FR2918667A1 - METHOD FOR COLORING USING A STYRYLIC OR IMINIC TYPE DISULFIDE / THIOL AND STIMULI COMPOUND, COMPOSITION AND DEVICE FOR CARRYING OUT THE METHOD - Google Patents

Abstract

The present invention relates to the dyeing of keratinous fibers from colorless or weakly colored styryl or iminic disulfide / thiol type compounds which are stained by stimuli. The subject of the present invention is a process for dyeing keratin materials, in particular keratinous fibers. such as hair, using a dye composition comprising at least one styrylic or imine disulfide / thiol type compound.It further relates to a device suitable for implementing said method.The present invention makes it possible in particular to obtain a coloring keratin fibers chromatic and tenacious, visible even on dark hair without prior lightening.It also allows to obtain a color that, under certain conditions, does not stain.

Description

METHOD FOR COLORING USING A STYRYLIC OR IMINIC TYPE COMPOUND

  The present invention relates to the dyeing of keratinous fibers from colorless or weakly colored styryl or iminic disulfide / thiol type compounds which stain by stimuli. SUMMARY OF THE INVENTION It is known to dye keratinous fibers, and in particular human keratinous fibers such as the hair, with dyeing compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds such as diaminopyrazole derivatives. These oxidation bases are colorless or weakly colored compounds which, combined with oxidizing products, give rise, by a process of oxidative condensation, to colored compounds. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds. Another advantage of this type of coloration is to be visible on dark hair. Indeed, the oxidative process being carried out in an alkaline medium, most generally in the presence of ammonia, it occurs, parallel to the condensation of color precursors, a discoloration of melanin, the natural pigment of keratin fibers and in particular the hair. The color obtained can also be visible even on dark hair. The colorations obtained have good toughness, especially with respect to shampoos. However, it is rare to be able to obtain by this method chromatic colorations.

  It is also known to dye keratinous fibers with compositions containing direct dyes. These compounds are colored molecules and dyes that have an affinity for keratin fibers. They are applied to the fibers for a time necessary to obtain the desired coloration, and then generally rinsed.

  The direct dyes conventionally used are in particular dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine or triarylmethane type or natural dyes.

  The direct dyes make it possible to advantageously achieve very chromatic colors but they always have the disadvantage of being temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or or the heart of the fiber are responsible for their low dyeing power and their poor resistance to washes or perspiration. Indeed, the tenacity of the direct dyes on the hair remains limited, which leads to a color fading, or even a turn of it over time, due to the departure of one or more dyes employed. Furthermore, the coloration of keratinous fibers from conventional direct dyes does not make it possible to significantly lighten the keratin fibers. Conventionally, to obtain a lighter coloration is implemented a chemical bleaching process. This method consists in treating keratin materials such as keratinous fibers, in particular the hair, by a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, most often in an alkaline medium. This bleaching system has the drawback of degrading keratin materials, in particular keratinous fibers, especially human fibers such as the hair, and of altering their cosmetic properties. The fibers tend to become rough, more difficult to disentangle and more fragile. Finally, the lightening or the bleaching of keratinous fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in the straightening treatments. Another lightening technique consists in applying fluorescent direct dyes to dark hair. This technique, described in particular in documents FR 2830189 and WO 2004/091473, makes it possible to respect the quality of the keratinous fiber during the treatment, but the fluorescent dyes employed do not exhibit satisfactory resistance to shampooing. To increase the tenacity of the direct dyes, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react dyes with reactive groups with the residues of cystine or cysteine very numerous in keratin fibers, see for example Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91, 259-264 ( 1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509. In addition, it is known to protect the thiol function (s) contained in a molecule to be grafted to the hair before applying them to said hair, for example see WO99 / 51194. However, this application does not mention the use of fluorescent dyes for coloring or lightening hair. Disulfide dyes known for dyeing keratinous fibers are disulfide derivatives of aminothiophenol derivatives. Such dyes are described, for example, in patent FR 1156407. These dyes can be used under relatively mild conditions, in the presence of a slightly reducing medium or after a reducing pretreatment of the hair. However, these dyes may cause color turns during application.

  WO 2005/097051 discloses aza-imidazolium disulfide dyes for the direct dyeing of keratinous fibers, EP1647580 discloses the use of azo disulfide dyes, hydrazones, anthraquinones and styrylics. Finally, WO 2006/134043 and WO 2006/136617 disclose other styryl disulfide dyes and styryl thiol dyes.

  A disadvantage of these dyes, such as those described in the above-mentioned staining modes, is that the compositions are initially stained, as in the case of staining compositions involving direct dyes, or become so during the application, such as this is the case for compositions comprising one or more oxidation dye precursors. Therefore, direct dyeing and oxidation dyeing have the disadvantage of being messy. Styryl or imine type compounds existing in a colored form and in a colorless form and their use in the field of cosmetics, and in particular in the field of skincare and nail polish, have been described in the documents JP 56-150006, JP 56-081522, JP 56-025106, JP 55-113710 and JP 55-031057. Recently, patent application FR 2,888,747 describes the use of existing styryl or imine type compounds in a colored form and in a colorless form, for dyeing keratinous fibers. Thus, under certain conditions, the composition used is colorless or weakly colored and the color is revealed in the keratinous fibers once the application is made, which makes it possible to solve the problem of staining the skin and the tissues used. If these compositions provide many advantages over existing compositions and provide some coloring efficiency, it is necessary to further improve the toughness of the coloring obtained. It is particularly desirable for the compound to be colorless or weakly colored for the duration of the application to the hair fibers while allowing the hair to be stained tenaciously, in particular with respect to the shampoos. The present invention therefore aims to provide a keratinous fiber dyeing process which does not have the disadvantages of known methods. In particular, one of the aims of the present invention is to provide methods for obtaining chromatic colorings, powerful and tenacious, especially vis-à-vis shampoos that do not degrade keratin fibers and which do not alter their cosmetic properties. The present invention also makes it possible to access keratin fibers which are lighter in color than the initial color without necessarily having to use an oxidizing composition. Finally, the method according to the invention makes it possible, under certain conditions, to propose a process which does not stain the skin or the tissues used for the coloration and involving new dyes. Thus, the subject of the invention is compounds of styrylic or imine disulfide / thiol type which can be stained by stimuli, chosen from compounds of the following formula (I): ## STR1 ## organic or inorganic acid, optical isomers, geometric isomers, and solvates such as hydrates; formula (I) in which: m is 1 or 2: when m is 1 then Y 'is present and when m is 2 then Y' is absent; p is 0 or 1; Csat represents a linear or branched, optionally substituted, optionally cyclic C1-C18i alkylene chain; - A represents a chromophore that can be colored, or can be stained and fluoresce, under the action of stimuli; said chromophore is for example selected from thermochromes, photochromes, halochromes, solvatochromes, ionochromes, acidochromes and electrochromes; in particular the chromophore is likely to stain in the presence of a proton source or a Lewis acid; X represents a C1-C30, particularly C1-C8, linear or branched, saturated or unsaturated, optionally substituted hydrocarbon-based chain, optionally interrupted by one or more divalent groups or combinations thereof chosen from: i) N (R) -; -N + (R) (R ') -, Q-; -O-; -S-; -CO-; -SO 2 - with R, R ', which may be identical or different, are chosen from hydrogen, a C1-C4 alkyl, hydroxyalkyl and aminoalkyl radical, Q- represents an anionic counterion; and ii) a radical (hetero) cyclic, aromatic or not, saturated or unsaturated, condensed or not, optionally comprising one or more identical or different heteroatoms, optionally substituted; Y 'represents i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + RaRRRYRs, M- or a phosphonium group: P + RaRRRYRs, M-with Ra, RR, R7 and R8, identical or different, representing a hydrogen atom or an alkyl group and M-represents an anionic counterion; or v) a thiol protecting group; it being understood that when m is 1, the function SY 'can be in the covalent form -S-Y' or ionic -S Y '+ depending on the nature of Y' and the pH of the medium.

  Another subject of the invention is a dyeing composition comprising, in a suitable cosmetic medium, at least one compound of formula (I) as defined above, and optionally a reducing agent.

  The subject of the invention is also a process for dyeing keratinous substances, in particular human keratinous fibers such as the hair, more particularly dark, consisting in applying to said materials the composition of the invention as defined above in the presence of a stimulus. Another subject of the invention relates to a method for staining and permanent deformation of particularly dark keratinous fibers, comprising applying to said materials a composition comprising at least one dye of formula (I) with at least one reducing agent followed by a step fixing by application of an oxidizing agent.

  Another subject of the invention is the use of at least one compound of formula (I) as defined above for the dyeing of keratin materials. The compounds of formula (I) can also be used for dyeing dark keratin materials, especially with a lightening effect, in particular for dyeing dark human keratin fibers such as dark hair.

  The dyeing method according to the invention makes it possible to visibly stain keratin materials, in particular dark human keratin fibers, especially dark hair. In addition, the process of the invention makes it possible to obtain a coloration of the keratin materials, in particular human keratinous fibers, in particular the hair, without degrading said material, which is persistent with respect to shampoos, of the common aggressions (sun, perspiration). , and other hair treatments. The process of the invention also makes it possible to obtain a lightening of keratin materials such as keratinous fibers, particularly dark keratinous fibers and more particularly dark hair. The invention makes it possible in particular to obtain a coloring of keratinous fibers which is chromatic and particularly stubborn, especially with respect to shampoos. In addition, they make it possible to achieve clean, non-staining colorations compared to direct and oxidation colorations. Indeed, under certain conditions of implementation of the invention, the compound of formula (I) applied to the keratinous fibers is colorless or weakly colored throughout the laying on the hair. Staining is only revealed by external stimulation after application to the keratinous fibers and a possible pause time. The dye composition applied to the keratinous fibers is therefore colorless, or slightly colored, transparent as well as the rinsing or shampooing water, thus making its application non-messy.

  Moreover, it is possible to delete the color obtained. The same color erasure property can be obtained with either the same stimulus as for the appearance of color, or with another type of stimulus. This stimulus reacts the colored compound of a colored form with the colorless form. The colored form obtained will structurally change to reversibly lead to the original unstained form. In practice, it suffices to treat the colored keratin materials, for example with a composition whose function is to increase the pH of the fibers above the pKa of the compounds of formulas (I) present on and in the fibers. Finally, it has been found that the application of the dyeing composition to dark hair, more particularly characterized by a pitch of less than or equal to 6, leads to an increase in the pitch of the coloration of at least one tone. corresponds to a visible lightening of the fiber, without resorting to the use of an oxidizing composition. The compounds of formula (I) can be neutralized by anionic or cationic counterion when they carry a charge. The negative counter-ions may for example be chosen from a halide such as a chloride, a bromide, an iodide or a fluoride, a perchlorate, a p-methylbenzene sulphonate, a tetrafluoroborate, a sulphate, an alkyl sulphate, a toluenesulphonate, a sulfonate. The cationic counterions can be chosen from cations derived from alkali metal or alkaline earth metal salts such as sodium or potassium ions.

  For the purposes of the invention, the term "dark keratin material" is understood to mean that which has a luminescence L * encoded in the CIEL * a * b * system, less than or equal to 45 and preferably less than or equal to 40, while also knowing that L * = 0 is equivalent to black and L * = 100 to white. For the purposes of the invention, the term naturally or artificially dark hair, hair whose pitch is less than or equal to 6 (dark blonde) and preferably less than or equal to 4 (chestnut). The lightening of the hair is evaluated by the pitch that characterizes the degree or level of lightening. The notion of tone is based on the classification of natural nuances, a tone separating each nuance from that which follows it or immediately precedes it. This definition and the classification of natural shades is well known to hair professionals and published in the book Science of hair treatments Charles ZVIAK 1988, Ed Masson, p. 215 and 278. The pitch ranges from 1 (black) to 10 (very light blonde), a unit corresponding to a tone; the higher the number, the clearer the nuance.

  An artificially colored hair is a hair whose color has been modified by a coloring treatment, for example a coloration with direct dyes or oxidation dyes.

  For the purposes of the present invention, and unless a different indication is given: the aryl or heteroaryl radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent carried by a carbon atom chosen among: • a C1-C16, preferably C1-C8, alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C1-C2 alkoxy, (C2-C4) poly (hydroxy) alkoxy, acylamino, amino radicals; substituted with two identical or different C1-C4 alkyl radicals, optionally bearing at least one hydroxyl group, or the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7; 5-membered, preferably 5-membered, optionally substituted saturated or unsaturated linkages optionally comprising another heteroatom identical to or different from nitrogen; A halogen atom such as chlorine, fluorine or bromine; • a hydroxyl group; A C1-C2 alkoxy radical; A C1-C2 alkylthio radical; A C2-C4 (poly) -hydroxyalkoxy radical; An amino radical; A 5- or 6-membered heterocycloalkyl radical; A 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferably methyl; An amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: i) a hydroxyl group, ii) an amino group optionally substituted with one or two C 1 -C 3 alkyl radicals optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom which is different from or different from nitrogen, iii ) a quaternary ammonium group -N + R'R "R" ', for which R', R ", R" ', which may be identical or different, represent a hydrogen atom, or a C1-C4 alkyl group; and M - represents the counter-ion of the organic acid, mineral or of the corresponding halide, iv) or a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted by a (C 1 -C 4) radical; alkyl, preferably methyl; -NR-C (O) -R 'in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C1-alkyl radical; -C2; a carbamoyl radical (R2N-C (O)) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R'S (O) 2-NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents an alkyl radical; C1-C4, a phenyl radical; an aminosulfonyl radical (R2N-S (O) 2-) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, • a radical; carboxylic acid in acid form C (0) OH or salified (preferably with an alkali metal or ammonium, substituted or not); • a cyano group; A polyhaloalkyl group comprising from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which are identical or different, the polyhaloalkyl group is, for example, trifluoromethyl; a cyclic, heterocyclic, or nonaromatic portion of an aryl or heteroaryl radical may also be substituted by one or more oxo or thioxo moieties; a hydrocarbon chain is unsaturated when it comprises one or more double bonds and / or one or more triple bonds; an aryl radical represents a mono or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl; a diarylalkyl radical represents a group comprising, on the same carbon atom of an alkyl group, two identical or different aryl groups, such as diphenylmethyl or 1,1-diphenylethyl; a heteroaryl radical represents a mono- or polycyclic group, fused or otherwise, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium, and at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and its ammonium salt; a diheteroarylalkyl radical represents a group comprising, on the same carbon atom of an alkyl group, two heteroaryl groups, which are identical or different, such as difurylmethyl, 1,1-difurylethyl, dipyrrolylmethyl and dithienylmethyl; a cyclic radical is a non-aromatic cycloalkyl radical, mono- or polycyclic, condensed or otherwise, containing from 5 to 22 carbon atoms, which can comprise from one to several unsaturations; particularly the cyclic radical is cyclohexyl; - A sterically hindered cyclic radical is a cyclic radical, aromatic or not, substituted or unsubstituted, hindered by steric effect or constraint, comprising from 6 to 14 members, which can be bridged, as sterically hindered radicals include bicyclo [1.1]. Butane, mesytyls such as 1,3,5-trimethylphenyl, 1,3,5-triterbutylphenyl, 1,3,5-isobutylphenyl, 1,3,5-trimethylsilylphenyl and adamantyl; a heterocyclic radical is a non-aromatic mono or polycyclic radical, condensed or otherwise, containing from 5 to 22 members, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium; an alkyl radical is a C1-C16 hydrocarbon radical, linear or branched, preferably C1-C8; an alkylene chain represents a divalent C1-C18 chain; especially C1-C6, more particularly C1-C2 when the chain is linear; optionally substituted by one or more, identical or different, halogen atoms or groups selected from hydroxy, alkoxy, (di) (alkyl) amino, R1a-Z1a-C (Z1b) - with Zia and Z1b, identical or different, representing an oxygen atom, sulfur atom, or a NRa 'and Ria group, representing an alkali metal, a hydrogen atom, or an alkyl group and Ra' representing a hydrogen atom or an alkyl group; a saturated or unsaturated C 1 -C 30 hydrocarbon-based chain, optionally substituted, represents a hydrocarbon chain, particularly C 1 -C 8, optionally comprising one or more conjugated or unsubstituted 7T double bonds, particularly the hydrocarbon chain is saturated; said chain is optionally substituted by one or more, identical or different, halogen atoms or groups selected from hydroxy, alkoxy, (di) (alkyl) amino, R1b-Z1b-C (Z1c) - with Z1b, Z10 same or different , representing an oxygen atom, sulfur atom, or NRb 'group, and Wb, representing an alkali metal, a hydrogen atom, or an alkyl group and Wb' representing a hydrogen atom or an alkyl group; the optionally substituted expression attributed to the alkyl radical, that is to say that said alkyl radical may be substituted by one or more radicals chosen from i) hydroxyl, ii) C 1 -C 4 alkoxy, iii) acylamino, iv) amino optionally substituted by a radical; or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom carrying them, a 5- to 7-membered heterocyl, optionally comprising another heteroatom which may or may not be different from nitrogen; ; v) or a quaternary ammonium group -N + R'R "R" ', for which R', R ", R" ', which may be identical or different, represent a hydrogen atom, or a C 1 -C 4 alkyl group, or else -N + R'R "R" 'forms a heteroaryl such as imidazolium optionally substituted by a C1-C4 alkyl group, and M represents the counterion; an alkoxy radical is an alkyl-oxy or alkyl-O- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, C1-C16 preferably C1-C8 i - an alkylthio radical is an alkyl-S- radical for wherein the alkyl radical is a hydrocarbon radical, linear or branched C1-C16 preferentially C1-C8; when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above; the condensed aryl or fused heteroaryl ring B of formulas (I '), (II') (III '), (IV'), (V ') or (VI') below may be substituted with one or several substituents, identical or different, chosen from: • a halogen atom (in particular chlorine, bromine, iodine or fluorine); A C1-C6 alkyl group; • a C1-C6 alkoxy group; An alkylsulfonyl group: -SO2C1-C6alkyl; A group of -SO3alkyl Cl-C6 type; • a cyano group (ON) • a group CF3; • -C (O) C 1 -C 6 alkyl groups; • a group -SO2CF3; • a group ùC (0) CF3; • a group -SO2Ph; • a group -SO3Ph; • a group ùC (0) Ph; A nitro group (NO2); a -C (O) O-alkyl: C1-C6 alkoxycarbonyl group; • a phosphonic group -PO3H2i • a (C 1 -C 6) alkyl phosphonic group; • a hydroxyl (OH) group; A group -NRaRb with Ra and Rb, identical or different, representing a hydrogen atom or a group selected from C1-C6 alkyl, C1-C6 hydroxy (C1-C6) alkyl (di) (alkyl) amino C1-C6 alkyl; A group -Alk-NRaRb with Ra and Rb as defined previously and Alk represents an alkylene chain; • C1-C6 hydroxyalkyl; Benzoyl optionally substituted with from one to three substituents chosen from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, cyano and (di) (C 1 -C 4) (alkyl) groups; amino; A phenyl (C 1 -C 6) group optionally substituted on the phenyl by from one to three substituents chosen from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, cyano and (di) (C) , -C4) (alkyl) amino; A quaternary ammonium group -N + R'R "R" ', for which R', R ", R" ', which may be identical or different, represent a hydrogen atom, or a C1-C4 alkyl group; and M - represents the counterion; A C 1 -C 6 ammonioalkyl group for which ammonium is as defined above; • a carboxylic group in the acid form C (0) OH or salified (preferably with an alkali metal or ammonium, substituted or not); A group Alk-C (O) OH with Alk as defined above; • a thiol or mercapto group (SH); A mercaptoalkyl group: Alk-SH with Alk as defined above; • a sulfonate group (SO3-); A group -Alk-SO3- with Alk as defined above; A (C 1 -C 6) alkylcarbonyl (C 1 -C 6) alkyl group; A (di) haloalkylamino group; • an acetamide group; A phenyloxy group; A phenyloxy (C1-C6) alkyl group; An acetylene group: -CH = CH 2; and a carbonylacetylene group: -C (O) -CH = CH 2; Two adjacent groups of B can form a bridge of the type -O-CsH2s-O- where s represents an integer equal to 1 or 2 (methylenedioxy or ethylenedioxy); B may also be substituted by one or more cationic groups of the oxazolium, thiazolium, imidazolium, pyrazolium, pyridinium, pyrrolium, triazolium, isooxazolium, isothiazolium, pyrimidinium, pyrazinium, triazinium, pyridazinium, indolium, quinolinium or isoquinolimiun type. These groups may be substituted, these groups being connectable to the ring B by any of their unsubstituted carbon atom; the divalent arylene or heteroarylene group G of the formula (I ') below or the aryl or heteroaryl group G' of formulas (II '), (III'), (IV '), (V') or (VI) ') below may be substituted by one or more substituents, identical or different, selected from those of the previous list of B, but also by a group - NR Rd with R and Rd which represent independently of each other a an alkylene chain which may contain an oxygen or sulfur atom and which may be terminated by a cyano (ON) or C 1 -C 6 alkylsulfonyl group, a C 1 -C 6 alkylcarbonyl group or else R and Rd may form together with the atom of nitrogen which carries them a heterocycle; the cyclic or heterocyclic part of a nonaromatic radical may be substituted by at least one substituent carried by a carbon atom selected from the groups: • hydroxy, • C 1 -C 4 alkoxy • (poly) hydroxyalkoxy at 02-04, • a C1-C2 alkylthio radical; RCO-NR'- in which the R 'radical is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R radical is a C 1 -C 2 alkyl substituted amino radical; by two identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated; optionally substituted optionally comprising at least one other heteroatom different or different from nitrogen; RC (O) -O- in which the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted saturated or unsaturated 5- to 7-membered heterocyclic ring optionally comprising at least one other heteroatom different from or different from nitrogen; • RO-C (O) - in which the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted saturated or unsaturated 5- to 7-membered heterocyclic ring optionally comprising at least one other heteroatom different from or different from nitrogen; a stimulus is an external physical or thermodynamic source such as light, electric current, heat, electromagnetic radiation or ultrasound (sonication); or else the stimulus may be a chemical external source such as the addition of organic, mineral or inorganic salt, the addition of Lewis acidic agents such as the addition of cosmetically acceptable zinc salt, or the addition of acidic Brdnsted agent, the addition of solvent including polar protic type such as those determined by C. Reichardt (Sc / Winds and Sc / Wind Effects in Organic Chemistry, VCH, Weinheim, 1988); advantageously the stimuli make use of external chemical sources such as acids, particularly Brdnsted acids i.e. proton-donating acids; the cosmetically acceptable zinc salts are salts comprising the zinc atom conventionally used in the field of cosmetics, in particular the zinc salt is a Zn2 + A'2- type derivative or a Zn2 + type derivative (B'- ) 2; with A 'and B' representing an organic radical, in particular a carboxylic acid; by way of example, mention may be made of zinc acetate, hydrated or not, zinc bromide, zinc carbonate, zinc hydroxide, zinc chloride, zinc cyanide, zinc cyclohexanebutyrate, zinc fluoride, zinc iodide, zinc nitrate, zinc selenide, zinc stearate, zinc sulphate, zinc sulphide, zinc tetrafluoroborate, zinc p-toluene sulphonate, acetylacetonate Zinc triflate, zinc bis (8-yroxyquinolate), zinc dibenzyldithiocarbamate, zinc diethyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc gluconate, zinc pyrithione, zinc zinc trifluoromethane sulfonate, zinc benzoate, zinc p-tert-butylbenzoate, zinc phenolsulfonate, zinc phosphate, zinc pyrophosphate, zinc terephthalate, zinc thiocyanate, zinc glycinate, aspartate of zinc, zinc lanolate, zinc dilaurate, zinc undecylenate, and Zinc lactate, the bounds delimiting the range of a range of values are within this range of values.

1. Compounds of formulas (1)

  The radical A of the formula (I) may contain one or more identical or different chromophores chosen from thermochromic, photochromic, halochromic, solvatochromic, ionochromic, acidochromic and electrochromic.

  1.1. Chromophore A For the purposes of the present invention, the chromophores are said to be different when they differ in their chemical structure. The chromophores useful in the invention exist in two forms: a closed cyclized form which is colorless or weakly colored, and a colored open form. The passage from one form to another is possible by several stimuli as defined above. The process of the form closed to the open form is reversible, and the reversibility of the process can appeal to another type of stimulus. Advantageously A is a colorless chromophore which can be colored under the action of stimuli. In particular, the chromophore may be stained in the presence of a proton source or a Lewis acid.

  These chromophores may also in open form be fluorescent chromophores. Fluorescent chromophore means a radical derived from a fluorescent compound. A fluorescent compound is a compound that is capable of absorbing in UV or visible radiation at an Xabs wavelength of between 250 and 800 nm and capable of reemitting in the visible range at an emission wavelength Xem between 400 and 800 nm. Preferably the fluorescent compounds are dyes capable of absorbing in the visible Xabs between 400 and 800 nm and reemitting in the visible Xem between 400 and 800 nm. More preferably, the fluorescent compounds are dyes capable of absorbing at an Xabs between 420 nm and 550 nm and reemitting in the visible at an Xem of between 470 and 600 nm.

  According to one variant, the radical A of formula (I) contains at least one radical derived from chromophore of merocyanine compounds. This radical A, derived from a chromophore, is connected by any part of said chromophore to the remainder of the molecule: ## STR5 ## of formula (I). For example, the radical A is colorless in heterocyclic (spiro) closed form and reveals its color, particularly at a different pH, by opening the heterocycle called merocyanine, as illustrated below with a Brenstead acid: Ar H + - H + spiroheterocyclic such as spirofuran or spiropyran open form protonated merocyanine open form heterocyclic protonated merocyanine n Ar H + - H + - _Ar n with - Het represents an optionally substituted dihydroheteroararyl group, heteroaryl being defined as defined above, the Het group is preferably fused with the heterocycle which comprises Z and Y; in particular, Het represents a dihydrooxazole, dihydrobenzoxazole, dihydrothiazole, dihydrobenzothiazole, dihydroimidazole, dihydrobenzimidazole, dihydropyridine, dihydropyrimidine, dihydropyrazine, dihydroquinoline, indoline, dihydrobenzoindole group; - Het + represents a cationic heteroaryl group; preferably, the cationic heteroaryl comprises an endocyclic heteroatom i.e. participating in the electronic delocalization of the electronic doublet mesomeric effect selected from the oxygen atom, sulfur, selenium and nitrogen; especially Het + represents an oxazolium, benzoxazolium, thiazolium, benzothiazolium, imidazolium, benzimidazolium, pyridinium, pyrimidinium, pyrazinium, quinolinium, indolium, benzoindolium or benzoselenium group; Ar represents an optionally substituted aryl or optionally substituted heteroaryl group as defined above; n represents an integer of 1 to 4; particularly n is 1 or 2; W, present or absent, represents a nitrogen atom or a group CR 2, it being understood that when n represents an integer greater than or equal to 2, W represents a group CR 2 and when n is 1 and W is absent, the double bond is find between CR3 and the Ar group; - R2 and R3, identical or different, represent a hydrogen atom, a halogen atom, a C1-C6 alkyl radical, a cyano radical, an aromatic group, a phenoxy group, a nitro radical; Y represents an oxygen atom, a sulfur atom, an NR5 group with R5 representing a hydrogen atom, a C1-C6 alkyl radical; Z represents i) a divalent group -CgH2q-, with q an integer between 2 and 4 inclusive, unsubstituted or substituted by one or more substituents selected from halogen atoms, and hydroxy, alkyl, haloalkyl, alkoxy, amino groups; (di) alkylamino, (di) hydroxyalkylamino, carboxyl; ii) a divalent group -CrH2rC (O) -orCrH2rC (S) - with r an integer inclusive of between 1 and 3, unsubstituted or substituted by one or more substituents selected from halogen atoms, and hydroxy, alkyl groups; , haloalkyl, alkoxy, amino, (di) alkylamino, (di) hydroxyalkylamino, carboxyl, especially Z is not substituted.

  The staining is revealed by opening the heterocyclic (spiro) chromophore to give chromophore (aza) merocyanine species, which are stained: stimulus stimulus 'closed form spiroheterocyclic open form merocyanine stimulus n Ar Yn z -Ar stimulus' I Het + - n N form heterocyclic form open merocyanine with Ar, Het, Het +, R2, R3, W, Y, Z, and n are as defined above, stimulus and stimulus', identical or different, are stimuli such as previously defined. The opening of the (spiro) heterocycle in the compounds compounds of the invention is carried out under the effect of a stimulus such as light, an electric current, heat, the addition of an acidifying agent, the addition solvent, the addition of salts, electromagnetic radiation or by sonication, and the return to the closed form of the (spiro) heterocycle can take place under the effect of the same stimulus used for the opening or under the effect of another type of stimulus.

  Such chromophores derived from styrylic or imine type compounds stain by stimuli are already described in the patents applied to fields other than hair coloring: JP 2001081342; JP 11034497; JP 11034489; JP 08222268; JP 02179618; JP 63280727; JP 61147235; JP 58048031; JP 56149489 (US 4380629); JP 57014652; JP 55113710; DE 2541665; JP 2001246862; and JP 56150006

  By way of example, which satisfies the sensitivity criteria for the stimuli according to the invention, mention may be made of the chromophores derived from the following compounds 1 to 5 and i) to Lxxxxi): N0 3,3-dimethyl-2- (p-dimethylamino) styryl) indolino [1,2-b] oxazoline: 1 CH3SO2CH3NCH3I / NOU 3,3-dimethyl-5-methylsulfonyl-2- (p-dimethylaminostyryl) indolino [1,2-b] oxazoline: 2 CH3 CH 3 SO 2 N- [N -3-dimethylaminocinnamylidenevinyl) indolino [1,2-b] -5 oxazoline: a] indole-7-carboxylic acid, 9- [2- [4- (dimethylamino) phenyl] -1,3-butadienyl] -2,3,9,9a-tetrahydro-9,9-dimethyl [620610-77] 7]; ii) Phosphonic acid, [9- [2- [4- (dimethylamino) phenyl] ethenyl] -2,3,9,9a-tetrahydro-9,9-dimethyloxazolo [3,2-a] indol-7-yl] [620610-76-6]; iii) Benzenamine, 4- [2- (9,9-diethyl-2,3-dihydro-7-methoxyoxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-diethyl [503529] 51-9]; iv) Phosphonic acid, [3- [9- [2- [4- (dimethylamino) phenyl] ethenyl] -2,3,9,9a-tetrahydro-9,9-dimethyloxazolo [3,2-a] indol-7 -yl] propyl] [475287-99-1]; v) Benzenamine, 4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N-methyl-N-phenyl [334475- 31-9]; vi) Benzenamine, 4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) yl) ethenyl] -3-ethoxy-N, N-diethyl [330625] -52-0]; (vii) Benzenamine, 4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N-ethyl-N- (2-methylpropyl) ) [303129-05-7]; viii) Benzenamine, 4- [2- (2,3-dihydrooxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [244146-17-6]; (ix) Benzenamine, 4- [4- (2,3-dihydro-7,9,9-trimethyloxa-zolo [3,2-a] indol-9a (9H) -yl) -1,3-butadienyl] -N N-dimethyl [220495-27-2]; x) Benzenamine, 4- [4- (2,3-dihydro-9,9-dimethyl-7-nitrooxazolo [3,2-a] indol-9a (9H) -yl) -1,3-butadienyl] - N, N-dimethyl [220495-26-1]; xi) Oxazolo [3,2-a] indole-7-carbonitrile, 9a- [4- [NO] -3,3-dimethyl-2- (p-acetylaminostyryl) indolino [1,2-b] oxazoline: 5 3 N 1 C2H5

  3,3-dimethyl-2- [2- (9-ethylcarbazolyl) vinyl] indolino [1,2-b] oxazoline: 4H3C-CH3H- [4- (dimethylamino) phenyl] -1,3-butadienyl ] -2,3,9,9a-tetrahydro-9,9-dimethyl [220495-25-0]; (xii) Oxazolo [3,2-a] indole-7-carbonitrile, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -2,3,9,9a-tetrahydro-9,9-dimethyl [220487] 74-1]; (xiii) Benzenamine, 4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [112025] 1]; xiv) Oxazolo [3,2-a] indole-7-sulfonic acid, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -2,3,9,9-tetrahydro-9,9-dimethyl-, methyl ester [ 93233-29-5]; (xv) Benzenamine, N, N-bis (2-chloroethyl) -4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] [86395-66-6]; (xvi) Oxazolo [3,2-a] indol-2 (3H) -one, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -9,9a-dihydro-9,9-dimethyl-7 ( octylsulfonyl) [82052-27-5]; (xvii) Oxazolo [3,2-a] indol-2 (3H) -one, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -9,9a-dihydro-9,9-dimethyl-7 (phenylsulfonyl) ) [82052-26-4]; (xviii) Oxazolo [3,2-a] indol-2 (3H) -one, 9- [2- [4- (dimethylamino) phenyl] -1-methylethenyl] -9,9a-dihydro-9,9-dimethyl- 7- (methylsulfonyl) [82052-22-0]; (xix) Oxazolo [3,2-a] indol-2 (3H) -one, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -9,9a-dihydro-9,9-dimethyl-7 ( methylsulfonyl) [82052-21-9]; xx) Benzenamine, 4- [2- [2,3-dihydro-9,9-dimethyl-7- (methylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] -N, N dimethyl [81979-29-5]; xxi) Benzenamine, 4- [2- [9- (ethoxymethyl) -2,3-dihydro-9-methyl-7- (methylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] N, N-dimethyl [81979-28-4]; xxii) Benzenamine, 4- [2- [2,3-dihydro-2,9,9-trimethyl-7- (methylsulfonyl) oxazolo [3,2-a] indol9a (9H) -yl] ethenyl] -N, N dimethyl [81979-27-3]; xxiii) Benzenamine, 4- [2- [2,3-dihydro-9,9-dimethyl-7- (methylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] -1-propenyl] N, N-dimethyl [81979-26-2]; (xxiv) Benzenamine, N, N-dibutyl-4- [2- [2,3-dihydro-9,9-dimethyl-7- (methylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] [81979-20-6]; xxv) 4- [2- [2,3-dihydro-9,9-dimethyl-7- (phenylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] -N, N-dimethyl [81979-14-8]; xxvi) Benzenamine, 4- [2- [2,3-dihydro-9,9-dimethyl-7- (octylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] -N, N dimethyl [81979-12-6]; xxvii) Acetamide, N- [4- [2- [7- (butylsulfonyl) -2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] phenyl] [81979-10-4]; xxviii) Benzenamine, 4- [2- [7- (butylsulfonyl) -2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] -N, N- dimethyl [81979-09-1]; xxix) Benzenamine, 4- [4- [2,3-dihydro-9,9-dimethyl-7- (methylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] -1,3-butadienyl N, N-dimethyl [81979-07-9]; xxx) Oxazolo [3,2-a] indole-9-ethanol, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -2,3,9,9a-tetrahydro-9-methyl [76202-26- 1]; xxxi) Benzenamine, 4- [2- (9,9-diethyl-2,3-dihydrooxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [74857-99-] 1]; xxxii) Benzenamine, 4- [2- [2,3-dihydro-9-methyl-9- (2-phenoxyethyl) oxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] -N, N dimethyl [74784-54-6]; xxxiii) Benzenamine, 4- [2- [9- (ethoxymethyl) -2,3-dihydro-9-methyloxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] -N, N-dimethyl [ 74784-53-5]; xxxiv) Benzenamine, 4- [2- (11,11-dimethylbenz [e] oxazolo [3,2-a] indol-10a (11H) -yl) ethenyl] -N, N-dimethyl [66180-27-6] ]; xxxv) Benzenamine, 4- [2- (7-methoxy-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [66180-26-5] ; xxxvi) Benzenamine, 4- [2- (9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [66180-24-3]; xxxvii) Oxazolo [3,2-a] indol-2 (3H) -one, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -3-ethyl-9,9-dihydro-9,9-dimethyl [65744] -31-2]; xxxviii) Oxazolo [3,2-a] indol-2 (3H) -one, 7-chloro-9- [2- [4- (dimethylamino) phenyl] ethenyl] -9,9a-dihydro-3,9,9 trimethyl [65744-30-1]; xxxix) Oxazolo [3,2-a] indol-2 (3H) -one, 9a- [2- [4- (dibutylamino) phenyl] ethenyl] -9,9-dihydro-9,9-dimethyl [65744-26] -5]; xxxx) Oxazolo [3,2-a] indol-2 (3H) -one, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -9,9a-dihydro-9- (2-hydroxyethyl) -9 methyl [65744-25-4]; xxxxi) Oxazolo [3,2-a] indol-2 (3H) -one, 9a- [2- [4- (dimethylamino) phenyl] -1-propenyl] -9,9a-dihydro-9,9-dimethyl [ 65744-24-3]; xxxxi) Oxazolo [3,2-a] indol-2 (3H) -one, 9,9-dihydro-7,9,9-trimethyl-9- [2- (4-nitrophenyl) ethenyl] [65744-02-7] ; xxxxii) Acetamide, N- [4- [2- (2,3-dihydro-9,9-dimethyl-2-oxooxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] phenyl] [65744] -01-6]; xxxxiii) Oxazolo [3,2-a] indol-2 (3H) -one, 9a- [2- [4- (dimethylamino) phenyl] -ethenyl] -9,9a-dihydro-6-methoxy-9,9- dimethyl [65743-99-9]; xxxxiv) Oxazolo [3,2-a] indole-7-carboxylic acid, 9a- [2- [4- (dimethylamino) phenyl] ethenyl] -2,3,9,9a-tetrahydro-9,9-dimethyl-2 oxo-ethyl ester [65743-98-8]; xxxxv) Oxazolo [3,2-a] indol-2 (3H) -one, 9a- [2- [4- (dimethylamino) phenyl] ethenyl] -9,9a-dihydro-7,9,9-trimethyl [65743] -94-4]; xxxxvi) Benz [e] oxazolo [3,2-a] indol-9 (8H) -one, 10- [2- [4- (dimethylamino) phenyl] ethenyl] -10a, 11 -dihydro-1, 1-di methyl [65743-93-3]; xxxxvii) Oxazolo [3,2-a] indol-2 (3H) -one, 9,9a-dihydro-9,9-dimethyl-9- [2- (4-nitrophenyl) ethenyl] [65743-92-2] ; xlviii) Oxazolo [3,2-a] indol-2 (3H) -one, 7-chloro-9- [2- [4- (dimethylamino) phenyl] ethenyl] -9,9a-dihydro-9,9 dimethyl [65743-90-0]; xxxxix) Oxazolo [3,2-a] indol-2 (3H) -one, 9- [2- [4- (dimethylamino) phenyl] ethenyl] -9,9a-dihydro-9,9-dimethyl [65743-88] -6]; xlix) Benzenamine, 4- [2- (7-chloro-2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [ 59380-46-0]; L) Benzenamine, 4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [59335-14] 7]; Li) Benzenamine, 4- [2- (7-Chloro-2,3-dihydro-2,9,9-trimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N- dimethyl [59335-03-4]; Lii) Benzenamine, 4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) -1-methylethenyl] -N, N-dimethyl [59335] -02-3]; xxxxxiii) Benzenamine, 4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-diethyl [59334-96] 2]; Liv) Oxazolo [3,2-a] indole, 2,3,9,9a-tetrahydro-7-methoxy-9,9-dimethyl-9- [2- (4-nitrophenyl) ethenyl] [59334-82-6 ]; Lv) Benzenamine, 4- [2- (2,3-dihydro-9,9-dimethyl-7-nitrooxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [ 59334-81-5]; Lvi) Benzenamine, N, N-dibutyl-4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] [59334-75- 7]; Lvii) Oxazolo [3,2-a] indole, 2,3,9,9a-tetrahydro-9,9-dimethyl-7-nitro-9- [2- (4-nitrophenyl) -ethenyl] [59334-70-] 2]; Lviii) Oxazolo [3,2-a] indole, 7-chloro-2,3,9,9a-tetrahydro-9,9-dimethyl-9- [2- (4-nitrophenyl) ethenyl] [59334-69-9 ]; Lix) Benzenamine, 4- [2- (2,3-dihydro-7-iodo-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [ 59334-68-8]; Lx) Benzenamine, 4- [2- (2,3-dihydro-5-methoxy-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [ 59334-54-2]; Lxi) Benzenamine, 4- [2- (2,3-dihydro-7-methoxy-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [ 59334-53-1]; Lxii) Benzenamine, 4- [4- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) -1,3-butadienyl] -N, N-diethyl [59334-40-6]; Lxiii) Benzenamine, 4- [4- (7-Chloro-2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) -1,3-butadienyl] -N N-dimethyl [59334-39-3]; Lxiv) Benzenamine, 4- [4- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) -1,3-butadienyl] -N, N-dimethyl [59334-38-2]; Lxv) Benzenamine, 4- [4- (2,3-dihydro-7-methoxy-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) -1,3-butadienyl] -N N-dimethyl [59334-37-1]; Lxvi) Oxazolo [3,2-a] indole, 2,3,9,9a-tetrahydro-7,9,9-trimethyl-9- [2- (4-nitrophenyl) ethenyl] [59334-30-4], Lxvii) Acetamide, N- [4- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] phenyl] [59334-28-0] ]; Lxviii) Benzenamine, 4- [2- (2,3-dihydro-6-methoxy-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [ 59334-25-7]; Lxix) Benzenamine, 4- [2- (8,9-dihydro-11,11-dimethylbenz [e] oxazolo [3,2-a] indol-10a (11H) -yl) ethenyl] -N, N-dimethyl [59334-23-5]; Lxx) Benzenamine, 4- [2- (2,3-dihydro-7,9,9-trimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -N, N-dimethyl [59334] -21-3]; Lxxi) Oxazolo [3,2-a] indole, 2,3,9,9a-tetrahydro-9,9-dimethyl-9- [2- (4-nitrophenyl) ethenyl] [59334-20-2]; Lxxii) Oxazolo [3,2-a] indol-2 (3H) -one, 9,9a-dihydro-9,9-dimethyl-9- [2- (9-methyl-9H-carbazol-3-yl) ethenyl) ] -7 (methylsulfonyl) [82052-23-1]; Lxxiii) Oxazolo [3,2-a] indole, 9a- [2- (9-hexyl-9H-carbazol-3-yl) ethenyl] -2,3,9,9a-tetrahydro-9,9-dimethyl-7 - (phenylsulfonyl) [81979-18-2]; Lxxiv) Oxazolo [3,2-a] indole, 2,3,9,9a-tetrahydro-9,9-dimethyl-7- (methylsulfonyl) -9a- [2 (9-octyl-9H-carbazol-3-yl) ethenyl] [81979-08-0]; Lxxv) Oxazolo [3,2-a] indole-7-carboxylic acid, 9a- [2- (9-butyl-6-methoxy-9H-carbazol-3-yl) ethenyl] -2,3,9,9a- tetrahydro-9,9-dimethyl-ethyl ester [81213-04-9]; Oxazolo [3,2-a] indole-7-sulfonic acid, 9- [2- (9-ethyl-9H-carbazol-3-yl) ethenyl] -2,3,9,9a-tetrahydro-9, 9-dimethyl-, methyl ester [81213-03-8]; 1H-carbazole, 3-chloro-6- [2- [2,3-dihydro-9,9-dimethyl-7- (methylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] -9-octyl [81213-02-7]; Lxxviii) 9H-Carbazole, 3- [2- [2,3-dihydro-9,9-dimethyl-7- (methylsulfonyl) oxazolo [3,2-a] indol-9a (9H) -yl] ethenyl] -9 -methyl [81213-01-6]; Lxxix) 9H-Carbazole, 3- [2- [9- (2-ethoxyethyl) -2,3-dihydro-9-methyl-7- (methylsulfonyl) oxazolo [3,2-a] indol-9a (9H) - yl] ethenyl] [81213-00-5]; Oxazolo [3,2-a] indole-7-carboxylic acid, 9a- [2- (9-hexyl-9H-carbazol-3-yl) ethenyl] -2,3,9,9a-tetrahydro-9 ( 2-hydroxyethyl) -9-methyl-ethyl ester [81212-99-9]; Oxazolo [3,2-a] indole-7-carboxylic acid, 2,3,9,9a-tetrahydro-9,9-dimethyl-9- [2- (9-octyl) -9H-carbazol-3-yl) ethenyl] - ethyl ester [81212-98-8]; Oxazolo [3,2-a] indole-7-carboxylic acid, 9- [2- (9-butyl-9H-carbazol-3-yl) ethenyl] -2,3,9,9a-tetrahydro-9, 9-dimethyl-ethyl ester [81212-97-7]; Lxxxiii) Oxazolo [3,2a] indole-7-carboxylic acid, 2,3,9,9a-tetrahydro-9,9-dimethyl-9- [2- (9-methyl-9H-carbazol-3-yl) ethenyl) ethyl ester [81212-96-6]; Lxxxiv) Oxazolo [3,2-a] indol-7-amine, 9a- [2- (9-butyl-6-ethoxy-9H-carbazol-3-yl) ethenyl] -2,3,9,9a-tetrahydro N, N, 9,9-tetramethyl [79512-57-5]; Oxazolo [3,2-a] indole-9-ethanol, 2,3,9,9a-tetrahydro-9-methyl-9- [2- (9-methyl-9H-carbazol-3-yl) ethenyl] [77939-33-4]; Oxazolo [3,2-a] indol-7-amine, 9a- [2- (9-butyl-9H-carbazol-3-yl) ethenyl] -2,3,9,9a-tetrahydro-N, N 9,9-tetramethyl [77912-91-5]; Lxxxvii) 9H-Carbazole, 3- [2- (2,3-dihydro-6-methoxy-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -9-methyl [ 77912-90-4]; 1Hxxviii) 9Hcarbazole, 3- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) -1-propenyl] -9-methyl [74784-55] -7]; Lxxxix) 9H-Carbazole, 3- [2- (7-chloro-2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -9-methyl [ 74784-52-4]; 1H-carbazole, 3-bromo-6- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -9-ethyl [1H NMR (CDCl3))? 74784-51-3]; 1H-carbazole, 3- [2- (2,3-dihydro-9,9-dimethyloxazolo [3,2-a] indol-9a (9H) -yl) ethenyl] -9-methyl [60449-28-] 7]; Lxxxxii) Lxxxxiii) \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ / \ Lxxxxv) O / \ N \ / \ / NS \ _ / Lxxxxix) C) Cl \% N / \ / Cl I \% ~ N / \ / OS \ S Ci) Cii) \% N / \ / N o NS S OH Ciii) Civ) / NC Cl I \ / NN ~ / N / \ / \ S \ _ / Cv) Cvi) OS 1 \% ~ N / / / \ N \ O \% ~ '\ \ N \ OS NSN Cvii) Cviii) \% e- / Cl ZNN `SQ Cix) Cx) NO Cl ZN ~ O) Cxi) Cxii) Cl% O Cl a N ~ Cxiii) Cxiv) I o CI OON ~ NJ N ~ Cxv) Cxvi ) Cxx) Nxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxixxxx ) Cxxiv) 0 = S Cl Z ~ NN N0 OZON ~ O Cxxv) Cxxvi) ~ N 4. NONN v N 1 Cxxvii) Cxxviii) O, S \ 0 ~ NN \ 0 N 0 NO \ O Cxxix) Cxxx) Cl ZNN ~ Cxxxi) 1.2. The Csa radical As indicated previously, in the formula (I) Csat represents a linear or branched, optionally substituted, optionally cyclic C 1 -C 18 alkylene chain. As a substituent, mention may be made of amino, (C 1 -C 4) alkylamino, (C 1 -C 4) dialkylamino groups, or the group Ra-Za-C (Zb) - (in which Za, Zb, identical or different , represent an oxygen atom, sulfur atom, or an NRa 'group, and Ra, represents an alkali metal, a hydrogen atom, or a C1-C4 alkyl group and Ra' represents a hydrogen atom or a grouping C1-C4 alkyl) preferably present on the carbon in the beta or gamma position of the sulfur atom. Preferably, Csat represents a chain - (CH2) k- with k integer, inclusive between 1 and 8. 1.3. The radical X According to a particular embodiment of the invention, in the formula (I) above, when p is equal to 1, x represents the following sequence: - (T) t- (Z) z- (T ' t - said sequence being connected in formulas (I) as follows -Csat- (T), - (Z) Z- (T '),' - (A); wherein: T and T ', which are identical or different, represent one or more radicals or combinations thereof selected from: ù SO 2 u; -Where; where; ùN (R) ù; ùN + (R) (R) ù; where; with R, R, which may be identical or different, representing a hydrogen atom, a C1-C4 alkyl, C1-C4 hydroxyalkyl or a (C1-C4) alkyl radical; and a heterocycloalkyl or heteroaryl radical, cationic or non-cationic, preferentially monocyclic, preferably containing two heteroatoms (more preferably two nitrogen atoms) and preferably comprising from 5 to 7 ring members, more preferably imidazolium; the indices t and t ', which are identical or different, are equal to 0 or 1; Z represents: - - (CH2) m1 - with m, an integer of between 1 and 8; - - (CH2CH2O) q, - or - (OCH2CH2) g - in which q, is an integer between 1 and 15, - an aryl, alkylaryl or arylalkyl radical whose alkyl radical is C1-C4 and the aryl radical is preferably C6i being optionally substituted with at least one SO3M group with M representing a hydrogen atom, an alkali metal or an ammonium ammonium group substituted with one or more identical or different linear or branched C 1 -C 18 alkyl radicals; optionally carrying at least one hydroxy; z is 0 or 1. Furthermore, according to one particular embodiment of the invention, Z represents: 1.4. The group Y 'when m is 1: A particular mode concerns the thiol compounds when m is 1 of formula (I) with SY' function where Y 'represents a hydrogen atom. According to another particular embodiment of the invention, in the formula (I) above, Y 'is a protective group and the protecting group is chosen from those known to those skilled in the art, for example those described in the literature. Protective Groups in Organic Synthesis, TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, chap. 5. Particularly when Y 'represents a protective group for the thiol function, Y' is chosen from the following radicals: alkyl optionally substituted with one or more groups, which may be identical or different, chosen from i) a halogen atom, ii ) alkylcarbonyl, iii) alkylthiocarbonyl, iv) alkoxycarbonyl, v) alkoxy-thiocarbonyl, vi) alkylthiothiocarbonyl, vii) (di) (alkyl) aminocarbonyl, viii) (di) (alkyl) aminothiocarbonyl, ix) carboxy and x cyano, such as 1,1-diacylethyl, 1,1-diamidoethyl; SO3; M + with M + representing a cationic counterion of alkali metal type such as sodium or potassium; optionally substituted aryl, such as phenyl, dibenzosuberyl, or optionally substituted 1,3,5-cycloheptatrienyl, heteroaryl, especially including aromatic groups, cationic or non-cationic, comprising from 1 to 4 following heteroatoms: i) monocyclic at 5, 6 or 7-membered groups such as furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl, isoxazolium, thiazolyl, thiazolium, isothiazolyl, isothiazolium, 1,2,4-triazolyl, 1,2,4-triazolium, 1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl, 1,2,4-oxazolium, 1,2,4-thiadiazolyl, 1,2,4-thiadiazolium, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine, azepinium, oxazepinyl, oxazepinium, thiepinyl, thiepinium, imidazolyl, imidazolium; ii) 8 to 11-membered bicyclic compounds such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazolium, thienocycloheptadienyl, these mono or bicyclic groups being optionally substituted by one or more groups such as alkyl as methyl, or polyhaloalkyl as trifluoromethyl; iii) or tricyclic ABC according to: wherein the two rings A, C optionally comprise a heteroatom, and the ring B is a 5-, 6- or 7-membered particularly 6-membered ring and contains at least one heteroatom such as pyperidyl, pyranyl; optionally substituted heterocycloalkyl, optionally cationic, the heterocycloalkyl group represents in particular a saturated or partially saturated 5, 6 or 7 membered monocyclic group comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as and / tetrahydrofuranyl, di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydroazepinyl, di / tetrahydropyrimidinyl these groups being optionally substituted with one or more groups such as alkyl, oxo or thioxo; or the heterocycle represents the following group: ## STR2 ## wherein R ', R'd, R'e, R R ', R'g and R'h, which may be identical or different, represent a hydrogen atom or an alkyl group, or two groups R'g with

  R'h, and / or R'e with R'f form an oxo or thioxo group, or R'g with R'e together form a cycloalkyl; and v represents an integer inclusive of between 1 and 3; preferably R 'to R'h represent a hydrogen atom; and An represents the counterion; -isothiouronium -C (NR 'R'd) = N + R'eR'f; With R ', R'd, R'e and R'f, identical or different, represent a hydrogen atom or an alkyl group; preferentially R 'to R' f represent a hydrogen atom; and An-represents the anionic counterion; optionally substituted (di) arylalkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl, optionally substituted by one or more groups chosen in particular from alkyl, alkoxy such as methoxy, hydroxy, alkylcarbonyl, nitro and nitroso, (di) (alkyl) amino, such as dimethylamino; - (di) heteroarylalkyl optionally substituted, the heteroaryl group is in particular, cationic or non-monocyclic, comprising 5 or 6 members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl groups, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium, triazinyl, optionally substituted with one or more groups such as alkyl particularly methyl, advantageously (di) heteroarylalkyl is (di) heteroarylmethyl or (di) heteroarylethyl; -CRIR2R3 with R ', R2 and R3 same or different, representing a halogen atom or a group selected from: optionally substituted alkyl such as methyl, ethyl;

  optionally substituted alkoxy such as methoxy or ethoxy; optionally substituted aryl such as phenyl optionally substituted with one or more groups such as alkyl, alkoxy, nitro, nitroso, hydroxy; optionally substituted heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted with an alkyl group; - P (Z ') R'1R'2R'3 with R'1, and R'2 identical or different represent a hydroxy, alkoxy or alkyl group, R'3 represents a hydroxyl or alkoxy group, and Z1 represents an atom oxygen or sulfur; - DES (0) O_2-alkû with i) ûalkû representing a divalent linear or branched hydrocarbon chain, C1-C18, preferably C1-C6 optionally substituted with a phenyl, ii) D represents a hydrogen atom, an aryl group optionally substituted such as phenyl or an optionally substituted heteroaryl group and iii) E representing an α, ûN (Ra) û link, ûalku, ûalkuOû, ûalkûN (Ra) û, with Ra and ûalkû as previously defined; especially D-E-S (O) O 2 -alku represents a methylsulfonylethyl group or -tosyl-1-phenylethyl; ## STR3 ## where E 'represents a bond a, uN (Ra) û, ûalku, ûalkuO0, ûalkûSû, ûalkûN (Ra) û; J and J ', which may be identical or different, represent an oxygen, sulfur or NRR atom; D, Ra, RR and ûalki are as previously defined; cyclic sterically hindered such as the adamantyl group; optionally substituted alkoxyalkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl; -Z2-C (Z ') -E'2 and Z2-S (O) with Z2 representing an optionally substituted alkyl group such as methyl, ethyl or M-H3N + - (CH2) 1-4; with M- corresponding to an anionic counterion such as a halide; optionally substituted alkoxy such as methoxy, ethoxy, M-H3N + O (CH2) 1-4000, benzoxy optionally substituted by one or more nitro or methoxy groups, or dibenzylmethyloxy optionally substituted with one or more nitro groups, optionally substituted alkylthio such as methylthio, ethylthio or M-H3N + û (CH2) 1-4-S-; optionally substituted aryl such as phenyl optionally substituted with one or more groups selected from amino, (di) alkylamino such as dimethylamino; nitro, nitroso, and alkoxy such as methoxy or ethoxy; optionally substituted arylalkyl such as benzyl optionally substituted with one or more groups selected from amino, (di) alkylamino such as dimethylamino, nitro, nitroso, and alkoxy such as methoxy or ethoxy; optionally substituted heteroaryl; optionally substituted heteroarylalkyl; NRZR'Z with RZ and R'Z, identical or different, representing a hydrogen atom or an alkyl group, or else RZ and R'Z together with the nitrogen atom carrying them a grouping: i) heterocycloalkyl such as piperazino, piperidino, or morpholino, ii) heteroaryl, cationic or non-cationic, such as the pyrrazolinium, indolinium, imidazolino, imidazolinium, benzoimidazolinium, oxazolinium, pyridinium, thiazolinium, triazolinium, tetrazolinium, quinolinium group optionally substituted with one or more substituents such as alkyl, especially methyl, or (di) (alkyl) amino such as dimethylamino; E 'representing a group as defined above; Z 'represents: an oxygen or sulfur atom; Embedded image wherein Alk represents an alkyl group, wherein R 1, R 2, Z, R 2, R 2 Z, which may be identical or different, represent a hydrogen atom, an optionally substituted alkyl group, optionally substituted aryl or optionally substituted heteroaryl, or optionally substituted alkoxy, for example -N + H2, Br or -N + Me2, Br and r representing an integer inclusive of between 1 and 2.

  Preferentially Y 'represents an alkali metal or a protective group such as: alkylcarbonyl; arylcarbonyl; - alkoxycarbonyl; aryloxycarbonyl; arylalkoxycarbonyl; - (di) (alkyl) aminocarbonyl; - (alkyl) arylaminocarbonyl; optionally substituted aryl such as phenyl; monocyclic 5-, 6- or 7-membered heteroaryl such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-triazolium thiadiazolyl, 1,2,4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; - 8 to 11-membered bicyclic heteroaryl such as benzoimidazolium, or benzoxazolium; - SO3, M +; heterocycle of the following formula: H - isothiouronium -C (NH 2) = N + H 2; Year-.

  1.5. Styrylia or iminipue disulfide / thiol-type compounds that can be stained with stimuli According to a preferred variant of the invention, the compounds of the invention of formula (I) are colored at basic pH and colorless at neutral or acidic pH. More specifically, it comprises at least one heterocyclic (spiro) chromophore as defined above, with p equal to 1 and: A represents a chromophore which in its protonated merocyanine form has the following formula W'u [C (Rd) = W "InuAru or'W'û [C (Rd) = W "], ûAr, where W 'is a heteroaryl, capable of closing, rendering the chromophore colorless or weakly colored; W "represents a nitrogen atom or a group C (Rd); Ar represents a (5- or 6-membered) heteroaryl radical of phenyl or pyridyl type or a (hetero) aromatic bicycle of the naphthyl, benzopyridyl or indolinyl type, or benzoindolinyl, optionally substituted by one or more halogen atoms, by one or more alkyl groups, preferably C1-C4, by one or more hydroxyl groups, by one or more alkoxy groups, by one or more hydroxyalkyl groups; or more amino or (di) alkylamino groups, preferably with the C 1 -C 4 alkyl part, with one or more acylamino groups, with one or more heterocycloalkyl or heteroaryl 5 or 6-membered groups preferentially chosen from pyrrolidinyl, piperazinyl, piperidinyl and imidazolinyl; Rd and Rd, identical or different, represent a hydrogen atom, a halogen atom, a C1-C6 alkyl radical, a cyano radical, a group an aromatic group, a phenoxy group, a nitro group; preferably R and Rd represent a hydrogen atom or a C 1 -C 4 alkyl group; n represents an integer inclusive between 1 and 3, preferably n is 1 or 2. According to a preferred variant p is 1, X represents the sequence (T), - (Z) Z- (T '),' -; z and t 'are 0; t is 1 and T is N (R) -, preferably in the para position on Ar with respect to the function C (R) = W "-.

  According to another preferred variant p is 1, X represents the sequence 32 An - (T) t- (Z) Z- (T ') t'-; z, t and t 'are 1; T represents N (R) -, preferably in the para position on Ar with respect to the function C (R) = W "- and T 'represents a group -N (R) -, - N + (R) (R) - or an imidazolium, and Z represents - (CH2) m- with m integer between 1 and 8, advantageously between 1 and 3.

  Preferably, W 'is a group chosen from imidazolyl, benzimidazolium, indolyl and benzoindolyl optionally substituted with one or more identical or different C 1 -C 4 alkyl radicals. More particularly, the compounds of the invention are chosen from compounds of formulas (I ') to (VI'):

[C = W Gù (X p Y. Cst

  R 3 R 3 (X ') p Csat S m Y' R 5 (X) P Cs ~ t SIY '(III') (X ') p Cisat SY' (V y 'm (VI') their salts of organic or inorganic acid, optical isomers, geometric isomers, tautomers, and solvates such as hydrates, formulas (I ') to (VI') in which: - m is 1 and Y 'is present or m is 2 and Y n is an integer of 1 to 4, particularly n is 1 or 2, p is 0 or 1, B is a condensed aryl or fused heteroaryl ring, n Rs ZC = WY 'm comprising 5 16-membered ring, particularly ring B represents a benzo or naphtho group, optionally substituted with one or more substituents selected from halogen such as chlorine or iodine, alkyl, alkoxy, alkylsulfonyl, phenylsulfonyl, alkoxycarbonyl and nitro; -Csa, represents a linear or branched, optionally substituted, optionally cyclic C 1 -C 18 alkylene chain; E represents an oxygen, sulfur or selenium atom; C 1 R 2 or NR 1, with R 1 and R 2, which may be identical or different, represent, a hydrogen atom, a C 1 -C 6 alkyl radical, a C 1 -C 6 hydroxyalkyl radical or a C 1 -C 6 alkoxyalkyl radical; R 'and R2 may together with the carbon atom carrying them form a 5- or 6-membered ring, optionally containing one or more heteroatoms such as a nitrogen, oxygen or sulfur atom; E 'represents a nitrogen atom or a CR2 group with R2 as defined for E; - R "represents a divalent radical (C 1 -C 6) alkylene, said radical may be an oxygen atom, sulfur and may be substituted by a hydroxyl or alkoxy group; G represents a divalent arylene or heteroarylene group comprising from 5 to 16 members; in particular G represents a phenylene, furanylene, thiophenylene, indolylene, benzoselenazolylene, benzothiazolylene, carbazolylene, pyridylene or benzopyranylene group, optionally substituted by one or more groups chosen from halogen, hydroxy, alkyl, alkoxy, (di) (alkyl) amino, nitro, cyano, alkylcarbonylamino, phenyl, or two adjacent substituents together form a methylenedioxy group; - G 'represents an aryl or heteroaryl group comprising from 5 to 16 members; in particular G 'represents a phenyl, furanyl, thiophenyl, indolyl, benzoselenazolyl, benzothiazolyl, carbazolyl, pyridyl or benzopyranyl group, optionally substituted by one or more groups chosen from halogen, hydroxy, alkyl, alkoxy, (di) (alkyl) amino, nitro , cyano, alkylcarbonylamino, phenyl, or two adjacent substituents together form a methylenedioxy group; W, present or absent, represents a nitrogen atom or a group CR 2 with R 2 representing a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl radical, a cyano radical, an aromatic group, a radical, phenoxy, a nitro radical; - R3 represents a hydrogen atom, a halogen atom, a C1-C6 alkyl radical, a cyano radical, an aromatic group, a phenoxy group, a nitro radical; R'3 and R'5 represent a divalent radical (C 1 -C 6) alkylene, arylene or -arylene, comprising from 5 to 16 members such as phenylene or phenoxyene; R4 represents a hydrogen atom, or a C1-C6 alkyl radical; - X 'represents a hydrocarbon chain C1-C3o, particularly C1-C8i linear or branched, saturated or unsaturated, optionally substituted, optionally interrupted and / or optionally terminated at one or both ends thereof by one or more divalent groups or combinations thereof selected from: N (R) -; -N + (R) (R ') -, Q-; -O-; -S-; -CO-; -SO2- with R, R ', which may be identical or different, are chosen from hydrogen, a C1-C4 alkyl, hydroxyalkyl and aminoalkyl radical, Q- representing an anionic counterion; and a radical (hetero) cyclic, aromatic or not, saturated or unsaturated, condensed or not, optionally comprising one or more identical or different heteroatoms, optionally substituted; particularly X 'represents a group chosen from: N (R) -, N (R) -CO-, -COON (R) -, -SO2-, -SO2- (R) - and -N (R) -SO2- Y represents an oxygen atom, a sulfur atom, an NR6 group with R6 representing a hydrogen atom, a C1-C6 alkyl radical; Y 'represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + RaRRRYRs or a phosphonium group: P + RaRRRYRs with Ra, RR, R7 and R8, identical or different, representing a hydrogen atom or an alkyl group; or v) a thiol protecting group; Z represents i) a divalent group -CgH2q-, with q an integer between 2 and 4 inclusive, unsubstituted or substituted by one or more substituents selected from halogen atoms, and hydroxy, alkyl, haloalkyl, alkoxy groups, amino, (di) alkylamino, (di) hydroxyalkylamino, carboxyl; ii) a divalent group -CrH2rC (O) - or -CrH2rC (S) -, with r an integer inclusive of between 1 and 3, unsubstituted or substituted by one or more substituents selected from halogen atoms, and hydroxy groups, alkyl, haloalkyl, alkoxy, amino, (di) alkylamino, (di) hydroxyalkylamino, carboxyl, particularly Z is unsubstituted; it being understood that: when m is 1, the -SY 'function may be in the covalent -S-Y' or ionic -S Y '+ form depending on the nature of Y and the pH of the medium; when n is 1 and W is absent then the double bond is directly connected to the group G or G '; when n is an integer greater than or equal to 2: the units [CR 3 = W] - are identical to or different from each other, W represents CR 2 or is absent; ^ W can be absent only on the last ground ù [CR3 = W] - directly connected to the group G or G '; The chain ùR'3ù (X) p CsatuSu of the formula (II ') or the chain ùR'5ù (X) p CsatuSu of the formula (III') can be connected only once to the chromophore via the groups ù [C = W] n or ù [CR3 = C] n respectively, the other groups then representing a group ù [C (R3) = W] ù.

  By way of example of a thiol / disulfide compound, mention may be made of the following compounds: ## STR1 ## N ~ 9 SS SS 11 SS 12 HO 13 SS 14 0, 0 S.NS-SN.SHH 1 N. 15 OO NS-S,) LN HH-N \ N- 16 SS NNHH 17 SS 18 0 0 O / OS SS NS HH 19 N- / 20 SS 21 OO SS 22 SS NNHH 23 OO SS 24 OO SS 25 OON SS 26 OO ss 27 OO ss 28 ss 29 OOON LJ NH ss 30 HH 31 HH 32 OO 33 35 34 37 36 38 39 40 41 43 42 N 44 45 N SH 46 47 NV M + OON '-js 48 49 / N \ ù \ N + S- <, Year N 50 51 NO SùS O SùS o o 53 52 54 55 i - \ o NvNùi ( - 1 M + o '57 56 and 58 59 With An-representative anionic counterion, and M + representing a cationic counterion

  1.6. The organic or inorganic salt and anionic counterion: By salt of organic or inorganic acid is more particularly understood a salt selected from a salt derived i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) d sulfuric acid H 2 SO 4, iv) alkylsulphonic acids: Alk-S (O) 2OH such as methylsulfonic acid and ethylsulphonic acid; v) arylsulfonic acids: Ar-S (O) 2OH such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4i xiii) acetic acid CH30OOH; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF4. By anionic counter-ion is understood an anion or an anionic group associated with the cationic charge of the compound of the invention; more particularly the anionic counterion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, including C1-C6 alkylsulfonates: Alk-S (O) 2O- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates Ar-S (O) 2O- such as benzenesulfonate and toluenesulphonate or tosylate; v) citrate; vi) succinate; (vii) tartrate; viii) lactate; ix) alkyl sulphates: Alk-O-S (O) O- such as methysulfate and ethylsulfate; x) arylsulfates: Ar-O-S (O) O-such as benzenesulphate and toluenesulphate; xi) alkoxysulfates: Alk-O-S (O) 2O- such as methoxy sulfate and ethoxysulfate; xii) aryloxysulfates: Ar-O-S (O) 2 O-, xiii) phosphate; (xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate. By cationic counter-ion is understood a cation or a cationic group associated with the anionic charge of the compound of the invention; more particularly, the cationic counterion is chosen from alkali metals such as Na *, K +, and N + ammoniums RaRbRcRd with Ra, Rb, R, and Rd, identical or different, representing a hydrogen atom or an alkyl group in C1-C6. 1.7. Preparation of thiol / disulfide compounds of the invention The protected thiol compounds of formula (I) for which m is 1 can be synthesized in two stages. The first step of preparing the unprotected thiol compound (Ia) according to the methods known to those skilled in the art, for example Thiols and organic Sulfides, Thiocyanates and Isothiocyanates, organic, Ullmann's Encyclopedia, Wiley-VCH, Weinheim, 2005 And the second step of protecting the thiol function according to conventional methods known to those skilled in the art to lead to the protected thiol compounds of formula (Ib). By way of example, to protect the thiol function of the thiol compound, the methods of Protective Groups in Organic Synthesis, T.W. Greene, John Willey & Sons, Ed., NY, 1981, pp.193-217; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, chap. 5.

  We can illustrate this method by the method consisting of i) generating thiol compounds of formula L by reduction of a compound with two chromophores, having a disulfide function -SS- such that (I) and ii) to be protected by conventional methods said thiol function of Q with reagent 7 Y "R to access the protected thiol compounds of formula (Ib) .The thiol compound 6 may also be metallized with an alkali metal or alkaline earth metal Met * to yield the thiolate compound of formula (Ic) A (((((((((réd réd ((((((((((((((((((())

  (la) Metallization A (X) p CtS Met * (Ic) with Y "representing a protective group of thiol function; Met * representing an alkali metal or an alkaline earth metal, particularly sodium or potassium, it being understood that when the metal is an alkaline-earth metal 2 chromophores with a thiolate function -S- may be associated with 1 Metal2 +, It being understood that A, X, p, and Csat are as defined above; Y "represents a protecting group of thiol function; and R represents a leaving group nucleofuge, such as, for example, mesylate, tosylate, triflate or halide. According to another possibility, it is possible to react a thiol compound protected by a protective group Y "as defined previously prepared according to one of the procedures described in the works cited above, said protected thiol compound comprising at least one nucleophilic function with a sufficient amount preferably, equimolar, of a "reactive chromophore" or of a compound comprising such a "reactive chromophore." j In other words, it comprises an electrophilic function to form a covalent bond E as can be schematized below in the preparation of compounds of formula (Id): Au (CR 1 R 2) m, E + -u (CR 3 R 4) SY "A (CRI R 2), 1 (CR 3 R 4) SY" (Id) with R 1, R 2, R 3, R 4, identical or different, representing a hydrogen atom, or an alkyl group; m 'and n', identical or different, represent an integer inclusive between 0 and 6 with m '+ n', represents an integer inclusive between 1 and 10; especially the sum m + n = m '+ n' = an integer inclusive between 2 and 4; preferentially m + n = m '+ n' = 2; W-u representing a nucleophilic group; E representing an electrophilic group; and 1 the generated bond after nucleophilic attack on the electrophile.

  By way of example, the covalent bonds E that can be generated are listed in the table below from the condensation of electrophiles with nucleophiles: Electrophilic E Nucleophiles ~ Covalent bonds E Activated esters * Amines Carboxamides Acyl azides ** Amines Carboxamides Acyl halides Amines Carboxamides Acyl halides Alcohols Esters Acyl cyanides Alcohols Esters Acyl cyanides Amines Carboxamides Alkyl halides Amines Alkylamines Halides of alkyls Carboxylic acids Esters Halides of alkyls Thiols Thioesters Halides of Alcohols Alcohols Ethers Sulphonic acids and their Thiols Thioethers salts Sulphonic acids and their carboxylic acids Esters salts Sulphonic acids and their alcohols Ethers salts Anhydrides Alcohols Esters Anhydrides Amines Carboxamides Halides aryls ThiolsThioethers Halides aryls Amines Arylamines Aziridines Thiols Thioethers Carboxylic acids Amines C arboxamides Carboxylic Acids Alcohols Esters Carbodiimides Carboxylic Acids N-acyluers or anhydrides Diazoalkanes Carboxylic Acids Esters Epoxides Thiols Thioethers Haloacetamides Thiols Thioethers Esters Imides Amines Amidines Isocyanates Amines Ureas Isocyanates Alcohols Urethanes Isothiocyanates Amines Thioureas Maleimides Thiols ThioethersSulphonic esters Amines Alkylamines Sulphonic esters Thiols Thioethers Esters sulfonic Acids carboxylic Esters 47 A (CR 1 R 2) Ta (CR 3 R 4) Hal (le) mal 2918667 Sulphonic esters Alcohols Ethers Sulfonyl halides Amines Sulfonamides * Activated esters of the general formula ûCO-Part with Part representing a leaving group such as oxysuccinimidyl, oxybenzotriazolyl, aryloxy optionally substituted; ** Acyl azides can rearrange to give isocyanates.

  An alternative to this method is to use a chromophore having an electrophilic acrylate function (-OCO-C = C-) on which an addition reaction is carried out which will generate an L bond.

  It is also possible to use a thiol reactant Y "-SH comprising a group Y" as defined previously, the nucleophilic function SH of which can react on the carbon atom alpha to the halogen atom carried by the chromophore j to lead to protected thiol compound of formula (Ic): MHS-Y "with R 1, R 2, R 3, R 4, Y", n ', and m' are as defined above, Hal represents a nucleofugal halogen atom such as bromine, iodine or chlorine and Ta represents: i) either a covalent bond a, ii) or one or more radicals or combinations thereof selected from -SO2-, -O2, -S0, -N (R) -N + (R) (R) ) with R and R, which may be identical or different, representing a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 hydroxyalkyl radical or a (C1-C4) alkyl radical; in particular, Ta represents a covalent link a or a group chosen from N (R) -, C (O) u, C (O) uN (R) u, uN (R) uC (O) u, uC (O) uN (R) ûC (O) û, ûOûC (O) û, ûC (O) ûOû and û N + (R) (R) û, with R, R being identical or different, representing a hydrogen atom, a C1-C4 group alkyl alkyl; particularly Ta represents a bond a; iii) a heterocycloalkyl or heteroaryl radical, cationic or otherwise, preferably monocyclic, containing in particular two heteroatoms, particularly two nitrogen atoms, and especially comprising from 5 to 7 members, such as imidazolium, piperidyl, homopiperidyl, piperidinium, homopiperidinium; optionally substituted with a (C1-C4) alkyl group such as methyl.

  More particularly, it will be possible to substitute a nucleofugal leaving group with a thiourea group (S = C (NRR) NRR) to generate the isothiouroniums. For example, if the thiourea group is a thioimidazolinium (R), the reaction scheme is as follows: SH R'c, (If) with R'c, R'd, Hal, An- and M 'are as defined above.

  An alternative is to use in place of the halide comprising the chromophore ai a chromophore comprising another type of nucleofuge such as tosylate, mesylate.

  According to another possibility, certain protected thiol compounds (Ig) can be obtained by reacting a protected thiol compound with a compound carrying two activated carboxylic acid functions according to conventional methods (for example reaction with a carbodiimide or with thionyl chloride ). The resulting product is then reacted with a chromophore carrying a nucleophilic function, for example of the primary or secondary amine type, or of the aliphatic alcohol type. Α (CR 1 R 2) Wu + E 1 (CR 3 R 4) SY "(Id) LcI with R 1, R 2, R 3, R 4, Y", m ', n', E, fu and (Id) as previously defined. A synthetic variant is to combine with the first route, the previous route ie from two equivalents of the nucleophilic reagent with a reagent diéléctrophile disulfide flil is possible to generate after condensation the product dichromophoric disulfide (I "), the latter can undergo a reduction to form the chromophore thiol compound which in turn can either be protected to form the protected thiol compound (I'c) or be metallized with an alkali metal to yield the metallated chromophore compound (I'c): No (+ "An A ^ / Hal An - H Hal N + A / \ VS I An

  R'd R'ON N 2 A- (CR 1 R 2) - Wu + E 1 (CR 3 R 4), 7S-S- (CR 3 R 4), 7E f A- (CR 1 R 2) m, - (CR 3 R 4) n, SS- ( CR3R4) n, ~ - (CR1 R2) 7 A (Ia) Ai (CR1 R2) Ei (CR3R4) n-SH protection Y "-R / - HR A- (CR1 R2) m, E- (CR3R4) n- According to another possibility, the protected thiol compounds of formula (Ib) can be obtained by reacting a compound comprising both a Y-protected thiol group and a previously activated hydroxy group. in group leaving nucleofuge Gp, such as mesylate, tosylate, triflate or halide with a chromophore comprising a nucleophilic part jj. Alternatively, the compound (1b) may be synthesized by reacting a reagent comprising a nucleofugal leaving group (c ") and a Y-protected thiol reagent having a nucleophilic moiety. Ù (X) + + + p C C f A A A ((((+ + + + + + + + + + + avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec avec (((((((((((((((sont sont sont sont sont sont sont sont sont sont sont sont sont sont sont sont sont sont sont

  According to another possibility, the thiol compounds according to the invention can be obtained by reaction of a compound comprising an electrophilic group or Lin with a compound comprising an Ar group with activated alkyl f. For example, an aldehyde or a thioaldehyde may be condensed when G 'represents an oxygen atom or a sulfur with an activated alkylene (methylene) such as the compound to generate an ethylene bond> C = C <. This reaction is commonly known as Knoevenagel condensation. The term "activated alkenes" refers to those which preferably contain in the 2 or 4-position of the heteroaryl group an alkyl group (i.e. Ar represents a heteroaryl). After condensation, the compound in the form merocyanine C or fi-ll can close, optionally by stimulus as seen above, to lead to the heterocyclic derivative ajj. G '- H2G' Z Z Het + / _ LU N Loj

  With Het, Het +, Ar, n, R2, R3, Y, G ', stimulus, and Z are as previously defined. According to another variant, the thiol compounds of formula (I) according to the invention can be obtained by reaction. of an activated alkyl compound, or a compound comprising an Ar group comprising an electrophilic group f or M. For example, an aldehyde or a thioaldehyde may be condensed when G 'represents an atom. oxygen or sulfur with an activated alkylene (methylene) such as the compound M, C or I to generate an ethylene bond> C = C <preferentially in position 2 or 4 of the Het group.

  After condensation the compound in merocyanine form or can be closed, optionally by stimulus as seen above, to lead to the derivative spiroheterocycle Qj, or heterocycle j: It is understood that the reagents jj, ~, j, (m ') can also exist in two forms, spiroheterocyclic or heterocyclic. The cyclization stimulus and the opening stimulus of the cycle may be different from the stimuli for respectively passing forms Ç to m and fln to (o). According to another possibility, in the case where n = 1 and W represents a nitrogen atom, the compounds according to the invention can also be obtained according to several modalities, such as the condensation of an amino group on a carbonyl group. (Imine formation reaction by dehydration) known to those skilled in the art (see, for example, J. Org Chem 65 (18), 5498-505 (2000) or Chem., Ber., 119 (11), 3316- 25 (1986)): Stimulus 1PI H2G 'Ar G' + H2N-H2G 'Ar frj + H2N Ar An alternative may consist in carrying out a condensation of an activated alkyl group on a nitroso Ar-NO group as described in Gazzetta Chim, Ital. 115 (4), 217-21, (1985). It being understood that the nitroso group of Ar-NO can be obtained by partial oxidation of an aromatic amine Ar-NH 2, by partial reduction of a nitro group Ar-NO 2, or finally by nitrosation of an aryl reagent Ar-H. Ar / Stimulus 0 = N + 2 Ar / Stimulus 0 = N + - H2G 'Given that the chromophores k, k' and I, the or n, n 'and o, o' can be connected by any part of the molecule via a group such as amino, halo, optionally activated hydroxy, or carboxylic acid for fixing the part - (X) p-Csat-SY '. Or else the chromophore already contains the group - (X) p-Csat-SY '.

  Reference may be made to Advanced Organic Chemistry, Reactions, Mechanisms and Structures, J. March, 4th Ed, John Willey & Sons, 1992 or TW Greene Protective Groups in Organic Synthesis, for further details on operating conditions. for the processes mentioned above. The thiol compounds formed can be converted to Y-protected thiol compounds by protection of the HSH thiol using conventional protecting groups. The thiol compounds are metallated using also conventional methods known to those skilled in the art such as those described in Advanced Organic Chemistry, Reactions, Mechanisms and Structures, J. March, 4th Ed, John Willey & Sons, NY, 1992. A As an example of a synthesis of the compound of the invention of formula (I) with Y representing an oxygen or sulfur atom, can be synthesized according to the following two reaction schemes by following the steps known to those skilled in the art. i) to vii): Rb Ra Rb Hal '(CH2) z-3 YH Hal ii) Rb Ra / Rd 1 M' YR (CH2) 2-3 Hal "Hal Rb R Hal NùNH2 i) HNY \ (H2) 2 3 Rb Ra / Rd iv) Hal vi) ~ GiNi (CH2) n Hal "Re NRI Rb GnN ~ (CH2) n Hal" Rf With Hal, Hal ', Hal "the same or different, represent a halogen atom, Ra , Rb, R and Rf, identical or different, represent a C1-C6 alkyl radical, a C1-C6 hydroxyalkyl radical, a C1-C6 alkoxyalkyl radical, an alkylene chain which may contain a carbonyl radical; oxygen or sulfur; Rd represents a hydrogen atom, a halogen atom, a C1-C6 alkyl radical, a cyano radical, an aromatic group, a phenoxy group or a nitro radical; advantageously Rd represents a hydrogen atom; Re represents a hydrogen atom, a halogen atom, a C1-C6 alkyl radical, a cyano radical, an aromatic group, a phenoxy radical, a nitro radical; M 'representing an anionic counterion; and G representing a group as defined above. According to another variant, it is possible to pass to the level of the synthesis route presented above of step vi), by a condensation of the alkylene groups on a nitrosoaryl reagent carrying a halogen, followed by the substitution of this halogenated by 4,5-dihydro-1H-imidazole-2-thiol thus allowing the preparation of the protected chromophore imine thiol. 0 Rb Ra N NGuN ~ (CH2) n Hal "Rb / Rd N Rf Ra / Rd / (CH2) n N NùGùNNR ~ Hal" R (CH 2) 23 HS-J N 10 For access in particular to the compounds of formula (I ') Another variant of synthesis resides in the use of a divergent method from a disulfide starting reagent igl also comprising a part that will become the chromophore by condensing with the reagent j. The latter being synthesized according to steps i) to iii) known to those skilled in the art, as described below. ## EQU1 ## where G, X, B, Rd, Hal and Re as previously defined. The intermediate disulfide compound of reaction can easily be obtained according to the following reaction schemes: by acylation, and preferably by formylation of a following diaryl disulfide compound, following, for example, the Vilsmeier-Haack reaction or the Duff reaction HùGu (X) p Csat SùSuCsa (X) p GùH o Re Csat SùSuCsa (X) p G j 0 Re) ùGu (X) p - by reaction between two aromatic aldehydes carrying an electrophilic group E, and a disulfide compound carrying two nucleophilic groups Wu - by reaction between two aromatic aldehydes carrying a soft nucleophilic group, and a disulfide compound bearing two electrophilic groups E According to the same divergent method it is possible to synthesize the compounds of formula ( It ') from electrophilic function reagent such as a carboxylic acid function on B, said function being able to undergo the nucleophilic attack of a reagent carrying laison also a disulphide, as described below. I ii) SOCl2 iii) H2NiCsiSuS • CsaiNH2 ONiSiSiSiHiCiuN sat sat IV) HaluZ YH voHiC'SiSAC sat v) OO HO G 'With G', p, Csat, E, Y, Z, B, Rd, Hal and Re as previously defined. Given that X represents here an amide bond, but the person skilled in the art can adapt instead of a carboxylic acid function on part B, another function, subsequently allowing the disulfide linker. According to another variant, the disulfide compounds can be obtained by following another divergent route which consists of preparing a compound with a disulfide-activated alkyl group and then condensing it on a carbonyl or nitroso group, as previously illustrated. Starting reagents are commercially available or accessible by conventional methods known to those skilled in the art. Electrochromic chromophore starting reagents can for example be prepared according to the methods of preparation as described in patents FR 2 285 439 and US Pat. No. 4 380 629. These modes of preparation can be adapted to cationic compounds of formula (I) by adding a quaternization step. Reference may be made to Advanced Organic Chemistry, Reactions, Mechanisms and Structures, J. March, 4th Ed, John Willey & Sons, 1992 or TW Greene Protective Groups in Organic Synthesis, for further details on operating conditions. for the processes mentioned above. Thiol or disulfide reaction intermediates as well as the thiol and disulfide compounds of the invention may be, for the purpose of the synthesis process, protected by conventional routes (such as those described in the books Protective Groups in Organic Synthesis, TW Greene, John Willey & Sons ed., NY, 1981, Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005) and once the chemical reaction (s) are complete they are deprotected by the pathways described in the same works mentioned previously.

  II. The dye composition: 11.1. The reducing agent The composition of the invention may contain a reducing agent. This reducing agent may be chosen from thiols, for example cysteamine, N-acetylcysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, in particular glycerol monothioglycolate, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catechol borane. The amount of reducing agent The amount of reducing agent in the composition is particularly between 0.1 and 15% by weight of the composition, more particularly between 0.5 and 10% by weight of the composition. 11.2. The dye (s) The dye composition useful in the invention generally contains a quantity of thiol / disulfide compound of formula (I) of between 0.001% and 50% relative to the total weight of the composition. Preferably, this amount is between 0.005 and 20% by weight and even more preferably between 0.01 and 5% by weight relative to the total weight of the composition. The dye composition may further contain additional direct dyes. These direct dyes are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

  Among the natural direct dyes that may be mentioned are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.

  The dye composition may also contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin materials. Among the oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among these couplers, it is possible to mention in particular, meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%. The oxidation base (s) present in the dyeing composition are in general each present in an amount of between 0.001% and 10% by weight relative to the total weight of the dyeing composition, preferably between 0.005% and 6% by weight.

  In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The solvents when present are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately. .

  According to one variant, the invention contains a reducing agent capable of reducing the disulfide bonds. This reducing agent is as defined above.

  11.3. Adjuvants: The dyeing composition may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic polymers, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as aminosilicones, chitosans and derivatives, film-forming agents, ceramides, preserving agents, opacifying agents and conductive polymers. The composition may also comprise at least one other additional disulfide compound different from that corresponding to the formulas (I), (I ') to (VI') detailed above. As an indication, the disulfide may be chosen from compounds comprising at least one fatty chain, more particularly at least one linear or branched, saturated or unsaturated C 5 -C 30 hydrocarbon-based chain, optionally substituted by a heteroatom, optionally interrupted by a group carboxylic acid, neutralized or not. By way of example of compounds of this type, mention may be made of the dimers of thioglycolic acid and its derivatives of the type CH3- (CH2) 17 -SH- (CH2) 17 -CH3i CH3- (CH2) 15 -SH- (CH 2) 15-CH 3 or CH 3 - (CH 2) 10 -SS- (CH 2) 10 -CH 3. The amount of adjuvants The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition. Of course, those skilled in the art will to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, impaired by the addition or additions envisaged.

  The pH of the composition The pH of the dyeing composition is generally between 2 and 12 approximately, and preferably between 3 and 11 approximately. It can be adjusted to the desired value by means of cosmetically acceptable acidic or alkaline agents, usually used for dyeing keratinous substances or else using conventional buffer systems. Among the acidic agents, mention may be made of Brnsted acids by way of example, such as inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids, an acid of formula (II) R6 (R7CR8) n2-COOH, or a precursor of such a compound, formula (II) in which: R 6 represents an aromatic or heteroaromatic type nucleus comprising at least one nitrogen atom, oxygen or sulfur, condensed or not, comprising from 5 to 16 members, optionally substituted with one or more hydroxyl groups, C1-C3 alkoxy groups; hydroxycarbonyl, alkoxycarbonyl with the alkoxy group C 1 -C 3 amino, cyano; n2 is an integer ranging from 0 to 6; R7 and R8 represent, independently of each other, a hydrogen atom, a branched or unsubstituted, substituted or unsubstituted C1-C6 alkyl group, a hydroxyl group, a C1-C6 methoxy group or a cyano group; an amino group, a hydroxycarbonyl group, alkoxycarbonyl.

  Particularly: R 6 represents an aromatic or heteroaromatic type nucleus comprising at least one nitrogen, oxygen or sulfur atom, condensed or not, comprising from 5 to 16 members, optionally substituted with one or more hydroxyl groups, C1 alkoxy groups. -C3, hydroxycarbonyl, alkoxycarbonyl with C1-C3 alkoxy, amino, cyano; n is an integer ranging from 0 to 6; R7 and R8 represent, independently of each other, a hydrogen atom, a branched or unsubstituted, substituted or unsubstituted C1-C6 alkyl group, a hydroxyl group, a C1-C6 methoxy group or a cyano group; an amino group, a hydroxycarbonyl group, alkoxycarbonyl.

  It is further recalled that the precursors of the acids of formula (II) are compounds capable of releasing into the medium of the composition containing the chemical stimulus, an acid of formula (II). More particularly, the esters of the acids corresponding to the formula (II) are designated capable of releasing the acid under conditions of acidic pH. By way of example, tannic acid is a precursor of gallic acid. In the acid of formula (II), the aromatic or heteroaromatic nucleus is more particularly chosen from furan, pyrrole, pyrazole, imidazole, oxazole, thiazole, oxadiazole, triazole, triazole, thiadiazole, benzene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, naphthalene, anthracene, quinoline, indole; these rings being optionally substituted with one or more hydroxyl groups, C 1 -C 3 alkoxy, hydroxycarbonyl, alkoxycarbonyl with the alkoxy group C 1 -C 3, amino, cyano, and preferably hydroxy. Preferably, the aromatic or heteroaromatic ring of the acid of formula (II) is chosen from benzene, pyridine, quinoline, triazine and indole nuclei; these rings being optionally substituted with one or more hydroxyl groups, C 1 -C 3 alkoxy, hydroxycarbonyl, alkoxycarbonyl with the alkoxy group C 1 -C 3, amino, cyano, and preferably hydroxy. According to a particularly advantageous embodiment, the aromatic or heteroaromatic ring of the acid of formula (II) is chosen from benzene optionally substituted with one or more hydroxyl groups. Preferably, the acid of formula (II) is chosen from gallic acid, 3,5-dihydroxybenzoic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid and 3,4-acid. dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,5-dihydroxyphenylacetic acid, their salts or their precursors, and preferably from 3,5-dihydroxybenzoic acid or its salts or precursors.

  The content of acid or precursor is usually between 0.001% and 50% by weight relative to the total weight of the dye composition, preferably between 0.1% and 30% by weight relative to the total weight of the dyeing composition, and even more advantageously, between 0.1 and 15% by weight relative to the total weight of the dyeing composition.

  Among the alkaline agents that may be mentioned, for example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (a): ## STR2 ## in which Wa is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; Raii Ra 2 Rai and Ra 4 or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

  11.4. The forms of the composition The dye composition may be in various forms, such as in the form of liquid, cream, gel, or in any other form suitable for dyeing keratin materials, and in particular hair.

  III. Staining process alone or in combination with permanent deformation The compounds of formula (I) may be applied to keratin materials, in particular keratin fibers such as naturally or artificially white or light hair or to naturally or artificially dark hair. According to one particular embodiment, the dyeing method uses the imine or styryl disulfide / thiol compounds of the invention in the absence of a reducing agent. According to a particular embodiment in the method of the invention, a reducing agent is applied in i.e. pre-treatment before the application of the composition containing at least one compound of formula (I). According to another particular embodiment, the composition comprising at least one compound of formula (I) is first applied to the keratin materials, said materials are then treated (reducing post-treatment) with a reducing agent. Another variant is to apply a composition comprising the compound of formula (I) and the reducing agent together to the keratin materials. Said reducing agent may be added to the composition at the time of use. This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catecholborane. In particular, the reducing agent is thiolated. Pretreatment or post-treatment with the reducing agent may be of short duration, in particular from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes with a reducing agent as mentioned above. A particular dyeing process is to apply the compound of formula (I), especially in its closed form, to keratinous materials, advantageously the keratinous materials are pre-treated with a reducing agent as defined above. The closed form of the compounds of the invention are particularly in a composition whose pH is greater than the pKa of said compound, particularly at an alkaline pH. After the application of the compound of formula (I) on keratin materials: 1) either no post-treatment is carried out, the hair is simply rinsed or shampooed and left in the open air; 2) either a post-treatment of the keratin materials is carried out by a stimulus as defined above to reveal the color optionally followed by a step of fixing the dyes with an oxidant; 3) a post-treatment of the keratin materials is carried out by fixing the compounds with an oxidant followed by a stimulus as defined above to reveal the color; 4) a post-treatment of the keratin materials is carried out using a composition comprising i) at least one oxidizing agent and ii) a stimulator stimulating the chemical color such as a salt such as a cosmetically acceptable zinc salt , a solvent or an acidic agent. Another object of the invention relates to a coloring process which is carried out at the same time as a permanent deformation process. The technique of permanent deformation of the hair consists, first of all, in opening the disulfide bonds of keratin (cystine) using a composition containing a reducing agent and then, after having preferably rinsed the hair, subsequently reconstituting said disulfide bonds by applying to the hair, previously tensioned by hair curlers or the like, or shaped or smoothed by other means, an oxidizing composition also called a fixing agent so as to give the hair the sought form. This technique allows indifferently to achieve either the waving of the hair, or their straightening or curing or smoothing.

  Thus, the invention relates in particular to a process for the permanent staining and deformation of keratinous fibers, especially human fibers, such as the hair comprising: a step of application to the keratinous fibers of a composition according to the invention comprising at least one compound of formula (I) as defined above and a reducing agent as defined above, for reducing the disulfide bonds of keratin and optionally the disulfide function of compound of formula (I) with m = 2 and Y 'absent; and a step of fixing by oxidation by contacting the keratin fibers with an oxidizing agent or by contacting said fibers with the oxygen of the air, to reform the disulfide bonds of the keratinous fibers together and form disulfide bonds between the S- bonds keratin fibers and -S compounds of formula (I). This process of coloring and permanent deformation may be followed by a stimulus, especially chemical, to reveal the color; or in a symmetrical manner, the dyeing process involves, in the application step, a composition comprising, in addition to at least one compound of formula (I) and at least one reducing agent, also at least one chemical stimulus; or else, in a symmetrical manner, the dyeing process involves, in the fixing step, the application of a composition comprising at least one oxidizing agent and at least one chemical stimulus. Another variant is to apply before the staining process, the staining and deformation process, a composition comprising at least one chemical stimulus. The oxidizing agent thus makes it possible to generate a disulfide bond between the thiol function of styrylic or imine compound according to the invention and a thiol function of keratin fibers. This step is called the fixation step. When a permanent deformation is performed at the same time the fixing step also comprises reforming the disulfide bonds of the keratinous fibers together once the desired shape is achieved.

  The oxidizing agent can be any oxidizing agent conventionally used in the field. Thus, it may be chosen from: - hydrogen peroxide or an agent capable of producing hydrogen peroxide by hydrolysis such as: urea peroxide, peroxygenic reagents such as persulfates, perborates, ammonium percarbonates or alkali metals, as well as enzymes including peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases; alkaline bromates; magnesium monoperoxyphthalate; nitrites and more particularly alkali metal, alkaline-earth metal or ammonium nitrites, organic derivatives of nitrites; the preferred nitrites being sodium nitrite or ammonium nitrite; the periodic acid and its water-soluble salts, the preferred salts being the salts of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, manganese, iron, copper, zinc, and aluminum, more particularly the sodium and potassium salts; - ferricyanides of alkali metals and in particular potassium ferricyanide; - silver oxide; - Fenton's reagent; lead oxide (IV); anions of a metal chosen from permanganates or dichromates, more particularly potassium permanganates and sodium dichromate; the metal salts of group III to VIII of the periodic table, such as the salts of manganese, cobalt, iron, copper and silver, for example manganese sulphate, manganese lactate or cobalt chloride; ferric chloride, cupric chloride, ammoniacal silver nitrate, copper salts are preferred, these metal salts may be in the free state or adsorbed to a support; rare earth salts, these being chosen particularly from lanthanide salts, cerium salts Ce3 +, Ce4 +, lanthanum salts Lai +, europium Eue +, Eu3 +, gadolinium salts Gd3 +, salts of Ytterbium Yb2 +, Yb3 +, dysprosium Dy3 +, the preferred salts are sulphates, chlorides or nitrates, more particularly, one will choose Ce3 + or Ce4 + as sulphate or chloride; and - sodium hypochlorite.

  In a preferred manner, the oxidant used is hydrogen peroxide, alkaline bromates and more particularly sodium bromate.

  Advantageously, when the staining and permanent deformation process is carried out at the same time as seen above, the fixing step is made with alkali metal bromate such as sodium bromate. The content of oxidizing agent is generally between 1 and 40% by weight, relative to the weight of the ready-to-use composition, preferably between 1 and 20% by weight relative to the weight of the ready-to-use composition. .

  When the compound of formula (I) is a thiol ie m is 1 and comprises an S-protected function, the method of the invention may be preceded by a step of deprotection of the S-protected function intended to restore in situ the SH function. By way of example, it is possible to deprotect the SY 'function with the protective group by adjusting the pH as follows: Y': alkylcarbonyl deprotecting protecting group, pH> 9 arylcarbonyl, pH> 9 alkoxycarbonyl, pH> 9 aryloxycarbonyl, pH > 9 arylalkoxycarbonyl pH> 9 (di) (alkyl) aminocarbonyl, pH> 9 (alkyl) arylaminocarbonyl pH> 9 aryl optionally substituted such pH> 9 as phenyl, monocyclic heteroaryl with 5, 6 or 7 pH> 9 members such as l oxazolium; 8 to 11-membered 9-membered bicyclic heteroaryl such as benzoimidazolium, or benzoxazolium The deprotection step may also be carried out in the course of a step of pretreatment of the keratin materials such as, for example, the reducing pretreatment of the hair. The application of the dyeing composition is generally carried out at room temperature, ie at 25 ° C. It may, however, be carried out at temperatures ranging from 25 to 80 ° C. According to another variant, the dyeing composition comprising at least one compound of formula ( I) disulphide ie m is 2, may contain an oxidizing agent as defined above, it is called ready-to-use composition. Usually, said composition is obtained by mixing said composition with an oxidizing composition before application to the keratin materials to be treated. In the keratinous material dyeing method according to the invention consisting in applying the composition of the invention to keratin materials, the exposure time is set between 5 minutes and 1 hour, particularly between 15 minutes and 1 hour. The temperature of the application is set between ambient temperature, ie 25 ° C. and 80 ° C., particularly at ambient temperature, ie 25 ° C.

  III. The device or dyeing kit: The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one compound of formula (I) and a second compartment contains a reducing agent capable of reducing the disulfide functions of keratin materials, and / or of the compound when said compound of formula (I) is a disulfide compound ie m is 2.

  It also relates to a multi-compartment device, one of which contains the compound (s) of formula (I) and another contains the chemical stimulus (s) as defined above. One of these compartments may further contain one or more other dyes of direct dye type or oxidation dye.

  It also relates to a multi-compartment device in which a first compartment contains a dye composition comprising at least one compound of formula (I); a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials and / or the compound of formula (I) when said compound is a disulphide compound i.e. m is 2; a third compartment contains an oxidizing agent. The invention also relates to a multi-compartment device in which a first compartment contains a dye composition comprising at least one compound of formula (I) protected thiol i.e. m is 1 and Y 'is a protecting group; a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials; a third compartment contains a deprotection agent to release Y '; and optionally a fourth compartment which contains an oxidizing agent. Each of the devices mentioned above can be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2 586 913.

  The examples which follow serve to illustrate the invention without, however, being limiting in nature. The disulfide compound A of formula (I) has been fully characterized by conventional spectroscopic and spectrometric methods. EXAMPLES EXAMPLE OF SYNTHESIS Synthesis of compound A: N, N = (disulfanediyldiethane-2,1-diyl) bis {4- [2- (9,9-dimethyl-2,3-dihydro [1,3] oxazolo [3] 2-a] indol-9a (9H) -yl) vinyl] -N-methylaniline Compound A / S N / N Synthesis scheme: ## STR2 ## \ N SS N \ \ _ / HO 2 / - \ N SS N [A] Operating Mode:

Step 1: 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde 82.3 g of phosphorus oxychloride are added to 500 ml of DMF at 0 ° C. After 30 minutes of stirring at 0 ° C., a solution of 47 g of N, N '(disulphanediyldiethane-2,1-diyl) bis (N-methylaniline) is added dropwise. The mixture is stirred for 90 min at 0 ° C. then 75 min at 10 ° C. and 105 min at 40 ° C. It is then poured into 2.5 L of ice water and 700 ml of 5N sodium hydroxide solution. The yellow precipitate obtained is filtered on celite, solubilized in 200 mL of dichloromethane and the solution obtained is washed with 200 mL of saturated aqueous sodium chloride solution. After drying over magnesium sulphate and evaporation of the dichloromethane, the yellow residue (80 g) is purified by chromatography on silica gel. After drying, a light yellow powder is collected. The analyzes show that the product conforms to the expected structure.

Step 2: Synthesis of N, N '- (disulfanediyldiethane-2,1-diyl) bis {4 - [(E) -2- (9,9-dimethyl-2,3-dihydro [1,3] oxazolo [3 , 2-a] indol-9a (9H) -yl) vinyl] -N-methylaniline} [A] 1.91 g of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde obtained in the previous step and 730 mg of pyrrolidine are suspended in 5 ml of methanol. 2 g of 2- (3,3-dimethyl-2-methylene-2,3-dihydro-1H-indol-1-yl) ethanol diluted in 15 ml of methanol are added to the mixture. After stirring for 30 minutes at 40 ° C., 630 mg of acetic acid are added and the mixture is refluxed for one week. 1.39 g of 2- (3,3-dimethyl-2-methylene-2,3-dihydro-1H-indol-1-yl) ethanol are added, the stirring at reflux is maintained for 24 h. After cooling the reaction mixture, the product is purified by liquid chromatography. 500 mg of light brown solid are collected. The analyzes show that the product conforms to the expected structure [A].

EXAMPLE OF COLORING

  Staining process Composition Composition 1 Compound A 8.5.10-5 mole% Benzyl alcohol 5% Ethanol 25.2% Monoethanolamine 2% Ammonium thioglycolate (71% MA *) 3.34% Hydroxyethyl cellulose (MW 720 000) 1, 5% Water qs 100% * MA: active ingredient

  The composition 1 is applied to gray hair comprising 90% natural (90% BN) and permed (90% BP) natural hair for 30 minutes at room temperature (24 C) and on dark hair of pitch HT = 5 A after the laying time, the locks are rinsed with clean water. Staining is revealed by the following post-treatment: Acidic 3,5-dihydroxybenzoic acid at a concentration of 500 mM in distilled water; pH of the solution adjusted to 3.0 by addition of sodium hydroxide. The post-treatment is applied in a non-rinsed manner at room temperature with a bath ratio of 2 (2 g of formulation per 1 g of hair).

  Results in the L * a * b System The color of the locks before and after treatment with the composition 1 was evaluated in the L * a * b * system by means of a CM 3600dMINOLTA 8 spectrophotometer, (D65 illuminant, including the secular component). angle of observation 10). In this system L * a * b *, L * represents the intensity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis. The higher the L value, the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color. The variation of the color between the locks of natural white hair (90% BN), permanent white (90% BP), and the same locks of hair after treatment is measured by AE according to the following equation: DE _. / (L * _Lo *) 2 + (a * _ao *) 2 + (b * _b0 *) 2 In this equation, L *, a * and b * represent the values measured after treatment and Lo *, ao * and bo * represent the values measured before treatment. L * a * b * AE Hair 90% BN before treatment 63.8 0.3 15.1 53.9 Hair 90% BN after treatment with 44.8 47.3 -3.1 Composition 1 hair 90% BN Hair 90% BP before treatment 63.4 0.7 14.5 56.3 Hair 90% BN after treatment with 40. 7 50.1 0.0 Composition 1 hair 90% BP Visual observations After the post-treatment the hair is dried at 60 C. The color obtained after treatment of the hair is fuchsia with chromatic reflections. Hair coloring is powerful, very aesthetic and homogeneous. After treatment of dark hair with compound A they appear visually clearer. COMPARATIVE STUDY: The compositions 2 and 3 below, containing respectively as compound the comparative compound and the compound A, are applied to natural hair and permed 90% white and chestnut (pitch HT = 5 international rating) for 30 minutes at room temperature. Compound Composition 2/3 Comparative Compound / Compound A 8.5.10-5 mole Benzyl alcohol 5 q Ethanol 25.2 g Ammonium thioglycolate 3 g Hydroxyethyl cellulose 1.5 g Polyethylene imine 10 g 0.5 M Na2CO3 qsp pH 10, 5 NaOH Distilled water qs 100 g At the end of the exposure time, the hair is rinsed with clear water to remove the excess of support and wrung out. The hair is fuchsia color.

  15 COLOR STABILITY DURING INSTALLATION Even after 30 minutes, the color of compound A does not change during the exposure time, whereas for comparison, the color changes. COMPARATIVE COLOR REVELATION Comparative 10 After applying compositions 2 and 3, laying, and rinsing, the hair is treated with the following compositions 4 or 5: Compound Composition 4 Composition 5 3,5-Dihydroxybenzoic acid 2.10-2 mole - succinic acid - 5.10-2 mole Zinc acetate 3.36 q 3.36 q HCl qsp pH 3 - NaOH - qsp pH 3 H2O2 - 0.5 g Distilled water qs 100 g qs 100 g For each step of the protocol color appearance below 1 and 2, after application according to the steps of the protocol the exposure time is 5 minutes, without being followed by rinsing. Protocol for the appearance of Step 1 Step 2 Color 1 Post-treatment with the composition 4 2 0.5% H 2 O 2 (1.7 vol) Post-treatment with the composition 5 3 Post-treatment with the composition 5 After application compositions 4 or 5 containing an acid as a color-stimulating stimulant on the hair, a hair coloring of 90% white hair colored in fushia is observed. The coloration is homogeneous, powerful and very chromatic. On hair chatain HT = 5 hair color after treatment is fuschia. This color is clearly observable, the hair is colored homogeneously with aesthetic reflections.

  During the application of the post-treatments, no disgorging of the strands stained with the compound A is observed in contrast to the strands dyed by the comparative compound.20 SHAMPOO TENACITY

  20 shampoos are made manually on the locks thus colored after revelation. During the shampoo, it appears visually that the hair mousse dyed by comparison is colored, unlike that obtained with the hair dyed by the compound A. In addition, during the rinsing of shampooed hair, the colored hair by comparative disgorge on the In contrast to what is observed with the hair dyed by compound A. Protocols Difference of AE before shampooing and after appearance color shampoos BN BP Protocol 1 Reference * -23 -18 Test ** -11 -4 Protocol 2 Reference * -27 -39 Test ** -8 -8 Protocol 3 Reference * -33 -26 Test ** -11 -12 * Reference: Wick not treated ** Test: treated wick

  According to this table, it is observed that the difference in AE for locks of hair BN before treatment and after shampooing is much higher than if the wick is treated with compound A according to protocols 1 to 3 (-23 vs. -11, -27 vs. -8 and -33 vs. -11). The same observation was made with the untreated BP strands vs treated according to the invention (-18 vs. -4, -39 vs. -8, -26 vs. -12). It follows that the toughness of the compound A is particularly improved with respect to the tenacity of the references or comparatives and whatever the nature of the hair.

  It has been noted that the tenacity of the compound A is significantly improved with respect to the tenacity of the comparative and whatever the nature of the hair. 73

Claims (24)

  A compound of the following formula (I): ## STR1 ## its organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates; formula (I) in which: m is 1 or 2: when m is 1 then Y 'is present and when m is 2 then Y' is absent; p is 0 or 1; Csat represents a linear or branched, optionally substituted, optionally cyclic C1-C18 alkylene chain; A represents a colorless chromophore which can be colored, or which can be stained and fluoresce, under the action of stimuli; X represents a linear or branched, saturated or unsaturated, optionally substituted C1-C30 hydrocarbon-based chain optionally interrupted by one or more divalent groups or combinations thereof chosen from: i) N (R) -; -N + (R) (R ') -, Q-; -O-; -S-; -CO- and -SO2-with R, R ', identical or different, are selected from hydrogen, C1-C4 alkyl, hydroxyalkyl and aminoalkyl, Qreprésente an anionic counter-ion; and ii) a radical (hetero) cyclic, aromatic or not, saturated or unsaturated, condensed or not, optionally comprising one or more identical or different heteroatoms, optionally substituted; Y 'represents i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + RaRaRYRs, M- or a phosphonium group: P + RaRaRYRs, Mavec Ra, Ra, R7 and R8, identical or different, representing a hydrogen atom or an alkyl group and M-represents a counter anionic ion; or v) a protecting group of thiol function, it being understood that when m is 1, the function SY 'may be in the covalent form -SY' or ionic -S Y '+ depending on the nature of Y' and the pH of the medium .   2. Compound of formula (I) according to the preceding claim characterized in that when m is 1, Y 'represents a hydrogen atom.   3. Compound of formula (I) according to claim 1 characterized in that when m is 1, Y 'is selected from the following radicals: alkyl optionally substituted with one or more groups, identical or different, selected from i) an atom halogen, ii) alkylcarbonyl, iii) alkylthiocarbonyl, iv) alkoxycarbonyl, v) alkoxy-thiocarbonyl, vi) alkylthiothiocarbonyl, vii) (di) (alkyl) aminocarbonyl, viii) (di) (alkyl) aminothiocarbonyl, ix) carboxy and x) cyano; - SO3; M + with M + representing a cationic counterion; optionally substituted aryl; optionally substituted heteroaryl; optionally substituted heterocycloalkyl; the following group: R '\ R'g Nom / R, h Ç'(CR'eR'f), R'd - An in which R', R'd, R'e, R'f, R'g and R'h, which are identical or different, represent a hydrogen atom or an alkyl group, or else two groups R'g with R'h and / or R'e with R'f form an oxo or thioxo group, or else R'g with R'e together form a cycloalkyl; and v represents an integer inclusive of between 1 and 3; and An represents the counterion; -isothiouronium -C (NR 'R'd) = N + R'eR'f; With R ', R'd, R'e and R'f, identical or different, represent a hydrogen atom or an alkyl group; - (di) arylalkyl optionally substituted; optionally substituted (di) heteroarylalkyl; - CR'R2R3 with R ', R2 and R3 identical or different, representing a halogen atom or a group selected from: alkyl optionally substituted; optionally substituted alkoxy; optionally substituted aryl; optionally substituted heteroaryl; - P (Z ') R'1R'2R'3 with R'1, and R'2 identical or different represent a hydroxy, alkoxy or alkyl group, R'3 represents a hydroxyl or alkoxy group, and Z' represents an atom oxygen or sulfur; - DES (0) O_2-alkû with i) ûalkû representing a divalent linear or branched hydrocarbon chain, C1-C13, ii) D represents a hydrogen atom, an optionally substituted aryl group or a heteroaryle group optionally substituted and iii) E representing a bond a, ùN (Ra) ù, ùalkù, ùalkùOù, ùalkùN (Ra) ù, with Ra and ùalkù as previously defined; - D-E'-C (J) -J'-alcu, with E ', representing a bond a, ùN (Ra) ù, ùalkù, ùcuùOù, ùalkùùùù,, ùalkùùN ((Ra) ù; J and J ', which may be identical or different, represent an oxygen, sulfur or NRR atom; D, Ra, RR and ùalkù are as previously defined; -cyclic sterically hindered; optionally substituted alkoxyalkyl; Z2-C (Z ') - wherein Z2-S (O) is with: Z2 representing an optionally substituted alkyl group; optionally substituted alkoxy; optionally substituted alkylthio; optionally substituted aryl; optionally substituted arylalkyl; optionally substituted heteroaryl; optionally substituted heteroarylalkyl; -NRZR'Z with RZ and R'z, identical or different, representing a hydrogen atom or an alkyl group, or else RZ and R'Z form together with the nitrogen atom which carries them a grouping: i) heterocycloalkyl, ii) heteroaryl, cationic or non-cationic; E 'representing a group as defined above; Z 'representing: an oxygen or sulfur atom; -M-, alk-O + u or M-, alk-S + u where alk represents an alkyl group and M- represents an anionic counterion, -NR "Z, ùN + R" ZR "'Z, Mdans which, R "Z and R" 'zf identical or different, represent a hydrogen atom, an optionally substituted alkyl group, optionally substituted aryl or optionally substituted heteroaryl, or optionally substituted alkoxy, r representing an integer inclusive between 1 and 2; .   4. Compound according to any one of the preceding claims, chosen from compounds of formulas (I ') to (VI'): ## STR1 ## ## STR2 ## wherein its salts of organic or inorganic acid, optical isomers, geometric isomers, tautomers, and solvates such as hydrates, formulas (I ') to (VI') in which: - m is 1 and Y 'is present or m is 2 and Y' is absent; - n represents an integer of 1 to 4; is 0 or 1; B is a condensed aryl or fused heteroaryl ring having from 5 to 16 members; -Csat is a straight or branched, optionally substituted, optionally cyclic C 1 -C 6 alkylene chain; represents an oxygen, sulfur or selenium atom, a group CRI R2 or NR1, with R 'and R2, which are identical or different, represent, a hydrogen atom, a C1-C6 alkyl radical or a hydroxyalkyl radical; C1-C6, a rad C1-C6 alkoxyalkyl radical; R 'and R2 may together with the carbon atom carrying them form a 5- or 6-membered ring, optionally containing one or more heteroatoms selected from the nitrogen atom, n, I3 c Oxygen or sulfur; -E 'represents a nitrogen atom or a CR2 group with R2 as defined for E, - R "represents a divalent (C 1 -C 6) alkylene radical, said radical possibly containing an oxygen, sulfur atom and may be substituted with a hydroxy or alkoxy group; G represents a divalent arylene or heteroarylene group comprising from 5 to 16 members; - G 'represents an aryl or heteroaryl group comprising from 5 to 16 members; - R3 represents a hydrogen atom, a halogen atom, a C1-C6 alkyl radical, a cyano radical, an aromatic group, a phenoxy group, a nitro radical; - R'3 and R'5, represent a divalent radical (C, -C6) alkylene, arylene or -uarylèneù comprising from 5 to 16 members; R4 represents a hydrogen atom, or a C1-C6 alkyl radical; W, present or absent, represents a nitrogen atom or a group CR 2 with R 2 representing a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl radical, a cyano radical, an aromatic group, a radical, phenoxy, a nitro radical; X 'represents a linear or branched, saturated or unsaturated, optionally substituted C1-C30 hydrocarbon chain, optionally interrupted and / or optionally terminated at one or both of its ends by one or more divalent groups or combinations thereof chosen from : N (R) -; -N + (R) (R ') -, Q-; -O-; -S-; -CO-; -SO2- with R, R ', which may be identical or different, are chosen from hydrogen, a C1-C4 alkyl, hydroxyalkyl and aminoalkyl radical, Q- represents an anionic counterion; and a radical (hetero) cyclic, aromatic or not, saturated or unsaturated, condensed or not, optionally comprising one or more identical or different heteroatoms, optionally substituted; Y represents an oxygen atom, a sulfur atom, an NR6 group with R6 representing a hydrogen atom or a C1-C6 alkyl radical; Y 'represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + RaRRRYRs or a phosphonium group: P + RaRRRYRs with Ra, RR, R7 and R8, identical or different, representing a hydrogen atom or an alkyl group; or v) a thiol protecting group; Z represents i) a divalent group -CgH2q-, with q an integer inclusive of 2 to 4, unsubstituted or substituted by one or more substituents selected from halogen atoms, and hydroxy, alkyl, haloalkyl, alkoxy, amino groups; (di) alkylamino, (di) hydroxyalkylamino, carboxyl; ii) a divalent group -CrH2rC (O) - or -CrH2rC (S) -, with r an integer inclusive of between 1 and 3, unsubstituted or substituted by one or more substituents selected from halogen atoms, and hydroxy groups, alkyl, haloalkyl, alkoxy, amino, (di) alkylamino, (di) hydroxyalkylamino, carboxyl; it being understood that: when m is 1, the -SY 'function may be in the covalent -S-Y' or ionic -S Y '+ form depending on the nature of Y and the pH of the medium; when n is 1 and W is absent then the double bond is directly connected to the group G or G '; when n is an integer greater than or equal to 2: the units [CR 3 = W] - are identical to or different from each other, W represents CR 2 or is absent; ^ W can be absent only on the last reason - [CR3 = W] - directly connected to the group G or G '; The chain R 3 (X) p Csat 2 O 2 of the formula (II ') or the chain R 5 (X) p Csat 2 O of the formula (III') can be linked only once to the chromophore via the groups û [C = W] n or û [CR3 = C] n respectively, the other groups then representing a group û [C (R3) = W] û.   5. Compounds according to any one of the preceding claims of the following formulas: ## STR2 ## SS 9 S-S10 NS-SN HH 11 12 HO OH 13 0 ,, O 0/0 s. S SS ~ N 14 0/0 0 0 SN ~ iS-S ~~ NS HH 15 OO NN HHN 16 ss 17s-s 18 19 -N N-20 ss 21 22 NS-SN HH 23 oo 24O o ss 25 O o N ss 26 O o ss 27 OO ss 28 NH ss 29 OO ss 30 NOOOU \ NN ~ N-SN HH 31H H 32 OO 33 35 34 O N + YEARS 37 N s' s 0 0 36 38 39 ## EQU1 ## where Y represents an anionic counterion, and M + represents a against cationic ion.   6. Cosmetically acceptable composition containing at least one compound according to any one of claims 1 to 5.   7. Composition according to the preceding claim further comprising at least one reducing agent.   8. Composition according to the preceding claim for which the reducing agent is selected from cysteine, cysteamine, N-acetylcysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites thioglycolic acid, as well as its esters, borohydrides and their derivatives, and catecholborane.   9. Composition according to any one of claims 7 or 8 for which the reducing agent is in amounts between 0.1 and 15% by weight of the composition.   10. Composition according to any one of claims 6 to 9 further comprising another additional disulfide compound, different from that of claims 1 to 6, selected from compounds comprising at least one fatty chain, linear or branched, saturated or unsaturated, optionally substituted. by a heteroatom, optionally interrupted by a carboxylic group, neutralized or not.   11. A method of dyeing keratin materials comprising contacting said materials with a composition as defined in any one of claims 6 to 10, optionally the keratin materials are pretreated with a reducing agent as defined in one of claims 8 or 9.   12. Method according to the preceding claim followed by a step of post-treatment of keratin materials by color-stimulating stimuli.   13. Method according to the preceding claim wherein the step of the post-treatment by stimuli is carried out using a composition containing at least one chemical stimulus and at least one oxidizing agent.   14. Method according to one of claims 11 or 12 wherein the process is followed by a step of fixing the compounds with an oxidizing agent.   15. A method of permanent deformation and dyeing of keratin fibers, comprising: a step of applying to the hair a composition comprising at least one dye of formula (I) according to at least one reducing agent according to any one of claims 7; at 10, for reducing lakeratin disulfide bonds, - an oxidation fixing step, for reforming said bonds, by applying an oxidizing composition to the hair or by contacting the hair with the oxygen of the air.   16. Method according to one of claims 13 or 15 wherein the oxidizing agent is selected from: - hydrogen peroxide or an agent capable of producing hydrogen peroxide by hydrolysis and the enzymes selected from peroxidases, 10 2-electron oxidoreductases and 4-electron oxygenases; - alkaline bromates; magnesium monoperoxyphthalate; nitrites; periodic acid and its water-soluble salts; Ferricyanides of alkali metals; - silver oxide; - Fenton's reagent; lead oxide (IV); anions of a metal chosen from permanganates or dichromates; The metal salts of group III to VIII of the periodic table; rare earth salts; and - sodium hypochlorite.   17. A staining method according to any one of claims 11 to 16 wherein when the compound of formula (I), m is 1 and Y 'is a protecting group of the thiol function, the application is preceded by a step of protection.   18. Multi-compartment device in which a first compartment 30 contains a dye composition comprising a compound as defined in claims 1 to 5 and a second compartment contains a reducing agent.   19. Device according to the preceding claim comprising a third compartment which contains an oxidizing agent.   20. Multi-compartment device in which a first compartment contains a dye composition comprising at least one compound of formula (I) protected thiol i.e. m is 1 and Y 'is a protective group according to any one of claims 1 to 4; a second compartment contains a reducing agent; a third compartment contains a deprotection agent to release Y '; and optionally a fourth compartment contains an oxidizing agent.   21. Use of the compounds as defined in claims 1 to 5 for dyeing human keratin materials.   22. Use according to the preceding claim for dyeing dark keratin fibers.   23. Use according to claims 21 or 22 for the lightening of dark keratin fibers.   24. Use according to any one of claims 21 to 23 characterized in that the keratinous fibers have a pitch of less than or equal to 6.20