CN108623434A - A method of preparing Alismoxide - Google Patents
A method of preparing Alismoxide Download PDFInfo
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- CN108623434A CN108623434A CN201810609729.7A CN201810609729A CN108623434A CN 108623434 A CN108623434 A CN 108623434A CN 201810609729 A CN201810609729 A CN 201810609729A CN 108623434 A CN108623434 A CN 108623434A
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- method described
- acetone
- alismoxide
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- soft coral
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/30—Azulenes; Hydrogenated azulenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Abstract
The invention discloses a kind of methods preparing Alismoxide, including：Step S1, extraction are concentrated to give soft coral acetone medicinal extract；Step S2, acetone medicinal extract XDA 1B macroporous resin enrichments collect 65% ethanol eluate of 4.5 5.0BV, are concentrated and dried to obtain enriched substance first with 30% ethanol elution, then with 65% ethanol elution；Step S3 carries out high-speed counter-current separation using ethyl acetate n-butanol trifluoroacetic acid water as dicyandiamide solution to enriched substance.The method of the present invention does not depend on silica gel column chromatography and/or gel filtration chromatography, has a extensive future.
Description
Technical field
The invention belongs to field of medicaments, and in particular to the preparation method of several medicinal activity compounds.
Background technology
Alismoxide、ent-spathulenol、4α,10α-aromadendranediol、aromadendrane-4β,
The chemical formula of 10 α-diol is as follows.Alismoxide is earliest by document (Terpenoids ofAlisma orientale
Rhizome andthe crude drug Alismatis rhizoma.Phytochemistry, 1994) it is open.ent-
Spathulenol is earliest by document (Three ent-secoaromadendrane-type sesquiterpene
hemiacetals and a bicyclogermacrene from Plagiochila ovalifolia
AndPlagiochilayokogurensis.Phytochemistry, 1980) it is open.4α,10α-aromadendranediol
With aromadendrane-4 β, 10 α-diol are earliest by document (Sesquiterpene lactones and a
Sesquiterpene diol from jamaican ambrosiaperuviana.Phytochemistry, 1987) it is open.
The study found that Alismoxide, ent-spathulenol, 4 α, 10 α-aromadendranediol,
There are a variety of pharmacological activity, patent medicine to have a extensive future by aromadendrane-4 β, 10 α-diol.But it prepares at present
Alismoxide、ent-spathulenol、4α,10α-aromadendranediol、aromadendrane-4β,10α-diol
Method without independent of silica gel column chromatography and/or gel filtration chromatography it is this can not industrial applications separating medium, industrialization
Production difficulty is big.
Invention content
The present invention is directed to overcome the shortage of prior art, one kind is provided independent of silica gel column chromatography and/or gel filtration chromatography
Preparation Alismoxide, ent-spathulenol, 4 α, 10 α-aromadendranediol, aromadendrane-4 β, 10
The method of α-diol.
The present invention includes following technical solution：
It is a kind of to prepare Alismoxide, ent-spathulenol, 4 α, 10 α-aromadendranediol,
Aromadendrane-4 β, the method for 10 α-diol include the following steps：
Step S1, extraction and concentration：
First soft coral is shredded, is freeze-dried, dry soft coral petroleum ether cold soaking is then extracted 3
Secondary, each 8h collects soft coral, then with acetone circumfluence distillation 3 times, each 2h, collects acetone extract, reduced pressure
Obtain soft coral acetone medicinal extract；
Step S2, macroporous resin enrichment：
Loading and absorption：It is 5 that XDA-1B macroporous absorbent resins, which are seated in draw ratio,:(per 200g beanpods in 1 resin column
Soft coral acetone medicinal extract use 100g resins), prepare soft coral acetone medicinal extract crude extract upper prop liquid (solvent be 15% second
Alcohol), loading under conditions of adsorption flow rate is 1.5BV/h closes resin column valve standing adsorption appropriate time after end of the sample；
Elution：First with 30% ethyl alcohol with 3BV/h elution flow rates elute 2h, then with 65% ethyl alcohol with 2BV/h elution flow rates into
Row elution, collects 65% ethanol eluate of 4.5-5.0BV, is concentrated and dried to obtain enriched substance；
Step S3, high-speed counter-current separation：
By dicyandiamide solution ethyl acetate-n-butanol-trifluoroacetic acid-water (volume ratio 30:5:1:30) it proportionally prepares, surpasses
Sound deaerates 2h, stands 0.5h, until after the layering completely of upper and lower two-phase, upper and lower two-phase is separated, then with plastic film by each container
It seals, places for 24 hours, the gas in system is made to drain；The enriched substance 0.5g after resin separation concentration is taken, with phase mobile phase 10mL
It is dissolved, sample liquid is used as after 0.45 μm of membrane filtration；Before separation, first high flow rate is pumped into stationary phase, and phase to be fixed is full of entire
After pipeline, termination of pumping starts work drum, rotating speed is adjusted to 800r/min, mobile phase is pumped into the speed of 1.5mL/min, waits for solvent
When system balances, sample introduction 10mL continues to be pumped into mobile phase with the speed of 1.5mL/min, and starts chromatographic work station record collection of illustrative plates,
Detection wavelength 225nm collects Alismoxide, ent-spathulenol, 4 α, 10 α-according to chromatogram
The corresponding elution fraction of aromadendranediol or aromadendrane-4 β, 10 α-diol.
Preferably, the solid-to-liquid ratio of petroleum ether cold soaking extraction is 1:30.
Preferably, the solid-to-liquid ratio of acetone circumfluence distillation is 1:20.
Preferably, concentration of alcohol refers to the ethanol water of different volumes percentage concentration.
Preferably, a concentration of 1mg/mL of crude extract upper prop liquid.
Preferably, it is filtered with absorbent cotton before crude extract upper prop liquid upper prop.
Preferably, resin column valve standing adsorption 0.5h is closed after end of the sample.
Preferably, ultrasound degassing 2h after high-speed counter-current dicyandiamide solution prepares.
Preferably, 0.5h is stood after the degassing of high-speed counter-current dicyandiamide solution ultrasound.
Preferably, the chromatogram is as shown in Figure 1.
Advantageous effect：
The method of the present invention is used to be detached with the macroporous absorbent resin combination high speed adverse current chromatogram of industrialized production and be prepared
Obtain (purity is more than 98%) alismoxide, ent-spathulenol, 4 α of high-purity, 10 α-
Aromadendranediol, aromadendrane-4 β, 10 α-diol, independent of silica gel column chromatography and/or gel column layer
Analysis, has a extensive future.
Description of the drawings
Fig. 1 is high-speed counter-current separation chromatogram；
Fig. 2 is that alismoxide corresponds to elution fraction and the HPLC retention times of alismoxide standard items compare；
Fig. 3 is the HPLC retention times that ent-spathulenol corresponds to elution fraction and ent-spathulenol standard items
It compares；
Fig. 4 is 4 α, and 10 α-aromadendranediol correspond to elution fraction and 4 α, 10 α-aromadendranediol marks
The HPLC retention times of quasi- product compare；
Fig. 5 is aromadendrane-4 β, and 10 α-diol correspond to elution fraction and aromadendrane-4 β, 10 α-diol
The HPLC retention times of standard items compare.
Specific implementation mode
The content of present invention is specifically introduced with reference to the accompanying drawings and examples.
Soft coral (Lobophytum sp.) picks up from the underwater 20m in China marine sites Sanya, Hainan Xi Dao, freezes immediately
It is spare.
TBE-300 type high-speed counter-current chromatographs are purchased from Tongtian Biochemical Technology Co., Ltd., Shanghai.
Preparation Alismoxide, ent-spathulenol, 4 α, 10 α-aromadendranediol,
Aromadendrane-4 β, the method for 10 α-diol include the following steps：
Step S1, extraction and concentration：
First soft coral is shredded, is freeze-dried, then extracts dry soft coral petroleum ether cold soaking 3 times
(solid-to-liquid ratio 1:30), each 8h collects soft coral, then with 3 (solid-to-liquid ratios 1 of acetone circumfluence distillation:20), every time
2h collects acetone extract, is concentrated under reduced pressure to give soft coral acetone medicinal extract；
Step S2, macroporous resin enrichment：
Loading and absorption：It is 5 that XDA-1B macroporous absorbent resins, which are seated in draw ratio,:(per 200g beanpods in 1 resin column
Soft coral acetone medicinal extract uses 100g resins), prepare the crude extract upper prop liquid of a concentration of 1mg/mL of soft coral acetone medicinal extract
(solvent be 15% ethyl alcohol, concentration expressed in percentage by volume, similarly hereinafter；Filtered with absorbent cotton before upper prop), in the item that adsorption flow rate is 1.5BV/h
Loading under part closes resin column valve standing adsorption 0.5h after end of the sample；
Elution：First with 30% ethyl alcohol with 3BV/h elution flow rates elute 2h, then with 65% ethyl alcohol with 2BV/h elution flow rates into
Row elution, collects 65% ethanol eluate of 4.5-5.0BV, is concentrated and dried to obtain enriched substance；
Step S3, high-speed counter-current separation：
By dicyandiamide solution ethyl acetate-n-butanol-trifluoroacetic acid-water (volume ratio 30:5:1:30) it proportionally prepares, surpasses
Sound deaerates 2h, stands 0.5h, until after the layering completely of upper and lower two-phase, upper and lower two-phase is separated, then with plastic film by each container
It seals, places for 24 hours, the gas in system is made to drain；The enriched substance 0.5g after resin separation concentration is taken, with phase mobile phase 10mL
It is dissolved, sample liquid is used as after 0.45 μm of membrane filtration；Before separation, first high flow rate is pumped into stationary phase, and phase to be fixed is full of entire
After pipeline, termination of pumping starts work drum, rotating speed is adjusted to 800r/min, mobile phase is pumped into the speed of 1.5mL/min, waits for solvent
When system balances, sample introduction 10mL continues to be pumped into mobile phase with the speed of 1.5mL/min, and starts chromatographic work station record collection of illustrative plates,
Detection wavelength 225nm collects Alismoxide, ent-spathulenol, 4 α, 10 α-according to chromatogram (Fig. 1)
The corresponding elution fraction of aromadendranediol or aromadendrane-4 β, 10 α-diol, is concentrated and dried to obtain the final product.
In Fig. 1, the corresponding elution fractions of alismoxide obtain the alismoxide of 155mg after being concentrated and dried, and HPLC returns
One change purity is 98.5%；The corresponding elution fractions of ent-spathulenol obtain the ent- of 92mg after being concentrated and dried
It is 99.2% that spathulenol, HPLC, which normalize purity,；The corresponding elution fraction concentration of 4 α, 10 α-aromadendranediol
4 α of 73mg are obtained after drying, 10 α-aromadendranediol, it is 98.1% that HPLC, which normalizes purity,；
The corresponding elution fractions of aromadendrane-4 β, 10 α-diol obtain the aromadendrane-4 β of 65mg after being concentrated and dried,
10 α-diol, it is 98.2% that HPLC, which normalizes purity,.
Fig. 2 is that alismoxide corresponds to elution fraction and the HPLC retention times of alismoxide standard items compare；Fig. 3 is
Ent-spathulenol corresponds to elution fraction and the HPLC retention times of ent-spathulenol standard items compare；Fig. 4 is 4 α,
10 α-aromadendranediol correspond to elution fraction and 4 α, when the HPLC of 10 α-aromadendranediol standard items retains
Between compare；Fig. 5 is aromadendrane-4 β, and 10 α-diol correspond to elution fraction and aromadendrane-4 β, 10 α-diol
The HPLC retention times of standard items compare.Each fraction concentrate corresponds to the mass spectrum of compound and nuclear magnetic data also discloses one with document
It causes.
The method of the present invention is used to be detached with the macroporous absorbent resin combination high speed adverse current chromatogram of industrialized production and be prepared
Obtain (purity is more than 98%) alismoxide, ent-spathulenol, 4 α of high-purity, 10 α-
Aromadendranediol, aromadendrane-4 β, 10 α-diol, independent of silica gel column chromatography and/or gel column layer
Analysis, has a extensive future.
The particular content that the scope of the present invention is not limited to the above embodiment.
Claims (10)
1. a kind of Alismoxide, which is characterized in that chemical constitution is as follows：
2. a kind of method preparing Alismoxide, which is characterized in that include the following steps：
Step S1, extraction and concentration：
First soft coral is shredded, is freeze-dried, then by the petroleum ether cold soaking extraction 3 times of dry soft coral, often
Secondary 8h, collects soft coral, then with acetone circumfluence distillation 3 times, each 2h, and collection acetone extract is concentrated under reduced pressure to give
Soft coral acetone medicinal extract；
Step S2, macroporous resin enrichment：
Loading and absorption：It is 5 that XDA-1B macroporous absorbent resins, which are seated in draw ratio,:(per the soft coral of 200g beanpods in 1 resin column
Coral acetone medicinal extract uses 100g resins), the crude extract upper prop liquid (solvent is 15% ethyl alcohol) of soft coral acetone medicinal extract is prepared,
Loading under conditions of adsorption flow rate is 1.5BV/h closes resin column valve standing adsorption appropriate time after end of the sample；
Elution：2h is first eluted with 3BV/h elution flow rates with 30% ethyl alcohol, then is washed with 2BV/h elution flow rates with 65% ethyl alcohol
It is de-, 65% ethanol eluate of 4.5-5.0BV is collected, enriched substance is concentrated and dried to obtain；
Step S3, high-speed counter-current separation：
By dicyandiamide solution ethyl acetate-n-butanol-trifluoroacetic acid-water (volume ratio 30:5:1:30) it proportionally prepares, ultrasound is de-
Gas 2h stands 0.5h, until after the layering completely of upper and lower two-phase, upper and lower two-phase is separated, is then sealed each container with plastic film,
It places for 24 hours, the gas in system is made to drain；Take resin separation concentration after enriched substance 0.5g, with phase mobile phase 10mL by its
It dissolves, sample liquid is used as after 0.45 μm of membrane filtration；Before separation, first high flow rate is pumped into stationary phase, and phase to be fixed is full of entire pipeline
Afterwards, termination of pumping starts work drum, rotating speed is adjusted to 800r/min, mobile phase is pumped into the speed of 1.5mL/min, waits for dicyandiamide solution
When balance, sample introduction 10mL continues to be pumped into mobile phase with the speed of 1.5mL/min, and starts chromatographic work station record collection of illustrative plates, detection
Wavelength 225nm collects the corresponding elution fractions of Alismoxide according to chromatogram.
3. according to the method described in claim 2, it is characterized in that：The solid-to-liquid ratio of petroleum ether cold soaking extraction is 1:30.
4. according to the method described in claim 2, it is characterized in that：The solid-to-liquid ratio of acetone circumfluence distillation is 1:20.
5. according to the method described in claim 2, it is characterized in that：Concentration of alcohol refers to the ethanol water of different volumes percentage concentration.
6. according to the method described in claim 2, it is characterized in that：A concentration of 1mg/mL of crude extract upper prop liquid.
7. according to the method described in claim 2, it is characterized in that：It is filtered with absorbent cotton before crude extract upper prop liquid upper prop.
8. according to the method described in claim 2, it is characterized in that：Resin column valve standing adsorption is closed after end of the sample
0.5h。
9. according to the method described in claim 2, it is characterized in that：Ultrasound degassing 2h after high-speed counter-current dicyandiamide solution prepares.
10. according to the method described in claim 2, it is characterized in that：0.5h is stood after the degassing of high-speed counter-current dicyandiamide solution ultrasound.
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| CN201810609729.7A CN108623434A (en) | 2018-06-13 | 2018-06-13 | A method of preparing Alismoxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717293A (en) * | 2021-08-09 | 2021-11-30 | 中山大学 | Soft coral polysaccharide, and preparation method and application thereof |
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2018
- 2018-06-13 CN CN201810609729.7A patent/CN108623434A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717293A (en) * | 2021-08-09 | 2021-11-30 | 中山大学 | Soft coral polysaccharide, and preparation method and application thereof |
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