CN104045648B - The method of 1,8,9-trihydroxy-3-methoxy-benzo[4,5 chemical reference substance is prepared in a kind of scale - Google Patents
The method of 1,8,9-trihydroxy-3-methoxy-benzo[4,5 chemical reference substance is prepared in a kind of scale Download PDFInfo
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Abstract
The present invention relates to a kind of scale and prepare the new preparation process of 1,8,9-trihydroxy-3-methoxy-benzo[4,5 chemical reference substance.Being optimized by 1,8,9-trihydroxy-3-methoxy-benzo[4,5 stability and preparation technology streaming, use and make large-scale middle pressure or decompression silica gel chromatography by oneself, batch obtains the purity 1,8,9-trihydroxy-3-methoxy-benzo[4,5 chemical reference substance more than 98%, and its scale is up to ten grams of levels.
Description
Present disclosure relates to a kind of scale and prepares the new preparation process of 1,8,9-trihydroxy-3-methoxy-benzo[4,5 (Wedelolactone) chemical reference substance.Mainly include ethyl acetate extraction, make large-scale middle pressure or decompression silica gel chromatography, three steps of recrystallization by oneself.
Background technology
1,8,9-trihydroxy-3-methoxy-benzo[4,5 is coumarin kind compound, have protect the liver, antiinflammatory, enhancing immunity etc. effect, Chinese Pharmacopoeia (2010 editions) is classified as the newly-increased quantitative target composition of Eclipta Prostrata L, actual application breach is huge, loaded down with trivial details plus this reference substance purification procedures, all cause this reference substance expensive (commercially available 1000-1500 unit, 20mg/ props up).Therefore batch obtains a large amount of reference substance, needed for the quality control of Herba Ecliptae correlated product can not only be met, and also significant for furtheing investigate its mechanism of action.
At present, the report preparing 1,8,9-trihydroxy-3-methoxy-benzo[4,5 from Herba Ecliptae mostly is laboratory scale, step is cumbersome, such as (Acta Pharmaceutica Sinicas such as Zhang Jinsheng, 36 (1): 34-37,2011) report uses petroleum ether-ether-methanol or 95% methanol diafiltration extraction, methanol dissolving remove impurity or ethyl acetate abstraction impurity removal, silicagel column separation acquisition 1,8,9-trihydroxy-3-methoxy-benzo[4,5, wherein separates eluant and uses toluene-acetone-acetic acid (6:8:1) or methylene chloride-methanol-water (14:9:4 lower floor)；Former red rosy clouds etc. (Chinese experimental pharmacology of Chinese medical formulae magazine, 17(16): 103-105,2011) report that employing 95% ethanol percolation extraction, ethyl acetate extraction, silicagel column petroleum ether-ethyl acetate gradient separations, sephadexLH-20 purification obtain 1,8,9-trihydroxy-3-methoxy-benzo[4,5；(the Ger.DE3525363 such as Wagner, Deutsche Bundespatent) use methanol soak extraction, ethyl acetate extracts, C18 reversed-phase HPLC gradient elution prepares 1,8,9-trihydroxy-3-methoxy-benzo[4,5, (the JP83228353 such as Kokai, Japan Patent) use water reflux, extract, butanol-water (1:1) countercurrently-adverse current distribution, SephadexLH-20, such document or use containing benzene and the bigger eluting solvent of dichloromethane toxicity, or use SephadexLH-20, the expensive separating filler of C18, and the most all use the most time-consuming diafiltration or soak extraction, cannot be carried out commercial scale and amplify production, it is required that reference substance yield cannot meet actual application.
The present invention passes through system extracting and developing Study of optimization, it is found that while in 1,8,9-trihydroxy-3-methoxy-benzo[4,5 structure containing a lactone bond and three phenolic hydroxyl groups (Fig. 1), structure less stable, but the ethanol extraction by alcohol content more than 70%, during 50 DEG C of concentrating under reduced pressure, its content has no significant change, prompting can replace diafiltration to extract by reflux, extract, greatly speeds up extraction efficiency；During extraction, the temperature of hot water is not more than 40 DEG C, and 1,8,9-trihydroxy-3-methoxy-benzo[4,5 can preferably keep stable.When silicagel column separates, employing post bed is closely, post imitates higher middle pressure or decompression chromatographic column separates, and is possible not only to obtain more preferable separating effect, and is greatly accelerated separation progress；Use the multiple stainless steel column of self-control as chromatographic column, can conveniently be processed as the most required major diameter post, significantly improve separation flux；Simultaneously by carefully optimizing eluting solvent, final selection is in petroleum ether-ethyl acetate mixed flow middle interpolation proper amount of acetic acid mutually, select this eluting solvent, the isocratic elution on silicagel column can be realized and the response rate is higher, prepare highly beneficial for batch, because the eluant of a kind of ratio only need to be allocated, greatly reduce the difficulty of solvent recovery allotment.Use this preparation technology of system optimization, prepared by the scale that can realize 1,8,9-trihydroxy-3-methoxy-benzo[4,5, its purity more than 98%, preparative-scale up to 10 grams of levels more than.
Summary of the invention
It is desirable to provide a kind of technique is simple, the novel preparation method of easy scale; can be with Herba Ecliptae ethanol extract as raw material; through ethyl acetate extraction, middle pressure or decompression silica gel chromatography, three steps of recrystallization; can obtain the purity 1,8,9-trihydroxy-3-methoxy-benzo[4,5 chemical reference substance more than 98%, its scale is up to ten grams of levels.
For achieving the above object, the technical solution used in the present invention:
1) ethyl acetate extraction:
Herba Ecliptae ethanol extract, or Herba Ecliptae medical material drying under reduced pressure acquisition ethanol extract after the ethanol extraction that volume fraction is not less than 70%, add the water of extract weight 3-5 times volume, and heating makes it dissolve, and temperature controls at 30 DEG C-40 DEG C；Add the ethyl acetate extraction of extract weight 1-2 times volume, repeat extraction 2-4 time, combining extraction liquid, be evaporated to 1/3～1/6 volume (ml/g) of ethanol extract weight, then admix the silica gel of equal proportion weight (g/ml), be dried and obtain acetic acid ethyl ester extract dry powder；
2) pressure or decompression silica gel chromatography in:
Take stainless steel column that blade diameter length ratio is 2～12.5 as chromatographic column, load the silica gel of extract 1-2 times of weight of dry powder as chromatography silica gel, dry method loading；With petroleum ether: ethyl acetate: acetic acid (volume ratio 8:2:1-6:4:1) mixed solvent eluting, middle compression leg pressure 0.2-0.3MPa, decompression column pressure is at-0.08-0.09MPa, thin layer chromatography detects, with petroleum ether: ethyl acetate: acetic acid (volume ratio 3:7:0.5-5:5:0.5) is as developing solvent, collecting the Rf value eluent at 0.40-0.48, concentrating under reduced pressure, separating out shallow white precipitate is 1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product；
3) recrystallization:
Above-mentioned reference substance crude product ethyl acetate or methanol dissolve ,-4 DEG C of-10 DEG C of crystallizes arranged below, can obtain the purity 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance more than 98%, and its outward appearance is white powder.
Mixing sample silica gel in described step 1) and necessarily use 100-200 mesh silica gel, otherwise loading silica gel is thinner than chromatographic silica gel granule, will sink, and have a strong impact on separating effect in pressurization and decompression.
Described step 2) design parameter be that chromatography silica gel is 100-200 mesh or 200-300 mesh, be not required to be dried activation processing before dress post, as by silica gel activating, its absorbability is too strong, will be substantially reduced the response rate of reference substance.Petroleum ether boiling range in eluant is 60-90 DEG C, and eluent controls at 8～12 times of column volumes, and flow velocity is 100-150ml/min.
The detailed process of described step 3) is, during recrystallization, ethyl acetate used is that analytical pure heavily steams solvent, and methanol is chromatographic grade, and mother solution is gone after need to filtering again and placed crystallization.
From Herba Ecliptae, separate 1,8,9-trihydroxy-3-methoxy-benzo[4,5 chemical reference substance with the present invention have the advantage that and improve:
1) present invention process is simple, it is simple to streaming produces
The present invention uses Herba Ecliptae alcohol thing to extract through ethyl acetate, extract is not required to be condensed into thick extractum when merging concentration can be directly added into the silica gel mixed sample of 100-200 mesh, fume hood volatilizes to obtain extract dry powder, can be used as the sample to be separated of second step silica gel column chromatography after appropriate grinding.Isocratic elution solvent is used during second step silica gel column chromatography, drying under reduced pressure is passed through after obtaining target stream part, on the one hand 1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product can be obtained, on the one hand recycling design is easy to redistribution recycling, still it is not required to during drying under reduced pressure drain solvent, it is concentrated into small size and i.e. may filter that placement crystallize, obtain 1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product, use heavily steaming ethyl acetate or Chromatographic Pure Methanol dissolution filter can carry out recrystallization subsequently.Three separating steps linking the best, is highly convenient for streaming and produces.Compare each step of document separating technology to be both needed to be concentrated to dryness or thick extractum, substantially increase separation efficiency.
2) technological means that the present invention uses is particularly suitable for amplification and carries out large-scale production.
This preparation technology is the highest to ingredient requirement, 70% ethanol extraction that technique employing is common, rather than the diafiltration used in document and dip operation, it is highly susceptible to batch and gets the raw materials ready；Silica gel column chromatography uses chromatography of pressing or reduce pressure in rustless steel, not only overcomes the pressure limit of compression leg in traditional glass, and the most stainless steel column is prone to processing, can conveniently be machined to required major diameter post, reaches to produce required extensive and high flux；Silica filler is cheap and easily-available, and solvent for use only relates to the Conventional solvents such as petroleum ether, ethyl acetate, acetic acid, and cost is inexpensive.
Accompanying drawing explanation
The structure of Fig. 1 1,8,9-trihydroxy-3-methoxy-benzo[4,5；
The HPLC of the 1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product obtained after Fig. 2 silica gel column chromatography analyzes collection of illustrative plates (351nm)；
HPLC after Fig. 3 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance recrystallization analyzes collection of illustrative plates (351nm)；
The ESI-MS negative ion mass spectrum collection of illustrative plates of Fig. 4 1,8,9-trihydroxy-3-methoxy-benzo[4,5；
The ultraviolet chromatogram of Fig. 5 1,8,9-trihydroxy-3-methoxy-benzo[4,5.
Detailed description of the invention
Being described in further details the present invention in conjunction with embodiment and accompanying drawing, embodiment is only limitted to the present invention, rather than limitation of the invention are described.
Embodiment 1
1) ethyl acetate extraction:
Herba Ecliptae alcohol takes thing 3kg(Sichuan Provincial Academy of Traditional Chinese Medicine and provides), add 15L water, 40 DEG C of heating make it dissolve, and add the extraction of 4.5L ethyl acetate, extract 3 times, combining extraction liquid, be evaporated to 500ml, admix the silica gel of 500 grams of 100-200 mesh, mixing thoroughly, fume hood dries, standby after grinding.
2) silica gel medium pressure column chromatography purification:
TakeStainless steel column as medium pressure chromatography post, load 1.5kg100-200 mesh silica gel as separating silica gel, acetic acid ethyl ester extract mixed sample powder and uniformly loads stigma, filling is closely；Use Shanghai with field TBP2H10 constant flow pump as medium lift pump, petroleum ether: ethyl acetate: acetic acid (7:3:1) mixed solvent as eluant, flow speed control at 150ml/min, pressure about 0.3MPa, eluting 10 times of column volumes, about 45L；Thin layer chromatography detect, with petroleum ether: ethyl acetate: acetic acid (4:6:0.5) as developing solvent, fluorescence viewing speckle uviol lamp 365nm at, collection RfValue is the eluent of 0.46, concentrates, and separates out pale precipitation 7.2g(1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product), its purity is about 70%(Fig. 2)；
3) recrystallization:
Above-mentioned 1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product is with chromatograph methanol heating for dissolving (< 40 DEG C), with the microporous filter membrane sucking filtration of 0.45 micron, clear liquid low temperature places (room temperature about 10 DEG C in winter), white precipitate is separated out after 24h, filter, 1,8,9-trihydroxy-3-methoxy-benzo[4,5 sterling can be obtained, mother solution can continue to concentrate places crystallization, different batches individually uses HPLC to detect, merge the purity batch more than 98% as 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance, final acquisition 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance 6.1g, detects through HPLC normalization, and its purity is 98.7%(Fig. 3)
UV, MS of above-mentioned reference substance are equal and document is consistent (Fig. 4,5).
Embodiment 2
1) ethyl acetate extraction:
Herba Ecliptae medical material 40kg, uses 70% alcohol reflux, for the first time 480L, for the second time 400L, each extraction 1.5 hours, merges twice extracting solution, obtains ethanol extract extractum about 7kg；Adding 35L water, 40 DEG C of heating make it dissolve, and add the extraction of 10.5L ethyl acetate, extract 3 times, combining extraction liquid, be evaporated to 2L, admix the silica gel of 2kg100-200 mesh, mix thoroughly, and fume hood dries, standby after grinding.
2) decompression silica gel chromatography:
TakeStainless steel column as decompression chromatographic column, under join 2.5L bottle,suction as catcher；Acetic acid ethyl ester extract, as separating silica gel, is mixed sample powder and is uniformly loaded stigma by loading 4.2kg200-300 mesh silica gel, and filling is closely；Use Gongyi, Henan give China board circulation vacuum pump as drawdown pump, pressure is about at-0.09MPa, petroleum ether: ethyl acetate: acetic acid (8:2:1) mixed solvent is as eluant, eluting 12 times of column volumes, about 180L；Thin layer chromatography detect, with petroleum ether: ethyl acetate: acetic acid (5:5:0.5) as developing solvent, fluorescence viewing speckle uviol lamp 365nm at, collection RfValue is the eluent of 0.40, concentrates, and separates out pale precipitation 15.3g(1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product), its purity is about 65%；
3) recrystallization:
Above-mentioned 1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product is heavily to steam ethyl acetate heating for dissolving (< 40 DEG C), with the microporous filter membrane sucking filtration of 0.45 micron, clear liquid low temperature places (room temperature about 10 DEG C in winter), separate out white precipitate after 24h, filter, 1,8,9-trihydroxy-3-methoxy-benzo[4,5 sterling can be obtained, it is similar to step with embodiment 1 and merges the purity batch more than 98% as 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance, final acquisition 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance 10.9g, detects through HPLC normalization, and its purity is 98.5%；
Embodiment 3
1) ethyl acetate extraction:
Herba Ecliptae alcohol takes thing 1kg(Sichuan Provincial Academy of Traditional Chinese Medicine and provides), add 5L water, 40 DEG C of heating make it dissolve, and add the extraction of 1.5L ethyl acetate, extract 3 times, combining extraction liquid, be evaporated to 200ml, admix the silica gel of 200 grams of 100-200 mesh, mixing thoroughly, fume hood dries, standby after grinding.
2) silica gel medium pressure column chromatography purification:
TakeStainless steel column as medium pressure chromatography post, load 750 grams of 100-200 mesh silica gel as separating silica gel, acetic acid ethyl ester extract mixed sample powder and uniformly loads stigma, filling is closely；Use Shanghai with field TBP2H10 constant flow pump as medium lift pump, petroleum ether: ethyl acetate: acetic acid (6:4:1) mixed solvent as eluant, flow speed control at 100ml/min, pressure about 0.2MPa, eluting 8 times of column volumes, about 24L；Thin layer chromatography detect, with petroleum ether: ethyl acetate: acetic acid (3:7:0.5) as developing solvent, fluorescence viewing speckle uviol lamp 365nm at, collection RfValue is the eluent of 0.48, concentrates, and separates out pale precipitation 2.5g(1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product), its purity is about 75%；
3) recrystallization:
Above-mentioned 1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product is with chromatograph methanol heating for dissolving (< 40 DEG C), with the microporous filter membrane sucking filtration of 0.22 micron, clear liquid low temperature places (room temperature about 10 DEG C in winter), separate out white precipitate after 24h, filter, 1,8,9-trihydroxy-3-methoxy-benzo[4,5 sterling can be obtained, the purity batch more than 98% is merged as 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance with embodiment 1, final acquisition 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance 1.9g, detects through HPLC normalization, and its purity is 99.0%.
Claims (7)
1. the method that 1,8,9-trihydroxy-3-methoxy-benzo[4,5 chemical reference substance is prepared in a scale; it is characterized in that: Herba Ecliptae ethanol extract; through ethyl acetate extraction, middle pressure or decompression silica gel chromatography, three steps of recrystallization, batch obtains the purity 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance more than 98%；Specifically comprise the following steps that
1) ethyl acetate extraction:
Herba Ecliptae ethanol extract, or Herba Ecliptae medical material drying under reduced pressure acquisition ethanol extract after the ethanol extraction that volume fraction is not less than 70%, add the water of extract weight 3-5 times volume, and heating makes it dissolve, and temperature controls at 30 DEG C-40 DEG C；Add the ethyl acetate extraction of extract weight 1-2 times volume, repeat extraction 2-4 time, combining extraction liquid, it is evaporated to concentrated solution volume/ethanol extract weight and is calculated as 1/3～1/6 with ml/g, then the silica gel of silica gel weight/concentrated solution volume equal proportion is admixed, silica gel weight/concentrated solution volume, in terms of g/ml, is dried and obtains acetic acid ethyl ester extract dry powder；
2) pressure or decompression silica gel chromatography in:
Take stainless steel column that blade diameter length ratio is 2～12.5 as chromatographic column, load the silica gel of extract 1-2 times of weight of dry powder as chromatography silica gel, dry method loading；With petroleum ether, ethyl acetate, the mixed solvent eluting of acetic acid, petroleum ether, ethyl acetate, the volume ratio of acetic acid are 7:3:1,8:2:1 or 6:4:1；Middle compression leg pressure 0.2-0.3MPa, decompression column pressure is at-0.08-0.09MPa, thin layer chromatography detect, with petroleum ether, ethyl acetate, acetic acid mixed solvent as developing solvent, petroleum ether, ethyl acetate, the volume ratio of acetic acid are 4:6:0.5,5:5:0.5 or 3:7:0.5；Collecting the Rf value eluent at 0.40-0.48, concentrating under reduced pressure, separating out shallow white precipitate is 1,8,9-trihydroxy-3-methoxy-benzo[4,5 crude product；
3) recrystallization:
Above-mentioned reference substance crude product ethyl acetate or methanol dissolve, and place crystallize for-4 DEG C-10 DEG C, can obtain the purity 1,8,9-trihydroxy-3-methoxy-benzo[4,5 reference substance more than 98%, and its outward appearance is white powder.
Method the most according to claim 1, it is characterised in that: step 1) in mix sample silica gel be 100-200 mesh.
Method the most according to claim 1, it is characterised in that: step 2) in chromatography divided silicon glue be 100-200 mesh or 200-300 mesh, dress post before be not required to be dried activation processing.
Method the most according to claim 1, it is characterised in that: step 2) in eluent 8～12 times of column volumes.
Method the most according to claim 1, it is characterised in that: step 3) in recrystallization time ethyl acetate used be that analytical pure heavily steams solvent, methanol is chromatographic grade, the mother solution after dissolving need to filter after filtrate again row place crystallization.
Method the most according to claim 5, it is characterised in that: filter the microporous filter membrane that microporous filter membrane is 0.22-0.45 micron used.
Method the most according to claim 1, it is characterized in that: Herba Ecliptae ethanol extract preparation process is, Herba Ecliptae medical material, add the ethanol solution of medical material weight 10-12 times volume, wherein the volume fraction of ethanol is 70%-100%, reflux, extract, 2-3 time, each 1-2 hour, united extraction liquid, drying under reduced pressure Herba Ecliptae ethanol extract.
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