CN101805388A - Method for preparing compounds with neuronal protection activity by using panaxatriol - Google Patents
Method for preparing compounds with neuronal protection activity by using panaxatriol Download PDFInfo
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Abstract
The invention relates to a method for preparing compounds with neuronal protection activity by using panaxatriol, and discloses the method for preparing the compounds: the acid degradation preparation method and the purification method thereof. Chemical names are respectively: a panaxatriol derivative, Gadamer-(E)-20(22)-alkene-3 beta, 6 beta, 12 beta, 25-tetra-alcohol, 20(R)-protopanaxatriol, 20(R)-25-methoxyl group (ethoxyl group)-3 beta, 6, beta, 12 beta, 20-tetra-alcohol, 20(R/S)-dammarane type-3 beta, 6 beta, 12 beta, 20 beta, 25-pentol. The method has the advantages of mild reaction condition, low cost, short period, controllable quality, easily separated and purified product, high yield, suitability for the industrial production and capacity of meeting the requirements on medicinal sources of neuronal protection and the like.
Description
Technical field:
The present invention relates to medical technical field, relate to the panoxatriol preparation and have the method for neuroprotective activity compound, be specifically related to panoxatriol and make the side chain open loop produce the method for neuroprotective activity compound by hydrolysis.
Background technology:
After the main effective constituent, chemical and medical worker is devoted to the conversion or the structural modification of the synthetic and effective monomer of some monomer saponin, reaches and improves its chemical property and improve bioactive purpose in ginsenoside is proved conclusively to genseng and Radix Panacis Quinquefolii.At present, mainly contain following several method in research and using, for example acid-hydrolysis method, alkali hydrolysis method, enzymolysis process, condensation method, dioxide giving etc.
Nineteen eighty-two, Hart B H reported first under the sour condition of gentleness, make ginsenoside degraded and determined the structure of degraded product.Chen Yingjie etc. find first, under suitable reaction conditions, the base catalysis edman degradation Edman, to the degraded of ginsenoside have reaction temperature and, advantage such as control is successfully synthesized ginsenoside Rh1 with the ginsenoside Rg2 with this method easily.Song Changchun in 1992 etc. use with quadrat method and have prepared monomer ginsenoside Rh1 and Rh2 from the Folium Panacis Quinquefolii saponin(e.Yang Ling etc. utilize basic hydrolysis natural ginseng saponin(e to prepare monomer rudimentary property ginsenoside and aglycon thereof.Yin Jianyuan etc. utilize ginsenoside to prepare new panoxadiol (patent No.: ZL 200710055693.4) through hydrolysis
Studies show that (22)-alkene-3 β of Da Ma-(E)-20,12 β, the 25-triol, 20 (R)-25-first (second) oxygen base-3 β, 12 β, the 20-triol, 20 (R/S)-dammarane-3 β, 12 β, 20, the 25-tetrol has tangible antitumour activity, can suppress people's growth of tumour cell and propagation, can also suppress the growth of prostate gland transplanted tumor, liver tumor and gastric tumor there is the obvious suppression effect, and increasing the susceptibility of tumour to chemicotherapy, inducing tumor cell breaks up, apoptosis suppresses tumor neogenetic blood vessels and generates, suppressing invading of tumour moistens and transfer, effects such as enhancing body immunizing power and reduction toxic and side.(22)-alkene-3 β of Da Ma-(E)-20,6 β, 12 β, the 25-tetrol, 20 (R)-25-first (second) oxygen base-3 β, 6 β, 12 β, 20-tetrol, 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, the 25-pentol has significant provide protection to neurone, obviously slow down the cortical neuron apoptosis, apoptotic cell is had the certain protection effect; Can obviously alleviate infringements such as rat hippocampus damage, apoptosis, memory function that infrasonic sound causes go down, the protection hippocampal neuron.
Summary of the invention:
The object of the present invention is to provide have the method for neuroprotective activity compound a kind of the preparation by panoxatriol.
The invention provides the open-loop method of panoxatriol, and have (22)-alkene-3 β of the Da Ma of neuroprotective activity-(E)-20,6 β; 12 β, 25-tetrol, 20 (R)-Protopanaxatriols; 20 (R))-and 25-first (second) oxygen base-3 β, 6 β, 12 β; the 20-tetrol; 20 (R/S)-dammarane-3 β, 6 β, 12 β; 20 β, the preparation method of 25-pentol.
The present invention is achieved through the following technical solutions:
Panoxatriol adds organic solvent in container, stirs, and heating, dissolving adds protective material; add acid again, back flow reaction, the reaction solution after the acid degradation neutralizes with alkali, steams and removes organic solvent; desalination gets the acid degradation thing, and through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of neuroprotective activity compound Da Ma-(E)-20,6 β, 12 β, the 25-tetrol, 20 (R)-Protopanaxatriols, 20 (R)-25-first (second) oxygen base-3 β, 6 β, 12 β, the 20-tetrol, 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, the 25-pentol, wherein material quantity is 1%～15% (g/ml) of organic solvent, the organic solvent concentration range is 35%～80%V/V, the protective material consumption is 1～10g/L, and the acid concentration scope is 1～25V/V%, and the acid degradation temperature is 40～90 ℃; Hydrolysis time is 2 hours～3 days.
The structure of the main active compound that is obtained and general formula are:
(22)-alkene-3 β of Da Ma-(E)-20,6 β, 12 β, 25-tetrol, 20 (R) and 20 (S)-dammarane-panoxatriol derivative
In the method provided by the invention, used raw material is that panoxatriol comprises panoxatriol, the panoxatriol that monomer saponin and plant total saponins obtain through several different methods such as acid degradation or alkaline degradation or bio-transformation or structural modifications.
In the method provided by the invention, the ring-opening reaction of raw material is the acid degradation reaction.
In the method provided by the invention, acid is protonic acid or Lewis acid, and example hydrochloric acid, sulfuric acid, phosphoric acid, Glacial acetic acid, oxalic acid, oxysuccinic acid, citric acid etc. are preferentially selected hydrochloric acid, sulfuric acid; Concentration range is 1～25V/V%; Protective material is xitix, sodium bisulfite, gallic acid, preferentially selects xitix, and consumption is 1～10g/L; Acidolysis is carried out at a kind of or its admixture solvent of organic solvent methyl alcohol, ethanol, propyl alcohol, butanols, acetone, dioxane, methyl-sulphoxide, pyridine, acetonitrile, preferentially selects methyl alcohol, ethanol, propyl alcohol, acetone, and optimum solvent is chosen as methyl alcohol or ethanol; Concentration range is 35%～80%V/V, preferred concentration range for 50%～75%V/V; Material quantity is 1%～15% (g/ml) of organic solvent; Be reflected in the container and stir, heating, backflow is carried out.The acid degradation temperature is 40～90 ℃; Hydrolysis time is 2 hours～3 days, and the preferred acid degradation temperature is 75～85 ℃; Preferred degradation time is 3 hours～8 hours.
In the method provided by the invention, be under the solvent condition, generate following compound at first (second) alcohol; be respectively (22)-alkene-3 β of the panoxatriol derivative with remarkable neuroprotective activity: Da Ma-(E)-20,6 β, 12 β; the 25-tetrol, 20 (R)-Protopanaxatriols, 20 (R)-25-first (second) oxygen base-3 β; 6 β, 12 β, 20-tetrol; 20 (R/S)-dammarane-3 β, 6 β, 12 β; 20 β, the 25-pentol.
Reaction conditions gentleness of the present invention, cost is low, and the cycle is short, and is quality controllable, the easily separated purifying of product, the yield height is fit to suitability for industrialized production, in order to satisfy antitumor and requirement of providing medicinal such as neuroprotective.
Embodiment:
Embodiment 1:
Get panoxatriol 10g, be dissolved among the methyl alcohol 250ml, add xitix 0.5g, add hydrochloric acid (1%～36%) 15ml, refluxed 2 hours～3 days in 40～90 ℃ of water bath with thermostatic control heated and stirred, adding sodium hydroxide solution accent pH is 7.0, reclaim methyl alcohol, desalination gets the acid degradation thing.Through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of panoxatriol derivative: Da Ma-(E)-20,6 β, 12 β, 25-tetrol (1.2g), 20 (R)-Protopanaxatriols (0.8g), 20 (R)-25-methoxyl group-3 β, 6 β, 12 β, 20-tetrol (0.7g), 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, 25-pentol (3.0g).
Embodiment 2:
Get panoxatriol 10g, be dissolved among the ethanol 250ml, add xitix 0.5g, add hydrochloric acid (1%～36%) 15ml, refluxed 8 hours in 75～85 ℃ of water bath with thermostatic control heated and stirred, adding sodium hydroxide solution accent pH is 7.0, reclaim ethanol, desalination gets the acid degradation thing.Through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of panoxatriol derivative: Da Ma-(E)-20,6 β, 12 β, 25-tetrol (1.3g), 20 (R)-Protopanaxatriols (0.8g), 20 (R)-25-oxyethyl group-3 β, 6 β, 12 β, 20-tetrol (0.8g), 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, 25-pentol (2.7g).
Embodiment 3:
Get panoxatriol 10g, be dissolved among the methyl alcohol 500ml, add xitix 0.5g, adding hydrochloric acid (1%～36%) 15ml refluxed 2 days in 40～55 ℃ of water bath with thermostatic control heated and stirred, and adding sodium hydroxide solution accent pH is 7.0, reclaims methyl alcohol, and desalination gets the acid degradation thing.Through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of panoxatriol derivative: Da Ma-(E)-20,6 β, 12 β, 25-tetrol (0.5g), 20 (R)-Protopanaxatriols (1.5g), 20 (R)-25-methoxyl group-3 β, 6 β, 12 β, 20-tetrol (0.9g), 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, 25-pentol (3.1g).
Embodiment 4:
Get panoxatriol 10g, be dissolved among the ethanol 500ml, add xitix 0.5g, add hydrochloric acid (1%～36%) 15ml, refluxed 24 hours in 40～90 ℃ of water bath with thermostatic control heated and stirred, adding sodium hydroxide solution accent pH is 7.0, reclaim ethanol, desalination gets the acid degradation thing.Through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of panoxatriol derivative: Da Ma-(E)-20,6 β, 12 β, 25-tetrol (0.6g), 20 (R)-Protopanaxatriols (1.4g), 20 (R)-25-oxyethyl group-3 β, 6 β, 12 β, 20-tetrol (1.0g), 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, 25-pentol (3.2g).
Embodiment 5:
Get panoxatriol 10g, be dissolved among the ethanol 250ml, adding hydrochloric acid (1%～36%) 15ml, in 12 hours skies of 60～70 ℃ of water bath with thermostatic control heated and stirred backflows, adding sodium hydroxide solution accent pH is 7.0, reclaims ethanol, desalination gets the acid degradation thing.Through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of panoxatriol derivative: Da Ma-(E)-20,6 β, 12 β, 25-tetrol (0.9g), 20 (R)-Protopanaxatriols (1.1g), 20 (R)-25-oxyethyl group-3 β, 6 β, 12 β, 20-tetrol (0.8g), 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, 25-pentol (2.9g).
Embodiment 6:
Get panoxatriol 10g, be dissolved among the ethanol 250ml, add xitix 0.5g, adding sulfuric acid (1%～35%) 15ml refluxed 6 hours in 75 ℃ of water bath with thermostatic control heated and stirred, and adding sodium hydroxide solution accent pH is 7.0, reclaims ethanol, and desalination gets the acid degradation thing.Through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of panoxatriol derivative: Da Ma-(E)-20,6 β, 12 β, 25-tetrol (1.0g), 20 (R)-Protopanaxatriols (1.0g), 20 (R)-25-methoxyl group-3 β, 6 β, 12 β, 20-tetrol (1.3g), 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, 25-pentol (3.2g).
Embodiment 7:
Get panoxatriol 10g, be dissolved among the ethanol 500ml, add xitix 0.5g, adding sulfuric acid (1%～35%) 15ml, in 2 hours skies of 90 ℃ of water bath with thermostatic control heated and stirred backflows, adding sodium hydroxide solution accent pH is 7.0, reclaims ethanol, desalination gets the acid degradation thing.Through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of panoxatriol derivative: Da Ma-(E)-20,6 β, 12 β, 25-tetrol (0.8g), 20 (R)-Protopanaxatriols (1.2g), 20 (R)-25-methoxyl group-3 β, 6 β, 12 β, 20-tetrol (1.0g), 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, 25-pentol (3.1g).
Embodiment 8:
Get panoxatriol 10g, be dissolved among the ethanol 250ml, add xitix 0.5g, add acetic acid (1%～50%) 15ml, refluxed 18 hours in 55～70 ℃ of water bath with thermostatic control heated and stirred, adding sodium hydroxide solution accent pH is 7.0, reclaim ethanol, desalination gets the acid degradation thing.Through (200～300 order silica gel) column chromatography, moving phase is CHCl repeatedly
3-MeOH-EtOAc-H
2O (2: 2: 4: 1, lower floor), the methanol-water recrystallization, obtain (22)-alkene-3 β of panoxatriol derivative: Da Ma-(E)-20,6 β, 12 β, 25-tetrol (0.9g), 20 (R)-Protopanaxatriols (1.1g), 20 (R)-25-oxyethyl group-3 β, 6 β, 12 β, 20-tetrol (0.8g), 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, 25-pentol (2.9g).
Claims (9)
1. a panoxatriol preparation has the method for neuroprotective activity compound, it is characterized in that panoxatriol adds organic solvent in container, stirs; heating, dissolving adds protective material; add acid again; back flow reaction, the reaction solution after the acid degradation neutralizes with alkali, steams and removes organic solvent; desalination; get the acid degradation thing, repeatedly through 200～300 order silica gel column chromatographies, moving phase is CHCl
3-MeOH-EtOAc-H
2The O ratio is 2: 2: 4: 1 lower floor, and the methanol-water recrystallization obtains (22)-alkene-3 β of neuroprotective activity compound Da Ma-(E)-20,6 β, 12 β, 25-tetrol, 20 (R)-Protopanaxatriols, 20 (R)-25-first (second) oxygen base-3 β, 6 β, 12 β, 20-tetrol, 20 (R/S)-dammarane-3 β, 6 β, 12 β, 20 β, the 25-pentol, wherein material quantity is 1%～15% of an organic solvent, and the organic solvent concentration range is 35%～80%V/V, and the protective material consumption is 1～10g/L, the acid concentration scope is 1～25V/V%, and the acid degradation temperature is 40～90 ℃; Hydrolysis time is 2 hours～3 days.
2. panoxatriol preparation according to claim 1 has the method for neuroprotective activity compound, and it is characterized in that: described acid is protonic acid or Lewis acid, example hydrochloric acid, sulfuric acid, phosphoric acid, Glacial acetic acid, oxalic acid, oxysuccinic acid, citric acid.
3. method according to claim 2 is characterized in that: described acid is hydrochloric acid or sulfuric acid.
4. panoxatriol preparation according to claim 1 has the method for neuroprotective activity compound, and it is characterized in that: described organic solvent is a kind of of methyl alcohol, ethanol, propyl alcohol, butanols, acetone, dioxane, methyl-sulphoxide, pyridine and acetonitrile or its admixture solvent.
5. panoxatriol preparation according to claim 4 has the method for neuroprotective activity compound, and it is characterized in that: described organic solvent is methyl alcohol or ethanol.
6. panoxatriol preparation according to claim 1 has the method for neuroprotective activity compound, and it is characterized in that: described protective material is xitix, sodium bisulfite or gallic acid.
7. panoxatriol preparation according to claim 6 has the method for neuroprotective activity compound, and it is characterized in that: described protective material is an xitix.
8. panoxatriol preparation according to claim 1 has the method for neuroprotective activity compound, and it is characterized in that: the acid degradation temperature is 75～85 ℃.
9. panoxatriol preparation according to claim 1 has the method for neuroprotective activity compound, and it is characterized in that: degradation time is 3 hours～8 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103211823A (en) * | 2012-01-18 | 2013-07-24 | 上海中药创新研究中心 | Use of 20(S)-protopanoxadiol derivatives and 20(S)-protopanaxatriol derivatives in preparation of antidepressant medicines |
| CN106389442A (en) * | 2016-01-14 | 2017-02-15 | 孙妙囡 | Application of pseudo protopanoxadiol |
| CN106608899A (en) * | 2015-10-23 | 2017-05-03 | 辽宁新中现代医药有限公司 | Preparation method of 20(R)-protopanaxatriol and derivative thereof and medical application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508144A (en) * | 2002-12-13 | 2004-06-30 | 中国科学院大连化学物理研究所 | Method for preparing true aglycone of ginseng saponin |
| CN101054400A (en) * | 2007-05-28 | 2007-10-17 | 尹建元 | Novel Panoxadiol and derivative, preparation method and medical use thereof |
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2010
- 2010-04-14 CN CN 201010145908 patent/CN101805388A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508144A (en) * | 2002-12-13 | 2004-06-30 | 中国科学院大连化学物理研究所 | Method for preparing true aglycone of ginseng saponin |
| CN101054400A (en) * | 2007-05-28 | 2007-10-17 | 尹建元 | Novel Panoxadiol and derivative, preparation method and medical use thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103211823A (en) * | 2012-01-18 | 2013-07-24 | 上海中药创新研究中心 | Use of 20(S)-protopanoxadiol derivatives and 20(S)-protopanaxatriol derivatives in preparation of antidepressant medicines |
| CN103211823B (en) * | 2012-01-18 | 2014-11-05 | 上海中药创新研究中心 | Use of 20(S)-protopanoxadiol derivatives and 20(S)-protopanaxatriol derivatives in preparation of antidepressant medicines |
| CN106608899A (en) * | 2015-10-23 | 2017-05-03 | 辽宁新中现代医药有限公司 | Preparation method of 20(R)-protopanaxatriol and derivative thereof and medical application |
| CN106608899B (en) * | 2015-10-23 | 2018-12-28 | 辽宁新中现代医药有限公司 | The preparation method and medical usage of 20 (R)-protopanaxatriols and derivative |
| CN106389442A (en) * | 2016-01-14 | 2017-02-15 | 孙妙囡 | Application of pseudo protopanoxadiol |
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Application publication date: 20100818 |