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WO1998038198A1 - Derives saponarine - Google Patents

Derives saponarine Download PDF

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Publication number
WO1998038198A1
WO1998038198A1 PCT/JP1998/000763 JP9800763W WO9838198A1 WO 1998038198 A1 WO1998038198 A1 WO 1998038198A1 JP 9800763 W JP9800763 W JP 9800763W WO 9838198 A1 WO9838198 A1 WO 9838198A1
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WO
WIPO (PCT)
Prior art keywords
aok
formula
group
water
derivative
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP1998/000763
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English (en)
Japanese (ja)
Inventor
Yoshihide Hagiwara
Hideaki Hagiwara
Toshihiro Nohara
Junei Kinjo
Hideo Ueyama
Masafumi Ohkawa
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Individual
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Individual
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Priority to AU61157/98A priority Critical patent/AU6115798A/en
Publication of WO1998038198A1 publication Critical patent/WO1998038198A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/733—Compounds of undetermined constitution obtained from animals or plants
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/771—Organic compounds containing hetero rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A61K8/602—Glycosides, e.g. rutin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
    • C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
    • C07H17/06—Benzopyran radicals
    • C07H17/065—Benzo[b]pyrans
    • C07H17/07—Benzo[b]pyran-4-ones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/522—Antioxidants; Radical scavengers

Definitions

  • the present invention relates to a saponalin derivative, a method for producing the same, and use as an antioxidant.
  • a green leaf of a barley plant particularly a young green leaf of barley, contains a substance having a strong antioxidant activity, and the substance is extracted and purified.
  • a substance having a strong antioxidant activity 0-glucosyl-isovitexin and rutonalin (JP-A-5-65480, US Pat. No. 5,346,890, EP-A-471,584; and JP-A-9 No. 235549).
  • the present inventors further studied antioxidant active substances contained in green leaves of wheat plants, and as a result, the green leaves of wheat plants contained a different fraction from that containing rutonalin. Also found that a fraction exhibiting strong antioxidant activity was present, and from the fraction, the body exhibiting antioxidant activity was separated and identified.
  • R 1 represents a hydrogen atom, a sinapyl group, a ferulyl group or a rhamnosyl group
  • R 2 represents a hydrogen atom or a dalkosyl group
  • the present invention provides a savonalin derivative represented by the above formula (I), provided that R 1 and R 2 do not simultaneously represent a hydrogen atom.
  • the present invention also provides a method for extracting and isolating a savonalin derivative represented by the above formula (I) from green leaves of a wheat plant.
  • the present invention further provides a use of the saponalin derivative represented by the above formula (I) as an antioxidant.
  • Figure 1 shows the mass spectrum obtained by the positive FAB-MS method of the antioxidant active substance AOK-II.
  • Figure 2 shows the ultraviolet absorption spectrum of the antioxidant active substance AOK-II.
  • Figure 3 shows the antioxidant active substance AOK—II ⁇ 1 !! — NMR spectrum (50 OMHz).
  • Figure 4 shows the 13 C-NMR spectrum (10 OMHz) of the antioxidant active substance AOK-II.
  • FIG. 5 shows the chemical structure of the antioxidant active substance AOK_II together with the 1 H-NMR signal assignment.
  • Figure 7 shows the mass spectrum of the antioxidant active substance AOK-IIIA by the positive FAB-MS method.
  • FIG. 8 is a 1 H-NMR spectrum (50 OMhz) of the antioxidant active substance AOK-IIIa.
  • FIG. 9 is a 13 C-NMR spectrum (10 MHZ) of the antioxidant active substance AOK-IIIa.
  • FIG. 10 shows the chemical structure of the antioxidant active substance AOK-IIIa together with the assignment of 1 H-NMR signals.
  • FIG. 11 shows the chemical structure of the antioxidant active substance AOK-Ilia, together with the assignment of the signal of 13 C-NMR.
  • FIG. 12 shows a mass spectrum of the antioxidant active substance A OK-Ia by the positive FAB-MS method.
  • FIG. 13 is the 1 H-NMR spectrum (50 OMHz) of the antioxidant active substance AOK-Ia.
  • FIG. 14 shows the 13 C-NMR spectrum (10 OMHz) of the antioxidant active substance AOK-Ia.
  • FIG. 15 shows the chemical structure of the antioxidant active substance AOK-Ia together with the assignment of 1 H-NMR signals.
  • FIG. 16 shows the chemical structure of the antioxidant active substance AOK-Ia together with the assignment of 13 C-NMR signals.
  • Figure 17 shows the mass spectrum of the antioxidant active substance A OK-I by positive FAB-MS method.
  • Figure 18 shows the 1 H-NMR spectrum of the antioxidant active substance AOK-Ib (5 0 OMH z).
  • FIG. 19 shows the 13 C-NMR spectrum (10 OMHz) of the antioxidant active substance AOK-Ib.
  • FIG. 20 shows the chemical structure of the antioxidant active substance A and K_Ib together with the assignment of 1 H-NMR signals.
  • FIG. 21 shows the chemical structure of the antioxidant active substance AOK-Ib together with the assignment of 13 C-NMR signals.
  • Figure 22 shows the infrared absorption spectrum of the antioxidant active substance AOK-IV.
  • FIG. 23 shows the 1 H-NMR spectrum (50 OMHz) of the antioxidant active substance AOK-IV.
  • FIG. 24 shows a 13 C-NMR spectrum (10 OMHz) of the antioxidant active substance AOK-IV.
  • FIG. 25 shows the chemical structure of the antioxidant active substance AOK-IV, together with the assignment of 13 C-NMR signals.
  • FIG. 26 shows the infrared absorption spectrum of the antioxidant active substance AOK-IIIB.
  • Fig. 27 shows the mass spectrum of the antioxidant active substance AOK-IIIB by the positive FAB-MS method.
  • FIG. 28 shows a 1 H-NMR spectrum (50 OMHz) of the antioxidant active substance AOK-IIIb.
  • FIG. 29 shows a 13 C-NMR spectrum (10 OMHz) of the antioxidant active substance AOK-IIIb.
  • Figure 30 shows the chemical structure of the antioxidant active substance AOK-IIIb as 13C- NM. It is described together with the assignment of the signal of R.
  • Examples of the barley plant used as a raw material for the extraction of the savonalin derivative of the above formula (I) include barley, wheat, naked barley, oats, barley, corn, millet, Italian diegrass, and the like. Above all, barley and naked barley are preferred, and barley is particularly preferred.
  • fresh stems and Z or leaf portions (collectively referred to as “green leaves” in the present specification) of young plants harvested before the maturity stage are particularly suitable.
  • the green leaves of wheat plants are first squeezed by mechanical crushing means such as a mixer, juicer, etc., and, if necessary, squeezed liquid (hereinafter referred to as squeezed liquid) by removing coarse solids by means such as sieving or filtration. Is called “green juice”).
  • the green juice powder obtained by drying the green juice as it is, or by drying it with an appropriate drying means such as freeze-drying or spray-drying or extracting the green juice with an anhydrous alcohol is sufficient.
  • Extraction with water (preferably hot water) or aqueous alcohol in this specification, the alcohol is preferably methanol or ethanol, particularly methanol) or n-hexane.
  • This extraction treatment can be usually performed at room temperature, and may be repeated twice or more depending on the case, whereby the components soluble in water or hydrous alcohol (hereinafter referred to as “water Separate and collect the components that are substantially insoluble in n-hexane (hereinafter referred to as “n-hexane insoluble components”) or n-hexane.
  • the recovered n-hexane-insoluble component can be dried and solidified at this stage in the same manner as described above.
  • n-hexane-insoluble component thus obtained is then treated with a water content of 5 to 80.
  • % Preferably 10 to 70%, more preferably 15 to 50% of a water-containing alcohol, for example, an extraction treatment with water-containing methanol having a water content of 20%, and the components soluble in the water-containing alcohol are separated and recovered.
  • the percentage of moisture content have your herein is vZ v%.
  • the extraction treatment with the hydroalcoholic alcohol is carried out by using a green juice prepared as described above, a water-soluble component of green leaves from which water-insoluble components have been substantially completely removed, or a suitable drying means such as freeze-drying or spray-drying. The drying can also be performed directly on the powder obtained.
  • the aqueous alcohol-soluble component thus recovered can be used as it is, or can be concentrated or the solvent can be distilled off.
  • the water-soluble component and the aqueous alcohol-soluble component obtained as described above are then treated with a porous resin adsorbent.
  • a porous resin adsorbent that can be used in the adsorption treatment include a non-ionic (preferably hydrophobic) resin having a large adsorption surface area such as a styrene-divinylpentene polymer and a phenol-formaldehyde. Resins and acrylic resins are used as bases.
  • Amberlite XAD-1, Amberlite XAD_2, Amberlite XAD-4, Amberlite XAD-7, Amberlite Light XAD-8, Amber Light XAD-11, Amber Light XAD-12 (or more, ROHM 'And Haas Diaion HP-10, Diaion HP-20, Diaion HP-30, Diaion HP-40, Diaion HP-50 (Mitsubishi Chemical Corporation), Imakty Syn-42, Imakti Syn-44 and Imakti Syn-46 (all manufactured by Imacti) can be mentioned.
  • the adsorbed porous resin adsorbent is then eluted with a water-containing alcohol having a water content of 10 to 70%, preferably 15 to 60%.
  • a water-containing alcohol having a water content of 10 to 70%, preferably 15 to 60%.
  • the compound and R 1 is a ferulyl group and R 2 of formula (I) and R 2 R 1 is a Shinapiru group is a hydrogen atom is a hydrogen atom
  • An eluate containing a compound of the formula (I) and optionally a compound of the formula (I) in which R 1 is a sinapyr group and R 2 is a darkosyl group is obtained.
  • These eluates can be used as antioxidants of the present invention as they are, after concentration, or after drying by drying means such as freeze drying, spray drying, etc.o
  • the aqueous methanol-soluble component obtained by the elution treatment as described above may be subjected to, for example, thin-layer chromatography using silica gel, reverse-phase silica gel (ODS, Amberlite XAD, etc.), or the like, if necessary.
  • ODS reverse-phase silica gel
  • individual compounds of the formula (I) can be recovered as crystals.
  • the collected crystals can be further recrystallized and purified, if necessary, using, for example, methanol or water-containing methanol having a water content of 90% or less.
  • the savonalin derivative of the formula (I)
  • R 1 and R 2 are both hydrogen atoms compounds of formula (I), 6 "'- Shinapirusaponari emissions: compound of formula (I) R 1 is and an Shinapiru group R 2 is water atom ,
  • rhamnosyl saponalin a compound of formula (I) wherein R 1 is a rhamnosyl group and R 2 is a hydrogen atom,
  • 4'-0-glucosyl-savonaline a compound of the formula (I) wherein R 1 is a hydrogen atom and R 2 is a glucosyl group;
  • an antioxidant characterized by containing at least one saponalin derivative of the formula (I) as an active ingredient.
  • the compound of the formula (I) produced as described above is free of various metal elements and substances that promote the denaturation of foods, etc., which are usually contained in the raw material of green leaves. Such as foods and beverages, cosmetics, It can be advantageously blended with various inorganic or organic (composition) compounds in the field.
  • the compound of the formula (I) of the present invention has substantially no adverse effect on the water solubility and transparency of the compounded composition, and can be sterilized by filtration in an aqueous composition. It is.
  • the compound of the formula (I) is optionally encapsulated with cyclodextrin, crown ether or the like, and then saccharides such as fructose, glucose, dextrin, starch; amino acids: citrate, lingo Organic acids such as acid, tartaric acid, succinic acid, etc .; various vitamins; coloring agents, fragrances, various thickeners and the like can be mixed.
  • saccharides such as fructose, glucose, dextrin, starch
  • amino acids citrate, lingo Organic acids such as acid, tartaric acid, succinic acid, etc .
  • various vitamins coloring agents, fragrances, various thickeners and the like can be mixed.
  • the compound of the formula (I) of the present invention includes medicaments such as talc, zinc white, sodium carbonate, sodium bicarbonate, titanium dioxide, kaolin and calcium phosphate, paints, cosmetics, foaming agents and the like.
  • medicaments such as talc, zinc white, sodium carbonate, sodium bicarbonate, titanium dioxide, kaolin and calcium phosphate
  • paints, cosmetics, foaming agents and the like By mixing with the raw materials or blending as a powder by spray drying, vacuum drying, etc., it is possible to produce a new industrial product, and it has the advantage that the quality of the product does not change.
  • the water-soluble and alcohol-soluble antioxidants of the present invention also help stabilize inorganic and organic compositions and are excellent new products, for example antioxidants for the production of volima; emulsion paints Cosmetics; Paper products; Foods and beverages; Pharmaceuticals;
  • the compound of the formula (I) of the present invention can be used for various foods and drinks, for example, fruits and processed foods (for example, fruits) for the purpose of, for example, maintaining the freshness of foods and drinks, maintaining quality, and improving preservability.
  • the compound of the formula (I) of the present invention is pale yellow to colorless, is water-soluble and alcohol-soluble, and has excellent absorbability in living organisms. It can be easily blended without substantially affecting the components and appearance.
  • sweeteners such as fructose, glucose, starch syrup and the like often used in foods and drinks; organic acids such as citric acid, linoleic acid, tartaric acid, and succinic acid or salts thereof: various vitamins, coloring agents, It can be freely mixed with fragrances, various edible ⁇ viscosity agents, etc., does not affect their water solubility, transparency, etc., and can be filtered, sterilized, etc.
  • the compound of formula (I) of the present invention can be advantageously used as a preservative of freshness or quality of foods and drinks, and is also useful for maintaining health by ingesting foods and drinks containing the compound. .
  • the compound of the formula (I) of the present invention can be added to food or drink alone or in combination of two or more.
  • the compounding amount of the compound of the formula (I) of the present invention with respect to the above-mentioned foods and drinks is not particularly limited, and can be varied over a wide range according to the kind and use of the foods and drinks to be compounded.
  • the compound of the formula (I) can be added in an amount of 0.0001 to 0.2% by weight, preferably 0.0005 to 0.1% by weight, based on the weight of the food or drink.
  • the compound of the formula (I) of the present invention is pale yellow or colorless, is water-soluble and alcohol-soluble, is excellent in the absorbability of living organisms, and is stain-free.
  • the present invention can provide cosmetics having excellent preventive effects such as blemishes, freckles, rough skin, and sunburn (sunburn), and hair protection effects.
  • the compound of the formula (I) of the present invention can be used alone or in combination of two or more of them in the cosmetic.
  • the amount of the compound in the cosmetic depends on the type and use of the cosmetic. Although it can be varied in a wide range, it is generally used in a range of 0.001 to 1% by weight, preferably 0.005 to 0.5% by weight based on the cosmetic base. Is appropriate.
  • Cosmetic bases that can be used for the above-mentioned skin and hair cosmetics are not limited at all, and include, for example, water, alcohol, propylene glycol, stearate, glycerin, cetyl alcohol, liquid paraffin, etc. Those conventionally used for skin and hair cosmetics can be used similarly.
  • the above-mentioned cosmetics may contain, if necessary, vitamins, crude drug extract extracts, hormones, and other externally-applicable drugs, as usual.
  • the skin and hair cosmetics containing the compound of the formula (I) of the present invention are effective in preventing spots, freckles, rough skin, ultraviolet rays (sunburn) and the like. It is worthwhile.
  • n-hexane insoluble component To this n-hexane insoluble component, add 500 ml of water-containing methanol having a water content of 20%, stir well at room temperature for about 5 minutes, and filter off the insoluble matter. Methanol is added to the filtrate to prepare a methanol solution having a water content of 60%, and the water-containing methanol solution is partitioned between ethyl acetate and the water-containing methanol layer.
  • the aqueous methanol extract (A) was adsorbed on a Diaion HP-20 column, and then eluted with aqueous methanol or methanol having a water content of 70, 60, 40 or 20% to obtain an eluate.
  • the eluate from aqueous methanol with a water content of 60% exhibiting antioxidant activity was subjected to silica gel column chromatography (manufactured by Merck), and mixed with a 1-butanol / acetic acid aqueous solution (volume ratio of 4: 1: 2).
  • the mixture was developed with an antioxidant active substance AOK-IIIa, and then developed with a mixed solvent of chloroform, methanol and water (volume ratio 6: 4: 1) to obtain an antioxidant active substance A OK-II.
  • This antioxidant active substance AOK-I was subjected to silylation gel chromatography using Chromatorex ODS (DU3 050MT) (manufactured by Fuji Silica Chemical Co., Ltd.) and developed with 35% water-containing methanol. The antioxidant active substances were classified into AOK-Ia and AOK-Ib.
  • each antioxidant active substance obtained above was identified as follows.
  • FIG. 1 shows the ultraviolet absorption spectrum measured by the KBr method using JASCO FT / IR-7000S.
  • AOK-II is identified as savonalin having the structure shown in FIGS.
  • AOK-IIIa was also heated to 90 ° C., and 1 H_NMR was measured. Compared to saponalin, the flavonoid portion was almost the same, but more signals derived from the sugar portion were observed. Then, 13 C-NMR was measured, and a new rhamnose signal was observed. Regarding the binding position of rhamnose, position 6 of glucose at position 7 was observed in a low magnetic field (568.0), and position 5 was observed in a high magnetic field (575.7) as a glycosylated shift. And the one that is bonded to the 6th position of glucose.
  • AOK-IIIa has the structure shown in Figs. 10 and 11 6 ⁇ 'with rhamnosyl saponalin was determined.
  • AOK-Ia gave a peak based on [M + H] + at mZz 801 in Positive FAV-MS, and the molecular weight was determined to be 800.
  • 'H-NMR of AOK-Ia showed a complex signal at room temperature. Then, when the temperature was raised to 90 ° C and observed, it became possible to assign signals. From the signal pattern, it was presumed to have a flavonoid skeleton.First, three phenolic hydroxyl groups were observed from a low magnetic field, and the 13.42 signal at the lowest magnetic field was assigned to the chelate-bonded 5-position hydroxyl group. Was.
  • AOK- I a was determined to 6 ⁇ 'single sinapyl support Na phosphorus have a structure shown in FIGS. 15 and 16 n (4)
  • a peak based on + was given and the molecular weight was determined to be 770. This molecular weight is 30 mass units less than AOK-Ia.
  • AOK-Ib was also heated to 90 ° C and measured by iH-NMR, and it was possible to assign a signal. The signal pattern was almost the same as that of AOK-Ia, but no signal derived from the synapyr group was observed, and instead, a signal of another aromatic compound was observed. When 13 C-NMR was measured, the aromatic compound was identified as a ferulyl group.
  • AOK-Ib was determined to be 6 ′ ′-ferrylsaponalin having the structure shown in FIGS. 20 and 21.
  • AOK—II Ia, AOK_II, AOK—Ia and AOK—Ib were 22.5, 27.8, 42.5, and 42.5 at a concentration of 100 1M, respectively.
  • Vita Mi down beta beta was prepared using T ris- HCL buffer (p H 7), a mixed solution of the solution 2.0 m 1 and 200 / M dissolved solution of various antioxidants 2.
  • p H 7 T ris- HCL buffer
  • Om 1 Into a quartz cell, and irradiate it with UV light using a light stability tester, Litetron LT-120 (Nagano Kagaku Kikai Seisakusho), under the conditions of UV intensity of 300 W / cm 2 and 20 ° C. The mobile phase was sampled over time and analyzed by Shimadzu High Performance Liquid Chromatograph TLC-6A equipped with a Shimp ac—CLC—ODS (M) (5 ⁇ m, 4.6 mm ⁇ 150 mm) column.
  • M Shimp ac—CLC—ODS
  • Example 8 5 g of the aqueous methanol extract (A) obtained in Example 1 and 500 g of talc were added to water 21 to prepare a suspension, which was spray-dried at an intake temperature of 190 ° C and an exhaust temperature of 120 ° C. Was performed to produce 450 g of a powder raw material.
  • Example 8 5 g of the aqueous methanol extract (A) obtained in Example 1 and 500 g of talc were added to water 21 to prepare a suspension, which was spray-dried at an intake temperature of 190 ° C and an exhaust temperature of 120 ° C. Was performed to produce 450 g of a powder raw material.
  • Example 9 A solution was prepared by adding 5 g of AOK-II and 400 g of dextrin obtained in the same manner as in Example 1 to water 11, and spray-dried at an intake temperature of 190 ° C and an exhaust temperature of 120 ° C. 370 g of a powder raw material was obtained.
  • Example 9 A solution was prepared by adding 5 g of AOK-II and 400 g of dextrin obtained in the same manner as in Example 1 to water 11, and spray-dried at an intake temperature of 190 ° C and an exhaust temperature of 120 ° C. 370 g of a powder raw material was obtained.
  • Example 9 A solution was prepared by adding 5 g of AOK-II and 400 g of dextrin obtained in the same manner as in Example 1 to water 11, and spray-dried at an intake temperature of 190 ° C and an exhaust temperature of 120 ° C. 370 g of a powder raw material was obtained.
  • Lintex-1 P (Cyclodextrin manufactured by Sanraku Co., Ltd.) was added to 5 Om 1 of water and mixed to form a slurry.
  • AOK—IIIa obtained by the same method as in Example 1 After adding 1 g and stirring at room temperature for 90 minutes, the mixture was freeze-dried to prepare 18.7 g of a freeze-dried product.
  • a solution was prepared by adding 100 g of water to 500 ml of water, and spray-dried at an intake temperature of 190 ° C and an exhaust temperature of 120 ° C to obtain 82 g of a powder raw material.
  • Lintex-P (Cyclodextrin manufactured by Sanraku Co., Ltd.) was added to 50 ml of water and mixed to form a slurry.
  • 0.5 g of AOK—Ib produced in the same manner as in Example 1 was added and stirred at room temperature for 90 minutes, followed by freeze-drying to prepare 19 g of a freeze-dried product.
  • a 0.1% mixture of each of AOK-Ia and AOK-Ib obtained in the same manner as in Example 1 was dissolved in squeezed liquid 11 of barley young leaves to prepare a 30% suspension. Spray drying was performed at a temperature of 170 ° C and an exhaust temperature of 110 ° C to produce 75 g of a powder raw material.
  • a mixture of 0.1 g of each of AOK-1 & & 01: -113 obtained in the same manner as in Example 1 was mixed with 80 g of dextrin, 150 g of purified fish oil and 25 g of miro wax.
  • the fish oil product was manufactured by filling 27 Omg each into a soft capsule by a conventional method.
  • the solvent was distilled off from the collected aqueous methanol layer under reduced pressure to obtain 35 g of an aqueous methanol extract.
  • the aqueous methanol extract (C) was adsorbed on a Diaion HP-20 column, and then eluted with aqueous methanol or anhydrous methanol having a water content of 60, 40 or 20% to obtain an eluate.
  • the eluate from aqueous methanol with a water content of 60% that exhibits antioxidant activity is subjected to silica gel column chromatography (manufactured by Merck), and mixed with a 1-butanol / acetic acid aqueous solution (volume ratio 4: 1: 2) using a mixed solvent.
  • silica gel column chromatography manufactured by Merck
  • a 1-butanol / acetic acid aqueous solution volume ratio 4: 1: 2
  • 45 mg of an antioxidant active substance A OK—IV was obtained.
  • the eluates of 40% water-containing methanol exhibiting antioxidant activity were subjected to silica gel column chromatography (manufactured by Merck), and developed with a mixed solvent of methanol and methanol in water (volume ratio 6: 4: 1).
  • the fraction was separated into a fraction containing the antioxidant active substance AOK-I and a fraction containing AOK-IIIa.
  • the fraction containing the antioxidant active substance AOK-I and the fraction containing AOK-IIIa were subjected to silica gel chromatography using Chromatorex ODS (DU 3050MT) (manufactured by Fuji Silysia Chemical Ltd.). Beave The mixture was developed with a mixed solvent of evening water and acetic acid in acetic acid (solvent ratio: 4: 1: 2) to obtain the antioxidant active substances AOK-V5Omg and AOK-IIIb4Omg. .
  • each antioxidant active substance obtained above was identified as follows.
  • Figure 22 shows the infrared absorption spectrum measured by the KBr method using JASCO FTZ IR-7000S.
  • the 13 C-NMR spectrum (100 MHz) of the AOK-IV crystal was converted into DMS 0 as a solvent using a JEOL GX-400 type nuclear magnetic resonance absorption spectrometer (manufactured by JEOL Ltd.).
  • the results shown in FIG. 24 were obtained.
  • Fig. 25 shows the assignment of each signal.
  • a new glucose signal was observed as compared with the data of the 13 C-NMR spectrum (100 MHz) of saponalin (see FIG. 4).
  • This substance, in a DMS 0- d 6, is for binding position of glucose, the glycosylated shift is not observed in the sugar moiety, B ring 4 'position upfield (5160.2), the 1-position of glucose 100. 1) in low magnetic field It is probable that it is linked to the 4'-position for reasons such as shifting.
  • 801: -1 ⁇ is identified as a 4'-O-glucosylsaponalin having the structure shown in Fig. 25.
  • AOK-IIIb was also heated to 90 ° C., and 1 H-NMR was measured. 6 "'Shinapirusabonari emissions were compared (see Fig. 7), where it Furabonoi head portion was filed nearly identical, measured more was observed. Thus 13 C-NMR is a signal derived from the sugar moiety, new The glucose binding position was thought to be binding to the 4 'position because the 4' position of the B ring was shifted (5160.2) to a high magnetic field.
  • AOK-II-Ib was determined to be 4'-0-darkosyl-1.6'-synapirsaponalin having the structure shown in Fig. 30.
  • the 200 ⁇ M solution of Vita Mi emissions B 2 prepared with T ris- HC L buffer (pH 7), the mixed solution of the solution 2.0 m 1 and 200 IM soluble liquid 2.0 m 1 of various antioxidants Pour into a quartz cell and add a light stability tester With Rye preparative Tron LT one 120 (Nagano Science Kikai Seisakusho), irradiating ultraviolet radiation under conditions of UV strength 300 Bruno 0:11 2, 20 ° C, over time sampled Ngushi, S hi mp ac- C LC- OD S (M) (5 / zm, 4.
  • a solution was prepared by adding 5 g of AOK-IIIb and 400 g of dextrin obtained in the same manner as in Example 14 to water 11 at an intake temperature of 190 ° C and an exhaust temperature of 120 ° C. Spray drying was performed to obtain 350 g of a powder raw material.
  • Lintex-1 P (Cyclodextrin manufactured by Sanraku Co., Ltd.) was added to 5 Om 1 of water and mixed to form a slurry.
  • AOK—IIIb obtained by the same method as in Example 14 was obtained. After adding 1 g and stirring at room temperature for 90 minutes, the mixture was freeze-dried to prepare 17 g of a freeze-dried product.
  • a solution was prepared by adding 1 g of the extract powder (A) obtained in the same manner as in Example 14 and 500 g of dextrin to 500 ml of water. Spray drying was performed at 190 ° C and an exhaust temperature of 120 ° C to obtain 87 g of a powder raw material.
  • Lintex-1 P (Cyclodextrin manufactured by Sanraku Co., Ltd.) was added to 5 Om 1 of water and mixed to form a slurry. To this, 0.5 g of AOK—IV manufactured by the same method as in Example 14 was added. After stirring at room temperature for 90 minutes, freeze-drying was performed to prepare 18 g of a freeze-dried product.
  • Example 14 0.5 g of the aqueous methanolic extract (C) obtained in the same manner as in Example 14 was dissolved in a concentrated solution 11 of the squeezed liquid of barley young leaves, and dextrin was added thereto to form a 30% suspension. It was prepared and spray-dried at an intake temperature of 170 ° C and an exhaust temperature of 110 ° C to produce 270 g of a powder raw material.
  • a mixture of 0.1 g of each of AOK-IIIb and AOK-IV obtained in the same manner as in Example 14 was mixed with 80 g of dextrin, 150 g of purified fish oil and 25 g of beeswax, and each was mixed in a conventional manner.
  • Soft oil capsules were filled with 27 Omg to produce fish oil products.
  • a lotion having the following formulation was prepared using 0.1 g of an equal mixture of AOK-Ia and AOK-Ib obtained in the same manner as in Example 1.
  • Example 27 The lotion obtained in Example 27 was used daily after washing the face and before going to bed to test the improvement of spots and freckles.
  • Table 7 shows the test results for 30 women. The test was performed for 6 months. The evaluation was based on the following criteria.
  • Example 27 An equivalent mixture of AOK-Ia, AOK-Ib, AOK-Ib and AOK-IIIa obtained in the same manner as in Example 1 was prepared as described in Example 27. Add a 0.1% concentration instead of AOK_Ia + AOK—lb (1: 1) to the lotion formulation to make a lotion.
  • Example 29 Using the cream obtained in Example 29 every day after washing the face and before going to bed, the effect on spots, freckles and rough skin was tested on 30 men and 30 women for 6 months. Judgment of spots and freckles was performed in accordance with Application Example 1, and skin roughness was judged based on the following criteria based on the degree of slippage of the cream on the skin.
  • a hair restorer of the following formulation was prepared using an extract powder (E) that was soluble in a 20% water-containing aqueous ethanol solution and was prepared from a spray-dried product of naked wheat juice obtained in the same manner as in Example 2. did.
  • Example 30 The effect of the obtained hair restorer was studied on 20 males and 20 females. The effect of daily use of hair restorer after 6 months
  • Example 31 The lotion obtained in Example 31 was used after washing the face and before going to bed to test the improvement of spots and freckles.
  • the test results for 30 women are shown in Table 11. The test was performed for 6 months. The evaluation was performed according to the same criteria as in Application Example 1.
  • Example 33 Using the cream obtained in Example 33 daily after washing the face and before going to bed, the effect on spots, freckles, and rough skin was tested on 30 men and 30 women for 6 months. Judgment for spots and freckles was performed in accordance with Application Example 4, and skin roughness was evaluated by feeling the degree of slippage of the cream on the skin according to the same criteria as in Application Example 2.
  • aqueous methanol extract (C) 1 g was dissolved in 95 ml of a 50% aqueous ethanol solution, and 5 ml of propylene glycol, 0.1 g of flavor and 0.1 g of coloring agent were added to prepare a hair restorer.
  • Example 34 The effect of the hair restorer obtained in Example 34 was evaluated for 20 males and 20 females. Examined. The effect of daily use of the hair restorer was determined after 6 months using the same criteria as in Application Example 3. The conditions before and after application are shown in Table 1.4 below. --Table 14
  • Carrot juice (A) and carrot juice (B) are 120. C. After pasteurization for 20 minutes and storage at room temperature for 150 days, juice (A) has less fading than juice (B), and juice (A) has a bright orange color, taste and aroma. Although the juice had a fresh flavor, the juice (B) had a slightly brownish orange color, the taste was a little poor, and the aroma unique to the carrot was significantly lower than that of the juice (A).
  • a soft drink was prepared by blending the aqueous methanol extract (A) produced in the same manner as in Example 1 with the following formulation. After preparation, soft drinks were heat-sterilized at 85 ° C for 30 minutes.
  • Example 37 A soft drink was prepared by blending the aqueous methyl extract (C) produced in the same manner as in Example 14 with the following formulation. After the preparation, the soft drink was heat-sterilized at 85 ° C for 30 minutes.
  • Example 36 an equivalent mixture of AOK-II, AOK-Ia and AOK-Ib was added in place of the aqueous methanol extract (A) so as to be 0.01% by weight, and the soft drink was added. Prepared. After leaving this product under natural light for 15 days, the residual ratios of riboflavin and pyridoxine were 75% and 72%, respectively, but an equivalent mixture of AOK-II, AOK-Ia and AOK-lb In soft drink without additives, the residual ratios of riboflavin and pyridoxine were 23% and 15%, respectively.
  • A aqueous methanol extract
  • the resulting bread had a bright green color and was a good-quality product with aroma.
  • AOK-IIIa 1.4mg, AOK-la 2.8mg, AOK-lb 0.7mg, AOK-II lb 5.6mg and AOK — Contained 5.7 mg of IV.
  • the cream was left in a room at a temperature of about 20 ° C and a relative humidity of about 55% for 15 days with little change in quality.
  • Example 45 The barley young leaf extract obtained in the same manner as in Example 42 was triturated with a medium flour to obtain a medium flour green juice powder. To 2.5 kg of flour, add 50 g of salt and 1 liter of water, and then add the above flour green juice powder to 2.5% of the raw material solids, and then add AOK—Illb 10111 8 and eight 01 ⁇ - to produce a hand total of noodles in a conventional manner by the addition of IV 1 Omg.
  • the obtained udon was bright green and had a good flavor.
  • the resulting udon is AOK-II 7.5mg, AOK-Ilia 2.3mg, AOK-Ia 1.
  • Omg. AOK-Ib 0.7mg, AOK-IIIb 1.2mg and A0K- It contained 1.2 mg of IV and was left in a room at a temperature of about 20 ° C and a relative humidity of about 57% for 180 days, but there was almost no change in quality.
  • This ice cream contains AOK-II 28.8mg, AOK-IIIa 3.Omg, AOK-la 2.0mg, AOK-lb 1.5mg, AOK-II lb 3.5mg and AOK-IV 3.7mg in 100g. After leaving it in the freezer of a home refrigerator (about 118 ° C) for 150 days, its quality was almost unchanged.
  • Example 47 Same as Example 14 in 100 g of wheat flour, 20 g of margarine, 30 g of sugar, 10 g of milk, 5 g of skim milk powder, 0.2 g of salt, 1 g of baking powder and 10 g of water, which are the raw materials of the woodpecker 10 g of the hydrated methanol extract (C) obtained in the above was added, mixed, molded and roasted in an oven at 200 ° C.

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Abstract

La présente invention concerne des dérivés saponarine représentés par la formule générale (I). Dans cette formule, R1 est hydrogène, sinapyl, férulyl ou rhamnosyl, et R2 est hydrogène ou glucosyl. Ces dérivés, qui sont extraits de feuilles de froment, d'orge ou similaire, font preuve d'une très bonne activité antioxydante et sont non toxiques, ce qui fait qu'ils sont très efficaces pour conserver la fraîcheur et d'autres qualités des aliments et boissons, et qu'ils conviennent notamment comme produits d'hygiène de la peau et des cheveux.
PCT/JP1998/000763 1997-02-26 1998-02-25 Derives saponarine Ceased WO1998038198A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61157/98A AU6115798A (en) 1997-02-26 1998-02-25 Saponarin derivatives

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP9/57118 1997-02-26
JP5711897 1997-02-26
JP10/32371 1998-01-30
JP3237198 1998-01-30

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WO1998038198A1 true WO1998038198A1 (fr) 1998-09-03

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PCT/JP1998/000763 Ceased WO1998038198A1 (fr) 1997-02-26 1998-02-25 Derives saponarine

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AU (1) AU6115798A (fr)
WO (1) WO1998038198A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005350436A (ja) * 2004-06-14 2005-12-22 Coletica 弾性繊維形成の不全、欠損又は無秩序による病状に対処するための、リシルオキシダーゼのアイソフォームの活性の誘導
WO2007094030A1 (fr) * 2006-02-13 2007-08-23 Sakamoto Bio Co., Ltd. Agent de blanchiment de la peau
JP2007217479A (ja) * 2006-02-15 2007-08-30 Toyo Shinyaku:Kk 大麦若葉石鹸
JP2009084194A (ja) * 2007-09-28 2009-04-23 Nippon Yakuhin Kaihatsu Kk １５−リポキシゲナーゼ阻害剤
JP2015127311A (ja) * 2013-12-27 2015-07-09 株式会社東洋新薬 美容組成物
JP2019073476A (ja) * 2017-10-17 2019-05-16 国立大学法人北海道大学 Ａｔｐ産生促進用剤

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JPH01179678A (ja) * 1988-01-12 1989-07-17 Nippon Oil & Fats Co Ltd 抗酸化剤
JPH05276909A (ja) * 1990-08-21 1993-10-26 Yoshihide Hagiwara 抗酸化性を有する飲食品類

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JPH01179678A (ja) * 1988-01-12 1989-07-17 Nippon Oil & Fats Co Ltd 抗酸化剤
JPH05276909A (ja) * 1990-08-21 1993-10-26 Yoshihide Hagiwara 抗酸化性を有する飲食品類

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BUDZIANOWSKI J., PAKULSKI G., ROBAK J.: "STUDIES ON ANTIOXIDATIVE ACTIVITY OF SOME C-GLYCOSYLFLAVONES.", POLISH JOURNAL OF PHARMACOLOGY AND PHARMACY., PHARMACOLOGY, KRAKOW, PL, vol. 43., 1 January 1991 (1991-01-01), PL, pages 395 - 401., XP002911728, ISSN: 0301-0244 *
HAYASHI T., ET AL.: "INHIBITION OF COW'S MILK XANTHINE OXIDASE BY FLAVONOIDS.", JOURNAL OF NATURAL PRODUCTS., AMERICAN CHEMICAL SOCIETY, US, vol. 51., no. 02., 1 March 1988 (1988-03-01), US, pages 345 - 348., XP002911729, ISSN: 0163-3864, DOI: 10.1021/np50056a030 *
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NIEMANN G. J.: "A NEW ACYLATED C-GLYCOFLAVONE GLYCOSIDE FROM SILENE PRATENSIS LEAVES.", ACTA BOTANICA NEERLANDICA., BLACKWELL SCIENTIFIC PUBLICATIONS, OXFORD., GB, vol. 30., no. 05/06., 1 November 1981 (1981-11-01), GB, pages 475 - 478., XP002911727, ISSN: 0044-5983 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005350436A (ja) * 2004-06-14 2005-12-22 Coletica 弾性繊維形成の不全、欠損又は無秩序による病状に対処するための、リシルオキシダーゼのアイソフォームの活性の誘導
WO2007094030A1 (fr) * 2006-02-13 2007-08-23 Sakamoto Bio Co., Ltd. Agent de blanchiment de la peau
JP2007217479A (ja) * 2006-02-15 2007-08-30 Toyo Shinyaku:Kk 大麦若葉石鹸
JP2009084194A (ja) * 2007-09-28 2009-04-23 Nippon Yakuhin Kaihatsu Kk １５−リポキシゲナーゼ阻害剤
JP2015127311A (ja) * 2013-12-27 2015-07-09 株式会社東洋新薬 美容組成物
JP2019073476A (ja) * 2017-10-17 2019-05-16 国立大学法人北海道大学 Ａｔｐ産生促進用剤

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