CN113968894B - Method for preparing cycloastragenol by degrading astragaloside IV - Google Patents
Method for preparing cycloastragenol by degrading astragaloside IV Download PDFInfo
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- QMNWISYXSJWHRY-YLNUDOOFSA-N astragaloside IV Chemical compound O1[C@H](C(C)(O)C)CC[C@]1(C)[C@@H]1[C@@]2(C)CC[C@]34C[C@]4(CC[C@H](O[C@H]4[C@@H]([C@@H](O)[C@H](O)CO4)O)C4(C)C)[C@H]4[C@@H](O[C@H]4[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O4)O)C[C@H]3[C@]2(C)C[C@@H]1O QMNWISYXSJWHRY-YLNUDOOFSA-N 0.000 title claims abstract description 32
- QMNWISYXSJWHRY-BCBPIKMJSA-N astragaloside IV Natural products CC(C)(O)[C@@H]1CC[C@@](C)(O1)[C@H]2[C@@H](O)C[C@@]3(C)[C@@H]4C[C@H](O[C@@H]5O[C@H](CO)[C@H](O)[C@@H](O)[C@H]5O)[C@H]6C(C)(C)[C@H](CC[C@@]67C[C@@]47CC[C@]23C)O[C@@H]8OC[C@@H](O)[C@H](O)[C@H]8O QMNWISYXSJWHRY-BCBPIKMJSA-N 0.000 title claims abstract description 32
- PFKIBRPYVNVMRU-UHFFFAOYSA-N cyclosieversioside F Natural products CC(C)(O)C1COC(C)(C1)C2C(O)CC3(C)C4CC(OC5OC(CO)C(O)C(O)C5O)C6C(C)(C)C(CCC67CC47CCC23C)OC8OCC(O)C(O)C8O PFKIBRPYVNVMRU-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000000593 degrading effect Effects 0.000 title claims abstract description 8
- WENNXORDXYGDTP-UOUCMYEWSA-N cycloastragenol Chemical compound O1[C@H](C(C)(O)C)CC[C@]1(C)[C@@H]1[C@@]2(C)CC[C@]34C[C@]4(CC[C@H](O)C4(C)C)[C@H]4[C@@H](O)C[C@H]3[C@]2(C)C[C@@H]1O WENNXORDXYGDTP-UOUCMYEWSA-N 0.000 title claims description 22
- WENNXORDXYGDTP-UHFFFAOYSA-N cyclosiversigenin Natural products O1C(C(C)(O)C)CCC1(C)C1C2(C)CCC34CC4(CCC(O)C4(C)C)C4C(O)CC3C2(C)CC1O WENNXORDXYGDTP-UHFFFAOYSA-N 0.000 title claims description 22
- 238000006731 degradation reaction Methods 0.000 claims abstract description 34
- 230000015556 catabolic process Effects 0.000 claims abstract description 30
- SMDOOINVMJSDPS-UHFFFAOYSA-N Astragaloside Natural products C1=C(O)C(OC)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)OC2C(C(OC3C(C(O)C(O)C(CO)O3)O)C(O)C(CO)O2)O)=C1 SMDOOINVMJSDPS-UHFFFAOYSA-N 0.000 claims abstract description 15
- QMNWISYXSJWHRY-XWJCTJPOSA-N astragaloside Chemical compound O1[C@H](C(C)(O)C)CC[C@]1(C)[C@@H]1[C@@]2(C)CC[C@]34C[C@]4(CC[C@H](O[C@H]4[C@@H]([C@@H](O)[C@H](O)CO4)O)C4(C)C)C4[C@@H](O[C@H]4[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O4)O)CC3[C@]2(C)C[C@@H]1O QMNWISYXSJWHRY-XWJCTJPOSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000011973 solid acid Substances 0.000 claims abstract description 14
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 11
- 241001061264 Astragalus Species 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 235000006533 astragalus Nutrition 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 230000005526 G1 to G0 transition Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 210000004233 talus Anatomy 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 5
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 3
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 abstract 1
- 239000002609 medium Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 241000045403 Astragalus propinquus Species 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- -1 KHSO 4 Chemical compound 0.000 description 1
- 108010017842 Telomerase Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229940107666 astragalus root Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000032677 cell aging Effects 0.000 description 1
- 230000032823 cell division Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 210000002997 osteoclast Anatomy 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 102000055501 telomere Human genes 0.000 description 1
- 108091035539 telomere Proteins 0.000 description 1
- 210000003411 telomere Anatomy 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a method for preparing cycloastragaloside by degrading astragaloside, which is a method for preparing cycloastragaloside by degrading astragaloside in a mixed medium formed by fatty alcohol-organic solvent by using solid acid slightly dissolved in a reaction medium as a catalyst. Specifically, astragaloside IV is used as a raw material, fatty alcohol is used as a degradation reagent in a medium formed by fatty alcohol-organic solvent, and under the catalysis of solid acid, the glycosidic bond of the astragaloside IV is degraded to remove xylosyl and glucosyl so as to obtain the cycloastragaloside. The degradation reaction condition is mild, the defect that the generated cycloastragal is further converted into the astragal or other byproducts is avoided, and the yield of the cycloastragal can reach more than 50 percent generally. The method has the advantages of simple operation steps, short degradation reaction time, high product purity and low preparation cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of pharmaceutical chemical industry, and in particular relates to a method for preparing cycloastragenol by degrading astragaloside IV.
Background
Astragalus root is used as a traditional important Chinese medicine, and the medicinal use has been two thousand years old so far. It has effects of strengthening body resistance, consolidating constitution, invigorating middle warmer and qi. Astragaloside IV is used as the most main saponin substance in Astragalus mongholicus, and has effects of enhancing organism immunity, improving organism disease resistance, resisting fatigue, protecting liver, scavenging free radicals in vivo, and inhibiting osteoclast. The content of astragaloside IV is an important index for judging the quality of astragalus Chinese medicinal materials at present.
Astragaloside IV can be degraded into cyclic Astragaloside alcohol which is easy to be absorbed and utilized by intestinal flora in the organism, and the molecular mass and the steric hindrance of the cyclic Astragaloside alcohol are smaller than those of the Astragaloside IV, and the cyclic Astragaloside IV has relatively good fat solubility and is easy to be absorbed by the organism through cell membranes. Related researches report that the cycloastragenol can be used as a telomerase activator to delay shortening of telomeres, increase cell division times and effectively inhibit cell aging. Therefore, the cycloastragenol has good application prospect in anti-aging.
The currently reported methods for preparing the cycloastragaloside from the astragaloside IV mainly comprise three conditions of an enzymolysis method, a Smith degradation method and an acid hydrolysis method. 1) Chinese invention discloses patent: CN105566434a; CN105734109a; CN106011213a; CN107058445A; CN111849959a; the preparation of cycloastragenol is mainly carried out by enzyme catalysis in CN111893158A and other documents. Although the enzymolysis method has higher conversion rate, the enzymolysis method has more severe requirements on reaction conditions, complicated steps and long preparation period, and is not beneficial to large-scale preparation. 2) Chinese invention discloses patent: CN13880910B; the CN106083979A and other documents prepare the cycloastragenol through Smith degradation by an oxidation-reduction method, but the preparation process needs to use an oxidant and a reducing agent to carry out oxidation-reduction reaction, so that the preparation steps are too many, and the practicability is not high. 3) Chinese invention discloses patent: CN102030799a; CN104817610a; CN1099942663a and the like are a method for preparing cyclic astragalus alcohol by acid hydrolysis of astragaloside iv with hydrochloric acid and sulfuric acid. The acid hydrolysis method is simple to operate and low in cost, and is the main method for preparing the cycloastragenol at present. However, the cyclic astragalus alcohol is easily converted into the byproduct astragalus alcohol under severe acidic conditions, the reaction conditions are difficult to control, and the yield is often low.
Disclosure of Invention
The invention aims to provide a method for preparing cycloastragenol by degrading astragaloside IV, which has the advantages of mild reaction conditions, higher yield and less byproducts.
The invention provides a method for preparing cycloastragaloside by catalyzing astragaloside IV with solid acid, which takes astragaloside IV as a raw material, takes bisulfate slightly dissolved in degradation medium as a solid acid catalyst, takes fatty alcohol such as methanol, absolute ethyl alcohol, n-propanol, n-butanol, ethylene glycol and the like as a degradation reagent, and degrades the astragaloside IV in the medium formed by the fatty alcohol, tetrahydrofuran, dioxane, ethyl acetate, methyl tertiary butyl ether and other organic solvents to obtain the cycloastragaloside.
According to the invention, the aliphatic alcohol-organic solvent mixed solvent is selected as the degradation medium for preparing the cycloastragaloside from the astragaloside, the solubility of the astragaloside in the aliphatic alcohol is relatively high, and the selected organic solvent has a certain solubility for the astragaloside, so that the solubility of the astragaloside in the degradation medium is increased. Meanwhile, as the bisulfate is slightly dissolved in the fatty alcohol, the solubility of the solid acid in the degradation medium can be controlled by adjusting the composition or the proportion of the degradation medium, so that the hydrogen ion concentration and the catalytic capability of the degradation reaction are changed, and the degradation and the conversion of the astragaloside IV into the cycloastragaloside are facilitated. The degradation medium contains a large amount of fatty alcohol, the degradation is realized mainly by alcoholysis, the reaction is mild, and the excessive hydrolysis of astragaloside IV in the aqueous medium is avoided.
The reaction formula:
The specific operation steps comprise:
1) Selecting fatty alcohol and organic solvent to form astragaloside IV degradation medium, adding astragaloside IV and solid acid into the degradation medium, stirring in water bath at 50-90 ℃ for reaction, tracking the reaction by high performance liquid chromatography, and stopping the reaction after the astragaloside IV raw material completely disappears to obtain degradation liquid;
2) Cooling and filtering the obtained degradation liquid, neutralizing the filtrate with dilute alkali solution, removing the organic solvent, extracting the residue with an extractant, drying, removing the solvent to obtain crude cycloastragenol, and purifying by column chromatography to obtain high-purity cycloastragenol;
The solid acid is bisulfate.
The mass volume ratio of astragaloside IV to solid acid and degradation medium is 1g:10-100g:100-1000mL, preferably 1g:20-30g:250-500mL.
The content of fatty alcohol in the degradation medium is more than 10 percent.
The fatty alcohol is methanol, absolute ethyl alcohol, n-propanol, n-butanol or ethylene glycol; preferably methanol or absolute ethanol, preferably in the range of 30-50%.
The organic solvent is tetrahydrofuran, dioxane, ethyl acetate or methyl tertiary butyl ether, etc.
The solid acid is bisulfate, such as KHSO 4、NaHSO4、(NH4)HSO4, and the like, preferably sodium bisulfate, and plays a role of a catalyst.
The extractant used in the step (2) is ethyl acetate or dichloromethane.
In the step (2), the column chromatography purification is performed by taking 100-200 meshes of silica gel as a stationary phase and taking methylene dichloride-methanol mixed solution as a mobile phase; the volume ratio of dichloromethane to methanol is 19:1.
Compared with the prior art, the invention has the beneficial effects that:
the prior literature reports that the preparation of the cycloastragal is realized by hydrolyzing the glycosidic bond of astragaloside, but the method for preparing the cycloastragal by alcoholysis of the glycosidic bond of astragaloside is not reported.
Aiming at the defects of the common method for preparing the cycloastragal, the invention establishes a method for preparing the cycloastragal by degrading astragaloside IV in a fatty alcohol-organic solvent mixed medium by taking solid acid as a catalyst, and realizes the degradation reaction under mild conditions by changing the solubility of the catalyst in the medium, thereby avoiding the excessive reaction of the cycloastragal under severe conditions, improving the stability of the cycloastragal in the medium, and ensuring that the yield is more than 50 percent and the purity is more than 95 percent. The preparation method has simple steps and low cost, and is suitable for industrial production.
Drawings
FIG. 1 high performance liquid chromatography (HPLC-ELSD) of astragaloside IV degradation solution, purified cycloastragaloside and cycloastragaloside alcohol standard substance
FIG. 2 1 H NMR (DMSO-d 6) spectrum of cycloastragenol
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical scheme of the invention is further described in detail through specific embodiments. These examples are not intended to limit the scope of the invention.
Example 1
To a mixed medium of 150mL of methanol and 150mL of tetrahydrofuran, 1g of astragaloside IV with the purity of 98%, 25g of sodium bisulfate are added, and in a water bath at 60 ℃, stirring reaction is carried out for 20 hours, cooling and filtering are carried out, the obtained filtrate is neutralized by dilute alkali solution, organic solvent is removed by rotary evaporation, water is added to 100mL, then the mixture is extracted three times by using ethyl acetate with the same volume, ethyl acetate is combined, and the mixture is dried by using anhydrous sodium sulfate. Removing ethyl acetate by rotary evaporation to obtain crude cycloastragenol. And then using 100-200 mesh silica gel as stationary phase, and using 19:1 dichloromethane-methanol mixed solution as mobile phase to make column chromatography purification so as to obtain 0.33g of cycloastragenol, its yield is 52.7% and purity is 97.5%.
Example 2
To a mixed medium of 50mL of ethylene glycol and 200mL of ethyl acetate, 1g of astragaloside IV with a purity of 85% and 20g of potassium bisulfate were added, and the mixture was stirred in a water bath at 90℃to react for 12 hours, cooled and filtered. The filtrate was neutralized with a dilute alkali solution, and 50mL of distilled water was added thereto, and the mixture was separated by a separating funnel, and the aqueous phase was extracted three times with 100mL of ethyl acetate, and the ethyl acetate was combined and dried over anhydrous sodium sulfate. Removing ethyl acetate by rotary evaporation to obtain crude cycloastragenol. And then using 100-200 mesh silica gel as stationary phase, and using 19:1 dichloromethane-methanol mixed solution as mobile phase to make column chromatography purification so as to obtain 0.28g of cycloastragenol, its yield is 50.5% and purity is 95.6%.
Example 3
1G of astragaloside with the purity of 98% and 20g of ammonium bisulfate are added into a mixed medium of 150mL of absolute ethyl alcohol and 150mL of dioxane, and the mixture is stirred and reacted for 16 hours in a water bath with the temperature of 80 ℃, cooled and filtered to obtain filtrate, the filtrate is neutralized by dilute alkali solution, organic solvent is removed by rotary evaporation, water is added to 150mL, the mixture is extracted three times by using ethyl acetate with the same volume, and the ethyl acetate is combined and dried by using absolute sodium sulfate. Removing ethyl acetate by rotary evaporation to obtain crude cycloastragenol. And then using 100-200 mesh silica gel as stationary phase, and using 19:1 dichloromethane-methanol mixed solution as mobile phase to make column chromatography purification so as to obtain 0.34g of cycloastragenol, its yield is 54.9% and purity is 98.5%.
Example 4
To a mixed medium of 400mL of methanol and 100mL of methyl tertiary butyl ether, 1g of astragaloside with the purity of 98%, 30g of sodium bisulfate are added, and in a water bath at 60 ℃, stirring reaction is carried out for 24 hours, cooling and filtering are carried out, the obtained filtrate is neutralized by dilute alkali solution, organic solvent is removed by rotary evaporation, water is added to 150mL, then the mixture is extracted three times by using ethyl acetate with the same volume, and the ethyl acetate is combined and dried by using anhydrous sodium sulfate. Removing ethyl acetate by rotary evaporation to obtain crude cycloastragenol. And then using 100-200 mesh silica gel as stationary phase, and using 19:1 dichloromethane-methanol mixed solution as mobile phase to make column chromatography purification so as to obtain 0.31g of cycloastragenol, its yield is 50.2% and purity is 98.8%.
Claims (5)
1. A method for preparing cycloastragaloside by degrading astragaloside IV, which is characterized by comprising the following steps:
1) Selecting fatty alcohol and organic solvent to form astragaloside IV degradation medium, adding astragaloside IV and solid acid into the degradation medium, stirring in water bath at 50-90 ℃ for reaction, tracking the reaction by high performance liquid chromatography, and stopping the reaction after the astragaloside IV raw material completely disappears to obtain degradation liquid;
2) Cooling and filtering the obtained degradation liquid, neutralizing the filtrate with dilute alkali solution, removing the organic solvent, extracting the residue with an extractant, drying, removing the solvent to obtain crude cycloastragenol, and purifying by column chromatography to obtain high-purity cycloastragenol;
The fatty alcohol is methanol, absolute ethyl alcohol or glycol, and the content of the fatty alcohol in the degradation medium is 30-50%; the organic solvent is tetrahydrofuran, dioxane, ethyl acetate or methyl tertiary butyl ether;
the solid acid is bisulfate: sodium bisulfate, potassium bisulfate and ammonium bisulfate;
The mass volume ratio of the astragaloside IV, the solid acid and the degradation medium is 1g:10-100g:100-1000mL.
2. The method for preparing cycloastragaloside by degradation of astragaloside according to claim 1, wherein the mass-volume ratio of astragaloside to solid acid to degradation medium is 1g:20-30g:250-500ml.
3. The method for preparing cyclic astragalus alcohol by degradation of astragaloside according to claim 1 or 2, wherein the extractant used in the step (2) is ethyl acetate or methylene chloride.
4. The method for preparing cyclic astragalus alcohol by degradation of astragaloside IV according to claim 1 or 2, wherein the column chromatography purification in the step (2) is performed by using 100-200 mesh silica gel as a stationary phase and methylene chloride-methanol mixed solution as a mobile phase.
5. The method for preparing cycloastragaloside by degradation according to claim 4, wherein the volume ratio of dichloromethane-methanol is 19:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111305277.1A CN113968894B (en) | 2021-11-05 | 2021-11-05 | Method for preparing cycloastragenol by degrading astragaloside IV |
Applications Claiming Priority (1)
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| CN1809364A (en) * | 2003-06-23 | 2006-07-26 | 杰龙公司 | Compositions and methods for increasing telomerase activity |
| CN104817610A (en) * | 2015-03-15 | 2015-08-05 | 北京化工大学 | Method for preparation of Cycloastragenol by sulfuric acid hydrolysis |
| CN106083979A (en) * | 2016-06-17 | 2016-11-09 | 浙江工业大学 | A kind of Cycloastragenol extract and preparation method thereof and purposes |
| 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 |
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| CN1809364A (en) * | 2003-06-23 | 2006-07-26 | 杰龙公司 | Compositions and methods for increasing telomerase activity |
| CN104817610A (en) * | 2015-03-15 | 2015-08-05 | 北京化工大学 | Method for preparation of Cycloastragenol by sulfuric acid hydrolysis |
| CN106083979A (en) * | 2016-06-17 | 2016-11-09 | 浙江工业大学 | A kind of Cycloastragenol extract and preparation method thereof and purposes |
| 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 |
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