CN104230680B - A kind of method preparing high-purity deoxyschizandrin - Google Patents
A kind of method preparing high-purity deoxyschizandrin Download PDFInfo
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- CN104230680B CN104230680B CN201310245419.9A CN201310245419A CN104230680B CN 104230680 B CN104230680 B CN 104230680B CN 201310245419 A CN201310245419 A CN 201310245419A CN 104230680 B CN104230680 B CN 104230680B
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- JEJFTTRHGBKKEI-OKILXGFUSA-N deoxyschizandrin Chemical compound C1[C@H](C)[C@H](C)CC2=CC(OC)=C(OC)C(OC)=C2C2=C1C=C(OC)C(OC)=C2OC JEJFTTRHGBKKEI-OKILXGFUSA-N 0.000 title claims abstract description 60
- JEJFTTRHGBKKEI-UHFFFAOYSA-N deoxyschizandrin Natural products C1C(C)C(C)CC2=CC(OC)=C(OC)C(OC)=C2C2=C1C=C(OC)C(OC)=C2OC JEJFTTRHGBKKEI-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000741 silica gel Substances 0.000 claims abstract description 17
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 17
- 238000001953 recrystallisation Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 240000006079 Schisandra chinensis Species 0.000 claims description 11
- 235000008422 Schisandra chinensis Nutrition 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 230000006835 compression Effects 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 5
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract 1
- 239000000287 crude extract Substances 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010829 isocratic elution Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 210000004185 liver Anatomy 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 230000008485 antagonism Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 210000003494 hepatocyte Anatomy 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 102000018832 Cytochromes Human genes 0.000 description 1
- 108010052832 Cytochromes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 241000218377 Magnoliaceae Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000736078 Schisandra sphenanthera Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 102000003929 Transaminases Human genes 0.000 description 1
- 108090000340 Transaminases Proteins 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- JEJFTTRHGBKKEI-KBPBESRZSA-N dimethylgomisin J Natural products C1[C@H](C)[C@@H](C)CC2=CC(OC)=C(OC)C(OC)=C2C2=C1C=C(OC)C(OC)=C2OC JEJFTTRHGBKKEI-KBPBESRZSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 230000002440 hepatic effect Effects 0.000 description 1
- 230000010224 hepatic metabolism Effects 0.000 description 1
- 238000010262 high-speed countercurrent chromatography Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000003859 lipid peroxidation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen free radical Chemical class 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- FYSHYFPJBONYCQ-UHFFFAOYSA-N schisanhenol Natural products C1C(C)C(C)CC2=CC(OC)=C(OC)C(OC)=C2C2=C1C=C(OC)C(OC)=C2O FYSHYFPJBONYCQ-UHFFFAOYSA-N 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/36—Ortho- or ortho- and peri-condensed systems containing three rings containing eight-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method preparing high-purity deoxyschizandrin, by the crude extract containing deoxyschizandrin through silicagel column, then carries out eluting with the solvent of different proportion, merges containing object component, carry out crystallizing and recrystallization, finally give deoxyschizandrin sterling after being evaporated.The inventive method volume containing the sample is big, and separation efficiency is good, and the response rate is high, with low cost, can realize mass industrialized production, and gained deoxyschizandrin content reaches more than 99%, and single contaminant is less than 0.1%.
Description
Technical field
The invention belongs to extracted form natural plant field, be specifically related to one and prepare high-purity deoxyschizandrin
Method.
Background technology
Fructus Schisandrae Chinensis is Magnoliaceae perennial fallen leaves bejuco, and the Pharmacopoeia of the People's Republic of China is received
Record has two kinds of schisandra chinensis medicinal materials, respectively Radix Schisandrae Bicoloris (Schisandra chinensis(Turcz) bail)
Fruit with Fructus Schisandrae Sphenantherae (schisandra chinensis) (Schisandra sphenanthera r&d.etwils.).
Fructus Schisandrae Chinensis plant contains the lignanoid of couplet benzene ring octadiene structure, is topmost pharmacology in Fructus Schisandrae Chinensis
Active component.Deoxyschizandrin (Schizandrin A), also known as wuweizisu A, deoxyschisandrin,
It is the lignanoid of isolated primary bioactivity in Fructus Schisandrae Chinensis, has been widely used as tonic many years.
A lot of researchs show, it has clear and definite pharmacological action, including: 1. there is significant hepatocyte injury
Antagonism, blocks the damage to liver plasma membrane of the multiple poisonous substance, the generation of suppression toxic product, reduces
Serum transaminase.2. induce the activity of cytochromes P450, strengthen the function of detoxification of liver；
3. to reactive oxygen free radical antagonism, the lipid peroxidation of suppression liver plasma membrane；4. hepatic glycogen is promoted
Generate and the anabolism of protein, beneficially hepatocyte function are recovered.Recently, Yang Ling research group
Find that deoxyschizandrin is the specific substrate of people liver metabolism enzyme P450 3A4, owing to its toxicity is extremely low,
It is therefore possible to as a kind of probe substrate for clinic.[Chinese patent 200910012552.3].
The method of currently acquired high-purity deoxyschizandrin has employing high speed adverse current chromatogram (HSCCC),
[J.Chromatogr.A, 2005,1082,203-207 and Chinese patent 200910242188.X], but
High-speed counter-current chromatograph device is expensive, and preparation amount is extremely limited, is unsuitable for large-scale production.Patent
(application number: 201010510828.3) discloses a kind of method preparing deoxyschizandrin, utilizes post color
Spectrum multiple techniques and recrystallization method, it is thus achieved that deoxyschizandrin monomer, but its technique is relatively complicated, and
Product purity is less than 98.5%, it is impossible to meet medicinal study in the future.Sun Wenjis etc. use vacuum liquid chromatograph
Deoxyschizandrin in Radix Schisandrae Bicoloris etc. is carried out extracting separation by method, and experimental technique is schisandra chinensis medicinal material water logging
After medicinal residues with 80% ethanol percolation, reclaim ethanol, concentrated solution refrigerator is placed, and takes off layer jelly and uses
Ether dissolution, after accompanying a small amount of silica gel, is flowing phase with petroleum ether-ethyl acetate (10:1), carries out true
Empty liquid chromatograph separates, the lignin that will collect, and with benzene-ethyl acetate (10:1) flowing phase, enters
The 2nd vacuum liquid phase chromatographic isolation of row, decile is collected, and after TLC checks, merges into two parts, its
Middle Part II normal hexane recrystallization obtains white needles through verifying as deoxyschizandrin.The method flows
Use benzene solvent in mutually, be not suitable for large-scale production.
Summary of the invention
It is an object of the invention to the shortcoming overcoming existing separation deoxyschizandrin production technology to exist, it is provided that
A kind of method preparing high-purity deoxyschizandrin, the method is a kind of simple process, is suitable for industrialization
The production technology produced.
The invention provides a kind of method preparing high-purity deoxyschizandrin, the method concrete steps are such as
Under:
(1) extraction of deoxyschizandrin: schisandra chinensis medicinal material is crushed to 60-80 mesh, 60-100% second
Alcohol reflux extraction 1-2 time, each 1-2 hour, united extraction liquid, extracting solution concentrating under reduced pressure removal ethanol,
Adding petroleum ether extraction, extraction phase is evaporated to do；
(2) chromatography: loaded by chromatographic silica gel in chromatographic column, flows step (1) sample
Loading after phased soln, then with flowing phase eluting, merges containing deoxyschizandrin part after eluting and is evaporated to
Dry；
(3) crystallization and recrystallization: after chromatographing, sample with ethanol dissolves, and adds appropriate normal hexane and enters
Row crystallize, left at room temperature over night is crystallized, and crystalline product is decompression drying again after filtering, and obtains five
Taste A prime sterling；Carry out recrystallization according to the method described above, it is thus achieved that final high-purity deoxyschizandrin
Product.
The method preparing high-purity deoxyschizandrin that the present invention provides, described step (2) chromatographic column is
Dynamic axial compression column, blade diameter length ratio is the preferred 1:3 of 1:1～10().
The method preparing high-purity deoxyschizandrin that the present invention provides, described step (2) sample and silicon
Glue mass ratio is the preferred 1:50 of 1:30～100(), chromatographic silica gel is 200-800 mesh (preferably 300-400).
The method preparing high-purity deoxyschizandrin that the present invention provides, described step (2) flowing is mutually
One or more low polar solvents and the mixed solution of one or more highly polar solvents.
The method preparing high-purity deoxyschizandrin that the present invention provides, described rudimentary property solvent is oil
One in ether, normal hexane, dichloromethane, chloroform；Described highly polar solvent is acetone, acetic acid
One in ethyl ester, ethanol；In view of the recycling of solvent, preferably, single low pole is selected
Property solvent and the combination of single highly polar solvent, more excellent, select petroleum ether and acetone.Described low pole
Property solvent and highly polar solvent volume are than for 100:0.1～100:5
The method preparing high-purity deoxyschizandrin that the present invention provides, described step (3) high-purity five
In taste A prime product, deoxyschizandrin content is more than 99%, and single impurity content is less than 0.1%.
High performance liquid chromatography (HPLC) is utilized to analyze each step sample.HPLC condition: chromatographic column:
Phenomenex PFP (250 × 4.6mm, 5 μ), detects wavelength: 220nm, column temperature: 30 DEG C, flowing
Phase: acetonitrile/water, flow rate of mobile phase: 1.0mL/min, sample size: 10uL.
Product identify: application Agilent G6410A QQQ Mass Spectrometer mass spectrograph and
Bruker500MHz nuclear magnetic resonance chemical analyser carries out MS respectively,1The mensuration of H-NMR spectrum.
The invention have the advantage that
1. in the inventive method, solvent can recycle repeatedly, with low cost.
Solvent safety the most used in the present invention, low toxicity, repeatable utilization, beneficially operator
Labor protection and environmental conservation.
3. present invention process route is simple to operation, can realize laboratory and be prepared into industrial mass in a small amount
Produce.
4. products obtained therefrom quality is high, and deoxyschizandrin content is more than 99%, and single impurity content is less than
0.1%。
Accompanying drawing explanation
The liquid chromatogram of Fig. 1 Fructus Schisandrae Chinensis extrat；
The liquid chromatogram of Fig. 2 finished product of the present invention；
The LC-MS figure of Fig. 3 finished product of the present invention and reference substance, wherein, draw above is reference substance
LC-MS schemes, and figure below is product LC-MS of the present invention figure；
Fig. 4 finished product of the present invention1H-NMR composes；
Fig. 5 finished product of the present invention13C-NMR composes.
Detailed description of the invention
The present invention will be further described by the following examples, but the most therefore limit this
Bright.
Embodiment 1
Schisandra chinensis medicinal material 1kg is crushed to 60 mesh, 80% alcohol reflux, extract concentrating under reduced pressure,
Solution must be concentrated.Concentrated solution petroleum ether extraction, obtains extract 55g, carries out column chromatography.Chromatographic column is
Axial compression column, internal diameter is 200mm, and 3kg silica gel is poured in post by silica gel granularity 200-300 mesh,
With the pressure of 30bar by real for pillar dress, flow and select dichloromethane mutually: ethyl acetate=98:2(volume
Than) carry out isocratic elution, collect the stream part containing deoxyschizandrin, detected by liquid chromatograph,
Obtaining 8.8g faint yellow solid by qualified clusters deciliter and after being evaporated, deoxyschizandrin content is 94.1%,
Yield is 90%.8.8g faint yellow solid 150ml ethanol dissolves, and is subsequently adding 50ml normal hexane,
Room temperature stands overnight, and has a large amount of white crystal to separate out, filtering drying, more heavily ties
Crystalline substance, after filtration, 70 degree of dry 8h of vacuum (vacuum-0.1Mpa) obtain deoxyschizandrin product 7.1g,
Product reaches 99.8% through liquid chromatogram measuring, deoxyschizandrin content, and remaining impurity is respectively less than 0.1%.
Embodiment 2
Schisandra chinensis medicinal material 1.5kg is crushed to 80 mesh, 90% alcohol reflux, and extract decompression is dense
Contracting, obtains concentration solution.Concentrated solution petroleum ether extraction, obtains extract 89g, carries out column chromatography.Chromatograph
Post is axial compression column, and internal diameter is 200mm, and 5kg silica gel is poured into by silica gel granularity 300-400 mesh
In post, with the pressure of 20bar by real for pillar dress, flow and select normal hexane mutually: ethanol=99:1(volume
Than) carry out isocratic elution, collect the stream part containing deoxyschizandrin, detected by liquid chromatograph,
Obtaining 14.3g faint yellow solid by qualified clusters deciliter and after being evaporated, deoxyschizandrin content is 93.6%,
Yield is 86%.14.3g faint yellow solid 400ml ethanol dissolves, and is subsequently adding 200ml normal hexane,
Room temperature stands overnight, and has a large amount of white crystal to separate out, filtering drying, more heavily ties
Crystalline substance, after filtration, 70 degree of dry 8h of vacuum (vacuum-0.1Mpa) obtain deoxyschizandrin product 12.2g,
Product reaches 99.6% through liquid chromatogram measuring, deoxyschizandrin content, and remaining impurity is respectively less than 0.1%.
Embodiment 3
Schisandra chinensis medicinal material 3kg is crushed to 80 mesh, 80% alcohol reflux, extract concentrating under reduced pressure,
Solution must be concentrated.Concentrated solution petroleum ether extraction, obtains extract 156g, carries out column chromatography.Chromatographic column
For axial compression column, internal diameter is 200mm, and silica gel granularity 600-800 mesh pours 5kg silica gel into post
In, with the pressure of 30bar by real for pillar dress, flow and select petroleum ether mutually: acetone=100:1(volume ratio)
Carry out isocratic elution, collect the stream part containing deoxyschizandrin, detected by liquid chromatograph, will close
The merging of lattice component obtains 24.9g faint yellow solid after being evaporated, and deoxyschizandrin content is 94.5%, yield
It is 89%.24.9g faint yellow solid 500ml ethanol dissolves, and is subsequently adding 200ml normal hexane, room
Temperature stands overnight, and has a large amount of white crystal to separate out, filtering drying, then carries out recrystallization as stated above,
After filtration, 70 degree of dry 12h of vacuum (vacuum-0.1Mpa) obtain deoxyschizandrin product 21.2g,
Product reaches 99.8% through liquid chromatogram measuring, deoxyschizandrin content, and remaining impurity is respectively less than 0.1%.
Embodiment 4
Schisandra chinensis medicinal material 1.3kg is crushed to 60 mesh, 90% alcohol reflux, and extract decompression is dense
Contracting, obtains concentration solution.Concentrated solution petroleum ether extraction, obtains extract 70g, carries out column chromatography.Chromatograph
Post is axial compression column, and internal diameter is 200mm, and 5kg silica gel is poured into by silica gel granularity 300-400 mesh
In post, with the pressure of 20bar by real for pillar dress, flow and select dichloromethane mutually: normal hexane: acetone
=90:7:3(volume ratio) carry out isocratic elution, collect the stream part containing deoxyschizandrin, by liquid phase color
Spectrum detects, and obtains 11.2g faint yellow solid by qualified clusters deciliter and after being evaporated, and deoxyschizandrin contains
Amount is 95.2%, and yield is 92%.11.2g faint yellow solid 400ml ethanol dissolves, and is subsequently adding
100ml normal hexane, room temperature stands overnight, and has a large amount of white crystal to separate out, filtering drying, then by above-mentioned
Method carries out recrystallization, and after filtration, 70 degree of dry 8h of vacuum (vacuum-0.1Mpa) obtain Fructus Schisandrae Chinensis
A prime product 9.5g, product reaches 99.7% through liquid chromatogram measuring, deoxyschizandrin content, and remaining is miscellaneous
Matter is respectively less than 0.1%.
Embodiment 5
Schisandra chinensis medicinal material 2.1kg is crushed to 70 mesh, 80% alcohol reflux, and extract decompression is dense
Contracting, obtains concentration solution.Concentrated solution petroleum ether extraction, obtains extract 103g, carries out column chromatography.Color
Spectrum post is axial compression column, and internal diameter is 200mm, silica gel granularity 300-400 mesh, is fallen by 5kg silica gel
Enter in post, with the pressure of 50bar by real for pillar dress, flow and select chloroform mutually: ethanol=100:05
(volume ratio) carries out isocratic elution, collects the stream part containing deoxyschizandrin, is carried out by liquid chromatograph
Detection, obtains 11.2g faint yellow solid by qualified clusters deciliter and after being evaporated, and deoxyschizandrin content is
93.2%, yield is 92%.16.4g faint yellow solid 300ml ethanol dissolves, and is subsequently adding 200ml
Normal hexane, room temperature stands overnight, and has a large amount of white crystal to separate out, filtering drying, more as stated above
Carrying out recrystallization, after filtration, 70 degree of dry 8h of vacuum (vacuum-0.1Mpa) obtain deoxyschizandrin
Product 13.9g, product reaches 99.5% through liquid chromatogram measuring, deoxyschizandrin content, remaining impurity
It is respectively less than 0.1%.
Claims (5)
1. the method preparing deoxyschizandrin, it is characterised in that: the method specifically comprises the following steps that
(1) extraction of deoxyschizandrin: schisandra chinensis medicinal material is crushed to 60-80 mesh, 60-100% second
Alcohol reflux extraction 1-2 time, each 1-2 hour, united extraction liquid, extracting solution concentrating under reduced pressure removal ethanol,
Adding petroleum ether extraction, extraction phase is evaporated to do；
(2) chromatography: loaded by chromatographic silica gel in chromatographic column, flows step (1) sample
Loading after phased soln, then with flowing phase eluting, merges containing deoxyschizandrin part after eluting and is evaporated to
Dry；
(3) crystallization and recrystallization: after chromatographing, sample with ethanol dissolves, and adds appropriate normal hexane and enters
Row crystallize, left at room temperature over night is crystallized, and crystalline product is decompression drying again after filtering, and obtains five
Taste A prime sterling；Carry out recrystallization according to the method described above, it is thus achieved that final deoxyschizandrin product；
Described step (2) chromatographic column is dynamic axial compression column, and blade diameter length ratio is 1:1～10.
2. according to the method preparing high-purity deoxyschizandrin described in claim 1, it is characterised in that:
Described step (2) sample and silica gel mass ratio are 1:30～100, and chromatographic silica gel is 200-800 mesh.
3. according to the method preparing deoxyschizandrin described in claim 1, it is characterised in that: described step
Suddenly (2) flowing is that one or more low polar solvents are molten with the mixing of one or more highly polar solvents mutually
Liquid；
Described rudimentary property solvent is a kind of in petroleum ether, normal hexane, dichloromethane, chloroform；
Described highly polar solvent is the one in acetone, ethyl acetate, ethanol.
4. according to the method preparing deoxyschizandrin described in claim 3, it is characterised in that: described low
Polar solvent and highly polar solvent volume are than for 100:0.1～100:5.
5. according to the method preparing deoxyschizandrin described in claim 1, it is characterised in that: described step
Suddenly in (3) deoxyschizandrin product, deoxyschizandrin content is more than 99%, and single impurity content is less than
0.1%.
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