WO2009037348A1

WO2009037348A1 - Indolinium-derived thiol/disulfide dye, dye composition comprisng this dye, process for lightening keratin materials using this dye

Info

Publication number: WO2009037348A1
Application number: PCT/EP2008/062570
Authority: WO
Inventors: Andrew Greaves; Nicolas Daubresse
Original assignee: L'oreal
Priority date: 2007-09-21
Filing date: 2008-09-19
Publication date: 2009-03-26
Also published as: FR2921374A1

Abstract

The invention relates to the dyeing of keratin materials using indolinium-derived thiol and disulfide fluorescent dyes. The invention relates to a dye composition comprising an indolinium-derived-chromophore thiol or disulfide dye and to a dyeing process with a lightening effect on keratin fibers such as the hair, using said composition. It similarly relates to novel indolinium-derived-chromophore thiol dyes and to the uses thereof in lightening keratin materials. This composition makes it possible to obtain a coloring with a lightening effect which is particularly resistant and visible on dark keratin fibers.

Description

INDOLINIUM-DERIVED THIOL/DISULFIDE DYE, DYE COMPOSITION

COMPRISNG THIS DYE, PROCESS FOR LIGHTENING KERATIN

MATERIALS USING THIS DYE

The invention relates to the dyeing of keratin materials using indolinium thiol and disulfide fluorescent dyes.

It is known practice to dye keratin fibers, in particular human keratin fibers, by direct dyeing. The process conventionally used in direct dyeing comprises applying to the keratin fibers direct dyes which are colored or coloring molecules having an affinity for the fibers, allowing them to diffuse and then rinsing the fibers.

The direct dyes which are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridine dyes, or dyes of the azo, xanthene, acridine, azine or triarlymethane type.

The coloring of keratin fibers using these conventional direct dyes does not make it possible to significantly lighten keratin fibers.

The lightening of the color of dark keratin fibers to lighter shades, by optionally modifying the shade thereof, constitutes an important demand.

Conventionally, in order to obtain a lighter coloring, a chemical bleaching process is used. This process comprises treating the keratin fibers, such as the hair, with a strong oxidizing system, generally composed of hydrogen peroxide, possibly in combination with persalts, generally in an alkaline medium.

This bleaching system has the drawback of damaging the keratin fibers and of detrimentally affecting their cosmetic properties. The fibers in fact have a tendency to become rough, more difficult to disentangle and more brittle. Finally, the lightening or the bleaching of keratin fibers with oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in hair straightening treatments.

Another lightening technique comprises applying fluorescent direct dyes to dark hair. This technique, described in particular in documents WO 03/028685 and WO 2004/091473, makes it possible to retain the quality of the keratin fiber during the treatment. However, these fluorescent direct dyes do not exhibit satisfactory fastness with respect to outside agents.

In order to increase the fastness of direct colorings, it is known practice to use disulfide dyes, in particular azaimidazolium chromophore dyes in patent applications WO 2005/097051 or EP 1647580, and pyridinium/indolinium styryl chromophore dyes in patent applications WO 2006/134043 and WO 2006/136617.

The aim of the present invention is to provide new systems for dyeing keratin materials, in particular human keratin fibers, especially the hair, which do not have the drawbacks of the existing bleaching processes.

In particular, one aim of the invention is to provide direct dyeing systems for obtaining lightening effects, especially on naturally or artificially dark keratin fibers, which are resistant to successive shampooing operations, which do not damage the keratin fibers and which do not detrimentally affect their cosmetic properties .

Another aim of the invention is to dye keratin materials chromatically and in a manner which is persistent with respect to outside attacks.

This aim is achieved with the present invention, a subject of which is a process for dyeing keratin materials, in particular keratin fibers, especially human keratin fibers such as the hair, more particularly dark hair, comprising applying, to the keratin materials, a dye composition comprising, in a suitable cosmetic medium, at least one indolinium- derived disulfide or thiol fluorescent dye, chosen from the dyes of formulae (I), (II) or (III) below:

the organic or mineral acid salts, optical isomers and geometric isomers thereof, and the solvates such as hydrates :

in which formulae (I) , (II) and (III) :

> p or p' represent an integer between 0 and 4 inclusive; in particular, p or p' is 0 or 1 ; > R¹ represents a halogen atom, or a (Ci-C₆) alkyl, (Ci-C₆) alkoxy, (Ci-C₆) alkylthio, (di) (Ci-C₆) (alkyl) - amino, (Ci-C₆) polyhaloalkyl, hydroxyl, (Ci-C₆)poly- hydroxyalkyl, polyhydroxy (Ci-C₆) alkoxy, cyano, R-G-C(G')-, R-C(C)-G-, R¹S(O)₂-N(R)- or RR¹N-S(O)₂- group with G or G', which may be identical or different, representing an oxygen or sulphur atom or a group NR', and R and R', which may be identical or different, representing a hydrogen atom or a (Ci-C₆) alkyl group; in particular, R¹ represents is at position 5 and more particularly R¹ represents a halogen such as chlorine or a (Ci-C₆) alkoxy group such as methoxy, an RR¹N-S(O)₂- group such as Me-S(O)₂- or an RR¹N-C(O)- group such as H₂N-C(O)-;

> R² and R³, which may be identical or different, represent a (Ci-C₆) alkyl group; in particular, R² and R³ are identical and represent a methyl group; > R⁴ and R⁵ represent an alkyl or aryl (Ci-C₆) alkyl group, it being understood that R⁴ represents a σ bond when the radical -L-S- of the disulphide dye of formula (I) is linked to R⁴;

> B represents an optionally substituted aryl or optionally substituted heteroaryl group, such as phenyl, naphthyl or indolyl optionally substituted in particular with one or more groups chosen from (di) (Ci-C₄) (hydroxyalkyl) amino, (di) (Ci-C₄) (carboxy- alkyl) amino, (di) (Ci-C₄) (alkyl) amino, hydroxyl- piperidino, hydroxyl and phenyl; advantageously substituents are chosen from (di) (Ci- C₄) (hydroxyalkyl) amino, (di) (Ci-C₄) (carboxyalkyl) - amino, (di) (Ci-C₄) (alkyl) amino, hydroxylpiperidino;

> L represents an optionally substituted Ci-C₂₀ divalent hydrocarbon-based chain which is optionally interrupted and/or optionally terminated at one or the other of its ends i) with one or more divalent groups or combinations thereof chosen from: -N(RJ-; -N⁺ (R_a) (R_b) -, An'^"; -O-, -S-, -C(O)- and -S(O)₂- with R_a and R_b, which may be identical or different, chosen from hydrogen, and a (Ci-C₆) alkyl, hydroxy (Ci-C₆) alkyl or

(di) (Ci-C₆) (alkyl) amino (Ci-C₆) alkyl radical, and An^" representing an anionic counterion, or ii) with a cationic heterocycle or cationic heteroaryl Het⁺, An^", with An'^" as defined above and Het⁺ representing a saturated or unsaturated heterocycle comprising from 5 to 10 members or a heteroaryl comprising from 5 to 10 members, such as imidazolium, pyridinium, piperazinium, piperidinium or benzimidazolium; in particular, L represents a (Ci-Cβ) alkylene chain linked to the rest of the molecule by an NR, -NRC (O) - or -C(O)NR- linkage;

^ Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N⁺RTR¹R , or a phosphonium group: P⁺R^αR^βR^γR^δ, with R^α, R^β, R^γ and R^δ, which may be identical or different, representing a hydrogen atom or a (Ci-C₄) alkyl group, or v) a thiol- function-protecting group; preferably Y cannot represent Au metal when L is (C2-C5) alkylene group; ^ An^" represents an anionic counterion; it being understood that: when p is between 2 and 4, the groups R¹ are identical or different, when p' is between 2 and 3, the groups R¹ are identical or different, - when the dye of formula (II) contains a group Y representing a hydrogen atom or an alkali metal, then the radical L cannot represent a divalent C2-C4 hydrocarbon-based chain, the chain -L-S- is linked to the indolinium- derived chromophore of formula (I) in particular via A, R⁴ or B, formula (I), (II) or (III) may contain other anionic counterions so as to achieve electro- neutrality.

Another subject of the invention is a dye composition for dyeing keratin fibers with a lightening effect, comprising, in a cosmetic medium, at least one indolinium-derived disulfide or thiol fluorescent dye of formula (I) , (II) or (III) as defined above, and optionally a reducing agent. A subject of the invention is also novel indolinium- derived disulfide or thiol fluorescent dyes of formula (I), (II) or (III) as defined above.

The dyeing process according to the invention makes it possible to visibly color dark keratin materials, in particular dark human keratin fibers, especially dark hair. Furthermore, the process of the invention makes it possible to obtain a coloring of the hair without damaging it, which is persistent with respect to shampooing operations, everyday attacks (sunlight, perspiration) and hair treatments. The process of the invention also makes it possible to obtain lightening of keratin materials such as keratin fibers, in particular dark keratin fibers, and more particularly dark hair.

This process also makes it possible to dye keratin fibers in a strong, relatively nonselective and homogeneous manner without observing any notable change in color over time. Moreover, the dye compositions according to the invention are particularly stable during the conservation or the storage thereof.

For the purpose of the present invention, the term "dark keratin material" is intended to mean that which exhibits a lightness L* measured in the C. I. E. L*a*b* system of less than or equal to 45, and preferably less than or equal to 40, given that, moreover, L* = 0 is equivalent to black and L* = 100 is equivalent to white .

For the purpose of the invention, the expression

"naturally or artificially dark hair" is intended to mean whose tone height is less than or equal to 6 (dark blond) and preferably less than or equal to 4

(chestnut-brown) . The lightening of the hair is evaluated by the variation in "tone height" before and after application of the compound of formula (I) , (II) or (III) . The notion of "tone" is based on the classification of the natural shades, one tone separating each shade from the shade immediately following or preceding it. This definition and the classification of the natural shades are well known to hair styling professionals and are published in the book "Science des traitements capillaires" [Hair Treatment Sciences], by Charles Zviak 1988, published by Masson, pp. 215 and 278.

The tone heights range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the figure, the lighter the shade.

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

For the purpose of the invention, the term "bleached hair" is intended to mean hair whose tone height is greater than 6 and preferably greater than 8.

One means for measuring the lightening effect given to the hair after application of the fluorescent dyes of the invention is to use the phenomenon of hair reflectance .

Preferably, the composition should, after application to dark hair, lead to the results below.

Interest is focused on the hair reflectance performance levels when said hair is irradiated with visible light in the wavelength range from 400 to 700 nanometers.

The curves of reflectance as a function of wavelength, of the hair treated with the composition of the invention and of untreated hair, are then compared.

The curve corresponding to the treated hair should show a reflectance in the wavelength range of from 500 to 700 nanometers which is higher than the curve corresponding to the untreated hair.

This means that, in the wavelength range of from

540 to 700 nanometers, there is at least one range where the reflectance curve corresponding to the treated hair is higher than the reflectance curve corresponding to the untreated hair. The term

"higher" is intended to mean a difference of at least 0.05% in reflectance, and preferably of at least 0.1%. All the same, there may be, in the wavelength range of from 540 to 700 nanometers, at least one range where the reflectance curve corresponding to the treated hair is superimposable on or lower than the reflectance curve corresponding to the untreated hair.

Preferably, the wavelength where the difference is at a maximum between the reflectance curve of the treated hair and that of the untreated hair is within the wavelength range of from 500 to 650 nanometers, and preferably within the wavelength range of from 550 to 620 nanometers.

For the purpose of the present invention, and unless otherwise indicated:

the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent chosen from:

• a C1-C16, preferably Ci-Cs, alkyl radical optionally substituted with one or more radicals chosen from the radicals: hydroxyl, C1-C2 alkoxy,

C2-C4 (poly) hydroxyalkoxy, acylamino and amino substituted with two Ci-C₄ alkyl radicals, which may be identical or different, optionally bearing at least one hydroxyl group, or the two radicals possibly forming, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, preferably 5 or 6 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises another heteroatom which may be identical or different from the nitrogen;

. a halogen atom such as chlorine, fluorine or bromine;

• a hydroxyl group;

• a C1-C2 alkoxy radical;

• C1-C2 alkylthio radical;

• a C2-C4 (poly) hydroxyalkoxy radical; • an amino radical;

• a 5- or 6-membered heterocycloalkyl radical which may be substituted with 1 to 3 groups, which may be identical or different, chosen from hydroxyl, amino, (di) alkylamino and Ci-C₄ hydroxyalkyl, such as morpholino, (hydroxyethyl) piperazino, (di) (hydroxy) -pyrrolidino, (di) (hydroxy) piperi- dino;

• an optionally cationic 5- or 6-membered heteroaryl radical, preferably imidazolium, optionally substituted with a Ci-C₄ alkyl radical, preferably methyl;

• a phenyl radical;

. an amino radical substituted with one or two Ci-Cβ alkyl radicals, which may be identical or different, optionally bearing at least: i) one hydroxyl group, ii) one amino group optionally substituted with one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen,

. -N(R)-C(O)R' in which the R radical is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, and the R' radical is a C1-C2 alkyl radical;

. R₂N-C(O)- in which the R radicals, which may or may not be identical, represent a hydrogen atom, or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group;

• R' S (0) 2-N (R) - in which the R radical represents a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, and the R' radical represents a Ci-C₄ alkyl radical or a phenyl radical;

• R₂N-S(O)₂- in which the R radicals, which may or may not be identical, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, • a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, which is substituted or unsubstituted) ;

• a cyano group;

• a polyhaloalkyl group containing from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which may be identical or different; the polyhaloalkyl group is, for example, trifluoromethyl; the cyclic or heterocyclic part of a nonaromatic radical may be substituted with at least one substituent borne by a carbon atom, chosen from the groups :

• hydroxyl ;

• C₁ -C₄ al koxy ;

• C₂-C₄ (poly) hydroxyalkoxy; • a Ci-C₂ alkylthio radical;

.RC(O)-N(R')- in which the R' radical is a hydrogen atom or a Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group, and the R radical is a Ci-C₂ alkyl radical or an amino radical substituted with two Ci-C₄ alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group;

.RC(O)-O- in which the R radical is a Ci-C₄ alkyl radical or an amino radical substituted with one or two Ci-C₄ alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen; .RO-C(O)- in which the R radical is a Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group; a cyclic or heterocyclic radical or a nonaromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo or thioxo groups; an "aryl" radical represents a condensed or noncondensed, monocyclic or polycyclic group containing from 6 to 22 carbon atoms, and at least one ring of which 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 aryl groups, which may be identical or different, such as diphenylmethyl or 1,1- diphenylethyl ; a "heteroaryl radical" represents an optionally cationic, condensed or noncondensed, monocyclic or polycyclic group comprising from 5 to 22 members and from 1 to 6 heteroatoms chosen from a nitrogen, oxygen, sulfur and selenium atom, and at least one ring of which is aromatic; preferably, a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenooxazolyl, 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 may be identical or different, such as difurylmethyl, 1 , 1-difurylethyl, dipyrrolylmethyl or dithienylmethyl ; - a "cyclic radical" is a condensed or noncondensed, monocyclic or polycyclic, nonaromatic cycloalkyl radical containing from 5 to 22 carbon atoms, possibly comprising one or more unsaturations; in particular, the cyclic radical is a cyclohexyl; - a "sterically hindered cyclic" radical is a substituted or unsubstituted, aromatic or nonaromatic, cyclic radical hindered by steric effect or constraint, comprising from 6 to 14 members, which may be bridged; by way of sterically hindered radicals, mention may be made of bicyclo [ 1.1.0 ] butane, mesityls such as 1,3,5- trimethylphenyl, 1, 3, 5-tri-tert-butylphenyl, 1, 3, 5-isobutylphenyl, 1, 3, 5-trimethylsilylphenyl and adamantyl; - a "heterocyclic radical or heterocycle" is a condensed or noncondensed, monocyclic or polycyclic, nonaromatic radical containing from 5 to 22 members, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium; an "alkyl radical" is a linear or branched, C1-C16, preferably Ci-Cs, hydrocarbon-based radical; the expression "optionally substituted" assigned to the alkyl radical implies that said alkyl radical may be substituted with one or more radicals chosen from the radicals: i) hydroxyl; ii) C1-C4 alkoxy; iii) acylamino; iv) amino optionally substituted with one or two Ci-C₄ alkyl radicals, which may be identical or different, said alkyl radicals possibly forming, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom which may or may not be different from nitrogen; v) or a quaternary ammonium group -N⁺R' R' ' R' ' ' , M^" for which R', R'', R' ' ' , which may be identical or different, represent a hydrogen atom or a Ci-C₄ alkyl group, or else -N⁺R' R' 'R''' forms a heteroaryl such as imidazolium optionally substituted with a Ci-C₄ alkyl group, and M^~ represents the counterion of the corresponding organic acid, mineral acid or halide; an "alkoxy radical" is an alkyloxy or alkyl-O- radical for which the alkyl radical is a linear or branched, C1-C16, preferably Ci-Cs, hydrocarbon- based radical; an "alkylthio radical" is an alkyl-S- radical for which the alkyl radical is a linear or branched, C1-C16, preferably Ci-Cs, hydrocarbon-based radical; when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above; an "alkylene chain" represents a divalent Ci-Cis chain; in particular, Ci-Cβ, more particularly C1-C2 when the chain is linear; optionally substituted with one or more, identical or different, halogen atoms or groups chosen from hydroxyl, alkoxy,

(di) (alkyl) amino and R^a-Z^a-C(Z^b)- with Z^a, Z^b, which may be identical or different, representing an oxygen or sulphur atom, or a group NR^a', and R^a representing an alkali metal, a hydrogen atom or an alkyl group and R^a' representing a hydrogen atom or an alkyl group; a "saturated or unsaturated, optionally substituted C1-C30 hydrocarbon-based chain" represents a hydrocarbon-based, in particular Ci-Cs, chain optionally comprising one or more π double bonds, which may or may not be conjugated; in particular, the hydrocarbon-based chain is saturated; said chain is optionally substituted with one or more, identical or different, halogen atoms or groups chosen from hydroxyl, alkoxy,

(di) (alkyl) amino and R^b-Z^b-C(Z^c)- with Z^b, Z^c, which may be identical or different, representing an oxygen or sulphur atom, or a group NR^b , and R^b representing an alkali metal, a hydrogen atom or an alkyl group, or else R^b is absent, in which case an anionic counterion belonging to formula (I), (II) or (III) is also absent, and R^b' representing a hydrogen atom or an alkyl group; the limits delimiting the extent of the range of values are included in this range of values; an "organic or mineral acid salt" is more particularly chosen from a salt derived: i) from hydrochloric acid HCl; ii) from hydrobromic acid HBr; iii) from sulfuric acid H₂SO₄; iv) from alkylsulfonic acids: AIk-S(O)₂OH such as methylsulfonic acid and ethylsulfonic acid; v) from arylsulfonic acids: Ar-S(O)₂OH such as from benzenesulfonic acid and from toluenesulfonic acid; vi) from citric acid; vii) from succinic acid; viii) from tartaric acid; ix) from lactic acid; x) from alkoxysulfinic acids: AIk-O-S(O)OH such as from methoxysulfinic acid and from ethoxysulfinic acid; xi) from aryloxysulfinic acids such as from tolueneoxysulfinic acid and from phenoxysulfinic acid; xii) from phosphoric acid H₃PO₄; xiii) from acetic acid CH₃C(O)OH; xiv) from triflic acid CF₃SO₃H and xv) from tetrafluoroboric acid HBF₄; an "anionic counterion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly, the anionic counterion is chosen from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, among which are Ci-Cβ alkyl sulfonates: AIk-S (O) 2θ^~ such as methyl sulfonate or mesylate and ethyl sulfonate; iv) aryl sulfonates: Ar-S(O)2θ^~ such as benzene sulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: AIk- O-S(O)O^~ such as methyl sulfate and ethyl sulfate; x) arylsulfates : Ar-O-S (O) 0^~ such as benzenesulfate and toluenesulfate; xi) alkoxysulfates : AIk-O- S(O)2θ^~ such as methoxy sulfate and ethoxy sulfate; xii) aryloxysulfates : Ar-O-S (0) 2θ^~; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate; the "solvates" represent the hydrates and also the association with linear or branched C₂-C₄ alcohols such as ethanol, isopropanol or n-propanol.

The indolinium-derived disulfide or thiol fluorescent dyes of formula (I) , (II) or (III) as defined above are fluorescent dyes, i.e. are capable of absorbing in the UV radiation or visible range at a wavelength γ_abs of between 250 and 800 nm and capable of re-emitting in the visible range at an emission wavelength γ_em of between 400 and 800 nm.

Preferably, the fluorescent compounds of formula (I) , (II) or (III) of the invention are dyes capable of absorbing in the visible range γ_abs of between 400 and 800 nm and of re-emitting in the visible range γ_em of between 400 and 800 nm. More preferably, the dyes of formula (I) , (II) or (III) are dyes capable of absorbing at a γ_abs of between 420 and 550 nm and of re- emitting in the visible range at a γ_em of between 470 and 600 nm.

The fluorescent compounds of the invention of formula (II) or (III) contain an SY function which may be in the covalent form -S-Y or ionic form -S^~Y⁺ depending on the nature of Y and on the pH of the medium.

A specific embodiment relates to the indolinium-derived disulfide or thiol fluorescent dyes of formula (II) or (III) where Y represents a hydrogen atom or an alkali metal. Advantageously, Y represents a hydrogen atom.

In accordance with another specific embodiment of the invention, in the abovementioned formula (II) or (III) ,

Y is a protecting group known to those skilled in the art, for instance those described in the books

"Protective Groups in Organic Synthesis", T. W. Greene,

John Wiley & Sons Ed., NY, 1981, pp. 193-217; "Protecting Groups", P. Kocienski, Thieme, 3rd Ed.,

2005, Chap. 5. It being understood that Y as protective group cannot constitute with the sulphur atom on which it is linked a disulfide dye i.e. cannot represent a group directly linked to the sulphur atom of formula (II) and (III) via another non oxidized sulphur atom.

Particularly when Y represents a thiol-function- protecting group, Y is chosen from the following radicals :

^■ (Ci-C₄) alkylcarbonyl;

^■ (Ci-C₄) alkylthiocarbonyl;

^■ (Ci-C₄) alkoxycarbonyl;

^■ (Ci-C₄) alkoxythiocarbonyl; ■ (Ci-C₄) alkylthiothiocarbonyl;

^■ (di) (Ci-C₄) (alkyl) aminocarbonyl;

^■ (di) (Ci-C₄) (alkyl) aminothiocarbonyl;

^■ arylcarbonyl such as phenylcarbonyl;

^■ aryloxycarbonyl; ^■ aryl (Ci-C₄) alkoxycarbonyl;

^■ (di) (Ci-C₄) (alkyl) aminocarbonyl such as dimethylaminocarbonyl ;

^■ (Ci-C₄) (alkyl) arylaminocarbonyl; ■ SO₃ , M⁺ with M⁺ representing a cationic counterion such as an alkali metal such as sodium or potassium, or else An^" of formula (II) or (III) and M⁺ are absent;

^■ optionally substituted aryl such as phenyl, dibenzosuberyl or 1, 3, 5-cycloheptatrienyl;

^■ optionally substituted heteroaryl; including in particular the cationic or noncationic heteroaryl comprising from 1 to 4 heteroatoms below: i) monocyclic comprising 5, 6 or 7 members, 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) bicyclic comprising 8 to 11 members, such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazolium, thienocycloheptadienyl, these monocyclic or bicyclic groups being optionally substituted with one or more groups such as (Ci-C₄) alkyl, for instance methyl, or polyhalo (Ci-C₄) alkyl, for instance trifluoromethyl; iii) or tricyclic ABC below:

in which 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, for instance piperidyl or pyranyl; optionally cationic, optionally substituted heterocycloalkyl, 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 di/tetrahydrofuranyl, di/tetrahydrothiophenyl, di/tetrahydropyrrolyl, di/tetrahydropyranyl, di/tetra/hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di/tetra/hexahydroazepinyl or di/tetrahydropyrimidinyl, these groups being optionally substituted with one or more groups such as (Ci-C₄) alkyl, oxo or thioxo; or the heterocycle represents the following group:

in which R'^c, R'^d, R'^e, R'^f, R'^g and R'^h, which may be identical or different, represent a hydrogen atom or a (Ci-C₄) 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 between 1 and 3 inclusive; preferably, R' ^c to R'^h represent a hydrogen atom; and An' ' ' represents a counterion;

^■ isothiouronium; ■ -C(NR'^cR'^d)=N⁺R'^eR'^f; An'"^" with R' ^c, R' ^d, R' ^e and R'^f, which may be identical or different, represent a hydrogen atom or a (Ci-C₄) alkyl group; preferably, R' ^c to R' ^f represent a hydrogen atom; and An'''^" represents a counterion; ■ isothiourea;

-C(NR'^cR'^d)=NR'^e; with R'^c, R' ^d and R' ^e as defined above;

^■ optionally substituted (di) aryl (Ci-C₄) alkyl, such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted with one or more groups in particular chosen from (Ci-C₄) alkyl, (Ci-C₄) alkoxy such as methoxy, hydroxyl, alkylcarbonyl and (di) (Ci-C₄) (alkyl) amino such as dimethy1amino; ■ optionally substituted (di) heteroaryl (Ci-C₄) alkyl, the heteroaryl group is in particular cationic or noncationic, and monocyclic, comprising 5 or 6 members and from 1 to 4 heteroatoms chosen from nitrogen, oxygen and sulfur, such as the groups pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such as 4-pyridyl or 2-pyridyl N-oxide, pyrylium, pyridinium or triazinyl, optionally substituted with one or more groups such as alkyl, particularly methyl, advantageously the (di) heteroaryl (Ci-C₄) alkyl is (di) heteroarylmethyl or (di) heteroarylethyl;

^■ CR¹R²R³ with R¹, R² and R³, which may be identical or different, representing a halogen atom or a group chosen from: - (Ci-C₄) alkyl;

(Ci-C₄) alkoxy; optionally substituted aryl, such as phenyl optionally substituted with one or more groups such as (Ci-C₄) alkyl, (Ci- C4)alkoxy or hydroxyl; optionally substituted heteroaryl, such as thiophenyl, furanyl, pyrrolyl, pyranyl or pyridyl, optionally substituted with a (Ci-C₄) alkyl group; P (Z¹) R' ¹R' ²R'³ with R'¹ and R'², which may be identical or different, representing a hydroxyl, (Ci-C₄) alkoxy or alkyl group, R'³ representing a hydroxyl or (Ci-

C₄) alkoxy group and Z¹ representing an oxygen or sulfur atom;

^■ a sterically hindered cyclic; and

^■ optionally substituted alkoxyalkyl, such as methoxymethyl (MOM) , ethoxyethyl (EOM) or isobutoxymethyl .

According to a specific embodiment, the protected thiol dyes of formula (II) or (III) comprise a group Y i) which is a cationic, aromatic 5- or 6-membered monocyclic heteroaryl group comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1, 2, 4-triazolium, 1, 2, 3-triazolium, 1, 2, 4-oxazolium, 1, 2, 4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, thiepinyl, thiepinium or imidazolium; ii) cationic 8- to 11-membered bicyclic heteroaryl group, such as indolinium, benzoimidazolium, benzoxazolium or benzothiazolium, these monocyclic or bicyclic heteroaryl groups being optionally substituted with one or more groups such as alkyl, for instance methyl, or polyhalo (Ci-C₄) alkyl, for instance trifluoromethyl; iii) or heterocyclic group below:

in which R' ^c and R'^d, which may be identical or different, represent a hydrogen atom or a (Ci-C₄) alkyl group; preferably, R' ^c to R'^d represent a (Ci-C₄) alkyl group such as methyl; and An''' represents an anionic counterion .

In particular, Y represents a group chosen from oxazolium, isoxazolium, thiazolium, isothiazolium, 1 , 2 , 4-triazolium, 1, 2, 3-triazolium, 1, 2, 4-oxazolium, 1, 2, 4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium, benzoimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted with one or more (Ci-C₄) alkyl groups, in particular methyl.

In particular, Y represents an alkali metal or a protecting group such as:

> (Ci-C₄) alkylcarbonyl, such as methylcarbonyl or ethylcarbonyl ;

^ arylcarbonyl such as phenylcarbonyl;

> (Ci-C₄) alkoxycarbonyl; > aryloxycarbonyl;

> aryl (Ci-C₄) alkoxycarbonyl;

> (di) (Ci-C₄) (alkyl) aminocarbonyl such as dimethylaminocarbonyl ;

> (Ci-C₄) (alkyl) arylaminocarbonyl; > optionally substituted aryl, such as phenyl;

^ 5- or 6-membered monocyclic heteroaryl, such as imidazolyl or pyridyl;

^ 5- or 6-membered cationic monocyclic heteroaryl, such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium or imidazolium; these groups being optionally substituted with one or more identical or different (Ci-C₄) alkyl groups, such as methyl;

> 8- to 11-membered cationic bicyclic heteroaryl, such as benzoimidazolium or benzoxazolium; these groups being optionally substituted with one or more identical or different (Ci-C₄) alkyl groups, such as methyl;

> cationic heterocycle of the following formula:

> isothiouronium -C (NH₂) =N⁺H₂; An'"^";

> isothiourea -C(NH₂)=NH; ^ SO₃ , M⁺ with M⁺ representing a cationic counterion such as an alkali metal such as sodium or potassium, or else An^" of formula (II) or (III) and M⁺ are absent.

According to a specific embodiment of the invention, the fluorescent dyes of the invention are disulphide dyes of formula (I) .

In particular, the disulphide fluorescent dyes of formula (I) of the invention are chosen from those of formulae (I_a) , (Ib) and (I_c) :

in which formulae (I_a) , (Ib) and (I_c) :

> Pr P' R¹ to R⁴, B and An are as defined above; > n and m, which may be identical or different, represent an integer between 1 and 6 inclusive, with the sum of n+m being between 2 and 4 inclusive, particularly 2 or 3 for (Ib);

> X represents a radical chosen from: -G-, -G' -C(G)- and -C(G)-G'-, with G and G', which may be identical or different, representing an oxygen or sulphur atom or NR, with R representing a hydrogen atom or a (Ci-Cβ) alkyl group, advantageously X represents a group -NR-, -NR-CO-, -C(O)-NR-, -S(O)₂-, -S(O)₂-NR-; or -NR-S(O)₂-, or -NR-; in particular, X of formula (I₀) is linked at position 5 on A or the X of formula (I_a) is in the para- position of B when B represents a phenyl group;

> T_a represents a σ covalent bond, a group -N(R'_a)-; -N⁺(R¹J (R'b)-, An^"; -C(O)-N(R¹J- or -N(R¹J-C(O)-, or a divalent cationic heteroaryl comprising from 5 to 7 members, such as imidazolium, with R'_a, R'b, which may be identical or different, representing a hydrogen atom or a (Ci-C₄) alkyl radical, An^" representing an anionic counteπon; in particular, T_a represents -C (O) -N (R' _a) - and -N (R' _a) -C (0) - .

By way of example, mention may be made of the fluorescent dyes of formulae (I_a) , (I_b) and (I_c) below:

10

14

15

19

27

30 with An^", which may be identical or different, representing an anionic counterion.

For all the exemplary embodiments, which follow, of preparation of the novel indolinium-derived disulphide or thiol fluorescent dyes of formulae (I) to (III) , those skilled in the art know how to pre-protect the reactive functions such as ketone functions and then to deprotect them for the needs of the synthesis reaction, by the known conventional methods of protection/deprotection such as those described in the books described above by T. W. Greene John Willey & Sons ed., NY, 1981, or P. Kocienski "Protecting Groups", P. Kocienski, Thieme, 3rd ed. 2005.

The protected thiol fluorescent dyes of formula (II-Y) or (III-Y) can be synthesized in two stages. The first stage consists in preparing the nonprotected thiol dye (II-H) or (III-H) according to the methods known to those skilled in the art, for instance "Thiols and organic sulfides", "Thiocyanates and isothiocyanates, organic", Ullmann' s Encyclopedia, Wiley-VCH, Weinheim, 2005. In addition, the second step consists in protecting the thiol function according to the conventional methods known to those skilled in the art in order to produce the protected thiol dyes of formula (II-Y) or (III-Y) . By way of example, for protecting the thiol function -SH of the thiol dye, use may be made of the methods in the books "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.

This method can be illustrated by means of the method consisting i) in generating indolinium-derived thiol fluorescent dyes of formula (II—H) or (III—H) by reduction of an indolinium-derived two-chromophore fluorescent dye bearing a disulfide function -S-S- such as (I') and ii) in protecting said thiol function of (II—H) or (III—H) , according to the conventional methods, with the reactant 1_ Y' R in order to obtain the protected thiol fluorescent dyes of formula (I' ) . The thiol compound (II-H) or (III-H) may also be metallated with an alkali metal or alkaline earth metal Met* so as to produce the thiolate fluorescent dye of formula (II- Met) or (Ill-Met) .

reducing agent reducing agent

(Ul-H)

(H-H)

with Y' representing a thiol-function-protecting group; 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 comprising a thiolate -S^~ function can be associated with 1 Metal²⁺; with R¹ to R⁵, A, B, An^", and p being as defined above; Y' represents a thiol-function-protecting group; and R represents a nucelofuge leaving group, for instance mesylate, tosylate, triflate or halide.

The indolinium-derived styryl thiol fluorescent dyes formed which are converted to -SY' protected thiol fluorescent dyes by protection of the thiol-SH using the conventional protecting groups. The indolinium- derived styryl thiol fluorescent dyes are metalated by also using the 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.

According to another possibility, a protected thiol compound (b) protected with a protecting group Y' as defined above, prepared according to one of the procedures described in the books described above, said protected thiol compound comprising at least one nucleophilic function, can be reacted with a sufficient, preferably equimolar, amount of an indoliium-derived styryl chromophore (a) or (ai) which comprises an electrophilic function so as to form a Σ covalent bond; see below, the preparation of dyes of formulae (II' -Y) and (III' -Y):

Ia₁I (iir-Y)

with R¹ to R⁵, A, B, An and p as defined above; m' and n' are integers between 1 and 6 inclusive with m' + n' being an integer between 2 and 6; JVu representing a nucleophilic group; E representing an electrophilic group; and Σ the linking group generated after attack by the nucleophile on the electrophile .

By way of example, the Σ covalent bonds that can be generated are listed in the table below based on condensation of electrophiles with nucleophiles :

Electrophiles E Nucleophiles Nu Σ Covalent bonds Activated esters* Amines Carboxamides Acyl nitrides** Amines Carboxamides Acyl halides Amines Carboxamides Acyl halides Alcohols Esters Acyl cyanides Alcohols Esters Acyl cyanides Amines Carboxamides Alkyl halides Amines Alkylamines Alkyl halides Carboxylic acids Esters Alkyl halides Thiols Thioesters Alkyl halides Alcohols Ethers Sulfonic acids Thiols Thioethers and salts thereof Sulfonic acids Carboxylic acids Esters and salts thereof Sulfonic acids Alcohols Ethers and salts thereof Anhydrides Alcohols Esters

Anhydrides Amines Carboxamides

Aryl halides Thiols Thioethers

Aryl halides Amines Arylamines

Aziridines Thiols Thioethers

Carboxylic acids Amines Carboxamides

Carboxylic acids Alcohols Esters

Carbodiimides Carboxylic acids N-acylureas

Diazoalkanes Carboxylic acids Esters

Epoxides Thiols Thioethers

Ha1oacetamides Thiols Thioethers

Imide esters Amines Amidines

Isocyanates Amines Ureas

Isocyanates Alcohols Urethanes

Isothiocyanates Amines Thioureas

Maleimides Thiols Thioethers

Sulfonic esters Amines Al kylamines

Sulfonic esters Thiols Thioethers

Sulfonic esters Carboxylic acids Esters

Sulfonic esters Alcohols Ethers

Sulfonyl halides Amines Sul fonamides

*the activated e sters of general formula -CO-Part with Part repre senting a leaving group such as oxysuccinimidyl , oxybenzotriazolyl , aryloxy which i s optional ly substituted; * *the acyl nitrides may rearrange to give i socyanates .

A variant to this process is to use an indolinium- derived styryl chromophore having an electrophilic acrylate function (-OCO-C=C-) on which is carried out an addition reaction that will generate a Σ bond.

It is also possible to use a thiol reactant (α) : Y' -SH comprising a Y' group as defined above, the nucleophilic SH function of which can react with the carbon atom of the radical L in the α-position with respect to the halogen atom borne by an indolinium- derived styryl chromophore of (a' ) or (a' ' 1) so as to give the protected thiol dye of formula (II-Y) or (III- Y) as defined above:

with R¹ to R⁵, A, B, An^", L, p, (II-Y) and (III-Y) as defined above, and Hal representing a nucleofuge halogen atom such as bromine, iodine or chlorine.

More particularly, a nucleofuge leaving group may be replaced with a derivative of a thiourea (S=C(NRR)NRR), so as to generate isothiouroniums; for example, based on chromophores (a' ) or (a' 1) as defined above if the thiourea group is a thioimidazolium (β) , so as to give the dye which is S-protected with an imidazolium group (II' '-Y) or (III' '-Y) :

with (a' ) , (a'l) , R'_c, R'_d, R¹ to R⁵, A, B, L, p, Hal and

An^" as defined above.

Another variant may make it possible to obtain the compound (11''-Y) or (111''-Y) using the cyclic thiourea derivative of imidazoline type (b' ) , followed by alkylation of said imidazole using R'_d-Lg, with Lg being a leaving group such as chloride, bromide, tosylate or mesylate:

with (a' ) , (a⁷!) , R'c, R' d, R¹ to R⁵, A, B, L, p and Gp as defined above.

A variant is to use, in place of the halide comprising the fluorescent chromophore (a' ) or (a' 1) , a chromophore comprising another type of nucleofuge such as tosylate or mesylate.

In accordance with another possibility, certain protected thiol dyes (II' -Y) or (III' -Y) can be obtained by reacting a protected thiol compound with a compound bearing two carboxylic acid functions that are activated, according to the conventional methods (for example, reaction with a carbodiimide or with thionyl chloride) . The resulting product (d) is subsequently reacted with an indolinium-derived styryl chromophore (c) or (cl) , the ketone functions of which are optionally protected beforehand as seen above, and which bears a nucleophilic function, for example of primary or secondary amine type, or of aliphatic alcohol type.

_£,!

with R¹ to R⁵, A, B, An , L, p, n' , m' , E, Nu, (II' -Y) and (III' -Y) as defined above.

Another variant is to use a thiolactone derivative based on specific nucleophilic chromophores (c' ) and (c' i) so as to give the derivatives (II' -H) or (III' -H) comprising a linker L interrupted with an amide function as represented by the scheme below:

With R¹ to R⁵, B, An , L, p, n' , m' as defined above, G' representing an oxygen or sulfur atom or an NR' group with R' representing a hydrogen atom or a alkyl radical, and R representing a hydrogen atom, a Ci-C₄ alkyl radical, a Ci-C₄ hydroxyalkyl radical or an aryl (Ci-C₄) alkyl . The thiolactone derivative is preferably chosen with m' = 3 and G' represents an oxygen atom.

The derivatives (II '-H) or (III '-H) comprising a free SH function may subsequently be protected or metalated as seen above.

In accordance with another possibility, the indolinium- derived styryl thiol fluorescent dyes of formula (II) or (III) according to the invention can be obtained by reaction of a compound comprising a thiol group optionally protected with Y' as defined above and an electrophilic group (e) , with an aryl or heteroaryl derivative comprising an electrophilic group. By way of example, an aldehyde or a thioaldehyde (e) when G' represents an oxygen atom or a sulfur may be condensed with an "activated methylene" derivative such as the methyl indolinium derivative (f) or (f' ) so as to generate an ethylene bond > C=C <. This reaction is commonly known as "Knoevenagel" condensation:

with R¹ to R⁵, B, An^", L, p, G', (H-Y) and (HI-Y) as defined above.

Reference may be made to the book Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4th Ed., John Willey & Sons, 1992 or T. W. Greene "Protective Groups in Organic Synthesis", for further details on the operating conditions used for the processes mentioned above.

The indolinium-derived styryl protected thiol fluorescent dyes can be deprotected by conventional pathways such as those described in the books "Protective Groups in Organic Synthesis", T. W. Greene, John Willey & Sons Ed., NY, 1981; "Protecting Groups", P. Kocienski, Thieme, 3rd Ed., 2005.

The starting reactants are commercially available or accessible by conventional methods known to those skilled in the art. By way of example, mention may be made of the synthesis of the dye (I), and subsequently the reactants (I¹) or (I"), using 2 equivalents of indolinium derivative _(£)_ and one equivalent of disulphide reactant 2 comprising two aryls or heteroaryls B comprising an electrophilic function such as aldehyde or thioaldehyde or an indolinium disulphide reactant comprising an activated methylene 3 comprising with two equivalents of aryl-derived or heteroaryl- derived electrophilic reactant (g¹), so as to give, by double Knoevenagel condensation, the styryl disulphide indolinium derivatives (I) .

with R¹ to R⁴, B, An^", L, p, G' and (I) as defined above .

Another subject of the invention relates to a composition for dyeing keratin fibers with a lightening effect, comprising, in a cosmetic medium, at least one indolinium-derived disulphide, thiol or protected thiol fluorescent dye of formula (I) , (ii) or (III) as defined above. In addition to the presence of at least one fluorescent dye of formula (I) , (II) or (III) , the composition of the invention may also contain a reducing agent.

This reducing agent may be chosen from thiols, for example cysteine, homocysteine or thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid, and also its esters, in particular glyceryl monothioglycolate, and thioglycerol . This reducing agent may also be chosen from borohydrides and derivatives thereof, for instance the salts of borohydride, of cyanoborohydride, of triacetoxyborohydride or of trimethoxyborohydride : sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-n-butylammonium or benzyltriethylammonium) salts; and catechol borane.

The dye composition that can be used in the invention generally contains an amount of dye of formula (I) , (II) or (III) 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 also contain additional direct dyes. These direct dyes are, for example, chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone, in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the natural direct dyes, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenindin. Extracts or decoctions containing these natural dyes, and in particular poultices or henna-based extracts, may also be used.

The dye composition may contain one or more oxidation bases and/or one or more couplers conventionally used for dyeing keratin fibers.

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

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

The coupler (s) is (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 dye composition is (are) in general each 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% by weight .

In general, the addition salts of the oxidation bases and of the couplers that can be used in the context of the invention are in particular chosen from addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and addition salts with a base, such as hydroxides of an alkali metal such as sodium or potassium, aqueous ammonia, amines or alkanolamines . The medium suitable for dyeing, also called dye support, is a cosmetic medium generally constituted of water or of a mixture of water and at least one organic solvent. By way of organic solvent, mention may, for example, be made of Ci-C₄ lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvents, when they are present, are preferably present in proportions of preferably 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. The solvents, including the water, are preferably present in proportions of preferably between 1% and 99% by weight approximately, relative to the total weight of the dye composition, and even more preferably between 5% and 95% by weight approximately.

The dye composition may also contain various adjuvants conventionally used in hair-dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers, or blends thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric associative polymer thickeners, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as, for example, modified or unmodified, volatile or nonvolatile silicones, such as amino silicones, film-forming agents, ceramides, preservatives, opacifiers or conductive polymers. The above adjuvants are in general present in an amount, for each of them, of between 0.01% and 20% by weight relative to the weight of the composition.

Of course, those skilled in the art will take care to select this or these possible additional compounds in such a way that the advantageous properties intrinsically associated with the dye composition in accordance with the invention are not, or are not substantially, impaired by the addition (s) envisaged.

The pH of the dye composition is generally between 3 and 14 approximately, and preferably between 4 and 10 approximately. It may be adjusted to the desired value by means of acidifying or basifying agents normally used in the dyeing of keratin fibers or else by means of conventional buffer systems.

Among the acidifying agents, mention may, by way of example, be made of mineral or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.

Among the basifying agents, mention may, by way of example, be made of aqueous ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines, and also derivatives thereof, sodium hydroxide or potassium hydroxide and the compounds of formula (γ) below:

in which W_a is a propylene residue optionally substituted with a hydroxyl group or a Ci-C₄ alkyl radical; R_ai, R_a2, R_a3 and R_a4, which may be identical or different, represent a hydrogen atom, a Ci-C₄ alkyl radical or a Ci-C₄ hydroxyalkyl radical.

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

Another subject of the invention is a process for dyeing keratin materials, in particular keratin fibers such as dark hair, consisting in applying a dye composition comprising, in a cosmetic medium, at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) as define above to the keratin materials.

According to a specific embodiment, in the process of the invention, the reducing agent may be applied as a pretreatment before the application of the composition containing at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I), (II) or (III) .

This pretreatment may be of short duration, in particular from 1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as mentioned above.

According to another process, the composition comprising at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) also contains at least one reducing agent as defined above. This composition is then applied to the hair.

When an indolinium-derived thiol or protected thiol fluorescent dye of formula (II) or (III) comprises a thiol-function-protecting group Y, the process of the invention may be preceded by a deprotection step aimed at restoring the SH function in situ.

By way of example, it is possible to deprotect the S-Y function of the dyes of the invention with a Y protecting group by adjusting the pH as follows:

The deprotection step can also be carried out during a hair pretreatment step, for instance reducing pretreatment of the hair.

According to one variant, the reducing agent is added to the dye composition containing at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) at the time of use. Advantageously, the reducing agent is added to the dye composition containing at least one fluorescent dye of formula (I) .

According to another process, the composition comprising at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula

(I) , (II) or (III) also contains at least one reducing agent as defined above. This composition is then applied to the hair. In particular, the composition containing at least one dye of formula (I) , also contains a reducing agent.

According to another variant, the reducing agent is applied as a post-treatment, after the application of the composition containing at least one indolinium- derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) . In particular, when the composition contains at least one fluorescent dye of formula (I) , the reducing agent is applied as a post-treatment. The duration of the post-treatment with the reducing agent may be short, for example from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above. According to a specific embodiment, the reducing agent is an agent of thiol or borohydride type as described above .

A specific embodiment of the invention relates to a process in which the indolinium-derived thiol or protected thiol fluorescent dye of formula (II) or (III) can be applied directly to the hair without reducing agents, free of reducing pretreatment or reducing post-treatment.

A treatment with an oxidizing agent may optionally be combined. Any type of oxidizing agent conventional in the field may be used. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred. The duration of the possible post-treatment with an oxidizing agent is between 1 second and 40 minutes. It is preferably between 1 and 10 minutes.

The application of the dye composition according to the invention is generally carried out at ambient temperature. It may, however, be carried out at temperatures ranging from 20 to 180⁰C.

A subject of the invention is also a multicompartment dyeing device or dyeing "kit" in which a first compartment contains a dye composition comprising at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or

(III) and a second compartment contains a reducing agent capable of reducing the disulfide functions of keratin fibers and/or of the indolinium fluorescent dye of formula (I) .

One of these compartments may also contain one or more other dyes of direct dye or oxidation dye type.

The invention also relates to a multicompartment device in which a first compartment contains a dye composition comprising an indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) ; a second compartment contains a reducing agent capable of reducing the disulfide bond of keratin fibers and/or of the indolinium-derived disulfide fluorescent dye of formula (I) ; a third compartment contains an oxidizing agent.

Alternatively, the dyeing device contains a first compartment containing a dye composition which comprises at least one indolinium-derived protected thiol fluorescent dye of formula (II) or (III) , a second compartment containing an agent capable of deprotecting the protected thiol so as to free the thiol, and optionally a third compartment comprising an oxidizing agent.

Each of the devices mentioned above may be equipped with a means for delivering the desired mixture to 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 dyes of the examples hereinafter have been entirely characterized by conventional spectroscopic and spectrometric methods.

EXAMPLES

Example 1 : Synthesis of 2, 2 ' -{disulphanediylbis [ethane- 2 , 1-diyl (methylimino) -4 , l-phenyleneethene-2 , 1- diyl] }bis (1, 3, 3-trimethyl-3H-indolium) dichloride [1]

[1]

Synthesis scheme :

[1]

Procedure : Stage 1: 4, 4 ' -{disulphanediylbis [ethane-2, 1-diyl- (methylimino) ] }dibenzaldehyde

82.3 g of phosphorus oxychloride are added to 500 ml of DMF at 0⁰C. After stirring for 30 minutes at 0⁰C, a solution of 47 g of JV, JV'- (disulphanediyldiethane-2, 1- diyl) bis (N-methylaniline) is added dropwise. The mixture is stirred at 0⁰C for 90 min and then at 10⁰C for 75 min and at 40⁰C for 105 min. It is subsequently poured into 2.5 1 of ice-cold water, and 700 ml of 5N sodium hydroxide are added. The yellow precipitate obtained is filtered off over celite and solubilized in 200 ml of dichloromethane and the solution obtained is washed with 200 ml of a saturated aqueous solution of sodium chloride. After drying over magnesium sulphate and evaporation of the dichloromethane, the yellow residue (80 g) is purified by silica gel chromatography. After drying, a light yellow powder is recovered. The analyses indicate that the product is in conformity with the expected structure.

Stage 2: Synthesis of 2, 2 ' -{disulphanediylbis [ethane- 2, 1-diyl (methylimino) -4, l-phenyleneethene-2 , 1-diyl] }- bis (1, 3, 3-trimethyl-3H-indolium) chloride [1]

4 g of 4 '-{ disulphanediylbis [ethane-2 , 1-diyl (methylimino) ] jdibenzaldehyde and 3.9 g of 1, 3, 3-trimethyl-2- methyleneindoline are mixed in 30 ml of methanol and then 5 ml of 5N hydrochloric isopropanol are added dropwise. After stirring for two hours at ambient temperature, the mixture is brought to 60⁰C for 2 h, 2 g of 1, 3, 3-trimethyl-2-methyleneindoline are added, and the stirring is maintained at 60⁰C for 2 h. Once cooled, the mixture is poured into 500 ml of ethyl acetate, and the resulting mixture is filtered and dried. The product is then purified by liquid/liquid water/butanol/tert-butyl methyl ether chromatography. 2.67 g of black powder are recovered after concentration and drying under vacuum. The analyses show that the product is in conformity.

¹H NMR (CD₃OD, multiplicity, proton number): 1.8 ppm, s,

12H; 3.05 ppm, t, 4H; 3.22 ppm, s, 6H; 3.92 ppm, t, 4H;

3.99 ppm, s, 6H; 6.97 ppm, d, 4H; 7.25 ppm, d, 2H; 7.54 ppm, 2m, 4H; 7.65 ppm, 2m, 4H; 7.96 ppm, d, 4H; 8.3 ppm, d, 2H

FIA/MS: The expected dication [C₄₄H₅₂N₄S₂J²⁺ is principally detected at m/z, ESP+=350.6. Example 2 : Synthesis of 5-chloro-2- (2-{2- [ (15-{2- [-2- (5-chloro-l, 3, 3-trimethyl-3H-indolium-2-yl) vinyl] - phenyl}-4, 4, 11, ll-tetramethyl-7, 8-dithia-15-aza-4, 11- diazoniahexadec-1-yl) (methyl) amino] phenyl}vinyl) -1,3,3- trimethyl-3H-indolium tetrabromide [2]

Synthesis scheme : [2]

Br

Procedure :

Stage 1 : Synthesis of 2- [ [3- (dimethylamino) propyl] (methyl) amino] benzaldehyde 1.75 ml of N, N, N' -trimethyl-1 , 3-propanediamine, 1 ml of 2-fluorobenzaldehyde and 1.45 g of potassium carbonate are stirred at 130⁰C for 16 h in 10 ml of dimethyl sulphoxide. After cooling to 75°C, 15 ml of water are added, and the mixture is conserved at 40⁰C for 3 h and then extracted with 3 times 25 ml of ethyl acetate. The ethyl acetate phases are combined, washed with three times 25 ml of water then 25 ml of a saturated solution of sodium chloride, dried over magnesium sulphate, and concentrated under vacuum. 2 g of a reddish-brown oil are recovered. The analyses show that the product is in conformity with the expected structure.

Stage 2: Synthesis of N, N' - (disulphanediyldiethane-2, 1- diyl)bis{3-[ (2-formylphenyl) (methyl) amino] -N, N- dimethylpropan-1-aminium} dibromide

1.4 g of 2, 2 ' -disulphanediylbis (1-bromoethane) and 2.64 g of 2- [ [3- (dimethylamino) propyl] -

(methyl) amino] benzaldehyde are heated at 80⁰C for

2.5 h. After distillation of the acetonitrile under vacuum, the mixture is diluted in 5 ml of methanol and the resulting mixture is mixed with 150 ml of ethyl acetate. The solid obtained is reprocessed by dispersion in 15 ml of methanol and then mixing in 150 ml of ethyl acetate. The mother liquors are combined and concentrated under vacuum, 70 ml of ethyl acetate are added to the residue and the mixture is brought to reflux. Methanol is added until there is complete dissolution under hot conditions, and the mixture is cooled. The precipitate that has been filtered off is combined with the first solid; 2.28 g of yellow solid are recovered. The analyses show that the product is in conformity with the expected structure .

Stage 3: Synthesis of 5-chloro-2- (-2-{2- [ (15-{2- [2- (5- chloro-1, 3, 3-trimethyl-3H-indolium-2-yl) vinyl] phenyl}- 4, 4, 11, ll-tetramethyl-7, 8-dithia-15-aza-4, 11-diazonia- hexadec-1-yl) (methyl) amino] phenyl}vinyl) -1,3,3- trimethyl-3H-indolium tetrachloride [2]

1.77 g of N, N ' - (disulphanediyldiethane-2, 1-diyl) bis { 3- [ (2-formylphenyl) (methyl) amino] -N, N-dimethylpropan-1- aminium} dibromide and 2 g of 5-chloro-l, 2, 3, 3- tetramethyl-3H-indolium are mixed for 18 h at ambient temperature in 150 ml of methanol. 443 mg of 5-chloro- 1, 2, 3, 3-tetramethyl-3H-indolium are added and the stirring is maintained for 6 h. The product is purified in several stages by sephadex column chromatography and the pure fractions collected are loaded onto an ion exchange resin (Dowex - chloride) and eluted with water. After lyophilization, 1.6 g of dark red powder are recovered. The analyses show that the product is in conformity with the expected structure.

Example 3 : synthesis of 2, 2 ' -{disulfanediylbis [ethane- 2, 1-diylimino (2-oxoethane-2, 1-diyl) (2-methyl-lH-indole- 1, 3-diyl) ethene-2, 1-diyl] }bis (1, 3, 3-trimethyl-3ff- indolium) dichloride [3]

2 Cf Synthesis scheme: [3]

tBuOK

[3]

Procedure :

Stage 1 : Synthesis of N, N'- (disulfanediyldiethane-2, 1- diyl) bis [2- (3-formyl-2-methyl-lH-indol-l-yl) acetamide]

10.43 g of 2-methyl-lH-indole-3-carbaldehyde are solubilized in 80 mL DMSO at room temperature, 7.8 g potassium tertiobutylate are added to the solution and the resulting mixture is heated at 100⁰C then cooled back to room temperature. A solution of 10 g of N, N'-

(disulfanediyldiethane-2, l-diyl)bis (2-chloroacetamide) in 80 mL DMSO is added. After stirring for 3h, the mixture is poured on 1.5L water, pH brought to 6.8 by addition of IN aqueous hydrochloric acid 150 mL of saturated aqueous sodium chloride solution are added. The resulting precipitate is washed three times with 100 mL water, twice with 100 mL diethyl ether. It is dried, washed with acetone at room temperature, stirred in 100 mL refluxing acetone for Ih, cooled and filtered after 1 day, washed again twice with 50 mL acetone. 9.47 g of solid are obtained. Analyses are in accordance with the expected structure. The product is used for following steps without further purification

Stage 2 : synthesis of 2, 2 ' -{disulfanediylbis [ethane- 5 2, 1-diylimino (2-oxoethane-2, 1-diyl) (2-methyl-lH-indole- 1, 3-diyl) ethene-2, 1-diyl] }bis- (1, 3, 3-trimethyl-3tf- indolium) dichloride [3]

0.55g of N, N'- (disulfanediyldiethane-2, 1-diyl) bis [2- (3- 10 formyl-2-methyl-lH-indol-l-yl) -acetamide] and 0.52 g of 1, 3, 3-trimethyl-2-methylidene-2, 3-dihydro-lH-indole are mixed in 10 mL ethanol and 5 mL N-methylpyrrolidinone (NMP) . After 10 min. 0.5 mL of hydrochloric acid in isopropanol is added and the mixture is stirred for 15 24h. It is then poured on 100 mL acetone. The resulting solid is filtered, washed with acetone and dried (626 mg - red orange powder) . Analyses are in accordance with the expected structure LCMS m/z = 431.8 (dication) λ_max : 472 nm. 20

Exemple 4 : Synthesis of 5, 5 '- [disulfanediylbis- (ethane- 2, 1-diylcarbamoyl) ] bis {2- [2-{4- [bis (2-hydroxyethyl) - amino] phenyl}ethenyl] -1, 3, 3-trimethyl-3H-indolium}bis methylsulfate

„ i- 2 MeOSO₃-

Synthesis scheme: [4]

^SNH,

^DIPEA

2 MeOSO₃-

[4]

Procedure :

Stage 1 : synthesis of N, N' - (disulfanediyldiethane-2, 1- diyl)bis (2,3, S-trimethyl-Sff-indole-S-carboxamide)

10 g of 2, 3, S-trimethyl-S-ff-indole-S-carboxylic acid (containing one molar equivalent of ammonia) were dispersed in 50 mL N-methyl-pyrrolidinone (NMP) . 9.07 g of carbonyldiimidazole were progressively added to the mixture (pH : 7) . 5.04 g of cystamine dichlorhydride and 7 mL diisopropylethylamine (DIPEA) (pH 9-10) were added. Apres 24 h stirring at room temperature, the reaction mixture was purified by chromatography. 2.2 g of yellowish oil were recovered. Analyses were in accordance with the expected structure. LCMS : m/z : 523 (M+l) ; 262 (M+2/2, double protonation] NMR ¹H (400 MHz, ppm, DMSO-d₆) : 1.29 (s, 12H) , 2 . 30 ( s , 6H) , 3 . 02 ( t , 4H) , 3 . 83 ( dt , 4H) , 7 . 03 ( t , 2H) , 7 . 52 ( d, 2H) , 7 . 77 ( dd, 2H) , 7 . 84 ( d, 2H) .

Stage 2 : synthesis of 5, 5 '- [disulfanediylbis (ethane- 2, 1-diylcarbamoyl) ] -bis (1, 2, 3, 3-tetramethyl-3H- indolium) ]bis methylsulfate

2 g of N, N¹- (disulfanediyldiethane-2, 1-diyl) bis (2, 3, 3- trimethyl-3iϊ-indole-5-carbox-amide) and 5 mL of dimethylsulfate were dispersed in 10 mL d' acetonitrile and heated at 140 ⁰C for 30 min. in a microwave apparatus. The resulting mixture was poured in 50 mL acetone and the solid was filtered, washed with acetone and dried under vaccum (1.39 g, pale pinkish powder) . The resulting product was used as such for following steps .

Stage 3 : of 5, 5 '-[disulfanediylbis (ethane-2, 1-diyl- carbamoyl) ]bis{2-[2-{4- [bis (2-hydroxyethyl) amino] - phenyl}ethenyl] -1, 3, 3-trimethyl-3ff-indolium}bis methylsulfate

100 mg of 5, 5 '- [disulfanediylbis (ethane-2, 1- diylcarbamoyl) ] bis (1, 2, 3, 3-tetramethyl-3iϊ-indolium) ] bis methylsulfate obtained as described above were mixed with 100 mg 4- [bis (2-hydroxyethyl) amino] - benzaldehyde in 4 mL isopropanol for 48 h at 50 ⁰C. The resulting mixture was poured on 25 mL acetone and triturated. The dark powder was filtered and washed with acetone. A hygroscopic black powder (132 mg) was collected.

Analyses were in accordance with the expected structure . LCMS : m/z : 467.5 (dication) λ_max : 560 nm.

Exemple 5 : Synthesis of 5,5'- [disulfanediylbis (ethane- 2, 1-diylcarbamoyl) ] -bis {2- [2-{4- [bis (2-hydroxyethyl) - amino] phenyl}ethenyl] -1, 3, 3-trimethyl-3ff-indolium}bis methylsulfate

Synthesis

MeOSO₃-

100 mg of 5, 5 '- [disulfanediylbis (ethane-2, 1- diylcarbamoyl) ] bis (1, 2, 3, 3-tetramethyl-3H-indolium) ] bis methylsulfate obtained as described above were mixed with 100 mg [ (4-formylphenyl) (methyl) amino] acetic acid in 4 mL isopropanol for 48h at 50⁰C. The resulting mixture was poured on 25 mL acetone and triturated, filtered and washed with acetone. A dark dull red solid

(134 mg) was collected.

Analyses were in accordance with the expected structure.

LCMS : m/z : 451.4 (dication) lambda_max : 544 nm.

Exemple 6 Synthesis 5,5'- [disulfanediylbis (ethane-

2, 1-diylcarbamoyl) ] -bis {2- [2- (9-ethyl-9H-carbazol-3- yl) ethenyl] -1, 3, 3-trimethyl-3H-indolium}bis methylsulfate

MeOSO₃- Reaction scheme :

2 MeOSO₃-

Procedure :

100 mg of 5, 5 ' - [disulfanediylbis (ethane-2, 1-diyl- carbamoyl) ] bis (1, 2, 3, 3-tetramethyl-3iϊ-indolium) ] bis methylsulfate obtained as described above were mixed with 100 mg 9-ethyl-9iϊ-carbazole-3-carbaldehyde in 4 mL isopropanol for 48 h at 50 ⁰C. The resulting mixture was poured on 25 mL acetone and triturated, filtered and washed with acetone. A dark red powder was collected (70 mg) .

Analyses were in accordance with the expected structure .

LCMS : m/ z : 4 8 1 . 6 ( di cat i on ) : λ_max : 50 6 nm .

DYEING EXAMPLE

Dyeing process - compounds [1] and [2]

Preparation of a composition A

5^χlO^"4

Compound [1] or [2] mol%

Benzyl alcohol 4 g

Polyethylene glycol 6 EO 6 g

Hydroxyethy1cellulose 0 7 g

Alkylpolyglucoside in an aqueous

4 5 g solution containing 65% AM Demineralized water qs lOOg

Preparation of a composition B

Thioglycolic acid IM

Sodium hydroxide qs pH 8.5

Demineralized water qs lOOg

At the time of use, compositions A (9 ml) and B (1 ml) are mixed, then the formulations are applied to locks of natural white hair containing 90% white hairs (NW) , permanent-waved white hair (PW) or chestnut-brown hair having a tone height of 4 (TH4) . The leave-in time is 20 minutes at ambient temperature AT.

After rinsing with running water, a fixer (Dulcia Vital II®) diluted 10-fold with water is applied for 5 minutes at AT. After rinsing with running water and shampooing, the locks are air-dried. During the shampooing operations, there is no visible bleeding of the color; the shampoo foam and the rinsing water are uncolored.

(i) Dyeing

Optical lightening:

Coloring of the hair thus treated with dye 1, 2 or 3 is observed. The TH4 dark locks became visibly lighter than untreated control locks.

Dyeing of white locks:

The natural white NW hair and the permanent-waved white

PW hair are colored fuchsia.

ii) Fastness with respect to successive shampooing operations :

The locks treated are divided into two, half are subjected to 5 successive shampooing operations according to a cycle which comprises wetting the locks with water, washing with a conventional shampoo, rinsing with water, followed by drying.

During the shampooing operations, there is no visible bleeding of the color; the shampoo foam and the rinsing water are not colored. The color observed remains visible on the TH4, NW and PW hair thus treated.

Claims

1. A fluorescent dye of formula (I), (II) or (III)

the organic or mineral acid salts, optical isomers and geometric isomers thereof, and the solvates such as hydrates: in which formulae (I) , (II) and (III) :

^ p or p' represent an integer between 0 and 4 inclusive;

> R¹ represents a halogen atom, or a (Ci-C₆) alkyl,

(Ci-C₆) alkoxy, (Ci-C₆) alkylthio, (di) (Ci-C₆) (alkyl) - amino, (Ci-C₆) polyhaloalkyl, hydroxyl, (Ci-C₆)poly- hydroxyalkyl, polyhydroxy (Ci-C₆) alkoxy, cyano, R-G-C(G')-, R-C (G') -G-, R' S (O) ₂-N (R) - or RR' N-S (O)₂- group with G or G', which may be identical or different, representing an oxygen or sulphur atom or a group NR' , and R and R' , which may be identical or different, representing a hydrogen atom or a (Ci-C₆) alkyl group;

^ R² and R³, which may be identical or different, represent a (Ci-C₆) alkyl group; in particular, R² and R³ are identical and represent a methyl group;

> R⁴ and R⁵ represent an alkyl or aryl (Ci-C₆) alkyl group, it being understood that R⁴ represents a σ bond when the radical -L-S- of the disulphide dye of formula (I) is linked to R⁴; > B represents an optionally substituted aryl or optionally substituted heteroaryl group;

> L represents an optionally substituted Ci-C₂O divalent hydrocarbon-based chain which is optionally interrupted and/or optionally terminated at one or the other of its ends i) with one or more divalent groups or combinations thereof chosen from: -N(R_a)-; -N⁺ (R_a) (R_b) -, An'^"; -O-, -S-, -C(O)- and -S(O)₂- with R_a and R_b, which may be identical or different, chosen from hydrogen, and a (Ci-Cβ) alkyl, hydroxy (Ci-Cβ) alkyl or

(di) (Ci-Cβ) (alkyl) amino (Ci-Cβ) alkyl radical, and An^" representing an anionic counterion, or ii) with a cationic heterocycle or cationic heteroaryl Het⁺, An^", with An'^" as defined above and Het⁺ representing a saturated or unsaturated heterocycle comprising from 5 to 10 members or a heteroaryl comprising from 5 to 10 members;

> Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N⁺R⁰¹R^R⁷R⁵, or a phosphonium group: P⁺R^αR^βR^γR^δ, with R^α, R^β, R^γ and R^δ, which may be identical or different, representing a hydrogen atom or a (Ci-C₄) alkyl group, or v) a thiol- function-protecting group;

^ An^" represents an anionic counterion; it being understood that: when p is between 2 and 4, the groups R¹ are identical or different, - when p' is between 2 and 3, the groups R¹ are identical or different, when the dye of formula (II) contains a group Y representing a hydrogen atom or an alkali metal, then the radical L cannot represent a divalent C₂-C₄ hydrocarbon-based chain, the chain -L-S- is linked to the indolinium- derived chromophore of formula (I) in particular via A, R⁴ or B, formula (I), (II) or (III) may contain other anionic counterions so as to achieve electro- neutrality.

2. The fluorescent dye of formula (II) or (III) as claimed in the preceding claim, in which Y represents a hydrogen atom or an alkali metal.

3. The fluorescent dye of formula (II) or (III) as claimed in claim 1, in which Y represents a protecting group.

4. The fluorescent dye of formula (II) or (III) as claimed in the preceding claim, in which Y represents a protecting group chosen from the following radicals:

• (Ci-C₄) alkylcarbonyl;

• (Ci-C₄) alkylthiocarbonyl;

• (Ci-C₄) alkoxycarbonyl;

• (Ci-C₄) alkoxythiocarbonyl; • (Ci-C₄) alkylthiothiocarbonyl;

• (di) (Ci-C₄) (alkyl) aminocarbonyl;

• (di) (Ci-C₄) (alkyl) aminothiocarbonyl;

• arylcarbonyl;

• aryloxycarbonyl; • aryl (Ci-C₄) alkoxycarbonyl;

• (di) (Ci-C₄) (alkyl) aminocarbonyl;

• (Ci-C₄) (alkyl) arylaminocarbonyl;

• carboxyl;

• SC>₃ ^~; M⁺ with M⁺ representing an alkali metal or else An^" of formula (II) or (III) and M⁺ are absent;

• optionally substituted aryl;

• optionally substituted heteroaryl;

• optionally cationic, optionally substituted heterocycloalkyl,

• the following group:

in which R'^c, R'^d, R'^e, R'^f, R'^g and R'^h, which may be identical or different, represent a hydrogen atom or a (Ci-C₄) 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 between 1 and 3 inclusive;

■ isothiouronium; ■ -C(NR'^cR'^d)=N⁺R'^eR'^f; An'"^" with R'^c, R'^d, R'^e and R'^f, which may be identical or different, representing a hydrogen atom or a (Ci-C₄) alkyl group and An'''^" being as defined above;

■ isothiourea; ■ -C (NR'^cR'^d)=NR'^e; with R'^c, R'^d and R'^e as defined above;

■ optionally substituted (di) aryl (Ci-C₄) alkyl;

■ optionally substituted (di) heteroaryl (Ci- C₄) alkyl; ■ -CR¹R²R³ with R¹, R² and R³, which may be identical or different, representing a halogen atom or a group chosen from:

(Ci-C₄) alkyl;

(Ci-C₄) alkoxy; - optionally substituted aryl; optionally substituted heteroaryl;

P (Z¹) R' ¹R' ²R'³ with R'¹ and R'², which may be identical or different, representing a hydroxyl, (Ci-C₄) alkoxy or alkyl group, R'³ representing a hydroxyl or (Ci-C₄) alkoxy group, and Z¹ representing an oxygen or sulfur atom;

■ a sterically hindered cyclic group; and

■ optionally substituted alkoxyalkyl.

5. The fluorescent dye of formula (I) as claimed in any one of the preceding claims, in which Y represents an alkali metal or a protecting group chosen from: > (Ci-C₄) alkylcarbonyl;

> arylcarbonyl;

> (Ci-C₄) alkoxycarbonyl;

> aryloxycarbonyl;

> aryl (Ci-C₄) alkoxycarbonyl; > (di) (Ci-C₄) (alkyl) aminocarbonyl;

> (Ci-C₄) (alkyl) arylaminocarbonyl;

> optionally aryl;

> 5- or 6-membered cationic monocyclic heteroaryl optionally substituted with one or more (Ci- C₄) alkyl groups which may be identical or different;

> 8- to 11-membered cationic bicyclic heteroaryl optionally substituted with one or more (Ci- C₄) alkyl groups which may be identical or different;

> cationic heterocycle of the following formula:

> isothiouronium;

> -C (NH₂) =N⁺H₂; An'''^"; with An'''^" representing an anionic counterion;

> isothiourea;

> -C(NH₂)=NH; and

^ Sθ₃ ^~; M⁺ with M⁺ representing an alkali metal or else An^" of formula (II) or (III) and M⁺ are absent.

6. The disulphide fluorescent dye of formula (I) as claimed in claim 1, chosen from those of formulae (I_a), (I_b) and (I_c) :

in which formulae ( I_a) , ( I_b) and ( I_c) :

> Pr P' , R¹ to R⁴ , B and An^" are as def ined in claim 1 ;

> n and m, which may be identical or different, represent an integer between 1 and 6 inclusive, with the sum of n+m being between 2 and 4 inclusive;

> X represents a radical chosen from: -G-, -G' -C (G) - and -C(G)-G'-, with G and G', which may be identical or different, representing an oxygen or sulphur atom or NR, with R representing a hydrogen atom or a (Ci-Cβ) alkyl group, advantageously X represents a group -NR-, -NR-CO-, -C(O)-NR-, -S(O)₂-, -S(O)₂-NR-; or -NR-S(O)₂-, or -NR-;

> T_a represents a σ covalent bond, a group -N(R'_a)-; -N⁺(R'_a) (R'_b)-, An^"; -C (0) -N (R' _a) - or -N (R' _a) -C (0) -, or a divalent cationic heteroaryl comprising from

5 to 7 members, such as imidazolium, with R' R' b/ which may be identical or different, representing a hydrogen atom or a (Ci-C₄) alkyl radical, An^" representing an anionic counterion.

7. The fluorescent dye of formulae (I), (I_a) , (Ib) and (I_c) and (II) as claimed in any one of the preceding claims, chosen from the following dyes:

10

15

19

27

30 with An , which may be identical or different, representing an anionic counterion.

A dye composition comprising, in a suitable cosmetic medium, at least one fluorescent dye of formula (I) , (II) or (III) as defined in any one of claims 1 to 7.

The dye composition as claimed in the preceding claim, comprising, in a suitable cosmetic medium: o at least one fluorescent dye of formula (I) , (II) or (III) as defined in any one of claims 1 to 7; o and at least one reducing agent.

10. A process for dyeing keratin fibers, in which a suitable dye composition comprising at least one fluorescent dye of formula (I) , (II) or (III) as defined in any one of claims 8 or 9 is applied to the materials.

11. The process for dyeing keratin materials as claimed in the preceding claim, wherein the keratin materials are dark keratin fibers having a tone height of less than or equal to 6.

12. The process as claimed in any one of claims 10 or 11, comprising an additional step consisting in applying an oxidizing agent to the keratin fibers.

13. A multicompartment device in which a first compartment contains a dye composition comprising a fluorescent dye of formula (I) , (II) or (III) as defined in claims 1 to 7, and a second compartment contains a reducing agent.

14. The use of fluorescent dyes of formula (I), (II) or (III) as defined in claims 1 to 7, for dyeing human keratin fibers, in particular dark human keratin fibers especially having a tone height of less than 6.

15. The use as claimed in the preceding claim, for lightening dark keratin fibers especially having a tone height of less than 6.