FR2980701A1 - Composition, useful to color human keratin fibers, comprises substituted iridoid compounds and/or furanol compounds, and nucleophilic carbonyl compound i.e. optionally comprises anion mixture to ensure electrical neutrality of composition - Google Patents

Abstract

Composition comprises, in a medium, substituted iridoid compounds (I) and/or 2,5-dihydro-furan-2-ol compounds (IA) or their plant extracts, and at least one nucleophilic carbonyl compound, which optionally comprises anions or their mixtures to ensure electrical neutrality of the composition. Composition comprises, in a medium, substituted iridoid compounds of formula (I) and/or 2,5-dihydro-furan-2-ol compounds of formula (IA) or their optical or geometrical isomers, or their mineral or organic acid salts, or solvates, or their plant extracts, where (I) optionally undergo a step comprising replacing the radical R with a hydrogen atom produced by an enzyme, prior to or simultaneously during the coloring of hair, and at least one nucleophilic carbonyl compound of formula (A1-C(=O)-C((R1b) 2)-C(=O)-B1) (II), (III), (IV) or (R25-O-C(=O)-CH 2-CN) (V) or its optical or geometrical isomer, organic or mineral acid salt or solvate, where the compounds (II)-(V) optionally comprise anions or their mixtures to ensure electrical neutrality of the composition, and are also from carbonyl oligomers or polymers comprising polymalonic acids or their esters, polysuccinic acids and/or sulfoacetic acid polymers. R1 : hydroxymethyl, -CO 2R4 or a sugar radical; R4 : H or 1-2C-alkyl; R2 : H, hydroxy or a sugar radical; R3 : H, hydroxy or 1-4C-alkyloxy, where the number of hydroxy groups is = 2; R : a sugar radical, where the sugar radical is a derivative obtained from an aldose or its derivative; n : 1-5; either A1 : A11-[C((R1a) 2)-C((R1a) 2)] n1-, A11a-[C(R1a)=C(R1a)] n1- or A22-O-; and B1 : B11-[C((R1a) 2)-C((R1a) 2)] m1-, B11a-[C(R1a)=C(R1a)] m1- or B22-O-; or A1+B1 : a 5- or 6-membered ring or heterocycle optionally comprising a heteroatom, preferably O, where the ring or heterocycle is optionally fused to a phenyl radical i.e. optionally substituted with at least one CH 3CO-, -COOR66 or -OCOR66; n1 : 0 or 1; m1 : 0 or 1; R1a : H or 1-4C-alkyl; either R1b : H or CH 3CO-, where one of the two radicals R1b represents H; and A11 , B11, A11a, B11a : 6C-aryl (optionally substituted with at least one linear or branched 1-20C-alkyl, hydroxy, -OR11, -OCOR44, -N +>(R55) 3or halo (preferably Cl), where the 6C-aryl is optionally fused to an unsaturated or aromatic 5- or 6-membered heterocycle comprising at least one heteroatom, preferably O), or pyridinyl or pyridinium, where the quaternized nitrogen atom is substituted with 1-4C-alkyl (optionally bearing hydroxy), 1-4C-alkyl; or two radicals R1b : a phenylmethylenyl, where the phenyl radical is optionally substituted with at least one hydroxyl or 1-4C-alkoxy; or R1b+A11a (where n is 1) : a 6-membered hydrocarbon-based ring (optionally substituted with 1-2C-alkyl or hydroxy); R11 : 1-4C-alkyl (optionally substituted with hydroxy) or -Si(R22)(OSi(R33) 3) 3; R22, R33 : 1-4C-alkyl, preferably CH 3; R44 : phenyl radical; R55 : 1-4C-alkyl (optionally bearing at least one hydroxy); R66, R22a : 1-4C-alkyl; either A22, B22 : a linear or branched 1-10C-alkyl (optionally contains one or more unsaturations and optionally substituted with a -Si(R22a) 3), 3-6C-alkenyl, H, alkali metal or alkaline-earth metal or ammonium group; or A22+B22 : 6-membered heterocycle optionally substituted with a 1-2C-alkyl; y : 0-3; D1 : -CR24-, O, -CO- or -C(R24)=C(R24)-; E1 : -CR23a- or O; R23a : H or R23; either R23 : hydroxy or 1-4C-alkyl (optionally substituted with at least one hydroxy); or R23+C+R23 : a fused aryl ring (optionally substituted with at least one 1-4C-alkoxy or a hydroxy); R24 : H or linear or branched 1-4C-alkyl; R25 : linear or branched 1-6C-alkyl (optionally substituted with -SO 3 ->Na +>or -C(NHR26)=NR26a); and R26, R26a : cyclic 4-8C-alkyl. Independent claims are included for: (1) coloring human keratin fibers, preferably hair comprising applying the composition on the fibers; and (2) a multicompartment device comprising a first compartment containing (I) and/or (IA) or their plant extracts, and a second compartment containing (II)-(V), carbonyl oligomers or polymers. [Image].

Description

The subject of the present invention is a coloring composition comprising, in a cosmetically acceptable medium, at least one compound of the family of non-glycosylated iridoids extracted from a non-GLYCOSYL IRIDOID COMPOUND AND A PARTICULAR CARBONYL NUCLEOPHILY. of plants, and at least one particular carbonyl nucleophilic compound, as well as a dyeing method using such a composition.

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-glycoside or (seco) iridoide non glycosylated (also called aglycon), extracted plants such as Rubiaceae, Euphorbiaceae, Valerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, Ericaceae, Loganiaceae, etc. The problem with such stains is that they are low intensity or require repeated application over several days or weeks of the composition to obtain a satisfactory color.

In addition, it is difficult to achieve natural nuances, which is a desired advantage. And when such nuances are achieved, it is not uncommon to observe a significant color shift over time. The present invention therefore aims to overcome the disadvantages described above.

Indeed, it has surprisingly been found that dye uptake could be significantly improved from non-glycosylated iridoid compounds and its derivatives, and generally any natural extract containing them, associating with this compound a particular carbonyl nucleophilic compound. It was also found that the structure of the treated fibers was not impaired by the coloring according to the invention. The subject of the present invention is therefore a composition for staining human keratinous fibers comprising, in a cosmetically acceptable medium: a compound of formula (I) and / or of formula (II) below, their optical or geometric isomers, their inorganic or organic acid, their solvates, or a plant extract comprising: R6 (I) (II) Formulas (I) and / or (II) wherein: - R1 represents a hydrogen atom, 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 or 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 between 1 and 5; - R5 represents a group -OO2R'6 in which R'6 represents a hydrogen atom, a C1-C2 alkyl radical, an alkali metal cation, an ammonium group; . R6 represents hydrogen, a group -OO2R'6 in which R'6 represents a hydrogen atom, a C1-C2 alkyl radical, an alkali metal cation, an ammonium group; at least one carbonyl nucleophilic compound chosen from the compounds of the following formulas, their optical or geometrical isomers, their organic or inorganic acid salts, their solvates: Rb (a) Formula in which: A represents: Ra Ra Ra A'1 n Ra; A2-0- B represents:; B2-0- * n is 0 or 1; m is 0 or 1; * Ra, identical or not, represent a hydrogen atom, a Cr 4 * alkyl radical Rb represents a hydrogen atom, an acetyl group (CH3CO-); one of the two radicals Rb representing a hydrogen atom, or two radicals Rb 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 R 10 alkoxy radical where R 1 represents a C 1 -C 4 alkyl radical optionally substituted by a hydroxyl group; a group - Si (R 2) (O Si (R 3) 3) 3 in which R 2, R 3, which may be identical or different, represent a C 1 -C 4 alkyl radical, preferably a methyl radical - a R 4 -R 4 radical group where R 4 represents a phenyl radical; ammonium group -1 \ r (R5) 3 where R5 identical or not, represent a C1-C4 alkyl radical optionally bearing at least one hydroxyl group - a halogen atom, preferably chlorine - optionally fused to a heterocycle 5- or 6-membered, unsaturated or aromatic group, comprising at least one heteroatom, preferably oxygen; a pyridinyl or pyridinium group; the quaternized nitrogen atom being substituted with a C1-C4 alkyl radical optionally bearing a hydroxyl group; o a C1-4-alkyl group; o 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 (CH3CO-), ester -COOR6 or -000R6 with R6 representing a C1-C4 alkyl radical; A2, B2, which are identical or different, represent: a linear or branched C1-C10 alkyl radical which may optionally have one or more unsaturations, optionally substituted with a group -SiR3, the radicals R, which may be identical or different, representing an alkyl radical; a C 3 -C 6 alkenyl radical; o a hydrogen atom, an alkaline metal, alkaline earth metal, an ammonium group, where the radicals A2 and B2 may optionally together form a 6-membered heterocycle where the radicals Rb and A '1, in the case where n is 1, may form in the form of a hydrocarbon ring with 6 members, optionally substituted by a C1-C2 alkyl group, a hydroxyl group; Wherein n is an integer from 0 to 3; the unsubstituted carbon atoms bear a hydrogen atom; A represents -CR24-, O, -CO-, -CR24 = CR24- * B represents -CR'23-, 0; R'23 represents an identical hydrogen atom or R23 * R23 represent a hydroxyl group, a C1-C4 alkyl radical optionally substituted with at least one hydroxyl group; two R23 radicals borne by two adjacent carbon atoms, may together form a fused aromatic ring optionally substituted by at least one C1-C4 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. In which R 25 represents a linear or branched C1-C6 alkyl radical optionally substituted with a group -SO3Na +, -C (NHR26) = NR'26 where R26, R'26, which may be identical or different, represent a C4 -C8 alkyl radical; the compounds of formulas (a) to (d) optionally comprising an anion An or a mixture of cosmetically acceptable anions, guaranteeing the electroneutrality of the formulas; as well as from carbonyl oligomers or nucleophilic polymers selected from polymalonic acids and their esters, polysuccinic acids, sulfoacetic acid polymers, or mixtures thereof. the compounds of formulas (a) to (d) optionally comprising an anion An or a mixture of cosmetically acceptable anions, guaranteeing the electroneutrality of the formulas.

Another subject of the present invention is represented by a process for staining human keratin fibers, in which such a composition is used. A final subject of the invention is constituted by a multi-compartment device comprising a first compartment containing at least one compound of formula (I) and / or (I1) or the plant extract comprising it, and a second compartment containing at least a compound of formula (a) to (d), oligomers or carbonyl polymers. The composition according to the invention makes it possible to obtain various colorations that do not degrade the hair and that are stubborn to shampooing.

Other characteristics and advantages of the invention will emerge more clearly on reading the description and examples which follow. It should be noted, unless otherwise indicated, that the limits of the value domains given in the description are included in the fields. The human keratinous fibers treated by the process according to the invention are preferably the hair In the following, the terms "at least one", "one or more" are considered synonymous. The mineral acid salts are more particularly hydrochlorides, hydrobromides, sulphates, phosphates; the organic acid salts are more particularly citrates, succincts, tartrates, lactates, tosylates, benzenesulfonates, and acetates. The solvates are more particularly hydrates. Compounds of formulas (I) and (II) or plant extract comprising as indicated above, the composition comprises, in a cosmetically acceptable medium, at least one compound of formula (I) and / or of formula (11) above, or a vegetable extract comprising It should be noted that the compounds used in the process according to the invention, and in particular those of formula (I) and / or of formula (11), are said to be unglycosylated insofar as they do not carry any patterns. sugar on the oxygen atom in the pseudo-anomeric position (on the alpha carbon atom of the intracyclic oxygen atom). Preferably, R 1 represents a hydrogen atom, a methyl radical, a hydroxymethyl radical, an aldehyde group; a hydroxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group.

Preferably, R2 represents a hydrogen atom or a hydroxyl radical.

Preferably, R 3, which may be identical or different, represent a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group or an n-butyloxy group. Preferably R5 represents a hydroxycarbonyl radical, a methoxycarbonyl radical or an ethoxycarbonyl radical. Preferably, R6 represents a hydrogen, a hydroxycarbonyl radical, a methoxycarbonyl radical or an ethoxycarbonyl radical. According to a particularly advantageous embodiment of the invention, the compound of formula (I) and / or of formula (II) is genipin (R1 represents a methoxycarbonyl group) and / or genipotic acid or one of its salts (R1 represents a carboxylic group in acid or salified form) and / or genipic acid (R5 represents a hydroxycarbonyl radical and R6, a hydrogen atom) and / or genipinic acid (R5 represents a hydroxycarbonyl radical and R6, a methoxycarbonyl radical).

The compounds of formula (I) and / or of formula (II) are generally found in plant extracts from the following plants: Veronica persica; Genipa americana; Apodytes dimidiata; Randia canthioides; Tarenna attenuata and preferably Genipa americana. It should be noted that by extract, juices, or powders obtained by one or more operations of separation of plant parts of the plant, of enrichment, concentration and, optionally, of drying, from natural plant substances are designated. These compounds of formula (I) and / or of formula (II) are in particular extracted from plants in a manner known per se.

It will be possible in particular to refer to the procedure described in the international application WO 2005/105020. Thus, in the case of the aerial parts, they are washed if necessary, or crushed, optionally in a frozen form, or cut at room temperature, and then macerated in a suitable solvent, in particular ethanol or water then filtered, concentrated and optionally dried. In the particular case of fruits, they are optionally frozen, washed with water to remove impurities present. It may optionally be sterilized, especially with a solution comprising ethanol and chlorine. For the actual extraction, the fruits are defrosted if necessary and pressed for example by means of a specially adapted hydraulic press. The juice thus recovered is filtered, degassed in the presence of nitrogen, this operation avoiding the oxidation of genipin or its derivatives, increasing the amount of dissolved gas. The juice is then stored in an airtight container protected from the air. The recovered juice can then, if necessary, be the subject of a concentration and drying step.

According to a preferred embodiment of the invention, the extract used is derived from Genipa americana. In this case, the extract is obtained from the immature fruit of Genipa americana. The first step of preparation of the extract consists of freezing the fruit beforehand and carrying out a cryomilling step, for example at a temperature of between -20 ° C. and -200 ° C. on the frozen fruit. A fine and homogeneous powder is thus collected. Once this operation is performed, the active ingredient (s) of formula (I) and / or (II) are extracted for example with water. The extract is then concentrated and then optionally dried. The content of compound of formula (I) and / or of formula (II) in the solids content varies from 0.01 to 30% by weight. The content of compound of formula (I) and / or of formula (II) of the composition is between 0.001 and 20% by weight relative to the weight of the composition. Additional dyes The dye composition may further comprise additional dyes, different from the compounds of formula (I) and / or formula (II) above. Among these additional dyes, mention may be made of natural or synthetic direct dyes, oxidation dyes with bases possibly associated with couplers, as well as their combinations.

These direct dyes may be, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinones, direct dyes azines, triarylmethane direct dyes, direct indoamine dyes and natural direct dyes. Among the natural direct dyes that may be mentioned are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, anthragallol, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, chlorophylls, chlorophyllins, orceins, haematein, hematoxylin, brazilin, braziline, safflower dyes (eg, carthamine), flavonoids (with examples are morine, apigenidine, sandalwood), anthocyans (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.

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. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

The oxidation base (s) present in the dyeing composition are in general each present in an amount of between 0.001% and 10% by weight relative to the total weight of the dyeing composition, preferably between 0.005% and 6% by weight. The coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. Carbonyl Nucleophilic Compounds As has been indicated previously, the composition according to the invention comprises at least one carbonyl nucleophilic compound of formulas (a) to (d) or at least one particular carbonyl nucleophilic polymer. Surprisingly, it has been found that the combination of the compounds of formulas (I) and / or (II) with these particular carbonyl nucleophilic compounds, makes it possible to improve the efficiency of the coloring reaction.

According to a first variant, the carbonyl nucleophilic compound is of formula (a) above, its isomers, or its salts, its solvates; this compound being alone or in mixture. By way of examples of compounds of this type, mention may be made of the following compounds, their isomers, their salts and their solvates; these compounds being alone or in admixture: Structure Chemical name 0 0 1 -phenyl-344- (propan-2-yl) phenyl] -propane-1,3-hydroxy-dione CH 3 OH OO 1 - (2,4-dihydroxyphenyl) N, N-trimethyl-4- (3-oxo-3-phenylpropanoypanilinium) -N, N -3-phenylpropane-1,3-dione 14α, 44α- (2-butoxyphenyl) -3-oxopropanoyl] -N, N, N-trimethylanilinium methyl ester of N- (2-hydroxyethyl) -bromide; N, N-dimethyl-4- (3-oxo-3-phenylpropanoyl) anilinium H, N '' C / OH H3 C Br 0 0 0 -CH 3 44342.4-dimethoxyphenyl methyl sulfate salt ) -3-oxopropanoyl] -N, N, N-11-trimethylanilinium O, -CH- ## STR2 ## methoxyphenyl) hepta-1,6-diene-3,5-dione 0 .0 'CH3 H30 Br 1- (2-hydroxyethyl) -3- (3-oxo-3-o-phenylpropanoyl) pyridinium bromide / N7 ° HOO 1-phenyl-3- (pyricin-3-yl) propane-1,3-dione * / NOO / N 1-phenyl-3- (pyridin-3-yl) propa ne-1,3-dione 0111 -. N, N, N-trimethyl-443- (4-methylphenyl) -3-oxopropanoyllanilinium methyl sulfate salt 1-ethyl-3- (3-methyl-3-yl) bromide -oxo-3-br nphenylpropanoyl) pyridinium C n 3 O 1H-indene-1,3 (2H) -dione Lele O 0 0 I CH 3 1H 1,3-bis (4-meoxyphenyl) propane-1,3-dione 10 ## STR1 ## wherein R 1 is bis (4-hydroxy-3-methoxyphenyl) heptane-3,5-HO ab 1-130, wherein O is 1H-O-OH-OH-1,4-bis (3,4-dihydroxyphenyl) heptane-3,5-dione HO - CH 3 OH OH (1 E, 6E) -1,7-bis (4-hydroxy-3) Methoxyphenyl) hepta-1,6-diene-3,5-dione OOHO and 1-phenyl-3- [4- (propan-2-yl) phenyl] propane-1,3-H-allyl CH 3 H 3 C. OO 1- (4-tert-butyphenyl) -3- (4- H3C CH3 0 -hexphenyl) -propane-1,3-dione C H x H3O N- (1- (6-methoxy-1-benzofuran) -5- O1 1- (4-tert-Butylphenyl) -3- (2-hydroxy-3,5-H30-O, 3-dimethylphenyl) propane-1,3-yl; dione CH 3 H 3 CH 3 0 ° 1-methyl-3 '(3-oxo-3-el, c-0-phenylpropanoyl) pyridinium methyl sulfate salt 144- [4-3-phenylpropane-1,3 H3C. ## STR1 ## 1,3-bis (1-hydroxyphenyl) propane-1,3-dione 5-dione \ \ ..-- II Structure Chemical name O` 0 dipropan-2-yl propanedioate, ry H3C y_o 0 ...... 0H 3 CH3 CH3 00 bis (2-methylpropyl) propanedioate, .- ## STR2 ## the 3-ethoxy-3-oxopropanoate salt of potassium. . Bis (2-ethylhexyl) propanedioate (CH 3 0) Bis (2,2-dimethylpropyl) propanedioate 0. ## STR2 ## 0 H, qH, 1 .... 4, CH, 1-1, C H, O 2,2-dimethyl-1,3-dioxane-4,6-dione O CH 3 YC H 3 O O 0 ethyl propanedioate 2-methylprop-2-en-1-yl) -LORCH 2 CH 3 0 0 L CH 3 O propanedioate of bis (4-methylpentan-2-yl) H 3 C CH 3 H 3 C CH 3 CH 3 CH 3 0. - CH3 3 bisprimethylsiemethA propanedioate 0) -Los i H3 I CH3 s CH3 CH3 CH3 CH3 CH3 oo CH3 propanedioate bis (2-ethylpentyl) (4-hydroxy-H3c) O 3,5-dimethoxybenzylidene In the case where the carbonyl nucleophilic compounds are of formula (b) or (c), the latter are preferably such that: n is an integer ranging from 0 to 2 * A represents -CO -, -CR24 = CR24- * B represents -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 borne by two adjacent carbon atoms, may together form a fused aromatic ring optionally substituted by at least one C1-C4 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 nucleophilic compounds of formulas (b) or (c) 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: Structure Chemical name HO 0 OH 2,5,7-trihydroxynaphthalene-1,4-dione; OH-O-OH-2-hydroxy-6-methoxynaphthalene-1,4-dione 1α-alkyl-2,5-dihydroxycyclohexa-2,5-diene; 1, 4-dione 2,5-dihydroxy-3-methylcyclohexa-2,5-diene-1,4-dione O-10 OH OH 2, 3,4,6-tetrahydroxy-5H benzo [7] annulen-5-one HO ee 1 1 ON 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one HO OH OH OH 2,5-dihydroxynaphthalene-1,4-dione O OH 2-hydroxy-5-methoxynaphthalene-1,4-dione ether OH-4-hydroxy-6-methyl-2H-pyran-2-one O-gli2-hydroxycyclohepta-2,4,6-trien-1 In the case of the carbonyl nucleophilic compounds of formula (d), there may be mentioned at least one of the carbonyl nucleophilic compounds of formula (d): ## STR2 ## as an example the compounds their isomers, their salts, their solvates, these compounds being alone or in mixtures: Structure Chemical name 2-methylpropyl cyanoacetate N = 0 0 H3C CH3 0 cyanoacetyl carbamimidate N, N'-Nr dicyclohexyl OyN CrNH N- ethyl cyanoacetate, the salt of sodium 2 - [(cyanoacetyl) oxy] ethanesulphonate. As for carbonyl oligomers or nucleophilic polymers these are selected from polymalonic acids and their esters, polysuccinic acids, sulfoacetic acid polymers, as well as 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: Preferably, the carbonyl-containing nucleophilic compound (s) are chosen from compounds of formulas (a) defined above, as well as than among the compounds of formulas (b) and (c), or mixtures thereof. More particularly, the content of the compound (s) of formula (s) (a) to (d) or carbonyl oligomers or nucleophilic polymers is between 0.001% and 30% by weight relative to the weight of the composition. In accordance with one embodiment of the invention, the composition may comprise at least one primary, secondary amine or its addition salts, ammonia, hydroxylamine, or mixtures thereof. 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, C = S, SO, SO 2 or their combinations ); 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. Among the groups present as substituents for hydrocarbon groups, heterocyclic groups, there may be mentioned the groups: carboxylic, sulphonic, phosphonic, in acid or salified form, hydroxyl, C 1 -C 4 alkoxy, (C 1 -C 8) alkoxycarbonyl, alkyl (C 1 -C 8), C4) sulfonate, (C1-C8) alkyl phosphonate, tri (C1-C4) alkylsilyl, tri (C1-C4) alkoxy silanyl, amino, (di) (C1-C4) alkylamino, tri (C1-C4) alkylammonium, thiol , (C1-C4) alkylthio, aminosulfonyl, (di-) (C1-C4) alkylaminosulfonyl, aminocarbonyl, (di-) (C1-C4) alkylaminocarbonyl, (C1-C4) alkylcarbonylamino, guanidine, ureido (N (R) 2-CO-NR'-) in which the radicals R and R ', independently of each other, represent a hydrogen atom, a C1-C4 alkyl radical, alkyl (CiC4) sulfonylamino; phenyl, indolyl, pyrolynyl, imidazolyl optionally substituted by one or more C1-C2 alkyl, hydroxyl.

Preferably, the groups present as substituents are chosen from carboxylic groups, in acid or salified form; hydroxyl; C1-C4 alkoxy,; C1-C8 alkoxycarbonyl; thiol; (C1-C4) alkylthio; amino; mono- and di-C 1 -C 4 alkylamino; aminocarbonyl; mono- and di-(C1-C2) alkylaminocarbonyl; (C1-C4) alkylcarbonylamino; phenyl, indolyl, pyrrolinyl, imidazolyl optionally substituted with one or more C1-C12 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 (III) 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), (IIIr) below, and also their addition salts: amines and / or derivatives of general formula (IIIa): O, H (IIIa) Formula (IIIa) in which: - R9 represents a hydrogen atom, a linear or branched C1-C6 alkyl radical, preferably substituted with one or several 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 by one or more hydroxyls, an imidazolyl radical, a pyrrolinyl radical optionally substituted with a C1-C2 alkyl group; or an unsubstituted phenyl radical - R "9 represents hydrogen, a C1-C4 alkyl radical, or an unsubstituted phenyl radical - R10 represents a hydrogen or a C1-C4 alkyl radical - R" 9 and R9 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) and most particularly 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 2-amino-2-methylpropanoic acid; alpha-methyl-DL-phenylalanine; D, L-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. o esters derived from amino acids and / or derivatives of general formula (IIIb): o, R11 (IIIb) Formula (IIIb) in which: - R9 represents a hydrogen atom a linear or branched C1-C6 alkyl radical , preferably substituted with one or more hydroxyl, hydroxycarbonyl, (C 1 -C 4) alkoxycarbonyl, thiol, (C 1 -C 4) alkylthio, amido, amino, guanidine, a phenyl radical, optionally substituted by one or more hydroxyl groups, indolyl radical optionally substituted by one or more hydroxyls, an imidazolyl radical, a pyrrolinyl radical optionally substituted with a C1-C2 alkyl group; or an unsubstituted phenyl radical - R "9 represents hydrogen, a C1-C4 alkyl radical, or an unsubstituted phenyl radical - R10 represents a hydrogen or a C1-C4 alkyl radical - R" 9 and R9 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 C1-C18 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, C = 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. As examples of formula (IIIb) there may be mentioned methoxytyrosine, ethylpiperidine-2 carboxylate; 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; L-cysteine 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. amides and thioesters derived from amino acids and / or derivatives of general formula (IIIc): (IIc) Formula (IIIc) in which: R9 represents a hydrogen atom or a C1-C6 alkyl radical; , linear or branched, preferably substituted by one or more hydroxyl groups, (C 1 -C 4) alkoxycarbonyl, hydroxycarbonyl, thiol, (C 1 -C 4) alkylthio, amido, amino, guanidine, a phenyl radical, optionally substituted with one or several hydroxyls, an indolyl radical optionally substituted by one or more hydroxyls, an imidazolyl radical or a pyrrolinyl radical optionally substituted by a C1-C2 alkyl group; R 9 represents a hydrogen or a C 1 -C 4 alkyl radical optionally substituted with 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 atom 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 hydroxyls, an indolyl radical optionally substituted by one or more hydroxyls, an imidazolyl radical or a pyrrolinyl radical optionally substituted by a C1-C2 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 3-amino-dihydrothiophene-2-one hydrochloride; DL homocysteine thiolactone; DL-leucyl-DL-alanine, aspartame; (5) -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 hydrochloride; L-Leucine amide hydrochloride; 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 hydrochloride; 2-amino-3-methylbutanamide; D-alaninamide hydrochloride; L-tyrosinamide hydrobromide; the amide of aspartic acid; L-tyrosine amide hydrochloride; L-arginine amide dihydrochloride; lysine amide dihydrochloride; threonine amide hydrochloride; isoleucine amide hydrochloride; histidine amide dihydrochloride; DL amide hydrochloride, alanine; 2-amino-3- (4-hydroxyphenyl) propionamide; DL-triptophanamide hydrochloride; N-hydroxy-L-arginine acetate (H-ARG-NH 2 2 AcOH); asparagine amide hydrochloride; alpha-diamide hydrochloride, L-glutamic acid gamma; D-phanylalanine amide; D-leucinamide hydrochloride; L-glutamic acid alpha-amide; L-methionineamide; L-cystine bisamide dihydrochloride; glycinamide acetate; D-lysine amide dihydrochloride; glycinamide; L-isoglutamine gamma-methyl ester hydrochloride; D-arginine amide dihydrochloride; (S) pyrrolidine carboxamide; prolyl histamine hydrochloride. Amino compounds of general formula (IIId): R15 R16 NI-1) (R18 R17 R13 R14 (IIId) Formula (IIId) in which: R13, R14, R15 and R16 represent independently of each other: hydrogen * a linear, branched and / or cyclic, saturated and / or unsaturated C 1 -C 20 hydrocarbon radical which may contain from 1 to 5 carbon-carbon double bonds, optionally aromatic, optionally substituted as indicated above, optionally interrupted by one or several heteroatoms and / or with 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 heteroatom; a hydroxyl or C1-C6 alkoxy group, said alkyl radicals R13 and R14 or R14 and R15 or R15 and R16 possibly being able to form, with the carbon atom to which each is attached, a saturated or unsaturated 5 or 7-membered heterocycle, detector may substituted as previously indicated, optionally aromatic, optionally comprising another heteroatom identical to 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 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; X represents a nitrogen, oxygen or sulfur atom. - R17 represents: * a hydrogen atom * a linear or branched, saturated or unsaturated C 1 -C 18 hydrocarbon-based 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 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, SO 2 or combinations thereof; the alkyl radical having no nitro, nitroso, peroxo or diazo function; more particularly R 17 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; - R18 represents: * a hydrogen atom 0 * 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, of 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.

As examples of compounds of formula (111d), mention may be made of L-2-aminohexanoic acid amide hydrochloride; 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 hydrochloride; 3-amino-3-ureido-N-butyric acid ethyl ester; dimethyl (S) -aminosuccinate hydrochloride; beta-L-alanine methyl ester hydrochloride; 4-carboxyyethoxypiperidine; 4-aminobutyric acid; DL-beta-amino adipic acid; 4- (methylamino) butyric hydrochloride; ethyl-gamma-aminobutyrate hydrochloride; hexahydronicotinamide; 4-carboxamide piperidine; 3-carbamoyl 2,2,5,5-tetramethylpyrrolidine. Amino compounds of general formula (III): ## STR5 ## in which: R13, R14, R15, R16 and R18 have the same structure; meaning than before. - 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.

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 enantiomers if they exist, and their salts, their hydrates: (1-aminoethyl) phosphonic acid, (aminomethyl) phosphonic acid, (1-aminoethyl) 1-cyclohexyl) phosphonic acid, (1-aminopropyl) phosphonic acid, (1-aminobutyl) 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-aminoopentyl) phosphonic acid, (1-amino-2-methylbutyl) phosphonic acid, aminooctyl) phosphonic acid, (1-amino-1-methylpropyl) phosphonic acid, (1-amino-1,2-dimethylpropyl) phosphonic acid, (1-amino-1,3-dimethylbutyl) phosphon (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 particular salt oxalate), 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-aminoethyl) 1-methyl-2-phenyl) ethyl phosphonic acid, (2-amino-2-phenyl) ethyl phosphonic acid diethyl ester, or mixtures thereof. Amino compounds of general formula (IIIf): ## STR2 ## 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 hydroxy radical, a (C1-C4) alkoxycarbonyl radical, a carboxaldehyde radical, an (C1-C3) alkoxy-q is a integer between 1 and 18 - X represents an oxygen atom, an SH or OH group, a methylene group optionally substituted by a hydroxyl radical. When X represents an oxygen atom, then R 18 forms a 5- or 6-membered ring optionally substituted by 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 be a [3-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 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, 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-methyl lphe-1-ol, 3-aminopropanethiol, 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, d 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. Amino compounds of general formula (IIIg): ## STR2 ## wherein: R 13, R 14, R 15, R 16 and R 18 have the same meaning as above. R 20 represents a linear C 1 -C 4 alkyl radical; a C 1 -C 4 linear alkoxy radical is an integer between 0 and 5. v is an integer equal to 1 or 2. When v is 2, then R 18 represents a hydrogen. By way of examples of compounds (111g) mention may be made of aminopropyl triethoxysilane, (aminomethyl) trimethylsilane, 2- (trimethylsilyl) ethanamine, 3- (trimethylsilyl) propan-1-amine, 4- (triethoxysilyl) butan-1-amine. N- [3- (trimethoxysilyl) propyl] ethylene diamine, 3- (trimethoxysilyl) propylamine, 3-triethoxysilyl-1-propanamine, (3-methylaminopropyl) trimethoxysilane, and mixtures thereof. o Amino compounds of general formula (IIIh): R 15 R NH R 1 (Formula (IIIh) in which: R 13, R 14, R 15, R 16 and R 18 have the same meaning as above, In addition, the radicals R 13, R 14, R 15 and R16 independently of each other may also be hydroxy, (C1-C4) alkoxycarbonyl, carboxaldehyde, (C1-C3) alkoxy; R21 and R22 independently represent one of other: * a hydrogen atom * a linear, branched and / or cyclic, saturated and / or unsaturated C 1 -C 20 hydrocarbon-based radical which may contain from 1 to 5 carbon-carbon double bonds, optionally substituted as indicated above, optionally terminated by one or more 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, optionally carrying at least one g hydroxyl or C1-C2 alkoxy group, more particularly an optionally substituted C1-C10 alkyl radical; and preferably, a linear or branched C1-C4 alkyl radical optionally substituted by 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 atom of carbon for R16 and the nitrogen atom for the radical R21 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 the '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 enantiomers if they exist, as well as their salts, their hydrates: gerontine, N43-aminopropyl] -1,4-butane-diamine, 1, 4-butanediamine, 4- (ethylamino) -N-butylamine, 243- (2-hydroxy-1,1-bis-hydroxymethyl-ethylamino) -propylamino] -2-hydroxyoxymethylpropane-1,3-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, piperazine-2-carboxylic acid, beta-N-methylaminoalanine , methyl ester of piperazine-2-carboxylic acid, ethyl 3-amino-prolinate, 2,4-diamino-N-butyric acid, N- [3- (trimethoxysilyl) propyl] ethylene diamine or mixtures thereof . The amino compounds of general formula (IIIi) and / or (IIIr): H 2 N (23) x NH 2 z "z 'Y (R 24) x. z (1111) (III) Formulas (IIIi) and / or (IIIr) in which: R23 and R24 represent, independently of each 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 selected from oxygen, nitrogen, sulfur, CO, SO, SO2 or combinations thereof, the alkyl radical not having a nitro, nitroso, peroxo or diazo function; an alkylcarbonyl radical (R-00-) 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) aminosulfonyl radical ((R) 2 N -SO 2 -) in which the R radicals independently represent a hydrogen, a C1-C4 alkyl radical; a (di-) (alkyl) aminocarbonyl radical (R) 2N-O-) in which the radicals R 2 independently represent a hydrogen or a C 1 -C 4 alkyl radical. a halogen atom preferably chosen from bromine, chlorine or fluorine. a C1-04 alkoxy group; a C2-04 (poly) hydroxyalkoxy group; a hydroxycarbonyl group (HO-00-) * an alkoxycarbonyl group (RO-CO-) in which R represents a C1-C4 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 (IIIr), there may be mentioned in particular the compounds listed below, their enantiomers if they exist, as well as their salts, their hydrates alpha-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-aminopyridine dimethylpyridine-4-amine, amino (4-) salicylic acid, methylpara-amino benzoate, benzocaine, aminobenzoic acid, 4-amino-M-anisic acid, 4-amino-3-hydroxy-benzoic acid, methyl ester of the 3,4-diaminobenzoic acid, 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-carbethoxy-1H-pyrazole, 5-amino -1-ethyl-pyraz ole, 1H-benzoimidazol-2-amine, 2-imidazolamine, 1-methylbenzoimidazol-2-amine, and mixtures thereof.

The following amines, in the form of salts or not, may also be used lauroyl Ethylenediamine, octopamine, oleamine, palmitamine, 2- (2-aminoethoxy) ethanol, 2-amino-4,5-dimethylthiazole, hexetidine, mecamylamine, tranylcypromine, triamterene methyl [2- (3-trimethoxysilylpropylamino) ethylamino], bis (triethoxysilylpropyl) amine, 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 of higher or lower molecular weight having one or more primary or secondary amine functions. By "polymer" is meant a compound having at least 5 repeating units chained by covalent bonds. The aminated polymer can be synthesized by radical reactions (polyacrylates, polymethacrylates, polyvinyls, etc.), by condensation reactions (polyesters, polyethers, polyamides, polyurethanes, polydimethylsiloxanes, polypeptides, etc.) by reaction reactions. ring opening (polyesters ...). It can be of natural origin, chemically modified or not, such as for example polysaccharides (cellulose, dextran, chitosan, guar and their amino or thiolated derivatives, The polymers can be in any type of topology: linear chain, branched, in star or hyperbranched (as dendrimers for example), sequenced, statistical 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 star-shaped or hyperbranched polymers Most preferably: 1 / polyamides having free OH, or NH 2 or SH or COOH groups, for example polylysine 2 / natural or modified polysaccharides having NH 2 or SH 3 functions / amino silicones 4 / synthetic polymers with NH 2 or SH functions, in particular polyvinyl vinyls by an amine function and the polymers made from the following commercial monomers: ## STR2 ## , NH 2 NH 2 N H 2 O, NH 2 H 2 O 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 comprises one or more amines, the latter are chosen from ammonia, the compounds of formulas (IIIa), (IIIb), (IIIc), (IIle), (IIIg), in particular when R20 represents a grouping. C1-C4 linear alkoxy, (IIIr), or mixtures thereof. If the composition comprises one or more primary or secondary amines, ammonia, hydroxylamine, their content represent 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. Enzyme The composition according to the invention may optionally comprise at least one enzyme chosen for example from isolase, β-glucosidase resulting for example from sweet almond (EC 3.2.1.21), alcohol oxidase (EC 1.1. 3.13), alcohol dehydrogenases EC 1.1.1.1, alcohol dehydrogenases EC 1.1.1.2, alcohol dehydrogenases EC 1.1.1.71, aromatic alcohol dehydrogenases EC 1.1.1.90 also called aryl alcohol dehydrogenases, aromatic alcohol dehydrogenases EC 1.1.1.97, 3-hydroxybenzyl alcohol dehydrogenases EC 1.1.1.97, alcohol coniferyl dehydrogenases EC 1.1.1.194, cinnamyl alcohol dehydrogenases EC 1.1.1.195, methanol dehydrogenases EC 1.1.1.244, aromatic alcohol oxidases EC 1.1.3.7 still called aryl alcohol oxidases , the alcohol oxidases EC 1.1.3.13, the 4-hydroxymandelate oxidases EC 1.1.3.19, the long chain alcohol hydrocarbon oxidases EC 1.1.3.20, the methanol oxidases EC 1.1.3.31, the alcohol d EC 1.1.99.20, EC 1.5.99.5 methylglutamate dehydrogenases, EC 4.1.1.1 2-oxoacid decarboxylases, EC 4.1.1.7 benzoylformate decarboxylases, EC 4.1.1.43 phenylpyruvate decarboxylases, threonine aldolase EC 4.1.2.5.

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.

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 composing these salts can be as well inorganic (chloride, carbonate, hydrogencarbonate, sulphate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate, hydroxide, etc.), as organic (aspartate, formate, acetate, lactate, citrate, gluconate, succinate, malate, fumarate, orotate ...) The cations composing these salts, associated with the anions above, can come from both alkali metals (preferably lithium, sodium, potassium) and alkaline earth metals (preferably magnesium, calcium), only 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 will be 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. Examples of organic solvents that may be mentioned are lower C1-C4 alkanols, 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 they are present are preferably present in proportions preferably of between 1 and 99% by weight relative to the weight of the composition, and still more preferably between 5 and 95% by weight, relative to the weight of the composition. 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. 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. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in dyeing keratinous fibers or even 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, the amines mentioned above. 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.

The ingredients of the aforementioned composition are advantageously stored separately. In particular, the compound of formula (I) or (II) and the carbonyl nucleophilic compound (s) of formulas (a) to (d) or the carbonyl oligomers or nucleophilic polymers are stored separately. It should also be noted that if one or more amino compounds are present, these are also stored separately from the compounds (I) and (II) or the plant extract comprising them. It may also be advantageous to store at least the compound (s) of formulas (I) / (11) or of the plant extract comprising, in a container protected from air. The composition used in the process according to the invention may also comprise one or more oxidizing agents. In this case, we speak of ready-to-use compositions.

Oxidizing agent In particular, when an oxidizing agent is present, the ready-to-use composition is advantageously obtained by extemporaneous mixing prior to the application of a previously described composition, with at least one composition comprising one or more oxidizing agents. The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for example alkali or alkaline earth metal persulfates, perborates and percarbonates. like sodium, potassium, magnesium.

Also suitable are enzymatic oxidizing agents such as 4-electron oxidoreductases (such as laccases), 2-electron oxidoreductases (such as uricase), where appropriate in the presence of their donor or respective co-factors. , peroxidases. The use of hydrogen peroxide is particularly preferred.

This 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. It should thus be noted that the composition used in the invention may result from the extemporaneous mixing of several compositions.

The composition which has just been described is therefore applied to human keratin fibers, in particular the hair. Coloring method According to a first embodiment, the composition applied does not comprise an oxidizing agent.

This embodiment is appropriate especially in the case where the composition does not comprise oxidation dye (bases / couplers). According to a second embodiment, the ready-to-use composition which has been described above and which is obtained by extemporaneous mixing before application of the composition previously described without any oxidizing agent is applied to the fibers. an oxidizing composition. This embodiment is particularly suitable in the case where the composition comprises one or more oxidation dyes (bases / couplers) or that it is desired to obtain a lightening effect. According to a second variant of this embodiment, the composition without an oxidizing agent and an oxidizing composition are applied successively and without intermediate rinsing. The oxidizing composition used comprises one or more oxidizing agents as defined above. Regarding the organic solvents that may be present in the oxidizing composition, reference may be made to the list indicated previously in the context of the description of the composition according to the invention. Usually, the pH of the oxidizing composition is less than 7. The oxidizing 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. Whatever the embodiment chosen (with or without oxidizing agent, extemporaneous mixture or successive applications of the composition and the oxidizing agent), the mixture applied to the fibers is left in place for a period, in general, of from 1 minute to 5 hours, preferably from 10 minutes to 3 hours. As for the temperature at which the composition or compositions are applied, this is generally between 20 and 200 ° C, advantageously between 20 ° C and 55 ° C. This operation can thus be carried out using, for example, a heating helmet, an infra-red lamp, a hair iron or curling iron. The process according to the invention can 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 40 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). Preferably, these compounds are alkali metal, alkaline earth metal or ammonium salts, carbonate, hydrogencarbonate, chloride, sulfate, silicate, monobasic phosphate, acetate. According to a preferred variant of the invention, this stimulus is carried out by using a composition, comprising in a cosmetically acceptable medium, at least one salt selected from lithium carbonate, sodium, potassium, calcium, ammonium; sodium hydrogencarbonates, potassium; calcium chloride, lithium, sodium; ammonium, sodium, magnesium sulphate; sodium silicate; sodium phosphate monobasic, potassium; sodium acetate. The composition advantageously has a salt content ranging from 0.001 to 40% by weight relative to the weight of the composition, and even more preferably from 0.001 to 20% by weight, relative to the weight of the composition.

It is not beyond the scope of the present invention by performing several successive steps combining stimuli different from each other. At the end of the pause time, the keratinous fibers may be rinsed with water, optionally washed with shampoo, rinsed with water and dried or allowed to dry.

A final subject of the invention is constituted by a multi-compartment device comprising a first compartment containing at least one compound of formula (I) and / or (11) or the plant extract comprising it, and a second compartment containing at least one a carbonyl nucleophilic compound of formulas (a) to (d), oligomer or carbonyl nucleophilic polymer. Preferably, the compound (s) of formulas (1) / (11) or the plant extract comprising it are (are) stored in the absence of air, advantageously under an inert atmosphere. The device may optionally comprise a third compartment comprising one or more amines. The examples below illustrate the invention without limiting its scope. EXAMPLES The staining compositions are obtained by dissolving the extract of Genipa americana (5.10-3mo1.%), Enriched at 9.4% with genipin and a carbonyl compound (10-2 mol%) in solution with a sonicator for 20 minutes. comprising a mixture of benzoic acid, benzyl alcohol, ethanol and water). Each composition is applied to natural gray hair with 90% white hair (1 g of lock to 12 g of solution) and said locks are put 30 minutes at 50 ° C (hotplate).

Each wick is then rinsed, washed with shampoo and dried with a hair dryer. The extract of Genipa americana is obtained by using the following method: The fruits of immature Genipa americana (100 g) are cut into pieces, frozen, freeze-dried and ground before being extracted with milliQ water. The bath ratio is 1/20 (= 1g of lyophilizate per 20m1 of solvent). The suspension is stirred for one hour at room temperature. The raw material is then separated from the solvent by centrifugation at 7500 rpm for 15 minutes, the supernatant is then filtered through Whatman GF / C filter. This filtered extract is then frozen and freeze-dried. HPLC analysis indicates that the extract is enriched to 9.4% genipin. The summary table below indicates the colorations obtained as a function of the carbonyl compounds added. Color structure observed on test wick 1 O OH black purple HO ele OH O 2 elessai O H- OH black 0 test 3 HO O OH black purple lei 0 test 4 0 gold OH

Claims (4)

REVENDICATIONS1. Coloring composition of human keratinous fibers comprising, in a cosmetically acceptable medium, a compound of formula (I) and / or of formula (II) below, their optical or geometric isomers, their mineral or organic acid salts, their solvates , or a plant extract comprising: R6 (I) (II) Formulas (I) and / or (II) wherein:. R1 represents a hydrogen atom, a methyl radical, a hydroxymethyl radical, an aldehyde group; a -CO2R4 group in which R4 represents a hydrogen atom or a C1-C2 alkyl radical; a -CH2-glucose group; R2 represents a hydrogen atom, a hydroxyl radical or 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 between 1 and 5; . R5 represents a -CO2R'6 group 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 wherein R'6 represents a hydrogen atom, a C1-C2 alkyl radical, an alkali metal cation, an ammonium group; at least one carbonyl nucleophilic compound chosen from the compounds of the following formulas, their optical or geometrical isomers, their organic or inorganic acid salts, their solvates: Rb (a) Formula in which: A represents: Ra A '1 n Ra; A2-O- * n is 0 or 1; m is 0 or 1; Ra, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical; Rb represents a hydrogen atom or an acetyl group (CH3CO-); one of the two radicals Rb representing a hydrogen atom, or two radicals Rb representing a phenyl-methylenyl group, the phenyl radical being optionally substituted by at least one hydroxyl radical, C1-C4 alkoxy, 15 * A1, B1, A '1, B'1, identical or not, represent; a C 6 aryl group optionally substituted with at least one C 1 -C 20 linear or branched alkyl radical; a hydroxyl radical; an R 1 alkoxy radical; R 1 represents a C 1 -C 4 alkyl radical optionally substituted by a hydroxyl group; a group -Si (R 2) (OSi (R 3) 3) 3 in which R 2, R 3, which may be identical or different, represent a C 1 -C 4 alkyl radical, preferably an ester-R 4 group where R 4 represents a phenyl radical or an ammonium group; (R 5) 3 where R 5, which may be identical or different, represent 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 chain members, unsaturated or aromatic, comprising at least one heteroatom, preferably oxygen; a pyridinyl or pyridinium group; the quaternized nitrogen atom being substituted by a C1-C4 alkyl radical optionally bearing a hydroxyl group; B represents: Ra; B2-0-o a C1-C4 alkyl group; o 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-), ester -COOR6 or -000R6 with R6 representing a C1-C4 alkyl radical; A2, B2, identical or different, represent: a linear or branched C1-C10 alkyl radical which may optionally have one or more unsaturations, optionally substituted with a group -SiR3, the radicals R, which may be identical or different, representing an alkyl radical; a C 3 -C 6 alkenyl radical; o a hydrogen atom, an alkaline metal, alkaline earth metal, an ammonium group, where the radicals A2 and B2 may optionally together form a 6-membered heterocycle where the radicals Rb and A '1, in the case where n is 1, may form in the form of a hydrocarbon ring with 6 members, optionally substituted by a C1-C2 alkyl group, a hydroxyl group; wherein n is an integer of from 0 to 3, wherein n is an integer of 0 to 3; the unsubstituted carbon atoms bear a hydrogen atom; A represents -CR24-, O, -CO-, -CR24 = CR24- * B represents -CR'23-, 0; R'23 represents an identical hydrogen atom or R23 * R23 represent a hydroxyl group, a C1-C4 alkyl radical optionally substituted with at least one hydroxyl group; two R23 radicals borne by two adjacent carbon atoms, may together form a fused aromatic ring optionally substituted by at least one C1-C4 alkoxy radical, a hydroxyl group; R24, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C4.35R2 CN (d) alkyl radical. In which R25 represents a linear or branched C1-C6 alkyl radical optionally substituted with a -SO3Na + group. , -C (NHR26) = NR'26 in which R26, R'26, which may be identical or different, represent a cyclic C4-C8 alkyl radical; the compounds of formulas (a) to (d) optionally comprising an anion An or a mixture of cosmetically acceptable anions, guaranteeing the electroneutrality of the formulas; as well as from carbonyl oligomers or nucleophilic polymers selected from polymalonic acids and their esters, polysuccinic acids, sulfoacetic acid polymers, or mixtures thereof. 2. Composition according to the preceding claim, wherein the plant extract is from the following plants: Veronica persica; Genipa americana; Apodytes dimidiata; Randia canthioides; Tarenna attenuata, preferably genipa americana. 8. Composition according to any one of the preceding claims, wherein the content of compound of formula (I) and / or of formula (II) of the composition is between 0.001 and 20% by weight relative to the weight of the composition. . 4. Composition according to any one of the preceding claims, wherein the carbonyl nucleophilic compound (s) are of formulas (a) and are chosen from the following compounds, their isomers, their salts, their solvates, alone or as a mixture: Structure Name Chemical 1-phenyl-344- (propan-2-yl) phenyl] propane-1,3-hydrogen dione CH 3 OH OO 1- (2,4-dihydroxyphenyl) -3-phenylpropane-1,3-dione H NN, N-trimethyl-4- (3-oxo-3-phenylpropanoypanilinium) chloride, - CH 2, C, H, C, O salt. 443- (2-butoxyphenyl) -3-oxopropanoyl] -N, N, N-trimethylanilinium methyl sulfate; N- (2-hydroxyethyp-N, N-dimethyl-4- (3-yl) bromide; oxo-3-phenylpropanoyl) anilinium ## STR1 ## N, N'-trimethylanilinium, ## STR1 ## ## STR5 ## wherein: ## STR2 ## nyl) hepta-1, 6-diene-3,5-dione 0 .0 'CH3 H30 Br 1- (2-hydroxyethyl) -3- (3-oxo-3-o-phenylpropanoyl) pyridinium bromide / N7 ° HOO 1-phenyl-3- (pyridin-3-yl) propane-1,3-dione * / NO O / N 1-phenyl-3- (pyridin-3-yl) propane-1,3-dione 0111 -. N, N, N-trimethyl-443- (4-methylphenyl) -3-oxopropanoyllanilinium methyl sulfate salt 1-ethyl-3- (3-methyl-3-yl) bromide -oxo-3-br nphenylpropanoyl) pyridinium C n 3 O 1H-indene-1,3 (2H) -dione Lele O 0 0 I CH 3 1H 1,3-bis (4-meoxyphenyl) propane-1,3-dione 10 ## STR1 ## wherein R 1 is bis (4-hydroxy-3-methoxyphenyl) heptane-3,5-HO ab 1-130, wherein O is 1H-O-OH-OH-1,4-bis (3,4-dihydroxyphenyl) heptane-3,5-dione HO-..-- "OH I HO .----- CH3 3 ---,. OH (1 E, 6E) -1,7-bis (4-hydroxy-3-methoxyphenyl) hepta-1,6-diene-3,5-dione OOHOO el 1-phenyl-3-one (propan-2-yl) phenylpropane-1,3-H30 el dione CH3 H3C. OO 1- (4-tert-butyphenyl) -3- (4- H3C CH3 0 -hexphenyl) -propane-1,3-dione C H x H3O N- (1- (6-methoxy-1-benzofuran) -5- O1 1- (4-tert-Butylphenyl) -3- (2-hydroxy-3,5-H30-O, 3-dimethylphenyl) propane-1,3-yl; 1-Methyl-3- (3-oxo-3-yl) -phenylpropanoyl) -pyridinium methyl ester salt; 3-phenylpropane-1,3 H3C. ## STR1 ## 1,3-bis (1-hydroxyphenyl) propane-1,3-dione 5-dione \ \ ..-- I IStructure Chemical name O` 0 dipropan-2-yl propanedioate, ry H3C y_o 0 ...... 0H 3 CH3 CH3 00 bis (2-methylpropyl) propanedioate, .- ## STR2 ## the 3-ethoxy-3-oxopropanoate salt of potassium. . Bis (2-ethylhexyl) propanedioate (CH 3 0) Bis (2,2-dimethylpropyl) propanedioate 0. ## STR2 ## 0 H, qH, 1 .... 4, CH, 1-1, C H, O 2,2-dimethyl-1,3-dioxane-4,6-dione O CH 3 YC H 3 O O 0 ethyl propanedioate 2-methylprop-2-en-1-yl) -LORCH 2 CH 3 0 0 L CH 3 O propanedioate of bis (4-methylpentan-2-yl) H 3 C CH 3 H 3 C CH 3 CH 3 CH 3 0. - 3-bis (2-ethylpentyl) (4-hydroxy-3H-diol) -3-hydroxy-3-hydroxypropanedioate bisprimethylsilylethoxypropanedioate (B) 3-CH 3 CH 3 CH 3 CH 3 CH 3 o CH 3 propanedioate 5. Composition according to any one of the preceding claims, in which the carbonyl nucleophilic compound (s) are of formula (b) or (c) and such that: n is an integer equal to 0 to 2 * A represents -CO-, -CR24 = CR24- * B represents -CR'23-, R'23 represents a hydrogen atom or R23 * R23, which may be identical or different, represent a hydrogen atom or a hydroxyl group a C1-C4 alkyl radical C4 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 C1-C4 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. 6. Composition according to any one of the preceding claims, in which the carbonyl nucleophilic compound (s) are of formula (b) and / or of formula (c), and are chosen from the following compounds, their isomers, their salts, their Solvates, alone or in admixture: Structure Chemical name HO 0 OH 2,5,7-trihydroxynaphthalene-1,4-dione OH O O O OH 2-hydroxy-6-nnethoxynaphthalene-1,4-dione 1 .el O He O OH 2,5-Dihydroxycyclohexa-2,5-diene-1,4-dione O OH OH 2,5-Dihydroxy-3-methylcyclohexa-2,5-diene-1,4 'eldion O-10 OH 0 OH 2, 3,4,6-tetrahydroxy-5H-benzo [7] annulen-5-one HEN 1 1 ON 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one OH OH OH OH 5-Dihydroxynaphthalene-1,4-dione in which OH 0 0 OH 2-hydroxy-5-methoxynaphthalene-1,4-dione 4-Hydroxy-6-methyl-2H-pyran-2-one O-gli2-hydroxycyclohepta-2,4,6-trien-1-one OH o 2-hydroxy-4- (propan-2-yl) cyclohepta-2 Composition according to any one of the preceding claims, wherein the carbonyl nucleophilic compound (s) are of formula (d) and chosen from the following compounds, their isomers, their Salts, alone or in mixtures: Structure Chemical name 2-methylpropyl cyanoacetate N = 0 0 H3C CH3 0 cyanoacetyl carbamimidate N, N'-Nr dicyclohexyl OyN CrNH N- ethyl cyanoacetate H 3 H Wherein the salt of sodium 2 - [(cyanoacetyl) oxy] ethanesulphonate is a compound of any one of the preceding claims, wherein compound (s) of formula (s) (a) to (d) or carbonyl oligomers or polymers is between 0.001% and 30% by weight relative to the weight of the composition. A composition according to any one of the preceding claims, wherein the composition comprises at least ammonia, hydroxylamine, a primary or secondary amine, or mixtures thereof. Composition according to the preceding claim, wherein the amine is chosen from the amines of formula (III) detailed below, the amine polymers, the purine bases, as well as their addition salts, and combinations thereof; R'7R'8NH (III) Formula (III) in which R'7, R'8, independently of one another represent: - a hydrogen atom - a linear, branched C1-C20 hydrocarbon radical and / or cyclic, saturated and / or unsaturated, aromatic or not, which may contain from 1 to 5 carbon-carbon double bonds and / or optionally substituted, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least a heteroatom or group comprising at least one heteroatom (preferably selected from oxygen, nitrogen, sulfur, C = O, C = S, SO, SO 2 or combinations thereof); 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. 11. Composition according to any one of claims 9 or 10, wherein the content of amine (s) primary (s) or secondary (s) present in the composition is between 0.001 and 65% by weight; and preferably between 0.001 and 30% by weight, based on the weight of the composition. 12. Composition according to any one of the preceding claims, comprising one or more inorganic organic salts chosen from: chloride, carbonate, hydrogencarbonate, sulphate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate, hydroxide, or organic anions chosen from: aspartate, formate, acetate, lactate, citrate, gluconate, succinate, malate, fumarate, orotate associated with * alkaline, alkaline earth metals, transition metals such as scandium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, silver, gold, or ammoniums. 13. Composition according to the preceding claim wherein the salt content (s) is 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. 14. A process for dyeing keratin fibers in which a composition according to any one of the preceding claims is applied. 15. Process according to the preceding claim, in which a temperature of between 20 and 200 ° C is applied. 16. Method according to one of claims 14 or 15, wherein UVA radiation is applied, in particular with an irradiance of between 0.01 and 0.40 milliwatt / cm 2, and / or UVB irradiation radiation in particular. between 0.01 and 0.20 milliwatt / cm2.17. Multi-compartment device comprising a first compartment containing at least one compound of formula (I) and / or (II) or the plant extract comprising, as described in one of claims 1 or 2 and a second compartment containing at least one compound of formula (a) to (d), carbonyl oligomers or nucleophilic polymers according to any one of claims 1, 4 to 7.