CN101891781A - A method for preparing high-purity geniposide - Google Patents

Abstract

The invention discloses a method for preparing high-purity geniposide. It uses gardenia fruit as raw material, extracts and concentrates with water, removes a large amount of sugar substances by alcohol precipitation, and then extracts with an appropriate single organic solvent to initially enrich geniposide, and finally extract the initially enriched gardenia The macroporous resin on the glycoside solution is adsorbed and desorbed to obtain coarse crystals of geniposide, and recrystallized to obtain a high-purity product. The present invention has the following advantages: 1. The extraction method of the present invention has fast and thorough advantages. 2. The present invention uses ethanol to precipitate the above-mentioned water extract, so that the subsequent extraction operation does not produce emulsification, and greatly shortens the extraction time. 3. The single solvent used for extraction of the present invention is convenient to recycle in industrial production, greatly reducing production costs.

Description

A method for preparing high-purity geniposide

technical field

The invention relates to a method for preparing chemical products, in particular to a method for preparing high-purity geniposide.

technical background

Gardenia is the dry and mature fruit of Gardenia jasminoides of the Rubiaceae plant, oblong or oval, dark red or yellow-red in color. "Compendium of Materia Medica" has detailed records: Gardenia has the functions of promoting gallbladder and protecting liver, clearing heat and detoxification, lowering blood pressure, antibacterial and anti-inflammatory. Traditional Chinese medicine is used clinically to treat jaundice hepatitis, sprains, high blood pressure, diabetes, etc. There are many chemical components in gardenia, and its main components are iridoids such as crocetin, crocetin and geniposide. Geniposide has many uses. After fermentation under different conditions, it can be made into natural food colorants gardenia blue and gardenia red. It is also a raw material drug for treating cardiovascular and cerebrovascular diseases, liver and gallbladder diseases and diabetes. Therefore, the separation, purification, crystallization and content determination of geniposide have become the key technologies for the in-depth development of geniposide.

At present, the separation and purification of geniposide reported in domestic literature mainly include: lead salt precipitation method, activated carbon impurity removal method, silica gel adsorption method, macroporous resin adsorption method, etc. The preliminary conclusion drawn through comparative research is that the above-mentioned first three methods are acceptable as research, but cannot be industrialized. Its main problems are: complex process, excessive material consumption, low yield, and the use of toxic and harmful reagents in large quantities, such as ether, chloroform, methanol, acetone, lead salt, etc. It does not meet the production specifications of food and medicine. The use of macroporous resin adsorption method can fully achieve the purpose of purifying geniposide. The process is to crush the gardenia fruit and then reflux extraction with ethanol aqueous solution to obtain a crude extract, which is concentrated and directly applied to a macroporous resin column. Finally, a certain concentration of ethanol was used as the eluent for elution, and the effluent was collected to purify geniposide. In this process, since the crude extract contains a large amount of carbohydrates, gardenia xanthin and other impurities, the amount of macroporous resin will be greatly increased and the regeneration of the resin will be difficult. Not conducive to industrialized production.

Contents of the invention

In order to overcome the deficiencies of the prior art, the invention provides a method for preparing high-purity geniposide.

The technical scheme that the present invention solves the problems of the technologies described above is:

A method for preparing high-purity geniposide, using gardenia fruit as a raw material, with the aid of ultrasonic waves, extracting and concentrating with water, removing a large amount of carbohydrates by alcohol precipitation, and then extracting with a suitable single organic solvent, to the effect of gardenia Glycosides are initially enriched, and finally the macroporous resin on the initially enriched geniposide solution is adsorbed and desorbed to obtain coarse crystals of geniposide, and recrystallized to obtain a high-purity product. The operation steps are as follows:

1. Preparation of the crude extract of gardenia fruit: crush the gardenia fruit, assisted by ultrasonic waves, soak in water 5 to 20 times the dry weight of gardenia fruit, and extract 1 to 4 times by ultrasonic waves at 20 to 70 °C, each time 1 to 4 hours, filter, combine the filtrate and concentrate under reduced pressure to form a dilute extract - geniposide crude extract;

2. Preliminary removal of impurities from the crude extract of geniposide: drop the thin extract prepared above into 95% ethanol 5 to 15 times the volume of the diluted extract to produce a large amount of precipitation, filter, and concentrate the filtrate under reduced pressure to form an extract ;

3. Preliminary enrichment of geniposide: after dissolving the extract obtained in step 2 in water with 1 to 10 times the weight of the extract, extract with a solvent of ethyl acetate, methyl acetate or ethyl formate 3 ~10 times, the combined extracts were concentrated under reduced pressure to form an extract, that is, geniposide was initially enriched;

4. Macroporous resin separation of geniposide: After the extract obtained in step 3 is saturated with macroporous resin DM130 or D101, it is first eluted with 3 to 10 times the column volume of water to remove geniposide which is more polar than geniposide. Larger substances are then eluted with 4 to 9 times the column volume of 10% to 40% ethanol solvent, the leaked liquid is collected and concentrated under reduced pressure, and then vacuum dried to obtain crude geniposide crystals;

5. Purification of geniposide: the crude crystals of geniposide obtained in step 4 are recrystallized with acetone to obtain high-purity geniposide.

In the above step 1, soak in water 10 times the dry weight of gardenia, and extract by ultrasonic wave at 65° C. for 4 times, each time for 1 hour.

In the above-mentioned step 2, dropping the dilute extract into 95% ethanol of 5.3 times the volume of the dilute extract produces a large amount of precipitation.

In the above step 3, the obtained extract was dissolved in water of 1.3 times the weight of the extract, and then extracted 10 times with ethyl formate.

In above-mentioned step 4, described macroporous resin is D101, carries out elution with the water of 9 times of column volumes, removes the impurity of large polarity, then with 7 times of column volumes 15% ethanol solvent elutions, collects leaking liquid and reduces Concentrate under reduced pressure and then dry in vacuum to obtain crude crystals of geniposide.

The present invention has the following advantages:

1. The present invention is assisted by ultrasonic waves, and water is extracted gardenia fruit coarse powder at a certain temperature, and this extraction method has fast, thorough advantage, can shorten the production cycle and improve the productive rate of geniposide in industrial production.

2. the present invention carries out precipitation to above-mentioned water extract with ethanol, can remove a large amount of sugar substances, and its advantage is that the extraction operation behind does not produce emulsification phenomenon, shortens extraction time greatly, and this is in industrial production quite advantageous.

3. The present invention uses a certain single solvent in ethyl acetate, methyl acetate or ethyl formate to extract the above-mentioned water extract after the sugar removal operation, and the purpose is to initially enrich the geniposide in the water extract. The advantage is that the adsorption capacity of macroporous resin to geniposide is greatly increased, the amount of macroporous resin and eluent is reduced, and the single solvent used for extraction is easy to recover in industrial production, which greatly reduces production costs.

Detailed ways

The present invention will be further described below in conjunction with embodiment. However, it should be noted that the examples do not limit the protection scope of the claims of the present invention.

Example 1

Weigh 500g of dried gardenia fruit powder, ultrasonically extract three times at 50°C, add 5000ml of distilled water for extraction for 1 hour each time, combine the three extractions and concentrate under reduced pressure to form 120ml of dilute extract, which is precipitated when added to 500ml of 95% ethanol A large amount of sugar precipitates, filters, and the filtrate is concentrated under reduced pressure into 90 g of extract, which is dissolved in 200 ml of distilled water, extracted continuously for 5 times with 200 ml of methyl acetate, and the combined extracts are concentrated under reduced pressure for 25 g of enriched extract. Dilute the extract with 1000ml of distilled water and put it on the pretreated DM130 macroporous resin column. After the adsorption is saturated, wash the column with 8 times of column volume of distilled water, discard the effluent, and then wash with 5 times of column volume of 20% ethanol aqueous solution. After elution, the eluent was concentrated under reduced pressure and dried in vacuo to obtain crude crystals of geniposide, which were recrystallized with acetone to obtain 16 g of crystals of geniposide with a purity greater than 98.9%, with a yield of 3.2%.

Example 2

Weigh 500g of dried gardenia fruit powder, ultrasonically extract three times at 50°C, add 5000ml of distilled water for extraction for 1 hour each time, combine the three extractions and concentrate under reduced pressure to form 120ml of dilute extract, which is precipitated when added to 500ml of 95% ethanol A large number of sugars precipitated, filtered, and the filtrate was concentrated under reduced pressure into 95g of extract, which was dissolved in 200ml of distilled water, extracted 8 times with 200ml of ethyl formate, and the extracts combined 8 times were concentrated under reduced pressure into 30g of extract, and 1000ml of extract was used After diluting with distilled water, put it on the pretreated DM130 macroporous resin column. After the adsorption is saturated, wash the column with distilled water of 8 times the column volume, discard the effluent, and then elute with 20% ethanol aqueous solution of 5 times the column volume. Concentrate under reduced pressure and dry in vacuo to obtain crude geniposide crystals, which can be recrystallized with acetone to obtain 18.5 g of geniposide crystals with a purity greater than 98.6%, with a yield of 3.7%.

Example 3

Weigh 500g of dried gardenia fruit powder, ultrasonically extract four times at 65°C, add 5000ml of distilled water for extraction for 1 hour each time, combine the four extractions and concentrate under reduced pressure to form 150ml of dilute extract, which is added to 600ml of 95% ethanol Promptly separate out a large amount of sugar precipitates, filter, and the filtrate is concentrated under reduced pressure into 110g of extractum, extractum is dissolved in 150ml distilled water, extracts 9 times with 200ml methyl acetate, and the extracts of merging 9 times are concentrated under reduced pressure into 34g of extractum, extractum After diluting with 800ml of distilled water, put it on the pretreated D101 macroporous resin column. After the adsorption is saturated, wash the column with distilled water of 8 times the column volume, discard the effluent, and then elute with 15% aqueous ethanol solution of 6 times the column volume. The crude crystals of geniposide were obtained after dehydration, concentration under reduced pressure and vacuum drying. The crude crystals were recrystallized with acetone to obtain 20.5 g of geniposide crystals with a purity greater than 99.1%, with a yield of 4.1%.

Example 4

Weigh 500g of gardenia fruit coarse powder, ultrasonically extract four times at 65°C, add 5000ml of distilled water to extract for 1.5 hours each time, combine the four extracts and concentrate under reduced pressure to form 150ml of dilute extract, which is added to 800ml of 95% ethanol Precipitate a large number of sugar precipitates, filter, concentrate the filtrate under reduced pressure into 120g of extract, dissolve the extract in 150ml of distilled water, extract 10 times with 300ml of ethyl formate, combine the extracts of 10 times under reduced pressure and concentrate into 38g of extract, which is used for extract Dilute with 1000ml of distilled water and put it on the pretreated D101 macroporous resin column. After the adsorption is saturated, wash the column with distilled water of 9 times the column volume, discard the effluent, and then elute with 15% ethanol aqueous solution of 7 times the column volume. The solution was concentrated under reduced pressure and dried in vacuo to obtain crude crystals of geniposide, which were recrystallized with acetone to obtain 22.5 g of crystals of geniposide with a purity greater than 99.2%, and the yield could reach 4.5%.

Claims (5)

1. method for preparing high-purity gardenoside, it is characterized in that, with cape jasmine really is raw material,, concentrate the back with water extraction and remove a large amount of glucides for auxiliary with ultrasonic wave, then with suitable single organic solvent extraction with the pure precipitator method, jasminoidin is carried out preliminary enrichment, at last macroporous resin on the jasminoidin liquid of preliminary enrichment is carried out adsorption-desorption and obtain the jasminoidin coarse crystal, recrystallization obtains high purity product, and operation steps is as follows:

(1) preparation of cape jasmine fruit crude extract: cape jasmine is really pulverized, for auxiliary, steep with the water logging of 5～20 times of cape jasmine dry weights with ultrasonic wave, ultrasonic extraction is 1～4 time under 20～70 ℃ of conditions, each 1～4 hour, filter, filtrate is merged concentrating under reduced pressure become rare medicinal extract-jasminoidin crude extract;

(2) the preliminary removal of impurities of jasminoidin crude extract: the above-mentioned rare medicinal extract that makes is splashed into promptly produce a large amount of precipitations in 95% ethanol of 5～15 times of rare medicinal extract volumes, filter, filtrate decompression is condensed into medicinal extract;

(3) the preliminary enrichment of jasminoidin: after the medicinal extract of step (2) gained being dissolved in the water of 1～10 times of medicinal extract weight, extract 3～10 times with a kind of solvent in ethyl acetate, methyl acetate or the ethyl formate, the combining extraction liquid concentrating under reduced pressure becomes medicinal extract, promptly jasminoidin has been carried out preliminary enrichment;

(4) macroporous resin of jasminoidin separates: with step (3) gained medicinal extract through macroporous resin DM130 or D101 absorption reach saturated after, water with 3～10 times of column volumes carries out wash-out earlier, remove the depolarization material bigger than jasminoidin, use the alcohol solvent wash-out of 4～9 times of column volumes 10%～40% then, collect leakage concentrating under reduced pressure final vacuum drying get final product the jasminoidin coarse crystal;

(5) purifying of jasminoidin: the jasminoidin coarse crystal of step (4) gained is carried out recrystallization with acetone can obtain highly purified jasminoidin.

2. a kind of method for preparing high-purity gardenoside according to claim 1 is characterized in that, in the described step (1), with the water logging bubble of 10 times of cape jasmine dry weights, ultrasonic extraction is 4 times under 65 ℃ of conditions, each 1 hour.

3. a kind of method for preparing high-purity gardenoside according to claim 1 is characterized in that in the described step (2), rare medicinal extract is splashed into promptly produce a large amount of precipitations in 95% ethanol of 5.3 times of rare medicinal extract volumes.

4. a kind of method for preparing high-purity gardenoside according to claim 1 is characterized in that in the described step (3), after the medicinal extract of gained is dissolved in the water of 1.3 times of medicinal extract weight, with extraction in the ethyl formate 10 times.

5. a kind of method for preparing high-purity gardenoside according to claim 1, it is characterized in that in the described step (4), described macroporous resin is D101, water with 9 times of column volumes carries out wash-out, remove the impurity of high polarity, use the alcohol solvent wash-out of 7 times of column volumes 15% then, collect leakage concentrating under reduced pressure final vacuum drying get final product the jasminoidin coarse crystal.