CN101863868A

CN101863868A - New method for preparing apiolin

Info

Publication number: CN101863868A
Application number: CN 201010206520
Authority: CN
Inventors: 孟继兰
Original assignee: Individual
Current assignee: Individual
Priority date: 2010-06-23
Filing date: 2010-06-23
Publication date: 2010-10-20
Anticipated expiration: 2030-06-23
Also published as: CN101863868B

Abstract

The invention provides a new method for preparing apiolin. In the method, old leaves of Adinandra nitida, which has not been developed and used so far, are used as raw materials, refluxing extraction in a water/alcohol solvent system and concentration under reduced pressure are performed, depigmentation is extracted by a solvent with a low polarity, a large amount of precipitate, which appears between two phases of solvents at the time, is filtered out, a proper amount of water is added into the precipitate filtered out to prepare mixed suspension, the mixed suspension is extracted by a solvent with a medium polarity, a white solid sample is obtained by removing the two phases of solvents by filtration, and the white solid sample is dissolved in the water/alcohol system, the solution is heated for acid hydrolysis, the reaction solution is cooled to precipitate a large amount of precipitate, the precipitate is washed by water repeatedly to be neutralized, and thus, the high-purity apiolin is obtained.

Description

A kind of novel method for preparing apigenin

Technical field: the invention belongs to natural medicine field, specially refer to the Lao Ye that utilizes Adinandra nitida and extract the preparation apigenin.

Background technology: Adinandra nitida (Adinandra nitida Merr.ex Li), for Theaceae (Theaceae) Yang Tong belongs to (Adinandra) plant, mainly be distributed in provinces and regions such as China Guangxi, Guangdong and Guizhou, it is perennial wild arbor, the strategically located and difficult of access part of mountain stone of short, the shady and cool humidity of weather at sunshine is born in happiness, the Guangxi people just are processed into tealeaves with its tender leaf a long time ago and are drunk, be commonly called as stone precipice tea, but, and pluck very reason such as difficulty and it is developed caused very big restriction because of its output rareness.In recent years, under the promotion of Guangxi local government, the domestication of Adinandra nitida has had bigger development, and at present at the existing tame Adinandra nitida of certain scale of Guangxi part counties and districts, the market sales revenue of the stone precipice tea of being processed into its tender leaf also increases gradually.Modern study shows in the tea of stone precipice and contains abundant flavones ingredient, and general flavone content reaches 28.4%, and its principal constituent camellin A, camellin B all are to be the flavonoid glycoside of parent nucleus with the apigenin.For a long time, application for Adinandra nitida only limits to its a spot of tender leaf is processed as stone precipice tea, and the Lao Ye of Adinandra nitida is a main by product in the tea industry of stone precipice, quantity is far away more than tender leaf, but at present a large amount of Adinandra nitida Lao Ye or withered with the wind, or be hung on the end of the branch for a long time, and nobody shows any interest in, more be not exploited.Do not see the research report of any relevant Adinandra nitida Lao Ye up to now, the author has carried out assay determination to its flavones ingredient on the basis of gathering a large amount of Adinandra nitida Lao Ye, finds wherein also to contain a large amount of flavones ingredients based on camellin A.Be the full-scale development Adinandra nitida, avoid the waste of resource, can be processed as on the basis of stone precipice tea,, thereby reach making full use of Adinandra nitida tender leaf and Lao Ye with the raw material of its Lao Ye as the extraction apigenin at its tender leaf.The objective of the invention is to produce apigenin as raw material, seek new resource for producing apigenin with the Lao Ye of Adinandra nitida.

Summary of the invention: the objective of the invention is to extract apigenin as raw material with the Lao Ye of Adinandra nitida.

For realizing above purpose, the invention provides a kind of preparation method of apigenin, may further comprise the steps:

(1), after the Lao Ye drying treatment with Adinandra nitida, add 30%～95% methyl alcohol or extraction using alcohol 2～3 times, each 0.5～2 hour, with extracting liquid filtering, merging filtrate, decompression and solvent recovery is distinguished the flavor of to there being alcohol substantially, gets concentrated solution:

(2), with concentrated solution with hexanaphthene or gasoline or petroleum ether extraction, extraction times is 1～2 time, profit two-phase solvent ratio is 0.3～1, remove pigment wherein, a large amount of precipitates appears in this moment in two phase solvent system, this precipitate is leached, add 1 to 2 times of water and make suspension, with ethyl acetate or methylene dichloride or chloroform extraction 2～3 times, solvent ratio is 0.3～1 with this suspension, behind the filtering two-phase solvent the white solid sample.

(3), with the white solid sample dissolution in 30～95% methyl alcohol or ethanol, 1%～10% adds hydrochloric acid or sulfuric acid or nitric acid or phosphoric acid or formic acid by volume, in 65～90 ℃ of following hydrolysis 10～30 minutes, hydrolyzed solution leaves standstill to put to be chilled to separates out a large amount of apigenins precipitations after the room temperature, with sedimentation and filtration and to be washed to neutrality, to be drying to obtain highly purified apigenin sample.

Embodiment:

Below, the present invention will be further detailed with embodiment, but it is not limited to any or the similar example of these embodiment.

Embodiment 1: get dry Adinandra nitida Lao Ye 500g, add 70% ethanol 4000mL extraction 1h, filter, residue merges filtrate twice with 3500mL 70% extraction using alcohol, and decompression recycling ethanol gets concentrated solution to there being the alcohol flavor substantially.Add isopyknic sherwood oil decolouring in concentrated solution, a large amount of precipitates appears in this moment between two-phase, filter, get the 174.5g precipitate, this precipitate is suspended in the 300mL water, in suspension, add the 300mL ethyl acetate then, shaking out is filtered, and gets white solid sample 112.3g.This white solid sample dissolution in 600mL70% ethanol, to wherein adding the 12mL concentrated hydrochloric acid, is stirred, 80 ℃ have a large amount of precipitations to separate out behind the heating 20min down, and this precipitation is leached, extremely neutral with the distilled water repetitive scrubbing, be drying to obtain the 40g apigenin, purity is 93.5%.

Embodiment 2: get dry Adinandra nitida Lao Ye 1000g, add 70% ethanol 7000mL extraction 1h, filter, residue merges filtrate twice with 6000mL 70% extraction using alcohol, and decompression recycling ethanol gets concentrated solution to there being the alcohol flavor substantially.Add isopyknic sherwood oil decolouring in concentrated solution, a large amount of precipitates appears in this moment between two-phase, filter, get the 347.6g precipitate, it is suspended in the 600mL water, in suspension, add the 600mL ethyl acetate then, shaking out is filtered, and gets white solid sample 210g.This white solid sample dissolution in 1100mL70% ethanol, to wherein adding the 20mL concentrated hydrochloric acid, is stirred, 80 ℃ have a large amount of precipitations to separate out behind the heating 20min down, and this precipitation is leached, extremely neutral with the distilled water repetitive scrubbing, be drying to obtain the 78g apigenin, purity is 96.6%.

Embodiment 3: get dry Adinandra nitida Lao Ye 3000g, add 70% ethanol 20000mL extraction 1h, filter, residue merges filtrate twice with 20000mL 70% extraction using alcohol, and decompression recycling ethanol gets concentrated solution to there being the alcohol flavor substantially.Add isopyknic sherwood oil decolouring in concentrated solution, a large amount of precipitates appears in this moment between two-phase, filter, get the 1000g precipitate, it is suspended in the 2000mL water, in suspension, add the 2000mL ethyl acetate then, shaking out is filtered, and gets white solid sample 600g.This white solid sample dissolution in 3000mL70% ethanol, to wherein adding the 60mL concentrated hydrochloric acid, is stirred, 80 ℃ have a large amount of precipitations to separate out behind the heating 20min down, and this precipitation is leached, extremely neutral with the distilled water repetitive scrubbing, be drying to obtain the 245g apigenin, purity is 95.7%.

Embodiment 4: get dry Adinandra nitida Lao Ye 5000g, add 70% ethanol 35000mL extraction 1h, filter, residue merges filtrate twice with 30000mL 70% extraction using alcohol, and decompression recycling ethanol gets concentrated solution to there being the alcohol flavor substantially.Add isopyknic sherwood oil decolouring in concentrated solution, a large amount of precipitates appears in this moment between two-phase, filter, get the 1645g precipitate, it is suspended in the 3200mL water, in suspension, add the 3200mL ethyl acetate then, shaking out is filtered, and gets white solid sample 1103g.This white solid sample dissolution in 5500mL70% ethanol, to wherein adding the 120mL concentrated hydrochloric acid, is stirred, 80 ℃ have a large amount of precipitations to separate out behind the heating 20min down, and this precipitation is leached, extremely neutral with the distilled water repetitive scrubbing, be drying to obtain the 405g apigenin, purity is 94.8%.

Claims

1. novel method for preparing apigenin is characterized in that step is as follows:

(1) raw material is added refluxing extraction behind the solvent

(2) with behind the extracting liquid filtering, decompression suitably concentrates

(3) with concentrated solution with little polar solvent extract, removing pigment wherein, a large amount of precipitates appear between two-phase this moment

(4) precipitate is leached, add an amount of water and make suspension

(5) with suspension with the Semi-polarity solvent extraction, behind the filtering two-phase solvent the white solid sample

(6) with the white solid sample dissolution in water/pure system, in this system, add acid then, and under heating condition, be hydrolyzed

(7) hydrolyzed solution is put cold after, a large amount of throw outs appears, throw out is promptly obtained highly purified apigenin with water washing to neutral after drying

2. the preparation method of apigenin as claimed in claim 1 is characterized in that, in the described step (1), used raw material is the Lao Ye of Adinandra nitida, and promptly growth time is longer, is not suitable for being processed as the Adinandra nitida leaf of stone precipice tea.

3. the preparation method of apigenin as claimed in claim 1 is characterized in that, in the described step (1), the extraction solvent is alcohol/water mixture, and used alcohol is methyl alcohol or ethanol, and determining alcohol is 30～95%, and extraction time is 2～3 times, extracts 0.5～2 hour at every turn.

4. the preparation method of apigenin as claimed in claim 1 is characterized in that, in the described step (2), should be evaporated to behind the extracting liquid filtering does not have the alcohol flavor substantially.

5. the preparation method of apigenin as claimed in claim 1 is characterized in that, in the described step (3), used little polar solvent is hexanaphthene or sherwood oil or gasoline, and extraction times is 1～2 time, and profit two-phase solvent ratio is 0.3～1.

6. the preparation method of apigenin as claimed in claim 1 is characterized in that, in the described step (4), amount of water should be 1～2 times of throw out amount.

7. the preparation method of apigenin as claimed in claim 1 is characterized in that, in the described step (5), used Semi-polarity solvent is ethyl acetate or methylene dichloride or trichloromethane, and extraction times is 2～3 times, and profit two-phase solvent ratio is 0.3～1.

8. the preparation method of apigenin as claimed in claim 1 is characterized in that, in the described step (6), in water/pure system, alcohol refers to methyl alcohol or ethanol, and determining alcohol is 30～95%.

9. the preparation method of apigenin as claimed in claim 1 is characterized in that, in the described step (6), the acid that adds in the system is hydrochloric acid or sulfuric acid or nitric acid or phosphoric acid or formic acid, and the volume fraction of acid is 1～10% in the hydrolyzed solution; The temperature of heating is 65～90 ℃, and the time of hydrolysis is 10～30 minutes.