CN107619401A - A kind of preparation method of senkyunolide Ⅰ - Google Patents
A kind of preparation method of senkyunolide Ⅰ Download PDFInfo
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- CN107619401A CN107619401A CN201711082169.6A CN201711082169A CN107619401A CN 107619401 A CN107619401 A CN 107619401A CN 201711082169 A CN201711082169 A CN 201711082169A CN 107619401 A CN107619401 A CN 107619401A
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Abstract
The invention discloses a kind of preparation method of senkyunolide Ⅰ, belong to traditional Chinese medicine ingredients preparing technical field, its method is using the extract containing Ligustilide as raw material, in basic aqueous solvent with after ammonium persulfate-sodium bisulfate heating response, reaction solution obtains senkyunolide Ⅰ sterling through extraction, column chromatography for separation；Extract of the invention containing Ligustilide is raw material, and senkyunolide Ⅰ is prepared with the method that chromatographic isolation is combined by chemical conversion, has the characteristics of few simple process, solvent consumption, high income, is adapted to a large amount of senkyunolide Ⅰs for preparing high-purity.
Description
Technical field
The present invention relates to traditional Chinese medicine ingredients preparing technical field, more particularly to a kind of preparation method of senkyunolide Ⅰ.
Background technology
Senkyunolide Ⅰ（senkyunolide Ⅰ）For pale yellow oil, belong to crude benzene phthalein compounds, mainly deposit
It is samphire, such as Ligusticum wallichii（Ligusticum chuanxiongHort.）, Radix Angelicae Sinensis（Angelica sinensis
(Oliv.) Diels）, Jehol Ligusticum Rhizome（Ligusticum sinenseOliv.）Deng volatile oil or fat-soluble extract in.
The chemical constitution of senkyunolide Ⅰ is as follows：
。
It is reported that senkyunolide Ⅰ is one of active component of chuanxiong and Radix Angelicae Sinensis, and can pass through blood-brain barrier, can
The hot plate method mouse threshold of pain is reduced, suppresses writhing response caused by glacial acetic acid, to nitric oxide in Migraine Rats body（NO）, 5- hydroxyls
Tryptamines（5-HT）, Calcitonin Gene Related to Peptide（CGRP）And beta-endorphin（β-EP）Deng the endogenous thing closely related with migraine
Matter has regulating and controlling effect.Therefore, senkyunolide Ⅰ has certain therapeutic action to antimigraine.Senkyunolide Ⅰ can also
Mitigate erythrocyte deformed injury, reduce erythrocyte aggregation；Reduce the nitric oxide in ischemia-reperfusion animal model brain stem
Content, suppress the activity of nitricoxide synthase.So based on current research and application, for senkyunolide Ⅰ demand very
Greatly.
However, the senkyunolide Ⅰ content contained by natural plants is very low, the content in Ligusticum wallichii, Radix Angelicae Sinensis is typically smaller than
0.1%（w/w）, such as, Liu Jinliang etc. " content of 5 kinds of effective components in HPLC measure Different Harvesting Time Ligusticum chuanxiong Horts " report river
Senkyunolide Ⅰ content is 0.58 mg/g in rhizome of chuanxiong medicinal material, i.e., 0.058%（w/w）." survey to be commented method while determines river field fine jade etc.
The content of a variety of chemical compositions in rhizome of chuanxiong, angelica sinensis " report 24 batch ligusticum wallichii decoction pieces in senkyunolide Ⅰ content be 1.09~
3.34 mg/g, senkyunolide Ⅰ content is 0.04~0.77 mg/g in 26 batch angelica sinensis.
The method that separation at present prepares senkyunolide Ⅰ mainly has repeatedly column chromatography, prepares thin-layer chromatography, half preparation efficiently
The shortcomings that different all be present in liquid chromatogram, preparative high-performance liquid chromatographic, high speed adverse current chromatogram etc., these methods：
For example Chinese patent CN200910200693.8 discloses a kind of side that senkyunolide Ⅰ is prepared from angelica extract
Method, using Radix Angelicae Sinensis medicinal material as raw material, the separation skill such as macroporous adsorbent resin column chromatography, solvent extraction, silica gel column chromatography is employed successively
Art, its complex steps, organic solvent consumption are big, and ultimate yield is only 0.07%~0.09%.
The A of Chinese patent CN 104003963 are prepared using high speed adverse current chromatogram, using partly preparing high-efficient liquid phase color
The methods of spectrum, preparative high-performance liquid chromatographic, is high for equipment requirement, and input is big.
To sum up, senkyunolide Ⅰ is largely prepared at present in the presence of consumption raw material is more, yield is low, reagent consumption is big, technique is complicated
Etc. difficulty, it is unfavorable for industrialized production.And limited source, the difficult further investigation limited to it of preparation of senkyunolide Ⅰ
And new drug development.
The content of the invention
The purpose of the present invention, which is that, provides a kind of preparation method of senkyunolide Ⅰ, to solve the above problems.
To achieve these goals, the technical solution adopted by the present invention is such：A kind of preparation method of senkyunolide Ⅰ,
Using the extract containing Ligustilide as raw material, with after ammonium persulfate-sodium bisulfate heating response, reacting in basic aqueous solvent
Liquid obtains senkyunolide Ⅰ sterling through extraction, column chromatography for separation.
Above-mentioned ammonium persulfate-sodium bisulfate is OXONE, and its chemical formula is 2KHSO5 · KHSO4 · K2SO4。
As preferable technical scheme：The aqueous solvent is selected from water-tetrahydrofuran, water -1,4- dioxane, water-fourth
Ketone, boiling, water-methanol, water-ethanol, water-isopropanol.
As further preferred technical scheme：The volume ratio of the aqueous solvent reclaimed water is 30%~70%.
As preferable technical scheme：The alkalescence is by toward adding sodium carbonate, potassium carbonate, bicarbonate in reaction system
Sodium, saleratus, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, the one or more of ammoniacal liquor are realized.
As preferable technical scheme：The reaction temperature of the heating is 30 DEG C~150 DEG C.
As further preferred technical scheme：The reaction temperature of the heating is 50 DEG C~100 DEG C.
As preferable technical scheme：The reaction time of the heating response is 0.5 hour~24 hours.
As further preferred technical scheme：The reaction time of the heating response is 1 hour~12 hours.
Compared with prior art, the advantage of the invention is that：The present invention is with Ligusticum wallichii, Radix Angelicae Sinensis and/or Jehol Ligusticum Rhizome etc. containing in Jehol Ligusticum Rhizome
The extract of ester is raw material, and the Ligustilide of wherein high content is changed into senkyunolide I by chemically reacting first, so as to
The content of senkyunolide I in extract is significantly improved, it is pure then with chromatography separating method to prepare senkyunolide I again
Product.It is low that the present invention significantly improves senkyunolide I content in plant, it is difficult to the problem of largely preparing.
Brief description of the drawings
Fig. 1 is the HPLC figures before Rhizoma Chuanxiong extract reaction；
Fig. 2 schemes for reacted HPLC.
In figure：A, senkyunolide Ⅰ；B, Ligustilide
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
Embodiment 1
A kind of preparation method of senkyunolide Ⅰ, its step are：
（1）The preparation of Rhizoma Chuanxiong extract：The kg of Ligusticum chuanxiong Hort 1, crush, extracted 2 times with 8 times of 80% alcohol refluxs of amount, merge extraction
Liquid, 45 DEG C of decompressions steam solvent, and gained medicinal extract is extracted with ethyl acetate after moisture dissipates, and merges organic layer, 45 DEG C of decompressions steam
Solvent, obtain oil-like extracts 56.4g, i.e. Rhizoma Chuanxiong extract；
（2）Reaction：By water-ethanol mixed solution（50:50, v/v）300 ml, step（1）The obtained g of Rhizoma Chuanxiong extract 15
（Ligustilide content 19.5%, w/w；Senkyunolide I 0.8%, w/w）Sequentially add in 500 ml round-bottomed flasks, stir at room temperature
Mix 5 minutes；The g of ammonium persulfate-sodium bisulfate 30, the finely ground mixings of the g of sodium acid carbonate 12 are taken, is slowly added in reaction system, room temperature
Lower stirring 10 minutes, then heat to 80 DEG C and react 3 hours；
Heating response 0 hour and separately sampled detection in 3 hours, obtained chromatogram is respectively as shown in Figure 1 and Figure 2；
HPLC detection methods are as follows：Waters Acquity UPLC chromatographic systems；Trifluoroacetic acid aqueous solution, Milli-Q ultra-pure waters, its
Remaining reagent is that analysis is pure；Chromatographic column is Waters BEH C18 (mm of 50 mm × 2.1 i.d., 1.7 μm)；Mobile phase is
Acetonitrile（A）- 0.1% phosphoric acid water（B）；The min of gradient elution 0~0.5（20% A）, 0.5~3.0 min（The A of 20% A~70%）,
3.0-3.5 min（The A of 70% A~100%）, 3.5~4.0 min（100% A）, 4.0~4.01 min（The A of 100% A~20%）,
4.01~5.0 min（20% A）；The mL/min of flow velocity 0.4；The C of column temperature 35；The nm of Detection wavelength 280；
As a result show：Before reaction, Ligustilide concentration in solution system（9.75 mg/ml）Far above senkyunolide I（0.43
mg/ml）；By reaction, Ligustilide substantially tails off（1.02 mg/ml）, it is converted primarily into as senkyunolide I（4.53 mg/
ml）；
（3）Separation：After reaction terminates, insoluble matter is filtered to remove, obtains filtrate.40 DEG C of gained filtrate is concentrated under reduced pressure after removing ethanol
It is extracted with ethyl acetate (100 ml × 3 time).Upper silicagel column after ethyl acetate layer concentration（φ40 mm×300 mm）Separation, stream
Dynamic is mutually petroleum ether-ethyl acetate（1:1, v/v）.TLC is detected, and condition is as follows：Silica G F254High Performance Thin plate, solvent are stone
Oily ether-ethyl acetate（1:2, v/v）, Rf value=0.35；
Merge cut after detection, remove solvent under reduced pressure, obtain the g of pale yellow oil 1.1.Contrast, confirm through NMR, UV and reference substance
For senkyunolide Ⅰ（HPLC purity 95.1%）；
The spectroscopic data of the senkyunolide Ⅰ of purifying：UVλmax (MeOH)：279 nm；ESI-MS shows quasi-molecular ion [M+
Na]+'sm/zFor 247.0968, molecular formula C is prompted12H16O4；1H-NMR (CD3COCD3) δ: 0.95 (3H, t, j =
7.2 Hz, H-13), 1.52 (2H, sext, j=7.2 Hz, H-12), 1.90~1.94 (1H, m, H-5),
2.33 (2H, q, H-9), 4.01 (1H, d, j =1.8 Hz, H-6), 4.28 (1H, d, j = 1.8 Hz, H-
7), 5.43(1H, d, j= 7.8 Hz , H-10)；13C-NMR (CD3COCD3)δ: 169.6 (C-1), 149.6 (
C-3), 24.8 (C-4), 22. 9 (C-5), 70.3 (C-6), 79.2 (C-7), 126.9 (C-8), 154.3 (C-
9), 112.6 (C-10), 28.7 (C-11), 17.8 (C-12), 14.1 (C-13)。
Embodiment 2
A kind of preparation method of senkyunolide Ⅰ, its step are：
（1）The preparation of angelica extract：The kg of Radix Angelicae Sinensis medicinal material 5, crush, cross No. 3 sieves, with extraction by steam distillation, obtain Radix Angelicae Sinensis and wave
The g of hair oil 27.8；
（2）Reaction：By water -1,4- dioxane（50:50, v/v）200 ml, step（1）The obtained g of Chinese angelica volatile oil 10
（Ligustilide content 55.1%, w/w；Senkyunolide I 3.2%, w/w）Sequentially add in 500 ml round-bottomed flasks, stir at room temperature
Mix 10 minutes.The g of ammonium persulfate-sodium bisulfate 45, the finely ground mixings of the g of sodium acid carbonate 16 are taken, is slowly added in reaction system, room temperature
Lower stirring 30 minutes, then heat to 100 DEG C and react 6 hours；
（3）Separation：After reaction terminates, be filtered to remove insoluble matter, 50 DEG C of filtrate is concentrated under reduced pressure remove Isosorbide-5-Nitrae-dioxane after use second
Acetoacetic ester extracts (100 ml × 3 time).After ethyl acetate layer concentration, add in a small amount of upper C18 silica gel of ethanol dissolving and suppress standby post（φ
49 mm×460 mm）Separation, mobile phase is water-ethanol（65:35, v/v）；
Merge cut after detection, remove solvent under reduced pressure, obtain the g of senkyunolide Ⅰ 2.9（HPLC purity 96.2%）.
Embodiment 3
A kind of preparation method of senkyunolide Ⅰ, its step are：
（1）The preparation of Rhizoma Ligustici extract：The kg of Raw Rhizoma Ligustici 2, crush, cross No. 3 sieves, with extraction by steam distillation, obtain Jehol Ligusticum Rhizome and wave
The g of hair oil 14.3；
（2）Reaction：By water-butanone（40:60, v/v）200 ml, step（1）The obtained g of ligusticum sinense volatile oil 10（Ligustilide
Content 28.2%, w/w；Senkyunolide I 1.4%, w/w）Sequentially add in 500 ml round-bottomed flasks, stir 5 minutes at room temperature.
The g of ammonium persulfate-sodium bisulfate 30, the finely ground mixings of the g of sodium acetate 12 are taken, is slowly added in reaction system, stirs 30 points at room temperature
Clock, then heat to 60 DEG C and react 12 hours；
（3）Separation：After reaction terminates, be filtered to remove insoluble matter, 50 DEG C of filtrate is concentrated under reduced pressure remove butanone after extracted with ethyl acetate
Take (100 ml × 3 time).After ethyl acetate layer concentration, add in a small amount of upper C18 silica gel of ethanol dissolving and suppress standby post（φ36 mm×
460 mm）Separation, mobile phase is water-ethanol（65:35, v/v）.Cut merges after HPLC is detected is evaporated off solvent, obtains foreign Ligusticum wallichii
The g of lactone I 1.22（HPLC purity 96.7%）.
Embodiment 4
A kind of preparation method of senkyunolide Ⅰ, its step are：
By water-ethanol（30:70, v/v）20 ml, Ligustilide crude product（Content 85%, w/w）1 g, sequentially add 50 ml round bottoms
In flask, stir 5 minutes at room temperature.The g of ammonium persulfate-sodium bisulfate 6, the finely ground mixings of the g of saleratus 2.4 are taken, is slowly added to
In reaction system, stir 30 minutes at room temperature, then heat to 50 DEG C and react 20 hours.After reaction terminates, it is filtered to remove insoluble
Thing, 50 DEG C of filtrate be concentrated under reduced pressure remove ethanol after be extracted with ethyl acetate (20 ml × 3 time).After ethyl acetate layer concentration, add few
Measure in the upper C18 silica gel of ethanol dissolving and suppress standby post（φ26 mm×460 mm）Separation, mobile phase is water-ethanol（65:35, v/
v）.Cut merges after HPLC is detected is evaporated off solvent, obtains the g of senkyunolide Ⅰ 0.43（Conversion yields 50.6%, HPLC purity
98.1%）.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
- A kind of 1. preparation method of senkyunolide Ⅰ, it is characterised in that：Using the extract containing Ligustilide as raw material, in alkalescence In aqueous solvent with after ammonium persulfate-sodium bisulfate heating response, reaction solution through extraction, column chromatography for separation, that is, obtain in foreign Ligusticum wallichii The sterling of ester I.
- 2. according to the method for claim 1, it is characterised in that：The aqueous solvent is selected from water-tetrahydrofuran, water -1,4- Dioxane, water-butanone, boiling, water-methanol, water-ethanol, water-isopropanol.
- 3. according to the method for claim 2, it is characterised in that：The volume ratio of the aqueous solvent reclaimed water be 30%~ 70%。
- 4. according to the method for claim 1, it is characterised in that：The alkalescence is by toward adding carbonic acid in reaction system Sodium, potassium carbonate, sodium acid carbonate, saleratus, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, the one or more of ammoniacal liquor Come what is realized.
- 5. according to the method for claim 1, it is characterised in that：The reaction temperature of the heating is 30 DEG C~150 DEG C.
- 6. according to the method for claim 5, it is characterised in that：The reaction temperature of the heating is 50 DEG C~100 DEG C.
- 7. according to the method for claim 1, it is characterised in that：The reaction time of the heating response is 0.5 hour~24 Hour.
- 8. according to the method for claim 7, it is characterised in that：The reaction time of the heating response is 1 hour~12 small When.
- 9. according to the method for claim 1, it is characterised in that：Ligustilide content is 10%~95% in the extract.
- 10. according to the method for claim 1, it is characterised in that：The extract is in Ligusticum wallichii, Radix Angelicae Sinensis, Jehol Ligusticum Rhizome Any one or more.
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Cited By (3)
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| CN108354077A (en) * | 2018-03-07 | 2018-08-03 | 余姚辉农农业科技有限公司 | A kind of first farrowing sow feed addictive, feed and preparation method thereof |
| CN110615798A (en) * | 2019-10-28 | 2019-12-27 | 四川省中医药科学院 | Preparation method of 6,7-epoxy ligustilide |
| CN113845501A (en) * | 2021-10-25 | 2021-12-28 | 四川省中医药科学院 | Preparation method of senkyunolide J |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108354077A (en) * | 2018-03-07 | 2018-08-03 | 余姚辉农农业科技有限公司 | A kind of first farrowing sow feed addictive, feed and preparation method thereof |
| CN110615798A (en) * | 2019-10-28 | 2019-12-27 | 四川省中医药科学院 | Preparation method of 6,7-epoxy ligustilide |
| CN113845501A (en) * | 2021-10-25 | 2021-12-28 | 四川省中医药科学院 | Preparation method of senkyunolide J |
| CN113845501B (en) * | 2021-10-25 | 2024-01-26 | 四川省中医药科学院 | Preparation method of senkyunolide J |
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