WO2013045701A2

WO2013045701A2 - Dyeing process using a composition comprising a glycosyl iridoid compound and a nucleophile or an amino or thio polymer, composition and devices therefor

Info

Publication number: WO2013045701A2
Application number: PCT/EP2012/069360
Authority: WO
Inventors: Hervé David; Gwenaëlle JEGOU
Original assignee: L'oreal
Priority date: 2011-09-29
Filing date: 2012-10-01
Publication date: 2013-04-04
Also published as: WO2013045701A3

Abstract

The present invention relates to a process of dyeing human keratin fibres by applying a composition, comprising, in a cosmetically acceptable medium: * a compound of the iridoid family of formula (I) below, or a plant extract comprising the same: formula (I) in which hydrogen, methyl, hydroxymethyl, aldehyde; -CO₂R₄ in which R₄: hydrogen, C₁-C₂ alkyl; sugar; R₂: a hydrogen atom, a hydroxyl radical, sugar radical; R₃: hydrogen, hydroxyl, alkyloxy; R: sugar radical (aldose or derivative); integer ranging from 1 to 5; the compound(s) of formula (I) having undergone prior to or simultaneously with the dyeing process, a step consisting in replacing the radical R with a hydrogen atom; ** at least one particular nucleophilic compound or at least one amino or thio polymer, in an amino or thio polymer(s)/compound(s) of formulae (I) and/or (II) weight ratio of at least 0.01. The invention also relates to multi-compartment devices.

Description

DYEING PROCESS USING A COMPOSITION COMPRISING A GLYCOSYL IRIDOID COMPOUND AND A NUCLEOPHILE OR AN AMINO OR THIO POLYMER,

COMPOSITION AND DEVICES THEREFOR The present invention relates to a process of dyeing human keratin hair using a composition comprising, in a cosmetically acceptable medium, at least one compound from the glycosyl iridoid family extracted from plants, optionally deglycosylated beforehand, and at least one particular nucleophilic compound or at least one amino or thio polymer.

Increasing interest has been shown in recent years for natural compounds that can be used as hair dyes.

For example, patent application EP 440 494 discloses a hair dyeing process using a composition comprising at least one compound of (seco)iridoid-glycoside or non-glycosyl (seco)iridoid (also known as aglycone), extracted from plants such as Rubiaceae, Euphorbiaceae, Valerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, Ericaceae, Loganiaceae, etc.

The problem encountered with such colorations is that they are not particularly strong or require repeated application of the composition over several days or several weeks in order to obtain a satisfactory coloration.

Furthermore, it is difficult to achieve natural shades, which is a desired advantage. What is more, when such shades are achieved, it is not uncommon to observe a substantial colour change over time.

The aim of the present invention is thus to overcome the drawbacks described above.

Specifically, it has been discovered, surprisingly, that the colour build-up can be substantially improved using compounds of non-glycosyl iridoid type and derivatives thereof, and, in general, any natural extract containing the same, by combining this compound with a particular carbonyl nucleophilic compound.

It has also been found that the structure of treated fibres is not impaired by the coloration according to the invention.

One subject of the present invention is thus a composition for dyeing human keratin fibres comprising, in a cosmetically acceptable medium:

^* a compound of the iridoid family of formula (I) below, optical or geometrical isomers thereof, mineral or organic acid salts thereof, solvates thereof, or a plant extract comprising the same:

in which:

i represents a hydroxymethyl radical, a group -CO₂R₄ 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 (CrC₄)alkyloxy 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 obtained from an aldose or an aldose derivative:

• The compound(s) of formula (I) have undergone, prior to or simultaneously with the dyeing process, a step consisting in replacing the radical R with a hydrogen atom;

the compound(s) of formula (I) having optionally undergone a preliminary step that consists in replacing the radical R with a hydrogen atom, performed by means of an enzyme;

** at least one nucleophilic compound

(1) Of the carbonyl nucleophile type chosen from the compounds having the following formulae, optical or geometrical isomers thereof, organic or mineral acid salts thereof, and solvates thereof:

B represents:

^* n is equal to 0 or 1 ; m is equal to 0 or 1 ;

* R_a, which may be identical or different, represent a hydrogen atom or a C₁-C4 alkyl radical,

* R_b represents a hydrogen atom, an acetyl group (CH₃CO-); one of the two radicals Rb representing a hydrogen atom, or alternatively two radicals Rb representing a phenylmethylenyl group, the phenyl radical being optionally substituted with at least one hydroxyl or C₁-C4 alkoxy radical;

^* Bi, ΑΊ and ΒΊ, which may be identical or different, represent:

o a C₆ aryl group

optionally substituted with at least

a linear or branched C₁-C₂₀ alkyl radical;

a hydroxyl radical;

an alkoxy radical -OR₁ in which Ri represents a C₁-C4 alkyl radical optionally substituted with a hydroxyl group, a group -Si(R₂)(OSi(R₃)3)3 in which R₂ and R₃, which may be identical or different, represent a C₁-C4 alkyl radical, preferably methyl;

an ester group -OCOR₄ in which R₄ represents a phenyl radical;

an ammonium group -N⁺(R₅)₃ in which R₅, which may be identical or different, represent a C₁-C4 alkyl radical optionally bearing at least one hydroxyl group;

a halogen atom, preferably chlorine;

optionally fused to an unsaturated or aromatic 5- or 6-membered heterocycle, comprising at least one heteroatom, preferably oxygen;

o a pyridynyl or pyridinium group; the quaternized nitrogen atom being substituted with a C₁-C4 alkyl radical optionally bearing a hydroxyl group; o a C₁-C4 alkyl group;

o the groups A and B possibly forming together a 5- or 6-membered ring or heterocycle optionally comprising a heteroatom, preferably oxygen; the said ring or heterocycle being optionally fused to a phenyl radical optionally substituted with at least one acetyl (CH3CO-), ester -COOR₆ or -OCOR₆ group with R₆ representing a C₁-C4 alkyl radical;

* A₂ and B₂, which may be identical or different, represent:

o a linear or branched C₁-C₁₀ alkyl radical, possibly containing one or more unsaturations, optionally substituted with a group -SiR₃, the radicals R, which may be identical or different, representing a C₁-C4 alkyl radical;

o a C₃-C₃ alkenyl radical; a hydrogen atom, an alkali metal or alkaline-earth metal or an ammonium group;

the radicals A₂ and B₂ together possibly forming a 6-membered heterocycle optionally substituted with a C₁-C₂ alkyl radical;

the radicals R_b and ΑΊ, in the case where n is equal to 1 , may together form a 6-membered hydrocarbon-based ring, optionally substituted with a C₁-C₂ alkyl group or a hydroxyl group;

in which:

^* y is an integer from 0 to 3; the unsubstituted carbon atoms bear a hydrogen atom;

^* D represents -CR₂₄-, O, -CO- or -CR₂4=CR₂4-;

^* E represents -CR'₂₃- or O; R'₂₃ represents a hydrogen atom or R_23;

^* R₂₃, which may be identical or different, represent a hydroxyl group or a C₁-C4 alkyl radical optionally substituted with at least one hydroxyl group;

^* two radicals R₂₃ borne by two adjacent carbon atoms may together form a fused aromatic ring optionally substituted with at least one C₁-C4 alkoxy radical or a hydroxyl group;

R24, which may be identical or different, represent a hydrogen atom or a linear or branched C₁-C4 alkyl radical

in which R₂₅ represents a linear or branched Ci-C₃ alkyl radical optionally substituted with a group -S0₃ ^"Na\ -C(NHR₂6)=NR'26 in which R₂6 and R'₂6, which may be identical or different, represent a cyclic C₄-C₈ alkyl radical;

the compounds of formulae (a1 ) to (d1 ) comprising, where appropriate, a cosmetically acceptable anion or mixture of anions An, ensuring the electrical neutrality of the formulations;

and also from carbonyl oligomers or polymers chosen from polymalonic acids and esters thereof, polysuccinic acids and sulfoacetic acid polymers, or mixtures thereof;

(2) Of the nucleophile type chosen from the compounds having the following formulae, optical or geometrical isomers thereof, organic or mineral acid salts thereof, and solvates thereof:

in which:

^* n is an integer from 0 to 4; the unsubstituted carbon atoms bear a hydrogen atom;

* A represents -CR-ιο-, -N- or -N⁺R_i with Rn representing a C C₄ alkyl radical;

* X represents N or CR'₇ and R'₇ represents a hydrogen atom or R_7;

* R₇, which may be identical or different, represent:

- a C1-C4 alkyl radical;

- a hydroxyl radical;

- a C C₄ alkoxy radical;

- an amino radical;

- a C1-C4 alkylamino radical;

^* two radicals R₇ located ortho to each other may form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms chosen from oxygen and nitrogen or a combination thereof,

* Rs and R10, which may be identical or different, represent:

a hydrogen atom,

• a hydroxyl radical,

an amino radical,

· a C1-C4 alkyl radical optionally substituted with at least one group -

COOR12 or -OCOR12 with R₁₂ representing a C C₄ alkyl radical, a group - COR13 with Ri3 representing a C1-C4 alkyl radical,

a group -COOR₁₄ or -OCOR₁₄ with R₁₄ representing a hydrogen atom, a C1-C4 alkyl radical optionally substituted with at least one C1-C4 alkoxy group;

• a group -OS0₃ ^",

preferably R10 is not a hydroxyl radical;

* R₉ represents a hydrogen atom, a C1-C4 alkyl radical, a (CrC₄)alkylcarbonyl group; an acetyl radical;

* the radicals R₈ and Rg may form a 5- or 6-membered heterocycle optionally comprising another heteroatom chosen from oxygen, nitrogen and sulfur, the said heterocycle also possibly being interrupted with a CO group,

^* when A represents N, n is 0, X represents CH and R₈ represents N H₂, then R_g is not a hydrogen atom or a methyl group;

(b'2)

in which:

^* n' is an integer from 0 to 2; the unsubstituted carbon atoms bear a hydrogen atom;

^* A' represents S, -(CRi₈)2- or

with R₁₈ representing a hydrogen atom or a C₁-C4 alkyl radical, R-ig and R'19, which may be identical or different, represent a hydrogen atom or a C₁-C4 alkyl radical;

^* B' represents S;

* Ri5, which may be identical or different, represent a C₁-C4 alkyl radical, a halogen atom, preferably chlorine, or a C₁-C4 alkoxy radical;

* Ri5', which may be identical or different, represent a C1-C2 alkyl radical;

* R16 represents a hydrogen atom or a C₁-C4 alkyl radical;

* 16' represents a hydrogen atom or a C1-C4 alkyl radical;

* Ri7 represents a C₁-C4 alkyl radical optionally bearing a hydroxyl group;

* Ri7' represents:

- a hydrogen atom;

- a C₁-C4 alkyl radical, optionally bearing a hydroxyl group, optionally interrupted with a CO group, optionally bearing a phenyl radical;

^* the radicals Ri₆ and R17 may together form a 5- or 6-membered fused heterocycle, optionally containing one or more unsaturations, optionally substituted with at least one C₁-C4 alkyl radical;

in which:

^* R₂o, which may be identical or different, represent a C₁-C4 alkyl radical, a halogen atom (preferably chlorine, bromine or iodine), a radical -COOR₂₁ or - OCOR₂₁ with R₂i representing a hydrogen atom, a C₁-C4 alkyl radical, an amino radical, or a C₆ aryl group (phenyl) optionally substituted with at least one hydroxyl radical;

^* X represents N, CR₂₂ or -CR'₂₂-CO-, CR'₂₂ being linked to Y or to X;

^* Y represents N or CR"_22;

* R22, R'22 and R"₂₂, which may be identical or different, represent a hydrogen atom, a linear or branched C1-C4 alkyl radical optionally substituted with an amino radical, a benzyl radical, a phenyl radical, -COOR₂₃ or -OCOR₂₃, R₂₃ representing a C1-C4 alkyl radical, -SOR₂4 in which R₂₄ represents a C1-C4 alkyl radical;

^* "₂₂ may together form a fused 6-membered aromatic ring;

Formulae (d2), (d'2), (d"2) and (d'"2) in which:

^* Y represents CH, CR₂₇ or N;

^* z represents N; z' represents N or 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 unsubstituted carbon atoms of the heterocycles bear a hydrogen atom;

^* R represents a hydrogen atom or a C1-C4 alkyl radical, at least one of the radicals R representing at least one hydrogen atom;

^* R₂₇, independently of each other, represent:

- a linear C1-C4 alkyl radical;

- a halogen chosen from chlorine, bromine and fluorine;

^* R"₂₇ represents a hydrogen atom, a C1-C4 alkyl radical or a phenyl radical;

^* R₂8 represents a hydrogen atom or a linear C1-C4 alkyl radical;

^* the radicals R₂₇ located ortho to the radical NHR₂₈ and R₂₈ may together form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms chosen from oxygen and nitrogen;

^* if Y represents CR₂₇, then q is preferably other than 0;

^* R₂₉, which may be identical or different, represent a linear C1-C4 alkyl radical, the two radicals R₂g together possibly forming a saturated 5-membered heterocycle; ^* R₃₀ represent, independently of each other, a hydroxyl radical, an amino radical or a pyrrolidyl radical;

^* R³¹, independently of each other, represent:

- a C1-C4 alkyl radical;

- a C1-C4 alkoxy radical optionally substituted with a hydroxyl group;

- an amino radical optionally substituted with an acetyl group (-COCH₃);

^* R^M27 and R₃₁ may form a 5- or 6-membered aromatic or non-aromatic heterocycle, optionally substituted with a C1-C4 alkyl radical;

^* in formula (d'2), at least one of the radicals R31 is other than hydrogen and/or at least u is equal to 1 ;

^* two radicals R31 may together form an aromatic ring optionally substituted with an amino radical;

^* the compounds of formulae (a2) to (d'"2) comprising, where appropriate, a cosmetically acceptable anion or mixture of anions An, ensuring the electrical neutrality of the formulations;

and also from oligomers or polymers of the polyallylimidazolium type;

or at least one amino or thio polymer, this polymer being present in an amino or thio polymer(s)/compound(s) of formula (I) weight ratio of at least 0.01. Another subject of the present invention is represented by a process for dyeing human keratin fibres, 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 the same, the said compound having undergone a preliminary step that consists in replacing the radical R with a hydrogen atom; and a second compartment containing at least one nucleophilic compound (1 ) or (2), nucleophilic oligomers or polymers, or at least one amino or thio polymer, the composition resulting from the mixing of the compartments having an [amino or thio polymer(s)/compound(s) of formula (I) or plant extract comprising the same] weight ratio of at least 0.01 , if it contains such amino or thio polymer(s).

Another subject of the invention also consists of a multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising the same; and a second compartment containing at least one nucleophilic compound (1 ) or (2), nucleophilic oligomers or polymers, or at least one amino or thio polymer, and an enzyme for replacing the radical R of formula (I) with a hydrogen atom; the composition resulting from the mixing of the compartments having an [amino or thio polymer(s)/compound(s) of formula (I) or plant extract comprising the same] weight ratio of at least 0.01 , if it contains such amino or thio polymer(s). Lastly, a final 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 the same; and a second compartment containing at least one nucleophilic compound (1 ) or (2), a carbonyl oligomer or polymer, and a third compartment containing an enzyme for replacing the radical R of formula (I) with a hydrogen atom; the composition resulting from the mixing of the compartments having an amino or thio polymer(s)/compound(s) of formula (I) or plant extract comprising the same] weight ratio of at least 0.01 , if it contains such amino or thio polymer(s).

The composition according to the invention makes it possible to obtain varied, shampoo-fast colorations, which do not degrade the hair.

Other features and advantages of the invention will become more clearly apparent on reading the description and the examples that follow.

It should be noted that, unless otherwise indicated, the limits of the ranges of values given in the description are included within the ranges.

The human keratin fibres treated via the process according to the invention are preferably the hair.

In the text hereinbelow, the terms "at least one" and "one or more" are considered as being synonymous.

The mineral acid salts are more particularly hydrochlorides, hydrobromides, sulfates and phosphates; the organic acid salts are more particularly citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates and acetates.

The solvates are more particularly hydrates.

Compounds of formula (I) or plant extract comprising the same

As indicated previously, the composition comprises, in a cosmetically acceptable medium, at least one compound of the abovementioned formula (I), or a plant extract comprising the same.

Preferably, Ri represents a hydrogen atom, a hydroxymethyl radical, a hydroxycarbonyl radical, a methoxycarbonyl group or an ethoxycarbonyl group.

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

Preferably, R₃, 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 or talose, preferably glucose. As regards the aldose derivatives, the deoxy derivatives are preferred, for instance rhamnose, and also diholosides, in particular maltose. In accordance with an even more particular embodiment of the invention, R represents a radical derived from glucose, rhamnose or maltose, and preferably derived from glucose.

In accordance with a particularly advantageous embodiment of the invention, the compound of formula (I) is geniposide (Ri represents a methoxycarbonyl group) or geniposidic acid or a salt thereof (Ri represents a hydroxycarbonyl group in acid or salified form).

The compounds of formula (I) are generally found in plant extracts originating 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 henryi, Cremaspora triflora, Crucianella sp, Daphniphyllum calycinum, Daphniphyllum humile, Daphniphyllum macropodum, Eremostachys glabra, Escallonia sp, Eucommia ulmoides, Feretia apodanthera, Galium humifusum, Galium verum, Gardenia jasminof^'des, 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 condensata, 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, Verbascum phlomoides, Verbascum salviifolium, Verbascum sinuatum, Verbascum thapsus, Verbascum undulatum, Veronica derwentiana, Vitex nigrum, Wendlandia formosana.

Preferably, the plant extract used is Gardenia jasminoides.

It should be noted that the term "extract" denotes juices or powders obtained via one or more extraction, enrichment or concentration operations and optionally drying, starting with natural plant substances.

These compounds of formula (I) are extracted from plants, in a manner known per se. Thus, in the case of the aerial parts, they are washed, if necessary, ground and then macerated in a suitable solvent, in particular ethanol or water, and then filtered, concentrated and optionally dried.

In the more particular case of fruit, it is optionally frozen, and washed with water to remove the impurities present. They may optionally be sterilized, in particular with a solution comprising ethanol and chlorine.

For the actual extraction, the fruit is thawed, if necessary, and pressed, for example using a specially adapted hydraulic press.

The juice recovered may then, where appropriate, undergo a step of concentration and drying.

In the case of Gardenia jasminoides, commercial extracts with varied contents of compound of formula (I) exist.

The content of compound of formula (I) in the dry extract ranges from 0.1 % to 70% by weight.

The content of compound of formula (I) in 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, prior to or simultaneously with the dyeing process, a step consisting in replacing the radical R with a hydrogen atom.

This reaction may be performed by any means known to those skilled in the art and may especially be performed using an enzyme chosen, for example, from isolase and β-glucosidase derived, for example, from sweet almond (EC 3.2.1 .21 ).

Thus, in the case where the operation takes place simultaneously with the dyeing process, the enzyme is added to the composition just before its application to the fibres.

In the case where the operation takes place before the application to the fibres, the enzyme is added to a buffered (acetate, pH between 5.5 and 6) aqueous solution of compound of formula (I). Preferably, the concentration of compound of formula (I) ranges between 10 and 30 mM. The enzyme is generally used at a concentration ranging between 5-100 units/ml (one enzymatic unit is in general defined by the number of μηηοΙ of substrate hydrolysed per minute).

The operation usually takes place at a temperature close to room temperature (between 20 and 45°C) and over a period ranging from 1 to 5 hours.

The reaction product may be used directly, or alternatively the compound obtained may be extracted, for example by employing a solvent such as ethyl acetate.

Additional dyes

The dye composition may also contain additional dyes other than the abovementioned compounds of formula (I). Among these additional dyes, mention may be made of natural or synthetic direct dyes, oxidation dyes with bases optionally combined with couplers, and also combinations thereof.

These direct dyes may be chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the natural direct dyes, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, anthragallol protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, chlorophylls, chlorophyllines, orceins, hematin, hematoxylin, brazilin, brazileine, safflower colorants (for instance carthamine), flavonoids (with, for example, morin, apigenidin and sandalwood), anthocyans (such as apigeninidin), carotenoids, tannins, sorghum and cochineal carmine, or mixtures thereof. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts, may also be used.

Among the oxidation bases, mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.

Among these couplers, mention may be made especially of meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers and heterocyclic couplers, and the addition salts thereof.

The oxidation base(s) present in the dye composition are each generally present in an amount of between 0.001% and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.

The coupler(s) are each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.

In general, the addition salts of the oxidation bases and couplers that can be used within the context of the invention are especially chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

Nucleophilic compounds

Carbonyl nucleophilic compounds (1)

As has been indicated previously, the composition according to the invention comprises at least one carbonyl nucleophilic compound (1 ) of formulae (a1 ) to (d1 ) or at least one particular carbonyl polymer. It has been observed, surprisingly, that the combination of the compound(s) of formula (I) with these particular carbonyl nucleophilic compounds (1 ) makes it possible to improve the efficacy of the dyeing reaction.

According to a first variant, the carbonyl nucleophilic compound (1 ) is of abovementioned formula (a1 ), isomers thereof, salts thereof or solvates thereof, this compound being alone or as a mixture.

As examples of compounds of this type, mention may be made of the following compounds, isomers thereof, salts thereof or solvates thereof, these compounds being alone or as a mixture:

bis(2-propyl) propanedioate

bis(2-methylpropyl) propanedioate

3-ethoxy-3-oxopropanoate potassium

bis(2-ethylhexyl) propanedioate

Bis(2,2- dimethylpropyl)propanedioate

2,2-dimethyl-1 ,3-dioxane-4,6-dione

ethyl 2 -methylprop-2-en-1 -yl propanedioate

bis (4-methylpentan-2-yl) propanedioate

In the case where the carbonyl nucleophilic compounds (1 ) are of formula (b1 ) or (c1 ), these compounds are preferably such that:

^* y is an integer ranging from 0 to 2;

* D represents -CO- or -CR₂4=CR₂4-;

^* E represents -CR'23- or O; R'23 represents a hydrogen atom or R₂3_;

^* R₂3, which may be identical or different, represent a hydroxyl group or a C1-C4 alkyl radical optionally substituted with at least one hydroxyl group;

^* two radicals 23 borne by two adjacent carbon atoms may together form a fused aromatic ring optionally substituted with at least one C1-C4 alkoxy radical or a hydroxyl group;

* R₂4, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C4 alkyl radical. As examples of particularly suitable carbonyl compounds of formula (b1 ) or (c1 ), mention may be made of the following compounds, isomers thereof, salts thereof or solvates thereof, these compounds being alone or as mixtures:

Structure Chemical name

2,5,7-trihydroxynapthalene-1 ,4-dione

OH O

2-hydro-6-methoxynaphtalene-1 ,4-dione

¹ 0

As regards the carbonyl nucleophilic compounds of formula (d1 ), examples that may be mentioned include the following compounds, isomers thereof, salts thereof or solvates thereof, these compounds being alone or as mixtures:

As regards the carbonyl oligomers or polymers, they are chosen from polymalonic acids and esters thereof, polysuccinic acids, sulfoacetic acid polymers, and also the salts of these polymers.

These compounds are known to those skilled in the art.

It should be noted that the polymalonic acid esters are especially described in US 4 the following polymer:

Preferably, the carbonyl nucleophilic compound(s) (1 ) are chosen from the compounds of formula (a1 ) defined previously, and also the compounds of formulae (b1 ) and (c1 ), or mixtures thereof.

More particularly, the content of compound(s) of formulae (a1 ) to (d1 ), or of carbonyl oligomers or polymers is between 0.001% and 30% by weight relative to the weight of the composition. Nucleophilic compounds (2)

As has been indicated previously, the composition according to the invention comprises at least one nucleophilic compound (2) of formulae (a2) to (d'"2) or at least one particular nucleophilic polymer.

It has been observed, surprisingly, that the combination of the compounds of formula (I) with these particular nucleophilic compounds (2) makes it possible to improve the efficacy of the dyeing reaction.

According to a first variant, the nucleophilic compound (2) is of abovementioned formula (a2), isomers thereof or salts thereof, this compound being alone or as a mixture.

As examples of compounds of this type (formula (a2)), mention may be made of the following compounds, isomers thereof, salts thereof or solvates thereof, these

5-methoxy-1 H-indole-2- ethyle carboxylate

H

1 H-indol-4-amine

3-methoxypropanoate de 1 H-indol-3-yle

1 H-indol-6-amine

1 H-indol-7-amine

h^2N" 1 H-indol-5-amine

H

N-ethyl- 1 H-indol-6-amine

H H

5-hydroxy-1 H-indole-2-ethyle carboxylate

2-methyl-1 H-indole-5,6-diol hydrobromide

6-hydroxy-1 H-indole-2-carboxylic acid

1 -(3-hydroxy-1 H-indol-1 -yl)ethanone

1 H-pyrrolo[2,3-b]pyridine-3-yl acetate

Preferably the compounds of formula (a2) are selected from those in which:

* A represents -CRi₀- or -N-;

* X represents CR'₇ and R'₇ represents a hydrogen atom or R_7;

* R₇, which may be identical or different, represent:

- a C1-C4 alkyl radical;

- a hydroxyl radical;

- a C1-C4 alkoxy radical;

- an amino radical;

- a C1-C4 alkylamino radical;

^* two radicals R₇ located ortho to each other may form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms chosen from oxygen and nitrogen or a combination thereof, preferably oxygen;

* R₈ and R10, which may be identical or different, represent:

• a hydrogen atom;

• a C1-C4 alkyl radical;

* Rg represents a hydrogen atom or a C1-C4 alkyl radical;

^* when A represents N, n is 0, X represents CH and R₈ represents N H₂, then R₉ is not a hydrogen atom or a methyl group.

As more particular examples of compounds (a2), mention may be made of the following compounds, isomers thereof, salts thereof or solvates thereof, these compounds being alone or as a mixture: Structure Chemical name

1 -butyl-2-methyl-1 H-benzimidazol-7-ol

1 H-benzimidazol-5-ol

OH

N 1 H-benzimidazol-4-ol

H

OH

N

\\ benzimidazol-4-ol hydrobromide

HBr

N

H

1 H-benzimidazol-5,6-diol hydrobromide

2-methyl-1 H-benzimidazol-4-amine HCI dihydrochloride

1 ,5,6-trimethyl— 1 H-benzimidazol-4-amine

I 1 H-benzimidazol-4-amine dihydrochloride

1 H-indol-5-ol

2-methyl- 1 H-indol-4-ol

1 H-indol-7-ol

1 H-indol-6-ol

1 H-indol-4-ol

5-methoxy-1 H-indole-2- ethyle carboxylate

5-hydroxy-1 H-indole-2-ethyle carboxylate

2-methyl-1 H-indole-5,6-diol hydrobromide

6-hydroxy-1 H-indole-2-carboxylic acid

As examples of suitable nucleophilic compounds(2) corresponding to formula (b2) or (b'2), mention may be made of the following compounds, isomers thereof, salts thereof or solvates thereof, these compounds being alone or as a mixture:

Preferably, the compound(s) are of formulae (b2) and (b'2) such that:

^* n and n' are 0; the unsubstituted carbon atoms bear a hydrogen atom;

^* A' represents S or -(CR¹⁸)2- with R ⁸ representing a hydrogen atom or a C1-C4 alkyl radical;

^* B' represents S;

* R16 represents a hydrogen atom or a C C₄ alkyl radical;

* R16' represents a hydrogen atom or a C1-C4 alkyl radical;

* Ri7 represents a C1-C4 alkyl radical optionally bearing a hydroxyl group;

* Ri represents:

- a hydrogen atom;

- a C1-C4 alkyl radical optionally bearing a hydroxyl group;

^* the radicals R16 and R17 may together form a 5- or 6-membered fused heterocycle, optionally containing one or more unsaturations, optionally substituted with at least one C1-C4 alkyl radical.

As more particular examples of compounds (b2) or (b'2), mention may be made of the following compounds, isomers thereof, salts thereof or solvates thereof, these compounds being alone or as a mixture:

According to one particular variant, the nucleophilic compound(s) (2) are of formula (c2) such that:

^* n' is an integer ranging from 0 to 2; the unsubstituted carbon atoms bear a hydrogen atom;

^* R₂o, which may be identical or different, represent a C1-C4 alkyl radical, a chlorine atom, a radical -COOR21 or -OCOR21 with ₂i representing a hydrogen atom, a C1-C4 alkyl radical, an amino radical, or a phenyl group;

^* X represents N, CR22 or -CR'₂₂ which is linked to Y or to X;

^* Y represents N or CR"_22;

* R22, R'22 and R"₂2, which may be identical or different, represent a hydrogen atom, a linear or branched C1-C4 alkyl radical optionally substituted with an amino radical, a benzyl radical, or a phenyl radical;

^* R₂₂ and R' 22 may together form a fused 6-membered aromatic ring. As regards the more particular nucleophilic compounds of formula (c2), examples that may be mentioned include the following compounds, isomers thereof, salts thereof or solvates thereof, these compounds being alone or as mixtures:

As regards the nucleophilic compound(s) of formulae (d2), (d'2), (d"2) and (d'"2), examples that may be mentioned include the following compounds, isomers thereof, salts thereof or solvates thereof, these compounds being alone or as mixtures:

As regards the nucleophilic oligomers or polymers, they are chosen from polymers of the polyallylimidazolium type, especially those prepared from 1 -allyl-3- butylimidazolium. Preferably, the carbonyl compound(s) (2) are chosen from the compounds of formulae (a2), (c2), (d2), (d'2), (d"2) and (d'"2), or mixtures thereof.

More particularly, the content of nucleophilic compound(s) (2) of formulae (a2) to (d'"2) or of nucleophilic oligomers or polymers is between 0.001 % and 30% by weight relative to the weight of the composition.

Amino or thio polymers

For the purposes of the invention, the term "amino or thio polymer" means macromolecules bearing at least one primary or secondary amine function or a thiol function.

The term "polymer" means a compound comprising at least five repeating units linked in sequence via covalent bonds.

The amino or thio polymer may be synthesized via radical, anionic or cationic polymerization reactions (polyacrylates, polymethacrylates, polyvinyls, etc.), via condensation reactions (polyesters, polyethers, polyamides, polyurethanes, polydimethylsiloxanes, polypeptides, etc.) or via ring-opening reactions (polyesters, etc.).

It may be of natural origin, optionally chemically modified, for instance polysaccharides such as cellulose, dextran, chitosan, guar, starch or inulin, and amino or thio derivatives thereof.

The polymers may be in the form of linear, branched, star or hyperbranched chains (for instance dendrimers). In addition, the chains may be in sequenced, statistical or alternating, or block form.

The amine or thiol chemical groups may be naturally present on the polymer chain, at the end of the chain, included in the main chain or side chains, or as a side function on the main chain or on the side chain, on the branches of the star or hyperbranched polymers or as an end group of these branches.

The following are most particularly preferred:

1 / polyamino acids containing free groups NH₂ or SH

21 natural or modified polysaccharides containing NH₂ or SH functions

3/ amino silicones

41 synthetic polymers containing NH₂ or SH functions

5/ polyethyleneimines 6/ oxyalkylenated polymers ending with an amine function; the oxyalkylene group comprising 2 to 5 linear or branched carbon atoms, preferably 2 to 3 carbon atoms

71 alkoxysilane-based polymers containing amine functions.

As regards the natural or modified polysaccharides containing primary or secondary amine functions, mention may be made of chitosan and derivatives thereof, polysaccharides amino-modified via standard methods known to those skilled in the art (in particular reductive amination reactions), for instance amino cellulose, and proteins such as gelatin or collagen.

As regards the amino silicones, these terms denote any silicone comprising at least one primary, secondary or tertiary amine or a quaternary ammonium group.

The following may thus be mentioned:

a ) the polysi l oxa nes co rres po nd i n g to form u l a (a 3) :

in which x' and y' are integers that are dependent on the molecular weight, generally such that the said weight-average molecular weight is between 5000 and 500 000 approximately;

b) the amino silicones corresponding to the formula:

R'_aG3-a-S i (OS i G₂ ) n- (O S i G_bR'2-b )m-0-S i G3-a-R'a (b3 )

in which:

G, which may be identical or different, denote a hydrogen atom or a phenyl, OH or C C₈ alkyl group, for example methyl, or a CrC₈ alkoxy, preferably methoxy,

a, which may be identical or different, denote the number 0 or an integer from 1 to 3, in particular 0,

b denotes 0 or 1 , and in particular 1 ,

m and n are numbers such that the sum (n + m) can range especially from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10;

R', which may be identical or different, denote a monovalent radical of formula -CqH2ql_ in which q is a number from 2 to 8 and L is an optionally quaternized amino group chosen from the following groups: -N "-Q-N(R")₂; -N(R")₂; -N⁺(R")₃ A^"; -N⁺H(R")₂ A^"; -N⁺H₂(R") A^"; -N(R")-Q-N⁺R"H₂ A^"; -NR"-Q-N⁺ (R")₂H A^"; -NR"-Q-N⁺ (R")₃ A^"; in which R" may denote hydrogen, phenyl, benzyl or a saturated monovalent hydrocarbon-based radical, for example an alkyl radical containing from 1 to 20 carbon atoms; Q denotes a linear or branched group of formula C_rH_2r, r being an integer ranging from 2 to 6 and preferably from 2 to 4; and A^" represents a halide ion, for instance fluoride, chloride, bromide or iodide.

A group of amino silicones corresponding to this definition is represented by the silicones known as "trimethylsilyl amodimethicone", corresponding to formula (c3):

in which n and m have the meanings given above (cf. formula b3).

Such polymers are described, for example, in patent application EP-A-95238. Another group of amino silicones corresponding to this definition is re e silicones of formulae (d3) and (e3) below:

in which:

m and n are numbers such that the sum (n + m) may range especially from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200,

n possibly denoting a number from 0 to 999, especially from 49 to 249 and more particularly from 125 to 175 and m possibly denoting a number from 1 to 1000, especially from 1 to 10 and more particularly from 1 to 5,

Ri, R₂ and R3, which may be identical or different, represent a hydroxyl or C₁-C4 alkoxy radical, at least one of the radicals Ri to R₃ denoting an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy mole ratio preferably ranges from 0.2:1 to 0.4:1 , preferably from 0.25:1 to 0.35:1 and is more particularly equal to 0.3:1. The weight-average molecular mass of the silicone preferably ranges from 2000 to 1 000 00

in which:

p and q are numbers such that the sum (p + q) may range especially from 1 to

1000, in particular from 50 to 350 and more particularly from 150 to 250,

p possibly denoting a number from 0 to 999, especially from 49 to 349 and more particularly from 159 to 239 and q possibly denoting a number from 1 to 1000, especially from 1 to 10 and more particularly from 1 to 5,

Ri and R₂, which may be identical or different, represent a hydroxyl or C₁-C4 alkoxy radical, at least one of the radicals Ri or R₂ denoting an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy mole ratio preferably ranges from 1 :0.8 to 1 :1 .1 , preferably from 1 :0.9 to 1 :1 and is more particularly equal to 1 :0.95.

The weight-average molecular mass of the silicone preferably ranges from 2000 to 200 000, even more particularly from 5000 to 100 000 and more particularly from 10 000 to 50 000.

The weight-average molecular masses of these amino silicones are measured by gel permeation chromatography (GPC) at room temperature, as polystyrene equivalents. The columns used are μ styragel columns. The eluent is THF and the flow rate is 1 ml/minute. 200 μΙ of a solution containing 0.5% by weight of silicone in THF are injected. Detection is performed by refractometry and UV-metry.

The commercial products corresponding to these silicones of structure (d3) or (e3) may include in their composition one or more other amino silicones whose structure is different from formula (d3) or (e3).

A product containing amino silicones of structure (d3) is sold by the company Wacker under the name Belsil® ADM 652.

A product containing amino silicones of structure (e3) is sold by Wacker under the name Fluid WR 1300®.

Another group of amino silicones corresponding to this definition is represented by formula (f3) below:

in which:

m and n are numbers such that the sum (n + m) can range especially from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and especially from 49 to 149, and m possibly denoting a number from 1 to 2000 and especially from 1 to 10;

A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.

The weight-average molecular mass of the amino silicones preferably ranges from 2000 to 1 000 000 and even more particularly from 3500 to 200 000.

Synthetic polymers that may be mentioned in particular include polyvinyls substituted with a pendent primary or secondary amine function (such as polyallylamine, polyvinylamines and copolymers thereof) and polymers prepared from the monomers below, via a radical route:

As regards the alkoxysilane derivatives, mention may be made in particular of polymers resulting from the condensation of at least one alkoxysilane having the following formula: H₂N -R_d-Si-R_b

R_c

in which formula:

R_a, R_b and R_c, which may be identical or different, denote a linear or branched Ci- C₂o alkoxy radical, the alkyl part of which is optionally interrupted with one or more oxygen atoms, and more particularly a linear or branched C₁-C₂0 and preferably C₁-C4 alkoxy radical,

R_d is a divalent C₁-C₂0 alkylene radical, optionally bearing at least one hydroxyl group, at least one group CH₂=CH-; optionally interrupted with at least one phenylene, -0-, -S-, -NH-CO-NH- group; -CO-NH-, =NH or =NR_e with R_e representing a C C₄ alkyl radical optionally bearing an amino group.

Preferably, the compound is (3-aminopropyl)triethoxysilane.

Examples that may be mentioned include the following amino or thio polymers:

- polylysines, sold in particular by Chisso,

- thiol-modified polylysines, in particular modified by reaction between an amino polymer and homocysteine thiolactone or n-acetyl-homocysteine thiolactone or gamma-thiobutyrolactone.

- amino-dextran, sold, for example, by Carbomer,

- amino-cellulose, for example those described in WO 01/25283 from BASF,

- chitosan and amino derivatives thereof,

- amino silicones, sold in particular by Dow Corning (e.g. Dow Corning 939 Emulsion or DC2-8566 Amino Fluid),

- dendrimer containing amine functions, for instance poly(amidoamines) (PAMAM), sold in particular by Dendritech, DSM and Sigma-Aldrich (Starburst, PAMAM Dendrimer, G(2, O) from Dendritech)),

- polyvinyl alcohol (Amino PVA), for example sold by Carbomer,

- poly(allylamine) sold especially by Beckman under the trade names PAA, polyvinylamines and poly(N-methyl)vinylamine,

- poly(diallylamines) and copolymers thereof,

- poly(vinylamine-co-vinylformamide) copolymers known especially under the trade name Catiofast by BASF,

- amine-terminated polyoxyalkylene polymers, for example of Jeffamine type sold by Huntsman,

- prepolymers such as Priamine C36 (Croda),

- alkoxysilane prepolymers, in particular aminopropyltriethoxysilane prepolymers,

- partially deprotected polyoxazolines,

- PEI (polyethyleneimine), sold in particular by BASF, under the name Lupasol, and thiol derivatives thereof (PEI thiols). Preferably, the polymers are chosen from amino polymers.

Among the preferred amino polymers, mention may be made of the polymers of classes 1/ and 21 mentioned previously.

As indicated previously, the content of amino or thio polymer(s) is such that the weight ratio of amino or thio polymer(s)/compound(s) of formula (I), in the composition, is at least 0.01.

Advantageously, the said weight ratio is between 0.01 -4/1 .

More particularly, the content of amino or thio polymer(s) is between 0.1 % and

10% by weight relative to the weight of the composition.

Amine

In accordance with one embodiment of the invention, the composition may comprise at least one primary or secondary amine or addition salts thereof, ammonia or hydroxylamine, or mixtures thereof.

In general, the addition salts of these amine compounds that may be used in the context of the invention are especially chosen from addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, dodecylbenzenesulfonates, phosphates and acetates, and preferably the hydrochlorides, citrates, succinates, tartrates, phosphates and lactates.

In particular, the primary or secondary amine(s) that may be used in the context of the invention are chosen from the amines of formula (III) that will be detailed below, amino polymers, purine bases, and also the addition salts thereof, and combinations thereof.

In particular, formula (I II) is as follows:

RVR'eNH (I II)

in which formula (I II) R'₇ and R's represent, independently of each other:

- a hydrogen atom;

- a linear, branched and/or cyclic, saturated and/or unsaturated, aromatic or non- aromatic C1-C20 hydrocarbon-based radical, which may contain from 1 to 5 carbon- carbon double bonds and/or may be optionally substituted, optionally interrupted with 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=0, C=S, SO and SO2 or combinations thereof); the said hydrocarbon-based radicals R'₇ and R'₈ possibly forming, with the nitrogen atom to which each is attached, a saturated or unsaturated 5- or 7-membered heterocycle, which is optionally substituted, optionally aromatic, optionally fused to a 6-membered aromatic or heteroaromatic nucleus, optionally comprising another nitrogen or non- nitrogen heteroatom; the hydrocarbon-based radical not comprising any nitro, nitroso, peroxo or diazo functions.

The compounds of formula (III) are advantageously not oxidation bases or oxidation couplers employed in the dyeing of keratin fibres.

Among the groups present as substituents of the heterocyclic hydrocarbon- based groups, mention may be made of the following groups:

carboxylic, sulfonic, phosphonic, in acid or salified form,

hydroxyl, C1-C4 alkoxy, (CrC₈)alkoxycarbonyl,

(Ci-C₄)alkylsulfonate, (CrC₈)alkylphosphonate,

tri(CrC₄)alkylsilyl, tri(Ci-C₄)alkoxysilanyl,

amino, (di)(Ci-C₄)alkylamino, tri(Ci-C₄)alkylammonium,

thiol, (Ci-C₄)alkylthio,

aminosulfonyl, (di)(Ci-C4)alkylaminosulfonyl,

aminocarbonyl, (di)(Ci-C₄)alkylaminocarbonyl,

(Ci-C )alkylcarbonylamino,

guanidine,

ureido (N( )₂-CO-NR'-) in which the radicals R and R\ independently of each other, represent a hydrogen atom or a C1-C4 alkyl or (Ci-C₄)alkylsulfonylamino radical; phenyl, indolyl, pyrrolyl, imidazolyl, optionally substituted with one or more C1-C2 alkyl or hydroxyl.

Preferably, the groups present as substituents are chosen from the following groups: carboxylic in acid or salified form; hydroxyl; C1-C4 alkoxy; (CrC₈)alkoxy carbonyl; thiol; (CrC₄)alkylthio; amino; mono- and di(Ci-C₄)alkylamino; aminocarbonyl; mono- and di(CrC2)alkylaminocarbonyl; (Ci-C4)alkylcarbonylamino; phenyl, indolyl, pyrrolinyl, imidazolyl optionally substituted with one or more CrC₂ alkyl or hydroxyl.

In particular, the amine(s) of formula (III), which may be identical or different, comprise from 1 to 5 primary and/or secondary amine functions; the amine(s) not comprising any N-N bonds. Also, the amine(s) of formula (III) do not comprise more than two heteroatoms bonded together.

Preferably, the amine(s) are compounds of formula (III), more particularly chosen from the compounds of formulae (Ilia) to (llli), (llli') below, and also the addition salts thereof.

amino acids an f general formula (Ilia):

(m )

in which formula (Ilia):

- R₉ represents a hydrogen atom, a linear or branched C C₆ alkyl radical, preferably substituted with one or more hydroxyl, hydroxycarbonyl, thiol, (Ci-C₄)alkylthio, amido, amino or guanidine groups, a phenyl radical, optionally substituted with one or more hydroxyl, an indolyl radical optionally substituted with one or more hydroxyl, an imidazolyl radical, a pyrrolinyl radical optionally substituted with a Ci-C₂ alkyl group; or an unsubstituted phenyl radical;

- R"₉ denotes a hydrogen, a C1-C4 alkyl radical or an unsubstituted phenyl radical;

- R10 represents a hydrogen or a C1-C4 alkyl radical;

- R"_g and R₉ possibly forming, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered heterocycle.

Examples of compounds of formula (Ilia) that may be mentioned most particularly include asparagine, cysteine, glutamine, histidine, lysine, methionine, phenylalanine, proline, pyrrolysine, serine, threonine, tryptophan and tyrosine, and the addition salts thereof.

According to another variant, the compounds of formula (Ilia) are advantageously chosen from 2-amino-2-methylpropanoic acid; a-methyl-D,L- phenylalanine; D,L-a-(hydroxymethyl)alanine; D,L-a-methyl-meta-tyrosine; omethyl- D,L-tryptophan; D,L-a-methylhistidine dihydrochloride; L-2-methylserine; (S)-2- methylcysteine dihydrochloride; (S)-2-methyl-2-pyrrolidinecarboxylic acid.

o esters derived from amino acids and/or derivatives of general formula (1Mb):

(1Mb)

in which formula (1Mb):

- R₉ represents a hydrogen atom, a linear or branched C C₆ alkyl radical, preferably substituted with one or more hydroxyl, hydroxycarbonyl, (Ci-C4)alkoxycarbonyl, thiol, (CrC₄)alkylthio, amido, amino or guanidine groups, a phenyl radical, optionally substituted with one or more hydroxyl, 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 a 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 possibly forming, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered heterocycle.

- R11 represents:

- a linear or branched, saturated or unsaturated C Ci₈ hydrocarbon-based radical optionally comprising from 1 to 5 conjugated or unconjugated carbon-carbon double bonds, optionally substituted as indicated previously, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, C=0, C=S, SO and SO2 or combinations thereof; the alkyi radical not comprising any nitro, nitroso, peroxo or diazo functions;

- an unsubstituted benzyl radical.

According to one particular variant, R₉ and Rn may optionally form a saturated 5-membered carbon-based ring.

Preferably, n represents a linear or branched, optionally substituted C1-C10 alkyi radical; a benzyl radical; and even more preferably a linear or branched C1-C4 alkyi radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups; a benzyl radical.

As examples of formula (1Mb), mention may be made of methoxytyrosine, 2- ethylpiperidine carboxylate; D,L-phenylalanine methyl ester; L-cystine dimethyl ester dihydrochloride; L-leucine methyl ester; methyl 2-amino-3-methylbutyrate; L- phenylalanine ethyl ester hydrochloride; L-glutamic acid diethyl ester hydrochloride; ethyl (S)-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; methyl (S)-pyrrolidine-2- carboxylate hydrochloride; methyl 2-aminoacetate hydrobromide; ethylglycine; H-D,L- alanine ethyl ester hydrochloride; D,L-tyrosine ethyl ester hydrochloride; methyl 2- (phenylamino)acetate; ethyl glutamate; bis(a, -tert-butyl) D,L-aspartate hydrochloride; ethyl L-a-aminoisocaproate hydrochloride; benzyl glycinate para-toluenesulfonate; D,L-alanine ethyl ester hydrochloride; 5-hydroxy-D,L-tryptophan methyl ester hydrochloride; D,L-threonine methyl ester hydrochloride; D,L-proline tert-butyl ester; D,L-phenylalanine methyl ester hydrochloride.

o amides and thioesters derived from amino acids and/or derivatives of general for

(IMC)

in which formula (lllc):

- R₉ represents a hydrogen atom, a linear or branched C C₆ alkyi radical, preferably substituted with one or more hydroxyl, (Ci-C₄)alkoxycarbonyl, hydroxycarbonyl, thiol, (CrC₄)alkylthio, amido, amino or guanidine groups, a phenyl radical, optionally substituted with one or more hydroxyl, an indolyl radical optionally substituted with one or more hydroxyl, an imidazolyl radical, a pyrrolinyl radical optionally substituted with a C1-C2 alkyi group;

- R"_g represents a hydrogen or a C1-C4 alkyi radical optionally substituted with a hydroxysulfonyl radical;

- R10 represents a hydrogen or a C1-C4 alkyi radical;

- R"g and R₉ possibly forming, together with the nitrogen atom to which they are attached, a saturated 5-membered heterocycle; - Ri2 represents:

^* a hydrogen atom;

^* a Ci-C₆ alkyl radical, preferably substituted with one or more hydroxyl, thiol, (Cr C4)alkylthio, amido or amino, a phenyl radical, optionally substituted with one or more hydroxyl, an indolyl radical optionally substituted with one or more hydroxyl, an imidazolyl radical, a pyrrolinyl radical optionally substituted with a C1-C2 alkyl group;

- X represents a sulfur or nitrogen atom.

According to one particular variant, R₉ and R12 may optionally form a saturated 5-, 6- or 7-membered carbon-based ring.

In the case where X represents a nitrogen atom and R₁₂ represents an alkyl radical defined as previously and most particularly an amino acid residue and/or the corresponding methyl or ethyl ester thereof chosen from alanine, arginine, asparagine, aspartate, cysteine, glutamate, glutamine, glycine, histidine, lysine, methionine, phenylalanine, proline, pyrrolysine, serine, threonine, tryptophan, tyrosine, valine, leucine or isoleucine, the compound of formula (I lie) represents a dipeptide or an oligopeptide.

As examples of compounds of formula (lllc), mention may be made of 3- aminodihydrothiophene-2-one hydrochloride; D,L-homocysteine thiolactone; D,L- leucyl-D,L-alanine, aspartame; (S)-pyrrolidine-2-carboxamide; [N-(-acetamido)]-2- aminoethanesulfonic acid; D,L-alanyl-D,L-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- aminopropanediamide; 2-(2-amino-3-methylbutanamido)propanoic acid; L-tyrosyl-L- alanine; L-valyl-L-phenylalanine; sarcosyl-L-phenylalanine; L-tyroyl-3-alanine; glycyl- L-proline; glycyl-D,L-valine; 2-aminomalonamide; L-methionamide hydrochloride; 2- amino-3-methylbutanamide; D-alaninamide hydrochloride; L-tyrosinamide hydrobromide; aspartate acid amide; L-tyrosine amide hydrochloride; L-arginine amide dihydrochloride; lysine amide dihydrochloride; threonine amide hydrochloride; isoleucine amide hydrochloride; histidine amide dihydrochloride; D,L-alanine amide hydrochloride; 2-amino-3-(4-hydroxyphenyl)propionamide; D,L-tryptophanamide hydrochloride; N-hydroxy-L-arginine acetate (H-ARG-NH2 2AcOH); asparagine amide hydrochloride; L-glutamic acid α,γ-diamide hydrochloride; D-phanylalanine amide; D- leucinamide hydrochloride; L-glutamic acid a-amide; L-methionineamide; L-cystine bisamide hydrochloride; glycinamide acetate; D-lysine amide dihydrochloride; glycinamide; L-isoglutamine γ-methyl ester hydrochloride; D-arginine amide dihydrochloride; (S)-pyrrolidine-2 carboxamide; prolylhistamine hydrochloride,

o Amino compounds of general formula (Hid):

(Hid)

l which formula (llld):

i3, Ri4. Ri5 and R₁₆ represent, independently of each other:

^* a hydrogen atom;

^* a linear, branched and/or cyclic, saturated and/or unsaturated Ci-C₂o hydrocarbon-based radical, which may contain from 1 to 5 optionally aromatic carbon-carbon double bonds, optionally substituted as indicated previously, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C=S, SO and S0₂ or combinations thereof, optionally bearing at least one hydroxyl or Ci-C₂ alkoxy group, the said radicals Ri₃ and Ri₄ or Ri₄ and R-I5 or R₁₅ and Ri₆ possibly forming, with the carbon atoms to which each is attached, a saturated or unsaturated 5- or 7-membered heterocycle, optionally substituted as indicated previously, which is optionally aromatic, optionally comprising another nitrogen or non-nitrogen heteroatom; the alkyl radical not comprising any nitro, nitroso, peroxo or diazo functions; more particularly an optionally substituted C₁-C₁₀ alkyl radical; and preferably a linear or branched Ci-C₈ alkyl radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups, a hydroxycarbonyl radical, a ureido radical, a (Ci- C₄)alkoxycarbonyl radical; an unsubstituted phenyl radical;

X represents a nitrogen, oxygen or sulfur atom;

Ri7 represents:

^* a hydrogen atom;

^* a linear or branched, saturated or unsaturated Ci-C₁₈ hydrocarbon-based radical, optionally comprising from 1 to 5 conjugated or non-conjugated carbon- carbon double bonds, optionally substituted as indicated previously, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C=S, SO and S0₂ or combinations thereof; the alkyl radical not comprising any nitro, nitroso, peroxo or diazo functions; more particularly, R₁₇ represents a hydrogen, an optionally substituted linear or branched C1-C10 alkyl radical; and preferably a hydrogen, a linear or branched C₁-C4 alkyl radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups;

R18 represents:

^* a hydrogen atom; ^* a linear or branched Ci-C₈ alkyl radical, optionally substituted as indicated previously, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C=S, SO and SO₂ or combinations thereof, optionally bearing at least one hydroxyl or Ci-C₂ alkoxy group; the alkyl radical not comprising any nitro, nitroso, peroxo or diazo functions;

- 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 Ri₆ and the atom X for the radical R17 to which each is attached, a saturated or unsaturated 5- or 6-membered heterocycle, optionally substituted as indicated previously, optionally aromatic, optionally comprising another nitrogen or non-nitrogen heteroatom.

According to another variant of the invention, the radicals R18 and R15 may optionally form, with the nitrogen atom for R ₈ and the carbon atom for the radical R15 to which each is attached, a saturated or unsaturated 5- or 6-membered heterocycle, optionally substituted as indicated previously, optionally aromatic, optionally comprising another nitrogen or non-nitrogen heteroatom.

As examples of compounds of formula (llld), mention may be made of L-2- aminohexanoic acid amide hydrochloride; L-phenylalanine amide; (S)-(+)- aminosuccinic acid; (R)-2-(methylamino)succinic acid; ethyl nipecotate; 3-piperidine carboxylic acid; 3-phenyl- -alanine; ethyl 3-aminobutyrate; 2-carboethylamine; ϋ,Ι,-β- aminoadipic acid; β-alanine ethyl ester hydrochloride; ethyl 3-amino-3-ureido-N- butyrate; dimethyl (S)-aminosuccinate hydrochloride; β-L-alanine methyl ester hydrochloride; 4-carboxyethoxypiperidine; 4-aminobutyric acid; D,L-3-aminoadipic acid; 4-(methylamino)butyric acid hydrochloride; ethyl γ-aminobutyrate hydrochloride; hexahydronicotinamide; piperidine-4-carboxamide; 3-carbamoyl-2, 2,5,5- tetramethylpyrrolidine.

previously, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C=S, SO and S0₂ or combinations thereof, optionally bearing at least one hydroxyl or C1-C2 alkoxy group; the alkyl radical not comprising any nitro, nitroso, peroxo or diazo functions;

- p is an integer between 0 and 7;

- u is an integer equal to 1 or 2. When u is equal to 2, then the radical R-is represents a hydrogen.

According to another variant of the invention, the radicals R13 and R14 may optionally form, with the carbon for R ₃ and R_M to which these substituents are attached, a saturated 5- or 6-membered heterocycle.

As examples of compounds (We), mention may be made of the following acids, enantiomers thereof if they exist, and also the salts thereof, and hydrates thereof: (1- aminoethyl)phosphonic, (aminomethyl)phosphonic, (1 -aminoethyl-1 - cyclohexyl)phosphonic, (l -aminopropyl)phosphonic, (l-aminobutyl)phosphonic, iminobis(methylphosphonic), (1-amino-2-methylpropyl)phosphonic, (1-amino-2- phenylethyl)phosphonic, (1 -amino-1 -methylethyl)phosphonic, (1 -amino-3- methylbutyl)phosphonic, 1 -aminobenzylphosphonic, 1 -aminohexylphosphonic, diethyl(aminoethyl)phosphonic (in particular oxalate salt), tetraethyl(aminomethylene)bisphosphonic (in particular salts thereof), (1 -amino-2,2- dimethylpropyl)phosphonic, N-methylaminomethylphosphonic, (1- aminopentyl)phosphonic, (1 -amino-2-methylbutyl)phosphonic, (1- aminooctyl)phosphonic, (1 -amino-1 -methylpropyl)phosphonic, (1 -amino-1 ,2- dimethylpropyl)phosphonic, (1-amino-1 ,3-dimethylbutyl)phosphonic, (1-amino-1- methylbutyl)phosphonic, (1 -amino-1 -cyclopentyl)phosphonic, (1 - aminohydroxycarbonyl)propylphosphonic, (1 -amino-1 -methylethyl)phosphonic, 1- amino-2-methylbutylphosphonic, 1 -phosphono-2-phenylethylamine, (aminomethyl)phosphonic, 3-aminopropylphosphonic, 2-amino-2-methyl-4- phosphonobutanoic and the ethyl esters thereof, (diethyl(3-aminopropyl)phosphonic (in particular oxalate salt), 3-(N-hydroxyamino)propyl phosphonic, 2-amino-2-methyl- 4-phosphonobutyric, diethyl (3-aminopropyl)phosphonate, 2-amino-4- phosphonobutyric, 2-aminoethylphosphonic, 2-amino-3-phosphonopropionic, diethyl (2-aminoethyl)phosphonate, diethyl (2-aminoethyl)phosphonic, (2-((2- pyrrolidinylcarbonyl)amino)ethyl)phosphonic, diethyl (2-amino-1 -methyl-2- phenyl)ethylphosphonate, diethyl (2-amino-2-phenyl)ethylphosphonate, and/or mixtures thereof.

o Amino compo rmula (lllf):

(lllf)

in which formula (lllf): - R-13, R₁₄, R₁₅, Ri6 and Ri₈ have the same meaning as previously. In addition, the radicals Ri₃, R-u, R15 and Ri₆, independently of each other, a hydroxyalkyl radical, a (CrC₄)alkoxycarbonyl radical, a carboxaldehyde radical, a (CrC₃)alkoxy

- q is an integer between 1 and 18;

- X represents an oxygen atom, an SH or OH group, or a methylene group optionally substituted with a hydroxyl radical;

- when X represents an oxygen atom, then R₁₈ forms a 5- or 6-membered rings optionally substituted with one or more hydroxy(methyl), preferably from 1 to 4 hydroxy(methyl) groups.

According to another variant of the invention, the radicals Ri₆ and R₁₈ or R₁₃ and

R18 may optionally form, with the carbon atom for Ri₆ (or for R_i3) and the nitrogen atom for the radical Ri₈ to which each is attached, a saturated or unsaturated 5- or 6- membered heterocycle, optionally substituted as indicated previously, optionally aromatic, optionally comprising another nitrogen or non-nitrogen heteroatom.

According to another variant of the invention, the amine of formula (II If) may be a β-amino alcohol originating from the reduction of the acid or ester function to an alcohol of one of the 20 esterified or non-esterified amino acids.

As examples of compounds (lllf), mention may be made of the following compounds, enantiomers thereof if they exist, and also the salts thereof and the hydrates thereof: isopropanolamine, isopropylamine, methylethanolamine, methylglucamine, stearamine, tromethamine, promethazine, 1 ,3-dimethylpentylamine, octodrine, spermidine, theanine, octamylamine, 2-amino-1-phenylpropane-1 ,3- diol, 1 ,3-dihydroxy-2-amino-2-methylpropane, 2-amino-2-(hydroxymethyl)propane-1 ,3-diol tris, 2-amino-1 ,3-dihydroxy-2-ethylpropane, 2-amino-3-methylbutan-1 -ol, 2-amino-2- methylpropan-1 -ol, phenylglycinol, 2-aminopropanol, 2-hydroxyethylamine, 2- aminohexan-1-ol, 1 -amino-1 -cyclopentanemethanol, histidinol, 2-amino-3-(3- indolyl)propanol, 3-(4-hydroxyphenyl)-2-amino-1-propanol, β-aminoisobutanol, 2- amino-1-propanol, 2-amino-1 ,3-propanediol, 2-amino-4-methyl-1-pentanol, 2-amino-3- methyl-1 -butanol, β-aminobenzenepropanol, 2-aminopropan-1 -ol, 2-amino-1-butanol, 2-amino-4-methylpetan-1-ol, 3-aminopropanethiol, ethyl 2-amino-4- mercaptobutanoate, 6-hydroxyhexylamine, β-D-galactopyranosylamine, β-D- glucopyranosylamine, 1-amino-2,5-anhydro-D-mannitol, 1-amino-1-deoxy-D-fructose, D-glucosamine, 2-pyrrolidinemethanol, 1 -amino-2,3-dihydroxypropane, 3- propanolamine, 3-[(2-hydroxyethyl)amino]propan-1 -ol, di-β-hydroethylamine, bis(3- hydroxypropyl)amine, N-2'-aminoethyl-N-propanolamine, 4-amino-N-butanol, methyl 3-amino-3-deoxy-a-D-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,

o Amino compounds of general formula (lllg):

in which formula (lllg):

- i3, Ri4, Ri5, i6 and Ris have the same meaning as previously;

- R₂o represents:

* a linear C1-C4 alkyl radical,

^* a linear C1-C4 alkoxy radical,

- o is an integer between 0 and 5,

- v is an integer equal to 1 or 2. When v is equal to 2, then R ₈ represents a hydrogen.

As examples of compounds (lllg), mention may be made of aminopropyltriethoxysilane, (aminomethyl)trimethylsilane, 2-

(trimethylsilyl)ethanamine, 3-(trimethylsilyl)propan-1 -amine, 4-(triethoxysilyl)butan-1 - amine, N-[3-(trimethoxysilyl)propyl]ethylenediamine, 3-(trimethoxysilyl)propylamine, 3- triethoxysilyl-1-propanamine and (3-methylaminopropyl)trimethoxysilane, and mixtures thereof.

o Amino compounds of general formula (lllh):

(lllh)

in which formula (lllh):

- R i4, i 5, and R₁₈ have the same meaning as previously. In addition, the radicals and Ri₆, independently of each other, may also represent a hydroxyl radical, a (Ci-C₄)alkoxycarbonyl radical, a carboxaldehyde radical, a (Ci- C₃)alkoxy;

- R21 and R22 represent, independently of each other:

^* a hydrogen atom;

^* a linear, branched and/or cyclic, saturated and/or unsaturated C1-C20 hydrocarbon-based radical, which may contain from 1 to 5 carbon-carbon double bonds, optionally substituted as indicated previously, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, C=S, SO and S0₂ or combinations thereof, optionally bearing at least one hydroxyl or C1-C2 alkoxy group, more particularly an optionally substituted C1-C10 alkyl radical; and preferably a linear or branched C C₄ alkyl radical optionally substituted with at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups;

- R21 and R22 possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated 5- or 7-membered heterocycle, optionally substituted as indicated previously, optionally aromatic, optionally comprising another nitrogen or non-nitrogen heteroatom; the alkyl radical not comprising any nitro, nitroso, peroxo or diazo functions,

- w is an integer between 1 and 10.

According to another variant of the invention, the alkyl radicals Ri₆ and R₂i may optionally form, with the carbon atom for R ₆ and the nitrogen atom for the radical R21 to which each is attached, a saturated or unsaturated 5- or 6-membered heterocycle, optionally substituted as indicated previously, optionally aromatic, optionally comprising another nitrogen or non-nitrogen heteroatom.

According to another variant of the invention, the alkyl radicals Ri₈ and R₂i may optionally form, with the first nitrogen atom for Ri₈ and the last nitrogen atom for the radical R₂i to which each is attached, a saturated or unsaturated 5- to 14-membered heterocycle, optionally substituted as indicated previously, optionally aromatic, optionally comprising another nitrogen or non-nitrogen heteroatom.

Among the compounds of formula (lllh), mention may be made in particular of the amines below, the enantiomers thereof if they exist, and also the salts thereof and the hydrates thereof: gerontine, N-[3-aminopropyl]-1 ,4- butanediamine, 1 ,4- butanediamine, 4-(ethylamino)-N-butylamine, 2-[3-(2-hydroxy-1 , 1 -bis- hydroxymethylethylamino)propylamino]-2-hydroxymethylpropane-1 ,3-diol, 1 ,4,8,1 1- tetraazacyclotetradecane, 1 ,4-diazacycloheptane, 1 ,3-diamino-2-hydroxypropane, N,N'-bis(2-aminoethyl)propane-1 ,3-diamine, 3-methylaminopropylamine, 1 ,3- diaminopropane, Ν,Ν'-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, β-Ν-methylaminoalanine, methyl piperazine-2-carboxylate, ethyl 3-aminoprolinate, 2,4-diamino-N-butyric acid, N-[3- (trimethoxysilyl)propyl]ethylenediamine, or mixtures thereof.

o Amino compounds of general formulae (llli) and/or (MM'):

in which general formulae (llli) and/or (llli'):

- R23 and R₂4 represent, independently of each other:

* an optionally substituted Ci-C₆ alkyl radical, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, C=0, SO and S0₂ or combinations thereof; the alkyl radical not comprising any nitro, nitroso, peroxo or diazo functions;

^* an alkylcarbonyl radical (R-CO-) in which R represents a C C₄ alkyl radical;

^* an alkylsulfonyl radical (RSO2-) in which R represents a C1-C4 alkyl radical; * a (di)(alkyl)aminosulfonyl radical ((R)₂N-S0₂-) in which the radicals R independently represent a hydrogen or a C1-C4 alkyl radical;

^* a (di)(alkyl)aminocarbonyl radical ((R)₂N-CO-) in which the radicals R independently represent a hydrogen or a C1-C4 alkyl radical;

^* a halogen atom preferably chosen from bromine, chlorine and fluorine;

* a C1-C4 alkoxy group;

^* a C2-C4 (poly)hydroxyalkoxy group;

^* a hydroxycarbonyl group (HO-CO-);

^* 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 alkylsulfonyl radical (RS0₂-) in which the radical R represents a C1-C4 alkyl radical;

- Y represents a carbon or nitrogen atom;

- z, z' and z" represent, independently of each other, a carbon atom, a nitrogen atom or a nitrogen atom substituted with a hydrogen;

- x is an integer between 0 and 2; when x is less than 2, the unsubstituted carbon atom(s) bear a hydrogen atom;

- x' is an integer equal to 0 or 1 ; when x' is less than 1 , the unsubstituted carbon atom(s) bear a hydrogen atom.

Among the compounds of formulae (llli) and/or (UN'), mention may be made in particular of the compounds listed below, the enantiomers thereof if they exist, and also the salts thereof and the hydrates thereof: a-pyridylamine, 2-amino-3- hydroxypyridine, 2 aminonicotinic acid, 2-amino-3-methylpyridine, 6-methoxy-3- pyridylamine, 3-aminopyridine, 3-amino-4-pyridinylamine, 2,5-aminopyridine, γ- pyridylamine, 2,3-dimethylpyridine-4-amine, 4-aminosalicylic acid, methyl para- aminobenzoate, benzocaine, aminobenzoic acid, 4-amino-m-anisic acid, 4-amino-3- hydroxybenzoic acid, methyl 3,4-diaminobenzoate, methyl-4-amino-3- methoxybenzenecarboxylic acid, 2-aminoanisole-4-carboxylic acid, 3-amino-4- hydroxybenzoic acid, ethyl 3-aminobenzoate, 1-amino-3-carboxybenzene, methyl 2- aminobenzoate, ethyl anthranilate, 1 H-pyrazol-3-ylamine, 3-amino-4-carbethoxy-1 H- pyrazole, 5-amino-1-ethylpyrazole, 1 H-benzimidazol-2-amine, 2-imidazolamine, 1- methylbenzimidazol-2-amine, and mixtures thereof.

Use may also be made of the following amines, which may or may not be in salt form: lauroylethylenediamine, octopamine, oleamine, palmitamine, 2-(2- aminoethoxy)ethanol, 2-amino-4,5-dimethylthiazole, hexetidine, mecamylamine, tranylcypromine, triamterene, methyl[2-(3-trimethoxysilylpropylamino)ethylamine], bis(triethoxysilylpropyl)amine, N 1 -(3-(trimethoxysilyl)propyl)hexane-1 ,6-diamine, diethylenetriaminopropyltrimethoxysilane, N-(3-triethoxysilylpropyl)ethylenediamine, N-(3-trimethoxysilylethyl)ethylenediamine.

According to another variant of the invention, the amine(s) are chosen from amino polymers, and also addition salts thereof, in particular when the composition comprises at least one nucleophilic compound (1 ) or (2). The term "amino polymers" means macromolecules of more or less high molecular weight containing one or more primary or secondary amine functions. The term "polymer" means a compound comprising at least five repeating units linked in sequence via covalent bonds.

The amino polymer may be synthesized:

- via radical reactions (polyacrylates, polymethacrylates, polyvinyls, etc.), - via condensation reactions (polyesters, polyethers, polyamides, polyurethanes, polydimethylsiloxanes, polypeptides, etc.),

- via ring-opening reactions (polyesters, etc.).

It may be of natural origin, optionally chemically modified, for instance polysaccharides (cellulose, dextran, chitosan, guar) and amino or thiol derivatives thereof.

The polymers may be in any type of topology: linear, branched, star or hyperbranched chain (for instance dendrimers), block, random or alternating chains.

The chemical groups may be naturally present on the polymer chain, at the end of the chain, grafted along the main chain or side chains, or on the branches of star or hyperbranched polymers.

The following are most particularly preferred:

1/ polyamino acids containing free OH or NH₂ or SH or COOH groups, for example polylysine,

21 natural or modified polysaccharides containing NH₂ or SH functions, 3/ amino silicones,

4/ synthetic polymers containing NH₂ or SH functions, in particular polyvinyl vinyls substituted with an amine function and polymers made from the commercial monomers below:

and in particular from polylysine; chitosan; polyethoxylated amines such as carboxyPEG-8 amine, carboxyPEG-12 amine or carboxyPEG-24 amine; or combinations thereof.

According to another variant of the invention, the amine(s) are chosen from purine bases, in particular chosen from adenine, adenosine, guanine, guanosine G, thymine, thymidine T, uracil, uridine U, cytosine, cytidine C, addition salts thereof, and combinations thereof.

It would not constitute a departure from the context of the invention to combine several of these variants.

Preferably, if the composition comprises one or more amines, they are chosen from ammonia, the compounds of formulae (Ilia), (lllb), (lllc), (llle) and (lllg) in particular when R₂o represents a linear C1-C4 alkoxy group, and (MM'), or mixtures thereof.

If the composition comprises one or more primary or secondary amines, ammonia or hydroxylamine, their content represents in the composition between 0.001 % and 65% by weight and preferably between 0.001% and 30% by weight relative to 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 derived, for example, from sweet almond (EC 3.2.1 .21 ), alcohol oxidase (EC 1.1.3.13), alcohol dehydrogenases EC 1.1.1 .1 , alcohol dehydrogenases EC 1.1.1.2, alcohol dehydrogenases EC 1.1.1.71 , aromatic alcohol dehydrogenases EC 1.1 .1.90, also known as aryl alcohol dehydrogenases, aromatic alcohol dehydrogenases EC 1 .1.1.97, 3-hydroxybenzyl alcohol dehydrogenases EC 1.1.1 .97, coniferyl alcohol 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 known as aryl alcohol oxidases, alcohol oxidases EC 1 .1.3.13, 4-hydroxymandelate oxidases EC 1.1.3.19, long-hydrocarbon-chain alcohol oxidases EC 1.1.3.20, methanol oxidases EC 1 .1.3.31 , alcohol dehydrogenases EC 1.1 .99.20, methylglutamate dehydrogenases EC 1.5.99.5, 2-oxo acid decarboxylases EC 4.1.1.1 , benzoylformate decarboxylases EC 4.1.1.7, phenylpyruvate decarboxylases EC 4.1.1.43 and threonine aldolases EC 4.1.2.5. If it is present, the concentration of the enzyme used in the dye composition is between 0.005% and 40% by weight relative to the total weight of the said composition and preferably between 0.05% and 10% by weight relative to the weight of this composition.

Salts

The composition comprising the compound(s) of formula (I) may optionally comprise one or more salts.

When they are present, these salts are generally chosen from organic solvents and/or mineral salts, and also combinations thereof.

In particular, the anions composing these salts may be either inorganic (chloride, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, silicate, phosphate, hydrogen phosphate, hydroxide, etc.) or organic (aspartate, formate, acetate, lactate, citrate, gluconate, succinate, malate, fumarate, orotate, etc.).

The cations composing these salts, associated with the above anions, may be derived either from alkali metals (preferably lithium, sodium or potassium), from alkaline-earth metals (preferably magnesium or calcium) or from transition metals (scandium, titanium, vanadium, manganese, molybdenum, iron, cobalt, nickel, copper, zinc, silver or gold). Other cations may also form salts, for instance ammoniums. Preferably, the cations will be chosen from alkali metals (lithium, sodium or potassium), alkaline-earth metals (magnesium or calcium), ammoniums, and also the following transition metals: manganese, molybdenum, iron, copper, zinc, silver and gold.

When they are present, their content represents from 0.001 % to 40% by weight relative to the weight of the composition, and even more preferentially 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 of at least one organic solvent. Examples of organic solvents that may be mentioned include Ci-C₄ lower alkanols, such as ethanol and isopropanol; polyols such as 1 ,3-propanediol or 1 ,6-hexanediol and polyol ethers, for instance 2- butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

When they are present, the solvents are preferably present in proportions preferably of between 1 % and 99% by weight relative to the weight of the composition and even more preferentially between 5% and 95% by weight relative to the weight of the composition. The composition used in the process according to the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or nonvolatile, modified or unmodified silicones such as amino silicones, film-forming agents, ceramides, preserving agents, opacifiers and conductive polymers.

The above adjuvants are generally present in an amount for each of them of between 0.01 % and 20% by weight relative to the weight of the composition.

Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the dye composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).

The pH of the composition is generally between 3 and 14 approximately and preferably between 4 and 1 1 approximately. It may be adjusted to the desired value by means of acidifying or basifying agents commonly used in the dyeing of keratin fibres, or alternatively using standard buffer systems.

Among the acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.

Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkali metal carbonates and the amines mentioned previously.

The composition may be in various forms, such as in the form of a liquid, a cream or gel, powders to be mixed before use to obtain poultices, infusions, or in any other form that is suitable for dyeing keratin fibres, and especially the hair.

The ingredients of the abovementioned composition are advantageously stored separately.

In particular, the compound(s) of formula (I) or the plant extract comprising the same, the compound optionally being lysed beforehand; where appropriate, the enzyme for replacing the radical R with a hydrogen atom if compound (I) has not been lysed beforehand; and the particular carbonyl nucleophilic compound(s) (1 ) of formulae (a1 ) to (d1 ) or the carbonyl oligomer(s) or polymer(s), or the nucleophile(s) (2) of formulae (a2) to (d'"2) or the nucleophilic oligomer(s) or polymer(s), or alternatively the amino or thio polymer(s), are stored separately.

It should also be noted that if one or more amine compounds are present, these compounds are also stored separately from the compounds (I) or from the plant extract comprising the same, which is or is not lysed. It may also be advantageous to store at least the compound(s) of formula (I) or the lysed or non-lysed plant extract comprising the same in an airtight container.

The composition used in the process according to the invention may also comprise one or more oxidizing agents. In this case, it is referred to as a ready-to-use composition.

Oxidizing agent

In particular, when an oxidizing agent is present, the ready-to-use composition is advantageously obtained by the extemporaneous mixing, before application, of a composition described previously 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 instance persulfates, perborates and percarbonates of alkali metals or alkaline-earth metals, such as sodium, potassium and magnesium.

Oxidizing agents that are also suitable for use include those of enzymatic type, for instance 4-electron oxidoreductases (such as laccases), 2-electron oxidoreductases (such as uricase), where appropriate in the presence of the respective donor or cofactor thereof, and peroxidases.

The use of hydrogen peroxide is particularly preferred.

This oxidizing agent is advantageously formed by hydrogen peroxide in aqueous solution (aqueous hydrogen peroxide solution), the titer of which may range more particularly from 1 to 40 volumes and even more preferentially 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 that has just been described is thus applied to human keratin fibres, in particular the hair.

Dyeing process

In accordance with a first embodiment, the applied composition does not comprise any oxidizing agent.

In this case, the ingredients (compound of formula (I) or lysed or non-lysed extract; where appropriate, the enzyme for replacing the radical R with a hydrogen atom, the carbonyl nucleophilic compound(s) of formulae (a) to (d) or the carbonyl oligomer(s) or polymer(s)) are mixed before application.

This embodiment is especially suitable in the case where the composition does not comprise an oxidation dye (bases or couplers).

In accordance with a second embodiment, the ready-to-use composition that has just been detailed and that is obtained by extemporaneous mixing, before application, of the composition described previously free of oxidizing agent with an oxidizing composition, is applied to the fibres.

This embodiment is particularly suitable in the case where the composition comprises one or more oxidation dyes (bases or couplers) or when it is desired to obtain a lightening effect.

According to a second variant of this embodiment, the composition free of oxidizing agent and an oxidizing composition are applied successively and without intermediate rinsing.

The oxidizing composition used comprises one or more oxidizing agents as defined above.

As regards the organic solvents that may be present in the oxidizing composition, reference may be made to the list indicated previously in the context of the description of the composition according to the invention.

Usually, the pH of the oxidizing composition is less than 7.

The oxidizing composition may take the form of a solution, an emulsion or a gel.

It may optionally comprise one or more additives conventionally used in the field of dyeing human keratin fibres, as a function of the desired galenical form. Once again, reference may be made to the list of additives given above.

Irrespective of the embodiment selected (with or without oxidizing agent, extemporaneous mixing or successive applications of the composition and of the oxidizing agent), the mixture applied to the fibres is left in place for a time generally from about 1 minute to 5 hours and preferably from 10 minutes to 3 hours.

As regards the temperature at which the composition(s) are applied, it is generally between 20 and 200°C and advantageously between 20°C and 55°C.

This operation may thus be performed using, for example, a heating hood, an infrared lamp or a straightening or curling iron.

The process according to the invention may advantageously be performed in the presence of a light stimulus.

It consists more particularly in applying to the keratin fibres thus treated UVA radiation (in particular an irradiance of between 0.01 and 0.40 milliwatt/cm² and preferably between 0.1 and 0.2 milliwatt/cm², delivered by continuous-spectrum lamps or line-spectrum lamps) and/or UVB radiation (in particular an irradiance of between 0.01 and 0.20 milliwatt/cm² and preferably between 0.01 and 0.1 milliwatt/cm² delivered by continuous-spectrum lamps or by line-spectrum lamps).

Preferably, the composition comprises alkali metal, alkaline-earth metal or ammonium, carbonate, hydrogen carbonate, chloride, sulfate, silicate, monobasic phosphate or acetate salts.

According to one preferred variant of the invention, this stimulus is performed by using a composition comprising, in a cosmetically acceptable medium, at least one salt chosen from lithium, sodium, potassium, calcium or ammonium carbonate; sodium or potassium hydrogen carbonate; calcium, lithium or sodium chloride; ammonium, sodium or magnesium sulfate; sodium silicate; monobasic sodium or potassium phosphate; 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 preferentially between 0.001 % and 20% by weight relative to the weight of the composition.

It would not constitute a departure from the context of the present invention to perform several successive steps combining stimuli that are different from each other.

After the leave-on time the keratin fibres may be rinsed with water, optionally washed with a shampoo, rinsed with water and dried or left 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 the same, the said compound having undergone a preliminary step that consists in replacing the radical R with a hydrogen atom; and a second compartment containing at least one carbonyl nucleophilic compound (1 ) of formulae (a1 ) to (d1 ), carbonyl oligomers or polymers, or containing at least one nucleophilic compound (2) of formulae (a2) to (d'"2), nucleophilic oligomer or polymer, or alternatively containing at least one amino or thio polymer.

Another subject of the invention also consists of a multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising the same; and a second compartment containing at least one carbonyl nucleophilic compound (1 ) of formulae (a1 ) to (d1 ), carbonyl oligomers or polymers, or containing at least one nucleophilic compound (2) of formulae (a2) to (d'"2), nucleophilic oligomer or polymer, or alternatively containing at least one amino or thio polymer, and containing an enzyme for replacing the radical R of formula (I) with a hydrogen atom. Lastly, a final 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 the same; a second compartment containing at least one carbonyl nucleophilic compound (1 ) of formulae (a1 ) to (d1 ), carbonyl oligomer or polymer, or containing at least one nucleophilic compound (2) of formulae (a2) to (d'"2), nucleophilic oligomer or polymer, or alternatively containing at least one amino or thio polymer; and a third compartment containing an enzyme for replacing the radical R of formula (I) with a hydrogen atom.

Preferably, the lysed or non-lysed compound(s) of formula (I) or the plant extract comprising the same are stored protected from air, advantageously under an inert atmosphere. The device may optionally comprise an additional compartment comprising one or more amines, or one or more salts.

The examples that follow illustrate the invention without limiting the scope thereof.

Example 1

The dye compositions are obtained by dissolving with a sonicator for 20 minutes the extract of lysed Gardenia jasminoides (5*10^"3 mol%), 93% or 99% enriched in genipin and the ingredient (10^"2 mol%) in a mixture of benzoic acid, benzyl alcohol, ethanol and water; the pH of the composition is of 9 (addition of NaOH; 0.1 M).

Each composition is applied to natural grey hair containing 90% white hair (1 g of lock per 10 g of solution) and the said locks are placed for 30 minutes at 50°C (hotplate).

The lock is then rinsed, washed with a shampoo and dried with a hairdryer.

Example 2

The dye compositions are obtained by dissolving with a sonicator for 20 minutes the extract of lysed Gardenia jasminoides (5*10^"3 mol%), 93% or 99% enriched in genipin and the ingredient (5x10^"3 mol%) in an aqueous solution or mixture of benzoic acid, benzyl alcohol, ethanol and water, buffered according to the desired pH.

Each composition is applied to natural and/or permanent-waved grey hair containing 90% white hairs (1 g of lock per 10 g of solution) and the said locks are placed for 30 minutes at 50°C (hotplate). The lock is then rinsed, washed with a shampoo and dried with a hairdryer.

Example 3

The lock is then rinsed, washed with a shampoo and dried with a hairdryer.

test 24/24' grey black grey black

test 25/25' grey black grey black

Example 3

The dye compositions are obtained by dissolving with a sonicator for 20 minutes the extract of lysed Gardenia jasminoides (1.13 g%), 93% enriched in genipin and a compound (1 .95%) in water at a pH of 8 (addition of KHC0₃).

Compound : 7-amino 1 H-imidazo[1 ,2-b]pyrazole dihydrochloride.

Each composition is applied to natural grey hair containing 90% white hair (1 g of lock per 5 g of solution) and the said locks are placed for 30 minutes at 50°C (hotplate).

The results are the following:

It is clear from the above results, that the colour obtained according to the invention is more intense than with the comparative composition.

Example 4

The dye composition is obtained by dissolving with a sonicator for 20 minutes the extract of lysed Gardenia jasminoides (1 .13 g%), 93% enriched in genipin and polylysine (0.022 g%) in water at a pH of 8 (addition of KHC0₃).

The composition is applied to natural grey hair containing 90% white hair (1 g of lock per 5 g of solution) and the said locks are placed for 60 minutes at 40°C (hotplate). The colour is a light orange.

As a comparison, no colour is observed when polyvinylpyrrolidone (PVP) is used. The conditions are the following:

The PVP (300mg) is solubilised in a prior step, in an aqueous solution comprising HCI (0.1 M) at 50°C during 1 hour; The dye composition is obtained by dissolving in water with a sonicator for 20 minutes the extract of lysed Gardenia jasminoides (1.13 g%), 93% enriched in genipin and the PVP solution (150μΙ) ; the pH is 8 (addition of KHC0₃).

The composition is applied to natural grey hair containing 90% white hairs (1 g of lock per 6 g of solution) and the said locks are placed for 60 minutes at 40°C (hotplate).

Claims

1. Process of dyeing human keratin fibres by applying a composition comprising, in a cosmetically acceptable medium:

^* a compound of the iridoid family of formula (f) below, optical or geometrical isomers thereof, mineral or organic acid salts thereof, solvates thereof, or a plant extract comprising the same:

• Ri represents a hydroxymethyl radical, a group -CO₂R₄ 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 (Ci-C₄)alkyloxy 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 compound(s) of formula (I) having undergone prior to or simultaneously with the dyeing process, a step consisting in replacing the radical R with a hydrogen atom;

** at least one nucleophilic compound:

in which formula:

A represents:

^* n is equal to 0 or 1 ; m is equal to 0 or 1 ;

* R_a, which may be identical or different, represent a hydrogen atom or a Ci-C₄ alkyl radical,

* R_b represents a hydrogen atom, an acetyl group (CH₃CO-); one of the two radicals Rb representing a hydrogen atom, or alternatively two radicals Rb representing a phenylmethylenyl group, the phenyl radical being optionally substituted with at least one hydroxyl or C1-C4 alkoxy radical;

* Ai , Bi , A'i and ΒΊ, which may be identical or different, represent:

o a C₆ aryl group

· optionally substituted with at least

a linear or branched C1-C20 alkyl radical;

a hydroxyl radical;

an alkoxy radical -OR1 in which represents a C1-C4 alkyl radical optionally substituted with a hydroxyl group, a group -Si(R₂)(OSi(R₃)3)3 in which R₂ and R₃, which may be identical or different, represent a C1-C4 alkyl radical, preferably methyl;

an ester group -OCOR₄ in which R₄ represents a phenyl radical;

an ammonium group -N⁺(R₅)₃ in which R₅, which may be identical or different, represent a C1-C4 alkyl radical optionally bearing at least one hydroxyl group;

a halogen atom, preferably chlorine;

optionally fused to an unsaturated or aromatic 5- or 6-membered heterocycle, comprising at least one heteroatom, preferably oxygen; o a pyridynyl or pyridinium group; the quaternized nitrogen atom being substituted with a C1-C4 alkyl radical optionally bearing a hydroxyl group; o a C1-C4 alkyl group;

o the groups A and B possibly forming together a 5- or 6-membered ring or heterocycle optionally comprising a heteroatom, preferably oxygen; the said ring or heterocycle being optionally fused to a phenyl radical optionally substituted with at least one acetyl (CH₃CO-), ester -COO ₆ or -OCOR₆ group with R₆ representing a C1-C4 alkyl radical;

* A₂ and B₂, which may be identical or different, represent:

o a linear or branched C1-C10 alkyl radical, possibly containing one or more unsaturations, optionally substituted with a group -SiR₃, the radicals R, which may be identical or different, representing a C1-C4 alkyl radical;

o a C₃-C₅ alkenyl radical;

o a hydrogen atom, an alkali metal or alkaline-earth metal or an ammonium group;

o the radicals A₂ and B₂ together possibly forming a 6-membered heterocycle optionally substituted with a Ci-C₂ alkyl radical;

o the radicals R_b and ΑΊ, in the case where n is equal to 1 , may together form a 6-membered hydrocarbon-based ring, optionally substituted with a Ci-C₂ alkyl group or a hydroxyl group;

in which:

* D represents -CR₂₄-, O, -CO- or -CR₂₄=CR₂₄-;

^* E represents -CR'₂₃- or O; R'₂₃ represents a hydrogen atom or R_23;

^* R₂₃, which may be identical or different, represent a hydroxyl group or a C1-C4 alkyl radical optionally substituted with at least one hydroxyl group;

^* two radicals R₂₃ borne by two adjacent carbon atoms may together form a fused aromatic ring optionally substituted with at least one C1-C4 alkoxy radical or a hydroxyl group;

R24, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C4 alkyl radical

in which R₂₅ represents a linear or branched Ci-Cs alkyl radical optionally substituted with a group -S0₃ ^"Na⁺, -C(N H R₂₆)=N R'₂₆ in which R₂₆ and R'₂₆, which may be identical or different, represent a cyclic C₄-C₈ alkyl radical; the compounds of formulae (a) to (d) comprising, where appropriate, a cosmetically acceptable anion or mixture of anions An, ensuring the electrical neutrality of the formulations;

in which:

^* A represents -CRi₀-, -N- or -N⁺R_i with Rn representing a C C₄ alkyl radical; ^* X represents N or CR'₇ and R'₇ represents a hydrogen atom or R_7;

* R₇, which may be identical or different, represent:

- a C1-C4 alkyl radical;

- a hydroxyl radical;

- a C C₄ alkoxy radical;

- an amino radical;

- a C1-C4 alkylamino radical;

* Rs and R10, which may be identical or different, represent:

a hydrogen atom,

• a hydroxyl radical,

an amino radical,

• a C1-C4 alkyl radical optionally substituted with at least one group - COOR12 or -OCOR12 with R₁₂ representing a C C₄ alkyl radical, a group -

COR13 with Ri3 representing a C1-C4 alkyl radical,

· a group -OS0₃ ^",

* Rg represents a hydrogen atom, a C1-C4 alkyl radical, a (Ci-C₄)alkylcarbonyl group; an acetyl radical; ^* the radicals R₈ and R₉ may form a 5- or 6-membered heterocycle optionally comprising another heteroatom chosen from oxygen, nitrogen and sulfur, the said heterocycle also possibly being interrupted with a CO group,

^* when A represents N, n is 0, X represents CH and R₈ represents NH₂, then R₉ is not a hydrogen atom or a methyl group;

in which:

^* A represents S, -(CRi₈)2- or

with R₁₈ representing a hydrogen atom or a Ci-C₄ alkyl radical, Rig and R' _9l which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical;

^* B' represents S;

^* R ₅, which may be identical or different, represent a C1-C4 alkyl radical, a halogen atom, preferably chlorine, or a C1-C4 alkoxy radical;

* R_15', which may be identical or different, represent a Ci-C₂ alkyl radical;

* R16 represents a hydrogen atom or a C1-C4 alkyl radical;

* R16' represents a hydrogen atom or a C1-C4 alkyl radical;

* Ri₇ represents a C1-C4 alkyl radical optionally bearing a hydroxyl group;

^* Ri₇' represents:

- a hydrogen atom;

- a C1-C4 alkyl radical, optionally bearing a hydroxyl group, optionally interrupted with a CO group, optionally bearing a phenyl radical;

^* the radicals Ri₆ and R₁₇ may together form a 5- or 6-membered fused heterocycle, optionally containing one or more unsaturations, optionally substituted with at least one C1-C4 alkyl radical;

in which: ^* n' is an integer from 0 to 2; the unsubstituted carbon atoms bear a hydrogen atom;

^* R₂o, which may be identical or different, represent a C C₄ alkyl radical, a halogen atom (preferably chlorine, bromine or iodine), a radical -COOR21 or - OCOR21 with R₂i representing a hydrogen atom, a C1-C4 alkyl radical, an amino radical, or a C₆ aryl group (phenyl) optionally substituted with at least one hydroxyl radical;

^* Y represents N or CR"₂2_;

* R22, R'22 and R"₂2, which may be identical or different, represent a hydrogen atom, a linear or branched C1-C4 alkyl radical optionally substituted with an amino radical, a benzyl radical, a phenyl radical, -COOR23 or -OCOR23, R23 representing a C1-C4 alkyl radical, -SOR24 in which R24 represents a C1-C4 alkyl radical;

* ' 22 may together form a fused 6-membered aromatic ring;

Formulae (d2), (d'2), (d"2) and (d'"2) in which:

^* Y represents CH, CR₂₇ or N;

^* z represents N; z' represents N or 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 unsubstituted carbon atoms of the heterocycles bear a hydrogen atom;

^* R²⁷, independently of each other, represent:

- a linear C1-C4 alkyl radical;

- a halogen chosen from chlorine, bromine and fluorine;

^* R"₂7 represents a hydrogen atom, a C1-C4 alkyl radical or a phenyl radical;

^* R₂8 represents a hydrogen atom or a linear C1-C4 alkyl radical;

^* the radicals R27 located ortho to the radical NHR₂8 and R28 may together form a 5- or 6-membered heterocycle comprising 1 or 2 heteroatoms chosen from oxygen and nitrogen; ^* if Y represents CR27, then q is preferably other than 0;

* R29, which may be identical or different, represent a linear C1-C4 alkyl radical, the two radicals R29 together possibly forming a saturated 5-membered heterocycle;

^* R₃₀ represent, independently of each other, a hydroxyl radical, an amino radical or a pyrrolidyl radical;

^* R³¹, independently of each other, represent:

- a C1-C4 alkyl radical;

- a C1-C4 alkoxy radical optionally substituted with a hydroxyl group;

- an amino radical optionally substituted with an acetyl group (-COCH₃);

^* R^M27 and R31 may form a 5- or 6-membered aromatic or non-aromatic heterocycle, optionally substituted with a C1-C4 alkyl radical;

and also from oligomers or polymers of the polyallylimidazolium type;

or at least one amino or thio polymer, this polymer being present in an amino or thio polymer(s)/compound(s) of formula (I) weight ratio of at least 0.01.

Process according to the preceding claim, characterized in that the plant extract is derived from the following plants: Abelia grandiflora, 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 henryi, Crucianella sp, Daphniphyllum calycinum, Daphniphyllum humile, Daphniphyllum macropodum, Eremostachys glabra, Escallonia sp, Eucommia ulmoides, Feretia apodanthera, Galium humifusum, Galium verum, Gardenia jasminoides, 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 condensata, 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, Rubia peregrina, Rubia tinctorum, Saprosma scortechinii, Scrophularia korainensis, Scrophularia lepidota, Scrophularia ningpoensis, Scyphiphora hydrophyllacea, Swida controversa, Syringa vulgaris, Tarenna kotoensis, Tecoma heptaphylla, Thevetia gaumeri, Thevetia peruviana, Verbascum laxum, Verbascum nigrum, Verbascum phlomoides, Verbascum salviifolium, Verbascum sinuatum, Verbascum thapsus, Verbascum undulatum, Veronica derwentiana, Veronica persica, Vitex nigrum, Wendlandia formosana, preferably Gardenia jasminoides.

Process according to any one of the preceding claims, in which the content of compound of formula (I) in the composition is between 0.001% and 10% by weight relative to the weight of the composition.

Process according to any one of the preceding claims, in which the carbonyl nucleophilic compound(s) (1 ) are of formula (a1 ) and are chosen from the following compounds, isomers thereof, salts thereof and solvates thereof, alone or as a mixture:

5. Process according to any one of the preceding claims, in which the carbonyl nucleophilic compound(s) (1 ) are of formula (b1 ) or (c1 ) and such that:

^* y is an integer ranging from 0 to 2;

^* D represents -CO- or -CR₂4=CR₂4-;

^* E represents -CR'23- or O; R'23 represents a hydrogen atom or R_23;

* R23, which may be identical or different, represent a hydrogen atom, a hydroxyl group or a C1-C4 alkyl radical optionally substituted with at least one hydroxyl group; ^* two radicals F½ borne by two adjacent carbon atoms may together form a fused aromatic ring optionally substituted with at least one C1-C4 alkoxy radical or a hydroxyl group;

6. Process according to any one of the preceding claims, in which the carbonyl nucleophilic compound(s) (1 ) are of formula (b1 ) and/or of formula (c1 ) and are chosen from the following compounds, isomers thereof, salts thereof and

Process according to any one of the preceding claims, in which the carbonyl nucleophilic compound(s) (1 ) are of formula (d1 ) and are chosen from the following compounds, isomers thereof, salts thereof and solvates thereof, alone or as mixtures:

Structure Chemical Name

N≡— \

2-methylpropyl cyanoacetate

CH₃

V^NT cyanoacetyl N,N'-dicyclohexyl carbamimidate

Process according to any one of Claims 1 to 3, in which the nucleophilic compound(s) (2) are of formula (a2) and are chosen from the following compounds, isomers thereof, salts thereof and solvates thereof, alone or as a mixture:

1 H-indole-5,6-diol

5H-[1 ,3]dioxolo[4,5-f]indole

5,6-dihydroxy-1 H-indole- carboxylate

6-dihydroxy-1 H-indole-2-ethyle carboxylate

1 H-indol-5-ol

2-methyl- 1 H-indol-4-ol

potassium salt of 1 H-indol— yl sulfate

1 H-indol-7-ol

1 H-indol-6-ol

4,6-dimethoxy-1 H-indole-2-carboxylic acid

Process according to any one of Claims 1 to 3 and 8, in which the nucleophilic compound(s) (2) are of formula (a2) such that:

^* A represents -CRi₀- or -N-;

^* X represents CR'₇ and R'₇ represents a hydrogen atom or R_7;

* R₇, which may be identical or different, represent:

- a C1-C4 alkyl radical;

- a hydroxyl radical;

- a C1-C4 alkoxy radical;

- an amino radical;

- a C1-C4 alkylamino radical;

^* R₈ and 10, which may be identical or different, represent:

a hydrogen atom,

• a C1-C4 alkyl radical;

a group -COOR14 or -OCOR14 with R₁₄ representing a hydrogen atom, a C1-C4 alkyl radical optionally substituted with at least one C1-C4 alkoxy group;

* R₉ represents a hydrogen atom or a C1-C4 alkyl radical; ^* when A represents N, n is 0, X represents CH and R₈ represents NH₂, then R₉ is not a hydrogen atom or a methyl group.

Procees according to any one of Claims 1 to3, in which the nucleophilic compound(s) (2) are of formulae (b2) and (b'2) and are chosen from the following compounds, isomers thereof, salts thereof and solvates thereof, alone or as a mixture:

1. Process according to any one of Claims 1 to 3 and 10, in which the nucleophilic compound(s) (2) are of formulae (b2) and (b'2) such that:

^* n and n' are 0; the unsubstituted carbon atoms bear a hydrogen atom;

* A' represents S or -(CR¹⁸)₂- with R¹⁸ representing a hydrogen atom or a CrC₄ alkyl radical;

^* B' represents S;

* i6 represents a hydrogen atom or a C1-C4 alkyl radical;

* Ri6' represents a hydrogen atom or a Ci-C₄ alkyl radical;

* Ri7 represents a Ci-C₄ alkyl radical optionally bearing a hydroxyl group;

* Ri represents:

- a hydrogen atom;

- a Ci-C₄ alkyl radical optionally bearing a hydroxyl group; ^* the radicals Ri₆ and Ri₇ may together form a 5- or 6-membered fused heterocycle, optionally containing one or more unsaturations, optionally substituted with at least one Ci-C₄ alkyl radical.

Process according to any one of Claims 1 to 3, in which the nucleophilic compound(s) (2) are of formula (c2) and such that:

^* R₂o, which may be identical or different, represent a C1-C4 alkyl radical, a chlorine atom, a radical -COOR21 or -OCOR21 with R₂i representing a hydrogen atom, a C1-C4 alkyl radical, an amino radical, or a phenyl group;

^* X represents N, CR22 or -CR'₂₂ which is linked to Y or to X;

^* Y represents N or CR"_22;

^* R₂₂ and R"₂2 may together form a fused 6-membered aromatic ring.

Process according to any one of Claims 1 to 3 and 12, in which the nucleophilic compound(s) (2) are of formula (c2) and are chosen from the following compounds, isomers thereof, salts thereof and solvates thereof, these compounds being alone or as a mixture:

Structure Chemical name

1 H-imidazol[1 ,2-b]pyrazole

N NH

3,6-dimethyl-1 H-pyrazolo[5,1-c][1 ,2,4]triazole

N NH

N NH 2-methyl-4H-pyrazolo[1 ,5,a]benzimidazole ft

Process according to any one of Claims 1 to 3, in which the nucleophilic compound(s) (2) are of formulae (d2), (d'2), (d"2) and (d'"2) and are chosen from the following compounds, isomers thereof, salts thereof and solvates thereof, alone or as mixtures:

i-2-chloro-6-methylphenol

CIH hydrochloride

3,4-dihydro-2H-1 ,4-benzoxanin-6-ol

2-[(3-aminopyrazolo[1 ,5-a]pyridin-2- yl)oxy]ethanol hydrochloride

2-aminopyridin-3-ol

15. Process according to any one of Claims 1 to 3 and 8 to 14, in which the nucleophilic compound(s) (2) are chosen from the compounds of formulae (a2), (c2), (d2), (d'2), (d"2) and (d'"2), or mixtures thereof.

16. Process according to any one of the preceding claims, in which the content of nucleophilic compound(s) (1 ) or (2) or of nucleophilic oligomers or polymers is between 0.001 % and 30% by weight relative to the weight of the composition. 17. Process according to any one of Claims 1 to 3, in which the amino or thio polymer(s) are chosen from:

1 / polyamino acids containing free groups NH₂ or SH

21 natural or modified polysaccharides containing NH₂ or SH functions

3/ amino silicones,

4/ synthetic polymers containing NH₂ or SH functions

5/ polyethyleneimines

6/ oxyalkylenated polymers ending with an amine function; the oxyalkylene group comprising 2 to 5 linear or branched carbon atoms, preferably 2 to 3 carbon atoms

71 alkoxysilane-based polymers containing amine functions.

18. Process according to any one of Claims 1 to 3 and 17, in which the amino or thio polymer(s) are chosen from:

- polylysines,

- thiol-modified polylysines,

- amino-dextran,

- amino-cellulose,

- chitosan and amino derivatives thereof,

- amino silicones,

- dendrimers containing amine functions such as poly(amidoamines), - amino polyvinyl alcohol,

- poly(allylamine), polyvinylamines and poly(N-methyl)vinylamine,

- poly(diallylamines) and copolymers thereof,

- poly(vinylamine-co-vinylformamide) copolymers,

- amine-terminated (C₂-C₅ alkyl) polyoxyalkylene polymers

- partially deprotected polyoxazolines,

- PEI (polyethyleneimine) and thiol derivatives thereof. 19. Process according to any one of Claims 1 to 3 and 17 or 18, in which the amino or thio polymer(s) are chosen from amino polymers, preferably of class 1/ or 21.

20. Process according to any one of Claims 1 to 3 and 17 to 19, in which the content of amino or thio polymer(s) is such that the weight ratio of amino or thio polymer(s)/compound(s) of formulae (I) and/or (I I), in the composition, is between 0.01 -4/1 .

21 . Process according to any one of Claims 1 to 3 and 17 to 20, in which the content of amino or thio polymer(s) is between 0.1 % and 10% by weight relative to the weight of the composition.

22. Process according to any one of the preceding claims, in which the composition comprises one or more organic or mineral salts chosen from:

* chloride, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, silicate, phosphate, hydrogen phosphate, hydroxide or organic anions chosen from aspartate, formate, acetate, lactate, citrate, gluconate, succinate, malate, fumarate, orotate combined with

^* alkali metals, alkaline-earth metals, transition metals such as scandium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, silver or gold, or ammoniums.

23. Process according to any one of the preceding claims, in which the content of salt(s) ranges between 0.001 % and 40% by weight relative to the weight of the composition and even more preferentially between 0.001 % and 20% by weight relative to the weight of the composition.

24. Process according to any one of the preceding claims, in which the step consisting in replacing the radical R with a hydrogen atom is performed using an enzyme chosen from isolase and β-glucosidase (EC 3.2.1.21 ).

25. Process according to any one of the preceding claims, in which a temperature of between 20 and 200°C is applied.

26. Process according to any one of the preceding claims, in which UVA radiation is applied, in particular an irradiance of between 0.01 and 0.40 milliwatt/cm² and/or

UVB radiation is applied, in particular an irradiance of between 0.01 and 0.20 milliwatt/cm².

27. Multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising the same, as described in either of Claims 1 and 2, which has undergone a preliminary step that consists in replacing the radical R with a hydrogen atom, and a second compartment containing at least one nucleophilic compound (1 ) or (2), carbonyl oligomers or polymers, according to any one of Claims 1 and 4 to 12, or at least one amino or thio polymer according to any one of Claims 1 , 13 to 16, the composition resulting from the mixing of the compartments having an [amino or thio polymer(s)/compound(s) of formula (I) or plant extract comprising the same] weight ratio of at least 0.01 , if it contains such amino or thio polymer(s). 28. Multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising the same, as described in either of Claims 1 and 2, and a second compartment containing at least one nucleophilic compound (1 ) or (2), carbonyl oligomers or polymers, according to any one of Claims 1 and 4 to 12, or at least one amino or thio polymer according to any one of Claims 1 , 13 to 14, and an enzyme for replacing the radical R of formula (I) with a hydrogen atom according to Claim 24; the composition resulting from the mixing of the compartments having an [amino or thio polymer(s)/compound(s) of formula (I) or plant extract comprising the same] weight ratio of at least 0.01 , if it contains such amino or thio polymer(s). Multi-compartment device comprising a first compartment containing at least one compound of formula (I) or the plant extract comprising the same, as described in either of Claims 1 and 2; a second compartment containing at least one nucleophilic compound (1 ) or (2), carbonyl oligomer or polymer, according to any one of Claims 1 and 4 to 13, or at least one amino or thio polymer according to any one of Claims 1 and 14 to 15; and a third compartment containing an enzyme for replacing the radical R of formula (I) with a hydrogen atom according to Claim 24; the composition resulting from the mixing of the compartments having an [amino or thio polymer(s)/compound(s) of formula (I) or plant extract comprising the same] weight ratio of at least 0.01 , if it contains such amino or thio polymer(s).