CN101434608B - Preparation of high-purity ellagic acid - Google Patents

Abstract

The invention discloses a preparation method of high-purity ellagic acid; tara powder is taken as raw material, extracted by purified water or 50-percent to 90-percent ethanol or a methanol water solution, hydrolyzed by concentrated sulfuric acid or hydrogen peroxide, purified by using diethylamine or triethylamine and crystallized, thus obtaining the high-purity ellagic acid; the method has simple technique and is suitable for industrialized production.

Description

A kind of preparation method of highly purified ellagic acid

Technical field

The present invention relates to the preparation method of activeconstituents in the kind of plant, specifically, relate to and a kind ofly draw method into the feedstock production ellagic acid with tower.

Background technology

Ellagic acid (Ellagic Acid) is a kind of pomegranate that extensively is present in, tower draws, strawberry, grape, apple, cranberry, polyphenolic compound in blackberry, blueberry and the English walnut, it is the very effectively polyphenoils of finding so far, can effectively resist melanic generation and intensification, compare with other traditional whitening compositions, its magical resistance to oxidation has unique double effects: at first, ellagic acid can in and cell in copper, it is compound to intercept cupric ion and tyrosine, thereby influence the generative process of melanocyte, directly intercept melanocyte and formed melanic possibility, greatly reduced the chance that new spot generates; Secondly, even if melanochrome forms, ellagic acid also can in and harmful free radical of producing when forming of melanochrome, suppress its diffusion, regulate oxidizing reaction, in and the environment of melanocyte, effectively suppress melanic further intensification, simultaneously, its natural polyphenol material can effectively be strengthened the reducing power of cell, desalination color spot when suppressing melanochrome to continue oxidation.

Ellagic acid can be widely used in fields such as medicine, food, healthcare products, makeup: be made into capsule in medicine, field of health care products, be mainly used in anti-cancer, step-down, anti-oxidant; At field of food, be mainly used in food antioxidant; At cosmetic field, effects such as Pear Power, removing beverage, anti-wrinkle, delaying decrepitude of skin.

In recent years, owing to found the anti-mutation of ellagic acid, anticancer change effect, and, caused that people pay close attention to widely to the restraining effect of chemical carcinogen.At present, the preparation method of ellagic acid mainly contains following several method:

A kind of is to extract ellagic acid from plant.Occurring in nature contains a small amount of ellagic acid ((1%) in the plants such as the redwood certain kind of berries, strawberry, pomegranate and fern.At present, it is raw material with strawberry, pomegranate that company is arranged in the world, can produce content and be the natural ellagic acid extract about 5-40%, be used for foodstuff additive, but be difficult to produce highly purified ellagic acid owing to be subjected to raw materials cost higher, and in the raw material ellagic acid content restriction and have little significance.

Another kind method is to produce ellagic acid by gallic acid or gallic acid ester by the oxypolymerization effect under the enzyme effect, the preparation method of this ellagic acid, productive rate is 20-30%, but the preparation process of used gallic acid (ester) itself is very complicated very, enzyme also needs refining purifying, and also has a kind of quinones substance of the unknown in the product, and the ratio of itself and ellagic acid is 1: 2.4, for the product separation purifying has brought very big difficulty, therefore present this method of less usefulness is carried out the production of ellagic acid.

European patent (EP 0390107A2Kiyoshi M., Yasuhiko I., Katsumi Y., etal) disclose another kind of method and prepared the ellagic acid that content is 50-60%, with the Turkey-galls is raw material, use methanol extraction, it is 7.9 that insolubles filtration rear filtrate is transferred pH by 40% NaOH solution, adds 1.89gNaHCO ₂In the U.S. Erlenmeyer flask of love he of 250mL, 25 ℃ of joltings of temperature 20 hours, shake fast 200rpm, every 20mL reaction solution adds 4mL0.1mol/L hydrochloric acid, and centrifugation obtains precipitation, precipitation is dissolved in 4mL methyl alcohol, with high performance liquid chromatography (255nm, the TSKODS120A post, 25cm), it is moving phase that the phosphate buffered saline buffer of M/30pH7.0 and methyl alcohol were made into mixed solution with 7: 3, reaction yield 48.0%.But but Turkey-galls is that the worm of animal is thin, though belong to Chinese medicine only limit to external application, therefore, is that the ellagic acid of production feedstock production can not be used for foodstuff additive with the Turkey-galls.The ellagic acid quality that obtains is lower, and outward appearance and color are relatively poor.Add that to state method steps various, the cycle is long, and the production cost height is difficult for extensive the operation.

Summary of the invention

The object of the present invention is to provide a kind of preparation method of highly purified ellagic acid, raw material can obtain the high purity ellagic acid through solvent extraction, hydrolysis, purifying, crystallization, and technology is simple, is suitable for industrial production.

A kind of preparation method of highly purified ellagic acid, the present invention adopt following technical scheme:

(1) extract: adopt the pure water of 5-12 times of raw material dry weight or 50-90% ethanol or methanol aqueous solution to boil raw material and extract twice, each 0.5-2.5 hour, united extraction liquid filtered, filtrate through vacuum concentration to there not being alcohol, medicinal extract;

(2) hydrolysis: add the vitriol oil or hydrogen peroxide in medicinal extract, the amount of adding is equivalent to 0.5-1 times of medicinal extract, and fully mixing leaves standstill solid-liquid separation, collecting precipitation;

(3) purifying: add the purifying agent of capacity in the precipitation, fully after the dissolving, the PH of regulator solution is 1-5, leaves standstill, and has crystal to separate out;

(4) collect crystallization, filter, drying obtains flaxen powder, and purity is more than 98%.

Raw material of the present invention is that tower draws powder, by beanpod gained after drying, pulverizing of trees Caesalpinia spinosaKuntze (Caesalpinia aspinosakuntze).

Hydrogen peroxide of the present invention, concentration 3%-50%.

Purifying agent of the present invention is diethylamine or triethylamine.

It is ellagic acid product more than 98% that the present invention adopts extraction, hydrolysis, purifying, crystalline method can obtain purity, compared with prior art:

1, this method technology is simple, is fit to scale operation;

2, find the new production of ellagic acid source, and be that directly to draw with tower be raw material, prepared highly purified ellagic acid, omitted intermediate products such as gallic acid or gallic acid ester.

Embodiment

Embodiment 1

(1) extract: adopt the pure water of 5 times of raw material dry weights to boil extraction twice raw material, each 0.5 hour, united extraction liquid filtered, and filtrate to there not being alcohol, gets medicinal extract through vacuum concentration;

(2) hydrolysis: add the vitriol oil in medicinal extract, the amount of adding is equivalent to 0.5 times of medicinal extract, and fully mixing leaves standstill solid-liquid separation, collecting precipitation;

(3) purifying: add the diethylamine of capacity in the precipitation, fully after the dissolving, the PH of regulator solution is 1, leaves standstill, and has crystal to separate out;

(4) collect crystallization, filter, drying obtains flaxen powder, purity 98.5%.

Embodiment 2

(1) extract: adopt the pure water of 12 times of raw material dry weights or 90% aqueous ethanolic solution to boil extraction twice raw material, each 2.5 hours, united extraction liquid filtered, and filtrate to there not being alcohol, gets medicinal extract through vacuum concentration;

(2) hydrolysis: adding concentration is 3% hydrogen peroxide in medicinal extract, and the amount of adding is equivalent to 1 times of medicinal extract, and fully mixing leaves standstill solid-liquid separation, collecting precipitation;

(3) purifying: add the triethylamine of capacity in the precipitation, fully after the dissolving, the PH of regulator solution is 5, leaves standstill, and has crystal to separate out;

(4) collect crystallization, filter, drying obtains flaxen powder, purity 99%.

Embodiment 3

(1) extract: adopt 50% methanol aqueous solution of 10 times of raw material dry weights to boil extraction twice raw material, each 2 hours, united extraction liquid filtered, and filtrate to there not being alcohol, gets medicinal extract through vacuum concentration;

(2) hydrolysis: adding concentration is 50% hydrogen peroxide in medicinal extract, and the amount of adding is equivalent to 0.8 times of medicinal extract, and fully mixing leaves standstill solid-liquid separation, collecting precipitation;

(3) purifying: add the triethylamine of capacity in the precipitation, fully after the dissolving, the PH of regulator solution is 3, leaves standstill, and has crystal to separate out;

(4) collect crystallization, filter, drying obtains flaxen powder, purity 99.1%.

Claims (2)

1. the preparation method of a highly purified ellagic acid is characterized in that comprising the following steps:

(1) extracts: adopt the pure water of 5-12 times of raw material dry weight or 50-90% ethanol or methanol aqueous solution to boil raw material and extract twice, each 0.5-2.5 hour, united extraction liquid, filter, filtrate is pure to not having through vacuum concentration, medicinal extract, raw material is that tower draws powder, it is beanpod gained after drying, pulverizing by the trees Caesalpinia spinosaKuntze that described tower draws powder;

(2) hydrolysis: add the vitriol oil or hydrogen peroxide in medicinal extract, the amount of adding is equivalent to 0.5-1 times of medicinal extract, and fully mixing leaves standstill solid-liquid separation, collecting precipitation;

(3) purifying: add the purifying agent of capacity in the precipitation, fully after the dissolving, the pH of regulator solution is 1-5, leaves standstill, and has crystal to separate out, and described purifying agent is diethylamine or triethylamine;

(4) collect crystallization, filter, drying obtains flaxen powder, and purity is more than 98%.

2. the preparation method of highly purified ellagic acid according to claim 1, it is characterized in that: described hydrogen peroxide concentration is 3%-50%.