FR2957924A1 - New dithiolane compounds useful for the cosmetic treatment of keratin materials such as skin, lips, eyelashes, eyebrows, nails or hair - Google Patents

Abstract

Dithiolane compounds (I) is new. Dithiolane compounds of formula (I) is new. u, v : 0-2; Y1 : O, NR1 or S; R1 : H, optionally saturated 1-32C hydrocarbon optionally comprising one or more heteroatoms of O, NR1aa or S, or phenyl optionally substituted by one or more OH and/ or 1-8C alkoxy; R1aa : H or 1-6C alkyl; p : 0 or 1; R : optionally saturated 1-6C divalent hydrocarbon group, optionally comprising one or more heteroatoms of O, NR1aa or S; n, m : 0-200, provided that m+n is not equal to 0; and R1a : H or optionally saturated 1-6C hydrocarbon group optionally comprising OH. An independent claim is included for cosmetic composition comprising (I) in a medium. [Image].

Description

The present invention relates to new compounds, to their use in particular in cosmetics, in particular in capillary, as well as compositions comprising them. The invention also relates to a method of hair treatment including protection and / or repair of keratin fibers, including damaged.

It is known that certain hair treatments such as coloring or perm, can attack the hair fiber and in particular cause the loss of some of its constituents present in the natural state, especially fatty acids.

It is also known that the cosmetic qualities of the hair can be improved by applying active-based compositions which make it possible to confer various properties on them such as shine, ease of disentangling, swelling, suppleness, nervousness or softness. In order to obtain good efficacy, it should of course be understood that these active agents have a certain affinity for keratin fibers and a good remanence. In other words, these assets must, as far as possible, remain attached to the hair in an amount sufficient to confer the desired properties. It is well known that hair which has been sensitized, in particular damaged and / or weakened, to varying degrees under the action of atmospheric agents or under the action of mechanical and / or chemical treatments, such as colorings, stains, discolorations and perms, are often difficult to disentangle and comb, and also lack sweetness. It has already been proposed for the treatment of keratin materials and in particular hair, cosmetic compositions containing conditioning cationic surfactants, such as those described in US2006 / 0078529. However, such compositions do not yet have the desired cosmetic qualities, in particular in terms of sensory properties, including touching the hair after treatment.

Now, the Applicant has now discovered, unexpectedly and surprisingly, that certain very particular compounds can bring interesting conditioning properties to the hair, especially concerning disentangling, lis-sage, combability and maneuverability of the hair; the hair is then more flexible and its shaping is easier. Its overall appearance would be improved, the hair would be softer and brighter.

The subject of the present invention is therefore a compound corresponding to formula (I): ## STR2 ## wherein: (embedded image) I) - u = 0.1 or 2; - v = 0, 1 or 2; Y denotes O, NR1 or S; with RI denoting: (i) a hydrogen atom; (ii) a saturated or unsaturated, linear or branched C 1 -C 32 hydrocarbon-based group optionally comprising one or more heteroatoms, which are identical or different, chosen from O, NR 'and S with R' = H or C 1 -C 6 alkyl; or (iii) a phenyl group optionally substituted with one or more hydroxyls and / or C1-C8 alkoxy radicals; -p = 0 or 1; - R denotes a divalent hydrocarbon group saturated or unsaturated, linear or branched C1-C6, optionally comprising one or more heteroatoms, identical or different, selected from O, NR 'and S with R' = H or alkyl C1 C6; n = 0 to 200, and m = 0 to 200, with the proviso that m + n # 0; - R 'denotes a hydrogen atom or a saturated or unsaturated hydrocarbon radical, linear or branched, C1-C6, optionally comprising an OH radical.

The invention also relates to a cosmetic composition comprising, in a cosmetically acceptable medium, at least one such compound.

Thanks to the compounds according to the invention, it would be possible to improve the cosmetic of damaged hair, for example following a discoloration, a permanent, a straightening, a smoothing or a coloration, or naturally fragile hair, or assaulted hair for example by UV, pollution or repeated brushing. One could also bring body and / or nervousness to the hair and make their surface shiny; we could also protect and / or repair damaged hair. The compounds according to the invention could make it possible to improve the surface state of the keratinous fibers, particularly in a humid medium.

Moreover, the compounds according to the invention provide good sensory properties to the hair, especially a very pleasant and fluid touch. In addition, the compounds according to the invention are easily transportable in the aqueous mid-places, which facilitates their implementation. The compounds according to the invention therefore correspond to formula (I): ## STR2 ## (R) + CH 2 CH 2 O in [OR 'CH 1 CH 2 / S] (0) U (O) v wherein: - u = 0.1 or 2; (I) - v = 0, 1 or 2; Y denotes O, NR1 or S; with RI denoting: (i) a hydrogen atom; (ii) a linear or branched C1-C32 saturated or unsaturated hydrocarbon group (alkyl or alkene) optionally comprising one or more heteroatoms, which are identical or different, chosen from O, NR 'and S with R' = H or C1-C6 alkyl; or (iii) a phenyl group optionally substituted with one or more hydroxyls and / or C1-C8 alkoxy radicals; - p = 0 or 1; - R denotes a divalent hydrocarbon group saturated or unsaturated, linear or branched C1-C6, optionally comprising one or more heteroatoms, identical or different, selected from O, NR 'and S with R' = H or alkyl C1 C6; n = 0 to 200, and m = 0 to 200, with the proviso that m + n # 0; - R 'denotes a hydrogen atom or a saturated or unsaturated hydrocarbon radical, linear or branched, C1-C6, optionally comprising an OH radical.

The chelates, solvates and optical isomers of the compounds of formula (I) are also part of the present invention. The solvates acceptable for the cosmetic use of the compounds according to the invention comprise conventional solvates such as those formed during the last step of preparation of said compounds due to the presence of solvents. There may be mentioned solvates due to the presence of water or linear or branched alcohols such as ethanol or isopropanol. Optical isomers include enantiomers and diastereoisomers.

Preferably, the C1-C8 alkoxy radicals are linear, preferably C1-C4, and preferentially chosen from methoxy, ethoxy, propoxy, butoxy and even better methoxy. Preferably u = 0. Preferably, v = 0.

Preferably, Y denotes O, NH or N (CH 3), preferentially O. Preferably, p = 0; there is therefore a single bond between Y and the oxyalkylenated group. Preferably, R, when it is present, denotes a linear, saturated divalent hydrocarbon group C1-C6, in particular C2-05, optionally comprising an oxygen atom. Preferably, n = 5 to 150, more preferably 8 to 130. Preferably, m = 5 to 150, more preferably 8 to 130. In a particular embodiment, m = 0 and n = 5 to 150, or even 8 to 130. Preferably, R 'denotes a hydrogen atom or a saturated hydrocarbon radical C1-C6 or even C2-05; and in particular methyl.

In a preferred embodiment, Y = O, p = 0 and R 'is selected from H and methyl.

Among the compounds of formula (I) that may be used in the context of the invention, alone or as a mixture, there may be mentioned in particular the following compounds, in which n may vary from 1 to 200, especially from 5 to 150: The compounds of formula (I) can be obtained according to the synthetic routes described below and documented: in the review by Lene Teuber, Sulfur reports, 9 (4), 257-349,1990 Naturally α-curing 1,2-dithiolanes and 1,2,3-tritians. Chemical and Biological Properties; in the patent application EP0869126 A1.

Starting from 2,2-bis (hydroxymethyl) propionic acid, the hydroxyls are functionalized to leaving groups X (alkyl or aryl sulfonate such as mesylate or tosylate, or halogen such as iodine, bromine or chlorine), and then the sulfur according to the following reaction scheme: introduction of sulfur / cyclization O BSH / BS-oxidation O ss YR ss YR XX: grouping leaving functionalization O functionalization BS OH introduction of sulfur / cyclization OH (A) 20 This introduction of sulfur can be carried out in one step using metal disulfide (such as Na2S2) or tetrathiomolybdate salts, in protic or aprotic polar solvents (for example water, DMF, methanol, acetonitrile) to give the dithiolane (A). in two steps, forming a dithiol intermediate, which in the presence of an oxidant (oxygen, DMSO, FeCl 3, 12, Br 2, sodium iodide, thallium trifluoroacetates, silver triflates, hydrogen peroxide, iodate and sodium periodate, sodium hypochlorite, potassium ferricyanide, chromium oxide in particular), in a neutral or basic medium, leads to the formation of dithiolane. The dithiol is obtained by conversion, in a basic or acid medium, in a polar or apolar solvent, of an intermediate species via derivatives of thioacetic acid CH3COSH (in the presence of base), or thiourea or NaSH, by the formation of dithiosulfonates (Bunte salts).

The transformation of the COOH function of dithiolane (A) into COYR function can be carried out according to the conventional methods of acid activation (notably described in Comprehensive Organic Transformation, by LAROCK Wiley VCH Ed. In the chapter Interconversion of nitriles, carboxylic acids and derivatives), then reaction of the activated function with RYH. Preferably, the activation methods are selected from acid chloride formation (by use of thionyl chloride or oxalyl, or 1-chloro-nn-2-trimethyl-1-propenamine), the formation of mixed anhydride (using alkyl chloroformate, for example), or the use of carbodiimides (DCC, DIC or EDC in particular) or of diethylcyanophosphate (as described in Phosphorus in organic synthesis-XI, Amino acids) and peptides-XXI, Reaction of diethyl phosphorocyanidate with carboxylic acids, A new synthesis of carboxylic esters and amides, Tetrahedron, 32, 1976, 2211-2217).

The solvents used may be polar or apolar, protic or aprotic, and especially chosen from toluene, dichloromethane, THF, DMF, acetonitrile, water, methanol and isopropanol. The reactions can be carried out at a temperature between 20 and 100 ° C.

The synthesis of the compounds of formula (I) in which m and / or n are different from 0 can be carried out according to the following reaction scheme: ## EQU1 ## oxidants such as oxygen, hydrogen peroxide, DMSO, sodium periodate, organic peracids, inorganic persulfates, inorganic permanganates, in the presence or absence of a catalyst such as Na2WO4, MoO2C12, or trichloro-oxo bis-triphenylphosphine-rhenium. Depending on the amount of oxidant used, the desired m and n values are obtained. The different oxidation steps are a function of the stoichiometry of the oxidants used. The solvents may be chosen from water, acetone, dichloromethane and methanol. These oxidations have in particular been described in the following publications: Oxidation of 1,2-Dithiolanes, Bernt Lindberg, Gôran Bergson, Arkiv Fôr Kemi, 1965, 23 (31), 319-333; - Selective oxidation of sulfides to sulfoxides and sulfones at room temperature using H2O2 and a Mo (VI) as catalyst, Kandasamy Jeyakumar, Dillip Kumar Chand, Tetrahedrons Letters 47 (2006), 4573-4576; 25 - Rhenium-Catalyzed Oxidation of Thiols and Disulfides with Sulfoxides, Jeffrey B. Arterburn, Marc C. Perry, Sherry L. Nelson, Benjamin R. Dible, Mylena S. Holguin, J. Am. Soc., 119, 9309-9310, 1997.

The compounds of formula (I) find a very particular application in the field of cosmetics, in particular capillary. They may be present in the composition in solubilized form, for example in water or an organic solvent, in particular ethanol, benzyl alcohol, butyl acetate, ethyl acetate or isopropyl myristate. PEG (polyethylene glycols) which are liquid at 25 ° C., isododecane, vegetable oils, liquid petroleum jelly, or in a silicone solvent such as volatile silicone oils, especially D5; as well as their mixtures. They may also be present in the form of an aqueous or organic or silicone dispersion, in particular in one of these solvents.

They can be used in cosmetic compositions, alone or as a mixture, in a proportion of 0.001 to 20% by weight of dry matter, especially 0.1 to 15% by weight, or even 1 to 10% by weight, and even better from 2 to 5% by weight, relative to the total weight of the composition.

The cosmetic compositions according to the invention comprise a cosmetically acceptable medium, that is to say a medium that is compatible with keratin materials such as the skin of the face or of the body, the lips, the hair, the eyelashes, the eyebrows and the skin. nails.

The composition may thus comprise a hydrophilic medium comprising water or a mixture of water and of hydrophilic organic solvent such as alcohols, and especially linear or branched C1-C6 monoalcohols, such as ethanol, tert-butanol, benzyl alcohol and the like. n-butanol, isopropanol or n-propanol, and polyols such as glycerine, diglycerine, propylene glycol, sorbitol, pentylene glycol, hexylene glycol, and polyethylene glycols, or even ethers glycols including C2 and hydrophilic C2-C4 aldehydes.

The composition may also comprise a fatty phase, especially consisting of fatty substances that are liquid at room temperature (generally 25 ° C.) and / or fatty substances that are solid at room temperature, such as waxes, pasty fatty substances, gums and their mixtures. . These fats can be of animal, vegetable, mineral or synthetic origin. This fatty phase may, in addition, contain lipophilic organic solvents. As fatty substances that are liquid at room temperature, often called oils, that can be used in the invention, mention may be made of: hydrocarbon-based oils of animal origin, such as perhydrosqualene; vegetable hydrocarbon-based oils such as liquid triglycerides of fatty acids with 4 to 10 carbon atoms, for instance triglycerides of heptanoic or octanoic acids, or sunflower, corn, soybean, grape seed or sesame oils, apricot, macadamia, castor oil, avocado, triglycerides of caprylic / capric acids, jojoba oil, shea butter; linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum jelly, polybutenes, hydrogenated polyisobutene such as Parleam; esters and synthetic ethers, in particular of fatty acids, for example purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, octyl-2-dodecyl stearate, erucate octyl-2-dodecyl, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; pentaerythritol esters; fatty alcohols having 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol; partially hydrocarbon and / or silicone fluorinated oils; silicone oils such as polymethylsiloxanes (PDMS) which may or may not be volatile, linear or cyclic, liquid or pasty at room temperature (25 ° C.), such as cyclomethicones or dimethicones, optionally comprising a phenyl group, such as phenyl trimethicones or phenyltrimethylsiloxydiphenyls; siloxanes, diphenylmethyldimethyl-trisiloxanes, diphenyl dimethicones, phenyl dimethicones, polymethylphenyl siloxanes; their mixtures.

The composition according to the invention may also comprise one or more organic solvents which are physiologically acceptable. Mention may in particular be made, in addition to the hydrophilic organic solvents mentioned above, ketones that are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone; propylene glycol ethers which are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether; short-chain esters (having 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, acetate of isopentyl; ethers which are liquid at 25 ° C., such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes liquid at 25 ° C such as decane, heptane, dodecane, isododecane, cyclohexane; aldehydes liquid at 25 ° C such as benzaldehyde, acetaldehyde and mixtures thereof.

The composition according to the invention may also comprise at least one ingredient commonly used in cosmetics, such as vitamins, perfumes, pearlescent agents, thickeners, gelling agents, trace elements, softeners, sequestering agents and alkalizing agents. or acidifying agents, preservatives, sunscreens, surfactants, emulsifiers, antioxidants, anti-hair loss agents, anti-dandruff agents, propellants, ceramides, polymers, especially film-forming polymers; fillers, nacres, dyestuffs and in particular pigments and dyes; reducers, as well as their mixtures. Of course, those skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, impaired by the addition envisaged.

Those skilled in the art may choose the appropriate dosage form, as well as its method of preparation, on the basis of its general knowledge, taking into account, on the one hand, the nature of the constituents used, in particular their solubility in the support, and on the other hand, of the application envisaged for the composition. Thus, the composition according to the invention can be in the form of a suspension, a dispersion including oil in water through vesicles; an aqueous, hydroalcoholic or oily solution, optionally thickened or even gelled; an oil-in-water, water-in-oil or multiple emulsion; an aqueous or hydroalcoholic gel, a foam; an oily or emulsified gel; a dispersion of vesicles, in particular lipids; a biphase or multiphase lotion; a spray. This composition may have the appearance of a lotion, a cream, an ointment, a soft paste, an ointment, a solid cast or molded and especially stick or cup, or compacted solid.

The cosmetic composition according to the invention may be in the form of a care product and / or makeup of the skin of the body or face, lips, nails, eyelashes and / or hair, a solar or self-tanning product, a hair product. In particular, it finds a particularly advantageous application in the hair field, in particular for the protection and / or the repair of keratinous fibers, in particular damaged keratin fibers (hair).

The hair compositions are preferably shampoos, gels, setting lotions, blow-drying lotions, fixing or styling compositions such as lacquers or spray, compositions for the care or repair of the hair, such as after-shampoos to rinse or not, hair care to rinse or not, aqueous or hydroalcoholic lotions for the care of the skin and / or hair; especially non-rinsed sprays; compositions for permanent, straightening, coloring or bleaching, or in the form of compositions to be rinsed, to be applied before or after coloring, discoloration, permanent or straightening, or between the two stages of a perm or a smoothing.

The compositions may also be in the form of shower gels or bubble baths. In a preferred embodiment, the compositions according to the invention may be used for washing, care, treatment, protection and / or treatment. repair of keratin materials such as hair, skin, eyelashes, eyebrows, nails, lips, scalp and more particularly hair, including damaged hair.

The subject of the invention is also a process for the cosmetic treatment of keratin materials such as the skin, the lips, the eyelashes, the eyebrows, the nails or the hair, in particular a hair treatment process, and in particular a method of hair protection and / or repair, in which a cosmetic composition comprising at least one compound of formula (I ') is applied to said keratin materials. In particular, it is a method of protecting and / or repairing hair, especially damaged hair. It is possible to envisage post-treatment of the hair after the application of the composition according to the invention, for example the application of heat and / or UV and / or oxidant such as hydrogen peroxide.

Claims (13)

REVENDICATIONS1. A compound having the formula (I): ## STR1 ## wherein: u = 0.1 or 2; - v = 0, 1 or 2; Y denotes O, NR1 or S; with RI denoting: (i) a hydrogen atom; (ii) a saturated or unsaturated, linear or branched C 1 -C 32 hydrocarbon-based group optionally comprising one or more heteroatoms, which are identical or different, chosen from O, NR 'and S with R' = H or C 1 -C 6 alkyl; or (iii) a phenyl group optionally substituted with one or more hydroxyls and / or C1-C8 alkoxy radicals; - p = 0 or 1; - R denotes a divalent hydrocarbon group saturated or unsaturated, linear or branched C1-C6, optionally comprising one or more heteroatoms, identical or different, selected from O, NR 'and S with R' = H or alkyl C1 C6; N = 0 to 200, and m = 0 to 200, with the proviso that m + n # 0; - R 'denotes a hydrogen atom or a saturated or unsaturated hydrocarbon radical, linear or branched, C1-C6, optionally comprising an OH radical. 2. Compound according to claim 1, wherein: u = 0, and / or - v = 0, and / or - Y denotes O, NH or N (CH3), preferably O; and / or - p = 0; and / or - R denotes a divalent saturated hydrocarbon group, linear, C1-C6, especially C2-05, optionally comprising an oxygen atom; and / or - n = 5 to 150, more preferably 8 to 130; and / or - m = 5 to 150, more preferably 8 to 130; and / or - R 'denotes a hydrogen atom or a linear saturated hydrocarbon radical having 1 to 6 carbon atoms, or even C2 to 5 carbon atoms; and in particular methyl. 35 3. Compound according to one of the preceding claims, in which m = 0 and n = 5 to 150, or even 8 to 130. (0) u (0) v (I) 11 4. Compound according to one of the preceding claims, wherein Y = O, p = 0 and R 'is selected from H and methyl. 5. Compound according to one of the preceding claims, corresponding to the following formula 5, in which n varies from 1 to 200, in particular from 5 to 150: ## STR2 ## 6. Cosmetic composition comprising, in a cosmetically acceptable medium, at least one compound as defined in one of claims 1 to 5. 7. Composition according to claim 6, wherein the compound of formula (I) is present, alone or as a mixture, in a proportion of 0.001 to 20% by weight of dry matter, especially 0.1 to 15% by weight, or even from 1 to 10% by weight, and more preferably from 2 to 5% by weight, relative to the total weight of the composition. 15 8. Composition according to one of claims 6 to 7, wherein the cosmetically acceptable medium comprises at least one ingredient selected from water, monoalcohols, linear or branched C1-C6; polyols such as glycerine, diglycerine, propylene glycol, sorbitol, pentylene glycol, hexylene glycol; polyethylene glycols; glycols ethers in particular C2 and hydrophilic C2-C4 aldehydes; waxes, pasty fatty substances, gums; lipophilic organic solvents; hydrocarbon oils of animal or vegetable origin; linear or branched hydrocarbons of mineral or synthetic origin; esters and synthetic ethers, in particular of fatty acids; polyol esters; the esters of pentaerythritol; fatty alcohols having 12 to 26 carbon atoms; partially hydrocarbon and / or silicone fluorinated oils; silicone oils; vitamins, perfumes, pearlescent agents, thickeners, gelling agents, trace elements, softeners, sequestering agents, basifying or acidifying agents, preservatives, sunscreens, surfactants, emulsifiers, antioxidants, anti-hair loss agents, anti-dandruff agents, propellants, ceramides, polymers, in particular film-forming polymers; fillers, nacres, dyestuffs and in particular pigments and dyes; reducers. 35 9. Composition according to one of claims 6 to 8, being in the form of a care product and / or makeup of the skin of the body or face, lips, nails, eyelashes and / or hair, a suntan or self-tanning product, a hair product. 10 10. Composition according to one of claims 6 to 9, being in the form of a hair product, in particular for the protection and / or repair of keratin fibers, including keratin fibers (hair) damaged. 11. A process for the cosmetic treatment of keratin materials such as the skin, the lips, the eyelashes, the eyebrows, the nails or the hair, in which a cosmetic composition as defined in one of the claims 6 is applied to said keratin materials. to 10. 12. The method of claim 11, characterized in that it is a capillary treatment method. 13. Method according to one of claims 11 to 12, characterized in that it is a method for protecting and / or repairing the hair, especially damaged che-15 want.