CN104817610A - Method for preparation of Cycloastragenol by sulfuric acid hydrolysis - Google Patents
Method for preparation of Cycloastragenol by sulfuric acid hydrolysis Download PDFInfo
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- CN104817610A CN104817610A CN201510112723.5A CN201510112723A CN104817610A CN 104817610 A CN104817610 A CN 104817610A CN 201510112723 A CN201510112723 A CN 201510112723A CN 104817610 A CN104817610 A CN 104817610A
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- cycloastragenol
- cyclosiversigenin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class
- C07J53/002—Carbocyclic rings fused
- C07J53/004—3 membered carbocyclic rings
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Abstract
The invention relates to a method for preparation of Cycloastragenol by sulfuric acid hydrolysis. The method provided by the invention utilizes sulfuric acid to hydrolyze the Chinese medicine astragalus crude extract astragaloside, and realizes conversion of astragaloside to Cycloastragenol under certain hydrolysis condition, then performs impurity separation on the Cycloastragenol crude extract obtained by acid hydrolysis by chloroform and n-butanol extraction, and further makes use of silica gel column chromatography purification to finally obtain high purity Cycloastragenol. The invention aims to provide the method that can overcome the disadvantages of complex production process, low yield, high cost and the like of Cycloastragenol production and is suitable for large-scale production of different purity Cycloastragenol.
Description
Technical field
The invention belongs to field of medicine and chemical technology, relating to a kind of take Chinese medicine astragalus as the novel method that prepared using sulphuric acid hydrolysis prepares Cyclosiversigenin.
Background technology
Effective constituent in the Radix Astragali comprises flavonoid, saponins, polyose and amino acids.Wherein Radix Astragali saponin have cardiac stimulant, step-down, antitumor, reduce blood glucose in diabetic rats and promote the effect such as insulin secretion.From astragalus root, isolation identification goes out tens of kinds of Radix Astragali saponins, and Cyclosiversioside F is the principle active component of saponin(e.Cyclosiversigenin (Cycloastragenol), belongs to triterpene saponin componds, and the hydrolysis primarily of Cyclosiversioside F (Astragaloside IV) obtains.Cyclosiversigenin is unique Activation of Telomerase agent found now, and shorten by increasing Telomerase thus delaying telomere, Cyclosiversigenin is considered to have antidotal effect.Process study at present about Cyclosiversigenin is few, the present invention seeks to a kind of method in order to set up simple economy, and the industrialization of producing for realizing Cyclosiversigenin lays the first stone.Preparation method at present about Cyclosiversigenin reports less, application number be 201410101515.0 Chinese invention patent application disclose a kind of Preparation method and use preparing Cyclosiversigenin, for raw material with Cyclosiversioside F or Radix Astragali saponin, highly purified Cyclosiversigenin is obtained by the method for oxidation, reduction, hydrolysis, extraction, purifying, the method can obtain the good Cyclosiversigenin product of quality, but complex steps, complicated operation, yield is lower.
Summary of the invention
The object of the invention is a kind of method setting up simple economy, realize the suitability for industrialized production of Cyclosiversigenin.Present method adopts Chinese medicine astragalus to be raw material, and utilize the Cyclosiversioside F in organic solvent rich material, then Cyclosiversioside F is converted into Cyclosiversigenin by sulphuric acid hydrolysis, eventually passes extraction, silica gel column chromatography separating purification obtains highly purified Cyclosiversigenin.
The chemical structural formula of Cyclosiversigenin
Utilize sulphuric acid hydrolysis to prepare the method for Cyclosiversigenin, it is characterized in that, in turn include the following steps:
A. Cyclosiversioside F crude extract preparation
Milkvetch Root methanol eddy extracts, and solid-liquid mass ratio 1:10, adds the ammoniacal liquor of methanol quality ratio 2%, and ammoniacal liquor reagent quality percentage concentration is 28%, temperature 65 DEG C, magnetic agitation, and the time is set to 2h, refluxes 2 times; After filtration, filtrate carrying out is revolved the crude extract steaming and obtain first glycosides;
B. Cyclosiversigenin is prepared in acid hydrolysis
Get above-mentioned crude extract, add the sulphuric acid soln of massfraction 5% in sealed reactor, solid-liquid mass ratio is 1:10,130 DEG C of reaction 6h; Neutralize with ammoniacal liquor after reaction; Take out material in still and be placed in beaker, add chloroform and shake up standing, removing chloroform layer impurity; Add n-butanol extraction twice, collect n-butanol layer and be spin-dried for as product;
C. the separation and purification of Cyclosiversigenin
Silica gel chloroform wet method fills out post, get product after stating extraction and be evenly dispersed in the top of silicagel column, silica gel and quality product ratio are 25:1, dry method loading, then constantly carry out wash-out with lower floor's solution that the chloroform-methanol prepared-water three volume ratio is 13:8:2, collect elutriant.
In the present invention, described sulphuric acid hydrolysis condition is realized by closed reactor; Described raw material Chinese medicine astragalus is Radix Astragali, purchased from Anguo City, Hebei province.
Feature of the present invention be with Chinese medicine astragalus be prepared using sulphuric acid hydrolysis method obtain Cyclosiversigenin.Described sulphuric acid hydrolysis, sulfuric acid is utilized to be broken by the xylose and glucose that Cyclosiversioside F female ring connects, generate aglycone structure Cyclosiversigenin, although loss part Cyclosiversioside F, but avoid a large amount of generations of intermediate product 6-O-glucoside-Cyclosiversigenin, because of the simple cost savings 30% ~ 50% of its step, be suitable for industrial production.
Accompanying drawing explanation
Fig. 1 is the liquid chromatography mass spectrometric figure of Cyclosiversigenin.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the object of these embodiments not lying in limits the scope of the invention.
Embodiment 1:
Prepared by Cyclosiversioside F crude extract: after being pulverized by Chinese medicine astragalus, get the 10g Radix Astragali and join solid-liquid mass ratio 1:10 in methyl alcohol, the massfraction adding 2% according to methanol quality ratio is again the ammoniacal liquor of 28%, in flask, place rotor carry out magnetic agitation, temperature is set at 65 DEG C, start timing when condenser occurring first phlegma, the time of once refluxing is set to 2h, and each back flow of sample is extracted for 2 times.Filter after backflow, filtrate being spin-dried for is obtained the crude extract of Cyclosiversioside F, it is 0.28% that HPLC records Cyclosiversioside F purity.
Cyclosiversigenin is prepared in acid hydrolysis: the Cyclosiversioside F crude extract accurately taking 5.00g, and adding 50ml massfraction is in the sulphuric acid soln of 5%, reacts in closed reactor, 130 DEG C of reaction 6h.Reaction terminates rear question response still and is down to room temperature, and the weak ammonia being 5% by solution massfraction in still neutralizes.Take out solidliquid mixture in still and be placed in beaker, the chloroform adding 50ml shakes up standing, removing chloroform layer impurity.The propyl carbinol adding 50ml again shakes up standing, extracting twice, collects n-butanol layer product.Carry out HPLC detection after being spin-dried for, Cyclosiversigenin purity is 8.01%.
The separation and purification of Cyclosiversigenin: get 50g silica gel chloroform wet method and fill out post, after getting the above-mentioned extraction of 2g, product is evenly dispersed in the top of silicagel column, dry method loading, then constantly carry out wash-out with lower floor's solution of the chloroform-methanol-water (volume ratio 13:8:2) prepared, it is 1ml/min that regulating piston makes flow velocity evenly.Every 50ml sampling once detects with thin-layer chromatography.
Embodiment 2:
Prepared by Cyclosiversioside F crude extract: get 10g Milkvetch Root and join solid-liquid mass ratio 1:10 in methyl alcohol, temperature is 65 DEG C, the massfraction adding methanol quality ratio 2% is the ammoniacal liquor of 28%, in flask, place rotor carry out magnetic agitation, timing is started when condenser occurring first phlegma, the time of once refluxing is set to 2h, and each back flow of sample is extracted for 2 times.Filter after backflow, filtrate being spin-dried for is obtained the crude extract of Cyclosiversioside F, it is 0.31% that HPLC records Cyclosiversioside F purity.
Cyclosiversigenin is prepared in acid hydrolysis: the first glycosides crude extract getting 5.00g, adds 50ml, and massfraction is in the sulphuric acid soln of 5%, in closed reactor 130 DEG C, and 6h reacts, and the ammoniacal liquor that reaction terminates rear massfraction 10% neutralizes.Take out material in still and be placed in beaker, add the chloroform removing chloroform layer impurity of 50ml.Add the n-butanol extraction twice of 50ml, collect n-butanol layer product.Carry out HPLC detection after being spin-dried for, Cyclosiversigenin purity is 7.81%.
The separation and purification of Cyclosiversigenin: get 50g silica gel chloroform wet method and fill out post, after getting the above-mentioned extraction of 2g, product is evenly dispersed in the top of silicagel column, dry method loading, then constantly carry out wash-out with lower floor's solution of the chloroform-methanol-water prepared (volume ratio 13:8:2), it is 1ml/min that regulating piston makes flow velocity evenly.Every 50ml sampling once detects with thin-layer chromatography.
Embodiment 3:
Prepared by Cyclosiversioside F crude extract: get 100g Milkvetch Root methanol eddy and extract, solid-liquid mass ratio 1:10, add the ammoniacal liquor of the massfraction 28% of mass ratio 2%, temperature 65 DEG C, carries out magnetic agitation.Time is set to 2h, refluxes 2 times.After filtration, filtrate carrying out is revolved the crude extract steaming and obtain first glycosides, it is 0.25% that HPLC records first glycosides purity.
Cyclosiversigenin is prepared in acid hydrolysis: the first glycosides crude extract claiming 20.00g, adds 200ml in closed reactor, and the sulphuric acid soln of massfraction 5% is at 130 DEG C of reaction 6h.Neutralize with the ammoniacal liquor of massfraction 10% after reaction.Take out material in still and be placed in beaker, the chloroform adding 200ml shakes up standing, removing chloroform layer impurity.Add the propyl carbinol of 200ml, extracting twice, collect n-butanol layer product.Carry out HPLC detection after being spin-dried for, Cyclosiversigenin purity is 7.67%.
The separation and purification of Cyclosiversigenin: fill out post by 250g silica gel chloroform wet method, after getting the above-mentioned extraction of 10g, product is evenly dispersed in the top of silicagel column, dry method loading, then constantly carry out wash-out with lower floor's solution of the chloroform-methanol-water prepared (volume ratio 13:8:2), it is 1ml/min that regulating piston makes flow velocity evenly.Every 50ml elutriant collecting and sampling once detects with thin-layer chromatography.
Claims (1)
1. utilize sulphuric acid hydrolysis to prepare the method for Cyclosiversigenin, it is characterized in that, in turn include the following steps:
A. Cyclosiversioside F crude extract preparation
Milkvetch Root methanol eddy extracts, and solid-liquid mass ratio 1:10, adds the ammoniacal liquor of methanol quality ratio 2%, and ammoniacal liquor reagent quality percentage concentration is 28%, temperature 65 DEG C, magnetic agitation, and the time is set to 2h, refluxes 2 times; After filtration, filtrate carrying out is revolved the crude extract steaming and obtain first glycosides;
B. Cyclosiversigenin is prepared in acid hydrolysis
Get above-mentioned crude extract, add the sulphuric acid soln of massfraction 5% in sealed reactor, solid-liquid mass ratio is 1:10,130 DEG C of reaction 6h; Neutralize with ammoniacal liquor after reaction; Take out material in still and be placed in beaker, add chloroform and shake up standing, removing chloroform layer impurity; Add n-butanol extraction twice, collect n-butanol layer and be spin-dried for as product;
C. the separation and purification of Cyclosiversigenin
Silica gel chloroform wet method fills out post, get product after stating extraction and be evenly dispersed in the top of silicagel column, silica gel and quality product ratio are 25:1, dry method loading, then constantly carry out wash-out with lower floor's solution that the chloroform-methanol prepared-water three volume ratio is 13:8:2, collect elutriant.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734109A (en) * | 2016-02-02 | 2016-07-06 | 成都锦泰和医药化学技术有限公司 | Producing and refining method for high-purity cycloastragenol |
| CN106831927A (en) * | 2017-02-07 | 2017-06-13 | 江西师范大学 | A kind of synthetic method of Astragaloside IV |
| CN109609581A (en) * | 2018-12-28 | 2019-04-12 | 北京化工大学 | A kind of method that microorganism mixed fermentation conversion degradation Astragaloside IV prepares cycloastragenol |
| CN109942663A (en) * | 2019-04-22 | 2019-06-28 | 中国人民解放军联勤保障部队第九八九医院 | The method for preparing cycloastragenol using two-phase sour water solution |
| CN111548385A (en) * | 2020-05-29 | 2020-08-18 | 中国科学院成都生物研究所 | Preparation method of astragaloside |
| CN113968894A (en) * | 2021-11-05 | 2022-01-25 | 山西大学 | Method for preparing cycloastragenol by degrading astragaloside |
Citations (1)
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| CN1809364A (en) * | 2003-06-23 | 2006-07-26 | 杰龙公司 | Compositions and methods for increasing telomerase activity |
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2015
- 2015-03-15 CN CN201510112723.5A patent/CN104817610A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1809364A (en) * | 2003-06-23 | 2006-07-26 | 杰龙公司 | Compositions and methods for increasing telomerase activity |
Non-Patent Citations (1)
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| 王立媛等: "黄芪甲苷的提取分离工艺的研究", 《2013中国化工学会年会论文集》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734109A (en) * | 2016-02-02 | 2016-07-06 | 成都锦泰和医药化学技术有限公司 | Producing and refining method for high-purity cycloastragenol |
| CN106831927A (en) * | 2017-02-07 | 2017-06-13 | 江西师范大学 | A kind of synthetic method of Astragaloside IV |
| CN106831927B (en) * | 2017-02-07 | 2018-02-09 | 江西师范大学 | A kind of synthetic method of Astragaloside IV |
| WO2018145578A1 (en) * | 2017-02-07 | 2018-08-16 | 江西师范大学 | Method for synthesizing astragaloside iv |
| CN109609581A (en) * | 2018-12-28 | 2019-04-12 | 北京化工大学 | A kind of method that microorganism mixed fermentation conversion degradation Astragaloside IV prepares cycloastragenol |
| CN109942663A (en) * | 2019-04-22 | 2019-06-28 | 中国人民解放军联勤保障部队第九八九医院 | The method for preparing cycloastragenol using two-phase sour water solution |
| CN109942663B (en) * | 2019-04-22 | 2021-10-26 | 中国人民解放军联勤保障部队第九八九医院 | Method for preparing cycloastragenol by using diphasic acid hydrolysis |
| CN111548385A (en) * | 2020-05-29 | 2020-08-18 | 中国科学院成都生物研究所 | Preparation method of astragaloside |
| CN111548385B (en) * | 2020-05-29 | 2024-03-26 | 中国科学院成都生物研究所 | Preparation method of astragaloside acid |
| CN113968894A (en) * | 2021-11-05 | 2022-01-25 | 山西大学 | Method for preparing cycloastragenol by degrading astragaloside |
| CN113968894B (en) * | 2021-11-05 | 2024-05-28 | 山西大学 | Method for preparing cycloastragenol by degrading astragaloside IV |
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