CN108671064A - A method of extracting couplet benzene ring octadiene system lignans from fructus schisandrae - Google Patents
A method of extracting couplet benzene ring octadiene system lignans from fructus schisandrae Download PDFInfo
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- CN108671064A CN108671064A CN201810620703.2A CN201810620703A CN108671064A CN 108671064 A CN108671064 A CN 108671064A CN 201810620703 A CN201810620703 A CN 201810620703A CN 108671064 A CN108671064 A CN 108671064A
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
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- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/57—Magnoliaceae (Magnolia family)
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- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/79—Schisandraceae (Schisandra family)
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- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/30—Extraction of the material
- A61K2236/33—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones
- A61K2236/333—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones using mixed solvents, e.g. 70% EtOH
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- A61K2236/50—Methods involving additional extraction steps
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- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/50—Methods involving additional extraction steps
- A61K2236/53—Liquid-solid separation, e.g. centrifugation, sedimentation or crystallization
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/50—Methods involving additional extraction steps
- A61K2236/55—Liquid-liquid separation; Phase separation
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Abstract
The present invention passes through the extraction in combination hydrolysis in situ, couplet benzene ring octadiene system lignans derivative can be made to hydrolyze, it is completely converted into free state couplet benzene ring octadiene system lignans, to increase the content of couplet benzene ring octadiene system lignans in extract liquor, and efficiently avoids couplet benzene ring octadiene system lignans and degrade because of basic conditions；Wherein, the OH‑Type ion exchange resin is the hydrolysis for promoting couplet benzene ring octadiene system lignans derivative as catalyst, and the chlorinated solvents are to extract free state couplet benzene ring octadiene system lignans derivative as extractant.Therefore, during extraction in combination hydrolysis in situ, the hydrolysis of couplet benzene ring octadiene system lignans derivative and the extraction of free state couplet benzene ring octadiene system lignans are completed at the same time.Meanwhile extraction in combination hydrolysis in situ method provided by the invention efficiently avoids hydrolysis and extracts the lengthy and tedious of two steps operation again, saves the usage amount of operational sequence and solvent, production cost is low, and couplet benzene ring octadiene system lignans yield is high.
Description
Technical field
The present invention relates to compound extractive technique fields, and in particular to one kind extracting couplet benzene ring octadiene from fructus schisandrae
The method of lignans.
Background technology
Fructus schisandrae is the dry mature fruit of magnoliaceae schisandra, and main product is in the Eastern Mountain Area in China northeast
Famous Changbai Mountain genunie medicinal materials, nourishing generate fluid, kidney tonifying nourishing heart, convergence astringent method, to nervous system, cardiovascular system, Digestive
System etc. has multiple pharmacological effect.The principle active component of fructus schisandrae is couplet benzene ring octadiene system lignans, with Schisandra chinensis first
Element, deoxyschizandrin, schizandrin, wuweizi alcohol B, Schisantherin C and schisantherin the second grade are representative.
Couplet benzene ring octadiene lignanoid skeleton is unique, and spatial chemistry is complicated, and bioactivity is extensive.The seventies, China face
Bed research finds that Schisandra chinensis can be substantially reduced hepatitis serum glutamic pyruvic transminase (SGPT) level, can so as to cause Schisandra chinensis
The upsurge of medicinal plants study, and thus develop treatment hepatitis medicament bifendate.In recent years, people by the study found that
Couplet benzene ring octadiene lignanoid is in addition to widely known protecting liver, lowering enzymes, the also bioactivity of other aspects, for example adjusts
Nervous centralis and anti peroxidation of lipid, antitumor, AntiHIV1 RT activity etc..Therefore, the bioactivity tool of research fructus schisandrae is continued deeper into
It is of great importance.
Currently, the method for couplet benzene ring octadiene lignanoid is typically that will be carried after extracting fructus schisandrae in extraction fructus schisandrae
It takes liquid directly to carry out extraction concentration, then is detached with macroporous absorbent resin or silica gel.Such methods have the disadvantage that：North five
In taste in addition to there are free state couplet benzene ring octadiene lignanoid, there is also reference state couplet benzene ring octadiene lignanoids；If not right
Reference state couplet benzene ring octadiene lignanoid extracts the loss that can cause about 30% couplet benzene ring octadiene lignanoid, meanwhile, tree
Fat or the separatory organic solvent recycling load of silica gel are big, cannot reuse, cause the waste in cost and energy.
Invention content
The method that the purpose of the present invention is to provide a kind of to extract couplet benzene ring octadiene system lignans from fructus schisandrae, this
The yield for inventing the method couplet benzene ring octadiene system lignans provided is high and at low cost, suitable for industrial-scale production.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The method that the present invention provides a kind of to extract couplet benzene ring octadiene system lignans from fructus schisandrae, including following step
Suddenly：
Fructus schisandrae is extracted using the first ethanol water, obtains extracting solution；
By the extracting solution and OH-Extraction in combination hydrolysis in situ is carried out after type ion exchange resin and chlorinated solvents mixing, is obtained
Extract liquor；
The organic phase in the extract liquor is isolated, the organic phase is concentrated to dryness, using the second ethanol water pair
Resulting material is dissolved, and lysate is obtained；
The lysate is enriched with using macroporous absorbent resin, using third ethanol water to the macropore after enrichment
Absorption resin is eluted, and the solvent in removal gained eluent obtains couplet benzene ring octadiene system lignans.
Preferably, the volumn concentration of first ethanol water is 60~90%；Second ethanol water
Volumn concentration be 20~30%；The volumn concentration of the third ethanol water is 70~90%.
Preferably, in terms of the absolute dry mass of the fructus schisandrae, the quality of the fructus schisandrae and the first ethanol water
Than being 1：(8~15).
Preferably, the temperature of the extraction is 75~90 DEG C, and the time is 1~5h.
Preferably, the OH-Type ion exchange resin is pre-processed before use, the pretreated method include with
Lower step：
(1) it is 88~92% ethanol water to OH to use volumn concentration-Type ion exchange resin is impregnated
Processing, by gained OH-Type ion exchange resin is washed；
(2) OH for using acid reagent to obtain the step (1)-Type ion exchange resin carries out immersion treatment, by gained
OH-Type ion exchange resin is washed to neutrality；
(3) OH for using base reagent to obtain the step (2)-Type ion exchange resin carries out immersion treatment, by gained
OH-Type ion exchange resin is washed to neutrality；
(4) OH for obtaining the step (3)-Type ion exchange resin carries out the place in step (2) and step (3) successively
Reason, obtains pretreated OH-Type ion exchange resin is spare.
Preferably, in terms of the absolute dry mass of the fructus schisandrae, the OH-Type ion exchange resin is fructus schisandrae quality
3~20%.
Preferably, the chlorinated solvents include dichloromethane, chloroform, 1,1- dichloroethanes or 1,2- dichloroethanes.
Preferably, the chlorinated solvents and the volume ratio of extracting solution are (0.4~2.5)：1.
Preferably, the extraction in combination hydrolysis in situ carries out under sealing condition；The temperature of the extraction in combination hydrolysis in situ be 50~
85 DEG C, the time is 0.5~4h.
Preferably, it the enrichment and is eluted under sealing condition and carries out；In the enrichment process sample concentration be 0.3~
1.0mg/mL。
The method that the present invention provides a kind of to extract couplet benzene ring octadiene system lignans from fructus schisandrae, using the first second
Alcohol solution extracts fructus schisandrae, obtains extracting solution；By the extracting solution and OH-Type ion exchange resin and containing chlorine it is molten
Extraction in combination hydrolysis in situ is carried out after agent mixing, obtains extract liquor；The organic phase in the extract liquor is isolated, the organic phase is dense
It is reduced to dry, resulting material is dissolved using the second ethanol water, obtains lysate；Using macroporous absorbent resin to described
Lysate is enriched with, and is eluted to the macroporous absorbent resin after enrichment using third ethanol water, removal gained elution
Solvent in liquid, obtains couplet benzene ring octadiene system lignans.The present invention can make cyclohexyl biphenyl pungent by the extraction in combination hydrolysis in situ
Dienes lignan derivatives (have the compound that ester group replaces, knot on C-6, C-9 or aromatic ring of couplet benzene ring octadiene system lignans
Close state couplet benzene ring octadiene system lignans) hydrolysis, free state couplet benzene ring octadiene system lignans are completely converted into, to increase extraction
The content of couplet benzene ring octadiene system lignans in liquid is taken, and efficiently avoids couplet benzene ring octadiene system lignans because of basic conditions
And it degrades；Wherein, the OH-Type ion exchange resin is to promote couplet benzene ring octadiene system lignans derivative as catalyst
Hydrolysis, the chlorinated solvents are to extract free state couplet benzene ring octadiene system lignans derivative as extractant.Therefore, it is hydrolyzing
During situ extracting, the hydrolysis of couplet benzene ring octadiene system lignans derivative and free state couplet benzene ring octadiene system lignans
Extraction is completed at the same time.Meanwhile extraction in combination hydrolysis in situ method provided by the invention efficiently avoids hydrolysis and extraction two again
Step operates lengthy and tedious, saves the usage amount of operational sequence and solvent, production cost is low, couplet benzene ring octadiene system lignans yield
It is high.Embodiment the experimental results showed that, by the yield of couplet benzene ring octadiene system lignans in extracting solution be 100% in terms of, according to this
For the yield for the couplet benzene ring octadiene system lignans that the method that invention provides obtains up to 143.24%, purity is higher than 26.7%.
Further, extraction in combination hydrolysis in situ, enrichment and elution process are carried out under sealing condition in the present invention, no dirt
Dye, solvent are recyclable；And the OH-Type ion exchange resin can recycle after through regeneration treatment.This into
One step reduces production cost, is produced convenient for industrial scale.
Description of the drawings
Fig. 1 is gained couplet benzene ring octadiene system lignans (b) and couplet benzene ring octadiene system lignans standard items in embodiment 1
(a) high-efficient liquid phase chromatogram, wherein 1- schizandrins, 2- Schisantherin Cs, 3- schizandrin As, 4- deoxyschizandrins.
Specific implementation mode
The method that the present invention provides a kind of to extract couplet benzene ring octadiene system lignans from fructus schisandrae, including following step
Suddenly：
Fructus schisandrae is extracted using the first ethanol water, obtains extracting solution；
By the extracting solution and OH-Extraction in combination hydrolysis in situ is carried out after type ion exchange resin and chlorinated solvents mixing, is obtained
Extract liquor；
The organic phase in the extract liquor is isolated, the organic phase is concentrated to dryness, using the second ethanol water pair
Resulting material is dissolved, and lysate is obtained；
The lysate is enriched with using macroporous absorbent resin, using third ethanol water to the macropore after enrichment
Absorption resin is eluted, and the solvent in removal gained eluent obtains couplet benzene ring octadiene system lignans.
The present invention extracts fructus schisandrae using the first ethanol water, obtains extracting solution.In the present invention, described
The volumn concentration of first ethanol water is preferably 60~90%, and more preferably 70~80%.In the present invention, with described
The mass ratio of the absolute dry mass meter of fructus schisandrae, the fructus schisandrae and the first ethanol water is preferably 1：(8~15), it is more excellent
It is selected as 1：(10~12).
In the present invention, the fructus schisandrae is preferably the fructus schisandrae after natural air drying；In the present invention, described northern five
For taste after natural air drying, moisture content is 20% hereinafter, in not necessary any drying process processing before.In the present invention,
The fructus schisandrae is preferably crushing processing using preceding, crosses 40 mesh sieve, obtains lower part of screen and divide fructus schisandrae powder for use.
In the present invention, the temperature of the extraction is preferably 75~90 DEG C, more preferably 80~85 DEG C；In the reality of the present invention
It applies in example, the temperature of the extraction is specially the reflux temperature of first ethanol water.In the present invention, the extraction
Time is preferably 1~5h, more preferably 2~4h.In the present invention, in order to ensure fully to extract couplet benzene ring octadiene class wood fat
The number of element, the extraction is preferably 2~4 times, more preferably 3 times.
After completing the extraction, gained system is preferably separated by solid-liquid separation by the present invention, using obtained liquid material as
Extracting solution.The present invention does not have the mode of the separation of solid and liquid special restriction, using side well known to those skilled in the art
Formula is specific as filtered.
The present invention extracts fructus schisandrae using the first ethanol water, and raw material is not required to additionally dry directly use,
Less energy consumption；And couplet benzene ring octadiene system lignans yield is high, fire safety evaluating hidden danger is low；Meanwhile the first ethanol water energy
Enough remove the larger substance of polarity in the fructus schisandrae, such as polysaccharide and protein.
After obtaining extracting solution, the present invention is by the extracting solution and OH-Type ion exchange resin and chlorinated solvents mixing are laggard
Row extraction in combination hydrolysis in situ, obtains extract liquor.In the present invention, the chlorinated solvents and the volume ratio of extracting solution be preferably (0.4~
2.5)：1, more preferably (1~2)：1.In the present invention, the chlorinated solvents preferably include dichloromethane, chloroform, 1,1-
Dichloroethanes or 1,2- dichloroethanes.
In the present invention, in terms of the absolute dry mass of the fructus schisandrae, the OH-Type ion exchange resin is preferably north five
The 3~20% of taste protonatomic mass, more preferably 5~17%, most preferably 8~12%.
The present invention is for the OH-The type of type ion exchange resin and source do not have special restriction, using this field
The OH of the known type of technical staff-The commercial goods of type ion exchange resin.In the present invention, the OH-Type ion exchange
The model of resin preferably includes 201*7, D261, D280, D290, D296, D301-G or D301-R.
In the present invention, the OH-The model and property of type ion exchange resin are as shown in the table：
OH-The model and property of type ion exchange resin
In the present invention, the OH-Type ion exchange resin is pre-processed before use, the pretreated method packet
Include following steps：
(1) it is 88~92% ethanol water to OH to use volumn concentration-Type ion exchange resin is impregnated
Processing, by gained OH-Type ion exchange resin is washed；
(2) OH for using acid reagent to obtain the step (1)-Type ion exchange resin carries out immersion treatment, by gained
OH-Type ion exchange resin is washed to neutrality；
(3) OH for using base reagent to obtain the step (2)-Type ion exchange resin carries out immersion treatment, by gained
OH-Type ion exchange resin is washed to neutrality；
(4) OH for obtaining the step (3)-Type ion exchange resin carries out the place in step (2) and step (3) successively
Reason, obtains pretreated OH-Type ion exchange resin is spare.
Present invention preferably employs volumn concentration be 88~92% ethanol water to OH-Type ion exchange resin into
Row immersion treatment, by gained OH-Type ion exchange resin is washed.In the present invention, the volume hundred of the ethanol water
Point content is preferably 90%.In the present invention, the time of the immersion treatment is preferably 22~26h, more preferably for 24 hours.At this
In invention, water used by the washing is preferably distilled water；The present invention can incite somebody to action the not special restriction of the washing
Gained OH after immersion treatment-Ethyl alcohol in type ion exchange resin is cleaned.
After the completion of using volumn concentration to carry out immersion treatment and washing for 88~92% ethanol water, the present invention
It is preferred that using acid reagent to gained OH-Type ion exchange resin carries out immersion treatment, by gained OH-Type ion exchange resin is washed
To neutrality.In the present invention, the acid reagent is preferably HCl solution.The present invention is not special for the concentration of the HCl solution
Restriction, using concentration well known to those skilled in the art；In an embodiment of the present invention, the concentration of the HCl solution
Specially 0.1mol/L.In the present invention, the time of the immersion treatment is preferably 3~5h, more preferably 4h.In the present invention
In, water used by the washing is preferably distilled water；The present invention can will impregnate the not special restriction of the washing
Gained OH after processing-Type ion exchange resin is washed till neutrality.
After the completion of carrying out immersion treatment and washing using acid reagent, present invention preferably employs base reagents to gained OH-Type from
Sub-exchange resin carries out immersion treatment, by gained OH-Type ion exchange resin is washed to neutrality.In the present invention, the alkali examination
Agent is preferably NaOH solution.The present invention does not have the concentration of the NaOH solution special restriction, using people in the art
Concentration known to member；In an embodiment of the present invention, the concentration of the NaOH solution is specially 0.1mol/L.In the present invention
In, the time of the immersion treatment is preferably 3~5h, more preferably 4h.In the present invention, water used by the washing is preferred
For distilled water；The present invention, can be by gained OH after immersion treatment for the not special restriction of the washing-Type amberlite
Fat is washed till neutrality.
After the completion of carrying out immersion treatment and washing using base reagent, the present invention is preferably tried according to above-mentioned technical proposal using acid
Agent is to gained OH-Type ion exchange resin carries out immersion treatment, by gained OH-Type ion exchange resin is washed to neutrality；Then it presses
According to above-mentioned technical proposal using base reagent to gained OH-Type ion exchange resin carries out immersion treatment, by gained OH-Type ion is handed over
It changes resin and is washed to neutrality, obtain pretreated OH-Type ion exchange resin is spare.
In the present invention, the OH-Often contain a small amount of oligomer in type ion exchange resin commercial goods and does not participate in anti-
The inorganic impurities such as the monomer answered, also iron, lead, copper, when it is contacted with other solution, above-mentioned substance will be transferred to solution
In, influence the quality of final product.Therefore, to the OH-Type ion exchange resin carry out pretreatment can prevent it is therein solvable
Property impurity is transferred in solution, using initial stage, pollutes the water quality of water outlet.
In the present invention, the extraction in combination hydrolysis in situ preferably carries out under sealing condition；The temperature of the extraction in combination hydrolysis in situ
Preferably 75~90 DEG C, more preferably 80~85 DEG C of degree；Time is preferably 0.5~4h, more preferably 1~3h.The present invention passes through
The extraction in combination hydrolysis in situ, can make couplet benzene ring octadiene system lignans derivative (C-6 of couplet benzene ring octadiene system lignans,
Have the compound that ester group replaces, reference state couplet benzene ring octadiene system lignans on C-9 or aromatic ring) hydrolysis, it is completely converted into free
State couplet benzene ring octadiene system lignans to increase the content of couplet benzene ring octadiene system lignans in extract liquor, and are effectively kept away
Exempt from couplet benzene ring octadiene system lignans to degrade because of basic conditions；Wherein, the OH-Type ion exchange resin is as catalysis
It is to extract free state biphenyl as extractant that agent, which promotes the hydrolysis of couplet benzene ring octadiene system lignans derivative, the chlorinated solvents,
Cyclo-octadiene lignans derivative.Therefore, during extraction in combination hydrolysis in situ, couplet benzene ring octadiene system lignans derivative
Hydrolysis and the extraction of free state couplet benzene ring octadiene system lignans are completed at the same time.Meanwhile hydrolysis provided by the invention is in situ
Extracting process efficiently avoids lengthy and tedious, the usage amount of saving operational sequence and solvent of the hydrolysis with extraction two steps operation again, raw
Produce at low cost, couplet benzene ring octadiene system lignans yield height.In addition, the extraction in combination hydrolysis in situ carries out under sealing condition, nothing
Pollution, solvent is recyclable, the OH-Through regeneration treatment (with the OH after type ion exchange resin use-Type ion is handed over
It is consistent using the pretreatment of preceding progress to change resin, is no longer repeated herein) it can recycle, it is convenient for commercial scale metaplasia
Production.
After obtaining extract liquor, the present invention isolates the organic phase in the extract liquor, and the organic phase is concentrated to dryness, is adopted
Resulting material is dissolved with the second ethanol water, obtains lysate.The present invention preferably by the extract liquor stratification,
To isolate organic phase.The present invention is for the not special restriction of the concentration, using well known to those skilled in the art dense
The technical solution of contracting.In the present invention, the volumn concentration of second ethanol water is preferably 20~30%, more
Preferably 23~27%.In the present invention, in terms of absolute dry mass, the organic phase is concentrated to dryness rear resulting material and the second ethyl alcohol
The mass ratio of aqueous solution is preferably 1：(25~35), more preferably 1：30.
After obtaining lysate, the present invention is enriched with the lysate using macroporous absorbent resin, using third ethyl alcohol
Aqueous solution elutes the macroporous absorbent resin after enrichment, and the solvent in removal gained eluent obtains couplet benzene ring octadiene
Lignans.The present invention does not have the type of the macroporous absorbent resin and source special restriction, using art technology
The commercial goods of the macroporous absorbent resin of the known type of personnel.In the present invention, the model of the macroporous absorbent resin is excellent
Choosing includes HPD80, HPD100, HPD300, HPD5000, AB-8, D101, HPD-D, DM-130, ADS-17, HPD826, ADS-7
Or DA-201.
In the present invention, the model and property of the macroporous absorbent resin are as shown in the table：
The model and property of macroporous absorbent resin
In the present invention, the macroporous absorbent resin is pre-processed before use, and the pretreated method is preferably wrapped
Include following steps：
Macroporous absorbent resin is impregnated into 8~12h in the ethyl alcohol that volumn concentration is 90~95%, using distilled water pair
Macroporous absorbent resin after immersion is washed to remove remaining ethyl alcohol, the filtering of family name's funnel, and port grinding bottle seals 22~26h balances up for safekeeping
It is for use to obtain pretreated macroporous absorbent resin for moisture.
In the present invention, sample concentration is preferably 0.3~1.0mg/mL in the enrichment process, more preferably 0.5~
0.8mg/mL.In the present invention, the volumn concentration of the third ethanol water is preferably 70~90%, and more preferably 75
~85%.
In the present invention, the enrichment and elution preferably carry out under sealing condition, and pollution-free, solvent is recyclable to be made
With convenient for industrial scale production.The present invention does not have special restriction for the concrete operation method of the enrichment and elution, adopts
With the technical solution of enrichment and elution well known to those skilled in the art.Macroporous absorbent resin is preferably filled column by the present invention,
Under sealing condition, the lysate is enriched with using gained closing column, then uses the third ethanol water pair
Closing column after enrichment is eluted.In the present invention, the blade diameter length ratio of the closing column is preferably 1：(15~20)；The dissolving
The volume of liquid is preferably close column volume 3~4 times, more preferably 3.5 times；The volume of the third ethanol water is preferably
Close column volume 15~25 times, more preferably 20 times.
The method of solvent does not have special restriction in gained eluent after the present invention elutes removal, using this field skill
The technical solution of removal solvent known to art personnel is specific as being evaporated under reduced pressure.In the present invention, molten in gained eluent
Agent preferably carries out recycling, to reduce production cost.
After solvent in removal gained eluent, preferably resulting material is dried by the present invention, obtains cyclohexyl biphenyl pungent two
Alkenes lignanoid.In the present invention, the drying is preferably dried in vacuo；In the present invention, the vacuum drying temperature is excellent
It is selected as 35~45 DEG C, more preferably 40 DEG C；The time is preferably 5~7h, more preferably 6h.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
Fructus schisandrae after natural air drying is crushed into processing, the fructus schisandrae powder that grain size is 40 mesh is obtained, weighs
50g fructus schisandraes powder is put into (in terms of absolute dry mass) in round-bottomed flask, then presses fructus schisandrae powder and ethanol water
Mass ratio is 1：8 meters, are added the ethanol water that volumn concentration is 80%, and the refluxing extraction 2h in 90 DEG C of water-baths continues
Repeat extraction 2 times, merges resulting material after extraction, filtering, using obtained liquid material as extracting solution；
To OH-Type ion exchange resin (model 201*7) is pre-processed, specifically use volumn concentration for
90% ethanol water is to OH-Type ion exchange resin carries out immersion treatment for 24 hours, by gained OH-Type ion exchange resin uses
Distilled water is washed；Using the HCl solution of 0.1mol/L to gained OH-Type ion exchange resin carries out immersion treatment 4h, will
Gained OH-Type ion exchange resin is washed to neutrality using distillation；Using the NaOH solution of 0.1mol/L to gained OH-Type ion
Exchanger resin carries out immersion treatment 4h, by gained OH-Type ion exchange resin is washed to neutrality using distillation；It repeats to use
The HCl solution of 0.1mol/L carries out immersion treatment, distillation is washed to neutral and is impregnated using the NaOH solution of 0.1mol/L
Processing, distillation are washed to neutral step, obtain pretreated OH-Type ion exchange resin；
By the extracting solution and pretreated OH-Type ion exchange resin 3.0g and 30mL1, the mixing of 2- dichloroethanes,
Under sealing condition, reflux progress extraction in combination hydrolysis in situ 2h, obtains extract liquor in 95 DEG C of water-baths；
By the extract liquor stratification, organic phase is isolated, the organic phase is concentrated to dryness, then presses resulting material
The mass ratio of (in terms of absolute dry mass) and ethanol water is 1：It is water-soluble that the ethyl alcohol that volumn concentration is 30% is added in 30 meters
Liquid makes the organic phase be concentrated to dryness rear resulting material dissolving, obtains lysate；
Macroporous absorbent resin (model AB-8) is impregnated into 10h in the ethyl alcohol that volumn concentration is 95%, using steaming
Distilled water washs the macroporous absorbent resin after immersion to remove remaining ethyl alcohol, and the filtering of family name's funnel, port grinding bottle is sealed up for safekeeping puts down for 24 hours
The pretreated macroporous absorbent resin of gained is filled column by Hengshui point, and under sealing condition, column (blade diameter length ratio 1 is closed using gained：
15, volume 9.5mL) lysate is enriched with, sample concentration is 0.6mg/mL in the enrichment process；Then it uses
The ethanol water (volume is close column volume 20 times) that volumn concentration is 90% washes the closing column after enrichment
De-, the solvent in vacuum distillation removal gained eluent obtains couplet benzene ring octadiene system lignans.
The content of couplet benzene ring octadiene system lignans in extracting solution is measured, yield is calculated；Meanwhile it calculating according to embodiment 1
The yield of couplet benzene ring octadiene system lignans obtained by middle method.The result shows that with couplet benzene ring octadiene system lignans in extracting solution
Yield be 100% meter, the yield according to couplet benzene ring octadiene system lignans obtained by method in embodiment 1 is 146.11%.This
Illustrate during extraction in combination hydrolysis in situ, couplet benzene ring octadiene system lignans derivative is converted into free state couplet benzene ring octadiene class
Lignanoid, to improve the yield of couplet benzene ring octadiene system lignans.To according to cyclohexyl biphenyl pungent two obtained by method in embodiment 1
Alkenes lignanoid carries out purity analysis, the results showed that, the purity of gained couplet benzene ring octadiene system lignans is up to 24.6%.Wherein,
The content and purity of the couplet benzene ring octadiene system lignans by high performance liquid chromatography detection and are calculated, specifically
As shown in Figure 1.
According to OH-Type ion exchange resin carries out pretreated method, and the OH after situ extracting will be hydrolyzed-Type from
Sub-exchange resin is regenerated.The result shows that by the OH after regeneration-Type ion exchange resin is reused 7 times, and hydrolysis efficiency is
The 90.2% of first hydrolysis efficiency.
Embodiment 2
Fructus schisandrae after natural air drying is crushed into processing, the fructus schisandrae powder that grain size is 40 mesh is obtained, weighs
500g fructus schisandraes powder is put into (in terms of absolute dry mass) in pilot scale round-bottomed flask, then presses fructus schisandrae powder and ethyl alcohol is water-soluble
The mass ratio of liquid is 1：12 meters, the ethanol water that addition volumn concentration is 80%, the refluxing extraction 3h in 90 DEG C of water-baths,
Continue to repeat extraction 2 times, merges resulting material after extraction, filtering, using obtained liquid material as extracting solution；
To OH-Type ion exchange resin (model 201*7) is pre-processed, specifically use volumn concentration for
90% ethanol water is to OH-Type ion exchange resin carries out immersion treatment for 24 hours, by gained OH-Type ion exchange resin uses
Distilled water is washed；Using the HCl solution of 0.1mol/L to gained OH-Type ion exchange resin carries out immersion treatment 4h, will
Gained OH-Type ion exchange resin is washed to neutrality using distillation；Using the NaOH solution of 0.1mol/L to gained OH-Type ion
Exchanger resin carries out immersion treatment 4h, by gained OH-Type ion exchange resin is washed to neutrality using distillation；It repeats to use
The HCl solution of 0.1mol/L carries out immersion treatment, distillation is washed to neutral and is impregnated using the NaOH solution of 0.1mol/L
Processing, distillation are washed to neutral step, obtain pretreated OH-Type ion exchange resin；
By the extracting solution and pretreated OH-Type ion exchange resin 3.0g and 30mL1, the mixing of 2- dichloroethanes,
Under sealing condition, reflux progress extraction in combination hydrolysis in situ 4h, obtains extract liquor in 85 DEG C of water-baths；
By the extract liquor stratification, organic phase is isolated, the organic phase is concentrated to dryness, then presses resulting material
The mass ratio of (in terms of absolute dry mass) and ethanol water is 1：It is water-soluble that the ethyl alcohol that volumn concentration is 25% is added in 30 meters
Liquid makes the organic phase be concentrated to dryness rear resulting material dissolving, obtains lysate；
Macroporous absorbent resin (model AB-8) is impregnated into 10h in the ethyl alcohol that volumn concentration is 95%, using steaming
Distilled water washs the macroporous absorbent resin after immersion to remove remaining ethyl alcohol, and the filtering of family name's funnel, port grinding bottle is sealed up for safekeeping puts down for 24 hours
The pretreated macroporous absorbent resin of gained is filled column by Hengshui point, and under sealing condition, column (blade diameter length ratio 1 is closed using gained：
20, volume 12mL) lysate is enriched with, sample concentration is 0.6mg/mL in the enrichment process；Then it uses
The ethanol water (volume is close column volume 15 times) that volumn concentration is 90% washes the closing column after enrichment
De-, the solvent in vacuum distillation removal gained eluent obtains couplet benzene ring octadiene system lignans.
The content of couplet benzene ring octadiene system lignans in extracting solution is measured, yield is calculated；Meanwhile it calculating according to embodiment 2
The yield of couplet benzene ring octadiene system lignans obtained by middle method.The result shows that with couplet benzene ring octadiene system lignans in extracting solution
Yield be 100% meter, the yield according to couplet benzene ring octadiene system lignans obtained by method in embodiment 2 is 143.24%.This
Illustrate during extraction in combination hydrolysis in situ, couplet benzene ring octadiene system lignans derivative is converted into free state couplet benzene ring octadiene class
Lignanoid, to improve the yield of couplet benzene ring octadiene system lignans.
To carrying out purity analysis according to couplet benzene ring octadiene system lignans obtained by method in embodiment 2, the results showed that, gained
The purity of couplet benzene ring octadiene system lignans is up to 26.7%.
According to OH-Type ion exchange resin carries out pretreated method, and the OH after situ extracting will be hydrolyzed-Type from
Sub-exchange resin is regenerated.The result shows that by the OH after regeneration-Type ion exchange resin is reused 7 times, and hydrolysis efficiency is
The 92.2% of first hydrolysis efficiency.
Embodiment 3
Fructus schisandrae after natural air drying is crushed into processing, the fructus schisandrae powder that grain size is 40 mesh is obtained, weighs
1000g fructus schisandraes powder is put into (in terms of absolute dry mass) in pilot scale round-bottomed flask, then presses fructus schisandrae powder and ethanol water
The mass ratio of solution is 1：The ethanol water that volumn concentration is 80%, the refluxing extraction in 90 DEG C of water-baths is added in 10 meters
2.5h continues to repeat extraction 2 times, merges resulting material after extraction, filtering, using obtained liquid material as extracting solution；
To OH-Type ion exchange resin (model 201*7) is pre-processed, specifically use volumn concentration for
90% ethanol water is to OH-Type ion exchange resin carries out immersion treatment for 24 hours, by gained OH-Type ion exchange resin uses
Distilled water is washed；Using the HCl solution of 0.1mol/L to gained OH-Type ion exchange resin carries out immersion treatment 4h, will
Gained OH-Type ion exchange resin is washed to neutrality using distillation；Using the NaOH solution of 0.1mol/L to gained OH-Type ion
Exchanger resin carries out immersion treatment 4h, by gained OH-Type ion exchange resin is washed to neutrality using distillation；It repeats to use
The HCl solution of 0.1mol/L carries out immersion treatment, distillation is washed to neutral and is impregnated using the NaOH solution of 0.1mol/L
Processing, distillation are washed to neutral step, obtain pretreated OH-Type ion exchange resin；
By the extracting solution and pretreated OH-Type ion exchange resin 3.0g and 30mL1, the mixing of 2- dichloroethanes,
Under sealing condition, reflux progress extraction in combination hydrolysis in situ 3h, obtains extract liquor in 95 DEG C of water-baths；
By the extract liquor stratification, organic phase is isolated, the organic phase is concentrated to dryness, then presses resulting material
The mass ratio of (in terms of absolute dry mass) and ethanol water is 1：It is water-soluble that the ethyl alcohol that volumn concentration is 30% is added in 25 meters
Liquid makes the organic phase be concentrated to dryness rear resulting material dissolving, obtains lysate；
Macroporous absorbent resin (model AB-8) is impregnated into 10h in the ethyl alcohol that volumn concentration is 95%, using steaming
Distilled water washs the macroporous absorbent resin after immersion to remove remaining ethyl alcohol, and the filtering of family name's funnel, port grinding bottle is sealed up for safekeeping puts down for 24 hours
The pretreated macroporous absorbent resin of gained is filled column by Hengshui point, and under sealing condition, column (blade diameter length ratio 1 is closed using gained：
20, volume 11.5mL) lysate is enriched with, sample concentration is 0.6mg/mL in the enrichment process；Then it adopts
The ethanol water for being 90% with volumn concentration (volume is close column volume 20 times) carries out the closing column after enrichment
Elution, vacuum distillation remove the solvent in gained eluent, obtain couplet benzene ring octadiene system lignans.
The content of couplet benzene ring octadiene system lignans in extracting solution is measured, yield is calculated；Meanwhile it calculating according to embodiment 3
The yield of couplet benzene ring octadiene system lignans obtained by middle method.The result shows that with couplet benzene ring octadiene system lignans in extracting solution
Yield be 100% meter, the yield according to couplet benzene ring octadiene system lignans obtained by method in embodiment 3 is 132.51%.This
Illustrate during extraction in combination hydrolysis in situ, couplet benzene ring octadiene system lignans derivative is converted into free state couplet benzene ring octadiene class
Lignanoid, to improve the yield of couplet benzene ring octadiene system lignans.
To carrying out purity analysis according to couplet benzene ring octadiene system lignans obtained by method in embodiment 3, the results showed that, gained
The purity of couplet benzene ring octadiene system lignans is up to 28.8%.
According to OH-Type ion exchange resin carries out pretreated method, and the OH after situ extracting will be hydrolyzed-Type from
Sub-exchange resin is regenerated.The result shows that by the OH after regeneration-Type ion exchange resin is reused 7 times, and hydrolysis efficiency is
The 91.4% of first hydrolysis efficiency.
As seen from the above embodiment, the present invention can make couplet benzene ring octadiene class wood fat by the extraction in combination hydrolysis in situ
Plain derivative (has the compound that ester group replaces, reference state cyclohexyl biphenyl on C-6, C-9 or aromatic ring of couplet benzene ring octadiene system lignans
Zinn diene class lignanoid) hydrolysis, free state couplet benzene ring octadiene system lignans are completely converted into, to increase biphenyl in extract liquor
The content of cyclo-octadiene lignans, and efficiently avoid couplet benzene ring octadiene system lignans and degrade because of basic conditions；Its
In, the OH-Type ion exchange resin is the hydrolysis for promoting couplet benzene ring octadiene system lignans derivative as catalyst, described
Chlorinated solvents are to extract free state couplet benzene ring octadiene system lignans derivative as extractant.Therefore, in extraction in combination hydrolysis in situ
In the process, the hydrolysis of couplet benzene ring octadiene system lignans derivative and the extraction of free state couplet benzene ring octadiene system lignans are same
When complete.Meanwhile extraction in combination hydrolysis in situ method provided by the invention efficiently avoids hydrolysis and extraction two steps operation again
It is lengthy and tedious, the usage amount of operational sequence and solvent is saved, production cost is low, and couplet benzene ring octadiene system lignans yield is high.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method for extracting couplet benzene ring octadiene system lignans from fructus schisandrae, includes the following steps：
Fructus schisandrae is extracted using the first ethanol water, obtains extracting solution；
By the extracting solution and OH-Extraction in combination hydrolysis in situ is carried out after type ion exchange resin and chlorinated solvents mixing, is extracted
Liquid；
The organic phase in the extract liquor is isolated, the organic phase is concentrated to dryness, using the second ethanol water to gained
Material is dissolved, and lysate is obtained；
The lysate is enriched with using macroporous absorbent resin, using third ethanol water to the macroporous absorption after enrichment
Resin is eluted, and the solvent in removal gained eluent obtains couplet benzene ring octadiene system lignans.
2. according to the method described in claim 1, it is characterized in that, the volumn concentration of first ethanol water is 60
~90%；The volumn concentration of second ethanol water is 20~30%；The volume hundred of the third ethanol water
It is 70~90% to divide content.
3. method according to claim 1 or 2, which is characterized in that in terms of the absolute dry mass of the fructus schisandrae, the north
The mass ratio of Schisandra chinensis and the first ethanol water is 1：(8~15).
4. according to the method described in claim 3, it is characterized in that, the temperature of the extraction be 75~90 DEG C, the time be 1~
5h。
5. according to the method described in claim 1, it is characterized in that, the OH-Type ion exchange resin is located in advance using preceding
Reason, the pretreated method include the following steps：
(1) it is 88~92% ethanol water to OH to use volumn concentration-Type ion exchange resin carries out immersion treatment,
By gained OH-Type ion exchange resin is washed；
(2) OH for using acid reagent to obtain the step (1)-Type ion exchange resin carries out immersion treatment, by gained OH-Type
Ion exchange resin is washed to neutrality；
(3) OH for using base reagent to obtain the step (2)-Type ion exchange resin carries out immersion treatment, by gained OH-Type
Ion exchange resin is washed to neutrality；
(4) OH for obtaining the step (3)-Type ion exchange resin carries out the processing in step (2) and step (3) successively, obtains
To pretreated OH-Type ion exchange resin is spare.
6. method according to claim 1 or 5, which is characterized in that in terms of the absolute dry mass of the fructus schisandrae, the OH-
Type ion exchange resin is the 3~20% of fructus schisandrae quality.
7. according to the method described in claim 1, it is characterized in that, the chlorinated solvents include dichloromethane, chloroform, 1,
1- dichloroethanes or 1,2- dichloroethanes.
8. method according to claim 1 or claim 7, which is characterized in that the chlorinated solvents and the volume ratio of extracting solution are
(0.4~2.5)：1.
9. according to the method described in claim 1, it is characterized in that, the extraction in combination hydrolysis in situ carries out under sealing condition；Institute
The temperature for stating extraction in combination hydrolysis in situ is 50~85 DEG C, and the time is 0.5~4h.
10. according to the method described in claim 1, it is characterized in that, the enrichment and being eluted under sealing condition and carrying out；It is described
Sample concentration is 0.3~1.0mg/mL in enrichment process.
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| CN111084885A (en) * | 2019-12-16 | 2020-05-01 | 云南中医药大学 | Antifungal medicine composition consisting of lignans active molecules SWL-1 and antifungal medicine |
| CN111084885B (en) * | 2019-12-16 | 2022-02-11 | 云南中医药大学 | Antifungal medicine composition consisting of lignans active molecules SWL-1 and antifungal medicine |
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Application publication date: 20181019 |