CN106831695A - A kind of preparation method of Strychnos nux-vomica aglycon - Google Patents
A kind of preparation method of Strychnos nux-vomica aglycon Download PDFInfo
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- CN106831695A CN106831695A CN201710054098.2A CN201710054098A CN106831695A CN 106831695 A CN106831695 A CN 106831695A CN 201710054098 A CN201710054098 A CN 201710054098A CN 106831695 A CN106831695 A CN 106831695A
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- vomica
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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Abstract
The invention discloses a kind of preparation method of Strychnos nux-vomica aglycon.The method is, with loganin as raw material, to be degraded by smith and purify the Strychnos nux-vomica aglycon for preparing high-purity.The present invention prepares Strychnos nux-vomica aglycon using smith edman degradation Edmans first, effectively solves sour water solution, and basic hydrolysis brings the problem of ester group cleavage, and this method is simple to operate, and mild condition, product purity is high, and accessory substance is few, the need for meeting Strychnos nux-vomica aglycon industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of Strychnos nux-vomica aglycon, belong to field of traditional Chinese medicine extraction.
Background technology
Fructus Corni is the ripe dry pulp of Cornaceae plant Fructus Corni, is the rare medicinal material of China's tradition rare with conventional
Chinese medicine, there is the effects such as puckery essence, arrest sweating, filling liver kidney, be usually used in treatment dizziness and tinnitus, soreness of waist and knee joint, impotence and seminal emission, enuresis frequent micturition,
The diseases such as uterine bleeding under band, Heat Diabetes, are one of parts of Liuwei Dihuang Wan.Iridoid glycoside is the main activity of Fructus Corni
One of composition, loganin with hypoglycemic, anti-platelet aggregation, is exempted from as the main component of iridoid glycosides in Fructus Corni
The effect such as epidemic disease regulation, Hemorrhagic shock, anti-oxidant, suppression PECTORAL LIMB SKELETON differentiation, the composition has turned into the focus to Fructus Corni research.
Strychnos nux-vomica aglycon sloughs the pale yellow oil obtained after a molecule glucose for loganin, and polarity is smaller than loganin, soluble in water,
Ethanol equal solvent, reports it seldom both at home and abroad at present, but has the special construction of ester group due to loganin, sour water solution,
Strychnos nux-vomica aglycon is hardly resulted under base hydrolysis conditions.
The content of the invention
In order to overcome shortcoming present in Strychnos nux-vomica aglycon preparation process, the present invention provides a kind of process is simple, environmentally friendly and suitable
Close the method for preparing Strychnos nux-vomica aglycon of industrialized production.
In order to reach object above, main technical schemes of the invention are：Degraded by smith, macroporous resin adsorption is pure
Change, the step such as charcoal absorption obtains the Strychnos nux-vomica aglycon of high-purity.
A kind of preparation method of Strychnos nux-vomica aglycon, it is characterised in that mainly include the following steps that：
(1) smith degradeds
Alcoholic solution is added to prepare loganin solution, to oxidant is added in loganin solution, lucifuge is anti-at ambient temperature
Should, add glycerine to terminate oxidation, neutralize, concentrate, oxidation product is obtained by extraction；Solvent dissolving oxidation product is added, is subsequently adding
Reducing agent, after reacting 12-48 hours, terminating reaction；To strong acid is added in reduction reaction liquid, be hydrolyzed reaction, obtains smith
Degradation solution；
(2) isolate and purify
To alkali is added in the smith degradation solutions of gained in step (1), pH is adjusted to extract to neutrality, then with isometric ethyl acetate
Take 3-5 times, combining extraction liquid, concentrate drying, obtain Strychnos nux-vomica aglycon crude product；Strychnos nux-vomica aglycon crude product is used into macroporous resin purification,
Charcoal absorption is that can obtain loganin unit.
Preferably, a kind of preparation method of Strychnos nux-vomica aglycon, it is characterised in that mainly include the following steps that：
(1) smith degradeds
Alcoholic solution is added to be configured to the solution that Determination of Loganin is 0.001-0.1mol/L, by rubbing for loganin and oxidant
You are than being 1:1-1:5 add oxidant, after lucifuge is reacted 12-96 hours at ambient temperature, add glycerine to terminate oxidation, in
With, concentrate, oxidation product be obtained by extraction；It is 1 to add with the mass ratio of loganin:1-40:1 solvent dissolving oxidation product, so
After add reducing agent, loganin is 1 with the mol ratio of reducing agent:2-1:8, after reacting 12-48 hours, terminating reaction；To reduction
It is 1 to be added in reaction solution with loganin mol ratio:1-3:1 strong acid, stirs 6-96 hours at 20-60 DEG C, obtains smith drops
Solution liquid；
(2) isolate and purify
To alkali is added in the smith degradation solutions of gained in step (1), pH is adjusted to extract to neutrality, then with isometric ethyl acetate
Take 3-5 times, combining extraction liquid, concentrate drying, obtain Strychnos nux-vomica aglycon crude product；Strychnos nux-vomica aglycon crude product is used into macroporous resin purification,
Charcoal absorption is that can obtain loganin unit.
Preferably, the alcoholic solution selected when preparing loganin solution in step (1) is 0-50% methyl alcohol or 0-50% ethanol.
Preferably, the concrete operations of extraction are in step (1)：Add with it is concentrated under reduced pressure after the isometric acetic acid of reaction solution
Ethyl ester is extracted 3-5 times；Combining extraction liquid, washes 2 times, then be evaporated ethyl acetate.
Preferably, the solvent of oxidation product is dissolved in step (1) for volume fraction is the methyl alcohol or 50-95% of 50-95%
Ethanol solution.
Preferably, the oxidant described in step (1) is any one in sodium metaperiodate, potassium metaperiodate, and reducing agent is
Any one in sodium borohydride, potassium borohydride, alkali is any one in NaOH, sodium carbonate, sodium acid carbonate, and strong acid is
Any one in sulfuric acid, hydrochloric acid, nitric acid.
Preferably, middle big pore resin model is isolated and purified described in step (2) in HPD450, HPD750, AB-8
Any one.
Useful achievement of the invention is as follows：
(1) degrade effectively to react loganin by smith and obtain Strychnos nux-vomica aglycon, and product purity after treatment
Up to more than 90%, sour water solution is successfully solved, basic hydrolysis causes the problem that ester group ftractures.
(2) whole preparation process mild condition, high income, operation is simple, environmental protection pressure is small, be adapted to industry metaplasia
Produce.
Specific embodiment
The present invention is further illustrated below in conjunction with specific implementation case, the scope of protection of present invention is not limited to
Implementation below.
Embodiment 1
(1) it is 0.001mol/L solution into Determination of Loganin that 2g loganins are added solution by smith degradeds, is pressed
Loganin is 1 with the mol ratio of oxidant：1 to sodium metaperiodate is added in solution, after lucifuge is reacted 96 hours at ambient temperature,
Add glycerine to terminate oxidation, neutralize, be extracted with ethyl acetate after concentration and obtain oxidation product；To add after oxidation product concentrate drying
Enter the dissolving of 50% ethanol, 50% ethanol of addition is 40 with the mass ratio of loganin:1, it is subsequently adding sodium borohydride, sodium borohydride
It is 2 with the mol ratio of loganin:1, after reacting 48 hours, terminating reaction；To adding 36% hydrochloric acid 0.5mL in reduction reaction liquid,
Stirred 6 hours at 60 DEG C, obtain smith degradation solutions.
(2) isolate and purify to sodium oxide molybdena is hydrogenated with the smith degradation solutions of gained in step (1), adjust pH to neutrality, then use
Isometric ethyl acetate is extracted 5 times, combining extraction liquid, is concentrated under reduced pressure into dry, obtains Strychnos nux-vomica aglycon crude product；By loganin crude product
Using HPD450 macroporous resin purifications, charcoal absorption is used after collecting the concentration of 40% ethanol eluate, filtering is dry by filtrate concentration
The Strychnos nux-vomica aglycon of purity 92% is can obtain after dry.
Embodiment 2
(1) it is 0.05mol/L's that 2g loganins are added 20% ethanol solution to be configured to Determination of Loganin by smith degradeds
Solution, is 1 by the mol ratio of loganin and oxidant：3 to potassium metaperiodate is added in solution, at ambient temperature lucifuge reaction 48
After hour, add glycerine to terminate oxidation, neutralize, to be concentrated into and obtain oxidation product without being extracted with ethyl acetate after alcohol taste；Will oxidation
Product adds the dissolving of 70% ethanol, and 70% ethanol of addition is 20 with the mass ratio of loganin:1；It is subsequently adding potassium borohydride, boron
Hydrofining is 4 with the mol ratio of loganin:1, after reacting 36 hours, terminate reduction reaction；To adding 5% sulphur in reduction reaction liquid
Sour 5.4mL, stirs 12 hours at 40 DEG C, obtains smith degradation solutions.
(2) isolate and purify to sodium carbonate is added in the smith degradation solutions of gained in step (1), adjust pH to neutrality, then with etc.
The ethyl acetate of volume is extracted 4 times, combining extraction liquid, is concentrated under reduced pressure into dry, obtains Strychnos nux-vomica aglycon crude product；Loganin crude product is made
Purified with macroreticular resin HPD750, charcoal absorption is used after collecting the concentration of 30% eluent, filtered, will be after filtrate concentrate drying i.e.
Can obtain the Strychnos nux-vomica aglycon of purity 93%.
Embodiment 3
(1) 2g loganins are added 50% ethanol to be configured to Determination of Loganin for 0.5mol/L solution by smith degradeds, are pressed
Loganin is 1 with the mol ratio of oxidant:1 to sodium metaperiodate is added in solution, after lucifuge is reacted 24 hours at ambient temperature,
Add glycerine to terminate oxidation, neutralize, be extracted with ethyl acetate after concentration and obtain oxidation product；To add after oxidation product concentrate drying
Enter the dissolving of 90% ethanol, 90% ethanol of addition is 10 with the mass ratio of loganin:1；It is subsequently adding sodium borohydride, sodium borohydride
It is 4 with the mol ratio of loganin:1, after reacting 24 hours, terminate reduction reaction；To adding 5% nitric acid 8mL in reduction reaction liquid,
Stirred 24 hours at 60 DEG C, obtain smith degradation solutions.
(2) isolate and purify to sodium oxide molybdena is hydrogenated with the smith degradation solutions of gained in step (1), adjust pH to neutrality, then use
Isometric ethyl acetate is extracted 3 times, combining extraction liquid, is concentrated under reduced pressure into dry, obtains Strychnos nux-vomica aglycon crude product；By loganin crude product
Using AB-8 macroporous resin purifications, charcoal absorption, filtering, by filtrate concentrate drying are used after collecting the concentration of 40% ethanol eluate
The Strychnos nux-vomica aglycon of purity 90% is can obtain afterwards.
Embodiment 4
(1) 2g loganins are added 30% methanol solution to be configured to Determination of Loganin for 0.5mol/L is molten by smith degradeds
Liquid, is 1 by the mol ratio of loganin and oxidant:5 to sodium metaperiodate is added in solution, lucifuge reaction 12 is small at ambient temperature
Shi Hou, adds glycerine to terminate oxidation, neutralizes, and is extracted with ethyl acetate after concentration and obtains oxidation product；Oxidation product concentration is dry
The dissolving of 70% ethanol is added after dry, 70% ethanol of addition is 1 with the mass ratio of loganin:1；It is subsequently adding sodium borohydride, boron
Sodium hydride is 8 with the mol ratio of loganin:1, after reacting 12 hours, terminate reduction reaction；To adding 36% in reduction reaction liquid
Hydrochloric acid 5mL, stirs 96 hours at ambient temperature, obtains smith degradation solutions.
(2) isolate and purify to sodium acid carbonate is added in the smith degradation solutions of gained in step (1), adjust pH to neutrality, then use
Isometric ethyl acetate is extracted 3 times, combining extraction liquid, is concentrated under reduced pressure into dry, obtains Strychnos nux-vomica aglycon crude product；By loganin crude product
Using HPD450 macroporous resin purifications, charcoal absorption is used after collecting the concentration of 40% ethanol eluate, filtering is dry by filtrate concentration
The Strychnos nux-vomica aglycon of purity 90% is can obtain after dry.
Claims (10)
1. a kind of method that Strychnos nux-vomica aglycon is prepared with smith degradeds.
2. preparation method as claimed in claim 1, it is characterised in that mainly include the following steps that：
(1) smith degradeds
Alcoholic solution is added to prepare loganin solution, to oxidant is added in loganin solution, lucifuge reaction at ambient temperature, plus
Enter glycerine and terminate oxidation, neutralize, concentrate, oxidation product is obtained by extraction；Solvent dissolving oxidation product is added, reduction is subsequently adding
Agent, after reacting 12-48 hours, terminating reaction；To strong acid is added in reduction reaction liquid, be hydrolyzed reaction, obtains smith degradeds
Liquid；
(2) isolate and purify
To alkali is added in the smith degradation solutions of gained in step (1), pH is adjusted to extract 3-5 to neutrality, then with isometric ethyl acetate
Secondary, combining extraction liquid, concentrate drying obtains Strychnos nux-vomica aglycon crude product；Strychnos nux-vomica aglycon crude product is used into macroporous resin purification, activated carbon
Absorption can obtain loganin unit.
3. the preparation method of Strychnos nux-vomica aglycon as claimed in claim 2, it is characterised in that loganin is prepared in the step (1)
The alcoholic solution selected during solution is 0-50% methyl alcohol or 0-50% ethanol.
4. the preparation method of Strychnos nux-vomica aglycon as claimed in claim 2, it is characterised in that loganin solution in the step (1)
Concentration be 0.001-0.1mol/L, loganin with add oxidant mol ratio be 1:1-1:5, the reaction time is 12-96
Hour.
5. the preparation method of Strychnos nux-vomica aglycon as claimed in claim 2, it is characterised in that extraction oxidation is produced in the step (1)
The concrete operations of thing are：Add with it is concentrated under reduced pressure after the isometric ethyl acetate of reaction solution extract 3-5 times；Combining extraction liquid,
Washing 2 times, then it is evaporated ethyl acetate.
6. the preparation method of Strychnos nux-vomica aglycon as claimed in claim 2, it is characterised in that dissolving oxidation is produced in the step (1)
The solvent of thing is methyl alcohol or 50-95% ethanol that volume fraction is 50-95%, is 1 with the mass ratio of loganin:1-40:1.
7. the preparation method of Strychnos nux-vomica aglycon as claimed in claim 2, it is characterised in that the reduction reaction in the step (1),
Loganin is 1 with the mol ratio of reducing agent:2-1:8.
8. the preparation method of Strychnos nux-vomica aglycon as claimed in claim 2, it is characterised in that hydrolysis in the step (1)
Concrete operations are：It is 1 to add with loganin mol ratio:1-10:1 strong acid is stirring reaction 6-96 hours at 20-60 DEG C.
9. the preparation method of Strychnos nux-vomica aglycon as claimed in claim 2, it is characterised in that described oxidant be sodium metaperiodate,
Any one in potassium metaperiodate, reducing agent is any one in sodium borohydride, potassium borohydride, and alkali is NaOH, carbonic acid
Any one in sodium, sodium acid carbonate, strong acid is any one in sulfuric acid, hydrochloric acid, nitric acid.
10. the preparation method of Strychnos nux-vomica aglycon as claimed in claim 2, it is characterised in that described to isolate and purify middle big pore
Resin model is any one in HPD450, HPD750, AB-8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988137A (en) * | 2017-12-30 | 2019-07-09 | 鲁南制药集团股份有限公司 | A kind of preparation method of epimedium aglucone |
-
2017
- 2017-01-22 CN CN201710054098.2A patent/CN106831695A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| MASAHIDE TANAKA，等，: "THE PRACTICAL METHOD FOR THE PREPARATION OF IRIDOID AGLYCONS FROM THEIR GLYCOSIDES", 《HETEROCYCLES》 * |
| TAKAO TANAHASHI，等，: "RADIOIMMUNOASSAY FOR THE DETERMINATION OF LOGANIN AND THE BIOTRANSFOTMATION OF LOGANIN TO SECOLOGANIN BY PLANT CELL CULTURES", 《PHYTOCHEMISTRY》 * |
| 沈彤 等，: "《天然药物化学》", 31 July 2010, 甘肃科学技术出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988137A (en) * | 2017-12-30 | 2019-07-09 | 鲁南制药集团股份有限公司 | A kind of preparation method of epimedium aglucone |
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Application publication date: 20170613 |