FR2908769A1 - New siliceous dithiolane-based derivatives useful as an agent for stimulating the intracellular synthesis of glutathione and useful as a photo-protective agent for the skin and for preparing the skin for exposure to sunlight - Google Patents

Abstract

Siliceous dithiolane-based derivatives (I) is new. Siliceous dithiolane-based derivatives of formula B1-Si(R)2-O[-Si(R)2-O-]-[-Si(R)(A)-O-]s-Si(R)2-B1 (I) and of formula (I') is new. A : dithiolane radical of formula (i); L : divalent radical for attaching the radical A to the silicone chain; m : 0-8; X : oxygen, nitrogen or sulfur atom; Y1oxygen or nitrogen atom, a group NR4 or sulfur atom; R4H, 1-20C linear, or branched 3-20C, saturated or unsaturated 2-20C alkyl, optionally substituted with an optionally substituted phenyl radical; R : denotes a linear 1-30C or branched 3-20C saturated, or 2-20C unsaturated hydrocarbon-based group, a halogenated 1-8C hydrocarbon-based group or a trimethylsilyloxy group; B1radical R or A; r : 0-50; s : 0-20; u : 1-6; t : 0-10; t+u : >= 3. Provided that if s is 0, at least one of the two radicals B1 is A. An independent claim is included for composition comprising at least one compound (I) in a medium. [Image] ACTIVITY : Dermatological. Evaluation of the photoprotective effect of (trimethylsilyl) methyl 5-(1,2-dithiolan-3-yl)-pentanoate (Ia) pentanoate with respect to UVA-induced DNA damage. The test was conducted by placing normal human fibroblasts (NHF) in contact with the active agent (compound (Ia) for 24 hours. The cells were then detached, included in an agarose gel and then deposited on a microscope slide. Following the UVA exposure (for 30 minutes), the cells were subjected to a cell lysis (so as to keep intact only the genetic material), to a DNA-denaturing step and then to an electrophoresis to make the damaged DNA migrate. The level of damaged DNA was measured. Pretreatment of the cells with the molecule (trimethylsilyl) methyl 5- (1, 2-dithiolan-3-yl) pentanoate gives the fibroblasts a protection of 42% at 1 mu M and 50% at 10 mu M as compared to the untreated fibroblast which did not showed any protection. MECHANISM OF ACTION : None given.

Description

The present invention relates to novel dithiolane derivative compounds

  silicones of formula (I) (I ') and (II), their use in compositions useful in the field of the treatment or prevention of disorders induced by oxidative stress, in particular caused by solar irradiation and compositions container. The skin is the outermost organ of our body and is therefore the first target of environmental stress, which is especially the ultraviolet radiation of sunlight, UVB and UVA. Indeed, acute or chronic exposure to the sun is known to induce deleterious biological and clinical effects on the body. Skin damage related to chronic (repeated irradiation) or acute (strong irradiation) exposure to UV-A or UV-B has been well studied; it is known in particular that: UV-B (290-300 nm, 5% of total UV), of the most energetic wavelengths, mainly affect the epidermal cells (keratinocytes), acting at the level of the DNA; - UV-A (320400 nm, 95% of total UV), more penetrating, reach dermal cells such as fibroblasts and act indirectly via the generation of free radicals; in addition, prolonged exposure to ultraviolet radiation has the effect of stimulating the expression of collagenases, particularly type 1 matrix metalloproteinase (MMP-1). At the cellular and molecular levels, the impact of UVB and UVA radiation induces various reactions, including the direct and indirect induction of DNA damage. Among the direct induction of DNA damage, some are specific for UV radiation, such as pyrimidine dimers and 6.4 photoproducts. In case of error during repair by specialized enzyme systems (nucleotide excision repair NER, or global excision repair GER), they can be responsible for mutations themselves at the origin of tumor process leading to the development of skin cancers. Moreover, cells found in these tumors have a very high incidence of mutations characteristic of the impact of solar UV. These DNA lesions are also at the origin of apoptotic processes inducing the formation of characteristic cells in the epidermis that are sunburn cells. It will also be noted that UV is responsible at the cellular level for the generation of reactive oxygen species, themselves at the origin of numerous biological effects such as the induction of oxidative damage to DNA (8). Guanine oxo) or many genes. Finally, in addition to the effects described mainly on the two major cell types of the skin, which are the keratinocytes that form the stratified and differentiated epidermis, and the fibroblasts responsible for the synthesis and renewal of the dermal extracellular matrix, UV also an impact on the melanocytes (cells responsible for pigmentation) and the Langerhans cells, having an antigen presenting immune function.

  The deleterious effects of UV in the skin (erythema, photocarcinogenesis, photoaging, photoimmunosuppression, disorders of pigmentation. . . ) are induced by a direct UV action on certain cell chromophores such as DNA, but also by an indirect action.  The energy transported by the UV is indeed capable of triggering the formation of activated species of oxygen (EAO), such as singlet oxygen and superoxide anion, through photosensitization reaction involving endogenous photosensitizers such as riboflavins, bilirubins, phaeomelanin and porphyrin derivatives.  The singlet oxygen and the superoxide anion will be the subject of a cascade of reactions leading to the production of other EAOs such as hydrogen peroxide and hydroxyl radicals.  The resulting EAOs damage DNA, cell membranes and certain proteins (enzymes, transcription factors). . . ).  The cells are equipped with an enzymatic antioxidant defense (superoxides Cu-Zn and Mn superoxide dismutases, catalases, glutathione peroxidases. . . ) and non-enzymatic (vitamins E and C, thiols including glutathione, [3-carotene, trace elements. . . ) whose role is to maintain the intracellular redox potential, but this defense capacity can be exceeded during intense oxidative stress.  The tripeptide glutathione (γ-L-glutamyl-L-cysteinyl-glycine or GSH) is the most ubiquitous and abundant non-protein thiol of low molecular weight.  Most of the intracellular GSH is in reduced form (GSH).  Glutathione disulfide (GSSG) is less than 0. 5% of the total GSH.  In most animal cells, the concentration of GSH is between 1 and 10 mM while it is of the order of 0. 5 and 10 μM in plasma.  The thiol function localized on the cysteine residue confers on it a redox potential (around -230 mV) predominant in the oxidation-reduction metabolic phenomena.  Its reducing and nucleophilic properties play a major role in the protection against oxidative alterations of lipids, proteins and nucleic acids.  Under oxidative stress, its protective and detoxifying role results mainly from its coenzyme function of glutathione peroxidases and glutathione-S-transferases.  It is also the subject of synergistic interactions with other components of the antioxidant protection system such as vitamin C, vitamin E, and superoxide dismutases.  Decreasing the level of glutathione will therefore affect the redox cell balance.  In particular, it is known that exposure to UV depletes the level of intracellular GSH thus increasing the sensitivity of cells to oxidative stress.  The skin can be protected from the harmful effects of UV radiation by the use of sunscreens.  These products contain molecules that absorb harmful wavelengths before they reach the skin and damage it, thus preventing acute and chronic effects of UV exposure.  Yet sunscreens do not have a global action.  Since there are no filters allowing total absorption of harmful wavelengths (UVB, UVA and long UVA), a photoprotection strategy based on the induction of endogenous antioxidant defense systems, offers perspectives. interesting.  There is therefore a real need to find complementary solutions in this field in order to restore endogenous glutathione levels after UV exposure.  This can be envisaged by the stimulation by an active endogenous natural systems of defense and / or cellular repair after UV stress.  Lipoic or thioctic acid (1,2-dithiacyclopentane-3-valeric) is an endogenous dithiol widely found in plants and animals.  It is a coenzyme for the metabolism of lipids and carbohydrates in mitochondrial multienzyme complexes such as pyruvate dehydrogenase and α-ketoglutarate dehydrogenase.  Lipoic acid also increases the glutathione cell level by oxidized glutathione regeneration (GSSG) and increases the activity of y-glutamylcysteine ligase (enzyme controlling GSH synthesis).  The Applicant has now discovered that certain novel derivatives possessing a silicon dithiolane unit and, in particular, siliconized lipoic acid derivatives make it possible to significantly increase the level of glutathione after induced UV depletion.  Thus, the present invention relates to compounds of the general formula of compounds (I) and (I '): ## STR1 ## wherein: ## STR2 ## wherein (1) following: L (1) in which: L is a divalent radical allowing the attachment of the radical A to the silicone chain; m represents an integer of 0, 1, 2, 3, 4, 5, 6; , 7, 8, - X represents an oxygen, nitrogen or sulfur atom, -Y represents an oxygen, nitrogen, NR4 or sulfur atom; -R4 represents a hydrogen, a linear alkyl C1-C20, or branched C3-20 C20, saturated or unsaturated C2-C20, optionally substituted with an optionally substituted phenyl radical, R 2908 denotes a linear saturated hydrocarbon group C1-C30 or branched C3-C20 or C2-C20 unsaturated, C1-C8 halogenated hydrocarbon group or trimethylsilyloxy group; B, identical or different for the same compound, is chosen from radicals R and A; R is an integer from 0 to 50 inclusive; ^ s is an integer from 0 to 20 inclusive, and if s is 0, at least one of the two radicals B is A; u is an integer from 1 to 6 inclusive; t is an integer from 0 to 10 inclusive; It being understood that t + u is equal to or greater than 3.  Preferably, L corresponds to one of the following formulas (a) or (a '): HCC (Z) p ù (Y') q (a) H2 Y "H (Z) p ù (Y) q (a) Wherein Y is 0 or NH; Z is a linear or branched, saturated or unsaturated C1-C6 alkanediyl radical optionally substituted with a linear or branched C2-C8 alkyl or hydroxyl radical; or branched, saturated or unsaturated • Y "represents a hydrogen atom, a hydroxyl radical or a linear or branched, saturated or unsaturated C 1 -C 8 alkyl radical • p and g are 0 or 1.  Preferably, the radicals R, which are identical or different, are chosen from linear C 1 -C 10 or branched C 3 -C 10 alkyl radicals, saturated or unsaturated radicals, the phenyl radical and the trifluoropropyl radical, at least 80% by weight. many of the radicals R being the methyl radical.  In formulas (I) and (I ') above, those compounds are preferred for which: A is a radical of formula (1) above with m = 4; Where Y is = O, Y "= H, Z = CH 2 and X is an oxygen atom, Y is an oxygen atom, a nitrogen atom NR 4 with R 4 is a hydrogen, a linear alkyl, C 1 -C 20 or branched C 3 -C 20, saturated or unsaturated, optionally substituted with an optionally substituted phenyl radical; R is methyl; B is methyl or a radical A; or is between 0 and 3 inclusive; between 1 and 3 inclusive, 10 o t + u is between 3 and 5.  In the formulas (I) and (I ') above, the compounds in which: A is a radical of formula (1) above with m = 4; Where Y represents an oxygen atom, Y represents an oxygen atom, nitrogen atom (NR4 with R4 = H), R is methyl, B is methyl or a radical A, or = 0, os = 1.  The invention also relates to the compounds of formula (II): R 3 (II) such that m represents an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8; X represents an oxygen, nitrogen or sulfur atom; Y is oxygen, nitrogen, NR4 or sulfur; V is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; R ', R 2, R 3 represent, independently of one another, a linear C 1 -C 10 or branched C 3 -C 10 alkyl radical, saturated or unsaturated, which may comprise one or more halogen atoms (for example Cl, Br, F); a phenyl radical, a benzyl radical; ## STR2 ## denotes hydrogen, a linear C 1 -C 8 or branched C 2 -C 8 alkyl radical, saturated or unsaturated, a phenyl radical; the group Si (CH 3) 3 with the proviso that when D is Si (CH 3) 3 then v = 0 and R ', R 2 and R 3 are methyl; W is a linear C 1 -C 8 or branched C 3 -C 8 linear alkyl radical or unsaturated, or C 2 -C 8 alkylene optionally substituted with hydroxyl; R 4 represents a hydrogen, a linear C 1 -C 20 or branched C 3 -C 20 alkyl, saturated or unsaturated, optionally substituted with an optionally substituted phenyl radical.  In formula (II) above, compounds are preferred for which: m = 4; ^ X = O; R 4 = R 3 or R 3 denote linear C 1 -C 4 or branched C 3 -C 4 alkyl and more particularly methyl; R 4 represents hydrogen, linear C 1 -C 20 or branched C 3 -C 20 alkyl, saturated or unsaturated, optionally substituted with an optionally substituted phenyl radical; W is methylene -CH2-.  In formula (II) above, compounds such as: m = 4; o X = O; o Y = OouNH; R 'to R3 denote C1-C4 alkyl and more particularly methyl; W is methylene -CH2-.  30 2.  5- (1,2-dithiolan-3-yl) pentanoate 2- (trimethylsilyl) ethyl S-3.  5- (1,2-dithiolan-3-yl) pentanoate of 3- (trimethylsilyl) propyl In particular, the compounds according to the invention are: 1.  5- (1,2-dithiolan-3-yl) pentanoate of (trimethylsilyl) methyl 8308769 5.  5- (2-hydroxy-3- (trimethylsilyl) propyl 5- (1,2-dithiolan-3-yl) pentanoate 6.  Dimethyl (phenyl) silyl] methyl 5- [1,2-dithiolan-3-yl] pentanoate 9.  N- [bis (trimethylsilyl) methyl] -5- (1,2-dithiolan-3-yl) pentanamide H 1 Si s 10.  5- (1,2-dithiolan-3-yl) -N- [3- (trimethylsilyl) propyl] pentanamide 4.  Ethyl (dimethyl) silyl] methyl 5- (1,2-dithiolan-3-yl) pentanoate 7.  5- [benzyl (dimethyl) silyl] methyl 5- (1,2-dithiolan-3-yl) pentanoate 10 8.  5- (1,2-dithiolan-3-yl) -N - [(trimethylsilyl) methyl] pentanamide, m.p.  5- (1,2-dithiolan-3-yl) -N- (3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) pentanamide 2908769 o O \ \ / 12.  N, N '- [(1,1,3,3-tetramethyldisiloxane-1,3-diyl) dipropane-3,1-diyl] bis [5- (1,2-dithiolan-3-yl) pentanamide] / NH The compounds of formula (I), (I ') and (II) can be obtained according to two general approaches.  The first conventionally employs a hydrosilylation reaction from the corresponding siloxane or silane derivative wherein, for example, all of the A radicals are hydrogen atoms.  This derivative is hereinafter referred to as SiH.  SiH groups may be present in the chain and / or at the ends of the chain.  These SiH derivatives are well known products in the silicone industry and are generally commercially available.  They are for example described in US Pat. Nos. 3,220,972, 3,679,473 and 4,340,709.  The SiH derivatives corresponding to the compounds of formulas (I), (I ') can therefore be represented by the following formulas (2) to (4): ## STR2 ## In which: R 1, R 2 and R 3 have the meaning given above for the formula (II), R, r, s, t and u have the meaning given above for the formulas (I) and (I '), - B', which are identical or different, are chosen from the radicals R and a hydrogen atom.  In order to prepare the compounds of the invention of formulas (I), (I ') and (II) above, the procedure is as follows: on the SiH derivative of formulas (2), (3) or (4), a hydrosilylation reaction is carried out in the presence of a catalytically effective amount of a platinum catalyst on a dithiolane organic derivative selected from those of the following formula (5): ## STR2 ## wherein X , Y, and m have the same meaning as in formula (1) above and L 'responds to one of two formulas (b) and (b'): H2C I (Z) pù (Y ') (b) Y, HC (Z) p (Y ') q (b') in which Y ', Y ", Z, p and q have the same meanings as in formulas (a) and (a ') above.  The hydrosilylation reaction is therefore carried out according to one of the following two reactions: ## STR2 # CH = CH- and / or Si-C = CH 2 (grafting on formula (b ')) For example on a lipoic derivative having an allylamide function: or SiO 2 OO 2. OH. A second route for preparing the compounds of formula (I) and (II) is to carry out esterification or ester, thioester or amide reactions from of carboxylic acid or derivatives synthetically compatible with the chosen route.  These derivatives can be obtained by one of the four routes described in the following scheme taken with skeleton as the lipoic acid: D i3 + HO H ". .  V v v + + + + + + + + + + + + où où où où où où où où où où où où où où où où où où où où où où où où où où où où où où and v have the same meanings as those indicated above for formula (II), Hal represents a halogen and more particularly chlorine and M + represents an alkali metal and more particularly sodium or potassium.  As reagents, mention may be made of hydroxymethyltrimethylsilane (RN 3219-63-4), 2- (trimethylsilyl) ethanol (RN 2916-68-9) or 3 (trimethylsilyl) propanol (RN 2917-47-7) which are commercial products.  As silane halide derivatives, there may be mentioned chloropropyltrimethylsilane (RN 2344-83-4) or chloromethyltrimethylsilane (RN 2344-80-1) sold by the company Wacker.  Also suitable are the following commercial products: iodomethyltrimethylsilane (RN 4206-67-1), (chloromethyl) dimethylethylsilane (RN 3121- 77-5), (chloromethyl) dimethyl-n-butylsilane (RN 3121-75 -3), (chloromethyl) dimethylpentylsilane (RN73013-39-5), (chloromethyl) dodecyldimethylsilane (RN 70851-47-7), (chloromethyl) triethylsilane (RN 757-34-6), 2-chloroethyltrimethylsilane (RN 7787 87-3), Bis (trimethylsilyl) methylchloride (RN 5926-35- Aminomethyltrimethylsilane (RN 18166-02-4) sold by the company Gelest and (phenyl) (trimethylsilyl) methylamine, the Bis (trimethylsilyl) methylamine (RN 134340-00-4), aminopropyltrimethylsilane (RN 18187-14-9) and other compounds cited by Speier JL, J.  Org.  Chem, 1971, 36, 21, 3120-3126 and Shina K, CAS RN 1961, 81299.  Particularly preferred compounds of formula (I), (I ') and (II) can be advantageously obtained from lipoic acid.  The Applicant has demonstrated that the daily UV (simulation of the average UV light, L'OREAL concept, Christiaens FJ et al, Standard ultraviolet daylight for nonextreme exposure conditions, Photochem Photobiol, 2005) resulted in a decrease in the level of intracellular GSH. on HaCaT cells (keratinocytes derived from a 2-implant), (chloromethyl) dimethyl-phenylsilane (RN 1833-51-8), (chloromethyl) diphenylmethylsilane (RN 18407-40-4) and (trimethylsilylmethyl) dimethylchloromethylsilane (RN 18306-73-5).  2908769 13 adult human skin spontaneously immortalized in vitro).  The depletion was maximum 6 hours after exposure (decrease of about 40%) and return to the basal state 24 hours after daily UV exposure (UVJ).  The compounds according to the invention can prevent and / or correct this depletion of GSH, they can thus boost endogenous antioxidant defenses systems, in order to prepare the skin to better undergo UV stress and help it repair itself.  Their activity was compared to a reference compound, lipoic acid, known to increase the level of GSH.  The Applicant has thus shown that the ability to increase the GSH level of the compounds according to the invention was much greater than that of lipoic acid measured under the same conditions (see Example 5).  The present invention also relates to the use of the compounds of general formula (I), (I ') and / or (II) as an agent stimulating intracellular synthesis of glutathione and / or maintaining an intracellular level of glutathione in a quantity sufficient to prevent oxidative damage caused by free radicals in the cells.  Thus, the use according to the invention makes it possible to increase the cellular antioxidant defense systems, in particular the antioxidant defense systems of the skin cells.  The cells of the skin are in particular fibroblates, keratinocytes, melanocytes, Langerhans cells. . .  According to an advantageous use of the invention, the compounds of general formula (I), (I ') and (II) are useful as photoprotective agent of the skin.  This use may be useful if the skin has been exposed to daylight at an intensity below the minimum erythemal dose and whose effects do not produce visible signs on the skin or where the UV damage is visible, for example by the appearance of redness on the skin.  As a result, the alterations range from simple discomfort such as a sensation of warming of the skin that is only perceptible to redness or irritation.  By skin is meant any cutaneous surface of the human body, including skin, mucous membrane, semi-mucous membrane, thus including lips, scalp. . . , as well as the appendages of the skin, in particular nails, hairs, hair.  Thus, the compounds of general formula (I), (I ') and / or (II) are useful for preventing and / or treating UV stresses and / or sensations of heating due to the sun's radiation, in particular UVA. and / or UVB.  The compounds of general formula (I), (I ') and / or (II) are also useful for the preparation of a composition, comprising a physiologically acceptable medium, for the prevention and / or treatment of alterations, such as redness and skin irritation, skin due to sun radiation.  The compounds of the general formula (I), (I ') and / or (II) are still useful for the preparation of a composition, comprising a physiologically acceptable medium, for preventing and / or treating DNA due to the sun's radiation and thus prevent the development of cancers, especially skin cancers.  The invention also relates to the use of at least one compound of formula (I), (I ') or (II) for the preparation of a composition containing a physiologically acceptable medium, said composition being intended for the prevention and / or treatment of disorders of the skin and / or mucous membranes induced by irradiation with UVA and / or UVB radiation.  The irradiation or sun exposure is characterized by exposure to the sun, it may in particular be an intense irradiation corresponding to exposure to the zenith sun or solar radiation varying by an angle of 30 around this zenith position. and / or when the skin is subjected to UV radiation capable of inducing a solar erythema (redness commonly called "sunburn"), and defined by a minimal erythemal dose (EMR or MED).  This dose varies according to the individual's phototype and the UVA / UVB ratio.  The invention aims in particular to prevent or reduce the damage induced in the skin, mucous membranes and / or integuments of a mammal, in particular of a human being, by short exposures to erythematous doses of solar radiation.  These solar exposure conditions include UVA and / or UVB radiation, at doses around the MED, in particular at a dose greater than or equal to 1 MED.  As explained above, by their ability to increase the level of GSH, the compounds of formula (I), (I ') and (II) according to the invention allow the establishment of the cutaneous antioxidant protective system.  Also, the cosmetic use according to the invention of at least one compound of formula (I), (I ') and (II) in a composition containing a physiologically acceptable medium is particularly suitable for preparing the skin for an exposure. solar.  A physiologically acceptable medium is according to the invention either a cosmetically or pharmaceutically acceptable medium compatible with the skin, the mucous membranes, the nails and / or the hair, or an orally administrable medium.  In particular, the preparation of the skin for sun exposure may be made by daily application to the skin of said cosmetic composition for one week before sun exposure and, preferably, for two weeks, up to at least one night (between 6 and 18 hours) before sun exposure.  Whether they have an endogenous or exogenous origin, free radicals cause significant oxidative damage, especially in cell membranes (lipid peroxidation causing degradation of membrane permeability), cell nuclei (destruction of DNA) and tissues, especially connective tissue (degradation of elastin and collagen fibers, depolymerization of polyuronic fibers).  This damage leads to dryness and loss of firmness and elasticity of the skin (Grinwald et al.  1980, Agren et al.  1997).  The specialists currently consider that one of the causes of cellular aging is the reduction of the defense capacities against free radicals and against the oxidation phenomena (in particular the formation of superoxide ions) that they initiate.  Thus, more generally, the compounds of general formula (I), (I ') and / or (II) according to the invention are useful as indirect antioxidant compounds for preventing and / or limiting the formation of free radicals and / or eliminate free radicals present in the cells and can be used for any skin disorder caused by oxidative stress.  This activity of the compounds of general formula (I), (I ') and (II) is enhanced by the intrinsic antioxidant property of these compounds related to their thiol function.  Thus, the use of the compounds according to the invention makes it possible to prevent and / or treat the clinical signs of aging.  Aging as a natural physiological phenomenon, the clinical signs of which are generally reflected on the skin by the appearance of wrinkles and fine lines, by loosening of the cutaneous and subcutaneous tissues, by a loss of cutaneous elasticity and by a sluggishness the texture of the skin.  The loss of firmness and tone of the skin, such as wrinkles and fine lines, can be explained at least in part by dermal atrophy and also by a smoothing of the dermal-epidermal junction; the skin is less firm and more flaccid, and the thickness of the epidermis diminishes.  In addition, the complexion of the skin is generally modified, it appears paler and more yellow.  This phenomenon seems essentially due to a disruption of microcirculation (less hemoglobin in the papillary dermis).  Another clinical sign of aging is the dry, rough appearance of the skin, which is essentially due to greater desquamation; these scales, by diffracting the light rays, also take part in the gray appearance of the complexion.  In addition, many colored spots and / or darker appear on the surface of the skin, and more especially on the hands, conferring on the skin a heterogeneity.  In general, these spots are due to a large production of melanin in the epidermis and / or dermis of the skin.  In addition, there may be diffuse irritations and sometimes telangiectasias on certain areas of the skin.  Some of these signs are more particularly related to intrinsic or physiological aging, that is, age-related aging, while others are more specific to extrinsic aging, i.e. aging caused in general by the environment; it is more particularly the photo-aging due to exposure to the sun, light or any other radiation or pollutants.  Thus the subject of the invention is particularly suitable for the cosmetic use of at least one compound of general formula (I), (I ') and / or (II) according to the invention in a composition containing a medium. physiologically acceptable, to prevent and / or treat the loss of firmness and / or elasticity of the skin.  Such use allows the skin to find a uniformly smooth appearance.  Another subject of the invention is the cosmetic use of at least one compound of general formula (I), (I ') and / or (II) according to the invention in a composition containing a physiologically acceptable medium, to prevent and / or treat dull complexion and / or restore radiance to the complexion.  The invention is also suitable for the cosmetic use of at least one compound of general formula (I), (I ') and / or (II) according to the invention in a composition containing a physiologically acceptable medium, for preventing and / or treat skin dehydration.  More generally, the subject of the invention is also suitable for the cosmetic use of at least one compound of general formula (I), (I ') and / or (II) according to the invention in a composition containing a physiologically acceptable medium, for preventing and / or treating the signs of skin aging.  By signs of skin aging is more particularly meant pigment spots and / or hyperkeratosis spots and / or epidermal atrophy and / or skin roughness and / or dryness.  Another subject of the invention relates to the cosmetic use of at least one compound of general formula (I), (I ') and / or (II) in a composition containing a cosmetically acceptable medium, for preventing and or treat the harmful effects of pollution on the skin.  It is known that the toxicity of atmospheric pollutants, in particular gaseous pollutants such as sulfur dioxide, ozone and nitrogen oxides on the constituents of the skin (fibers, cells, enzymes) and on the sebum secreted by the body. skin is linked in particular to their activity of initiators of free radicals, source of oxidation phenomena which cause in living beings cellular damages.  The living cells, which are in direct and permanent contact with the external environment (in particular the skin, the scalp and certain mucous membranes) are particularly sensitive to these effects of gaseous pollutants, which result in particular in accelerated aging of the skin, with a lack of radiance and early formation of wrinkles or fine lines, and also a decrease in vigor and dullness of the hair.  As previously explained, an undesirable effect of the presence of free radicals in the skin is that they cause a phenomenon of lipid peroxidation.  With age (more particularly from the age of forty), the accumulation of these peroxidized lipids is responsible for bad body odors such as a rancid odor (Haze S.  et al.  J.  5 Invest.  Dermatol.  2001, 116 (4): 520-4).  The object of the invention is adapted to the cosmetic use of at least one compound of general formula (I), (I ') and / or (II) according to the invention in a composition containing a physiologically acceptable medium, to prevent and / or limit and / or eliminate peroxidation of cutaneous lipids.  Thus the object of the invention is also useful for preventing and / or limiting and / or eliminating bad body odor.  The compositions according to the invention may be for cosmetic and / or dermatological use.  These may be compositions adapted for topical application, in particular external topical application to the skin, mucous membranes and / or integuments.  According to another embodiment, the compositions according to the invention are adapted to the oral route, and are especially intended for applications in oral cosmetics.  The amount of usable compound according to the invention is of course a function of the desired effect and can therefore vary to a large extent.  To give an order of magnitude, it is possible to use, for the topical route, an extract as defined above in an amount representing from 0.001% to 20% of the total weight of the composition and preferably in a quantity representing 0.01% at 10% of the total weight of the composition.  Formulation of the compositions Preferably, the compositions according to the invention comprising at least one compound of formula (I), (I ') and / or (II) consists of a cosmetically acceptable medium, that is to say which has a pleasant color, smell and feel and does not generate unacceptable discomfort.  The compositions are preferably cosmetic compositions or products.  By "cosmetic product" is meant especially any substance or preparation intended to be put in contact with the various superficial parts of the human body (epidermis, hair and hair system, nails, lips and external genital organs) or with the teeth and 5 oral mucosa in view, exclusively or mainly, of cleaning, perfuming, modifying its appearance and / or correcting body odor and / or protecting or maintaining it in good condition (cosmetic directive 76 / 768 / EEC as amended).  The composition according to the invention may especially be in the form of alcoholic, hydro-alcoholic or oily solution, suspension, dispersion, W / O, O / W or multiple emulsions, aqueous or anhydrous gels, vesicular dispersion. ionic or nonionic type.  It can have a liquid, semi-liquid, pasty, or solid consistency.  For a topical application, the composition that may be used according to the invention may especially be in the form of a hydroalcoholic or oily solution or of the lotion or serum dispersion, of emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous (O / W) or reverse (W / O) or multiple phase, a free or compacted powder to be used as such or incorporated in a physiologically acceptable medium, or suspensions or soft-consistency emulsions of the cream or gel type, aqueous or anhydrous, or microcapsules or microparticles, or vesicular dispersions of ionic and / or nonionic type.  It can thus be in the form of ointment, tincture, cream, ointment, powder, patch, impregnated buffer, solution, emulsion or vesicular dispersion, lotion, gel, spray, suspension, shampoo, aerosol or foam.  It can be anhydrous or aqueous.  It may also consist of solid preparations constituting soaps or cleaning bars.  These compositions are prepared according to the usual methods.  According to another embodiment of the invention, the composition is suitable for oral use, in particular in "oral cosmetics".  For oral use, the composition may especially be in the form of capsules, capsules, dragees, granules, tablets, chewable, gels or oral syrups or any other form known to man. of career.  The amounts of the various constituents of the compositions which can be used according to the invention are those conventionally used in the fields under consideration.  The compositions according to the invention may also contain agents which enhance or supplement the activity of the compound of formula (I), (I ') or (II), and in particular at least one compound selected from the group consisting of oxidizers, anti-pollution agents, anti-UVA filters, anti-UVB filters, depigmenting agents, DNA repair stimulating agents.  The compounds of formula (I), (I ') and (II) according to the invention may also be advantageously combined with extracts (total biomass, culture medium, ribosomal fraction, fraction of cell membranes, LPS fraction, lipid A . . . ) of non-photosynthetic non-fruiting filamentous bacteria such as Vitreoscilla filiformis or {2- [acetyl- (3-trifluoromethyl-phenyl) -amino] -3-methyl-butyrylamino} -acetic acid.  Thus, it is possible, for example, to use an antioxidant agent chosen from: vitamin E (tocopherol) and its derivatives, among other acetate, linoleate or nicotinate, preferably at concentrations of the order of 0.1 to 5%, - y-orizanol (0.1 to 5%), - lysine or arginine pidolates (0.5 to 10%), - plant extracts such as melissa extract (0.01 to 2%) ), silimarine extract (0.01 to 2%), gingko biloba extract (0.05 to 2%), sage extract (0.05 to 2%), kola nut (0,05 to 2%), rutin extract (0,1 to 2%) or thyme extract (0,1 to 2%), the% being given in dry matter, - carotenoids, such as α and β-carotene or lycopene in a purified form or in an extract (for example tomato paste titrated with lycopene resulting in a final concentration of lycopene of between 10-12% and 10% and more preferentially from 10% to 0.1%), the proanthocyanolidic oligomers of pine, hawthorn or grape (0.1 to 2%), - di-tert-butyl-hydroxybenzylidene camphor (0.1 to 2%), - green tea (0.1 to 2%), - caffeine (0 , 1 to 5%), - glycerol (2 to 30%), - mannitol (2 to 30%), - carnosine (0.1 to 2%), - superoxide dismutase (100 to 10 000 IU / 100 g), guanosine (0.01 to 1%), 2908769 21 microalgae containing ethoxyquin such as Hematococcus (0.005 to 1%), pentasodium aminotrimethylene phosphonate (0.001 to 0.5%). %), - lactoperoxidase (0.01 to 0.1%), - vitamin C and its derivatives, - lactoferrin (0.01 to me. isopropyl (benzyl {2- [benzyl (2-isopropoxy-2-oxoethyl) amino] ethyl} amino) acetate, phloretin, hesperidine, neohesperidinedihydrochalcone, ferulic acid, Eukarions (including EUK-8, EUK-134 and EUK-189 developed by Proteome Systems), L-2-oxo-4-thiazolidine carboxylic acid, ergothioneine, Caffeic acid, desferal, 4,4 '- (2,3-dimethylbutane-1,4-diyl) dibenzene-1,2-diol.  It is also possible to use a mixture of several antioxidants.  Anti-free radical agents may also be mentioned, in particular bioflavonoids; coenzyme Q10 or ubiquinone; certain enzymes such as catalase, glutathione peroxidase and quinone reductases; glutathione; benzylidene camphor; benzylcyclanones; substituted naphthalenones; pidolates; phytantriol; lignans; melatonin; hydroxylated chalcones and their reduced derivatives.  Preferably, the antioxidant is selected from vitamin C, vitamin E, isopropyl (benzyl {2- [benzyl (2-isopropoxy-2-oxoethyl) amino] ethyl} amino) acetate, ferulic acid , phloretin and SOD.  By the term "anti-pollution agent" is meant any compound capable of trapping ozone, mono- or polycyclic aromatic compounds such as benzopyrene and / or heavy metals such as cobalt, mercury, cadmium and / or nickel.  By "antiradical agent" is meant any compound capable of trapping free radicals.  As ozone scavengers for use in the composition according to the invention, there may be mentioned in particular vitamin C and its derivatives including ascorbyl glucoside; phenols and polyphenols, especially tannins, ellagic acid and tannic acid; epigallocatechin and natural extracts containing it; olive leaf extracts; tea extracts, especially green tea; anthocyanins; rosemary extracts; phenolic acids, in particular chorogenic acid; stilbenes, especially resveratrol; sulfur-containing amino acid derivatives, in particular S-carboxymethylcysteine; ergothioneine; N-acetylcysteine; chelating agents such as N, N'-bis- (3,4,5-trimethoxybenzyl) ethylenediamine or a salt thereof, metal complexes or esters; carotenoids such as crocetin; and various raw materials such as the mixture of arginine, histidine ribonucleate, mannitol, adenosinetriphosphate, pyridoxine, phenylalanine, tyrosine and hydrolysed RNA marketed by Serobiological Laboratories under the trade name CPP LS 2633-12F, the water-soluble corn fraction. sold by the company SOLABIA under the trade name Phytovityl, the mixture of fumitory extract and lemon extract marketed under the name Unicotrozon C-49 by Induchem, and the mixture of extracts of ginseng, apple, peach, wheat and barley sold by the company PROVITAL under the trade name Pronalen Bioprotect.  As scavengers for mono- or polycyclic aromatic compounds which can be used in the composition according to the invention, mention may be made in particular of tannins such as ellagic acid; indole derivatives, in particular indol-3-carbinol; tea extracts especially green tea, extracts of water hyacinth or eichornia crassipes; and the water soluble fraction of corn marketed by the company SOLABIA under the trade name Phytovityl.  Finally, as heavy metal scavengers for use in the composition according to the invention, mention may in particular be made of chelating agents such as EDTA, the pentasodium salt of ethylenediamine tetramethylene phosphonic acid, and N, N'-bis- (3,4,5-trimethoxybenzyl) ethylenediamine or a salt thereof, metal complexes or esters; phytic acid; chitosan derivatives; tea extracts, especially green tea; tannins such as ellagic acid; sulfur-containing amino acids such as cysteine; water hyacinth (Eichornia crassipes) extracts; and the water soluble fraction of corn marketed by the company SOLABIA under the trade name Phytovityl.  Advantageously, the compositions according to the invention contain at least one UVA filter and / or at least one UVB filter, preferably a combination of at least one UVA filter and at least one UVB filter.  Sunscreens are molecules that absorb UV radiation and thus prevent them from reaching the cells of the skin.  They can absorb either UVB or mainly UVA, depending on their nature.  There are two main categories of solar filters, either organic or mineral (zinc or titanium oxides).  By using them in cosmetic compositions in combination and in sufficient quantity, they make it possible to stop a large part of the UV radiation.  However, it is generally accepted that, in order to be effective, these formulas must be used under good conditions of application (sufficient quantity, frequent renewal, homogeneous spreading).  These conditions of application are not always respected by the user, which increases the risk that a significant amount of UV radiation reaches the cells of the skin, and therefore generates the biological effects mentioned above.  Moreover, in order to obtain an absorption with respect to all the wavelengths of the UV UV + UVA solar spectrum, it is necessary to associate several absorbing molecules in domains of complementary wavelengths.  The compositions according to the invention may further comprise at least one organic photoprotective agent and / or at least one active inorganic photoprotective agent in the UVA and / or UVB (absorbers), which are water-soluble or fat-soluble or insoluble in the

  cosmetic solvents commonly used. The complementary organic screening agents are chosen in particular from anthranilates; salicylic derivatives, camphor derivatives; benzophenone derivatives; 13,13-diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives as described in patents EP 0 669 323 and US 2,463,264; paminobenzoic acid derivatives (PABA); methylene bis- (hydroxyphenylbenzotriazole) derivatives as described in US 5,237,071, US 5,166,355, GB2303549, DE 197 26 184 and EP 0 893 119; filter polymers and silicone filters such as those described in particular in the application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadienes as described in EP 0 967 200, DE19746654, DE19755649, EP1 008 586, EP 1 133 980 and EP 0 133 981 and mixtures thereof. Examples of additional organic screening agents that may be mentioned are those designated below by their INCI name: para-aminobenzoic acid derivatives PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name Escalol 507 by ISP, Glyceryl PABA, PEG-25 PABA sold under the name UVINUL P25 by BASF. Salicylic Derivatives Homosalate sold under the name Eusolex HMS by Rona / EM Industries, Ethylhexyl Salicylate sold under the name NEO HELIOPAN OS by HAARMANN and REIMER, Dipropylene Glycol Salicylate sold under the name DIPSAL by SCHER, TEA Salicylate, sold under the name NEO HELIOPAN TS by HAARMANN and REIMER. Derivatives of 13,1'd iphénylacrylate Octocrylene sold in particular under the trade name UVINUL N539 by BASF, Etocrylene, sold in particular under the trade name UVINUL N35 by BASF. Benzophenone derivatives Benzophenone-1 sold under the trade name UVINUL 400 by BASF, Benzophenone-2 sold under the trade name UVINUL D50 by BASF, Benzophenone-3 or Oxybenzone, sold under the trade name UVINUL M40 by BASF, Benzophenone 4 sold under the trade name UVINUL MS40 by BASF, Benzophenone-5 Benzophenone-6 sold under the trade name Helisorb 11 by Norquay Benzophenone-8 sold under the trade name Spectra-Sorb UV-24 by American Cyanamid 30 Benzophenone-9 sold under the trade name Trade name UVINUL DS-49 by BASF, Benzophenone-12 Diethylamino Hydroxybenzoyl Hexyl Benzoate sold under the trade name UVINUL A PLUS by BASF. Derivatives of benzylidene camphor 3-Benzylidene camphor manufactured under the name MEXORYL SD by CHIMEX, 2908769 4-Methylbenzylidene camphor sold under the name EUSOLEX 6300 by MERCK, Benzylidene Camphor Sulfonic Acid manufactured under the name MEXORYL SL by CHIMEX, Camphor Benzalkonium Methosulfate manufactured under the name MEXORYL SO by CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name MEXORYL SX by CHIMEX, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MEXORYL SW by CHIMEX. Derivatives of Phenylbenzimidazole Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name Eusolex 232 by Merck, Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name NEO HELIOPAN AP by HAARMANN and REIMER. Derivatives of phenyl benzotriazole Drometrizole Trisiloxane sold under the name Silatrizole by Rhodia Chimie Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold in solid form under the trade name MIXXIM BB / 100 by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion under the trade name TINOSORB M by CIBA SPECIALTY CHEMICALS. Anthranilic Derivatives Menthyl anthranilate sold under the trade name NEO HELIOPAN MA by HAARMANN and REIMER. Derivatives of imidazolines Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate. Derivatives of benzalmalonate Benzalmalonate-functional polyorganosiloxanes such as Polysilicone-15 sold under the trade name PARSOL SLX by HOFFMANN LA ROCHE. Derivatives of 4,4-diarylbutadiene 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene. Benzoxazole 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6 (2-ethylhexyl) imino-1,3,5-triazine derivatives sold under the name of Uvasorb K2A by Sigma 3V and their mixtures. The preferred organic UV filters present in the compositions are selected from: Ethylhexyl Salicylate, Homosalate, Octocrylene, Phenylbenzimidazole Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Benzophenone-3, Benzophenone-4, Benzophenone-5, 2- ( N-hexyl 4-diethylamino-2-hydroxybenzoyl) benzoate. 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Methylene bis-Benzotriazolyl Tetramethylbutylphenol Drometrizole Trisiloxane Polysilicone-1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene 2,4-bis- [ 5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6 (2-ethylhexyl) imino-1,3,5-triazine and mixtures thereof. The inorganic complementary photoprotective agents are chosen from pigments and even more preferentially nanopigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) of metal oxides, whether or not treated, such as examples of nanopigments of titanium oxide (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium. The treated nanopigments are pigments which have undergone one or more surface treatments of chemical, electronic, mechanochemical and / or mechanical nature with compounds as described for example in Cosmetics & Toiletries, February 1990, Vol. 105, p 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron, or aluminum salts. of fatty acids, metal alkoxides (of titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides, sodium hexametaphosphate, alumina or glycerine. The nanopigments treated may more particularly be titanium oxides treated with: silica and alumina, such as the products Microtitanium Dioxide MT 500 SA and Microtitanium Dioxide MT 100 SA from the company Tayca, and the products Tioveil Fin, 5 Tioveil OP, Tioveil MOTG and TIOVEIL IPM from the company TIOXIDE, aluminum alumina and stearate such as the product Microtitanium Dioxide MT 100 T from TAYCA, aluminum alumina and laurate such as the product Dioxide MT 100 S microtitanium from the company TAYCA, 10-iron oxides and iron stearate, such as the product Microtitanium Dioxide MT 100 F from TAYCA, silica, alumina and silicone such as Microtitanium products Dioxide MT 100 SAS, Microtitanium Dioxide MT 600 SAS and Microtitanium Dioxide MT 500 SAS from TAYCA, 15 - sodium hexametaphosphate such as Microtitanium Dioxide MT product 150 W from the company TAYCA, - octyltrimethoxysilane such as the product T-805 from the company Degussa, - alumina and stearic acid such as the product UVT-M160 from the company KEMIRA, -alumina and the glycerin such as the UVT-M212 product from the company KEMIRA, 20 - alumina and silicone such as the UVT-M262 product from KEMIRA. Other titanium oxide nanopigments treated with a silicone are preferably TiO 2 treated with octyl trimethyl silane and whose average elementary particle size is between 25 and 40 nm, such as that sold under the trade name 25 ". T 805 "by the company Degussa Silices, the TiO 2 treated with a polydimethylsiloxane and whose average elementary particle size is 21 nm such as that sold under the trade name" 70250 Cardre UF Ti02S13 "by CARDRE, TiO2 anatase / rutile treated with a polydimethylhydrogensiloxane and whose average elementary particle size is 25 nm such as that sold under the trade name "MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC" by the company COLOR TECHNIQUES. Uncoated titanium oxide nanopigments are for example sold by the company Tayca under the trade names "MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM DIOXIDE MT600 B" by DEGUSSA under the name "P 2908769 28 25" , by the company WACKHER under the name "transparent titanium oxide PW", by the company MIYOSHI KASEI under the name "UFTR", by the company TOMEN under the name "ITS" and by the company TIOXIDE under the name "TIOVEIL AQ" . Non-coated zinc oxide nanopigments are for example: those sold under the name Z-cote by the company Sunsmart; those marketed under the name "Nanox" by Elementis; those marketed under the name "Nanogard WCD 2025" by Nanophase Technologies; The coated zinc oxide nanopigments are, for example, those sold under the name "Zinc Oxide CS-5" by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane); those marketed under the name "Nanogard Zinc Oxide FN" by Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alcohol benzoate); these sold under the name "DAITOPERSION ZN-30" and "DAITOPERSION Zn-50" by the company Daito (dispersions in cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 30% or 50% of zinc nano-oxides coated with silica and 20 polymethylhydrogensiloxane); those marketed under the name "NFD Ultrafine ZnO" by the company Daikin (ZnO coated with perfluoroalkyl phosphate and a copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane); those marketed under the name "SPD-Z1" by the company Shin-Etsu (ZnO 25 coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z100" by the company ISP (ZnO treated alumina and dispersed in the mixture methoxycinnamate ethylhexyl / copolymer PVP-hexadecene / methicone); those marketed under the name "Fuji ZnO-SMS-10" by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); those marketed under the name "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in C12-C15 alcohols benzoate with hydroxystearic acid polycondensate). The uncoated cerium oxide nanopigments are sold under the name "COLLOIDAL CERIUM OXIDE" by the company RHONE POULENC. The uncoated iron oxide nanopigments are for example sold by the company ARNAUD under the names "Nanogard WCD 2002 (FE 45B)", "Nanogard IRON FE 45 BL AQ", "Nanogard FE 45R AQ," NANOGARD WCD 2006 (FE 45R) ", or by the company MITSUBISHI under the name" TY-220 "The coated iron oxide nanopigments are for example sold by the company ARNAUD 10 under the names" NANOGARD WCD 2008 (FE 45B FN) " , "NANOGARD WCD 2009 (FE 45B 556)", "NANOGARD FE 45 BL 345", "NANOGARD FE 45 BL", or by BASF under the name "TRANSPARENT IRON OXIDE". metal oxides, in particular of titanium dioxide and cerium dioxide, of which the titanium dioxide and silica-coated cerium dioxide equivalent compound, sold by the company IKEDA under the name "SUNVEIL A", and the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as product "M 261" sold by the company KEMIRA or coated with alumina, silica and glycerin such as the product "M 211" sold by the company KEMIRA 20. The nanopigments may be introduced into the compositions according to the invention as such or in the form of a pigment paste, that is to say in a mixture with a dispersant, as described for example in GB-A-2206339. The additional photoprotective agents are generally present in the compositions according to the invention in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.1% to 10% by weight relative to to the total weight of the composition. The depigmenting or anti-pigmenting agents which may be incorporated in the composition according to the present invention comprise, for example, the following compounds: kojic acid; ellagic acid; arbutin and its derivatives such as those described in EP-895,779 and EP-524,109; hydroquinone; aminophenol derivatives such as those described in WO 99/10318 and WO 99/32077, and in particular N-cholesteryloxycarbonyl-para-aminophenol and N-ethyloxycarbonyl-para-aminophenol; iminophenol derivatives, in particular those described in application WO 99/22707; L-2-oxothiazolidine-4-carboxylic acid or procysteine, as well as its salts and esters; calcium d-pantheterine sulfonate, ascorbic acid and its derivatives, especially ascorbyl glucoside; and plant extracts, in particular licorice, mulberry, skullcap and Bacopa monnieri, without this list being limiting. A useful vitamin E derivative is in particular tocopheryl acetate. The DNA repair stimulating agents include repair promoting enzymes such as photolyase and / or T4 endonuclease. The composition may further contain moisturizing agents, NO-synthase inhibitors, anti-radical agents or agents stimulating the synthesis of epidermal macromolecules and / or preventing their degradation. The amounts of these various components will be adapted by those skilled in the art. In a 25 mL three-neck flask surmounted by a condenser and a thermometer, 4.23 g (20.5 mmol) of 5- (1,2-dithiolan-3-yl) pentanoic acid and 2.9 mL (22.5 mmol) of (trimethylsilyl) methanol are introduced into 5 mL of toluene. 0.11 ml (2.05 mmol) of 98% sulfuric acid is added and then heated at T = 80 ° C. for 2.5 hours. After standing at room temperature, the reaction medium is taken up in 100 ml of ethyl acetate and then washed with water and with saturated sodium chloride solution, the organic phase is dried over sodium sulphate, filtered and then concentrated under vacuum P = 240 mbar at 40 ° C. After purification on a silica column, eluent Heptane / ethyl acetate: 95/5, 2 g of trimethylsilyl 5- (1,2-dithiolan-3-yl) pentanoate are isolated. ) methyl (Yield = 33%). The quasi-molecular ions [M + H] +, [M + Na] +, [M + Na + CH3OH] +, [2M + Na] + as well as the fragment [M + H-C4H12OSi] + of the expected molecule C12H24O2S2Si , M = 292 are mainly detected. The expected product is not detected in ESI-. Example 1 - Preparation of (trimethylsilyl) methyl 5- (1,2-dithiolan-3-yl) pentanoate 2908769 31 Anal. Calculated for C 12 H 24 O 2 S 2 Si: C 49.27, H 8.27, O 10.94, Si 9.6, S 21.92 Found: C (49.44); H (8.3); S (21.72) 1H NMR (DMSO-d6) Signal or signal center Multiplicity Integration (ppm) 0.05 s 9H 1.36m 2H 1.55m 3H 1.65m 1H 1.87m 1H 2.3 t 2H 2.4m 1H 3.11m 1H 3.18m 1H 3.59m 1H 3.73 2s 2H Example 2 Preparation of N-bis (trimethylsilyl) methyl-5- (1,2-dithiolan-3-yl) pentanamido, 5- (1,2-dithiolan-3-yl) -N-compounds 3- (trimethylsilyl) propylpentanamide and N, N'-f (1,3,3-tetramethyldisiloxane-1,3-divl) dipropane-3,1-divyl-5- (1,2-dithiolan-3-yl) pentanamide. synthesis of the three compounds N- [bis (trimethylsilyl) methyl] -5- (1,2-dithiolan-3-yl) pentanamide, 5- (1,2-dithiolan-3-yl) -N- [3- (trimethylsilyl) ) propyl] pentanamide, N, N '- [(1,1,3,3-tetramethyldisiloxane-1,3-diyl) dipropane-3,1-diyl] bis [5- (1,2-dithiolan-3-yl) pentanamide], is carried out from a common intermediate: 1 - {[5- (1,2-dithiolan-3-yl) pentanoyl] oxy} pyrrolidine-2,5-dione, the synthesis of which will be described at prior. Synthesis of 1 - {[5- (1,2-dithiolan-3-yl) pentanoyl] oxy} pyrrolidine-2,5-dione In a dry, 500 mL three-neck, under nitrogen, surmounted by a condenser, a thermometer and an isobaric dropping funnel, 30 g (145 mmol) of 5- (1,2-dithiolan-3-yl) pentanoic acid and 16.85 g (0.145 mol) of N-Hydroxysuccinimide are suspended in 200 mL 2908769 32 of anhydrous acetonitrile. A solution of 30 g (145 mmol) of N, N'-dicyclohexylcarbodiimide in 50 mL of anhydrous acetonitrile is introduced dropwise at T = 0-5 ° C, then 20 mL (145 mmol) of triethylamine are added. The reaction medium is stirred at 0 ° C. for 1 h and then left at room temperature for 24 hours. After filtration of the white insoluble material, the reaction mixture is concentrated under vacuum P = 200 mbar at 40 ° C. and then taken up in approximately 500 ml of ethyl acetate. The organic phase is washed with water, with a saturated solution of sodium hydrogencarbonate and with a saturated solution of sodium chloride. The organic phase is then dried over sodium sulfate, filtered and then concentrated under vacuum P = 240 mbar at 40 ° C. The crude product obtained (30 g) is recrystallized under heat in 150 mL of ethanol. After drying over P2O5 under vacuum, 25.8 g of 1 - {[5- (1,2-dithiolan-3-yl) pentanoyl] oxy} pyrrolidine-2,5-dione, crystalline yellow solid, R0058450A 001 L 002, are obtained. (Yield = 60%). 1. Synthesis of N-fbis (trimethylsilyl) methyl-5- (1,2-dithiolan-3-yl) pentanamide In a 50 ml bicol, under nitrogen, a solution of 1.5 g (5 mmol) of {[5- (1,2-dithiolan-3-yl) pentanoyl] oxy} pyrrolidine-2,5-dione in 20 mL of anhydrous acetonitrile followed by 0.86 g (5 mmol) of 1,1-bis (trimethylsilyl) methanamine. and 0.68 mL (5 mmol) of triethylamine. The mixture is stirred at room temperature for 20 h, concentrated under vacuum P = 200 mbar at 40 ° C. and then taken up in 100 ml of dichloromethane. The organic phase is washed with water and then with a saturated solution of sodium chloride. The organic phase is then dried over sodium sulphate, filtered and then concentrated under vacuum P = 700 mbar at 40 ° C. After purification on a column of silica, eluent Heptane / ethyl acetate: 8/2, we obtain 25 0.68 g of N- [bis (trimethylsilyl) methyl] -5- (1,2-dithiolan-3-yl) pentanamide, yellow oil (Yield = 40%). The analysis in ESI + and ESI- makes it possible to confirm the molecular mass of the expected product C15H33NOS2Si2, M = 363 (detection of [M + H] +, [M + Na] +, [2M + Na] +, [MH] - , [M + Cl] -, [2M-3H + Na] + and [MH-H 2 S] -) fragment. Also in ESI + and ESI- are uncharacterized secondary ions of very low intensity. Anal. calculated for C15H33NOS2Si2: C 49.5, H 9.1, N 3.9.0 4.4, S 17.6, Si 15.4. Found: C (49.90); H (9.47); N (3.75); S (17.22) 1H NMR 2908769 (DMSO-d6) Signal or center Multiplicity Signal integration (ppm) 0.002 s 18H 1.35 m 2H 1. 52 m 3H 1.67 m 1H 1.86 m 1H 2.11 t 2H 2.41 m 1H 3 d 1H 3.11 m 1H 3.17 m 1H 3.58 m 1H 7.43 d 1H 2. Synthesis of 5- (1,2-dithiolan-3-yl) -N- [3- (trimethylsilyl) propyllpentanamide 5- (1,2-dithiolan-3-) yl) -N- [3- (trimethylsilyl) propyl] pentanamide is obtained from 3- (trimethylsilyl) propan-1-amine, the synthesis of which is described below. 2.a. Synthesis of 3- (trimethylsilyl) propan-amine in two steps In a dry, 50 ml three-necked flask under argon, surmounted by a condenser and a thermometer, 2.6 g (14 mmol) of potassium phthalimide are added. in suspension in 20 ml of anhydrous N, N-dimethylformamide and 2.3 ml (13 mmol) of chloropropyltrimethylsilane are introduced dropwise into the reaction medium. The mixture is heated at T = 85 ° C. for 20 hours, allowed to come back to RT and then concentrated under vacuum P = 1 mbar at 40 ° C. The crude product is taken up in 100 ml of ethyl ether. After filtration of the salts, the ethereal phase is washed with water and then dried over sodium sulfate, filtered and concentrated under vacuum P = 700 mbar at 40 ° C. 2.7 g of 2- [3- (trimethylsilyl) are thus obtained. propyl] -1H-isoindole-1,3 (2H) -dione with a yield of 71%. For the phthalimide reduction step, 2.16 g (8.3 mmol) of 2- [3- (trimethylsilyl) propyl] -1H-isoindole-1,3 (2H) -dione are solubilized at 40.degree. In 100 mL of the isopropanol / water mixture: 6/1. At room temperature, 1.57 g (41 mmol) of sodium borohydride are gradually added and the reaction mixture is stirred for 20 hours. 9 ml of acetic acid are then added slowly before refluxing for 3 hours. The reaction medium is concentrated under vacuum P = 40 mbar at 40 ° C. and the residue is taken up in 100 ml of water. In acid medium (pH 4-5), the aqueous phase is washed with ether, the pH brought to 12-14 with a 20% aqueous solution of ammonia and then extracted with ethyl acetate. After washing with a saturated solution of sodium chloride, the organic phase is dried over sodium sulfate, filtered and then concentrated under vacuum P = 240 mbar at 40 ° C. 0.5 g of 3- (trimethylsilyl) propan-1 are thus obtained. amine (Yield = 41%). 5- (1,2-dithiolan-3-yl) -N- [3- (trimethylsilyl) propyl] pentanamide is obtained in a yield of 66% by introducing an equivalent of 1 - {[5- (1, 2-dithiolan-3-yl) pentanoyl] oxy} pyrrolidine-2,5-dione for 1 eq of 13- (trimethylsilyl) propan-1-amine. The analysis in ESI + and ESI- makes it possible to confirm the molecular mass of the expected product C14H29NOS2Si, M = 319 (detection of [M + H] +, [M + Na] +, [2M + H] +, [2M + Na] ] +, [MH] -, [M + Cl] -, [M + CH3COO] - and the fragment in ESI-m / z = 272 [MH-H2S] -). Anal. Calc'd for C 14 H 29 NOS 2 Si: C 52.6, H 9.1, N 4.4.0 5.0, S 20.1, Si 8.8 Found: C (52.47); H (9.10); N (4.51) 1H NMR (DMSO - d6) Signal or signal center Multiplicity Integration (ppm) -0.028 s 9H 0.4 m 2H 1.35 m 4H 1.51 m 2H 1.56 m 1H 1.65 m 1H 1.86 m 1H 2.04 t 2H 2908769 35 2.41 m 1H 2.99 m 2H 3.11 m 1H 3.18 m 1H 3.6 m 1H 7.74 t 1H 3. Synthesis of N, N '- [(1,1,3,3-tetramethyldisiloxane-1,3-diyl) dipropane-3,1-diyllbis [ 5- (1, 2-dithiolan-3-yl) pentanamide The compound N, N '- [(1,1,3,3-tetramethyldisiloxane-1,3-diyl) dipropane-3,1-diyl] bis [ 5- (1, 2-dithiolan-3-yl) pentanamide] was synthesized by introducing two equivalents of 1 - {[5- (1,2-dithiolan-3-yl) pentanoyl] oxy} pyrrolidine-2,5- dione for 1 eq of 1,3-bis (3-aminopropyl) -1,3,3,3-tetramethyldisiloxane. Yield = 37% Quasi molecular ions [M + H] +, [M + Na] +, [MH] -, [M + Cl] - as well as fragments [M + H-C13H27NO2S2Si] + and [MH- C13H25NOS2Si] - of the expected molecule C26H52N2O3S4Si2, M = 624 are mainly detected. Detection of weak signals in ESI + and ESI- in the 65-800 mass range that may correspond to any impurities. Anal. Calculated for C26H52N2O3S4Si2: C50.0, H 8.4, N 4.5.0 7.7, S 20.5, Si 9.0. Found: C (49.55); H (8.46); N (4.4) 1H NMR (DMSO- d6) Signal or signal center Multiplicity Integration (ppm) 0.031 s 12 0.46 m 4 1.36 m 8 1.53 m 6 2908769 36 1.65 m 2 1.85 m 2 2.05 t 4 2.41 m 2 2.99 m 4 3.12 m 2 3.17 m 2 3.59 m 2 7.76 t 2 EXAMPLE 3 Preparation of 5- (1,2-dithiolan-3-yl) -NF (trimethylsilyl) methyllpentanamide in a dry 50 ml bicol under argon, 0.2 ml (1.5 g) 1 mmol) of 1-chloro-N, N-2-trimethylpropenylamine are added dropwise to a solution of 0.3 g (1.5 mmol) of 5- (1,2-dithiolan-3-yl) pentanoic acid in 10 ml of anhydrous tetrahydrofuran. . The reaction medium is stirred for one hour at ambient temperature and then the mixture of 0.3 ml (2.25 mmol) of aminomethyltrimethylsilane and 0.3 ml (2.25 mmol) of triethylamine is added dropwise. The mixture is stirred under magnetic stirring for 20 hours, the white insoluble material is filtered off and the filtrate is concentrated under vacuum at 350 ° C. at 40 ° C. After filtration through silica, eluting with dichloromethane, 0.24 g of 5- (1,2-dithiolene) are isolated. 3-yl) -N - [(trimethylsilyl) methyl] pentanamide (Yd = 70%). The analysis in ESI + and ESI- makes it possible to confirm the molecular mass of the expected product C12H25NOS2Si, M = 291 (detection of [M + H] +, [M + Na] +, [2M + Na] +, [MH] -, [M + Cl] -] - and fragment [MH-H2S] -). Anal. Calculated for C 12 H 25 NOS 2 Si: C 49.4, H 8.6, N 4.8, 5.5, Si 9.6, S 22.0 Found: C (49.24); H (8.71); N (4.76); S (22.31) 1H NMR (DMSO-d6) Si-1 5 2908769 37 Signal or signal center Multiplicity Integration (ppm) 0.003 s 9H 1.33m 2H 1.49m 2H 1.54m 1H 1.65m 1H 1.85m 1H 2.06 t 2H 2.4m 1H 2.54 d 2H 3.11 m 1H 3.17 m 1H 3.59 m 1H 7.56 t 1H EXAMPLE 4 Preparation of 5- (1,2-dithiolan-3-yl) -N- (3- {1,3,3,3-tetramethylamine) 1-F (trimethylsilyl) oxyldisiloxanylpropyl) pentanamide I-Si SiO 2 O 3 SiO 2 In a 50 ml dry bicol under argon, 0.4 ml (3 mmol) of 1-chloro-N, N, 2-trimethylpropenylamine are added dropwise to a solution of 0.620 g (3 mmol) of 5- (1,2-dithiolan-3-yl) pentanoic acid in 5 mL of anhydrous tetrahydrofuran. The reaction medium is stirred for 1.5 hours at room temperature and is then added dropwise to a mixture of 0.924 g (3.3 mmol) of siloxane amine and 0.63 ml (4.5 mmol) of triethylamine in 5 ml of anhydrous THF. . The mixture is left stirring for 20 h, the white insoluble material is filtered off and the filtrate is concentrated under vacuum. After flash chromatography on silica, eluting with dichloromethane, is isolated after evaporation under vacuum 1.1 g of 5- (1,2-dithiolan-3-yl) -N- (3- {1,3,3,3 -tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) pentanamide (Yd = 80%). The analysis in ESI + and ESI-confirms the molecular mass of the expected product C18H41 NO3S2Si3, M = 467 1H NMR (DMSO-d6) Signal or signal center Multiplicity Integration (ppm) 0.004 s 3H 0.082 s 18H 0.4 m 2H 1.35 m 4H 1.51 m 2H 1. 55 m 1 H 1.66 m 1 H 1.86 m 1 H 2.04 t 2H 2.41 m 1 H 2.98 m 2H 3.11 m 1H 3.17 m 1H 3.59 m 1 H 7.75 t 1 H Example 5 - Measurement of the GSH level increase activity of the compounds according to the invention The study consisted in evaluating at the cellular level the protective effect of the reference molecule, lipoic acid, as well as lipoic acid derivatives according to the invention. the invention with respect to UVJ induced intracellular GSH depletion. To this end, HaCaT cells were exposed to UVJ, the level of intracellular GSH was then measured, allowing then the evaluation of the possible protection provided by the addition in the culture medium of the lipoic acid derivatives according to the invention. UVJs are radiation from a non-zenithal sun and for average spectral illumination they simulate the radiation received by an individual's skin over a day and not just those corresponding to zenith exposure. Devices for reproducing these radiations are described in FR 2 863 356. The evaluation technique uses a fluorescent probe, Monochlorobimane (MCB). The MCB has the particularity of presenting, unlike other biman compounds such as monobromobiman, a more selective reactivity with respect to glutathione: the blue fluorescent compound (GSH-monochlorobimane) measured, results from a enzymatic reaction catalysed by glutathione-S-transferase. The specificity of MCB with respect to GSH in our keratinocyte model (HaCaT line) was previously verified. Pretreatment of the cells with the reference molecule, lipoic acid, for 24 hours at 1 mM provides about 100% protection against UVJ-induced UVJ depletion (see Figure 1 showing the evaluation of protective effect of lipoic acid at 1 mm in the MCB test on HaCaT: The measurement of intracellular GSH level is performed on keratinocytes pretreated and not pretreated with lipoic acid at 1 mm and exposed to UVJ, at t = 0, t = 6h, t = 24h after UVJ exposure), this protection is about 83% to 500μM and about 10% to 100μM. Both lipoic acid derivatives, (trimethylsilyl) methyl 5- (1,2-dithiolan-3-yl) pentanoate and 5- (1,2-dithiolan-3-yl) -N- [3- ( trimethylsilyl) propyl] pentanamide, evaluated under the same operating conditions give the keratinocytes a protection of about 40% to 100 μM. The protection afforded by these two active agents with respect to the daily UV-induced depletion of GSH is greater than the reference molecule, lipoic acid (see Figure 2: evaluation of the protective effect of derivatives). lipoic acid at 0.1 mm in the MCB test on HaCaT: the measurement of intracellular GSH level is performed on pretreated keratinocytes and not pretreated with the active ingredients and exposed to UVJ, t = 6h after exposure to UVJ). 30 Ë -.ah. where Assets = L

  .................................................. ........................ DTD: ........................ .................................................. DTD: ................................................ .......................... DTD: ................... D ëetirm% 4 a ë Q Q Q et et et et et et et et signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal signal . ~ ............... {, t F 43 {t ai .3 ~. '. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~. ~ ~ u ~ ~ ~ ~ ~ _yï ~ 42: e û-f, 1,7 ', # o1ar. 3 `~~ -N [3 (## - t'R.hrwv'1l and2t: the? ~~ d` ay I.

EXAMPLE 6 Measurement of Protection Against Damage to DNA Solar UV is capable of generating a great deal of oxidative damage in skin cells, and especially in DNA. Nucleic acids absorb UVB photons, thereby inducing DNA damage directly. UVAs, even if they are not directly absorbed by DNA, will have a genotoxic action mediated by reactive oxygen species.

The comet test makes it possible to quantify UV-induced DNA damage (here, UVA): strand breaks as well as oxidative DNA damage (labile alkali sites cleaved under alkaline conditions) are detected. The principle of this test is based on the ability of the denatured and cleaved DNA fragments to migrate out of the cell nuclei under the influence of an electric field, while the undamaged DNA remains confined in the nucleus. The damaged DNA fragments form a trail behind the nucleus of the cells. These then take on the appearance of comets. The tail of each comet is all the more important and intense as the damage to the DNA is important. (Alapetite, C. et al., 1996, Int J Rad, Klaude M. et al., 1996, Mut Res, Lehmann J et al., 1998, Mut Res, Singh NP, and al., 1988, Exp. Ce / 1 Res.) The study consisted in evaluating the photoprotective effect of 2 molecules derived from lipoic acid, 5- (1,2-dithiolan-3-yl) pentanoate. (trimethylsilyl) methyl (compound of Example 1) and 5- (1,2-dithiolan-3-yl) -N- [3- (trimethylsilyl) propyl] pentamide, (compound of Example 2 2) with respect to UVA-induced DNA damage. For this, normal human fibroblasts (FHN) were put in contact with the assets for 24 hours. The cells were then detached, included in an agarose gel, and then deposited on a microscope slide.

Following exposure to UVA (for 30 minutes), the cells were subjected to cell lysis (so as to keep intact only the genetic material), to a DNA denaturation step, and then to electrophoresis. to migrate the damaged DNA. The level of damaged DNA was measured using a fluorescence microscope combined with suitable image analysis software.

Pretreatment of the cells with the (trimethylsilyl) methyl 5- (1,2-dithiolan-3-yl) pentanoate molecule gives the fibroblasts a protection of 42% at 1 μM and 50% at 10 μM (see Figure 3). ). 5- (1,2-dithiolan-3-yl) -N- [3- (trimethylsilyl) propyl] pentanamide was evaluated under the same operating conditions. It provides 18% protection at 1 μM and 47% at 10 μM (see Figure 4). These two compounds therefore have the ability to protect UV-induced DNA degradation. Summary Table: Assets Assessed 5- (1,2-dithiolan-3-yl) pentanoate TM Mean Deviation% of% (trimethylsilyl) methyl (standard damage damage protection to DNA) to DNA Control (UVA = 30 13.99 1.34 100 0 1pM 8.12 0.88 58 42 10pM 7.04 0.76 50.3 49.7 5- (1,2-dithiolan-3-yl) -N- [3] - Mean TM deviation% of% (trimethylsilyl) propyl] pentanamide (standard damage damage protection to DNA) to DNA Control (UVA = 30 ') 14.23 1.39 100 0 1 pM 11.74 1, 1 82.5 17.5 10pM 7.54 0.74 53 47 Example 7 - Formulations 15 Sunscreen (oil-in-water emulsion) • Compound of Example 1, 2, 3 or 4 • Mixture of cetylstearyl alcohol and oxyethylenated cetylstearyl alcohol (33 units 0E) 80/20 sold by the company TENSIA under the trade name DEHSCONET 390 • Mixture of mono- and distearate of glycerol sold under 10 3g 3g 2908769 42 the trade name CERASYNTH SD 2 g by the company ISP • Cetyl alcohol 1,5 g • Pol ydimethylsiloxane sold under the name DC200FIuid by the company Dow Corning 1.5 g Glycerine 15 g Parleam = ISOPARAFFIN (6-8 MOLES ISOBUTYLENE) HYDROGENEE by the company NOF CORPORATION 20 g Preservatives q.s. • Demineralized water qsp 77 g The fatty phase containing the compound is heated to about 70 ù 80 C until complete melting. The water is then added with vigorous stirring all at once at 80 ° C. Stirring is maintained for 10 to 15 minutes, then allowed to cool with moderate stirring to about 40 ° C. and the preservatives are added. Sunscreen composition (oil-in-water emulsion) • Compound of Example 1, 2, 3 or 4: 2 g • Mixture of cetylstearyl alcohol and oxyethylenated cetylstearyl alcohol (33 EO units) 80/20 sold by the TENSIA company under the trade name DEHSCONET 390 3 g • Mixture of glycerol mono- and distearate sold under the trade name CERASYNTH SD 25 by the company ISP 2 g • Cetyl alcohol 2.5 g • Benzoate of C12-C15 alcohols sold under the trade name FINSOLV TN by WITCO 20 g • Polydimethylsiloxane sold under the name 30 DC200FIuid by the company Dow Corning 1.5 g • Glycerin 15 g • Preservatives, perfumes qs • Demineralized water qs 97 g 2908769 43 This cream is prepared according to standard emulsion preparation techniques by dissolving the filter in the fatty phase containing the emulsifiers, heating this fatty phase to 70-80 ° C and adding, with vigorous stirring , water heated to the same temperature. Stirring is maintained for 10 to 15 minutes, then allowed to cool with moderate stirring, and at about 40 ° C., perfume and preservative are finally added. FT: NEW SILICY DITHIOLAN DERIVATIVE COMPOUNDS AND THEIR USE

Claims (37)

  1. Compound of general formula (I) and (I ') RRR 1 Si o AO rs (1) in which: ^ A is a radical of the following formula (1): L (1) in which: - L is a divalent radical allowing the attachment of the radical A to the silicone chain; m represents an integer 0, 1, 2, 3, 4, 5, 6, 7, 8, X represents an oxygen atom, nitrogen, sulfur, -Y is oxygen, nitrogen, NR4 or sulfur, R4 is hydrogen, linear C1-C20 alkyl, or branched C3-20 C20, saturated or unsaturated, C2-C20, optionally substituted with an optionally substituted phenyl radical, R5 denotes a C1-C30 linear or branched C3-C20 or unsaturated C2-C20 saturated hydrocarbon group, a C1-C8 halogenated hydrocarbon group or a trimethylsilyloxy group; B, identical or different for the same compound, is chosen from radicals R and A; R is an integer from 0 to 50 inclusive; ^ s is an integer from 0 to 20 inclusive, and if s is 0, at least one of the two radicals B is A; u is an integer from 1 to 6 inclusive; t is an integer from 0 to 10 inclusive; It being understood that t + u is equal to or greater than 3.   2. Compound according to claim 1, characterized in that L corresponds to one of the following formulas (a) or (a '): HC (Z) p (Y) q Y', (Z) p (Y ') in which: Y 'represents O or NH; • Z is a linear or branched, saturated or unsaturated C1-C6 alkane di-yl radical, optionally substituted with a hydroxyl radical or C2 alkyl; -C8, linear or branched, saturated or unsaturated; Y "represents a hydrogen atom, a hydroxyl radical or a linear or branched, saturated or unsaturated C 1 -C 8 alkyl radical; • p and g are 0 or 1. 25   3. Compound according to claim 1 or 2, characterized in that the radicals R, which are identical or different, are chosen from linear C 1 -C 10 or branched C 3 -C 10 alkyl radicals, saturated or unsaturated radicals, the phenyl radical and the trifluoropropyl radical and at least 80% by number of the radicals R is a methyl radical. 30   4. Compound according to any one of the preceding claims, characterized in that o A is a radical of formula (1) above with m = 4; o Lest such that q = 0, Y "= H, Z = CH2 and p = 1; C H2 (a) 2908769 46 where X represents an oxygen atom; Y represents an oxygen atom, nitrogen NR4 with R4 represents hydrogen, linear C 1 -C 20 or branched C 3 -C 20 alkyl, saturated or unsaturated, optionally substituted with an optionally substituted phenyl radical; R 5 is methyl; B is methyl or an A radical; between 0 and 3 inclusive, where os is between 1 and 3 inclusive, where t + u is between 3 and   5. Compound according to any one of the preceding claims, characterized in that o A is a radical of formula (1) above with m = 4; where X represents an oxygen atom, Y represents an oxygen atom, nitrogen atom (NR4 with R4 = H), R is methyl, B is methyl or a radical A, gold = 0, os = 1.   6. Compound of general formula (II) ## STR1 ## in which m represents an integer which can be 0, 1, 2, 3, 4, 5, 6, 7, 8; X represents an oxygen, nitrogen or sulfur atom; Y is oxygen, nitrogen, NR4 or sulfur; ν represents an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; R 1, R 2, R 3 represent, independently of each other, a saturated or unsaturated, linear C 1 -C 10 or branched C 3 -C 10 alkyl radical which may comprise one or more halogen atoms (for example Cl, Br, F ), a phenyl radical, a benzyl radical; D denotes hydrogen, a linear C1-C8, or branched C2-C8 alkyl radical, saturated or unsaturated, a phenyl radical; the group Si (CH 3) 3 with the proviso that when D is Si (CH 3) 3 then v = 0 and R ', R 2 and R 3 are methyl; W is a linear C 1 -C 8 or branched C 3 -C 8 linear alkyl radical or unsaturated, or C 2 -C 8 alkylene optionally substituted with hydroxyl; R 4 represents a hydrogen, a linear C 1 -C 20 or branched C 3 -C 20 alkyl, saturated or unsaturated, optionally substituted with an optionally substituted phenyl radical.   Compound according to claim 6, characterized in that: 10 m = 4; ^ X = 0; ^ Y = OouNR4. R 1 to R 3 denote linear C 1 -C 4 or branched C 3 -C 4 alkyl and more particularly methyl; R4 represents a hydrogen, a linear C-C20 or branched C3-C20 alkyl, saturated or unsaturated, optionally substituted with an optionally substituted phenyl radical; W is methylene -CH2-. 20   8. Compound according to claim 6 or 7, characterized in that: m = 4; o X = O; o Y = OouNH; R 'to R3 denote C1-C4 alkyl and more particularly methyl; W is methylene -CH2-.   9. Compound according to any one of the preceding claims, characterized in that it is obtained from lipoic acid.   10. A compound according to any one of the preceding claims selected from: 1- (5-trimethylsilyl) methyl 5- (1,2-dithiolan-3-yl) pentanoate; 2- (trimethylsilyl) ethyl 5- (1,2-dithiolan-3-yl) pentanoate; 3- (trimethylsilyl) propyl 5- (1,2-dithiolan-3-yl) pentanoate; 4. [ethyl (dimethyl) silyl] methyl 5- (1,2-dithiolan-3-yl) pentanoate; 5- (2-hydroxy-3- (trimethylsilyl) propyl) 5- (1,2-dithiolan-3-yl) pentanoate; 6. Dimethyl (phenyl) silyl] -methyl 5- (1,2-dithiolan-3-yl) pentanoate; 7. [benzyl (dimethyl) silyl] methyl 5- (1,2-dithiolan-3-yl) pentanoate; 8. 5- (1,2-dithiolan-3-yl) -N - [(trimethylsilyl) methyl] pentanamide; 9. N- [bis (trimethylsilyl) methyl] -5- (1,2-dithiolan-3-yl) pentanamide; 10. 5- (1,2-dithiolan-3-yl) -N- [3- (trimethylsilyl) propyl] pentanamide; 11. 5- (1,2-dithiolan-3-yl) -N- (3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) pentanamide; 12. N, N '- [(1,1,3,3-tetramethyldisiloxane-1,3-diyl) dipropane-3,1-diyl] bis [5- (1,2-dithiolan-3-yl) pentanamide] . 11. Use of at least one compound according to any one of claims 1 to 10 for preventing oxidative damage caused by free radicals in cells. 12. Use according to claim 11 as a photoprotective agent of the skin.   13. Use according to claim 11 for preparing the skin for sun exposure.   14. Use according to any one of claims 11 to 13, for preventing and / or treating sensations of heating due to sunlight.   15. Use of at least one compound according to any one of claims 1 to 10 for the preparation of a composition for preventing and / or treating redness and / or irritation due to sunlight. 25   16. Use of at least one compound according to any one of claims 1 to 10, for the preparation of a composition for preventing and / or treating DNA lesions due to sunlight.   17. Use of at least one compound according to any one of claims 1 to 10, for the preparation of a composition for the prevention and / or treatment of disorders of the skin and / or mucous membranes induced by a intense irradiation with UVA and / or UVB radiation. 15 20 2908769 49   18. Use of at least one compound according to any one of claims 1 to 10, for preventing and / or limiting the formation of free radicals and / or eliminating free radicals present in the cells. 5   19. Use according to claim 18, for preventing and / or treating cutaneous alterations caused by oxidative stress.   20. Use according to claim 18 or 19, for preventing and / or treating the harmful effects of pollution on the skin.   21. Use according to any one of claims 18 to 20, for preventing and / or treating the loss of firmness and / or elasticity of the skin.   22. Use according to any one of claims 18 to 20, to allow the skin 15 to regain a uniformly smooth appearance.   23. Use according to any one of claims 18 to 20, for preventing and / or treating the dull complexion and / or promoting the radiance of the complexion. 20   24. Use according to any one of claims 18 to 20 for preventing and / or treating cutaneous dehydration.   25. Use according to any one of claims 18 to 20, for preventing and / or treating the signs of skin aging.   26. Use according to claim 25 for preventing and / or treating pigment spots and / or hyperkeratosis spots and / or epidermal atrophy and / or skin roughness and / or dryness. 30   27. Use according to any one of claims 18 to 20, for preventing and / or limiting and / or eliminating the peroxidation of cutaneous lipids.   28. Use according to claim 27, for preventing and / or limiting and / or eliminating bad body odor. 10 25 35 2908769 50   29. Use according to any one of claims 10 to 28, characterized in that the composition is for external topical use.   30. Use according to claim 29, characterized in that said compound according to any one of claims 1 to 10 is present in the composition at a concentration of 0.001% to 20% of the total weight of the composition.   31. Use according to claim 30, characterized in that said compound is present in the composition at a concentration of 0.01% to 10% of the total weight of the composition.   32. Use according to any one of claims 10 to 28, characterized in that the composition is a composition for the oral route.   33. Use according to claim 32, characterized in that said compound is present in an amount between 0.1 and 100 mg per dose.   34. Composition comprising, in a physiologically acceptable medium, at least one compound according to any one of Claims 1 to 10.   35. Composition according to claim 34, characterized in that it further comprises at least one compound chosen from antioxidants, anti-pollution agents, anti-UVA filters, anti-UVB filters, depigmenting agents, DNA repair stimulating agents   36. Composition according to Claim 35, characterized in that the antioxidant is chosen from vitamin C, vitamin E and isopropyl (benzyl {2- [benzyl (2-isopropoxy-2-oxoethyl) amino} ethyl} amino) acetate. , ferulic acid, phloretin and SOD.   37. A cosmetic method for preparing the skin for sunlight comprising at least one step of administering at least one compound according to any one of claims 1 to 10. 10