Ascorbic acid derivative or salt thereof, and cosmetic product thereof

Abstract

The present invention relates to a novel ascorbic acid derivative or a salt thereof, which has excellent intrinsic functions of ascorbic acid such as a whitening effect, a collagen production promoting effect, and a moisturizing effect, while being stable even when stored for a long period of time, and exhibiting little change in color, smell, or activity, etc. The present invention provides an ascorbic acid derivative or a salt thereof, wherein one hydrogen among hydroxyl groups at a second position and a third position of ascorbic acid has been substituted with R-O-CH2-CH (OH)-CH2-, R-O-CH2-CH (CH2OH)-, R-CH (CH2OH)-, R-CH (OH)-CH2-(R is H, alkyl, alkenyl, or phenyl), HO-C (CH3) 2-CH2-, or HO-CH2-C (CH3) 2-. The invention also provides a cosmetic containing the ascorbic acid derivative or the salt thereof.

Description

Technical Field

[0001] The present invention relates to an ascorbic acid derivative or a salt thereof which is suitable as a raw material for cosmetics, and also to a cosmetic containing the ascorbic acid derivative or a salt thereof. Background Art

[0002] Ascorbic acid is a safe and useful antioxidant and is known as a compound with excellent whitening effect. On the other hand, it is unstable to light, heat and oxidation, which hinders its application in the field of cosmetics. Therefore, various ascorbic acid derivatives or salts thereof have been proposed, which have improved stability over time compared with ascorbic acid, and have been proposed to be incorporated into skin external preparations for whitening (Patent Document 1, Patent Document 2) and into cosmetics (Patent Document 3).

[0003] However, many of the above-mentioned ascorbic acid derivatives and salts thereof have problems such as discoloration and odor generation over time, and their stability over time is still insufficient. In addition, their activity in vivo lasts only for a short period of time, and improvements in these aspects are desired.

[0004] The present inventors have proposed ascorbic acid derivatives that solve these problems (Patent Document 4), but further improvements are desired.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 62-221611

[0008] Patent Document 2: JP 2005-060239 A

[0009] Patent Document 3: Japanese Patent Application Publication No. 1-228978

[0010] Patent Document 4: JP 4681670 B Summary of the invention

[0011] Problems to be solved by the present invention

[0012] An object of the present invention is to provide an ascorbic acid derivative or a salt thereof which has excellent effects inherent to ascorbic acid, such as whitening effect and moisturizing effect, and is highly stable over time (almost no discoloration, odor generation, activity reduction, etc.), and further has excellent physiological activity effects, and to provide a cosmetic preparation containing the same.

[0013] Means of solving the problem

[0014] The present inventors have conducted intensive research on the above-mentioned situation, and have found that a novel ascorbic acid derivative or a salt thereof represented by the following formula (I) has excellent effects such as whitening and moisturizing, is stable over time (almost no discoloration, odor generation, activity reduction, etc.), and has excellent physiological activity effects such as hyaluronic acid production promotion effect. Based on these findings, the present invention has been completed.

[0015] The present invention provides an ascorbic acid derivative or a salt thereof, characterized in that it is represented by the following general formula (I) (claim 1).

[0016] [Chemical formula 1]

[0017]

[0018] [Where R 1 and R 2 is H, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a benzyl group, R 3 -O-CH2-CH(OH)-CH2-、R 3 -O-CH2-CH(CH2OH)-、R 3 -CH(CH2OH)-, R 3 -CH(OH)-CH2-, HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 3 is H, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group, provided that R 1 and R 2 At least one of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-.]

[0019] The salt of ascorbic acid derivative means a compound wherein R 1 or R 2 The H in the ascorbic acid derivative represented by the formula (I) is replaced by a cation such as a metal ion or an ammonium ion. Such salts are also included in the present invention.

[0020] The ascorbic acid derivative or its salt represented by the general formula (I) has excellent stability over time (compared with ascorbic acid or conventional ascorbic acid derivatives), maintains a high residual rate even when stored for several weeks in a high temperature environment higher than room temperature, and suppresses the problems of odor generation and coloration. In addition, it has excellent antioxidant effect compared with conventional ascorbic acid derivatives such as glyceryl ascorbic acid. Among them, an ascorbic acid derivative or its salt having a hydroxyisobutyl group at the 3-position is preferred.

[0021] From which R 1 or R2 The ascorbic acid derivative represented by the general formula (I) wherein H is H can be obtained by reacting ascorbic acid with isobutylene oxide or tert-butyl halide and regiospecifically etherifying only the 2-position and / or 3-position among the four hydroxyl groups at the 2-position, 3-position, 5-position and 6-position of ascorbic acid with HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, as described below.

[0022] In the reaction of ascorbic acid with isobutylene oxide or tert-butyl halide, depending on the etherification reaction conditions, the hydroxyl group at the 2-position may be mainly etherified, or the hydroxyl group at the 3-position may be mainly etherified. When the hydroxyl group at the 2-position is mainly etherified, R 1 is HO-C(CH3)2-CH2- and R 1 It is a mixture of HO-CH2-C(CH3)2-. When the hydroxyl group at the 3-position is mainly etherified, R 2 is HO-C(CH3)2-CH2- and R 2 It is a mixture of HO-CH2-C(CH3)2-.

[0023] Among the ascorbic acid derivatives represented by the general formula (I), the ascorbic acid derivatives wherein R 1 is H and R 2 Those ascorbic acid derivatives which are HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- have excellent melanin production inhibitory effects and collagen production promoting effects.

[0024] Among the ascorbic acid derivatives represented by the general formula (I), the ascorbic acid derivatives wherein R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- and the other is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a benzyl group, a R 3 -O-CH2-CH(OH)-CH2-、R 3 -O-CH2-CH(CH2OH)-、R 3 -CH(CH2OH)- or R 3 -CH(OH)-CH2- and those ascorbic acid derivatives wherein R 1 and R 2 Those ascorbic acid derivatives which are HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- have excellent melanin production inhibitory effect, collagen production promoting effect and hyaluronic acid production promoting effect.

[0025] Among the ascorbic acid derivatives represented by the general formula (I), wherein R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- and the other is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a benzyl group, a R 3 -O-CH2-CH(OH)-CH2-、R 3 -O-CH2-CH(CH2OH)-、R 3 -CH(CH2OH)- or R 3 Those ascorbic acid derivatives containing -CH(OH)-CH2- can be obtained by making R 1 and R 2 One of them is a compound of HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- (which is obtained by reacting ascorbic acid with isobutylene oxide or halogenated tert-butyl alcohol) with glycidol, alkyl glycidyl ether of a specific structure, alkenyl glycidyl ether, phenyl glycidyl ether, sulfate, alkylene oxide, alkenyl oxide, styrene oxide, alkyl halide, hydroxyalkyl halide, benzyl halide, alkenyl halide, hydroxyalkenyl halide, halogenated phenylethanol, etc.; or it can be obtained by reacting ascorbic acid with glycidol, alkyl glycidyl ether of a specific structure, alkenyl glycidyl ether, phenyl glycidyl ether, sulfate, alkylene oxide, alkenyl oxide, styrene oxide, alkyl halide, hydroxyalkyl halide, benzyl halide, alkenyl halide, hydroxyalkenyl halide, halogenated phenylethanol, etc. (having R 1 or R 2 ) and then reacting the resulting compound with isobutylene oxide or tert-butyl halide.

[0026] The invention according to claim 2 is the ascorbic acid derivative or a salt thereof according to claim 1, wherein in the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 Another of the glyceryl groups is an alkyl group having 2 to 20 carbon atoms or a branched alkylglyceryl group having 6 to 20 carbon atoms.

[0027] In the ascorbic acid derivative according to claim 1, wherein R 1 and R 2Those ascorbic acid derivatives in which one of the glyceryl groups is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- and the other is an alkyl group having 2 to 20 carbon atoms (preferably 6 to 16 carbon atoms) or a branched alkylglyceryl group having 6 to 20 carbon atoms (preferably 8 to 14 carbon atoms) are preferred because they have a particularly high hyaluronic acid production promoting effect. Claim 2 corresponds to this particularly preferred embodiment.

[0028] The invention according to claim 3 is the ascorbic acid derivative or a salt thereof according to claim 1, wherein in the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other one is benzyl.

[0029] In the ascorbic acid derivative according to claim 1, wherein R 1 and R 2 Those ascorbic acid derivatives in which one of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- and the other is benzyl are preferred because they exhibit high physiologically active effects such as hyaluronic acid production promoting effect and melanin production inhibiting effect. Claim 3 corresponds to this particularly preferred embodiment.

[0030] The invention according to claim 4 is the ascorbic acid derivative or a salt thereof according to claim 1, wherein in the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other one is R 3 -O-CH2-CH(OH)-CH2- or R 3 -O-CH2-CH(CH2OH)-.

[0031] The ascorbic acid derivatives according to claim 1 have excellent stability over time compared to ascorbic acid, and among them, wherein R 1 and R 2 one of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- and the other is R 3 -O-CH2-CH(OH)-CH2- or R 3Those ascorbic acid derivatives of -O-CH2-CH(CH2OH)- are preferred because they have less odor generation among the ascorbic acid derivatives of the present invention. Claim 4 corresponds to this particularly preferred embodiment.

[0032] The invention according to claim 5 is the ascorbic acid derivative or a salt thereof according to claim 1, wherein in the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other of which is H, alkyl or alkenyl, and R 1 and R 2 The total number of carbon atoms in the 1 and R 2 The other one is R 3 -O-CH2-CH(OH)-CH2-、R 3 -O-CH2-CH(CH2OH)-, HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 3 The number of carbon atoms in is 4 or less.

[0033] The ascorbic acid derivatives according to claim 1 have excellent stability over time compared to ascorbic acid, and among them, those ascorbic acid derivatives are preferred, wherein in the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other of which is H, alkyl or alkenyl, and R 1 and R 2 The total number of carbon atoms in the 1 and R 2 The other one is R 3 -O-CH2-CH(OH)-CH2-、R 3 -O-CH2-CH(CH2OH)-, HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 3 The number of carbon atoms in the esters is 4 or less because they have a high moisturizing effect when incorporated into cosmetics. Claim 5 corresponds to this particularly preferred embodiment.

[0034] The invention according to claim 6 is the ascorbic acid derivative or a salt thereof according to claim 1, wherein in the general formula (I), R1 and R 2 one of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- and R 1 and R 2 The other one is R 3 -CH(CH2OH)- or R 3 -CH(OH)-CH2-, and R 3 is H, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a phenyl group.

[0035] The ascorbic acid derivatives according to claim 1 have excellent stability over time compared to ascorbic acid, and among them, those ascorbic acid derivatives are preferred, wherein in the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other one is R 3 -CH(CH2OH)- or R 3 -CH(OH)-CH2-, and R 3 is H, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a phenyl group, because coloration is suppressed in the ascorbic acid derivatives of the present invention. Claim 6 corresponds to this particularly preferred embodiment.

[0036] By incorporating the ascorbic acid derivative or its salt of the present invention into cosmetics, a cosmetic having excellent whitening and moisturizing effects, being stable even when stored for a long time, and having high physiological activity can be obtained. Therefore, the present invention provides a cosmetic containing the ascorbic acid derivative or its salt of the present invention (claim 7). In addition, since the effect of the present invention is particularly exhibited when the ascorbic acid derivative or its salt is incorporated into cosmetics at 1 to 20% by mass, the present invention also provides a cosmetic in which the ascorbic acid derivative or its salt of the present invention is incorporated in an amount of 1 to 20% by mass (claim 8).

[0037] Effects of the Invention

[0038] The ascorbic acid or its salt represented by the general formula (I) of the present invention has excellent functions inherent to ascorbic acid derivatives such as whitening and moisturizing effects, is stable even after long-term storage (less discoloration, odor generation and activity reduction over time), and has high physiological activities such as antioxidant effects, melanin production inhibitory effects, collagen production promoting effects and hyaluronic acid production promoting effects. Therefore, by incorporating the compound into cosmetics such as skin external preparations and hair cosmetics, cosmetics with excellent whitening and moisturizing effects, stable even after long-term storage and high physiological activity can be obtained. The cosmetics of the present invention are cosmetics (whitening cosmetics, moisturizing cosmetics, etc.) with excellent whitening and moisturizing effects, stable even after long-term storage and high physiological activity. DETAILED DESCRIPTION

[0039] Hereinafter, HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2- will be referred to as "hydroxyisobutyl". Hydroxyisobutyl ascorbic acid refers to ascorbic acid in which a hydroxyisobutyl group is bonded to any one or more oxygens of each hydroxyl group. The ascorbic acid derivative of the present invention is a hydroxyisobutyl ascorbic acid in which a hydroxyisobutyl group is bonded to the 2-position and / or the 3-position.

[0040] Specific examples of the ascorbic acid derivative represented by the general formula (I) include the compounds shown below, but the scope of the present invention is not limited thereto.

[0041] In the following example,

[0042] "Glyceryl" means HOCH2-CH(OH)-CH2- or HOCH2-CH(CH2OH)-;

[0043] "Alkylglyceryl" means RO-CH2-CH(OH)CH2- or RO-CH2-CH(CH2OH)- (R represents an alkyl group);

[0044] "Hydroxyalkyl" refers to a 1-alkyl-2-hydroxyethyl group represented by R-CH(OH)-CH2- (R represents an alkyl group);

[0045] "Hydroxyalkenyl" refers to a 1-alkenyl-2-hydroxyethyl group represented by R-CH(OH)-CH2- (R represents alkenyl);

[0046] The "alkyl" refers to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl and the like.

[0047] The "alkenyl group" refers to vinyl, allyl, butenyl, isobutenyl, crotyl, octenyl, decenyl, dodecenyl and the like.

[0048] (1) 3-O-Hydroxyisobutylascorbic acid

[0049] Examples include

[0050] 3-O-hydroxyisobutyl-2-O-alkyl ascorbic acids, such as 3-O-hydroxyisobutyl-2-O-ethyl ascorbic acid, 3-O-hydroxyisobutyl-2-O-butyl ascorbic acid, 3-O-hydroxyisobutyl-2-O-hexyl ascorbic acid, 3-O-hydroxyisobutyl-2-O-octyl ascorbic acid, 3-O-hydroxyisobutyl-2-O-decyl ascorbic acid, 3-O-hydroxyisobutyl-2-O-ethylhexyl ascorbic acid, 3-O-hydroxyisobutyl-2-O-dodecyl ascorbic acid, 3-O-hydroxyisobutyl-2-O-tetradecyl ascorbic acid and 3-O-hydroxyisobutyl-2-O-hexadecyl ascorbic acid;

[0051] 3-O-hydroxyisobutyl-2-O-alkenyl ascorbic acid, such as 3-O-hydroxyisobutyl-2-O-allyl ascorbic acid, 3-O-hydroxyisobutyl-2-O-octenyl ascorbic acid and 3-O-hydroxyisobutyl-2-O-dodecenyl ascorbic acid;

[0052] 3-O-Hydroxyisobutyl-2-O-glyceryl ascorbic acid;

[0053] 3-O-hydroxyisobutyl-2-O-alkylglyceryl ascorbic acid, such as 3-O-hydroxyisobutyl-2-O-butylglyceryl ascorbic acid, 3-O-hydroxyisobutyl-2-O-ethylhexylglyceryl ascorbic acid and 3-O-hydroxyisobutyl-2-O-dodecylglyceryl ascorbic acid;

[0054] 3-O-hydroxyisobutyl-2-O-enylglyceryl ascorbic acid, such as 3-O-hydroxyisobutyl-2-O-dodecenylglyceryl ascorbic acid;

[0055] 3-O-Hydroxyisobutyl-2-O-phenylglyceryl ascorbic acid;

[0056] 3-O-Hydroxyisobutyl-2-O-benzyl ascorbic acid;

[0057] 3-O-hydroxyisobutyl-2-O-(2-hydroxyalkyl)ascorbic acid, such as 3-O-hydroxyisobutyl-2-O-(2-hydroxypropyl)ascorbic acid, 3-O-hydroxyisobutyl-2-O-(2-hydroxydecyl)ascorbic acid, 3-O-hydroxyisobutyl-2-O-(2-hydroxyhexadecyl)ascorbic acid, and 3-O-hydroxyisobutyl-2-O-(2-hydroxyethylphenyl)ascorbic acid; and

[0058] 3-O-hydroxyisobutyl-2-O-(1-alkyl-2-hydroxyethyl)ascorbic acid, such as 3-O-hydroxyisobutyl-2-O-(1-methyl-2-hydroxyethyl)ascorbic acid, 3-O-hydroxyisobutyl-2-O-(1-ethyl-2-hydroxyethyl)ascorbic acid, 3-O-hydroxyisobutyl-2-O-(1-octyl-2-hydroxyethyl)ascorbic acid, 3-O-hydroxyisobutyl-2-O-(1-tetradecyl-2-hydroxyethyl)ascorbic acid and 3-O-hydroxyisobutyl-2-O-(1-phenyl-2-hydroxyethyl)ascorbic acid.

[0059] (2) 2-O-Hydroxyisobutylascorbic acid

[0060] Examples include

[0061] 2-O-hydroxyisobutyl-3-O-alkyl ascorbic acids, such as 2-O-hydroxyisobutyl-3-O-ethyl ascorbic acid, 2-O-hydroxyisobutyl-3-O-butyl ascorbic acid, 2-O-hydroxyisobutyl-3-O-hexyl ascorbic acid, 2-O-hydroxyisobutyl-3-O-octyl ascorbic acid, 2-O-hydroxyisobutyl-3-O-decyl ascorbic acid, 2-O-hydroxyisobutyl-3-O-ethylhexyl ascorbic acid, 2-O-hydroxyisobutyl-3-O-dodecyl ascorbic acid, 2-O-hydroxyisobutyl-3-O-tetradecyl ascorbic acid and 2-O-hydroxyisobutyl-3-O-hexadecyl ascorbic acid;

[0062] 2-O-hydroxyisobutyl-3-O-alkenyl ascorbic acid, such as 2-O-hydroxyisobutyl-3-O-allyl ascorbic acid, 2-O-hydroxyisobutyl-3-O-octenyl ascorbic acid and 2-O-hydroxyisobutyl-3-O-dodecenyl ascorbic acid;

[0063] 2-O-Hydroxyisobutyl-3-O-glyceryl ascorbic acid;

[0064] 2-O-hydroxyisobutyl-3-O-alkylglyceryl ascorbic acid, such as 2-O-hydroxyisobutyl-3-O-butylglyceryl ascorbic acid, 2-O-hydroxyisobutyl-3-O-ethylhexylglyceryl ascorbic acid and 2-O-hydroxyisobutyl-3-O-dodecylglyceryl ascorbic acid;

[0065] 2-O-hydroxyisobutyl-3-O-enylglyceryl ascorbic acid, such as 2-O-hydroxyisobutyl-3-O-dodecenylglyceryl ascorbic acid;

[0066] 2-O-Hydroxyisobutyl-3-O-phenylglyceryl ascorbic acid;

[0067] 2-O-Hydroxyisobutyl-3-O-benzyl ascorbic acid;

[0068] 2-O-hydroxyisobutyl-3-O-(2-hydroxyalkyl)ascorbic acids, such as 2-O-hydroxyisobutyl-3-O-(2-hydroxypropyl)ascorbic acid, 2-O-hydroxyisobutyl-3-O-(2-hydroxydecyl)ascorbic acid, 2-O-hydroxyisobutyl-3-O-(2-hydroxyhexadecyl)ascorbic acid and 2-O-hydroxyisobutyl-3-O-(2-hydroxyethylphenyl)ascorbic acid;

[0069] 2-O-hydroxyisobutyl-3-O-(1-alkyl-2-hydroxyethyl)ascorbic acid, such as 2-O-hydroxyisobutyl-3-O-(1-methyl-2-hydroxyethyl)ascorbic acid, 2-O-hydroxyisobutyl-3-O-(1-ethyl-2-hydroxyethyl)ascorbic acid, 2-O-hydroxyisobutyl-3-O-(1-octyl-2-hydroxyethyl)ascorbic acid, 2-O-hydroxyisobutyl-3-O-(1-tetradecyl-2-hydroxyethyl)ascorbic acid and 2-O-hydroxyisobutyl-3-O-(1-phenyl-2-hydroxyethyl)ascorbic acid.

[0070] (3) 2,3-Di-O-hydroxyisobutyl ascorbic acid.

[0071] The ascorbic acid derivatives or salts thereof of the present invention can be produced by various methods. For example, by reacting ascorbic acid with isobutylene oxide or tert-butyl halogenate, a hydroxyisobutyl group is introduced into the oxygen atom bonded to the 2- or 3-position of ascorbic acid, thereby synthesizing 2-O-hydroxyisobutyl ascorbic acid or 3-O-hydroxyisobutyl ascorbic acid. Thereafter, another oxygen atom bonded to the 2- or 3-position is alkylated or alkenylated by a known method to obtain the ascorbic acid derivatives of the present invention. The compounds of the present invention can be obtained in the following manner: first, an oxygen atom bonded to the 2- or 3-position of ascorbic acid is alkylated or alkenylated, and then the reaction product is reacted with isobutylene oxide or tert-butyl halogenate.

[0072] Examples of the compound used to introduce a hydroxyisobutyl group in the present invention include, but are not limited to, isobutylene oxide and tert-butyl halide. Examples of tert-butyl halide include tert-butyl fluoride, tert-butyl chloride and tert-butyl bromide.

[0073] In the reaction of ascorbic acid or hydroxyalkylated ascorbic acid with isobutylene oxide or tert-butyl halide, the hydroxyl group at the 2-position may be mainly etherified, or the hydroxyl group at the 3-position may be mainly etherified, depending on the etherification reaction conditions. When the hydroxyl group at the 2-position is mainly etherified, R 1 is HO-C(CH3)2-CH2- and R 1is a mixture of HO-CH2-C(CH3)2-, and when the hydroxyl group at the 3-position is mainly etherified, R 2 is HO-C(CH3)2-CH2- and R 2 It is a mixture of HO-CH2-C(CH3)2-.

[0074] The amount of the isobutylene oxide or the halogenated tert-butyl alcohol used in the present invention is not particularly limited, but is preferably 0.8 to 1.5 mol / mol of ascorbic acid, more preferably 1.0 to 1.2 mol / mol of ascorbic acid.

[0075] The reaction for introducing hydroxyisobutyl in the production of the present invention can be carried out in various solvents. Examples of solvents include, but are not limited to, water, lower alcohols (such as methanol, ethanol and isopropanol), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dioxane, tetrahydrofuran (THF), N-methylpyrrolidone and mixtures thereof. The reaction temperature is not particularly limited, but is preferably in the range of 30 to 100° C., more preferably in the range of 50 to 90° C., and particularly preferably in the range of 60 to 90° C.

[0076] The pH of the reaction solvent is not particularly limited, but when producing an ascorbic acid derivative in which the 2-position of the ascorbic acid structure is H or a salt thereof, acidic conditions are preferred, and a pH of 2 to 6 is particularly preferred. Whereas, when producing an ascorbic acid derivative in which the 3-position of the ascorbic acid structure is H or a salt thereof, alkaline conditions are preferred, and a pH of 8 to 11 is particularly preferred.

[0077] Examples of the pH adjuster used during the reaction include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, gluconic acid, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, and triethylamine.

[0078] The ascorbic acid derivative of the present invention or a salt thereof produced as described above can be purified by means of column chromatography using silica gel, column chromatography using a resin such as an ion exchange resin, treatment with activated carbon, extraction, distillation, crystallization, or the like.

[0079] From which R 1 or R 2The ascorbic acid derivative represented by the above-mentioned general formula (I) wherein H can be formed into salts by replacing the hydrogen ions dissociated from H with cations such as metal ions or ammonium ions, and such salts are also included in the scope of the present invention. Examples of such salts include inorganic salts and organic salts, and examples of inorganic salts include salts of alkali metals (such as sodium and potassium), salts of alkaline earth metals (such as calcium and magnesium), and ammonium salts. Examples of organic salts include diethanolamine salts, triethanolamine salts, and basic amino acid salts. Salts can be formed by methods similar to known salt formation methods, such as by neutralizing R with an alkaline substance. 1 or R 2 A method for forming an aqueous solution of an ascorbic acid derivative of H.

[0080] The hydroxyisobutyl ascorbic acid synthesized as described above can be alkylated, alkenylated, benzylated, hydroxyalkylated, etc. with glycidol, alkyl glycidyl ether of a specific structure, alkenyl glycidyl ether, phenyl glycidyl ether, sulfate, alkylene oxide, alkenyl oxide, styrene oxide, alkyl halide, hydroxyalkyl halide, benzyl alcohol halide, alkenyl halide, hydroxyalkenyl halide, phenylethyl alcohol halide, etc. to obtain the ascorbic acid derivative of claim 2, 3, 4 or 6.

[0081] The amount of glycidol, alkyl glycidyl ether, alkylene oxide, alkylene oxide, styrene oxide or the like used in alkylation, alkenylation, benzylation, phenylation or the like is not particularly limited but is preferably 0.8 to 2.0 mol / mol of hydroxyisobutylascorbic acid.

[0082] The reaction with glycidol, alkyl glycidyl ether, alkylene oxide, alkylene oxide, styrene oxide, etc. can be carried out under the same solvent, the same reaction temperature and the same pH as in the reaction for introducing the hydroxyisobutylene group, and the ascorbic acid derivative of the present invention can be synthesized by purifying the reaction product by means of column chromatography using silica gel, column chromatography using a resin (such as an ion exchange resin), activated carbon treatment, extraction, distillation, crystallization, etc.

[0083] In addition, even when the oxygen atom bonded to the 2- or 3-position of ascorbic acid is first reacted with glycidol, alkyl glycidyl ether, alkylene oxide, alkylene oxide, styrene oxide or the like and then a hydroxyisobutyl group is introduced onto the other oxygen atom, each reaction can be performed under the same conditions as described above.

[0084] The ascorbic acid derivative or a salt thereof of the present invention can be suitably used as a component of various cosmetics such as external preparations for skin and hair cosmetics, and can also be used as a food additive, feed, and the like.

[0085] When the ascorbic acid derivative or its salt of the present invention is compounded into various cosmetics, the compounding amount is preferably 1 wt % to 20 wt %, and particularly preferably in the range of 3 wt % to 10 wt %. If the compounding amount is less than 1 wt %, the effects of the ascorbic acid derivative or its salt of the present invention such as whitening effect and hyaluronic acid production promoting effect are usually not fully exhibited. On the other hand, if it exceeds 20 wt %, the effect commensurate with the compounding amount is usually not expected, and there is a risk of damaging the formulation system.

[0086] In addition to these essential components, the cosmetics of the present invention may contain, as appropriate, commonly used components such as oily raw materials, surfactants, humectants, polymer compounds, antioxidants, whitening agents, drugs, ultraviolet absorbers, chelating agents, proteins, protein hydrolyzates or derivatives thereof, amino acids or derivatives thereof, pH adjusters, preservatives, etc. The ascorbic acid derivatives or salts thereof of the present invention are also effective as humectants, and other humectants may also be compounded in the cosmetics of the present invention.

[0087] Examples of the oil-based raw materials, surfactants, other moisturizers, polymer compounds, antioxidants, other whitening agents, other drugs, ultraviolet absorbers, chelating agents, proteins, protein hydrolysates or derivatives thereof, amino acids or derivatives thereof, pH adjusters, preservatives, and the like include those similar to those described in JP 2022-028125A.

[0088] The cosmetic composition of the present invention may have any reagent system (including a solution system, a solubilization system, an emulsion system, a gel system, a powder dispersion system and a water-oil double-layer system), and may be produced by mixing the ascorbic acid derivative represented by the above general formula (I) or a salt thereof with the above-mentioned optional mixing components according to the desired product.

[0089] Example

[0090] Next, specific embodiments for implementing the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to these examples.Before the examples, examples of production of the ascorbic acid derivatives of the present invention used in the examples and comparative examples will be described as synthesis examples.

[0091] Synthesis Example 1 Synthesis of 2-O-(2-hydroxyisobutyl)ascorbic acid

[0092] In an eggplant-shaped flask, water (10.5mL), DMF (5mL), ascorbic acid (10.0g), sodium hydroxide (2.50g) and isobutylene oxide (4.50g) were added, and the resulting mixture was stirred at 60°C for 4 hours. After the reaction was complete, 5mol / L hydrochloric acid was added to make the pH acidic. Then, the mixture was concentrated under reduced pressure, and isopropanol was added, followed by filtration and concentration under reduced pressure. The resulting residue (10.1g) was subjected to silica gel chromatography, eluted with a mixture of chloroform / methanol=10 / 0 to 6 / 4, and concentrated under reduced pressure to obtain 2-O-(2-hydroxyisobutyl) ascorbic acid (8.83g).

[0093] The obtained product was subjected to mass spectrometry, 1 H-NMR and 13 C-NMR measurement was performed, and the measurement results confirmed that the product was 2-O-(2-hydroxyisobutyl)ascorbic acid represented by the following structural formula:

[0094] [Chemical formula 2]

[0095]

[0096] In this structural formula, carbon atoms and hydrogen atoms bonded to carbon atoms are omitted. For example, in this formula, positions 1, 2, 4, 6, and 7 are carbon, position 5 is a CH3 group, positions 3 and 9 are CH2 groups, and position 8 is a CH group. In the following structural formula, hydrogen atoms and carbon atoms are omitted in the same manner as in this formula.

[0097] In the following synthesis examples, the obtained products were also subjected to mass spectrometry, 1 H-NMR and 13 C-NMR measurement was performed, and the measurement results confirmed that each product was an ascorbic acid derivative represented by the structural formula or compound name shown in each synthesis example. 1 H-NMR and 13 The measurement results of the C-NMR measurement are shown in Tables 1 to 8.

[0098] Synthesis Example 2 Synthesis of 3-O-(2-hydroxyisobutyl)ascorbic acid

[0099] In the same manner as in Synthesis Example 1, except using DMF (50 mL) instead of water, DMF and using triethylamine (1.72 g) instead of sodium hydroxide, the title 3-O-(2-hydroxyisobutyl)ascorbic acid (7.42 g) was obtained.

[0100] [Chemical formula 3]

[0101]

[0102] Synthesis Example 3 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-ethyl ascorbic acid

[0103] In an eggplant-shaped flask, 2-O-(2-hydroxyisobutyl) ascorbic acid (1.50 g), DMF (6 mL), triethylamine (1.22 g) and diethyl sulfate (1.86 g) obtained in Synthesis Example 1 were added, and the mixture was stirred at 70 ° C for 4 hours. After the reaction was completed, ion exchange water and ethyl acetate were added, and the separation operation of the mixture was performed. The ethyl acetate layer was collected, and the extract was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting residue (1.16 g) was subjected to silica gel chromatography, eluted with a mixture of chloroform / methanol=10 / 0 to 7 / 3, and concentrated under reduced pressure to obtain 2-O-(2-hydroxyisobutyl)-3-O-ethyl ascorbic acid (148.5 mg) represented by the following structural formula.

[0104] [Chemical formula 4]

[0105]

[0106] Synthesis Example 4 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-butyl ascorbic acid

[0107] In the same manner as in Synthesis Example 3, except using sodium bicarbonate (1.27 g) instead of triethylamine and butyl bromide (1.08 g) instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-butylascorbic acid (710.3 mg) was obtained.

[0108] [Chemical formula 5]

[0109]

[0110] Synthesis Example 5 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-hexylascorbic acid

[0111] In the same manner as in Synthesis Example 3, except using sodium bicarbonate (1.27 g) instead of triethylamine and using hexyl bromide (1.30 g) instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-hexylascorbic acid (473.7 mg) was obtained.

[0112] [Chemical formula 6]

[0113]

[0114] Synthesis Example 6 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-octylascorbic acid

[0115] The title 2-O-(2-hydroxyisobutyl)-3-O-octylascorbic acid (148.5 mg) was obtained in the same manner as in Synthesis Example 3, except that sodium bicarbonate (1.52 g) was used instead of triethylamine and octyl bromide (1.75 g) was used instead of diethyl sulfate.

[0116] [Chemical formula 7]

[0117]

[0118] Synthesis Example 7 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-decyl ascorbic acid

[0119] In the same manner as in Synthesis Example 3, except using sodium bicarbonate (1.27 g) instead of triethylamine and using decyl bromide (1.74 g) instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-decylascorbic acid (371.2 mg) was obtained.

[0120] [Chemical formula 8]

[0121]

[0122] Synthesis Example 8 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-dodecyl ascorbic acid

[0123] In the same manner as in Synthesis Example 3, except using sodium bicarbonate (1.27 g) instead of triethylamine and using dodecyl bromide (1.96 g) instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-dodecylascorbic acid (358.8 mg) was obtained.

[0124] [Chemical formula 9]

[0125]

[0126] Synthesis Example 9 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-tetradecyl ascorbic acid

[0127] In the same manner as in Synthesis Example 3, except using sodium bicarbonate (1.27 g) instead of triethylamine and using tetradecyl bromide (2.18 g) instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-tetradecylascorbic acid (328.8 mg) was obtained.

[0128] [Chemical formula 10]

[0129]

[0130] Synthesis Example 10: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-hexadecyl ascorbic acid

[0131] In the same manner as in Synthesis Example 3, except that sodium bicarbonate (1.27 g) was used instead of triethylamine and cetyl bromide (1.85 g) was used instead of diethyl sulfate, 2-O-(2-hydroxyisobutyl)-3-O-hexadecylascorbic acid (258.0 mg) of the title was obtained.

[0132] [Chemical formula 11]

[0133]

[0134] Synthesis Example 11 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-allyl ascorbic acid

[0135] In the same manner as in Synthesis Example 3, except using sodium bicarbonate (1.52 g) instead of triethylamine and allyl bromide (1.10 g) instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-allyl ascorbic acid (366.4 mg) was obtained.

[0136] [Chemical formula 12]

[0137]

[0138] Synthesis Example 12 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-benzyl ascorbic acid

[0139] In the same manner as in Synthesis Example 3, except using sodium bicarbonate (1.52 g) instead of triethylamine and benzyl bromide (1.55 g) instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-benzylascorbic acid (602.2 mg) was obtained.

[0140] [Chemical formula 13]

[0141]

[0142] Synthesis Example 13: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-glyceryl ascorbic acid

[0143] In an eggplant-shaped flask, 3-O-glyceryl ascorbic acid (3.00 g), DMF (12 mL), triethylamine (0.24 g) and isobutylene oxide (1.04 g) were added, and the mixture was stirred at 85 ° C for 18 hours. After the reaction was completed, ion exchange water and ethyl acetate were added, and the separation operation of the mixture was performed. The ethyl acetate layer was collected, and the extract was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting residue (1.12 g) was subjected to silica gel chromatography, eluted with a mixture of chloroform / methanol = 9.5 / 0.5 to 7 / 3, and concentrated under reduced pressure to obtain 2-O-(2-hydroxyisobutyl)-3-O-glyceryl ascorbic acid (178.6 mg) represented by the following structural formula.

[0144] [Chemical formula 14]

[0145]

[0146] Synthesis Example 14: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxy-3-O-butyl)ascorbic acid

[0147] The title 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxy-3-O-butyl)ascorbic acid (216.6 mg) was obtained in the same manner as in Synthesis Example 3, except that sodium bicarbonate (0.20 g) was used instead of triethylamine and butyl glycidyl ether (1.89 g) was used instead of diethyl sulfate.

[0148] [Chemical formula 15]

[0149]

[0150] Synthesis Example 15: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxy-3-O-ethylhexyl)ascorbic acid

[0151] The title 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxy-3-O-ethylhexyl)ascorbic acid (375.9 mg) was obtained in the same manner as in Synthesis Example 3, except that sodium bicarbonate (0.20 g) was used instead of triethylamine and ethylhexyl glycidyl ether (2.70 g) was used instead of diethyl sulfate.

[0152] [Chemical formula 16]

[0153]

[0154] Synthesis Example 16: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxy-3-O-dodecyl)ascorbic acid

[0155] The title 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxy-3-O-dodecyl)ascorbic acid (450.3 mg) was obtained in the same manner as in Synthesis Example 3, except that sodium bicarbonate (0.20 g) was used instead of triethylamine and lauryl glycidyl ether (3.52 g) was used instead of diethyl sulfate.

[0156] [Chemical formula 17]

[0157]

[0158] Synthesis Example 17 Synthesis of 2,3-di-O-(2-hydroxyisobutyl)ascorbic acid

[0159] The title 2,3-di-O-(2-hydroxyisobutyl)ascorbic acid (500.9 mg) was obtained in the same manner as in Synthesis Example 3, except that isobutylene oxide (1.05 g) was used instead of diethyl sulfate.

[0160] [Chemical formula 18]

[0161]

[0162] Synthesis Example 18 Synthesis of 2-O-ethyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0163] In an eggplant-shaped flask, 3-O-(2-hydroxyisobutyl) ascorbic acid (3.00 g), DMF (12 mL), triethylamine (1.35 g) and diethyl sulfate (2.42 g) obtained in Synthesis Example 2 were added, and the mixture was stirred at 80 ° C for 5 hours. After the reaction was completed, ion exchange water and ethyl acetate were added, and the separation operation of the mixture was performed. The ethyl acetate layer was collected, and the extract was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting residue (2.41 g) was subjected to silica gel chromatography, eluted with a mixture of chloroform / methanol=10 / 0 to 9 / 1, and concentrated under reduced pressure to obtain 2-O-ethyl-3-O-(2-hydroxyisobutyl) ascorbic acid (443.0 mg) represented by the following structural formula.

[0164] [Chemical formula 19]

[0165]

[0166] Synthesis Example 19: Synthesis of 2-O-butyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0167] The title 2-O-butyl-3-O-(2-hydroxyisobutyl)ascorbic acid (464.8 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.56 g) was used instead of triethylamine and butyl bromide (0.99 g) was used instead of diethyl sulfate.

[0168] [Chemical formula 20]

[0169]

[0170] Synthesis Example 20: Synthesis of 2-O-hexyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0171] The title 2-O-hexyl-3-O-(2-hydroxyisobutyl)ascorbic acid (617.8 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.56 g) was used instead of triethylamine and hexyl bromide (1.20 g) was used instead of diethyl sulfate.

[0172] [Chemical formula 21]

[0173]

[0174] Synthesis Example 21 Synthesis of 2-O-octyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0175] The title 2-O-octyl-3-O-(2-hydroxyisobutyl)ascorbic acid (1.05 g) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (1.12 g) was used instead of triethylamine and octyl bromide (2.80 g) was used instead of diethyl sulfate.

[0176] [Chemical formula 22]

[0177]

[0178] Synthesis Example 22 Synthesis of 2-O-decyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0179] The title 2-O-decyl-3-O-(2-hydroxyisobutyl)ascorbic acid (216.7 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.56 g) was used instead of triethylamine and decyl bromide (1.60 g) was used instead of diethyl sulfate.

[0180] [Chemical formula 23]

[0181]

[0182] Synthesis Example 23: Synthesis of 2-O-dodecyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0183] The title 2-O-dodecyl-3-O-(2-hydroxyisobutyl)ascorbic acid (248.9 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.56 g) was used instead of triethylamine and dodecyl bromide (1.81 g) was used instead of diethyl sulfate.

[0184] [Chemical formula 24]

[0185]

[0186] Synthesis Example 24: Synthesis of 2-O-tetradecyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0187] The title 2-O-tetradecyl-3-O-(2-hydroxyisobutyl)ascorbic acid (383.9 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.56 g) was used instead of triethylamine and tetradecyl bromide (2.01 g) was used instead of diethyl sulfate.

[0188] [Chemical formula 25]

[0189]

[0190] Synthesis Example 25: Synthesis of 2-O-hexadecyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0191] In the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.56 g) was used instead of triethylamine and cetyl bromide (2.21 g) was used instead of diethyl sulfate, 2-O-hexadecyl-3-O-(2-hydroxyisobutyl)ascorbic acid (234.5 mg) of the title was obtained.

[0192] [Chemical formula 26]

[0193]

[0194] Synthesis Example 26: Synthesis of 2-O-allyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0195] In the same manner as in Synthesis Example 18, except using sodium bicarbonate (0.70 g) instead of triethylamine and allyl bromide (0.88 g) instead of diethyl sulfate, the title 2-O-allyl-3-O-(2-hydroxyisobutyl)ascorbic acid (276.0 mg) was obtained.

[0196] [Chemical formula 27]

[0197]

[0198] Synthesis Example 27 Synthesis of 2-O-benzyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0199] In the same manner as in Synthesis Example 18, except using sodium bicarbonate (1.12 g) instead of triethylamine and using benzyl bromide (2.07 g) instead of diethyl sulfate, the title 2-O-benzyl-3-O-(2-hydroxyisobutyl)ascorbic acid (511.5 mg) was obtained.

[0200] [Chemical formula 28]

[0201]

[0202] Synthesis Example 28: Synthesis of 2-O-glyceryl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0203] In the same manner as in Synthesis Example 13, except that 2-O-glyceryl ascorbic acid (3.0 g) was used instead of 3-O-glyceryl ascorbic acid, the title 2-O-glyceryl-3-O-(2-hydroxyisobutyl)ascorbic acid (243.7 mg) was obtained.

[0204] [Chemical formula 29]

[0205]

[0206] Synthesis Example 29: Synthesis of 2-O-(2-hydroxy-3-O-butyl)-3-O-(2-hydroxyisobutyl)ascorbic acid

[0207] 2-O-(2-hydroxy-3-O-butyl)-3-O-(2-hydroxyisobutyl)ascorbic acid (579.4 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.20 g) was used instead of triethylamine and butyl glycidyl ether (1.89 g) was used instead of diethyl sulfate.

[0208] [Chemical formula 30]

[0209]

[0210] Synthesis Example 30: Synthesis of 2-O-(2-hydroxy-3-O-ethylhexyl)-3-O-(2-hydroxyisobutyl)ascorbic acid

[0211] 2-O-(2-hydroxy-3-O-ethylhexyl)-3-O-(2-hydroxyisobutyl)ascorbic acid (358.8 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.20 g) was used instead of triethylamine and ethylhexyl glycidyl ether (2.70 g) was used instead of diethyl sulfate.

[0212] [Chemical formula 31]

[0213]

[0214] Synthesis Example 31 Synthesis of 2-O-(2-hydroxy-3-O-dodecyl)-3-O-(2-hydroxyisobutyl)ascorbic acid

[0215] The title 2-O-(2-hydroxy-3-O-dodecyl)-3-O-(2-hydroxyisobutyl)ascorbic acid (458.0 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.10 g) was used instead of triethylamine and lauryl glycidyl ether (1.76 g) was used instead of diethyl sulfate.

[0216] [Chemical formula 32]

[0217]

[0218] Synthesis Example 32 Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-propyl ascorbic acid

[0219] In the same manner as in Synthesis Example 3, except using sodium bicarbonate (1.27 g) instead of triethylamine and propyl bromide (0.97 g) instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-butyl ascorbic acid (642.7 mg) was obtained.

[0220] [Chemical formula 33]

[0221]

[0222] Synthesis Example 33: Synthesis of 2-O-propyl-3-O-(2-hydroxyisobutyl)ascorbic acid

[0223] The title 2-O-propyl-3-O-(2-hydroxyisobutyl)ascorbic acid (423.7 mg) was obtained in the same manner as in Synthesis Example 18, except that sodium bicarbonate (0.56 g) was used instead of triethylamine and propyl bromide (1.26 g) was used instead of diethyl sulfate.

[0224] [Chemical formula 34]

[0225]

[0226] Synthesis Example 34: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxypropyl)ascorbic acid

[0227] The title 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxypropyl)ascorbic acid (0.17 g) was obtained in the same manner as in Synthesis Example 3, except that propylene oxide (0.64 g) was used instead of diethyl sulfate.

[0228] [Chemical formula 35]

[0229]

[0230] Synthesis Example 35: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxybutyl)ascorbic acid

[0231] The title 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxybutyl)ascorbic acid (0.18 g) was obtained in the same manner as in Synthesis Example 3, except that butylene oxide (0.80 g) was used instead of diethyl sulfate.

[0232] [Chemical formula 36]

[0233]

[0234] Synthesis Example 36: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxydecyl)ascorbic acid

[0235] 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxydecyl)ascorbic acid (0.11 g) was obtained in the same manner as in Synthesis Example 3, except that sodium bicarbonate (0.14 g) and tetrabutylammonium bromide (0.77 g) were used instead of triethylamine and decyl oxide (1.63 g) was used instead of diethyl sulfate.

[0236] [Chemical formula 37]

[0237]

[0238] Synthesis Example 37: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxyhexadecyl)ascorbic acid

[0239] The title 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxyhexadecyl)ascorbic acid (0.55 g) was obtained in the same manner as in Synthesis Example 3, except that hexadecane oxide (2.65 g) was used instead of diethyl sulfate.

[0240] [Chemical formula 38]

[0241]

[0242] Synthesis Example 38: Synthesis of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxyethylbenzene)ascorbic acid

[0243] In the same manner as in Synthesis Example 3, except that styrene oxide (1.32 g) was used instead of diethyl sulfate, the title 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxyethylphenyl)ascorbic acid (0.65 g) was obtained.

[0244] [Chemical formula 39]

[0245]

[0246] Synthesis Example 39: Synthesis of 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxypropyl)ascorbic acid

[0247] The title 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxypropyl)ascorbic acid (0.38 g) was obtained in the same manner as in Synthesis Example 18, except that diazabicycloundecene (0.15 g) was used instead of DMF, DMAc (5.0 mL) was used instead of triethylamine, and propylene oxide (0.35 g) was used instead of diethyl sulfate.

[0248] [Chemical formula 40]

[0249]

[0250] Synthesis Example 40: Synthesis of 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxybutyl)ascorbic acid

[0251] The title 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxybutyl)ascorbic acid (0.27 g) was obtained in the same manner as in Synthesis Example 18, except that diazabicycloundecene (0.15 g) was used instead of DMF, DMAc (5.0 mL) was used instead of triethylamine, and butylene oxide (0.43 g) was used instead of diethyl sulfate.

[0252] [Chemical formula 41]

[0253]

[0254] Synthesis Example 41 Synthesis of 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxydecyl)ascorbic acid

[0255] The title 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxydecyl) ascorbic acid (0.30 g) was obtained in the same manner as in Synthesis Example 18, except that diazabicycloundecene (0.15 g) was used instead of DMF, DMAc (5.0 mL) was used instead of triethylamine, and decene oxide (0.94 g) was used instead of diethyl sulfate.

[0256] [Chemical formula 42]

[0257]

[0258] Synthesis Example 42: Synthesis of 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxyhexadecyl)ascorbic acid

[0259] In the same manner as in Synthesis Example 18, except that diazabicycloundecene (0.15 g) was used instead of DMF, DMAc (5.0 mL) was used instead of triethylamine, and hexadecane oxide (1.44 g) was used instead of diethyl sulfate, 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxyhexadecyl)ascorbic acid (0.30 g) was obtained.

[0260] [Chemical formula 43]

[0261]

[0262] Synthesis Example 43: Synthesis of 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxyethylbenzene)ascorbic acid

[0263] The title 3-O-(2-hydroxyisobutyl)-2-O-(2-hydroxyethylbenzene) ascorbic acid (0.48 g) was obtained in the same manner as in Synthesis Example 18, except that diazabicycloundecene (0.15 g) was used instead of DMF, DMAc (5.0 mL) was used instead of triethylamine, and styrene oxide (0.74 g) was used instead of diethyl sulfate.

[0264] [Chemical formula 44]

[0265]

[0266] The mass spectrometry analysis of the reaction products obtained in Synthesis Examples 1 to 43 was performed using LCMS-2020 (manufactured by Shimadzu Corporation).

[0267] [Table 1]

[0268]

[0269]

[0270] *Ionization was performed by electrospray ionization (ESI).

[0271] The reaction products obtained in Synthesis Examples 1 to 43 were subjected to 1 H-NMR The measurement results are shown in Tables 2 to 5.

[0272] [Table 2]

[0273]

[0274]

[0275] [Table 3]

[0276]

[0277]

[0278] [Table 4]

[0279]

[0280]

[0281] [Table 5]

[0282]

[0283]

[0284] The products obtained in Synthesis Examples 1 to 43 were subjected to 13 C-NMR. The measurement results are shown in Tables 6 to 8.

[0285] [Table 6]

[0286]

[0287]

[0288] [Table 7]

[0289]

[0290]

[0291] [Table 8]

[0292]

[0293]

[0294] Test Example 1 [Melanin production inhibition effect]

[0295] As a test of whitening effect, the effect of the ascorbic acid derivatives of the present invention on theophylline-induced melanin production in B16 melanoma 4A5 cells was evaluated according to the following procedure. For comparison, similar evaluations were also performed on known ascorbic acid derivatives. The results are shown in Tables 9 to 11.

[0296] (1) B16 mouse melanoma 4A5 cells were cultured at 8.0×10 3 The cells were seeded into 48-well plates at a density of 10 cells / well.

[0297] (2) After culturing in Dulbecco's modified Eagle's medium (manufactured by SIGMA, hereinafter referred to as "D-MEM") containing 10% fetal bovine serum for 24 hours, the medium was replaced with D-MEM containing 10% fetal bovine serum, which contained theophylline (final concentration 1 mmol / L) and a sample at a specified concentration.

[0298] (3) After culturing for 3 days in the presence of the sample, the culture medium was removed using an aspirator, distilled water was added, and the cells were disrupted by ultrasonic treatment.

[0299] (4) The amount of protein was then quantified using a BCA protein assay kit (manufactured by PIERCE), and the amount of melanin produced was measured by alkaline dissolution. Sodium hydroxide was added to the cell lysate to a final concentration of 1 mol / L, and the solution was dissolved by heating (60°C, 30 minutes), after which the absorbance at 405 nm was measured using a microplate reader. The amount of melanin was calculated based on a calibration curve prepared using synthetic melanin (SIGMA) as a standard. The amount of melanin per unit protein was calculated by dividing the amount of melanin by the amount of protein.

[0300] (5) The melanin production inhibition rate was calculated using the following formula.

[0301] Melanin production inhibition rate (%) = [1-(AB) / (CB)] × 100

[0302] [In this formula, A represents the amount of melanin per unit protein (g / g) when the sample is added, B represents the amount of melanin per unit protein in the normal group (g / g), and C represents the amount of melanin per unit protein in the control group (g / g).]

[0303] The melanin production inhibition rate when the sample was measured at a concentration of 10 mM or less is expressed as follows. The measurement was performed with N=4.

[0304] <20%: ±

[0305] 20-40%: +

[0306] 40-60%: ++

[0307] 60-100%: +++

[0308] [Table 9]

[0309]

[0310] [Table 10]

[0311]

[0312]

[0313] [Table 11]

[0314]

[0315]

[0316] The results in Tables 9 to 11 show that the ascorbic acid derivatives of the present invention have whitening effects equal to or greater than those of known ascorbic acid derivatives (ie, 2-O-glyceryl ascorbic acid and 3-O-glyceryl ascorbic acid).

[0317] Test Example 2 [Stability Test]

[0318] Utilize dilute potassium hydroxide aqueous solution, the 1% aqueous solution of each test sample is adjusted to pH 6, is placed in 50mL screw cap tube, is sealed, and is stored at 50 ℃ for 4 weeks, then is measured by HPLC (using the liquid chromatography manufactured by Shimadzu Corporation) to determine the residual rate according to the peak area. The residual rate, odor and coloration degree are evaluated according to the following methods and standards. The results are shown in Tables 12 and 13.

[0319] Residual rate:

[0320] ◎:More than 90%

[0321] 〇: 80% or more, less than 90%

[0322] △: 60% or more, less than 80%

[0323] ×: 20% or more, less than 60%

[0324] ××: less than 20%

[0325] Odor: Evaluation was conducted by 10 panelists according to the following criteria.

[0326] 3: Almost no odor.

[0327] 2: There is a slight strange smell.

[0328] 1: A strong odor is detected.

[0329] Based on the evaluation results, the following classification is made:

[0330] ◎: Total score of 10 team members is 25 or above

[0331] 0:Total score of 10 team members is 20-24

[0332] △: Total score of 10 team members is 16-19

[0333] ×: The total score of 10 panelists was 15 or less Coloring: Evaluation was performed by 10 panelists according to the following criteria.

[0334] 3: Almost no change compared to just after preparation.

[0335] 2: The color has changed compared to that immediately after preparation.

[0336] 1: Strongly colored compared to just after preparation.

[0337] Based on the evaluation results, the following classification is made:

[0338] 0:Total score of 10 team members is 25 or above

[0339] △: Total score of 10 team members is 16-24

[0340] ×: The total score of the 10 team members is less than 15

[0341] [Table 12]

[0342]

[0343]

[0344] [Table 13]

[0345]

[0346]

[0347] Compared with ascorbic acid, the ascorbic acid derivative of the present invention has excellent stability over time when stored at 50°C, and shows almost no odor generation or coloration, etc. In other words, the results shown in Tables 12 and 13 show that the ascorbic acid derivative of the present invention has excellent properties inherent to ascorbic acid such as excellent whitening effect, and also has improved stability over time, which is a problem with conventional ascorbic acid derivatives, and is therefore more suitable as an ingredient for cosmetics.

[0348] Test Example 3 [Antioxidant Test]

[0349] Normal human epidermal keratinocytes were seeded into 96-well plates using KG2 medium to a cell density of 2.0 × 104 Cells / well. After pre-incubation for 24 hours, a sample adjusted to a predetermined concentration with KG2 medium was added to each well. After culturing for 24 hours and removing the medium, the wells were washed with HBSS (-), and the ROS-responsive fluorescent probe DCFHDA was incorporated for 30 minutes. The wells were washed with HBSS (-) again, treated with 0.2mM H2O2, and cultured for 2 hours. The fluorescence intensity was measured, and the amount of ROS produced per unit protein was calculated by dividing the fluorescence intensity by the amount of protein quantified by the BCA method. The results are shown in Table 14.

[0350] The antioxidant effect when the sample was measured at a concentration of 10 mM or less is shown below. The measurement was performed with N=4.

[0351] <20%: ±

[0352] 20-40%: +

[0353] 40-70%: ++

[0354] 70-100%: +++

[0355] [Table 14]

[0356] Example No. Ascorbic acid derivative or its salt Antioxidant Effect Compare 2-O-Glyceryl Ascorbic Acid ± Compare 3-O-Glyceryl Ascorbic Acid + 57 2-O-(2-Hydroxyisobutyl)ascorbic acid (Synthesis Example 1) ++ 58 3-O-(2-Hydroxyisobutyl)ascorbic acid (Synthesis Example 2) ++ 59 2-O-(2-Hydroxyisobutyl)-3-O-ethylascorbic acid (Synthesis Example 3) ++ 60 2-O-Ethyl-3-O-(2-hydroxyisobutyl)ascorbic acid (Synthesis Example 18) ++

[0357] The results in Table 14 show that the ascorbic acid derivatives of the present invention have excellent antioxidant effects compared to known ascorbic acid derivatives or salts thereof (ie, 2-O-glyceryl ascorbic acid and 3-O-glyceryl ascorbic acid).

[0358] Test Example 4 [Collagen production promotion effect]

[0359] Normal human dermal fibroblasts were cultured in D-MEM containing 5% (v / v) fetal bovine serum at a concentration of 2.5 × 10 4 The cells were cultured at a cell density of 10 cells / well and pre-incubated in a 96-well plate for 24 hours. After removing the culture medium, a sample prepared at a predetermined concentration in D-MEM containing 5% (v / v) fetal bovine serum was added to each well and cultured for 48 hours. After the culture was completed, the amount of free collagen in the supernatant was quantified by ELISA. The measurement was performed with N=3.

[0360] The amount of collagen produced when the samples were measured at a concentration of 10 mmol / L or less was compared with the control group, and the results (% values ​​when the control group was taken as 100%) are shown in Tables 15 to 17 based on the following criteria.

[0361] <100%: ±

[0362] 100-120%: +

[0363] 120% <: ++

[0364] [Table 15]

[0365]

[0366] [Table 16]

[0367]

[0368]

[0369] [Table 17]

[0370]

[0371]

[0372] The results in Tables 15 to 17 clearly show that the ascorbic acid derivatives of the present invention have a collagen production promoting effect equal to or greater than that of known ascorbic acid derivatives or salts thereof (ie, 2-O-glyceryl ascorbic acid and 3-O-glyceryl ascorbic acid).

[0373] Test Example 5 [Hyaluronic acid production promoting effect]

[0374] Normal human dermal fibroblasts (NHDF) were cultured in D-MEM containing 5% (v / v) fetal bovine serum at a volume of 2.5 × 10 4 The cells were cultured at a cell density of 10 cells / well and then pre-incubated in a 96-well plate for 24 hours. After removing the culture medium, samples prepared in serum-free D-MEM were added to each well and cultured for 48 hours. After the culture was completed, the amount of hyaluronic acid in the supernatant was quantified by ELISA. The measurement was performed with N=3.

[0375] The amount of hyaluronic acid produced when the sample was measured at a concentration of 10 mmol / L or less was compared with that of the control group, and the results (% value when the control group was taken as 100%) are shown in Tables 18 to 20 based on the following criteria.

[0376] <100%: ±

[0377] 100-120%: +

[0378] 120-150%: ++

[0379] 150% <:+++

[0380] [Table 18]

[0381]

[0382]

[0383] [Table 19]

[0384]

[0385] [Table 20]

[0386]

[0387]

[0388] The results in Tables 18 to 20 clearly show that the ascorbic acid derivatives of the present invention have a hyaluronic acid production-promoting effect equal to or greater than that of known ascorbic acid derivatives such as 2-O-glyceryl ascorbic acid.

[0389] Example 131 Cream

[0390] The oil phase components (1) to (5) and the water phase components (6) to (10) shown in Table 21 were each heated to 70°C and dissolved to prepare an oil phase and a water phase, respectively. The oil phase was then added to the water phase and pre-emulsified, and the mixture was uniformly emulsified using a homogenizer. The mixture was then cooled to room temperature while being fully stirred to prepare a cream having an excellent whitening effect. In Table 22 and subsequent tables, the amounts are all expressed in parts by mass.

[0391] [Table 21]

[0392] serial number Ingredient name Formula Quantity 1 Squalane 9.0 2 Vaseline 6.0 3 Stearyl Alcohol 5.0 4 Polyoxyethylene (25) hexadecyl ether 2.5 5 Glyceryl Monostearate 1.5 6 2-O-Benzyl-3-O-(2-hydroxyisobutyl)ascorbic acid (Synthesis Example 27) 2.0 7 glycerin 6.0 8 preservative Moderate 9 pH Adjusters Moderate 10 Purify water margin*

[0393] *The amount required to make the total blending amount 100 parts by mass. The same applies to the following table.

[0394] Example 132 Emulsion

[0395] The oil phase components (1) to (9) and the water phase components (10) to (13) shown in Table 22 were each heated to 70° C. and dissolved to prepare an oil phase and a water phase, respectively. The oil phase was then added to the water phase and pre-emulsified, and the mixture was uniformly emulsified using a homogenizer. The mixture was then cooled to room temperature while being fully stirred to prepare an emulsion having an excellent whitening effect.

[0396] [Table 22]

[0397]

[0398]

[0399] Example 133 Emulsion

[0400] The oil phase components (5) to (10) and the water phase components (1) to (4) and (11) to (12) in the composition shown in Table 23 were each heated to 70°C and dissolved to prepare an oil phase and a water phase, respectively. The oil phase was then added to the water phase and pre-emulsified, and the mixture was uniformly emulsified using a homogenizer. The mixture was then cooled to room temperature while being fully stirred to prepare an emulsion having an excellent whitening effect.

[0401] [Table 23]

[0402] serial number Ingredient name Formula Quantity 1 Dipropylene glycol 5.0 2 2-O-Octyl-3-O-(2-hydroxyisobutyl)ascorbic acid (Synthesis Example 21) 1.0 3 Sorbitan sesquioleate 4.0 4 Polyoxyethylene (20) sorbitan monooleate 1.0 5 Microcrystalline wax 1.0 6 beeswax 2.0 7 Lanolin 2.0 8 Liquid paraffin 18.0 9 Squalane 12.0 10 spices Moderate 11 preservative Moderate 12 Purify water margin

[0403] Example 134 Cream

[0404] The oil phase components (1) and (2) and the water phase components (3) to (10) shown in Table 24 were each heated to 70°C and dissolved to prepare an oil phase and a water phase, respectively. The oil phase was then added to the water phase and pre-emulsified, and the mixture was uniformly emulsified using a homomixer. The mixture was then cooled to room temperature while being fully stirred to prepare a cream. The cream was used as a skin cosmetic having an excellent whitening effect.

[0405] [Table 24]

[0406]

[0407] Example 135 Lotion

[0408] The lotion can be prepared by fully mixing the raw materials (1) to (6) shown in Table 25. The lotion contains 7% by weight of 2,3-di-O-(2-hydroxyisobutyl)ascorbic acid and thus has an excellent whitening effect.

[0409] [Table 25]

[0410] serial number Ingredient name Formula Quantity 1 2,3-Di-O-(2-hydroxyisobutyl)ascorbic acid (Synthesis Example 17) 7.0 2 Ethanol 8.0 3 Citric Acid 0.01 4 Sodium Citrate 0.015 5 Potassium Glycyrrhizinate 0.03 6 Purify water margin

[0411] Example 136 Cream

[0412] The oil phases (1) to (6) and the water phases (7) to (10) shown in Table 26 were each heated to 70°C and dissolved. The oil phase was added to the water phase and pre-emulsified, and then emulsified with a homomixer. The mixture was then cooled to room temperature while being fully stirred to prepare a cream. The cream contained 3% by weight of 3-O-(2-hydroxyisobutyl)ascorbic acid and can be used as a skin cosmetic having an excellent melanin production inhibitory effect and an excellent whitening effect.

[0413] [Table 26]

[0414] serial number Ingredient name Formula Quantity 1 Cetyl Alcohol 2.0 2 Stearyl Alcohol 3.0 3 Squalane 7.5 4 Glyceryl tri-2-ethylhexanoate 7.5 5 Methyl polysiloxane 5.5 6 3-O-(2-Hydroxyisobutyl)ascorbic acid (Synthesis Example 2) 3.0 7 1,3-Butanediol 5.0 8 Hydroxyethyl Cellulose 0.2 9 preservative Moderate 10 Purify water margin

[0415] Example 137 Cream

[0416] The oil phase components (1) to (5) and the water phase components (6) to (10) shown in Table 27 were each heated to 70° C. and dissolved to prepare an oil phase and a water phase, respectively. The oil phase was then added to the water phase and pre-emulsified, and the mixture was uniformly emulsified using a homogenizer. The mixture was then cooled to room temperature while being sufficiently stirred to prepare a cream having an excellent whitening effect.

[0417] [Table 27]

[0418]

[0419]

[0420] Example 138 Emulsion

[0421] The oil phase components (1) to (9) and the water phase components (10) to (13) shown in Table 28 were each heated to 70° C. and dissolved to prepare an oil phase and a water phase, respectively. The oil phase was then added to the water phase and pre-emulsified, and the mixture was uniformly emulsified using a homogenizer. The mixture was then cooled to room temperature while being fully stirred to prepare an emulsion having an excellent whitening effect.

[0422] [Table 28]

[0423]

[0424] Example 139 Emulsion

[0425] The oil phase components (5) to (10) and the water phase components (1) to (4) and (11) to (12) in the composition shown in Table 29 were each heated to 70°C and dissolved to prepare an oil phase and a water phase, respectively. The oil phase was then added to the water phase and pre-emulsified, and the mixture was uniformly emulsified using a homogenizer. The mixture was then cooled to room temperature while being fully stirred to prepare an emulsion having an excellent whitening effect.

[0426] [Table 29]

[0427]

[0428] Example 140 Cream

[0429] The oil phase components (1) and (2) and the water phase components (3) to (10) in the composition shown in Table 30 were each heated to 70°C and dissolved to prepare an oil phase and a water phase, respectively, and then the oil phase was added to the water phase and pre-emulsified, and the mixture was uniformly emulsified using a homomixer. The mixture was then cooled to room temperature while being sufficiently stirred to prepare a cream. The cream was used as a skin cosmetic having an excellent whitening effect.

[0430] [Table 30]

[0431]

[0432]

[0433] Example 141 Lotion

[0434] A lotion was prepared by thoroughly mixing raw materials (1) to (6) in the composition shown in Table 31. The lotion contained 7% by mass of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxybutyl)ascorbic acid and thus had an excellent whitening effect.

[0435] [Table 31]

[0436]

[0437] Example 142 Cream

[0438] The oil phases (1) to (6) and the water phases (7) to (10) in the composition shown in Table 32 were each heated to 70°C and dissolved. The oil phase was added to the water phase and pre-emulsified, and then emulsified with a homomixer. The mixture was then cooled to room temperature while being fully stirred to prepare a cream. The cream contains 3% by mass of 2-O-(2-hydroxyisobutyl)-3-O-(2-hydroxydecyl) ascorbic acid and can be used as a skin cosmetic having an excellent melanin production inhibitory effect and an excellent whitening effect.

[0439] [Table 32]

[0440]

Claims

1. An ascorbic acid derivative or a salt thereof, characterized in that: It is represented by the following general formula (I): [Chemical formula 1] [Where R 1 and R 2 is H, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a benzyl group, R 3 -O-CH2-CH(OH)-CH2-、R 3 -O-CH2-CH(CH2OH)-、R 3 -CH(CH2OH)-, R 3 -CH(OH)-CH2-, HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 3 is H, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group, provided that R 1 and R 2 At least one of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-].

2. The ascorbic acid derivative or a salt thereof according to claim 1, wherein In the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 Another one of the glyceryl groups is an alkyl group having 2 to 20 carbon atoms or a branched alkylglyceryl group having 6 to 20 carbon atoms.

3. The ascorbic acid derivative or a salt thereof according to claim 1, wherein In the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other one is benzyl.

4. The ascorbic acid derivative or a salt thereof according to claim 1, wherein In the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other one is R 3 -O-CH2-CH(OH)-CH2- or R 3 -O-CH2-CH(CH2OH)-.

5. The ascorbic acid derivative or a salt thereof according to claim 1, wherein In the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other of which is H, alkyl or alkenyl, and R 1 and R 2 The total number of carbon atoms in the 1 and R 2 The other one is R 3 -O-CH2-CH(OH)-CH2-、R 3 -O-CH2-CH(CH2OH)-, HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 3 The number of carbon atoms in is 4 or less.

6. The ascorbic acid derivative or a salt thereof according to claim 1, wherein In the general formula (I), R 1 and R 2 One of them is HO-C(CH3)2-CH2- or HO-CH2-C(CH3)2-, and R 1 and R 2 The other one is R 3 -CH(CH2OH)- or R 3 -CH(OH)-CH2-.

7. A cosmetic comprising the ascorbic acid derivative or a salt thereof according to any one of claims 1 to 6.

8. A cosmetic, wherein the ascorbic acid derivative or the salt thereof according to any one of claims 1 to 6 is incorporated in an amount of 1 to 20% by mass.

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