CN101891775B - 6-hydroxy-2-O-beta-D-glucopyranose base heptane, and preparation method and application thereof - Google Patents
6-hydroxy-2-O-beta-D-glucopyranose base heptane, and preparation method and application thereof Download PDFInfo
- Publication number
- CN101891775B CN101891775B CN201010228966.2A CN201010228966A CN101891775B CN 101891775 B CN101891775 B CN 101891775B CN 201010228966 A CN201010228966 A CN 201010228966A CN 101891775 B CN101891775 B CN 101891775B
- Authority
- CN
- China
- Prior art keywords
- water
- methanol
- acetonitrile
- mixed solvent
- methyl alcohol
- 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
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention belongs to the technical field of medicine and provides 6-hydroxy-2-O-beta-D-glucopyranose base heptane, and a preparation method and application thereof. The compound has the following structure shown in the specification. The invention also provides a preparation method of the compound. Anti-tumour in vivtro and anti-inflammatory tests prove that the compound has favorable anti-inflammatory and anti-tumour activities, and can be used for development and application of anti-inflammatory and anti-tumour drugs.
Description
Technical field
The invention belongs to medical technical field, relate to glucoside compound separation, preparation and application, be specifically related to 6-hydroxy-2-O-beta-D-glucopyranose base heptane and preparation method thereof and the application in anti-inflammatory, antitumor drug.
Background technology
Codonopsis lanceolata (Codonopsis lanceolata) has another name called Root of Lance Asiabell, sheep breast, tetraphyllous ginseng etc., is campanulaceae per nnial herb, and main product is in China, Japan and Korea S.Among the people using codonopsis lanceolata as the integration of drinking and medicinal herbs product simply with strengthening by means of tonics effect.Bibliographical information shows, contains a large amount of triterpenes components, and have certain anti-inflammatory, anti-tumor activity in codonopsis lanceolata.Researcher in this field is devoted to the mask work of codonopsis lanceolata always, and separation has obtained a series of small molecules fatty alcohol glucoside constituents, 6-hydroxy-2-O-beta-D-glucopyranose base heptane is a kind of new compound separated in codonopsis lanceolata, and has good anti-inflammatory and anti-tumor activity.But in prior art, also there is no extraction Separation Research that 6-hydroxy-2-O-beta-D-glucopyranose base heptane is relevant and the research of anti-inflammatory anti-tumor activity.
Summary of the invention
The object of this invention is to provide 6-hydroxy-2-O-beta-D-glucopyranose base heptane and its preparation method and application.
6-hydroxy-2-O-beta-D-glucopyranose base heptane provided by the invention, has following structure:
The present invention also provides the preparation method of 6-hydroxy-2-O-beta-D-glucopyranose base heptane, by following two kinds of methods, any one prepares,
Method one
(1), after codonopsis lanceolata pulverizing medicinal materials, through solvent-extraction process, adopt the ethanol of 50%-100% or methyl alcohol to soak rear refluxing extraction, extract 2-3 time, united extraction liquid, reclaim under reduced pressure extracting solution to determining alcohol lower than 5%, contained crude drug concentration 20-40g/mL, after filtration, get filtrate or centrifugal after get supernatant liquor;
(2) in step (1), gained filtrate or supernatant liquor are processed through non-polar macroporous resin column chromatography, and water and methyl alcohol or ethanol gradient elution, obtain 60%-90% alcohol wash-out position, decompression and solvent recovery successively;
(3) step (2) gained alcohol washing is separated through silica gel column chromatography, with chloroform, methyl alcohol or chloroform, methyl alcohol, water mixed solvent gradient elution;
(4) gained flow point is processed through ODS column chromatography in above-mentioned steps (3), take methanol/water or acetonitrile/water to obtain wash-out flow point as moving phase wash-out;
(5) in above-mentioned steps (4), gained flow point is through half preparation or preparation HPLC chromatographic separation, and with methanol/water, acetonitrile/water or methyl alcohol/acetonitrile/water are moving phase wash-out, obtain target new compound;
Method two
(1), after codonopsis lanceolata pulverizing medicinal materials, through solvent-extraction process, adopt the ethanol of 50%-100% or methyl alcohol to soak rear refluxing extraction, extract 2-3 time, united extraction liquid, reclaim under reduced pressure extracting solution to determining alcohol lower than 5%, contained crude drug concentration 20-40g/mL, after filtration, get filtrate or centrifugal after get supernatant liquor;
(2) gained filtrate or supernatant liquor are through the n-butanol extraction with volume ratio 1:1～1:2 2-4 time in step (1), and decompression and solvent recovery obtains n-butanol extraction position;
(3) step (2) gained n-butyl alcohol extract is separated through silica gel column chromatography, with chloroform, methyl alcohol or chloroform, methyl alcohol, water mixed solvent gradient elution;
(4) gained flow point is processed through ODS column chromatography in above-mentioned steps (3), take methanol/water or acetonitrile/water to obtain wash-out flow point as moving phase wash-out;
(5) in above-mentioned steps (4), gained flow point is through half preparation or preparation HPLC chromatographic separation, and with methanol/water, acetonitrile/water or methyl alcohol/acetonitrile/water are moving phase wash-out, obtain target new compound;
The preparation method of new 6-hydroxy-2-O-beta-D-glucopyranose base heptane provided by the invention, the alcohol of the step (2) in described method one and method two is methyl alcohol or ethanol, its gradient elution concentration is 60%-90%.
The preparation method of new 6-hydroxy-2-O-beta-D-glucopyranose base heptane provided by the invention, step (3) in described method one is that alcohol eluate is separated through silica gel column chromatography, eluting solvent is the chloroform/methanol of different ratios, chloroform/methanol/water, chloroform/methanol blending ratio is that the flow point of 5:1～3:1 contains target compound, and the flow point that chloroform/methanol/water blending ratio is 12:3:1～7:3:1 contains target compound.
The preparation method of new 6-hydroxy-2-O-beta-D-glucopyranose base heptane provided by the invention, step in described method two (3) is that n-butyl alcohol extract is separated through silica gel column chromatography, eluting solvent is the chloroform/methanol of different ratios, chloroform/methanol/water, chloroform/methanol blending ratio is that the flow point of 5:1～3:1 contains target compound, and the flow point that chloroform/methanol/water blending ratio is 12:3:1～7:3:1 contains target compound.
The preparation method of new 6-hydroxy-2-O-beta-D-glucopyranose base heptane provided by the invention, described method one is that step (3) gained flow point is further separated through ODS column chromatography with the step (4) in method two, eluting solvent is methanol/water or acetonitrile/water.Methanol/water mixed solvent ratio is that 1:9～8:2, acetonitrile/water mixed solvent ratio are 1:20～2:1.Methanol/water mixed solvent ratio is to contain target compound in 1:4～4:6, the acetonitrile/water mixed solvent ratio wash-out flow point that is 1:8～1:3.
The preparation method of new 6-hydroxy-2-O-beta-D-glucopyranose base heptane provided by the invention, described method one is that step (4) gained wash-out flow point is separated through high performance liquid chromatography with the step (5) in method two, moving phase is methanol/water, acetonitrile/water or methyl alcohol/acetonitrile/water, from methanol/water mixed solvent ratio, is that 1:5～3:7, acetonitrile/water mixed solvent ratio are that 1:10～2:8, the methyl alcohol/acetonitrile/water mixed solvent ratio flow point that is 1:1:12～1:1:6, separation obtains compound.
New 6-hydroxy-2-O-beta-D-glucopyranose base heptane compound provided by the invention has anti-inflammatory, anti-tumor activity, can be used for the exploitation of anti-inflammatory and antitumor drug.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
(1) dry codonopsis lanceolata root 10kg, pulverizes by 75% alcohol reflux three times, and each 1.5 hours, united extraction liquid reclaim under reduced pressure extracting solution was to determining alcohol lower than 5%, and contained crude drug concentration 30g/mL, gets filtrate after filtration;
(2) filtrate is through equal-volume n-butanol extraction three times, combining extraction liquid, and decompression and solvent recovery obtains n-butyl alcohol extract;
(3) step (2) gained n-butyl alcohol extract is separated through silica gel column chromatography, with chloroform: methyl alcohol 8:1,7:1,6:1,5:1,4:1,3:1,2:1 gradient elution;
(4) gained chloroform in above-mentioned steps (3): methyl alcohol 4:1 flow point is separated through ODS column chromatography, with methyl alcohol: water 3:7,5:5,6:4,7:3,8:2 gradient elution.
(5) gained 6:4 wash-out flow point in step (4), through half preparative HPLC chromatographic separation, take 15% acetonitrile/water as moving phase wash-out, and retention time locates to obtain new compound for 16 minutes, through physico-chemical property and spectral data (in Table 1), is accredited as 6-hydroxy-2-O-beta-D-glucopyranose base heptane.
Embodiment 2
(1) dry codonopsis lanceolata medicine materical crude slice 5kg is through 70% alcohol reflux twice, and each 2 hours, reclaim under reduced pressure extracting solution was to determining alcohol lower than 3%, and contained crude drug concentration 40g/mL, gets supernatant liquor after centrifugal;
(2) supernatant liquor is processed through HPD400 macroporous resin column chromatography, successively water and 60% ethanol and 90% ethanol gradient elution;
(3) step (2) gained 60% ethanol elution thing is separated through silica gel column chromatography, with chloroform: methyl alcohol: water 15:3:1,10:3:1,7:3:1,4:3:1 gradient elution;
(4) gained chloroform in above-mentioned steps (3): methyl alcohol: water 10:3:1 flow point is separated through ODS column chromatography, with methyl alcohol: water 1:9,2:8,3:7,5:5,6:4,7:3,8:2 gradient elution.
(5) gained 6:4 wash-out flow point in step (4), through half preparative HPLC chromatographic separation, take 23% methanol/water as moving phase wash-out, and retention time locates to obtain new compound for 21 minutes, through physico-chemical property and spectral data (in Table 1), is accredited as 6-hydroxy-2-O-beta-D-glucopyranose base heptane.
This compound is colourless needle (methyl alcohol).In FABMS spectrum, provide quasi-molecular ion peak m/z317[M+Na]
+, in HRFABMS spectrum, provide m/z317.1570[M+Na]
+(calcd.317.1576), determine that thus molecular weight is 294, molecular formula is C
13h
26o
7.
The NMR data of table 1 compound
The anticancer experiment in vitro test of embodiment 3 compounds 1 (6-hydroxy-2-O-beta-D-glucopyranose base heptane)
Experimental technique:
(1) cultivation of cell
The culture condition of HL-60 cell strain cell strain is RMPI1640 nutrient solution, 10% foetal calf serum, the culture condition of MCF-7 cell strain is low sugar DMEM nutrient solution 10% foetal calf serum, the culture condition of HepG2 cell strain is DMEM in high glucose nutrient solution 10% foetal calf serum, the culture condition of A549 cell strain is RMPI1640 nutrient solution, 10% calf serum.Above cell strain is all incubated at 5%CO
2, in the incubator of 37 ℃.
(2) preparation of medicine
Measured 6-hydroxy-2-O-beta-D-glucopyranose base heptane (1 and 2) is made into the mother liquor that concentration is 50mmol/L, is stored in-20 ℃.
Cell strain is used the RMPI1640 nutrient solution of serum-free that the mother liquor of medicine is diluted to 1000umol/L, 500umol/L, and 100umol/L, 10umol/L, every hole adds 10uL, and the final concentration that makes medicine is 100umol/L, 50umol/L, 10umol/L, 1umol/L.
(3) MTT experiment
Adjust cell density to 1.0～1.5 * 10
5/ ml, adds every hole 100ul in 96 well culture plates, after cultivation 24h, adds above-mentioned each concentration medicine, every hole 10ul.Every concentration is 6 multiple holes.Hatch after 72h, every hole adds 10uLMTT, hatches after 4h in incubator, detects.By supernatant liquor sucking-off, add 100ulDMSO, after vibration evenly, in microplate reader, 492nm place records OD value.
Mean value * 100% of the mean value of cell survival rate %=administration group OD value/blank breast group OD value
(4) statistical procedures method
Employing SPSS(13.0) statistical software analyzes.Result is used
represent.
Every kind of medicine will be in triplicate for the screening of three kinds of cells.Experimental result is in Table 2
The anti tumor activity in vitro experimental result of table 2 compound 1
The anti-inflammatory activity test of embodiment 4 compounds 1 (6-hydroxy-2-O-beta-D-glucopyranose base heptane)
Adopt the mice ear model of dimethylbenzene induction, the anti-inflammatory activity of test compounds 1.
Laboratory animal: the male mouse of kunming of body weight 30 ± 3g
Test method: mouse is divided into 3 groups at random by body weight, every group 8, each is organized after mouse etherization, and before and after Yu Zuoer, two sides is coated with each the 20 μ l of xylene solution that contain each compound 1 or positive drug (acetylsalicylic acid) 1mg/ml, and model control group is directly coated with 20 μ l dimethylbenzene.After three hours, mouse dislocation is put to death, with diameter 9mm punch tool, in left and right ear same position, lay ear sheet, weigh, the weight difference of left and right ear sheet is as swelling, and the significance of difference between comparative group.
Experimental result: in Table 3
The impact of table 3 compound 1 p-Xylol inducing mouse ear swelling degree
Compare *: P<0101 with model control group, compared significant difference with control group.
Claims (8)
1. the 6-hydroxy-2-O-beta-D-glucopyranose base heptane with following structure,
2. the preparation method of 6-hydroxy-2-O-beta-D-glucopyranose base heptane as claimed in claim 1, is characterized in that: comprise the steps:
(1), after codonopsis lanceolata pulverizing medicinal materials, through solvent-extraction process, adopt the ethanol of 50%-100% or methyl alcohol to soak rear refluxing extraction, extract 2-3 time, united extraction liquid, reclaim under reduced pressure extracting solution to determining alcohol lower than 5%, contained crude drug concentration 20-40g/mL, after filtration, get filtrate or centrifugal after get supernatant liquor;
(2) in step (1), gained filtrate or supernatant liquor are processed through non-polar macroporous resin column chromatography, and water and methyl alcohol or ethanol gradient elution, obtain 60%-90% alcohol wash-out position, decompression and solvent recovery successively;
(3) step (2) gained alcohol washing is separated through silica gel column chromatography, with chloroform, methyl alcohol or chloroform, methyl alcohol, water mixed solvent gradient elution; Wherein, chloroform/methanol blending ratio is 8:1～1:1; Chloroform/methanol/water blending ratio is 15:3:1～4:3:1;
(4) gained flow point is processed through ODS column chromatography in above-mentioned steps (3), take methanol/water or acetonitrile/water to obtain wash-out flow point as moving phase wash-out; Methanol/water mixed solvent ratio is that 1:9～8:2, acetonitrile/water mixed solvent ratio are 1:20～2:1;
(5) in above-mentioned steps (4), gained flow point is through half preparation or preparation HPLC chromatographic separation, and with methanol/water, acetonitrile/water or methyl alcohol/acetonitrile/water are moving phase wash-out, obtain 6-hydroxy-2-O-beta-D-glucopyranose base heptane; Methanol/water mixed solvent ratio is that 1:5～3:7, acetonitrile/water mixed solvent ratio are that 1:10～2:8, methyl alcohol/acetonitrile/water mixed solvent ratio are 1:1:12～1:1:6.
3. the preparation method of 6-hydroxy-2-O-beta-D-glucopyranose base heptane as claimed in claim 1, is characterized in that: comprise the steps:
(1), after codonopsis lanceolata pulverizing medicinal materials, through solvent-extraction process, adopt the ethanol of 50%-100% or methyl alcohol to soak rear refluxing extraction, extract 2-3 time, united extraction liquid, reclaim under reduced pressure extracting solution to determining alcohol lower than 5%, contained crude drug concentration 20-40g/mL, after filtration, get filtrate or centrifugal after get supernatant liquor;
(2) gained filtrate or supernatant liquor are through the n-butanol extraction with volume ratio 1:1～1:2 2-4 time in step (1), and decompression and solvent recovery obtains n-butanol extraction position;
(3) step (2) gained n-butyl alcohol extract is separated through silica gel column chromatography, with chloroform, methyl alcohol or chloroform, methyl alcohol, water mixed solvent gradient elution; Wherein, chloroform/methanol blending ratio is 8:1～1:1; Chloroform/methanol/water blending ratio is 15:3:1～4:3:1;
(4) gained flow point is processed through ODS column chromatography in above-mentioned steps (3), take methanol/water or acetonitrile/water to obtain wash-out flow point as moving phase wash-out; Methanol/water mixed solvent ratio is that 1:9～8:2, acetonitrile/water mixed solvent ratio are 1:20～2:1;
(5) in above-mentioned steps (4), gained flow point is through half preparation or preparation HPLC chromatographic separation, and with methanol/water, acetonitrile/water or methyl alcohol/acetonitrile/water are moving phase wash-out, obtain target new compound; Methanol/water mixed solvent ratio is that 1:5～3:7, acetonitrile/water mixed solvent ratio are that 1:10～2:8, methyl alcohol/acetonitrile/water mixed solvent ratio are 1:1:12～1:1:6.
4. according to the preparation method of 6-hydroxy-2-O-beta-D-glucopyranose base heptane claimed in claim 2, it is characterized in that: in described step (2), alcohol used is ethanol or methyl alcohol, its gradient elution concentration is 60%-90%.
5. according to the preparation method of the 6-hydroxy-2-O-beta-D-glucopyranose base heptane described in claim 2 or 3, it is characterized in that: in described step (3), chloroform/methanol blending ratio is that the flow point of 5:1～3:1 contains target compound, and the flow point that chloroform/methanol/water blending ratio is 12:3:1～7:3:1 contains target compound.
6. according to the preparation method of the 6-hydroxy-2-O-beta-D-glucopyranose base heptane described in claim 2 or 3, it is characterized in that: in described step (4), in methanol/water mixed solvent ratio, be to contain target compound in 1:4～4:6, the acetonitrile/water mixed solvent ratio wash-out flow point that is 1:8～1:3.
7. according to the preparation method of the 6-hydroxy-2-O-beta-D-glucopyranose base heptane described in claim 2 or 3, it is characterized in that: in described step (5), methanol/water mixed solvent ratio is that 1:5～3:7, acetonitrile/water mixed solvent ratio are that in 1:10～2:8, the methyl alcohol/acetonitrile/water mixed solvent ratio flow point that is 1:1:12～1:1:6, separation obtains compound.
8. the application of 6-hydroxy-2-O-beta-D-glucopyranose base heptane in preparing anti-inflammatory, antitumor drug described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010228966.2A CN101891775B (en) | 2010-07-16 | 2010-07-16 | 6-hydroxy-2-O-beta-D-glucopyranose base heptane, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010228966.2A CN101891775B (en) | 2010-07-16 | 2010-07-16 | 6-hydroxy-2-O-beta-D-glucopyranose base heptane, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101891775A CN101891775A (en) | 2010-11-24 |
| CN101891775B true CN101891775B (en) | 2014-03-12 |
Family
ID=43101146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010228966.2A Expired - Fee Related CN101891775B (en) | 2010-07-16 | 2010-07-16 | 6-hydroxy-2-O-beta-D-glucopyranose base heptane, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101891775B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2645763B2 (en) * | 1991-05-23 | 1997-08-25 | 長谷川香料株式会社 | Plant fragrance enhancer and fragrance enhancement method |
| CN1421453A (en) * | 2002-12-11 | 2003-06-04 | 中国科学院南海海洋研究所 | Structure and use of acanthus illicifolius glycoside B as one fatty alcohol glycoside compound |
| CN101322734A (en) * | 2008-07-22 | 2008-12-17 | 沈阳药科大学 | Codonopsis lanceolata total saponins with antiinflammatory immunity function and preparation thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0648B2 (en) * | 1989-09-25 | 1994-01-05 | 鐘紡株式会社 | Flavor enhancer / improver for food and drink and method for enhancing or improving flavor of food and drink |
| JP4088459B2 (en) * | 2002-02-28 | 2008-05-21 | 日本食品化工株式会社 | Novel carbohydrate and process for producing the same |
-
2010
- 2010-07-16 CN CN201010228966.2A patent/CN101891775B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2645763B2 (en) * | 1991-05-23 | 1997-08-25 | 長谷川香料株式会社 | Plant fragrance enhancer and fragrance enhancement method |
| CN1421453A (en) * | 2002-12-11 | 2003-06-04 | 中国科学院南海海洋研究所 | Structure and use of acanthus illicifolius glycoside B as one fatty alcohol glycoside compound |
| CN101322734A (en) * | 2008-07-22 | 2008-12-17 | 沈阳药科大学 | Codonopsis lanceolata total saponins with antiinflammatory immunity function and preparation thereof |
Non-Patent Citations (7)
| Title |
|---|
| JP平3-112460A 1991.05.14 |
| JP特开2003-252892A 2003.09.10 |
| KYUNG-TAE LEE，等.Structure of a New Echinocystic Acid Bisdesmoside Isolated from Codonopsis lanceolata Roots and the Cytotoxic Activity of Prosapogenins.《J. Agric. Food Chem.》.2002,第50卷(第15期),第4190-4193页. * |
| Mitsuyasu USHIJIMA，等.Triterpene Glycosides from the Roots of Codonopsis lanceolata.《Chem. Pharm. Bull.》.2008,第56卷(第3期),第308-314页. |
| Mitsuyasu USHIJIMA,等.Triterpene Glycosides from the Roots of Codonopsis lanceolata.《Chem. Pharm. Bull.》.2008,第56卷(第3期),第308-314页. * |
| 付成国,等.轮叶党参化学成分与药理作用研究进展.《中药材》.2007,第30卷(第4期),第497-499页. * |
| 梁志敏，等.轮叶党参化学成分研究.《中国中药杂志》.2007,第32卷(第13期),第1363-1364页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101891775A (en) | 2010-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101904968B (en) | Preparation method of Chinese paris rhizome yam type saponin and anti-tumor medicinal preparation thereof | |
| CN101863871B (en) | Total glycosides of Rhodiola rosea, medical application and preparation method thereof | |
| CN113307785B (en) | Abietane diterpenoid compound with anti-tumor effect, preparation method, pharmaceutical composition and application | |
| CN102977114B (en) | Inoscavin A as a monomeric component in phellinus as well as prepearation method and application thereof | |
| CN101824067A (en) | Barrigenol-type triterpenoid saponins compound, preparation method and application thereof | |
| CN104825463A (en) | Metabolic-regulation and anti-hypoxia application of ganoderma leucocontextum extract | |
| CN113336634B (en) | 17(15 → 16) -methyl abietane type diterpene compound, preparation method, pharmaceutical composition and application | |
| CN102286056A (en) | Oleanolic acid derivative and preparation method thereof | |
| CN105017345B (en) | The method of four kinds of compounds of extraction and the application simultaneously from selfheal | |
| CN101824068B (en) | Cyclic-ahltin type triterpenoid saponin compound and preparation method and application thereof | |
| CN104958330A (en) | Oroxylum indicum general flavone extraction and purification method and application thereof | |
| CN104817609B (en) | Arasaponin compound with resisting liver cancer activity and preparation method and application | |
| CN101880306B (en) | Stauntonia brachyanthera Hand-Mazz saponins components as well as preparation method and application thereof | |
| CN105198943B (en) | A kind of entitled tea hill how glycosides A acylated flavonoids glucosides and its preparation method and application | |
| CN101891775B (en) | 6-hydroxy-2-O-beta-D-glucopyranose base heptane, and preparation method and application thereof | |
| CN103191143B (en) | New application of cardiac glycoside compound | |
| CN101028322A (en) | Use of Maoliefengdou extract for preparing anti-cancer medicine | |
| CN102731464B (en) | Sesquiterpene lactone compound, its preparation methods and application | |
| CN110156859A (en) | Mustard seed acid compounds and its preparation method and application | |
| CN101537027A (en) | Extract with anti-lung cancer activity of streptocaulon juventas (Loureiro) Merrill and preparation process of compounds thereof | |
| CN114133422B (en) | Cucurbitane triterpenoid compound and preparation method and application thereof | |
| CN104926773A (en) | Method for extracting flavanone framework compounds in spina gleditsiae and application of flavanone framework compounds | |
| CN101156865A (en) | Antineoplastic new usage of cardiac glycoside compound in antiar | |
| CN104861010B (en) | A kind of new laudanum alkane type diterpene glycoside compound and its production and use | |
| CN107722087B (en) | Gynostemma pentaphylla flavonoid compound, preparation method thereof and application thereof in antitumor drugs |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140312 Termination date: 20180716 |