FR3003860A1 - COMPOUNDS DERIVED FROM PROTEIN OR NON-PROTEIN IRIDOIDS, COMPOSITION COMPRISING THEM, USE AS COLORING KERATIN FIBERS AND DEVICES - Google Patents

Abstract

The subject of the present invention is compounds of the following formula (I): wherein R 1 and R "1 represent -CH 3; -CH 2 O 2; -CHO; -COOR 10, R 10: H, aklyl; -CONR 11 R 12, R 11, R 12: H, W; at least one of the radicals being different from H; -CH 2 NR 13 R 14, R 13, R 14: H, W, at least one of the radicals being different from H; -COR 15, R 15: alkyl, R 2 and R "2 represent H; -CH3; -CH2OZ; -COR20, R20: alkyl; -COOR21, R21: H, alkyl; -CONR22R23, R22, R23: H, W, at least one of which is different from H; -CH2NR24R25, R24 and R25: H, W, at least one of which is different from H; - C (OH) R 26 R 27, R 26, R 27: alkyl, phenyl, unsubstituted benzyl; R3 and R "3 represent: -OZ; -CH3; -NR31R32, R31 and R32: H, W, at least one of which is different from H; alkylthio; R'3 may additionally be H; R4 and R; "4 represent H; an alkyl; a sugar pattern; -COR40, R40: alkyl; -COOR41, R41: alkyl; -CONR42R43, R42, R43: H, W; -Si (R44) 3 R44: alkyl; Z is H; alkyl; sulfonic, alkylsulphonate, phenylsulphonate or alkylphenylsulphonate group; a -COR 2 group with R 2: alkyl, sugar unit; W represents a hydrocarbon radical C1-C40, linear, branched and / or cyclic, saturated, unsaturated, aromatic or otherwise, optionally substituted; and / or optionally interrupted by one or more heteroatoms and / or groups comprising; n integer varies from 0 to 5; Exclusions of formula (I): * when R4 represents a sugar unit, a (C1-C4) alkylcarbonyl, a mono- or di (C1-C4) alkylaminocarbonyl, then R2 does not represent an alkoxy (C1- C2) carbonyl, hydroxycarbonyl, -CH2OH, R2 also does not represent H when R4 is a sugar; when R4 is H and R1 is -CH3, -CH2OH, then R2 is not H, -CH3, -COOH, -COOCH3. The invention also relates to a composition comprising such compounds and a process for dyeing keratinous fibers implementing it.

Description

The subject of the present invention is novel compounds derived from protected or unreproduced iridoids, as well as compositions comprising them and their use as inhibiting agents. BACKGROUND OF THE INVENTION dyeing keratinous fibers, especially human fibers, such as the hair. In recent years, there has been a growing interest in natural compounds that can be used as hair dyes.

For example, in the application EP 440 494, there is described a hair dyeing method using a composition comprising at least one compound of the type (seco) iridoide glycosylated or not (also called aglycon), extracted from plants such as Rubiaceae, Euphorbiaceae, Valerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, Ericaceae, Loganiaceae, etc.

These dyes, when they are brought into contact with the keratinous material, react with the free amine functions thereof, in particular the hair and give a blue color. In order to modulate the color obtained from these compounds, it is known to react with additional amines, such as aromatic amines, amino acids. The resulting color then changes to dark blues, night blues and greens. However, we are still looking for compounds derived from natural species, which would expand the color range obtained. The subject of the present invention is therefore compounds of the following formula (I) and / or (II), their organic or inorganic acid salts, their solvates, their optical, geometric, tautomeric and enantiomeric isomers, if they exist: Wherein R1 and R "1 independently of one another represent a radical selected from: -CH2OZ; -CHO; -000R10, R10 representing a hydrogen atom, an alkyl radical C1-O HO 012; -00NR11R12, wherein R11 and R12, identical or not, represent a hydrogen atom, a group VV, at least one of the two groups being different from hydrogen; -CH2NR13R14 with R13 and R14 representing independently of one another a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen; -COR15 with R15 representing a C1-C12 alkyl radical, R2 and R "2 represent, independently of each other, a radical chosen from: a hydrogen atom, a methyl radical, -CH2OZ, -COR20 with R20 representing an alkyl radical C1-C12, -000R21, R21 representing a hydrogen atom, an alkyl radical C1-C12; -CON R22R23, R22, R23, identical or not, represent a hydrogen atom, a group VV, at least one of the two groups being different from hydrogen; -CH 2 NR 24 R 25 with R 24 and R 25 representing, independently of one another, a hydrogen atom or a group V V, at least one of the two groups being different hydrogen - C (OH) R 26 R 27 with R 26, R 27, identical or different, representing a linear or branched C 1 -C 12 alkyl radical, unsubstituted phenyl or unsubstituted benzyl.

R3 and R "3 represent, independently of each other, a radical -OZ, a methyl, a radical -N R31 R32 with R31 and R32 representing, independently of one another, a hydrogen atom or a group VV at least one of the two groups being different from hydrogen, a C1-C12 alkylthio radical; R "3 may also represent a hydrogen atom; R4 and R "4 represent, independently of one another, a radical chosen from: a hydrogen atom, a C1-C12 alkyl radical, a sugar unit, -COR40, with R40 representing a C1-C12 alkyl radical; -000R41, with R41 represents a C1-C12 alkyl radical; -00NR42R43, with R42, R43, identical or not, representing a hydrogen atom, a W; -Si (R44) 3 group in which R44 represents an alkyl radical; C1-C4; Z represents a hydrogen atom, a C1-C2 alkyl radical, a sulphonic group, alkyl (01-02) sulphonate, phenyl sulphonate or alkyl (01-02) -phenyl sulphonate, a -CORz group with Rz representing a C1-C12 alkyl radical, a sugar unit, VV represents a linear, branched and / or cyclic, saturated unsaturated, aromatic or non-aromatic hydrocarbon radical, which may contain from 1 to 5 carbon-carbon double bonds, optionally substituted and / or optionally interrupted by one or more heteroatoms and / or by one or more groups compositions comprising at least one heteroatom (preferably selected from oxygen, nitrogen, sulfur, O = O, C = S, P = O, SO, SO 2 or combinations thereof) and / or silicon; the hydrocarbon radical having no nitro, nitroso, peroxo or diazo function; said radicals (R11, R12), (R13, R14), (R22, R23), (R24, R25), (R31, R32) and (R42, R43), which can optionally form with the nitrogen atom to which each is attached, an optionally substituted 5- or 7-membered saturated or unsaturated heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; integer ranges from 0 to 5; more preferably from 0 to 3, preferably from 0 to 2; Exclusions of formula (I): when R 4 represents a sugar unit, a (1-4C) alkylcarbonyl group, a mono- or di-(1-4C) aminocarbonyl group, then R2 does not represent an alkoxy group ( -02) carbonyl, hydroxycarbonyl, hydroxymethyl (-CH2OH), R2 also does not represent a hydrogen atom when R4 represents a sugar; When R4 represents a hydrogen atom and R1 represents -0H3, -CH2OH, then R2 does not represent H, -0H3, -COOH, -0000H3.

Another subject of the present invention is represented by a composition comprising, in a cosmetically acceptable medium, the compounds of formula (I) and / or (II) as defined above. Another subject of the invention is a method for dyeing keratinous fibers in which a composition according to the invention comprising at least one compound of formula (I) and / or (II) is applied. A final subject of the invention relates to the use of the abovementioned compounds as dyes for keratinous fibers, in particular human fibers, such as the hair. Other features and advantages of the invention will emerge more clearly on reading the description and the examples that follow. It should be noted, unless otherwise indicated, that the boundaries of the value domains given in the description are included in the domains. The human keratinous fibers treated by the process according to the invention are preferably the hair. In what follows, the terms "at least one", "one or more" are considered synonymous.

The alkyl, alkenyl radicals are linear or branched unless specified more precisely. It should be noted that when the hydrocarbon radical is substituted, the substituent or substituents are chosen from the following: - carboxylic acid, in acid or salified form, - hydroxyl, C 1 -C 4 alkoxy, C 1 -C 8 alkoxycarbonyl, - alkyl (C1-C4) sulfonate, (C1-C8) alkyl phosphonate, tri (C1-C4) alkyloxy silanyl, amino, mono- or di (C1-C4) alkylamino, tri (C1-C4) alkylammonium, thiol (C1-C4) alkylthio-aminosulphonyl, mono- or di-(C1-C4) alkylaminosulfonyl, aminocarbonyl, mono- or di-(C1-C4) alkylaminocarbonyl, -alkyl (C1-C4) carbonylamino, guanidine, ureido (N (R) 2-CO-NR'-) in which the radicals R and R ', independently of each other, represent a hydrogen atom, a C 1 -C 4 alkyl, alkyl radical ( C1-C4) sulfonylamino; phenyl, indolyl, pyrolynyl, imidazolyl optionally substituted with one or more C 1 -C 2 alkyl, hydroxyl. Preferably, the groups present as substituents are chosen from carboxylic groups, in acid or salified form; hydroxyl; C1-4 alkoxy; C1-C8 alkoxycarbonyl; thiol; (C1-C4) alkylthio; amino; mono- and dialkyl (C1-C4) amino; aminocarbonyl; mono- and di-alkyl (C1-C2) aminocarbonyl; (C1-C4) alkylcarbonylamino; phenyl, indolyl, pyrolynyl, imidazolyl optionally substituted with one or more C 1 -C 2 alkyl, hydroxyl.

In general, the addition salts of the compounds of formula (I) and / or (II) of the invention are especially chosen from acid addition salts such as hydrochlorides, hydrobromides and sulphates. citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, dodecylbenzenesulfonates, phosphates and acetates, preferably hydrochlorides, citrates, succinates, tartrates, phosphates, lactates.

The solvates more particularly represent the hydrates of such compounds and / or the combination of a compound of formula (I) and / or (II) with a linear or branched C1-C4 alcohol such as methanol or ethanol. , isopropanol, n-propanol.

Compounds of formula (I) and / or (II) The compounds of formulas (I) and (II) are therefore substituted respectively with radicals R1, R2, R40-, and optionally one or more radicals R3; radicals R "1, R" 2, R "3, R" 40-, hydroxyl.

Preferably, the compounds of formula (I) and (II) are such that R1 and R "1 represent independently of each other: -CH3, -CHO, -CH2OZ, Z representing an atom of hydrogen, a C1-C20 alkyl radical, a sulfonic group, alkyl (O1-02) sulphonate, phenyl sulphonate or alkyl (O2-O2) phenyl sulphonate, a CORz group with Rz representing a C1-C6 alkyl radical; sugar unit; -000R10, R10 representing a hydrogen atom, a C1-C10 alkyl radical; -CH2NR13R14 with R13 and R14 representing, independently of one another, a hydrogen atom or a VV group, at least one of the two groups being different from hydrogen; R11 and R12 representing, independently of one another, a hydrogen atom or a group VV, at least one of the two groups being different hydrogen.

With regard to R 2 and R "2, the latter are independently of one another more advantageously: -CH 3 * -CH 2 OZ with Z representing a hydrogen, a C 1 -C 2 alkyl radical, -COR 2 with R 2 representing a C1-C6 alkyl radical, -000 R21, R21 representing a hydrogen atom, a C1-C6 alkyl radical; -CON R22 R23 R22, R23, which may be identical or different, represent a hydrogen atom, a group VV, at least one of the two groups being different from hydrogen. -OH2NR24R25 with R24 and R25 representing independently of one another a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen; -C (OH) R 26 R 27 with R 26, R 27, which may be identical or different, representing a linear or branched C 1 -C 12 alkyl radical, unsubstituted phenyl or unsubstituted benzyl. As regards R3 resulting from formula (I), this radical represents more particularly a hydroxyl radical, a methox radical y, ethoxy, a radical -N R31R32 with R31 and R32 representing independently of one another a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen. As regards R "3 derived from formula (II), this radical represents more particularly a hydrogen atom, a hydroxyl radical, a methoxy radical, ethoxy, a radical -NR31R32 with R31 and R32 independently representing one of the other a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen, a dodecylthio radical, R4 and R "4 represent, independently of one another, a radical chosen from a hydrogen atom, a C1-C12 alkyl radical, a sugar unit, -COR40, with R40 representing a C1-C6 alkyl radical; -000R41, with R41 represents a C1-C6 alkyl radical; -00NR42R43, with R42, R43, identical or not, representing a hydrogen atom, a group W; -Si (R44) 3 where R44 represents a C1-C4 alkyl radical. Within the meaning of the invention, the sugar unit or units mentioned in formula (I) and / or (II), independently of one another, denote a radical derived from a sugar, in cyclized form, comprising a or two sugar units, identical or not, selected from pentoses, hexoses. More particularly, the pentoses are chosen from the cyclized forms of ribulose, xylulose, arabinose, lyxose, ribose, xylose or deoxyribose. As regards the hexoses, the latter may advantageously be chosen from the cyclized forms of fructose, psicose, sorbose, tagatose, allose, altrose, galactose, glucose, gulose, idose, mannose, fucose, fuculose, pneumose, quinovose, rhamnose. With regard to the sugar units comprising two cyclized units, mention may be made of the following diholosides: cellobiose, gentiobiose, inulobiose, isomaltose, isomaltulose, kojibiose, lactose, lactulose, laminaribiose, leucrose, maltose, maltulose, melibiose, nigerose, robinose, rutinose, sucrose, sophorose, trehalose, trehalulose, turanose. Preferably, the sugar unit (s) of the formula (I) and / or (II), independently of one another, is / are chosen from allose, altrose, galactose, glucose, gulose, idose, mannose, talose, xylose, fructose, rhamnose and preferably glucose.

As regards the aldose derivatives, deoxy derivatives, such as rhamnose, as well as diholosides, in particular maltose, are preferred. According to an even more particular embodiment of the invention, the sugar unit (s) of the formula (I) and / or (II), independently of one another, is / are chosen from a radical derived from glucose, rhamnose, maltose, and preferably glucose. As indicated previously, the VV group represents a linear, branched and / or cyclic, saturated and / or unsaturated, aromatic or non-aromatic C1-C40 hydrocarbon radical which may contain from 1 to 5 carbon-carbon double bonds, optionally substituted, and or optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom or group comprising at least one heteroatom (preferably chosen from oxygen, nitrogen, sulfur, C = O, C = S, P = 0, SO, SO2 or combinations thereof) and / or silicon; said radicals (R11, R12), (R13, R14), (R22, R23), (R24, R25), (R31, R32) and (R42, R43) may optionally form with the nitrogen atom to which each is attached, an optionally substituted 5- or 7-membered saturated or unsaturated heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; the hydrocarbon radical having no nitro, nitroso, peroxo or diazo function. With regard to the VV group, the latter represents more particularly a C 1 -C 14 alkyl radical, optionally substituted with one or two hydroxyl groups, with one or two amino groups optionally substituted with a fluorenylmethyloxycarbonyl group or one of following groups, R 'R'1 (3) o O' 5 (4) R F7 F8 R 'ti (6) Formulas in which: R'1 represents: Si R'11 R'11 (7) o an atom of hydrogen or a linear or branched C1-C6 alkyl radical, preferably substituted by one or more hydroxyl, hydroxycarbonyl, thiol, alkyl (O1-C4) thio, amido, amino, guanidine, a phenyl radical, optionally substituted by a or more hydroxyl, an indolyl radical optionally substituted by one or more hydroxyls, an imidazolyl radical, a pyrrolinyl radical optionally substituted by a C1-C12 alkyl group; or an unsubstituted phenyl radical R'2 represents a hydrogen or a C1-C4 alkyl radical.

R '3 represents: a linear or branched, saturated or unsaturated C 1 -C 18 hydrocarbon radical and optionally comprising one to five conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and or by one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, O = O, C = S, SO, SO 2 or combinations thereof; the alkyl radical having no nitro, nitroso, peroxo or diazo function; an unsubstituted benzyl radical; * link attaching the radical VV to the molecule. Preferably R'3 represents an optionally substituted linear or branched C1-C10 alkyl radical; a benzyl radical; and even more preferably, a linear or branched C1-C4 alkyl radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups; a benzyl radical; R'1 and R'3 can form a saturated carbon ring with 5 members; R'4 represents: * a hydrogen atom * a C1-C6 alkyl radical, optionally substituted by one or more hydroxyl, thiol, alkyl (O-C4) thio, amido or amino groups, a phenyl radical, optionally substituted with one or more several hydroxyl groups, an indolyl radical optionally substituted with one or more hydroxyls, an imidazolyl radical or a pyrrolinyl radical optionally substituted with a C1-C12 alkyl group; R'1 and R'4 can form a saturated carbon ring with 5, 6, 7 members. In the case where X represents a nitrogen atom and R'4 represents an alkyl radical defined as above and very particularly an amino acid residue and / or their corresponding methyl or ethyl ester chosen from alanine, arginine, asparagine, aspartate, cysteine, glutamate, glutamine, glycine, histidine, lysine, methionine, phenylalanine, proline, pyrrolysine, serine, threonine, tryptophan, tyrosine , valine, leucine, isoleucine, the compound of formula (3) represents a dipeptide, an oligopeptide. R'6, R'6, R'8 represent independently of each other: * a hydrogen atom * a linear, branched and / or cyclic, saturated and / or unsaturated C-020 hydrocarbon radical which may contain from 1 to with 5 carbon-carbon double bonds, optionally aromatic, optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C = S, SO, SO 2 or combinations thereof, optionally carrying at least one hydroxyl or alkoxy group at 01-02, said alkyl radicals R '5 and R' 6 OR R '7 and R' 8 optionally capable of forming, with the carbon atom to which each is attached, a 5- or 7-membered, saturated or unsaturated heterocycle, optionally substituted as indicated above, optionally aromatic, optionally comprising another identical or different heteroatom are nitrogen; the alkyl radical having no nitro, nitroso, peroxo or diazo function; more particularly an optionally substituted C1-C10 alkyl radical; and preferably, a linear or branched C 1 -C 8 alkyl radical optionally substituted by at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups, a hydroxycarbonyl radical, a ureido radical or a (C 1 -C 4) alkoxycarbonyl radical; an unsubstituted phenyl radical; In the case of formula (6), the radicals R'6, R'6, R'8 independently of each other may also represent a hydroxyl radical, a (C1-C4) alkoxycarbonyl radical, a carboxaldehyde radical, an alkoxy (C1-03) R'5 and R'6 can form, with the carbon atom to which they are attached, a saturated 5- or 6-membered heterocyclic ring; R'9 represents: * a hydrogen atom * a linear or branched, saturated or unsaturated C 1 -C 18 hydrocarbon radical and optionally comprising one to five conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as indicated above, optionally interrupted by a or more heteroatoms and / or one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO, SO 2 or combinations thereof; the alkyl radical having no nitro, nitroso, peroxo or diazo function; more particularly R '9 represents a hydrogen, a linear or branched, optionally substituted C1-C10 alkyl radical; and preferably, hydrogen, a linear or branched C1-C4 alkyl radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups R'10 represents: * a hydrogen atom * an alkyl radical Cl-08 linear or branched optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO, SO 2 or combinations thereof, optionally carrying at least one hydroxyl group or C 1 -C 2 alkoxy; the alkyl radical having no nitro, nitroso, peroxo or diazo function, R '11 represents a linear C1-C4 alkyl radical; a linear C1-C4 alkoxy radical represents a sulfur atom; or nitrogen; an amino group (-NH-); Y represents a nitrogen, oxygen or sulfur atom; an amino group (-NH-); T represents an oxygen atom, an SH or OH group, a methylene group optionally substituted by a hydroxyl radical; when T represents an oxygen atom, then R11 or R12, R13 or R14, R22 or R23, R24 or R25, R42 or R43 form with T a 5- or 6-membered ring optionally substituted by one or more hydroxy (methyl) preferably 1 to 4 hydroxy groups (methyl); p is an integer from 0 to 7; q is an integer between 1 and 18 o is an integer between 0 and 5. More particularly, the radicals of formula (1) are derived from the following amino acids and derivatives, their enantiomers if they exist, their salts, their solvates asparagine, cysteine, glutamine, histidine, lysine, methionine, phenylalanine, proline, pyrrolysine, serine, threonine, tryptophan, tyrosine, and their addition salts. According to another variant, the radicals of formula (1) are derived from 2-amino-2-methylpropandic acid; alpha-methyl-DL-phenylalanine; DL-alpha- (hydroxymethyl) alanine; D, L-alpha-methyl-meta-tyrosine; alpha-methyl-D, L-tryptophan; D, L-alpha-methylhistidine dihydrochloride; L-2-methylserine; (S) -2-methylcysteine dihydrochloride; (S) -2-methyl-2-pyrrolidine carboxylic acid. As more specific examples of radicals of formula (2), mention may be made of those derived from the following amino acid and / or derivative esters, their enantiomers if they exist, their salts, their solvates: methoxytyrosine, carboxylate ethylpiperidine-2; the methyl ester of D, L phenylalanine; L-cystine dimethyl ester dihydrochloride; the methyl ester of L-leucine; methyl ester of 2-amino-3-methyl-butyric acid; L-phenylalanine ethyl ester hydrochloride; L-glutamic acid diethyl ester hydrochloride; (S) ethyl-2-amino-3-methylbutanoate hydrochloride; D, L, serine methyl ester hydrochloride; tyrosine methyl ester hydrochloride; Lysteine ethyl ester hydrochloride; L-histidine methyl ester hydrochloride; (S) pyrrolidine-2-carboxylic acid methyl ester hydrochloride; methyl 2-aminoacetate hydrobromide; ethylglycine; H-DL-alanine ethyl ester hydrochloride; DL tyrosine ethyl ester hydrochloride; methyl-2- (phenylamino) acetate; ethylglutamate; aspartic acid diester alpha, beta, tert-butyl dichloride hydrochloride; L-alpha-aminoisocaproic acid ethyl ester hydrochloride; paratoluene benzyl glycinate sulphonate; DL alanine methyl ester hydrochloride; 5-hydroxy-DL-tryptophan methyl ester hydrochloride; DL-threonine methyl ester hydrochloride; tert-butyl ester of DL proline; DL phenylalanine methyl ester hydrochloride. As regards the radicals of formula (3), there may be mentioned more particularly the radicals derived from amides and the thioesters originating from amino acids and / or derivatives, their enantiomers if they exist, their salts, their solvates, such as 3-amino-dihydrothiophene-2-one hydrochloride; DL homocysteine thiolactone; DL-leucyl-DL-alanine, aspartame; (S) -pyrrolidine 2 carboxamide; [N - (- acetamido)] 2-aminoethanesulfonic acid, DL-Alanyl-DL-phenylalanine; 2- (2-aminoacetamido) -3- (4-hydroxyphenyl) propanoic acid; 2- (2-aminoacetylamino) acetic acid; (R) -3-aminoazepan-2-one; glycinamide; L-Leucinamide; 2-aminopropane diamide; 2- (2-amino-3-methylbutanamido) propanoic acid; L-tyrosyl-L-alanine; L-valyl-L-phenylalanine; sarcosyl-L-phenylalanine; L-tyroyl-beta-alanine; glycyl-L-proline; glycyl-DL-valine; 2-aminomalonamide; L-methionamide; 2-amino-3-methylbutanamide; D-alaninamide; L-tyrosinamide hydrobromide; the amide of aspartic acid; L-arginine amide dihydrochloride; lysinamide; threonine; the isoleucine amide; histidine amide; DL amide, alanine; 2-amino-3- (4-hydroxyphenyl) propionamide; DL-triptophanamide; N-hydroxy-L-arginine acetate (HARG-NH 2 2 AcOH); asparagine amide; alpha diamide, gamma of L-glutamic acid; D-phanylalanine amide; D-leucinamide; L-glutamic acid alpha-amide; L-methionineamide; L-cystine bisamide; glycinamide acetate; D-lysine amide; glycinamide; gamma-methyl ester of L-isoglutamine; the amide of D-arginine; (S) pyrrolidine carboxamide; prolyl histamine. As regards the radicals of formula (4), mention may be made of those resulting from the following amino compounds, their enantiomers, if they exist, their salts, their solvates: L-2-aminohexandic acid amide; L-phenylalanine amide; (S) (+) aminosuccinic acid; (R) -2- (methylamino) succinic acid; ethyl nipecotate; the carboxylic acid 3-piperidine; 3-phenyl-beta-alanine; ethyl-3-aminobutyrate; 2-carboyethylamine; DL beta-amino adipic acid; beta-alanine ethyl ester; 3-amino-3-ureido-N-butyric acid ethyl ester; dimethyl (S) -aminosuccinate; beta-L-alanine methyl ester; 4-carboxyyethoxypiperidine; 4-aminobutyric acid; DL-beta-amino adipic acid; 4- (methylamino) butyric hydrochloride; ethyl-gamma-aminobutyrate; hexahydronicotinamide; 4-carboxamide piperidine; 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine.

As regards the radicals of formula (5), mention may be made of those resulting from the following acids, their enantiomers if they exist, their salts, their solvates: (1-aminoethyl) phosphonic acid, (aminomethyl) phosphonic acid, (1-aminoethyl) -1- (cyclohexyl) phosphonic acid, (1-aminopropyl) phosphonic acid, (1-amino-butyl) phosphonic acid, imino-bis (methylphosphonic), (1-amino-2-methylpropyl) phosphonic acid, (1-amino-2-phenylethyl) phosphonic acid, (1-amino-1-methylethyl) phosphonic acid, (1-amino-3-methylbutyl) phosphonic acid, 1-amino-benzyl phosphonic acid, 1-amino hexyl phosphonic acid, diethyl (aminoethyl) phosphonic acid (especially oxalate salt), tetraethyl (aminomethylene) ) bisphosphonic acid (especially its salts), (1-amino-2,2-dimethylpropyl) phosphonic acid, N-methylaminomethylphosphonic acid, (1-aminopentyl) phosphonic acid, (1-amino-2-methylbutyl) phosphonic acid, (1-aminooctyl) ) phosphonic acid, (1-amino-1-methylpropyl) phosphonic acid, (1-amino-1,2-dimethylpropyl) phosphonic acid, (1-amino-1,3-dimethylbutyl) phosphoni (1-amino-1-methylbutyl) phosphonic acid, (1-amino-1-cyclopentyl) phosphonic acid, (1-amino-hydroxycarbonyl) propyl phosphonic acid, (1-amino-1-methylethyl) phosphonic acid, 1-amino-2 methyl-butyl phosphonic acid, 1-phosphono-2-phenylethylamine, (aminomethyl) phosphonic acid, 3-aminopropyl phosphonic acid, 2-amino-2-methyl-4-phosphonobutanoic acid and their ethyl esters, (diethyl (3-aminopropyl) phosphonic acid (in especially the oxalate salt) 3- (N-hydroxyamino) propyl phosphonic acid, 2-amino-2-methyl-4-phosphonobutyric acid, (3-aminopropyl) phosphonic acid diethyl ester, 2-amino-4-phosphonobutyric acid, 2-aminoethylphosphonic acid, 2 -amino-3-phosphonopropionic acid, (2-aminoethyl) phosphonic diethyl ester, diethyl (2-aminoethyl) phosphonic acid, (2 - ((2-pyrrolidinylcarbonyl) amino) ethyl) phosphonic acid, diethyl ester of (2-amino-1 -methyl-2-phenyl) ethyl phosphonic acid, (2-amino-2-phenyl) ethyl phosphonic acid diethyl ester, or mixtures thereof. According to another variant of the invention, the radicals of formula (6) may be the β-aminoalcohol resulting from the reduction of the acid or ester function to the alcohol of one of the twenty esterified or non-esterified amino acids. By way of examples of compounds (6), mention may be made of the following compounds, their enantiomers if they exist, their salts, their solvates: isopropanolamine, isopropylamine, methylethanolamine, methylglucamine, stearamine, tromethamine, promethazine, 1,3 Dimethylpentylamine, octodrine, spermidine, theanine, octamylamine-2-amino-1-phenylpropane-1,3-diol, 1,3-dihydroxy-2-amino-2-methylpropane, 2-amino-2- (hydroxymethyl) propane-1,3-diol tris, 2-amino-1,3-dihydroxy-2-ethylpropane, 2-amino-3-methylbutan-1-ol, 2-amino-2-methylpropan-1-01, phenylglycinol, alcohol 2-aminopropyl, 2-hydroxyethylamine, 2-aminohexan-1-ol, 1-amino-1-cyclopentanemethanol, histidinol, 2-amino-3- (3-indolyl) propanol, 3- (4-hydroxyphenyl) -2-amino -1-propanol, beta-aminoisobutanol, 2-amino-1-propanol, 2-amino-1,3-propanediol, 2-amino-4-methyl-1-pentanol, 1-butano-2-amino-3-methyl , beta-amino benzenepropanol, 2-aminopropan-1-ol, 2-amino-1-butanol, 2-amino-4-methylpetan-1-ol, 3-aminopropanet hiol, ethyl 2-amino-4-mercaptobutanoate, 6-hydroxyhexylamine, beta-D-galactopyranosylamine, BD-glucopyranosylamine, 1-amino-2,5-anhydro-D-mannitol, 1-amino-1-deosy-D-fructose D-glucosamine, 2-pyrrolidinemethanol, 1-amino-2,3-dihydroxypropane, 3-propanolamine, 3 - [(2-hydroxyethyl) amino] propan-1-ol, di-beta-hydroethylamine, bis (3-hydroxypropyl) ) amine, N-2'-aminoethyl-N-propanolamine, 4-amino-N-butyl alcohol, methyl 3-amino-3-deoxy-AD-mannopyranoside, N-butyl-4-hydroxybutylamine, 4-amino-4- (3-hydroxypropyl) -1,7-heptanediol, 1-hexylamine, 1-octylamine, 1-nonylamine, 1-decylamine, laurylamine, 1-tetradecylamine, 1-hexadecylamine, 3-amino-2-hydroxypropionic acid, 3-amino-2-hydroxy-4-phenylbutanoic acid, 4-amino-3-hydroxybutyric acid, ethyl 4-hydroxy-2-pyrrolidinecarboxylate and mixtures thereof. The radicals of formula (7) are in particular derived from the following compounds, their enantiomers if they exist, their salts, their solvates: aminopropyl triethoxysilane, (aminomethyl) trimethylsilane, 2- (trimethylsilyl) ethanamine, 3- (trimethylsilyl) propane 1-amine, 4- (triethoxysilyl) butan-1-amine, N- [3- (trimethoxysilyl) propyl] ethylene diamine, 3- (trimethoxysilyl) propylamine, 3-triethoxysilyl-1-propanamine, (3-methylaminopropyl) trimethoxysilane, and their mixtures. According to an advantageous variant of the invention, the VV group, more particularly represents a C1-C14 alkyl radical, optionally substituted with one or two hydroxyl groups, or one of the following groups, even more preferably the compounds of formula (I) and / or (II) are such that R1 and R "1 independently of each other represent: * -CH3, * -CHO, * -CH2OH, * -CH2OCH3, * - CH2OSO2CH3, -CH2OSO2PhCH3, (Ph = phenyl) * -COOH, -0000H3, -0000H2CH3, -000 (CH2) 5CH3, -000 (CH2) 9CH3 * -CH2NR13R14 with R13 and R14 representing independently of one another a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen; R11 and R12 representing, independently of one another, hydrogen, a group VV; one of the two groups being different from hydrogen.

As regards R2 and R "2, the latter represent, independently of one another, even more advantageously: -CH 3 -CH 2 OH * -COOH, -0000H 3, -0000H 2 CH 3 -C (OH) (CH 3 ) 2, -C (OH) (CH 2 Cl-13) 2, -C (OH) (CH 2 Ph) 2 * -CON R 22 R 23, R 22, R 23, which may be identical or different, represent a hydrogen atom, a VV group, at least one of the two groups being different from hydrogen. * -OH2NR24R25 with R24 and R25 representing independently of one another a hydrogen atom or a group VV, at least one of the two groups being different hydrogen, * -0H20000H3, -0H20000H20H3, -0H20000H20H201-13, -0H20000H20H20H20H3, 0H20000H20H20H20H201-13, -0H20000H20H20H20H20H20H20H3 As regards R3, this radical represents more particularly a hydroxyl radical.

As regards R "3, this radical represents more particularly a hydrogen, a hydroxyl radical, an ethoxy, dodecylthio, methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, 2-methylpropanoate amino radical. preferably, is 0 or 1.

Of course, when n is zero, the carbon atoms of the ring (s) carry the required number of hydrogen atoms.

With regard to R4 OR R "4, this preferably represents a radical chosen from: * H, methyl, ethyl, propyl, butyl, pentyl, hexyl * a glucose unit, * -000H3, -000H2CH3, -000H2CH2CH3, - 000H2CH2CH2CH3, -000H2CH2CH2CH2CH3, -000H2CH2CH2CH2CH2CH3; -000 (CH3) 3; -0000H3, -0000H2CH3, -0000H2CH2CH3, -0000H2CH2CH2CH3, -0000H2CH2CH2CH2CH3. -00NR42R43, with R42, R43, identical or not, representing a hydrogen atom, a W 2 -Si (R 44) 3 group in which R 44 represents a C 1 -C 4 alkyl radical The compounds of formula (I) and / or (II) may be chosen from the following compounds, their optical isomers, geometric isomers, their tautomers, their enantiomers if they exist, their salts, their solvates, and their mixtures: Compounds of formula (I) with n being the preferred value of 0 or 1 R1 R3 R4 H OC 1-12-CH300 (0) -, HOC (0) -, HO-CH3CH2-, OH-, CH3 [CH212-, CH3 [CH213-, CH3 [CH214-, CH3CO-, CH3CH2C (O) -, CH3 [CHIC (O) -, CH3 [CH2] 3C (0 ) -, (CH3) 3Si, CH3CH200 (O) -, (CH3) 3000 (0) -, CH3CHCH2-, pd-glucose HOCH2- CH300 (O) -, HOC (O) -, HO- CH3CH2-, -CH2OH CH3 [CH212-, CH3 [CH213-, CH3 [CH214-, (CH3) 3Si-, CH3CH200 (O) -, (CH3) 3000 (O) -, CH3CHCH2-HC (O) - CH300 (O) -, HOC (O) -, HO- H-, CH3CH2-, CH3 [CH212- , CH3 [CH213-, CH3 [CH214-, HOCH2-, CH3-CH3CO-, CH3CH2C (O) -, CH3 [CHIC (O) -, CH3 [CH2] 3C (O) -, (CH3) 3Si, CH3CH200 (0) -, (CH3) 3000 (O) -, (CH3) 2NC (O) -, CH3CHCH2-, pd-glucose CH3CH200 (O) -, HOC (O) -, CH300 (O) -, HOC (0) - ) -, HO- H-, CH3CH2-, CH3 [CHINHC (O) -, HOCI-12-, CH3 [CH2] 2-, CH3 [CHINHCH2-, CH3-CH3 [CH2] 3-, CH3 [CH2] 4NHCH) -, CH3 [CH2] 4-, CH3 [CH2] 3NHCH-, CH300-, CH3CH2CH2NHCH-, CH3CH2C (O) -, CH3CH2NHCH-, CH3 [CHIC (O) -, CH3NHCH-, CH3 [CH2] 3C (O) -, CH300 (O) CH (CH3) NHC (O) - (CH3) 3Si, CH3CH200 (O) -, (CH3) 3000 (O) -, (CH3) 2NC (O) -, CH3CHCH2-, pd- Glucose HOCI-12-CH3CH2NHC (O) -, HO- H-, CH3CH2-, HO [CHINHC (O) -, CH3 [CH2] 2-, CH3 [CHINHC (O) -, CH3 [CH2] 3-, CH3 [CH2] 3NHC (O) -, CH3 [CH2] 4-, CH3 [CH2] 4NHC (O) -, CH3O-, CH3 [CHINHC (O) -, CH3CH2C (O) -, FmocNH [CH2] 6NHC (0 ) -, CH3 [CHIC (O) -, NH2 [CH2] 6NHC (O) -, CH3 [CH2] 3C (O) - , CH3 [CH2] 200 (O) -, -CH (O), (CH3) 3Si-, -C (OH) (Cl-13) 2, CH3CH200 (O) -, -C (OH) (C61-15 ) 2, - (C (OH) (CH2C61-15) 2, CH3) 3000 (O) -, -C (O) N (C4H8), (CH3) 2NC (O) -, -C (O) NHCH ( CH3) C (O) OCH3 CH3CHCH2-, -C (O) NH (CH2) 13CH3, pd-glucose-CH20000H3, -CH20000H2CH3, -CH2000 [CHICH3, -CH2000 [CH2] 3CH3, -CH2000 [CH2] 4CH3, CH2000 [CHICH3 Preferably n is 0.

Preferred Compounds of Formula (II) ## STR2 ## wherein -, CH3-, H, -CH2OH CH3 [CH2] 4NH-, CH3 [CH213-, CH3 [CH2] 3NH-, CH3 [CH214-, CH3 [CHINH-, CH3CO-, CH3CH2NH-, CH3CH2C (O) -, CH3NH-, CH3 [CHIC (O) -, C12H25S-, CH3 [CH2] 3C (O) -, -NHCH (CH3) C (O) OCH3 (CH3) 3Si-, CH3CH2O-CH3CH2O (O) -, H ( CH3) 3COC (O) -, (CH3) 2NC (O) -, CH2CHCH2-, pd-glucose HOCH2-CH3CH2NHC (O) -, H-, HO- H-, CH3CH2-, HO [CHINHC (0) -, CH3 [CH212-, CH3 [CHINHC (O) -, CH3 [CH213-, CH3 [CH2] 3NHC (O) -, CH3 [CH214-, CH3 [CH2] 4NHC (O) -, CH3CO-, CH3 [CHINHC ( 0) -, CH3CH2C (O) -, FmocNH [CH2] 6NHC (O) -, CH3 [CHIC (O) -, NH2 [CH2] 6NHC (O) -, CH3 [CH2] 3C (O) -, CH3 [ CH2] 20C (O) -, (CH3) 3Si, -CH (O), CH3CH2Oc (O) -, -C (OH) (Cl-13) 2, (CH3) 3COC (O) -, -C ( OH) (C61-15) 2, - (CH3) 2NC (O) -, C (OH) (CH2C61-15) 2, CH2CHCH2-, -C (O) N (C4H8), pd-glucose -C (0) ) NHCH (CH3) C (O) OCH3 -C (O) NH (CH2) 13CH3, -CH2OCOCH3, -CH2OCOCH2CH3, -CH2OCO [CHICH3, -CH2OCO [CH2] 3CH3, -CH2OCO [CH2] 4CH3, CH2OCO [CHICH3 A] title of particularly suitable compound The following compounds may be mentioned, as well as their tautomers, their enantiomers if they exist, their salts, their solvates, and their mixtures: ## STR2 ## ## STR2 ## ## EQU1 ##, ## EQU1 ##, ## STR2 ## Another object of the invention is represented by a composition comprising, in a cosmetically-compatible medium, a cosmetically compatible medium. one or more compounds of formula (I) and / or (II) as defined above The content of compound of formula (I) and / or (II) of the composition is more particularly between 0.001 and 20% by weight. weight in relation to the weight of the composition Additional dyes The composition may optionally comprise at least one additional dye different from the compounds of formula (I) and / or (II), Among these additional dyes, mention may be made of natural or synthetic direct dyes , the oxidation dyes with the bases possibly associated with couplers, as well as their combinations These direct dyes may be chosen, for example, from among the colorants neutral, acidic or cationic nitro-benzene direct feeders, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, direct dyes indoamines and natural direct dyes. Among the natural direct dyes that may be mentioned are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, anthragallol, indigo, curcumin, spinulosin, apigenidine, chlorophylls, chlorophyllins, orceins, haematin, brazilin, braziline, safflower dyes (such as, for example, carthamine), flavonoids (with, for example, morine, apigenidine, sandalwood) anthocyanins (of the apigeninidine type), carotenoids, tannins, sorghum, and cochineal carmine, or mixtures thereof. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. The direct dye content, of synthetic or natural origin, when the composition contains, is more particularly between 0.001 and 10% by weight relative to the weight of the composition. Among the oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts, and their solvates. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts, their solvates. The oxidation base (s) possibly present in the dyeing composition are generally each present in an amount of between 0.001% and 10% by weight relative to the total weight of the composition, preferably between 0.005% and 6% by weight. The coupler (s), if present, are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the composition, preferably between 0.005 and 6% by weight. Optional Compounds The composition may also comprise optional compounds such as the non-glycosylated or glycosylated iridoid derivatives defined below, these compounds being alone or in mixtures: the non-glycosylated iridoides of formula (a) and / or of formula ( b) following, their optical or geometric isomers, their salts of mineral or organic acid, their solvates: R 2 OH R, (a) (b) Formulas (a) and / or (b) in which: R1 represents an atom of hydrogen, a methyl radical, a hydroxymethyl radical, an aldehyde group; a group -OO 2 R 4 in which R 4 represents a hydrogen atom or a C 1 -C 2 alkyl radical; a -CH2-glucose group; R2 represents a hydrogen atom, a hydroxyl radical, a glucose radical; R3, which may be identical or different, represent a hydrogen atom, a hydroxyl radical or a (C1-C4) alkyl radical; the number of hydroxyl groups not being greater than 2; n is an integer from 1 to 5; R5 represents a group -CO2R'6 in which R'6 represents a hydrogen atom, a C1-C2 alkyl radical, an alkali metal cation, an ammonium group; R6 represents a hydrogen, a -CO2R'6 group in which R'6 represents a hydrogen atom, a C1-C2 alkyl radical, an alkali metal cation, an ammonium group; or a plant extract comprising said compounds of formula (a) and / or of formula (b) selected from the following plant extracts: Veronica persica; Apodytes dimidiata; Randia canthioides; Tarenna attenuata, il) non-glycosyl iridoides of formula (c) below, their optical or geometric isomers, their salts of mineral or organic acid, their solvates: (R) ', R2 OR - - - - - - 25 (c) (C) wherein: R1 represents a hydroxymethyl radical, a group -O2R4 in which R4 represents a hydrogen atom or a C1-C2 alkyl radical; a sugar radical; R2 represents a hydrogen atom, a hydroxyl radical, a sugar radical; R3, which may be identical or different, represent a hydrogen atom, a hydroxyl radical or a (C1-C4) alkyl radical; the number of hydroxyl groups not being greater than 2; R represents a sugar radical; n is an integer from 1 to 5; the sugar radical is a derivative derived from an aldose or an aldose derivative: The compound (s) of formula (c) having undergone, before or simultaneously with the dyeing process, a step of replacing the radical R with a hydrogen atom; the compound or compounds of formula (c) having optionally undergone a preliminary step consisting in replacing the radical R with a hydrogen atom produced by means of an enzyme; or a plant extract comprising said compound of formula (c), chosen from the following plant extracts: Abelia grandiflora, Adenorandia kalbreyeri, Adina polycephala, Aeginetia indica var. gracilis, Asperula sp, Asystasia bella, Aucuba japan ica, Avicennia marina, Bartsia trixago, Buddleja Americana, Buddleja crispa, Buddleja japonica, Canthium schimperianum, Castilleja wightii, Chaenorhinum minus, Clerodendrum serratum, Coprosma sp, Cornus officinalis, Craibiodendron henryi, Cremaspora triflora , Crucianella sp, Daphniphyllum calcinum, Daphniphyllum humile, Daphniphyllum macropodum, Eremostachys glabra, Escallonia sp, Eucommia ulmoides, Feretia apodanthera, Galium humifusum, Galium verum, Jasmine gardenia, Garrya elliptica, Globularia dumulosa, Hedyotis corymbosa, Hygrophila difformis, Ixeris chinensis, Lamiastrum galeobdolon (Lamium galeobdolon), Lamiophlomis rotata (Phlomis rotata), Leonotis nepetaefolia, Lin aria sp, Morinda coreia, Mussaenda pubescens, Nepeta cilicia, Nepeta nuda ssp. Albiflora, Odeontites verna, Oldenlandia corymbosa, Paederia scandens, Pedicularis chinensis, Pedicularis condensata, Pedicularis dolichocymba, Penstemon con fertus, Penstemon deutus, Penstemon richardsonii, Penstemon serrulatus, Pithecoctenium crucigerum, Plantago alpina, Plantago carinata, Plantago lagopus, Plantago lanceolata, Plantago subulata , Premna barbata, Randia dumetorum, Rhododendron latoucheae, Rothmannia withfieldii, Rubia peregrina, Rubia tinctorum, Saprosma scortechinii, Scrophularia korainensis, Scrophularia lepidota, Scrophularia ningpoensis, Scyphiphora hydrophyllacea, Swida controversa, Syringa vulgaris, Tarenna kotoensis, Tecoma heptaphylla, Thevetia gaumeri, Thevetia Peruviana, Verbascum laxum, Verbascum nigrum, Verbascum phlomoides, Verbascum salviifolium, Verbascum sinuatum, Verbascum thapsus, Verbascum undulatum, Veronica derwentiana, Vit ex nigrum, Wendlandia formosana, preferably Gardenia jasmine oïdes and their mixtures Lewis acid According to a mode of re the composition according to the invention comprises at least one Lewis acid, in particular chosen from boron halides and aluminum halides.

The Lewis acid may be present in a content ranging from 0.001 to 10%, preferably from 0.01 to 5% by weight relative to the total weight of the composition. Salts The composition comprising the compound (s) of formula (I) and / or (II) may optionally comprise one or more salts. When present, they are generally chosen from organic salts and / or inorganic salts, as well as combinations thereof. In particular, the anions comprising these salts can be as well inorganic (chloride, carbonate, hydrogencarbonate, sulphate, hydrogen sulphate, hydroxide, silicate, phosphate, hydrogen phosphate, etc.), as organic (aspartate, formate, acetate, lactate, citrate, gluconate, succinate, malate, fumarate, orotate ...). The cations composing these salts, associated with the above anions, may be derived from both alkali metals (preferably lithium, sodium, potassium), alkaline earth metals (preferably magnesium, calcium) and transition metals. (scandium, titanium, vanadium, manganese, molybdenum, iron, cobalt, nickel, copper, zinc, silver, gold). Other cations may also form salts such as ammoniums. Preferably, the cations comprising these salts, associated with the above-mentioned anions, are chosen from alkali metals (lithium, sodium, potassium), alkaline earth metals (magnesium, calcium), ammoniums, as well as the following transition metals: manganese, molybdenum, iron, copper, zinc, silver and gold. When present, their content represents 0.001 and 40% by weight relative to the weight of the composition, and even more preferably between 0.001 and 20% by weight, relative to the weight of the composition.

Other ingredients The cosmetically acceptable medium generally comprises at least water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned for example lower alkanols in Cl-04, such as ethanol and isopropanol; polyols such as 1,3-propanediol or else 1,6-hexanediol and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The solvents when present are preferably present in proportions preferably of between 1 and 99% by weight relative to the weight of the composition, and even more preferably between 5 and 95% by weight, relative to the weight. of the composition.

The composition used in the process according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers. cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or not, such as amino silicones, film-forming agents, ceramides, preserving agents, opacifying agents, polymers conductors. In particular, the composition used may comprise at least one additional compound chosen from dihydroxyacetone, vitamin C, oxidized vitamin C, protocatechaldehyde, isatin, hematoxylin and mixtures thereof. The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.

Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, impaired by the or the additions envisaged. The pH of the composition is generally between 3 and 14 approximately, and preferably between 4 and 11 approximately, more preferably between 6 and 11 and even more preferably between 7 and 9.5. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, for example, ammonia, alkaline carbonates, amines which will be detailed below. The composition may be in various forms, such as in the form of liquid, cream, gel, powders to be mixed before use to obtain poultices, infusions, or in any other form suitable for dyeing keratinous fibers, and in particular hair. Staining process The method according to the invention therefore consists in applying the abovementioned composition to keratinous fibers. Deprotection of the group R4, R "4 It should be noted that if the compound (s) of formula (I) and / or (II) is (are) protected by a protective group R4 OR R" 4 different from one sugar, these are advantageously subjected before or simultaneously to the dyeing process, at a step of replacing the radical R4 OR R "4 with a hydrogen atom.

This reaction can be carried out by any means known to those skilled in the art and in particular it can be carried out using an acidic agent, chosen, for example, from citric acid, tartaric acid, lactic acid, benzoic acid, ascorbic acid, or an alkaline agent, chosen for example from soda, a primary or secondary amine.

Thus, in the case where the operation takes place simultaneously with the dyeing process, the alkaline agent or the acidic agent is added to the composition just before its application to the fibers.

In the case where the operation takes place before application to the fibers, the alkaline agent or the acidic agent is more particularly added to an aqueous solution of compound of formula (I) and / or (II). The operation is usually carried out at a temperature between 20 and 70 ° C and for a time ranging from 1 minute to 5 hours. The reaction product can be used directly in the dyeing process according to the invention, or else can be extracted. the compound obtained, for example by employing a solvent such as ethyl acetate.

Deglycosylation It should be noted that if the compound (s) of formula (I) and / or (II) is (are) glycosylated, the latter are advantageously subjected before or simultaneously to the dyeing process, at a step of replacing the radical R4 OR R "4 by a hydrogen atom.

This reaction can be carried out by any means known to those skilled in the art and in particular it can be carried out using an enzyme, chosen for example from the isolase, p-glucosidase resulting for example from sweet almond (EC 3.2 .1.21), Thus, in the case where the operation takes place simultaneously with the staining process, the enzyme is added to the composition just before its application to the fibers. In the case where the operation takes place before application to the fibers, the enzyme is more particularly added to an aqueous solution of compound of formula (I) and / or (II), buffered (for example acetate, pH between 5.5 and 6). Preferably, the concentration of compound of formula (I) and / or (II) varies between 10 and 30 mM. If it is present, the concentration of the enzyme used in the dyeing composition is between 0.005% and 40% by weight relative to the total weight of said composition and preferably between 0.05% and 10% by weight per relative to the weight of this composition. The operation is usually carried out at a temperature between 20 and 45 ° C and for a period of 1 to 5 hours.

The reaction product can be used directly in the dyeing process according to the invention, or else the compound obtained can be extracted, for example by using a solvent such as ethyl acetate.

Second composition According to one particular variant of the invention, the composition is applied in the presence of at least a second composition comprising at least one ingredient chosen from amines, aldehyde or imine compounds, nucleophilic compounds, nucleophilic carbonyl compounds, salts, alone or in combination.

According to a first embodiment, the composition according to the invention is applied successively and without intermediate rinsing to the second composition comprising one or more of the aforementioned ingredients. According to a second preferred embodiment, the composition according to the invention is mixed before application to the fibers with at least one composition comprising at least one or more of said ingredients. It should thus be noted that the composition used in the invention may result from the extemporaneous mixing of several compositions.

As indicated above, the second composition comprises at least one ingredient selected from amines, aldehyde or imine compounds, nucleophilic compounds, nucleophilic carbonyl compounds, salts, alone or in combination.

Amine According to this embodiment of the invention, the amine or amines are chosen from primary amines, secondary amines or their addition salts, ammonia, hydroxylamine, or their mixtures. In general, the addition salts of these amine compounds that may be used in the context of the invention are chosen especially from acid addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, dodecylbenzenesulfonates, phosphates and acetates, preferably hydrochlorides, citrates, succinates, tartrates, phosphates, lactates.

In particular, the primary or secondary amine or amines which can be used in the context of the invention are chosen from the amines of formula (III) which will be detailed below, the amine polymers, the purine bases and their salts. addition, and their combinations. In particular, the formula (III) is the following: R'7R'8NH (III) Formula (III) in which R'7, R'8, represent independently of one another - a hydrogen atom - a linear, branched and / or cyclic, saturated and / or unsaturated, aromatic or non-aromatic, C1-C20 hydrocarbon radical which may contain from 1 to 5 carbon-carbon and / or optionally substituted double bonds, optionally interrupted by one or more heteroatoms; and / or with one or more groups comprising at least one heteroatom or group comprising at least one heteroatom (preferably chosen from oxygen, nitrogen, sulfur, C = O, P = 0, C = S, SO, SO2 or combinations thereof) and / or silicon; said R'7 and R'8 hydrocarbon radicals possibly being able to form, with the nitrogen atom to which each is attached, a 5- or 7-membered, optionally substituted, optionally aromatic, saturated or unsaturated heterocycle, optionally fused to an aromatic ring or heteroaromatic 6-membered ring, optionally comprising another heteroatom identical to or different from nitrogen; the hydrocarbon radical having no nitro, nitroso, peroxo or diazo function.

The compounds of formula (III) are advantageously not oxidation bases or oxidation couplers used in the dyeing of keratinous fibers. Preferably, the groups present as substituents, if they are, are chosen from carboxylic groups, in acid or salified form; hydroxyl; C1-4 alkoxy, C1-8 alkoxycarbonyl; thiol; alkyl (01-04) thio; amino; mono- and di-alkyl (01-04) amino; aminocarbonyl; mono- and di-alkyl (01-02) aminocarbonyl; alkyl (01-04) carbonylamino; phenyl, indolyl, pyrrolinyl, imidazolyl optionally substituted by one or more C 1 -C 2 alkyl, hydroxyl. In particular, the amine (s) of formula (III), which may be identical or different, comprise from one to five primary and / or secondary amine functions; the amine or amines having no N-N bond. Also, the amine (s) of formula (111) do not comprise more than two heteroatoms bonded together. Preferably, the amine or amines are compounds of formula (III), more particularly chosen from compounds of formulas (IIIa) to (IIIi), (IIIi ') below, as well as their addition salts, their solvates. amino acids and / or derivatives of general formula (IIIa): ## STR2 ## in which: R 9 represents a hydrogen atom, a linear or branched C 1 -C 6 alkyl radical; , preferably substituted with one or more hydroxyl, hydroxycarbonyl, thiol, (C 1 -C 4) alkylthio, amido, amino, guanidine groups, a phenyl radical, optionally substituted with one or more hydroxyls, an indolyl radical optionally substituted with one or more hydroxyl, an imidazolyl radical, a pyrrolinyl radical optionally substituted by a C1-C12 alkyl group; or an unsubstituted phenyl radical - R "9 represents hydrogen, a C 1 -C 4 alkyl radical, or an unsubstituted phenyl radical - R 10 represents a hydrogen or a C 1 -C 4 alkyl radical - R" 9 and R 9 may form together with the nitrogen atom to which they are attached, a 5- or 6-membered saturated heterocycle. By way of example of compounds of formula (IIIa) mention may be made in particular of the following compounds, their salts, their hydrates, their optical or geometrical isomers, their enantiomers: asparagine, cysteine, glutamine, histidine, lysine, methionine, phenylalanine, proline, pyrrolysine, serine, threonine, tryptophan, tyrosine, and their addition salts. According to another variant, the compounds of formula (IIIa) are advantageously chosen from the following compounds, their salts, their hydrates, their optical or geometrical isomers, their enantiomers: 2-amino-2-methylpropandic acid; alpha-methyl-DL-phenylalanine; D, L-alpha- (hydroxymethyl) alanine; D, L-alpha-methyl-meta-tyrosine; alpha-methyl-D, tryptophan; D, L-alpha-methylhistidine dihydrochloride; L-2-methylserine; (S) -2-methylcysteine; (S) -2-methyl-2-pyrrolidine carboxylic acid. esters derived from amino acids and / or derivatives of general formula (IIIb): (IIIb) Formula (IIIb) in which: R9 represents a hydrogen atom or a linear or branched C1-C6 alkyl radical, preferably substituted by one or more hydroxyl, hydroxycarbonyl, (C 1 -C 4) alkoxycarbonyl, thiol, (C 1 -C 4) alkylthio, amido, amino, guanidine groups, a phenyl radical, optionally substituted by one or more hydroxyls, an optionally substituted indolyl radical; substituted with one or more hydroxyls, an imidazolyl radical, a pyrrolinyl radical optionally substituted with a C1-C12 alkyl group; or an unsubstituted phenyl radical - R "9 represents hydrogen, a C 1 -C 4 alkyl radical, or an unsubstituted phenyl radical - R 10 represents a hydrogen or a C 1 -C 4 alkyl radical - R" 9 and R 9 may form together with the nitrogen atom to which they are attached, a 5- or 6-membered saturated heterocycle. R11 represents: a linear or branched, saturated or unsaturated C 1 -C 18 hydrocarbon-based radical optionally comprising one to five conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as indicated above, optionally interrupted by one or more heteroatoms, and or by one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, O = O, C = S, SO, SO 2 or combinations thereof; the alkyl radical having no nitro, nitroso, peroxo or diazo function; an unsubstituted benzyl radical. According to a particular variant, R 9 and R 11 may optionally form a saturated carbon ring with 5 members.

Preferably, R 11 represents a linear or branched, optionally substituted C 1 -C 10 alkyl radical; a benzyl radical; and even more preferably, a linear or branched C1-C4 alkyl radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups; a benzyl radical. By way of examples of formula (IIIb), mention may be made of the following compounds, their salts, their hydrates, their optical or geometrical isomers, their enantiomers: methoxytyrosine, ethylpiperidine-2 carboxylate; the methyl ester of D, L phenylalanine; L-cystine dimethyl ester; the methyl ester of L-leucine; methyl ester of 2-amino-3-methyl-butyric acid; L-phenylalanine ethyl ester; L-glutamic acid diethyl ester; ethyl-2-amino-3-methylbutanoate; the methyl ester of D, L, serine; tyrosine methyl ester; Lysteine ethyl ester; L-histidine methyl ester; (S) pyrrolidine-2-carboxylic acid methyl ester; methyl 2-aminoacetate; ethylglycine; ethyl ester of H-DL-alanine; the ethyl ester of DL tyrosine; methyl-2- (phenylamino) acetate; ethylglutamate; alpha, beta, tert-butyl DL aspartic acid diester; L-alpha-aminoisocaproic acid ethyl ester; paratoluene benzyl glycinate sulphonate; DL alanine methyl ester; 5-hydroxyDL-tryptophan methyl ester; DL-threonine methyl ester; tert-butyl ester of DL proline; the methyl ester of DL phenylalanine. amides and thioesters derived from amino acids and / or derivatives of general formula (IIIc): ## STR2 ## Formula (IIIc) in which: R 9 represents a hydrogen atom or a C 1 -C 6 alkyl radical; , linear or branched, preferably substituted by one or more hydroxyl groups, alkoxy (ClC 4) carbonyl, hydroxycarbonyl, thiol, (C 1 -C 4) alkylthio, amido, amino, guanidine, a phenyl radical, optionally substituted by one or more hydroxyl groups an indolyl radical optionally substituted by one or more hydroxyls, an imidazolyl radical, a pyrrolinyl radical optionally substituted with a C1-C2 alkyl group; R 9 is a hydrogen or a C 1 -C 4 alkyl radical optionally substituted by a hydroxysulfonyl radical; R 10 represents a hydrogen or a C 1 -C 4 alkyl radical; R 9 and R 9 may form together with the to which they are attached, a saturated 5-membered heterocycle; - R12 represents: * a hydrogen atom * a C1-C6 alkyl radical, preferably substituted by one or more hydroxyl, thiol, (C1-C4) alkylthio, amido, amino groups, a phenyl radical, optionally substituted with one or several hydroxyl groups, an indolyl radical optionally substituted with one or more hydroxyls, an imidazolyl radical or a pyrrolinyl radical optionally substituted with a C1-C12 alkyl group; X represents a sulfur or nitrogen atom. According to a particular variant, R 9 and R 12 may optionally form a saturated carbon ring with 5, 6, 7 members. In the case where X represents a nitrogen atom and R12 represents an alkyl radical defined as above and very particularly an amino acid residue and / or their corresponding methyl or ethyl ester chosen from alanine, arginine, asparagine, aspartate, cysteine, glutamate, glutamine, glycine, histidine, lysine, methionine, phenylalanine, proline, pyrrolysine, serine, threonine, tryptophan, tyrosine, valine, leucine, isoleucine, the compound of formula (IIIc) represents a dipeptide, an oligopeptide. By way of examples of compounds of formula (IIIc), mention may be made of the following compounds, their salts, their hydrates, their optical or geometrical isomers, their enantiomers: 3-amino-dihydrothiophene-2-one; DL homocysteine thiolactone; DL-leucyl-DL-alanine, aspartame; (S) -pyrrolidine 2 carboxamide; [N - (- acetamido)] 2-aminoethanesulfonic acid, DL-Alanyl-DL-phenylalanine; 2- (2-aminoacetamido) -3- (4-hydroxyphenyl) propanoic acid; 2- (2-aminoacetylamino) -acetic acid; (R) -3-aminoazepan-2-one; glycinamide; L-Leucine amide; 2-aminopropane diamide; 2- (2-amino-3-methylbutanamido) propanoic acid; L-tyrosyl-L-alanine; L-valyl-L-phenylalanine; sarcosyl-L-phenylalanine; L-tyroyl-beta-alanine; glycyl-L-proline; glycyl-DL-valine; 2-aminomalonamide; L-methionamide; 2-amino-3-methylbutanamide; D-alaninamide; L-tyrosinamide; the amide of aspartic acid; L-tyrosine lamide; L-arginine amide; lysine amide; threonine amide; the isoleucine amide; histidine lamide; DL amide, alanine; 2-amino-3- (4-hydroxyphenyl) propionamide; DL-triptophanamide; N-hydroxy-L-arginine acetate (H-ARG-NH 2 2 AcOH); asparagine amide; alpha-diamide hydrochloride, L-glutamic acid gamma; D-phanylalanine amide; D-leucinamide; L-glutamic acid alpha-amide; L-methionineamide; L-cystine bisamide; glycinamide acetate; D-lysine amide; glycinamide; the gamma-methyl ester of L-isoglutamine; D-arginine lamide; (S) pyrrolidine carboxamide; prolyl histamine, or mixtures thereof. Amino compounds of general formula (IIId): R17 (IIId) Formula (IIId) in which: R13, R14, R15 and R16 represent, independently of one another: a hydrogen atom, a C 1 -C 20 hydrocarbon-based radical, linear, branched and / or cyclic, saturated and / or unsaturated, which may contain from 1 to 5 carbon-carbon double bonds, optionally aromatic, optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C = S, SO, SO 2 or combinations thereof, optionally carrying at least one hydroxyl or alkoxy group at 01-02, said alkyl radicals R13 and R14 or R14 and R15 or R15 and R16 may optionally form with the carbon atom to which each is attached, a 5- or 7-membered saturated or unsaturated heterocycle, optionally substituted as indiq ué previously, optionally aromatic, optionally comprising another heteroatom identical or different from nitrogen; the alkyl radical having no nitro, nitroso, peroxo or diazo function; more particularly an optionally substituted C1-C10 alkyl radical; and preferably, a linear or branched C 1 -C 8 alkyl radical optionally substituted by at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups, a hydroxycarbonyl radical, an ureido radical or an alkoxy (C 1 -C 4) carbonyl radical; an unsubstituted phenyl radical; X represents a nitrogen, oxygen or sulfur atom. R 17 represents: a hydrogen atom, a linear or branched, saturated or unsaturated C 1 -C 18 hydrocarbon radical and optionally comprising one to five conjugated or unsubstituted carbon-carbon double bonds, optionally substituted as indicated above, optionally interrupted by one or a plurality of heteroatoms and / or one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO, SO2 or combinations thereof; the alkyl radical having no nitro, nitroso, peroxo or diazo function; more particularly R 17 represents a hydrogen, a C 1 -C 10 alkyl radical, linear or branched, optionally substituted; and preferably, hydrogen, a linear or branched C1-C4 alkyl radical optionally substituted by at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups; - R18 represents: * a hydrogen atom * a linear or branched C1-C8 alkyl radical optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO, SO2 or combinations thereof, optionally carrying at least one hydroxyl group or C1-C2 alkoxy; the alkyl radical having no nitro, nitroso, peroxo or diazo function, o is an integer between 0 and 5. According to another variant of the invention, the radicals R16 and R17 may optionally form with the carbon atom for R16 and the X atom for the radical R17 to which each is attached, a 5- or 6-membered, saturated or unsaturated heterocycle, optionally substituted as indicated above, optionally aromatic, optionally comprising another heteroatom identical to or different from nitrogen. According to another variant of the invention, the radicals R18 and R15 may optionally form, with the nitrogen atom for R18 and the carbon atom for the radical R15 to which each is attached, a 5- or 6-membered heterocycle, saturated or unsaturated, optionally substituted as indicated above, optionally aromatic, optionally comprising another heteroatom identical to or different from nitrogen. By way of examples of compounds of formula (IIId), mention may be made of the following compounds, their salts, their hydrates, their optical or geometrical isomers, their enantiomers, if they exist: the amide of L-2 acid amino hexane; L-phenylalanine amide; (S) (+) aminosuccinic acid; (R) -2- (methylamino) succinic acid; ethyl nipecotate; the carboxylic acid 3-piperidine; 3-phenyl-beta-alanine; ethyl-3-aminobutyrate; 2-carboyethylamine; DL betamino adipic acid; beta-alanine ethyl ester; 3-amino-3-ureido-N-butyric acid ethyl ester; dimethyl (S) -aminosuccinate; beta-L-alanine methyl ester; 4-carboxyyethoxypiperidine; 4-aminobutyric acid; DL-beta-amino adipic acid; 4- (methylamino) butyric; ethyl-gamma-aminobutyrate; hexahydronicotinamide; 4-carboxamide piperidine; 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine; or their mixtures. o Amino compounds of general formula (IIl) R15R16 R19 N (H), R18 'R14 Pe0 R19 o (Ille) Formula (IIle) in which: - R13, R14, R15, R16 and R18 have the same meaning as above. - R19 represents: * a hydrogen atom * a linear or branched C1-C8 alkyl radical optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO, SO2 or combinations thereof, optionally carrying at least one hydroxyl group or C1-C2 alkoxy; the alkyl radical having no nitro, nitroso, peroxo or diazo function, - p is an integer between 0 and 7. - u is an integer equal to 1 or 2. When u is 2 then the radical R 18 represents a hydrogen; - r is 0 or 1, being extended that when u is 1 then r is 1 and when u is 2, then r is 0; According to another variant of the invention, the radicals R13 and R14 may optionally form, with the carbon atom for R13 and R14 to which these substituents are attached, a saturated 5- or 6-membered heterocycle. By way of examples of compounds (III), mention may be made of the following acids, their optical isomers, geometric isomers, their enantiomers if they exist, and their salts, their hydrates: (1-aminoethyl) phosphonic acid, (aminomethyl) phosphonic acid (1-aminoethyl-1-cyclohexyl) -phosphonic, (1-aminopropyl) phosphonic, (1-aminobutyl) -phosphonic, imino-bis (methylphosphonic), (1-amino-2-methylpropyl) -phosphonic, (1- amino-2-phenylethyl) phosphonic acid, (1-amino-1-methylethyl) -phosphonic acid, (1-amino-3-methylbutyl) phosphonic acid, 1-amino-benzyl phosphonic acid, 1-amino hexyl phosphonic acid, diethyl (aminoethyl) phosphonic acid (in particular salt oxalate), tetraethyl (aminomethylene) bisphosphonic acid (in particular its salts), (1-amino-2,2-dimethylpropyl) phosphonic acid, N-methyl aminomethyl phosphonic acid, (1-aminopentyl) phosphonic acid, (1-amino -2-methylbutyl) phosphonic acid, (1-Aminoctyl) phosphonic acid, (1-amino-1-methylpropyl) phosphonic acid, (1-amino-1,2-dimethylpropyl) phosphine honic, (1-amino-1,3-dimethylbutyl) phosphonic acid, (1-amino-1-methylbutyl) phosphonic acid, (1-amino-1-cyclopentyl) phosphonic acid, (1-amino-hydroxycarbonyl) propyl phosphonic acid (1-amino-1-methylethyl) phosphonic acid, 1-amino-2-methyl-butyl phosphonic acid, 1-phosphono-2-phenylethylamine, (aminomethyl) phosphonic acid, 3-aminopropyl phosphonic acid 2-amino-2-methyl-4 phosphonobutane and their ethyl esters, (diethyl (3-aminopropyl) phosphonic acid (in particular oxalate salt), 3- (N-hydroxyamino) propyl phosphonic acid '2-amino-2-methyl-4-phosphonobutyric acid, (3-aminopropyl) diethyl ester ) phosphonic, 2-amino-4-phosphonobutyric, 2-aminoethylphosphonic, 2-amino-3-phosphonopropionic, (2-aminoethyl) phosphonic diethyl ester, diethyl (2-aminoethyl) phosphonic acid, (2 - ((2-pyrrolidinyl) carbonyl) amino) ethyl) phosphonic acid, (2-amino-1-methyl-2-phenyl) ethyl phosphonic diethyl ester, (2-amino-2-phenyl) ethyl phosphonic acid diethyl ester, or mixtures thereof. Amino compounds of general formula (IIIf): R1, Formula (IIIf) in which: R13, R14, R15, R16 and R18 have the same meaning as above; In addition, the radicals R13, R14, R15 and R16 independently of each other may also represent a hydroxyl radical, a (C1-C4) alkoxycarbonyl radical, a carboxaldehyde radical or a (C1-C3) alkoxy radical; q is an integer incusitively between 1 and 18; X represents, an oxygen atom, or sulfur, a methylene group optionally substituted by a hydroxyl radical; it being understood that when X represents an oxygen atom, then R18 forms a 5- or 6-membered ring optionally substituted with one or more hydroxy (methyl), preferably from 1 to 4, hydroxy (methyl) groups. According to another variant of the invention, the radicals R16 and R18 OR R13 and R18 may optionally form with the carbon atom for R16 (or for R13) and the nitrogen atom for the radical R18 to which each is attached, a 5- or 6-membered saturated or unsaturated heterocycle, optionally substituted as indicated above, optionally aromatic, optionally comprising another heteroatom identical to or different from nitrogen. According to another variant of the invention, the amine of formula (IIIf) may contain a 13-aminoalcohol resulting from the reduction of the acid or ester function to alcohol of one of the twenty esterified or non-esterified amino acids. By way of examples of compounds (IIIf), mention may be made of the following compounds, their optical, geometric isomers, their enantiomers if they exist, as well as their salts, their hydrates: isopropanolamine, isopropylamine, methylethanolamine, methylglucamine, stearamine, tromethamine, promethazine, 1,3-dimethylpentylamine, octodrine, spermidine, theanine, octamylamine, 2-amino-1-phenylpropane-1,3-diol, 1,3-dihydroxy-2-amino-2-methylpropane, 2- amino-2- (hydroxymethyl) propane-1,3-diol tris, 2-amino-1,3-dihydroxy-2-ethylpropane, 2-amino-3-methylbutan-1-ol, 2-amino-2-methylpropan 1-ol, phenylglycinol, 2-aminopropyl alcohol, 2-hydroxyethylamine, 2-aminohexan-1-ol, 1-amino-1-cyclopentanemethanol, histidinol, 2-amino-3- (3-indolyl) propanol, 3- ( 4-hydroxyphenyl) -2-amino-1-propanol, beta-aminoisobutanol, 2-amino-1-propanol, 2-amino-1,3-propanediol, 2-amino-4-methyl-1-pentanol, 1-butanoic acid 2-amino-3-methyl, beta-amino benzenepropanol, 2-aminopropan-1-ol, 2- amino-1-butanol, 2-amino-4-methylpetan-1-ol, 3-aminopropanethiol, ethyl-2-amino-4-mercaptobutanoate, 6-hydroxyhexylamine, beta-D-galactopyranosylamine, B-Dglucopyranosylamine, 1-amino-2 , 5-anhydro-D-mannitol, 1-amino-1-deosy-D-fructose, D-glucosamine, 2-pyrrolidinemethanol, 1-amino-2,3-dihydroxypropane, 3-propanolamine, 3 - [(2-hydroxyethyl) ) amino] propan-1-ol, di-beta-hydroethylamine, bis (3-hydroxypropyl) amine, N-2'-aminoethyl-N-propanolamine, 4-amino-N-butyl alcohol, methyl 3-amino-3- deoxy-AD-mannopyranoside, N-butyl-4-hydroxybutylamine, 4-amino-4- (3-hydroxypropyl) -1,7-heptanediol, 1-hexylamine, 1-octylamine, 1-nonylamine, 1-decylamine, laurylamine, 1-tetradecylamine, 1-hexadecylamine, 3-amino-2-hydroxypropionic acid, 3-amino-2-hydroxy-4-phenylbutandic acid, 4-amino-3-hydroxybutyric acid, ethyl 4- hydroxy-2-pyrrolidinecarboxylate and mixtures thereof. Amino compounds of general formula (IIIg): (IIIg) Formula (IIIg) in which: R13, R14, R15, R16 and R18 have the same meaning as above. R20 represents a linear C1-C4 alkyl radical; a linear C1-C4 alkoxy radical; o is an integer between 0 and 5. v is an integer equal to 1 or 2. When v is 2, then R18 represents a hydrogen; - r is 0 or 1, being extended that when v is 1 then r is 1 and when v is 2, then r is 0. Examples of compounds (111g) include aminopropyl triethoxysilane, (aminomethyl) trimethylsilane 2- (trimethylsilyl) ethanamine, 3- (trimethylsilyl) propan-1-amine, 4- (triethoxysilyl) butan-1-amine, N43- (trimethoxysilyl) propyl] ethylene diamine, 3- (trimethoxysilyl) propylamine, 3- triethoxysilyl-1-propanamine, (3-methylaminopropyl) trimethoxysilane, and mixtures thereof. Amino compounds of general formula (IIIh): embedded image in which R 13, R 14, R 15, R 16 and R 18 have the same meaning as above. furthermore, the radicals R 13, R 14, R 15 and R 16 independently of each other may also represent a hydroxyl radical, a (C 1 -C 4) alkoxycarbonyl radical, a carboxaldehyde radical or a C 1 -C 3 alkoxy radical; R21 and R22 represent independently of one another: a hydrogen atom, a linear, branched and / or cyclic, saturated and / or unsaturated C 1 -C 20 hydrocarbon radical which may contain from 1 to 5 double bonds; carbon-carbon, optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C = S, SO, SO2 or combinations thereof, optionally carrying at least one gro hydroxyl or C 1 -C 2 alkoxy, more particularly C 1 -C 10 alkyl, optionally substituted; and preferably, a linear or branched C1-C4 alkyl radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups; - R21 and R22 may optionally form with the nitrogen atom to which they are attached, a 5- or 7-membered heterocycle, saturated or unsaturated, optionally substituted as indicated above, optionally aromatic, optionally comprising another heteroatom identical to or different from the 'nitrogen; the alkyl radical having no nitro, nitroso, peroxo or diazo function, - w is an integer between 1 and 10.

According to another variant of the invention, the alkyl radicals R16 and R21 may optionally form with the carbon atom for R16 and the nitrogen atom for the radical R21 to which each is attached, a 5- or 6-membered heterocycle, saturated or unsaturated, optionally substituted as indicated above, optionally aromatic, optionally comprising another heteroatom identical to or different from nitrogen. According to another variant of the invention, the alkyl radicals R18 and R21 may optionally form with the first nitrogen atom for R18 and the last nitrogen atom for the radical R21 to which each is attached, a heterocycle comprising from 5 to 14-membered, saturated or unsaturated, optionally substituted as indicated above, optionally aromatic, optionally comprising another heteroatom identical to or different from nitrogen. Among the compounds of formula (IIIh), mention may be made of the amines below, their optical isomers, their geometrical enantiomers, if they exist, as well as their salts and their hydrates: gerenterine, N [3-aminopropyl] -1, 4-butanediamine, 1,4-butanediamine, 4- (ethylamino) -N-butylamine, 243- (2-hydroxy-1,1-bishydroxymethyl-ethylamino) -propylamino] -2-hydroxymethyl-1,3-propane Diol, 1,4,8,11-tetraazacyclotetradecane, 1,4-diazacycloheptane, 1,3-diamino-2-hydroxypropane, N, N'-bis (2-aminoethyl) propane-1,3-diamine, 3- methylamino propylamine, 1,3-bisamino propane, N, N'-dimethyltrimethylenediamine, 2,2-dimethyltrimethylenediamine, 2,2-dimethyl-1,3-diaminopropane, N- (2-hydroxyethyl) -1,3-diaminopropane, N- (2-hydroxyethyl) -1,3-diaminopropane, cystamine, 1,5-diaminopentane, 1,6-diaminohexane, lauraminopropylamine, 2-methylheptylamine (2- (N-methyl) heptylamine), ethylenediamine, N, N- bis (2-hydroxyethyl) ethylenediamine, 3-aminoalanine, 2-piperazine boxylic acid, beta-N-methylamino-alanine, the methyl ester of piperazine-2-carboxylic acid, ethyl 3-amino-prolinate, 2,4-diamino-N-butyric acid, N [3- ( trimethoxysilyl) propyl] ethylenediamine or mixtures thereof. The amino compounds of general formula (IIIi) and / or (IIIi '): NH2 Y (R2) x, O10 Formulas (IIIi) and / or (IIIi') in which: R23 and R24 independently represent one of the other: an optionally substituted C1-C6 alkyl radical, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, SO, SO2 or combinations thereof; the alkyl radical having no nitro, nitroso, peroxo or diazo function; an alkylcarbonyl radical (R-O-) in which R represents a C 1 -C 4 alkyl radical. an alkylsulphonyl radical (RSO 2 -) in which R represents a C 1 -C 4 alkyl radical. a (di-) (alkyl) aminosulphonyl radical ((R) 2 N -SO 2 -) in which the radicals R independently represent a hydrogen or a C 1 -C 4 alkyl radical. a radical (di-) (alkyl) aminocarbonyl (R) 2N-O-) in which the radicals R independently represent a hydrogen or a C 1 -C 4 alkyl radical. a halogen atom preferably chosen from bromine, chlorine or fluorine. a C1-C4 alkoxy group; a (poly) hydroxyalkoxy group at 02-04; a hydroxycarbonyl group (HO-00-) * an alkoxycarbonyl group (R0-00-) in which R represents a C 1 -C 4 alkyl radical, * an alkylcarbonylamino group (RCO-NR'-) in which the radical R represents a C1-C4 alkyl radical and the radical R 'represents a hydrogen atom or a C1-C4 alkyl radical; an alkylsulphonyl radical (RSO 2 -) in which the radical R represents a C 1 -C 4 alkyl radical; - Y represents a carbon or nitrogen atom - z, z ', z "represents independently of each other a carbon atom, a nitrogen atom or a nitrogen atom substituted by a hydrogen - x is an integer between 0 and 2, when x is less than 2, the unsubstituted carbon atom (s) bear (s) a hydrogen atom - x 'is an integer equal to 0 or 1, when x' is less than 1, the unsubstituted carbon atom (s) carries (s) a hydrogen atom.

Among the compounds of formula (IIIi) and / or (IIIi '), mention may be made in particular of the compounds listed below, their optical isomers, geometric, their enantiomers if they exist, as well as their salts, their alpha hydrates, pyridylamine, 2-amino-3-hydroxypyridine, 2-amino-nicotinic acid, 2-amino-3-methylpyridine, 6-methoxy-3-pyridylamine, 3-aminopyridine, 3-amino-4-pyridinylamine, 2,5-aminopyridine, gamma-pyridylamine, 2,3-dimethyl-pyridine-4-amine, amino (4-) salicylic acid, methylpara-amino benzoate, benzocaine, aminobenzoic acid, 4-amino-M-anisic acid, 4-amino-3-acid hydroxy-benzoic acid, 3,4-diaminobenzoic acid methyl ester, methyl 4-amino-3-methoxybenzene carboxylic acid, 2-aminoanisole-4-carboxylic acid, 3-amino-4-hydroxy-benzoic acid, 3-Aminobenzoic acid ethyl ester, 1-amino-3-carboxybenzene, 2-aminobenzoic acid methyl ester, ethyl anthranylate, 1H-pyrazol-3-ylamine, 3-amino-4 - vs arbethoxy-1H-pyrazole, 5-amino-1-ethyl-pyrazole, 1H-benzoimidazol-2-amine, 2-imidazolamine, 1-methyl-benzoimidazol-2-amine, and mixtures thereof. It is also possible to use the following amines, in the form of salts or not, lauroyl ethylenediamine, octopamine, oleamine, palmitamine, 2- (2-aminoethoxy) ethanol, 2-amino-4,5-dimethylthiazole, hexetidine, mecamylamine, tranylcypromine, triamterene, methyl [2- (3-trimethoxysilylpropylamino) ethylamino], bis (triethoxysilylpropylamine, N1- (3- (trimethoxysilyl) propyl) hexane-1,6-diamine, diethylene triaminopropyl trimethoxy silane, N- (3-triethoxysilylpropyl) ethylene diamine, N- (3-trimethoxysilylethyl) ethylenediamine According to another variant of the invention, the amine or amines are chosen from amino polymers, as well as their addition salts Amino polymer is understood to mean macromolecules having a or several primary or secondary amine functions, comprising at least 5 repeating units linked by covalent bonds The amino polymer may be synthesized: by radical reactions (polyacrylates, polymethacrylates, polyvinyl ...), - by condensation reactions (polyesters, polyethers, polyamides, polyurethanes, polydimethylsiloxanes, polypeptides, etc.) - by ring opening reactions (polyesters, etc.). It can be of natural origin, chemically modified or not, such as for example oligosaccharides, polysaccharides (cellulose, dextran, chitosan, guar and their amino or thiolated derivatives, polymers can be in any type of topology: linear chain, branched, star-shaped or hyperbranched (like dendrimers for example), sequenced, random or alternating chains Chemical groups can be naturally present on the polymer chain, at the end of the chain, grafted along the main chain or secondary chains, on the branches of star-shaped or hyperbranched polymers, the following are particularly preferred: 1 / polyamides containing free OH, or SH or COOH groups, in addition to NH 2 groups, for example polylysine 2 / oligosaccharides, natural or modified polysaccharides having NH2 functions and optionally SH 3 / amino silicones 4 / synthetic polymers with NH 2 or SH functional groups, in particular vinyl polyvinyls substituted by an amine function and polymers made from commercial monomers, as well as their mineral or organic acid salts, hereinafter: ## STR2 ## NH 2 NH 2 NH 2 NH 2 and in particular from polylysine; chitosan; polyethoxylated amines, such as carboxyPEG8 amine, carboxyPEG12 amine, carboxyPEG24 amine; or their combinations. According to another variant of the invention, the amine or amines are chosen from purine bases, in particular chosen from adenine, adenosine, guanine, guanosine G, thymine, thymidine T, uracil, uridine U, cytosine, cytidine C, their addition salts, and combinations thereof. It would not be outside the scope of the invention by combining several of these variants. Preferably, if the composition is used in the presence of one or more amines, the latter are chosen from ammonia, the compounds of the formulas (IIIa), (IIIb), (IIIc), (IIle), ( 111f) (111g) in particular when R20 is a C1-C4 linear alkoxy group, (1110, or mixtures thereof.

Even more preferably, the methyl, ethyl esters of the compounds of formula (IIIb), amino acids (IIIa) (III), (IIIf) (IIIg) and amino polymers such as polylysine and amine-functional oligosaccharides are used. According to an even more advantageous embodiment, mention may be made of compounds of formulas (IIIa), (IIIb) (methyl, ethyl esters), (IIIf) (IIIg) and amino polymers such as polylysine. If the composition is used in the presence of one or more primary or secondary amines, ammonia, hydroxylamine, their content represents in the composition between 0.001 and 65% by weight; and preferably between 0.001 and 30% by weight, based on the weight of the composition. Aldehyde or imine compound According to another embodiment of the invention, the composition is used in the presence of at least one compound chosen from the following formulas (a) and (b) below, their optical isomers or geometric, their organic or inorganic acid salts, their solvates, as well as the oxidized oligo- or polysaccharides comprising at least one aldehyde or imine function: R ', -2 (a) (b) Formulas (a) and (b) in which: - m is an integer of 0 or 1. - X represents an oxygen atom, NR "i with R" 1 representing a hydrogen atom, a C1-C10 alkyl radical; when X represents an oxygen atom, the compounds may also be: in the form of cyclic acetal with 5 or 6-membered or acyclic ring resulting from the condensation of an additional primary monoalcohol (R'30H) in which R 3 represents a C1-C5 alkyl radical or a symmetrical 1,2- or 1,3-diol having a C2-C3 alkyl chain. 0 in the form of hemiacetal resulting from the condensation of a hydroxyl group present on A or A1 when A or A1 represents an alkyl radical and when n is 0; - The radicals R'1 and R'2, independently of one another represent a hydrogen atom, an unsubstituted linear C1-C6 alkyl radical; the monovalent and divalent A radicals represent a group chosen from: a hydroxycarbonyl group (-CO-OH), a C6 aryl group optionally substituted by at least: a hydroxyl group, a C 1 -C 4 alkyl radical; - an aryl-ethylenyl radical, the aryl group being at 06 and optionally substituted by at least one alkyl radical at 01-02, alkoxy at 01-02, - a group -00-OR'4 or -O-COR'4 where R'4 represents a C1-C2 alkyl radical, a phenyl group; a -COOH group, in acid or salified form, a group -OR'5 in which R'5 represents a C1-C8 alkyl radical optionally substituted by at least one hydroxyl group, an ammonium group -N + R "8 with R "8, identical or not, representing a C1-C2 alkyl radical, a group -SiR'7 with R'7, identical or different, representing a C1-C12 alkyl radical; a benzyl radical (-OH 2 -O61-16), - according to a particular variant, two radicals -OR '5 located in ortho of the aryl group at 06 can form a 5- or 6-membered heterocycle via the two radicals R' A group -N (R'8) 2 in which R'8, which may be identical or different, represents a C1-C8 alkyl radical optionally substituted by a hydroxyl, carboxylic (-000H) group in acid or salified form, or sulphonic acid (- S031-1) in acid or salified form; the radicals R'8 may optionally form a 5- or 6-membered heterocycle with the nitrogen atom which carries them, saturated or not, optionally comprising another heteroatom selected from O, N, NR'9 where R'9 represents a C1-C₂ alkyl radical; the heterocycle being optionally substituted by a hydroxyl group, a -COR'10 group in which R'10 represents a 6-membered aryl group fused to a 6-membered hydrocarbon ring, optionally substituted by at least one C 1 -C 2 alkyl radical, one in which R '11 represents a C1-C2 alkyl radical, a halogen atom preferably chosen from chlorine, bromine, a -O-SO2-061-16 group, a -SO31-1 group, a unsaturated, cationic or non-cationic 5- or 6-membered heterocycle comprising one or two heteroatoms, selected from O, N, NR'12 wherein R'12 represents a C1-C2 alkyl group, optionally fused to a 5- or 6-membered ring linkages, saturated or unsaturated, aromatic or not, one of the heteroatoms possibly being included in both rings; the heterocycle or the fused ring may be substituted by at least one C1-C2 alkoxy radical - said aryl group being optionally fused to a 5- or 6-membered heterocyclic group, comprising one or two heteroatoms selected from O, N, NR '; Wherein R'13 represents a C 1 -C 4 alkyl radical, the heterocycle being optionally fused to an aryl group at O 6 - said aryl group being optionally fused to a 6-aryl group optionally substituted with at least one alkoxy group at 0- 02; a 5- or 6-membered cationic or non-cationic heterocyclic group, unsaturated or unsaturated, aromatic or non-aromatic, comprising one or two heteroatoms, which may be identical or different, chosen preferably from O, N, NR '14 with R' 14 representing a hydrogen atom, a C1-C6 alkyl radical or a 6-aryl radical optionally substituted by a group (R'15) 2N00- or (R'16) OO-NHoù R'16, which may be identical or different, represent an alkyl radical in 01 -02; said heterocyclic group being optionally fused to a 6-membered aryl group which is itself optionally substituted with at least one C1-C4 alkyl group and C1-C4 alkoxy; phenoxy; said heterocyclic group being optionally substituted by at least one hydroxyl group, a C1-C12 alkyl radical optionally substituted with a hydroxyl radical, or an amino radical -N (R'16) 2, where R'16, which may be identical or no, represent a C 1 -C 4 alkyl radical optionally substituted by a hydroxyl group, the R '16 radicals possibly being able to form a 5- or 6-membered heterocycle with the saturated or unsaturated nitrogen atom, optionally comprising a another heteroatom selected from O, N, NR '17 where R' 17 represents a C 1 -C 12 alkyl radical, a C 6 aryl radical optionally substituted with at least one -COOH group, R'1800NH- with R '18 representing a C1-4 alkyl radical; said aryl radical at 06 being optionally connected to a nitrogen atom of the heterocyclic group; When the aryl radical is not substituted by a previously mentioned radical, the carbon atoms are represented by a hydrogen atom; a linear or branched C1-C10 alkyl radical, or an alkenyl radical containing one or more carbon-carbon unsaturations, conjugated with each other or not; said alkyl or alkenyl radical being optionally substituted with at least one hydroxyl group; The divalent radical A2 represents a linear alkylene chain linking two A1 radicals via a carbon, oxygen or nitrogen atom; the compounds of formulas (i) and (ii) optionally comprising an anion An or a mixture of cosmetically acceptable anions, guaranteeing the electroneutrality of the formulas. According to a first variant of the invention, the compound or compounds of formulas (a) and (b) are such that X represents an oxygen atom. Compounds (a) and (b) may also be in the form of cyclic acetal with 5 or 6-membered or acyclic ring resulting from the condensation of an additional primary monoalcohol (R'30H) in which R'3 represents a radical C1-C5 alkyl or a symmetrical 1,2- or 1,3-diol having a 02-03 alkyl chain. These compounds may also be in the form of hemiacetal resulting from the condensation of a hydroxyl group present on A or A1 when A or A1 represents an alkyl radical and when n is O.

It should be noted that the electroneutrality of the formulas (a) and (b) is verified if necessary by means of an anion or a mixture of organic or inorganic anions making it possible to balance the charge (s) of said compounds, for example selected from a halide such as chloride, bromide, fluoride, iodide; a hydroxide; sulphate; a hydrogen sulfate; an alkyl sulphate for which the linear or branched alkyl part is C 1 -C 6, such as the methyl sulphate or ethyl sulphate ion; carbonates and hydrogen carbonates; salts of carboxylic acids such as formate, acetate, citrate, tartrate, oxalate; alkylsulphonates for which the linear or branched alkyl part is C 1-6 such as the methylsulphonate ion; arylsulphonates for which the aryl part, preferably phenyl, is optionally substituted by one or more C 1 -C 4 alkyl radicals such as, for example, 4-toluylsulfonate; alkylsulfonyls such as mesylate. The nonionic or anionic oxidized oligosaccharides or polysaccharides comprise one or more aldehyde groups and optionally one or more anionic groups. These anionic groups are preferably carboxylic or carboxylate groups. The oligosaccharides or nonionic or oxidized anionic polysaccharides used may be represented by the following formula (c): P- (CHO) m (COOX) n (c) in which: P represents an oligosaccharide or polysaccharide chain consisting of monosaccharides comprising at least 5 carbon atoms, preferably at least 6 carbon atoms and more particularly 6 carbon atoms.

X is chosen from a hydrogen atom, ions derived from an alkali metal or alkaline earth metal such as sodium, potassium, ammonia, organic amines such as monoethanolamine, diethanolamine, triethanolamine and 3-aminopropanedio1; -1,2 and the basic amino acids such as lysine, arginine, sarcosine, ornithine, citrulline, m + n is greater than or equal to 1, m is such that the degree of substitution of the oligosaccharide or the polysaccharide with one or more aldehyde groups (DS (CHO)) is in the range of from 0.001 to 2, preferably from 0.005 to 1.5. n is such that the degree of substitution of the oligosaccharide or polysaccharide by one or more carboxylic groups (DS (COOX)) is in the range from 0 to 2, preferably from 0.001 to 1.5. By degree of substitution DS (CHO) or DS (COOX) oligosaccharides or polysaccharides according to the invention means the ratio between the number of carbons oxidized to an aldehyde or carboxylic group for all the repeating units and the number of elemental monosaccharides ( even opened by preoxidation) constituting the polysaccharide. The CHO and COOX groups can be obtained during the oxidation of certain carbon atoms, for example in position 02, O3 or O6, of a saccharide unit 6 carbon atoms; Preferably, the oxidation may be O 2 and O 3, more preferably from 0.01% to 75% by number, and preferably from 0.1% to 50% by number of the cycles that may have been opened. The oligosaccharide or polysaccharide chain, represented by P, is preferably selected from among inulins, celluloses, starches, pectins, guar gums, xanthan gums, pullulan gums, alginate gums, agar gums and the like. agar, carrageenan gums, gellan gums, gum arabic, xyloses and gum tragacanth and their derivatives. By derivative is meant the compounds obtained by chemical modification of the compounds mentioned. It can be esters, amides, ethers of said compounds. The oxidation can be carried out according to a process known in the art, for example according to the process described in FR 2 842 200, in document FR2854161 or in the article "Hydrophobic films from maize bran hemicelluloses" of E. Fredon et al. Carbohydrate Polymers 49, 2002, pages 1 to 12. Another oxidation process is described in the article "water soluble oxidized starches by peroxide reaction extrusion" Industril Crops and Products 75 (1997) 45-52 - RE VVing, JL VVillet . These oxidation processes are simple to implement, are effective, do not generate toxic byproducts or difficult to eliminate. The peroxide may be a percarbonate or an alkali metal or alkaline earth metal perborate, an alkyl peroxide, peracetic acid or hydrogen peroxide. The amount of peroxide in the reaction medium is generally between 0.05 and 1 molar equivalent per glucose unit of the oligosaccharide or polysaccharide. A single phthalocyanine or a mixture of phthalocyanines, for example a mixture of Co phthalocyanine and Fe phthalocyanine, can be used as catalyst. The amount of catalyst depends on the degree of substitution desired. In general a small amount, for example, an amount corresponding to 0.003 to 0.016 molar equivalents per 100 glucose units of oligosaccharide or polysaccharide is suitable. The process can also be carried out by contacting the oligosaccharide or the polysaccharide in powder form with the catalyst dissolved in a small volume of water and with the peroxide. This process is referred to as a "semi-dry" process. More preferably, the oligosaccharide or polysaccharide is obtained by oxidation of inulin, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, starch, starch acetate, hydroxyethyl starch, hydroxypropyl starch, guar gum, carboxymethylguar gum. , carboxymethylhydroxypropyl guar gum, hydroxyethylguar gum, hydroxypropylguar gum, xylose or xanthan gum, carrageenan gum, or mixtures thereof. The oligosaccharides or polysaccharides most particularly preferred in the invention are those corresponding to the formula (c) in which P represents a polymer chain derived from inulin and starch; m is such that the degree of substitution of the oligosaccharide or polysaccharide by one or more aldehyde groups (DS (CHO)) is in the range of 0.005 to 2.5; n is such that the degree of substitution of the oligosaccharide or polysaccharide by one or more carboxylic groups (DS (COOX)) is in the range of 0.001 to 2. Preferably, the composition comprises at least one compound of formula (a). Advantageously, the formula (a) is such that: * m is 0 or 1 * the R'1 and R'2 radicals, independently of one another represent a hydrogen atom, a C1-C6 alkyl radical linear unsubstituted; X represents an oxygen atom A represents: a linear or branched C 5 -C 10 alkyl radical, optionally substituted with at least one hydroxyl group; * a C2-08 alkenyl radical comprising a carbon-carbon double bond * a hydroxycarbonyl group (-000H) * a 6-aryl group optionally substituted by at least: 0 a hydroxyl group, O a C1-C4 alkyl radical, a group -00-OR'4 or -O-COR'4 where R'4 represents an alkyl radical at 01-02, O a group -OR'5 where R'6 represents an alkyl radical at 01-06, 0 a aryl-ethylenyl radical, the aryl group being C6 and optionally substituted by at least one C1-C2 alkyl radical, C1-C20 alkoxy, an unsaturated 5- or 6-membered cationic or non-cationic heterocycle comprising one or two heteroatoms, chosen from O, N, NR'12 where R'12 represents a C1-C12 alkyl group, optionally fused to a 5- or 6-membered ring, saturated or unsaturated, aromatic or otherwise, one of the heteroatoms possibly being be included in both cycles; the heterocycle or the fused ring may be substituted by at least one C1-C2 alkoxy radical - said aryl group being optionally fused to a 5- or 6-membered heterocyclic group, comprising one or two heteroatoms selected from O, N, NR '; Wherein R'13 represents a C1-C4 alkyl radical; a 5- or 6-membered heterocyclic group, cationic or non-cationic, unsaturated or unsaturated, aromatic or otherwise, comprising one or two heteroatoms, identical or different, preferably chosen from 0, N, NR '14 with R' 14 representing a hydrogen atom, a C1-C6 alkyl radical, or a 6-aryl optionally substituted with a group (R'15) 2N00- or (R'15) CO-NH- where R'15 represent an alkyl radical; Cl-02; Said heterocyclic group being optionally fused to a 6-membered aryl group, itself optionally substituted with at least one C 1 -C 20 alkyl, C 1 -C 4 alkoxy radical; said heterocyclic group being optionally substituted by at least one hydroxyl group, a C1-C2 alkyl radical optionally substituted by a hydroxyl radical; O an amino radical -N (R'16) 2, where R'16, which may be identical or different, represents a C 1 -C 4 alkyl radical optionally substituted by a hydroxyl group, the radicals R'16 possibly being able to form a 5-membered heterocyclic ring; 6-membered ring with the saturated or unsaturated nitrogen atom, optionally comprising another heteroatom selected from O, N, NR'17 where R'17 is a C 1 -C 2 alkyl radical, compounds of formulas (a) optionally comprising an anion An or a cosmetically acceptable mixture of anions, guaranteeing the electroneutrality of the formulas; The compound (s) of formula (a) which can be in the form of acetal or hemiacetal, as described above. As examples of preferred compounds (a), mention may be made of the following compounds, their isomers, their salts and their solvates, these compounds being alone or in mixtures: 2,4,6 trihydroxybenzaldehyde, 2,3,4 trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, vanillin, ethyl vanillin, 4-formyl-1-methylquinolinium-4-methylbenzene sulfonate, oxyacetic acid, methyl 4-formylbenzoate, benzaldehyde, 3-phenylprop-2-enal, 2-hydroxy-5- (hydroxymethyl) -2-methylpyridine 4-carbaldehyde, 4-formyl-1-methylpyridinium, 1- (4-Formylphenyl) -6-methoxy-1-methylimidazo [1,2-a] pyridin-1-ium, 8-methyl-6- (morpholin-4-yl) quinoline-3-carbaldehyde, N44- (3-formyl-5,5-dimethyl-4,5-dihydro-1H-pyrazol-1-yl) phenyl] acetamide; 6-deoxyhexose, D-mannopyranose, D-glucose, D-galactose, D-fructose, 1,3-benzodioxole-5-carboxaldehyde, D-yyxopyranose, 3,7-dimethylocta-2, 6-Dienal, D-ribose, 4 - [- 2- (4-methoxy-2,3,6-trimethylphenyl) ethenyl] benzaldehyde, methyl-4- [-2-methyl-3-oxoprop-1-en 1-yl] benzoate, 4-formyl-2-methoxyphenyl acetate, 1H-indole-3-carbaldehyde, 1-butyl-1H-indole-3-carbaldehyde, 2-hydroxy-3,4-dimethoxy 6 -méthylbenzaldéhyde. More particularly, when they are present, the content of compound (s) of formula (a), (b), or of oxidized oligo- or polysaccharides comprising at least one aldehyde or imine function is between 0.001% and 30%. % by weight relative to the weight of the composition. As examples of preferred oxidized oligo- or polysaccharides, mention may be made of the following compounds: oxidized starch (Rn 9047-50-1), starch known under the following trade names: Caldas 10; Caldas 5; Caldas 5H; Caldas 5S; Caldas C 5; Caldas C 5GP; Caldas C 5GT; Caldas No. 5; DAS 100; Dialdehyde starch; Dialdehydostarch; Formamyl; Periodate starch; Polyaldehyde starch; Starch dialdehyde; Sumstar; Sumstar 150; Sumstar 190 - oxidized cellulose (Rn 9032-52-4) known under the names 2,3dialdehyde cellulose; 2,3-Dialdehydocellulose; Aldehydocellulose; Cellulose 2,3dialdehyde; Dialdehyde cellulose; Dialdehyde cellulose; oxidized inulin (Rn 82446-43-3) - dextran dialdehyde (Rn 37317-99-0). Nucleophilic compounds According to another embodiment of the invention, the composition is used in the presence of at least one nucleophilic compound chosen from compounds of the following formulas, their optical or geometrical isomers, their organic acid salts or mineral, their solvates: (R7) n R8 N R9 (c) wherein: * n is an integer from 0 to 4; the unsubstituted carbon atoms bearing a hydrogen atom * A represents -CRio-, -N-, -N + Ri- with R11 representing a C1-C4 alkyl radical X represents N, CR'7 and R'7 represents a hydrogen atom or R7 * R7, which may be identical or different, represent: a C1-C4 alkyl radical, a hydroxyl radical, a C1-C4 alkoxy radical, an amino radical or a C1-C4 alkylamino radical; ortho from each other may form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms selected from oxygen, nitrogen or their combination, R8, R10, identical or different, represent an atom of hydrogen, a hydroxyl radical, an amino radical or a C1-C4 alkyl radical optionally substituted with at least one -000R12 or -000R12 group with R12 representing a C1-C4 alkyl radical, a -COR13-group with R13 representing a radical; C1-C4 alkyl, - a group -000R14 or -000R14 with R14 representing a hydrogen atom, a radica C1-4 alkyl optionally substituted with at least one C1-4 alkoxy group; a group -OSO3- * R9 represents a hydrogen atom, a C1-C4 alkyl radical or a (C1-C4) alkylcarbonyl group; an acetyl radical R8 and R9 radicals may form a 5- or 6-membered heterocycle optionally comprising another heteroatom selected from oxygen, nitrogen or sulfur, said heterocycle may be further interrupted by a CO group, when A represents N, that n is 0, X represents CH, and R8 represents NH2, then R9 is neither a hydrogen atom nor a methyl group; Where: B (R15) n, C-R16. An R17, (e) * n is an integer from 0 to 4; unsubstituted carbon atoms carry a hydrogen atom * n 'is an integer from 0 to 2; the unsubstituted carbon atoms carry a hydrogen atom * A 'represents S, - (CR18) 2-, -CR19 = CR'19-, with R18, representing a hydrogen atom, a C1-C4 alkyl radical, R19, R'19, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical; B 'represents S * R15, which may be identical or different, represent a C 1 -C 4 alkyl radical, a halogen atom, preferably chlorine or a C 1 -C 4 alkoxy radical; R15, which may be identical or different, represents a C1-C2 alkyl radical. R16 represents a hydrogen atom or a C1-C4 alkyl radical; R16 represents a hydrogen atom or a C1-C4 alkyl radical; R17 represents a C1-C4 alkyl radical, optionally bearing a hydroxyl group. R17 represents: a hydrogen atom, a C1-C4 alkyl radical, optionally bearing a hydroxyl group, optionally interrupted by a CO group, optionally carrying a phenyl radical; R16 and R17 radicals may form together a 5- or 6-membered fused heterocycle, optionally having one or more unsaturations, optionally substituted with at least one C 1 -C 4 alkyl radical; In which * n 'is an integer ranging from 0 to 2, the unsubstituted carbon atoms carry a hydrogen atom * R 20, which may be identical or different, represent a C 1 -C 4 alkyl radical, a hydrogen atom or a hydrogen atom. halogen (preferably chlorine, bromine, iodine), a radical -000R21 or -000R21 with R21 representing a hydrogen atom, a C1-4 alkyl radical, an amino radical, an aryl group at phenyl) optionally substituted with at least one hydroxyl radical * X represents N, CR22, -CR'22-00-, CR'22 being connected to Y or X. * Y is N, CR "22 * R22, R" 22 , identical or not, represent a hydrogen atom, a linear or branched C 1 -C 4 alkyl radical optionally substituted by an amino radical, a benzyl radical, a phenyl radical, -000 R 23 or -000 R 23 R 23 representing a C 1 -C 6 alkyl radical; 04, -SOR24 wherein R24 represents an alkyl radical in n - 4 * R22 and R "22 may together form an aromatic 6-membered aromatic ring (R30), N R2 (R30) 1NNNN (R) O R29 (g ") (g) Formulas (g), (g '), (g"), (g-) in which: * Y is CH, CR27, N * z is N; z 'is N, NR "27 * q is an integer between 0 and 3 * r is 1 or 2 * s is 1 or 2 * t is an integer between 0 and 4 * u is 0 or 1 * the atoms of unsubstituted carbon heterocycles carry a hydrogen atom * R represents a hydrogen atom or a C 1 -C 4 alkyl radical, at least one of R radicals representing at least one hydrogen atom * R27 independently represent one of the others: a C1-C4 linear alkyl radical; a halogen selected from chlorine, bromine and fluorine; R27 represents a hydrogen atom, a linear C1-C4 alkyl radical or a phenyl radical; R 28 represents a hydrogen atom or a linear C 1 -C 4 alkyl radical; the R 27 radicals located in ortho of the NHR 28 and R 28 radical may together form a 5- or 6-membered heterocycle comprising 1 to 2 heteroatoms selected from oxygen and nitrogen. * if Y represents CR27, then q is preferably different from 0 * R29, which may be identical or different, represent a linear C 1 -C 4 alkyl radical, the two radicals R 29 which may together form a saturated 5-membered heterocycle, R 30 represent independently others a hydroxyl radical, an amino radical, a pyrrolidinyl radical * R31 represent independently of each other: - a C 1 -C 4 alkyl radical - a C 1 -C 4 alkoxy radical optionally substituted by a hydroxyl group - an optionally substituted amino radical by an acetyl group (-COCH3) * R "27 and R31 may form a 5- or 6-membered heterocycle having aromatic or non-aromatic optionally substituted by a C1-C4 alkyl radical; in the formula (g '), at least 1 one of the radicals R 31 is different from hydrogen and / or at least one is equal to 1; two radicals R 31 may together form an aromatic ring optionally substituted with an amino radical; mposés formulas (d) to (g-) comprising optionally an anion An or cosmetically acceptable mixture of anions, ensuring the electroneutrality of said formulas; as well as among oligomers or polymers of the polyallylimidazolium type. Preferably, the compounds of formula (c) are chosen from those in which: n is an integer ranging from 0 to 4; the unsubstituted carbon atoms carry a hydrogen atom, A represents -CRio-, -N-, X represents CR'7 and R'7 represents a hydrogen atom or R7 * R7, which may be identical or different, represents a radical; C1-C4 alkyl, a hydroxy radical, a C1-C4 alkoxy radical, an amino radical, a C1-C4 alkylamino radical, and two R7 radicals located ortho to one another may form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatom (s) chosen from oxygen, nitrogen or their combination, preferably oxygen, R8, R10, identical or not, represent - a hydrogen atom, - an alkyl radical in Cl -04 - a group -000R14 or -000R14 with R14 representing a hydrogen atom, a C1-C4 alkyl radical optionally substituted with at least one C1-C4 alkoxy group; R 9 represents a hydrogen atom, a C 1 -C 4 alkyl radical, when A represents N, n is 0, X represents CH, and R 8 represents NH 2, then R 9 is neither a hydrogen atom nor a methyl group. By way of examples of more particular compounds (c), mention may be made of the following compounds, their isomers, their salts, their solvates, these compounds being alone or in a mixture: 1-butyl-2-methyl-1H-benzimidazole 7-ol, 1H-benzimidazol-5-ol, 1H-benzimidazol-4-ol, 1H-benzimidazol-5,6-diol, 2-methyl-1H-benzimidazol-4-amine, 1.5 6-trimethyl-1H-benzimidazol-4-amine, 1H-benzimidazol-4-amine, 1H-benzimidazol-5-amine, 2-methyl-1H-benzimidazol-5-amine, 1H-benzimidazol-2,5,6-triamine 1H-benzimidazol-2,5-diamine, 4-amino-1H-benzimidazol-7-ol, 1H-indole-5,6-diol, 5H41,3] dioxolo [4,5-f] indole, Ethyl 5,6-dihydroxy-1H-indole-2-carboxylate, ethyl 6-hydroxy-1H-indole-2-carboxylate, 1H-indol-5-ol, 2-methyl-1H-indol 4-ol, 1H-indol-7-ol, 1H-indol-6-ol, 1H-indol-4-ol, 5-methoxy-1H-indole-2-carboxylic acid ethyl ester, 5- ethyl-1H-indole-2-carboxylate, 2-methyl-1H-indole-5,6-diol, 6-hydroxy-1H-indole-2-carbo acid xyl, 1H-indol-4-amine, 1H-indol-3-yl 3-methoxypropanoate, 1H-indol-6-amine, 1H-indol-7-amine, 1H-indol-5-amine, N-ethyl-1H-indol-6-amine. Preferably, the compound (s) are of formulas (d) and (e) such that: n and n are 0; the unsubstituted carbon atoms carry a hydrogen atom; * A 'represents S, - (CR18) 2-, with R18, representing a hydrogen atom, a C1-C4 alkyl radical; * B 'represents S * R16, represents a hydrogen atom, a C1-C4 alkyl radical; R16 represents a hydrogen atom or a C1-C4 alkyl radical; R17 represents a C1-C4 alkyl radical, optionally bearing a hydroxyl group. R17 represents: a hydrogen atom or a C1-C4 alkyl radical, optionally bearing a hydroxyl group; the radicals R16 and R17 may together form a fused 5- or 6-membered heterocycle, optionally having one or more unsaturations, optionally substituted with at least one C 1 -C 4 alkyl radical.

By way of examples of more particular nucleophilic compounds corresponding to formulas (d) or (e), mention may be made of the salts of the following compounds, their isomers, their solvates, these compounds being alone or in a mixture: 1,4- dimethylquinolinium, 1,2-dimethylquinolinium, 10,10-dimethyl-7,8,9,10-tetrahydro-6H-pyrido [1,2-a] indolium, 2,3-dimethyl-1,3-thiazol 3-ium, 3- (2-hydroxyethyl) -2-methyl-1,3-benzothiazol-3-ium. According to a particular variant, the compound or compounds are of formulas (f) such that * n 'is an integer ranging from 0 to 2, the unsubstituted carbon atoms carry a hydrogen atom * R20, which may be identical or different, represent a C1-C4 alkyl radical, a chlorine atom, a radical -000R21 or -000R21 with R21 representing a hydrogen atom, a C1-C4 alkyl radical, an amino radical, a phenyl group * X represents N, CR22, CR'22 being connected to Y or X. * Y represents N, CR "22 * R22, R" 22, which may be identical or different, represent a hydrogen atom, a linear or branched C1-C4 alkyl radical optionally substituted with an amino radical, a benzyl radical, a phenyl radical, - * R22 and R "22 may together form an aromatic 6-membered fused ring, and in the case of the more particular nucleophilic compounds of formula (f), by way of example, the following compounds, their isomers, their salts, their solvates, these compounds either alone or in mixtures: 1H-imidazo [1,2-b] pyrazole, 3,6-dimethyl-1H-pyrazolo [5,1-c] [1,2,4] triazole, 2- Methyl-4H-pyrazolo [1,5-a] benzimidazole, 7-chloro-2,6-dimethyl-1H-pyrazolo [1,5-b] [1,2,4] triazole, 7-chloro-3 6-dimethyl-1H-pyrazolo [5,1-c] [1,2,4] triazole, 6-ethyl-3-methyl-1H-pyrazolo [5,1-c] [1,2], 4] triazole, 3,6-diethyl-1H-pyrazolo [5,1-c] [1,2,4] triazole, 3-ethyl-6-methyl-1H-pyrazolo [5,1-c] [1,2,4] triazole, 3-phenyl-1H-pyrazolo [5,1-c] [1,2,4] triazole 6-carboxylate, 3-phenyl-1H-pyrazolo [5.1 -c] [1,2,4] triazol-6-yl) methanol, 6-ethyl-3- (propan-2-yl) -1H-pyrazolo [5,1-c] [1,2,4] triazole, 3,6-dimethyl-1H-pyrazolo [5,1-c] [1,2,4] triazol-7-amine, 1H-imidazol [1,2-b] pyrazol-7-amine 2- (7-Chloro-6-methyl-1H-pyrazolo [1,5-b] [1,2,4] triazol-2-yeropan-1-amine, 2-methyl-4H-pyrazolo [1] , 5-a] benzimidazol-3-amine. With respect to the nucleophilic compound (s) of formula (g), (g '), (g "), (g"), the following compounds, for example, their isomers, their salts, their solvates, these compounds being alone or in mixtures: 3-amino-1H-pyrazol-5-ol, N- (5-hydroxy-1-phenyl-1H-pyrazol-3-yl) acetamide, 3- Methyl-1H-pyrazol-5-ol, 5- (pyrrolidin-1-emidazo [1,2-a] pyridin-8-amine, 2-methyl-2H-indazole-3,5-diamine, 2 3-Diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 3-amino6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 4-amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-3H-pyrazol-3-one, 4,5-diamino-1,2- diethyl-1,2-dihydro-3H-pyrazol-3-one, 3-amino-2-chloro-6-methylphenol, 3,4-dihydro-2H-1,4-benzoxazin-6-ol, 2- (3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethanol, 2-aminopyridin-3-ol, The oligomers or nucleophilic polymers are chosen from polymers of type of polyallylimidazolium, no especially those made from 1-allyl-3-butylimidazolium. Preferably, the carbonyl compound (s) are chosen from the compounds of formulas (c), (f), (g), (g '), (g "), (g-) or mixtures thereof. they are present, the content of compound (s) of formula (s) (c) to (g-) or oligomers or nucleophilic polymers is between 0.001% and 30% by weight relative to the weight of the composition. carbonyl nucleophiles According to another embodiment of the invention, the composition is used in the presence of at least one carbonophilic nucleophilic compound chosen from compounds of the following formulas (h) to (I), their optical or geometric isomers their salts of organic or inorganic acid, their solvates: A (h) Formula wherein: A represents: Ra Ra Ra A'1 Ra B represents: Ra * n is 0 or 1; m is 0 or 1; * Ra , which may be identical or different, represent a hydrogen atom, a Ci-Ca alkyl radical; Rb represents a hydrogen atom, an acetyl group (CH 3C0-), one of the two Rb radicals representing a hydrogen atom, or two Rb radicals representing a phenyl-methylenyl group, the phenyl radical being optionally substituted with at least one hydroxyl, C1-C4 alkoxy radical; * A1, B1, A'1, B'1, identical or not, represent; A C 6 aryl group optionally substituted with at least one linear or branched C 1 -C 20 alkyl radical; a hydroxyl radical; an alkoxy -O R 1 radical in which R 1 represents a C 1 -C 4 alkyl radical optionally substituted by a hydroxyl group; a If (R 2) (O Si (R 3) 3) 3 Ot 1 R 2, R 3, which may be identical or different, represent a C 1 -C 4 alkyl radical, preferably an -R 4 R 4 ester group where R 4 represents a phenyl radical or an ammonium group; W (R 5) 3 where R 5, which may be identical or different, represents a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group, a halogen atom, preferably chlorine - optionally fused to a 5- or 6-membered heterocycle, unsaturated or aromatic, comprising at least one heteroatom preferably oxygen; O a pyridinyl or pyridinium group; the quaternized nitrogen atom being substituted with a C1-C4 alkyl radical optionally bearing a hydroxyl group; O a C 1 -C 4 alkyl group; The groups A and B may together form a 5- or 6-membered ring or heterocycle optionally comprising a heteroatom, preferably oxygen; said ring or heterocycle being optionally fused to a phenyl radical optionally substituted with at least one acetyl group (CH300-), -000R6 or -000R6 ester with R6 representing a C1-C4 alkyl radical; * A2, B2, identical or not, represent: O a linear or branched C1-C10 alkyl radical, which may optionally have one or more unsaturations, optionally substituted with a -SiR3 group, the radicals R, which may be identical or different, representing an alkyl radical; in a Cl-O 4 O 3 -Alkenyl radical, a hydrogen atom, an alkali metal, alkaline-earth metal, an ammonium group O, the radicals A2 and B2 may optionally form together a 6-membered heterocycle optionally substituted with a radical in the case where n is 1, the radicals Rb and A'1 may form, in the same way, a 6-membered hydrocarbon-based ring, optionally substituted by a C1-C20 alkyl group, a hydroxyl group; ) -OH (R23) y (R23) y D (j) (k) wherein * y is an integer from 0 to 3; the unsubstituted carbon atoms carry a hydrogen atom; D represents -CR24-, O, -CO-, -CR24 = CR24- * E represents -CR'23-, 0; R'23 represents a hydrogen atom or R23 * R23 identical or different represent a hydroxyl group, a C1-C4 alkyl radical optionally substituted by at least one hydroxyl group; two R23 radicals carried by two adjacent carbon atoms, may together form a fused aromatic ring optionally substituted by at least one C 1 -C 4 alkoxy radical, a hydroxyl group; R24, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C4 alkyl radical. (I) wherein R 25 represents a linear or branched C1-C6 alkyl radical optionally substituted with a group -SO3-Na +, -C (NHR26) = NR'26 where R26, R'26, which may be identical or different, represent an alkyl radical; in 04-08 cyclic; the compounds of formulas (h) to (1) optionally comprising an anion An or a cosmetically acceptable mixture of anions, guaranteeing the electroneutrality of the formulas; and among carbonyl oligomers or polymers selected from polymalonic acids and their esters, polysuccinic acids, sulfoacetic acid polymers, or mixtures thereof.

According to a first variant, the carbonyl nucleophilic compound is of formula (h) above, its isomers, or its salts, its solvates; this compound being alone or in a mixture, in particular chosen from: 1-phenyl-344- (propan-2-yl) phenyl] propan-1,3-dione, 1- (2,4-dihydroxyphenyl) -3- phenylpropane-1,3-dione, N, N, N-trimethyl-4- (3-oxo-3-phenylpropanoyl) anilinium salt, 443- (2-butoxyphenyl) -3-oxopropanoyl] -N salt; N, N-trimethylanilinium, N- (2-hydroxyethyl) -N, N-dimethyl-4- (3-oxo-3-phenylpropanoyl) anilinium salt, 443- (2,4-dimethoxyphenyl) -3 salt oxopropanoyl N, N, N-trimethylanilinium, 1,7-bis (4-hydroxy-3-methoxyphenyl) hepta-1,6-diene-3,5-dione, 1- (2-hydroxyethyl) salt 3- (3-oxo-3-phenylpropanoyl) pyridinium, 1-phenyl-3- (pyridin-3-yl) propane-1,3-dione, N, N, N-trimethyl-443- (4-phenylpropanoyl) salt; methylphenyl) -3-oxopropanoyl] anilinium salt, 1-ethyl-3- (3-oxo-3-phenylpropanoyl) pyridinium salt, 1H-indene-1,3 (2H) -dione, bis (4-methoxyphenyl) propane-1,3-dione, 1,7-bis (4-hydroxy-3-methoxyphenyl) heptane3,5-dione, 1,7-bis (3,4-dihydroxyphenyl) heptane; 3,5-dione, 1,7-bis (4-hydroxy-3-methoxyphenyl) hepta-1,6-diene-3,5-dione, 1-phenyl-3- [4- (propan-2-yl) phenyl] propane -1,3-dione, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, 1- (6-methoxy-1-benzofuran-5-yl) 3-phenylpropane-1,3-dione, 1- (4-tert-butylphenyl) -3- (2-hydroxy-3,5-dimethylphenyl) propane-1,3-dione, 1-methyl-3-salt - (oxo-3-phenylpropanoyl) pyridinium, 144- (dimethylamino) phenyl] -3-phenylpropane-1,3-dione, 1,3-bis (4-hydroxyphenyl) propane-1,3-dione, 1, 7-bis (4-hydroxyphenyl) haptane-3,5-dione, dipropan-2-yl propanedioate, bis (2-methylpropyl) propanedioate, 3-ethoxy-3-oxopropanoate salt, bispropanedioate (2-ethylhexyl), bis (2,2-dimethylpropyl) propanedioate, 2,2-dimethyl-1,3-dioxane-4,6-dione, ethyl propanedioate 2-methylprop-2-in-1 -yl, bis (4-methylpentan-2-yl) propanedioate, bis [[(trimethylsilyl) methyl] propanedioate, bis (2-ethylpentyl) (4-hydroxy-3,5-dimethyl) propanedioate thoxybenzylidène.

In the case where the carbonyl nucleophilic compounds are of formula (j) or (k), the latter are preferably such that: * y is an integer ranging from 0 to 2 * D represents -CO-, -CR24 = CR24- * E is -CR'23-, 0; R'23 represents a hydrogen atom or R23, R23, which may be identical or different, represent a hydroxyl group or a C1-C4 alkyl radical optionally substituted with at least one hydroxyl group; two R23 radicals carried by two adjacent carbon atoms, may together form a fused aromatic ring optionally substituted by at least one C 1 -C 4 alkoxy radical, a hydroxyl group; R24, identical or different, represent a hydrogen atom, a linear or branched C1-C4 alkyl radical. By way of examples of carbonyl compounds of formulas (j) or (k) which are particularly suitable, mention may be made of the following compounds, their isomers, their salts, their solvates, these compounds being alone or in mixtures: 2.5.7 trihydroxynaphthalene-1,4-dione, 2-hydroxy-6-methoxynaphthalene-1,4-dione, 2,5-dihydroxycyclohexa-2,5-diene-1,4-dione, 2,5-dihydroxy- 3-methylcyclohexa-2,5-diene-1,4-dione, 2,3,4,6-tetrahydroxy-5H-benzo [7] annulen-5-one, 5-hydroxy-2- (hydroxymethyl) - 4H-pyran-4-one, 2,5-dihydroxynaphthalene-1,4-dione, 2-hydroxy-5-methoxynaphthalene-1,4-dione, 4-hydroxy-6-methyl-2H-pyran-2 -one, 2-hydroxycyclohepta-2,4,6-trien-1-one, 2-hydroxy-4- (propan-2-yl) cyclohepta-2,4,6-trien-1-one. As regards the carbonyl nucleophilic compounds of formula (1), the following compounds may be mentioned by way of example, their isomers, their salts, their solvates, these compounds being alone or in mixtures: 2-methylpropyl cyanoacetate, cyanoacetyl carbamimidate N, N'-dicyclohexyl, ethyl cyanoacetate, salt of 24 (cyanoacetyl) oxy] ethanesulfonate.

As for the carbonyl oligomers or polymers, these are chosen from polymalonic acids and their esters, polysuccinic acids, sulfoacetic acid polymers, and the salts of these polymers. These compounds are known to those skilled in the art.

It should be noted that the polymalonic acid esters are in particular described in US Pat. No. 4,444,928, and more particularly the following polymer: ## STR1 ## Preferably, the carbonyl nucleophilic compound (s) are chosen from compounds of formula (h) defined before as well as among the compounds of formulas (j) and (k), or mixtures thereof. More particularly, if they are present, the content of compound (s) of formula (s) (h) to (I) or carbonyl oligomers or polymers is between 0.001% and 30% by weight relative to the weight of the composition. Salts In accordance with another embodiment of the invention, the composition is used in the presence of at least one salt. These salts may be present in the composition according to the invention or in a distinct composition. We can refer to the list of ingredients of this type indicated before. When present, their content represents 0.001 and 40% by weight relative to the weight of the composition, and even more preferably between 0.001 and 20% by weight, relative to the weight of the composition.

Third Composition The composition according to the invention may advantageously be used in the presence of a composition comprising at least one oxidizing agent different from the oxygen in the air (third composition).

The oxidizing agent present in the third composition is preferably a chemical oxidizing agent. It is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as, for example, persulfates, perborates and alkali or alkaline earth metal percarbonates, such as sodium, potassium, magnesium, transition metal salts selected from salts of zinc, copper, manganese, iron, salts which may be of organic or mineral nature. When the transition metal salts are organic acid salts, they may contain one or more carboxylic acid (-000H) and / or sulfonic acid (-SO 3 H), and / or phosphonic acid (-H 2 PO 3) functions, and or phosphinic acid (-H2PO2 or = HPO2), and / or phosphinous acid (= POH). Preferably, the organic acid contains one or more carboxylic acid and / or sulfonic acid functions. The organic acid according to the invention may be saturated or unsaturated, linear, branched or cyclic. The organic acid according to the invention can. in particular be selected from gluconate, lactate, glycinate, aspartate, pyrrolidone carboxylate, phenolsulfonate, salicylate, citrate, acetate and mixtures thereof. For the purposes of the present invention, the term "inorganic salts" means inorganic salts, that is to say not having in their structure a carbon atom bonded to at least one hydrogen atom. Mineral salts are salts resulting from the action of a mineral acid or a mineral base on the metal. Among the salts, mention may be made of halides such as chloride, fluoride and iodide; sulphate, phosphate, nitrate, carbonate, perchlorate and mixtures thereof. Preferably, the inorganic salts used are sulphate, phosphate and zinc chloride. Also suitable are enzymatic oxidizing agents such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase), where appropriate in the presence of their donor or respective co-factors.

The use of hydrogen peroxide is particularly preferred. The oxidizing agent is advantageously constituted by hydrogen peroxide in aqueous solution (hydrogen peroxide), the titre of which may vary, more particularly, from 1 to 40 volumes, and even more preferably from 5 to 40 volumes. The third composition may optionally comprise one or more organic solvents. Reference may be made to the list indicated earlier in the context of the description of the composition according to the invention.

Usually, the pH of this third composition is less than 7. Said composition may be in the form of a solution, an emulsion or a gel. It may optionally comprise one or more additives conventionally used in the field of human keratin fiber staining, depending on the desired dosage form. We can again refer to the list of additives given above.

Application conditions The composition according to the invention comprising the compound (s) of formula (I) and / or (II), optionally deglycosylated or deprotected, and which has no oxidizing agent other than oxygen air, as it has just been described, is therefore applied to keratin fibers, especially human fibers, in particular the hair. According to a first embodiment, the formulation applied to the fibers (that is to say the composition according to the invention and, where appropriate, the second composition), does not comprise any oxidizing agent other than oxygen from the air. The formulation applied to the fibers may result from the extemporaneous mixing before the application of the composition according to the invention with the second composition described above (simultaneous application). It may also result from the successive application without intermediate rinsing, of the composition according to the invention and of the second composition. Preferably, the applied formulation results from extemporaneous mixing before application, of the composition according to the invention and of the second composition. The pause time is then more particularly between 1 minute to 5 hours, preferably from 15 minutes to 3 hours. The temperature is usually between 20 and 200 ° C, preferably between 20 ° C and 55 ° C. This operation can thus be carried out, when necessary, by using heating means, for example a heating helmet, an infrared lamp, a hair iron or curling iron. According to a second embodiment, the formulation applied to the fibers (that is to say the composition according to the invention and, if appropriate, the second composition, the whole being devoid of an oxidizing agent other than oxygen air) is applied in the presence of at least a third composition comprising at least one oxidizing agent different from the oxygen of the air. According to a first variant of this embodiment, the formulation is applied simultaneously to the third composition.

According to this variant, said formulation preferably results from extemporaneous mixing before application, of the composition according to the invention with the second composition and with the third composition (oxidizing composition). According to a second variant of this embodiment, the formulation and the third composition are applied successively and without intermediate rinsing.

In a particularly advantageous manner, the said formulation is applied first and then the third composition comprising at least one oxidizing agent. The first step is therefore to apply the formulation devoid of oxidizing agent. Preferably, said formulation comprises the composition according to the invention and the second composition. Even more preferably, said formulation results from extemporaneous mixing before application of the composition according to the invention with the second composition. However, it is not impossible to proceed in two successive stages without intermediate rinsing. It is thus possible to apply the composition according to the invention and then the second composition or vice versa. Preferably, the third composition comprising at least one oxidizing agent is introduced after a pause time of at least 5 minutes, after the application of the formulation (composition according to the invention and, where appropriate, of the second composition), and preferably after a pause of between 10 minutes and 1 hour. The temperature at which the first step is carried out is generally between 20 and 200 ° C, advantageously between 20 ° C and 55 ° C. This operation can thus be carried out, when necessary, by using heating means, for example a heating helmet, an infrared lamp, a hair iron or curling iron. After the pause time of the first step, the third composition comprising the oxidizing agent is applied, preferably at room temperature (25 ° C.), with a pause time of preferably between 1 minute and 20 minutes. minutes. The process according to the invention may advantageously be carried out in the presence of a light stimulus. It consists more particularly in applying to the keratinous fibers thus treated, a UVA radiation, (in particular with an irradiance of between 0.01 and 0.40 milliwatt / cm 2, preferably between 0.1 and 0.2 milliwatt / cm 2, delivered by continuous spectrum lamps or by line-spectrum lamps) and / or UVB radiation (in particular with an irradiance of between 0.01 and 0.20 milliwatt / cm 2, preferably between 0.01 and 0 , 1 milliwatt / cm2 delivered by continuous spectrum lamps or line-of-sight lamps). After the pause time, the keratinous fibers may be rinsed with water, optionally washed with shampoo, rinsed with water and dried or allowed to dry.

Processes for the Preparation of the Compounds of Formula (I) and / or (II) from Geniposide Various synthetic processes may be envisaged to obtain the compounds according to the invention. Qeniposide is a natural product derived from Gardenia iasminoides extract. It is present at various levels. Process 1: According to a first variant, the following reaction scheme may be used: In part 1 of the above reaction scheme, a transacetalization step is first carried out to substitute the "sugar" group of the compound (a). ) by a group R4 alkyl Cl-06 (step 1). This transacetalization step takes place in a manner known per se, for example by bringing the compound into contact in the presence of an organic or inorganic acid, preferably a mineral acid such as hydrochloric acid (0.1N to 1N), in the presence of R4OH alcohol. This operation is advantageously carried out in an aqueous medium. The stirring is usually carried out at a temperature of between 0 ° C. and 80 ° C., more particularly at a temperature of between 20 ° C. and 60 ° C. Generally, the reaction time is between 1 and 24 hours.

At the end of the reaction, the resulting product is preferably separated by using conventional methods such as precipitation, purification on a column, extraction.

In part 2 of the above reaction scheme, a saponification step is then carried out to substitute the "ester" group of compound (b) with an "OH" group. This saponification step takes place in a manner known per se, for example by bringing the compound into contact in the presence of a base, preferably a mineral base, such as sodium hydroxide or potassium hydroxide. This operation is advantageously carried out in an aqueous medium. The reaction is usually carried out at a temperature of between 0 ° C. and room temperature (20 ° C.), more particularly at a temperature close to room temperature. Generally, the reaction time is between 1 and 24 hours. At the end of the reaction, the resulting product is preferably separated by using conventional methods such as precipitation, purification in a column, extraction.

In a step 3, N-acetylation is carried out, employing a coupling agent conventionally used for this purpose. By way of example, mention may be made of HOBT (1-hydroxybenzotriazole), EDCI (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide), DCC (dicyclohexylcarbodiimide) and DIC (diisopropylcarbodiimide).

The operation is generally carried out with 1 to 2 equivalents of coupling agent in the presence optionally of an organic base such as DMAP (4- (N, N-dimethylamino) pyridine). The reaction is advantageously carried out at a temperature between 0 ° C. and 35 ° C., and more particularly at a temperature close to room temperature. This reaction is preferably carried out in the presence of an aprotic polar solvent, such as in particular dichloromethane or ethyl acetate. The contacting of the reagents, usually with stirring, lasts approximately between 1 minute and 30 minutes. This same step involves contacting the resulting product with an amine to obtain the product (d). The amine used corresponds to the following formula HNR 2 R 3, in which R 2 and R 3 represent, preferably and independently of each other, a hydrogen, a VV radical mentioned above. Conventionally and advantageously, the product directly from the previous step 3 is brought into contact with said amine. But it would not be excluded to separate the resulting product in a conventional manner. The amine is introduced into the reaction mixture, preferably with stirring.

Once the amine is introduced, the whole is left for a period of up to 48 hours. The solvent is more particularly an aprotic polar solvent, such as in particular dichloromethane, ethyl acetate.

At the end of the reaction, the product (d) is preferably separated from the reaction mixture and optionally purified in a manner conventional to those skilled in the art. Step 4 of the optional method consists of deprotecting the acetal function to transform it into a hemiacetal (elimination of the R4 group).

This operation is carried out in acidic medium, so that the amide function is not eliminated. The acid is advantageously chosen from organic or inorganic acids such as, for example, citric acid, acetic acid, dilute hydrochloric acid whose pH in solution is between 2 and 6.

This reaction is advantageously carried out in a polar protic medium, preferably in an aqueous medium. The reaction temperature is preferably between 0 ° C and 60 ° C, more especially close to room temperature. As for the duration of the reaction, it is between 1 and 24 hours, more particularly between 1 and 5 hours. The resulting product (e) is advantageously separated and purified using any conventional method. As indicated above, step 4. of the process is optional. It can indeed be carried out during the preparation of the dyeing composition comprising said compound, as soon as the pH of this composition is acidic, more particularly between 3 and 7. However, it is preferable to use Step 4 of the process. Method 2: A transacetalization step is carried out beforehand in order to substitute the "sugar" group of the compound (a) with a R4 alkyl C1-C6 group (step 1, obtaining the compound b). The conditions are the same as those indicated in method 1.

Step 1 of the reaction scheme above, the step makes it possible to pass from compound (b) to compound (f) and consists in replacing the methyl group of the ester function in another ester group in which Ra preferably represents a radical. ethyl, pentyl, decyl.

It can be carried out in two stages, by carrying out a saponification and then an esterification, or in a time, carrying out a transesterification in an acid medium to obtain the compound (f). It is also possible to carry out a so-called peptide coupling reaction (O-alkylation). This latter method makes it possible to obtain compounds (f) for which Ra and R4 are different. According to the saponification / esterification route, the compound obtained from the first stage is first saponified under the same conditions as that of the first stage described above.

It is not necessary to separate the product from the saponification reaction to carry out the esterification step. This esterification step is preferably carried out in the presence of organic or inorganic acid, preferably in a catalytic amount such as, for example, APTS (para-toluenesulphonic acid). This in particular plays the role of desiccant. The reaction medium advantageously comprises the corresponding alcohol RaOH as a solvent in the case of ethanol or optionally pentanol. In the case of decyl alcohol, another apolar aprotic solvent such as toluene is preferably used. Usually, the temperature at which the reaction is carried out varies from room temperature to reflux temperature of the selected alcohol or solvent. In a conventional manner one operates in a Dean Stark or other apparatus allowing to shift the equilibrium towards the formation of the ester. If a transesterification step is carried out, this reaction being reversible, it is generally catalyzed by an acid or a base. To make the reaction complete, the compound from the first step, optionally purified, is brought into contact with the alkali metal alkoxide (R, O-M +) conventionally in a polar (a) protic reaction medium. The solvent is advantageously chosen from tetrahydrofuran, methyl tetrahydrofuran, diethyl ether and the alcohol corresponding to the aforementioned alcoholate. Similarly, step 2. of this process, leading to compound (g) is similar to that of the previous process and can be referred to. Process 3: A transacetalization step is carried out beforehand in order to substitute the "sugar" group of compound (a) with a C1-C6 alkyl group (step 1, obtaining compound b). The conditions are the same as those indicated in method 1. Step 1, represented in the above reaction scheme, consists in carrying out a step of functionalization of the double bond of the 5-membered ring, in particular a step of epoxidation of the double bond, followed by a step of opening the same epoxide. Classically, this epoxidation step is carried out using reagents of the peracid type of formula R-00001-1 such as mCPBA (metachloroperoxybenzoic acid), hydrogen peroxide (H 2 O 2) both known to the man of the art and classically used in this kind of reaction. The reaction may also be advantageously carried out in the presence of urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as, for example, persulfates, perborates, peracids and their precursors and alkali or alkaline-earth metal percarbonates. . In general, the peracid is used in an amount such that it advantageously represents from 1 to 2 equivalents of peracid with respect to one equivalent of compound comprising the double bond to be functionalized.

Generally, the reaction medium comprises a polar aprotic solvent, such as, for example, dimethylformamide or dichloromethane. The reaction temperature is conventionally between 0 ° C. and room temperature.

The duration of the reaction varies from a few minutes to less than 10 hours. Once the reaction is complete, the reaction medium is preferably neutralized by introducing an alkaline agent to reach a pH ranging from about 7 to 8. The resulting compound is then separated from the reaction mixture and purified in a conventional manner. consists in opening the epoxide obtained during the previous step. Thus, according to a first variant, the epoxidized product resulting from the preceding step is brought into contact in the presence of a catalytic amount of organic, inorganic acid in an aqueous medium to obtain the corresponding 1,2-diol.

An acid and acid contents such as the pH of the reaction mixture are chosen, in the range 3 to 5. For example, citric acid, dilute hydrochloric acid and dilute sulfuric acid are suitable. Usually, the reaction time is between 1 minute and 5 hours.

According to a second variant, the compound obtained from the preceding step can be brought into contact with a nucleophilic agent advantageously chosen from primary, secondary or tertiary amines, in the presence or absence of a Lewis acid, in order to obtain the 13-amino corresponding alcohol. The amines particularly correspond to the following formula -N R31 R32 with R31 and R32 representing independently of one another a hydrogen atom or a group VV defined above, at least one of the two groups being different from the hydrogen. The Lewis acids may be chosen, for example, from aluminum chloride, ytterbium triflate, zinc perchlorate hexahydrate, vanadium chloride, tin chloride, etc. Depending on the nature of the lewis acid used, the reaction can be with or without a solvent. When the reaction is carried out in the presence of solvent, it may be chosen from ethereal solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, tert-butylmethylether or other solvents such as water. The duration of the reaction varies more particularly from 5 minutes to 5 hours. As for the temperature, it is usually between 0 ° C. and 80 ° C., preferably between room temperature and 80 ° C.

According to a third variant, the epoxide from the preceding stage can be brought into contact with a nucleophilic agent advantageously chosen from alcohols or alkali metal alkoxides in order to obtain the corresponding α-hydroxy-alkoxy compound. The alcohols and alcoholates correspond particularly to the following formula ROM with R represents a methyl, ethyl, M represents a hydrogen atom, a sodium ion, potassium. They are generally introduced with contents ranging from 1 to 2 equivalents relative to the compound carrying the epoxide. The solvent advantageously corresponds to the alcohol used or its alcoholate. The duration of the reaction varies more particularly from one to 4 hours.

As for the temperature, it is usually between 0 ° C and reflux of the alcohol present. Whatever the variant used, the reaction mixture is neutralized by introducing either a base or an acid. Step 2 of the optional method is similar to that used for method 1 and reference may be made here again.

Process 4: A transacetalization step is carried out beforehand in order to substitute the "sugar" group of compound (a) with a C1-C6 alkyl group (step 1, obtaining compound b). The conditions are the same as those indicated in method 1. In step 1 of the above reaction scheme, the step in question consists in reacting the allyl alcohol (b) so that the C-bond 0 of the 5-chain cycle is replaced by a CN, or CC. Thus, the compound resulting from stage 1 is reacted in the presence of a metal catalyst, for example a catalyst based on iron, iridium, palladium, platinum, nickel or gold, under a inert atmosphere. The reaction is carried out in the presence of an amine NR13R14 with R13 and R14 representing independently of one another a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen Usually 1 to 2 equivalent (s) of amine compound are used relative to the allyl alcohol (b). The reaction medium is preferably an aprotic polar solvent such as, for example, dichloromethane, tetrahydrofuran. The reaction temperature is conventionally between 0 ° C. and 60 ° C., and advantageously close to room temperature. The duration of the reaction varies from a few minutes to 48 hours. At the end of the reaction, the reaction mixture is filtered to recover the metal catalyst, for example on alumina, silica deactivated, celite column.

The reaction mixture is then concentrated and the product separated using any conventional means for those skilled in the art. According to a second variant, this step also consists of functionalizing the hydroxyl group of the 5-membered ring. A first embodiment consists of carrying out this step to etherify the hydroxyl group. Thus, the allyl alcohol (b) is contacted with an alkyl or aryl halide, preferably an alkyl chloride.

Said compound is usually employed at 1 to 2 equivalents relative to the allyl alcohol (b). The reaction is preferably carried out in the presence of an alkaline agent, for example sodium hydride, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate or cesium carbonate. The content is such that the pH of the reaction mixture is between 8 and 11 approximately. The reaction is usually carried out in polar aprotic medium, such as, for example, dimethylformamide, dichloromethane or ethereal solvents such as tetrahydrofuran. In order to accelerate the reaction kinetics, it is possible to add a catalytic amount of sodium or potassium iodide. As for the temperature of the reaction, it depends on the boiling temperature of the halogenated reagent. By way of example, it is less than 100 ° C., of the order more particularly of the order of 60 to 70 ° C. The reaction is generally carried out for a period of between a few minutes and 48 hours. At the end of the reaction, the mixture is neutralized by addition of a base. A second embodiment consists of carrying out this step to esterify the hydroxyl group.

Thus, the allyl alcohol (b) is contacted with an organic acid of formula R15COOH, wherein R15 represents a linear or branched C1-C12 alkyl radical. Said compound is usually employed at 1 to 5 equivalents relative to the allyl alcohol (b).

In the case where an organic acid of formula R15COOH is reacted, it may be carried out in the presence of a particularly mineral acid, such as dilute hydrochloric acid. As for the temperature of the reaction, it may range from room temperature to reflux.

The allylic alcohol (b) can also be contacted with a carboxylic or sulfonic acid halide. Said halide is usually used in amounts of 1 to 5 equivalents relative to the allyl alcohol (b). .

The reaction is preferably carried out in the presence of a base, for example chosen from amines, such as triethylamine, diisopropylethylamine or dimethylaminopridine. The base content is such that the pH of the reaction mixture is greater than 7. Usually, 1 to 2 equivalents by weight of amine is used.

The temperature at which the reaction is carried out is usually below room temperature, preferably close to 0 ° C. At the end of the reaction, the temperature of the reaction mixture is allowed to rise to room temperature or close. The reaction mixture is then neutralized by addition of an acid.

A third embodiment consists of carrying out this step by oxidizing the hydroxyl group, to the aldehyde, to the acid, to the ester or to the amide. Thus, the allyl alcohol (b) can be brought into contact with an oxidizing agent, for example a manganese derivative, of the MnO 2 type, barium permanganate, potassium dichromate, ammonium nitrate cerium, etc. then obtains an aldehyde derivative. The oxidizing compound is usually employed at 1 to 20 equivalents relative to the compound from step 1.

The reaction is advantageously carried out at room temperature. The reaction is generally carried out for a period of between a few minutes and 96 hours. The reaction is usually carried out in an apolar aprotic medium, such as, for example, toluene or dichloromethane.

At the end of the reaction, the reaction mixture is filtered to recover the oxidant, for example on alumina, silica deactivated, celite column. The reaction mixture is then concentrated and the product separated using any conventional means for those skilled in the art. The allyl alcohol (b) can also be brought into contact with an oxidizing agent, such as chromic acid, potassium permanganate, nitric acid, 30% hydrogen peroxide, tetrabutylammonium hydrogen sulphate and a tungsten catalyst, orthoperiodic acid / chromic acid combinations, to obtain the carboxylic acid derivative. The oxidizing agent is more particularly employed at a level of 1 to 5 equivalents relative to the compound resulting from stage 1.

The temperature at which this step is carried out is more particularly between 0 ° C. and 100 ° C. It is also possible to carry out the reaction by microwave irradiation. Depending on the nature of the oxidant, the reaction usually takes place in a polar protic medium (a), such as, for example, dimethylformamide, water. Some oxidation reactions sometimes do not require a solvent. At the end of the reaction, the reaction mixture is filtered to recover the oxidant, for example on alumina, silica deactivated, celite column. The reaction mixture is then concentrated and the product separated using any conventional means for those skilled in the art. The acid derivative thus obtained can be esterified in a conventional manner. Reference can be made to the description given in method 2.

The amide derivative can be obtained for example by employing a coupling agent conventionally used for this purpose. Reference may be made to the description given in method 1. After the steps previously described, the compound obtained is purified in a conventional manner. Step 2 of the optional method is similar to that used for method 1 and can be referred to. Method 5: A transacetalization step is previously carried out in order to substitute the "sugar" group of the compound (a) with a R4 alkyl C1-C6 group (step 1, obtaining the compound b). The conditions are the same as those indicated in method 1.

The compound (b) is in a first variant, brought into contact with a reducing agent, in order to reduce the ester function carried by the heterocycle to an alcohol function (R2 = -CH2OH). More particularly, for this step, a reducing agent such as AlLiH4, DIBALH, lithium triethylborohydride, LiAlH (Ot-Bu) 3, BH3-SMe2 is used.

Usually, the solvent is selected from aprotic polar compounds, such as, for example, ethereal solvents such as ethereal solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, tert-butylmethylether. The temperature at which this reaction is carried out is conventionally between 0 ° C. and 80 ° C. The reaction time is usually between 1 minute and 24 hours At the end of the reaction, the temperature of the reaction mixture is allowed to rise to a temperature close to room temperature.

If the alcohol is desired, the compound (I) obtained during this step is then separated and purified in a manner known per se. If the compound (I) is an ether (R2 = -CH2OZ), then the alcohol obtained by reducing the ester function is treated as indicated previously in the etherification step of the process 4. It will first be necessary to protect prior to the alcohol function of the compound (b) before reduction, in particular by a protective group chemically inert vis-à-vis the reducer used. If the compound (I) is an ester (R2 = -CH 2 O (O) R 28), then the alcohol obtained by reducing the ester function is treated similarly to the esterification described in method 4. As before, it will first be necessary to protect beforehand the alcohol function of the compound (b) before reduction, more particularly by a protective group chemically inert vis-à-vis the reducer used and esterification conditions. According to a second variant, the compound (b) is treated in such a way that the ester is reduced to tertiary alcohol (R2 = -C (OH) R26R27). This operation usually takes place by bringing the compound obtained (b) into contact with an organomagnesium compound of formula R26MgBr or R27MgBr with R26, R27 representing a linear or branched C1-C12 alkyl radical, unsubstituted phenyl, or non-benzyl benzyl. substituted.

The number of equivalents of organomagnesium compound is between 2 and 3. Usually the solvent of the reaction is chosen from polar aprotic compounds such as tetrahydrofuran, diethyl ether and diisopropyl ether. The temperature at which this reaction is carried out is conventionally below room temperature, more particularly below 10 ° C. The reaction time is usually between 1 minute and 5 hours. The reaction is also carried out under an inert atmosphere.

At the end of the reaction, the reaction mixture is neutralized by adding an acid in an amount such that the pH is about 7.

At the end of the steps previously described, the compound (I) obtained is purified in a conventional manner. Step 2 of the optional method is similar to that used for method 1 and can be referred to. The examples below illustrate the invention without limiting its scope.

Examples Reaction of transacetalization of the geniposide by an alkyl group. Synthesis of: - Methyl (1R, 4a5,7a5) -1-ethoxy-7- (hydroxymethyl) -1,4a, 5,7-tetrahydrocyclopenta [c] pyran-4-carboxylate-methyl (1S, 4a5,7a5) - 1-ethoxy-7- (hydroxymethyl) -1,4a, 5,7-tetrahydrocyclopenta [c] pyran-4-carboxylate In a three-necked flask surmounted by a condenser, a thermometer and a dropping funnel, 10 g of geniposide are added to a solution of 200 ml of ethanol at 70 ° C. 0.44 g of p-toluenesulfonyl acid (PTSA) is then added and the mixture is stirred for 6 hours. The solution is colored in dark brown. The solvent is evaporated and 15.94 g of a brown oil is recovered. The recovered mixture is extracted with dichloromethane / water solution. The aqueous phase is at pH 9. The organic phase is then evaporated and a brown oil is obtained. The analyzes confirm the presence of the desired product. Saponification reaction of transacetalized geniposide Synthesis of: - (1R, 4a5,7a5) -1-ethoxy-7- (hydroxymethyl) -1,4a, 5,7a-tetrahydrocyclopenta [c] pyranic acid 4-carboxylic acid (2a) APTS Ethanol. 6h 70 ° C - Yield = 58 ° / 0 la / lb 2a / 2b (600/0/400/0) In a three-necked flask surmounted by a condenser, a thermometer and a dropping funnel, one 4mL of methanol is introduced and 500 mg of transacetalized geniposide are added as and when. Once the product is completely dissolved, a solution of 10 ml of 0.5 N sodium hydroxide (1 equivalent) is poured onto the reaction medium at room temperature.

The solution initially colorless to light yellow when adding. The resulting mixture is stirred at room temperature for 4 hours and then a solution of hydrochloric acid is added until a pH of 3 is obtained. The aqueous phase is then extracted with ethyl acetate (3 × 20mL) and the organic phase is dried with Na 2 SO 3. The organic phase is then concentrated and a colorless oil is recovered. The product is then purified with an ether / heptane mixture. A white solid is recovered which precipitates at the bottom of the flask. The analyzes confirm the presence of the desired product.

Reaction of N-acetylation of amine with transacetalized adipose acid In a three-necked flask surmounted by a condenser, a thermometer and a dropping funnel, 47.2 mg of N-hydroxysuccinimide are introduced into a solution of transacetalized geniposic acid (100 mg) in solution in 2 ml of dichloromethane under argon at 5 ° C. H 4h 74 - (1S, 4aS, 7aS) -1-ethoxy-7- (hydroxymethyl) -1,4a, 5,7a-tetrahydrocyclopenta [c] pyran-4-carboxylic acid (2b) O HO NaOH HO OH The mixture is stirred at 0 ° C. for 30 minutes and then 82.4 mg of dicyclohexylcarbodiimide dissolved in 1 ml of dichloromethane are added to the reaction medium at room temperature for 1 hour. The formation of a white precipitate is observed.

The reaction medium is filtered and 60 microliters of hexylamine are added to the reaction medium. The whole is stirred at room temperature for 10 minutes. A first extraction is then carried out with a dichloromethane / water mixture: pH of the water = 2 to remove the amine.

A second extraction is carried out with a dichloromethane / water mixture: pH of the water = 9 to remove the acid. The organic phase obtained is dried with Na 2 SO 4. And we evaporate the organic phase.

The following products are obtained: Amine used N ° molecules Pyrrolidine 3a / 3b Hexylamine 4a / 4b Decylamine 5a / 5b Tetradecylamine 6a / 6b The analyzes confirm the presence of the desired product.

Claims (9)

REVENDICATIONS1. Compounds of formula (I) below, their salts of organic or inorganic acid, and their solvates, their optical isomers, geometries, their isomers, their tautomers if they exist: Formulas (I) and (II) in which: R1 and R "1 represent, independently of one another, a radical chosen from: -CH3; -CH2OZ; -CHO; -COOR10, R10 representing a hydrogen atom, a C1-C12 alkyl radical; -00NR11R12, in which R11 and R12, which may be identical or different, represent a hydrogen atom, a VV group, at least one of the two groups being different from hydrogen; -CH2NR13R14 with R13 and R14 representing, independently of one another, a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen; -COR15 with R15 representing a C1-C12 alkyl radical, R2 and R "2 independently represent one of the two groups; another a radical selected from: a hydrogen atom; a methyl radical; -CH2OZ; -COR20 with R20 representing a C1-C12 alkyl radical, -000R21, R21 representing a hydrogen atom, a C1-C12 alkyl radical; -00NR22R23, R22, R23, identical or not, represent a hydrogen atom, a group VV, at least one of the two groups being different from hydrogen; -CH2NR24R25 with R24 and R25 independently of one another representing a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen; - C (OH) R 26 R 27 with R 26, R 27, identical or different, representing a linear or branched C 1 -C 12 alkyl radical, unsubstituted phenyl, or unsubstituted benzyl. (R 3) n, R, K R "R 3 and R" 3 represent, independently of one another, a radical -OZ, a methyl; an -N R31R32 radical with R31 and R32 representing, independently of one another, a hydrogen atom or a VV group, at least one of the two groups being different from hydrogen; a C1-C12 alkylthio radical; R'3 may further represent a hydrogen atom; R4 and R "4 represent, independently of one another, a radical chosen from: a hydrogen atom, a C1-C12 alkyl radical, a sugar unit, -COR40, with R40 representing a C1-C12 alkyl radical; -000R41, with R41 represents a C1-C12 alkyl radical; -00NR42R43, with R42, R43, identical or not, representing a hydrogen atom, a W; -Si (R44) 3 group in which R44 represents an alkyl radical; Cl-04; Z represents a hydrogen atom, a C1-C2 alkyl radical, a sulphonic group, alkyl (01-02) sulphonate, phenyl sulphonate or alkyl (01-02) -phenyl sulphonate, a -COR 2 group with Rz represents a C1-C12 alkyl radical, a sugar unit, VV represents a linear, branched and / or cyclic, saturated unsaturated, aromatic or non-aromatic hydrocarbon radical, which may contain from 1 to 5 carbon-carbon double bonds; optionally substituted and / or optionally interrupted by one or more heteroatoms and / or by one or more gro upsets comprising at least one heteroatom (preferably selected from oxygen, nitrogen, sulfur, O = O, C = S, P = O, SO, SO 2 or combinations thereof) and / or silicon; the hydrocarbon radical having no nitro, nitroso, peroxo or diazo function, said radicals (R 11, R 12), (R 13, R 14), (R 22, R 23), (R 24, R 25), (R 31, R 32) and (R 42 , R43), which can optionally form with the nitrogen atom to which each is attached, a 5- or 7-membered, optionally substituted, saturated or unsaturated heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; n integer varies from 0 to 5; more preferably from 0 to 3, preferably from 0 to 2; Exclusions of formula (I): when R 4 represents a sugar unit, a (1-4C) alkylcarbonyl group, a mono- or di-(1-4C) aminocarbonyl group, then R2 does not represent an alkoxy group ( -02) carbonyl, hydroxycarbonyl, hydroxymethyl (-C1-1201-1), R2 also does not represent a hydrogen atom when R4 represents a sugar; When R4 is hydrogen and R1 is -CH3, -CH2OH, then R2 is not H, -CH3, -COOH, -0000H3. 2. Compounds according to the preceding claim, characterized in that R1 and R "1 represent independently of one another: * -CH3, * -CHO, * -CH2OZ, Z representing a hydrogen atom, an alkyl radical in 01-02, a sulphonic group, alkyl (01-02) -, phenyl or alkyl (01-02) -phenyl sulphonate group, a CORz group with Rz representing a C6 alkyl radical, a sugar unit; * -000R10, R10 representing a hydrogen atom, a C1-C10 alkyl radical, with R13 and R14 representing, independently of one another, a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen; R11 and R12 represent, independently of one another, a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen. 3. Compounds according to any one of the preceding claims, characterized in that R2 and R "2, the latter represent independently of one another: * -CH3 * -CH2OZ with Z representing a hydrogen, an alkyl radical C1-C2, -CORz with Rz representing a C1-C6 alkyl radical, * -000R21, R21 representing a hydrogen atom, a C1-C6 alkyl radical; -CON R22R23, R22, R23, identical or different, represent a hydrogen atom, a group VV, at least one of the two groups being different from hydrogen. -CH2NR24R25 with R24 and R25 representing, independently of one another, a hydrogen atom or a grouping VV, at least one of the two groups being different from hydrogen; -C (OH) R 26 R 27 with R 26, R 27, identical or different, representing a linear or branched C 1 -C 12 alkyl radical, unsubstituted phenyl, or unsubstituted benzyl. 4. Compounds according to any one of the preceding claims, characterized in that R3 represents a hydroxyl radical, a methoxy radical, ethoxy, a radical - NR31R32 with R31 and R32 representing independently of one another a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen. 5. Compounds according to any one of the preceding claims, characterized in that R "3 derived from the formula (II), this radical represents more particularly a hydrogen atom, a hydroxyl radical, a methoxy radical, ethoxy, a radical - NR31R32 with R31 and R32 representing independently of one another a hydrogen atom or a group VV, at least one of the two groups being different from hydrogen, a dodecylthio radical. 6. Compounds according to any one of the preceding claims, characterized in that R4 R "4 represent, independently of one another, a radical chosen from: a hydrogen atom, a C1-C12 alkyl radical, a unit sugar, -COR40, with R40 representing a C1-C6 alkyl radical; -000R41, with R41 represents a C1-C6 alkyl radical; -00NR42R43, with R42, R43, identical or different, representing a hydrogen atom, a grouping Wherein R44 represents a C1-C4 alkyl radical. 7. Compounds according to any one of the preceding claims, characterized in that the sugar unit contains one or two sugar units, in cyclized form, chosen from pentoses, hexoses, or diholosides. 8. Compounds according to the preceding claim, characterized in that the sugar unit is chosen from pentoses such as cyclized forms of ribulose, xylulose, arabinose, lyxose, ribose, xylose, deoxyribose; among hexoses such as cyclized forms of fructose, psicose, sorbose, tagatose, allose, altrose, galactose, glucose, gulose, idose, mannose, fucose, fuculose, pneumose, quinovose, rhamnose; among diholosides such as cellobiose, gentiobiose, inulobiosis, isomaltose, isomaltulose, kojibiose, lactose, lactulose, laminaribiose, leucrose, maltose, maltulose, melibiose, nigerose, robinose, rutinose, sucrose, sophorose, trehalose, trehalulose, turanose; and preferably maltose, glucose, rhamnose. 9. Compounds according to any one of the preceding claims, characterized in that the W group is chosen from a C 1 -C 14 alkyl radical, optionally substituted with one or two hydroxyl groups, with one or two optionally substituted amino groups. by a fluorenylmethyloxycarbonyl group or one of the following groups, (2) R'7 R'8 OR '/ 10 P Il 0 -R'10 0 (5) R'8 (6) R'11 (7) Formulas in which R '1 represents: a hydrogen atom o a linear or branched C1-C6 alkyl radical, preferably substituted by one or more hydroxyl, hydroxycarbonyl, thiol, alkyl (O-C4) thio, amido or amino groups, guanidine, a phenyl radical, optionally substituted by one or more hydroxyls, an indolyl radical optionally substituted with one or more hydroxyls, an imidazolyl radical or a pyrrolinyl radical optionally substituted with a C1-C12 alkyl group; or an unsubstituted phenyl radical R'2 represents a hydrogen or a C1-C4 alkyl radical. R'3 represents: a linear or branched, saturated or unsaturated C 1 -C 18 hydrocarbon radical and optionally comprising one to five conjugated or unsubstituted conjugated carbon-carbon double bonds, as optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and or by one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, O = O, C = S, SO, SO 2 or combinations thereof; the alkyl radical having no nitro, nitroso, peroxo or diazo function; an unsubstituted benzyl radical; * link attaching the radical VV to the molecule. R'1 and R'3 can form a saturated carbon ring with 5 members; R'4 represents: * a hydrogen atom * a C1-C6 alkyl radical, optionally substituted by one or more hydroxyl, thiol, alkyl (O-C4) thio, amido or amino groups, a phenyl radical, optionally substituted with one or more a plurality of hydroxyls, an indolyl radical optionally substituted with one or more hydroxyls, a 4 (3) O (4) imidazolyl radical or a pyrrolinyl radical optionally substituted by a C 1 -C 20 alkyl group; R'1 and R'4 can form a saturated carbon ring with 5, 6, 7 members. In the case where X represents a nitrogen atom and R'4 represents an alkyl radical defined as above and very particularly an amino acid residue and / or their corresponding methyl or ethyl ester chosen from alanine, arginine, asparagine, aspartate, cysteine, glutamate, glutamine, glycine, histidine, lysine, methionine, phenylalanine, proline, pyrrolysine, serine, threonine, tryptophan, tyrosine , valine, leucine, isoleucine, the compound of formula (3) represents a dipeptide, an oligopeptide. R'6, R'6, R'8 represent independently of each other: * a hydrogen atom * a linear, branched and / or cyclic, saturated and / or unsaturated hydrocarbon radical, which may contain from 1 to with 5 carbon-carbon double bonds, optionally aromatic, optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C = S, SO, SO 2 or combinations thereof, optionally carrying at least one hydroxyl or alkoxy group at 01-02, said alkyl radicals R '5 and R' 6 OR R '7 and R' 8 optionally capable of forming, with the carbon atom to which each is attached, a 5- or 7-membered, saturated or unsaturated heterocycle, optionally substituted as indicated above, optionally aromatic, optionally comprising another identical or different heteroatom are nitrogen; the alkyl radical having no nitro, nitroso, peroxo or diazo function; more particularly an optionally substituted C1-C10 alkyl radical; and preferably, a linear or branched C1-C8 alkyl radical optionally substituted by at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups, a hydroxycarbonyl radical, an ureido radical or a (C1-C4) alkoxycarbonyl radical; an unsubstituted phenyl radical; In the case of the formula (6), the radicals R'6, R'6, R'8 independently of each other may also represent a hydroxyl radical, an alkoxy (ClC4) carbonyl radical, a carboxaldehyde radical or an alkoxy radical. (C1-03) R'5 and R'6 can form, with the carbon atom to which they are attached, a 5- or 6-membered saturated heterocycle; R'9 represents: * a hydrogen atom * a linear or branched, saturated or unsaturated C 1 -C 18 hydrocarbon radical and optionally comprising one to five conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as indicated above, optionally interrupted by a or more heteroatoms and / or one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO, SO 2 or combinations thereof; the alkyl radical having no nitro, nitroso, peroxo or diazo function; more particularly R '9 represents a hydrogen, a linear or branched, optionally substituted C 1 -C 10 alkyl radical; and preferably, hydrogen, a linear or branched C1-C4 alkyl radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups R'10 represents: * a hydrogen atom * an alkyl radical 01-00 linear or branched optionally substituted as indicated above, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO, SO2 or combinations thereof, optionally bearing at least one hydroxyl group or alkoxy group at 01-02; the alkyl radical having no nitro, nitroso, peroxo or diazo function, R '11 represents a linear C 1 -C 4 alkyl radical; a linear C 1 -C 4 alkoxy radical represents a sulfur or nitrogen atom; an amino group; Y represents a nitrogen, oxygen or sulfur atom; an amino group; T represents an oxygen atom, an SH or OH group, a methylene group optionally substituted by a hydroxyl radical; When T represents an oxygen atom, then R11 or R12, R13 OR R14, R22 or R23, R24 or R25, R42 OR R43, form a 5- or 6-membered ring optionally substituted with one or more hydroxy (methyl), preferably 1 to 4 hydroxy groups (methyl); p is an integer from 0 to 7; q is an integer between 1 and 18 o is an integer between 0 and 5. / 0. Compounds according to any one of the preceding claims, characterized in that the compounds of formula (I) are chosen from the following compounds, their optical isomers, geometric, their tautomers, their enantiomers if they exist, their salts, their solvates, and mixtures thereof: Preferred compounds of formula (I) with n being 0 or 1, and preferably n being 0, R1 R2 R3 R4 HOCH2-CH300 (O) -, HOC (O) -, HO-CH3CH2-, CH3- ## STR2 ## (CH3) 3Si, CH3CH200 (O) -, (CH3) 3000 (O) -, CH3CHCH2-, pd-glucose HOCH2-CH300 (O) -, HOC (O) -, HO-CH3CH2-, -CH2OH CH3 [ CH2] 2-, CH3 [CH2] 3-, CH3 [CH2] 4-, (CH3) 3Si-, CH3CH200 (O) -, (CH3) 3000 (O) -, CH3CHCH2-HC (O) -CH300 ( 0) -, HOC (O) -, HO- H-, CH3CH2-, HOCH2-, CH3 [CH2] 2-, CH3-CH3 [CH2] 3-, CH3 [CH2] 4-, CH3CO-, CH3CH2C (0) ) -, CH3 [CHIC (O) -, CH3 [CH2] 3C (O) -, (CH3) 3Si, CH3CH200 (O) -, (CH3) 3000 (O) -, (CH3) 2NC (O) - , CH3CHCH2-, pd-glucose CH3CH200 (0) -, CH300 (0) -, HOC (0) -, HO- H-, CH3CH2-, HOC (O) -, HOCH2-, CH3 [CH2] 2-, CH3 [CHINHC (O) -, CH3-CH3 [CH2] 3-, CH3 [CHINHCH2-, CH3 [ CH2] 4-, CH3 [CH2] 4NHCH-, CH300-, CH3 [CH2] 3NHCH-, CH3CH2C (O) -, CH3CH2CH2NHCH-, CH3 [CHIC (O) -, CH3CH2NHCH-, CH3 [CH2] 3C (O) -, CH3NHCH-, (CH3) 3Si, CH300 (O) CH (CH3) N CH3CH200 (O) -, HC (O) - (CH3) 3000 (O) -, (CH3) 2NC (O) -, CH3CHCH2 -, pd-glucose HOCH2-CH3CH2NHC (O) -, HO- H-, CH3CH2-, HO [CHINHC (O) -, CH3 [CH2] 2-, CH3 [CH2] 2NHC (O) -, CH3 [CH2] 3-, CH3 [CH2] 3NHC (O) -, CH3 [CH2] 4-, CH3 [CH2] 4NHC (O) -, CH300-, CH3 [CHINHC (O) -, CH3CH2C (O) -, FmocNH [CH2 ] 8NHC (O) -, CH3 [CHIC (O) -, NH2 [CH2] 8NHC (O) -, CH3 [CH2] 3C (O) -, Cl-13 [C1-12] 200 (O) -, - CH (O), (CH 3) 3 Si-, -C (OH) (Cl-13) 2, CH 3 CH 2 O (-) -, (-C (OH) (C 61-15) 2, -CH 3) 3000 (O) - , C (OH) (CH2C61-15) 2, (CH3) 2NC (O) -, -C (O) N (C4H8), CH3CHCH2-, -C (O) NHCH (CH3) C (O) OCH3 pd- Glucose -C (O) NH (CH2) 13CH3, -CH20000H3, -CH20000H2CH3, -CH2000 [CHICH3, -CH2000 [CH2] 3CH3, -CH2000 [CH2] 4CH3, CH2000 [CHCl3]. Compounds according to any one of the preceding claims, characterized in that the compounds of formula (II) are chosen from the following compounds: their optical isomers, geometric, their tautomers, their enantiomers if they exist, their salts, their solvates, and mixtures thereof: Compounds of formula (II) ## STR2 ## [CH212-, CH3-, H, -CH2OHCH3 [CH2] 4NH-, CH3 [CH213-, CH3 [CH2] 3NH-, CH3 [CH2] 4-, CH3CO-, CH3 [CHINH-, CH3CH2C (O) - , CH3CH2NH-, CH3 [CHIC (O) -, CH3NH-, CH3 [CH2] 3C (O) -, C12H25S-, (CH3) 3Si-, -NHCH (CH3) C (O) OCH3CH3CH2O (O) -, CH3CH20- (CH3) 3COC (O) -, (CH3) 2NC (O) -, CH2CHCH2-, pd-glucose HOCH2 CH3CH2NHC (O) -, HO [CHINHC (O) -, CH3 [CHINHC (O) -, CH3 [CH2] 3NHC (O) -, CH3 [CH2] 4NHC (O) -, CH3 [CHINHC (O) -, H-, HO- H-, CH3CH2-, - FmocNH [CH2] 8NHC (O) -, CH3 [CH212-, CH3 [CH213-, CH3 [CH2] 4-, CH3CO-, CH3CH2C (O) -, CH3 [CHIC (O) -, CH3 [CH2] 3C (O) -, NH2 [CH2] 6NHC (0 ) -, (CH3) 3Si-, CH3 [CH2] 200 (O) -, CH3CH200 (O) -, -CH (O), (CH3) 00 (0) -, -C (OH) (Cl-13) 2, (CH 3) 2 NC (O) -, -C (OH) (C 61-15) 2, - CH 2 CHCH 2 -, C (OH) (CH 2 Cl 2) 15) 2, pd-glucose -C (O) N (C4H8), -C (O) NHCH (CH3) C (O) OCH3 -C (O) NH (CH2) 13CH3, -CH2OCOCH3, -CH20000H2CH3, -CH2000 [CHICH3, - CH2000 [CH2] 3CH3, - CH2000 [CH2] 4CH3, CH2000 [CHICH3] 12. Composition comprising, in a cosmetically acceptable medium, one or more compounds of formula (I) and / or (II) as defined in US Pat. any preceding claim. 13. Composition according to the preceding claim, characterized in that the content of compounds of formulas (I) and / or (II) is between 0.001 and 10% by weight relative to the weight of the composition. 14. A process for dyeing keratinous fibers, especially human fibers, in which a composition according to any one of claims 12 or 13, comprising the compounds of formulas (I) and / or (II), is applied. 15. The method of dyeing according to the preceding claim, characterized in that the composition is applied in the presence of a second composition comprising at least one ingredient selected from amines, aldehyde or imine compounds, nucleophilic compounds, nucleophilic carbonyl compounds, salts, alone or in combination. 16. A method of dyeing according to any one of claims 14 or 15, characterized in that the composition and the second composition are applied simultaneously or successively and without intermediate rinsing, preferably simultaneously. 17. The method of dyeing according to any one of claims 14 to 16, characterized in that the composition, if necessary the second composition, is applied in the presence of a third composition comprising at least one oxidizing agent other than oxygen air ; the composition, if necessary the second composition, on the one hand, and the third composition, on the other hand, which can be applied simultaneously or successively without intermediate rinsing, preferably successively, 18. Use of compounds of formulas (I) and / or (II) as defined according to any one of Claims 1 to 11 as dyes for keratinous fibers, in particular human fibers, in particular the hair.