JP2014210721A - Process for producing 1,5-anhydro-d-glucitol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing 1,5-AG (1,5-anhydro-D-glucitol), capable of producing 1,5-AG in high purity, high yield, and high efficiency.SOLUTION: Provided is a process for producing 1,5-anhydro-D-glucitol using plants as raw material, comprising the steps of: (i) obtaining an extract by subjecting the raw material to extraction by water or a water-containing organic solvent; (ii) obtaining a treatment liquid by subjecting the extract to at least one treatment selected from the group consisting of treatment by contact with a synthetic adsorption resin, treatment using a dialysis membrane, and treatment using a reverse osmosis membrane; and (iii) separating a fraction containing 1,5-anhydro-D-glucitol from the obtained treatment liquid by using an ion exchange resin and/or by using an ion exchange membrane.

Description

  The present invention relates to a method for producing 1,5-anhydro-D-glucitol (sometimes abbreviated as “1,5-AG” in the present specification). More specifically, the present invention relates to a method for producing 1,5-AG using a plant as a raw material.

  1,5-AG is a non-reducing sugar in which the 1-position of D-glucose is reduced. Therefore, 1,5-AG is less reactive than reducing sugar and is chemically stable under conditions such as acidic, alkaline, and high temperature. is there. In addition, 1,5-AG is a saccharide that is present in the body next to D-glucose, and has excellent characteristics such as high biocompatibility and no safety problem. Therefore, its use is drawing attention.

  1,5-AG is known to be contained in plants called Onji and Senega, which are known as herbal medicines for herbal medicine. As a report to try to isolate 1,5-AG from these plants, for example, by extracting with alcohol from dry roots of Senega and then fractionating with activated carbon column, arabinose, fructose, sucrose, maltose, It has been reported that 1,5-AG is isolated together with melibiose, manninotriose, raffinose and the like (see Non-Patent Document 1).

  Non-Patent Document 2 discloses a method of isolating 1,5-AG by using amaranth seeds and banana fruits, extracting with trichloroacetic acid, and performing column fractionation with an ion exchange resin. Yes. Non-Patent Document 3 discloses that 1,5-AG can be isolated by silica gel chromatography after extraction with methanol from a Protea plant.

  Onzi and Senega, on the other hand, in addition to 1,5-AG, dementia ameliorating effects such as Alzheimer's syndrome, brain function improvement and treatment, expectoration, bronchitis improvement and treatment, bronchial asthma improvement and treatment, It is also known to contain ondisaponins known to have such actions as sleep prolongation, immunostimulation, anti-stress ulcer, congestive edema suppression, PDE (phosphodiesterase) inhibition, and sedative tonic Yes.

  As a method for obtaining ondisaponin, for example, a raw material plant is extracted with a lower alcohol such as methanol, ethanol, propanol and butanol, an organic solvent such as chloroform, the solvent is distilled off, and the extract is then subjected to silica gel column chromatography. Etc. are disclosed (see Patent Document 1, Non-Patent Documents 4 and 5).

Japanese Patent Laid-Open No. 11-43440

Pharmaceutical Journal, 94 (8), 998-1003, 1974 Biosci. Biotechnol. Biochem., 64 (11), 2462-2465, 2000 Phytochemistry, Vol.22, No.9, 1959-1960, 1983 Chem. Pharm. Bull., 29 (9), 2431-2441, 1981 Chem. Pharm. Bull., 30 (3), 810-821, 1981

  However, the above-mentioned method using an organic solvent for extraction has problems such as a large environmental load and a large number of times of concentration, which requires time, cost and energy. In addition, when performing purification by column chromatography, a large number of eluents are generated, so the number of times of concentration increases, and time, cost, and energy are required.

  In addition, when water is used alone as the extraction solvent, since the extract contains a large amount of saponins, when general vacuum concentration is performed, foaming becomes intense and concentration is difficult. Therefore, it is necessary to take measures such as normal pressure concentration, concentration under weak reduced pressure, reduced pressure concentration after adding a defoaming agent, or freeze drying. However, when these measures are taken, there are problems such as decomposition and coloring of components due to longer working time, addition of a defoaming agent removing step, and lowering of working efficiency.

  An object of the present invention is to provide a method for producing 1,5-AG, which is capable of producing 1,5-AG with high purity, high yield and high efficiency.

The present invention relates to the following [1] to [2].
[1] A method for producing 1,5-anhydro-D-glucitol from plant,
(I) A step of subjecting the raw material to extraction with water or a water-containing organic solvent to obtain an extract,
(Ii) The extract is subjected to at least one treatment selected from the group consisting of a contact treatment with a synthetic adsorption resin, a treatment using a dialysis membrane, and a treatment using a reverse osmosis membrane to obtain a treatment liquid. And (iii) a step of separating a fraction containing 1,5-anhydro-D-glucitol from the obtained treatment liquid using an ion exchange resin and / or using an ion exchange membrane,
A process for producing 1,5-anhydro-D-glucitol, comprising:
[2] After the step (ii) in the production method according to the above [1], when a contact treatment with a synthetic adsorption resin is performed, a desorption treatment of ondisaponins from the resin is performed or a dialysis membrane is used. On-saponin is collected by at least one method that collects the dialysis internal solution when the treatment is performed, or collects the reverse osmosis membrane non-permeate when the treatment using the reverse osmosis membrane is performed. The manufacturing method of the ondisaponins containing composition which obtains a containing composition.

  The method for producing 1,5-AG of the present invention has an excellent effect that 1,5-AG can be produced with high purity, high yield and high efficiency. In the production method, ondisaponins can also be obtained from components other than 1,5-AG contained in the 1,5-AG extract.

The method for producing 1,5-AG of the present invention uses a plant as a raw material,
(I) A step of subjecting the raw material to extraction with water or a water-containing organic solvent to obtain an extract,
(Ii) The extract is subjected to at least one treatment selected from the group consisting of a contact treatment with a synthetic adsorption resin, a treatment using a dialysis membrane, and a treatment using a reverse osmosis membrane to obtain a treatment liquid. And (iii) a step of separating a fraction containing 1,5-anhydro-D-glucitol from the obtained treatment liquid using an ion exchange resin and / or using an ion exchange membrane,
including. By such a method, 1,5-AG can be produced with high purity, high yield and high efficiency.

  The present invention is characterized in that a specific treatment is performed on the extract of step (i) in step (ii). In step (i), water or a water-containing organic solvent is used for extraction, so that the obtained extract contains other saccharides (monosaccharides, oligosaccharides), glycosides (ondisaponins) in addition to 1,5-AG. Etc.), fat-soluble components, ionic substances (salts), and highly polar organic substances (amino acids and the like). In the step (ii), a fraction containing mainly a fat-soluble component and ondisaponins is separated from the extract by a separation treatment using a synthetic adsorption resin, a dialysis membrane, and / or a reverse osmosis membrane. -Separation into fractions containing AG and other sugars, ionic substances, and highly polar organics. In the present invention, other saccharides are glucose, fructose, sucrose, maltose and the like, glycosides are ondisaponins, senegin and the like, and fat-soluble components are gaurterin, 3,4,5- Trimethoxycinnamic acid and the like, the ionic substance means salts such as calcium carbonate, and the highly polar organic substance means amino acids such as arginine.

  For example, when the extract is brought into contact with a synthetic adsorption resin, fat-soluble components and glycosides are adsorbed on the synthetic adsorption resin and can be easily removed by filtration or the like. The containing fraction is collected as a filtrate. In addition, since a pigment | dye is also adsorb | sucked by synthetic adsorption resin, decoloring can also be performed.

  In addition, when the extract is treated with a dialysis membrane or reverse osmosis membrane having an appropriate fractional molecular weight or pore size, fat-soluble components and glycosides having a large molecular structure cannot pass through the dialysis membrane, Since 1,5-AG has a molecular size of about 0.6 nm, it can pass through with ionic substances, amino acids, etc., so it is possible to pass dialysis internal solution and dialysis external solution, or reverse osmosis membrane nonpermeate and reverse osmosis membrane permeate. Separation is easy.

  The treatment may be performed alone or in combination, and since the obtained treatment liquid does not contain ondisaponin, concentration under reduced pressure is also possible at this stage.

  Further, the present invention is characterized in that the treatment liquid in step (ii) is contacted with an ion exchange resin and / or treated with an ion exchange membrane. In other words, in the present invention, since the fat-soluble components and glycosides have already been removed from the treatment liquid used in step (iii), an ion exchange resin and / or an ion exchange membrane is used in step (iii). Thus, amino acids and other ionic substances can be removed.

  In the present specification, “yield” means a part by weight of 1,5-AG obtained by the operation of the present invention when the weight of a plant as a raw material is 100 parts by weight, and “recovery rate” "Means parts by weight of 1,5-AG obtained by the operation of the present invention when the amount of 1,5-AG contained in the plant as a raw material is 100 parts by weight.

<Process (i)>
In step (i), the raw material is subjected to extraction with water or a water-containing organic solvent to obtain an extract.

In the present invention, a plant is used as a raw material. The plant used in the present invention is not particularly limited as long as it contains 1,5-AG. Examples thereof include plants belonging to the family Polygalaceae , plants belonging to the bean ( Fabaceae ) family, plants belonging to the Proteaceae family, and the like.

As plants belonging to Polygala (Polygalaceae) family, include plants belonging to Polygala (Polygala) genus, Polygala (P.japonica) species, luchuensis Polygala (P.longifolia) species, scintigraphy click Polygala (P.polifolia) species , Kakinohagusa (P.reinii) species, Hinano Kin Chak (P.tatarinowii) species, Harihimehagi (P.ambigua) species, Kobanahimehagi (P.paniculata) species, hairpin Polygala (P.sanguinea) species, Senegal (P.senega) species , Oohimehagi (P.sibirica) species, Ihitomehagi (P.tenuifolia) species, preferably car bar Polygala (P.verticillata) species, Polygala tenuifolia (P. tenuifolia) species and Senegal (P. senega) species are more preferred. Specifically, Itohimehagi, Senega, Hiroha Senega are exemplified.

Examples of the plant belonging to the family of bean ( Fabaceae ) include plants belonging to the genus Soybean ( Glycine ), soy bean ( G.max ) species, and sour bean ( G.soja ) species are preferable, and soy bean and sour bean are exemplified.

Yamamogashi Examples of the plant belonging to the (Proteaceae) family, Protea (Protea) include plants belonging to the genus, King Protea (P.cynaroides) species, Peach Protea (P.grandiceps) species, blond leaf Sugarbush (P.eximia) Species, Southern Cross Protea ( P. obtusifolia xmagnifica ) Species, Oleander Leaf Protea ( P. neriiforia ) Species, Common Sugar Bush ( P. repens ) Species, Protea Aurea ( P. aurea) Species, Protea Compactor ( P. compacta) Species are preferred, and examples include king protea, blond leaf sugar bush, and repens.

  As these plants, the living body of the plant itself may be used, but parts such as leaves, fruits, seeds and roots may be selected and used. For example, it is preferable to use Itohimehagi root, Senega root, and Hirosanega root as raw materials.

  In addition, about the plant used as a raw material, the growth period, freshness, completeness of a plant body, etc. are not specifically limited. As the growing period, the germination period is preferred because the 1,5-AG content in the plant is high.

  The plant as a raw material may be subjected to extraction as it is, or may be used after chopping, pulverizing, etc. to an appropriate size. Moreover, although a plant may be used raw, the dried thing may be used and the juice from a plant may be used as a raw material.

  In the present invention, water or a water-containing organic solvent is used as the extraction solvent.

  There is no limitation in particular as water used for extraction, A tap water, distilled water, ion-exchange water, an ultrapure water etc. are mentioned. Although pH of water is not specifically limited, About 4-8 is preferable. To adjust the pH, for example, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen carbonate, carbon sodium, aqueous ammonia, potassium carbonate, sodium hydroxide, potassium hydroxide, or the like may be used.

  Further, the organic solvent in the water-containing organic solvent is not particularly limited, but a polar organic solvent is preferable from the viewpoint of extraction efficiency. Examples of the polar organic solvent include methanol, ethanol, propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, 2,2-dimethylethanol, 1-pentanol, 2-pentanol, 3-pentanol, 2- Lower alcohols having 1 to 5 carbon atoms such as methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol; Lower aliphatic ketones such as acetone and methyl ethyl ketone; polyhydric alcohols having 2 to 5 carbon atoms such as 1,3-butylene glycol, propylene glycol and glycerin; ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monopropyl ether Glycol ethers such as ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol diethyl ether, propylene glycol monoethyl ether; glycols such as ethylene glycol diacetyl ester, ethylene glycol monoacetyl ester, propylene glycol diacetyl ester, propylene glycol monoacetyl ester Esters; cyclic ethers such as furan, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, etc. Examples thereof include amide compounds. Of these, methanol and ethanol are preferable from the viewpoints of safety and price.

  The water in the water-containing organic solvent is the same as the water used when extracting with water alone, and the above-mentioned ones can be used.

  The amount of the organic solvent in the water-containing organic solvent is preferably 30 v / v% or less from the viewpoint of the adsorption efficiency of the fat-soluble substance and glycoside to the synthetic adsorption resin, the resistance of the dialysis membrane and the reverse osmosis membrane to the organic solvent, and the like. 20v / v% or less is more preferable, and 10v / v% or less is more preferable. The lower limit is not particularly limited.

  The extraction operation is performed, for example, by putting the raw material into a treatment tank filled with the extraction solvent, and preferably eluting soluble components with stirring. The amount of raw material and extraction solvent used for the extraction process can be adjusted as appropriate according to the extraction conditions (equipment scale and processing capacity) and cannot be determined in general. For example, when water is used as the extraction solvent The extraction is usually performed with 300 to 1000 parts by weight of water with respect to 100 parts by weight of the total amount of raw materials. Moreover, when hydrous alcohol is used as an extraction solvent, extraction is usually performed with 300 to 1000 parts by weight of hydrous alcohol with respect to 100 parts by weight of the total amount of raw materials.

  The extraction is performed within the range from room temperature to a temperature near the boiling point of the extraction solvent. For example, when water is used as the extraction solvent, the reaction is preferably performed at 80 to 100 ° C, more preferably 85 to 100 ° C for about 1 to 2 hours. When hydrous alcohol is used as the extraction solvent, it is preferably performed at 70 to 100 ° C. for about 1 to 2 hours. The pressure at the time of extraction is not particularly limited, and may be normal pressure (101.3 kPa) or under pressure and / or under reduced pressure.

  After the extraction, the extract is removed by filtration to obtain an extract (also referred to as an extract). The resulting extract may be concentrated according to known methods if desired. As a filter used for filtration, filter paper made of cellulose, glass fiber, polyethylene resin, polypropylene resin, cloth, or the like can be used, and the shape thereof is not particularly limited. A tube type, a flat plate type, etc. are mentioned. Examples of these include qualitative filter paper manufactured by Advantech Toyo Co., Ltd. and membrane filter manufactured by Nihon Millipore Co., Ltd. The material, shape, and manufacturer of the filter paper are not particularly limited as long as they do not hinder the implementation of the present invention.

  In the present invention, extraction work using a water-insoluble organic solvent can be performed before, during and / or after step (i) from the viewpoint of improving work efficiency in step (ii). The fat-soluble component can be removed in advance by extraction with this water-insoluble organic solvent, and as a result, the amount of the synthetic adsorption resin, dialysis membrane, and reverse osmosis membrane used in step (ii) can be suppressed. Specifically, for example, before the step (i), a raw material to be extracted with water or a water-containing organic solvent is subjected to extraction with a water-insoluble organic solvent. Thereafter, the residue is subjected to extraction with water or a water-containing organic solvent. When extraction with a water-insoluble organic solvent is performed during and / or after step (i), extraction in step (i) is preferably extraction with water. In addition, the extraction method can be performed according to a known method, and extraction is usually performed with 300 to 1000 parts by weight of a water-insoluble organic solvent with respect to 100 parts by weight of the total amount of raw materials used for extraction with water or a water-containing organic solvent.

  Non-water-soluble organic solvents include halogen-based solvents such as chloroform and chlorobenzene, ester-based solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, toluene from the viewpoint of extraction efficiency of fat-soluble components, versatility, market distribution, etc. And aromatic solvents such as xylene and mesitylene, higher alcohols such as heptanol and octanol, and aliphatic solvents such as pentane, hexane and octane.

  The extraction operation may be repeated as desired. For example, an extraction solvent may be added to the extraction residue, an extraction operation may be performed under the above-described conditions, and the resulting extract may be combined into one and used for the next step. As a typical example, when dried onji root is used as a raw material and water is used as an extraction solvent, 1,5-AG eluted in the extract is approximately 8.5% in the first extraction and the second in the extraction. The yield is 0.9% for extraction and 0.2% for the third extraction. The number of extraction operations is preferably 2 to 4 times because the extract can be obtained in high yield.

  Also, from the viewpoint of reducing the amount of synthetic adsorption resin used in step (ii), shortening the service life due to clogging of dialysis membranes and reverse osmosis membranes, and shortening each processing time, the extract is filtered immediately before mixing with the synthetic adsorption resin. And it is preferable to use for process (ii). If desired, the extract may be cooled prior to filtration.

  The extract thus obtained is subjected to step (ii).

<Step (ii)>
In step (ii), the extract obtained in step (i) is contacted with a synthetic adsorption resin (processing A), processing using a dialysis membrane (processing B), and processing using a reverse osmosis membrane. (Process C), one or more processes selected from the group consisting of are performed to obtain a process liquid. That is, in step (ii), the above-mentioned treatment is performed to collect a fraction containing 1,5-AG, an ionic substance, and a highly polar organic substance.

  In the process A, specifically, the extract obtained in the step (i) and the synthetic adsorption resin are mixed, the mixture is filtered to obtain a filtrate, and the extract obtained in the step (i) is synthesized. An embodiment in which a filtrate is obtained by passing through a column filled with an adsorbent resin can be mentioned.

The synthetic adsorption resin used in the present invention is not particularly limited, and for example, crosslinked polymer particles having a porous structure with a specific surface area of about 300 to about 1500 m ² / g are used. Examples of the crosslinked polymer include styrene-based polymers, acrylic polymers, methacrylic polymers, and the like. Specifically, HP resins such as Diaion (registered trademark) HP20SS, HP20, and HP21, Sepapies (registered trademark). ) Styrene-divinylbenzene resins such as SP resins such as SP825L, SP850, and SP700 (above, manufactured by Mitsubishi Chemical Corporation), Amberlite (registered trademark) XAD-2000, XAD-4, etc. (above, manufactured by Organo); Examples thereof include acrylic resins such as Diaion (registered trademark) HP2MG (manufactured by Mitsubishi Chemical Corporation) and Amberlite (registered trademark) XAD-7HP (manufactured by Organo Corporation).

  The column packed with the synthetic adsorption resin is not particularly limited, and can be appropriately selected and used according to the technical common knowledge of those skilled in the art.

  The amount of the synthetic adsorption resin used when mixing with the extract of step (i) is not generally determined by the purity of the extract, but for example, in terms of dry resin weight, 100 parts by weight of the raw material, Usually, it is 10 to 2000 parts by weight.

  For the mixing of the extract and the synthetic adsorption resin, for example, the extract and the synthetic adsorption resin are put into a treatment tank having a stirring device, and are preferably mixed at 15 to 40 ° C. The mixing time is not generally determined. It should be noted that the extraction and the synthetic adsorption resin may be charged into the treatment tank as long as the mixing can be performed in a batch manner, or may be performed simultaneously or separately, and may be performed collectively or dividedly.

  Next, the mixture of the extract and the synthetic adsorption resin is filtered to separate the filtrate. As the filtration filter, the same filter as used in step (i) can be used.

  In addition, the amount used when the column is filled with the synthetic adsorption resin is not generally determined depending on the capacity of the column to be used. For example, in terms of dry resin weight, 10 to 2000 parts by weight. The liquid passing through the column may be single time or multiple times.

  The obtained filtrate may be concentrated according to a known method if desired.

  In the treatment B, specifically, the extract obtained in the step (i) is applied to a dialysis membrane to remove a component that does not permeate the dialysis membrane (dialysis internal solution) to obtain an external dialysis solution.

  The dialysis membrane used in the present invention is not particularly limited, and a cellulose membrane or a synthetic polymer membrane is used. Examples of the cellulose film include a regenerated cellulose film, a surface-modified regenerated cellulose film, and a cellulose acetate film. Examples of the regenerated cellulose film include a cupra ammonium rayon film and a saponified cellulose film. Examples of the surface-modified regenerated cellulose membrane include a PC membrane (Polyethylene glycol grafted membrane) and a vitamin E coating membrane. Examples of the cellulose acetate film include a cellulose diacetate film and a cellulose triacetate film. Examples of the synthetic polymer film include a polyacrylonitrile film, a polymethyl methacrylate film, an ethylene vinyl alcohol copolymer film, a polysulfone film, a polyamide film, and a polyester polymer alloy film.

  Examples of the shape of the dialysis membrane include tubular, hollow fiber, spiral, disk, sheet, pleat and the like, and are not particularly limited.

The effective surface area of the dialysis membrane is not generally determined by the amount of components in the extract, the dialysis speed, the processing temperature, etc., but when considering the processing time and decomposition of components other than 1,5-AG, for example, dry onji root Preferably it is 0.2-10 m < ² > with respect to 100 g, More preferably, it is 0.5-7 m < ² >, More preferably, it is 0.8-5 m < ² >.

  The molecular weight cut off of the dialysis membrane is not particularly limited as long as the present invention can be suitably carried out, and is not generally determined depending on the amount of components in the extract. For example, about 300 to 1000D is usually preferable.

  Examples of suitable commercially available products include Spectra / Por (registered trademark) Float-A-Lyzer, Tube-A-Lyzer, Dialysis tube, 6 Dialysing tube, 7 Dialyzing tube (manufactured by Spectrum Laboratories).

  In the dialysis treatment, for example, a dialysis treatment is performed using a liquid to be treated as a dialysis inner solution of a hollow fiber type dialyzer or a dialysis membrane and purified water as an outer dialysis solution. The dialysis temperature is not particularly limited as long as it does not affect the performance of the dialysis membrane and the dialysis machine, but it is preferably 5 to 60 ° C and 10 to 50 ° C in consideration of decomposition and coloring of components other than 1,5-AG. More preferred is 20 to 45 ° C. The dialysis time can be determined according to a known technique according to the type of dialysis membrane to be used, the molecular weight cut off, the concentration of the liquid to be dialyzed, the processing temperature, and the like.

  The obtained dialysis external solution may be concentrated according to a known method if desired.

  In the treatment C, specifically, the extract obtained in the step (i) is subjected to a reverse osmosis membrane to remove components that do not permeate the reverse osmosis membrane (reverse osmosis membrane non-permeate), and the reverse osmosis membrane A permeate is obtained. The reverse osmosis membrane in the present invention includes so-called reverse osmosis membranes and NF membranes (Nanofiltration membranes, nanofilters).

  The reverse osmosis membrane used in the present invention is not particularly limited, and is a cellulose acetate membrane, a sulfonated polyethersulfone membrane, a polyvinyl alcohol membrane, an aromatic polyamide membrane, a polysulfone membrane, a polytetraphthalate ester (PTFE). ) System membranes and composite membranes thereof are used. Further, the pore diameter and the molecular weight cut off are not particularly limited as long as the present invention can be carried out. However, considering the steric size, molecular weight and the like of the separation component, the pore diameter is 8 to 10 nm. Preferably, the molecular weight cutoff is about 2000D.

  Examples of the shape of the reverse osmosis membrane include a flat membrane type, a hollow fiber type, a spiral type, and a tube type, and are not particularly limited.

The effective surface area of the reverse osmosis membrane is not generally determined by the type of membrane used, the pore size, the molecular weight cut off, the number of pores per unit area, the processing temperature, the amount of insoluble particles, etc., but the processing time and 1,5 In consideration of decomposition of components other than -AG, for example, it is usually 20 to 5,000 cm ² for 100 g of dried onji root.

  Examples of suitable commercial products include NTR-7410, NTR-7450, NTR-7250, NTR-729HF, NTR-759HR, ES-20, LES-90 (manufactured by Nitto Denko Corporation) and the like.

  The reverse osmosis membrane treatment can be performed, for example, by passing a liquid to be treated through a hollow fiber type reverse osmosis membrane. The treatment temperature is not generally determined by the type of membrane used, pore size, fractional molecular weight, number of pores per unit area, treatment temperature, insoluble matter amount, etc. -60 degreeC is preferable, 10-50 degreeC is more preferable, and 20-45 degreeC is further more preferable. The treatment pressure is not determined unconditionally depending on the pore diameter of the reverse osmosis membrane to be used, the number of pores per unit area, the treatment temperature, the amount of insoluble particles, etc., and is used within the range where the performance of the membrane to be used can be exhibited. The treatment time cannot be generally determined by the pore size of the reverse osmosis membrane to be used, the number of pores per unit area, the treatment temperature, the amount of insoluble matter, and the like.

  The obtained reverse osmosis membrane permeate may be concentrated according to a known method if desired.

  In step (ii), processing A, processing B, and processing C may be appropriately selected and combined, and any order may be used first.

  The treated product thus obtained is subjected to step (iii).

<Step (iii)>
In step (iii), a fraction containing 1,5-anhydro-D-glucitol and other components (ions) from the treatment liquid obtained in step (ii) using an ion exchange resin and / or an ion exchange membrane. Active substances and highly polar components). Depending on the plant material used, the fraction containing 1,5-anhydro-D-glucitol includes monosaccharides such as glucose and fructose and oligosaccharides such as sucrose and maltose in addition to 1,5-AG. May be included.

  Specifically, the ion exchange resin is contacted with the treatment liquid obtained in step (ii) and filtered (the aspect 1) and the treatment liquid obtained in step (ii) is treated using an ion exchange membrane. Aspect (Aspect 2) may be mentioned.

  In Embodiment 1, the fraction containing 1,5-AG and the other components (ionic substance, highly polar component, etc.) are separated by the difference in adsorptivity to the ion exchange resin. More specifically, the treatment liquid obtained in step (ii) is mixed with an ion exchange resin, and the mixture is filtered to obtain a filtrate, and the treatment liquid obtained in step (ii) is filled with an ion exchange resin. An embodiment in which a filtrate containing a fraction containing 1,5-AG is obtained by passing through a column can be mentioned.

  As an ion exchange resin used in the present invention, it exhibits high adsorption ability for components other than 1,5-AG contained in the treatment liquid, but is substantially non-adsorbable for 1,5-AG. An adsorbent is preferred. Specific examples include cation exchange resins and anion exchange resins.

  Examples of the cation exchange resin include strong acid cation exchange resins and weak acid cation exchange resins, such as styrene-divinylbenzene crosslinked polymers containing sulfonic acid groups or carboxyl groups as ion exchange groups. It is done.

  Examples of the anion exchange resin include strongly basic anion exchange resins and weakly basic anion exchange resins. For example, a styrene-divinylbenzene crosslinked polymer containing a dimethylamino group or a monomethyl group as an ion exchange group. Is mentioned.

  These resins can be used alone or in combination of two or more. Also, a both ion exchange resin having both a cation portion and an anion portion in one resin can be used.

  The shape of the ion exchange resin is not particularly limited, and examples thereof include a gel type and a porous type. Further, the particle size of the ion exchange resin and the degree of crosslinking are not limited.

  Examples of suitable commercially available ion exchange resins used in the present invention include gel-type strongly acidic cation exchange resins such as Diaion (registered trademark) SK104, SK110, SK112, Diaion (registered trademark) PK208, PK212, PK216, Porous type strongly acidic cation exchange resins such as PK218, PK220, PK228, gel type uniform particle size strongly acidic cation exchange resins such as Diaion (registered trademark) UBK08, UBK10, UBK12; Diaion (registered trademark) SA10A, SA12 Gel I type strongly basic anion exchange resin such as NSA100, Gel II type strongly basic anion exchange resin such as Diaion (registered trademark) SA20A, SA21A, Diaion (registered trademark) PA306S, PA308, PA312, PA316 , PA318L and other porous type I strongly basic Anion exchange resin, Acrylic weakly basic anion exchange resin such as Diaion (registered trademark) WA10, Styrene polyamine type weakly basic anion exchange resin such as Diaion (registered trademark) WA20, WA21J, Diaion ( (Registered trademark) WA30 and other styrenic dimethylamine type weakly basic anion exchange resins, Diaion (registered trademark) AMP03 and other amphoteric ion exchange resins (above, manufactured by Mitsubishi Chemical Corporation); Dowex (registered trademark) 50W × 8, etc. Strongly basic cation exchange resin such as Dowex (registered trademark) 1 × 2, 1 × 4, 1 × 8 (made by Dow Chemical Co.); Amberlite (registered trademark) IR120B, IR124 Strongly basic cation exchange resins such as Amberlite (registered trademark) IRA400J, IRA411, etc. (Above, manufactured by Organo Co., Ltd.) and the like.

  The column packed with the ion exchange resin is not particularly limited, and can be appropriately selected and used according to common technical knowledge of those skilled in the art.

  The amount used when mixing the ion exchange resin with the treatment liquid is not generally determined by the impurity content in the filtrate obtained in step (ii), but for example, 100 weight of raw material in terms of dry resin weight The amount is usually 10 to 2000 parts by weight with respect to parts.

  For the mixing of the treatment liquid obtained in the step (ii) and the ion exchange resin, for example, the treatment liquid and the ion exchange resin are introduced into a treatment tank having a stirring device, and are preferably mixed at 10 to 40 ° C. The mixing time is not generally determined. The treatment liquid obtained in step (ii) and the ion exchange resin may be charged into the treatment tank at the same time or separately as long as the mixing can be performed batchwise. It may be input or split input.

  In addition, the amount used when the ion-exchange resin is packed in a column is not generally determined by the capacity of the column to be used, but for example, in terms of dry resin weight, 10 to 2000 parts by weight. The liquid passing through the column may be single time or multiple times.

  In the aspect 2, the fraction containing 1,5-AG and the other components (ionic substance, highly polar component, etc.) are separated by the difference in permeability to the ion exchange membrane. More specifically, the treatment liquid obtained in step (ii) is subjected to treatment such as dialysis using an ion exchange membrane.

  As an ion exchange membrane used in the present invention, it is possible to selectively permeate or remain ionic substances (salts) and highly polar organic substances (amino acids, etc.) contained in the treatment liquid to separate them from the target substance. Therefore, any material can be used as long as it can separate and collect the fraction containing 1,5-AG by collecting the permeate or non-permeate. Specific examples include a cation exchange membrane and an anion exchange membrane.

  The cation exchange membrane does not permeate anionic substances and neutral lysates in the solution, and allows only small cations and hydrogen ions to permeate. For example, a cation exchange membrane having a cation exchange group such as a sulfone group, a carboxyl group, a phosphonic acid group, a sulfuric acid ester group, and a phosphoric acid ester group can be mentioned. Of these, a sulfonic acid group and a carboxyl group are preferable.

  The anion exchange membrane does not permeate cationic substances and neutral lysates in the solution, but permeates small anions. For example, an anion exchange membrane having an anion exchange group such as primary amino group, secondary amino group, tertiary amino group, and quaternary amino group can be mentioned. Of these, a quaternary amino group is preferred.

  Examples of suitable commercially available ion exchange membranes used in the present invention include cation exchange membranes such as Selemion (registered trademark) CMW, CDM, HSF, CSO, CMF, Selemion (registered trademark) AMV, AMT, DSV, AAV, Anion exchange membranes such as ASV, AHO, APS4 (made by Asahi Glass Co., Ltd.); Cation exchange membranes such as Neoceptor (registered trademark) CMX, AMX, Neoceptor (registered trademark) CIMS, CMB, AHA, ACM, ACS, Anion exchange membranes such as AFN and AFX (above, manufactured by Tokuyama Corporation) can be mentioned.

The effective surface area of the ion exchange membrane is not particularly limited as long as the present invention can be suitably carried out, and is necessary for processing depending on the composition and concentration of separation components in the processing stock solution, pH, and performance of the ion exchange membrane used. Although the time and the like vary, for example, it is usually 200 to 10,000 cm ² with respect to 100 g of dried onji root.

  In the present invention, electrodialysis is preferably performed using the ion exchange membrane. In addition, as an electrodialysis apparatus, a well-known thing can be used and there is no limitation in particular.

  Thus, a fraction containing 1,5-AG can be selectively separated from the treatment liquid obtained in step (ii). The obtained treatment liquid may be concentrated according to a known method if desired.

  In addition, in process (iii), you may carry out combining the aspect 1 and the aspect 2, and the order may be any first.

  If the resulting fraction containing 1,5-AG contains monosaccharides or oligosaccharides in addition to 1,5-AG, a further purification step is carried out to obtain only 1,5-AG. Can be separated.

  Purification methods include, for example, a method in which a fraction containing 1,5-AG is concentrated and / or cooled and crystallized, or a fraction containing 1,5-AG is insoluble or difficult. A method of adding a soluble solvent (for example, 2-propanol, 1,4-dioxane, tetrahydrofuran, etc.) to crystallize, adding yeast such as baker's yeast or brewer's yeast, and monosaccharides other than 1,5-AG and A method of separating 1,5-AG by decomposing oligosaccharides into alcohol, carbon dioxide and the like can be mentioned.

  As a crystallization method, for example, a fraction containing 1,5-AG is concentrated until the concentration of 1,5-AG is about 60 to 85% (w / v), and the temperature is raised to 65 to 75 ° C. once. Then, a method of crystallizing by slowly cooling to 5 ° C. over 8 hours can be mentioned.

  Moreover, when refine | purifying by adding yeast, as yeast used, commercially available baker's yeast, beer yeast, etc. can be used, for example. Examples of the strain include those belonging to the genus Saccharomyces, the genus Saccharomycodes, and the genus Schizosaccaromyces. Specific examples include Saccharomyces cerevisiae, Saccharomyces pastorianus, Saccharomyces carlsbergensis, and Saccharomyces diastaticus.

  The yeast reaction may be anaerobic or aerobic. Moreover, reaction temperature should just be a range with the activity of yeast, However About 30-40 degreeC is preferable. The pH of the reaction solution is not particularly limited as long as the yeast activity is maintained within a certain level, and is preferably pH 5.5 to 8.0, more preferably pH 5.8 to 6.5.

  The method for removing the yeast after the reaction is not particularly limited, and may be adsorption removal with activated carbon or centrifugation, or a combination of adsorption removal with activated carbon and centrifugation.

  The amount of yeast used is not particularly limited. Usually, it is 5-50 weight part with respect to 100 weight part of raw materials.

  In addition, since the said refinement | purification process removes saccharides (monosaccharide and oligosaccharide) other than 1,5-AG in a raw material plant, between process (i) and process (ii), process (ii) and process (iii) ) May be performed at any stage after step (iii). By performing such purification, the content ratio of 1,5-AG in the obtained fraction is increased, and a purity of preferably 60% or more, more preferably 80% or more is obtained.

  Thus, according to the method of the present invention, 1,5-AG can be produced with high purity, high yield and high efficiency.

  In the present invention, step (ii) and step (iii) can be performed simultaneously from the viewpoint of improving work efficiency. Specifically, for example, a synthetic adsorption resin and an ion exchange resin are added to and mixed with the extract obtained in the step (i), and the obtained mixture is filtered to obtain a filtrate. 5-AG can be obtained by concentration under reduced pressure.

  Further, from the same viewpoint, step (i), step (ii) and step (iii) can be performed simultaneously. Specifically, for example, a raw material plant, a synthetic adsorption resin, and an ion exchange resin are added to water or a water-containing organic solvent and mixed, and after performing an extraction operation, the resulting mixture is filtered to obtain a filtrate. After acquisition, 1,5-AG can be obtained by concentration and crystallization of the filtrate.

  In the production method of the present invention, for example, when dried onji root is used as a raw material, the yield is preferably 5% or more, more preferably 7% or more, and even more preferably 9% or more. is there. The content of 1,5-AG in the roots of dried onji is approximately 12%, although it varies depending on the cultivation method, production area, harvest time, weather during the cultivation period, preservation method, drying method, and the like. Therefore, according to the production method of the present invention, the recovery rate of 1,5-AG in the plant is preferably 40% or more, more preferably 60% or more, and further preferably 75% or more.

  1,5-AG thus obtained has high biocompatibility, has no problem in safety, and has an excellent property that it does not accumulate in the living body. It can be used as a postprandial hyperglycemia inhibitor, a postprandial hyperlipidemia preventive agent, a glycogenolytic enzyme inhibitor, a sweetener, an osmotic pressure regulator, an anti-cariogenic agent and the like.

  Further, in the method for producing 1,5-AG of the present invention, for example, when the extract is brought into contact with the synthetic adsorption resin in the treatment A, ondisaponin or a fat-soluble substance is adsorbed on the synthetic adsorption resin. Further, when dialysis treatment is performed in the treatment B, ondisaponin, a fat-soluble substance, and the like are present in the dialysis internal solution. When the reverse osmosis membrane treatment is performed in the treatment C, ondisaponins and fat-soluble substances are present in the reverse osmosis membrane non-permeate. Ondisaponin can also be obtained by treating this synthetic adsorbent resin with an organic solvent, or collecting the dialysis internal solution and reverse osmosis membrane non-permeate. Therefore, as another embodiment of the present invention, a method for producing an ondisaponin-containing composition can also be provided. Since ondisaponin is also difficult to synthesize like 1,5-AG, a highly efficient production method of those compounds that can be provided by the present invention is very useful.

  The ondisaponin-containing composition is present in the form adsorbed on the synthetic adsorption resin after step (ii) in the method for producing 1,5-AG, or in the dialysis internal solution or reverse osmosis membrane non-permeate.

  For example, such a synthetic adsorption resin and, for example, an organic solvent capable of dissolving ondisaponin can be mixed to elute ondisaponins from the synthetic adsorption resin into the solvent. If the synthetic adsorption resin is packed in an arbitrary column, ondisaponins can be separated by a liquid chromatography technique using the solvent as a mobile phase. The target ondisaponin-containing composition can be obtained by appropriately removing the solvent.

  Examples of organic solvents that can dissolve ondisaponin adsorbed on the synthetic adsorption resin include polar organic solvents such as methanol, ethanol, propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, and 2,2-dimethylethanol. 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2, Lower alcohols having 1 to 5 carbon atoms such as 2-dimethyl-1-propanol; Lower aliphatic ketones such as acetone and methyl ethyl ketone; Polyhydric alcohols having 2 to 5 carbon atoms such as 1,3-butylene glycol, propylene glycol and glycerin Ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol diethyl ether Glycol glycol such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol diethyl ether, propylene glycol monoethyl ether; ethylene glycol diacetyl ester, ethylene glycol monoacetyl ester, propylene Glycol esters such as glycol diacetyl ester and propylene glycol monoacetyl ester; Cyclic ethers such as furan, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane; N-methylpyrrolidone, N, N And amide compounds such as dimethylformamide and N, N-dimethylacetamide. Of these, methanol and ethanol are preferable from the viewpoints of safety and price.

  Moreover, the target ondisaponin-containing composition can be obtained by collecting the dialysis internal solution and the reverse osmosis membrane non-permeate as they are.

  For example, ondisaponin such as butanol can be dissolved in the collected dialysis inner solution or reverse osmosis membrane non-permeate, and a certain amount or more is used for the dialysis inner solution or reverse osmosis membrane non-permeate. Thus, an organic solvent that can be separated from the aqueous phase is mixed, and an extraction / separation operation is further performed according to a known method, whereby a highly pure ondisaponin-containing composition can be obtained in the organic solvent phase.

  Examples of organic solvents that can extract ondisaponin from dialysis internal fluid and reverse osmosis membrane non-permeate include 1-butanol, 2-butanol, 2,2-dimethylethanol, 1-pentanol, 2-pentanol, Carbon number such as 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol Examples include 4 to 5 lower alcohols. Among these, 1-butanol is preferable from the viewpoints of safety, price, and the like.

  In addition, the organic solvent solution of the obtained ondisaponin-containing composition was concentrated to remove most or all of the organic solvent, and then the resulting residue was mixed with water to obtain an aqueous solution. By concentrating the aqueous phase obtained by washing with a relatively low-polarity water-insoluble organic solvent, an ondisaponin-containing composition with higher purity can be obtained.

That is, as another aspect of the present invention,
A method for producing an ondisaponin-containing composition using a plant as a raw material,
(I) A step of subjecting the raw material to extraction with water or a water-containing organic solvent to obtain an extract,
(Ii) The extract is subjected to one or more treatments selected from the group consisting of contact treatment with a synthetic adsorption resin, treatment using a dialysis membrane, and treatment using a reverse osmosis membrane, and then synthetic adsorption. When the contact treatment with the resin is performed, the desorption treatment of ondisaponins from the resin is performed, or when the treatment using the dialysis membrane is performed, the dialysis internal solution is recovered, or the reverse osmosis membrane A step of obtaining an ondisaponin-containing composition by at least one method of collecting a reverse osmosis membrane non-permeate when the treatment using
A method for producing an ondisaponin-containing composition is provided. The raw materials used, solvent, implementation conditions, and preferred embodiments may be the same as those in the method for producing 1,5-AG. The desorption treatment of ondisaponins from the synthetic adsorption resin may be performed according to a known method using the organic solvent. If necessary, extraction treatment of ondisaponins from the dialysis internal solution or reverse osmosis membrane non-permeate may be performed, and in this case, the extraction may be performed according to the above method.

  The thus-obtained ondisaponin-containing composition is effective in improving dementia such as Alzheimer's syndrome, improving and treating brain function, expectorant action, improving and treating bronchitis, improving and treating bronchial asthma, sleep-extending action, immunity Because of its stimulating action, anti-stress ulcer action, congestive edema inhibitory action, PDE (phosphodiesterase) inhibitory action, sedation tonic action, etc., it has the effect of improving dementia such as Alzheimer's syndrome, brain function improvement and therapeutic action, and expectorant action For bronchitis improvement and treatment, bronchial asthma improvement and treatment, sleep prolongation, immunostimulation, anti-stress ulcer, congestive edema inhibition, PDE (phosphodiesterase) inhibition, sedation and tonic It can be used for pharmaceuticals, quasi drugs, foods for specified health use, pharmaceutical raw materials, foods, and the like.

  Hereinafter, the present invention will be specifically described with reference to examples. Note that this example is merely illustrative of the present invention and is not meant to be limiting. The parts in the examples are parts by mass unless otherwise specified. “Normal pressure” indicates 101.3 kPa, and “normal temperature” indicates 15 to 25 ° C.

Reference example 1
1,500 g of dried onji root (manufactured by Tochimoto Tenkaido Co., Ltd.) was put into 10 L of ion-exchanged water and extracted by heating at 90 to 100 ° C. for 1 hour. After this operation was repeated twice, the onji was removed, and all the obtained extracts were combined and allowed to cool to below room temperature. By filtering this liquid using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., an on-distilled liquid (16.43 kg) was obtained. When this extract was analyzed by high performance liquid chromatography under the following conditions, the content of 1,5-AG was 138.2 g.
[Analysis conditions for 1,5-AG (high performance liquid chromatography)]
Column: Cosmosil Sugar-D manufactured by Nacalai tesque
φ4.6 × 250mm
Column temperature: 40 ° C
Detector: Differential refractive index detector Mobile phase flow rate: 1 mL / min
Mobile phase composition: acetonitrile / water = 85/15 (v / v)

Reference example 2
An orange-colored onji extract (16.15 kg) prepared in the same manner as in Reference Example 1 is divided into three equal parts, one is untreated, and one is a synthetic adsorption resin Diaion (registered trademark) manufactured by Mitsubishi Chemical Corporation. ) HP20 (2.5 L) and activated carbon (crushed, 2 to 5 mm) (2.5 L) manufactured by Wako Pure Chemical Industries, Ltd. were added to each, and stirred gently for 1 hour. Thereafter, for each of the three types of solutions, each supernatant was filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd. In order to measure the degree of decolorization, a microplate reader MTP-310 manufactured by CORONA ( The absorbance (Abs) at each wavelength was measured using Ver1.09). The results are shown in Table 1. The control was distilled water.

  From Table 1, it was found that the synthetic adsorption resin treatment and the activated carbon treatment have the same degree of decolorization effect.

Reference example 3
450 g of dried onji root (manufactured by Tochimoto Tenkaido Co., Ltd.) was added to 3,000 mL of ion-exchanged water and extracted by heating at 90 to 100 ° C. for 1 hour. After this operation was repeated twice, the onji was removed, and all the obtained extracts were combined and cooled to room temperature or lower. By filtering this liquid using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., an onji extract (5.02 kg) was obtained. The obtained extract was divided into nine equal parts, and synthetic adsorption resin Diaion (registered trademark) HP20 manufactured by Mitsubishi Chemical Corporation, powdered activated carbon (Taiko K type) manufactured by Phutamura Chemical Co., Ltd., activated carbon (crushed, 2 ˜5 mm) was added to 150 mL, 200 mL, and 250 mL, respectively, and gently stirred for 1 hour. Thereafter, a part of the supernatant (about 20 mL) was filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd., and poured into a glass sample bottle (content 50 mL). When each liquid was turned upside down and shaken vigorously, and the state of foaming was observed, the results shown in Table 2 below were obtained.

  From the above results, it was found that the foam-causing substance contained in the Onji water extract can be removed by using a synthetic adsorption resin. In addition, after confirming foaming with 250 mL of activated carbon (2 locations in the above table), after adding 250 mL of activated carbon (and 1000 mL of ion-exchanged water) and stirring for 1 hour, foaming was confirmed again in the same manner. It turns out that the condition does not change.

  That is, even if this result uses the same volume part synthetic adsorption resin and activated carbon for the raw material parts by weight, or uses the same part by weight synthetic adsorption resin and activated carbon for the raw material parts by weight, This means that the synthetic adsorption resin has a higher firing removal effect than activated carbon.

Reference example 4
Synthetic adsorption resin Diaion (registered trademark) HP20 (7.5 L) manufactured by Mitsubishi Chemical Corporation was added to the ONI extract (16.43 kg) obtained in Reference Example 1, and after gently stirring for 1 hour, filtered. The filtrate was collected. On the other hand, the filtered resin was put into 20 L of ion exchange water and gently stirred for 15 minutes, followed by filtration to recover the filtrate. This operation was repeated twice, and all the filtrates obtained (55.21 kg) were analyzed under the same conditions as in the high performance liquid chromatography of Test Example 1. As a result, 1,5-AG contained in this liquid was analyzed. It was found that there was almost no loss of 1,5-AG due to the synthetic adsorption resin treatment. In addition, the usage-amount of synthetic adsorption resin was 180 weight part with respect to 100 weight part of raw materials in conversion of the resin weight of a dry state.

Reference Example 5
150 g of dried onji root (manufactured by Tochimoto Tenkaido Co., Ltd.) was put into 1,000 mL of ion-exchanged water and extracted by heating at 90 to 100 ° C. for 1 hour. After this operation was repeated twice, the onji was removed, and all the obtained extracts were combined and cooled to room temperature or lower. By filtering this liquid using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., an onji extract (1.87 kg) was obtained. When this extract was analyzed by high performance liquid chromatography under the conditions described in Reference Example 1, the content of 1,5-AG was 14.9 g.

  Next, the Onji extract is divided into four equal parts, one untreated, one synthetic adsorption resin Diaion (registered trademark) HP20 made by Mitsubishi Chemical, and one powdered activated carbon (Taiko K type made by Futamura Chemical). ), 188 mL each of activated carbon (crushed, 2 to 5 mm) manufactured by Wako Pure Chemical Industries, Ltd. was added and stirred gently for 1 hour. After that, each was filtered using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., and each remaining residue (synthetic adsorption resin, powdered activated carbon, activated carbon) was put into 1,000 mL of ion-exchanged water, and gently After stirring for 1 hour, the mixture was filtered through a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd., and combined with the above filtrate. Each solution was analyzed by high performance liquid chromatography under the conditions described in Reference Example 1. The amount of 1,5-AG contained in each solution was shown in Table 3 below.

  As is clear from the above table, it was found that there was almost no loss of 1,5-AG due to the synthetic adsorption resin, and the loss when using activated carbon was larger than the loss due to the synthetic adsorption resin.

Example 1
Cation exchange resin Amberlite (registered trademark) IR120B (4.5 L) manufactured by Organo Co., Ltd., acidified in advance, was added to the synthetic adsorption resin treatment liquid (55.21 kg) obtained in Reference Example 4 and gently stirred for 15 minutes. And the filtrate was separated. Next, the filtered resin was put into 10 L of ion exchange water and gently stirred for 15 minutes to collect the filtrate. This operation was repeated twice, and all the filtrates (74.44 kg) obtained were combined and filtered using a coated type cartridge filter TCYE-NS manufactured by Advantech Toyo. The resulting aqueous solution was concentrated under reduced pressure, and the resulting crystals were dried to obtain 128.1 g of 1,5-AG (yield 8.54%). The obtained 1,5-AG was subjected to ¹ H-NMR, ¹³ C-NMR, IR, HPLC analysis, and mass spectrometry (mass spectrum) to obtain commercially available 1,5-AG (Wako Pure Chemical Industries, Ltd.). The product was confirmed to be highly pure 1,5-AG (area percentage: 100%, quantitative purity: 101% (Wako Pure Chemical Industries 1,5-anhydro-D-) Glucitol was the standard product)). In addition, the usage-amount of the cation exchange resin was 210 weight part with respect to 100 weight part of raw materials in conversion of resin weight of a dry state.

Example 2
Onji extract (15.87 kg) prepared by the same method as in Reference Example 1, 15 cm in diameter (inner diameter) and 80 cm in height (inner volume: filled with synthetic adsorption resin Diaion (registered trademark) HP20 manufactured by Mitsubishi Chemical Corporation) After circulating through the cylindrical container of 14.1 L) at a flow rate of 0.5 L / min for 3 hours, the circulating liquid was taken out. Next, 12 L of ion-exchanged water was passed through the cylindrical container, and all the aqueous solutions obtained were combined to form a synthetic adsorption resin treatment liquid (a part of this synthetic adsorption resin treatment liquid (about 20 mL) was 50 mL in volume. No bubbling was observed when transferred to a sample container and shaken vigorously). Next, this synthetic adsorption resin treatment liquid was made into a cylindrical shape having a diameter (inner diameter) of 15 cm and a height of 80 cm (inner volume: 14.1 L) by using Cation Exchange Resin Amberlite (registered trademark) IR120B manufactured by Organo Co. The vessel was passed at a flow rate of 1 L / min. Next, 12 L of ion exchange water was passed through the cylindrical container, and all the obtained aqueous solutions were combined and filtered using a coated type cartridge filter TCYE-NS manufactured by Advantech Toyo Co., Ltd. to obtain an ion exchange resin treatment solution. The obtained treatment liquid was concentrated under reduced pressure, and the resulting crystals were dried to obtain 125.0 g of 1,5-AG (yield 8.33%). The amount of synthetic adsorption resin used is 338 parts by weight based on 100 parts by weight of the raw material in terms of dry resin weight, and the amount of cation exchange resin used is 100 parts by weight of raw material in terms of dry resin weight. It was 675 weight part with respect to this.

Example 3
Onji extract (16.25 kg) prepared by the same method as in Reference Example 1 was used, and the type of cation exchange resin in Example 2 was changed to an anion exchange resin (anion exchange resin Amberlite (registered trademark) IRA400J manufactured by Organo Corporation). Except for the change to 1), it was treated in the same manner as in Example 2 to obtain 118.4 g of 1,5-AG (yield 7.89%). The amount of the anion exchange resin used was 482 parts by weight with respect to 100 parts by weight of the raw material in terms of the weight of the resin in the dry state.

Example 4
10 g of dried onji root (manufactured by Tochimoto Tenkaido Co., Ltd.) was put into 100 mL of ion-exchanged water and extracted by heating at 90 to 100 ° C. for 1 hour. After this operation was repeated twice, the onji was removed, and all the obtained extracts were combined and allowed to cool to below room temperature. By filtering this liquid using qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., an orange Onji extract (171 g) was obtained. Next, this solution was used using SPECTRUM (registered trademark) LABORATORIES, INC. Dialysis membrane (Spectrum / Por (registered trademark) Dialysis Tubing) (fractionated molecular weight (MWCO): 100-500 D, effective surface area 0.08 m ² ). Then, ion-exchanged water (1,000 mL) was dialyzed for 18 hours at 20 to 25 ° C. as an external dialysis solution. Even when the obtained dialysis solution was shaken well, foaming was not confirmed, and the color was slightly yellow. An anion exchange resin Amberlite (registered trademark) IRA400J (100 mL) manufactured by Organo Co., Ltd., prepared in advance in a basic form, was added to the obtained liquid (1,005 g), and the mixture was gently stirred for 1 hour. Next, the resin obtained by filtering this liquid was put into 400 mL of ion-exchanged water, and gently stirred for 30 minutes to collect the filtrate. This operation was repeated twice, and all the obtained aqueous solutions (1,821 g) were combined and filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo. The obtained treatment liquid was concentrated under reduced pressure, and the resulting crystals were dried to obtain 0.55 g of 1,5-AG (yield 5.5%). In addition, the usage-amount of the anion exchange resin was 500 weight part with respect to 100 weight part of raw materials in conversion of resin weight of a dry state.

Example 5
30 g of dried Onji root (manufactured by Tochimoto Tenkaido Co., Ltd.) was put into 200 mL of ion-exchanged water and extracted by heating at 90 to 100 ° C. for 1 hour. After this operation was repeated twice, the onji was removed, and all the obtained extracts were combined and allowed to cool to below room temperature. This solution was filtered using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd. to obtain an onji extract (337 g). Next, this solution was filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd. An NF membrane manufactured by Nitto Denko Corporation (NTR-7250, molecular weight cutoff 3000D, effective surface area 84.2 cm ² ). Was filtered at 30 to 40 ° C. with a pressure of 1.0 to 2.5 MPa (the pressure was gradually increased from 1.0 MPa to 2.5 MPa) while stirring the stock solution. Also, ion-exchanged water (200 mL) is added to the inside of the filtration container, and the filtrate is filtered at a pressure of 1.0 to 2.5 MPa (the pressure is gradually increased from 1.0 MPa to 2.5 MPa) while stirring. It was collected. To the obtained total filtrate (520 mL), cation exchange resin Amberlite (registered trademark) IR120B (120 mL) made by Organo Co., Ltd., which was previously made acidic, was added and gently stirred for 1 hour. Next, the resin obtained by filtering this liquid was put into 420 mL of ion-exchanged water, and gently stirred for 30 minutes to collect the filtrate. This operation was repeated twice, and all the obtained aqueous solutions (1,341 g) were combined and filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo. The obtained treatment liquid was concentrated under reduced pressure, and the resulting crystals were dried to obtain 1.83 g of 1,5-AG (yield 6.1%). In addition, the usage-amount of the cation exchange resin was 280 weight part with respect to 100 weight part of raw materials in conversion of resin weight of a dry state.

Example 6
100 g of dried onji root (manufactured by Tochimoto Tenkaido Co., Ltd.) was put into 700 mL of ion-exchanged water and extracted by heating at 90 to 100 ° C. for 1 hour. After this operation was repeated twice, the onji was removed, and all the obtained extracts were combined and allowed to cool to below room temperature. By filtering this liquid using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., an onji extract (1,142 g) was obtained. To the obtained onji extract, 3,000 mL of ion exchange water and synthetic adsorption resin Diaion (registered trademark) HP20 (500 mL) were added and gently stirred for 1 hour. Next, what filtered this liquid using the membrane filter (pore size: 0.5 micrometer) made from Advantech Toyo Co., Ltd. Electrodialyzer Micro Acylizer S3 (Ion exchange membrane cartridge: AC-220-550 made from Sanactis) And an effective membrane area of 550 cm ² ), the sample liquid was processed until the electric conductivity became 0.3 mS or less. The obtained treatment liquid was concentrated under reduced pressure, and the resulting crystals were dried to obtain 7.1 g of 1,5-AG (yield 7.1%). In addition, the usage-amount of synthetic adsorption resin was 180 weight part with respect to 100 weight part of raw materials in conversion of the resin weight of a dry state.

Example 7
100 g of dried onji root (produced by Tochimoto Tenkaido Co., Ltd.) and 1,000 mL of ion-exchanged water are placed in a glass eggplant-shaped flask having a capacity of 2,000 mL equipped with a Dimroth cooler. Heat extraction was performed at 90 to 97 ° C for 1 hour while circulating a cooling solvent at 5 ° C. After this operation was repeated twice, the Onji was removed, and all the obtained extracts were combined and filtered using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd. 888 mL). Synthetic adsorption resin Diaion (registered trademark) HP20 (400 mL) and a pre-acidified cation exchange resin Amberlite (registered trademark) IR120B (300 mL) were added to the obtained onji extract and slowly added for 1 hour. Stir. Next, the liquid obtained by filtering this liquid using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd. was electrodialyzed by the San Actis Microdialyzer S3 (ion exchange membrane cartridge: AC-220-550). ) Was used until the electrical conductivity of the sample liquid became 0.3 mS or less. The obtained treatment liquid was concentrated under reduced pressure, and the resulting crystals were dried to obtain 8.2 g of 1,5-AG (yield 8.2%). The amount of the synthetic adsorption resin used is 144 parts by weight with respect to 100 parts by weight of the raw material in terms of dry resin weight, and the amount of the cation exchange resin used is 100 parts by weight of the raw material in terms of dry resin weight. The amount was 210 parts by weight.

Example 8
100 g of dried Onji root (manufactured by Tochimoto Tenkaido Co., Ltd.) was put into 700 mL of ion-exchanged water and extracted by heating at 89 to 97 ° C. for 1 hour. After this operation was repeated twice, the onji was removed, and all the obtained extracts were combined and allowed to cool to below room temperature. By filtering this liquid using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., an onji extract (1,210 g) was obtained. 3,000 mL of ion exchange water, synthetic adsorption resin Diaion (registered trademark) HP20 (500 mL), and cation exchange resin made by Organo Co., Ltd., Amberlite (registered trademark) IR120B (300 mL) were added to the obtained ondi extract. And gently stirred for 1 hour. Next, the resin obtained by filtering this liquid was put into 3 L of ion-exchanged water, and gently stirred for 30 minutes to collect the filtrate. This operation was repeated twice, and all the obtained aqueous solutions (9.91 kg) were combined and filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo. The obtained treatment liquid was concentrated under reduced pressure, and the resulting crystals were dried to obtain 6.9 g of 1,5-AG (yield 6.9%). The amount of synthetic adsorption resin used is 180 parts by weight in terms of dry resin weight, and 100 parts by weight of the raw material. The amount of cation exchange resin used is 100 parts by weight of raw material in terms of dry resin weight. The amount was 210 parts by weight.

Example 9
100 g of dried onji root (produced by Tochimoto Tenkaido Co., Ltd.) and 1,000 mL of ion-exchanged water are placed in a glass eggplant-shaped flask having a capacity of 2,000 mL equipped with a Dimroth cooler. Heat extraction was performed at 90 to 97 ° C for 1 hour while circulating a cooling solvent at 5 ° C. After this operation was repeated twice, the Onji was removed, and all the obtained extracts were combined and filtered using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd. 935 g) was obtained. Synthetic adsorption resin Diaion (registered trademark) HP20 (400 mL) and pre-acidified cation exchange resin Amberlite (registered trademark) IR120B (300 mL), preliminarily alkalinized in the obtained onji extract Anion exchange resin Amberlite (registered trademark) IRA400J (400 mL) was added, and the mixture was gently stirred for 1 hour. Next, this liquid was filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd., and then concentrated under reduced pressure, and the resulting crystals were dried to give 9.1 g (yield). 9.1%). The amount of the synthetic adsorption resin used is 144 parts by weight with respect to 100 parts by weight of the raw material in terms of dry resin weight, and the amount of the cation exchange resin used is 100 parts by weight of the raw material in terms of dry resin weight. The amount of the anion exchange resin used was 210 parts by weight with respect to 100 parts by weight of the raw material in terms of dry resin weight.

Example 10
150 g of dried onji root (manufactured by Tochimoto Tenkaido Co., Ltd.), synthetic adsorption resin Diaion (registered trademark) HP20 (1,500 mL), and a pre-acidic type made by Organo Co., Ltd. each packed in a non-woven bag Ion exchange resin Amberlite (registered trademark) IR120B (450 mL) was added to 4,500 mL of ion-exchanged water and extracted by heating at 90 to 100 ° C. for 2 hours. After cooling to near room temperature, the nonwoven fabric bag in the liquid was taken out, and the resulting aqueous solution was filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo. The obtained filtrate was concentrated under reduced pressure, and the resulting crystals were dried to obtain 12.9 g of 1,5-AG (yield 8.6%). The amount of synthetic adsorption resin used is 360 parts by weight in terms of dry resin weight, and 100 parts by weight of the raw material. The amount of cation exchange resin used is 100 parts by weight of raw material in terms of dry resin weight. The amount was 210 parts by weight.

Example 11
200 g of dried onji root (produced by Tochimoto Tenkaido Co., Ltd.) and 1,500 mL of ion-exchanged water containing ethanol (ethanol / ion-exchanged water = 10/90 (v / v)), the inner volume equipped with a Jimroth cooler The mixture was put into a 5,000 mL glass eggplant-shaped flask, and extracted by heating at 78 to 85 ° C. for 1 hour while circulating a cooling solvent at 0 to 5 ° C. through a Dimroth condenser. After this operation was repeated twice, the onji was removed, and all the obtained extracts were combined and allowed to cool to below room temperature. By filtering this liquid using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., an on-distilled liquid (2,944 mL) was obtained. Synthetic adsorption resin Diaion (registered trademark) HP20 (800 mL) and pre-acidified cation exchange resin Amberlite (registered trademark) IR120B (300 mL) were added to the obtained ondi extract and slowly added for 1 hour. Stir. Next, this liquid was filtered using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., and then a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd. The obtained treatment liquid was concentrated under reduced pressure, and the resulting crystals were dried to obtain 19.9 g of 1,5-AG (yield 10.0%). The amount of the synthetic adsorption resin used is 144 parts by weight with respect to 100 parts by weight of the raw material in terms of dry resin weight, and the amount of the cation exchange resin used is 100 parts by weight of the raw material in terms of dry resin weight. It was 105 weight part with respect to this.

Example 12
200 g of dried onji root (produced by Tochimoto Tenkaido Co., Ltd.) and 1,500 mL of ion-exchanged water containing ethanol (ethanol / ion-exchanged water = 90/10 (v / v)), the internal capacity equipped with a Jimroth cooler The mixture was put into a 5,000 mL glass eggplant-shaped flask, and extracted by heating at 70 to 80 ° C. for 1 hour while circulating a cooling solvent at 0 to 5 ° C. through a Dimroth condenser. After this operation was repeated twice, the Onji was removed, and all the obtained extracts were combined and concentrated under reduced pressure until the liquid volume was approximately 600 mL. By filtering this liquid using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., an on-distilled liquid (582 mL) was obtained. To the obtained Onji extract, ion-exchanged water (2,500 mL) and synthetic adsorption resin Diaion (registered trademark) HP20 (800 mL) and an anion-exchange resin made by Organo Co., Ltd. made in advance, Amberlite (registered trademark) IRA400J ( (500 mL) was added and gently stirred for 1 hour. Next, this liquid was filtered using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd., and then a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd. The obtained treatment liquid was concentrated under reduced pressure, and the resulting crystals were dried to obtain 16.7 g (yield 8.4%) of 1,5-AG. The amount of synthetic adsorption resin used is 144 parts by weight in terms of dry resin weight and 100 parts by weight of raw material, and the amount of anion exchange resin used is 100 parts by weight of raw material in terms of dry resin weight. It was 125 weight part with respect to this.

Example 13
100 g of dried Onji root (manufactured by Tochimoto Tenkaido Co., Ltd.), 700 mL of ion exchange water and 500 mL of toluene (toluene / ion exchange water = 500/700 (v / v)), with a capacity of 2, equipped with a Jimroth cooler It was put into a 000 mL glass eggplant-shaped flask, and heated and extracted at 95 to 100 ° C. for 1 hour while circulating a cooling solvent at 0 to 5 ° C. through a Dimroth condenser. After this operation was repeated twice, the Onji was removed, and all the obtained extracts were combined and the organic layer was removed. Then, the resulting aqueous layer was filtered with qualitative filter paper (No. 5C) manufactured by Advantech Toyo. On-distillation liquid (1,422g) was obtained by filtering using. Synthetic adsorption resin Diaion (registered trademark) HP20 (300 mL) was added to the obtained Onji extract and gently stirred for 1 hour. Next, this liquid was filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo. Next, ion-exchanged water (500 mL), a cation exchange resin Amberlite (registered trademark) IR120B (400 mL) made by Organo in advance, and an anion exchange resin Amberlite made by Organo in advance (registered) (Trademark) IRA400J (400 mL) was added and gently stirred for 1 hour. Next, this liquid was filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo Co., Ltd., and the resulting crystals were dried by concentration under reduced pressure to obtain 9.2 g of 1,5-AG (yield 9.2%). The amount of the synthetic adsorption resin used is 108 parts by weight based on 100 parts by weight of the raw material in terms of dry resin weight, and the amount of the cation exchange resin used is 100 parts by weight of the raw material in terms of dry resin weight. The amount of the anion exchange resin used was 280 parts by weight with respect to 100 parts by weight of the raw material in terms of the weight of the resin in the dry state.

Example 14
100 g of dried Onji root (produced by Tochimoto Tenkaido Co., Ltd.) and 1,000 mL of ion-exchanged water are put into a glass eggplant-shaped flask having an internal volume of 2,000 mL equipped with a Dimroth cooler. Heat extraction was performed at 92 to 100 ° C. for 1 hour while circulating a cooling solvent at 5 ° C. through the circulation. After this operation was repeated twice, the Onji was removed, and all the obtained extracts were combined and filtered using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo Co., Ltd. 911 g) was obtained. Synthetic adsorption resin Diaion (registered trademark) HP20 (400 mL) and pre-acidified cation exchange resin Amberlite (registered trademark) IR120B (300 mL), preliminarily alkalinized in the obtained onji extract Anion exchange resin made by Organo Corp. Amberlite (registered trademark) IRA400J (400 mL) was added and gently stirred for 1 hour. Next, this liquid was filtered using a qualitative filter paper (No. 5C) manufactured by Advantech Toyo. Add 4.5 g of US yeast manufactured by Oriental Yeast Co., Ltd. to the resulting solution, and use Jar Fermenter BMS-C manufactured by Able for 15 hours under conditions of a solution temperature of 30 ° C., a stirring speed of 200 rpm, and an aeration rate of 2 L / min. did. After adding 5 g of powdered activated carbon (Taiko K type) manufactured by Futamura Chemical Co., Ltd. to the obtained reaction liquid and stirring for 1 hour, it was filtered using a membrane filter (pore size: 0.5 μm) manufactured by Advantech Toyo. The obtained solution was concentrated under reduced pressure, and the resulting crystal was dried to obtain 8.1 g of 1,5-AG (yield 8.1%). The amount of the synthetic adsorption resin used is 144 parts by weight with respect to 100 parts by weight of the raw material in terms of dry resin weight, and the amount of the cation exchange resin used is 100 parts by weight of the raw material in terms of dry resin weight. The amount of the anion exchange resin used was 210 parts by weight with respect to 100 parts by weight of the raw material in terms of dry resin weight.

Example 15
20 L of ion-exchanged water was added to the synthetic adsorption resin (7.5 L) collected by filtration in Reference Example 4, and the mixture was gently stirred at 20 to 25 ° C. for 15 minutes, followed by filtration to recover the resin. This operation was repeated twice, 20 L of ethanol was added to the resultant synthetic adsorption resin, and the mixture was gently stirred at 20 to 25 ° C. for 15 minutes to collect the filtrate. This operation was repeated twice, and all the ethanol layers obtained were collected and concentrated to dryness under reduced pressure to obtain 181 g (yield 12.1%) of a brownish ondisaponin-containing composition.

Example 16
In the cylindrical container filled with the used synthetic adsorption resin used in Example 2, an aqueous sodium hydroxide solution (pH 8.0, 12 L), an aqueous hydrochloric acid solution (pH 5.5, 12 L), and then ion-exchanged water (20 L) Were sequentially passed, and then 20 L of ethanol was passed at a flow rate of 0.5 L / min. The obtained ethanol fraction was concentrated to dryness under reduced pressure to obtain 199 g (yield: 13.3%) of a brown-colored ondisaponin-containing composition.

Example 17
The used synthetic adsorption resin used in Example 4 was filled in a glass chromatograph tube having a diameter of 6 cm, and an aqueous sodium hydroxide solution (pH 8.0, 1,000 mL) and an aqueous hydrochloric acid solution (pH 5.5, 1,000 mL). Then, ion exchange water (1,500 mL) was sequentially passed at a flow rate of about 5 mL / min. Next, ethanol (1,500 mL) was passed at a flow rate of 5 mL / min. The obtained ethanol fraction was concentrated to dryness under reduced pressure to obtain 6.1 g (yield 6.1%) of a brown-colored ondisaponin-containing composition.

Example 18
Ion exchange water (1,000 mL) and hexane (2,000 mL) were added to 181 g of the ondisaponin-containing composition obtained in Example 15, mixed and stirred, the organic layer was removed, and the remaining aqueous layer was converted to butanol. Extracted twice (1,000 mL x 2). The resulting butanol layer was concentrated to dryness under reduced pressure to obtain 108.3 g (yield: 7.22%) of a brown-colored ondisaponin-containing composition from which most of the fat-soluble substance was removed.

  The method for producing 1,5-AG of the present invention can produce 1,5-AG in high purity, high yield, and high efficiency, and therefore provides 1,5-AG in large quantities with high productivity. Can do. In the production method, ondisaponins can also be obtained from components other than 1,5-AG contained in the 1,5-AG extract.

Claims (11)

A method for producing 1,5-anhydro-D-glucitol from plant,
(I) A step of subjecting the raw material to extraction with water or a water-containing organic solvent to obtain an extract,
(Ii) The extract is subjected to at least one treatment selected from the group consisting of a contact treatment with a synthetic adsorption resin, a treatment using a dialysis membrane, and a treatment using a reverse osmosis membrane to obtain a treatment liquid. And (iii) a step of separating a fraction containing 1,5-anhydro-D-glucitol from the obtained treatment liquid using an ion exchange resin and / or using an ion exchange membrane,
A process for producing 1,5-anhydro-D-glucitol, comprising: The production method according to claim 1, wherein the plant is at least one plant selected from the group consisting of plants belonging to the family Polygalaceae and plants belonging to the family Fabaceae . The production method according to claim 1 or 2, wherein the plant is at least one plant selected from the group consisting of plants belonging to the genus Polygala and plants belonging to the genus Soybean ( Glycine ). The production method according to any one of claims 1 to 3, wherein the plant is at least one plant selected from the group consisting of P. tenuifolia species and S. senega species.   The production method according to any one of claims 1 to 4, wherein the plant is at least one plant selected from the group consisting of Itohimehagi, Senega, and Hirosanega.   The manufacturing method of Claim 5 which uses the root of Itohimehagi, Senega and / or the root of Hirosanega as a raw material.   The synthetic adsorption resin in the step (ii) is at least one selected from the group consisting of a styrene synthetic adsorbent, an acrylic synthetic adsorbent, and a methacrylic synthetic adsorbent. Production method.   The dialysis membrane in the step (ii) is at least one selected from the group consisting of a regenerated cellulose membrane, a surface-modified regenerated cellulose membrane, a cellulose acetate membrane, and a synthetic polymer membrane. The manufacturing method in any one.   The reverse osmosis membrane in the step (ii) comprises a cellulose acetate membrane, a sulfonated polyethersulfone membrane, an aromatic polyamide membrane, a polyvinyl alcohol membrane, a polytetraphthalate ester (PTFE) membrane, and a polysulfone membrane. The manufacturing method in any one of Claims 1-6 which is 1 or more types chosen from a group.   The production according to any one of claims 1 to 9, wherein the separation in the step (iii) includes a step of mixing the ion exchange resin with the filtrate and filtering, and / or a step of treating the filtrate with an electrodialysis membrane. Method.   After the step (ii) in the production method according to any one of claims 1 to 10, when a contact treatment with a synthetic adsorption resin is performed, a desorption treatment of ondisaponins from the resin is performed, or a dialysis membrane is used. When the treatment used is collected, the dialysis internal solution is collected, or when the treatment using the reverse osmosis membrane is conducted, the reverse osmosis membrane non-permeate is collected by at least one method. A method for producing an ondisaponins-containing composition to obtain a saponin-containing composition.