JP7061767B2 - 1-Method for producing acetoxychavicol acetate-containing material - Google Patents

Description

The present invention relates to a method for producing a 1-acetoxychavicol acetate-containing substance, and is particularly useful in the fields of foods and drinks, food additives, pharmaceuticals, quasi-drugs, pesticides, cosmetics, feeds, etc. The present invention relates to a method for producing an acetoxychavicol acetate-containing substance.

1-Acetoxychabicol acetate (hereinafter abbreviated as ACA) is useful in foods and drinks, food and drink additives, cosmetics, pharmaceuticals, quasi-drugs, pesticides, feeds, etc., and is particularly strong. It is known to have an antioxidant effect (Non-Patent Document 1).

As a method for obtaining ACA, a production method by a chemical synthesis method (Patent Document 1) and a production method by extraction derived from a natural product are known. In particular, when ACA is used as food or drink, food additives, or cosmetics, those derived from natural products are desirable. As a production method by extraction derived from natural substances, for example, a method of extracting from Galangal (scientific name: Alpinia galanga, Zingiberaceae), which is a plant native to tropical Asia, is known (see Patent Documents 2 to 5). Galangal, also known as Nankyo (Japanese name) or Kah (Thai), has long been used as a spice for soups such as Tom Yum Kung. It has also been used as a crude drug for a long time as a drug for suppressing inflammation of the gastric mucosa, throat and bronchi. On the other hand, ginger mainly produced in Japan has a pungent ingredient such as gingerol and shogaol as its main active ingredients, and is a plant completely different from the above-mentioned galangal.

In addition to the above-mentioned actions, ACA contained in galangal is expected to have pharmacological actions such as antitumor activity, suppression of interleukin 2 production, and inhibition of angiotensin converting enzyme, and demand is increasing. However, there is a problem in supplying a large amount at low cost. For example, supply by chemical synthesis requires processes such as column purification and optical resolution, resulting in high cost. There was also concern about safety to the human body.

On the other hand, Galangal, which is derived from natural plants and is native to tropical Asia, has long been used as a spice for soups such as Tom Yum Kung. Therefore, the supply by extraction using Galangal has less concern in terms of safety to the human body.
However, the known natural product extraction supply contained a large amount of extra components other than ACA, and Galangal was decomposed during the extraction process to provide a low ACA content. Therefore, the production efficiency is low and the cost is high, which is not satisfactory as an industrial manufacturing method.

For example, Patent Document 2 describes a method of extracting the juice of the rhizome of Galangal with chloroform and separating it by liquid chromatography. However, it is clear that the juice, which is a water-soluble component, does not originally contain oil-soluble ACA. Therefore, the obtained extract contains almost no ACA.

Patent Document 3 describes a method of shredding a galangal rhizome, extracting it with methanol, and then purifying it by column. However, column purification results in high cost and low yield, so it cannot be used industrially.

Patent Document 4 describes a method for extracting a dried product of a galangal site (for example, rhizome) as it is with alcohol or ethyl acetate. However, there is no description such as the content of ACA.

Patent Document 5 is not satisfactory as an industrial manufacturing method because the manufacturing process includes a freeze-drying operation and the cost is high.

Japanese Unexamined Patent Publication No. 2013-19393 Japanese Patent No. 4194744 Japanese Unexamined Patent Publication No. 2005-179201 Japanese Patent Application Laid-Open No. 2003-73288 WO2014 / 195479

Kikueda Kubota Urakami Foundation Research Report (1996) Vol.5 p132-138

An object of the present invention is to provide an industrial method for producing a high-ACA-containing material, which can efficiently and inexpensively produce a "high-ACA-containing material" containing a large amount of 1-acetoxychabicol acetate (ACA). be.

The means for solving the above-mentioned problems are
(I) (1) Shredding step of shredding gallangal to obtain shredded material (2) Water treatment step of obtaining a slurry containing the shredded material and water (3) Solid-liquid separation of the slurry. A method for producing an ACA-containing material, which comprises a solid-liquid separation step of obtaining a solid substance and (4) an oil-soluble component extraction step of extracting and separating an oil-soluble component from the solid substance with an organic solvent.
A preferred embodiment of the method for producing an ACA-containing material of the present invention is
(II) In the water treatment step (2) in the method for producing an ACA-containing material according to (I), the amount of water with respect to the shredded material is 0.1 to 100 times the weight of the shredded material. And
(III) In the solid-liquid separation step of (3) in the method for producing an ACA-containing material according to (I) or (II), a squeezing means is included.
(IV) In the solid-liquid separation step (3) in the method for producing an ACA-containing material according to any one of (I) to (III), the solid matter has an absolute dry solids content of 30%. That's all,
(V) The organic solvent in the method for producing an ACA-containing material according to any one of (I) to (IV) above is a water-soluble organic solvent.

According to the production method according to the present invention, hydrophilic contaminants can be effectively removed from galangal, and oil-soluble components are extracted and removed from the solid matter obtained in the solid-liquid separation step (3) with an organic solvent. Therefore, it is possible to obtain an ACA-containing substance having a high concentration of ACA and having excellent storage stability.

FIG. 1 is a diagram showing one aspect of the manufacturing method of the present invention.

前記ＡＣＡ含有物には前記化１で示される化合物１のほかに、化合物１の幾何異性体、又は、光学異性体、ラセミ体等を含んでいてもよい。また、前記ＡＣＡ含有物には、この発明の製造方法に係る工程中に含まれる水によってＡＣＡが変性してなる以下の化合物２～化合物４を含んでいてもよい。

The ACA-containing substance obtained by the production method of the present invention is a mixture containing ACA (Compound 1) as a main component.

In addition to the compound 1 shown in Chemical formula 1, the ACA-containing substance may contain a geometric isomer, an optical isomer, a racemate, or the like of the compound 1. Further, the ACA-containing material may contain the following compounds 2 to 4 in which ACA is modified by water contained in the step according to the production method of the present invention.

One aspect of the production method of the present invention can be shown by the procedure shown in FIG. That is, one aspect of the present invention includes the following steps (1) to (6).

<Shredding process (1)>
In this shredding step (1), galangal is shredded to obtain shredded material.
The galangal is a plant native to tropical Asia (scientific name: Alpinia galanga, Zingiberaceae), and is also called Nankyo (Japanese name) or Kah (Thai).
The galangal may be in a dry state or may be in a non-dry state.
The galangal can be adopted as a shredding target in this shredding step (1) regardless of any part of the plant such as roots, rhizomes, stems, flowers, leaves, fruits, seeds and the like. Suitable sites for shredding the galangal are roots, rhizomes, and leaves, and particularly suitable sites are roots and rhizomes. This is because these sites have a high content of ACA.
In addition, since Galangal is already distributed as an edible product, a commercially available product can also be used. Galangal can be used in the production method of the present invention regardless of whether it is a refrigerated product, a frozen product or a dried product.

The method for shredding galangal is not particularly limited as long as the galangal can be shredded, and machines, utensils, and devices generally used in the field of food processing can be used. Further, as a machine, an instrument, or an apparatus for shredding, for example, a shredding machine and a crushing machine that utilize a force such as a cutting force, a shearing force, a crushing force, a crushing force, and a pressure such as water pressure or air pressure. Etc., and specific examples thereof include a cutter, a chopper, a slicer, a dicer, a mixer, a mill, and a grinder.
When shredding the galangal, the galangal may be preliminarily shredded to an appropriate size so that the galangal can be easily shredded according to the shredding machine, the crusher, or the like. For example, when using a household or industrial mixer, it is preferable to cut the galangal into a shape having a length and width of several cm and put the cut piece into the mixer.

The galangal shreds obtained by this shredding step (1) are aggregates of shredded particles. The shredded particles may be substantially spherical, spheroidal, needle-shaped, fibrous or the like. In the next water treatment step (2), if the contact area of the shredded material with water is large, the contaminants can be efficiently extracted by the water, but the shredded material and the handling of the shredded material obtained after the shredded material can be efficiently extracted. For convenience such as, the major axis of the shredded particles along the length direction is 0.1 to 20 mm, preferably 0.1 to 5 mm, and the minor axis in the direction orthogonal to the major axis is 0.1 to 5 mm. It is preferably 0.1 to 3 mm.
In this shredding step (1), the galangal can be shredded in a state where the galangal is immersed in water, or the galangal in a dry state or a semi-dry state can be shredded without water. can.

<Water treatment process (2)>
In this water treatment step (2), a slurry of the shredded material and water is obtained.
When the shredded product is obtained by shredding the dried or non-dried galangal without using water in the shredding step (1), the shredding step (2) is performed in the water treatment step (2). The shredded product obtained in 1) and water are mixed to obtain a slurry containing the shredded product and water.
Further, in the case of shredding the galangal in a state where the galangal is immersed in water in the shredding step (1) to obtain a shredded product, in the water treatment step (2), the shredding step (1) is performed. To obtain a slurry containing water and shreds, with or without water added to the mixture of water and shreds obtained in.

The weight ratio of shredded material to water in the slurry obtained in this step is 0.1 to 100 times the weight of water, preferably 0.5 to 20 times the weight of the shredded material, particularly. It is preferably appropriately selected from the range of 2 to 10 times the weight.

In this water treatment step (2), impurities contained in the shredded material are removed by forming a slurry of the shredded material and water. The fact that impurities are removed by water by this water treatment step (2) is supported by the following test.
That is, as shown in Table 1, in Test Examples 1 to 6, the amount of shredded material shown in Table 1 and the amount of water shown in Table 1 were mixed and then allowed to stand for 30 minutes, and then allowed to stand. When the solid content obtained by filtering the slurry and evaporating and drying the obtained aqueous phase was analyzed, the amount of ACA in the solid content and the amount of components other than ACA were as shown in Table 1.

As shown in Table 1, since ACA was not contained in the aqueous phase obtained by solid-liquid separation of the slurry, it is judged that the solid content contained in the aqueous phase is a contaminant. .. In addition, it was clarified that the contaminants in the shredded material moved to the aqueous phase by forming the slurry.

In addition, in order to increase the effect of elution of impurities into water from shredded substances (that is, elution effect), water-soluble alcohols such as methanol, ethanol and propanol, water-soluble ketones such as formaldehyde and acetone, and water-soluble substances such as dimethyl ether are added together with water. A water-soluble organic solvent such as sex ether can also be mixed with the shredded material.
The amount of these water-soluble organic solvents is appropriately selected within the range of 1 to 20% by mass with respect to water.
It is preferable to employ a stirring means for mixing the shredded material, water and a water-soluble organic solvent added as needed. The stirring duration for stirring by the stirring means is usually 30 minutes to 8 hours. The stirring by the stirring means may be performed at room temperature, or may be performed under heating.

The slurry obtained by mixing shredded material, water and a water-soluble organic solvent added as needed is preferably allowed to stand for another 10 minutes to several hours after the completion of stirring by the stirring means. By leaving it to stand, the slurry is separated into a solid phase and an aqueous phase, facilitating the solid-liquid separation operation which is the next step, and the elution of contaminants into the aqueous phase sufficiently progresses to solidify. The content of impurities contained in the phase separation can be reduced as much as possible.
During the period in which the slurry is allowed to stand, the slurry may be kept at room temperature or may be heated. Since there is a risk of decomposition of ACA when heated, it is preferable that the heating temperature is as low as possible and the heating time is shortened.

Since this water treatment step (2) is a step of exerting an action of elution of impurities contained in the shredded material into water, another aspect of the water treatment step (2) is to add water to the shredded material. Examples thereof include an operation of continuously refluxing the water-soluble organic solvent added as needed at room temperature or heating.

<Solid-liquid separation step (3)>
In this solid-liquid separation step (3), a solid substance is obtained from the slurry obtained in the water treatment step (2).
In order to separate the solid matter from the slurry, a filtration means such as natural filtration, pressure filtration, or vacuum filtration can be adopted by using a filter such as filter paper or filter cloth which is usually performed. It is also possible to adopt a filter press that applies pressure during filtration. Centrifugal separation means can be adopted instead of the filtration means. In short, there is no particular limitation as long as it is a method capable of solid-liquid separation of the slurry.

When the solid matter separated in the solid-liquid separation step (3) is further squeezed by a squeezing means, the liquid (moisture) can be squeezed out from the solid matter. The squeezed liquid, that is, the juice thereof, does not contain ACA, which is oil-soluble because it is aqueous. Therefore, the liquid contained in the juice and the solid matter contained in the liquid are impurities. Therefore, the squeezing means is a suitable means capable of further increasing the purity of the final product (ACA-containing material).
The pressing means is not particularly limited, but for example, a hydraulic press machine or a roll press machine is suitable. The squeezing pressure can be appropriately selected in the range of 50 to 250 kg / cm ² , but is preferably 150 kg / cm ² or more.

In this solid-liquid separation step (3), it is preferable to efficiently separate the liquid from the solid matter. The solid matter obtained by the filtration means, the centrifugation means, and the squeezing means contains water and liquid components contained in the shredded galangal structure. If there is concern that the water or liquid components contained in the solids obtained at this stage contain impurities, the solids obtained at this stage and water or water and water solubility added as needed It is preferable to mix with an organic solvent and use the resulting mixture in the filtration means, centrifugation means or squeezing means to reduce the content of impurities in the solid content to a negligible level.

Since the solid thus obtained contains some water, it is preferable to further dry the solid. When the solid content containing water is subjected to the next extraction step (4), the extract contains water, which forces an extra operation of further separating the extract into an oil phase and an aqueous phase. Because.
An absolutely dry solid (hereinafter referred to as an absolutely dry solid) can be obtained by heating the solid and completely drying it.
The solid matter obtained in this solid-liquid separation step (3) has an absolute dry solid content of 7% or more, particularly 7 to 95%, preferably 30 to 95%, and more preferably 50 to 95%. The absolute dry solids content is adjusted to be appropriately determined. In particular, if it is 30% or more, emulsification is less likely to occur in the ACA extraction step in the subsequent extraction step, and the extraction workability (efficiency) is improved.

In the present invention, the absolute dry solids content (%) is calculated as follows.
Absolutely dry solids content (%) = [Weight of solids in an absolutely dry state (g) / Weight of solids (g)] x 100
In order to adjust the absolute dry solid content ratio, it is preferable to subject the solid material to a vacuum drying operation, a hot air drying operation, and a blower drying operation.

<Oil-soluble component extraction step (4)>
In this oil-soluble component extraction step (4), the oil-soluble component is extracted from the solid substance obtained in the solid-liquid separation step (3) with an extraction solvent.
The extraction solvent is not particularly limited as long as it can stably extract ACA, and for example, alcohol-based solvents such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, butyl alcohol, and diethylene glycol, methyl acetate, and acetic acid. Examples thereof include ester solvents such as ethyl, isopropyl acetate and butyl acetate, hydrocarbon solvents such as hexane and heptane, glycerin and acetone. Further, two or more kinds of solvents can be mixed and used, and the mixing ratio at the time of mixed use can be arbitrarily determined. Among the extraction solvents, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, ethyl acetate, hexane and heptane are preferable, and in particular, water-soluble from the viewpoint of ACA extraction efficiency and safety to the human body. Organic solvents, especially ethanol, are preferred.
The amount of the extraction solvent used in the oil-soluble component extraction step (4) is appropriately selected in the range of 0.1 to 1000 parts by mass with respect to 1 part by mass of the solid-liquid content obtained in the solid-liquid separation step (3). It is appropriately selected in the range of preferably 0.5 to 500 parts by mass, more preferably 1.0 to 150 parts by mass.

The extraction treatment in this oil-soluble component extraction step (4) is a solid under normal pressure or a pressurized atmosphere, usually under heating at 0 to 200 ° C., preferably 25 to 150 ° C., more preferably 50 to 120 ° C. The operation is performed by heating a mixture of the substance and the extraction solvent, or heating and refluxing the absolute dry solid content with the extraction solvent. Usually, the extraction processing time is preferably 30 minutes or more.

If the shredded product obtained in the shredding step (1) is subjected to the oil-soluble component extraction step (4) by omitting the water treatment step (2) and the solid-liquid separation step (3), ACA can be used. An ACA-containing product having a low content and poor storage stability can be obtained. Therefore, the water treatment step (2) and the solid-liquid separation step (3) should not be omitted.

Further, in this oil-soluble component extraction step (4), an acid or a base may be appropriately added when adjusting the pH, if necessary.
The acid that can be used is not particularly limited as long as it can stably extract ACA. Examples thereof include hydrochloric acid, phosphoric acid, acetic acid, adipic acid, citric acid, gluconic acid, succinic acid, lactic acid, tartaric acid, fumaric acid, malic acid and the like, which are also recognized as food additives.
The base that can be used is not particularly limited as long as it can stably extract ACA. For example, sodium acetate, ammonium acetate, sodium hydroxide, potassium carbonate, sodium hydrogencarbonate and the like, which are also recognized as food additives, can be mentioned.

<Concentration step (5)>
In the production method of the present invention, an ACA-containing substance containing ACA at a high concentration can be produced by going through the steps from the shredding step (1) to the oil-soluble component extraction step (4).
The extract obtained in the oil-soluble component extraction step (4) is an ACA-containing substance having excellent storage stability of ACA.
However, since the extract contains an organic solvent for extraction, it is preferable to include a step of removing the organic solvent, that is, a step of performing a concentration operation.
For the concentration operation excluding the organic solvent, a known method generally used conventionally can be used.
Examples of known concentration methods include known drying methods such as vacuum drying method, hot air drying method, blast drying method, freeze drying method, oven drying method, microwave heating drying method, and sun drying method. Further, in order to perform pulverization, known means such as a spray dryer, a drum dryer, a freeze dryer, and an air dryer can be appropriately adopted.
The components other than ACA contained in the ACA-containing material are components that do not significantly reduce the storage stability, and specifically include various oils and fats.

Further, in order to produce a high-concentration concentrated ACA-containing liquid containing at least ACA of high purity, or a powder containing at least ACA with high purity, it is preferable to use an adsorbent. The adsorbent may be added to the extract obtained in the oil-soluble component extraction step (4), or may be used in the post-treatment step (5).
The adsorbent is not particularly limited as long as it does not affect ACA, and examples thereof include activated carbon, silica gel, activated alumina, and activated clay. In particular, it is preferable to use activated carbon and silica gel because it is possible to produce an ACA-containing substance containing ACA at a high concentration.

Further, in the case of applications such as pharmaceuticals, quasi-drugs, some functional foods, and cosmetics, it is necessary to produce a higher concentration of ACA-containing substances. In that case, the ACA-containing material obtained in the present invention can be purified by solvent extraction or column chromatography to increase the purity to 95% or more.

The ACA-containing material obtained by the production method according to the present invention can be made into various useful derivatives using this as a starting material.
By hydrolyzing the ACA, 4-((E) -3-hydroxy-1-propenyl) phenylacetate and further acetylated acetylated product can be easily obtained.
Further, the ACA-containing material obtained in the present invention can be blended as it is in various foods as a food material, particularly as a pungency-enhancing material. Alternatively, it can be used for pharmaceuticals, quasi-drugs, foods for specified health use, functional foods, dietary supplements and the like. The form may be ampoules, capsules, pills, tablets, powders, granules, solids, liquids, gels, bubbles and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are specific examples shown for a deeper understanding of the present invention, and the present invention is the embodiment thereof. It is not limited to any examples. The identification and purity measurement of the compound were confirmed by R-90H type high resolution NMR (90 MHz, manufactured by Hitachi, Ltd.) and liquid high performance chromatography "LaChon ELITE series (manufactured by Hitachi High-Tech Science Co., Ltd.).

(Example 1)
As a shredding process, a non-dried, that is, raw galangal rhizome 1000 g (absolute dry weight 80 g) is shredded with a crusher "Cutter Mixer 25S" (manufactured by Aikosha Seisakusho Co., Ltd.) to obtain shredded material. rice field.
As a water treatment step, 1000 g of this shredded product and 3000 g of water were mixed, and the obtained mixture was heated to 50 ° C. for 1 hour with stirring to obtain a slurry.
As a solid-liquid separation step, this slurry was squeezed at a pressure of 150 kg / cm ² using "Oil Press KSP-5M" (manufactured by Shin-Komagata Machinery Mfg. Co., Ltd.) to obtain a solid substance. The absolute dry solid content of this solid was 31%.
As an extraction step, 2000 g of ethanol was added to the solid substance, and the mixture was slowly stirred at 65 ° C. for 2 hours for extraction. After filtering the residue after extraction, ethanol was distilled off under reduced pressure to obtain 11.1 g of concentrated ACA content. The ACA content was 55%.

The ACA content (%) was calculated by preparing a calibration curve by liquid chromatography.
In the present invention, the ACA extraction efficiency (%) is calculated as follows.
ACA extraction efficiency (%) = [weight of ACA content (g) / absolute dry weight of raw material (g)] x ACA content (%)
In this example, the ACA extraction efficiency was 7.6%.

(Example 2)
Except for the fact that vacuum filtration was performed instead of squeezing in the solid-liquid separation step, the same procedure as in Example 1 was carried out. As a result, a solid substance having an absolute dry solid content of 7% was obtained. The obtained ACA content was 12.1 g, the ACA content was 35%, and the ACA extraction efficiency was 5.3%.
(Example 3)
Except for the centrifugal filtration (1760G) performed in the solid-liquid separation step, the same procedure as in Example 1 was carried out. As a result, a solid substance having an absolute dry solid content of 13% was obtained. The ACA content was 10.5 g, the ACA content was 39%, and the ACA extraction efficiency was 5.1%.
(Example 4)
In the solid-liquid separation step, the process was carried out in the same manner as in Example 1 except that the press was pressed with a pressure of 100 kg / cm ² in the same manner as in Example 1. As a result, a solid substance having an absolute dry solid content of 21% was obtained. The ACA content was 12.3 g, the ACA content was 50%, and the ACA extraction efficiency was 7.7%.

(Example 5)
In the water treatment step of Example 1, the same operation as in Example 1 was performed except that the amount of water to be added was changed to 2000 g (twice the weight of the raw material). As a result, the ACA content was 11.9 g, the ACA content was 50%, and the ACA extraction efficiency was 7.4%.
(Example 6)
In the water treatment step of Example 1, the same operation as in Example 1 was performed except that the amount of water to be added was changed to 1000 g (1 times the weight of the raw material). As a result, the ACA content was 10.9 g, the ACA content was 35%, and the ACA extraction efficiency was 4.8%.

(Example 7)
Instead of using ethanol as the extraction solvent of Example 1, the same operation as in Example 1 was carried out except that the solution was changed to methanol. As a result, the ACA content was 12.1 g, the ACA content was 41%, and the ACA extraction efficiency was 6.2%.
(Example 8)
In Example 1, the same operation as in Example 1 was carried out except that the extraction solvent was changed to ethyl acetate instead of ethanol. As a result, the ACA content was 8.4 g, the ACA content was 45%, and the ACA extraction efficiency was 4.7%.
(Example 9)
In Example 1, instead of using ethanol as the extraction solvent, the same operation as in Example 1 was carried out except that the extraction solvent was changed to hexane. As a result, the ACA content was 4.9 g, the ACA content was 55%, and the ACA extraction efficiency was 3.4%.
(Example 10)
In Example 1, the same operation as in Example 1 was carried out except that instead of using ethanol as the extraction solvent, the solution was changed to a 75% ethanol aqueous solution. As a result, the ACA content was 7.5 g, the ACA content was 31%, and the ACA extraction efficiency was 2.9%.

(Example 11)
As a shredding process, using a crusher "Cutter Mixer 25S" (manufactured by Aikosha Seisakusho Co., Ltd.) using 100 g of dried galangal rhizome (absolute dry weight 90 g) from which some water has been removed from the galangal in advance, the galangal is shredded. 100 g of cut pieces were obtained.
As a water treatment step, a slurry obtained by mixing 100 g of the shredded product and 300 g of water and stirring the mixture at 50 ° C. for 3 hours was obtained.
As a solid-liquid separation step, this slurry was squeezed at a pressure of 150 kg / cm ² using "Oil Press KSP-5M" (manufactured by Shin-Komagata Machinery Mfg. Co., Ltd.) to obtain a solid substance. When this solid substance was further subjected to an absolute dry treatment, the absolute dry solid content was 80%.
As an extraction step, 890 g of ethanol was added to the solid substance, and the mixture was slowly stirred at 65 ° C. for 2 hours for extraction. After filtering the residue after extraction, the solvent was distilled off under reduced pressure and concentrated to obtain 10.1 g of ACA-containing material. The ACA content was 53%. The ACA extraction efficiency was 5.9%.

(Example 12)
After crushing the dried galangal in the same manner as in Example 11, in the water treatment step, ethanol was added to 300 g of water (three times the weight of the raw material) so that the concentration was 5% by weight, and the mixture was added to 50 ° C. The same procedure as in Example 11 was carried out except that the mixture was heated, immersed for 1 hour and stirred to form a slurry. As a result, the ACA content was 10.5 g, the ACA content was 55%, and the ACA extraction efficiency was 6.4%.

(Example 13)
Instead of using ethanol as the extraction solvent of Example 11, the same procedure as in Example 11 was carried out except that the mixture was changed to ethyl acetate. As a result, the ACA content was 8.2 g, the ACA content was 55%, and the ACA extraction efficiency was 5.0%.

(Example 14)
As a shredding process, a non-dried, that is, raw galangal rhizome 1000 g (absolute dry weight 80 g) is shredded with a crusher "Cutter Mixer 25S" (manufactured by Aikosha Seisakusho Co., Ltd.) to obtain shredded material. rice field.
As a water treatment step, 1000 g of this shredded product and 3000 g of water were mixed, and the obtained mixture was heated to 50 ° C. for 1 hour with stirring to obtain a slurry.
As a solid-liquid separation step, this slurry was squeezed at a pressure of 150 kg / cm ² using "Oil Press KSP-" (manufactured by Shin-Komagata Machinery Mfg. Co., Ltd.) to obtain a solid substance. The solid was further dried with warm air at 50 ° C. for 5 hours to obtain a solid having an absolute dry solid content of 50%.
As an extraction step, 2000 g of ethanol was added to the solid substance, and the mixture was slowly stirred at 65 ° C. for 2 hours for extraction. After filtering the residue after extraction, ethanol was distilled off under reduced pressure to obtain 11.3 g of a concentrated ACA content. The ACA content is 57%,
The ACA extraction efficiency was 8.1%.

(Example 15)
The galangal solid having an absolute dry solid content of 31% obtained in the solid-liquid separation step in Example 1 was further dried under reduced pressure at 60 ° C. for 5 hours to obtain a solid having an absolute dry solid content of 88%. ..
As an extraction step, 2000 g of ethanol was added to the solid substance, and the mixture was slowly stirred at 65 ° C. for 2 hours for extraction. After filtering the residue after extraction, ethanol was distilled off under reduced pressure to obtain 11.5 g of a concentrated ACA content. The ACA content was 59% and the ACA extraction efficiency was 8.5%.

(Comparative Example 1)
As a shredding step, 1000 g (absolute dry weight 80 g) of non-dried (raw) galangal rhizome was crushed using a crusher "Cutter Mixer 25S" (manufactured by Aikosha Seisakusho Co., Ltd.) to obtain shredded products.
The water treatment step and the solid-liquid separation step of Example 1 were omitted, and as an oil-soluble component extraction step, 2000 g of ethanol was added to the shredded product, and the mixture was slowly stirred at 65 ° C. for 2 hours for extraction. After filtering the residue after extraction, the solvent was distilled off under reduced pressure and concentrated to obtain 11.4 g of ACA-containing material. The ACA content was 24% and the ACA extraction efficiency was 3.4%.

(Comparative Example 2)
1000 g of non-dried (raw) galangal rhizome (absolute dry weight 80 g) was crushed using a crusher "Cutter Mixer 25S" (manufactured by Aikosha Seisakusho Co., Ltd.). Grinding gave a mixture of water and shreds contained in Galangal itself.
For the mixture, the water treatment step of Example 1 was omitted, and the same solid-liquid separation step as in Example 1 was carried out, whereby a solid substance was obtained, and 2000 g of ethanol was added to the solid substance as an oil-soluble component extraction step. Extraction was performed by gently stirring at 65 ° C. for 2 hours. The residue after extraction was filtered, and then the solvent was distilled off under reduced pressure to concentrate the residue to obtain 11.9 g of ACA-containing material. The ACA content was 26%. The ACA extraction efficiency was 3.9%.

(Comparative Example 3)
The water treatment step was omitted and the outside was carried out in the same manner as in Example 8. As a result, 7.6 g of ACA-containing material was obtained. The ACA content was 29% and the ACA extraction efficiency was 2.8%.

(Comparative Example 4)
The oil-soluble component extraction step was carried out in the same manner as in Comparative Example 1 except that 3000 mL of water was added under the extraction conditions shown in Table 2 and the mixture was extracted at 90 ° C. for 6 hours. After filtering the residue after extraction, the solvent was distilled off under reduced pressure and concentrated to obtain 5.2 g of a solid substance. ACA was not detected.

(Comparative Example 5)
A shredded galangal was obtained using a crusher "Cutter Mixer 25S" (manufactured by Aikosha Seisakusho Co., Ltd.) using 100 g of dried galangal rhizome (absolute dry weight 90 g) from which some water was removed from the galangal in advance. .. The water treatment step and the squeezing step of Example 11 were omitted, 2000 g of ethanol was added to the shredded product, and the mixture was slowly stirred at 65 ° C. for 2 hours to extract the oil-soluble component. It was carried out in the same manner. After filtering the residue after the oil-soluble component extraction treatment, the solvent was distilled off under reduced pressure and concentrated to obtain 9.2 g of an ACA content. The ACA content was 33%. The ACA extraction efficiency was 3.4%.

(Comparative Example 6)
The same operation as in Comparative Example 5 was carried out except that ethanol was used as the extraction solvent of Comparative Example 5 and was changed to ethyl acetate. As a result, 9.4 g of ACA-containing material was obtained. The ACA content was 28%. The ACA extraction efficiency was 2.9%.

The results of Examples 1 to 15 and Comparative Examples 1 to 6 are shown in Table 2.

表１及び２から明らかなように、本発明の方法を用いれば、従来公知の方法と比較して、高い含有量のＡＣＡ含有物を提供可能で、更に、ＡＣＡ抽出効率が高いため、製造にも適していることが明らかである。また、保存安定性にも優れる。 Regarding the storage stability of the ACA-containing material, 0.1 g of the obtained ACA-containing material was dissolved in 10 ml of a 40% ethanol solution and stored at 60 ° C. for 10 days to examine the progress of coloring.
Regarding the evaluation of "storage stability" in Table 2,
Those with a change in absorbance at 400 nm of less than 5% are marked with a circle.
Those with a change of 5% or more and less than 10% are marked as △.
Those in which a color change of 10% or more was observed were marked with x.
The comprehensive evaluation in Table 2 was based on the following criteria.
Evaluation A: ACA content is 40% or more and storage stability is 〇 Evaluation B: ACA content is 30% or more and less than 40% and storage stability is 〇 Evaluation C: ACA content is less than 30% At the same time, the storage stability is △ or ×, or even if the ACA content exceeds 30%, the storage stability is ×.

As is clear from Tables 1 and 2, by using the method of the present invention, it is possible to provide an ACA-containing material having a higher content than that of a conventionally known method, and further, since the ACA extraction efficiency is high, it is suitable for production. It is clear that is also suitable. It also has excellent storage stability.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an industrial production method for obtaining a high ACA-containing substance containing a large amount of ACA, which is an active ingredient thereof, from galangal, which is a natural product that has been used for food as a spice for soups such as Tom Yum kung for a long time. can. In particular, according to the present invention, it is possible to provide an efficient and inexpensive method for industrially producing a high ACA-containing product with less concern about safety to the human body. Further, the ACA-containing material provided by the present invention has a feature that deterioration of quality is suppressed. Further, the high ACA-containing material provided by the present invention is useful as an additive in the fields of foods and drinks, pharmaceuticals, quasi-drugs, pesticides, cosmetics, feeds, especially health foods.

Claims (4)

(1) Shredding step of shredding galangal to obtain shredded material (2) Water treatment step of adding water to the shredded material to obtain shredded material and a slurry containing water (3) Solidifying the slurry It includes a solid-liquid separation step of liquid separation to obtain a solid substance and a liquid phase containing impurities , and (4) an oil-soluble component extraction step of extracting and separating an oil-soluble component from the solid substance with an organic solvent. A method for producing a 1-acetoxychavicol acetate (ACA) -containing material.
The 1-acetoxychabi according to claim 1, wherein in the (2) water treatment step, the amount of water with respect to the shredded material is 0.1 to 100 times the weight of the shredded material. A method for producing a colacetate (ACA) -containing material. The method for producing a 1-acetoxychabicol acetate (ACA)-containing material according to claim 1 or 2, wherein the solid-liquid separation step includes a pressing means. The method for producing a 1-acetoxychabicol acetate (ACA)-containing material according to any one of claims 1 to 3, wherein the organic solvent is a water-soluble organic solvent.

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