CN101585825B - Method for preparing amentoflavone - Google Patents
Method for preparing amentoflavone Download PDFInfo
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- CN101585825B CN101585825B CN200910012091XA CN200910012091A CN101585825B CN 101585825 B CN101585825 B CN 101585825B CN 200910012091X A CN200910012091X A CN 200910012091XA CN 200910012091 A CN200910012091 A CN 200910012091A CN 101585825 B CN101585825 B CN 101585825B
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Abstract
The invention belongs to the technical field of medicaments, and provides a method for preparing amentoflavone of which the content is over 95 percent from a Chinese medicament of herba selaginellae. The compound has a structure as shown in the formula (I). A dried herbal material of selaginella tamariscina(Beauv.)spring or selaginella pulvinata(Hook.et Grev.)maxim. is taken as an initial raw material, extracted by organic solvent and/or water, and separated by a column chromatography separation method to obtain the amentoflavone. The method has the advantages of simple process operation, goodrepeatability, high yield and the suitability for industrialized production; and the product is high in purity, and the content of the product is measured to be over 95 percent by an HPLC method.
Description
Technical field:
The present invention relates to the preparation method of Tridemethylsciadopitysin in Selaginella tamariscina (amentoflavone), its content adopts the HPLC method to detect should be more than 95%.Belong to traditional Chinese medicine extraction separation, purifying field.
Background technology:
In Chinese Pharmacopoeia version in 2005, the regulation Selaginella tamariscina is the dry herb of Spikemoss plant Selaginella tamariscina Selaginellatamariscina (Beauv.) Spring or cushion Selaginella tamariscina Selaginella pulvinata (Hook.et Grev.) Maxim..All can gather the whole year, removes fibrous root and silt, dries.Suffering, flat.Return liver, the heart channel of Hang-Shaoyin.Has promoting blood circulation to restore menstrual flow.Be used for through closing dysmenorrhoea ， Disorder lump in the abdomen lump in the abdomen, injury from falling down.The hemostasis of the Selaginella tamariscina charing stasis of blood.For spitting blood, uterine bleeding, have blood in stool, prolapse of the anus.In Selaginella tamariscina, contain the number of chemical composition, as flavonoid, have now found that in Selaginella tamariscina and contain apigenin (apigenin), Tridemethylsciadopitysin (amentoflavone), hinokiflavone (hinokiflavone), isocryptomerin (isocryptomerin) and Oman's holder yellow (amentoflavone) etc.; The compounds such as Phenylpropanoid Glycosides class, alkaloids, phenols, organic acid.Pharmacological action shows to have: immunity and antitumor action, to effects such as the effect of blood system, antiviral, antibacterial and anti-inflammatory action, antalgic and sedatives.The invention provides a kind of convenience, easy, the method for preparing fast the high purity Tridemethylsciadopitysin.In currently available technology, have no the extracting method of this Tridemethylsciadopitysin.
Summary of the invention:
Technical problem to be solved by this invention is to provide in a kind of therefrom powder stick cypress extracts the preparation method of a kind of content at the Tridemethylsciadopitysin more than 95% (amentoflavone), and purpose is by simple technological process, to obtain the Tridemethylsciadopitysin (amentoflavone) of content higher (content is greater than 95%).
Technical scheme of the present invention is: therefrom in the powder stick cypress, extract the preparation method of a kind of content at the Tridemethylsciadopitysin more than 95% (amentoflavone), its concrete grammar step is:
A) the dry herb raw material of Spikemoss plant Selaginella tamariscina Selaginella tamariscina (Beauv.) Spring or cushion Selaginella tamariscina Selaginella pulvinata (Hook.et Grev.) Maxim. is cut into to a cun section;
B) by (1: 10～10: 1) the mixed solvent refluxing extraction of mixing and/or mixing with water in proportion of a kind of and water in a kind of or ethanol and methyl alcohol in ethanol, methyl alcohol, water, add the 2-16 times of solvent that is equivalent to medicinal material weight, refluxing extraction 1-5 time, each 0.5 to 6 hour, united extraction liquid, filter, obtain extracting solution;
C) extracting solution reclaimed to solvent and be concentrated into clear cream or the thick paste that relative density is 1.05-1.40 (60 ℃), placing 0.5-24 hour, filtering, obtaining solid sediment.
D) in the sherwood oil doubly measured with 2-100 of solid sediment, ether, ethyl acetate, acetone, trichloromethane, ethanol, methyl alcohol a kind of or any two kinds in proportion (1: 10～10: 1) mixed solvent of mixing dissolve.
E) organic solvent of solid sediment or mixed organic solvents are added and take silica gel and adsorb on the chromatography column of sorbent material.
The silica gel column chromatography that f) will adsorb solid sediment with sherwood oil, ether, ethyl acetate, acetone, trichloromethane is a kind of or any two kinds in proportion (1: 10～10: 1) mixed solvent of mixing respectively with the mixed solvent wash-out of ethanol or methyl alcohol (10: 1～1: 1), with the volume of every part of 1/100～1/20 total amount eluent, collect eluent stream part respectively, take trichloromethane: methyl alcohol (10: 1～1: 1) is that developping agent adopts TLC to check spot, merges identical yellow spotting wash-out stream part.
The identical yellow spotting wash-out stream part that g) will merge reclaims solvent, obtains the yellow solid powder.
H) one or more in the sherwood oil of the yellow solid powder doubly being measured with 2-100, ether, ethyl acetate, acetone, trichloromethane, ethanol, the methyl alcohol mixed organic solvents of (1: 10～10: 1) mixing are in proportion dissolved.
I) organic solvent of yellow solid powder or mixed organic solvents are added and take Sephadex LH-20 and adsorb on the chromatography column of sorbent material.
The Sephadex LH-20 chromatography column that j) will adsorb the yellow solid powder with sherwood oil, ether, ethyl acetate, acetone, trichloromethane is a kind of or any two kinds in proportion (1: 10～10: 1) mixed solvent of mixing respectively with the mixed solvent wash-out of ethanol or methyl alcohol (10: 1～1: 1), with the volume of every part of 1/100～1/20 total amount eluent, collect respectively the yellow colour band of Sephadex LH-20 chromatography column, until fully.Take trichloromethane: methyl alcohol (10: 1～1: 1) is that developping agent adopts TLC follow-up investigations spots, merges identical yellow spotting wash-out stream part.
The identical yellow spotting wash-out stream part that k) will merge reclaims a solvent, obtains the yellow solid powder, i.e. Tridemethylsciadopitysin (amentoflavone) highly finished product, and its content adopts the HPLC method to detect should be more than 95%.
Tridemethylsciadopitysin
The Tridemethylsciadopitysin structure elucidation:
Figure The structure of amentoflavone
Yellow powder, FeCL
3Reaction, hydrochloric acid-magnesium powder reaction all is positive, and points out it may be flavonoid compound.
1H NMR (300MHz, DMSO-d
6) compose with single flavones hydrogen spectrogram and relatively find δ 6.78 (H-II 3 for 1H, s), 6.82 (H-I 3 for 1H, s) are two 3 proton signals of biflavone; And in the low place of hydrogen spectrum, 6 hydroxyl proton signals are arranged: be respectively δ 13.09 (H-I 5 for 1H, s), 12.96 (H-II 5 for 1H, s) are the 5-hydroxyl of two flavones; δ 10.55 (2H, brs, 4 " OH and H-4 " '-OH); (10.82 1H, s, 7-OH), 10.28 (1H, s, 7 " OH), in conjunction with
13C NMR (75MHz, DMSO-d
6) 30 carbon signals providing in spectrum, further point out this compound may be biflavone.δ 6.45 (1H, d, J=2.0Hz, H-8) in the hydrogen spectrum, 6.18 (1H, d, J=2.0Hz, H-6) prompt for flavone A interannular digit pair and close proton, illustrate that some flavone A rings are that 5,7-dihydroxyl replaces; In the hydrogen spectrum, a Last sharp-pointed unimodal signal is δ 6.39 (1H, s), supposition may be 6 or 8 protons of another flavones, illustrates that this biflavone compound is to be connected with certain proton of another flavones B ring by 6 on a flavones structural unit A ring or 8.δ 7.58 (2H, d, J=8.7Hz, H-2 " ', 6 " '), AA ' BB ' Coupling System that δ 6.72 (2H, d, J=8.7Hz, H-3 " ', 5 " ') forms while prompting for one of them flavones B ring para-orientation.
Now in the hydrogen spectrum, also be left 3 hydrogen signals, according to peak type and coupling constant, infer that one of them flavones B ring is the ABX Coupling System, also further illustrate simultaneously these two flavones by 3 of one of them B ring ' or 5 ' position and another flavones 6 or 8 protons be connected, specifically belong to as follows: δ 7.15 (1H, d, J=9.3Hz), δ 8.01 (1H, d, J=2.0Hz, 6.9Hz), δ 7.99 (1H, d, J=2.0Hz) (above formation ABX system).By with single flavones
13C NMR compares, and the C-8 of one of them flavones shifts to low place, and chemical displacement value increases about 6ppm, shows and really has other group to be connected, and in conjunction with the ABX Coupling System that flavones B ring in the hydrogen spectrum exists, infers that further two single flavones are really with 3 '-8 and " connects.According to above proton distribution situation, this compound is amentoflavone therefore infer.Structure such as Figure.
Table amentoflavone
1HNMR and
13C NMR attribution data (300,75MHz, DMSO-d
6)
Advantage of the present invention is:
(1) technological operation is simple, reproducible, and productive rate is high, is suitable for suitability for industrialized production.
(2) purity of this product is higher, and its content adopts the HPLC method to detect more than 95%.
The application of Tridemethylsciadopitysin (amentoflavone):
(1) Tridemethylsciadopitysin of the present invention (amentoflavone) is suitable for preparing the a kind new medicine preparation used clinically.
(2) Tridemethylsciadopitysin of the present invention (amentoflavone) also can with other compound or Drug combination, the new drug preparation that preparation is used clinically.
(3) Tridemethylsciadopitysin of the present invention (amentoflavone) can be made the various pharmaceutical dosage forms that use clinically.
(3) Tridemethylsciadopitysin of the present invention (amentoflavone) also can be used as reference substance.
(4) Tridemethylsciadopitysin of the present invention (amentoflavone) also can be made various protective foods and the functional cosmetics that use clinically.
Embodiment:
Below in conjunction with embodiment, carry out more detailed description the present invention, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1:
By dry Selaginella tamariscina herb 100g, be cut into a cun section, add 30% alcohol reflux three times, add 11 times of amounts at every turn, each 2 hours, united extraction liquid, filtered, and obtains extracting solution.Extracting solution is reclaimed to ethanol and be concentrated into the clear cream that relative density is 1.30 (60 ℃), placed 12 hours, filter, obtain solid sediment.By after the dissolve with methanol of solid sediment by 40 times of amounts, adding, take silica gel and adsorb on the chromatography column of sorbent material.The silica gel column chromatography mixed solvent gradient elution of trichloromethane and methyl alcohol (10: 1～1: 1), volume with every part of 1/40 total amount eluent is collected eluent stream part, adopt TLC to check spot (take trichloromethane: methyl alcohol be developping agent at 3: 1), merges identical yellow spotting wash-out and flow part.The identical yellow spotting wash-out stream part merged is reclaimed to solvent, obtain the yellow solid powder.By after the acetone solution of yellow solid powder by 30 times of amounts, add and take Sephadex LH-20 and adsorb on the chromatography column of sorbent material.By the mixed solvent wash-out of Sephadex LH-20 chromatography column with trichloromethane and methyl alcohol (3: 1), with the volume of every part of 1/30 total amount eluent, collect respectively the yellow colour band of Sephadex LH-20 chromatography column, until fully.Adopt TLC follow-up investigations spot (take trichloromethane: methyl alcohol be developping agent at 4: 1), merges identical yellow spotting wash-out and flow part.The identical yellow spotting wash-out stream part merged is reclaimed to a solvent, obtain the yellow solid powder, i.e. Tridemethylsciadopitysin (amentoflavone) highly finished product, it is on 98.1% that its content adopts the HPLC method to detect.
Embodiment 2:
By dry Selaginella tamariscina herb 2kg, be cut into a cun section, add 75% alcohol reflux three times, add 10 times of amounts at every turn, each 1.5 hours, united extraction liquid, filtered, and obtains extracting solution.Extracting solution is reclaimed to ethanol and be concentrated into the clear cream that relative density is 1.10 (60 ℃), placed 8 hours, filter, obtain solid sediment.By after the acetic acid ethyl dissolution of solid sediment by 30 times of amounts, adding, take silica gel and adsorb on the chromatography column of sorbent material.The silica gel column chromatography mixed solvent gradient elution of trichloromethane and methyl alcohol (10: 1～1: 1), volume with every part of 1/30 total amount eluent is collected eluent stream part, adopt TLC to check spot (take trichloromethane: methyl alcohol be developping agent at 2: 1), merges identical yellow spotting wash-out and flow part.The identical yellow spotting wash-out stream part merged is reclaimed to solvent, obtain the yellow solid powder.By after the acetone solution of yellow solid powder by 20 times of amounts, add and take Sephadex LH-20 and adsorb on the chromatography column of sorbent material.By the mixed solvent wash-out of Sephadex LH-20 chromatography column with trichloromethane and methyl alcohol (4: 1), with the volume of every part of 1/20 total amount eluent, collect respectively the yellow colour band of SephadexLH-20 chromatography column, until fully.Adopt TLC follow-up investigations spot (take trichloromethane: methyl alcohol be developping agent at 2: 1), merges identical yellow spotting wash-out and flow part.The identical yellow spotting wash-out stream part merged is reclaimed to a solvent, obtain the yellow solid powder, i.e. Tridemethylsciadopitysin (amentoflavone) highly finished product, it is 96.6% that its content adopts the HPLC method to detect.
Embodiment 3:
By dry Selaginella tamariscina herb 30kg, be cut into a cun section, add 50% alcohol reflux three times, add 9 times of amounts at every turn, each 1.5 hours, united extraction liquid, filtered, and obtains extracting solution.Extracting solution is reclaimed to ethanol and be concentrated into the clear cream that relative density is 1.25 (60 ℃), placed 6 hours, centrifugal, obtain solid sediment.By after the acetone solution of solid sediment by 20 times of amounts, adding, take silica gel and adsorb on the chromatography column of sorbent material.The silica gel column chromatography mixed solvent gradient elution of trichloromethane and methyl alcohol (10: 1～1: 1), volume with every part of 1/20 total amount eluent is collected eluent stream part, adopt TLC to check spot (take trichloromethane: methyl alcohol be developping agent at 3: 1), merges identical yellow spotting wash-out and flow part.The identical yellow spotting wash-out stream part merged is reclaimed to solvent, obtain the yellow solid powder.By after the acetone solution of yellow solid powder by 10 times of amounts, add and take Sephadex LH-20 and adsorb on the chromatography column of sorbent material.By the mixed solvent wash-out of Sephadex LH-20 chromatography column with trichloromethane and methyl alcohol (3: 1), with the volume of every part of 1/30 total amount eluent, collect respectively the yellow colour band of Sephadex LH-20 chromatography column, until fully.Adopt TLC follow-up investigations spot (take trichloromethane: methyl alcohol be developping agent at 3: 1), merges identical yellow spotting wash-out and flow part.The identical yellow spotting wash-out stream part merged is reclaimed to a solvent, obtain the yellow solid powder, i.e. Tridemethylsciadopitysin (amentoflavone) highly finished product, it is 95.3% that its content adopts the HPLC method to detect.
Claims (3)
1. the preparation method of a Tridemethylsciadopitysin, it is characterized in that: described concrete grammar comprises the following steps:
The dry herb raw material of Spikemoss plant Selaginella tamariscina Selaginella tamariscina (Beauv.) Spring or cushion Selaginella tamariscina Selaginella pulvinata (Hook.et Grev.) Maxim. is cut into to a cun section;
By the 1:10～10:1 mixed solvent refluxing extraction of mixing in proportion of a kind of and water in a kind of or ethanol in ethanol, methyl alcohol, water and methyl alcohol, add the 2-16 times of solvent that is equivalent to medicinal material weight, refluxing extraction 1-5 time, each 0.5 to 6 hour, united extraction liquid, filter, and obtains extracting solution;
Extracting solution is reclaimed to solvent and be concentrated into clear cream or the thick paste that 60 ℃ of lower relative densities are 1.05-1.40, place 0.5-24 hour, filter, obtain solid sediment;
A kind of or any two kinds of mixed solvent dissolvings of 1:10～10:1 mixing in proportion in the sherwood oil that solid sediment is doubly measured with weight/volume 2-100, ether, ethyl acetate, acetone, trichloromethane, ethanol, methyl alcohol;
The organic solvent of solid sediment or mixed organic solvents are added and take silica gel and adsorb on the chromatography column of sorbent material;
By the silica gel column chromatography of absorption solid sediment with sherwood oil, ether, ethyl acetate, acetone, trichloromethane is a kind of or any two kinds in proportion the mixed solvent that mixes of 1:10～10:1 respectively with the mixed solvent wash-out of ethanol or methyl alcohol 10:1～1:1, with the volume of every part of 1/100～1/20 total amount eluent, collect eluent stream part respectively, take trichloromethane: methyl alcohol 10:1～1:1 is that developping agent adopts TLC to check spot, merges identical yellow spotting wash-out stream part;
The identical yellow spotting wash-out stream part merged is reclaimed to solvent, obtain the yellow solid powder;
In the sherwood oil that the yellow solid powder is doubly measured with 2-100, ether, ethyl acetate, acetone, trichloromethane, ethanol, methyl alcohol a kind of or any two kinds in proportion the mixed organic solvents that mixes of 1:10～10:1 dissolve;
The organic solvent of yellow solid powder or mixed organic solvents are added and take Sephadex LH-20 and adsorb on the chromatography column of sorbent material;
By the Sephadex LH-20 chromatography column of absorption yellow solid powder with sherwood oil, ether, ethyl acetate, acetone, trichloromethane is a kind of or any two kinds in proportion the mixed solvent that mixes of 1:10～10:1 respectively with the mixed solvent wash-out of ethanol or methyl alcohol 10:1～1:1, with the volume of every part of 1/100～1/20 total amount eluent, collect respectively the yellow colour band of Sephadex LH-20 chromatography column, until fully; Take trichloromethane: methyl alcohol 10:1～1:1 is that developping agent adopts TLC follow-up investigations spots, merges identical yellow spotting wash-out stream part;
The identical yellow spotting wash-out stream part merged is reclaimed to a solvent, obtain the yellow solid powder, i.e. Tridemethylsciadopitysin highly finished product, its content adopts the HPLC method to detect should be more than 95%.
2. preparation method according to claim 1 is characterized in that: prepared Tridemethylsciadopitysin and pharmaceutically acceptable carrier or vehicle are in conjunction with being prepared into acceptable various preparation clinically.
3. preparation method according to claim 2, it is characterized in that: described preparation is tablet, capsule, granule, injection or dripping pill.
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| CN101732306B (en) * | 2009-12-03 | 2013-11-06 | 沈阳药科大学 | New application of natural product amentoflavone in treating cancers |
| CN102285950B (en) * | 2011-09-07 | 2013-03-20 | 上海交通大学 | Application of amentoflavone |
| CN102731592B (en) * | 2012-06-25 | 2015-09-23 | 湖南农业大学 | A kind of method extracting oleuropein and Tridemethylsciadopitysin from olive leaf |
| CN103087025A (en) * | 2013-02-22 | 2013-05-08 | 天津科技大学 | Complete synthesis method of secondary metabolic active component amentoflavone |
| CN109320486A (en) * | 2017-08-01 | 2019-02-12 | 复旦大学 | A kind of method of amentoflavone in infrared extraction Selaginella tamariscina |
| CN114394950B (en) * | 2022-01-19 | 2023-03-28 | 四川省中医药科学院 | Biflavonoid compound for resisting I-type simplex herpes virus as well as preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101361765A (en) * | 2008-09-19 | 2009-02-11 | 湖北中医学院 | Anti-coxsackie and anti-herpesvirus extract of selaginella tamariscina and extraction technique and formulation thereof |
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| JPH09263534A (en) * | 1996-03-29 | 1997-10-07 | Sunstar Inc | Promoter for melanogenesis |
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| CN101361765A (en) * | 2008-09-19 | 2009-02-11 | 湖北中医学院 | Anti-coxsackie and anti-herpesvirus extract of selaginella tamariscina and extraction technique and formulation thereof |
Non-Patent Citations (3)
| Title |
|---|
| Hyun Jun Jung，等.Antifungal Effect of Amentoflavone derived from Selaginella tamariscina.《Arch. Pharm. Res.》.2006,第29卷(第9期), * |
| JP特开平9-263534A 1997.10.07 |
| Shuang-Cheng MA，等.Antiviral Amentoflavone from Selaginella sinensis.《Biol. Pharm. Bull.》.2001,第24卷(第3期), * |
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