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EP-3813785-B1 - 5-OXAZOLIDINE-2,4-DIONE C-GLYCOSIDE DERIVATIVES AND THEIR USE AS MOISTURIZER FOR THE SKIN

EP3813785B1EP 3813785 B1EP3813785 B1EP 3813785B1EP-3813785-B1

Inventors

  • DALKO, MARIA
  • PREVOT-GUEGUINIAT, Amélie
  • FRANTZ, Marie-Céline
  • DROPSIT, Sébastien

Dates

Publication Date
20260506
Application Date
20190619

Claims (19)

  1. Cosmetic use, as moisturizer for keratin materials, preferably the skin, of one or more 5-oxazolidine-2,4-dione C-glycoside derivatives corresponding to formula (I) below, and also the solvates thereof such as hydrates, the optical and geometric isomers and tautomers thereof and the organic or mineral base or acid salts thereof, in which formula (I): - S* denotes a monosaccharide sugar radical or denotes a polysaccharide sugar radical comprising from 2 to 5 saccharide units, each saccharide unit (the saccharide unit in the case of a monosaccharide or each saccharide unit in the case of polysaccharides) comprising one or more hydroxyl groups optionally substituted with a radical R' chosen from: i) (C 1 -C 6 )alkyl or (C 2 -C 6 )alkenyl; or ii) an acetyl radical; or iii) a protective group (PG) for hydroxyl function(s), such as (C 2 -C 6 )alkyl(thio)carbonyl or benzyl; said monosaccharide radical possibly also being deoxygenated in position 2 (on its C 2 carbon atom); said monosaccharide or polysaccharide radical possibly also comprising one or more amino groups NR b R c with R b and R c , which may be identical or different, representing a hydrogen atom, or an acetyl group, or a protective group for the amino function, such as (C 2 -C 6 )alkyl(thio)carbonyl; said monosaccharide or polysaccharide radical being connected to the rest of the molecule by a bond between the C 1 carbon atom of one of the sugars of said monosaccharide or polysaccharide radical, this bond possibly being α or β anomeric; - R represents i) a hydrogen atom; ii) a (C 1 -C 18 )alkyl group; iii) an aryl(C 1 -C 4 )alkyl group optionally substituted with at least one hydroxyl and/or (C 1 -C 4 )alkoxy group, such as benzyl; iv) a cycloalkyl group.
  2. Use according to Claim 1, in which the compound(s) of formula (I) comprise(s) a radical R chosen from: i) a hydrogen atom; ii) a (C 1 -C 18 )alkyl group, in particular a (C 1 -C 6 )alkyl group and more particularly a (C 1 -C 4 )alkyl group such as a methyl group.
  3. Use according to Claim 1 or 2, in which the compound(s) of formula (I) comprise(s) a sugar radical S* which represents a monosaccharide radical in which the heterocycle which forms it contains 4 or 5 carbon atoms, of formula S*' below: R a representing a hydrogen atom, a (C 1 -C 4 )alkyl group such as methyl or a (poly)hydroxy(C 1 -C 4 )alkyl group such as hydroxymethyl or 1,2-dihydroxyethyl, the hydroxyl function(s) of the (poly)hydroxy(C 1 -C 4 )alkyl group being substituted with A as defined below; it being understood that the R a radical is in the C 5 position if the sugar unit is in pyranose form or in the C 4 position if it is in furanose form; R b representing a hydrogen atom or a (C 1 -C 4 )alkyl group, preferably hydrogen; R c representing a hydrogen atom, or a protective group for the amine function, such as R d -C(X')-, identical in the case of several hydroxyl functions, with X' representing an oxygen or sulfur atom, in particular an oxygen atom, and R d representing a (C 1 -C 4 )alkyl group, R c preferably representing an acetyl group CH 3 -C(O)-; R e represents a hydrogen atom or a -CH 2 -O-A group; A representing a hydrogen atom, a (C 1 -C 6 )alkyl group or a hydroxyl-function-protective group, or else, when n is greater than or equal to 2 and two groups A-O are contiguous, then two A groups can together form a linear or branched (C 1 -C 6 )alkylene chain; preferably, when A is different from a hydrogen atom and from a (C 1 -C 6 )alkyl group, all the protective groups A are identical; more preferentially, A represents a hydrogen atom, n is equal to 1, 2 or 3 and m is equal to 0 or 1; preferably, m is equal to 0.
  4. Use according to either one of Claims 1 and 2, in which the compound(s) of formula (I) comprise(s) a sugar radical S* which represents a polysaccharide radical constituted of 2 to 5 saccharide units, in particular of 2 to 3 and preferably of 2 saccharide units, linked together via an oxygen atom (oxy), 1→4 (C 1 of one saccharide unit →C 4 of the other saccharide unit) or 1→3 (C 1 of one saccharide unit →C 3 of the other saccharide unit) or 1→6 (C 1 of one saccharide unit →C 6 of the other saccharide unit), each saccharide unit of which is constituted of a heterocycle comprising 4 or 5 carbon atoms, of formula S*" below: in which formula S*": - p and q represent integers inclusively between 0 and 4, with p + q inclusively between 1 and 4, particularly between 1 and 2, preferentially p + q = 1; - R a , R b , R c , R e , A, m, and n, which may be identical or different, are as defined in any one of the preceding claims, it being understood that the two sugar units between the square brackets q and p can be reversed, i.e. can represent the following sequence:
  5. Use according to any one of Claims 1 to 3, in which the compound(s) of formula (I) comprise(s) a sugar radical S* or S*' which represents a monosaccharide radical chosen from glucose, galactose, mannose, xylose, lyxose, fucose, arabinose, rhamnose, ribose, deoxyribose, quinovose, fructose, sorbose, talose, 2-deoxyglucose, threose, erythrose, N-acetylglucosamine, N-acetylgalactosamine, glucosamine and galactosamine; in particular, S* or S*' represents a monosaccharide radical chosen from D-glucose, D-galactose, D-mannose, D-xylose, L-xylose, D-lyxose, L-lyxose, L-fucose, L-arabinose, D-arabinose, L-rhamnose, L-ribose, D-ribose, 2-deoxy-D-ribose, 2-deoxy-L-ribose, D-quinovose, D-fructose, L-sorbose, D-talose, 2-deoxy-D-glucose, D-threose, D-erythrose, L-threose, L-erythrose, N-acetyl-D-glucosamine, N-acetyl-D-galactosamine, D-glucosamine and D-galactosamine. Preferably, S* or S*' denotes a monosaccharide radical chosen from D-glucose, D-galactose, D-mannose, D-xylose, D-lyxose, L-fucose, L-arabinose, L-rhamnose, D-ribose, 2-deoxy-D-ribose, D-quinovose, D-fructose, L-sorbose, D-talose, 2-deoxy-D-glucose, D-threose, D-erythrose, N-acetyl-D-glucosamine, N-acetyl-D-galactosamine, D-glucosamine and D-galactosamine, advantageously chosen from glucose, xylose, rhamnose, mannose and galactose; in particular, S* or S*' denotes a monosaccharide radical chosen from D-glucose, D-xylose, L-rhamnose, D-mannose and D-galactose, and more particularly a D-glucose or D-xylose radical.
  6. Use according to any one of Claims 1 to 2 and 5, in which the compound(s) of formula (I) comprise(s) a sugar radical S* or S*' which represents a monosaccharide radical chosen from glucose, xylose and rhamnose; particularly, S* or S*' denotes a sugar radical chosen from D-glucose, D-xylose and L-rhamnose, more particularly S* or S*' denotes a glucose or xylose radical, preferentially S* or S*' denotes a D-glucose or D-xylose radical.
  7. Use according to any one of Claims 1, 2 and 4, in which the compound(s) of formula (I) comprise(s) a sugar radical S* or S*" which represents a polysaccharide radical and in particular a disaccharide radical preferably chosen from lactose, maltulose, palatinose, lactulose, amygdalose, turanose, cellobiose, isomaltose, rutinose and maltose; more particularly chosen from D-lactose, maltulose, palatinose, lactulose, amygdalose, D-turanose, D-cellobiose, isomaltose, rutinose and D-maltose, in particular a disaccharide radical chosen from lactose, maltose and cellobiose. In particular, S* and S*" represent a disaccharide radical chosen from D-lactose, D-maltose and D-cellobiose.
  8. Use according to any one of the preceding claims, in which the compound(s) of formula (I) is (are) chosen from the compounds of formulae (I'), (I"), (Iʺʺ), (I'a), (I"a) and (Iʺʺa) below: and also the solvates thereof such as hydrates, the optical and geometric isomers and tautomers thereof and the salts thereof, in which formulae (I'), (I"), (Iʺʺ), (I'a), (I"a) and (Iʺʺa): - R' 1 has the same definition as that of R for the compounds of formula (I); preferably, R' 1 represents a hydrogen atom; or a (C 1 -C 6 )alkyl, in particular (C 1 -C 4 )alkyl, radical, such as a methyl radical; - R' 2 represents a hydrogen atom or the group -OR" with R" as defined below; - R" represents i) (C 1 -C 6 )alkyl; or ii) an acetyl radical; or iii) a protective group (PG) for hydroxyl function(s), such as (C 2 -C 6 )alkyl(thio)carbonyl or benzyl; or iv) a hydrogen atom; preferably, R" represents a hydrogen atom or an acetyl radical, and more particularly a hydrogen atom; - R‴ represents a hydrogen atom, or a (C 1 -C 4 )alkyl group, or a -CH 2 -OR" group with R" as defined previously, in particular hydrogen or an acetyl radical, and preferably a hydrogen atom.
  9. Use according to any one of the preceding claims, in which the compound(s) of formula (I) are chosen from the following compounds: compound structure 1a 2a 3a 4a compound sugar structure 1 D-glucose 2 D-xylose 3 D-glucose 4 L-rhamnose 5 D-mannose 6 D-mannose 7 D-galactose 8 D-galactose and also the solvates thereof such as hydrates, and the organic or mineral base or acid salts thereof.
  10. Composition comprising one or more compounds of formula (I) as defined in any one of the preceding claims, preferably at least one compound of formula (I) chosen from (I'), (I"), (Iʺʺ), (I'a), (I"a) and (Iʺʺa) as defined in Claim 8 and compounds 1a, 1b, 1c and 1d, and 1 to 8 as defined in the preceding claim.
  11. Composition according to Claim 10, in which the compound(s) of formula (I) are present in amounts ranging from 0.01% to 10% by weight, preferentially from 0.1% to 5% by weight, relative to the total weight of the composition.
  12. Composition comprising one or more compounds of formula (I) as defined in any one of Claims 1 to 9 and one or more additional moisturizing active agents other than the compounds of formula (I), preferably one or more additional moisturizing active agents chosen from glycerol, urea, hydroxyethylurea, hyaluronic acid, propanediol, trehalose, mannitol, xylitol, sorbitol, glycine, β-alanine, taurine, trimethylglycine, and polyethylene glycol (PEG) derivatives.
  13. Compounds of formula (I) and also the solvates thereof such as hydrates, the optical and geometric isomers and tautomers thereof and the organic or mineral base or acid salts thereof, in which formula (I): - S* denotes a monosaccharide sugar radical or denotes a polysaccharide sugar radical comprising from 2 to 5 saccharide units, each saccharide unit (the saccharide unit in the case of a monosaccharide or each saccharide unit in the case of polysaccharides) comprising one or more hydroxyl groups optionally substituted with a radical R' chosen from: i) (C 1 -C 6 )alkyl or (C 2 -C 6 )alkenyl; or ii) an acetyl radical; or iii) a protective group (PG) for hydroxyl function(s), such as (C 2 -C 6 )alkyl(thio)carbonyl or benzyl; said monosaccharide radical possibly also being deoxygenated in position 2 (on its C 2 carbon atom); said monosaccharide or polysaccharide radical possibly also comprising one or more amino groups NR b R c with R b and R c , which may be identical or different, representing a hydrogen atom, or an acetyl group, or a protective group for the amino function, such as (C 2 -C 6 )alkyl(thio)carbonyl; said monosaccharide or polysaccharide radical being connected to the rest of the molecule by a bond between the C 1 carbon atom of one of the sugars of said monosaccharide or polysaccharide radical, this bond possibly being α or β anomeric; - R represents i) a hydrogen atom; ii) a (C 1 -C 18 )alkyl group; iii) an aryl(C 1 -C 4 )alkyl group optionally substituted with at least one hydroxyl and/or (C 1 -C 4 )alkoxy group, such as benzyl; iv) a cycloalkyl group.
  14. Compound of formula (I) according to the preceding claim, comprising a radical R chosen from: i) a hydrogen atom; ii) a (C 1 -C 18 )alkyl group, in particular a (C 1 -C 6 )alkyl group and more particularly a (C 1 -C 4 )alkyl group such as a methyl group.
  15. Cosmetic process for moisturizing keratin materials, in particular the skin, which consists in applying to said keratin materials, preferably to the skin, a composition as defined in any one of Claims 10 to 12.
  16. Cosmetic process according to Claim 15, characterized in that said composition is applied to dry skin and/or to a cutaneous region chosen from: - the hands, - the face, in particular the forehead, the cheeks or the contour of an eye (periocular), and in particular the crow's feet, the region below the eye (bag), or the eyelids, - the neck, - the feet, - the legs, - the arms and forearms.
  17. Process for the synthesis of compounds of formula (I) as defined in any one of Claims 1 to 9 according to scheme (1) below: in which (II) denotes a monosaccharide represented by: or a polysaccharide PS-OH, in which A, R a , R b , R c , R e , n, and m are as defined above, p' and q' representing an integer inclusively between 0 and 4, with p' + q' inclusively between 0 and 4, in particular between 0 and 2, preferably p'+q' = 0 or 1, it being understood that the two units between square brackets can be reversed; PS-OH denoting a polysaccharide having the structure (gg) below: (gg) - step 1 consisting in reacting a monosaccharide or a polysaccharide PS-OH of formula (II) with a barbituric acid derivative (III), in particular in the presence of a mineral base such as M + OH - , M + representing a cationic counterion or preferably a weak base such as (bi)carbonate, in particular with alkali metal (bi)carbonate, or in the presence of an organic base such as triethylamine or diisopropylethylamine; in particular in a polar protic solvent such as water, by heating optionally at a temperature of between 30°C and 100°C, in particular at 80°C, preferably for a period of between 1 hour and 24 hours, in particular between 3 hours and 10 hours, such as 5 hours, so as to give the compound comprising a sugar unit (IV); - step 2 consisting in reacting the compound (IV) with a chemical oxidizing agent such as hydrogen peroxide or a hydrogen peroxide-generating agent such as oxone or else a biological agent such as an enzyme of oxidase type, in particular in a polar solvent (or solvent mixture) with a boiling point of between 40°C and 100°C at atmospheric pressure, such as acetone or acetonitrile, or a polar protic solvent such as water, optionally in a basic medium and/or in the presence of a chelating agent such as ethylenediaminetetraacetic acid (EDTA) optionally in salt form, so as to give a C-glycoside compound (I) according to the invention, ▪ it being understood that, if A represents a hydrogen atom and it is desired to have a protective group PG, then a protection step is added, ▪ that, if R b and R c of NR b R c optionally present on the monosaccharide or the polysaccharide (II) represent hydrogen atoms and it is desired to protect the amino group(s), a protection step is carried out, ▪ that, if the group R comprises a function sensitive to these synthesis steps, it will be advisable to add a protection/deprotection sequence, wherein, under certain reaction temperature and time conditions during step 2, it is possible to isolate the intermediate (V) according to step 2a: wherein step 2b consists in treating the compound (V) in a polar solvent (or solvent mixture) with a boiling point of between 40°C and 100°C at atmospheric pressure, such as acetone or acetonitrile, or a polar protic solvent such as water, optionally in a medium that is basic, in particular by addition of a mineral base such as sodium hydroxide or potassium hydroxide, and/or in the presence of a chelating agent such as ethylenediaminetetraacetic acid (EDTA) optionally in salt form, and optionally in the presence of a chemical oxidizing agent, such as hydrogen peroxide or a hydrogen peroxide-generating agent, such as oxone, or else a biological agent such as an enzyme of oxidase type, to give a C-glycoside compound (I) according to the invention.
  18. Compounds of formula (V), and also the solvates and/or isomers and/or salts thereof, having the general formula below with S* and R as described in Claims 1 to 9.
  19. Compound according to the preceding claim of formula 9 compound sugar structure 9 D-glucose

Description

The present invention relates to novel C-glycoside compounds, to a cosmetic composition comprising same, to a preparation process, to the use of said C-glycosides for treating keratin materials and in particular the skin, and to a process for treating keratin materials using said C-glycosides. More particularly, the invention relates to the use of 5-oxazolidine-2,4-dione C-glycoside derivatives in the field of caring for keratin materials such as the skin, and especially as a moisturizer for keratin materials, preferably the skin. The skin, which is a protective and exchange barrier with the environment, is both strong and fragile, it may lose its suppleness and its capacity to retain water decreases, then causing skin dryness. It is known that the stratum corneum or corneal layer, which is the outermost region of the epidermis, is most particularly involved in moisturizing the skin. Located at the interface with the external environment, its function is especially to delay excessive water loss arising from the deeper layers of the epidermis. The stratum corneum also protects against mechanical attack. It also constitutes the first line of defence against UV radiation. With a thickness of 10 µm, it is composed of vertically stacked corneocytes surrounded by a matrix of lipid-enriched membranes. Thus, it is a two-compartment system that may be compared to a wall of bricks, composed of anuclear cells (the "bricks") and of intercellular lamellar membranes (the "cement"). By virtue of this compact stratified structure, the stratum corneum performs its barrier function by opposing transcutaneous water loss. It thus efficiently contributes towards the moisturization of the skin via its capacity to take up and retain water, which is mainly located in the intercellular spaces. For obvious reasons, it is important to ensure a sufficient level of skin moisturization in order to preserve its suppleness, softness, tonicity and/or appearance. In general, a decrease in this level of moisturization may be prevented or treated by acting on the stratum corneum via moisturizers, for instance glycerol, which are the reference active agents in this field. However, drawbacks are observed with active agents of these types. For example, glycerol has the drawback of making formulations tacky, especially when it is used in high concentration. There is thus a need to find other active agents in the field of skin moisturization that are free of the abovementioned drawbacks. Patent application WO2018/083341 A1 relates to a method for the cosmetic treatment of keratin materials, comprising the application of a composition to the keratin materials, such as the skin, said composition comprising amide C-glycoside derivatives. The inventors have discovered that 5-oxazolidine-2,4-dione C-glycoside derivatives of general formula (I) as described below are good moisturizers, and especially have a beneficial effect in terms of elasticity of the stratum corneum and/or improve the barrier function. The 5-oxazolidine-2,4-dione C-glycoside derivatives of general formula (I), which are the subject of the present invention, make it possible especially to provide, while at the same time having a moisturizing effect, compositions that have good stability and/or that remain pleasant for the consumer, i.e. being sparingly tacky, having a pleasant feel, and/or having no discomfort sensations such as tautness. Thus, the subject of the present invention is the cosmetic use of one or more 5-oxazolidine-2,4-dione C-glycoside derivatives corresponding to the formula (I) below, and also the solvates thereof such as hydrates, the optical and geometric isomers and tautomers thereof and the organic or mineral base or acid salts thereof, in which formula (I): S* denotes a monosaccharide sugar radical or denotes a polysaccharide sugar radical comprising from 2 to 5 saccharide units, each saccharide unit (the saccharide unit in the case of a monosaccharide or each saccharide unit in the case of polysaccharides) comprising one or more hydroxyl groups optionally substituted with a radical R' chosen from: i) (C1-C6)alkyl or (C2-C6)alkenyl; orii) an acetyl radical; oriii) a protective group (PG) for hydroxyl function(s), such as (C2-C6)alkyl(thio)carbonyl or benzyl; said monosaccharide radical possibly also being deoxygenated in position 2 (on its C2 carbon atom);said monosaccharide or polysaccharide radical possibly also comprising one or more amino groups NRbRc with Rb and Rc, which may be identical or different, representing a hydrogen atom, or an acetyl group, or a protective group for the amino function, such as (C2-C6)alkyl(thio)carbonyl; said monosaccharide or polysaccharide radical being connected to the rest of the molecule by a bond between the C1 carbon atom of one of the sugars of said monosaccharide or polysaccharide radical, this bond possibly being α or β anomeric;R represents i) a hydrogen atom;ii) a (C1-C18)alkyl group;iii) an aryl(C1-C4)alkyl group op