WO2007110540A2 - Dyeing composition containing a thiol/disulphide fluorescent colorant comprising an alkoxy/hydroxy grouping, with an internal cationic charge, and method for lightening keratin materials using said colorant - Google Patents

Abstract

The invention relates to a dyeing composition containing a thiol/disulphide fluorescent colorant comprising an alkoxy and/or hydroxy grouping, and to a method for colouring keratin materials, especially keratin fibres, particularly human keratin fibres such as hair, with a lightening effect, using said composition. The invention also relates to novel thiol or disulphide fluorescent colorants and the uses thereof for lightening keratin materials. Said composition produces a lightening effect which is especially tenacious and visible on dark keratin fibres.

Description

 DYE COMPOSITION COMPRISING A FLUORESCENT COLOR

THIOL / DISULFIDE WITH ALCOXY / HYDROXY AND CHARGING

INTERNAL CATIONIC, METHOD OF CLARIFYING MATERIALS

KERATINICS FROM THIS COLOR

The invention relates to the dyeing of keratin materials using fluorescent dyes thiols or disulfides alkoxy group and / or hydroxy.

It is known to dye keratinous fibers, especially human fibers, by direct dyeing. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and dyeing 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, nitropyridines, dyes of the azo, xanthene, acridine, azine or triaryl methane type.

The colorings that result from the use of direct dyes are temporary or semi-permanent dyes because the nature of the interactions that bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible their low dyeing power and their poor resistance to washes or perspiration.

Furthermore, the coloration of keratinous fibers from conventional direct dyes does not make it possible to significantly lighten the keratin fibers.

The lightening of the color of keratinous fibers, more particularly dark to lighter shades, possibly modifying the shade of these, constitutes an important demand.

Conventionally, to obtain a lighter coloration is implemented a chemical bleaching process. This method consists in treating keratin materials such as keratinous fibers, in particular the hair, by a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, most often in an alkaline medium.

This bleaching system has the drawback of degrading keratin materials, in particular keratinous fibers, especially human fibers such as the hair, and of altering their cosmetic properties. Fibers indeed tend to become rough, more difficult to disentangle and more fragile. Finally, the lightening or the bleaching of keratinous fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in the straightening treatments. Another lightening technique consists in applying fluorescent direct dyes to dark hair. This technique described in particular in the documents FR 2830189 and WO 2004/091473 makes it possible to respect the quality of the keratinous fiber during the treatment, but the fluorescent dyes employed do not exhibit satisfactory resistance to shampooing. To increase the tenacity of the direct dyes, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react dyes with reactive groups with the residues of cystine or cysteine very numerous in keratin fibers, see for example Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, AZ _x 1-17 (1991); CA 2024509. In addition, it is known to protect the thiol function (s) contained in a molecule to be grafted to the hair before applying them to said hair WO 99/51194. However, this application does not mention the use of fluorescent dyes for coloring or lightening hair.

Other disulfide dyes known for dyeing keratinous fibers are disulfide derivatives of aminothiophenol derivatives. Such dyes are described, for example, in patent FR 1156407. These dyes can be used under relatively mild conditions, in the presence of a slightly reducing medium or after a reducing pretreatment of the hair. However, these dyes may cause color turns during application. Finally, the document WO 2005/097051 describes disulfide aza-imidazolium dyes for the direct dyeing of keratin fibers.

The object of the present invention is to provide novel systems for dyeing keratin materials, in particular human keratinous fibers, in particular the hair, which do not have the drawbacks of existing bleaching processes. In particular, one of the aims of the present invention is to provide direct dyeing systems which make it possible to obtain lightening effects, in particular on naturally or artificially dark keratin fibers, which are stubborn in the face of successive shampoos, which do not degrade keratin fibers and which do not alter their cosmetic properties. This object is achieved with the present invention which relates to a process for dyeing keratin materials, in particular keratinous fibers, in particular human fibers such as the hair, more particularly the dark hair, consisting in applying to the keratin materials a dye composition. comprising, in a suitable cosmetic medium, at least one disulfide or thiol fluorescent dye containing an alkoxy and / or hydroxyl group chosen from the following dyes of formula (I) and (II):

(H) their organic or inorganic acid salts, optical isomers, geometric, and solvates such as hydrates, formulas (I) or (II) in which:

R and R ', which may be identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl or benzyl group; particularly a hydrogen atom or a group (dC ₄ ) alkyl; R ₁ , R ' ₁ , R "1 and R'", which may be identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group; especially a hydrogen atom;

> M 'represents an anionic counterion

m and m ', identical or different, represent an integer inclusive between 1 and 6, particularly m and m'valent 2; > p and p ', which may be identical or different, represent an integer between 1 and 5; particularly 2 or 3; more particularly p and p 'are 2;

Y represents i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N ⁺ R ^α R ^β R ^γ R ^δ or a phosphonium group: P ⁺ R ^α R ^β R ^γ R ^δ with R ^α , R ^β , R ^γ and R ^δ , identical or different, representing a hydrogen atom or a (dC ₄ ) alkyl group; or v) a protecting group of thiol function; Being heard that :

- When the compound of formula (I) or (II) contains other cationic parts, it is associated with one or more anionic counter-ions to achieve the electroneutrality of formula (I) or (II);

when p and / or p 'is an integer greater than or equal to 2, the groups R 0 may be identical or different; and

when two groups RO and / or two groups R'O are adjacent, the two radicals R and / or the two radicals R 'can form together an alkylene chain - (CRi R ₂ ) _q -, with Ri and R ₂ , identical or different, represent a hydrogen atom or a group (C ₁ -C ₄ ) alkyl and q represents an integer inclusive between 1 and 3; particularly Ri and R ₂ represent a hydrogen atom and q represents 1 or 2.

Another subject of the invention is a dye composition comprising, in a suitable cosmetic medium, at least one fluorescent dye of formula (I) or (II) as defined previously and optionally a reducing agent.

The invention also relates to new fluorescent dyes of formula (I) or (II) as defined above.

The dyeing process according to the invention makes it possible to visibly stain dark keratin materials, in particular dark human keratin fibers, especially dark hair.

In addition, the process of the invention makes it possible to obtain a coloration of the keratin materials, in particular human keratinous fibers, in particular the hair, without degrading said material, which is persistent with respect to shampoos, of the common aggressions (sun, perspiration). , and other hair treatments. The process of the invention also makes it possible to obtain a lightening of keratin materials such as keratinous fibers, particularly dark keratinous fibers and more particularly dark hair.

For the purposes of the invention, the term "dark keratin material" is understood to mean that which has a luminescence L * encoded in the CIEL L * a * b * system, less than or equal to 45 and preferably less than or equal to 40, while also knowing that L * = 0 is equivalent to black and L * = 100 is white.

For the purposes of the invention, the term naturally or artificially dark hair means hair whose pitch is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut).

The lightening of the hair is evaluated by the variation of "pitch" before and after application of the compound of formula (I) or (II). The notion "tone" is based on the classification of natural nuances, a tone separating each nuance from that which follows or immediately precedes it. This definition and the classification of natural shades is well known to hair professionals and published in the book "Science of hair treatments" Charles ZVIAK 1988, Ed Masson, p. 215 and 278.

Heights range from 1 (black) to 10 (very light blond), a unit corresponding to a tone; the higher the number, the clearer the nuance.

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

Preferably, the composition must, after application to hair, for example chestnut, bring to the results below.

- We are interested in the reflectance performance of the hair when irradiated with visible light in the wavelength range from 400 to 700 nanometers. The reflectance curves are then compared as a function of the wavelength, of the hair treated with the composition of the invention and of the untreated hair.

- The curve corresponding to the treated hair must show a reflectance in the wavelength range from 500 to 700 nanometers higher than the curve corresponding to untreated hair. This means that, in the wavelength range of 540 to 700 nanometers, there is at least one range where the reflectance curve corresponding to the treated hair is greater than the reflectance curve corresponding to the untreated hair. The term "superior" means a difference of at least 0.05% reflectance, and preferably at least 0.1%. This does not prevent that there may exist in the wavelength range from 540 to 700 nanometers, at least one range where the reflectance curve corresponding to the treated hair is superimposable, or less than the reflectance curve corresponding to the untreated hair.

Preferably, the wavelength where the difference is maximum between the curve of The reflectance of treated hair and untreated hair is in the wavelength range of 500 to 650 nanometers, and preferably in the wavelength range of 550 to 620 nanometers.

For the purposes of the present invention, and unless a different indication is given:

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

. a C ₁ -C ₁₆ , preferably C ₁ -C ₈ , alkyl radical optionally substituted with one or more radicals chosen from hydroxyl and C ₁ -C ₄ alkoxy radicals;

C ₂ , (poly) -hydroxyalkoxy C ₂ -C ₄ , acylamino, amino substituted with two identical or different alkyl radicals, C ₁ -C ₄ , optionally carrying at least one hydroxyl group or both radicals may forming, with the nitrogen atom to which they are attached, a 5- to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated heterocycle optionally comprising another heteroatom which is identical or different from nitrogen;

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

• a hydroxyl group; . a C ₁ -C ₂ alkoxy radical;

A C ₁ -C ₂ alkylthio radical;

. a (C ₂ -C ₄ ) polyhydroxyalkoxy radical;

An amino radical;

. a 5- or 6-membered heterocycloalkyl radical; A 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C ₁ -C ₄ ) alkyl radical, preferably methyl;

An amino radical substituted with one or two identical or different C ₁ -C ₆ alkyl radicals optionally carrying at least: i) a hydroxyl group; ii) an amino group optionally substituted with one or two C ₁ -C ₂ alkyl radicals; ₁ -Cs optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or different from nitrogen,

. an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a Ci-C ₄ alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C 1 -C alkyl radical; ₂ ; a carbamoyl radical ((R) ₂ N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C ₁ -C ₄ alkyl radical optionally carrying at least one hydroxyl group; an alkylsulphonylamino radical (R ¹ SO ₂ -NR-) in which the radical R represents a hydrogen atom, a C ₁ -C ₄ alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents an alkyl radical; in C ₁ -C ₄ , a phenyl radical; an aminosulphonyl radical ((R) ₂ N-SO ₂ -) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C ₁ -C ₄ 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, substituted or unsubstituted);

• a cyano group;

. a polyhaloalkyl group comprising from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which are identical or different, the polyhaloalkyl group is, for example, trifluoromethyl;

the cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom chosen from the groups:

. hydroxy, • C ₁ -C ₄ alkoxy,

. (poly) hydroxyalkoxy C ₂ -C ₄ ,

A C ₁ -C ₂ alkylthio radical;

. RCO-NR'- in which the radical R 'is a hydrogen atom, an alkyl radical in dC ₄ optionally bearing at least one hydroxyl group and the radical R is a C ₁ -C ₂ alkyl radical, amino substituted by two identical or different C ₁ -C ₄ alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, saturated or unsaturated; optionally substituted comprising optionally at least one other heteroatom different or different from nitrogen; RCO-O- in which the radical R is a C ₁ -C ₄ alkyl radical, amino substituted with two identical or different C ₁ -C ₄ alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted 5- to 7-membered heterocyclic ring, saturated or unsaturated optionally comprising at least one other heteroatom different or different from nitrogen; . RO-CO- wherein the radical R is a C ₁ -C ₄ alkyl radical, amino substituted with two identical or different C ₁ -C ₄ alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted saturated or unsaturated 5- to 7-membered heterocyclic ring optionally comprising at least one other heteroatom different from or different from nitrogen;

a cyclic, heterocyclic radical or a non-aromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo or thioxo groups;

an "aryl" radical represents a mono or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;

a "diarylalkyl" radical represents a group comprising, on the same carbon atom of an alkyl group, two identical or different aryl groups, such as diphenylmethyl or 1,1-diphenylethyl;

a "heteroaryl radical" represents a mono- or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium; , and of which at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl , phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyryl, 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, identical or different, such as difurylmethyl, 1,1-difurylethyl, dipyrrolylmethyl, dithienylmethyl;

a "cyclic radical" is a non-aromatic, mono or polycyclic cycloalkyl radical, condensed or not, containing from 5 to 22 carbon atoms, which may contain from 1 to several unsaturations; particularly the cyclic radical is cyclohexyl;

a "cyclic sterically hindered" radical is a cyclic radical, aromatic or not, substituted or unsubstituted, hindered by steric effect or constraint, comprising from 6 to 14 members, which can be bridged, as sterically hindered radicals, mention may be made of bicyclo [1.1.0] butane, mesytyls such as 1,3,5-trimethylphenyl, 1,3,5-triterbutylphenyl, 1,3,5-isobutylphenyl, 1,3,5-trimethylsillylphenyl and adamantyl ;

a "heterocyclic radical" is a non-aromatic mono or polycyclic radical, condensed or not, containing from 5 to 22 members, containing from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium ;

- an "alkyl radical" is a hydrocarbon radical Ci-Ci ₆ linear or branched, preferably Ci-Cs;

the expression "optionally substituted" ascribed to the alkyl radical, meaning that said alkyl radical may be substituted with one or more radicals chosen from the radicals i) hydroxy, ii) alkoxy, C _r C ₄ , iii) acylamino, iv) amino optionally substituted with one or two identical or different C ₁ -C ₄ alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 ring members, optionally comprising another different heteroatom or not nitrogen; v) or a quaternary ammonium group -

N R'R "R '", M ^" for which R', R", R '", which are identical or different, represent a

+ hydrogen atom, or a dC ₄ alkyl group, or else -N R'R "R '" forms a heteroaryl such as imidazolium optionally substituted with a group C _r C ₄ alkyl, and M represents the counter-ion of the organic acid, mineral or corresponding halide,

an "alkoxy radical" is an alkyl-oxy or alkyl-O- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, preferably of CrCl ₆ ;

an "alkylthio radical" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, Ci-Ci ₆ preferentially in dC ₈ ; when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above; the bounds defining the range of a range of values lie within this range of values; an "organic or inorganic acid salt" is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H ₂ SO ₄ , iv) acids alkylsulfonic: Alk-S (O) ₂ OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulphonic acids: Ar-

S (O) ₂ OH such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid

H ₃ PO ₄ ; xiii) acetic acid CH ₃ COOH; xiv) triflic acid CF ₃ SO ₃ H and xv) tetrafluoroboric acid HBF ₄ ; an "anionic counterion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly the anionic counterion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, among which C _r -C ₆ alkylsulfonates: AIk-S (O) ₂ O ^", such as methylsulfonate or mesylate and ethyl sulfonate; iv) arylsulfonates: Ar-S (O) ₂ ^O" as the benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; (vii) tartrate; viii) lactate; ix) Alkyl sulphates: Alk-OS (O) O ^" such as methysulphate and ethyl sulphate; x) aryl sulphates: Ar-OS (O) O ^- such as benzenesulphate and toluenesulphate; xi) alkoxysulphates: Alk - OS (O) ₂ O ^- such as methoxy sulfate and ethoxysulphate; xii) aryloxysulphates: Ar - OS (O) ₂ O ^- (xiii) phosphate; (xiv) acetate; xv) triflate; and (xvi) borates such as tetrafluoroborate.

The fluorescent dyes of formula (I) or (II) are compounds capable of absorbing in UV or visible radiation at a wavelength λ _abs of between 250 and 800 nm and capable of reemitting in the visible range at a emission wavelength λ _em between 400 and 800 nm.

Preferably, the fluorescent compounds of the invention of formula (I) or (II) are dyes capable of absorbing in the visible λ _abs between 400 and 800 nm and reemitting in the visible λ _em between 400 and 800 nm. . More preferably, the fluorescent dyes of formula (I) or (II) are dyes capable of absorbing at an _abs λ between 420 nm and 550 nm and reemitting in the visible at an λ _em between 470 and 600 nm.

The fluorescent compounds of the invention which contain a function SY may be in the covalent -SY or ionic -S ^" Y ^{+ form} depending on the nature of Y and the pH of the medium. of the invention are thiol dyes with Y representing a hydrogen atom.

Another particular mode relates to thiol fluorescent dyes of formula (II) with SY function where Y represents an alkali metal.

According to another particular embodiment of the invention, in the formula (II) above, Y is a protective group known to those skilled in the art such as those described 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, 3 ^ΘmΘ ed., 2005, c. 5.

Especially when Y represents a protective group of the thiol function, Y is chosen from the following radicals:

(Ci-C ₄ ) alkylcarbonyl,

(Ci-C ₄ ) alkylthiocarbonyl,

• (CrC ₄ ) alkoxycarbonyl,

• (Ci-C ₄ ) alkoxythiocarbonyl, • (CrOOalkylthio-thiocarbonyl,

(Di) (CrC ₄ ) (alkyl) aminocarbonyl,

(Di) (CrC ₄ ) (alkyl) aminothiocarbonyl,

Arylcarbonyl as phenylcarbonyl; Aryloxycarbonyl;

• aryl (Ci-C ₄₎ alkoxycarbonyl;

(Di) (CrC ₄ ) (alkyl) aminocarbonyl as dimethylaminocarbonyl;

(C ₁ -C ₄ ) (alkyl) arylaminocarbonyl • carboxy;

• SO ₃ ^" M ⁺ with M ⁺ representing an alkali metal such as sodium or potassium or M ⁺ and M 'of the formula (II) are absent;

Optionally substituted aryl such as phenyl, dibenzosuberyl, or 1,3,5-cycloheptatrienyl, optionally substituted heteroaryl; including in particular cationic or non-cationic heteroaryl, comprising from 1 to 4 following heteroatoms: i) monocyclic with 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) 8 to 11-membered bicyclic compounds such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazolium, thienocycloheptadienyl, these mono or bicyclic groups being optionally substituted by one or more groups such as dC ₄ ) alkyl as methyl, or polyhalo (dC ₄ ) alkyl as trifluoromethyl; iii) or tricyclic ABC following:

wherein the two rings A, C optionally comprise a heteroatom, and the ring B is a 5-, 6- or 7-membered particularly 6-membered ring and contains at least one heteroatom such as pyperidyl, pyranyl; optionally substituted heterocycloalkyl, optionally cationic heterocycloalkyl represents in particular a saturated or partially saturated 5, 6 or 7 membered monocyclic group comprising 1 to 4 heteroatoms selected 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, di / tetrahydropyrimidinyl these groups being optionally substituted with one or more groups such as CrC ₄ ) alkyl, oxo or thioxo; or the heterocycle represents the following group:

wherein R ^'c, R' ^d, R ^'Θ, R' ^f, R ^'9 and R' ^h, identical or different, represent a hydrogen atom or a (Ci-C ₄₎ alkyl, or else two groups R ' ⁹ with R' ^h , and / or R ' ^Θ with R' ^f form an oxo or thioxo group, or else R ' ⁹ with R' ^Θ together form a cycloalkyl; and v represents an integer inclusive of between 1 and 3; preferentially R ' ^c to R' ^h represent a hydrogen atom; and An ^" represents a counterion;

• isothiouronium -C (NR ' ^c R' ^d ) = N ⁺ R ' ^Θ R'^f; An ^"with R ^'c, R' ^d, R ^'Θ and R' ^f, like or different, represent a hydrogen atom or a (dC ₄₎ alkyl; preferably, R ^'c to R' ^f represent a hydrogen atom, hydrogen, and An ^" represents a counterion;

• isothiourea -C (NR ' ^c R' ^d ) = NR '^Θ; with R ' ^c , R' ^d , R ' ^Θ as defined above;

Optionally substituted (di) aryl (C _r C ₄ ) alkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted with one or more groups chosen in particular from (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy such as methoxy, hydroxy and alkylcarbonyl, (di) (C ₁ -C ₄ ) (alkyl) amino such as dimethylamino;

(Di) heteroaryl (C _r C ₄ ) optionally substituted alkyl, the heteroaryl group is in particular, cationic or otherwise, monocyclic, comprising 5 or 6 members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide groups such as the

4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium, triazinyl, optionally substituted by one or more groups such as alkyl particularly methyl, advantageously (di) heteroaryl (CrC ₄ ) alkyl is

(di) heteroarylmethyl or (di) heteroarylethyl;

• CR ¹ R ² R ³ with R ¹ , R ² and R ^{3, which may be} identical or different, representing a halogen atom or a group chosen from: - (C ₁ -C ₄ ) alkyl;

- (C ₁ -C ₄ ) alkoxy;

optionally substituted aryl such as phenyl optionally substituted by one or more groups such as (CrC ₄ ) alkyl, (CrC ₄ ) alkoxy, hydroxy; optionally substituted heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl or pyridyl, optionally substituted with a (C ₁ -C ₄ ) alkyl group;

- P (Z ¹ ) R ' ¹ R ¹² R' ³ with R ' ¹ , and R' ² identical or different represent a hydroxyl group, (C ₁ -C ₄ ) alkyl or alkyl, R ' ³ represents a hydroxyl group or C _r C ₄ ) alkoxy, and Z ¹ represents an oxygen or sulfur atom;

Sterically hindered cyclic such as the adamantyl group;

Optionally substituted alkoxy (CrC ₄ ) alkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.

According to a particular embodiment, the thiol fluorescent dyes of formula (II) contain a cationic aromatic 5- or 6-membered monocyclic moiety Y i) heteroaryl comprising 1 to 4 heteroatoms selected 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, imidazolium; ii) cationic 8 to 11-membered bicyclic heteroaryl such as indolinium, benzoimidazolium, benzoxazolium, benzothiazolium, these mono or bicyclic heteroaryl groups optionally being substituted by one or more groups such as alkyl like methyl, or polyhalo (Ci-C ₄₎ alkyl ∞mme trifluoromethyl; iii) or heterocyclic according to:

wherein R ' ^c and R' ^d , identical or different, represent a hydrogen atom or a group (dC ₄ ) alkyl; preferentially R ' ^c to R' ^d represent a grouping

(dC ₄ ) alkyl such as methyl; and An ^" represents a counterion.

Especially 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 by one or more (CrC ₄ ) alkyl groups including methyl.

In particular Y represents an alkali metal or a protective group such as:> (C _r C ₄ ) alkylcarbonyl such as methylcarbonyl or ethylcarbonyl;

arylcarbonyl, such as phenylcarbonyl;

(C _r C ₄ ) alkoxycarbonyl;

> aryloxycarbonyl;

> aryl (C ₁ -C ₄ ) alkoxycarbonyl; (di) (CrC ₄ ) (alkyl) aminocarbonyl as dimethylaminocarbonyl;

(C _r C ₄ ) (alkyl) arylaminocarbonyl;

optionally substituted aryl such as phenyl;

Cationic monocyclic 5- to 6-membered heteroaryl such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted by one or more, identical or different, (C ₁ -C ₄ ) alkyl groups such as methyl;

8 to 11-membered cationic bicyclic heteroaryl such as benzoimidazolium, or benzoxazolium; these groups being optionally substituted by one or more, identical or different, (C ₁ -C ₄ ) alkyl groups such as methyl; cationic heterocycle of following formula:

> isothiouronium -C (NH ₂ ) = N ⁺ H ₂ ; An ^" ;

> isothiourea -C (NH ₂ ) = NH; or

> SO ₃ ^" , M ⁺ with M ⁺ representing an alkali metal such as sodium or potassium or M ⁺ and M 'of the formula (II) are absent.

According to one particular embodiment of the invention, the thiol fluorescent dyes are of formula (Ia) or (IIa):

formulas (Ia) or (Ma) in which the group (s) RO- and / or R'O-, identical or different, positioned particularly at 2 'and / or 4' and the styryl group is connected to the pyridinium ring in position 2 or 4, particularly in position 2. Preferably the dyes of formula (Ia) contain one or more groups RO- with RO- identical to R ¹ O-. In particular, the dyes of formula (Ia) are symmetrical.

By way of example of thiol and disulfide fluorescent dyes, mention may be made in particular of the following compounds:

(26)

(27)

(28)

2An ^" (29)

(30)

With An ^" representing an anionic counterion.

The protected thiol dyes of formula (M ") can be synthesized in two steps: the first step of preparing the unprotected thiol dye (II) according to the methods known to those skilled in the art, for example" Thiols and organic Sulfides "," Thiocyanates and Isothiocyanates, organic ", Ullmann's Encyclopedia, Wiley-VCH, Weinheim, 2005. And the second step of protecting the thiol function according to conventional methods known to those skilled in the art to lead to protected thiol dyes of formula (M "). By way of example, to protect the thiol -SH function of the thiol dye, the methods of the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217; "Protecting Groups", P. Kocienski, Thieme, 3 ^èmΘ ed., 2005, c. 5.

We can illustrate this method by the method consisting of i) generating thiol fluorescent dyes of formula (M ') by reduction of a heterocyclic, two-chromophore fluorescent dye bearing a disulfide function -SS- such that (O and ii) to protect, according to conventional methods, said thiol function of (H ') with the reagent 7 Y'R to access the protected thiol fluorescent dyes of formula (H "). The thiol compound (M') may also be" metallated "with a alkali metal or alkaline earth metal Met * to yield the thiolate fluorescent dye of formula (M ''). It is also clear that when the compound (H ') is metallized with an alkaline earth metal, the dye may comprise 2 -S ^" chromophores for a metal ²⁺ .

(I ¹ ) (H ")

with Y 'representing a protecting group of thiol function; Met * representing an alkali metal or an alkaline earth metal, particularly sodium or potassium; and Gp ^" representing a subsequent anionic counterion from the leaving group, it being understood that when the metal is an alkaline earth metal 2 thiolate-functional chromophores-S ^" may be associated with 1 Metal ²⁺ .

The counter ions Gp ^" of the compounds (M '), (M") and (M'") above can be replaced by counterions An ^" of other natures from methods known to the human being. craft especially ion exchange resin.

It is also possible to use a thiol reagent (α) Y'-SH comprising a group Y 'as defined previously, whose nucleophilic function SH can react on the carbon atom alpha of the halogen atom borne by the fluorescent chromophore (al to yield the protected thiol fluorescent dye of formula (M "):

(Al with R, Ri, R'i, m and p as defined above and HaI representing a nucleofugal halogen atom such as bromine, iodine or chlorine.

More particularly, it will be possible to substitute a nucleofugal leaving group with a thiourea group (S = C (NRR) NRR) to generate the isothiouroniums. For example, if the thiourea group is a thioimidazolinium (β), the reaction scheme is as follows:

with R, R, R'i, R ' _c , R' _d , HaI, m, p, An ^" and Gp as defined above are as defined above.

An alternative is to use in place of the halide comprising the fluorescent chromophore (al a chromophore comprising another type of nucleofuge such as tosylate, mesylate or triflate.

In another method, the protected thiol thiol dyes can be generated from substituted phenylstyrylpyridine derivatives (b) and thiol reagent comprising a leaving group Gp such that (ç). For example, the leaving group can be a mesylate, tosylate, triflate or halide:

M with R ₁ , R'i, R ' _c , R' _d , HaI, p, m and Gp ^" are as previously defined

According to another possibility, the protected thiol fluorescent dyes of formula (II) according to the invention can be obtained by condensation of phenylaldehyde / thioaldehyde derivatives with a reagent containing "activated alkylene" such as the alkylpyridinium derivative (d) also comprising the thiol function. This reaction is commonly known as "Knoevenagel" condensation.

with R, R, R'i, Y and An ^" as defined above and G representing an oxygen or sulfur atom.

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

The thiol fluorescent dyes formed can be converted to protected thiol stain -SY 'by protecting the thiol -SH using conventional protecting groups. The thiol fluorescent dyes are metallated by also using the conventional methods known in the art such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4 ^èmΘ Ed, John Wiley & Sons, NY , 1992.

Protected thiol dyes may be deprotected by conventional routes such as those described in the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981; "Protecting Groups", P. Kocienski, Thieme, 3 ^èmΘ ed. 2005.

The starting reagents are commercial or accessible by conventional methods known to those skilled in the art. For example, it is possible to synthesizing the reagent (I ') from 2 equivalents of pyridine derivative I and one equivalent of disulfide reactant comprising two leaving groups Gp, to yield dipyridinium disulfide salt 3 which can in turn be condensed with two equivalents of aryl compound aldehyde / thioaldehyde group 4 to yield 5.

with Gp representing a leaving group nucleofuge, such as mesylate, tosylate, triflate or halide.

The disymmetric disulfide dyes of formula (I) may be synthesized in one step by reacting an unprotected thiol fluorescent dye with a protected thiol fluorescent dye to form the disulfide dye of formula (I).

with R, R ', Ri, R'i, R ", R'", m, m ', p, p' and M 'are as previously defined; Y 'represents a protecting group of thiol function. The composition of the invention contains at least one fluorescent dye of formula (I) or (II). In addition to the presence of at least one fluorescent dye of formula (I) or (II), the composition of the invention may also contain a reducing agent. This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, in particular monothioglycolate glycerol, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catechol borane. The dye composition useful in the invention generally contains a quantity of fluorescent dye of formula (I) or (II) of between 0.001 and 50% relative to the total weight of the composition. Preferably, this amount is between 0.005 and 20% by weight and even more preferably between 0.01 and 5% by weight relative to the total weight of the composition. The dye composition may further contain additional direct dyes. These direct dyes are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

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

The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratinous fibers. Among the oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

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

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

In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned, for example lower alkanols dC ₄ , such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvents when present are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

According to one variant, the invention contains a reducing agent capable of reducing the disulfide bonds of keratin. This reducing agent is as defined above. The dye composition may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers. or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic polymeric associative thickeners, ionic and amphoteric agents, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as amino silicones film-forming agents, ceramides, preservatives, opacifying agents, conductive polymers.

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

Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, impaired by the or the additions envisaged.

The pH of the dyeing composition is generally between 3 and 14 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (γ):

^ I / 32

NW ₈ -N

R ₃ 4 ^R a3 ( _γ ) wherein W _a is a propylene residue optionally substituted by a hydroxyl group or a C ₁ -C ₄ alkyl radical; _R i, R _32, R _a3 and R _a4, identical or different, represent a hydrogen atom, an alkyl radical in C ₁ -C ₄ hydroxyalkyl or C _r C _4.

The dye composition may be in various forms, such as in the form of liquid, cream, gel, or in any other form suitable for dyeing keratinous fibers, and in particular hair. According to a particular embodiment in the method of the invention, a reducing agent may be applied pre-treatment before the application of the composition containing at least one fluorescent dye of formula (I) or (II).

This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catecholborane.

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 method, the composition comprising at least one fluorescent dye of formula (I) or (II) 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 in post-treatment, after the application of the composition containing at least one fluorescent dye (I) or (II). 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 particular embodiment, the reducing agent is a thiol or borohydride type agent as described above. A particular embodiment of the invention relates to a process in which the fluorescent dye of formula (I) or (II), particularly (II), can be applied directly to hair without reducing agents, free of pre or post-treatment reducers.

A treatment with an oxidizing agent may optionally be associated. Any type of conventional oxidizing agent may be used in the art. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, as well as the enzymes among which may be mentioned peroxidases, oxides, 2-electron reductases such as uricases and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.

This oxidizing agent may be applied to the fibers before or after the application of the composition containing at least one fluorescent dye of formula (I) or (II).

When the thiol fluorescent dye of formula (II) comprises a group Y protecting the thiol function, the process of the invention may be preceded by a deprotection step aimed at rendering the SH function in situ.

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

The deprotection step can also be carried out in the course of a hair pretreatment step such as, for example, the reducing pretreatment of the hair.

According to one variant, the reducing agent is added to the dyeing composition containing at least one fluorescent dye of formula (I) or (II) at the time of use.

The application of the dye composition according to the invention is generally carried out at room temperature. However, it can be carried out at temperatures ranging from 20 to 180 ^° C.

The invention also relates to a device with several compartments or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one fluorescent dye of formula (I) or (II) and a second compartment contains a reducing agent capable of reducing the disulfide functions of the keratin materials and / or the dye of formula ( I). One of these compartments may further contain one or more other dyes of direct dye type or oxidation dye.

It also relates to a multi-compartment device in which a first compartment contains a dye composition comprising at least one fluorescent dye of formula (I) or (II); a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials; 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 (II) and a second compartment containing an agent capable of deprotecting the protected thiol to release the thiol.

Each of the devices mentioned above can be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2 586 913.

The examples which follow serve to illustrate the invention without, however, being limiting in nature. The thiol fluorescent dyes of the examples below have been fully characterized by conventional spectroscopic and spectrometric methods.

EXAMPLES

EXAMPLES OF SYNTHESIS

Example 1 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4 - [(E) -2- (4-hydroxy-2-methoxyphenyl) vinyl] pyridinium dimethanesulfonate [1] Scheme of synthesis

[1] Operating mode

Step 1: Synthesis of dimethanesulfonate disulfanediyldiethane-2,1-diyl

10 g of 2,2 -dithiodiéthanol ¹ and 14.44 g of triethylamine (TEA) are diluted in 100 ml of ethyl acetate (AcOEt). At 0 ^° C., 16.35 g of dilute methanesulfonyl chloride in 35 ml of AcO Et are added dropwise to the reaction medium with rapid stirring. 7.22 g of TEΞA are introduced, the stirring is continued at room temperature for 4 h 30. 8.2 g of methanesulfonyl chloride are added dropwise at 15 ° C., and the stirring is then maintained at room temperature for 17 h. The precipitate is filtered and washed with 3 times 50 ml of AcOEt. The organic phases are extracted with 100 ml of ice water, 100 ml of water, 3 times 50 ml of a saturated solution of sodium hydrogencarbonate (NaHCO ₃ ), with 2 times 20 ml of saturated solution of sodium chloride (NaCl), and are then dried over anhydrous sodium sulphate (Na ₂ SO ₄ ). L ¹ AcOEt is evaporated and 17.49 g of pale yellow clear oil are collected and stored at -25 ⁰ C. The analyzes indicate that the product complies.

Step 2: Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4-methylpyridinium) Dimethanesulfonate

3.51 g of 4 picoline and 5 g of disulfanediyldiethane-2,1-diyl dimethanesulphonate are diluted in 5 ml of N-methylpyrrolidinone (NMP) and then heated at 80 ^° C. with stirring for 2 h. Stirring is maintained at room temperature for 17 hours. The reaction medium is supplemented with 50 ml of ethyl acetate, then filtered, washed with 3 times 100 ml of AcOEt, and dried under vacuum under P ₂ O ₅ . 7.29 g of brown powder are collected. The analyzes indicate that the product is compliant.

Step 3: Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis {4 - [(E) -2- (4-hydroxy-2-methoxyphenyl) vinyl] pyridinium} [1] 1 g dimethanesulphonate of 4-hydroxy-2-methoxybenzaldehyde, 10 ml of isopropanol (iPrOH), and 1.69 ml of pyrrolidine are mixed with stirring for 10 minutes. 1.18 mL of acetic acid is added and the mixture is stirred at room temperature for 20 minutes. Dimethanesulfonate 5 g of 1, 1 ^l - (disulfanediyldiéthane-2,1-diyl) bis (4-methylpyridinium) was suspended in 7 mL of iPrOH and 2 ml of methanol are added. The reaction mixture is stirred for 24 h at room temperature. The precipitate obtained is filtered, washed with 100 mL of acetone and then dried. 2.32 g of powder are collected. The analyzes indicate that the product is compliant.

¹ H NMR (400 MHz, MeOH-O ₄ ) 2.71 (s, 4.7 H), 3.37 (t, 4H), 3.9 (s, 6H), 4.78 (t, 4H), 6.45-6.47 (d and dd, 4H), 7.23 (d, 2H), 7.58 (d, 2H), 8 (d, 4H), 8.07 (d, 2H), 8.61 (d, 4H). Example 2 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis {4 - [(E) -2- (3,4,5-trimethoxyphenyl) vinyl] pyridinium dibromide [2]

[2] Diagram of synthesis

[2]

Step 1: Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4-methyl-pyridinium) dibromide

67 g of 4-picoline are diluted in 100 ml of acetonitrile and the mixture is heated to 80 ^° C. A mixture of 60 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] ethane and 15 ml of N - methylpyrrolidinone (NMP) is added in 5 min. After stirring for 4 h at 85 ^° C., the mixture is cooled. The solid obtained is filtered, rinsed with 3 x 200 mL of acetonitrile and then dissolved in 800 mL of iPrOH at reflux. After cooling, 1 L of ethyl ether is added. The precipitate formed is filtered, rinsed with 3 × 200 ml of ethyl ether and then dried. The off-white powder obtained (73.77 g) contains for the most part (> 90%) the expected product which is used as it is for the next step.

Step 2: Synthesis of dibromide 1,1 ^l - (disulfanediyldiéthane-2,1-diyl) bis {4- [(E) -2- (3,4,5-trimethoxyphenyl) vinyl] pyridinium} [2]

785 mg of 3,4,5-trimethoxybenzaldehyde and 932 mg of 1,1'- (disulfanediyldiethane-2,1-diyl) bis (4-methylpyridinium) dibromide obtained in the previous step suspended in 10 ml of iPrOH. 232 μl of acetic acid and 328 μl of pyrrolidine are added to the mixture. After stirring at room temperature for 2 h 30, the mixture is poured into acetone. 600 mg of orange powder are collected after filtration. ¹ H NMR (400 MHz, MeOH-Of _4): 3.31 (t, 4H), 3.68 (s, 6H), 3.78 (s, 12H), 4.71 (t, 4H), 6.94 (s, 4 H), 7.27 (d, 2H), 7.76 (d, 2H), 8.04 (d, 4H), 8.67 (d, 4H).

Example 3 Synthesis of 4 - [(E) -2- (4-hydroxy-2-methoxyphenyl) vinyl] -1- (2-sulfanylethyl) pyridinium methanesulfonate [3]

[3]

Diagram of synthesis

Operating mode Synthesis of 4 - [(E) -2- (4-hydroxy-2-methoxyphenyl) vinyl] -1- (2-sulfanylethyl) pyridinium salt [3]

76 mg of the compound [1] are dissolved in 10 ml of water / ethanol mixture 1: 1); 60 mg

(2 eq.) Of 3- [bis (2-carboxy-ethyl) phosphino] -propanoic acid hydrochloride hydrate in solution in 1 mL of water and 21 mg (4 eq) of sodium bicarbonate in solution in 1 mL of water is added to the mixture. After 30 minutes of agitation at

40 ^° C. under an inert atmosphere, the analyzes indicate that the product is compliant [3].

LC-MS analysis: LC-DAD (400-700 nm)

Column: Waters XTerra MS C18 5μm (4.6 x 50) mm

Mobile phase: A: Water + formic acid 0.1% / B: acetonitrile

Linear gradient: T (min) A% / B%: 0 min 95/5; 8min 0/100

Flow: 1mL / min.

Detection: UV diode array λ = 400-700nm

Retention time t = 3.5 min.

Relative purity> 95%,

MS (ESI +) m / z = 288 corresponds to the mass peak of the expected product monocation [3]

EXAMPLE OF COLORING

Staining process with compounds [1] and [2]

Preparation of a composition A

of a composition B

Thioglycolic acid 1 M

Sodium hydroxide qsp pH 8.5

Demineralized water qs 100g

At the time of use, the compositions A (9 ml) and B (1 ml) are mixed, then apply the resulting mixture to a lock of 1 g of dark hair (pitch 4) placed at the bottom of a bowl, for 30 minutes at room temperature (the locks are returned and re-impregnated after 15 minutes). After rinsing with running water and drying, a lightening of the hair thus treated is observed: the lock of pitch 4 became visually clearer than untreated control locks.

Staining process - dye [3]

10 ml of fresh solution of the compound [5] of Example 5 are applied to a lock of 1 g of hair of pitch 4 arranged at the bottom of a bowl for 30 minutes at room temperature (the locks are turned and re-impregnated after 15 minutes). The locks are then rinsed with running water and dried.

After staining, the pitch lock 4 became visually brighter than untreated control locks.

Remanence vis-à-vis successive shampoos:

The locks thus treated are divided in two, one half is subjected to 5 successive shampoos in a cycle which comprises wetting the locks with water, washing with a conventional shampoo, rinsing with water followed by drying.

Visual Observations When shampooing, there is no visible bleeding, shampoo foam and rinsing water are not colored.

The observed color and the lightening effect remain visible on the hair of pitch 4 thus treated.

Reflectance results:

The lightening performance of the compositions according to the invention and their persistence with respect to successive shampoos were expressed as a function of the reflectance of the hair. These reflectances are compared with the reflectance of a lock of untreated HT4 pitch hair.

The reflectance is measured using a KONIKA-MINOLTA®, CM 260Od spectrophotocolorimeter and after irradiation of the hair with visible light in the wavelength range of 400 to 700 nanometers.

Reflectance of wicks treated with compounds 1 and 2 at application and after 5 shampoos

1 1 - 5 shampoos 2 2 - 5 shampoos

oooooooo CM - * co oo o (N CD OO O CM • * "* • * • * ^• <* m io LO IO CD CO (8D § (O 8 N

Wavelength (nm)

It is firstly noted that the reflectance of a lock of hair treated with a composition according to the invention is greater than that of untreated hair. The treated locks therefore appear clearer.

In addition, the results of FIG. 1 show that the reflectance of the locks of hair of pitch 4 treated with the composition of the invention changes very little even after 5 shampoos. Thus the coloration and the lightening effect on the hair remains almost unchanged which shows a very good resistance to shampoos dyes of the invention.

Results in the L ^* a ^* b ^{* system} :

The color of the locks before and after the 5 washes was evaluated in the L * a * b * system by means of a MINOLTA® CM 2600D spectrophotometer (Illuminant D65).

In this system L ^* a ^* b ^* , L * represents the brightness, a * indicates the green / red color axis and b ^* the blue / yellow color axis. The higher the L value, the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color. The variation of the coloration between the locks of HT4 hair, stained and washed is measured by ΔE according to the following equation:

Δ E = V (L ^* - L ₀ ^* ) ² + (a ^* - a ₀ ^* ) ² + (b ^* - b ₀ ^* f

In this equation, L *, a * and b * represent the values measured after staining and L ₀ *, ao * and bo * represent the values measured before staining (or shampooing).

The results of the table above show that the color changes very little even after 5 shampoos. Thus the coloration and the lightening effect on the hair remains almost unchanged which shows a very good resistance to shampoos dyes of the invention.

Claims

1. Fluorescent dye of formula (I) or (II):

(I) its organic or inorganic acid salts, optical isomers, geometrical, and solvates such as hydrates, formulas (I) or (II) in which:

> R and R ', which may be identical or different, represent a hydrogen atom, a (CrC ₄ ) alkyl or benzyl group; R 1, R '1, R "1 and R"", identical or different, represent a hydrogen atom, or a (C ₁ -C ₄ ) alkyl group;

> M 'represents an anionic counterion

m and m ', identical or different, represent an integer inclusive between 1 and 6; > p and p ', which may be identical or different, represent an integer between 1 and 5;

Y represents i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N ⁺ R ^α R ^β R ^γ R ^δ or a phosphonium group: P ⁺ R ^α R ^β R ^γ R ^δ with R ^α , R ^β , R ^γ and R ^δ , identical or different, representing a hydrogen atom or a (dC ₄ ) alkyl group; or v) a thiol protecting group; Being heard that :

- When the compound of formula (I) or (II) contains other cationic parts, it is associated with one or more anionic counter-ions to achieve the electroneutrality of formula (I) or (II); when p and / or p 'is an integer greater than or equal to 2, the groups RO may be the same or different;

when two groups RO and / or two groups R'O are adjacent, the two radicals R and / or the two radicals R 'can form together an alkylene chain - (CRi R ₂ V, with R 1 and R ₂ , identical or different , represent a hydrogen atom or a group (CrC ₄ ) alkyl and q represents an integer inclusive between 1 and 3.

2. Fluorescent dye of formula (II) according to the preceding claim wherein

Y represents a hydrogen atom.

3. Fluorescent dye of formula (II) according to the preceding claim wherein Y represents an alkali metal.

4. Fluorescent dye of formula (II) according to claim 1 wherein Y represents a protective group.

5. Fluorescent dye of formula (II) according to the preceding claim wherein

Y represents a protective group chosen from the following radicals: • (Ci-C ₄ ) alkylcarbonyl;

. (Ci-C ₄₎ alkylthiocarbonyl;

• (Ci-C ₄₎ alkoxycarbonyl;

. (Ci-C ₄₎ alkoxythiocarbonyl;

• (Ci-C ₄₎ alkylthio-thiocarbonyl; . (di) (CrC ₄ ) (alkyl) aminocarbonyl;

(Di) (CrC ₄ ) (alkyl) aminothiocarbonyl; . arylcarbonyl;

Aryloxycarbonyl;

. aryl (C ₁ -C ₄ ) alkoxycarbonyl; (Di) (CrC ₄ ) (alkyl) aminocarbonyl;

• (CrC ₄ ) (alkyl) arylaminocarbonyl;

• carboxy;

SO ₃ ^" ; M ⁺ with M ⁺ representing an alkali metal or M ⁺ and M 'of the formula (II) are absent; optionally substituted aryl;

Optionally substituted heteroaryl;

. optionally substituted heterocycloalkyl, optionally cationic;

The heterocycle represents the following grouping:

wherein R ^'c, R' ^d, R ^'Θ, R' ^f, R ^'9 and R' ^h, identical or different, represent a hydrogen atom or a (Ci-C ₄₎ alkyl, or else two groups R ' ⁹ with R' ^h , and / or R ' ^Θ with R' ^f form an oxo or thioxo group, or else R ' ⁹ with R' ^Θ together form a cycloalkyl; and v represents an integer inclusive of between 1 and 3;

. isothiouronium -C (NR ' ^c R' ^d ) = N ⁺ R ' ^Θ R'^f; An ^"with R ^'c, R' ^d, R ^'Θ and R' ^f, like or different, represent a hydrogen atom or a (dC ₄₎ alkyl;. Isothiourea -C (NR ^'c R' ^d) = NR ' ^Θ with R' ^c , R ' ^d , R' ^Θ as defined above: (di) aryl (Ci-C ₄ ) alkyl optionally substituted;

(Di) optionally substituted heteroaryl (CrC ₄ ) alkyl;

. CR ¹ R ² R ³ with R ¹ , R ² and R ^{3, which may be} identical or different, representing a halogen atom or a group chosen from:

- (Ci-C ₄₎ alkyl; - (Ci-C ₄₎ alkoxy;

optionally substituted aryl;

optionally substituted heteroaryl;

- P (Z ¹ ) R ' ¹ R ¹² R' ³ with R ' ¹ , and R' ² identical or different represent a hydroxyl group, (CrC ₄ ) alkoxy or alkyl, R ' ³ represents a hydroxyl group or (dC ₄ alkoxy, and Z ¹ represents an oxygen or sulfur atom;

. sterically hindered cyclic such as adamantyl group; and

• optionally substituted alkoxy (dC ₄ ) alkyl.

6. Fluorescent dye according to the preceding claim wherein Y represents a protective group chosen from:> (C _r C ₄ ) alkylcarbonyl;

> arylcarbonyl;

(C _r C ₄ ) alkoxycarbonyl;

> aryloxycarbonyl;

> aryl (CrC ₄ ) alkoxycarbonyl; (di) (CrC ₄ ) (alkyl) aminocarbonyl;

> (CrC ₄ ) (alkyl) arylaminocarbonyl;

optionally substituted aryl;

cationic monocyclic heteroaryl with 5, 6 members; 8 to 11-membered cationic bicyclic heteroaryl;

cationic heterocycle of following formula:

> isothiouronium -C (NH ₂ ) = N ⁺ H ₂ ; An ^" ;

> isothiourea -C (NH ₂ ) = NH; and> SO ₃ ^" ; M ⁺ with M ⁺ representing an alkali metal or else M ⁺ and M 'of the formula

(II) are absent.

Fluorescent dye according to any one of the preceding claims of formula (Ia) or (IIa):

formulas (Ia) or (Ma) in which the group (s) RO- and / or R ¹ O-, identical or different, positioned particularly in 2 'and / or 4' and the styryl group is connected to the pyridinium ring in position 2 or 4.

8. Fluorescent dye according to the preceding claim of formula (Ma) wherein RO- and RO'- are identical.

9. Fluorescent dye according to any one of the preceding claims, chosen from the following colorants:

With An ^" representing an anionic counterion.

10. Dyeing composition comprising in a suitable cosmetic medium, a fluorescent dye of formula (I) or (II) as defined in any one of claims 1 to 9.

11. dye composition comprising in a suitable cosmetic medium, at least one fluorescent dye of formula (I) or (II) as defined in any one of claims 1 to 9 and at least one reducing agent.

12. Dyeing composition according to the preceding claim wherein the reducing agent is chosen from: cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid, as well as its esters, borohydrides and their derivatives, the sodium, lithium, potassium, calcium and quaternary ammonium salts; catecholborane.

13. Composition according to any one of claims 10 to 12, wherein the fluorescent dye of formula (I) or (II) is present in an amount of between 0.001 and 50% by weight relative to the total weight of the composition.

14. A process for dyeing keratin materials, in which materials, a dye composition as defined in any one of claims 10 to 13, comprising in a suitable cosmetic medium, at least one fluorescent dye of formula (I) or (II) as defined in any one of claims 1 to 9, optionally in the presence of a reducing agent.

15. The method of dyeing according to the preceding claim wherein when the thiol fluorescent dye of formula (II) comprises a protective Y group, the application is preceded by a deprotection step.

16. A method of dyeing keratin materials according to claim 14 or 15 characterized in that the keratin materials are dark keratinous fibers having a pitch of less than or equal to 6.

The method of any one of claims 14 to 16 wherein the reducing agent is applied before or after the application of the thiol fluorescent dye.

18. The method of any one of claims 14 to 17, wherein the composition comprises an oxidizing agent.

19. A method according to any one of claims 14 to 17 comprising a further step of applying to the keratin fibers an oxidizing agent.

20. Multi-compartment device wherein a first compartment contains a dye composition comprising a fluorescent dye as defined in claims 1 to 9 and a second compartment contains a reducing agent.

21. Device according to the preceding claim comprising a third compartment which contains an oxidizing agent.

22. Use of fluorescent dyes of formula (I) or (II) as defined in claims 1 to 9 for dyeing dark human keratin fibers.

23. Use according to the preceding claim for lightening dark keratin fibers.

24. Use according to claims 22 and 23 characterized in that the keratin fibers have a pitch of less than 6.