JP2011099020A - Antioxidant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent antioxidant applicable to cosmetics, drugs, foods, and the like. <P>SOLUTION: The antioxidant is an ascorbic acid derivative or its salt prepared by reacting a hydroxyl group in the second place and/or the third place of an ascorbic acid with glycidol, alkyl glycidyl ether, alkenyl glycidyl ether, phenyl glycidyl ether, epoxyalkane, epoxyalkene and the like and etherifying the resultant reaction product. For the ascorbic acid derivative, in particular, a reaction product prepared by reacting glycidol with a hydroxyl group in the second place and/or the third place of the ascorbic acid is preferable. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antioxidant that can be used in cosmetics, pharmaceuticals, foods and the like.

  Cosmetics, pharmaceuticals, foods, etc. are often oxidized by oxygen in the air. The deterioration of quality is prevented by adding an antioxidant to a composition that is particularly susceptible to oxidation and a composition containing the same.

  Many cosmetics currently produced are blended with oily raw materials, thereby imparting smoothness, oiliness, glossiness and flexibility to the skin and hair. Moreover, the moisturizing effect by prevention of drying, etc. are acquired. Examples of oily raw materials include natural fats and oils, hydrocarbons, synthetic triglycerides, ester oils, and silicone oils.

  However, among these useful oily raw materials, unsaturated fatty acids having a double bond between carbon and carbon are extremely unstable and easily oxidized. As a result, substances such as peroxides and oxidation polymers are generated, which affect odors, coloring, deterioration in feeling of use, changes in the agent system, and the like. Therefore, cosmetics containing raw materials that are easily oxidized often include raw materials for the purpose of antioxidants of cosmetics.

  In the production of cosmetics, a wide variety of polyoxyethylene type surfactants and polyhydric alcohol ester type surfactants are widely used for the purpose of emulsification and solubilization. However, these have an ether bond site and may have a double bond site derived from an unsaturated fatty acid in the lipophilic group. Therefore, they tend to be altered by oxidation and are generally used together with an antioxidant. is there.

  Further, in foods, antioxidants are used for the purpose of preventing browning of food, maintaining flavor, maintaining freshness, and the like.

  Thus, there is a demand for antioxidants in cosmetics, foods, pharmaceuticals, etc., and ascorbic acid, ascorbic acid derivatives, etc. are frequently used for reasons such as high safety and high antioxidant power. Yes.

  However, ascorbic acid and its salts blended for the purpose of antioxidation are decomposed over time, and there are problems such as coloring, generation of odors, and reduction of effects. Thus, ascorbic acid derivatives such as magnesium ascorbate phosphate and glucoside ascorbate have been proposed as an improvement of these problems. (Patent Document 1, Patent Document 2)

  However, ascorbic acid derivatives such as magnesium ascorbate and ascorbic acid glucoside formulated for the purpose of antioxidant effect are also less to the extent of ascorbic acid, but they decompose over time, causing coloring, odor generation, and reduced effectiveness There are problems such as. Further, magnesium ascorbate phosphate has low solubility in water, and the amount that can be blended in cosmetics is limited, making it difficult to blend in cosmetics. Furthermore, the antioxidant effect of these ascorbic acid derivatives is low. For these reasons, ascorbic acid derivatives such as magnesium ascorbate phosphate and ascorbic acid glucoside have not been satisfactory.

  Patent Document 3 discloses an ascorbic acid derivative having a glyceryl group, but does not describe its antioxidant effect, and it is difficult to expect an excellent antioxidant effect from these derivatives. In addition, the stability is not described for other ingredients that are susceptible to oxidation, and the stability when blended into cosmetics is not necessarily good.

JP 2005-60239 A JP 2005-120023 A WO2009 / 0253328

  This invention solves the problem of the said prior art, and makes it a subject to provide the outstanding antioxidant which can be utilized for cosmetics, a pharmaceutical, a foodstuff, etc.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that an ascorbic acid derivative having a specific structure and a salt thereof have excellent antioxidant power and stability, and completed the present invention. The present invention has been completed based on these findings.

  The present invention is an antioxidant comprising an ascorbic acid derivative represented by the following general formula (I) or a salt thereof (Claim 1).

[Wherein, R ¹ and R ² are each a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a benzyl group, R ³ —O—CH ₂ —CH (OH) —CH. Selected from the group consisting of _2- , R ⁴ —O—CH ₂ —CH (CH ₂ OH) —, R ⁵ —CH (CH ₂ OH) —, R ⁶ —CH (OH) —CH ₂ —, and a hydroxycyclohexyl group. Wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group, and R ⁵ and R ⁶ are hydrogen atoms. , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a phenyl group. However, when R ¹ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a benzyl group, R ² is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or 2 to 2 carbon atoms. Neither 22 alkenyl groups nor benzyl groups]

In this general formula (I), a carbon atom and a hydrogen atom bonded to the carbon atom are omitted. For example, the position of 1-4 in the formula is a carbon, the position of the 5 are CH groups, the position of 6 is CH ₂ group. The same applies to the following equations.

  The ascorbic acid derivative represented by the general formula (I), which is an antioxidant of the present invention, has glycidol, alkyl glycidyl ether having a specific structure, alkenyl glycidyl ether, phenyl glycidyl at the 2-position and / or 3-position hydroxyl group of ascorbic acid A compound (epoxy compound) having an epoxy ring selected from ether, ethylene oxide, epoxy alkane, epoxy alkene, styrene oxide, and alicyclic epoxy is reacted. By substituting at least one of the hydrogen atoms of the 2- and 3-position hydroxyl groups with a glyceryl group, an alkyl glyceryl group or a hydroxyalkyl group, problems such as the stability of ascorbic acid over time and generation of odor over time are improved. An ascorbic acid derivative which is stable even during storage for a period and has little discoloration, odor change, reduced activity, etc. can be obtained.

Moreover, when ^one of R ¹ or R ² is H, it can be converted to a salt.

Specific examples of the ascorbic acid derivative represented by the general formula (I) are shown below. In the following examples,
The glyceryl group represents HOCH ₂ —CH (OH) —CH ₂ — or HOCH ₂ —CH (CH ₂ OH) —,
The alkyl glyceryl group refers to R—O—CH ₂ —CH (OH) CH ₂ — or R—O—CH ₂ —CH (CH ₂ OH) — (R represents an alkyl group).
The alkyl group is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, A pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a behenyl group, etc .;
An alkenyl group refers to a vinyl group, an allyl group, a butenyl group, an isobutenyl group, a crotyl group, an octenyl group, a decenyl group, a dodecenyl group, etc.
The hydroxyalkyl group represents R—CH ₂ —CH (OH) — or R—CH (OH) —CH ₂ — (R represents an alkyl group), and examples thereof include a hydroxyethyl group, a hydroxypropyl group, a hydroxy group. Butyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl, hydroxypentadecyl , Hydroxyhexadecyl group, hydroxyheptadecyl group, hydroxyoctadecyl group, hydroxynonadecyl group, hydroxyeicosyl group, and hydroxybehenyl group.

(1) 3-O-glyceryl ascorbic acid,
3-O-alkyl glyceryl ascorbic acid, such as 3-O-methyl glyceryl ascorbic acid, 3-O-eicosyl glyceryl ascorbic acid,
3-O-alkenyl glyceryl ascorbic acid, such as 3-O-allyl glyceryl ascorbic acid, 3-O-crotyl glyceryl ascorbic acid, 3-O-vinyl glyceryl ascorbic acid, 3-O-isobutenyl glyceryl ascorbic acid, 3-O-octenyl glyceryl ascorbic acid, 3-O-decenyl glyceryl ascorbic acid, 3-O-dodecenyl glyceryl ascorbic acid, and 3-O-phenyl glyceryl ascorbic acid

(2) 2-O-glyceryl ascorbic acid,
2-O-alkyl glyceryl ascorbic acid, such as 2-O-methyl glyceryl ascorbic acid, 2-O-eicosyl glyceryl ascorbic acid,
2-O-alkenyl glyceryl ascorbic acid, such as 2-O-allyl glyceryl ascorbic acid, 2-O-dodecenyl glyceryl ascorbic acid, and 2-O-phenyl glyceryl ascorbic acid,
(3) 2,3-di-O-glyceryl ascorbic acid,
2,3-di-O-alkylglyceryl ascorbic acid, 2,3-di-O-alkenyl glyceryl ascorbic acid, 2,3-di-O-phenylglyceryl ascorbic acid (4) 3-O-hydroxyalkylascorbic acid, 3-O-hydroxyphenylethyl ascorbic acid (5) 2-O-hydroxyalkylascorbic acid, 2-O-hydroxyphenylethylascorbic acid (6) 2,3-di-O-hydroxyalkylascorbic acid, 2,3- Di-O-hydroxyphenylethyl ascorbic acid

(7) 3-O-glyceryl-2-O-alkylglyceryl ascorbic acid, 3-O-glyceryl-2-O-alkenyl glyceryl ascorbic acid, 3-O-glyceryl-2-O-phenylglyceryl ascorbic acid (8) 3-O-glyceryl-2-O-hydroxyalkylascorbic acid, 3-O-glyceryl-2-O-hydroxyphenylethylascorbic acid (9) 3-O-glyceryl-2-O-alkylascorbic acid, 3-O -Glyceryl-2-O-alkenyl ascorbic acid,
(10) 3-O-alkylglyceryl-2-O-alkylglyceryl ascorbic acid (however, 3-alkyl and 2-alkyl are different), 3-O-alkylglyceryl-2-O-alkenyl glyceryl ascorbic acid 3-O-alkylglyceryl-2-O-phenylglyceryl ascorbic acid,

(11) 3-O-alkyl glyceryl-2-O-hydroxyalkyl glyceryl ascorbic acid, 3-O-alkenyl glyceryl-2-O-hydroxyalkyl glyceryl ascorbic acid, 3-O-alkyl glyceryl-2-O-hydroxy alkenyl Glyceryl ascorbic acid, 3-O-alkenyl glyceryl-2-O-hydroxyalkenyl glyceryl ascorbic acid, 3-O-alkyl glyceryl-2-O-phenyl glyceryl ascorbic acid (12) 3-O-alkyl glyceryl-2-O- Alkyl ascorbic acid, 3-O-alkyl glyceryl-2-O-alkenyl ascorbic acid (13) 3-O-hydroxyalkyl-2-O-alkyl ascorbic acid, 3-O-hydroxyalkyl-2-O-alkenyl ascorbic acid (14 3-O-hydroxyalkyl-2-O-alkyl glyceryl ascorbic acid, 3-O-hydroxyalkyl-2-O-alkenyl glyceryl ascorbic acid (15) 3-O-hydroxyalkyl-2-O-hydroxyalkyl ascorbic acid, 3-O-hydroxyalkyl-2-O-hydroxyphenylethyl ascorbic acid (16) 3-O-hydroxycyclohexyl ascorbic acid, 2-O-hydroxycyclohexyl ascorbic acid, 3-O-glyceryl-2-O-benzylascorbic acid 2-O-glyceryl-3-O-benzylascorbic acid.

  Examples of the salt of the ascorbic acid derivative represented by the general formula (I) include inorganic salts and organic salts. Examples of the inorganic salt include alkali metal salts such as sodium and potassium, and alkaline earth metals such as calcium and magnesium. A metal salt, an ammonium salt, etc. are mentioned, As an organic salt, a diethanolamine salt, a triethanolamine salt, an amino acid salt etc. can be mentioned. The salt can be formed by a known method.

  Examples of the epoxy compound include compounds selected from a compound represented by the following formula (II), a compound represented by the following formula (III), and 1,2-epoxycyclohexane.

[Wherein, R ¹¹ represents H, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group. ]

[Wherein, R ¹² represents H, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a phenyl group. ]

As a compound represented by the formula (II),
Glycidol, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether , Dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether, octadecyl glycidyl ether, nonadecyl glycidyl ether, vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl D Ether, isobutenyl glycidyl ether, Black lipped glycidyl ether, octenyl glycidyl ether, de Seni glycidyl ether, dodecane Seni glycidyl ether, phenyl glycidyl ether and the like.

As the compound represented by the formula (III),
Ethylene oxide, methyloxirane, ethyloxirane, propyloxirane, isopropyloxirane, butyloxirane, pentyloxirane, hexyloxirane, heptyloxirane, octyloxirane, nonyloxirane, decyloxirane, undecyloxirane, dodecyloxirane, tridecyloxirane, tetradecyloxirane , Pentadecyloxirane, hexadecyloxirane, heptadecyloxirane, octadecyloxirane, nonadecyloxirane, isopropyleneoxirane, buteneoxirane, penteneoxirane, hexeneoxirane, hepteneoxirane, octeneoxirane, noneneoxirane, deceneoxirane, undecenoxirane, Dodecene oxirane, tridecene oxirane, La Defense Sen oxirane, penta-decene oxirane, hexa decene oxirane, hepta-decene oxirane, octadecene oxirane, Roh pat Sen oxirane is exemplified.

A commercially available product may be used as glycidyl ether, but it can also be obtained by reacting an epihalo (chloro) hydrin with an alcohol.

  Ascorbic acid used for the production of an ascorbic acid derivative which is an antioxidant of the present invention may have either the S configuration or the R configuration of the 4- and 5-position carbon. Similarly, glycidol, alkyl glycidyl ether, alkenyl glycidyl ether, or epoxy compounds such as epoxy alkene and epoxy alkane, which are raw materials for producing the ascorbic acid derivative which is the antioxidant of the present invention, are also in the S form and R form. Or a mixture thereof.

  The ascorbic acid derivative represented by the formula (I) or a salt thereof is obtained by using 3-halo-1,2-propanediol such as 3-chloro-1,2-propanediol or the like instead of glycidol. It can be also produced by a method of reacting with ascorbic acid and etherifying only the 2-position and / or 3-position of ascorbic acid. In this case, however, it is necessary to further add a basic substance to the reaction system for dehalogenation.

  For example, a compound in which an epoxy compound is added to both the 2-position and the 3-position is obtained by, for example, obtaining an adduct in which an epoxy compound is added to only one side, and then performing purification by the method described later, etc. It is possible to obtain it by a method in which only 0.5 to 1.5 mol of an epoxy compound is reacted with the adduct. By changing the epoxy compound used in the reaction before and after purification, a compound in which different epoxy compounds are added to both the 2-position and the 3-position can be obtained.

The ascorbic acid derivative of general formula (I) or a salt thereof, wherein R ¹ or R ² is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having ² to 22 carbon atoms, or a benzyl group, the reaction of the, the use amount of the epoxy compound to the ascorbic acid, carried out in the range of about 0.5 to 1.5 mol, to obtain ascorbic acid derivatives etherifying one of R ¹ or R ² only, It can be obtained by alkylating, alkenylating or benzylating the remaining hydroxyl group among the hydroxyl groups at the 2-position or 3-position. Alkylation, alkenylation, or benzylation can be performed by a known method, for example, a reaction with an alkyl halide, an alkenyl halide, a benzyl halide or the like.

  The ascorbic acid derivative or salt thereof produced as described above is purified by means such as column chromatography using silica gel, column chromatography using a resin such as an ion exchange resin, activated carbon treatment, extraction, distillation, crystallization, etc. can do.

  The ascorbic acid derivative represented by the general formula (I) of the present invention or a salt thereof exhibits an excellent antioxidant effect when blended in cosmetics, pharmaceuticals, foods and the like containing raw materials that are susceptible to oxidation. As a result, deterioration of the texture and shape of the product is suppressed. Furthermore, compared to conventional ascorbic acid derivatives, there is less deterioration such as degradation and coloring of the product itself, and it is difficult to adversely affect the feel and shape of the product.

  The ascorbic acid derivative represented by the general formula (I) or a salt thereof can be dissolved in water, and can be dissolved as it is when blended in an aqueous composition. Alternatively, it is used as an oil-in-water or water-in-oil emulsion composition obtained by emulsifying a water phase containing it and an oil phase containing an unsaturated fatty acid, preferably in the presence of an emulsifier.

  In such an emulsion, the emulsifier is known, for example, nonionic surfactants such as POE fatty acid ester, polyglycerin fatty acid ester, POE higher alcohol ether, POE.POP block polymer, fatty acid potassium, fatty acid Anionic surfactants such as sodium, higher alkyl sulfates, alkyl ether sulfates, acyl sarcosinates, sulfosuccinates, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylpyridinium salts, benzalkonium chloride Cationic surfactants such as imidazoline-based and betaine-based amphoteric surfactants can be blended.

Among the compounds of the general formula (I), R ¹ is hydrogen, HOCH ₂ —CH (OH) —CH ₂ —, or HOCH ₂ —CH (CH ₂ OH) —, and R ² is H, HOCH Those that are _2- CH (OH) —CH ₂ — or HOCH ₂ —CH (CH ₂ OH) — (wherein at least one of R ¹ and R ² is not H) are also particularly soluble in aqueous systems. It is excellent and can be suitably used in water-based base materials such as lotion (claim 2).

  In emulsification, water phase / oil phase = 5/95 to 95/5 (mass ratio, the same shall apply hereinafter) is preferable, and in the case of an oil-in-water emulsion composition, water phase / oil phase = 5/95 is particularly preferable. In the case of a water-in-oil emulsion composition, water phase / oil phase = 5/95 to 95/5 and emulsified by a normal phase or phase inversion emulsification method.

  The amount of an ascorbic acid derivative or a salt thereof to be blended in a composition for the purpose of antioxidants varies depending on the use, but is preferably 0.01 to 10.0% by weight of the entire composition, In order to exhibit a sufficient antioxidant effect, it is more preferable to be contained in an amount of 0.1 to 5.0% by weight.

  Antioxidants of the present invention include glycerol and glycerol derivatives such as polyglycerol, polyglycerol fatty acid ester, polyglycerol alkyl ether, polyethylene glycol, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, and the like. It exhibits an effect on a substance having an oxyalkylene chain or an oil having an unsaturated bond, or various cosmetics, pharmaceuticals, foods and the like in which these are blended regardless of whether they are aqueous or oily. Especially effective for polar substances and water-based products.

  In addition to this essential component, cosmetics containing the antioxidant of the present invention usually include components such as oily raw materials, surfactants, polymer compounds, ultraviolet absorbers, humectants, sequestering agents, A whitening agent, a drug, a protein hydrolyzate, an amino acid or a derivative thereof, a pH adjuster, a preservative, a thickener, a pigment, a fragrance and the like can be appropriately blended. Further, other antioxidants can be appropriately blended.

  Examples of the oily raw material include oils and fats such as olive oil, coconut oil, macadamia nut oil, tea seed oil, castor oil, and tri (caprin / capryl) glyceryl, jojoba oil, carnauba wax, candelilla wax, lanolin, beeswax and other waxes, Hydrocarbons such as liquid paraffin, paraffin, petrolatum, ceresin, microcrystalline wax, squalane, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, cetyl alcohol, stearyl alcohol, isostearyl Higher alcohols such as alcohol and chimyl alcohol, esters such as isopropyl myristate, 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, diisostearyl malate, and tri-2-ethylhexanoin Methyl polysiloxane, methylphenyl polysiloxane, silicones such as decamethylcyclopentasiloxane or the like.

  Examples of surfactants include anionic surfactants such as higher fatty acid soaps, polyoxyethylene alkyl ether sulfates, acyl-N-methyl taurate salts, N-acyl amino acid salts, alkyl phosphate ester salts, and alkyltrimethyl chlorides. Cationic surfactants such as ammonium and dialkyldimethylammonium chloride, amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, alkylamidoaminoacetic acid betaine, 2-alkyl-N-carboxy-N-hydroxyimidazolinium betaine, polyoxy Nonionic surfactants such as ethylene alkyl ether, polyethylene glycol fatty acid ester, polyhydric alcohol fatty acid ester, and polyether-modified silicone are listed.

  Examples of the polymer compound include carboxyvinyl polymer, sodium carboxymethyl cellulose, xanthan gum, polyvinyl alcohol, and polymer dimethylpolysiloxane.

  Examples of the ultraviolet absorber include ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, potassium paramethoxycinnamate and mono-2-paramethoxycinnamate. Glyceryl ethylhexanoate, glyceryl octyl diparamethoxycinnamate, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, dihydroxydimethoxybenzophenone, Dihydroxydimethoxybenzophenone-sodium sulfonate, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, Octyl chill acid, phenyl salicylate, ethylene glycol salicylate, salicylic acid, myristyl, methyl salicylate, urocanic acid, ethyl urocanate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, methyl anthranilate and the like.

  Examples of the humectant include propylene glycol, 1,3-butylene glycol, sodium lactate, polyethylene glycol, sodium pyrrolidonecarboxylate, sodium hyaluronate and the like.

  Examples of the sequestering agent include ethylenediaminetetraacetic acid, alanine, sodium edetate, phosphoric acid, citric acid, ascorbic acid, succinic acid, and gluconic acid.

  Examples of the whitening agent include arbutin, vitamin C derivatives, ellagic acid, chamomile extract, licorice extract, lucinol, rosemary extract and the like.

  Examples of other drugs include rough skin prevention agents and anti-inflammatory agents. Examples of the rough skin preventive agent or anti-inflammatory agent include dipotassium glycyrrhizinate, stearyl glycyrrhetinate, methyl salicylate, pyridoxine hydrochloride, allantoin, sea salt, persimmon extract, aloe extract, gardenia extract, chamomile extract, licorice extract, mukuroji extract, Kyounin extract, Ogon extract, strawberry tea extract, loquat extract, ginkgo biloba extract, hypericum extract, sorghum extract, safflower extract, spruce extract, salvia extract, birch extract, chimpi extract, tonin extract, gayo extract, altea extract, arnica extract, carrot extract, peony extract , Cucumber extract, gentian extract, cordyceps extract, duckweed extract, ginseng extract, ginseng extract, peach leaf Kiss, kumazasa extract, Yokuininekisu, horse chestnut extract, hawthorn extract, Coptis extract, litchi extract, Toukinsenkaekisu, peppermint extract, comfrey extract, Butcher bloom extract, mortar Beni mallow extract, YAG Rumaru Saw extract, Togenashiekisu, and the like. In addition, other agents such as hair-growth agents, acne agents, dandruff and itching agents, and odor-preventing agents can also be mentioned.

  Examples of protein hydrolysates include protein hydrolysates such as milk protein, silk protein, wheat protein, rice protein, pea protein, collagen, keratin, soybean, sesame, conchiolin, marine collagen, and derivatives thereof.

  As amino acids or derivatives thereof, for example, amino acids such as glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, asparagine, aspartic acid, glutamine, glutamic acid, cystine, cysteine, methionine, tryptophan, proline, histidine, etc. And derivatives thereof.

  Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like.

  Examples of the preservative include paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and phenoxyethanol.

  Examples of thickeners include gum arabic, gum tragacanth, cabbage gum, guar gum, pectin, agar, quince seed, starch, alge colloid, xanthan gum, dextran, succinoglucan, collagen, gelatin, casein, albumin, carboxymethyl starch, methylcellulose, Ethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, sodium arginate, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, polyethylene acrylate, polyacrylamide , Cationic polymers, etc. It is.

  Examples of the dye include tar dyes, natural dyes, inorganic pigments, and polymer powders. Examples of the fragrances include natural fragrances, synthetic fragrances, and blended fragrances.

  Examples of other antioxidants include ascorbic acid and salts thereof, ascorbic acid derivatives, tocopherol, BHT (tert-butylhydroxytoluene), plant extracts, and the like.

  The ascorbic acid derivative represented by the above general formula (I), which is the antioxidant of the present invention, has an excellent antioxidant ability, can suppress the odor change, discoloration, and deterioration in feeling of use of the blended product, Can be used for pharmaceuticals, foods, etc.

  Next, specific modes for carrying out the present invention will be described by way of examples. However, the scope of the present invention is not limited by the following examples. Prior to the examples, production examples of ascorbic acid derivatives used in the examples are shown.

Production Example 1 Synthesis of 3-O-glyceryl ascorbic acid L-ascorbic acid (300 g) and sodium hydrogen carbonate (42.9 g) were added to water under an argon atmosphere, and the mixture was stirred at room temperature for 30 minutes, and then glycidol (126 g). Was added. Thereafter, the mixture was heated to 50 ° C. and stirred for 5 hours. Methanol was added and filtered, the filtrate was concentrated under reduced pressure, and 457 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with chloroform / methanol / water = 65/35/5, and concentration was performed under reduced pressure to obtain 3-O-glyceryl ascorbic acid (296 g) represented by Chemical formula 4.

The obtained product was subjected to ¹ H-NMR and ¹³ C-NMR measurements, and from this measurement result, it was confirmed that the product was 3-O-glyceryl ascorbic acid represented by the following structural formula. It was.

In addition, also in the manufacture example shown below, about the obtained product, < ¹ > H-NMR and / or < ¹³ > C-NMR measurement is performed and the measurement result is shown.

In this formula, a carbon atom and a hydrogen atom bonded to the carbon atom are omitted. For example, positions 1 to 4 in this formula are carbon, positions 6, 7, and 9 are CH ₂ groups (methylene), and positions 5 and 8 are CH groups. The same applies to the following equations.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (600 MHz, CD ₃ OD):
δ ppm 3.59 (2H, m), 3.66 (2H, m), 3.89 (1H, m), 3.92 (1H, m), 4.45 / 4.49 (1H, dd) , 4.59 / 4.62 (1H, dd), 4.82 (1H, d)
¹³ C-NMR (150 MHz, CD ₃ OD):
δ ppm 63.4, 63.7, 70.56, 70.61, 71.79, 71.89, 73.4, 73.6, 76.9, 121.17, 121.24, 151.84 151.88, 173.04, 173.07

Production Example 2 Synthesis of 2-O-glyceryl ascorbic acid In an argon atmosphere, L-ascorbic acid (10.0 g) and sodium hydrogen carbonate (9.54 g) were added to water, and the mixture was stirred at room temperature for 30 minutes to give glycidol (8 .41 g) was added. The mixture was heated to 60 ° C. and stirred for 5 hours. Methanol was added and filtered, the filtrate was concentrated under reduced pressure, and 19.0 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with chloroform / methanol / water = 6/4/1, and concentration was performed under reduced pressure to obtain 2-O-glyceryl ascorbic acid (1.21 g) represented by Chemical formula 5. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (400 MHz, CD ₃ OD): δ ppm 3.61 (2H, m), 3.67 (2H, m), 3.90 (1H, m), 3.92 (1H, dt-like) ), 3.92 (1H, m), 4.07 / 4.09 (1H, dd), 4.86 (1H, d)
¹³ C-NMR (100 MHz, CD ₃ OD): δ ppm 63.3, 63.7, 70.4, 72.0, 74.6, 76.8, 122.2, 161.6, 172.9

Production Example 3 Synthesis of 2,3-di-O-glyceryl ascorbic acid In an argon atmosphere, L-ascorbic acid (100 g) and sodium hydrogen carbonate (14.4 g) were added to water, and the mixture was stirred at room temperature for 30 minutes to give glycidol. (42.0 g) was added. The mixture was heated to 50 ° C. and stirred for 5 hours. Thereafter, glycidol (57.5 g) was added, heated to 80 ° C., stirred for 4 hours, and then concentrated under reduced pressure. 232 g of the obtained residue was subjected to alumina column chromatography, eluted with a mixture of chloroform / methanol / water = 6/4/1, concentrated under reduced pressure, and 2,3-diglyceryl represented by Chemical formula 6 Ascorbic acid (23.0 g) was obtained. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (400 MHz, CD ₃ OD):
δ ppm 3.58 (2H, m), 3.61 (2H, m), 3.65 (2H, m), 3.88 (1H, m), 3.91 (1H, m), 3.93 (1H, m), 3.99 (1H, m), 4.16 (1H, m), 4.53 (1H, m), 4.65 (1H, dd), 4.88 (1H, m)
¹³ C-NMR (100 MHz, CD ₃ OD):
δ ppm 63.22, 63.60, 63.63, 63.95, 63.98, 64.44, 70.57, 70.60, 71.68, 71.94, 71.98, 73.87, 74.27, 74.33, 75.06, 76.83, 123.02, 159.48, 172.29

Production Example 4 Synthesis of 3-O- (1,3-dihydroxy-2-propyl) ascorbic acid Ascorbic acid (1.00 g) and sodium hydrogen carbonate (0.14 g) were added to water in an argon atmosphere at room temperature. After stirring for 30 minutes, glycidol (0.42 g) was added. Thereafter, the mixture was heated to 50 ° C. and stirred for 5 hours. After the reaction, water was added and subjected to silica gel column chromatography. Elution was performed with a mixed solution of chloroform / methanol / water = 65/35/5, followed by concentration under reduced pressure to obtain 0.99 g of a crude product. The obtained crude product was fractionated by HPLC using a COSMOSIL 5C ₁₈ -MS-II Waters (20 mm × 250 mm) column at 100% water at a flow rate of 9.9 ml / min. The peak of -O- (1 ', 3'-dihydroxy-2'-propyl) ascorbic acid (8 minutes, 52 mg) was separated and purified. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (500 MHz, CD ₃ OD):
δ ppm 3.67 (2H, m), 3.75 (2H, dd), 3.78 (1H, dd), 3.81 (1H, dd), 3.84 (1H, dd), 4.84 (1H, d), 4.99 (1H, m)
¹³ C-NMR (125 MHz, CD ₃ OD):
δ ppm 62.3, 62.4, 63.3, 70.6, 77.1, 83.3, 120.9, 151.2, 172.9

Production Example 5 Synthesis of 3-O-butylglyceryl ascorbic acid L-ascorbic acid (100 g) and sodium hydrogen carbonate (14.3 g) were added to water under an argon atmosphere, and the mixture was stirred at room temperature for 30 minutes, and butyl glycidyl ether. (73.8 g) was added. The mixture was heated to 80 ° C. and stirred for 12 hours. Then, it extracted with n-butanol. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 96.8 g of the obtained residue was subjected to silica gel column chromatography. Elution was performed with a mixed solution of chloroform / methanol / water = 20/3 / 0.3, and concentration was performed under reduced pressure to obtain 3-O-butylglyceryl ascorbic acid (74.2 g) represented by Chemical formula 8. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (500 MHz, CD ₃ OD):
δ ppm 0.93 (3H, m), 1.38 (2H, m), 1.56 (2H, m), 3.49 (2H, m), 3.50 (2H, m), 3.66 (2H, m), 3.88 (1H, m), 4.03 (1H, m), 4.44 (1H, dd), 4.46 (1H, dd), 4.59 (1H, dd) 4.62 (1H, dd), 4.81 (1H, d)
¹³ C-NMR (125 MHz, CD ₃ OD):
δ ppm 14.2, 20.3, 32.8, 63.36, 63.39, 70.2, 70.4, 70.56, 70.61, 72.4, 72.5, 72.6 73.8, 73.9, 76.8, 121.1, 121.2, 151.7, 151.8, 172.9, 173.0

Production Example 6 Synthesis of 3-O- (2-hydroxyhexyl) ascorbic acid Under argon atmosphere, 30 ml of DMF was added to L-ascorbic acid (5.00 g), and 1,2-epoxyhexane (3.45 g) was further added. It was. The mixture was heated to 80 ° C. and stirred for 24 hours, and then extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 7.56 g of the obtained residue was subjected to silica gel column chromatography, eluted with chloroform / methanol / water = 20/3 / 0.3 mixed solution, concentrated under reduced pressure, and 3- O- (2-hydroxyhexyl) ascorbic acid (1.93 g) was obtained. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (600 MHz, CD ₃ OD):
δ ppm 0.93 (3H, m), 1.36 (2H, m), 1.48 (4H, m), 3.65 (2H, m), 3.88 (1H, m), 4.27 (1H, dd), 4.31 (1H, dd), 4.51 (1H, dd), 4.53 (1H, dd), 4.81 (1H, d)
¹³ C-NMR (150 MHz, CD ₃ OD):
δ ppm 14.3, 23.68, 23.70, 26.68, 28.75, 33.70, 33.74, 63.36, 63.40, 70.6, 70.7, 70.9, 71.1, 76.3, 76.4, 76.8, 120.9, 121.0, 151.8, 151.9, 172.96, 173.02

Production Example 7 Synthesis of 2-O-butylglyceryl ascorbic acid Under argon atmosphere, L-ascorbic acid (5.00 g) and sodium carbonate (6.02 g) were added to water, followed by stirring at room temperature for 30 minutes, and then butylglycidyl. Ether (14.8 g) was added, and the mixture was heated to 80 ° C. and stirred for 12 hours. Thereafter, methanol was added for filtration, and the filtrate was concentrated under reduced pressure, and 20.1 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with a mixed solution of chloroform / methanol / water = 75/35/5, and concentration was performed under reduced pressure to obtain 2-O-butylglyceryl ascorbic acid (1.74 g) represented by Chemical formula 10. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (400 MHz, CD ₃ OD):
δ ppm 0.92 (3H, t), 1.37 (2H, m), 1.55 (2H, m), 3.49 (4H, m), 3.67 (2H, brd), 3.92 (2H, m), 3.99 (1H, m), 4.06 / 4.07 (1H, dd), 4.81 (1H, brs)
¹³ C-NMR (100 MHz, CD ₃ OD):
δ ppm 14.24, 20.25, 32.77, 63.29, 70.55, 70.61, 72.34, 72.64, 72.66, 75.01, 75.09, 77.10, 121.78, 121.82, 163.76, 163.84, 173.32, 173.34

Production Example 8 Synthesis of 3-O-glyceryl-2-O-octylascorbic acid 3-O-glycerylascorbic acid (54.1 g) obtained in Production Example 1 was stirred in DMSO (200 mL) under an argon atmosphere. Further, sodium hydrogen carbonate (18.5 g) was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, octyl bromide (63.7 g) was added, the mixture was heated to 100 ° C., stirred for 3 hours, and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 131 g of the obtained residue was subjected to silica gel column chromatography. Elution was performed with a mixed solution of chloroform / methanol / water = 10/3 / 0.4, and the mixture was concentrated under reduced pressure. 3-O-glyceryl-2-O-octylascorbic acid represented by the chemical formula 11 (48.0 g) Got. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (600 MHz, CD ₃ OD):
δ ppm 0.90 (3H, t), 1.32 (8H, m), 1.42 (2H, m), 1.70 (2H, m), 3.60 (2H, brd), 3.65 (2H, m), 3.89 (1H, m), 3.91 (1H, m), 4.02 (1H, m), 4.47 (1H, dd), 4.48 (1H, dd) , 4.57 (1H, dd), 4.59 (1H, dd), 4.86 (1H, d)
¹³ C-NMR (150 MHz, CD ₃ OD):
δ ppm 14.4, 23.7, 26.9, 30.37, 30.44, 30.8, 33.0, 63.2, 63.56, 63.59, 70.5, 70.6, 71.5, 71.6, 74.01, 74.04, 74.1, 76.7, 123.27, 123.30, 159.2, 159.3, 172.2

Production Example 9 Synthesis of 3-O-glyceryl-2-O-benzylascorbic acid Under argon atmosphere, 3-O-glyceryl ascorbic acid (2.93 g) obtained in Production Example 1 was added to water and sodium hydrogen carbonate (1 .42 g) was added and stirred at room temperature for 30 minutes, benzyl bromide (2.61 g) was added, and the mixture was heated to 50 ° C. and stirred for 2 hours. Then, it concentrated under pressure reduction and melt | dissolved in methanol. The resulting solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and 6.13 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with a mixed solution of chloroform / methanol / water = 10/3 / 0.4, followed by concentration under reduced pressure, and 3-O-glyceryl-2-O-benzylascorbic acid represented by the chemical formula 12 (2.47 g). Got. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (500 MHz, CD ₃ OD):
δ ppm 3.49 (2H, m), 3.65 (2H, m), 3.81 (1H, m), 3.88 (1H, m), 4.47 (1H, dd), 4.28 (1H, dd), 4.36 (1H, dd), 4.37 (1H, dd), 4.85 (1H, brs), 5.05 (2H, m), 7.35 (3H, m) , 7.43 (2H, m)
¹³ C-NMR (175 MHz, CD ₃ OD):
δ ppm 63.21, 63.51, 63.54, 70.54, 70.57, 71.42, 71.49, 74.12, 74.20, 75.25, 75.28, 76.80, 76.82, 122.27, 122.31, 129.60, 129.95, 130.11, 137.61, 159.90, 159.94, 172.17

Production Example 10 Synthesis of 3-O-butylglyceryl-2-O-allyl ascorbic acid Under argon atmosphere, 3-O-butylglyceryl ascorbic acid (3.56 g) obtained in Production Example 5 was mixed with water and sodium bicarbonate. (0.98 g) was added and stirred at room temperature for 30 minutes. Thereafter, allyl bromide (1.68 g) was added, and the mixture was heated to 60 ° C. and stirred for 5 hours, followed by extraction with ethyl acetate. The extract was dried over anhydrous sodium sulfate and then concentrated under reduced pressure, and 3.53 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with chloroform / methanol / water = 30/3 / 0.3 mixed solution, followed by concentration under reduced pressure, and 3-O-butylglyceryl-2-O-allyl ascorbic acid (3.00 g) represented by Chemical formula 13 ) Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (500 MHz, CD ₃ OD):
δ ppm 0.93 (3H, t), 1.39 (2H, m), 1.55 (2H, m), 3.48 (4H, m), 3.65 (2H, m), 3.89 (1H, m), 4.01 (1H, m), 4.457 / 4.464 (1H, dd), 4.54 (2H, m), 4.586 / 4.594 (1H, dd), 4.87 (1H, 1d), 5.25 (1H, m), 5.35 (1H, m), 6.04 (1H, m)
¹³ C-NMR (175 MHz, CD ₃ OD):
δ ppm 14.24, 20.33, 32.83, 63.19, 70.00, 70.10, 70.50, 70.54, 72.42, 72.45, 72.50, 74.14, 74.63, 74.63, 76.77, 76.79, 119.25, 122.50, 122.54, 134.52, 159.67, 159.72, 172.08

Production Example 11 Synthesis of 3-O-octylglyceryl-2-O-hexadecylascorbic acid Under argon atmosphere, sodium hydrogen carbonate (14.3 g) and 200 ml of DMSO were added to L-ascorbic acid (100 g), and octylglycidyl ether was further added. (127 g) was added. The mixture was heated to 80 ° C. and stirred for 24 hours, and then extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and 150 g of the resulting residue was subjected to silica gel column chromatography. Thereafter, elution was performed with a chloroform / methanol / water = 30/3 / 0.3 mixed solution, followed by concentration under reduced pressure to obtain 3-O-octylglyceryl ascorbic acid (36 g). The obtained 3-O-octylglyceryl ascorbic acid (5.17 g) was stirred in DMSO (10 mL) under an argon atmosphere, sodium hydrogen carbonate (1.20 g) and hexadecyl bromide (5.22 g) were added, The mixture was heated to 100 ° C. and stirred for 3 hours. Then, it extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and 9.06 g of the residue was subjected to silica gel column chromatography, eluting with chloroform / methanol / water = 50/3 / 0.3 mixed solution. Then, concentration was performed under reduced pressure to obtain 3-O-octylglyceryl-2-O-hexadecylascorbic acid (3.41 g) represented by Chemical formula 14. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (600 MHz, d ₆ -DMSO):
δ ppm 0.90 (6H, m), 1.24 (34H, brs), 1.34 (2H, m), 1.48 (2H, m), 1.60 (2H, m), 3.38 (4H, m), 3.46 (2H, m), 3.72 (1H, m), 3.87 (1H, m), 3.94 (2H, m), 4.25 (1H, dd) , 4.31 (1H, dd), 4.42 (1H, dd), 4.45 (1H, dd), 4.82 (1H, d)
¹³ C-NMR (150 MHz, d ₆ -DMSO, 40 ° C.):
δ ppm 13.95, 22.13, 25.40, 25.42, 25.63, 25.71, 28.74, 28.78, 28.87, 28.97, 29.09, 29.20, 29.28, 29.30, 31.34, 61.72, 68.04, 68.09, 68.81, 70.88, 71.48, 71.52, 72.14, 73.24, 73. 43, 74.55, 121.29, 157.71, 157.85, 169.42.

Example 1 Antioxidation Test for Oxyalkylene Chain 2 mg of each compound produced in the production example shown in Table 1 as a sample was added and dissolved in 5 g of a 30% aqueous solution of triethylene glycol. This was stored in a constant temperature bath at 50 ° C. for 3 days or 6 days, and the amount of formalin was measured by a colorimetric method. As a comparative product, the same test was carried out using antioxidant-free (triethylene glycol only), ascorbic acid, and ascorbic acid glucoside. The amount of formalin produced is expressed as follows, and the results are shown in Table 1.
○: 30 mg or less Δ: 30 mg or more and 60 mg or less ×: 60 mg or more

  As is apparent from Table 1, the ascorbic acid derivatives of the present invention produced in Production Examples 1 to 11 have a remarkable antioxidant effect as compared with ascorbic acid and ascorbic acid derivatives.

Example 2 Cream Stability Test The raw material of the oil phase part having the composition shown in Table 2 and the raw material of the aqueous phase part containing the compound produced in the production example were each heated to 70 ° C. so that the total amount became 100 g and dissolved. To prepare an oil phase and an aqueous phase, respectively. Thereafter, an oil phase was added to the aqueous phase, preliminary emulsification was performed, and the mixture was uniformly emulsified with a homomixer, and then cooled to room temperature with good stirring to prepare a cream. In addition, a compounding quantity represents a mass part and a residue means the quantity required in order to make a compounding quantity 100 mass parts in total.

  Each cream prepared as described above was stored at 50 ° C. for 1 week and evaluated by 10 panelists based on the following criteria. The results are shown in Table 3.

1. Appearance (state):
3: No separation between the aqueous layer and the oil layer is observed, and there is no precipitation.
2: The water layer is slightly raised or precipitation is slightly confirmed.
1: Separation of the water layer and the oil layer into two layers is not observed, and no precipitation is confirmed.
2. Appearance (color):
3: changed to dark brown 2: changed to brown 1: changed to white or slightly brown Odor:
3: Severe acid odor is observed 2: Acid odor is confirmed 1: Almost no acid odor is observed Feeling of use:
3: There is a feeling of foreign matter and it is difficult to spread 2: There is almost no foreign matter feeling and it is difficult to spread 1: There is almost no foreign matter feeling and it is easy to spread

Each evaluation result of appearance, odor, and feeling of use was classified as follows.
○: Total score of 10 people is 15 or less △: Total score of 10 people is 16-24
×: Total score of 10 people is 25 or more

  As is clear from the results in Table 3, the cream containing the ascorbic acid derivative of the present invention is important for cosmetics in a cream containing an unsaturated bond that undergoes oxidation to change color, odor, and the like. It showed an excellent antioxidant effect without deterioration in a certain color or smell.

Example 3 Antioxidant effect on edible oils and fats 100 g of cottonseed oil was added to a 200 mL beaker, 1 g of each ascorbic acid derivative produced in Production Examples 1 to 11 was added, heated to 80 ° C., and oxygen gas was bubbled at about 50 mL / min. The mixture was stirred for 24 hours. Sampling was performed at 8 and 24 hours from the start of stirring, and the peroxide value (POV) was measured according to the Japan Oil Chemical Society method. As a comparative product, the same test was carried out for antioxidants added (cotton seed oil only), ascorbic acid and ascorbic acid glucoside, and the peroxide value was measured. Peroxide values are classified as follows, and the results are shown in Table 4.

○: 0 to 20 meq / kg or less △: 20 to 40 meq / kg
×: 40 meq / kg or more

  From the results shown in Table 4, when compared with ascorbic acid, the ascorbic acid derivative of the present invention showed the same effect in the results after 8 hours, and the antioxidant ability superior to ascorbic acid in the results after 24 hours. It has a sustained antioxidant effect.

Example 4 Test of retention effect of color and aroma in tea After adding 1500 mL of water to 150 g of tea leaves and refluxing for 5 minutes, the tea leaves were removed by filtration with filter paper. Ascorbic acid derivatives produced in Synthesis Examples 1 to 11 were added to 100 mL of the obtained tea so as to be 0.5% by mass, respectively, and stored in a 200 mL sealable container at room temperature (25 ° C.). As a comparative product, the same test was performed for antioxidant-free (tea liquid only), ascorbic acid and ascorbic acid glucoside. Changes in the color and aroma of the solution after storage for 30 days and 90 days were observed. The changes in the color and aroma were observed after 30 days and 90 days, and were evaluated by 10 panelists based on the following criteria. The results are shown in Table 4.

1. Color 3: Almost unchanged 2: Brown changed 1: Dark brown Fragrance Evaluation was performed by 10 panelists according to the following criteria.
3: Almost unchanged 2: Slightly fragrant 1: Little smell

Each evaluation result of color and aroma was classified as follows.
○: Total score of 10 people is 25 or more Δ: Total score of 10 people is 16-24
×: Total score of 10 people is 15 or less

  From the results of Table 5, the ascorbic acid derivative of the present invention shows good results in both color and aroma after 30 days and after 90 days as compared with ascorbic acid and other ascorbic acid derivatives. It was clear that the ascorbic acid derivative of the present invention has an excellent antioxidant effect.

Claims (2)

An antioxidant comprising an ascorbic acid derivative represented by the following general formula (I) or a salt thereof.
[Wherein, R ¹ and R ² are each a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a benzyl group, R ³ —O—CH ₂ —CH (OH) —CH. Selected from the group consisting of _2- , R ⁴ —O—CH ₂ —CH (CH ₂ OH) —, R ⁵ —CH (CH ₂ OH) —, R ⁶ —CH (OH) —CH ₂ —, and a hydroxycyclohexyl group. Wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group, and R ⁵ and R ⁶ are hydrogen atoms. , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a phenyl group. However, when R ¹ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a benzyl group, R ² is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or 2 to 2 carbon atoms. Neither 22 alkenyl groups nor benzyl groups] In the general formula (I), R ¹ is a hydrogen atom, —CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH, and R ² is —CH ₂ —CH. (OH) _-CH 2 OH or _{-CH (CH 2 OH) -CH 2} OH according to claim 1, characterized in that the (wherein, ^{R 1} and ^{R 2} are not simultaneously represent a hydrogen atom) An antioxidant comprising an ascorbic acid derivative.