WO2023245459A1 - Anti-oxidizing composition comprising a thiopyridinone compound - Google Patents

Anti-oxidizing composition comprising a thiopyridinone compound Download PDF

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Publication number
WO2023245459A1
WO2023245459A1 PCT/CN2022/100256 CN2022100256W WO2023245459A1 WO 2023245459 A1 WO2023245459 A1 WO 2023245459A1 CN 2022100256 W CN2022100256 W CN 2022100256W WO 2023245459 A1 WO2023245459 A1 WO 2023245459A1
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Prior art keywords
alkyl group
formula
branched
linear
group
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PCT/CN2022/100256
Other languages
French (fr)
Inventor
Wenyan Xu
Lixuan KE
Rui Huang
Jun Wu
Original Assignee
L'oreal
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Publication date
Application filed by L'oreal filed Critical L'oreal
Priority to PCT/CN2022/100256 priority Critical patent/WO2023245459A1/en
Priority to FR2207483A priority patent/FR3136662A1/en
Priority to PCT/US2023/025678 priority patent/WO2023249912A1/en
Publication of WO2023245459A1 publication Critical patent/WO2023245459A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4933—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having sulfur as an exocyclic substituent, e.g. pyridinethione
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A61K8/676—Ascorbic acid, i.e. vitamin C
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/522—Antioxidants; Radical scavengers

Definitions

  • the present invention relates to an anti-oxidizing composition
  • an anti-oxidizing composition comprising a thiopyridinone compound, which is useful for caring for keratin materials, and in particular the skin.
  • thiopyridinone compounds exhibit good depigmenting activity, even at low concentration, see for example WO2012080075 and WO2017/102349.
  • the thiopyridinone compound can show strong depigmenting or brightening effects by reducing the production of melanin.
  • compositions comprising the components of: A) a compound of formula (I) or (I’) , , which can be deemed as a thiopyridinone compound, or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture; B) an antioxidant, comprising ascorbic acid or a stabilized derivative thereof in an amount of at least 5%by weight of the composition, can not only achieve the depigmenting or brightening effect desired, but also promote the antioxidizing effect.
  • R 1 denotes a radical chosen from:
  • R 2 denotes a radical chosen from:
  • R 3 denotes a radical chosen from:
  • the compound (I’) is the tautomer form of the compound (I) when a tautomeric equilibrium exists according to the following scheme:
  • R 1 represents one hydrogen atom.
  • R 1 represents a linear (C 1 -C 10 ) alkyl group or branched (C 3 -C 10 ) alkyl group, especially a linear (C 1 -C 6 ) alkyl group or branched (C 3 -C 6 ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably ethyl. Particularly the said alkyl group of R 1 is not substituted.
  • R 2 represents one hydrogen atom.
  • R 2 represents a linear (C 1 -C 10 ) alkyl group or branched (C 3 -C 10 ) alkyl group, especially a linear (C 1 -C 6 ) alkyl group or branched (C 3 -C 6 ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl group; the said alkyl group of R 2 being not substituted.
  • R 2 represents a linear (C 1 -C 10 ) alkyl group or branched (C 3 -C 10 ) alkyl group, especially a linear (C 1 -C 6 ) alkyl group or branched (C 3 -C 6 ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl; the said alkyl group being substituted by one or more groups selected from i) , ii) , iii) and iv) as defined herein before.
  • the said alkyl group being substituted by one or two groups selected from i) , ii) and iii) , more preferably by one or two groups selected from i) and iii) , better substituted by one group iii) as carboxy.
  • radical R 2 Another variant for radical R 2 is that the said alkyl group being substituted by one group iv) especially substituted by one phenyl group.
  • R 2 represents a (C 3 -C 8 ) cycloalkyl group, preferably a (C 5 -C 7 ) cycloalkyl group such cyclohexyl.
  • R 2 represents C 5 -C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1 -C 8 alkoxy radicals, preferably a phenyl group particularly not substituted.
  • R 3 represents a hydrogen atom.
  • R 3 represents a saturated linear C 1 -C 10 or branched C 3 -C 10 alkyl group; particularly a linear (C 1 -C 6 ) alkyl group or a branched (C 3 -C 6 ) alkyl group, preferably (C 1 -C 4 ) alkyl group such as methyl group.
  • a “saturated hydrocarbonated group linear C 1 -C 12 or branched C 3 -C 12 ” is equivalent to a “linear (C 1 -C 12 ) alkyl or branched (C 3 -C 12 ) alkyl group” which correspond to a saturated C 1 -C 12 linear or branched C 3 -C 12 hydrocarbon based group, and preferably C 1 -C 10 linear or C 3 -C 10 branched hydrocarbon based group, more preferably C 1 -C 6 linear or C 3 -C 6 branched hydrocarbon-based;
  • the linear or branched groups may be chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.
  • the saturated linear or branched alkyl groups may be chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, pentyl, hexyl, heptyl and octyl, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl.
  • ⁇ a saturated hydrocarbonated cyclic C 3 -C 8 group is a mono or bicyclic cycloalkyl group containing from 3 to 8 carbon atoms especially is a monocyclic cycloalkyl group in C5 to C7 such as cyclohexyl group,
  • alkoxy radical is an alkyl-oxy radical for which the alkyl radical is a linear or branched C 1 -C 16 and preferentially C 1 -C 8 hydrocarbon-based radical;
  • aryl group represents a fused or non-fused monocyclic or bicyclic carbon-based group comprising from 5 to 12 carbon atoms, preferably from 6 to 10 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, more preferably a phenyl group;
  • the salts of the compounds of formula (I) , (I’) , (II) or (II’) as defined herein after comprise the conventional non-toxic salts of said compounds, such as those formed from organic or inorganic acid or from organic or inorganic base.
  • a mineral base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, magnesium hydroxide, lithium hydroxide, and sodium, potassium or calcium carbonate or hydrogen carbonate for example;
  • an organic base such as a primary, secondary or tertiary alkylamine, for example triethylamine or butylamine.
  • This primary, secondary or tertiary alkylamine may comprise one or more nitrogen and/or oxygen atoms and may thus comprise, for example, one or more alcohol functions; mention may be made in particular of 2-amino-2-methylpropanol, ethanolamine, triethanolamine, 2-dimethylaminopropanol, 2-amino-2- (hydroxymethyl) -1, 3-propanediol and 3- (dimethylamino) propylamine.
  • salts of amino acids for instance lysine, arginine, guanidine, glutamic acid and aspartic acid.
  • the salts of the compounds of formula (I) or (II) may be chosen from alkali metal or alkaline-earth metal salts such as sodium, potassium, calcium or magnesium salts and ammonium salts.
  • organic or inorganic acid salt is more particularly chosen from salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4 , iv) alkylsulfonic acids: Alk-S (O) 2 OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S (O) 2 OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid
  • the acceptable solvates of the compounds described in the present invention comprise conventional solvates such as those formed during the preparation of said compounds owing to the presence of solvents. Mention may be made, by way of example, of the solvates due to the presence of water or of linear or branched alcohols, such as ethanol or isopropanol.
  • optical isomers are in particular, the enantiomers and the diastereoisomers.
  • the “keratin material” is the skin.
  • skin we intend all the body skin.
  • the keratin material is the face, or the neck, especially the face.
  • a numeric range is defined with a lower and an upper limit when needed, such as one or more lower limits and one or more upper limits are given to form a range optionally along with one or more preferred ranges.
  • a given range can be defined by selecting a lower limit and an upper limit that define the boundaries of the given range. All ranges defined in this manner are inclusive and combinable, that is, any lower limit can be combined with any upper limit to form a range, as long as the lower and upper limits are provided to modify the same subject. For example, when ranges of 60-110 and 80-120 are listed for a specific subject, it is to be understood that ranges 60-120 and 80-110 are also contemplated and encompassed. Further, if the lower limits listed are 1 and 2 and the upper limits are listed as 3, 4 and 5, the following ranges are all predictable and within the scope of the present disclosure: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
  • the present invention provides a composition comprising the components of: A) a compound of formula (I) or (I’) , and B) a specific antioxidant.
  • composition according to the invention comprises a compound of formula (I) or (I’) below or tautomer (I’) below or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture, as component A) :
  • R 1 denotes a radical chosen from:
  • R 2 denotes a radical chosen from:
  • R 3 denotes a radical chosen from:
  • the compound (I’) is the tautomer form of the compound (I) when a tautomeric equilibrium exists according to the following scheme:
  • R 1 represents one hydrogen atom.
  • R 1 represents a linear (C 1 -C 10 ) alkyl group or branched (C 3 -C 10 ) alkyl group, especially a linear (C 1 -C 6 ) alkyl group or branched (C 3 -C 6 ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably ethyl. Particularly the said alkyl group of R 1 is not substituted.
  • R 2 represents one hydrogen atom.
  • R 2 represents a linear (C 1 -C 10 ) alkyl group or branched (C 3 -C 10 ) alkyl group, especially a linear (C 1 -C 6 ) alkyl group or branched (C 3 -C 6 ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl group; the said alkyl group of R 2 being not substituted.
  • R 2 represents a linear (C 1 -C 10 ) alkyl group or branched (C 3 -C 10 ) alkyl group, especially a linear (C 1 -C 6 ) alkyl group or branched (C 3 -C 6 ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl; the said alkyl group being substituted by one or more groups selected from i) , ii) , iii) and iv) as defined herein before.
  • the said alkyl group being substituted by one or two groups selected from i) , ii) and iii) , more preferably by one or two groups selected from i) and iii) , better substituted by one group iii) as carboxy.
  • radical R 2 Another variant for radical R 2 is that the said alkyl group being substituted by one group iv) especially substituted by one phenyl group.
  • R 2 represents a (C 3 -C 8 ) cycloalkyl group, preferably a (C 5 -C 7 ) cycloalkyl group such cyclohexyl.
  • R 2 represents C 5 -C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1 -C 8 alkoxy radicals, preferably a phenyl group particularly not substituted.
  • R 3 represents a hydrogen atom.
  • R 3 represents a saturated linear C 1 -C 10 or branched C 3 -C 10 alkyl group; particularly a linear (C 1 -C 6 ) alkyl group or a branched (C 3 -C 6 ) alkyl group, preferably (C 1 -C 4 ) alkyl group such as methyl group.
  • the compounds of formula (I) and tautomer (I’) or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture;
  • R 1 denotes a radical chosen from:
  • R 2 denotes a radical chosen from:
  • a phenyl group optionally substituted with one or more hydroxyls and/or with one or more C 1 -C 4 alkoxy radicals such as methoxy;
  • R 3 denotes a radical chosen from:
  • the compounds of formula (I) and tautomer (I’) or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture;
  • R 1 denotes a radical chosen from:
  • R 2 denotes a radical chosen from:
  • R 3 denotes a radical chosen from:
  • the compounds of formula (I) and tautomer (I’) or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture;
  • R 1 is a hydrogen atom
  • R 2 denotes a radical chosen from:
  • R 2 is even more preferably a saturated hydrocarbonated group linear C 1 -C 4 or branched C 3 -C 4 substituted with one group iii) -C (O) -OR 3 .
  • compounds of formula (I) and tautomer (I’) are selected among compounds of formula (II) and also the tautomers thereof, the salts thereof, the solvates thereof and the optical isomers thereof, and the racemates thereof, alone or as a mixture:
  • R1 and R3 have the same meaning than for compounds of formula (I) and (I’) and X denotes an alkylene radical- (CH 2 ) n -with n being an integer ranging inclusively from 1 to 10, preferably ranging from 1 to 6, more preferably ranging from 1 to 4, such as 1, preferably R 3 represents a hydrogen atom.
  • the following compounds are preferably used and their tautomer or their salts, their optical isomers, racemates, and/o r solvates such as hydrates and the thereof, alone or as a mixture:
  • the compound according to the present invention is the following:
  • the compound 20, N- [ (2-thioxo-1, 2-dihydropyridin-3-yl) carbonyl] glycine may also be nominated as 3-carboxymethylaminocarbonyl-2-thiopyridinone, is a typical representative of the useful thiopyridinone compounds according to the present invention.
  • the component A) , compound may be present in an amount ranging for example from 0.01%to 10%by weight, preferably from 0.1%to 5%by weight, or preferably from 0.5%to 3%by weight, relative to the total weight of the composition.
  • composition according to the invention comprises an antioxidant, as component B) .
  • vitamin C or stabilized derivatives thereof is particularly useful in component B) .
  • the composition comprises essentially vitamin C or stabilized derivatives thereof in component B) .
  • vitamin C and derivatives can be used, including ascorbic acid, erythorbic acid, or derivatives, especially stabilized derivatives, thereof, e.g., sodium ascorbate/erythorbate and the fat-soluble ester tetrahexyl decyl ascorbate/erythorbate and ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl glucoside, glucosamine ascorbate, ascorbyl acetate, and the like.
  • ascorbic acid erythorbic acid, or derivatives, especially stabilized derivatives, thereof, e.g., sodium ascorbate/erythorbate and the fat-soluble ester tetrahexyl decyl ascorbate/erythorbate and ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl glucoside, glucosamine ascorbate, ascorbyl acetate, and the like.
  • the component B) may also comprise an “additional antioxidant” different from vitamin C or derivatives thereof, which may be cinnamic acid or a derivative thereof, e.g., a phenylpropanoid.
  • Phenylpropanoids include: cinnamic acid, caffeic acid, ferulic acid, trans-ferulic acid (including its antioxidant pharmacore 2, 6-dihydroxy acetophenome) , 5-hydroxyferic acid, sinapic acid, Coumarin, coniferyl alcohol, sinapyl alcohol, eugenol, Chavicol, baicalein, P-coumaric acid and sinapinic acid.
  • phenylpropanoids can neutralize free radicals.
  • useful cinnamic acid derivatives may comprise 2-ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, diisopropyl methoxycinnamate, pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate (Tinogard TT) , octadecyl di-t-butyl-4-hydroxyhydrocinnamate, caffeic acid, ferulic acid. Caffeic acid and ferulic acid may be preferable, and ferulic acid may be more preferable.
  • the vitamin C or stabilized derivatives thereof can be present in the composition in an amount of 15%to 30%by weight, or preferably 15%to 20%by weight, relative to the total weight of the composition according to the present invention.
  • the “additional antioxidant” can be present in the composition from 0%to 2%by weight, preferably 0%to 1%by weight, or preferably 0.1%to 0.5%by weight, relative to the total weight of the composition according to the present invention.
  • composition according to the invention can advantageously comprise at least one medium/solvent, including water and/or organic medium/solvent.
  • the composition according to the invention may advantageously comprise water in various amounts.
  • a relatively high amount of water may be used.
  • water is used in a content of greater than or equal to 40%by weight relative to the total weight of composition.
  • the water content in the low viscosity composition according to the invention preferably ranges from 40%to 99%by weight, or preferably from 50%to 90%by weight, or from 60%to 80%by weight, relative to the total weight of the composition.
  • the high viscosity composition according to the invention advantageously comprises water in a content of less than or equal to 40%by weight relative to the total weight of composition.
  • the water content in the high viscosity composition according to the invention preferably ranges from 10%to 40%by weight, or preferably from 15%to 35%by weight, or from 20%to 30%by weight, relative to the total weight of the composition.
  • composition according to the invention may also comprise one or more organic medium/solvents, preferably water-soluble organic medium/solvents (solubility of greater than or equal to 5%in water at 25°C and at atmospheric pressure) .
  • organic medium/solvents preferably water-soluble organic medium/solvents (solubility of greater than or equal to 5%in water at 25°C and at atmospheric pressure) .
  • organic medium/solvents examples include linear or branched, and preferably saturated, monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethanol, (iso) propanol, butanol, hexylene glycol (2-methyl-2, 4-pentanediol) , neopentyl glycol and 3-methyl-1, 5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as phenylethyl alcohol; polyols containing more than two hydroxyl functions, in particular C3-C6 polyols, such as glycerol; polyol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, especially C 1 -C 4 alkyl
  • the organic medium/solvents when they are present in an amount ranging from 0.1%to 40%by weight, preferably from 1%to 30%by weight, or from 5%to 20%by weight, relative to the total weight of the composition according to the invention.
  • composition according to the present invention can be used for various use, comprising application directly on keratin materials, or use to formulate other cosmetic products, such as body cream and in particular various masks.
  • compositions may be incorporated into the composition, or used together with the composition according to the present invention.
  • active agents for improving the condition of the skin in the case of mask, such as moisturizers or agents serving to improve the natural lipid barrier. It is also possible to use enzymes that have activity on the skin.
  • active agents there are agents for drugs, peptides, proteins, detectable labels, contrast reagents, pain-killing, anesthetics, antibacterial agents, anti-yeast agents, antifungal agents, antiviral agents, anti-dermititis agents, anti-pruritic agents, anti-emetics, vascular protectors, agents against motion sickness, anti-irritants, anti-inflammatory agents, immunomodulators, anti-hyperkeratolytic agents, agents for treating dry skin, antiperspirants, anti-psoriatic agents, antidandruff agents, anti-aging agents, anti-asthmatic agents and bronchodilators, sunscreen agents, antihistamines, healing agents, corticosteroids, tanning agents, and mixtures thereof.
  • the content of the other active agent in the composition according to the present invention may be adjusted as a function of the intended purpose of the kit.
  • composition according to the present invention may comprise at least on preservative.
  • the preservative useful according to the present invention can be any one conventionally used for cosmetics, in particular for masks.
  • the content of the preservative is 0.01%to 5%by weight, preferably 0.01%to 3%by weight, preferably 0.01%to 1%by weight, based on the weight of the composition.
  • composition according to the present invention may optionally comprise at least one pH adjuster.
  • pH adjusters include, but are not limited to, aminomethyl propanol, aminomethylpropane diol, triethanolamine, triethylamine, citric acid, sodium hydroxide, acetic acid, potassium hydroxide, lactic acid, and any combination thereof.
  • the amount of the pH adjuster in the composition according to the present invention can be adjusted and determined by those skilled depending on the pH desired, as long as the amount thereof will not bring other substantially harmful effect.
  • the pH adjuster can be present in an amount of 1%to 20%by weight, such as from 5%to 15 %by weight, relative to the total weight of the composition.
  • the composition of the present invention may also contain adjuvants which are customary in the cosmetic, pharmaceutical and/or dermatological field depending on the final uses and/or the specific product forms, such as hydrophilic or lipophilic gelling agents, emulsifiers, hydrophilic or lipophilic active agents, fragrances, fillers, odor absorbers and dyes.
  • adjuvants which are customary in the cosmetic, pharmaceutical and/or dermatological field depending on the final uses and/or the specific product forms, such as hydrophilic or lipophilic gelling agents, emulsifiers, hydrophilic or lipophilic active agents, fragrances, fillers, odor absorbers and dyes.
  • the amounts of these various adjuvants are those conventionally used in the field under consideration, and for example from 0.01%to 20%by weight of the total weight of the composition.
  • compositions according to the invention can be manufactured by known processes, generally used in the cosmetic or dermatological field.
  • composition according to the invention finds its application in a large number of cosmetic treatments for keratin materials such as the skin, the scalp or the mucous membranes (lips) , and more particularly the skin, in particular in the care of the face, to brighten the skin.
  • the composition according to the invention may be particularly useful for a mask product.
  • the subject of the invention is also a cosmetic process for the care or makeup of keratin materials, comprising the application to the keratin materials of a composition as defined above.
  • the subject of the invention is also a non-therapeutic cosmetic process for the care or makeup of keratin materials, comprising the application to the keratin materials of a composition as defined above.
  • the invention also relates to the cosmetic use of a composition as defined above, for the care or makeup of keratin materials.
  • the subject of the invention is the cosmetic use of a composition as defined above, for the care of the skin, preferably for brightening the skin, and/or reducing or lightening darker and/or more coloured spots on the skin.
  • the composition is suitable for the treatment of darker and/or more coloured spots on the skin.
  • compositions according to the invention are given by way of illustration and without limitation.
  • the compounds are indicated in chemical name or INCI name.
  • Compound 20 is synthesized as disclosed in example 2 of patent EP3 390 363.
  • compositions/formulas described below are expressed in %by weight, relative to the total weight of each composition/formula, unless otherwise indicated.
  • compositions of Ex. 1-Ex. 2 were prepared, from the ingredients indicated in the table 1 below (in which the contents were indicated in%by weight of materials with regard to the total weight of the composition) :
  • compositions were prepared by the steps of, taking Ex. 1 as an example:
  • compositions of Ex. 1-Ex. 2, as well as comparative compositions of CE. 1-CE. 4, prepared in Example A were evaluated for the anti-oxidant performance by a thin layer squalene oxidation test, comprising the steps of:
  • Detection of the response of SQOOH&SQ is a test to measure the antioxidant performance well known in the art. The smaller value of the SQOOH/SQ, the better the antioxidant performance is.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Birds (AREA)
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  • Gerontology & Geriatric Medicine (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

A composition comprises A) a thiopyridinone compound and B) an antioxidant selected from ascorbic acid or a stabilized derivative thereof in an amount of 15% to 30% by weight of the composition.

Description

ANTI-OXIDIZING COMPOSITION COMPRISING A THIOPYRIDINONE COMPOUND TECHNICAL FIELD
The present invention relates to an anti-oxidizing composition comprising a thiopyridinone compound, which is useful for caring for keratin materials, and in particular the skin.
BACKGROUND
It has always been an ultimate target of the cosmetic filed to deliver products with skin benefits such as hydration, moisturizing, anti-aging, brightening, cleansing, and so on. Brightening of the skin is always high interest of the consumers, especially those who have a dark or dull skin tone. Unfortunately, at various periods of their life, some people see the appearance on their skin, and more in particular on the hands, of darker and/or more colored spots, which give the skin heterogeneity. These spots are in particular due to a high concentration of melanin in the keratinocytes located at the surface of the skin.
It is known that certain thiopyridinone compounds exhibit good depigmenting activity, even at low concentration, see for example WO2012080075 and WO2017/102349. The thiopyridinone compound can show strong depigmenting or brightening effects by reducing the production of melanin.
However, there is still a need in the art for new use of thiopyridinone.
SUMMARY OF THE INVENTION
The inventors have unexpectedly discovered that a composition comprising the components of: A) a compound of formula (I) or (I’) , , which can be deemed as a thiopyridinone compound, or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture; B) an antioxidant, comprising ascorbic acid or a stabilized derivative thereof in an amount of at least 5%by weight of the composition, can not only achieve the depigmenting or brightening effect desired, but also promote the antioxidizing effect.
Figure PCTCN2022100256-appb-000001
In which Formulas (I) and (I’) :
R 1 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group optionally substituted with one or more groups, which may be identical or different, chosen from:
i) -O-R 3
ii) -S-R 3;
R 2 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated hydrocarbonated group linear C 1-C 12 or branched C 3-C 12 or cyclic C 3-C 8, optionally substituted with one or more groups, which may be identical or different, chosen from:
i) -O-R 3
ii) -S-R 3
iii) -C (O) -O-R 3;
iv) a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals;
c) a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals
R 3 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group;
The compound (I’) is the tautomer form of the compound (I) when a tautomeric equilibrium exists according to the following scheme:
Figure PCTCN2022100256-appb-000002
According to one embodiment of the invention R 1 represents one hydrogen atom.
According to another embodiment of the invention R 1 represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably ethyl. Particularly the said alkyl group of R 1 is not substituted.
According to one embodiment of the invention R 2 represents one hydrogen atom.
According to another embodiment of the invention R 2 represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl group; the said alkyl group of R 2 being not substituted.
According to another embodiment of the invention R 2 represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl; the said alkyl group being substituted by one or more groups selected from i) , ii) , iii) and iv) as defined herein before. Preferably the said alkyl group being substituted by one or two groups selected from i) , ii) and iii) , more preferably by one or two groups selected from i) and iii) , better substituted by one group iii) as carboxy.
Another variant for radical R 2 is that the said alkyl group being substituted by one group iv) especially substituted by one phenyl group.
According to another embodiment of the invention R 2 represents a (C 3-C 8) cycloalkyl group, preferably a (C 5-C 7) cycloalkyl group such cyclohexyl.
According to another embodiment of the invention R 2 represents C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals, preferably a phenyl group particularly not substituted.
According to an embodiment R 3 represents a hydrogen atom.
According to another embodiment R 3 represents a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group; particularly a linear (C 1-C 6) alkyl group or a branched (C 3-C 6) alkyl group, preferably (C 1-C 4) alkyl group such as methyl group.
EMBODIMENTS OF INVENTION
Throughout the description, including the claims, the term "comprising a" should be understood as being synonymous with "comprising at least one" , unless otherwise mentioned. Moreover, the expression "at least one" used in the present description is equivalent to the expression "one or more" .
For the purposes of the present invention, and unless otherwise indicated:
a “saturated hydrocarbonated group linear C 1-C 12 or branched C 3-C 12” is equivalent to a “linear (C 1-C 12) alkyl or branched (C 3-C 12) alkyl group” which correspond to a saturated C 1-C 12 linear or branched C 3-C 12 hydrocarbon based group, and preferably C 1-C 10 linear or C 3-C 10 branched hydrocarbon based group, more preferably C 1-C 6 linear or C 3-C 6 branched hydrocarbon-based; Preferentially, the linear or branched groups may be chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.
More preferentially, the saturated linear or branched alkyl groups may be chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, pentyl, hexyl, heptyl and octyl, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl.
■a saturated hydrocarbonated cyclic C 3-C 8 group is a mono or bicyclic cycloalkyl group containing from 3 to 8 carbon atoms especially is a monocyclic cycloalkyl group in C5 to C7 such as cyclohexyl group,
■an "alkoxy radical" is an alkyl-oxy radical for which the alkyl radical is a linear or branched C 1-C 16 and preferentially C 1-C 8 hydrocarbon-based radical;
■when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined hereinabove;
■an "aryl" group represents a fused or non-fused monocyclic or bicyclic carbon-based group comprising from 5 to 12 carbon atoms, preferably from 6 to 10 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, more preferably a phenyl group;
■the term "at least one" is equivalent to the term "one or more" ; and
■the term "inclusive" for a range of concentrations means that the limits of that range are included in the defined range.
The salts of the compounds of formula (I) , (I’) , (II) or (II’) as defined herein after comprise the conventional non-toxic salts of said compounds, such as those formed from organic or inorganic acid or from organic or inorganic base.
As salts of the compounds of formula (I) , (I’) , (II) or (II’) mention may be made of:
the salts obtained by addition of the compound of formula (I) or (II) to:
- a mineral base, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, magnesium hydroxide, lithium hydroxide, and sodium, potassium or calcium carbonate or hydrogen carbonate for example;
or
- an organic base such as a primary, secondary or tertiary alkylamine, for example triethylamine or butylamine. This primary, secondary or tertiary alkylamine may comprise one or more nitrogen and/or oxygen atoms and may thus comprise, for example, one or more alcohol functions; mention may be made in particular of 2-amino-2-methylpropanol, ethanolamine, triethanolamine, 2-dimethylaminopropanol, 2-amino-2- (hydroxymethyl) -1, 3-propanediol and 3- (dimethylamino) propylamine.
Mention may also be made of the salts of amino acids, for instance lysine, arginine, guanidine, glutamic acid and aspartic acid. Advantageously, the salts of the compounds of formula (I) or (II) (when it comprises a carboxy group) may be chosen from alkali metal or alkaline-earth metal salts such as sodium, potassium, calcium or magnesium salts and ammonium salts.
■as "organic or inorganic acid salt" is more particularly chosen from salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2SO 4, iv) alkylsulfonic acids: Alk-S (O)  2OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S (O)  2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H 3PO 4; xiii) acetic acid CH 3C (O) OH; xiv) triflic acid CF 3SO 3H; and xv) tetrafluoroboric acid HBF 4;
■The acceptable solvates of the compounds described in the present invention  comprise conventional solvates such as those formed during the preparation of said compounds owing to the presence of solvents. Mention may be made, by way of example, of the solvates due to the presence of water or of linear or branched alcohols, such as ethanol or isopropanol.
■The optical isomers are in particular, the enantiomers and the diastereoisomers.
Preferably, the “keratin material” according to the present invention is the skin. By “skin” , we intend all the body skin. Still preferably, the keratin material is the face, or the neck, especially the face.
In the application, unless specifically mentioned otherwise, amounts, contents, parts and percentages are expressed on a weight basis.
In the application, a numeric range is defined with a lower and an upper limit when needed, such as one or more lower limits and one or more upper limits are given to form a range optionally along with one or more preferred ranges. A given range can be defined by selecting a lower limit and an upper limit that define the boundaries of the given range. All ranges defined in this manner are inclusive and combinable, that is, any lower limit can be combined with any upper limit to form a range, as long as the lower and upper limits are provided to modify the same subject. For example, when ranges of 60-110 and 80-120 are listed for a specific subject, it is to be understood that ranges 60-120 and 80-110 are also contemplated and encompassed. Further, if the lower limits listed are 1 and 2 and the upper limits are listed as 3, 4 and 5, the following ranges are all predictable and within the scope of the present disclosure: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of components and/or reaction conditions are to be understood as being modified in all instances by the term "about" , with conventionally known meaning in the art, e.g., within 10%of the indicated number (such as "about 10%" means 9%-11 %and "about 2%" means 1.8%-2.2%) .
The present invention provides a composition comprising the components of: A) a compound of formula (I) or (I’) , and B) a specific antioxidant.
Component A)
The composition according to the invention comprises a compound of formula (I) or (I’) below or tautomer (I’) below or their salts, their optical isomers, racemates, and/or  solvates such as hydrates and the thereof, alone or as a mixture, as component A) :
Figure PCTCN2022100256-appb-000003
In which Formulas (I) and (I’) :
R 1 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group optionally substituted with one or more groups, which may be identical or different, chosen from:
i) -O-R 3
ii) -S-R 3;
R 2 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated hydrocarbonated group linear C 1-C 12 or branched C 3-C 12 or cyclic C 3-C 8, optionally substituted with one or more groups, which may be identical or different, chosen from:
i) -O-R 3
ii) -S-R 3
iii) -C (O) -O-R 3;
iv) a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals;
c) a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals
R 3 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group;
The compound (I’) is the tautomer form of the compound (I) when a tautomeric equilibrium exists according to the following scheme:
Figure PCTCN2022100256-appb-000004
According to one embodiment of the invention R 1 represents one hydrogen atom.
According to another embodiment of the invention R 1 represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably ethyl. Particularly the said alkyl group of R 1 is not substituted.
According to one embodiment of the invention R 2 represents one hydrogen atom.
According to another embodiment of the invention R 2 represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl group; the said alkyl group of R 2 being not substituted.
According to another embodiment of the invention R 2 represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl; the said alkyl group being substituted by one or more groups selected from i) , ii) , iii) and iv) as defined herein before. Preferably the said alkyl group being substituted by one or two groups selected from i) , ii) and iii) , more preferably by one or two groups selected from i) and iii) , better substituted by one group iii) as carboxy.
Another variant for radical R 2 is that the said alkyl group being substituted by one group iv) especially substituted by one phenyl group.
According to another embodiment of the invention R 2 represents a (C 3-C 8) cycloalkyl group, preferably a (C 5-C 7) cycloalkyl group such cyclohexyl.
According to another embodiment of the invention R 2 represents C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals, preferably a phenyl group particularly not substituted.
According to an embodiment R 3 represents a hydrogen atom.
According to another embodiment R 3 represents a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group; particularly a linear (C 1-C 6) alkyl group or a branched (C 3-C 6) alkyl group, preferably (C 1-C 4) alkyl group such as methyl group.
Preferably, the compounds of formula (I) and tautomer (I’) or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture;
have the following meanings:
R 1 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated linear C 1-C 6 or branched C 3-C 6 alkyl group optionally substituted with one or more groups, which may be identical or different, chosen from:
i) -O-R 3
ii) -S-R 3;
preferably optionally substituted with one or more groups i)
R 2 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated hydrocarbonated group linear C 1-C 10 or branched C 3-C 10 or cyclic C 3-C 8 such as C5-C6, optionally substituted with one or more groups, which may be identical or different, chosen from:
i) -O-R 3
ii) -SR- 3
iii) -C (O) -O-R 3;
iv) a phenyl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 4 alkoxy radicals such as methoxy;
preferably substituted with one or more groups selected from i) and iii) , preferably iii) such as carboxy
R 3 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated linear C 1-C 6 or branched C 3-C 6 alkyl group
Preferentially, the compounds of formula (I) and tautomer (I’) or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a  mixture;
have the following meanings:
R 1 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated linear C 1-C 4 or branched C 3-C 4 alkyl group optionally substituted with one or more groups, which may be identical or different, chosen from i) -OR 3, more preferably not substituted;
R 2 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated hydrocarbonated group linear C 1-C 10 or branched C 3-C 10 or cyclic C 3-C 8 as C5-C6, optionally substituted with one or more groups, which may be identical or different, chosen from:
i) -O-R 3
iii) -C (O) -O-R 3;
iv) a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 4 alkoxy radicals;
R 3 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated linear C 1-C 4 or branched C 3-C 4 alkyl group such as methyl or ethyl.
Preferentially, the compounds of formula (I) and tautomer (I’) or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture;
have the following meanings:
R 1 is a hydrogen atom; and
R 2 denotes a radical chosen from:
a) a hydrogen atom;
b) a saturated hydrocarbonated group linear C 1-C 5 or branched C 3-C 5 or cyclic C 3-C 8 as C5-C6, substituted with one or more groups, which may be identical or different, chosen from v) -C (O) -O-R 3, preferably substituted with one group iii) -C (O) -O-R 3;
R 2 is even more preferably a saturated hydrocarbonated group linear C 1-C 4 or branched C 3-C 4 substituted with one group iii) -C (O) -OR 3.
According to another preferred embodiment, compounds of formula (I) and  tautomer (I’) are selected among compounds of formula (II) and also the tautomers thereof, the salts thereof, the solvates thereof and the optical isomers thereof, and the racemates thereof, alone or as a mixture:
Figure PCTCN2022100256-appb-000005
Formula (II) and (II’) Wherein R1 and R3 have the same meaning than for compounds of formula (I) and (I’) and X denotes an alkylene radical- (CH 2)  n-with n being an integer ranging inclusively from 1 to 10, preferably ranging from 1 to 6, more preferably ranging from 1 to 4, such as 1, preferably R 3 represents a hydrogen atom.
Among the compounds of formula (I) , the following compounds are preferably used and their tautomer or their salts, their optical isomers, racemates, and/o r solvates such as hydrates and the thereof, alone or as a mixture:
Figure PCTCN2022100256-appb-000006
Figure PCTCN2022100256-appb-000007
Figure PCTCN2022100256-appb-000008
Figure PCTCN2022100256-appb-000009
Among these compounds, the following compounds are more particularly preferred:
Figure PCTCN2022100256-appb-000010
Figure PCTCN2022100256-appb-000011
Figure PCTCN2022100256-appb-000012
Figure PCTCN2022100256-appb-000013
More preferably, among these compounds, the following compounds are more particularly preferred:
Figure PCTCN2022100256-appb-000014
Figure PCTCN2022100256-appb-000015
Even more preferably, among these compounds, the following compounds are more particularly preferred:
Figure PCTCN2022100256-appb-000016
Figure PCTCN2022100256-appb-000017
In a most preferred embodiment, the compound according to the present invention is the following:
Figure PCTCN2022100256-appb-000018
All compounds can be obtained by chemical method known by man skilled in the art, from commercially available reagents. For example, the synthetic method disclosed in the European patent application EP3 390 363 can be used.
The compound 20, N- [ (2-thioxo-1, 2-dihydropyridin-3-yl) carbonyl] glycine, may also be nominated as 3-carboxymethylaminocarbonyl-2-thiopyridinone, is a typical representative of the useful thiopyridinone compounds according to the present invention.
The component A) , compound, may be present in an amount ranging for example from 0.01%to 10%by weight, preferably from 0.1%to 5%by weight, or preferably from 0.5%to 3%by weight, relative to the total weight of the composition.
Component B) , antioxidant
The composition according to the invention comprises an antioxidant, as component B) .
Without being limited by any known theory, it is surprisingly to discover that for  the component A) , vitamin C or stabilized derivatives thereof is particularly useful in component B) .
Thus, according to an embodiment of the invention, the composition comprises essentially vitamin C or stabilized derivatives thereof in component B) .
As a useful antioxidant, vitamin C and derivatives can be used, including ascorbic acid, erythorbic acid, or derivatives, especially stabilized derivatives, thereof, e.g., sodium ascorbate/erythorbate and the fat-soluble ester tetrahexyl decyl ascorbate/erythorbate and ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl glucoside, glucosamine ascorbate, ascorbyl acetate, and the like. In addition, it is also possible to use plants derived from a large amount of vitamin C, such as extracts of Myrciaria dubia, acerola, emblica officinalis, and bioflavonoids from rose hips and citrus, including Water-soluble bioflavonoids such as hesperidin methyl chalcone.
The component B) may also comprise an “additional antioxidant” different from vitamin C or derivatives thereof, which may be cinnamic acid or a derivative thereof, e.g., a phenylpropanoid. Phenylpropanoids include: cinnamic acid, caffeic acid, ferulic acid, trans-ferulic acid (including its antioxidant pharmacore 2, 6-dihydroxy acetophenome) , 5-hydroxyferic acid, sinapic acid, Coumarin, coniferyl alcohol, sinapyl alcohol, eugenol, Chavicol, baicalein, P-coumaric acid and sinapinic acid. Without limiting the mode of action of the present invention, phenylpropanoids can neutralize free radicals.
Amongst others, useful cinnamic acid derivatives may comprise 2-ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, diisopropyl methoxycinnamate, pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate (Tinogard TT) , octadecyl di-t-butyl-4-hydroxyhydrocinnamate, caffeic acid, ferulic acid. Caffeic acid and ferulic acid may be preferable, and ferulic acid may be more preferable.
According to the present invention, the vitamin C or stabilized derivatives thereof can be present in the composition in an amount of 15%to 30%by weight, or preferably 15%to 20%by weight, relative to the total weight of the composition according to the present invention.
According to an embodiment of the present invention, the “additional antioxidant” can be present in the composition from 0%to 2%by weight, preferably 0%to 1%by weight, or preferably 0.1%to 0.5%by weight, relative to the total weight of the composition according to the present invention.
Medium/solvent
The composition according to the invention can advantageously comprise at least one medium/solvent, including water and/or organic medium/solvent.
Water
The composition according to the invention may advantageously comprise water in various amounts. For low viscosity applications of the composition, e.g., in form of leave-on lotion, a relatively high amount of water may be used. For example, water is used in a content of greater than or equal to 40%by weight relative to the total weight of composition. The water content in the low viscosity composition according to the invention preferably ranges from 40%to 99%by weight, or preferably from 50%to 90%by weight, or from 60%to 80%by weight, relative to the total weight of the composition.
For high viscosity applications of the composition, e.g., in form of leave-on cream, a relatively lower amount of water may be used. The high viscosity composition according to the invention advantageously comprises water in a content of less than or equal to 40%by weight relative to the total weight of composition. The water content in the high viscosity composition according to the invention preferably ranges from 10%to 40%by weight, or preferably from 15%to 35%by weight, or from 20%to 30%by weight, relative to the total weight of the composition.
Organic medium/solvent
The composition according to the invention may also comprise one or more organic medium/solvents, preferably water-soluble organic medium/solvents (solubility of greater than or equal to 5%in water at 25℃ and at atmospheric pressure) .
Examples of the organic medium/solvents that may be mentioned include linear or branched, and preferably saturated, monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethanol, (iso) propanol, butanol, hexylene glycol (2-methyl-2, 4-pentanediol) , neopentyl glycol and 3-methyl-1, 5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as phenylethyl alcohol; polyols containing more than two hydroxyl functions, in particular C3-C6 polyols, such as glycerol; polyol ethers, for instance ethylene glycol monomethyl,  monoethyl and monobutyl ether, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, especially C 1-C 4 alkyl ethers, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
The organic medium/solvents, when they are present in an amount ranging from 0.1%to 40%by weight, preferably from 1%to 30%by weight, or from 5%to 20%by weight, relative to the total weight of the composition according to the invention.
The composition according to the present invention can be used for various use, comprising application directly on keratin materials, or use to formulate other cosmetic products, such as body cream and in particular various masks.
Accordingly, depending on specific use, various additional components may be incorporated into the composition, or used together with the composition according to the present invention.
Other active agents
It is also possible to use active agents for improving the condition of the skin in the case of mask, such as moisturizers or agents serving to improve the natural lipid barrier. It is also possible to use enzymes that have activity on the skin.
As other examples of active agents that can be suitable for implementing the present invention there are agents for drugs, peptides, proteins, detectable labels, contrast reagents, pain-killing, anesthetics, antibacterial agents, anti-yeast agents, antifungal agents, antiviral agents, anti-dermititis agents, anti-pruritic agents, anti-emetics, vascular protectors, agents against motion sickness, anti-irritants, anti-inflammatory agents, immunomodulators, anti-hyperkeratolytic agents, agents for treating dry skin, antiperspirants, anti-psoriatic agents, antidandruff agents, anti-aging agents, anti-asthmatic agents and bronchodilators, sunscreen agents, antihistamines, healing agents, corticosteroids, tanning agents, and mixtures thereof.
The content of the other active agent in the composition according to the present invention may be adjusted as a function of the intended purpose of the kit.
Preservative
For use of the present invention, the composition according to the present invention  may comprise at least on preservative. The preservative useful according to the present invention can be any one conventionally used for cosmetics, in particular for masks.
Preferably, the content of the preservative is 0.01%to 5%by weight, preferably 0.01%to 3%by weight, preferably 0.01%to 1%by weight, based on the weight of the composition.
pH adjuster
The composition according to the present invention may optionally comprise at least one pH adjuster.
Examples of pH adjusters include, but are not limited to, aminomethyl propanol, aminomethylpropane diol, triethanolamine, triethylamine, citric acid, sodium hydroxide, acetic acid, potassium hydroxide, lactic acid, and any combination thereof.
The amount of the pH adjuster in the composition according to the present invention can be adjusted and determined by those skilled depending on the pH desired, as long as the amount thereof will not bring other substantially harmful effect. For example, the pH adjuster can be present in an amount of 1%to 20%by weight, such as from 5%to 15 %by weight, relative to the total weight of the composition.
Adjuvant
In a known manner, the composition of the present invention may also contain adjuvants which are customary in the cosmetic, pharmaceutical and/or dermatological field depending on the final uses and/or the specific product forms, such as hydrophilic or lipophilic gelling agents, emulsifiers, hydrophilic or lipophilic active agents, fragrances, fillers, odor absorbers and dyes. The amounts of these various adjuvants are those conventionally used in the field under consideration, and for example from 0.01%to 20%by weight of the total weight of the composition.
These adjuvants and their concentrations must be such that they do not modify the desired property for the composition of the invention.
The compositions according to the invention can be manufactured by known processes, generally used in the cosmetic or dermatological field.
The composition according to the invention finds its application in a large number of cosmetic treatments for keratin materials such as the skin, the scalp or the mucous  membranes (lips) , and more particularly the skin, in particular in the care of the face, to brighten the skin. For example, the composition according to the invention may be particularly useful for a mask product.
The subject of the invention is also a cosmetic process for the care or makeup of keratin materials, comprising the application to the keratin materials of a composition as defined above.
The subject of the invention is also a non-therapeutic cosmetic process for the care or makeup of keratin materials, comprising the application to the keratin materials of a composition as defined above.
The invention also relates to the cosmetic use of a composition as defined above, for the care or makeup of keratin materials.
More particularly, the subject of the invention is the cosmetic use of a composition as defined above, for the care of the skin, preferably for brightening the skin, and/or reducing or lightening darker and/or more coloured spots on the skin.
In a particular embodiment, the composition is suitable for the treatment of darker and/or more coloured spots on the skin.
EXAMPLES
The following examples of compositions according to the invention are given by way of illustration and without limitation. The compounds are indicated in chemical name or INCI name.
Figure PCTCN2022100256-appb-000019
Compound 20 is synthesized as disclosed in example 2 of patent EP3 390 363.
The ingredient amounts/concentrations in the compositions/formulas described below are expressed in %by weight, relative to the total weight of each composition/formula, unless otherwise indicated.
Example A
The inventive compositions of Ex. 1-Ex. 2, as well as comparative compositions of CE. 1-CE. 4, were prepared, from the ingredients indicated in the table 1 below (in which the contents were indicated in%by weight of materials with regard to the total weight of the composition) :
Table 1
Figure PCTCN2022100256-appb-000020
Figure PCTCN2022100256-appb-000021
The compositions were prepared by the steps of, taking Ex. 1 as an example:
1) . preparing a water solution of COMPOUND 20 (or ferulic acid) ;
2) . heating the solution with 60℃ for 20mins, then cooling down to room temperature;
3) . adding ascorbic acid and chlorphenesin; and
4) . add potassium hydroxide to adjust PH.
Example B
The inventive compositions of Ex. 1-Ex. 2, as well as comparative compositions of CE. 1-CE. 4, prepared in Example A were evaluated for the anti-oxidant performance by a thin layer squalene oxidation test, comprising the steps of:
1. applying artificial serum on squalene solution;
2. preparing a smoke solution, which was known in the art as an aqueous acetonitrile absorbed with smoke;
3. applying respectively the inventive compositions of Ex. 1-Ex. 2, as well as comparative compositions of CE. 1-CE. 4, and applying the smoke solution (5 plate/composition) , both to glass slide with 2.5cm*2cm sequentially;
4. simulating sunlight (5J/cm 2, 17mins) ;
5. standing by for reaction overnight;
6. cutting glass into pieces, extracting by 5ml MeOH, and vibrating for 1hr;
7. filtering all of the extractions; and
8. detecting the response of SQOOH&SQ by LCMS
Detection of the response of SQOOH&SQ is a test to measure the antioxidant performance well known in the art. The smaller value of the SQOOH/SQ, the better the antioxidant performance is.
The results were given in Table 2 below.
Table 2
Properties Ex. 1 Ex. 2 CE. 1 CE. 2 CE. 3 CE. 4
SQOOH/SQ 9 10.2 10.8 15.9 13 16

Claims (13)

  1. A composition comprising the components of:
    A) at least one compound selected from compounds of formula (I) and tautomer of formula (I’) herein below; and their salts, optical isomers, racemates, and/or solvates such as hydrates, alone or as a mixture:
    Figure PCTCN2022100256-appb-100001
    In which Formulas (I) and (I’) :
    - R 1 denotes a radical chosen from:
    a) a hydrogen atom;
    b) a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group optionally substituted with one or more groups, which may be identical or different, chosen from:
    i) -O-R 3
    ii) -S-R 3;
    - R 2 denotes a radical chosen from:
    a) a hydrogen atom;
    b) a saturated hydrocarbonated group linear C 1-C 12 or branched C 3-C 12 or cyclic C 3-C 8, optionally substituted with one or more groups, which may be identical or different, chosen from:
    i) -O-R 3
    ii) -S-R 3
    iii) -C (O) -O-R 3;
    iv) a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals;
    c) a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals
    - R 3 denotes a radical chosen from:
    a) a hydrogen atom;
    b) a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group;
    B) an antioxidant, comprising vitamin C or a stabilized derivative thereof, selected from the group consisting of ascorbic acid, erythorbic acid, sodium ascorbate/erythorbate, tetrahexyl decyl ascorbate/erythorbate, ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl glucoside, glucosamine ascorbate, and ascorbyl acetate, in an amount of 15%to 30%by weight of the composition.
  2. The composition according to claim 1, wherein:
    - R 1 of formula (I) and (I’) represents a hydrogen atom,
    or
    - R 1 of formula (I) and (I’) represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably ethyl, particularly the said alkyl group ofR 1 is not substituted.
  3. The composition according to any one of the preceding claims, wherein:
    - R 2 of formula (I) and (I’) represents a hydrogen atom;
    or
    - R 2 of formula (I) and (I’) represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl group; the said alkyl group of R 2 being not substituted.
  4. The composition according to claim 1 or 2, wherein:
    - R 2 of formula (I) and (I’) represents a linear (C 1-C 10) alkyl group or branched (C 3-C 10) alkyl group, especially a linear (C 1-C 6) alkyl group or branched (C 3-C 6) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl; the said alkyl group being substituted by one or more groups selected from i) , ii) , iii) and iv) as defined in claim 1, preferably the said alkyl group being substituted by one or two groups selected from i) , ii) and iii) , more preferably by one or two groups selected from i)  and iii) , better substituted by one group iii) as carboxy.
  5. The composition according to claim 1 or 2, wherein
    - R 2 of formula (I) and (I’) represents a (C 3-C 8) cycloalkyl group, preferably a (C 5-C 7) cycloalkyl group such cyclohexyl;
    or
    - R 2 of formula (I) and (I’) represents a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 8 alkoxy radicals, preferably a phenyl group particularly not substituted.
  6. The composition according to any one of the preceding claims, wherein
    - R 3 of formula (I) and (I’) represents a hydrogen atom;
    or
    - R 3 of formula (I) and (I’) represents a saturated linear C 1-C 10 or branched C 3-C 10 alkyl group; particularly a linear (C 1-C 6) alkyl group or a branched (C 3-C 6) alkyl group, preferably (C 1-C 4) alkyl group such as methyl group.
  7. The composition according to any one of the preceding claims, wherein:
    - R 1 of formula (I) and (I’) represents a radical chosen from:
    a) a hydrogen atom;
    b) a saturated linear C 1-C 6 or branched C 3-C 6 alkyl group optionally substituted with one or more groups, which may be identical or different, chosen from:
    i) -O-R 3
    ii) -S-R 3;
    preferably optionally substituted with one or more groups i)
    - R 2 of formula (I) and (I’) represents a radical chosen from:
    - a) a hydrogen atom;
    - b) a saturated hydrocarbonated group linear C 1-C 10 or branched C 3-C 10 or cyclic C 3-C 8 such as C5-C6, optionally substituted with one or more groups, which may be identical or different, chosen from:
    - i) -O-R 3
    - ii) -SR- 3
    - iii) -C (O) -O-R 3;
    - iv) a phenyl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 4 alkoxy radicals such as methoxy;
    - preferably substituted with one or more groups selected from i) and iii) , preferably iii) such as carboxy
    - R 3 of formula (I) and (I’) represents a radical chosen from:
    - a) a hydrogen atom;
    - b) a saturated linear C 1-C 6 or branched C 3-C 6 alkyl group;
    - preferentially, the compounds of formula (I) and tautomer (I’) or their salts, their optical isomers, racemates, and/or solvates such as hydrates and the thereof, alone or as a mixture;
    - have the following meanings:
    - R 1 of formula (I) and (I’) represents a radical chosen from:
    - a) a hydrogen atom;
    - b) a saturated linear C 1-C 4 or branched C 3-C 4 alkyl group optionally substituted with one or more groups, which may be identical or different, chosen from i) -OR 3, more preferably not substituted;
    - R 2 of formula (I) and (I’) represents a radical chosen from:
    - a) a hydrogen atom;
    - b) a saturated hydrocarbonated group linear C 1-C 10 or branched C 3-C 10 or cyclic C 3-C 8 as C5-C6, optionally substituted with one or more groups, which may be identical or different, chosen from:
    - i) -O-R 3
    - iii) -C (O) -O-R 3;
    - iv) a C 5-C 12 aryl group optionally substituted with one or more hydroxyls and/or with one or more C 1-C 4 alkoxy radicals;
    - R 3 of formula (I) and (I’) represents a radical chosen from:
    - a) a hydrogen atom;
    - b) a saturated linear C 1-C 4 or branched C 3-C 4 alkyl group such as methyl or ethyl.
  8. The composition according to any one of the preceding claims, wherein
    the compound of formula (I) selected out from the group consisting of the  compounds 1 to 24 below and their tautomer or their salts, their optical isomers, racemates, and/or solvates suchas hydrates, alone or as a mixture, particularly compounds 1, 2, 4, 6, 7, 9, 11, 12, 14, 15, 16, 17, 18, 19, 20, or 21, morre particularly 1, 9, 16, 18, 19, 20, or 21, preferably 18, 19, 20, or 21, more preferably 20:
    Figure PCTCN2022100256-appb-100002
    Figure PCTCN2022100256-appb-100003
    Figure PCTCN2022100256-appb-100004
    Figure PCTCN2022100256-appb-100005
  9. The composition according to any one of the preceding claims, wherein the compound of formula (I) or (I’) is present in an amount ranging from 0.01%to 20%by weight, preferably from 0.05%to 10%by weight, or preferably from 0.1%to 5%by weight, relative to the total weight of the composition.
  10. The composition according to any one of the preceding claims, wherein the vitamin C or stabilized derivatives thereof is present in the composition in an amount of 15%to 20%by weight, relative to the total weight of the composition.
  11. The composition according to any one of the preceding claims, wherein the component B) further comprises an additional antioxidant selected from cinnamic acid or a derivative thereof; and
    the additional antioxidant is present in the composition from 0%to 2%by weight, preferably 0%to 1%by weight, or preferably 0.1%to 0.5%by weight, relative to the total weight of the composition.
  12. Use of ascorbic acid or a stabilized derivative thereof, selected from the group consisting of ascorbic acid, erythorbic acid, sodium ascorbate/erythorbate, tetrahexyl decyl ascorbate/erythorbate, ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl glucoside, glucosamine ascorbate, and ascorbyl acetate, in an amount of at least 5%by weight relative to the final composition to be applied to keratin materials,
    for stabilizing the compound of formula (I) and tautomer of formula (I’) as defined in any one of claims 1 to 8, e.g., for stabilizing the compound 20.
  13. A non-therapeutic cosmetic process for depigmenting, lightening and/or bleaching keratin materials, preferably skin, comprising the step of:
    applying to the keratin substance the composition according to any one of claims 1 to 11.
PCT/CN2022/100256 2022-06-21 2022-06-21 Anti-oxidizing composition comprising a thiopyridinone compound WO2023245459A1 (en)

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FR2207483A FR3136662A1 (en) 2022-06-21 2022-07-21 ANTIOXIDANT COMPOSITION COMPRISING A THIOPYRIDINONE COMPOUND
PCT/US2023/025678 WO2023249912A1 (en) 2022-06-21 2023-06-19 Cosmetic composition comprising hydrophilic antioxidants and thiopyridinone compounds

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CN117554550B (en) * 2023-12-29 2024-06-04 大连博源医学科技有限公司 Liquid chromatography tandem mass spectrometry detection method for catecholamine metabolites in plasma and combined stabilizer

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US20020012639A1 (en) * 1999-01-08 2002-01-31 Glenn Robert Wayne Topical compositions comprising protected functional thiols
FR2879929A1 (en) * 2004-02-27 2006-06-30 Oreal Tinctorial composition, useful for the dyeing of keratinous fibers in human, comprises a mixed dye comprising two different chromophores
CN103228630A (en) * 2010-12-14 2013-07-31 莱雅公司 Process for depigmenting keratin materials using thiopyridinone compounds
CN108473432A (en) * 2015-12-18 2018-08-31 莱雅公司 Use the method for thiopyridine ketone compound decoloration keratin material
WO2022079122A1 (en) * 2020-10-15 2022-04-21 L'oreal Use of thiopyridinone compounds for preventing the formation of cutaneous blackheads

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GB2141626B (en) * 1983-04-25 1987-01-28 Kao Corp Cinnamic acid derivatives for lightening melanin pigmentation of skin
FR2848846B1 (en) * 2002-12-18 2005-01-28 Oreal COSMETIC USE OF ASCORBIC ACID DERIVATIVES AS BLANCHING AGENTS
WO2022138471A1 (en) * 2020-12-22 2022-06-30 L'oreal Stabilization of thiopyridinone compound and yellowing reduction of composition comprising same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020012639A1 (en) * 1999-01-08 2002-01-31 Glenn Robert Wayne Topical compositions comprising protected functional thiols
FR2879929A1 (en) * 2004-02-27 2006-06-30 Oreal Tinctorial composition, useful for the dyeing of keratinous fibers in human, comprises a mixed dye comprising two different chromophores
CN103228630A (en) * 2010-12-14 2013-07-31 莱雅公司 Process for depigmenting keratin materials using thiopyridinone compounds
CN108473432A (en) * 2015-12-18 2018-08-31 莱雅公司 Use the method for thiopyridine ketone compound decoloration keratin material
CN114533579A (en) * 2015-12-18 2022-05-27 莱雅公司 Process for bleaching keratin materials using thiopyridone compounds
WO2022079122A1 (en) * 2020-10-15 2022-04-21 L'oreal Use of thiopyridinone compounds for preventing the formation of cutaneous blackheads

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