | External application of rhizoma corydalis composition for treating pain of gall-stone |
-
2018
- 2018-09-29 CN CN201811144625.XA patent/CN110960577A/en active Pending
- 2018-11-30 WO PCT/CN2018/118603 patent/WO2020062545A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816152A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院大连化学物理研究所 | Application and preparation method of berberine compound |
| CN104415573A (en) * | 2013-09-10 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for classifying and preparing tertiary amine alkaloid and quaternary ammonium alkaloid from corydalis extract |
| CN106117197A (en) * | 2016-06-16 | 2016-11-16 | 长春工业大学 | A kind of method being prepared 2,3,9,10 4 butoxy protoberberines by Rhizoma Coptidis mixed biologic alkali |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021212535A1 (en) * | 2020-04-25 | 2021-10-28 | 江苏天士力帝益药业有限公司 | Method for refining benzhexol hydrochloride |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020062545A1 (en) | 2020-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101433565B (en) | Total alkaloid extract of seeds of harmel genus, and preparation thereof | |
| CN102976909B (en) | Method for extracting and purifying 6-gingerol from ginger | |
| CN102001947A (en) | Method for preparing honeysuckle chlorogenic acid | |
| CN105001285A (en) | Method for extracting baicalin from radix scutellariae | |
| CN100439319C (en) | Method for preparing salviol acid A | |
| CN108299453B (en) | Method for separating psoralen, isopsoralen and bakuchiol from fructus psoraleae | |
| CN101812098B (en) | Method for extracting monotropein monomers from medicinal indianmulberry root | |
| CN114989185A (en) | Extraction and preparation method of cepharanthine | |
| CN101607964B (en) | Preparation method of cycle epimedium aglucone | |
| CN110960577A (en) | Preparation method of tertiary amine alkali component in rhizoma corydalis | |
| CN111018819B (en) | Preparation method of luteolin | |
| CN101891740A (en) | Method for extracting laburnine from upper part of thermopsis lanceolate | |
| CN101177426B (en) | Process for separating extracting spherosinin from gansu whin | |
| CN100522981C (en) | Method for purifying Ramoplanin | |
| CN103275049B (en) | Method for preparing myricetin by using vine tea and application of pyrosulfite | |
| CN111053808A (en) | Preparation method of quaternary ammonium base component in corydalis tuber extract | |
| CN101606976B (en) | Method for preparing tetrandrine alkaloids by coupling in-situ conversion-adsorptive separation technology | |
| CN102532023A (en) | Purification method of yunaconitine | |
| CN105294793A (en) | Separation method for naringin in aizoon stonecrop herb | |
| CN102267877A (en) | Method for extracting and separating magnolol and honokiol from leaf of magnolia officinalis | |
| CN101759549A (en) | Method for preparing hypericins | |
| CN107473996A (en) | The extraction separation method of 4,5,9-trithiadodeca-1,6,11-triene 9-oxide in a kind of garlic | |
| CN102731606B (en) | Method for extracting corosolic acid from globeflower | |
| CN103524578B (en) | A kind of method of extraction and isolation paeoniflorin compound from tree peony stamen | |
| CN102391328B (en) | Method for simultaneously preparing chemical reference substances magnoloside A and magnoloside B |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200407 |