CN102212092A - Preparation method for high-purity jasminoidin - Google Patents

Abstract

The invention relates to a preparation method for high-purity jasminoidin, particularly a preparation method for high-purity jasminoidin based on liquid-liquid partitioning extraction, which comprises the following steps: pulverizing gardenia, soaking in water, carrying out ultrasonic-assisted extraction, filtering, combining the extraction liquids, and concentrating while depressurizing to obtain a gardenia extraction concentrate; regulating the pH value of the gardenia extraction concentrate to alkaline, and extracting while stirring at high speed by using a low-carbon alcohol as a solvent, thus obtaining an extraction liquid rich in jasminoidin; decolorizing the obtained extraction liquid, and concentrating the decolorized extraction liquid while depressurizing to obtain a decolorized concentrate; pouring the decolorized concentrate into an organic acid ester while stirring so as to crystallize and precipitate jasminoidin; and separating out crystallized jasminoidin precipitate, washing with the organic acid ester, and repeatedly washing the precipitate to obtain the high-purity jasminoidin. The preparation method provided by the invention completely discards chromatography, has the advantages of simple operation process, short production period, high efficiency and high yield and purity of the product, and is suitable for industrial production.

Description

A kind of preparation method of high-purity geniposide

technical field

The invention relates to a method for preparing high-purity geniposide, in particular to a method for preparing high-purity geniposide based on liquid-liquid distribution and extraction.

Background technique

Gardenia is an evergreen shrub of the Rubiaceae Gardenia genus, also known as Mudan, Shanzhi, etc., widely distributed in southern my country. Gardenia fruit is dark red or yellow-red, and is commonly used as traditional Chinese medicine in my country. "Compendium of Materia Medica" has detailed records: Gardenia fruit has the functions of clearing heat and purging fire, promoting gallbladder and protecting liver, lowering blood pressure, anti-inflammatory and bactericidal, and anti-thrombosis. There are many chemical components in gardenia, among which geniposide and gardenia yellow pigment are the substances with higher content. Geniposide is an active ingredient in Gardenia jasminoides, an effective monomer for the production of gardenia blue pigment and gardenia red pigment, and also a raw material drug for the treatment of cardiovascular and cerebrovascular diseases, liver and gallbladder diseases, and diabetes. Therefore, the efficient separation and purification of geniposide is the key technology for the in-depth development of geniposide.

At present, domestic and foreign studies on Gardenia jasminoides are more about the separation and purification of the active ingredient geniposide. Mainly used methods: lead salt precipitation method, silica gel adsorption method, two-phase extraction method, supercritical CO- ₂ fluid method, macroporous resin adsorption method, etc. Lead salt precipitation method, silica gel adsorption method, supercritical CO- ₂ fluid method are acceptable as research, but can't carry out industrialized production. The main problems are: complex process, excessive material consumption, low yield, and a large amount of toxic and harmful reagents, such as ether, chloroform, methanol, acetone, lead salt, etc. It does not meet the production specifications of food and medicine. The selection of geniposide by the aqueous two-phase method is not high, and high-purity geniposide cannot be obtained. The macroporous resin method is also not suitable for large-scale production of enterprises due to its low preparation volume. Utilize the conventional extraction method to enrich geniposide, and then use macroporous adsorption resin to refine and prepare high-purity geniposide. Although compared with the traditional macroporous adsorption resin method, the output per unit time can be obviously improved, but it is still not reached. relatively satisfactory results.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing high-purity geniposide that completely abandons chromatography, has simple operation methods, short production cycle, high efficiency, high product yield and purity, and is suitable for industrial production. The method is to adopt a pure extraction method to obtain a high-purity geniposide product, which overcomes the shortcomings in the above-mentioned prior art.

The technical solution for solving the above-mentioned technical problems is: a preparation method of high-purity geniposide, which comprises pulverizing gardenia jasminoides, soaking in water, ultrasonically assisted extraction, filtering and merging the extracts, and concentrating under reduced pressure to form gardenia jasminoides extract concentrate; The pH value of the fruit extract concentrate is adjusted to alkaline, and then the low-carbon alcohol is used as a solvent to extract under high-speed stirring to obtain an extract rich in geniposide; the obtained extract is decolorized, and the decolorized extract is decompressed Concentrate to obtain the decolorized concentrated solution; pour the decolorized concentrated solution into the organic acid ester under stirring, so that the crystals of geniposide are precipitated; after the crystallized precipitate is separated, it is washed with the organic acid ester, and the precipitate is washed repeatedly to obtain high-purity geniposide. The preparation method specifically comprises the following steps:

(1) Preparation of gardenia extract concentrate: crush gardenia, soak in water, ultrasonically extract 3 to 4 times at room temperature, add water for each extraction 5 to 6 times the dry weight of gardenia, each extraction After 1-2 hours, filter and combine the extracts, concentrate the extracts under reduced pressure to form an extract concentrate with a solid content of 30-60% by weight, to obtain a gardenia extract concentrate;

(2) Enrichment of geniposide: at room temperature, adjust the pH value of the concentrated gardenia extract prepared in step (1) to 9-11, and use four-carbon alcohol or five-carbon alcohol as the extractant under high-speed stirring, The gardenia extract concentrate is extracted 2 to 6 times, the volume of the extractant used for each extraction is equal to the volume of the extracted gardenia extract concentrate, each extraction is 20 to 60 minutes, and the combined extract is the geniposide Efficient enrichment was carried out;

(3) Decolorization and impurity removal of the extract: the extract obtained in step (2) is decolorized with granular activated carbon, and the decolorized extract is concentrated under reduced pressure into a decolorized concentrate with a solid content of 40-60% by weight;

(4) Further purification of geniposide: Add low-carbon organic acid ester to the decolorized concentrated solution prepared in step (3) to precipitate geniposide, and the volume of added low-carbon organic acid ester is 5% of the volume of the decolorized concentrated solution. ~9 times, after filtration, the precipitate is washed with low-carbon organic acid ester for 3 to 4 times, and high-purity geniposide can be obtained after drying.

The four-carbon alcohol in step (2) is n-butanol, and the five-carbon alcohol is isoamyl alcohol.

The rotating speed of the high-speed stirring described in step (2) is 400-600 rpm.

In step (2), sodium carbonate is used to adjust the pH value of the gardenia extract concentrate to 9-11.

The low-carbon organic acid ester described in step (4) is methyl acetate or ethyl acetate.

The purity of the geniposide prepared by the invention is greater than or equal to 94.5%.

The present invention is a method for preparing high-purity geniposide based on liquid-liquid partition extraction, which has the following beneficial effects:

The invention uses ultrasonic waves as an aid to extract the gardenia coarse powder with water at a certain temperature. The extraction method has the advantages of rapidity and thoroughness, and can shorten the production cycle and increase the yield of geniposide in industrial production. In the present invention, the pH value of the above-mentioned water extract is adjusted to 9-11, and then four-carbon alcohol and five-carbon alcohol are used for extraction, geniposide is extracted, and most of the impurities are left in the water phase, thereby achieving high-efficiency enrichment of Gardenia jasminoides The purpose of glycosides. Then use activated carbon to decolorize the above extract, which can efficiently remove the pigment, while geniposide is not adsorbed by activated carbon. The decolorized extract is concentrated, and then a low-carbon organic acid ester is added to the concentrated solution to precipitate geniposide crystals, while colorless impurities remain in the mother liquor, achieving the effect of efficient separation and purification of geniposide. The invention adopts a pure extraction method to obtain high-purity geniposide products. In the preparation process of the present invention, no toxic and harmful reagents such as ether, chloroform, methanol, acetone and lead salt are used, and the production standard of food and medicine is met. In addition, the present invention completely abandons the chromatography method, has simple operation method, short production cycle, high efficiency, high product yield and purity, and is suitable for industrial production.

Below, the technical characteristics of a method for preparing high-purity geniposide of the present invention will be further described in conjunction with examples.

Detailed ways

Example 1:

Weigh 100g (dry weight) of gardenia coarse powder, ultrasonically extract 3 times at room temperature, add 500g distilled water for extraction for 1 hour each time, combine three extracts and concentrate under reduced pressure, and concentrate to obtain gardenia with a solid weight content of 30%. Extract the concentrate. At room temperature, adjust the pH value of the gardenia extract concentrate to 9 with sodium carbonate, stir the gardenia extract concentrate at a speed of 400 rpm, and then use the same volume of the extracted gardenia extract concentrate each time Under the condition of n-butanol at a rotating speed of 400 r/min, stir and extract the concentrated solution of Gardenia jasminoides extract, extract twice for 30 minutes each time, and combine the n-butanol extracts. The extract is decolorized with granular activated carbon. After decolorization, the extract is clear and transparent, and the decolorized extract is concentrated under reduced pressure to a solid content of 40% by weight to obtain a decolorized concentrated solution. Add ethyl acetate 5 times the volume of the decolorizing concentrated solution to the decolorized concentrated solution to precipitate geniposide. After filtration, the precipitate was washed three times with methyl acetate and dried to obtain geniposide with a purity of 95.5% and a yield of 3.4%.

Embodiment 2～embodiment 16:

Weigh 100g (dry weight) of gardenia coarse powder, ultrasonically extract 3 times at room temperature, add 500g distilled water for extraction for 1 hour each time, combine the extracts three times and concentrate under reduced pressure to obtain a solid weight content of 30% ~ 60% (Condition 1) Gardenia extract concentrate. At room temperature, use sodium carbonate to adjust the pH value of the gardenia extract concentrate to 9~11 (condition 2), stir the gardenia extract concentrate at a speed of 400~600 rpm (condition 3), and then use it each time With the same volume of n-butanol or isoamyl alcohol (condition 4) as the extracted gardenia extract concentrate, stir and extract the gardenia extract concentrate at a speed of 400-600 rpm, and extract for 20-60 minutes each time (Condition 5), extract 2 to 6 times (Condition 6), and combine n-butanol or isoamyl alcohol extracts. The extract is decolorized with granular activated carbon. After decolorization, the extract is clear and transparent, and it is qualified. The decolorized extract is concentrated under reduced pressure to a solid content of 40% to 60% by weight (condition 7) to obtain a decolorized concentrate. Add 5 to 9 times the volume of the decolorized concentrated solution (condition 8) of ethyl acetate to the decolorized concentrated solution to precipitate geniposide. After filtration, the precipitate was washed three times with methyl acetate and dried to obtain geniposide with a purity of ≥94.5% and a yield of ≥3.4%.

The specific conditions of Examples 2 to 16 are shown in Attached Table 1, which shows that high-purity geniposide products can be obtained by using the pure extraction method.

Attached Table 1: List of Specific Conditions of Embodiment 2 to Embodiment 16

The weight content of solids in the solution in the present invention refers to the ratio of the weight of solids obtained by evaporation by conventional methods (that is, under normal pressure, the evaporation temperature is 100° C.) to the total weight of the solution.

As a transformation of each embodiment of the present invention, the low-carbon organic acid ester added to the decolorized concentrated solution to precipitate geniposide, in addition to using ethyl acetate, can also use methyl acetate to wash the precipitate The low-carbon organic acid ester can also adopt ethyl acetate except methyl acetate, and the low-carbon organic acid ester used for precipitation and washing precipitation can be the same or different.

Claims (6)

1. the preparation method of a high-purity gardenoside is characterized in that: may further comprise the steps:

(1) cape jasmine is extracted the preparation of concentrated solution: cape jasmine is pulverized, soak, the ultrasonic wave lixiviate is 3～4 times under the room temperature, it is 5～6 times of cape jasmine dry weight that each lixiviate adds water weight, each extraction time 1～2 hour, filter and united extraction liquid, it is 30～60% extraction concentrated solution that the extracting solution concentrating under reduced pressure is become the solid substance weight content, obtains cape jasmine and extracts concentrated solution;

(2) enrichment of jasminoidin: under the room temperature, the pH value that the cape jasmine that step (1) is made is extracted concentrated solution is adjusted to 9～11, be extraction agent with four carbon alcohols or five carbon alcohol under the high-speed stirring, cape jasmine is extracted concentrated solution to extract 2～6 times, each extraction equates with the cape jasmine extraction concentrated solution volume that is extracted with the volume of extraction agent, each extraction 20～60 minutes, combining extraction liquid has promptly carried out enrichment efficiently to jasminoidin;

(3) the decolouring removal of impurities of extraction liquid: the extraction liquid of step (2) gained is decoloured with granular carbon, and it is 40～60% decolouring concentrated solution that the extraction liquid concentrating under reduced pressure after the decolouring becomes the solid substance weight content;

(4) being further purified of jasminoidin: add the low carbon organic acid ester in the decolouring concentrated solution that makes toward step (3) and make the jasminoidin precipitation separate out, the low carbon organic acid ester volume that adds is 5～9 times of decolouring concentrated solution volume, after the filtration, precipitation can obtain high-purity gardenoside with low carbon organic acid ester washing 3～4 times after the drying.

2. the preparation method of a kind of high-purity gardenoside according to claim 1, it is characterized in that: the described four carbon alcohols of step (2) is a propyl carbinol, described five carbon alcohol are primary isoamyl alcohol.

3. the preparation method of a kind of high-purity gardenoside according to claim 1, it is characterized in that: the rotating speed of the described high-speed stirring of step (2) is 400～600 rev/mins.

4. the preparation method of a kind of high-purity gardenoside according to claim 1 is characterized in that: regulate pH value to 9～11 that cape jasmine is extracted concentrated solution with yellow soda ash in the step (2).

5. the preparation method of a kind of high-purity gardenoside according to claim 1, it is characterized in that: the described low carbon organic acid ester of step (4) is methyl acetate or ethyl acetate.

6. according to the preparation method of claim 1,2,3,4 or 5 described a kind of high-purity gardenosides, it is characterized in that: the jasminoidin purity that makes is more than or equal to 94.5%.