Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
• • 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
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P17/00—Drugs for dermatological disorders
  • A61P17/16—Emollients or protectives, e.g. against radiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P39/00—General protective or antinoxious agents
  • A61P39/06—Free radical scavengers or antioxidants
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
  • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
• • 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 novel silicone derivatives of ascorbic acid, which are liposoluble and stable.
• the invention also relates to compositions, in particular cosmetic or pharmaceutical compositions comprising these new derivatives, as well as their use.
• patent application FR2645863 describes molecular complexes formed from a compound belonging to the family of silanols and from an alkali or ammonium derivative of an organic or mineral acid. Molecular combinations are thus obtained which have the advantage of being soluble in water.
• This document cites in particular the molecular complex formed of a monomethylsilane triol and potassium ascorbate.
• the stability of these complexes is not very good, in particular when they are in concentrated solution. In particular, they tend to polymerize which causes their partial insolubilization.
• the object of the present invention is to provide new silicon compounds derived from ascorbic acid, said compounds being liposoluble and having - good stability both in the dry state and in dilute or concentrated solution.
• a subject of the invention is therefore new silicon compounds derived from ascorbic acid as defined below.
• Another subject of the invention is a process for the preparation of the compounds of formulas (2) to (4) defined below, by hydrosilylation of the corresponding siloxane or silane derivative represented by one of formulas (5) to (7) defined below, on an organic derivative of ascorbic acid chosen from the compounds of formula
• Another subject of the invention is a process for preparing the silane derivatives of formula (2) hereinafter defined, by reaction of a derivative of formula (I "') hereinafter defined, with a silane derivative of formula ( 8) following:
• Hal represents a halogen and more particularly chlorine or iodine and the radicals Ri, R'i, R ' 2 , R' 3 , V, p and q have the same meanings as above.
• compositions in particular a cosmetic or pharmaceutical composition, comprising a cosmetically or pharmaceutically acceptable medium and at least one silicon compound derived from ascorbic acid as defined above.
• Another object of the invention is the use of at least one such silicon compound derived from ascorbic acid as an antioxidant and / or anti-free radical agent, in particular in a cosmetic or pharmaceutical composition.
• this use can be cosmetic for, or in a cosmetic composition intended for, treating oxidative stress and / or treating the effects of exposure to the sun and / or preventing aging, in particular of the skin, hair, eyelashes. , eyebrows and / or nails.
• This use can also be for the preparation of a pharmaceutical composition intended to treat oxidative stress and / or treat the effects of exposure to ionizing or solar radiation, and / or prevent aging, in particular of the skin, hair, eyelashes, eyebrows and / or
• the Applicant has found that by grafting covalently on a silicone chain, one or more derivatives of ascorbic acid, new compounds were obtained which exhibited very good solubility properties in the usual organic solvents, in particular in bodies. fats such as oils, as well as great stability in these media or as such.
• - R denotes a hydrocarbon radical, linear, cyclic or branched, saturated or unsaturated in C1-C 3 0, optionally partially or completely halogen, or a tr imethylsilyloxy group of formula -O-SiMe 3 ;
• R -i, R 2 , R 3 are chosen from linear or branched alkyl radicals in C ⁇ -C 8 , linear or branched alkenyl radicals in C r Cs, or a trimethylsilyloxy group;
• - A is a radical of formula (I) below: in which Li, L 2 , L 3 and L represent hydrogen or a divalent radical of formula (a) or (a ') allowing the attachment of the radical A on the silicone chain, provided that at least one of the radicals Li, L 2 , L 3 and L, preferably only one of said radicals Li, L 2 , L 3 and L 4 , represents said divalent radical of formula (a) or (a ') below:
• - V is a linear or branched, saturated or unsaturated CC 6 divalent hydrocarbon radical, optionally substituted by a linear or branched, saturated or unsaturated hydroxyl or C 2 -C 8 alkoxy radical;
• - Ri represents a hydrogen atom, a hydroxyl radical or a C-i-C ⁇ hydrocarbon radical, linear or branched, saturated or unsaturated;
• the compounds according to the invention consisting of a silicone chain comprising at least one unit of formula (1) above therefore comprise, in particular, at least one unit of formula (1a):
• they can also comprise at least one other unit, for example of the (di-) alkylsiloxane type of formula (1c):
• radicals B which are identical or different, are chosen from the radicals R and A,
• - r is an integer between 0 and 50 inclusive, preferably between 0 and 5,
• - u is an integer between 1 and 6 inclusive, preferably chosen from 1 or 2,
• - 1 is an integer between 0 and 9 inclusive, preferably chosen from 2, 3 or 4,
• t + u is between 3 and 10 inclusive, preferably is worth 3, 4, 5 or 6.
• the radicals R which are identical or different, are chosen from the C- I -C- IS hydrocarbon radicals, linear, cyclic or branched, saturated or unsaturated, and the C 1 -C 6 hydrocarbon radicals, linear or branched, saturated or unsaturated, partially halogenated, in particular fluorinated.
• the radicals R which are identical or different, are chosen from the linear or branched C 1 -C 10 alkyl radicals; the phenyl radical; linear or branched fluorinated C-i-Cs alkyl radicals.
• the radicals R 1, R 3 , R 3 which are identical or different, are chosen from linear or branched C 1 -C 6 alkyl radicals, in particular methyl or ethyl, and the trimethylsilyloxy group.
• silicon derivatives corresponding to one of the formulas (1), (2), (3) or (4) will be more particularly preferred, and having at least one of the following characteristics:
• R ' i, R 2 , R 3 represent CH 3 or the trimethylsilyioxy group
• - Ri is hydrogen or CH 3 ;
• - V is -CH 2 - or -CH 2 -CH (OH) CH 2 -;
• - r is between 0 and 5 inclusive
• - s is between 1 and 2 inclusive, - 1 + u is between 3 and 6.
• the divalent radicals corresponding to formulas (a) or (a ') are chosen from hydrocarbon radicals, linear or branched, saturated or unsaturated, optionally hydroxylated, divalent in CrC 6 such as methylene radicals (-CH 2 -) , ethylene (-CH 2 -CH 2 -), propylene (-CH 2 -CH 2 -CH 2 -), n-butylene
• siloxane or silane derivative in which, for example, all the radicals A are atoms of hydrogen.
• SiH derivative This siloxane or silane derivative is referred to in the following description as "SiH derivative".
• the SiH groups can be present in the chain and / or at the ends of the silicic chain. These SiH derivatives are well known products in the silicone industry and are generally available commercially. They are for example described in patents US-A-3220972, US-A-3697473 and US-A-4340709.
• a hydrosilylation reaction of the SiH derivative of formula (5), (6) or (7) is carried out, preferably in the presence of a catalytically effective amount of a platinum catalyst, on an organic derivative of ascorbic acid. chosen from the compounds of formula (Y) below:
• radicals L'i and L ' 2 being able, moreover, to form together with the residue of ascorbic acid a methylene dioxy ring substituted by at least one C alkyl group - ⁇ - 6 or a phenyl group, in particular by a methyl, ethyl or phenyl group, or even by two alkyl or phenyl groups; provided that at least one of the radicals L'i, L ' 2l L' 3 and L 'represents the radical
• the hydrosilylation reaction can therefore be carried out according to one of the following two reactions:
• L " ⁇ , L” 2 , L “ 3 and L” 4 represent benzyloxy groups or a hydrogen atom, provided that at least one of the radicals L “ ⁇ , L” 2 , L “ 3 and L "represents hydrogen.
• radicals L “ ⁇ and L” 2 can also form together with the rest of ascorbic acid a methylenedioxy ring substituted with at least one alkyl group in C- ⁇ - 6 or a phenyl group, in particular by methyl, ethyl or phenyl, or two alkyl or phenyl; provided that at least one of the radicals L “ ⁇ , L” 2 , L “ 3 and L” 4 represents hydrogen, - - with a silane derivative of formula (8) below:
• Hal represents a halogen and more particularly chlorine or iodine and the radicals Ri, R'i, R ' 2 , R' 3 , V, p and q have the same meanings as above.
• the compounds according to the invention are generally present in the compositions of the invention in proportions of between 0.1% and 10% by weight, preferably between 0.5% and 5% by weight, relative to the total weight of the composition.
• compositions which can in particular be cosmetic or pharmaceutical compositions, therefore also comprise a cosmetically or pharmaceutically acceptable medium, that is to say a medium compatible with all keratin materials such as the skin of the body or of the face, mucous membranes, semi-mucous membranes, scalp, as well as integuments such as nails, hair, eyelashes and eyebrows.
• a cosmetically or pharmaceutically acceptable medium that is to say a medium compatible with all keratin materials such as the skin of the body or of the face, mucous membranes, semi-mucous membranes, scalp, as well as integuments such as nails, hair, eyelashes and eyebrows.
• compositions according to the invention can be presented in any cosmetically or pharmaceutically acceptable gaiic form, such as in the form of a lotion, suspension, dispersion, solution in solvent or hydroalcoholic medium, optionally multiphase, optionally thickened or even gelled; form a gel, a foam, a spray, an oil-in-water, water-in-oil or multiple emulsion; in the form of a loose, compact or cast powder; as a solid or an anhydrous paste.
• a cosmetically or pharmaceutically acceptable gaiic form such as in the form of a lotion, suspension, dispersion, solution in solvent or hydroalcoholic medium, optionally multiphase, optionally thickened or even gelled; form a gel, a foam, a spray, an oil-in-water, water-in-oil or multiple emulsion; in the form of a loose, compact or cast powder; as a solid or an anhydrous paste.
• the composition can comprise at least one ingredient chosen from the adjuvants usually used in the field under consideration, such as fatty substances, organic solvents, water, silicones, thickeners, softeners, sunscreens, anti-foaming agents, moisturizing agents, perfumes, preservatives, surfactants, fillers, sequestrants, anionic, cationic, nonionic and / or amphoteric polymers, propellants, basifying or acidifying agents, colorants, pigments or nanopigments, cosmetic active ingredients.
• the adjuvants usually used in the field under consideration such as fatty substances, organic solvents, water, silicones, thickeners, softeners, sunscreens, anti-foaming agents, moisturizing agents, perfumes, preservatives, surfactants, fillers, sequestrants, anionic, cationic, nonionic and / or amphoteric polymers, propellants, basifying or acidifying agents, colorants, pigments or nanopigments, cosmetic active ingredients.
• oils and / or waxes in particular of animal, vegetable, mineral or synthetic origin; C ⁇ -C 32 fatty acids; esters of Cs-C 32 fatty acids; C 8 -C 32 fatty alcohols. Mention may more particularly be made of petrolatum, paraffin, lanolin, hydrogenated lanolin, acetylated lanolin, hydrogenated palm oil, hydrogenated castor oil, petrolatum oil, paraffin oil, Purcellin oil, silicone oils, volatile or not, isoparaffins.
• organic solvents mention may be made of lower CeC alcohols and polyols, such as ethanol, isopropanol, propylene glycol, glycerin and sorbitol.
• the compounds of the invention exhibit excellent lipid solubility, in particular in fatty substances such as Miglyol, alcohols (ethanol in particular), glycols (propylene glycol in particular) and silicone oils (PDMS in particular). Furthermore, they are distributed uniformly in conventional cosmetic carriers containing at least one fatty phase or a cosmetically acceptable organic solvent.
• the compounds according to the invention can have good antioxidant and / or anti-free radical properties. They therefore find a very particular application in cosmetic or pharmaceutical compositions intended to treat oxidative stress and / or treat the effects of sun exposure and / or prevent aging, in particular of the skin, hair, eyelashes, eyebrows. and / or nails.
• compositions comprising them therefore find a very particular application as a composition to be applied to the skin of the body and / or of the face, and / or to the hair, eyelashes, eyebrows and / or nails.
• these compositions can be used:
• a cosmetic composition for protecting or treating or caring for the hair in particular in the form of a shampoo, lotion, gel or rinsing composition, to be applied before or after shampooing, before or after coloring or bleaching, before, during or after permanent or straightening, styling or treating lotion or gel, brushing or styling lotion or gel, hair spray, composition for permanent waving or straightening, coloring or bleaching of hair;
• a care composition for the skin of the body and / or of the face such as an epidermis treatment cream, day cream, night cream, anti-wrinkle cream, moisturizer, hand or foot cream;
• makeup composition for eyelashes, eyebrows, hair, body - or face such as foundation, lipstick, eyeshadows, blushes, liner also called "eyeliner", mascara, coloring gel, nail polish.
• the whole is heated at 55 ° C for 19 hours. Cool and pour into 150 ml of water. The mixture is stirred for 1 hour at room temperature (25 ° C). The precipitate is filtered. It is rinsed with water and dried under vacuum.
• the above derivative (6.4 g, 0.021 mole) is heated to 50 ° C. in a mixture of 80 ml of methanol and 40 ml of aqueous 2N HCl for 2 hours. The mixture is evaporated in vacuo at 40 ° C to remove most of the methanol. The residue is poured into 200 ml of water. The mixture is neutralized with sodium bicarbonate. We extract with ethyl acetate. The organic phase is washed with salt water and dried over Na 2 SO. The solvent is evaporated.
• a colorless oil is obtained which is purified on silica (eluent: cyclohexane / ethyl acetate 50/50). 4.0 g (72% yield) of the desired product are obtained in the form of a colorless oil.
• a brown oil is obtained which is purified on silica (eluent: cyclohexane / ethyl acetate 75/25) to give 13.8 g (yield 45%) of the desired product in the form of a slightly yellow oil.
• the organic phase is washed with salt water and dried over Na 2 SO 4 .
• the preceding product (10.5 g, 0.026 mole) is dissolved in 100 ml of methanol. 50 ml of an aqueous 2N HCl solution are added. The mixture is heated at 50 ° C for 2 hours. The mixture is evaporated under vacuum at 40 ° C to remove the methanol. The residue is poured into 200 ml of water. The mixture is neutralized with sodium bicarbonate. Extraction is carried out with ethyl acetate. The organic phase is washed with salt water and dried over Na 2 S0. The solvent is evaporated to give a yellow oil which is purified on silica (eluent: cyclohexane / ethyl acetate 60/40).
• Step 1 Preparation of 5- (2,2-dimethyl- [1, 3] dioxolan-4-yl) -3-hydroxy-4- (3 thméthylsilanyl-propyloxy) -5H-furan-2-one
• a brown oil is obtained which is purified on silica (eluent: cyclohexane / ethyl acetate 75/25) to give 8.8 g (yield 67%) of the desired product in the form of a slightly yellow oil.
• the above product (8.89 g, 0.03 mole) is dissolved in 100 ml of methanol. 50 ml of an aqueous 2N HCl solution are added. The mixture is heated at 50 ° C for 2 hours. The mixture is evaporated under vacuum at 40 ° C to remove the methanol. The residue is poured into 100 ml of water. The mixture is neutralized with sodium bicarbonate. Extraction is carried out with ethyl acetate. The organic phase is washed with salt water and dried over Na 2 S0 4 . The solvent is evaporated. The yellowish oil obtained is purified on silica (eluent: cyclohexane / ethyl acetate 50/50).
• the above product is dissolved (9.4 g, 0.025 mole) in 80 ml of methanol. 40 ml of an aqueous 2N HCl solution are added. The mixture is heated at 50 ° C for 2 hours. The mixture is evaporated under vacuum at 40 ° C to remove the methanol. The residue is poured into 200 ml of water. The mixture is neutralized with sodium bicarbonate. Extraction is carried out with ethyl acetate. The organic phase is washed with salt water and dried over Na 2 SO 4 . The solvent is evaporated to give a yellow oil which is purified on silica (eluent: cyclohexane / ethyl acetate 2/1). 8.0 g (94% yield) of the desired product are obtained in the form of a yellowish oil.
• the preceding derivative (7.6 g, 0.02 mole) is dissolved in 100 ml of ethyl acetate. 100 ml of absolute ethanol are added. 1.2 g of 5% palladium on charcoal are then added. The mixture is stirred under 12 bar of hydrogen for 7 hours at room temperature. The catalyst is filtered.
• An anti-sun oil-in-water emulsion comprising:
• a protective conditioner gel for the hair is prepared, comprising:

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• 1999
  • 1999-10-26 FR FR9913355A patent/FR2800073B1/fr not_active Expired - Fee Related
• 2000
  • 2000-09-29 ES ES00966244T patent/ES2200946T3/es not_active Expired - Lifetime
  • 2000-09-29 DE DE60003452T patent/DE60003452D1/de not_active Expired - Fee Related
  • 2000-09-29 EP EP00966244A patent/EP1228075B1/fr not_active Expired - Lifetime
  • 2000-09-29 CN CN00817830A patent/CN1414967A/zh active Pending
  • 2000-09-29 MX MXPA02004138A patent/MXPA02004138A/es unknown
  • 2000-09-29 CA CA002388313A patent/CA2388313A1/fr not_active Abandoned
  • 2000-09-29 KR KR1020027005353A patent/KR20020044579A/ko not_active Application Discontinuation
  • 2000-09-29 BR BR0015058-4A patent/BR0015058A/pt not_active IP Right Cessation
  • 2000-09-29 AU AU76697/00A patent/AU7669700A/en not_active Abandoned
  • 2000-09-29 AT AT00966244T patent/ATE243213T1/de not_active IP Right Cessation
  • 2000-09-29 WO PCT/FR2000/002713 patent/WO2001030784A1/fr not_active Application Discontinuation
  • 2000-09-29 JP JP2001533137A patent/JP2003512469A/ja not_active Withdrawn
  • 2000-09-29 PL PL00354959A patent/PL354959A1/xx unknown
  • 2000-09-29 US US10/111,537 patent/US6780888B1/en not_active Expired - Fee Related
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