CN101343331B - Synthesis of substituted pachyman - Google Patents
Synthesis of substituted pachyman Download PDFInfo
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- CN101343331B CN101343331B CN2008101202310A CN200810120231A CN101343331B CN 101343331 B CN101343331 B CN 101343331B CN 2008101202310 A CN2008101202310 A CN 2008101202310A CN 200810120231 A CN200810120231 A CN 200810120231A CN 101343331 B CN101343331 B CN 101343331B
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Abstract
The invention relates to a preparation method of polysaccharide, which aims at providing a synthetic method replacing pachymaran. In order to realize the purpose, the preparation method adopts the detailed technical steps: firstly, the ethanol aqueous solution of NaOH or NaOH/ urea aqueous solution is added in poria powder and is alkalified under the effect of ultrasonic wave for 30 minutes to 90 minutes; secondly, the reaction reagent is added in a reaction system to react for 50 minutes to 90 minuets under the effect of ultrasonic wave and the temperature of 50 DEG C to 70 DEG C, the mol ratio of the NaOH and the reaction reagent is 2 to 6 : 1, and the use amount of the ethanol aqueous solution or the urea aqueous solution is 20 mL/1g to 30 mL/1g of poria powder; and thirdly, the target product is obtained through leaching and acid washing the mixture obtained after reaction to neutrality and edulcoration. The preparation method has the advantages that the preparation method can perform one-step synthesis replacing pachymaran, the operation is convenient and time saving, and the cost is reduced; the ultrasonic wave is used to assist, the reaction speed is accelerated, and the substitution degree of the product is enhanced; the solution is secure, nontoxic and tractable.
Description
Technical field
The present invention relates to a kind of preparation method of polysaccharide, particularly a kind of compound method of substituted pachyman.
Background technology
Poria cocos (Poria cocos (Schw.) Wolf) is the Chinese medicinal materials of medicine-food two-purpose, is a kind of fungi that colonizes on pinaceae plant such as the tree roots such as Pinus massoniana Lamb, Japanese red pine.Pachymose is the main functional component of Poria cocos, in its medicinal part poria cocos sclerotium, contains 93% approximately.Pachymose can be divided into water-soluble Pachymose and caustic solubility Pachymose etc., wherein is the caustic solubility polysaccharide mostly, and its monosaccharide component mainly is a glucose.Caustic solubility Pachymose activity is low; Almost there is not anti-tumor activity (0～3%); Obtain substituted water-soluble Pachymose and have higher anti-tumor activity and the caustic solubility Pachymose is carried out chemically modified; In the antitumor test to mouse, inhibiting rate reaches as high as more than 90%, therefore has excellent development and is worth and application prospect.
With the example that synthesizes of CMP, at present, its synthesis route mainly contains three kinds.Method one: under alkaline condition and certain temperature, be reaction medium with the Virahol, Pachymose and chloroacetate reaction, separate then product.Method two: under alkaline condition and certain temperature, be reaction medium with ethanol, Pachymose and chloroacetate reaction, separate then product.Method three: with ethanol is reaction medium, at a certain temperature, adopts the secondary alkali adding method to make Pachymose and chloroacetate reaction, separate then product.In above three kinds of methods, method one Virahol is poisonous, not only contaminate environment but also there is unsafe factor in the application of CMP.Although method two has adopted safety solvent, substitution value is lower.Method three adopts the secondary alkali adding methods, and substitution value is improved, but long reaction time, operates loaded down with trivial detailsly, is unfavorable for industriallization.Above method all need make Pachymose earlier, and the method for traditional preparation process Pachymose mainly contains two kinds of flooding-organic solvent precipitation method and alkali lixiviate-acid precipitation methods.The former yield is low, and the organic solvent consumption is big, and cost is high; The latter with the alkali lye lixiviate after, add acid neutralization Pachymose separated out, Pachymose is heavy-gravity peptone shape in acidic medium, be difficult to suction filtration or spinning.
Summary of the invention
The object of the present invention is to provide a kind of compound method of substituted pachyman, in order to realize this purpose, the present invention has adopted following concrete technological step:
(1) Poria powder is added in the aqueous ethanolic solution or NaOH/ aqueous solution of urea of NaOH, alkalization is 30～90 minutes under the UW effect;
(2) reaction reagent is added in the reaction system, under the UW effect, under 50～70 ℃ of temperature, reacted 50～90 minutes;
Reaction equation is illustrated as follows:
A. working as reaction reagent is ClCH
2COOH or ClCH
2CH
2During OH:
PCS-(OH)+RCl+2NaOH→PCS-OR+NaCl
PCS-(OH) represents Pachymose, R=CH
2COOH or CH
2CH
2OH
B. working as reaction reagent is (CH
3)
2SO
4The time:
PCS-(OH)+(CH
3)
2SO
4+NaOH→PCS-OCH
3+NaOSO
2OCH
3
C. when reaction reagent is propylene oxide:
D. when reaction reagent is γ-propane sultone:
The molar ratio of NaOH and said reaction reagent is 2～6: 1, and aqueous ethanolic solution or aqueous solution of urea consumption are 20～30mL/1g Poria powder;
(3) reaction gained mixture is through suction filtration, and acid elution to neutral and purifying promptly gets title product.
As a kind of improvement, said temperature of reaction is 60 ℃.
As a kind of improvement, the said reaction times is 60 minutes.
As a kind of improvement, said acid elution solvent for use is a Glacial acetic acid min. 99.5.
As a kind of improvement, behind purifying, comprise that also freeze-drying makes the step of powdered product.
The beneficial effect that the present invention had is:
(1) one-step synthesis substituted pachyman, easy and simple to handle saving time reduced cost;
(2) use UW auxiliary, accelerated speed of response greatly, the product substitution value is improved;
(3) aqueous ethanolic solution or aqueous solution of urea safe in utilization, nontoxic, that be easy to get are made solvent, are convenient to operation and handle the easy recovery use of ethanol.
Embodiment
Through specific embodiment the present invention is described further below:
Embodiment 1 in the NaOH aqueous ethanolic solution, CMP synthetic
(3.0g 75mmol), 85% ethanol (20mL), makes the NaOH dissolving, adds Poria powder 1.0g then, and the UW effect is alkalization 0.5h down in the 50mL single necked round bottom flask, to add solid NaOH successively; (1.17g 12.4mmol), reacted layering 50 minutes in 50 ℃ under the ultrasonic continuation effect to add Mono Chloro Acetic Acid again; The supernatant liquid that inclines, lower floor's mashed prod is dissolved in the small amount of alkali, with Glacial acetic acid min. 99.5 neutralization, alcohol precipitation; Suction filtration, washing, freeze-drying gets white powder, and recording substitution value is 0.68.
Embodiment 2 in the NaOH aqueous solution of urea, methyl Pachymose synthetic
In the 50mL single necked round bottom flask, add 1.5MNaOH/0.5M aqueous solution of urea (18.5mL), add Poria powder 1.0g then, the UW effect is alkalization 1.0h down; (1.75g 13.9mmol), reacted 60 minutes in 60 ℃ under the ultrasonic continuation effect to add methyl-sulfate again; With Glacial acetic acid min. 99.5 neutralization, suction filtration, washing; Freeze-drying gets white powder, and recording substitution value is 0.51.
Embodiment 3 in the NaOH aqueous solution of urea, hydroxyethyl pachyman synthetic
In the 50mL single necked round bottom flask, add 1.5MNaOH/0.5M aqueous solution of urea (25mL), add Poria powder 1.0g then, the UW effect is alkalization 1.0h down; (1.0g 12.4mmol) slowly splashes in the reaction system, reacts 90 minutes in 60 ℃ under the ultrasonication with ethylene chlorhydrin again; With Glacial acetic acid min. 99.5 neutralization, suction filtration, washing; Freeze-drying gets white powder, and recording substitution value is 0.42.
Embodiment 4 in the NaOH aqueous solution of urea, hydroxypropyl Pachymose synthetic
In the 50mL single necked round bottom flask, add 1.5MNaOH/0.5M aqueous solution of urea (17.2mL), add Poria powder 1.0g then, the UW effect is alkalization 1.5h down; (0.5g 8.6mmol) slowly splashes in the reaction system, reacts 75 minutes in 70 ℃ under the ultrasonication with propylene oxide again; With Glacial acetic acid min. 99.5 neutralization, suction filtration, washing; Freeze-drying gets white powder, and recording substitution value is 0.38.
Embodiment 5 in the NaOH aqueous ethanolic solution, γ-propanesulfonic acid Pachymose synthetic
(3.0g 75mmol), 85% ethanol (30mL), makes the NaOH dissolving, adds Poria powder 1.0g then, and the UW effect is alkalization 1.0h down in the 50mL single necked round bottom flask, to add solid NaOH successively; (2.44g 20.0mmol), reacted layering 90 minutes in 60 ℃ under the ultrasonic continuation effect to add γ-propane sultone again; The supernatant liquid that inclines, lower floor's mashed prod is dissolved in the small amount of alkali, with Glacial acetic acid min. 99.5 neutralization, alcohol precipitation; Suction filtration, washing, freeze-drying gets white powder, and recording substitution value is 0.60.
At last, it is also to be noted that what more than enumerate only is practical implementation example of the present invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (5)
1. the compound method of a substituted pachyman is characterized in that, may further comprise the steps:
(1) Poria powder is added in the aqueous ethanolic solution or NaOH/ aqueous solution of urea of NaOH, alkalization is 30～90 minutes under the UW effect;
(2) reaction reagent is slowly splashed in the reaction system, under the UW effect, under 50～70 ℃ of temperature, reacted 50～90 minutes;
Reaction equation is illustrated as follows:
A. working as reaction reagent is ClCH
2COOH or ClCH
2CH
2During OH:
PCS-(OH) represents Pachymose, R=CH
2COOH or CH
2CH
2OH
B. working as reaction reagent is (CH
3)
2SO
4The time:
C. when reaction reagent is propylene oxide:
D. when reaction reagent is γ-propane sultone:
The molar ratio of NaOH and said reaction reagent is 2～6: 1, and aqueous ethanolic solution or aqueous solution of urea consumption are 20～30mL/1g Poria powder;
(3) previous reaction gained mixture is through suction filtration, and acid elution to neutral and purifying promptly gets title product.
2. according to the compound method of the said substituted pachyman of claim 1, it is characterized in that said temperature of reaction is 60 ℃.
3. according to the compound method of the said substituted pachyman of claim 1, it is characterized in that the said reaction times is 60 minutes.
4. according to the compound method of the said substituted pachyman of claim 1, it is characterized in that said acid elution solvent for use is a Glacial acetic acid min. 99.5.
5. according to the compound method of the said substituted pachyman of claim 1, it is characterized in that, behind purifying, comprise that also freeze-drying makes the step of powdered product.
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| CN2008101202310A CN101343331B (en) | 2008-08-12 | 2008-08-12 | Synthesis of substituted pachyman |
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| CN2008101202310A CN101343331B (en) | 2008-08-12 | 2008-08-12 | Synthesis of substituted pachyman |
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| CN101343331A CN101343331A (en) | 2009-01-14 |
| CN101343331B true CN101343331B (en) | 2012-03-21 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399299B (en) * | 2011-12-05 | 2013-05-22 | 湖北泱盛生物科技有限公司 | Preparation method for tuckahoe acidic polysaccharide extract and application of tuckahoe acidic polysaccharide extract |
| CN103484510B (en) * | 2013-10-09 | 2015-10-28 | 武汉工程大学 | A kind of preparation method of carboxymethylpachymaran |
| CN105348407B (en) * | 2015-12-04 | 2018-10-09 | 徐晓飞 | The preparation process of carboxymethylpachymaran and its application |
| CN106046192A (en) * | 2016-07-20 | 2016-10-26 | 潜山县三新茶叶专业合作社 | Process for extracting pachyman from poria coccus wolf |
| CN106509852B (en) * | 2016-11-04 | 2020-01-07 | 河北苓秀中药科技有限公司 | Preparation method of poria cocos colloid capable of self-stabilizing and dispersing in water, health food and preparation method of poria cocos colloid |
| CN108864314B (en) * | 2017-05-10 | 2022-06-07 | 华中农业大学 | Novel ultrasonic-assisted preparation method of carboxymethyl pachymaran (CMP) |
| CN110655590A (en) * | 2019-10-22 | 2020-01-07 | 靖州县金茶油科技开发有限责任公司 | Production method of pachyman |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554667A (en) * | 2003-12-26 | 2004-12-15 | 三明市真菌研究所 | Process for producing carboxymethyl pachyman |
| CN1970579A (en) * | 2006-11-28 | 2007-05-30 | 戴甲木 | High substitution degree carboxymethyl indianbread polysaccharide and its preparation method and uses |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554667A (en) * | 2003-12-26 | 2004-12-15 | 三明市真菌研究所 | Process for producing carboxymethyl pachyman |
| CN1970579A (en) * | 2006-11-28 | 2007-05-30 | 戴甲木 | High substitution degree carboxymethyl indianbread polysaccharide and its preparation method and uses |
Non-Patent Citations (2)
| Title |
|---|
| JP昭60-219202A 1985.11.01 |
| 伍焜贤等.羧甲基多糖制备及其应用.《现代化工》.2001,21(12),全文. * |
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