CN110143920A - The extraction preparation method of Sinomenine in a kind of caulis sinomenii - Google Patents
The extraction preparation method of Sinomenine in a kind of caulis sinomenii Download PDFInfo
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- CN110143920A CN110143920A CN201910566222.2A CN201910566222A CN110143920A CN 110143920 A CN110143920 A CN 110143920A CN 201910566222 A CN201910566222 A CN 201910566222A CN 110143920 A CN110143920 A CN 110143920A
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- sinomenine
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
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Abstract
The present invention provides a kind of extraction preparation methods of Sinomenine in caulis sinomenii.By under the conditions of low-concentration hcl, being translated into Sinomenine, improving water solubility, so as to use pure water as solvent, dissolved out active ingredient hydrochloric acid cucoline from caulis sinomenii by leaching mode to active constituent cucoline in caulis sinomenii；To leaching liquid, pH value of solution first is adjusted with lye, flocculant is added and precipitates vegetable protein in leaching liquid in a step-wise fashion.The present invention makes the use concentration that bronsted lowry acids and bases bronsted lowry is reduced in the extraction and preparation technique of Sinomenine, decomposition of the Sinomenine in high concentration bronsted lowry acids and bases bronsted lowry environment is prevented to occur, reduce impurity new in the final product to generate, using the yield of method Sinomenine provided by the invention up to 1.5% or more of caulis sinomenii.
Description
[technical field]
The invention belongs to pharmaceutical technology fields, and in particular to the extraction preparation method of Sinomenine in a kind of caulis sinomenii.
[background technique]
Sinomenine has the pharmacological actions such as anti-inflammatory, analgesia, decompression and anti-arrhythmia, and existing several formulations are answered at present
For clinic, for treating rheumatic and rheumatoid arthritis etc..
Traditional Sinomenine mostly uses alkalization water extraction technique, for water and a certain amount of ripe stone are added in cocculi
Alkalization a period of time, a certain amount of technical benzene is then added in ash, then the refluxing extraction in water-bath is acidified, stands, crystallization.It is this
Method is that Extraction solvent needs cumbersome technique that can just meet ring in terms of the recovery processing of solvent using a large amount of organic benzene, organic
Guaranteed request, and be easy in obtained Sinomenine product containing impurity.
Number of patent application is CN201110361882.0, and the applying date is on November 15th, 2011, patentee be Hunan just
Joint-stock company, clear pharmacy group, Changsha Yuandao Medicine Science and Technology Development Co. Ltd., a kind of entitled " side for preparing Sinomenine
Method " discloses a kind of Sinomenine crude product and process for refining, which passes through 0.1~1mol.L-1Hydrochloric acid diacolation mode separates
Then active constituent in caulis sinomenii by the way that milk of lime is added adjusts pH to 10.5~12, with salt acid for adjusting pH to 7.0~9.5, use
Chloroform extraction, then concentrated plus hydrochloric acid crystallization obtain Sinomenine crude product, then pass through absorbent charcoal fine purification.The patent at
Realizing for function extracts Sinomenine using only non-prohibitive organic solvent (chloroform) mode from caulis sinomenii, instead of tradition
Using benzene as the extraction preparation method of solvent.However the patent is there is also some problems, it is specific as follows:
Firstly, soaked in the method disclosed in the patent, hydrochloric acid (HCl) concentration that dipping, diacolation use is 0.1~
1.0mol.L-1.It is soaking, in dipping, diacolation, if controlling hydrochloric acid (HCl) concentration in this range, especially when hydrochloric acid is dense
Degree is greater than 0.3mol.L-1When, concentration of hydrochloric acid is excessively high, and the acid for easily causing cucoline decomposes, and acid dissolution is other from caulis sinomenii
Impurity can also increase because of the excessive concentration of acid；And excessively high concentration of hydrochloric acid is used, also make hydrochloric acid consumption big, latter step processing needs
It to use milk of lime to neutralize hydrochloric acid, cause the alkali number of consumption big, wastewater treatment is difficult；
Moreover, the patent extracts Sinomenine using diacolation mode from caulis sinomenii, will be blocked up after being crushed there are caulis sinomenii
The problem of plug percolator causes diacolation that can not carry out；
Furthermore the patent of invention uses the milk of lime of high concentration, i.e. Ca (OH) in the precipitation and separation impurity stage2Saturation
Solution adjusts percolate pH=10.5~12, and since the dissolution dispersity of milk of lime is bad, adjusting pH value of solution is excessively high, is easy hair
The caustic digestion of raw Sinomenine, causes Sinomenine to lose or increase new impurity.
Therefore, in order to solve the above technical problems, it is necessary to research and develop a kind of extraction preparation method of new Sinomenine.
[summary of the invention]
The object of the invention is that solve the deficiencies in the prior art, and one kind is provided and is taken water as a solvent, from caulis sinomenii
In Sinomenine is prepared by leaching mode extraction method, to effectively prevent Sinomenine under high salt concentration acid environment
Acid decompose, also avoid in the subsequent process, when because of neutralisation treatment residue hydrochloric acid, using the lime milk solution of high concentration, band
The problem of caustic digestion come, while also the difficulty of wastewater treatment is reduced because the usage amount of bronsted lowry acids and bases bronsted lowry is greatly reduced.
The purpose of the present invention is what is solved by the following technical programs:
The extraction preparation method of Sinomenine in a kind of caulis sinomenii, comprising the following steps:
(1) caulis sinomenii is taken, it is 1.0 × 10 that concentration, which is added,-4~0.3mol.L-1Hydrochloric acid wetting, makes the cucoline in caulis sinomenii
It is converted into Sinomenine；
(2) the caulis sinomenii water extraction for taking step (1) to soak collects leaching liquid；
(3) leaching liquid for taking step (2) to obtain, adjusts pH to 7~11 with alkali, and flocculant then is added until sinking without new
It forms sediment and generates；
(4) precipitating and leaching liquid supernatant separation obtained step (3)；
(5) the leaching liquid supernatant for taking step (4) to obtain, is adjusted with acid pH to 7~9, then obtains salt through extraction, crystallization
Sour cucoline.
Preferably, caulis sinomenii crushed 10 meshes first in the step (1) to soak again.
Preferably, concentration of hydrochloric acid solution is 1.0 × 10 in the step (1)-4~0.1mol.L-1。
Preferably, the volume for hydrochloric acid being added in the step (1) when wetting is at least higher by caulis sinomenii surface 1mm or more, moistens
Wet temp is room temperature~60 DEG C, and the time is 0.5~4h.
Preferably, the volume ratio of the caulis sinomenii and water that have soaked when the step (2) leaches is 1:(1~2), leach number
It is 2 times or more, 1~2.5h every time.
Preferably, the step (3) uses 0.1~3mol.L-1NaOH solution adjust pH, used flocculant be height
Valence metal ion flocculant.
Preferably, the flocculant is saturation calcium chloride solution.
Preferably, the step (5) uses 0.1~6mol.L-1Salt acid for adjusting pH.
Preferably, the step (5) is extracted using chloroform, and the ratio of leaching liquid supernatant and chloroform is 1:(1/4~1/2)
(V/V), extraction times are 2 times or more, are concentrated into chloroform volume to chloroformic solution after extraction and measure less than 1/10 times, then are analysed
It is brilliant.
Preferably, the step (5) carries out crystallization using hydrochloric acid, the crystal of precipitation is washed using ethanol solution,
It is dried to obtain Sinomenine.
The present invention is by being translated into hydrochloric acid under the conditions of low-concentration hcl to active constituent cucoline in caulis sinomenii
Cucoline is dissolved out active ingredient hydrochloric acid cucoline from caulis sinomenii by leaching mode so as to use pure water as solvent.
Sinomenine is extracted by leaching mode using pure water as solvent, the hydrochloric acid reduced in Sinomenine extraction and preparation technique makes
With concentration and total amount, further decrease the non-active ingredient impurity content dissolved out in leaching liquid.
To leaching liquid, pH value of solution first is adjusted with lye, adds the plant egg in flocculant stepping mode precipitating leaching liquid
White, substitution is directly added into milk of lime mode in the prior art, makes to reduce bronsted lowry acids and bases bronsted lowry in the extraction and preparation technique of Sinomenine
Use concentration, it is therefore prevented that decomposition of the Sinomenine in high concentration bronsted lowry acids and bases bronsted lowry environment occurs, and reduces in the final product
New impurity generates, using the yield of method Sinomenine provided by the invention up to 1.5% or more of caulis sinomenii.
Meanwhile the present invention can moisten the hydrochloric acid of caulis sinomenii in the prior art, the merging of dipping, three step of diacolation is set same
It is carried out in standby (such as leaching pond), significantly shortens process flow, reduce production cost, and the use by reducing bronsted lowry acids and bases bronsted lowry
Amount, decreases the pressure of wastewater treatment, reduces the pollution to environment.
[Detailed description of the invention]
Fig. 1 is the color change of Sinomenine solution in different pH environments.
[specific embodiment]
The invention will be further described with embodiment with reference to the accompanying drawing.
The present invention provides a kind of extraction preparation methods of Sinomenine in caulis sinomenii, comprising the following steps:
(1) caulis sinomenii is taken, it is 1.0 × 10 that concentration, which is added,-4~0.3mol.L-1Hydrochloric acid wetting, makes the cucoline in caulis sinomenii
It is converted into Sinomenine；The main function of hydrochloric acid wetting is that the cucoline in caulis sinomenii is converted Sinomenine；Cucoline
Water solubility it is poor, need using organic solvent, such as: benzene could be dissolved out from caulis sinomenii；And the water solubility of Sinomenine is very
It is good, it can be directly dissolved in water, therefore after converting Sinomenine for the cucoline in caulis sinomenii, can largely it improve
Water solubility is used only pure water to realize, Sinomenine is leached from caulis sinomenii.Also because of this principle, in the salt of caulis sinomenii
Sour wetting stage, concentration of hydrochloric acid and dosage, it is only necessary to which control is converted into Sinomenine in realization cucoline, does not need
Use more hydrochloric acid；
(2) the caulis sinomenii water extraction for taking step (1) to soak collects leaching liquid；
(3) leaching liquid for taking step (2) to obtain, adjusts pH to 7~11 with alkali, and flocculant then is added until sinking without new
It forms sediment and generates；A certain amount of phytoprotein is generally dissolved in leaching liquid, these vegetable proteins lotus positive electricity under acidic environment can
It is dissolved in water；The presence of vegetable protein in aqueous solution has large effect to subsequent extraction process, it is therefore desirable to pass through before extraction
Coprecipitation mode is separated off；Using remaining hydrochloric acid, adjusting leaching liquid pH value are 7 in certain density aqueous slkali and in leaching liquid
~11, it keeps leaching to be in weakly alkaline environment, the charging characteristic of a part of phytoprotein can be made to be converted into isoelectric point (positive negative electricity
Property it is equal), another part protein bear is electrical；NaOH, KOH, Na can be selected in aqueous slkali2CO3, the solution such as CaO.Isoelectric point electricity
Under the conditions of phytoprotein can directly agglomerate to form precipitating, however the vegetable protein of bear electricity is still solvable, therefore by appropriate
Flocculant is added can coagulative precipitation；
(4) precipitating and leaching liquid supernatant separation obtained step (3)；
(5) the leaching liquid supernatant for taking step (4) to obtain is adjusted with acid pH to 7~9, then obtains salt through extraction, crystallization
Sour cucoline；To guarantee that the precipitating of vegetable protein is completed, leaching liquid is generally adjusted to the isoelectric pH value of vegetable protein or is made
Vegetable protein bear is electrical, and leaching liquid at this time is in alkalescent；But under higher pH environment, Sinomenine some will turn
The phenates form for turning to cucoline, is unfavorable for subsequent extraction；Therefore the cucoline sodium phenolate in leaching liquid should be led to before extraction
Solution ph is overregulated, it is made to be converted into cucoline, to guarantee that effective component can all be extracted agent extraction, this solution ph
It is 7~9；The prior art can be used in present invention extraction, Devitrification step, is such as extracted using chloroform, and hydrochloric acid crystallization is added.
Caulis sinomenii can be carried out appropriate crushing by controlling the time with medicinal herb grinder by above-mentioned steps (1), make caulis sinomenii powder
It crosses No.1 pharmacopeia sieve (10 mesh) to crush unsifted caulis sinomenii medicinal material with medicinal herb grinder again, its whole is made to pass through No.1
Pharmacopeia sieve, the smashing fineness by increasing caulis sinomenii can increase the reference area of caulis sinomenii, to accelerate Sinomenine
Dissolution；
Step (1) moistening step is preferable are as follows: when wetting be added hydrochloric acid volume be at least higher by caulis sinomenii surface 1mm with
On, wetting temperature is room temperature~60 DEG C, and the time is 0.5~4h, be can guarantee by control hydrochloric acid additional amount, wetting temperature, time
The quick and complete wetting of caulis sinomenii sample；
Step (2) leaching step is preferable are as follows: the volume ratio of the caulis sinomenii and water that have soaked is 1:(1~2), leach number
It is 2 times or more, 1~2.5h every time；Sinomenine can be made to obtain by control extraction solid-liquid ratio, extracting times, extraction time
Dissolution to the limit；
Step (3), which is neutralized, further preferably uses 0.1~3mol.L with settling step-1NaOH solution adjust pH, made
Flocculant is preferably high volence metal ion flocculant, and the application high-valency metal refers to divalent and the above metal ion；Such as: Al3+、
Mg2+、Ca2+, due to Mg2+Higher cost, effect is relatively poor, Al3+It is forbidden to use by medicinal industry, therefore more preferably uses Ca2 +It (can be further using saturation CaCl2Solution).
Step (4) separating step is preferable are as follows: and the leaching liquid and precipitating standing 4 for taking step (3) to obtain~for 24 hours, make to leach
Vegetable protein cohesion and sedimentation, filter supernatant liquor, are centrifugated at 2000~6000r/min to lower sediment liquid in liquid
Sediment, sediment make fixed-end forces, collect leaching liquid clear liquid after precipitation and separation；
The acid solution that step (5) extraction and Devitrification step adjust pH can select hydrochloric acid, dilute sulfuric acid etc., due to previous step
It is soaked using hydrochloric acid, therefore it is preferable to use hydrochloric acid solutions, can reduce the generation of impurity；Step (5) is further preferred are as follows: to step
(4) the caulis sinomenii leaching liquid clear liquid being collected into, with 0.1~6.0mol.L-1Hydrochloric acid, under the detection of wide pH value test paper, adjust
Solution ph is 7~9 ranges.To the leaching liquid after adjusting pH value, the chloroformic solution of 1/4~1/2 amount of leaching liquid volume is added,
It is extracted in separatory funnel, this step operation more than twice, collects the chloroformic solution of lower layer, separates leaching liquid and make liquid waste processing；Merge
Resulting chloroformic solution is extracted every time, is placed in decompression rotary evaporator, and vacuum distillation to chloroform volume is measured less than 1/10 times, will
Cucoline chloroformic solution filtering after being concentrated, to filtrate, is slowly added dropwise 6mol.L-1Hydrochloric acid solution, be precipitated hydrochloric acid sinomenium acutum
Alkali yellow crystals, until stopping that hydrochloric acid is added after cannot precipitating crystal.To the crystal (i.e. Sinomenine crystal) of precipitation, decompression is taken out
Filter, to filter cake, with a small amount of 95% ethanol washing twice, be placed at 60 DEG C and dry to obtain Sinomenine crude product (Sinomenine
Molecular formula: C19H23NO4HCl；Molecular weight: 365.8512).
Experimental example one
1, experiment purpose
After this experiment carries out preliminary working to caulis sinomenii, under room temperature (water-bath controls 30 DEG C of constant temperature) environment, by using not
With the hydrochloric acid of concentration, caulis sinomenii powder is leached, investigating it, cucoline is converted into Sinomenine in a static condition, and from
Situation is dissolved out in caulis sinomenii.
2, experimental material and instrument
2.1 material
Caulis sinomenii: buying is in Baoji, Shaanxi province area
2.2 chemical reagent
Hydrochloric acid (analysis is pure): Chengdu Kingsoft chemical reagent Co., Ltd
Pure water is the water obtained by secondary reverse osmosis treatment.
2.3 laboratory apparatus
HH-21-4 type constant water bath box: Jin Cheng Guo Sheng laboratory apparatus factory, Community of Jin Tan County city
LC-15C high performance liquid chromatograph: Shimadzu Corporation, Japan, Suzhou City produces
2.4 chromatographic test strip parts
Mobile phase: 0.5% sodium dihydrogen phosphate buffered aqueous solution: second cyanogen, 87:13；
Chromatographic column: ODSC18；
Column temperature: 25 DEG C；
20 μ L of sample volume.
3, experimental method
The processing of 3.1 caulis sinomenii crude products
For convenience of leaching, the caulis sinomenii rhizome item that will be bought is cut into of length no more than 1 cun of billet with scissors, this is claimed to add
Work is a cun section, and the caulis sinomenii after this processing claims caulis sinomenii crude product.
The conversion of the dipping and cucoline of 3.2 caulis sinomenii crude products
50 grams 5 parts of caulis sinomenii crude product (handling to obtain by 3.1 sections) is weighed with electronic balance, is transferred to 5 500ml respectively
In beaker, number 1,2,3,4,5.0.3,0.1,1.0 × 10 are measured respectively with 500mL graduated cylinder-2、1.0×10-3、1.0×10- 4mol.L-1Hydrochloric acid solution, be added in the beaker equipped with caulis sinomenii crude product, be placed in 30 DEG C of water-baths of constant temperature, stirred with glass bar
It mixes uniformly, it is primary at interval of glass bar stirring in 5 minutes.
The sampling and chromatography of 3.3 maceration extracts
It is fixed by 15,30,60,120,240,1200 minutes interval times to the caulis sinomenii of the salt acid dip of various concentration
When sample, sampling 5ml pipette pipettes 5ml maceration extract, and be transferred in 50mL scale colorimetric cylinder, constant volume dilution, until 6
Sub-sampling is completed.To the maceration extract after diluting constant volume, 5mL is taken to be filtered with syringe-driven filter, with 2.4 section chromatographic conditions,
Direct injection analysis.
The assay of Sinomenine in 3.4 maceration extracts
Under 1 room temperature of table in the various concentration hydrochloric acid leaching liquid of caulis sinomenii crude product Sinomenine the amount of dissolution (with peak area table
Show) it changes with time
It is shown by upper experimental result: 0.1mol.L-1Hydrochloric acid and acidity are 1.0 × 10-4Under aqueous solution, be maceration extract, it is green
Cucoline can be converted into Sinomenine in wind rattan, and the content difference of Sinomenine is simultaneously in 1200 minutes latter two maceration extracts
Less, the former, which is higher by, is only about 20% or so.Description of test is 1.0 × 10 in acidity-4mol.L-1Under aqueous solution in cucoline
It can be converted into Sinomenine, and can be dissolved out in aqueous solution.
Experimental example two
1, experiment purpose
This experiment is to the caulis sinomenii after preliminary working, then carries out crushing and processing, makes all to cross No. 1 pharmacopeia sieve (10 mesh).Normal
Under temperature (water-bath controls 30 DEG C of constant temperature) environment, by using the hydrochloric acid of various concentration, caulis sinomenii powder is impregnated, investigates and crushes
Fineness is converted into Sinomenine to determination of sinomenine in Caulis Sinomenii, and situation is dissolved out from caulis sinomenii in a static condition.
2, experimental material and instrument
2.1 material
Caulis sinomenii: buying is in Baoji, Shaanxi province area
2.2 chemical reagent
Hydrochloric acid (analysis is pure): Chengdu Kingsoft chemical reagent Co., Ltd
Pure water is the water obtained by secondary reverse osmosis treatment.
2.3 laboratory apparatus
Medicinal herb grinder
HH-21-4 type constant water bath box: Jin Cheng Guo Sheng laboratory apparatus factory, Community of Jin Tan County city
LC-15C high performance liquid chromatograph: Shimadzu Corporation, Japan, Suzhou City produces
2.4 chromatographic test strip parts
Mobile phase: 0.5% sodium dihydrogen phosphate buffered aqueous solution: second cyanogen, 87:13；
Chromatographic column: ODSC18；
Column temperature: 25 DEG C；
20 μ L of sample volume.
3, experimental method
The thin product processing of 3.1 caulis sinomeniis
For the influence for investigating caulis sinomenii smashing fineness, it will be processed into the sample of caulis sinomenii crude product, further crushed with Chinese medicine
Machine crushes 3 minutes, so that caulis sinomenii powder is crossed No.1 pharmacopeia sieve (10 mesh) and is crushed again with Chinese medicine to unsifted caulis sinomenii medicinal material
Machine crushes, its whole is made to pass through No.1 pharmacopeia sieve, and the caulis sinomenii powder after this processing claims caulis sinomenii thin product.
The conversion of the dipping and cucoline of the thin product of 3.2 caulis sinomeniis
50 grams 5 parts of the thin product of caulis sinomenii (handling to obtain by 3.1 sections) are weighed with electronic balance, are transferred to 5 500ml respectively
In beaker, number 1,2,3,4,5.0.3,0.1,1.0 × 10 are measured respectively with 500mL graduated cylinder-2、1.0×10-3、1.0×10- 4mol.L-1Hydrochloric acid solution, be added in the beaker equipped with caulis sinomenii crude product, be placed in 30 DEG C of water-baths of constant temperature, stirred with glass bar
It mixes uniformly, it is primary at interval of glass bar stirring in 5 minutes.
The sampling and chromatography of 3.3 maceration extracts
It is fixed by 15,30,60,120,240,1200 minutes interval times to the caulis sinomenii of the salt acid dip of various concentration
When sample, sampling 5ml pipette pipettes 5ml maceration extract, and be transferred in 50mL scale colorimetric cylinder, constant volume dilution, until 6
Sub-sampling is completed.To the maceration extract after diluting constant volume, 5mL is taken to be filtered with syringe-driven filter, with 2.4 section chromatographic conditions,
Direct injection analysis.
The assay of Sinomenine in 3.4 maceration extracts
Under 2 room temperature of table the thin product of caulis sinomenii in various concentration hydrochloric acid leaching liquid Sinomenine the amount of dissolution (with peak area table
Show) it changes with time
Shown by upper experimental result: after caulis sinomenii degree of grinding improves, first feature is the dissolution time of Sinomenine
It shortens dramatically, substantially close to maximum, increasing dip time can not increase the dissolution concentration of Sinomenine after dipping 15 minutes
Solubilization goes out the concentration of Sinomenine.Second feature after degree of grinding improves is that high salt concentration acid dip is not conducive to hydrochloric acid
The dissolution of cucoline, experimental result show 0.1mol.L-1The dissolution of Sinomenine is the largest under concentration of hydrochloric acid.Caulis sinomenii powder
After broken degree improves, third feature is impregnated under different concentration of hydrochloric acid, and the maximum dissolution concentration of Sinomenine is above green wind
The dissolution concentration of rattan crude product.
Description of test is 1.0 × 10 in acidity-4mol.L-1Under aqueous solution in cucoline can be converted into hydrochloric acid sinomenium acutum
Alkali, and can dissolve out in aqueous solution.
Experimental example three
1, experiment purpose
After this experiment carries out preliminary working to caulis sinomenii, under 50 DEG C of environment of constant temperature water bath, by using the salt of various concentration
Acid impregnates caulis sinomenii powder, and investigating it, cucoline is converted into Sinomenine in a static condition, and molten from caulis sinomenii
Artificial situation.
2 experimental materials and instrument
2.1 material
Caulis sinomenii: buying is in Baoji, Shaanxi province area
2.2 chemical reagent
Hydrochloric acid (analysis is pure): Chengdu Kingsoft chemical reagent Co., Ltd
Pure water is the water obtained by secondary reverse osmosis treatment.
2.3 laboratory apparatus
HH-21-4 type constant water bath box: Jin Cheng Guo Sheng laboratory apparatus factory, Community of Jin Tan County city
LC-15C high performance liquid chromatograph: Shimadzu Corporation, Japan, Suzhou City produces
2.4 chromatographic test strip parts
Mobile phase: 0.5% sodium dihydrogen phosphate buffered aqueous solution: second cyanogen, 87:13；
Chromatographic column: ODSC18；
Column temperature: 25 DEG C；
20 μ L of sample volume.
3 experimental methods
The processing of 3.1 caulis sinomenii crude products
For convenience of dipping, the caulis sinomenii rhizome item that will be bought is cut into of length no more than 1 cun of billet with scissors, this is claimed to add
Work is a cun section, and the caulis sinomenii after this processing claims caulis sinomenii crude product.
The conversion of the dipping and cucoline of 3.2 caulis sinomenii crude products
50 grams 5 parts of caulis sinomenii crude product (handling to obtain by 3.1 sections) is weighed with electronic balance, is transferred to 5 500ml respectively
In beaker, number 1,2,3,4,5.0.3,0.1,1.0 × 10 are measured respectively with 500mL graduated cylinder-2、1.0×10-3、1.0×10- 4mol.L-1Hydrochloric acid solution, be added in the beaker equipped with caulis sinomenii crude product, be placed in 50 DEG C of water-baths of constant temperature, stirred with glass bar
It mixes uniformly, it is primary at interval of glass bar stirring in 5 minutes.
The sampling and chromatography of 3.3 maceration extracts
It is fixed by 15,30,60,120,240,1200 minutes interval times to the caulis sinomenii of the salt acid dip of various concentration
When sample, sampling 5ml pipette pipettes 5ml maceration extract, and be transferred in 50mL scale colorimetric cylinder, constant volume dilution, until 6
Sub-sampling is completed.To the maceration extract after diluting constant volume, after taking 5mL to be filtered with syringe-driven filter, with 2.4 section chromatostrips
Part, direct injection analysis.
The assay of Sinomenine in 3.4 maceration extracts
At 3 50 DEG C of table middle caulis sinomenii crude product in various concentration hydrochloric acid leaching liquid Sinomenine the amount of dissolution (with peak area
Indicate) it changes with time
Shown by upper experimental result: after the dipping temperature of caulis sinomenii powder improves, first feature is to high salt concentration acidleach
Stain caulis sinomenii is conducive to the dissolution of Sinomenine.Second feature is when shortening Sinomenine to reach equilibrium concentration
Between, for experimental result display dipping after 120 minutes, Sinomenine can reach equilibrium concentration.Description of test acidity be 1.0 ×
10-4mol.L-1Under aqueous solution in cucoline can be converted into Sinomenine, and can therefrom dissolve out in aqueous solution.
Three above experiment can illustrate that determination of sinomenine in Caulis Sinomenii is 1.0 × 10-4mol.L-1It can in aqueous hydrochloric acid solution
It is converted into Sinomenine, and can therefrom dissolve out Yu Shuizhong.
Experimental example four
1, experiment purpose
Sinomenine not only has sour decomposition, also there is caustic digestion.Higher alkaline environment, sinomenium acutum in extraction and preparation technique
Caustic digestion will occur for alkali.The online value of Sinomenine caustic digestion pH is grasped by this experiment.
2, experimental material and instrument
2.1 chemical reagent
Sinomenine: self-control
Hydrochloric acid (analysis is pure): Chengdu Kingsoft chemical reagent Co., Ltd
Pure water is the water obtained by secondary reverse osmosis treatment.
2.2 laboratory apparatus
CLJ2000 magnetic stirring apparatus: Tianjin Lan Like Co., Ltd
PHSJ-4A thunder magnetic acidometer: upper Co., Ltd, Nereid section
Thunder magnetic 231-01 type pH glass electrode: upper Co., Ltd, Nereid section；
218 type reference electrode (saturated calomel electrode) of thunder magnetic: upper Co., Ltd, Nereid section
T-818-B-6 type temperature sensor: upper Co., Ltd, Nereid section
3, experimental method
One is taken to clean, drying places to the beaker of the 250mL of room temperature, hydrochloric acid sinomenium acutum is accurately weighed on assay balance
Alkali 10.0000g.0.3mol.L is accurately measured with 100mL graduated cylinder-1Hydrochloric acid 100mL, be added in three times, by 10g Sinomenine
All dissolutions, are quantitatively transferred to constant volume in 1000mL volumetric flask, sufficiently shake up, and stand half an hour.
The beaker of a clean 1000mL is separately taken, the Sinomenine stock solution 900mL prepared by the above method is measured.
The solution is first used into 2mol.L-1NaOH solution be tentatively adjusted to pH nearly 5, then use 0.2mol.L-1Guide of the NaOH in acidometer
Accurately it is adjusted to pH=5.0 down.Then 100mL graduated cylinder is used, by the above-mentioned adjusted Sinomenine solution for pH=5.0, respectively
It is accurate to measure 100mL, it totally 9 parts, pours into 9 250mL beakers.
To above-mentioned Sinomenine solution, 5 parts are taken, uses 0.2mol.L respectively-1NaOH respectively will under the guide of acidometer
Solution is adjusted to pH=5.0, and 6.0,7.0,8.0,9.0.2 parts separately are taken, under the guide of acidometer, with 2mol.L-1NaOH solution,
Accurately it is adjusted to pH=10.0,11.0.To remaining two parts of Sinomenine solution, under the guide of pH test paper, a copy of it slowly adds
Enter 0.0400g NaOH solid, stirring and dissolving obtains the Sinomenine solution of pH=12, another is slowly added to 0.4000g
NaOH solid, stirring and dissolving obtain the Sinomenine solution of pH=13.The variation of observation solution colour, such as Fig. 1 after standing 30 minutes.
Description of test: red is presented in pH value of solution >=10 Sinomenine solution, caustic digestion has occurred.Experimental example five
1, experiment purpose
Caulis sinomenii powder salt Acid leaching liquid not only has Sinomenine dissolution wherein, also there is a large amount of Soluble plant albumen
Dissolution.There are carboxyl and amino in the end of vegetable protein, therefore vegetable protein is with double electrical.Under acidic environment, vegetable protein
Lotus positive electricity can be dissolved in the water.By adjusting solution ph, it is in vegetable protein under isoelectric point, vegetable protein can be made solidifying
Gather and precipitates.Or make vegetable protein bear electricity, and high price Ca is added2+It is set to agglomerate and precipitate, realization is isolated from maceration extract
The purpose of vegetable protein.
2, experimental method
The preparation of hydrochloric acid leaching liquid:
Dry caulis sinomenii is put in medicinal herb grinder and is crushed, No.1 pharmacopeia sieve is smashed it through；Accurately weigh 100.0g blueness
1000mL0.3mol.L is added in the beaker of 3000mL in wind rattan powder-1Hydrochloric acid, (beaker mouth is sealed with preservative film within 12 hours for leaching
Mouthful)；Part leaching liquid is transferred in 8 50mL centrifuge tubes, is centrifuged 4 minutes at 4000r/min；It is clear to upper layer after centrifugation
Liquid, decompression filter to obtain leaching liquid stock solution.
The hydrochloric acid leaching liquid that will be prepared by above-mentioned steps pours into 7 50mL scale color-comparison tubes, every respectively
25mL；To leaching liquid, mode is added dropwise with saturation sodium hydroxide solution respectively, adjusting pH value of solution is 6,7,8,9,10,11, pH value of solution
Value is tested with wide pH value test paper；With maximum volume constant volume in six brace plug pipes, separately take a tool plug test tube that 25mL leaching is only added
Liquid compares, and observation solution precipitating generates situation.
After adjusting solution ph to above-mentioned 6 brace plug pipe, observes that precipitating generates, stood 30min, shake up precipitating
Liquid is transferred completely into 50mL centrifuge tube, is centrifuged 4 minutes at 4000r/min, isolates supernatant, weighs the precipitating matter of formation
Amount deducts centrifuge tube quality, obtains precipitation capacity under each pH value condition, record is as in table 4.
To centrifugal clear liquid obtained in above-mentioned experiment, saturation CaCl is added dropwise respectively2Solution 2mL, observation precipitating generate situation,
30min is stood, precipitated liquid is shaken up, is transferred completely into 50mL centrifuge tube, be centrifuged 4 minutes at 4000r/min, isolate supernatant
Liquid weighs the precipitating quality of formation, deducts centrifuge tube quality, obtains that saturation CaCl is added under each pH value condition2After solution
Newly-generated precipitation capacity, record is as in table 4.
The precipitation capacity that 4 caulis sinomenii hydrochloric acid leaching liquid of table produces under condition of different pH
| It leaches liquid acidity (pH) | 6 | 7 | 8 | 9 | 10 | 11 | Control |
| The precipitation capacity (g) of formation | 0.2457 | 0.4772 | 0.6991 | 0.7271 | 0.1307 | 0.0807 | 0.0 |
| +CaCl2 | 0 | 0 | 0.2003 | 0.2551 | 0.6630 | 0.6466 | 0.0 |
| NaOH+CaCl2 | 0.2457 | 0.4772 | 0.8994 | 0.9822 | 0.7937 | 0.7273 | 0.0 |
Description of test: behind pH >=8, saturation CaCl is added2The equal newly-generated precipitating of energy, illustrates in pH value of solution >=8 after solution
After, solvent portions phytoprotein bear electricity can only make its cohesion heavy the protein part of bear electricity with high volence metal ion
Drop.Experimental result also illustrates, obtains precipitation capacity maximum when maceration extract pH=9 with NaOH solution to adjust, adds saturation CaCl2
Solution precipitates the vegetable protein of bear electricity further, and precipitation capacity maximum is obtained when being still pH=9.Experiment also illustrates: dipping
Liquid can generate precipitating in pH value of solution=6~11.
Embodiment one
Wetting and leaching: it takes caulis sinomenii coarse powder 1000g to be put into plastic barrel, at room temperature (16 DEG C), uses 1000mL
0.1mol.L-1HCl infiltration, and be sufficiently stirred with glass bar, until caulis sinomenii complete wetting can be made wet.After 2 hours, high purity water is added
1500mL.It after 2 hours, is filtered with double gauze, obtains filtrate about 1700mL.High purity water 1000mL, glass is added in caulis sinomenii filter cake
Glass stick is sufficiently stirred, and leaches 2 hours.Filtering, can obtain filtrate 1700mL.1000mL pure water is continuously added to filter cake, leaches third
Secondary, merging filtrate obtains volume about 5000mL, and filter cake discards.
Precipitation and separation: filtrate is concentrated in a plastic barrel, under glass bar stirring, uses 1mol.L-1NaOH solution is adjusted
PH value is 9, and 10%CaCl is added in the test of wide pH value test paper2(g/mL) solution 100mL stands 8 hours, makes insoluble matter in filtrate
It precipitates.Supernatant liquor decompression filters, and lower layer, which is centrifugated out, to be precipitated, and merges and collects filtrate and centrifugate, obtains precipitation and separation
Liquid totality 5000mL.
Extraction and separation: it to above-mentioned precipitation and separation acquired solution is passed through, is dispensed with 3000mL separatory funnel to two parts, is used in combination
500mL chloroform is extracted twice, and separates lower layer's extract liquor, merges to obtain 2000mL.
Vacuum distillation: on a rotary evaporator, being evaporated under reduced pressure at 40 DEG C, and tail washings temperature is increased to 60 DEG C, steams to residue and evaporates
Divide 100mL, stop distillation, steams chloroform recycling.
It crystallizes crude: to remaining fraction, in evaporative flask, with 50mL 6mol.L-1HCl is slowly added dropwise, and has a large amount of yellow brilliant
Body is precipitated, until stopping that hydrochloric acid is added after being precipitated without crystal again.Decompression filters, to yellow crystals, with a small amount of 95% ethanol washing
Twice, it is placed in clean and dry beaker and is dried at 60 DEG C, weigh to obtain Sinomenine crude product 18.3g, measured through chromatography
Sinomenine content is 88.1% (normalization method) in crude product, and crude yield 1.83%, pure Sinomenine yield is
1.61%.
Embodiment two
Wetting and leaching: take caulis sinomenii coarse powder 1000g to be put into plastic barrel, at room temperature (16 DEG C), with 1000mL 1.0 ×
10-2mol.L-1HCl infiltration, and be sufficiently stirred with glass bar, until caulis sinomenii complete wetting can be made wet.After 2 hours, it is added high-purity
Water 1500mL.It after 4 hours, is filtered with double gauze, obtains filtrate about 1800mL.High purity water 1000mL is added in caulis sinomenii filter cake,
Glass bar is sufficiently stirred, and leaches 4 hours.Filtering, can obtain filtrate 1100mL.1000mL pure water continuously added to filter cake, leaching the
Three times, merging filtrate obtains volume about 3900mL, and filter cake discards.
Precipitation and separation: filtrate is concentrated in a plastic barrel, under glass bar stirring, uses 1mol.L-1NaOH solution is adjusted
PH value is 9, and 10%CaCl is added in the test of wide pH value test paper2Solution 100mL stands 12 hours, makes in filtrate under insoluble matter precipitating
Come.Supernatant liquor decompression filters, and lower layer, which is centrifugated out, to be precipitated, and merges and collects filtrate and centrifugate, and it is overall to obtain precipitation and separation liquid
4900mL。
Extraction and separation: it to above-mentioned precipitation and separation acquired solution is passed through, is dispensed with 3000mL separatory funnel to two parts, is used in combination
500mL chloroform is extracted twice, and separates lower layer's extract liquor, merges to obtain 2000mL.
Vacuum distillation: on a rotary evaporator, being evaporated under reduced pressure at 40 DEG C, and tail washings temperature is increased to 60 DEG C, steams to residue and evaporates
Divide 100mL, stop distillation, steams chloroform recycling.
It crystallizes crude: to remaining fraction, in evaporative flask, with 50mL 6mol.L-1HCl is slowly added dropwise, and has a large amount of yellow brilliant
Body is precipitated, until stopping that hydrochloric acid is added after being precipitated without crystal again.Decompression filters, to yellow crystals, with a small amount of 95% ethanol washing
Twice, it is placed in clean and dry beaker and is dried at 60 DEG C, weigh to obtain Sinomenine crude product 17.3g, measured through chromatography
Sinomenine content is 90.1% (normalization method) in crude product, and crude yield 1.73%, pure Sinomenine yield is
1.56%.
Embodiment three
Wetting and leaching: taking caulis sinomenii coarse powder 1000g, and medicinal herb grinder crushes, and caulis sinomenii powder is made all to pass through No.1
Pharmacopeia sieve.It is put into plastic barrel, at room temperature (16 DEG C), with 1000mL 1.0 × 10-4mol.L-1HCl infiltration, and filled with glass bar
Divide stirring, until caulis sinomenii complete wetting can be made wet.After 2 hours, high purity water 1500mL is added.After 2 hours, with double gauze mistake
Filter, obtains filtrate about 1600mL.High purity water 1000mL is added in caulis sinomenii filter cake, and glass bar is sufficiently stirred, and leaches 2 hours.Filtering,
Filtrate 1200mL can be obtained.1000mL pure water, leaching third time are continuously added to filter cake, merging filtrate obtains volume about 3800mL, filters
Cake discards.
Precipitation and separation: filtrate is concentrated in a plastic barrel, under glass bar stirring, uses 1mol.L-1NaOH solution is adjusted
PH value is 9, and 10%CaCl is added in the test of wide pH value test paper2Solution 100mL stands 12 hours, makes in filtrate under insoluble matter precipitating
Come.Supernatant liquor decompression filters, and lower layer, which is centrifugated out, to be precipitated, and merges and collects filtrate and centrifugate, and it is overall to obtain precipitation and separation liquid
4800mL。
Extraction and separation: it to above-mentioned precipitation and separation acquired solution is passed through, is dispensed with 3000mL separatory funnel to two parts, is used in combination
500mL chloroform is extracted twice, and separates lower layer's extract liquor, merges to obtain 2000mL.
Vacuum distillation: on a rotary evaporator, being evaporated under reduced pressure at 40 DEG C, and tail washings temperature is increased to 60 DEG C, steams to residue and evaporates
Divide 100mL, stop distillation, steams chloroform recycling.
It crystallizes crude: to remaining fraction, in evaporative flask, with 50mL 6mol.L-1HCl is slowly added dropwise, and has a large amount of yellow brilliant
Body is precipitated, until stopping that hydrochloric acid is added after being precipitated without crystal again.Decompression filters, to yellow crystals, with a small amount of 95% ethanol washing
Twice, it is placed in clean and dry beaker and is dried at 60 DEG C, weigh to obtain Sinomenine crude product 15.7g, chromatography 91.3%
(normalization method), crude yield 1.57%, Sinomenine yield are 1.43%.
Above-described is only embodiments of the present invention, it should be noted here that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, improvement can also be made, but these belong to protection model of the invention
It encloses.
Claims (10)
1. the extraction preparation method of Sinomenine in a kind of caulis sinomenii, it is characterised in that the following steps are included:
(1) caulis sinomenii is taken, it is 1.0 × 10 that concentration, which is added,-4~0.3mol.L-1Hydrochloric acid wetting, converts the cucoline in caulis sinomenii
For Sinomenine；
(2) the caulis sinomenii water extraction for taking step (1) to soak collects leaching liquid；
(3) leaching liquid for taking step (2) to obtain, adjusts pH to 7~11 with alkali, and flocculant then is added until raw without new precipitating
At；
(4) precipitating and leaching liquid supernatant separation obtained step (3)；
(5) the leaching liquid supernatant for taking step (4) to obtain is adjusted with acid pH to 7~9, then obtains hydrochloric acid blueness through extraction, crystallization
Rattan alkali.
2. the extraction preparation method of Sinomenine in caulis sinomenii as described in claim 1, it is characterised in that the step (1)
In caulis sinomenii be crushed into 10 meshes first soak again.
3. the extraction preparation method of Sinomenine in caulis sinomenii as described in claim 1, it is characterised in that the step (1)
Middle concentration of hydrochloric acid solution is 1.0 × 10-4~0.1mol.L-1。
4. the extraction preparation method of Sinomenine in caulis sinomenii as described in claim 1, it is characterised in that the step (1)
The volume that hydrochloric acid is added when middle wetting is at least higher by caulis sinomenii powder surface 1mm or more, and wetting temperature is room temperature~60 DEG C, and the time is
0.5~4h.
5. the extraction preparation method of Sinomenine in caulis sinomenii as described in claim 1, it is characterised in that the step (2)
The volume ratio of the caulis sinomenii and water that have soaked when leaching is 1:(1~2), leaching number is 2 times or more, every time 1~2.5h.
6. the extraction preparation method of Sinomenine in caulis sinomenii as described in claim 1, it is characterised in that the step (3)
Use 0.1~3mol.L-1NaOH solution adjust pH, used flocculant be high volence metal ion flocculant.
7. the extraction preparation method of Sinomenine in caulis sinomenii as claimed in claim 6, it is characterised in that the flocculant
To be saturated calcium chloride solution.
8. the extraction preparation method of Sinomenine in caulis sinomenii as described in claim 1, it is characterised in that the step (5)
Use 0.1~6mol.L-1Salt acid for adjusting pH.
9. the extraction preparation method of Sinomenine in caulis sinomenii as described in claim 1, it is characterised in that the step (5)
Extracted using chloroform, the ratio of leaching liquid supernatant and chloroform is 1:(1/4~1/2) (V/V), extraction times are 2 times or more, extraction
Chloroform volume is concentrated into chloroformic solution after taking to measure less than 1/10 times, then carries out crystallization.
10. the extraction preparation method of Sinomenine in caulis sinomenii as described in claim 1, it is characterised in that the step
(5) crystallization is carried out using hydrochloric acid, the crystal of precipitation is washed using ethanol solution, is dried to obtain Sinomenine.
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| CN113209161A (en) * | 2021-05-28 | 2021-08-06 | 湖南农业大学 | Extract of vine fruit of Sinomenium acutum and preparation method and application thereof |
| CN114252522A (en) * | 2021-11-03 | 2022-03-29 | 湖南正清制药集团股份有限公司 | Impurity fingerprint spectrum analysis method of sinomenine hydrochloride raw material medicine |
| CN114957118A (en) * | 2021-02-22 | 2022-08-30 | 湖南正清制药集团股份有限公司 | Extraction method of sinomenine hydrochloride |
| CN115504936A (en) * | 2021-06-22 | 2022-12-23 | 湖南正清制药集团股份有限公司 | Alkalization equipment and method for sinomenine hydrochloride |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957118A (en) * | 2021-02-22 | 2022-08-30 | 湖南正清制药集团股份有限公司 | Extraction method of sinomenine hydrochloride |
| CN113209161A (en) * | 2021-05-28 | 2021-08-06 | 湖南农业大学 | Extract of vine fruit of Sinomenium acutum and preparation method and application thereof |
| CN115504936A (en) * | 2021-06-22 | 2022-12-23 | 湖南正清制药集团股份有限公司 | Alkalization equipment and method for sinomenine hydrochloride |
| CN114252522A (en) * | 2021-11-03 | 2022-03-29 | 湖南正清制药集团股份有限公司 | Impurity fingerprint spectrum analysis method of sinomenine hydrochloride raw material medicine |
| CN114252522B (en) * | 2021-11-03 | 2023-12-26 | 湖南正清制药集团股份有限公司 | Impurity fingerprint analysis method for sinomenine hydrochloride bulk drug |
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