CN1569887A - Method for preparing spirosta saponin TTS-12 from traditional Chinese medicine caltrop - Google Patents
Method for preparing spirosta saponin TTS-12 from traditional Chinese medicine caltrop Download PDFInfo
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- CN1569887A CN1569887A CN 200410018318 CN200410018318A CN1569887A CN 1569887 A CN1569887 A CN 1569887A CN 200410018318 CN200410018318 CN 200410018318 CN 200410018318 A CN200410018318 A CN 200410018318A CN 1569887 A CN1569887 A CN 1569887A
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Abstract
The invention provides a novel process for preparing steroidal saponin tigogenin -0-3-beta-D-xylopyranose (1,2)-[beta-D-xylopyranose (1,3)-[beta-D-glucopyranose (1,4)-[alpha-L-pyranrhamnose (1,2)]-beta-D-galactopyranoside (TTS-12) from caltrop, which consists of, (1) extracting steroid saponin TTS-12 extract through ethanol backflow, (2) decompressing, concentrating the extract, stewing, obtaining deposition by centrifugation, (3) subjecting the deposition to silica gel column chromatography for segregation and purification, thus obtaining semifinished product of TTS-12, recrystallizing with methanol or alcohol to obtain the TTS-12 refined produce.
Description
Technical field
The present invention relates to medical technical field, is that the preparation spirostanol saponin replaces the novel method of accusing sapogenin-O-3-β-D-xylopyranose (1 → 2)-[β-D-xylopyranose (1 → 3)]-β-D-Glucopyranose (1 → 4)-[α-L-pyrans rhamnosyl (1 → 2)]-β-D-galactopyranoside (abbreviation TTS-12) from the Chinese medicine puncturevine herb.
Background technology
The thick saponin(e preparation (as XINNAOSHUTONG JIAONANG and Xinnao Shutong sheet) that extracts in the Chinese medicine puncture vine (Tribulus terrestris L.) is mainly used in the treatment cardiovascular and cerebrovascular diseases clinically.The total saponins that extracts from puncture vine mainly comprises compositions such as spirostanol saponin and furostanol saponin, 17 kinds of spirostanol saponin composition [Xu YX had been reported at present, Chen HS, Liang HQ, et al.Three new saponins from Tribulus terrestris.Planta Med.2000; 66 (6): 545～50; Yan W, Ohtani K, Kasai R, et al.Steroidal Saponins from fruits ofTriblus terrestris.Phytochemistry 1996; 42 (5): 1417～22; Yan W, Ohtani K, KasaiR, et al.Steroidal Saponins from fruits of Triblus terrestris.Phytochemistry 1997; 45 (4); 811; S.B.Mahato, N.P.Sahu et al.J.Chem.Soc.Perkin Trans.I 1981; (9): 2405; Wu, G., Jiang, S.H., and Jiang, F.X.et al.Phytochemistry 1996; 42 (6): 1677].TTS-12 is a kind of spirostanol saponin wherein, promptly for accusing sapogenin-O-3-β-D-xylopyranose (1 → 2)-[β-D-xylopyranose (1 → 3)]-β-D-Glucopyranose (1 → 4)-[α-L-pyrans rhamnosyl (1 → 2)]-β-D-galactopyranoside, its chemical structure is:
Wherein
TTS-12 is a kind of antifungal compound efficiently, and the preparation method of bibliographical information is: Chinese medicine puncture vine raw material 80% alcohol reflux, behind the extracting solution concentrating under reduced pressure, concentrated solution is used sherwood oil, chloroform and n-butanol extraction respectively.After butanol extraction liquid reclaims solvent, residue carries out the macroporous resin adsorption chromatography again, difference water, 50%, 70%, 90% ethanol elution, 90% ethanol elution part, reclaim solvent to doing, residue carries out chromatography processes such as silica gel column chromatography and the anti-phase medium pressure column chromatography of C18 again and just obtains pure compound TTS-12[XuYX, Chen HS, Liang HQ, et al.Three new saponins from Tribulus terrestris.PlantaMed.2000; 66 (6): 545～50, inclined to one side number of this compound is 8 in the document].This preparation method's complexity, step is many, the preparation cost height, and be not suitable for a large amount of preparations or suitability for industrialized production.
Summary of the invention
The invention provides a kind of fast and convenient, with low cost, applicable to the TTS-12 preparation method of a large amount of preparations or suitability for industrialized production.Concrete preparation method is as follows:
1.TTS-12 the extraction puncturevine herb with extracting the solvent reflux, extract solvent and select 60～95% ethanol for use, preferred 70～80% ethanol, consumption are 15～25 times of sandbur weight, preferred 20 times.With the puncturevine herb of the section of the being chopped into multi-function extractor of packing into, divided three refluxing extraction each 2 hours, merge ethanol extract.
2.TTS-12 separation and purification said extracted liquid decompression recycling ethanol to distillate is not had ethanol flavor, be cooled to precipitation fully, centrifugal collection extract precipitation, precipitation is with adding 100～200 or 200～300 order column chromatography silica gels (about 10 kilograms of puncturevine herb extracts add 1 kilogram of order silica gel) after the 95% ethanol heating for dissolving, dispersed with stirring, drying, last 100～200 orders or 200～300 order silica gel column chromatographies are used the mixed solvent wash-out.Mixed solvent is selected from chloroform-methanol or methylene chloride-methanol, or elder generation's chloroform: methyl alcohol=5: 1 (V/V) wash-out, do not flow out to there being eluate, use chloroform again: methyl alcohol=4: 1 (V/V) wash-out, or elder generation's methylene dichloride: methyl alcohol=4: 1 (V/V) wash-out, do not flow out to there being eluate, use methylene dichloride again: methyl alcohol=3: 1 (V/V) wash-out, TLC detects elutriant, collection contains the elutriant of TTS-12, place crystallization after adding an amount of methyl alcohol or ethanol thermosol behind the recovery solvent, obtain the TTS-12 crude product, promptly get the pure product of TTS-12 with methyl alcohol or 80% ethyl alcohol recrystallization again.Preparation method of the present invention is easy, has reduced cost, and applicable to a large amount of preparations or suitability for industrialized production.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1 preparation compound TTS-12
40 kilograms of puncturevine herbs, the section of the being chopped into multi-function extractor of packing into adds 70% ethanol as extracting solvent, make and flood whole medicinal materials, soak after 24 hours heating and refluxing extraction three times, each 2 hours, extracting solution was 20 times of puncture vine weight, united extraction liquid, filter back decompression recycling ethanol to distillate and do not have the ethanol flavor, concentrated solution is placed cooling, makes abundant precipitation, centrifugal collection extract precipitation, to precipitate and use the distilled water wash secondary, use 1 liter of distilled water at every turn.Add 3 liters of heating for dissolving of 95% ethanol in throw out, add 5 kilograms of dispersed with stirring of 100～200 order column chromatography silica gels, fling to 80 ℃ of dryings behind the ethanol, porphyrize is crossed 60 mesh sieves, promptly gets extract and silica gel blended sample.With 100～200 order column chromatography silica gel 6kg decompression 30cm * 150cm stainless steel chromatography post of packing into, decompression is taken out tight back and is added said extracted thing and silica gel blended sample, earlier use chloroform: 100 liters of wash-outs of the mixed solvent of methyl alcohol=5: 1 (V/V), (developping agent is CHCl to the TLC detection procedure
3: CH
3OH: H
2O=65: 35: 10, use lower floor, developer is 20%H
2SO
4Ethanol liquid), behind no washings spot in the elutriant, with chloroform: the mixed solvent wash-out that methyl alcohol=4: 1 (V/V) is 40 liters, collect this part elutriant, decompression and solvent recovery, add 3 liters of methyl alcohol in the residuum, heating makes dissolving, places, cooling, separate out needle crystal, filter, get TTS-12 crude product 25.4 grams.Crude product after with recrystallizing methanol the pure product 23.0g of TTS-12, purity＞98%.
Embodiment 2 preparation compound TTS-12
40 kilograms of puncturevine herbs, the section of the being chopped into multi-function extractor of packing into adds 70% ethanol as extracting solvent, make and flood whole medicinal materials, soak after 24 hours heating and refluxing extraction three times, each 2 hours, extracting solution was 20 times of puncture vine weight, united extraction liquid, filtering back decompression recycling ethanol to distillate does not have the ethanol flavor, and concentrated solution is placed, cooling, make abundant precipitation, centrifugal collection extract precipitation will precipitate and use the distilled water wash secondary, use 1 liter of distilled water at every turn.Add 3 liters of heating for dissolving of 95% ethanol in throw out, add 5 kilograms of dispersed with stirring of 200～300 order column chromatography silica gels, fling to 80 ℃ of dryings behind the ethanol, porphyrize is crossed 60 mesh sieves, promptly gets extract and silica gel blended sample.With 200～300 order column chromatography silica gel 6kg, 30cm * 150cm stainless steel chromatography the post of packing into reduces pressure, decompression is taken out tight back and is added said extracted thing and silica gel blended sample, and use methylene dichloride earlier: 100 liters of wash-outs of the mixed solvent of methyl alcohol=4: 1 (V/V), (developping agent is CHCl to the TLC detection procedure
3: CH
3OH: H
2O=65: 35: 10, use lower floor, developer is 20%H
2SO
4Ethanol liquid), behind no washings spot in the elutriant, again with methylene dichloride: the mixed solvent wash-out that methyl alcohol=3: 1 (V/V) is 40 liters, collect this part elutriant, decompression and solvent recovery, add 4 liters of methyl alcohol in the residuum, heating makes dissolving, places, cooling, separate out needle crystal, filter, get TTS-12 crude product 28.6 grams.Crude product after with 80% ethyl alcohol recrystallization the pure product 20.5g of TTS-12, purity＞98%.
Claims (2)
1. method that from the Chinese medicine puncturevine herb, prepares spirostanol saponin TTS-12, the structural formula of TTS-12 is:
Wherein
The concrete operations step is as follows:
(1) the extraction puncturevine herb of TTS-12 is with extracting the solvent heating and refluxing extraction, and extracting solvent is 60～95% ethanol, and consumption is 15～25 times of puncture vine weight, gets extracting solution;
(2) separation and purification of TTS-12 does not have the ethanol flavor with extracting solution decompression recycling ethanol to debris, be cooled to precipitation fully, centrifugal collection extract precipitation, precipitate with 95% ethanol heating for dissolving, add an amount of 100～200 or 200～300 order column chromatography silica gel dispersed with stirring, drying and screening, last 100～200 orders or 200～300 order silica gel column chromatographies, use the mixed solvent wash-out, mixed solvent is selected from chloroform-methanol or methylene chloride-methanol, or uses earlier chloroform: methyl alcohol=5: 1 (V/V) wash-out, do not flow out to there being eluate, use chloroform again: methyl alcohol=4: 1 (V/V) wash-out, or use earlier methylene dichloride: methyl alcohol=4: 1 (V/V) wash-out, do not flow out to there being eluate, use methylene dichloride again: methyl alcohol=3: 1 (V/V) wash-out, TLC detects elutriant, collects the elutriant that contains TTS-12, reclaims solvent, add an amount of methyl alcohol or ethanol thermosol, place crystallization, obtain the TTS-12 crude product, promptly get the pure product of TTS-12 with methyl alcohol or 80% ethyl alcohol recrystallization then.
2, by the described method that from the Chinese medicine puncturevine herb, prepares spirostanol saponin TTS-12 of claim 1, it is characterized in that said extraction solvent is 70～80% ethanol.
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| CN 200410018318 CN1254481C (en) | 2004-05-13 | 2004-05-13 | Method for preparing spirosta saponin TTS-12 from traditional Chinese medicine caltrop |
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| CN1254481C CN1254481C (en) | 2006-05-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106924279A (en) * | 2017-03-01 | 2017-07-07 | 广州军区广州总医院 | The new opplication of puncture vine TTS 12, the traditional Chinese medicine gel for suppressing alpha fungus and preparation method thereof |
-
2004
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106924279A (en) * | 2017-03-01 | 2017-07-07 | 广州军区广州总医院 | The new opplication of puncture vine TTS 12, the traditional Chinese medicine gel for suppressing alpha fungus and preparation method thereof |
| CN106924279B (en) * | 2017-03-01 | 2020-03-17 | 广州军区广州总医院 | Application of TTS-12 of caltrops, traditional Chinese medicine gel for inhibiting trichophyton mentagrophytes and preparation method of traditional Chinese medicine gel |
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Granted publication date: 20060503 Termination date: 20110513 |