CN104402950B - A kind of picroside Ⅰ crystallization preparation method - Google Patents
A kind of picroside Ⅰ crystallization preparation method Download PDFInfo
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- CN104402950B CN104402950B CN201410830534.7A CN201410830534A CN104402950B CN 104402950 B CN104402950 B CN 104402950B CN 201410830534 A CN201410830534 A CN 201410830534A CN 104402950 B CN104402950 B CN 104402950B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
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Abstract
Patent of the present invention is related to a kind of purification process of picroside Ⅰ：75% picrorhiza rhizome is not less than as raw material with picroside Ⅰ purity, picroside Ⅰ is crystallized as solvent with the mixture of ethanol or ethanol-water and recrystallization purifying.The method of the present invention is easy, with favorable reproducibility, purity is high, yield is high the characteristics of, it is and workable, be particularly suitable for heavy industrialization.
Description
Technical field
The present invention relates to a kind of method for preparing purified of picroside Ⅰ monomer.
Technical background
Radix picrorrhizae is the traditional Chinese medicine of China, is recorded in earliest《Tang materia medica》, with reducing the asthenic fever, except sore heat, clearing away damp-heat
Effect, for osteopyrexia and fever, children's sore heat, damp-heat dysentery, yellow subcutaneous ulcer urinates red, hemorrhoid gall etc..Chemical composition mainly has cyclenes ether
Terpene glycoside, cucurbitacine, benzyl carbinol glycoside and phenolic glycoside class.Picroside Ⅰ (Picroside I) is the master of iridoid glycosides
Want one of active ingredient.It is reported that picroside Ⅰ has the pharmacological actions such as hepatic cholagogic, protection nerve.Through retrieving its medical usage
And preparation technology patent applied for (Chinese Patent Application No.：200410098646.4[1]；200710164321 .5[2]；
201310618996. 8[3], U.S. Patent number：US005145955[4]) method therefor is prepared for chromatography, macroporous absorption, lead salt sink
The method such as form sediment, gained material is noncrystalline product or the crystallization product for not obtaining simple picroside Ⅰ with the mixed crystal of other materials,
The patent crystallized on picroside Ⅰ is had no through retrieval, also has no that related scientific paper is delivered.
The chemical structural formula of picroside Ⅰ is as follows：
Bibliography：
| Sequence number | Country origin | Classification number | The applying date | Shen Qing Publication day | Application number（The patent No.） |
| 1 | China | A61K31/7048(2006.01); | 2004.12.15 | 2008.05.07 | 2004100986464 |
| 2 | China | C07H17/04(2006.01)I | 2004.12.15 | 2012.04.18 | 2007101643215 |
| 3 | China | C07H1/08(2006.01)I C07H17/04(2006.01)I; | 2013.11.27 | 2014.02.26 | 2013106189968 |
| 4 | The U.S. | A01N65/00;A65K35/78 | 1991.10.28 | 1992.09.08 | 5145955 |
The content of the invention
Simple to operate it is an object of the invention to provide one kind, prepared by the crystallization of product purity picroside Ⅰ monomer high
Method.The method can apply to prepare picroside Ⅰ reference substance, or industrialized production high-purity picroside Ⅰ bulk drug.
The present invention is not less than 75% picrorhiza rhizome as raw material with picroside Ⅰ purity, the Radix picrorrhizae that the present invention is used
Extract is the extracted solvent extraction of Radix picrorrhizae rhizome, extract obtained through adsorption column A after extract solution concentration, uses eluting solvent a
Wash-out, takes picroside Ⅰ concentrated part in eluent and, through adsorption column B, is eluted with eluting solvent b, and picroside Ⅰ is not in eluent
Part less than 75%, by assay, drying under reduced pressure after concentration.
1. said extracted solvent, eluting solvent 1 and eluting solvent 2 can be water, methyl alcohol, ethanol, acetone, ethyl acetate,
Both can be used alone, it is also possible to which two or more is used in mixed way.
2. above-mentioned adsorption column A, adsorption column B can be that silica gel, macroreticular resin, aluminum oxide, activated carbon, polyamide individually make
With.
A kind of method for preparing purified specific embodiment of picroside Ⅰ monomer of the invention is:With kutkin I purity
75% picrorhiza rhizome is not less than for raw material, the mixture with ethanol or ethanol-water as solvent, using cooling after intensification
Mode is crystallized, crystallization and recrystallization purifying under appropriate temperature conditions, and suction filtration crystallization, is then washed with cold solvent after 24h
Wash, freeze-drying or 50 1 65 DEG C of reduced vacuums are drying to obtain kutkin I crystallization.Wherein picrorhiza rhizome and water weighing body
Product is 1g than scope:The 1g of 40mL mono-:4mL.Temperature is in the range of -20 one 20 DEG C when crystallization and recrystallization.
Assay of the present invention is with HPLC detection methods:
The preparation of standard sample liquid
Precision weighs 5mg kutkin I reference substances and is placed in the volumetric flask of 25m1, adds water, ultrasonic dissolution constant volume, as mark
Quasi- sample liquid, concentration is 0. 2mg/ml,
The preparation of test sample liquid
Precision weighs kutkin I sample and is placed in the volumetric flask of 25m1, adds water, ultrasonic dissolution constant volume, as test specimens
Product liquid, concentration is 0. 2mg/ml,
Testing conditions:
Mobile phase:Methanol-water-glacial acetic acid（25:75:0.5）Blended, filtering is used after degassing;Chromatographic column:ODS-
C18 4. 6 × 250mm of post, flow velocity:0.8ml/min, sampling volume:10ul, Detection wavelength:282nm, when kutkin I retains
Between:It is 13 1 14min.
Specific embodiment
Following examples are illustrated to the present invention, but the scope of the present invention is not limited to what the following example was included
Content.
Embodiment 1. learnt from else's experience column chromatography twice picroside Ⅰ purity be 80% picrorhiza rhizome 10g, in 50 DEG C
It is dissolved under environment in the ethanol that 100ml concentration is 85%, is filtered while hot, filtrate is placed in -13 DEG C of refrigerators, by picroside after 24h
I crystallization is leached, and freeze-drying obtains the picroside Ⅰ 4.5g that purity is 93%.
Embodiment 2. learnt from else's experience column chromatography twice picroside Ⅰ purity be 85% picrorhiza rhizome 10g, in 20 DEG C
It is dissolved under environment in the ethanol that 130ml concentration is 95%, is filtered while hot, filtrate is placed in 0 DEG C of constant temperature refrigerator, by Radix picrorrhizae after 24h
The crystallization of glycosides I is leached, and 60 DEG C of reduced vacuums are dried, and obtain the picroside Ⅰ 6.33g that purity is 96%.
Embodiment 3. learnt from else's experience column chromatography twice picroside Ⅰ purity be 75% picrorhiza rhizome 10g, in 30 DEG C
It is dissolved under environment in 50ml absolute ethyl alcohols, is filtered while hot, filtrate is placed in 4 DEG C of constant temperature refrigerators, crystallizes picroside Ⅰ after 24h
Leach, freeze-drying, obtain the picroside Ⅰ 3g that purity is 93%.
Embodiment 4. was learnt from else's experience the picroside Ⅰ 10g that primary crystallization purity is 96%, in be dissolved under 60 DEG C of environment 100ml without
In water-ethanol, filter while hot, filtrate is placed in 13 DEG C of environment, 24h has no that picroside Ⅰ crystallization occurs, and is added thereto to purity
It is 96% crystalline powder 0.1g, leaches picroside Ⅰ crystallization after 6h is placed at room temperature, freeze-drying, it is 98.3% to obtain purity
Picroside Ⅰ 8.68g.
Embodiment 5. was learnt from else's experience the picroside Ⅰ 10g that primary crystallization purity is 96%, dense in 100ml is dissolved under 60 DEG C of environment
Spend in the ethanol for 80%, filter while hot, filtrate is placed in -10 ~ 11 DEG C of outdoor environments, leach picroside Ⅰ crystallization after 24h,
Freeze-drying, obtains the picroside Ⅰ 6g that purity is 99.1%.
Claims (3)
1. a kind of picroside Ⅰ crystallization preparation method, it is characterised in that carried with the Radix picrorrhizae that picroside Ⅰ purity is not less than 75%
Thing is taken for raw material, is recrystallisation solvent with 75% -100% ethanol water, crystallized by the way of being cooled down afterwards using first heating up,
Crystallization and recrystallization purifying under -20 DEG C -20 DEG C of temperature conditionss, suction filtration crystallization after 24h, then with cold 80% -100%
Ethanol water is washed for cleaning solvent, and freeze-drying or 50 ~ 60 DEG C of reduced vacuums are drying to obtain picroside Ⅰ crystallization.
2. according to the picroside Ⅰ crystallization preparation method described in claim 1, it is characterised in that wherein picrorhiza rhizome with
Recrystallisation solvent w/v scope is 1g：40ml~1g：4ml.
3. according to the picroside Ⅰ crystallization preparation method described in claim 1, it is characterised in that wherein crystallize and recrystallize institute
The picroside Ⅰ purity for obtaining reaches more than 90%, and form is little particle type.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104693253A (en) * | 2015-03-30 | 2015-06-10 | 济南东源生物医药技术有限公司 | Industrial preparation method for high-purity 6'-O-trans-cinnamyl catalpol |
| CN104892699A (en) * | 2015-05-05 | 2015-09-09 | 济南东源生物医药技术有限公司 | Method for preparing high-purity 6'-O-trans-cinnamylcatalpol |
| CN105111257B (en) * | 2015-09-19 | 2017-10-10 | 济南同生生物医药科技有限公司 | It is a kind of to prepare glucose acetyl vanilla glycosides, the process of 10 fragrant pod acyl Catalpols and the trans cinnamyl Catalpols of 6 ' O simultaneously |
| CN105198941A (en) * | 2015-09-21 | 2015-12-30 | 济南同生生物医药科技有限公司 | Aluminum oxide pressurized column chromatography preparation of 6'-O-trans cinnamyl catalpa alcohol |
| CN106397510A (en) * | 2016-08-31 | 2017-02-15 | 防城港市防城区那梭香料厂 | Method for separating pure 6'-O- trans-cinnamyl catalpol |
| CN106749451B (en) * | 2017-03-27 | 2019-04-05 | 山东康裕生物科技有限公司 | A method of extracting separation picroside Ⅰ and picroside Ⅱ |
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