FR2980706A1 - Composition, useful for coloring human keratin fibers, comprises iridoid compounds and nucleophilic compounds optionally comprising anion(s) to ensure electrical neutrality of composition, and polyallylimidazolium oligomers or polymers - Google Patents

Abstract

Composition comprises, in a medium, iridoid compounds (I) or their plant extracts, and at least one nucleophilic compound or its optical or geometrical isomer, organic or mineral acid salt or solvate, where the nucleophilic compounds optionally comprise an anion or its mixture to ensure electrical neutrality of the composition. Composition comprises, in a medium, iridoid compounds of formula (I) 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 compound of formula (a)-(h) or its optical or geometrical isomer, organic or mineral acid salt or solvate, where the nucleophilic compounds optionally comprise an anion or its mixture to ensure electrical neutrality of the composition, and polyallylimidazolium oligomers or 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 derived from an aldose or its derivative; n : 1-5; n1 : 0-4; n2 : 0-2, where the unsubstituted carbon atoms bear a hydrogen atom; A : -CR-10-, -N- or -N +>R11; R11 : 1-4C alkyl; X : N or CR7a; R7a : H or R7; R7 : 1-4C alkyl, OH, 1-4C alkoxy, amino, 1-4C alkylamino, where two radicals R7 located ortho to each other may form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms containing O and/or N; either R8, R10 : 1-4C alkyl (optionally substituted with at least one group of -COOR12 or -OCOR12), H, OH, amino, -COR13, -COOR14, -OCOR14 or -OSO 3 ->; and R9 : H, 1-4C alkyl, 1-4C alkylcarbonyl or acetyl; or R8R9 : 5- or 6-membered heterocycle optionally comprising another heteroatom containing O, N or S, where the heterocycle is optionally interrupted with CO group; R12, R13 : 1-4C alkyl; R14 : H, 1-4C alkyl (optionally substituted with at least one 1-4C alkoxy); A1 : S, -(CR18) 2- or -C(R19)=C(R19a)-; R18 : H or 1-4C alkyl; B1 : S; R19, R19a : H or 1-4C alkyl; R15 : 1-4C alkyl, halo, preferably Cl, or 1-4C alkoxy; R15a : 1-2C alkyl; either R16 : H or 1-4C alkyl; and R17 : 1-4C alkyl optionally bearing a hydroxyl group; or R16R17 : 5- or 6-membered fused heterocycle optionally containing one or more unsaturations (optionally substituted with at least one 1-4C alkyl radical); R16a : H or 1-4C alkyl; R17a : H or 1-4C alkyl, where the alkyl group is optionally bearing a hydroxyl or phenyl radical and optionally interrupted with a CO group; R20 : 1-4C alkyl, halo (preferably Cl, Br or I), -COOR21 or -OCOR21; R21 : H, 1-4C alkyl, amino or 6C aryl (optionally substituted with at least one hydroxyl radical); X : N, -CR22 or -CR22a-CO-, where CR22a is linked to Y1 or X; Y1 : N or -CR22aa; either R22, R22a, R22aa : H or linear or branched 1-4C alkyl (optionally substituted with amino, benzyl, phenyl, -COOR23 or -OCOR23); R23 : 1-4C alkyl or -SOR24; or R22, R22aa : fused 6-membered aryl ring; R24 : 1-4C alkyl; Y2 : CH, CR27 or N; Z : N; Z1 : N or NR27a; q : 0-3; r, s : 1 or 2; t : 0-4; u : 0 or 1, where the unsubstituted carbon atoms of the heterocycles contain a hydrogen atom; R27 : linear 1-4C alkyl, halo, preferably Cl, Br or F; R28 : H or linear 1-4C alkyl radical, where the radicals R27 located ortho to the radical NHR28 and R28 is together to form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms of O or N; R29 : linear 1-4C alkyl, where the two radicals R29 together optionally forming a saturated 5-membered heterocycle; either R27a : H, 1-4C alkyl or phenyl radicals; and R31 : 1-4C alkyl, 1-4C alkoxy (optionally substituted with OH) or amino (optionally substituted with -COCH 3); or R27aR31 : 5- or 6-membered (non)aromatic heterocycle (optionally substituted with 1-4C alkyl); or R31R31 : aromatic ring (optionally substituted with an amino radical); and R30 : OH, amino or pyrrolidyl group. Provided that: when A is N, n is 0, X is CH and R8 is NH 2, then R9 is not H or CH 3; if Y2 is CR27, then q is preferably other than 0; and at least one of the radicals R31 is other than hydrogen and/or at least u is 1. 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) or their plant extracts, and a second compartment containing (a)-(h), carbonyl oligomers or polymers, and optionally containing an enzyme for replacing the radical R of (I) with a hydrogen atom or a third compartment containing the enzyme. [Image].

Description

The subject of the present invention is a dyeing composition comprising, in a cosmetically acceptable medium, at least one compound of the family of glycosylated iridoids extracted from plants, prior to or in the form of a hair dyeing compound. non-deglycosylated and at least one particular 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 the rise of dye could be significantly improved from compounds of the glycosylated or non-glycosylated type and of its derivatives, and in a general manner any natural extract containing them, by associating with this compound a particular nucleophilic compound. It has also been found that the structure of the treated fibers is 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 the iridoid family of formula (I) below, their optical or geometrical isomers, their acid salts mineral or organic, their solvates, or a plant extract comprising: (I) wherein: - R1 represents a hydroxymethyl radical, a -CO2R4 group in which R4 represents a hydrogen atom or a C1-C2 alkyl radical; a sugar radical; R2 represents a hydrogen atom, a hydroxyl radical or 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 between 1 and 5; the sugar radical is a derivative derived from an aldose or an aldose derivative: the compound or compounds of formula (I) having optionally undergone a preliminary step consisting in replacing the radical R with a hydrogen atom carried out by means of an enzyme; at least one compound chosen from compounds of the following formulas, their optical or geometric isomers, their organic or inorganic acid salts, their solvates: (R7) n R8 N R9 (a) in which: n is an integer ranging from 0 to 4; 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 ', and R'7 represents a hydrogen atom or R7 * R7, which may be identical or different, represents: 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 can form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms selected from oxygen, nitrogen or their combination, R8, R10, identical or not, represent a hydrogen atom, - a hydroxyl radical, - an amino radical - a C 1 -C 4 alkyl radical optionally substituted with at least one -000 R 12 or -000 R 12 group with R 12 representing a C 1 -C 4 alkyl radical, a -COR 13 group with R13 representing a Cr 4 alkyl radical, a -000R14 or -000R14 group with R14 representing a hydrogen atom, a n is a C 1 -C 4 alkyl radical optionally substituted with at least one C 1 -C 4 alkoxy group; a group -OSO3 * R9 represents a hydrogen atom, a C1-C4 alkyl radical, 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; (R15.) No. + -R.16. In which: 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 C1-4 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, a C 1 -C 4 alkoxy radical; R15 ', which may be identical or different, represents a C1-C12 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 carrying a hydroxyl group, optionally interrupted by a CO group, optionally carrying a phenyl radical * R16 and R17 radicals may forming together a 5- or 6-membered fused heterocycle, optionally having one or more unsaturations, optionally substituted with at least one C1-C4 alkyl radical; In which * n 'is an integer ranging from 0 to 2, the unsubstituted carbon atoms carry a hydrogen atom * R20, identical or different, represent a C1-C4 alkyl radical, a halogen atom (preferably chlorine, bromine, iodine), a radical -COOR21 or -000R21 with R21 representing a hydrogen atom, a C1-C4 alkyl radical, an amino radical, a C6 aryl (phenyl) group optionally substituted with at least one hydroxyl radical * X represents N, CR22, -CR'22-00-, CR'22 being connected to Y or X. * Y represents N, CR "22 * R22, R'22, R" 22, identical or different, represent a hydrogen atom, a linear or branched C1-C4 alkyl radical optionally substituted by an amino radical, a benzyl radical, a phenyl radical, -COOR23 or -000R23 R23 representing a C1-C4 alkyl radical; Where R 24 represents a C 1 -C 4 alkyl radical; R 22 and R 22 may together form a 6-membered aromatic 6-chain fused ring; Y. NHR2, (d) (d ') wherein (d), (d'), (d "), (d-) wherein: (d") * 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 C1-4 alkyl radical, at least one of the radicals R representing at least one hydrogen atom * R27 independently represent one of the others: a linear C1-C4 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, 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 identical or not, represent a linear C1-C4 alkyl radical, the two radicals R29 may together form a saturated 5-membered heterocycle, * R30 independently represent others a hydroxyl radical, an amino radical, a pyrrolidinyl radical * R31 represent independently of each other: - a C1-C4 alkyl radical - a C1-C4 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 formula (d '), at least one 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 (a) to (d-) comprising optionally an anion An or a cosmetically acceptable mixture of anions, guaranteeing the electroneutrality of said formulas; as well as among oligomers or nucleophilic polymers of the polyallylimidazolium type. Another subject of the present invention is represented by a process for staining human keratin fibers, in which such a composition is used. Another subject of the invention consists of a multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising, said compound having undergone a prior stage of replacing the radical R by a hydrogen atom; and a second compartment containing at least one compound of formula (a) to (d "), oligomers or nucleophilic polymers Another object is also constituted by a multi-compartment device comprising a first compartment containing at least one compound of formula (I) ) or the plant extract comprising, and a second compartment containing at least one compound of formula (a) to (d "), oligomers or nucleophilic polymers, and an enzyme for replacing the radical R of formula (I) with a hydrogen atom.

Finally, a last subject of the invention is represented by a multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising it; a second compartment containing at least one compound of formula (a) to (d "), oligomers or nucleophilic polymers, and a third compartment containing an enzyme for replacing the radical R of formula (I) with a hydrogen atom. The composition according to the invention makes it possible to obtain various shades which are not hair-degrading and resistant to shampoos.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 ranges of values given in the description are included in the ranges. The human keratin 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 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 formula (I) or plant extract comprising as indicated above, the composition comprises, in a cosmetically acceptable medium, at least one compound of formula (I) above, or a plant extract comprising. Preferably, R 1 represents a hydrogen atom or a hydroxymethyl radical; 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, R represents a radical derived from a C6 aldose, such as allose, altrose, galactose, glucose, gulose, idose, mannose, talose, 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, R represents a radical derived from glucose, rhamnose, maltose, and preferably from glucose. According to a particularly advantageous embodiment of the invention, the compound of formula (I) is the geniposide (R1 represents a methoxycarbonyl group) or the genipotic acid or one of its salts (R1 represents a hydroxycarbonyl group in the form of acidic or salified). The compounds of formula (I) are generally found in plant extracts from the following plants: Abelia grandiflora, Adenorandia kalbreyeri, Adina polycephala, Aeginetia indica var. gracilis, Asperula sp, Asystasia bella, Aucuba japonica, Avicennia marina, Bartsia trixago, Buddleja Americana, Buddleja crispa, Buddleja japonica, Canthium schimperianum, Castilleja wightii, Chaenorhinum minus, Clerodendrum serratum, Coprosma sp, Cornus officinalis, Craibiodendron hentyi, Cremaspora triflora , Crucianella sp, Daphniphyllum calycinum, 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, 35 Lamiastrum galeobdolon (Lamium galeobdolon), Lamiophlomis rotata (Phlomis rotata), Leonotis nepetaefolia, Linaria sp, Morinda coreia, Mussaenda pubescens, Nepeta cilicia, Nepeta nuda ssp. Albiflora, Odeontites verna, Oldenlandia corymbosa, Paederia scandens, Pedicularis chinensis, Pedicularis condensa ta, Pedicularis dolichocymba, Penstemon confertus, Penstemon deutus, Penstemon richardsonii, Penstemon serrulatus, 40 Pithecoctenium crucigerum, Plantago alpina, Plantago carinata, Plantago lagopus, Plantago lanceolata, Plantago subtilis, Premna barbata, Randia dumetorum, Rhododendron latoucheae, Rothmannia withfieldii, Rubia peregrina, Rubia tinctorum, Saprosma scortechinfi, 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 salvfifofium, Verbascum sinuatum, Verbascum thapsus, Verbascum undulatum, Veronica derwentiana, Vitex nigrum, Wendlandia formosana. Preferably, the plant extract used is Gardenia jasmine. It should be noted that, by extract, means juices, or powders obtained by one or more extraction, enrichment, concentration and possibly drying operations, from natural plant substances. These compounds of formula (I) are extracted from plants in a manner known per se. Thus, in the case of aerial parts, they are washed if necessary, crushed 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 recovered juice can then, if necessary, be the subject of a concentration and drying step. In the case of Gardenia Jasminoïdes, there are commercial extracts having various contents of compound of formula (I).

The content of compound of formula (I) in the solids content ranges from 0.1 to 70% by weight. The content of compound of formula (I) of the composition is between 0.001 and 10% by weight relative to the weight of the composition. It should be noted that the compound (s) of formula (I) have undergone, before or simultaneously with the dyeing process, a step of replacing the radical R 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 enzyme, chosen for example from the isolase, β-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 added to an aqueous solution of compound of formula (I), buffered (acetate, pH between 5.5 and 6). Preferably, the concentration of compound of formula (I) varies between 10 and 30 mM. The enzyme is generally used at a concentration of between 5 - 100 Units / ml (an enzyme unit is generally defined as the number of pmoles of hydrolyzed substrate per minute). The operation is usually carried out at a temperature close to room temperature (between 20 and 45 ° C) and for a period ranging from 1 to 5 hours.

The reaction product can be used directly or else the compound obtained can be extracted, for example by employing a solvent such as ethyl acetate. Additional dyes The dye composition may further comprise additional dyes, different from the compounds of formula (I) 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. Nucleophilic Compounds As has been indicated previously, the composition according to the invention comprises at least one nucleophilic compound of formulas (a) to (d-) or at least one particular nucleophilic polymer. Surprisingly, it has been found that the combination of the compounds of formulas (I) and / or (II) with these particular nucleophilic compounds makes it possible to improve the efficiency of the coloring reaction. According to a first variant, the nucleophilic compound is of formula (a) above, its isomers, or its salts, this compound being alone or in mixture. By way of examples of compounds of this type (formula (a)), mention may be made of the following compounds, their isomers, their salts, their solvates, these compounds being alone or as a mixture: Structure Chemical name OH CH3 1-buty1 2-Methyl-1H-benzimidazol-7-ol 1H-benzimidazol-5-01 (1H-benzimidazol-4-ol) 1H-benzimidazol-5-01 (1H-benzimidazol-4-ol) 1H-N-OH-1H-bromhydrate benzimidazol-4-ol el Ni-la [1,3] thiazolo [3,2-appenzimidazol-3 (2H) -one HO N 1H-benzimidazole-5,6-diol hydrobromide HO NH am 013 H3C 2- (2-methoxy-2-oxoethyl) -1,3-dimethyl-1H-3,1-benzimidazol-3-ium methosulphate. ## STR2 ## Structure Chemical name NH , CH3 CIH 2-methyl-1H-benzimidazol-4-aminoamine dihydrochloride N 1,... N-NH 2 Nil 1,5,6-trimethyl-1H-benzimidazol-4- 1H-benzimidazol-4-amine dihydrochloride, the dihydrochloride MH 2 HNH-benzimidazol-5-amine / H 2 N 2 -methyl-1F-1-dihydrochloride; benzimidazol-5-amine CH, NH Structure Chemical name H2N - HN NH2 1H-benzimidazole-2,5-2-dihydrochloride 1H-dihydrochloride 1H-benzimidazole-2,5,6-H2N 2H-benzimidazole-2,5-dihydrochloride 1H-1H-benzimidazole dihydrochloride 1H-dihydrochloride 4-amino-dihydrochloride 1H-benzimidazol-7-OH OH Structure Chemical Name HO of \ 1H-indole-5,6-diol HO 0 0 \ H 5H-0, 31dioxolo [4,5-tlindole 0 HO el \ / le Ethyl 5,6-dihydroxy-11-1-indole-2-carboxylate HO H 0. Ethyl 6-hydroxy-1H-indole-2-carboxylate HO NH 11 I-indol-5-ol OH 2-methyl-1H-indol-4-ol PI * - Os / '(:) - K + the salt of 1 H-indol-3-yl potassium sulfate 0 [^ N 0. 1H-indol-7-ol-1H-1H-indol-6-ol. Embedded image 4,6-Dimethoxy-1H-indole-2-carboxylic acid and N-methyl-1-indol-4-ol. Ethyl-1H-indole-2-carboxylate N 0 ----- \ H Structure Chemical name 1H-indo1-4-amine N H2 1H-indo1-3-yl 3-methoxypropanoate IN \ 0 1H-1H-indol-6-amine and 1H-indol-1-amine NH 2 NH. 2H-1H-indol-5-amine H-leila N-ethyl-1H-indol-6-amine H-ethyl-5-hydroxy-1H-indole-2-carboxylate ## STR2 ## 2-methyl-1H-indole-5,6-diol hydrobromide HBr HO 1H-indole-2-carboxyl acid 6-h droxide YYN OH H o. 1- (3-Hydroxy-1H-indol-1-yl) ethanone N OH 10 O -H-pyrrolo [2,3-b] pyridin-3-ylacetate The compounds of formula (a) are selected from those wherein * n is an integer of 0 to 4; the unsubstituted carbon atoms carry a hydrogen atom, A represents -CR10-, -N-, X represents CR ', and R' 7 represents a hydrogen atom or R7 * R7, which may be identical or different, represent: C1-C4 alkyl radical, hydroxy radical, C1-C4 alkoxy radical, amino radical, C1-C4 alkylamino radical, two R7 radicals located ortho to each other may form a 5- or 6-membered heterocycle linkages comprising 1 or 2 heteroatom (s) selected from oxygen, nitrogen or combination thereof, preferably oxygen, with R14 representing an atom * R8, R10, identical or different, represent - an atom of hydrogen, - a C1-C4 alkyl radical - a -COOR14 or -000R14 group of hydrogen, 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. As examples of compounds (a) which are more particular, the following compounds may be mentioned, their isomers, their salts, their solvates, these compounds being alone or as a mixture: Structure Chemical name OH CH3 1-butyl-2-methylene 1H-benzimidazol-5-ol 1H-benzinnidazol-4-ol 1H-benzimidazol-7-ol 1H-benzinnidazol-4-ol (. of 1 H-benzimidazol-4-ol HO 0111 N 1 H-benzimidazole-5,6-diol hydrobromide HO HB rH 10 Structure Chemical name N 0111 CH3 CIH 2-methyl-1H-benzimidazol-4H dihydrochloride , 2 amine N 1,...,... N-NH 2 Nile 1,5,6-trimethyl-1H-benzimidazol-4-amine H 3 C 6 CH 3 H, C 2 O 3 1H-benzimidazol-4-amine dihydrochloride MH 2 HNH 3H-benzimidazol-5-amine / H 2 N 2 H 2 -methyl-1H-1-benzimidazol-5-amine CH 3 NH 2 HN NH 2 1H-dihydrochloride 2H-benzimidazole-2H-benzimidazole-1H-benzimidazole-2,5,6-H2N 2 -HCl 2H-dihydrochloride 1H-dihydrochloride 1H-dihydrochloride 4-aminhydrochloride o-1H-benzimidazol-7-OH OH Structure Chemical name HO of 1H-indole-5,6-diol HO 0 0 \ H 5H-0, 31dioxolo [4,5-tlindole 0 HO el \ ethyl 5,6-dihydroxy-11-1-indole-2-carboxylate HO H 0. Ethyl 6-hydroxy-1H-indole-2-carboxylate HO NH 1 I-indol-5-ol OH 2-methyl-1H-indol-4-ol PI lel 1 H-indol-7-ol OH NH. 1 F-1-Indol-6-ol HO N. 1H-ethyl-4-ol-1-ethyl-5-ethoxy-1H-indole-2-carboxylic acid, and 5-hydroxy-1H. Ethyl-indole-2-carboxylate 2-methyl-1H-indole-5,6-diol hydrochloride HO NH HBr. hydroxy-1H-indole-2-carboxylic acid H Structure Chemical name 1H-indol-3-yl 1H-indol-4-amine NH 2 I e O 0 / 1H-indol-3-yl 3-methoxypropanoate 1H-indol-6-amine-NH-1H-indol-7-amine NH 2 NH 2 N 1H-indol-5-amine N lei NH N-ethyl-1H-indol-6-amine Examples of suitable nucleophilic compounds corresponding to formulas (b) or (b ') include the following compounds, their isomers, their salts, their solvates, these compounds being alone or as a mixture: Structure Chemical name CH the methylsulfate salt of 4-dimethylquinolinium is added to the salt of methylsulfate of 1,2-N-dimethylquinolinium 1, wherein o, oo cii, CH 6-m methylsulfate salt ethoxy-1,2- (1,3,1-dimethylquinolinium) = 2-methyl-1H-pyrrolo [1,2-cil] chloride; a] quinolinium Cl el ...- 1-ethyl-2-methylquinolinium iodide CH3 H3C I-CH3 6,8-dimethoxy-1,4-H, C-0 1101 N 0 dimethylquinolinium methylsulphate salt ## STR4 ## Structure Chemical Name H3C CI-13 10,10-dimethy-7,8,9,10-tetrahydro6H- chloride pyrido [1,2-alindolium / N Cl Structure Chemical name S 0 the salt of 2,3-dimethy1-1,3-> - CH3 isobenzyl-3-thium sulfate 113C 0 \ C) N 0 \ CH3 ## STR5 ## 4.5-Dimethyl-3- (2-oxo-2-scH, phenylethyl) -1,3-thiazol-3-ium bromide. N + C ,,, Io the salt of 4-methylbenzenesulfonate 5-chloro-3. ethy1-2-methyl-1,3-benzothiazol-3-lum 0 -S = D H,. 1-1, 3- (2-oxo-2-phenylethyl) -1,3-thiazol-3-yl bromide, N, el, s / 1, methyl sulfate salt. 2-Amino-4-methoxy-3-methyl-1,3-benzothiazol-3-ium-bromide 3- (2-hydroxyethyl) -bromide Preferably, the compound (s) are of formulas (b) and (b ') such that: n and n are 0, unsubstituted carbon atoms have 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; hydrogen, 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 carrying a hydroxyl group, * the radicals R16 and R17 may together form a heterocycle condensed 5- or 6-membered, optionally having one or more unsaturations, optionally substituted by at least one C1-C4 alkyl radical. As examples of compounds (b) or (b ') that are more specific, mention may be made of the following compounds, their isomers, their solvates, or their salts, these compounds being alone or as a mixture: Structure Chemical name S 0 S le 2,3-dimethyl-1,3-thiazol-3-ium methyl sulfate salt; CH 3, CH 3, ID 3, N, CH 3; N + 3- (2-hydroxyethyl) -2-methy1-1,3-OH benzothiazol-3-ium bromide 1-13C CH3 10,10-dimethy-7,8,9,10-tetrahydro6H-pyrido chloride [1,2-ajindolium till 1 Cl 2 CH, the 1,4-dimethylquinolinium methylsulfate salt CH 3 (C) 14, and the salt of 1,2-CH 3 dimethylquinolinium methylsulfate CH 3 ( :) s, o. According to a particular variant, the compound or compounds are of formulas (c) such that: ## STR5 ## is an integer ranging from 0 to 2, the unsubstituted carbon atoms carry a hydrogen atom identical or different, represent a C1-C4 alkyl radical, a chlorine atom, a radical -COOR21 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, R" 22, identical or different, represent a hydrogen atom, an alkyl radical linear or branched C1-C4 optionally substituted with an amino radical, a benzyl radical, a phenyl radical, - * R22 and R "22 may together form an aromatic 6-membered aromatic fused ring With respect to the more specific nucleophilic compounds of formula (c), there may be mentioned by way of example the following compounds, their isomers, their salts, their solvates, these compounds being alone or in mixtures: Structure Chemical name 1 H-imidazo [1,2-b] pyrazole [N] N NH N 3,6-dinnethyl-1H-pyrazolo [5,1-c] [1, 2,4] riazole NI-N 2 -methyl-4H-pyrazolo [1,5-a] benzimidazine) NN-1-G 7-chloro-2,6-methyl-1H-pyrazolo [1,5-b] ] [1,2,4] triazole N, N, N - CI 7-chloro-3,6-dimethyl-1H-pyrazolo [5,1-c] [1,2,4] triazol NH 4 N 6 ethy1-3-methyl-1H-pyrazolo [5,1-c] [1,2,4] briazole N NH) = ---- Ni Ni3,6-diethyl-1H-pyrazolo [5, 1 NH 3 -ethyl-6-methyl-1H-pyrazolo [5,1-c] [1,2,4] triazole NH 3 -alkyl] triazole [1, 2,4] triazole 3-phenyl-1H sodium pyrazolop, 1-c] [1,2,4] triazole-6-carboxylate / N- [CH] 3-phenyl-1H-pyrazolo [5,1-c] [1] 2,4,4-Triazol-6- (N-yl) methanol NNH / 41 -6-ethyl-3- (propan-2-yl) -1H-pyrazolo [5,1-c] [1,2,4] triazole NNNiNNH = i \ li NI-11} the hydrate and hydrochloride of 3,6-dinnethy1-11-1- \ H2O pyrazolo [5,1-c] [1,2,4] triazol-7-amine NH) - 1H-Imidazo [1,2-b] pyrazol-7-NH amine hydrochloride 1H-1H-1H-1H-1H-imidazo [1,2-b] pyrazol-7-NH amine NH 2 2- (7-chloro-6-methyl-1H-pyrazolo [1.5-N b] [1,2,4] triazol-2-yl) propan-1-amine N 2 H 2 Cl 2 dihydrochloride 2-Methyl-4H-pyrazolo [1,5-NH a] benzimidazol-3-amine N - With respect to the nucleophilic compound (s) of formula (d), (d '), (d "), (d') The following compounds may be mentioned by way of example, their isomers, their salts, their solvates, these compounds being alone or in mixtures: Structure Chemical name H2 OH 3-amino-1H-pyrazol-5-ol H. N-(5-hydroxy-1-phenyl-1H-pyrazol-3-yl) acetamide of N, N-3-methyl-1H-pyrazol-5-ol, N 1-12 sulphate of 5- (1-pyrrolidin-1-yepimidazo [1,2-a] pyridin-8-amine HO-S-OH N 0H 2 NH, the dihydrochloride and hydrate of 2 Methyl-2H-H₂O-N-indazole-3,5-diamine N-HClN 2 H 2 Cl 2 2,3-diarnino-6,7-dihydro-NH 2 -5-pyrzolo dihydrochloride 12-a] pyrazol-1-one, 3-amino-6,7-dihydro-11-1,51-1-pyrazolo [1,2-alpyrazol] hydrochloride; 4-Amino-1,2,2-dihydro-3H-pyrazol-3-chlorohydro-3H-dihydro-3H-pyrazol-3-hydrochloride -one o NI-1 Ecl 4-amino-12-diethyl-5-hydroxy-1, 2-dihydro-3H-pyrazol-3-one hydrochloride 0-1.) ----- VNIN N-12 J-13 4,5-diamino-1,2-diethy1,1,2-dihydro-31-1-pyrazol-3-one dihydrochloride. amino-2-chloro-6H-2-methylphenol HO 3,4-dihydro-2H-1,4-benzoxazin-6-ol H 2 NH 2 FCl 2 - [(3-aminopyrazolo [1,5-y] hydrochloride) Oh a] pyr idin-2-yl) oxylethanol NNH 2 OH 2-aminopyridin-3-ol As regards oligomers or nucleophilic polymers, these are chosen from polymers of the polyallylimidazolium type, in particular those made from 1-allyl-3 -butylimidazolium. Preferably, the carbonyl compound (s) are chosen from compounds of formulas (a), (c), (d), (d '), (d "), (d-) or mixtures thereof.

More particularly, the content of compound (s) of formula (s) (a) to (d-) or oligomers or nucleophilic polymers is between 0.001% and 30% by weight relative to the weight of the composition. Amine According to one embodiment of the invention, the composition may comprise at least one primary amine, 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, mention may be made of the following 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 one another, represent a hydrogen atom, a C1-C4 alkyl radical or a (C1-C4) alkylsulphonylamino; 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 1-4 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: amino and / or derivatives of general formula (IIIa): ## STR5 ## in which: R 9 represents a hydrogen atom, a linear or branched C 1 -C 6 alkyl radical; , preferably substituted by 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 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-methylD, 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 by 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. o amides and thioesters derived from amino acids and / or derivatives of general formula (IIIc): 2 o (11c) Formula (IIIc) in which: - R9 represents a hydrogen atom, 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; (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 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): ## STR1 ## in which: R13, R14, R15 and R16 represent independently of one another: hydrogen atom * a linear, branched and / or cyclic, saturated and / or unsaturated, C1-C20 hydrocarbon radical which may contain from 1 to 5 carbon-carbon double bonds, optionally aromatic, optionally substituted as indicated above, optionally interrupted by a or more heteroatoms and / or with 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 having at least one hydroxyl or C1-C2 alkoxy group, 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 , possible lementarily substituted as indicated above, 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 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 C1-C18 hydrocarbon radical and optionally comprising one to five carbon-carbon conjugated or non-conjugated 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 C 1 -C 10 alkyl radical; 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 C1-02 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 atom X for the radical R17 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 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 (IIl): embedded image in which: R 13, R 14, R 15, R 16 and R 18 have the same meaning; 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, 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, - p is an integer between 0 and 7. 35 - u is an integer equal to 1 or 2. When u is 2 then the radical R 18 represents a hydrogen atom .

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 (in particular 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, aminooctyl) phosphonic acid, (1-amino-1-methylpropyl) phosphonic acid, (1-amino-1,2-dimethylpropyl) phosphonic acid, (1-amino-1,3-dim thylbutyl) 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-phosphonobutanoic acid and their ethyl esters, (diethyl (3-aminopropyl) phosphonic acid (especially 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 diethyl ester, (2-aminoethyl) phosphonic acid 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. Amino compounds of general formula (IIIf): embedded image in which: R 13, R 14, R 15, R 16 and R 18 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 ci X R14 - X represents, an oxygen atom, an SH or OH group, a methylene group optionally substituted by a hydroxy 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 the 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-butanol-2-amino-3-methyl beta-amino benzenepropanol, 2-aminopropan-1-ol, 2-amino-1-butanol, 2-amino-4-methylpetan-1-ol, 3-am inopropanethiol, 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, Dglucosamine 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 alcohol 4-amino-N-butyl, 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): R18N R20 (IIIg) Formula (IIIg) in which: R13, R14, R15, R16 and R18 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. Y is an integer equal to 1 or 2. When y 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. Amino compounds of general formula (IIIh): ## STR2 ## in which: . 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; - R21 and R22 represent independently of one another: * a hydrogen atom * a linear, branched and / or cyclic, saturated and / or unsaturated hydrocarbon-based radical, which may contain 1 to 5 double bonds, carbon-carbon 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 chosen from oxygen, nitrogen, sulfur, CO, C = S, SO, SO2 or combinations thereof, optionally bearing at least one hydroxyl group or C1-C2 alkoxy, 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 and their hydrates: gerenterine, N- [3-aminopropyl] -1,4-butane-diamine 1,4-butanediamine, 4- (ethylamino) -N-butylamine, 243- (2-hydroxy-1,1-bis-hydroxymethyl-ethylamino) -propylamino] -2-hydroxymethyl-propane-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-methylamino-alanine, the 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): ## STR2 ## which: R23 and R24 represent, independently of one another, 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, of preferably selected from oxygen, nitrogen, sulfur, CO, SO, SO 2 or combinations thereof, the alkyl radical not having a nitro, nitroso, peroxo or diazo function, an alkylcarbonyl radical (R-00-) in wherein R represents a C 1 -C 4 alkyl radical; an alkylsulfonyl radical (RSO 2 -) wherein 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 C 1 -C 4 alkyl radical or a (di-) (alkyl) aminocarbonyl (R) 2N-O- radical in which the radicals R independently represent a hydrogen, 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) bears (s) a hydrogen atom, Among the compounds of formula (IIIi) and / or (IIIr), mention may be made in particular of the compounds listed below, their enantiomers if 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 Pyridinylamine, 2,5-aminopyridine, gamma-pyridylamine, 2,3-dimethylpyridine-4-amine, amino (4-) salicylic acid, methylpara-amino benzoate, benzocaine, amino acid obenzoic acid, 4-amino-M-anisic acid, 4-amino-3-hydroxy-benzoic acid, 3,4-diaminobenzoic acid methyl ester, methyl 4-amino-3-methoxybenzene carboxylic acid, 2-aminoanisole acid 4-carboxylic acid, 3-amino-4-hydroxy benzoic acid, 3-aminobenzoic acid ethyl ester, 1-amino-3-carboxybenzene, 2-aminobenzoic acid methyl ester, anthranylate ethyl, 1H-pyrazol-3-ylamine, 3-amino-4-carbethoxy-1H-pyrazole, 5-amino-1-ethyl-pyrazole, 1H-benzoimidazol-2-amine, 2-imidazolamine, 1-methylbenzoimidazole, 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 (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 together 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 reactions. ring opening (polyesters ...). It may be of natural origin, chemically modified or not, as for example polysaccharides (cellulose, dextran, chitosan, guar and their amino or thiolated derivatives. The polymers may be in any type of topology: linear, branched chain, star-shaped or hyperbranched (like 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 of star-shaped or hyperbranched polymers Very particularly preferred are: 1 / polyamides containing OH groups, or free NH 2 or SH or COOH, 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 functional groups, in particular vinyl polyvinyls and substituted by an amine function and polymers made from the following commercial monomers: ## STR1 ## 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 still called aryl alcohol dehydrogenases, aromatic alcohol dehydrogenases EC 1.1.1.97, 3-hydroxybenzyl alcohol dehydrogenases EC 1.1.1.97, alcohol coniferylic 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 also 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 dies Hydrogenases EC 1.1.99.20, methylglutamate dehydrogenases EC 1.5.99.5, 2-oxo-acids decarboxylases EC 4.1.1.1, benzoylformate decarboxylases EC 4.1.1.7, phenylpyruvate decarboxylases EC 4.1.1.43, 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, those skilled in the art will take care to choose this or these optional complementary 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 proposed additions. 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 alkalinizing agents usually used in dyeing of keratinous 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, sulfonic 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 (s) of formula (I) or the plant extract comprising it, the compound being or not previously lysed; where appropriate, the enzyme allowing the radical R to be replaced by a hydrogen atom if the compound (I) has not been previously lysed; and the compound or compounds of formulas (a) to (d-) or the oligomer or nucleophilic polymer are stored separately. It should also be noted that if one or more amino compounds are present, they are also stored separately from the compound (s) (I) or the plant extract including, lysed or not. It may also be advantageous to store at least the compound (s) of formula (I) or the plant extract, lysed or not, including 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.

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 composition previously described, 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. Staining Process According to a first embodiment, the applied composition does not comprise an oxidizing agent.

In this case, the ingredients (compound of formula (I) or extract, lysed or not, optionally the enzyme to replace the radical R with a hydrogen atom, the compound or compounds of formulas (a) to ( d-) or the oligomer (s) or nucleophilic polymer (s) are mixed before application.

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, with a coating, is applied to the fibers. 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 oxidizing agent is applied, and an oxidizing composition, successively and without intermediate rinsing. The oxidizing composition used comprises one or more oxidizing agents as defined above. Regarding the organic solvents possibly 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 mixing 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 the 1 minute to 5 hours, preferably 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 method according to the invention can advantageously be implemented 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). 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.

Another subject of the invention consists of a multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising, said compound having undergone a prior stage of replacing the radical R by a hydrogen atom; and a second compartment containing at least one compound of formula (a) to (d "), oligomers or nucleophilic polymers Another object is also constituted by a multi-compartment device comprising a first compartment containing at least one compound of formula (I) ) or the plant extract comprising and a second compartment containing at least one compound of formula (a) to (d "'), oligomers or nucleophilic polymers, and an enzyme for replacing the radical R of formula (I) by a hydrogen atom. Finally, a last subject of the invention is represented by a multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising it; a second compartment containing at least one compound of formula (a) to (d "), oligomers or nucleophilic polymers, and a third compartment containing an enzyme for replacing the radical R of formula (I) with a hydrogen atom.

Preferably, the compound (s) of formula (I) or the plant extract comprising lysed (s) or not, is (are) stored in the absence of air, preferably in an inert atmosphere . The device may optionally comprise an additional 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 gardenia extract lysed enriched with 93% or 99% genipin (5.10-3 mol%) with the sonicator for 20 minutes, and the ingredient (10-2 mol%). ) in 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 10 g of solution) and said locks are put 30 minutes at 50 ° C (hotplate). The wick is then rinsed, washed with shampoo and dried in the hair dryer. test 9 Chemistry HO black purple O OH O 4 test 10 H2N Chemistry black gOl \ NH test 11 N-12 N 2 gray black ® HCI H Chemistry 6 test 12/12 'NH2 gray black gray black ® \ H Chemistry 7 test 13 H2N Chemistry gray black the \ 8 test 14/14 'H2N gOl gray gray Chemistry IN NH 9 test 15 N Chemistry N black H el H 11 test 16 N NI-12 0 H black Chemistry 17 test 17/17' NH2 black black - ) NH C9te set tr y211, - 1 test 18/18 'H2 Chemistry H gray black gray black N / N 13 test 19/19' H2N NHZ N gray black gray black Chemistry Hp / - cI 14 test 20/20 ' NH2 2HC I black purple black purple 15 // N \ NH Chemistry test 21 NH2 ei gray H20 NO NH) 'i \ i Chemistry 15 test 22/22' NH2 gray gray black gray black NH 17 N-Chemistry test 23/23 ' NH2 2HCI gray black gray black 18 i N NH Chemistry test 24/24 'HN) gray black gray black. H N N 2 21-13 Chemistry NH2 19 test 25/25 '\ NH, HCI gray black gray black - 0 \ \ OH Chemistry 14

Claims (12)

REVENDICATIONS1. A composition for staining human keratinous fibers comprising, in a cosmetically acceptable medium, a compound of the following iridoid family of formula (I), their optical or geometrical isomers, their mineral or organic acid salts, their solvates, or a vegetable extract comprising: (I) wherein: - R1 represents a hydroxymethyl radical, a -CO2R4 group in which R4 represents a hydrogen atom or a C1-C2 alkyl radical; a sugar radical; R2 represents a hydrogen atom, a hydroxyl radical or 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 between 1 and 5; the sugar radical is a derivative derived from an aldose or an aldose derivative: the compound or compounds of formula (I) having optionally undergone a preliminary step consisting in replacing the radical R with a hydrogen atom carried out by means of an enzyme; at least one nucleophilic compound chosen from the compounds of the following formulas, their optical or geometrical isomers, their organic or inorganic acid salts, their solvates: ## STR2 ## a) in which: n is an integer of 0 to 4, the unsubstituted carbon atoms bear a hydrogen atom, A represents -OR10-, -N-, -N + Ri- with R11 representing a radical; C1-C4alkyl * X represents N, CR ', and R'7 represents a hydrogen atom or R7 * R7, which may be identical or different, represents: a C1-C4 alkyl radical, a hydroxyl radical or a C1-C4 alkoxy radical; , an amino radical or a C1-C4 alkylamino radical; two R7 radicals located ortho to each other may form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms (s) chosen from oxygen, nitrogen or their combination, R8, R10, identical or different, represent a hydrogen atom, a hydroxyl radical, an amino radical or a C1-C4 alkyl radical substituted by at least one -COOR12 or -000R12 group with R12 representing a C1-C4 alkyl radical, a -COR13 group with R13 representing a C1-C4 alkyl radical, a group -COOR14 or -000R14 with R14 representing a hydrogen atom or a C1-C4 alkyl radical optionally substituted with at least one C1-C4 alkoxy group; a group -OSO3 * R9 represents a hydrogen atom, a C1-4 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; (RA '(R15.) N., B1-Ri16-R16, N' IV + R17 R17, An An (b) (b ') in which: n is an integer ranging from 0 to 4; unsubstituted carbon 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, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical; B 'represents S * R15, which may be identical or different, and represents a C 1 -C 4 alkyl radical, a halogen atom, preferably chlorine or a C 1 -C 4 alkoxy radical; R 1', which may be identical or different, represent a C 1 -C 4 alkyl radical; 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, a C1-C4 alkyl radical, optionally bearing a hydroxyl group, optionally interrupted by a CO group, optionally carrying a phenyl radical; the radicals R16 and R17 may together form a heterocycle; 5- or 6-membered fused compound, optionally having one or more unsaturations, optionally substituted with at least one C1-C4 alkyl radical; Wherein * n 'is an integer 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 halogen atom (preferably chlorine, bromine or iodine), a radical -COOR21 or -000R21 with R21 representing a hydrogen atom, a Cr4 alkyl radical, an amino radical, a C6 aryl group (phenyl) optionally substituted with at least one hydroxyl radical * X represents N, CR22, -CR -22-, CR'22 being connected to Y or X. * Y is N, CR "22 * R22, R'22, R" 22, identical or not, represent a hydrogen atom, an alkyl radical linear or branched C1-C4 optionally substituted with unradical amino, a benzyl radical, a phenyl radical, -COOR23 or -000R23 R23 representing a C1-C4 alkyl radical, -SOR24 where R24 represents a C1-C4 alkyl radical R22 and R "22 may together form an aromatic 6-membered condensed ring (R 30) HO HO u (R 31) ,: z (d) (d ') N x 29 / N o R 29 (d") Formula (d), (d '), (d ") wherein: 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 C1-C4 alkyl radical, at least one of R radicals representing at least one hydrogen atom * R27 independently represent one of the others: a linear C1-C4 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, 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 identical or not, represent a linear C1-C4 alkyl radical, the two radicals R29 may together form a saturated 5-membered heterocycle, * R30 independently represent others a hydroxyl radical, an amino radical, a pyrrolidinyl radical * R31 represent independently of each other: - a C1-C4 alkyl radical - a C1-C4 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 formula (d '), at least one 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; poses of formulas (a) to (d-) comprising, where appropriate, an anion An or a cosmetically acceptable mixture of anions, guaranteeing the electroneutrality of said formulas; as well as among oligomers or polymers of the polyallylimidazolium type. 2. Composition according to the preceding claim, wherein the plant extract is derived from the following plants Abelia grandiflora, Adenorandia kalbreyeri, Adina polycephala, Aeginetia indica var. gracilis, Asperula sp, Asystasia balla, Aucuba japonica, Avicennia marina, Bartsia trixago, Buddleja Americana, Buddleja crispa, Buddleja japonica, Canthium schimperianum, Castilleja wightii, Chaenorhinum minus, Clerodendrum serratum, Coprosma sp, Cornus officinalis, Craibiodendron hentyi, Cremaspora triflora, Crucianella sp, Daphniphyllum calycinum, Daphniphyllum humile, Daphniphyllum macropodum, Eremostachys glabra, Escallonia sp, Eucommia ulmoides, Feretia apodanthera, Galium humifusum, Galium varum, Jasmine gardenia, Garrya elliptica, Globularia dumulosa, Hedyotis corymbosa, Hygrophila difformis, Ixeris chinensis, Lamiastrum galeobdolon (Lamium galeobdolon), Lamiophlomis rotata (Phlomis rotata), Leonotis nepetaefolia, Linaria sp, Morinda coreia, Mussaenda pubescens, Nepeta cilicia, Nepeta nuda ssp. Albiflora, Odeontites verna, Oldenlandia corymbosa, Paederia scandens, Pedicularis chinensis, Pedicularis condensa ta, Pedicularis dolichocymba, Penstemon confertus, 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, 3. 4. 5. Verbascum phlomoides, Verbascum salviifolium, Verbascum sinuatum, Verbascum thapsus, Verbascum undulatum, Veronica derwentiana, Vitex nigrum, Wendlandia formosana, preferably Gardenia jasminoides. Composition according to the preceding claim, in which the preceding step of replacing the radical R with a hydrogen atom is carried out using an enzyme chosen from isolase, beta-glucosidase (EC 3.2.1.21) Composition according to any one of the preceding claims, wherein the content of compound of formula (I) of the composition is between 0.001 and 10% by weight relative to the weight of the composition. Composition according to any one of the preceding claims, in which the compound or compounds are of formulas (a) and are chosen from the following compounds, their isomers, their salts, their solvates, alone or as a mixture: Structure Chemical name OH CH3 1-Butyl-2-methyl-1H-benzimidazol-7-ol 1H-benzimidazol-5-01 1H-benzimidazol-4-ol (1 N-OH) 1H-benzimidazol-4-ol hydrobromide el Ni-la [1,3] thiazolo [3,2-appenzimidazol-3 (2H) -one HO N 1H-benzimidazole-5,6-diol hydrobromide HO NH embedded image 2- (2-methoxy-2-oxoethyl) -1,3-dimethyl-1H-3,1-benzimidazol-3-ium methosulphate, ## STR2 ## Chemical Name NH, CH3 CIH 2-Methyl-1H-benzimidazol-4-amino-1-amine dihydrochloride N 1, ..., ..., n-NH 2 Nile 1,5,6-trimethyl-1H-benzimidazol 4-amine H 3 C 6 H, C 1 H 2 -benzimidazol-4-amin dihydrochloride dihydrochloride MH 2 N.sub.H 111 -benzimidazol-5-amine / H2N go N 2 -methyl-1F -1-benzimidazol 5-amine CH, NH Structure Chemical name H2N-HN NH2 1H-benzimidazole-2,5-2-dihydrochloride 1H-CIH / diamine H 2 N 2 H NH 2 1H-benzimidazole-2,5,6-H 2 N 2 dihydrochloride CIH / 1riannine NH2 N 2 CIH dihydrochloride 4-amino-1H-benzimidazol-7-OH OH Structure Chemical name HO of 1H-indole-5,6-diol HO 0 0H 5H-O, 31dioxolo [4,5-triol 0H ethyl 5,6-dihydroxy-11-1-indole-2-carboxylate HO H 0. Ethyl 6-hydroxy-1H-indole-2-carboxylate HO NH 11 I-indol-5-ol OH 2-methyl-1H-indol-4-ol PI * - Os / '(:) - K + the salt of 1 H-indol-3-yl potassium sulfate 0 [^ N 0. 1 H-indol-7-ol-1 H-indol-6-ol. N-OH-4,6-dimethoxy-1H-indole-2-carboxylic acid and N-methyl-1-indolol-4-ol. Ethyl 5-methoxy-1H-indole-2-carboxylate ## STR1 ## The chemical name 1H-indol-4-amine NH 2 -NH 3H-indol-3-methoxypropanoate 3H-NMR 1H-indol-6-amine and NH-1H-indol-7-amine NH 2 NH. 2H 1H-indol-5-amine H leila N-ethyl-1H-indol-6-amine H A composition according to any one of the preceding claims, wherein the compound (s) are of formulas (a) such that: n is an integer of 0 to 4; the unsubstituted carbon atoms carry a hydrogen atom, A represents -CR10-, -N-, X represents CR ', and R' 7 represents a hydrogen atom or R7 * R7, which may be identical or different, represent: C1-C4 alkyl radical, hydroxy radical, C1-C4 alkoxy radical, amino radical, C1-C4 alkylamino radical, and 5-hydroxy-1H-inclole-2-carboxylate. Ethyl H 2 HNH 2-methyl-11-indole-5,6-diol glycol hydrobromide HO 6-hydroxy-1-1H-indole-2-carboxyl acid 6-hi YY cl N OH H 1H-pyrrolo [2,3-b] pyridin-3-yl acetate OH 1- (3-hydroxy-1H-indol-1-yl) ethanone O * two R7 radicals located ortho to each other may forming a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms selected from oxygen, nitrogen or their combination, preferably oxygen, R8, R10, identical or different, represent a hydrogen atom , a C1-C4 alkyl radical - a -COOR14 or -000R14 group with R14 representing an atom of hy 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. 7. Composition according to any one of the preceding claims, in which the compound or compounds are of formulas (b) and (b ') and are chosen from the following compounds, their isomers, their salts, their solvates, alone or as a mixture. Chemical name CH, methylsulfate salt del, 4-dimethylquinolinium. ## STR1 ## The 1,2-methyl dimethylquinolinium methylsulfate salt is used in the preparation of the formula. ## STR1 ## wherein the salt of 6-methoxy-1,2- (1,3,100-dimethylquinolinium) methylsulphatesulphonate is used as 2-Methyl-1H-pyrrolo [1,2-cla] quinolinium el-1-ethyl-2-methylquinolinium iodide cIl, H3CI-CH, 6,8-dimethoxy-1 methylsulphate salt 4-H, C-0 1101 N 0 dimethylquinolinium I 0,,,,,,,,,,,,, C, O-Structure Structure Chemical Name H3C CH3 10,10- dimethy1-7,8,9,10-tetrahydro6H-pyhdo [1,2-a] indolium / N Cl Structure Chemical Name S 0 the methyl sulfate salt of 2,3-dimethy1-1,3-> - CH3 is thiazol- 3-ium 113C 0 \ C) N 0 \ CH3 o \ 1 .... B .. -... 1 .7CH 4.5-dimethyl-3- (2-oxo-2-scH, phenylethyl) bromide 1,3-thiazol-3-ium 11 Cl. N + C ,,, Io the salt of 4-methylbenzenesulfonate 5-chloro-3. ethy1-2-methyl-1,3-benzothiazol-3-lum 0 -S = D H,. 1-1, 3- (2-oxo-2-phenylethyl) -1,3-thiazol-3-yl bromide, N, el, s / 1, methyl sulfate salt. 2-Amino-4-methoxy-3-methyl-1,3-benzothiazol-3-ium-bromide 3- (2-hydroxyethyl) -bromide 1,3-methyl-N-benzothiazol-3-ium OH 8. A composition according to any one of the preceding claims, wherein the one or more compounds are of formulas (b) and (b ') 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; R 17 represents a C 1 -C 4 alkyl radical, optionally bearing a hydroxyl group. R 17 'represents: a hydrogen atom, a C 1 -C 4 alkyl radical, optionally carrying a hydroxyl group, radicals R16 and R17 may together form 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. 9. Composition according to any one of the preceding claims, in which the compound (s) are of formulas (c) and such that: n 'is an integer ranging from 0 to 2, the unsubstituted carbon atoms carry an atom of hydrogen or R20, which may be identical or different, represent a C1-C4 alkyl radical, a chlorine atom, a -COOR21 or -000R21 radical with R21 representing a hydrogen atom, a C1-C4 alkyl radical or 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, R" 22, identical or different, represent an atom of hydrogen, a linear or branched C1-C4 alkyl radical optionally substituted by an amino radical, a benzyl radical, a phenyl radical, - * R22 and R "22 may together form an aromatic 6-membered fused ring. 10. Composition according to any one of the preceding claims, wherein the carbonyl compounds are of formula (c) and are chosen from the following compounds, their isomers, their salts, their solvates, these compounds being alone or as a mixture: Structure Name 1H-Imidazo [1,2-b] pyrazole NNH N 3,6-dinnethyl-1H-pyrazolo [5,1-c] [1,2,4] riazole NI-N 2 -methyl 4H-pyrazolo [1,5-a] benzimidazin) NN-1-G-7-chloro-2,6-methyl-1H-pyrazolo [1,5-b] [1,2,4] triazole N NI - 7-chloro-3,6-dimethyl-1H-pyrazolo [5,1-c] [1,2,4] triazole NH) 4 N-6-ethyl-3-methyl-1H-pyrazolo [5,1- c] [1,2,4] briazole N NH) = N-N-3,6-diethyl-1H-pyrazolo [5,1-c] [1,2,4] triazole "NH 3 6-Methyl-6-methyl-1H-pyrazolo [5,1-c] [1,2,4] triazole N / NH 3-phenyl-1H-pyrazolo [5,1-cl] [1, 2] 4] triazol-6- /%, sodium carboxylate II 'N' '' ', 1H [si.NNN NH (3-phenyl) -1H-pyrazolo [5.1-c] [1,2,4] triazol -G 1-N-yl) methanol-6-ethyl-3- (propan-2-yl) -1H-pyrazolo [5,1-c] [1,2,4] triazo The hydrate and hydrochloride of 3,6-dinnethyl-11-l-1H-pyrazolo [5,1-c] [1,2,4] triazol-7- amine NH) 1H-1H-imidazo [1,2-b] pyrazol-7-NH-amine // N- [] - ________________________ NH 2 2- (7-chloro-6-methyl-1H-pyrazolo [1.5-N b] [1,2,4] triazol-2-yl) propan-1-amine N 2 H 2 Cl 2 dihydrochloride 2-Methyl-4H-pyrazolo [1,5-NHa] benzimidazol-3-amine N - 11. Composition according to any one of the preceding claims, in which the compound or compounds are of formulas (d), (d '), (d "), (d-) and chosen from the following compounds, their isomers, their salts, their solvates, alone or in mixtures: Structure Chemical name H2 OH 3-Amino-1H-pyrazol-5-ol / H.- [N- (5-hydroxy-1-phenyl) -1H-pyrazol) 3-yl) acetamide of HN-N-3-methyl-1H-pyrazol-5-ol, N 2 O 5- (pyrrolidin-1-yl) pyrimidazo [1,2-i]; 0 a] py ridin-8-amine HO-S-OH 0 N H2 NH, dihydrochloride and 2-methy1-2H-H20 \ 1N-indazole-3,5-diamine hydrate. N Ï-ICI 0 N H2 HCl 2 2,3-diarnino-6,7-dihydro-NH 2 -5-pyrzolo [12-a] pyrazol-1-one dihydrochloride, α, NNH 2 HCl, 3-chlorohydrate. annino-67-dihydro-11-1,51-1-pyrazolo [1,2-ajpyrazol-1-one] IN-4-chlorhydrate Annino4,2-diethyl-5-Ni (pyrrolidin-1-yl) -1,2-dihydro-3H-pyrazol-3-one N-12 I-Cl 4-amino-1,2-diethyl-hydrochloride -hydroxy1,2-dihydro-3H-py razol-3-one CH. ## STR1 ## The 4,5-diamino-1,2-diethy1,1,2-dihydro-3H-pyrazol-3-one Di-N-12 Dihydroxy-N-diol The hydrochloride of 3-amino-2-chloro-6-methylphenol H 2 O 3 3,4-dihydro-2H-1,4-benzoxazin-6-ol H 2 NH 2 F 2 hydrochloride [(3-aminopyrazolo [1,5-a-1H-OH] pyridin-2-yl) oxylethanol NNH 2 2-aminopyridin-3-ol OH 12. A composition according to any one of the preceding claims, wherein the compound (s) are selected from the compounds of formulas (a), (c), (d), (d '), (d ") (d-) or mixtures thereof A composition according to any one of the preceding claims wherein the content of the compound (s) of the formula (s) (a) to (d "') or oligomers or nucleophilic polymers is included 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. Composition according to any one of claims 14 and 15, wherein the content of primary amine (s) or secondary (s) present (s) 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. 17. Composition according to any one of the preceding claims, comprising one or more inorganic organic salts chosen from: chloride, carbonate, hydrogencarbonate, sulfate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate, hydroxide or organic anions chosen from aspartate , formate, acetate, lactate, citrate, gluconate, succinate, malate, fumarate, orotate associated with * alkali metals, alkaline earth metals, transition metals such as scandium, titanium, vanadium, manganese, iron, cobalt, nickel, copper , zinc, silver, gold, or ammoniums. 18. 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. 19. A process for staining human keratinous fibers in which a composition according to any one of the preceding claims is applied.Dyeing process according to the preceding claim, characterized in that the compound (s) of formula (I) undergo, before or simultaneously to the staining process, a step of replacing the radical R with a hydrogen atom. A staining method according to the preceding claim, wherein the step of replacing the radical R with a hydrogen atom is carried out by means of an enzyme selected from isolase, beta-glucosidase (EC 3.2.1.21). Process according to any one of the preceding claims, wherein a temperature of between 20 and 200 ° C is applied. Process according to one of Claims 19 to 22, in which UVA radiation, in particular of irradiance of between 0.01 and 0.40 milliwatt / cm 2, and / or UVB radiation, in particular of irradiance between 0.01 and 0.20 milliwatt / cm 2. Multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising, as described in one of claims 1 or 2, said compound having undergone a preliminary step of replacing the radical R with a hydrogen atom; and a second compartment containing at least one compound of formula (a) to (e), oligomers or nucleophilic polymers, according to any one of claims 1, 5 to 12. Multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising such as described in one of claims 1 or 2; and a second compartment containing at least one compound of formula (a) to (e), oligomers or nucleophilic polymers, according to any one of claims 1, 5 to 12, and an enzyme for replacing the radical R of the formula (I) with a hydrogen atom according to claim 3. 26. A multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising such as described (s) ) in one of claims 1 or 2; a second compartment containing at least one compound of formula (a) to (e), oligomers or nucleophilic polymers according to any one of claims 1, 5 to 12; and a third compartment containing an enzyme 20. 21. 22. 23. 24.allowing to replace the radical R of the formula (I) with a hydrogen atom according to claim 3.