WO2009037350A2 - DIKETOPYRROLO[3,4-c]PYRROLE THIOL/DISULFIDE DYE, COMPOSITION COMPRISING THIS DYE, PROCESS FOR LIGHTENING KERATIN MATERIALS USING THIS DYE - Google Patents

Abstract

The invention relates to the dyeing of keratin materials using diketopyrrolo [3, 4-c] pyrrole thiol and disulfide dyes. The invention relates to a dye composition comprising a diketopyrrolo [3, 4-c] pyrrole chromophore thiol or disulfide dye and to a dyeing process with a lightening effect on keratin materials, in particular keratin fibers, especially human keratin fibers, such as the hair, using said composition. It similarly relates to novel diketopyrrolo [ 3, 4-c] pyrrole 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

DIKETOPYRROLO [3, 4-C]PYRROLE THIOL/DISULFIDE DYE,

COMPOSITION COMPRISING THIS DYE, PROCESS FOR LIGHTENING

KERATIN MATERIALS USING THIS DYE

The invention relates to the dyeing of keratin materials using diketopyrrolo [3, 4-c] pyrrole thiol and disulfide 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 triarylmethane type.

It is also known practice to use, in patent application WO 01/062759, disubstituted diketopyrrolo [3, 4-c] pyrrole dyes for dyeing keratin fibers; however, the colorings do not have satisfactory fastness with respect to outside agents.

Moreover, the coloring of keratin fibers using conventional direct dyes does not make it possible to significantly lighten keratin fibers.

The lightening of the color of keratin fibers, more particularly 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, especially 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, especially the hair, 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 FR2830189 and WO 2004/091473, makes it possible to retain the quality of the keratin fiber during the treatment.

In order to increase the fastness of direct colorings, it is known practice to use disulfide dyes, in particular azo-imidazolium dyes in patent applications WO 2005/097051 or EP 1647580 for direct dyeing of light keratin fibers. Another patent application WO 2005/0395 concerns formulations containing at least a pyrrolopyrrole derivative pigment for making-up, among other things, keratin fibres such as human hair. This document does not disclose any pyrrolopyrrole with thiol, protected thiol or disulfide functions. Moreover, none of those documents mentions the problem of lightening keratin fibers without the use of chemical oxidation agents.

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

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 diketopyrrolo [3, 4-c] pyrrole disulfide or thiol dye, chosen from the dyes of formula (I) :

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

in which formula (I) :

> n represents 1 or 2 ;

> m represents 0 or 1 ;

> R¹ represents a hydrogen atom or an optionally substituted (Ci-Cs) alkyl group;

> R² represents an optionally substituted aryl group, such as a phenyl group optionally substituted in particular with a halogen atom;

> R³ represents a hydrogen atom, an optionally substituted (Ci-Cs) alkyl group, or an optionally substituted aryl group, such as a phenyl group optionally substituted in particular with a halogen atom, particularly in the para-position;

> L represents a linear or branched, Ci-C₂O, preferably C₂-Cs, divalent hydrocarbon-based chain which is optionally substituted and optionally interrupted i) with one or more divalent groups or combinations thereof chosen from: -N(R)-; -N⁺(R) (R⁰)- An^"; -O-; -S-; -C(O)-; and -S(O)₂-, with R, R°, which may be identical or different, chosen from a hydrogen, and a Ci-C₄ alkyl, hydroxyalkyl or aminoalkyl radical, and An^" representing an anionic counterion, or ii) with a cationic heterocycle Heti⁺ An^", with An^" as defined above and Heti⁺ representing a saturated or unsaturated, optionally aromatic heterocycle comprising from 5 to 10 members, such as imidazolium, pyridinium, piperazinium, piperidinium, pyrrolidinium, benzoimidazolium, thiazolium, triazolium, pyrimidinium, pyrazinium, pyridazinyl, pyridazinium or imidazolium;

> Z represents: i) a σ covalent bond or ii) an optionally substituted cationic heteroaryl group comprising at least one nitrogen atom Het₂ ⁺ An^"; in particular, Het₂ ⁺ represents a heteroaryl comprising from 5 to 10 members and from 1 to 3 nitrogen atoms, such as pyridinium, An'^", pyrazinium An'^", pyrimidinium An'^", pyridazinium An'^", quinolinium An'^", isoquinolinium An'^", naphthyridinium An^", quinoxalinium An^", quinazolinium An^", cinnolinium An^", with An'^" representing an anionic counterion; more particularly, Het₂ ⁺ represents a pyridinium group;

^ Y represents : i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N⁺R⁰¹R^R⁷R⁵, An''^" or a phosphonium group: P⁺R^αR^βR^γR^δ, An"^" 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, and An''- representing an anionic counterion; or v) a thiol- function-protecting group; it being understood that:

- when n is 2, then m is zero, and when n is 1, then m is 1 ; - when the radical R of formula (I) is on Ni, then the chain -Z-L-S- (Y) _m is attached on the carbon atom at position 5, and when the radical R³ is attached on the carbon atom at position 5, then the chain is on the nitrogen atom Ni; - when the radical Z of formula (I) represents a σ covalent bond, the group L is on the nitrogen atom Ni and the radical R³ represents an optionally substituted aryl group;

- when the radical Z of formula (I) represents a group Het2⁺ An^", the radical Z is on the carbon atom at position 5 and the radical R³ is on the nitrogen atom Ni and represents a hydrogen atom or an optionally substituted (Ci-Cs) alkyl group.

Another subject of the invention is a dye composition comprising, in a suitable cosmetic medium, at least one diketopyrrolo [3, 4-c] pyrrole disulfide or thiol dye of formula (I) as defined above, and optionally a reducing agent .

A subject of the invention is also novel diketopyrrolo [3, 4-c] pyrrole disulfide or thiol dyes of formula (I) 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. This process also makes it possible to dye bleached keratin fibers in a strong, relatively unselective, homogeneous and chromatic manner.

Furthermore, the process of the invention makes it possible to obtain a coloring of keratin materials, in particular human keratin fibers, especially the hair, without damaging said material, which is persistent with respect to shampooing operations, common attacks

(sunlight, perspiration) and other 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.

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) . 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 7.

Preferably, the composition should, after application to hair, for example chestnut-brown 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; • an optionally cationic 5- or 6-membered heteroaryl radical, preferably imidazolium, optionally substituted with a Ci-C₄ alkyl radical, preferably methyl; . 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,

. -NR-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 Ci-C₄ alkyl radical optionally bearing at least one hydroxyl group;

• R' S (O) 2-NR- in which the R radical represents a hydrogen atom or a Ci-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 Ci-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; . Ci-C₄ alkoxy;

• C2-C4 (poly) hydroxyalkoxy;

• a C1-C2 alkylthio radical;

• RC (O) -NR' - 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 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, Ci-Ciβ, 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; 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)₂θH 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 CH₃COOH; 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- 0-S(0)0^~ such as methyl sulfate and ethyl sulfate; x) arylsulfates : Ar-O-S (O)O^" 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 Ci-C₄ alcohols such as ethanol, isopropanol or n-propanol.

The diketopyrrolo [3, 4-c] pyrrole disulfide or thiol dyes of formula (I) as defined above are dyes capable of fluorescing, i.e. 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) 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) or (II) 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 compounds of the invention of formula (I) when n and m are 1 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 diketopyrrolo [3, 4- c] pyrrole thiol dyes of formula (I) where n and m are 1 and Y represents a hydrogen atom or an alkali metal. Advantageously, Y represents a hydrogen atom. According to a specific embodiment relates to the diketopyrrolo [3, 4-c] pyrrole thiol dyes of formula (I), said formula (I) contains at least one cationic charged group or radical, associated or not, with it anionic counterion .

In accordance with another specific embodiment of the invention, in the abovementioned formula (I), 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 constitute a formula (I) in which n=m=l . Y as protective group cannot represent a group directly linked to the sulphur atom of formula (I) 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 an alkali metal such as sodium or potassium, or else An^" or An'^~ of formula (I) 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 dimethylamino;

^■ 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 (I) for which m and n are 1 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:

An 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 a 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 an alkali metal such as sodium or potassium, or else An^" or An'^~ of formula (I) and M⁺ are absent.

According to a specific embodiment of the invention, the dyes of the invention belong to one of the four formulae (Ia), (Ib), (Ha) and (lib):

in which formulae (Ia) , (Ib) , (Ha) and (lib) :

> T_a represents a σ covalent bond or a group chosen from: -N(R)-, -C(O)-N(R)-, -N(R)-C(O)- and -N⁺(R) (R⁰)-, An^", with R, R°, which may be identical or different, representing a hydrogen atom or a (Ci-C₄) alkyl group, and An^" representing an anionic counterion;

> m' and n' , which may be identical or different, represent an integer between 0 and 6 inclusive, with m'+n' representing an integer between 2 and 6 inclusive;

(preferably, m'+n'= 2 or 5; p' represents an integer between 0 and 4, or else two contiguous groups R⁴ form, with the carbon atoms which bear them, a benzo group; in particular, p' is 0;

R⁴ represents a halogen atom or a group chosen from hydroxyl, (Ci-C₆) alkyl, (Ci-C₆) alkoxy,

(Ci-C₆) alkylthio, (di) (Ci-C₆) (alkyl) amino, trihalo (Ci-C₆) alkyl, cyano and carboxyl;

> Y, R¹, R² and R³ are as defined above; and An- represents an anionic counterion.

By way of example, mention may be made of the following diketopyrrolo [3, 4-c] pyrrole dyes

8

10

11

12

13

14

15

16

17

20

21

22

23

24

with An representing an anionic counterion.

For all the exemplary embodiments, which follow, of preparation of the novel diketopyrrolo [3, 4-c] pyrrole thiol and disulfide dyes, those skilled in the art know how to pre-protect the reactive functions such as the ketone functions of the chromophore 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 mentioned above, by T. W Greene or P. Kocienski.

The protected thiol dyes of formula (I-Y) for which m and n are 1 can be synthesized in two stages. The first stage consists in preparing the nonprotected thiol dye (I—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 (I-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 thiol fluorescent dyes of formula (I-H) by reduction of a heterocyclic, two-chromophore fluorescent dye bearing a disulfide function -S-S- such as (I—S) and ii) in protecting said thiol function of (I-H) , according to the conventional methods, with the reactant 7 Y' R in order to obtain the protected thiol fluorescent dyes of formula (I—Y) . The thiol compound (I—H) may also be metallated with an alkali metal or alkaline earth metal Met* so as to produce the thiolate fluorescent dye of formula (I-Met) .

(I-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⁺; and with R¹, R², R³, Z and L 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.

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 a diketopyrrolo [3, 4-c] pyrrole chromophore (a) , the ketone functions of which are optionally pre-protected as seen above and which comprises an electrophilic function so as to form a Σ covalent bond; see below in the preparation of dyes of formula (I' -Y):

with R¹, R², R³, m' , n' , and Y' as defined above; Nu representing a nucleophilic group; E representing an electrophilic group; and Σ the bond 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 Nucleophi les JVu 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 Alkylamines Sulfonic esters Thiols Thioethers Sulfonic esters Carboxylic acids Esters Sulfonic esters Alcohols Ethers Sulfonyl halides Amines Sulfonamides *the activated esters of general formula -CO-Part with Part representing a leaving group such as oxysuccinimidyl, oxybenzotriazolyl, aryloxy which is optionally substituted; **the acyl nitrides may rearrange to give isocyanates .

A variant to this process is to use a fluorescent 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 a diketopyrrolo [3, 4-c] pyrrole chromphore, the ketone functions of which are optionally pre-protected as seen above, so as to give the protected thiol dye of formula (I-Y) :

with R¹, R², R³, Z, L and (I-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, if the thiourea derivative is a thioimidazolinium (β) , so as to give the dye which is S-protected with an imidazolium group (1''-Y):

with R' _c, R'_d, R , R , R , Z, L, Hal and An as defined above .

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

with R' _c, R' _d, R¹ , R² , R³ , Z , L , ( a ' ) , Hal and Lg as def ined above .

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

In accordance with another possibility, certain protected thiol dyes (I' -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 a diketopyrrolo [3, 4-c] pyrrole chromophore (c) , the ketone functions of which are optionally pre-protected as seen above, on which bears a nucleophilic function, for example of primary or secondary amine type, or of aliphatic alcohol type.

with R¹, R², R³, m' , n' , E, Nu and (I'-Y) as defined above .

Another variant is to use a thiolactone derivative as represented by the scheme below:

τ^ 2 τ^ 3 vv±Lii K , K , K , -t\ g, i , i^vie L " , Ii , aiiu in aa ueiineu 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 n' = 3 and G' represents an oxygen atom.

One synthesis variant is to combine the above pathway with the first pathway, i.e., using two equivalents of the nucleophile reactant (c) with a dielectrophilic disulfide reactant (i) , it is possible to generate, after condensation, the dichromophoric disulfide product (I'-S), it being possible for the latter to undergo a reduction so as to form the heterocyclic thiol dye (I' -H) which, in turn, may be either protected so as to form the protected thiol fluorescent dye in (I' -Y) or metallated with an alkali metal so as to give the metallated heterocyclic thiol fluorescent dye (I" '-Metai) :

In accordance with another possibility, the protected thiol dyes of formula (1'''-Y) and (11'''-Y) can be obtained by reaction of a compound comprising a thiol group protected with a Y' group, and a nucleofuge leaving group Lg, for instance mesylate, tosylate, triflate or halide, with a diketopyrrolo [3, 4-c] pyrrole chromophore (c' ) or (c' ' ) , the ketone functions of which are optionally pre-protected as seen above.

With R¹, R², R³, R⁴, p' , Y', Z and L as defined above. By way of example, the quaternization of the pyridine group (c' ' ) to (11'''-Y) is carried out by adapting the quaternization described in document WO 2006/134043.

By way of example, a compound containing a protected thiol group (1'''-Y) or (11'''-Y) contains a nucleofuge leaving group R, for instance mesylate, tosylate or triflate, which can undergo nucleophilic attack from the amine of the pyridine chromophore (c' ' ) or diketo- pyrrole [3, 4-c] pyrrole chromophore (c' ) , the ketone functions of which are optionally pre-protected as seen 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 thiol fluorescent dyes formed can be converted to -S Y' protected thiol fluorescent dyes by protection of the -SH thiol using the conventional protecting groups. The thiol fluorescent dyes are metallated 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.

The protected thiol 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 documents US 4579949 and US 4666455, which describe syntheses of substituted diketopyrrolo [3, 4- c] pyrroles .

The synthesis of non-disulfide diketopyrrolo [3, 4-c] - pyrroles is described in the book Color Chemistry, 3rd edition, H. Zollinger, Wiley-VCH, 2003, pages 330-345.

The composition of the invention contains at least one disulfide, thiol or protected thiol dye of formula (I) . In addition to the presence of at least one dye of formula (I), 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) 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 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 5 and 11 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. According to a specific embodiment, in the process of the invention, a reducing agent may be applied as a pretreatment before the application of the composition containing at least one dye of formula (I) .

This pretreatment 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.

According to another process, the composition comprising at least one dye of formula (I) and also contains at least one reducing agent as defined above. This composition is then applied to the hair.

When the thiol dye of formula (I) for which m and n are 1 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 dye of formula (I) at the time of use.

According to another process, the composition comprising at least one dye of formula (I) also contains at least one reducing agent as defined above. This composition is then applied to the hair.

According to another variant, the reducing agent is applied as a post-treatment, after the application of the composition containing at least one dye of formula (I) . 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 dye of formula (I) 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 optional post-treatment with an oxidizing agent is between 1 second 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 dye of formula (I) and a second compartment contains a reducing agent capable of reducing the disulfide functions of the keratin materials and/or of the disulfide 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 at least one dye of formula (I); a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials and/or of the disulfide dye of formula (I); and a third compartment contains an oxidizing agent.

Alternatively, the dyeing device contains a first compartment containing a dye composition which comprises at least one protected thiol fluorescent dye of formula (I) with m and n being 1, 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.

EXAMPLE 1

Synthesis of N₁ N'- (disulfanediyldiethane-2, 1-diyl) bis {4- [3, 6-bis (4-chlorophenyl) -1, 4-dioxo-4, 5-dihydro- pyrrolo[3, 4-c]pyrrol-2 (IH) -yl] -N, N-dimethylbutan-l- aminium}dibromide

Synthesis scheme

Procedure

Stage 1 :

Synthesis of 2- (4-bromobutyl) -3, 6-bis (4-chlorophenyl) - 2, 5-dihydropyrrolo [3, 4-c] pyrrole-1, 4-dione (DPP-2)

3, 6-bis (4-Chlorophenyl) -2, 5-dihydropyrrolo [3, 4-c] - pyrrole-1 , 4-dione (DPP-I) is dispersed in N-methyl- pyrrolidinone (NMP) at ambient temperature, and then sodium hydride (2.5 equivalents) is added at 0⁰C. The reaction mixture is heated with stirring at 100⁰C for 10 minutes and then at ambient temperature for 10 minutes. Dibromobutane (3 equivalents) is then added dropwise and the mixture is stirred for 3 days. An orangey-red paste forms.

The reaction mixture is poured into ice and then heptane is added. The mixture is left to stir for 30 minutes and is then filtered. The resulting product is washed with water and then with heptane. An orangey- red powder is recovered after air-drying.

Stage 2

N, N'- (Disulfanediyldiethane-2, 1-diyl) bis { 4- [3, 6-bis (4- chlorophenyl) -1, 4-dioxo-4, 5-dihydropyrrolo [3, 4-c] - pyrrol-2 (IH) -yl] -JV, JV-dimethylbutan-1-aminium} dibromide

The 2- (4-bromobutyl) -3, 6-bis (4-chlorophenyl) -2, 5-dihydropyrrolo [3, 4-c] pyrrole-1, 4-dione (DPP-2) prepared in the preceding stage is mixed in dimethylformamide

(DMF) with JV, JV, JV, JV-tetramethylcysteamine and the mixture is stirred for 24 h at 80⁰C. The reaction mixture is poured into toluene. The resulting mixture is left to stir for 30 minutes and then filtered. The resulting product is washed with acetone. An orangey- red powder is recovered after air-drying.

This mixture is purified by chromatography. DYEING EXAMPLE

Example 1 : Dyeing process - compound [1]

Preparation of a composition A

5^χlO^~4

Compound [1] 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 q£ 3 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 (22.5 ml) and B

(2.5 ml) are mixed, then the mixture obtained is applied to two locks of gray hair comprising 90% white hairs (NW), two locks of permanent-waved hair (PW) and one lock of dark hair (tone height 4, TH4) for 20 minutes at ambient temperature (the locks are turned over and reimpregnated after 10 minutes) . The locks are rinsed with running water, shampooed once, and then air-dried.

Visual observations :

During the rinsing and shampooing of example [1], there is very little visible bleeding of the color; the shampoo foam and the rinsing water are virtually uncolored.

The coloring obtained on the NW and PW locks is a strong orange. The dark hair appears visually lighter. Fastness with respect to successive shampooing operations :

The locks thus 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.

Visual observations

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 on the locks is retained and the lightening effect remains visible on the dark hair thus treated.

Claims

1. A dye of formula (I) :

the organic or mineral acid salts, optical isomers and geometric isomers thereof, and the solvates such as hydrates: in which formula (I) : ^ n represents 1 or 2 ;

> m represents 0 or 1 ;

^ R¹ represents a hydrogen atom or an optionally substituted (Ci-Cs) alkyl group; > R² represents an optionally substituted aryl group;

> R³ represents a hydrogen atom, an optionally substituted (Ci-Cs) alkyl group, or an optionally substituted aryl group; > L represents a linear or branched, C1-C20, divalent hydrocarbon-based chain which is optionally substituted, 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)-; -N⁺(R) (R⁰)-, An^"; -O-; -S-; -C(O)-; and -S(O)₂-, with R, R°, which may be identical or different, chosen from a hydrogen, and a C₁-C₄ alkyl, hydroxyalkyl or aminoalkyl radical, and An^" representing an anionic counterion, or ii) with a cationic heterocycle Het⁺, An^", with An^" as defined above and Het⁺ representing a saturated or unsaturated, optionally aromatic heterocycle comprising from 5 to 10 members; > Z represents: i) a σ covalent bond or ii) an optionally substituted cationic heteroaryl group comprising at least one nitrogen atom Het2⁺ An^", with An'^" representing an anionic counterion; > Y represents : i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N⁺R⁰¹R^R⁷R⁵, An''^" or a phosphonium group: P⁺R^αR^βR^γR^δ, An"^" 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, and An''- representing an anionic counterion; or v) a thiol- function-protecting group; it being understood that:

- when n is 2, then m is zero, and when n is 1, then m is 1;

- when the radical R of formula (I) is on Ni, then the chain -Z-L-S- (Y) _m is attached on the carbon atom at position 5, and when the radical R³ is attached on the carbon atom at position 5, then the chain is on the nitrogen atom Ni;

- when the radical Z of formula (I) represents a σ covalent bond, the group L is on the nitrogen atom Ni and the radical R³ represents an optionally substituted aryl group; - when the radical Z of formula (I) represents a group Het2⁺ An^", the radical Z is on the carbon atom at position 5 and the radical R³ is on the nitrogen atom Ni and represents a hydrogen atom or an optionally substituted (Ci-Cs) alkyl group.

2. The fluorescent dye of formula (I) as claimed in the preceding claim, in which m and n are 1 and Y represents a hydrogen atom or an alkali metal.

3. The fluorescent dye of formula (I) as claimed in claim 1, in which m and n are 1 and Y represents a protecting group.

4. The fluorescent dye of formula (I) 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^" or An'^~ of formula (I) 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; 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, 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 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

> SO₃ ^"; M⁺ with M⁺ representing an alkali metal or else An^" or An'^" of formula (I) and M⁺ are absent .

6. The dye as claimed in any one of the preceding claims, belonging to one of the four formulae (Ia), (Ib), (Ha) and (lib):

in which formulae (Ia) , (Ib) , (Ha) and (lib) :

> T_a represents a σ covalent bond or a group chosen from: -N(R)-, -C(O)-N(R)-, -N(R)-C(O)- and -N⁺(R) (R⁰)-, An^", with R, R°, which may be identical or different, representing a hydrogen atom or a (Ci-C₄) alkyl group, and An^" representing an anionic counterion;

^ m' and n' , which may be identical or different, represent an integer between 0 and 6 inclusive, with m'+n' representing an integer between 2 and 6 inclusive;

^ p' represents an integer between 0 and 4, or else two contiguous groups R⁴ form, with the carbon atoms which bear them, a benzo group; > R⁴ represents a halogen atom or a group chosen from hydroxyl, (Ci-C₆) alkyl, (Ci-C₆) alkoxy, (Ci-C₆) alkylthio, (di) (Ci-C₆) (alkyl) amino, trihalo (Ci-C₆) alkyl, cyano and carboxyl;

> Y, R¹, R² and R³ are as defined in any one of the preceding claims;

> and An- represents an anionic counterion.

7. The fluorescent dye as claimed in any one of the preceding claims, having the formula below:

8

10

11

12

13

14

15

16

17

20

21

22

23

24 with An^" representing an anionic counterion.

8. A dye composition comprising, in a suitable cosmetic medium, a dye of formula (I) as defined in any one of claims 1 to 7.

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

10. A process for dyeing keratin materials, in which a suitable dye composition comprising at least one dye of formula (I) as claimed 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 dye of formula (I) as defined in claims 1 to 7, and a second compartment contains a reducing agent .

14. The use of the dyes of formula (I) as defined in claims 1 to 7, 9, for dyeing 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.