CN1880326A - Two-step resin method for preparing salidrose - Google Patents
Two-step resin method for preparing salidrose Download PDFInfo
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- CN1880326A CN1880326A CN 200510026830 CN200510026830A CN1880326A CN 1880326 A CN1880326 A CN 1880326A CN 200510026830 CN200510026830 CN 200510026830 CN 200510026830 A CN200510026830 A CN 200510026830A CN 1880326 A CN1880326 A CN 1880326A
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- organic solvent
- filtrate
- chromatography
- polymeric adsorbent
- low
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- 229920005989 resin Polymers 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 21
- 241001165494 Rhodiola Species 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000000287 crude extract Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012141 concentrate Substances 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229920001429 chelating resin Polymers 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 6
- 229930182470 glycoside Natural products 0.000 abstract 3
- 150000002338 glycosides Chemical class 0.000 abstract 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000003480 eluent Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- ILRCGYURZSFMEG-UHFFFAOYSA-N Salidroside Natural products OC1C(O)C(O)C(CO)OC1OCCC1=CC=C(O)C=C1 ILRCGYURZSFMEG-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ILRCGYURZSFMEG-RQICVUQASA-N salidroside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)OC1OCCC1=CC=C(O)C=C1 ILRCGYURZSFMEG-RQICVUQASA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000004237 preparative chromatography Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 241000220284 Crassulaceae Species 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 235000014327 Sedum acre Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 1
- 238000002953 preparative HPLC Methods 0.000 description 1
- 230000004223 radioprotective effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Landscapes
- Medicines Containing Plant Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
This invention relates to a method for separating and preparing high-purity rhodiola root glycosides from natural rhodiola root crude extract using two-step resin method, comprising: dissolve the rhodiola root crude extract in the 20-90Def C water with stirring followed by filtration, adjust the filtrate pH to 1-5 then load on the absorption resin column at room temperature, elute with organic solvent like acetone, low-carbon alcohol or acetate, concentrate the eluent, and load on the chromatography column at room temperature, concentrate and evaporate the chromatography liquid to dryness, then add in organic solvent like low-carbon alcohol or acetate and heat to re-dissolve, filtrate and concentrate the filtrate to precipitate the crystals, then obtain the high-purity rhodiola root glycosides after filtration. By using one resin absorption and one resin chromatography, this invention can prepare high-purity rhodiola root glycosides with 90%-98% purity from low-content(1%-5%) natural rhodiola root crude extract, and the absorption and chromatography process is done at room temperature. Besides, the process is easy and qualified for industrial production.
Description
Technical field
The present invention relates to a kind of method for preparing rhodioside (salidroside) of from the rhodiola root of natural plant crude extract, separating, belong to technical field of biochemical industry.
Background technology
The Crassulaceae Rhodida plant is perennial herb or semishrub plant, and the whole world has kind more than 90, in state-owned nearly 80 kinds, major part is grown on the limestone, granites mountain region, mountain valley rock of height above sea level 3500～5000m.The Root of Kirilow Rhodiola resource of China mainly is distributed in some areas in northeast, northwest, North China and southwest.Studies show that Root of Kirilow Rhodiola has anti-hypoxia, antifatigue, anti-ageing, radioprotective, antitumor, reducing blood-fat prevents and treats biological medical actions such as cardiovascular disorder.Rhodioside (salidroside) is the main effective constituent in the Root of Kirilow Rhodiola.
The preparation of bibliographical information rhodioside adopts multistep column chromatography or preparative high performance liquid chromatography to finish more.Traditional extraction process has the employing charcoal absorption, with ethanol or methanol-eluted fractions, elutriant is concentrated the back with making with extra care with preparative chromatography behind the membrane filtration.Because the preparation amount of preparative chromatography is very little, can't scale operation.Also there is alcohol extract to prepare rhodioside through polymeric amide, macroporous adsorbent resin, silica gel and four kinds of column chromatography for separation of dextrane gel successively with Root of Kirilow Rhodiola.The separating medium that this method is used is wide in variety, and the dextrane gel price is expensive, and silica gel can't recycle, and the whole sepn process time is long, and the cost height is not suitable for suitability for industrialized production.Adopt the high-speed counter-current liquid phase chromatography to prepare rhodioside, made gram level product at present, products obtained therefrom purity height, shortcoming is that preparation amount is few, and high-speed counter-current liquid chromatography device costliness, can't large-scale production.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, product purity is high, be fit to the preparation method of the rhodioside of suitability for industrialized production.
The technical solution used in the present invention is in order to achieve the above object: with Root of Kirilow Rhodiola crude extract temperature is 20～90 ℃ water stirring and dissolving 20 minutes～3 hours, filters and obtains clear filtrate.Regulating filtrate pH is 1～5, and normal temperature descended adsorption resin column to adsorb, and used 10%～40% acetone, low-carbon alcohol or acetate esters organic solvent wash-out then.Collect elutriant, concentrate eluant is to syrupy shape, and the adding polymeric adsorbent mixes the back oven dry, and the amount that adds resin is good to dry the not mutual adhesion of back resin.The polymeric adsorbent adding of oven dry has been filled in the chromatography column of polymeric adsorbent, the polymeric adsorbent of oven dry: polymeric adsorbent=1 of having adorned post: (1～10), normal temperature carries out chromatography with 5%～25% low-carbon (LC) alcohol organic solvent down, collects chromatography and sees through liquid, with its concentrated evaporate to dryness.Add low-carbon alcohol or acetate esters organic solvent heating for dissolving, Heating temperature is no more than 60 ℃, filtered while hot, concentrated filtrate, be cooled to 0 ℃, separate out crystallization, wash crystalline substance with low-carbon alcohol or acetate esters organic solvent again, dry below 70 ℃, obtain product, the filtrate recovery set is used.
Polymeric adsorbent described in the such scheme is a nonpolar adsorption resin, as the product HZ-816 of Shanghai Huazhen Science and Technology Co., Ltd., the product A mberlite XAD-4 of U.S. RohmHass company, Amberlite XAD-16, Amberlite XAD-1600 or Amberchrom CG161.The low-carbon (LC) alcohol organic solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, the Virahol in the scheme; Described acetate esters organic solvent is vinyl acetic monomer or N-BUTYL ACETATE.
Compare with other extraction processes of rhodioside, positively effect of the present invention is: only just can prepare purity from the neutral red red-spotted stonecrop crude extract of low levels (1%～5%) through resin absorption, resin chromatography and crystallization is 90%～98% rhodioside, and absorption, chromatography process are all carried out at normal temperatures, technology is simple, each separating step all is sophisticated biochemical industry unit operation, is fit to suitability for industrialized production.
Embodiment
Below by preparing high-purity salidroside embodiment from commercially available Root of Kirilow Rhodiola crude extract (content 1%～5%), the invention will be further described.
Embodiment 1
Get Root of Kirilow Rhodiola crude extract 500 grams, add water 5000ml dissolving, be heated to 30 ℃, stir insulation 2.5 hours.Filtration obtains clear filtrate.Filtrate is regulated pH to 3, flows through HZ-816 polymeric adsorbent (Shanghai Huazhen Science and Technology Co., Ltd.) post under the normal temperature, feeds 30% ethanol 1200ml then, collects effluent liquid.Effluent liquid is concentrated into syrupy shape, adds the HZ-816 polymeric adsorbent and mixes and dry.Polymeric adsorbent according to oven dry: adorned the ratio of the polymeric adsorbent of post=1: 6, the resin of oven dry has been added the chromatography column of having filled the HZ-816 polymeric adsorbent,, normal temperature feeds 15% ethanolic soln down and carries out chromatography.Collect chromatographic solution, be concentrated into dried.Add dissolve with ethanol, be heated to 50 ℃, filtered while hot.Concentrated filtrate is cooled to 0 ℃, separates out crystallization, and the filtrate recovery set is used.After the rhodioside crystallization was cleaned with ethanol, 60 ℃ of vacuum-dryings obtained the rhodioside white powder, measure through HPLC, and purity is 97.2%.
Embodiment 2
Get Root of Kirilow Rhodiola crude extract 500 grams, add water 5000ml dissolving, be heated to 70 ℃, stir insulation 1 hour.Filtration obtains clear filtrate.Filtrate is regulated pH to 4, flows through Amberlite XAD-4 polymeric adsorbent (U.S. RohmHaas company product) post under the normal temperature, feeds 25% ethanol 2000ml then, collects effluent liquid.Adding Amberlite XAD-4 polymeric adsorbent mixed and dries after effluent liquid was concentrated into syrupy shape.Polymeric adsorbent according to oven dry: the ratio of having adorned the polymeric adsorbent of post=1: 2, the resin of oven dry is added the chromatography column of having filled Amberlite XAD-1600 polymeric adsorbent (U.S. RohmHass company product), the normal temperature ethanolic soln of feeding 20% down carries out chromatography, collect chromatographic solution, be concentrated into dried.Add the propyl carbinol dissolving, be heated to 50 ℃, filtered while hot.Concentrated filtrate is cooled to 0 ℃, separates out crystallization, and the filtrate recovery set is used.After the rhodioside crystallization was cleaned with propyl carbinol, 60 ℃ of vacuum-dryings obtained the rhodioside white powder, measure through HPLC, and purity is 95.6%.
Embodiment 3
Get Root of Kirilow Rhodiola crude extract 500 grams, add water 5000ml dissolving, be heated to 60 ℃, stir insulation 1.5 hours.Filtration obtains clear filtrate.Filtrate is regulated pH to 3, flows through HZ-816 polymeric adsorbent (Shanghai Huazhen Science and Technology Co., Ltd.) post under the normal temperature, feeds 15% methyl alcohol 2500ml then, collects effluent liquid.Adding HZ-816 polymeric adsorbent mixed and dries after effluent liquid was concentrated into syrupy shape.Polymeric adsorbent according to oven dry: adorned the ratio of the polymeric adsorbent of post=1: 10, the resin of oven dry has been added filled the chromatography column that HZ-816 has adsorbed resin, normal temperature feeds 5% methanol solution down and carries out chromatography, collects chromatographic solution, is concentrated into dried.Add the propyl carbinol dissolving, be heated to 50 ℃, filtered while hot.Concentrated filtrate is cooled to 0 ℃, separates out crystallization, and the filtrate recovery set is used.After the rhodioside crystallization was cleaned with propyl carbinol, 60 ℃ of vacuum-dryings obtained the rhodioside white powder, measure through HPLC, and purity is 96.0%.
Embodiment 4
Get Root of Kirilow Rhodiola crude extract 500 grams, add water 5000ml dissolving, be heated to 80 ℃, stir insulation 40 minutes.Filtration obtains clear filtrate.Filtrate is regulated pH to 1, flows through HZ-816 polymeric adsorbent (Shanghai Huazhen Science and Technology Co., Ltd.) post under the normal temperature, feeds 40% acetone 1500ml then, collects effluent liquid.Adding HZ-816 polymeric adsorbent mixed and dries after effluent liquid was concentrated into syrupy shape.The resin of oven dry is added the chromatography column filled the HZ-816 polymeric adsorbent, the polymeric adsorbent of oven dry: adorned the polymeric adsorbent of post=1: 3, normal temperature feeds 25% aqueous isopropanol down and carries out chromatography, collects chromatographic solution, is concentrated into dried.Add the N-BUTYL ACETATE dissolving, be heated to 50 ℃, filtered while hot.Concentrated filtrate is cooled to 0 ℃, separates out crystallization, and the filtrate recovery set is used.After the rhodioside crystallization was cleaned with N-BUTYL ACETATE, 60 ℃ of vacuum-dryings obtained the rhodioside white powder, measure through HPLC, and purity is 92.9%.
Claims (4)
1. the preparation method of a rhodioside: (1) is 20～90 ℃ water stirring and dissolving 20 minutes～3 hours with Root of Kirilow Rhodiola crude extract temperature, filters and obtains clear filtrate; (2) regulating filtrate pH is 1～5, and normal temperature descended adsorption resin column to adsorb, and used 10%～40% acetone, low-carbon alcohol or acetate esters organic solvent wash-out then; (3) concentrate eluant adds polymeric adsorbent and mixes the back oven dry to syrupy shape; (4) the polymeric adsorbent adding of oven dry has been filled in the chromatography column of polymeric adsorbent, normal temperature carries out chromatography with 5%～25% low-carbon (LC) alcohol organic solvent down, collects chromatography and sees through liquid, with its concentrated evaporate to dryness; (5) add low-carbon alcohol or acetate esters organic solvent heating for dissolving, Heating temperature is no more than 60 ℃, filtered while hot, concentrated filtrate, be cooled to 0 ℃, separate out crystallization, wash crystalline substance with low-carbon alcohol or acetate esters organic solvent, dry below 70 ℃, obtain product, the filtrate recovery set is used.
2. according to the preparation method of the described rhodioside of claim 1, it is characterized in that described polymeric adsorbent is a nonpolar adsorption resin.
3. according to the preparation method of claim 1 and 2 described rhodiosides, it is characterized in that described polymeric adsorbent is HZ-816 (Shanghai Huazhen Science and Technology Co., Ltd.'s product), Amberlite XAD-4, AmberliteXAD-16, Amberlite XAD-1600 or Amberchrom CG161 (U.S. RohmHass company product).
4. according to the preparation method of the described rhodioside of claim 1, it is characterized in that described low-carbon (LC) alcohol organic solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, the Virahol; Described acetate esters organic solvent is vinyl acetic monomer or N-BUTYL ACETATE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100268302A CN1880326B (en) | 2005-06-16 | 2005-06-16 | Two-step resin method for preparing salidrose |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100268302A CN1880326B (en) | 2005-06-16 | 2005-06-16 | Two-step resin method for preparing salidrose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1880326A true CN1880326A (en) | 2006-12-20 |
| CN1880326B CN1880326B (en) | 2010-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005100268302A Expired - Fee Related CN1880326B (en) | 2005-06-16 | 2005-06-16 | Two-step resin method for preparing salidrose |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130561B (en) * | 2007-08-10 | 2010-10-06 | 成都诺迪康生物制药有限公司 | Method for producing salidroside and injection containing the same |
| CN113603734A (en) * | 2021-08-12 | 2021-11-05 | 内蒙古泓兴生物科技有限公司 | Method for extracting salidroside |
-
2005
- 2005-06-16 CN CN2005100268302A patent/CN1880326B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130561B (en) * | 2007-08-10 | 2010-10-06 | 成都诺迪康生物制药有限公司 | Method for producing salidroside and injection containing the same |
| CN113603734A (en) * | 2021-08-12 | 2021-11-05 | 内蒙古泓兴生物科技有限公司 | Method for extracting salidroside |
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| Publication number | Publication date |
|---|---|
| CN1880326B (en) | 2010-11-03 |
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