CN107814826A - A kind of method that pachymic acid and pachymaran are extracted from fuling peel - Google Patents

A kind of method that pachymic acid and pachymaran are extracted from fuling peel Download PDF

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CN107814826A
CN107814826A CN201711076766.8A CN201711076766A CN107814826A CN 107814826 A CN107814826 A CN 107814826A CN 201711076766 A CN201711076766 A CN 201711076766A CN 107814826 A CN107814826 A CN 107814826A
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filtrate
ethanol
fuling peel
pachymaran
filter residue
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姚蓉
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Changsha Aiyang Medical Technology Co Ltd
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Changsha Aiyang Medical Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J9/00Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C07J9/005Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane containing a carboxylic function directly attached or attached by a chain containing only carbon atoms to the cyclopenta[a]hydrophenanthrene skeleton
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0003General processes for their isolation or fractionation, e.g. purification or extraction from biomass

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Sustainable Development (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
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Abstract

The present invention relates to a kind of method that pachymic acid and pachymaran are extracted from fuling peel, and fuling peel is extracted using alcohol reflux, filtering, filtrate concentration, obtains filtrate and filter residue;Filtrate concentration plus ethyl acetate extraction, the upper silicagel column purifying of extract concentration, crystallize to obtain pachymic acid;Filter residue is hydrogenated with sodium hydroxide solution refluxing extraction, filtering, and filtrate acid adding adjusts pH value, adds alcohol to precipitate, and precipitation washing and drying obtains pachymaran.This method can make full use of the active ingredient of fuling peel, can obtain the pachymic acid and pachymaran of high-purity simultaneously, substantially increase the utilization rate of fuling peel, solve problem of resource waste, while reduce production cost.

Description

A kind of method that pachymic acid and pachymaran are extracted from fuling peel
Art
The present invention relates to a kind of method that pachymic acid and pachymaran are extracted from fuling peel, belong to natural product chemistry Technical field.
Background technology
Fuling peel, it is the drying crust of On Polyporaceae Poria cocos Poria cocos (Schw.) Wolf sclerotium.More than 7~ September is excavated, and when processing " Indian buead tablet ", " Poria cocos block ", is collected the crust under cutting, is dried in the shade.Fuling peel is the Poria cocos crust under cutting, shape Shape is not of uniform size, mild-natured, sweet, light, special material gain water, detumescence, mainly contains the compositions such as tetracyclo-triterpene acid and polysaccharide, triterpenes Compound has extensive pharmacological activity, as diuresis, anti-hemolysis, anticancer, anti-inflammatory, antibacterial, it is antiviral, reduce cholesterol, kill software Animal and antifertility etc..Pachymaran has liver protection, glutamate pyruvate transaminase lowering, enhancing immune, calmness, anti-aging, hypoglycemic and anti- Tumour etc. acts on, and is widely used in Chinese patent drug, health food, medicinal diet for beautifying, has preferable DEVELOPMENT PROSPECT.Pachymic acid belongs to One of main active in Poria cocos in main component tetracyclo-triterpene acid (general designation su-fuling), have enhancing body immunity, Anticancer etc. acts on.Poria cocos is On Polyporaceae Poria cocos (Schw.) Wolf dry sclerotia, mild-natured, sweet, light, is returned The heart, lung, spleen, kidney channel, it is clearing damp and promoting diuresis conventional simply, strengthening the spleen and stomach, the Chinese medicine of antitoxic heart-soothing and sedative.Poria cocos is exactly one since ancient times Taste medicine-food two-purpose, very important Chinese medicine, in China, the usage amount of Poria cocos is more much larger than fuling peel, cause fuling peel in large quantities by It is discarded, serious waste of resources.
A kind of isolation and purification method of pachymic acid monomer of Publication No. CN103665079A Introduction To Cn Patent.With Fu Siberian cocklebur is raw material by extracting, extracting, crystallizing and obtain pachymic acid monomer, specifically includes following key steps:A is extracted:By Poria cocos powder Coarse powder is broken into, equivalent extract is extracted to obtain with alcohol reflux;B is extracted:Equivalent extract extracts to obtain Poria cocos acid crude with ethyl acetate;C is crystallized: Crude product is dissolved with organic solvent, obtains the pachymic acid monomer product of purity >=98% after crystallized and filtered.The whole work of the present invention Skill process operation simplicity, process stabilizing, cost are cheap, and separative efficiency is high, product purity is high, is adapted to industrialized production high-purity Pachymic acid monomer.
Publication No. CN104688782A Introduction To Cn Patent one kind high efficiency extraction triterpenes activity from fuling peel The method of composition.The present invention adds the immersion of alcohol liquid, refluxing extraction and to putting forward using fuling peel as raw material, after crushing according to a certain percentage Take liquid to be concentrated under reduced pressure, obtain Poria cocos bark extract;Poria cocos bark extract is entered by heating ultrasonic dissolution by macroreticular resin Row purifying, is finally prepared fuling peel total triterpene.The yield of fuling peel total-triterpene extract obtained by the present invention is reachable 5.6%, the Poria cocos total triterpene yield 2.32% significantly larger than extracted using Poria cocos block as raw material.Extraction effect of the present invention is good, No or seldom chemical solvent residual, the content of fuling peel total triterpene are more than 60%.The inventive method extraction cost relative moderate, It can be mass-produced, turn waste into wealth, there is good economic benefit and social benefit.
A kind of extracting method of fuling peel of Publication No. CN104666369A Introduction To Cn Patent.Methods described includes Following steps:Chinese medicine fuling peel is taken, is crushed after cleaning, 8 mesh sieves is crossed, produces fuling peel particle;Gained fuling peel particle is taken, is added The aqueous alkali of pH value 7.5~8.0, refluxing extraction at 100~110 DEG C, filtering, obtain the dregs of a decoction and buck extract solution;Gained buck Pachymaran can be further prepared as raw material in extract solution;The gained dregs of a decoction can be further prepared rich in three as raw material The fuling peel alcohol extracting thing of terpenoid.Application of the further protection methods described of the invention in fuling peel is extracted, and The application of pachymaran, fuling peel alcohol extracting thing and the material that methods described is prepared.
A kind of extracting method of fuling peel active ingredient of Publication No. CN103550265A Introduction To Cn Patent, bag Include:Fuling peel is rinsed with hydrochloric acid, neutrality is washed to, dries;Fuling peel is extracted with alcohol reflux, extract solution recovery ethanol is extremely It is dry;Dry is dissolved with water, adds the mixture extraction of n-butanol and ethyl acetate, organic phase recycling design obtains slightly to doing Product;Crude product is dissolved with ethanol, wiring solution-forming, neutral alumina chromatographic column in resulting solution, then with ethanol and ethyl acetate Mixture is eluted, and collects eluent;Activated carbon is added into eluent, is filtered, filtrate concentration, stands, filter, drying, Obtain active ingredient.Extracting method of the present invention is stable, extraction efficiency is high, substantially increases the yield of extract and containing for active ingredient Amount, it is extract obtained in 3 beta-hydroxies-wool steroid 7,9 (11), 24- triolefins -21- acid and dehydrogenation Yi Buli acid contents it is larger, extraction Thing has the function that hypoglycemic, reducing blood lipid, has preferable application prospect.
A kind of Poria cocos bark extract of Publication No. CN102697820A Introduction To Cn Patent, it is obtained by following steps Arrive:(1) fuling peel ethanol immersion, diacolation, reclaims ethanol, is concentrated to give brown paste after drying, crushing;(2) brown paste Thing is dissolved with water, ethyl acetate extraction, is reclaimed ethyl acetate, is concentrated to give paste;(3) paste obtained by step (2) is dissolved in second Alcohol, with silica gel mixed sample, the silicagel column of upper 100-200 mesh, petroleum ether-ethyl acetate elution, eluent is collected, merged, Concentration, finally obtain Poria cocos bark extract.Extract of the present invention plays the role of to protect potassium row's sodium, and its diuresis is than furosemide action time It is long, have the characteristics that long-acting, toxic side effect is low, a kind of new diuretic drug candidate can be provided for clinic.
A kind of preparation method of Poria cocos acidity polyoses extract of Publication No. CN102399299A Introduction To Cn Patent, Its step:Poria cocos is taken, adds the 60-80v/v% ethanol immersion 3-12h of 4-8 times of weight, refluxing extraction 1-3 times, each 1-2h, mistake Filter, obtains filter residue;By water refluxing extraction 1-3 times, each 1-3h of 4-10 times of weight of filter residue, filtering, filter residue is obtained;Add 30-70 The 0.1-0.5M of times weight NaOH extraction 0.5-2h, filtering, filtrate is neutralized with HCl, then water-washing desalting, must be precipitated;Again will be heavy Form sediment and be spray-dried, obtain Poria cocos acidity polyoses extract.This method is simple, and solvent used is repeatable to be recycled, and reduces life Cost is produced, has saved the energy, the content of extract obtained middle Poria cocos acidic polysaccharose is using glucose meter as 1.9-50.0wt%.This is carried Take thing to have and significantly adjust immune and antitumor function.
At present, because fuling peel price is far below Poria cocos, fuling peel survival dose is less so that and a large amount of fuling peels are dropped, Cause the significant wastage of resource.Existing research data shows, tetracyclo-triterpene acid and polysaccharide isoreactivity composition are contained in fuling peel, Wherein Poria cocos acid content is far above Poria cocos, and pharmacological testing shows, pachymic acid has the effects such as enhancing body immunity, anticancer. Fuling peel exploitation dynamics is little, does not obtain comprehensive development and utilization, in order to preferably rationally utilize fuling peel, explores from fuling peel Extract pachymic acid simultaneously and pachymaran means a great.
The content of the invention
For the problem of resource waste of fuling peel, in order to more rationally utilize fuling peel, the present invention provide one kind it is simple to operate, Rational technology, the quick production technology for extracting pachymic acid and pachymaran simultaneously.
The technical solution adopted by the present invention includes:Fuling peel is extracted using alcohol reflux, filtering, filtrate concentration, obtains filtrate And filter residue;Filtrate concentration plus ethyl acetate extraction, the upper silicagel column purifying of extract concentration, crystallize to obtain pachymic acid;Filter residue is hydrogenated with oxygen Change sodium solution refluxing extraction, filtering, filtrate acid adding adjusts pH value, adds alcohol to precipitate, and precipitation washing and drying obtains pachymaran.
Therefore, the present invention provides a kind of method that pachymic acid and pachymaran are extracted from fuling peel, and specific steps include It is as follows:
(1) fuling peel is crushed to the mesh of 80 mesh~120, adds 95% ethanol solution refluxing extraction 3 times, 2 hours every time, mistake Filter, merging filtrate, obtains filtrate I and filter residue I;
(2) filtrate I is concentrated under reduced pressure at 55 DEG C~65 DEG C, obtains medicinal extract I;
(3) medicinal extract I plus the ethyl acetate of two volumes are extracted 2 times, 1 hour every time, combined ethyl acetate extract was dense It is reduced to dry, obtains medicinal extract II;
(4) by medicinal extract II plus the dissolving of 80~95% ethanol, upper silica gel column chromatography (200~300 mesh), after adsorbing 30min, use The 40-70% ethanol elutions of 1-3BV upper prop liquid, eluent is discarded, then 95% ethanol elution with 3-5BV upper prop liquid, collection are washed De- liquid I, it is concentrated into crystallization and separates out, ceramic membrane filter 1 time, obtain coarse crystallization;
(5) coarse crystallization adds 95% ethanol to dissolve, and adds the water of 2-5 times of volume, refrigerates, crystallization, dry pachymic acid sterling;
(6) by the filter residue I in step (1) plus 0.1-1mol/L sodium hydroxide solution refluxing extraction 2 times, 2 hours every time, Filtering, merging filtrate, obtains filtrate II;
(7) concentrated hydrochloric acid tune pH value is added dropwise to 6.5-7 in filtrate II, it is 70~80% to add ethanol to alcohol content, stirring, is put Put overnight, ceramic membrane filter 1 time, obtain filter residue II;
(8) dried after filter residue II is washed with a small amount, produce pachymaran.
Ceramic membrane filter in the step, fenestra pore size are 0.22 μm;BV refers to a times column volume.
95% ethanol solution is added described in the step (1), is 8-10 by volume L/ fuling peel weight kg ratios:1.
80~95% ethanol solutions are added described in the step (4), are 8-10 by the weight kg ratios of volume L/ medicinal extract II:1.
95% ethanol solution is added described in the step (5), is 2-5 by volume L/ coarse crystallization weight kg ratios:1.
0.1-1mol/L sodium hydroxide solution is added described in the step (6), is by the weight kg ratios of volume L/ filter residues I 8-10:1。
Technique effect:
1st, extracted simultaneously by using fuling peel and obtain the pachymic acid and pachymaran of high-purity, substantially increase fuling peel Utilization rate, improve added value;The production cost of pachymic acid is reduced simultaneously, saves Chinese material medicine resource.
2nd, the present invention extracts active component from fuling peel, and Poria cocos acid content is far above Poria cocos in fuling peel, rationally utilizes Fuling peel, solves problem of resource waste;The production cost of pachymic acid is reduced simultaneously.
3rd, equipment used in the inventive method, method for extraction and purification are common conventional equipment and method, are avoided For the dependence of expensive instrument and equipment in commercial process, its production cost is greatly reduced.
4th, the reagent used in the present invention is low toxicity, the cheap, chemical reagent of volume production, using maturation in whole process The routine techniques of reagent recovery, significantly reduces the risk to environmental emission discarded object.
Embodiment
With reference to specific embodiment, the invention will be further described, following examples be intended to illustrate invention rather than Limitation of the invention further.
Embodiment 1
Fuling peel is crushed, 100 mesh sieves is crossed, weighs 5kg, adds 50L 95% ethanol solution refluxing extraction 3 times, 2 is small every time When, filtering, merging filtrate, obtain filtrate I and filter residue I.Filtrate I is concentrated under reduced pressure at 55 DEG C~65 DEG C, obtains 5L medicinal extract I.By medicinal extract I Add 10L ethyl acetate to extract 2 times, 1 hour every time, combined ethyl acetate extract, be concentrated to dryness, obtain 0.3kg medicinal extract II.Will The dissolving of medicinal extract II plus 3L 80% ethanol, upper silica gel column chromatography (200~300 mesh), after adsorbing 30min, with 8L 40% ethanol Elution, eluent, then 95% ethanol elution with 15L are discarded, collect eluent I, be concentrated into crystallization and separate out, filter to obtain 48.2g Coarse crystallization.Coarse crystallization adds 0.2L 95% ethanol to dissolve, and adds 0.6L water, refrigeration crystallization, obtains 20.3g pachymic acid sterlings.Will Filter residue I plus 40L 0.2mol/L sodium hydroxide solution refluxing extraction 2 times, 2 hours every time, filtering, merging filtrate, obtain filtrate Ⅱ.Concentrated hydrochloric acid tune pH value is added dropwise to 6.5-7 in filtrate II, addition ethanol to alcohol content is 70~80%, stirring, is stood overnight, Filtering, obtains filter residue II.Dried after filter residue II is washed with a small amount, produce pachymaran.After testing, the purity of pachymic acid is 99.45%, pachymaran yield is 16.3%.
Embodiment 2
Fuling peel is crushed, 80 mesh sieves is crossed, weighs 10kg, adds 80L 95% ethanol solution refluxing extraction 3 times, 2 is small every time When, filtering, merging filtrate, obtain filtrate I and filter residue I.Filtrate I is concentrated under reduced pressure at 55 DEG C~65 DEG C, obtains 8L medicinal extract I.By medicinal extract I Add 16L ethyl acetate to extract 2 times, 1 hour every time, combined ethyl acetate extract, be concentrated to dryness, obtain 0.7kg medicinal extract II.Will The dissolving of medicinal extract II plus 6L 90% ethanol, upper silica gel column chromatography (200~300 mesh), after adsorbing 30min, with 10L 50% ethanol Elution, eluent, then 95% ethanol elution with 30L are discarded, collect eluent I, be concentrated into crystallization and separate out, filter to obtain 0.1kg Coarse crystallization.Coarse crystallization adds 0.4L 95% ethanol to dissolve, and adds 1L water, refrigeration crystallization, obtains 45.1g pachymic acid sterlings.Will filter Slag I plus 80L 0.5mol/L sodium hydroxide solution refluxing extraction 2 times, 2 hours every time, filtering, merging filtrate, obtain filtrate II. Concentrated hydrochloric acid tune pH value is added dropwise to 6.5-7 in filtrate II, it is 70~80% to add ethanol to alcohol content, stirring, is stood overnight, mistake Filter, obtains filter residue II.Dried after filter residue II is washed with a small amount, produce pachymaran.After testing, the purity of pachymic acid is 99.39%, pachymaran yield is 17.5%.
Embodiment 3
Fuling peel is crushed, 120 mesh sieves is crossed, weighs 15kg, adds 120L 95% ethanol solution refluxing extraction 3 times, 2 is small every time When, filtering, merging filtrate, obtain filtrate I and filter residue I.Filtrate I is concentrated under reduced pressure at 55 DEG C~65 DEG C, obtains 20L medicinal extract I.By medicinal extract I plus 40L ethyl acetate extracts 2 times, 1 hour every time, combined ethyl acetate extract, is concentrated to dryness, obtains 1.2kg medicinal extract II. Medicinal extract II plus 10L 80% ethanol are dissolved, upper silica gel column chromatography (200~300 mesh), after adsorbing 30min, with the 70% of 30L Ethanol elution, eluent, then 95% ethanol elution with 45L are discarded, collect eluent I, be concentrated into crystallization and separate out, filter 0.16kg coarse crystallization.Coarse crystallization adds 0.8L 95% ethanol to dissolve, and adds 2L water, refrigeration crystallization, it is pure to obtain 65.8g pachymic acids Product.By filter residue I plus 120L 0.8mol/L sodium hydroxide solution refluxing extraction 2 times, 2 hours every time, filtering, merging filtrate, Obtain filtrate II.Concentrated hydrochloric acid tune pH value is added dropwise to 6.5-7 in filtrate II, it is 70~80% to add ethanol to alcohol content, is stirred, and is placed Overnight, filtering, obtains filter residue II.Dried after filter residue II is washed with a small amount, produce pachymaran.After testing, pachymic acid is pure Spend for 98.98%, pachymaran yield is 17.1%.

Claims (6)

1. a kind of method that pachymic acid and pachymaran are extracted from fuling peel, specific steps include as follows:
(1) fuling peel is crushed to the mesh of 80 mesh~120, adds 95% ethanol solution refluxing extraction 3 times, 2 hours every time, filtered, close And filtrate, obtain filtrate I and filter residue I;
(2) filtrate I is concentrated under reduced pressure at 55 DEG C~65 DEG C, obtains medicinal extract I;
(3) medicinal extract I plus the ethyl acetate of two volumes are extracted 2 times, 1 hour every time, combined ethyl acetate extract, are concentrated into It is dry, obtain medicinal extract II;
(4) by medicinal extract II plus the dissolving of 80~95% ethanol, upper 200~300 mesh silica gel column chromatography, after adsorbing 30min, 1-3BV is used The 40-70% ethanol elutions of upper prop liquid, eluent, then 95% ethanol elution with 3-5BV upper prop liquid are discarded, collect eluent I, It is concentrated into crystallization to separate out, ceramic membrane filter 1 time, obtains coarse crystallization;
(5) coarse crystallization adds 95% ethanol to dissolve, and adds the water of 2-5 times of volume, refrigerates, crystallization, dry pachymic acid sterling;
(6) by the filter residue I in step (1) plus 0.1-1mol/L sodium hydroxide solution refluxing extraction 2 times, 2 hours every time, mistake Filter, merging filtrate, obtains filtrate II;
(7) concentrated hydrochloric acid tune pH value is added dropwise to 6.5-7 in filtrate II, it is 70~80% to add ethanol to alcohol content, stirring, is placed At night, ceramic membrane filter 1 time, obtain filter residue II;
(8) dried after filter residue II is washed with a small amount, produce pachymaran.
2. claim 1 method, ceramic membrane filter in its described step, fenestra pore size is 0.22 μm;BV refers to a times cylinder Product.
3. claim 1 method, wherein step add 95% ethanol solution described in (1), by volume L/ fuling peel weight kg ratios For 8-10:1.
4. 80~95% ethanol solutions are added described in claim 1 method, wherein step (4), by the weight of volume L/ medicinal extract II Kg ratios are 8-10:1.
5. claim 1 method, wherein step add 95% ethanol solution described in (5), by volume L/ coarse crystallization weight kg ratios For 2-5:1.
6. adding 0.1-1mol/L sodium hydroxide solution described in claim 1 method, wherein step (6), filtered by volume L/ The weight kg ratios of slag I are 8-10:1.
CN201711076766.8A 2017-11-06 2017-11-06 A kind of method that pachymic acid and pachymaran are extracted from fuling peel Pending CN107814826A (en)

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