KR20240130919A - Novel compounds and cosmetic compositions containing them - Google Patents

Abstract

The present invention relates to a novel compound and a cosmetic composition comprising the same, wherein the compound according to one aspect is a tocopherol derivative and not only has an antioxidant effect, but also increases compatibility with various cosmetic raw materials and increases solubility, so that it can be usefully used in a wider variety of cosmetics.

Description

{Novel compounds and cosmetic compositions containing them}

It relates to a novel compound and a cosmetic composition containing the same.

Vitamin E is a fat-soluble vitamin that exists in foods in the form of four types of tocopherols (α, β, γ, δ) and four types of tocotrienols (α, β, γ, δ). Of these, the most common and bioactive is α-tocopherol, commonly referred to as vitamin E.

Its important functions include acting as an antioxidant in the human body, inhibiting the oxidation of unsaturated fatty acids that make up cell membranes, which are prone to oxidation within cells, thereby preventing damage to cell membranes and tissues, and also contributing to protecting the lipid bilayer of enzymes and various proteins. It is used as an antioxidant, skin conditioning agent, and moisture blocking agent due to the above characteristics, and is used in the form of creams, basic cosmetics, and lotions that prevent skin damage caused by ultraviolet rays.

Vitamin E can be obtained from synthetic and natural sources, and is abundant in vegetable oils such as nuts such as almonds, sunflower seeds, and rapeseed, and is also present in small amounts in animal oils such as fish and crustaceans. Synthetic vitamin E is DL-tocopherol or DL-tocopherol acetate, which is converted to esters from natural sources using acetic acid or succinic acid.

Although vitamin E has various useful properties as described above, its compatibility and solubility with cosmetic raw materials are significantly low, and therefore, there is a need to develop a compound that solves these problems while maintaining its useful properties.

One aspect is to provide a compound represented by the chemical formula 1 or a cosmetically acceptable salt thereof:

[Chemical Formula 1]

wherein R1, R2 or R3 are each independently hydrogen, halogen, alkylsulfonyl, hydroxyl, an amino group, a nitro group, or a substituted or unsubstituted C ₁ to C ₁₀ alkyl; wherein R4 is hydrogen, a substituted or unsubstituted C ₂ to C ₂₀ alkyl, or a substituted or unsubstituted C ₂ to C ₂₀ alkenyl; wherein R5 is hydrogen, or a substituted or unsubstituted C ₁ to C ₁₀ alkyl; wherein R6 is a substituted or unsubstituted silyl, or a substituted or unsubstituted siloxy; and wherein n is 0 to 20.

Another aspect is to provide a cosmetic composition comprising the compound or a cosmetically acceptable salt thereof.

One aspect provides a compound represented by the formula 1 or a cosmetically acceptable salt thereof:

[Chemical Formula 1]

wherein R1, R2 or R3 are each independently hydrogen, halogen, alkylsulfonyl, hydroxyl, an amino group, a nitro group, or a substituted or unsubstituted C ₁ to C ₁₀ alkyl; wherein R4 is hydrogen, a substituted or unsubstituted C ₂ to C ₂₀ alkyl, or a substituted or unsubstituted C ₂ to C ₂₀ alkenyl; wherein R5 is hydrogen, or a substituted or unsubstituted C ₁ to C ₁₀ alkyl; wherein R6 is a substituted or unsubstituted silyl, or a substituted or unsubstituted siloxy; and wherein n is 0 to 20.

As used herein, the term “unsubstituted” means that the specified group does not bear any substituents.

The term "substituted," as used herein, means substituted with one or more substituents, for example, a hydroxy group, an alkyl group, an alkoxy group, a mercapto group, a cycloalkyl group, a substituted cycloalkyl group, a heterocyclic group, a substituted heterocyclic group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, an aryloxy group, a substituted aryloxy group, a halogen group, a trifluoromethyl group, a cyano group, a nitro group, an oxo group, an amino group, an amido group, an aldehyde group, an acyl group, an oxyacyl group, a carboxyl group, a carbamate group, a sulfonyl group, sulfonamide, sulfuryl, and the like.

As used herein, the term "alkyl" means a saturated aliphatic hydrocarbon group containing 1 to 20 carbon atoms, for example, 1 to 10, 1 to 8, 1 to 6, or 1 to 4, wherein the alkyl group may be straight-chain or branched. Additionally, the alkyl includes cycloalkyl, heteroalkyl, and heterocycloalkyl. Examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl.

The alkyl may be substituted with one or more substituents, for example, halo, phospho, cycloaliphatic (e.g., cycloalkyl or cycloalkenyl), heterocycloaliphatic (e.g., heterocycloalkyl or heterocycloalkenyl), aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl (e.g., (aliphatic)carbonyl, (cycloaliphatic)carbonyl, or (heterocycloaliphatic)carbonyl), nitro, cyano, amido (e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl), amino (e.g., aliphaticamino, cycloaliphaticamino, or heterocycloaliphaticamino), sulfonyl (e.g., aliphatic-SO ₂ -), sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl, cycloaliphaticoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. The substituted alkyl can be a carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl or alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO ₂ -amino)alkyl), aminoalkyl, amidoalkyl, (cycloaliphatic)alkyl, haloalkyl, an amine cation, a quaternary ammonium or a quaternary phosphonium.

As used herein, the term "heteroalkyl" means an alkyl composed of carbon atoms and one or more heteroatoms selected from the group consisting of O, N, and S. The nitrogen and sulfur atoms may be optionally oxidized, and the heteroatoms O, N and/or S may be located at any internal position of the heteroalkyl group.

As used herein, the term "alkenyl" means an aliphatic carbon group containing 2 to 10, for example, 2 to 8, 2 to 6, or 2 to 4 carbon atoms and one or more double bonds. Similar to alkyl groups, alkenyl groups can be straight-chain or branched. Additionally, the alkenyl includes cycloalkenyl, heteroalkenyl, and cycloheteroalkenyl. The alkenyl can be, but is not limited to, allyl, isoprenyl, 2-butenyl, or 2-hexenyl.

The above alkenyl may be substituted with one or more substituents, for example, halo, phospho, cycloaliphatic (e.g., cycloalkyl or cycloalkenyl), heterocycloaliphatic (e.g., heterocycloalkyl or heterocycloalkenyl), aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl (e.g., (aliphatic)carbonyl, (cycloaliphatic)carbonyl, or (heterocycloaliphatic)carbonyl), nitro, cyano, amido (e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl), amino (e.g., aliphaticamino, cycloaliphaticamino, heterocycloaliphaticamino, or aliphaticsulfonylamino), sulfonyl (e.g., alkyl-SO ₂ -, cycloaliphatic-SO ₂ -, or aryl-SO ₂ -), sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl, cycloaliphaticoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. A substituted alkenyl can be cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO ₂ -amino)alkenyl), aminoalkenyl, amidoalkenyl, (cycloaliphatic)alkenyl, or haloalkenyl.

As used herein, the term "heteroalkenyl" means an alkenyl composed of carbon atoms and one or more heteroatoms selected from the group consisting of O, N, and S. The nitrogen and sulfur atoms may be optionally oxidized, and the heteroatoms O, N and/or S may be located at any internal position of the heteroalkenyl group.

As used herein, the term "alkynyl" means an aliphatic carbon group containing 2 to 10, for example, 2 to 8, 2 to 6, or 2 to 4 carbon atoms and having at least one triple bond, wherein the alkynyl group may be straight-chain or branched. The alkynyl includes cycloalkynyl, heteroalkynyl and cycloheteroalkynyl. For example, the alkynyl group can be propargyl or butynyl.

Alkynyl may be substituted with one or more substituents, for example, aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl (e.g., aliphaticsulfanyl or cycloaliphaticsulfanyl), sulfinyl (e.g., aliphaticsulfinyl or cycloaliphaticsulfinyl), sulfonyl (e.g., aliphatic-SO ₂ -, aliphaticamino-SO ₂ -, or cycloaliphatic-SO ₂ -), amido (e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, arylaminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino or heteroarylaminocarbonyl), urea, thiourea, sulfamoyl, sulfamide, alkoxycarbonyl, alkylcarbonyloxy, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, acyl (e.g., (cycloaliphatic)carbonyl or (heterocycloaliphatic)carbonyl), amino (e.g., aliphaticamino), sulfoxy, oxo, carboxy, carbamoyl, (cycloaliphatic)oxy, (heterocycloaliphatic)oxy, or (heteroaryl)alkoxy.

The term "heteroalkynyl" as used herein means an alkynyl consisting of carbon atoms and one or more heteroatoms selected from the group consisting of O, N, and S. The nitrogen and sulfur atoms may be optionally oxidized, and the heteroatoms O, N and/or S may be located at any internal position of the heteroalkynyl group.

As used herein, the term "alkoxy" means a group in which a hydrogen atom of a hydroxyl group is replaced by the above alkyl, alkenyl or alkynyl. The alkoxy may be a C ₁ to C ₁₀ alkoxy such as methoxy, ethoxy, propoxy, butoxy and pentoxy.

As used herein, the term "alkoxyalkyl" means an alkyl group substituted with an alkoxy group. Examples thereof include CH ₃ CH ₂ OCH ₂ -, CH ₃ OCH ₂ CH ₂ -, and CH ₃ OCH ₂ -.

As used herein, the term "aryl" means an aromatic ring system containing 6 to 16 ring atoms, including heteroaryl. The aryl group may be a monocyclic, bicyclic or tricyclic group, or may be linked by a bond to form a biaryl group. Typically, the aryl group may be phenyl, naphthyl or biphenyl. In one specific embodiment, the aryl group may include an alkylene linkage to form an arylalkyl group, for example, a benzyl group. The aryl group may have 6 to 12 ring members, such as phenyl, naphthyl or biphenyl, and the aryl may be substituted or unsubstituted.

As used herein, the term "heteroaryl" means a monocyclic, fused bicyclic or tricyclic aromatic ring assembly containing from 5 to 16 ring atoms, wherein 1 to 5 of the ring atoms can be heteroatoms, such as N, O or S. The heteroatoms can be oxidized, including but not limited to N-oxides, -S(O)- and -S(O) ₂ -. A heteroaryl group can contain any number of ring atoms, for example, 3 to 6, 4 to 6, 5 to 6, 3 to 8, 4 to 8, 5 to 8, 6 to 8, 3 to 9, 3 to 10, 3 to 11, or 3 to 12 ring members. In one embodiment, the heteroaryl group can have 5 to 8 ring members and 1 to 4 heteroatoms, or 5 to 8 ring members and 1 to 3 heteroatoms, or 5 to 6 ring members and 1 to 4 heteroatoms, or 5 to 6 ring members and 1 to 3 heteroatoms. The heteroaryl group can include groups such as pyrrole, pyridine, imidazole, pyrazole, triazole, tetrazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiophene, furan, thiazole, isothiazole, oxazole, and isoxazole. The heteroaryl group may also be fused to an aromatic ring system, for example, a phenyl ring, including but not limited to benzopyrroles such as indole and isoindole, benzopyridines such as quinoline and isoquinoline, benzopyrazine, benzopyrimidine, benzopyridazines such as phthalazine and cinnoline, benzothiophene, and benzofuran. In addition, the heteroaryl group may include heteroaryl rings linked by a bond, for example, bipyridine, and the heteroaryl group may be substituted or unsubstituted.

The heteroaryl group can be linked at any position on the ring. For example, pyrrole includes 1-, 2- and 3-pyrrole; pyridine includes 2-, 3- and 4-pyridine; imidazole includes 1-, 2-, 4- and 5-imidazole; pyrazole includes 1-, 3-, 4- and 5-pyrazole; triazole includes 1-, 4- and 5-triazole; tetrazole includes 1- and 5-tetrazole; pyrimidine includes 2-, 4-, 5- and 6-pyrimidine; pyridazine includes 3- and 4-pyridazine; 1,2,3-triazine includes 4- and 5-triazine; 1,2,4-Triazines include 3-, 5- and 6-triazines; 1,3,5-Triazines include 2-triazines; thiophenes include 2- and 3-thiophenes; furans include 2- and 3-furan; thiazoles include 2-, 4- and 5-thiazoles; isothiazoles include 3-, 4- and 5-isothiazoles; oxazoles include 2-, 4- and 5-oxazoles; isoxazoles include 3-, 4- and 5-isoxazoles; indoles include 1-, 2- and 3-indoles; isoindoles include 1- and 2-isoindoles; quinolines include 2-, 3- and 4-quinolines; Isoquinolines include 1-, 3- and 4-isoquinolines; quinazolines include 2- and 4-quinazoline; cinnolines include 3- and 4-cinnoline; benzothiophenes include 2- and 3-benzothiophene; and benzofurans can include 2- and 3-benzofuran.

As used herein, the term “halo” or “halogen” means F, Cl, Br, or I.

As used herein, the term "haloalkyl" means an alkyl group substituted with one or more halogen atoms. For example, haloC _1-6 alkyl means a straight-chain or branched alkyl group of 1-6 carbon atoms substituted with one or more halogen atoms. Examples include, but are not limited to, CH ₂ F-, CHCl ₂ -, -CHF ₂ , CF ₃ -, CF ₃ CH ₂ -, CH ₃ CF ₂ , CF ₃ CCl ₂ -, and CF ₃ CF ₂ -.

As used herein, the term "carbonyl" means the nonradical -C(O)-.

As used herein, the term “hydroxy” or “hydroxyl” means the radical -OH.

As used herein, the term "hydroxyalkyl" means an alkyl group substituted with one or more hydroxy groups. Examples include, but are not limited to, HOCH ₂ -, HOCH ₂ CH ₂ -, CH ₃ CH(OH)CH ₂ -, and HOCH ₂ CH(OH)CH ₂ -.

As used herein, the term "hydroxyalkoxy" means an alkoxy group substituted with one or more hydroxy groups. Examples include, but are not limited to, HOCH ₂ O-, HOCH ₂ CH ₂ O-, CH ₃ CH(OH)CH ₂ O-, and HOCH ₂ CH(OH)CH ₂ O-.

As used herein, the term “amino group” means -NH ₂ .

The term "alkylsulfonyl" as used herein denotes a straight-chain or branched alkylsulfonyl having 1 to 10 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, s-butylsulfonyl and t-butylsulfonyl. Alkylsulfonyl groups having 1 to 4 carbon atoms are also preferred. The alkylsulfonyl groups of the present invention may be substituted by one or more identical or different radicals.

As used herein, the term “sulfonyl” means -SO ₂ -.

As used herein, the term “nitro group” means -NO ₂ .

The term "silyl group" as used herein can be represented by the chemical formula of -SiR _a R _b R _c , wherein R _a , R _b and R _c can each independently be hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.

As used herein, the term "siloxy group" refers to a monovalent functional group of the chemical formula -[OSiR _x R _y ] _g R _z , wherein R _x , R _y and R _z are each independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group, a substituted alkenyl group, a cycloalkenyl group, a substituted cycloalkenyl group, a heterocyclyl group, a substituted heterocyclyl group, an aryl group, a substituted aryl group, a heteroaryl group and a substituted heteroaryl group, and the variable g is an integer of 1 or greater. Specifically, R _x , R _y and R _z are each independently selected from the group consisting of an alkyl group (e.g., a C ₁ -C ₈ alkyl group), and the variable g is 1 to 50, more preferably 1 to 20.

In one specific example, R1, R2 or R3 may each independently be hydrogen or a substituted or unsubstituted C ₁ to C ₁₀ alkyl. For example, R1, R2 or R3 may each independently be hydrogen or -CH ₃ .

In one specific embodiment, the R4 may be a C ₂ to C ₂₀ alkyl substituted or unsubstituted with a C ₁ to C ₁₀ alkyl, or a C ₂ to C ₂₀ alkenyl substituted or unsubstituted with a C ₁ to C ₁₀ alkyl. For example, the R4 may be -(CH ₂ CH ₂ CH ₂ CH(CH ₃ )) ₃ CH ₃ or -(CH ₂ CH ₂ CH=C(CH ₃ )) ₃ CH ₃ .

In one specific example, R6 may be a compound of any one of formulae 2 to 4:

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

The above R8 to R16 are each independently hydrogen, or substituted or unsubstituted C ₁ to C ₁₀ alkyl, and m may be 0 to 20. For example, the above R8 to R16 may each independently be hydrogen or -CH ₃ .

In one specific example, the compound of formula 1 may be a compound of formula 5. The compound of formula 5 is a compound that embodies the above compound, and therefore, the compound according to the present invention is not limited thereto.

[Chemical Formula 5]

.

In one specific example, the compound may be a tocopherol derivative. Accordingly, the compound may have antioxidant properties.

As used herein, the term “acceptable” means exhibiting the property of being non-toxic to cells or humans exposed to the composition.

As used herein, the term "acceptable salt" means a salt prepared using a particular compound according to one aspect and a relatively nontoxic acid or base. When the compound contains a relatively acidic functional group, a base addition salt can be obtained by contacting a neutral form of such compound with a sufficient amount of a base, either in a pure solution or in a suitable inert solvent. Pharmaceutically acceptable base addition salts include salts of sodium, potassium, calcium, ammonium, organic amines, or magnesium, or similar salts. When the compound contains a relatively basic functional group, an acid addition salt can be obtained by contacting a neutral form of such compound with a sufficient amount of an acid, either in a pure solution or in a suitable inert solvent. Pharmaceutically acceptable acid addition salts include salts of inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, carbonic acid, hydrogen carbonate ion, phosphoric acid, monohydrogen phosphate ion, dihydrogen phosphate ion, sulfuric acid, hydrogen sulfate ion, hydroiodic acid or phosphorous acid, and salts of organic acids such as acetic acid, propionic acid, isobutyric acid, maleic acid, malonic acid, benzoic acid, succinic acid, suberic acid, fumaric acid, lactic acid, mandelic acid, phthalic acid, benzenesulfonic acid, p-tolylsulfonic acid, citric acid, tartaric acid and methanesulfonic acid, and further include salts of amino acids (e.g., arginine, etc.) and salts of organic acids such as glucuronic acid.

The above acceptable salts can be synthesized by conventional chemical methods from parent compounds containing acidic or basic moieties. Typically, these salts are prepared by reacting the free acid or base form of these compounds with a stoichiometric amount of base or acid in water or an organic solvent or a mixture of the two. Typically, a non-aqueous medium such as ether, ethyl acetate, ethanol, isopropanol or acetonitrile is preferred.

Another aspect provides a cosmetic composition comprising the compound or a cosmetically acceptable salt thereof.

The above compounds are as described above.

The above compound has an antioxidant effect, and thus a cosmetic composition containing the compound may have an antioxidant effect. In addition, a cosmetic composition containing the above compound may have high compatibility and solubility, and thus may be used in various cosmetics.

The above cosmetic composition can be manufactured in any formulation commonly manufactured in the technical field to which the present invention belongs. For example, it can be any one selected from the group consisting of lotion, cream, powder, essence, sunscreen, makeup primer, foundation, lipstick, eye shadow, soap, pack, stick type, balm type, and spray.

In one specific example, the cosmetic composition may be formulated as a solid or semi-solid. The term "semi-solid" means softer than a solid but viscous and capable of forming a certain shape.

In one specific example, the compound or a cosmetically acceptable salt thereof may be included in an amount of 0.001 to 50.00 wt%. For example, 0.001 to 50.00 wt%, 0.001 to 40.00 wt%, 0.001 to 30.00 wt%, 0.001 to 20.00 wt%, 0.001 to 10.00 wt%, 0.001 to 1.00 wt%, 0.01 to 50.00 wt%, 0.01 to 40.00 wt%, 0.01 to 30.00 wt%, 0.01 to 20.00 wt%, 0.01 to 10.00 wt%, 0.01 to 1.00 wt%, 0.1 to 50.00 wt%, 0.1 to 40.00 wt%, 0.1 to 30.00 wt%, 0.1 to 20.00 wt%, It may be included in an amount of 0.1 to 10.00 wt% or 0.1 to 1.00 wt%.

In one specific example, the cosmetic composition may further include an oily component.

The above oil component may be at least one of oil or wax. The oil and wax may be any of those commonly used as ingredients of cosmetics in the art. For example, the oil may be a silicone oil, an ester oil, a triglyceride oil, a hydrocarbon oil, or a vegetable oil, and one or more of these ingredients may be mixed and used as needed.

For example, the silicone-based oil may be a silicone-based fluid oil or a silicone-based crosspolymer dispersed in oil. For example, silicone-based fluid oils that can be used include cyclopentasiloxane, cyclohexasiloxane, cycloheptasiloxane, cyclomethicone, cyclophenylmethicone, cyclotetrasiloxane, cyclotrisiloxane, dimethicone, capryl dimethicone, caprylyl trimethicone, caprylyl methicone, cetearyl methicone, hexadecyl methicone, hexyl methicone, lauryl methicone, myristyl methicone, phenyl methicone, stearyl methicone, stearyl dimethicone, trifluoropropyl methicone, cetyl dimethicone, diphenylsiloxyphenyl trimethicone, dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, methyl trimethicone, or phenyl trimethicone. The above silicone oil components can be used alone or in combination of two or more types of oil. As silicone crosspolymers, dimethicone crosspolymer, dimethicone/vinyl dimethicone crosspolymer, dimethicone PEG-10/15 crosspolymer, or PEG-12 dimethicone/PPG-20 crosspolymer can be used, but are not limited thereto.

Ester oils include ascorbyl palmitate, ascorbilinolate, ascorbyl stearate, diisostearyl malate, benzyl benzoate, benzyl laurate, butylene glycol dicaprylate/dicaprate, butylene glycol diisononanoate, butylene glycol aurate, butylene glycol stearate, butyl isostearate, cetearyl isononanoate, cetearyl nonanoate, cetyl caprylate, cetyl ethylhexanoate, cetyl isononanoate, ethylhexyl caprylate/caprate, ethylhexyl isononanoate, ethylhexyl isostearate, ethylhexyl laurate, hexyl laurate, octyldodecyl isostearate, isopropyl isostearate, Isostearyl isononanoate, isostearyl isostearate, isocetyl ethylhexanoate, neopentyl glycol dicaprate, neopentyl glycol diethylhexanoate, neopentyl glycol diisostearate, pentaerythrityl stearate, pentaerythrityl tetraethylhexanoate, dipentaerythrityl hexaacid ester, polyglyceryl-2 diisostearate, polyglyceryl-2 sesquiisostearate, polyglyceryl-2 isostearate, polyglyceryl-2 tetraisostearate, polyglyceryl-2 triisostearate, polyglyceryl-3 diisostearate, polyglyceryl-3 isostearate, polyglyceryl-4 diisostearate, Polyglyceryl-4 isostearate, polyglyceryl-6 diisostearate, polyglyceryl-6 sesquiisostearate, or triethylhexanoin can be used.

Triglyceride oils that can be used include C8-C12 acid triglycerides, C12-C18 acid triglycerides, caprylic/capric/triglycerides, caprylic/capric/lauric triglycerides, C10-C40 isoalkyl acid triglycerides, C10-C18 triglycerides, glyceryl triacetyl hydrostearate, soybean glycerides, tribehenin, tricaprin, triethylhexanoin, triheptanoin, triisostearin, tripalmitin, or tristearin.

Hydrocarbon oils that can be used include liquid paraffin (mineral oil), paraffin, petroleum jelly, microcrystalline wax, or squalene.

Vegetable oils that can be used include avocado oil, wheat germ oil, rosehip oil, shea butter, almond oil, olive oil, macadamia oil, argan oil, meadowfoam oil, sunflower oil, castor oil, camellia oil, corn oil, safflower oil, soybean oil, rapeseed oil, macadamia nut oil, jojoba oil, peony oil, palm oil, palm kernel oil, or coconut oil.

As the wax, any wax, such as hydrocarbon wax, vegetable wax, or silicone wax, which are generally used in cosmetics, can be used. For example, it can include, but is not limited to, candelilla wax, carnauba wax, rice wax, beeswax, lanolin, ozokerite, ceresin wax, paraffin wax, microcrystalline wax, C30-C45 alkyldimethylsilylpolypropylsilsesquioxane, ethylene/propylene copolymer, or polyethylene wax.

The above cosmetic composition may further comprise one or more additional ingredients commonly used in cosmetics, for example, selected from the group consisting of preservatives, stabilizers, surfactants, thickeners, solubilizers, moisturizers, antiseptics, emulsifiers, bactericides, antioxidants, pH adjusters and fragrances. A person skilled in the art can select any additional ingredient and/or its amount such that the advantageous properties of the composition according to the present disclosure are not or are substantially not adversely affected by the expected addition.

The numerical ranges disclosed herein are approximate and thus may include values outside the range unless otherwise indicated. The numerical range includes all values, including lower and upper values, including fractions or decimals. The disclosure of a range includes not only the range itself and what is subsumed therein, but also the endpoints. For example, the disclosure of a range of 1 to 20 includes not only the range of 1 to 20, including the endpoints, but also 1, 2, 3, 4, 6, 10, and 20 individually, and also any other numbers subsumed therein. Furthermore, for example, the disclosure of a range of 1 to 20 includes, for example, the subsets of 1 to 3, 2 to 6, 10 to 20, and 2 to 10, as well as any other subsets subsumed therein.

Similarly, disclosure of a Markush group includes the entire group and also any individual members and subgroups contained therein. For example, disclosure of a Markush group, a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group includes the member alkyl individually; the subgroups hydrogen, alkyl, and aryl; the subgroups hydrogen and alkyl; and any other individual members and subgroups contained therein.

The compound according to the aspect of the invention is a tocopherol derivative that not only has an antioxidant effect, but also increases compatibility with various cosmetic raw materials and increases solubility, so that it can be usefully used in a wider range of cosmetics.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are intended to exemplify the present invention and the scope of the present invention is not limited to these examples.

Example 1. Preparation of a siloxane-based tocopherol derivative compound

1.1. Preparation of modified acetyl chloride intermediate compound based on siloxane

To prepare a siloxane-based tocopherol derivative, a siloxane-based modified acetyl chloride intermediate compound was first prepared as follows.

Specifically, 0.5 L of toluene, from which moisture had been removed in a nitrogen atmosphere, was added to a 2 L four-necked flask equipped with a stirrer, a heating mantle, a reflux condenser, and a thermometer, and then 222.5 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and a platinum catalyst of Chemical Formula 9 or 10 were added and stirred for 10 minutes. 161.47 g of allyloxyacetyl chloride was slowly added while stirring at a constant speed, and the mixture was stirred while maintaining reflux for 5 hours. After cooling, toluene mixed with the reaction mixture was evaporated to obtain 368 g of a siloxane-based modified acetyl chloride intermediate compound.

The above reaction is shown in Scheme 1.

[Reaction Formula 1]

1.2. Preparation of siloxane-based tocopherol derivative compounds

A 2 L four-necked flask equipped with a new clean stirrer, heating mantle, reflux condenser, and thermometer was charged with _0.7 L of _CH2Cl2 , from which moisture had been removed under a nitrogen atmosphere, then 100 g of the synthesized siloxane-based modified acetyl chloride intermediate compound and 56 g of triethylamine were slowly added while stirring at a constant speed, and 118.7 g of α-tocopherol was added over 30 minutes. During this, care should be taken that the internal temperature of the flask does not exceed 70℃, and stirring was maintained for an additional 24 hours after the addition was completed. The mixture was cooled to room temperature, 100 ml of water was added to the mixture, and the lower organic layer was separated from the aqueous layer and washed three times with 2 L of water. The organic layer was separated and subjected to vacuum distillation to obtain 164 g of a siloxane-based tocopherol derivative compound. The refractive index was measured to be 1.4275 and the viscosity was measured to be 655 cSt at 25°C.

The above reaction is shown in Scheme 2.

[Reaction Formula 2]

Manufacturing Examples 1 to 14 and Comparative Manufacturing Example 1. Manufacturing of a Balm-type cosmetic composition

Cosmetic compositions of the night type of Preparation Examples 1 to 14 including the siloxane-based tocopherol derivative compound of Example 1 were prepared as follows.

Specifically, a 100 ml beaker was placed in a magnetic stirrer, and jojoba oil, camellia oil, Bebe Bo blending oil, and beeswax, etc. were measured and added according to the compositions in Table 1 below, and the magnetic bar was slowly stirred so that the beeswax was evenly mixed. In Table 1, CP904 refers to dimethicone and a dimethicone/vinyl dimethicone crosspolymer mixture. Next, a thermometer was used to heat the internal temperature to 80 to 85°C, and when the temperature reached 80 to 85°C, the beeswax melted. At this time, the siloxane-based tocopherol derivative compound was slowly added and mixed. As a comparative manufacturing example, α-tocopherol was added and mixed instead of the siloxane-based tocopherol derivative compound. After 30 minutes of mixing, the liquid composition was poured into a chestnut mold and cooled to room temperature to complete the chestnut.

Manufacturing example Comparative manufacturing example Ingredients (g) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 Jojoba oil 5.7 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 4 4 4 5.6 Camellia oil 5.7 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 4 4 4 5.6 Bebe Bo Blending Oil ^TM - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Beeswax 3 3.1 4 4.4 6 4 4 4 4 4 4 4.4 4.4 4.4 4 Tocopherol derivative compound of Example 1 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 - α-Tocopherol - - - - - - - - - - - - - - 0.7 Peony oil - - - - - - - 1.6 - - 0.8 - - 3.2 - CP904 - - - - - 1.6 - - 0.8 - - 3.2 - - 1.6 PCADimethicone - - - - - - 1.6 - - 0.8 - - 3.2 - -

Experimental Example 1. Confirmation of compatibility, spreadability, and curability

The spreadability, compatibility, and curability of the night type compositions of the above-mentioned Manufacturing Examples 1 to 14 and Comparative Examples were confirmed.

The compatibility test was conducted by visually observing whether the raw materials used were mixed evenly when stirring at an internal temperature of 80 to 85℃ during the manufacture of the chestnut. The spreadability test was conducted to evaluate whether the chestnut was applied smoothly or had a smooth feeling when applied to the skin after manufacture. The hardening test was conducted to evaluate whether the raw materials were separated from the surface of the test specimen and came out to the surface when the solidified test specimen was stored at room temperature for 7 days after manufacture of the chestnut.

As a result, as shown in Table 2 below, it was confirmed that the composition containing the siloxane-based tocopherol derivative compound of the above example had better compatibility, spreadability, and curability than the comparative manufacturing example using α-tocopherol.

These results imply that the compound according to one specific example can be usefully used as a cosmetic composition.

Manufacturing example comparison
Manufacturing example item 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 Compatibility ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ Spreadability ○ ○ ○ ○ ○ ◎ ○ ○ ◎ ○ ○ ○ ○ ○ △ Hardening ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○

Claims (12)

A compound represented by the chemical formula 1 or a cosmetically acceptable salt thereof:
[Chemical Formula 1]

wherein R1, R2 or R3 are each independently hydrogen, halogen, alkylsulfonyl, hydroxyl, an amino group, a nitro group, or a substituted or unsubstituted C ₁ to C ₁₀ alkyl;
wherein R4 is hydrogen, a substituted or unsubstituted C ₂ to C ₂₀ alkyl, or a substituted or unsubstituted C ₂ to C ₂₀ alkenyl;
wherein R5 is hydrogen, or substituted or unsubstituted C ₁ to C ₁₀ alkyl;
wherein R6 is substituted or unsubstituted silyl, or substituted or unsubstituted siloxy; and
The above n is 0 to 20. A compound or a cosmetically acceptable salt thereof according to claim 1, wherein R1, R2 or R3 are each independently hydrogen, or substituted or unsubstituted C ₁ to C ₁₀ alkyl. A compound or a cosmetically acceptable salt thereof according to claim 1, wherein R4 is a C ₂ to C ₂₀ alkyl substituted or unsubstituted with a C ₁ to C ₁₀ alkyl, or a C ₂ to C ₂₀ alkenyl substituted or unsubstituted with a C ₁ to C ₁₀ alkyl. A compound or a cosmetically acceptable salt thereof, wherein in claim 3, R4 is -(CH ₂ CH ₂ CH ₂ CH(CH ₃ )) ₃ CH ₃ or -(CH ₂ CH ₂ CH=C(CH ₃ )) ₃ CH ₃ . In claim 1, R6 is a compound of any one of chemical formulas 2 to 4, or a cosmetically acceptable salt thereof:
[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

A compound or a cosmetically acceptable salt thereof, wherein R8 to R16 are each independently hydrogen, or substituted or unsubstituted C ₁ to C ₁₀ alkyl, and m is 0 to 20. A compound or a cosmetically acceptable salt thereof according to claim 5, wherein R8 to R16 are each independently hydrogen or -CH ₃ . In claim 1, the compound of chemical formula 1 is a compound of chemical formula 5, or a cosmetically acceptable salt thereof:
[Chemical Formula 5]
. A cosmetic composition comprising the compound of claim 1 or a cosmetically acceptable salt thereof. A cosmetic composition according to claim 8, wherein the cosmetic composition is any one selected from the group consisting of lotion, cream, powder, essence, sunscreen, makeup primer, foundation, lipstick, eye shadow, soap, pack, stick type, balm type, and spray. A cosmetic composition according to claim 8, wherein the cosmetic composition is formulated in a solid or semi-solid form. A cosmetic composition according to claim 8, wherein the compound or a cosmetically acceptable salt thereof is contained in an amount of 0.001 to 50.00 wt%. A cosmetic composition according to claim 8, wherein the cosmetic composition further comprises at least one selected from the group consisting of a preservative, a stabilizer, a surfactant, a thickener, a solubilizer, a moisturizer, an antiseptic, an emulsifier, a bactericide, an antioxidant, a pH adjuster, and a fragrance.