CN105001243B - A kind of method that preparing chromatograph in industry purifies vinorelbine - Google Patents
A kind of method that preparing chromatograph in industry purifies vinorelbine Download PDFInfo
- Publication number
- CN105001243B CN105001243B CN201510398974.4A CN201510398974A CN105001243B CN 105001243 B CN105001243 B CN 105001243B CN 201510398974 A CN201510398974 A CN 201510398974A CN 105001243 B CN105001243 B CN 105001243B
- Authority
- CN
- China
- Prior art keywords
- eluent
- vinorelbine
- silica gel
- methanol
- purity
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
- C07D519/04—Dimeric indole alkaloids, e.g. vincaleucoblastine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that preparing chromatograph in industry purifies vinorelbine.Including(1)Use organic solvent A be swelled after silica gel for chromatographic column filler prepare chromatographic column;(2)Vinorelbine crude product organic solvent A solution is added into above-mentioned chromatographic column;(3)Chromatographic column is eluted using the method for gradient elution, the organic solvent A being gradually reduced successively with volume ratio/organic solvent B mixed liquor is eluted as eluent, collect main composition efflux, finally wash lower residue;(4)Be concentrated under reduced pressure recovery eluant, eluent, obtains high-purity vinorelbine.Products obtained therefrom purity of the present invention is high, and this method can make the purity of vinorelbine reach more than 98%, and yield is 60~98%.Stationary phase is stable, reusable.
Description
Technical field
The present invention relates to the separating and purifying technology of vinorelbine, more particularly to a kind of preparing chromatograph in industry purifying length
Spring Rui Bin method, belongs to chemical pharmacy field.
Background technology
Vinorelbine(English name:vinorelbine)It is the plant series antineoplastic medicament of the listing nineties in last century, so far
It is still the First-line chemotherapy medicine of the common cancers such as breast cancer, non-small cell lung cancer that the comprehensive cancer guide of American National is recommended
Thing, and it is widely used in other malignant tumours such as oophoroma, lymthoma.It by with tubulin binding, cell is being had silk
Micro-pipe formation obstacle in fission process, structural formula is as follows:
Vinorelbine
It is few that the country is studied vinorelbine technical grade isolation and purification method.Chinese patent CN10781322A is disclosed
A kind of isolation and purification method of vinorelbine crude product, after crude product is eluted through alkali alumina post, obtains just sterling, then through C18It is anti-phase
Filled column is eluted, and eluent is extracted through dichloromethane, again with methanol is recrystallized to give vinorelbine sterling;
Chinese patent CN 102199165A disclose vinorelbine crude product through silica gel column chromatography, alkali alumina column chromatography
The technique for obtaining high purity product afterwards, but the processing step is various, and production cost is high, is not suitable for industrialized production.
Chinese patent CN103788117A discloses lab scale purifying process of the vinorelbine as intermediate products, by silica gel
Column chromatography, product purity is up to more than 99%, but yield is only 27% or so, and the process economy is low, is not suitable for industrialized production.
The present invention have studied a kind of method that preparing chromatograph in industry prepares high-purity vinorelbine, and product purity is high(98% with
On), and process recovery ratio is stable, is adapted to industrialized production.
The content of the invention
For problems such as the low, complex process of vinorelbine purification efficiency, it is an object of the invention to provide a kind of high-purity, behaviour
The property made is strong, be adapted to the purification process of the vinorelbine of industrialized production.
To achieve these goals, the present invention is adopted the following technical scheme that:
A kind of purification process of vinorelbine, comprises the following steps:
(1)Use organic solvent A be swelled after silica gel for chromatographic column filler prepare chromatographic column;
(2)Above-mentioned chromatographic column will be added with organic solvent A after vinorelbine dissolving crude product;
(3)Chromatographic column is eluted using the method for gradient elution, the organic solvent being gradually reduced successively with volume ratio
A/ organic solvent B mixed liquors are eluted as eluent, collect main composition efflux, lower residue is finally washed with solvent;
(4)Be concentrated under reduced pressure recovery eluant, eluent, obtains high-purity vinorelbine, more than the wt% of purity 98, and yield is 60~
98%。
In above-mentioned preparation method:
Step(1)In, silica gel is used for 100~400 mesh;
Step(1)In, the organic solvent A is dichloromethane, n-butanol, methyl isopropyl ketone, ethyl acetate, chloroform, two
One kind in the ring of oxygen six;
Step(2)In, vinorelbine applied sample amount is 1~6 (w/w%), and inlet amount is the 1~12% of preparation chromatogram column volume;
Step(3)In, the organic solvent B is one in acetone, acetonitrile, dimethylformamide, methanol, dimethyl sulfoxide
Kind;
Step(3)In, eluant, eluent is entered using constant pressure and flow pump, eluant, eluent is followed successively by solvent orange 2 A:B=99:1~75:1(v/v)、
Solvent orange 2 A:B=65:1~45:1 (v/v), solvent orange 2 A:B=45:1~15:1 (v/v), eluting agent for column volume 200~
500%, elution flow rate is the 1~10% of elution column volume per minute;The pressure for preparing chromatographic column operation is 0.1~0.7 MPa;
Step(3)In, eluent Fractional Collections, collection is divided to two sections, and first paragraph collects solvent orange 2 A:B=65:1~45:1(v/v)
Cut, is the relatively low vinorelbine eluent of content;Second segment collects solvent orange 2 A:B=45:1~15:1 (v/v) cut, predominantly
High concentration vinorelbine eluent.
Step(3)In, using solvent orange 2 A:B=15:1~5:1 (v/v) elutes residue.
The present invention, by silica gel preparing chromatograph in industry purifies and separates, is realized high-purity using vinorelbine crude product as initiation material
Spend the preparation of vinorelbine.The invention has the advantages that:
1st, product purity is high, and this method can make the purity of vinorelbine reach more than 98%, and yield is 60~98%.Stationary phase
It is stable, it is reusable;
2nd, the eluant, eluent that uses of the present invention is easily reclaimed, can Reusability, production cost is low;
3rd, technical process is simple, and equipment disposably puts into small, and energy consumption is low, workable, is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the liquid-phase chromatographic analysis collection of illustrative plates for the vinorelbine crude material that the embodiment of the present invention 1 is used.
Fig. 2 is the liquid-phase chromatographic analysis collection of illustrative plates for the vinorelbine product that the embodiment of the present invention 1 is obtained.
Embodiment
Embodiment 1
1) the mesh silica gel of 5.96 kg 300 is weighed, chloroform is added and stirs, bubble in discharge silica gel is then uniform by silica gel
Ground is attached in preparation chromatogram, and column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, is filled
Good preparation chromatographic column;
2) by 270g vinorelbine crude products(Purity is 67.00%)Dissolved, fed, inlet amount is 300ml with chloroform;
3) eluant, eluent is entered using constant pressure and flow pump, first uses chloroform:Methanol=90:1 solvent elutes 2 beds, uses chloroform instead:
Methanol=40:1 solvent elutes 3 beds and collects eluent a, then uses chloroform instead:Methanol=30:1 solvent elutes 4 beds and received
Collect eluent b, finally use chloroform instead:Methanol=15:1 elution prepares residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 116g is obtained, liquid chromatographic detection purity is 99.72%, and yield is
63.94%。
The liquid-phase chromatographic analysis collection of illustrative plates of vinorelbine crude material is as shown in figure 1, the liquid chromatogram point of vinorelbine product
Analyse collection of illustrative plates as shown in Figure 2.
Embodiment 2
1) the mesh silica gel of 6.05 kg 400 is weighed, chloroform is added and stirs, bubble in discharge silica gel is then uniform by silica gel
Ground is attached in preparation chromatogram, and column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, is filled
Good preparation chromatographic column;
2) by 268g vinorelbine crude products(Purity is 67%)Dissolved, fed, inlet amount is 280ml with chloroform;
3) eluant, eluent is entered using constant pressure and flow pump, first uses chloroform:Methanol=95:1 solvent elutes 2 beds, uses chloroform instead:
Methanol=45:1 solvent elutes 3 beds and collects eluent a, then uses chloroform instead:Methanol=35:1 solvent elutes 4 beds and received
Collect eluent b, finally use chloroform instead:Methanol=15:1 elution prepares residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 178g is obtained, liquid chromatographic detection purity is 99.1%, and yield is
98.24%。
Embodiment 3
1) the mesh silica gel of 5.98 kg 200 is weighed, chloroform is added and stirs, bubble in discharge silica gel is then uniform by silica gel
Ground is attached in preparation chromatogram, and column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, is filled
Good preparation chromatographic column;
2) by 290g vinorelbine crude products(Purity is 79.21%)Dissolved, fed, inlet amount is 320ml with chloroform;
3) eluant, eluent is entered using constant pressure and flow pump, first uses chloroform:Methanol=90:1 solvent elutes 3 beds, uses chloroform instead:
Methanol=40:1 solvent elutes 3 beds and collects eluent a, then uses chloroform instead:Methanol=30:1 solvent elutes 4 beds and received
Collect eluent b, finally use chloroform instead:Methanol=10:1 elution prepares residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 187g is obtained, liquid chromatographic detection purity is 98.31%, and yield is
80.03%。
Embodiment 4
1) the mesh silica gel of 5.96 kg 300 is weighed, dichloromethane is added and stirs, bubble in discharge silica gel, then by silica gel
Equably it is attached in preparation chromatogram, column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, obtains
To the preparation chromatographic column installed;
2) by 290g vinorelbine crude products(Purity is 79.21%)Dissolved, fed, inlet amount is 320ml with dichloromethane;
3) eluant, eluent is entered using constant pressure and flow pump, first uses dichloromethane:Acetonitrile=80:1 solvent elutes 2 beds, uses two instead
Chloromethanes:Acetonitrile=35:1 solvent elutes 3 beds and collects eluent a, then uses dichloromethane instead:Acetonitrile=25:1 solvent is eluted
4 beds simultaneously collect eluent b, finally use dichloromethane instead:Acetonitrile=5:1 elution prepares residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 212g is obtained, liquid chromatographic detection purity is 98.18%, and yield is
90.62%。
Embodiment 5
1) the mesh silica gel of 5.97 kg 400 is weighed, dichloromethane is added and stirs, bubble in discharge silica gel, then by silica gel
Equably it is attached in preparation chromatogram, column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, obtains
To the preparation chromatographic column installed;
2) by 255g vinorelbine crude products(Purity is 79.65%)Dissolved, fed, inlet amount is 290ml with dichloromethane;
3) eluant, eluent is entered using constant pressure and flow pump, first uses dichloromethane:Acetonitrile=85:1 solvent elutes 3 beds, uses two instead
Chloromethanes:Acetonitrile=45:1 solvent elutes 4 beds and collects eluent a, then uses dichloromethane instead:Acetonitrile=30:1 solvent is eluted
4 beds simultaneously collect eluent b, finally use dichloromethane instead:Acetonitrile=5:1 elution prepares residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 189.5g is obtained, liquid chromatographic detection purity is 98.12%, and yield is
91.55%。
Embodiment 6
1) the mesh silica gel of 6.20 kg 300 is weighed, ethyl acetate is added and stirs, bubble in discharge silica gel, then by silica gel
Equably it is attached in preparation chromatogram, column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, obtains
To the preparation chromatographic column installed;
2) by 250g vinorelbine crude products(Purity is 79.65%)Dissolved, fed, inlet amount is 290ml with ethyl acetate;
3) eluant, eluent is entered using constant pressure and flow pump, first uses ethyl acetate:Methanol=99:1 solvent elutes 2 beds, uses second instead
Acetoacetic ester:Methanol=50:1 solvent elutes 3 beds and collects eluent a, then uses ethyl acetate instead:Methanol=35:1 solvent is eluted
3 beds simultaneously collect eluent b, finally use ethyl acetate instead:Methanol=10:1 elution is prepared in chromatographic column and remained
Thing;
4)Eluent b is recovered under reduced pressure, vinorelbine 196.6g is obtained, liquid chromatographic detection purity is 98.35%, and yield is
97.1%。
Embodiment 7
1) the mesh silica gel of 6.10 kg 400 is weighed, ethyl acetate is added and stirs, bubble in discharge silica gel, then by silica gel
Equably it is attached in preparation chromatogram, column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, the preparation chromatogram installed
Post;
2) by 260g vinorelbine crude products(Purity is 70.57%)Dissolved, fed, inlet amount is 280ml with ethyl acetate;
3) eluant, eluent is entered using constant pressure and flow pump, first uses ethyl acetate:Methanol=98:1 solvent elutes 2 beds, uses second instead
Acetoacetic ester:Methanol=48:1 solvent elutes 3 beds and collects eluent a, then uses ethyl acetate instead:Methanol=30:1 solvent is eluted
2 beds simultaneously collect eluent b, finally use ethyl acetate instead:Methanol=10:1 elution is prepared in chromatographic column and remained
Thing;
4)Eluent b is recovered under reduced pressure, vinorelbine 130g is obtained, liquid chromatographic detection purity is 98.47%, and yield is
69.77%。
Embodiment 8
1) the mesh silica gel of 5.90 kg 400 is weighed, chloroform is added and stirs, bubble in discharge silica gel is then uniform by silica gel
Ground is attached in preparation chromatogram, and column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, is filled
Good preparation chromatographic column;
2) by 220g vinorelbine crude products(Purity is 82.79%)Dissolved, fed, inlet amount is 250ml with chloroform;
3) eluant, eluent is entered using constant pressure and flow pump, first uses chloroform:Acetone=75:1 solvent elutes 3 beds, uses chloroform instead:
Acetone=40:1 solvent elutes 3 beds and collects eluent a, then uses chloroform instead:Acetone=25:1 solvent elutes 2 beds and received
Collect eluent b, finally use chloroform instead:Acetone=5:1 elution prepares residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 122g is obtained, liquid chromatographic detection purity is 98.43%, and yield is
65.93%。
Embodiment 9
1) the mesh silica gel of 5.80 kg 300 is weighed, chloroform is added and stirs, bubble in discharge silica gel is then uniform by silica gel
Ground is attached in preparation chromatogram, and column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, is filled
Good preparation chromatographic column;
2) by 216g vinorelbine crude products(Purity is 79.19%)Dissolved, fed, inlet amount is 240ml with chloroform;
3) eluant, eluent is entered using constant pressure and flow pump, first uses chloroform:Acetone=80:1 solvent elutes 3 beds, uses chloroform instead:
Acetone=45:1 solvent elutes 3 beds and collects eluent a, then uses chloroform instead:Acetone=30:1 solvent elutes 2 beds and received
Collect eluent b, finally use chloroform instead:Acetone=5:1 elution prepares residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 156g is obtained, liquid chromatographic detection purity is 98.57%, and yield is
89.90%。
Embodiment 10
1) the mesh silica gel of 6.20 kg 300 is weighed, chloroform is added and stirs, bubble in discharge silica gel is then uniform by silica gel
Ground is attached in preparation chromatogram, and column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, is filled
Good preparation chromatographic column;
2) by 216g vinorelbine crude products(Purity is 79.19%)Dissolved, fed, inlet amount is 250ml with chloroform;
3) eluant, eluent is entered using constant pressure and flow pump, first uses chloroform:Acetone=75:1 solvent elutes 3 beds, uses chloroform instead:
Acetone=45:1 solvent elutes 3 beds and collects eluent a, then uses chloroform instead:Acetone=30:1 solvent elutes 2 beds and received
Collect eluent b, finally use chloroform instead:Acetone=5:1 elution prepares residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 160g is obtained, liquid chromatographic detection purity is 98.1%, and yield is
91.76%。
Claims (2)
1. a kind of purification process of vinorelbine, it is characterised in that comprise the following steps:
1) the mesh silica gel of 6.05 kg 400 is weighed, chloroform is added and stirs, then bubble in discharge silica gel equably fills silica gel
To preparing in chromatogram, column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, is installed
Prepare chromatographic column;
2) by the vinorelbine crude product that 268g purity is 67%, dissolved, fed, inlet amount is 280ml with chloroform;
3) eluant, eluent is entered using constant pressure and flow pump, first uses chloroform:Methanol=95:1 (v/v) solvent elutes 2 beds, uses chloroform instead:
Methanol=45:1 (v/v) solvent elutes 3 beds and collects eluent a, then uses chloroform instead:Methanol=35:1 (v/v) solvent elution 4
Individual bed simultaneously collects eluent b, finally uses chloroform instead:Methanol=15:1 (v/v) elution is prepared in chromatographic column and remained
Thing;
4)Eluent b is recovered under reduced pressure, vinorelbine 178g is obtained, liquid chromatographic detection purity is 99.1%, and yield is 98.24%.
2. a kind of purification process of vinorelbine, it is characterised in that comprise the following steps:
1) the mesh silica gel of 6.20 kg 300 is weighed, ethyl acetate is added and stirs, bubble in discharge silica gel is then uniform by silica gel
Ground is attached in preparation chromatogram, and column dimension is Φ 20cm × 52cm, after the compacting of stationary phase silica gel, rinses 2h with eluant, eluent, is filled
Good preparation chromatographic column;
2) by the vinorelbine crude product that 250g purity is 79.65%, dissolved, fed, inlet amount is 290ml with ethyl acetate;
3) eluant, eluent is entered using constant pressure and flow pump, first uses ethyl acetate:Methanol=99:1 (v/v) solvent elutes 2 beds, uses instead
Ethyl acetate:Methanol=50:1 (v/v) solvent elutes 3 beds and collects eluent a, then uses ethyl acetate instead:Methanol=35:1
(v/v) solvent elutes 3 beds and collects eluent b, finally uses ethyl acetate instead:Methanol=10:1 (v/v) elution
Prepare residue in chromatographic column;
4)Eluent b is recovered under reduced pressure, vinorelbine 196.6g is obtained, liquid chromatographic detection purity is 98.35%, and yield is
97.1%。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510398974.4A CN105001243B (en) | 2015-07-08 | 2015-07-08 | A kind of method that preparing chromatograph in industry purifies vinorelbine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510398974.4A CN105001243B (en) | 2015-07-08 | 2015-07-08 | A kind of method that preparing chromatograph in industry purifies vinorelbine |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105001243A CN105001243A (en) | 2015-10-28 |
CN105001243B true CN105001243B (en) | 2017-07-14 |
Family
ID=54374142
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510398974.4A Active CN105001243B (en) | 2015-07-08 | 2015-07-08 | A kind of method that preparing chromatograph in industry purifies vinorelbine |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105001243B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109206442A (en) * | 2017-06-29 | 2019-01-15 | 江苏汉邦科技有限公司 | A kind of preparation method of vinorelbine monomer |
CN109988184B (en) * | 2017-12-29 | 2021-12-17 | 江苏豪森药业集团有限公司 | Purification method of vinorelbine |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104725405A (en) * | 2013-12-20 | 2015-06-24 | 中国医药研究开发中心有限公司 | Preparation method of vinorelbine |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101638413B (en) * | 2009-08-28 | 2011-12-14 | 广州汉方现代中药研究开发有限公司 | Separation and purification method for vinca alkaloids |
-
2015
- 2015-07-08 CN CN201510398974.4A patent/CN105001243B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104725405A (en) * | 2013-12-20 | 2015-06-24 | 中国医药研究开发中心有限公司 | Preparation method of vinorelbine |
Non-Patent Citations (1)
Title |
---|
抗肿瘤药长春碱的提取分离工艺研究;李晓蕾;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20040915(第3期);B016-238 * |
Also Published As
Publication number | Publication date |
---|---|
CN105001243A (en) | 2015-10-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105001243B (en) | A kind of method that preparing chromatograph in industry purifies vinorelbine | |
CN105384746B (en) | The method that ungernine is extracted from the bulb of vegetation water ghost any of several broadleaf plants | |
CN106243078B (en) | The preparation method and purposes of compound in Fu Kangshu | |
CN105601693B (en) | Ginseng saponin F1Preparation and its antitumor action | |
CN107011170A (en) | Fucoxanthine derivative and its preparation method and application | |
CN107880063B (en) | A kind of synthetic method of dauricine | |
CN104892642A (en) | Method for purifying vindesine | |
CN109942663A (en) | The method for preparing cycloastragenol using two-phase sour water solution | |
CN105924484B (en) | The method of quercetin derivative is extracted from Camellia Leaves | |
CN110790777B (en) | Vincristine compound impurity and preparation method and application thereof | |
CN107759448B (en) | Preparation method of beta-asarone reference substance and product thereof | |
CN107074798B (en) | Method for extracting phytoxin from rhodiola rosea | |
CN108299519A (en) | A method of preparing poliumoside and 2 '-acetyl group poliumosides from husky desert cistanche | |
CN105294802B (en) | A kind of preparation method of ganodermenonol | |
CN113372407B (en) | Steroid saponin compound and preparation method and application thereof | |
CN113943332B (en) | Method for preparing high-purity paeoniflorin by dynamic axial compression chromatography | |
CN109879850A (en) | A method of preparing three kinds of polyester catechins monomers | |
CN104628799B (en) | Impurity A and its separation method in a kind of Troxerutin | |
CN103965298B (en) | A kind of purification process of anidulafungin | |
CN113735922B (en) | Method for extracting lignans or terpenoids from cymbidium sinense | |
CN109251232B (en) | New active ingredient of kudzuvine root and application thereof | |
CN114702388B (en) | Compound in rabdosia rubescens and extraction and separation method and application thereof | |
CN108250217A (en) | A kind of method for preparing immunosuppressor sirolimus | |
CN101270143B (en) | Triterpene saponin antineoplastic compound, preparing method and uses | |
CN107298695A (en) | A kind of method for extracting pecan shell sterol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |