CN101735030A - Method for preparing 6-shogaol - Google Patents
Method for preparing 6-shogaol Download PDFInfo
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- CN101735030A CN101735030A CN200910232593A CN200910232593A CN101735030A CN 101735030 A CN101735030 A CN 101735030A CN 200910232593 A CN200910232593 A CN 200910232593A CN 200910232593 A CN200910232593 A CN 200910232593A CN 101735030 A CN101735030 A CN 101735030A
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- shogaol
- ethyl acetate
- supercritical fluid
- sherwood oil
- ginger
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- OQWKEEOHDMUXEO-UHFFFAOYSA-N (6)-shogaol Natural products CCCCCC=CC(=O)CCC1=CC=C(O)C(OC)=C1 OQWKEEOHDMUXEO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- OQWKEEOHDMUXEO-BQYQJAHWSA-N [6]-Shogaol Chemical compound CCCCC\C=C\C(=O)CCC1=CC=C(O)C(OC)=C1 OQWKEEOHDMUXEO-BQYQJAHWSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 25
- 235000006886 Zingiber officinale Nutrition 0.000 claims abstract description 31
- 235000008397 ginger Nutrition 0.000 claims abstract description 31
- 241000234314 Zingiber Species 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007670 refining Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 89
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 18
- 238000000194 supercritical-fluid extraction Methods 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 12
- 230000001476 alcoholic effect Effects 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract 3
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 19
- 238000010812 external standard method Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- 230000005526 G1 to G0 transition Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000010828 elution Methods 0.000 description 4
- NLDDIKRKFXEWBK-AWEZNQCLSA-N gingerol Chemical compound CCCCC[C@H](O)CC(=O)CCC1=CC=C(O)C(OC)=C1 NLDDIKRKFXEWBK-AWEZNQCLSA-N 0.000 description 4
- JZLXEKNVCWMYHI-UHFFFAOYSA-N gingerol Natural products CCCCC(O)CC(=O)CCC1=CC=C(O)C(OC)=C1 JZLXEKNVCWMYHI-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003146 anticoagulant agent Substances 0.000 description 2
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000002780 gingerol Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 102000011727 Caspases Human genes 0.000 description 1
- 108010076667 Caspases Proteins 0.000 description 1
- 102100035591 POU domain, class 2, transcription factor 2 Human genes 0.000 description 1
- 101710084411 POU domain, class 2, transcription factor 2 Proteins 0.000 description 1
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 102000013530 TOR Serine-Threonine Kinases Human genes 0.000 description 1
- 108010065917 TOR Serine-Threonine Kinases Proteins 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000702 anti-platelet effect Effects 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229930006739 camphene Natural products 0.000 description 1
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 1
- 239000000496 cardiotonic agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000010649 ginger oil Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 208000002154 non-small cell lung carcinoma Diseases 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 208000029729 tumor suppressor gene on chromosome 11 Diseases 0.000 description 1
- 239000001841 zingiber officinale Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The invention relates to the field of natural medicines, in particular to a method for preparing 6-shogaol, which is a method for preparing the efficient component 6-shogaol from the extract of ginger supercritical fluid. The method comprises the following steps of: mixing the extract of ginger supercritical fluid with an ethanol-containing acid water liquid before conversion, heating and refluxing, then separating and refining. The content of the 6-shogaol in the original extract of ginger supercritical fluid is about 2.5%, and the content of the 6-shogaol in the extract after the acid water reaction can reach 20%.
Description
Technical field
The present invention relates to natural medicine field, be specifically related to the preparation method of effective constituent 6-shogaol (6-shogaol), promptly utilize the orderly couplings of multiple means such as transforming pre-treatment, chromatographic separation and purification to prepare the method for effective constituent 6-shogaol in the Chinese medicine ginger.
Background technology
Ginger and rhizoma zingiberis are respectively fresh rhizome and the dry rhizome of zingiber Zingiber officinale Rosc., are conventional Chinese medicine.Main component in the ginger is pungent and fragrance ingredient, comprises gingerol, ginger oil terpene, Herba Limnophilae rugosae, camphene, folium eucalypti olein, starch, mucus etc.6-shogaol (6-shogaol) is one of volatile component in the ginger, and its molecular formula is C
17H
24O
3, molecular weight is 276.37, for yellow meal or crystallisate, is soluble in ethanol, is insoluble in water, its chemical structural formula is as follows:
The 6-shogaol has biological activitys such as cardiac stimulant, antiplatelet or antithrombotic, the easypro blood vessel that contracts.In recent years, there is research report 6-shogaol that very strong antitumour activity [6-Shogaol is arranged, an Active Constituent of Dietary Ginger, InducesAutophagy by Inhibiting the AKT/mTOR Pathway in Human Non-Small Cell Lung Cancer A549Cells.J Agric Food Chem.2009 Oct 2; 6-Shogaol induces apoptosis in human colorectal carcinomacells via ROS production, caspase activation, and GADD 153 expression.Mol Nutr Food Res.2008,52,527-537].Therefore, the preparation of 6-shogaol is significant to the pharmacology activity research that advances this composition and ginger class Chinese medicine.
Preparation 6-shogaol difficulty is very big from ginger, the one because the content of 6-shogaol in ginger extremely low (＜0.05mg/g); The 2nd, owing to 8-hydroxyketone structure is arranged, the physico-chemical property less stable in its molecule; The 3rd, in ginger, the chemical ingredients of this compound and multiple similar is also deposited, and separating difficulty is very big.By literature search and data check, still find no the 6-shogaol reference substance of company's supplied goodsization both at home and abroad; Through patent retrieval both at home and abroad, also still find no the relevant patent of preparation 6-shogaol from ginger.Domestic existing preparation method often will adopt some separating power higher but method such as thin layer scraper plate method and analysis mode HPLC method that output is less.Though reported in literature (Cytotoxic Components from the Dried Rhizomes ofZingiber officinale Roscoe.Arch Pharm Res is arranged at present, 2008,31,415-41) adopt the silica gel method from ginger, to prepare the 6-shogaol, but its productive rate very low (25mg/600g).This method is only applicable to the laboratory and prepares usefulness on a small quantity, is not suitable for large-scale application.
Just because of content low, yield poorly, factor such as cost is big, mass preparation 6-shogaol is difficult to realize always from ginger, has also restricted the activity research of 6-shogaol, and is pharmacology and the activity research that ginger class Chinese medicine is carried out on the basis with the 6-shogaol.
China's supercritical fluid extraction research starts from early 1980s, has entered the commodity application stage at present, existing ripe commodity ginger supercritical fluid extraction thing supply on the market.Ginger supercritical fluid extraction owner will contain gingerol and shogaol compounds such as 6-gingerol, 6-shogaol, quality homogeneous, stable.Based on ginger supercritical fluid extraction thing, use multimedia combination, study a kind of output that can increase substantially the 6-shogaol, fast, the method for preparing the 6-shogaol of easy handling, be the subject matter that the present technique field faces.
Summary of the invention
The invention discloses a kind of can increase substantially output, fast, the method for preparing the 6-shogaol of easy handling.
The present invention is a raw material with ginger supercritical fluid extraction thing, on traditional extraction, separation and refining basis, improve, when extracting with ginger supercritical fluid extraction thing with contain the backflow of alcoholic acid acid liquid mixing post-heating.
Wherein ginger supercritical fluid extraction thing preferably was not less than 3: 80 with the weightmeasurement ratio that contains the alcoholic acid acid liquid.
Contain wherein that concentration of ethanol is preferably 40%～80v/v% in the alcoholic acid acid liquid, the concentration of hydrochloric acid is 0.2～0.8M more preferably, and under this concentration, corresponding pH value is about 0.1～0.7.Described acid can be selected from hydrochloric acid, sulfuric acid etc., the preferred hydrochloric acid of the present invention.
By the external standard method quantitative Analysis, the content of 6-shogaol is about 2.5% in the former supercritical fluid extraction thing, and the content of 6-shogaol can reach 20% in the extract after carrying out the sour water reaction treatment, sees Fig. 1.Infer that part 6-gingerol has converted the 6-shogaol in the former supercritical fluid extraction thing of possibility.
Test finds, when the concentration of acid not simultaneously, the yield of product is had certain influence, be example with hydrochloric acid, the hydrochloric acid of different concns causes the difference (HPLC detects, and external standard method is quantitative) of 6-shogaol output.See Table 1:
Table 1. concentration of hydrochloric acid is to the influence of 6-shogaol content in the extract
| Concentration (M) | ??0.1 | ??0.2 | ??0.4 | ??0.8 | ??1.0 |
| The content of 6-shogaol (%) | ??12 | ??16 | ??17 | ??20 | ??13 |
As can be seen from Table 1, when the concentration of hydrochloric acid is 0.1～1.0M (corresponding pH value is 0～1.0), 2.5% height in all more former supercritical fluid extraction thing of product 6-shogaol, explanation is reacted in the sour water that contains alcohol, converted other molecule to the 6-shogaol, the concentration of hydrochloric acid is 0.2～0.8M (corresponding pH value is about 0.1～0.7) more preferably.
Discover that reflux variation of temperature and time are also influential to product, see Table 2, table 3:
Table 2. reflux temperature is to the influence of 6-shogaol content in the extract
| Temperature (℃) | ??60 | ??70 | ??80 | ??100 |
| The content of 6-shogaol (%) | ??10 | ??15 | ??19 | ??21 |
The table 3. reflux time is to the influence of 6-shogaol (6-shogaol) content in the extract
| Time (h) | ??0.5 | ??1 | ??2 | ??4 |
| The content of 6-shogaol (%) | ??5 | ??7 | ??18 | ??20 |
Therefore the preferred 70-100 of temperature ℃ of reflux.The preferred 2-4h of return time.
Reaction solution after the reflux is reclaimed ethanol, reclaimed the alcoholic acid acid liquid and separate, separating step can comprise for two steps: extract and cross silica gel chromatographic column.Chosen multiple extraction solvent commonly used, yield is better when finding to make extraction solvent with sherwood oil or ethyl acetate, and effect is also different when selecting sherwood oil with ethyl acetate for use, sees Table 4, and therefore, most preferred extraction solvent is an ethyl acetate among this preparation method.
Table 4 extraction solvent is to reacting the influence of 6-shogaol content in the extract of back
| Extraction agent | Sherwood oil | Ethyl acetate |
| The content of 6-shogaol (%) | ??10 | ??19 |
After the extraction, the extraction liquid reheat reclaims the solvent of extraction usefulness.The preferred 40-55 of extraction liquid recovered temperature ℃, temperature is too high, and the yield of 6-shogaol can reduce.
To extract the back enriched material is raw material, mixes sample, and silica gel for chromatography is as stationary phase, gradient elution, preferred sherwood oil of eluent and ethyl acetate mixed solution are collected and are contained 6-shogaol part, concentrate and promptly get 6-shogaol crude product, general concentrated the employing put evaporate to dryness on the Rotary Evaporators.The volume ratio of sherwood oil and ethyl acetate is preferably 25～50: 1.
With the crude product acetic acid ethyl dissolution that makes, cross middle compression leg, wash-out, elutriant that the thin layer silica gel H is a stationary phase and concentrate and promptly get 6-shogaol highly finished product, wherein the moving phase used of wash-out is the mixed solvent of sherwood oil and ethyl acetate.The volume ratio of sherwood oil and ethyl acetate is preferably 15～20: 1.
Can also further use the HPLC purifying through above-mentioned purified product, moving phase is collected main chromatographic peak for containing methanol aqueous solution, and evaporate to dryness promptly gets the pure product of 6-shogaol.Preferred 60～the 90%v/v of methanol concentration, methanol concentration is 70～80%v/v more preferably.
The present invention can increase substantially output, quick, easy handling, and the yield in each step is as follows:
| Step | Reaction and extraction | Silica gel column chromatography separates | Middle compression leg is refining | The HPLC purifying |
| Yield | Target product content is elevated to 20% by original 2.5% | ??10-20％ | About 35% | About 50% |
Description of drawings
Fig. 1 is the HPLC comparative analysis figure of ginger supercritical fluid extraction thing before and after handling (color atlas above among the figure after containing the alcoholic acid sour water and handling, following chromatogram is graphic handled without sour water)
Embodiment
Ginger supercritical fluid extraction thing in the present embodiment is purchased in Guangzhou and rich bio tech ltd
Embodiment 1
Accurately take by weighing the about 75g of ginger supercritical fluid extraction thing (purchasing) in Guangzhou and rich bio tech ltd, with the abundant mixing of itself and 2000ml 60% alcoholic acid aqueous hydrochloric acid (0.8M hydrochloric acid), 60 ℃ of reflux 4h, after question response is complete, 55 ℃ are reclaimed ethanol, add the 40ml ethyl acetate extraction, reclaim ethyl acetate, acquisition to be containing the product of 6-shogaol, and the content of 6-shogaol is elevated to 20% (external standard method is quantitative) by original 2.5% in the extract.With reacted product 300g is raw material, silica gel column chromatography separates, gradient elution, eluent polarity is followed successively by sherwood oil: ethyl acetate=45: 1, and sherwood oil: ethyl acetate=37: 1 and sherwood oil: ethyl acetate=27: 1, collect back two portions, TLC checks merging, put evaporate to dryness on the Rotary Evaporators, promptly get 6-shogaol crude product 50g, it is 80% that the HPLC external standard method detects its purity.Then that middle compression leg on the crude product is refining, as stationary phase, eluent is a sherwood oil with the thin layer silica gel H: ethyl acetate=20: 1, get 6-shogaol highly finished product 18g, and it is 90% that the HPLC external standard method detects its purity.(methyl alcohol: water volume ratio is a moving phase at 70: 30, C with Angilent1100 series preparation HPLC purifying on the highly finished product at last
18Be stationary phase, flow velocity 10mL/min, UV-detector, the detection wavelength is 280nm), getting the pure product 8g of 6-shogaol, its purity is 98% (HPLC check, external standard method is quantitative).
Embodiment 2
Accurately take by weighing the about 0.75g of ginger supercritical fluid extraction thing, with the abundant mixing of itself and 20ml 80% alcoholic acid acid liquid (0.6M hydrochloric acid), 80 ℃ of reflux 1h, after question response is complete, 50 ℃ are reclaimed ethanol, add the 40ml ethyl acetate extraction, reclaim ethyl acetate, acquisition is based on the product of 6-shogaol, and the content of 6-shogaol is elevated to 18% (external standard method is quantitative) by original 2.5% in the extract.With reacted product 300g is raw material, silica gel column chromatography separates, gradient elution, eluent polarity is followed successively by sherwood oil: ethyl acetate=50: 1, and sherwood oil: ethyl acetate=33: 1 and sherwood oil: ethyl acetate=25: 1, collect back two portions, TLC checks merging, put evaporate to dryness on the Rotary Evaporators, promptly get 6-shogaol crude product 55g, it is 80% that the HPLC external standard method detects its purity.Then that middle compression leg on the crude product is refining, as stationary phase, eluent is a sherwood oil with the thin layer silica gel H: ethyl acetate=17: 1, get 6-shogaol highly finished product 19g, and it is 90% that the HPLC external standard method detects its purity.At last with Angilent1100 series preparation HPLC purifying (methyl alcohol: water volume ratio 75: 25) be moving phase, C on the highly finished product
18Be stationary phase, flow velocity 10mL/min, UV-detector, the detection wavelength is 280nm), getting the pure product 8.5g of 6-shogaol, its purity is 98% (HPLC check, external standard method is quantitative).
Embodiment 3
Accurately take by weighing the about 0.75g of ginger supercritical fluid extraction thing, with the abundant mixing of itself and 20ml 80% alcoholic acid acid liquid (0.4M hydrochloric acid), 100 ℃ of reflux 2h, after question response is complete, 45 ℃ are reclaimed ethanol, add the 40ml ethyl acetate extraction, reclaim ethyl acetate, acquisition is based on the product of 6-shogaol, and the content of 6-shogaol is elevated to 25% (external standard method is quantitative) by original 2.5% in the extract.With reacted product 300g is raw material, silica gel column chromatography separates, gradient elution, eluent polarity is followed successively by sherwood oil: ethyl acetate=48: 1, and sherwood oil: ethyl acetate=35: 1 and sherwood oil: ethyl acetate=28: 1, collect back two portions, TLC checks merging, put evaporate to dryness on the Rotary Evaporators, promptly get 6-shogaol crude product 60g, it is 80% that the HPLC external standard method detects its purity.Then that middle compression leg on the crude product is refining, as stationary phase, eluent is a sherwood oil with the thin layer silica gel H: ethyl acetate=15: 1, get 6-shogaol highly finished product 21g, and it is 90% that the HPLC external standard method detects its purity.(methyl alcohol: water volume ratio is a moving phase at 80: 20, C with Angilent1100 series preparation HPLC purifying on the highly finished product at last
18Be stationary phase, flow velocity 10mL/min, UV-detector, the detection wavelength is 280nm), getting the pure product 10g of 6-shogaol, its purity is 98% (HPLC check, external standard method is quantitative).
Claims (10)
1. method for preparing the 6-shogaol from ginger supercritical fluid extraction thing comprises extraction, separates and refining, it is characterized in that: when extracting with ginger supercritical fluid extraction thing with contain the backflow of alcoholic acid acid liquid mixing post-heating.
2. the process of claim 1 wherein that ginger supercritical fluid extraction thing and the weightmeasurement ratio that contains the alcoholic acid acid liquid were not less than 3: 80.
3. the process of claim 1 wherein to contain that concentration of ethanol is 40%～80v/v% in the alcoholic acid acid liquid, the concentration of hydrochloric acid is 0.2-0.8M.
4. the process of claim 1 wherein that the temperature of reflux is 70-100 ℃, return time is 2-4h.
5. the method for claim 1, the isolating method in back that wherein refluxes comprises: reclaim ethanol, acid liquid obtains extracting the back enriched material with ethyl acetate extraction, reclaim under reduced pressure ethyl acetate, and enriched material is crossed silica gel chromatographic column, wash-out, the collection elutriant concentrates, and promptly gets 6-shogaol raw product.
6. the method for claim 5, the eluent when wherein silica gel column chromatography separates are the mixed solvent of sherwood oil and ethyl acetate, and sherwood oil and ethyl acetate volume ratio are 25～50: 1.
7. the method for claim 5, the temperature that wherein reclaims ethanol and ethyl acetate is 40-55 ℃.
8. the process of claim 1 wherein that process for purification comprises: with the crude product acetic acid ethyl dissolution that makes, compression leg, wash-out, elutriant concentrate and promptly get 6-shogaol highly finished product in crossing, and wherein the moving phase used of wash-out is the mixed solvent of sherwood oil and ethyl acetate.
9. the method for claim 8, wherein the volume ratio of sherwood oil and ethyl acetate is preferably 15～20: 1.
10. the method for claim 8, also comprise: with the highly finished product dissolve with methanol that makes, with the HPLC purifying, moving phase is collected main chromatographic peak for containing methanol in water, and 40-55 ℃ of evaporated under reduced pressure promptly gets the pure product of 6-shogaol.
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|---|---|---|---|---|
| CN102028689A (en) * | 2010-12-10 | 2011-04-27 | 中国药科大学 | Compound medicinal composition for treating acute lymphocytic leukemia |
| CN102260152A (en) * | 2011-06-02 | 2011-11-30 | 中国药科大学 | Preparation method and medicinal application of shogaol extract |
| CN102266547A (en) * | 2011-08-31 | 2011-12-07 | 南京财经大学 | Preparation method of ginger extract with detoxifying effect on exogenous carcinogens and product |
| CN106187727A (en) * | 2016-07-27 | 2016-12-07 | 陕西嘉禾生物科技股份有限公司 | A kind of method extracting 6 paradol from paradise green pepper fruit |
| CN106800502A (en) * | 2016-12-05 | 2017-06-06 | 陕西嘉禾药业有限公司 | A kind of purposes of paradise green pepper and the method that 6 salad oils of separation are extracted from paradise green pepper |
| JP2018027082A (en) * | 2016-08-10 | 2018-02-22 | 株式会社エヌ・エル・エー | Processed ginger and manufacturing method thereof |
| CN112239399A (en) * | 2020-09-21 | 2021-01-19 | 华南理工大学 | Gingerol pulse electric field treatment preparation method with high 6-shogaol content |
| CN113925948A (en) * | 2020-07-14 | 2022-01-14 | 香港大学 | Application of ginger total extract or active ingredients thereof, pharmaceutical composition and preparation method |
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Cited By (11)
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| CN102028689A (en) * | 2010-12-10 | 2011-04-27 | 中国药科大学 | Compound medicinal composition for treating acute lymphocytic leukemia |
| CN102260152A (en) * | 2011-06-02 | 2011-11-30 | 中国药科大学 | Preparation method and medicinal application of shogaol extract |
| CN102266547A (en) * | 2011-08-31 | 2011-12-07 | 南京财经大学 | Preparation method of ginger extract with detoxifying effect on exogenous carcinogens and product |
| CN102266547B (en) * | 2011-08-31 | 2013-06-12 | 南京财经大学 | Preparation method of ginger extract with detoxifying effect on exogenous carcinogens and product |
| CN106187727A (en) * | 2016-07-27 | 2016-12-07 | 陕西嘉禾生物科技股份有限公司 | A kind of method extracting 6 paradol from paradise green pepper fruit |
| JP2018027082A (en) * | 2016-08-10 | 2018-02-22 | 株式会社エヌ・エル・エー | Processed ginger and manufacturing method thereof |
| CN106800502A (en) * | 2016-12-05 | 2017-06-06 | 陕西嘉禾药业有限公司 | A kind of purposes of paradise green pepper and the method that 6 salad oils of separation are extracted from paradise green pepper |
| CN113925948A (en) * | 2020-07-14 | 2022-01-14 | 香港大学 | Application of ginger total extract or active ingredients thereof, pharmaceutical composition and preparation method |
| CN113925948B (en) * | 2020-07-14 | 2023-10-10 | 香港大学 | Use of rhizoma Zingiberis recens total extract or its active component, pharmaceutical composition and preparation method |
| CN112239399A (en) * | 2020-09-21 | 2021-01-19 | 华南理工大学 | Gingerol pulse electric field treatment preparation method with high 6-shogaol content |
| CN112239399B (en) * | 2020-09-21 | 2022-01-18 | 华南理工大学 | Gingerol pulse electric field treatment preparation method with high 6-shogaol content |
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| CN101735030B (en) | 2012-12-12 |
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