FR2912142A1 - New naphthalimido- or naphthalimidylamino-substituted thiol derivative fluorescent dye compounds, useful for dyeing keratin fibers, especially for lightening dark human hair - Google Patents

Abstract

New fluorescent dye compounds consist of omega -(substituted alkylamino-naphthalimido)-alkanethiol compounds (I), omega -(naphthalimidyl-amino)-alkanethiol compounds (II) or their S-substituted derivatives. Naphthalimido- or naphthalimidylamino-substituted thiol derivative fluorescent dye compounds of formulae (I) and (II) and their mineral or organic acid addition salts, optical and geometric isomers, hydrates and other solvates are new. R aarylalkyl or 1-6C alkyl (optionally substituted (os) by OH, NH 2, mono- or dialkylamino or 5-7 membered N-heterocyclyl (optionally containing additional heteroatom(s)); R bH, arylalkyl or os 1-6C alkyl (especially H, 1-3C alkyl or benzyl); R eoptionally unsaturated 1-6C alkylene; R f-N +>R''R'''R''''.M', os cationic N-heteroaryl residue (plus M'), OH, NH 2, mono- or dialkylamino or os, non-cationic heteroaryl; R'', R''', R'''' : H or alkyl; R gH, halo, NH 2, mono- or dialkylamino, CN, COOH, OH, CF 3, acylamino, alkoxy, 2-4C mono- or polyhydroxyalkoxy, alkylcarbonyloxy, alkoxycarbonyl, alkylcarbonylamino, acylamino, CONH 2, alkylsulfonylamino, SO 2NH 2 or 1-16C alkyl (os by 1-12C alkoxy, OH, CN, COOH, NH 2, mono- or dialkylamino or 5-7 membered N-heterocyclyl (optionally containing additional heteroatom(s)); R 1 - R 4H, alkyl, alkoxy, OH, CN, COOH, NH 2, mono- or dialkylamino or 5-7 membered N-heterocyclyl (optionally containing additional heteroatom(s)); T adirect bond; one or more of SO 2, O, S, N(R), -N +>(R)(R 0>)- or CO; or cationic or non-cationic heterocycloalkyl or heteroaryl; m, n : 0-6; m + n : 1-10; M' : counter-anion; Y : H, alkali(ne earth) metal, NH 4 +>, PH 4 +>, mono-, di-, tri- or tetraalkyl-ammonium, mono-, di-, tri- or tetraalkyl-phosphonium or thiol protecting group; alkyl moieties have 1-4C unless specified otherwise; if (I) or (II) contains additional cationic moieties, at least one further counter-anion is present to preserve electro-neutrality. Independent claims are included for: (1) a dyeing composition (A) comprising (I) or (II) and optionally a reducing agent (III) in a cosmetic medium; (2) a method for dyeing keratin fibers, involving application of (A); and (3) a multi-compartment dyeing device, having a first compartment containing (I) or (II), a second compartment containing (III) and optionally a third compartment containing an oxidizing agent. [Image].

Description

DYE COMPOSITION COMPRISING A NAPHTHYLIMIDE FLUORESCENT COLOR,

  The invention relates to the dyeing of keratin materials using fluorescent dyes thiols naphthylimide.

  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 triarylmethane type. The colorations 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. The fibers tend to become rough, more difficult to disentangle and more fragile. Finally, the lightening or the bleaching of keratinous fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in the straightening treatments. Another lightening technique consists in applying fluorescent direct dyes to dark hair. This technique described in particular in 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, 42, 1-17 (1991); CA 2024509; In addition it is known to protect the thiol function (s) contained in a molecule to be grafted to the hair before applying them to said hair WO99 / 51194. However, this application does not mention the use of fluorescent dyes for coloring or lightening hair.

  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 fluorescent dye thiol, chosen from the following dyes of formulas (I) and (II): N (I) and their organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates; formulas (I) and (II) in which:

  Ra represents an aryl (C 1 -C 4) alkyl group or a (C 1 -C 6) alkyl group optionally substituted by a hydroxyl group, or (di) (C 1 -C 4) (alkyl) amino, said alkyl radicals being able to form with the nitrogen atom carrying them a 5- to 7-membered heterocyl, optionally comprising another heteroatom different or different from nitrogen; preferably Ra represents a (C 1 -C 3) alkyl group optionally substituted by a hydroxyl group, or a benzyl group;

  - Rb represents a hydrogen atom, an aryl (C 1 -C 4) alkyl group or an optionally substituted (C 1 -C 6) alkyl group; especially Rb represents

  a hydrogen atom or a C1-C3 alkyl or benzyl group;

  Re represents a divalent (C 1 -C 6) alkylenyl hydrocarbon chain,

  linear or branched, possibly unsaturated; + - Rf represents i) a quaternary ammonium group (R ") (R" ') (R "") N -, M' where R ", R" 'and R "", which are identical or different, represent an atom of hydrogen + or a (C 1 -C 4) alkyl group or else (R ") (R" ') (R "") N - represents an optionally substituted cationic heteroaryl group, in particular an imidazolium group optionally substituted by a group (C 1 - C3) alkyl and M 'represents an anionic counterion; ii) a hydroxyl group; iii) (C1-C6) (di) (alkyl) amino; or iv) optionally substituted non-cationic heteroaryl such as imidazolyl;

  - Rg represents a hydrogen, halogen, amino, (di) (C 1 -C 4) alkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, C 1 -C 4 alkoxy, (poly) hydroxyalkoxy group; C2-C4, (C1-C4) alkylcarbonyloxy (C1-C4) alkoxycarbonyl, (C1-C4) alkylcarbonylamino, acylamino, carbamoyl, (C1-C4) alkylsulfonylamino, amino-sulfonyl, or (C) -C16) alkyl optionally substituted with a group selected from (C 1 -C 12) alkoxy, hydroxy, cyano, carboxy, amino, (di) (C 1 -C 4) alkylamino, or both alkyl radicals borne by the atom nitrogen of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom; especially Rg represents a hydrogen atom; -R ,, R2, R3, R4, identical or different, represent a hydrogen atom or a (C1-C4) alkyl, (C1-C4) alkoxy, hydroxy, cyano, carboxy, (di) (C1-C4) ) (alkyl) amino, said alkyl radicals being capable of forming, with the nitrogen atom which carries them, a 5- to 7-membered heterocyl, optionally comprising another heteroatom which may or may not be different from nitrogen; in particular R 1, R 2, R 3 and R 4 are hydrogen atoms or an amino group; especially R 1, R 2, R 3 and R 4 represent a hydrogen atom; Ta is: i) either a covalent bond a, ii) or one or more radicals or combinations thereof selected from -SO2-, where Where?, Where N (R) ù, ùN + (R) (R) ù, ùC ( Wherein R and R, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 hydroxyalkyl radical or a (C1-C4) alkyl radical; in particular, Ta represents a covalent bond a or a group chosen from ùN (R) -, ùC (O) ù, ùC (O) ùN (R) ù, ùN (R) ùC (O) ù, ùC (O) ùN (R) ùC (O) ù, where ùC (O) ù, ùC (O) ùOù and ùN + (R) (R) ù, with R, R being identical or different, representing a hydrogen atom, a C1-C4 alkyl group alkyl; especially Ta represent a bond a; iii) a heterocycloalkyl or heteroaryl radical, cationic or non-cationic, preferentially monocyclic, containing in particular two heteroatoms, particularly two nitrogen atoms, and comprising especially from 5 to 7 members such as imidazolium, piperidyl, homopiperidyl, piperidinium, homopiperidinium, if appropriate; substituted with a (C1-C4) alkyl group such as methyl; m and n, identical or different, represent an integer inclusive between 0 and 6 with m + n represents an integer inclusive between 1 and 10; particularly the sum m + n is an integer inclusive between 2 and 4; preferentially m + n is an integer equal to 2; and Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + RaRRRYR8 or a phosphonium group: P + RaRRRYR8 with Ra, RR, R7 and R8, which may be identical or different, representing a hydrogen atom or a (C 1 -C 4) alkyl group; or v) a thiol protecting group;

  it being understood that: when the compound of formula (I) or (II) contains one or more cationic parts, it is associated with one or more anionic counter-ions making it possible to reach the electroneutrality of formula (I) or (He).

  Another subject of the invention is a dye composition comprising, in a suitable cosmetic medium, at least one thiol fluorescent dye of formula (I) or (II) as defined above, and optionally a reducing agent. The invention also relates to new thiol 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 regard 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" means that which has a luminescence L * encoded in the C.I.E. L * a * b *, less than or equal to 45 and preferably less than or equal to 40, knowing moreover that L * = 0 is equivalent to black and L * = 100 to white. For the purposes of the invention, the term naturally or artificially dark hair is understood to mean hair whose pitch is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut). hair is evaluated by the variation in pitch before and after application of the compound of formula (I) or (II). The notion of tone is based on the classification of natural nuances, a tone separating each nuance from that which follows it or immediately precedes it. This definition and the classification of natural shades is well known to hair professionals and published in the book Science of hair treatment Charles ZVIAK 1988, Ed Masson, p. 215 and 278. The pitch ranges from 1 (black) to 10 (very light blonde), a unit corresponding to a tone; the higher the number, the clearer the nuance.

  An artificially colored hair is a hair whose color has been modified by a coloring treatment, for example a coloration with direct dyes or oxidation dyes. Preferably, the composition must after application to hair, for example, chestnut, bring to the results below. - We are interested in the reflectance performance of hair when irradiated with visible light in the wavelength range of 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 range of wavelengths ranging from 450 to 700 nanometers greater than the curve corresponding to untreated hair. This means that, in the wavelength range of 450 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 it can exist in the range of wavelength from 450 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 greatest between the reflectance curve of the treated hair and that of the untreated hair is in the wavelength range of 450 to 650 nanometers, and preferably in the wavelength range from 450 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 C1-C16, preferably C1-C8, alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C1-C2 alkoxy and (C2-C4) poly (-hydroxyalkoxy) acylamino radicals; amino substituted with two identical or different C 1 -C 4 alkyl radicals, optionally carrying at least one hydroxyl group, or the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated ring optionally comprising another heteroatom identical to or different from nitrogen; A halogen atom such as chlorine, fluorine or bromine; • a hydroxyl group; A C1-C2 alkoxy radical; A C1-C2 alkylthio radical; A C2-C4 (poly) -hydroxyalkoxy radical; An amino radical; A 5- or 6-membered heterocycloalkyl radical; A 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl; An amino radical substituted with one or two identical or different C1-C6 alkyl radicals optionally carrying at least: i) a hydroxyl group; ii) an amino group optionally substituted by one or two C1-C3 alkyl radicals; optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or different from nitrogen, -NR-COR 'in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C1-C2 alkyl radical; (R) 2N-CO- in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; R'SO2-NR- in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C1-C4 alkyl radical; phenyl radical; (R) 2N-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 form or salified (preferably with an alkali metal or 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 following groups: • hydroxy, • C 1 -C 4 alkoxy, • (poly) C 2 -C 4 hydroxyalkoxy, A C1-C2 alkylthio radical; RCO-NR'- in which the R 'radical is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R radical is a C 1 -C 2 alkyl substituted amino radical; by two identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group; RCO-O- in which the radical R is a C 1 -C 4 alkyl radical, amino substituted with one or 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 optionally substituted saturated or unsaturated heterocycle optionally comprising at least one other non-nitrogen heteroatom; RO-CO- wherein the radical R is a C1-C4 alkyl radical optionally bearing at least one hydroxyl group; 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, fused or otherwise, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium, and at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and its ammonium salt; a diheteroarylalkyl radical represents a group comprising, on the same carbon atom of an alkyl group, two heteroaryl groups, which are identical or different, such as difurylmethyl, 1,1-difurylethyl, dipyrrolylmethyl and dithienylmethyl; a cyclic radical is a non-aromatic cycloalkyl radical, mono- or polycyclic, condensed or otherwise, containing from 5 to 22 carbon atoms, which can comprise from 1 to several unsaturations; particularly the cyclic radical is cyclohexyl; - A sterically hindered cyclic radical is a cyclic radical, aromatic or not, substituted or unsubstituted, hindered by steric effect or constraint, comprising from 6 to 14 members, which can be bridged, as sterically hindered radicals include bicyclo [1.1]. Butane, mesytyls such as 1,3,5-trimethylphenyl, 1,3,5-triterbutylphenyl, 1,3,5-isobutylphenyl, 1,3,5-trimethylsilylphenyl and adamantyl;

  a heterocyclic radical or heterocycle is a mono or non-aromatic radical;

  polycyclic, condensed or not, containing from 5 to 22 members, having from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium;

  an alkyl radical is a linear or branched C1-C16 hydrocarbon radical of

C1-C8 preference;

  the optionally substituted expression attributed to the alkyl radical, that is to say that said alkyl radical may be substituted by one or more radicals chosen from i) hydroxyl, ii) C 1 -C 4 alkoxy, iii) acylamino, iv) amino optionally substituted by one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being capable of forming, with the nitrogen atom carrying them, a 5- to 7-membered heterocyl, optionally comprising another heteroatom different from or different from nitrogen; v) or a quaternary ammonium group -N R'R "R" ', M for which R', R ", R" ', identical or different, represent a + hydrogen atom, or a C 1 -C 4 alkyl group, or else -N R'R "R" 'form

  a heteroaryl such as imidazolium optionally substituted by a C1-C4 alkyl group, and M represents the counter-ion of the corresponding organic acid, mineral or halide, - an alkoxy radical is an alkyl-oxy or alkyl-O radical; for which the alkyl radical is a hydrocarbon radical, linear or branched, C1-C16 preferentially C1-C8;

  an alkylthio radical is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, C1-C16 preferably C1-C8; when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above;

  the boundaries delimiting 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) alkylsulphonic acids: Alk- S (O) 2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2OH such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3COOH; xiv) triflic acid CF3SO3H and xv) 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 selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulphonates, including C1-C6 alkylsulphonates: Alk-S (O) 2O- such as methylsulphonate or mesylate and ethylsulphonate; iv) arylsulfonates: Ar-S (O) 20- such as benzenesulphonate and toluenesulphonate or tosylate; v) citrate; vi) succinate; (vii) tartrate; viii) lactate; ix) alkyl sulfites: Alk-O-S (O) O- such as methysulfite and ethylsulfite; x) arylsulfites: Ar-O-S (O) O-such as benzenesulphite and toluenesulphite; xi) alkylsulfates: Alk-O-S (O) 2O- such as methyl sulfate and ethylsulfate; xii) arylsulfates: Ar-O-S (O) 2O-, xiii) phosphate; (xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate. The thiol fluorescent dyes of formula (I) or (II) are compounds capable of absorbing in the UV or visible radiation at an Xabs wavelength of between 250 and 800 nm and capable of reemitting in the visible range at a Xem emission wavelength between 400 and 700 nm. Preferably thiol fluorescent compounds of the invention are dyes capable of absorbing in the visible Xabs between 400 and 700 nm and reemitting in the visible Xem between 400 and 700 nm. More preferably, the thiol fluorescent dyes with formula (I) or (II) are dyes capable of absorbing at an Xabs between 400 nm and 550 nm and reemitting in the visible at an Xem of between 450 and 620 nm. The fluorescent compounds of the invention contain a SY function which may be in the covalent -S-Y or ion -S-Y + form depending on the nature of Y and the pH of the medium. One particular embodiment relates to thiol fluorescent dyes of formula (I) or (II) with SY function where Y represents a hydrogen atom, or an alkali metal. Advantageously, Y represents a hydrogen atom.

  According to another particular embodiment of the invention, in the formula (I) or (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 , TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, chap. 5. Particularly when Y is a protecting group for the thiol function, Y is selected from the following radicals: (C 1 -C 4) alkylcarbonyl; (C 1 -C 4) alkylthiocarbonyl; (C1-C4) alkoxycarbonyl; (C 1 -C 4) alkoxythiocarbonyl; C 1 -C 4 alkylthio thiocarbonyl; ^ (di) (C1-C4) (alkyl) aminocarbonyl; ^ (di) (C1-C4) (alkyl) aminothiocarbonyl; arylcarbonyl as phenylcarbonyl; aryloxycarbonyl; aryl (C1-C4) alkoxycarbonyl; (di) (C1-C4) (alkyl) aminocarbonyl as dimethylaminocarbonyl; (C 1 -C 4) (alkyl) arylaminocarbonyl; carboxy; ^ S03; W with M + representing an alkali metal such as sodium or potassium or W and M 'of the formula (I) 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 C 1 -C 4) alkyl as methyl, or polyhalo (C 1 -C 4) alkyl as trifluoromethyl; iii) or tricyclic ABC according to: wherein the two rings A, C optionally comprise a heteroatom, and the ring B is a 5-, 6- or 7-membered particularly 6-membered ring and contains at least one heteroatom such as pyperidyl, pyranyl; optionally substituted heterocycloalkyl, optionally cationic heterocycloalkyl represents in particular a saturated or partially saturated 5, 6 or 7 membered monocyclic group comprising from 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 (C1-C4) alkyl, oxo or thioxo; or the heterocycle represents the following group: R '\ R'g R, where R', R'g, R'e, R'f, R'g and R '", which are identical or different, represent a hydrogen atom or a (C1-C4) alkyl group, or else two R'g groups with R'", and / or R'e with R'f form an oxo or thioxo group, or else R'g with R'e together form a cycloalkyl, and v represents an integer inclusive between 1 and 3, preferentially R 'to R' "represent a hydrogen atom; and An represents a counterion; isothiouronium -C (NR 'R'd) = N + R'eR'f; With R ', R'g, R'e and R'f, identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl group; preferentially R 'to R' f represent a hydrogen atom; and An- represents a counterion; isothiourea -C (NR 'R'd) = NR'e; with R'd, R'e, as defined previously; optionally substituted di (aryl) (C 1 -C 4) alkyl, such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl, optionally substituted by one or more groups chosen in particular from (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy, such as methoxy, hydroxy, (C1-C4) alkylcarbonyl, (di) (C1-C4) (alkyl) amino such as dimethylamino; optionally substituted heteroaryl (C 1 -C 4) alkyl, the heteroaryl group is in particular, cationic or non-monocyclic, comprising 5 or 6 members and 1 to 4 heteroatoms chosen from nitrogen, oxygen and sulfur; , such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium, triazinyl, optionally substituted with one or more group such as alkyl particularly methyl preferably (di) heteroaryl (C 1 -C 4) alkyl is (di) heteroarylmethyl or (di) heteroarylethyl; CR'R 2 R 3 with R ', 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; - (C1-C4) alkoxy; optionally substituted aryl such as phenyl optionally substituted by one or more groups such as (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy, hydroxy; - optionally substituted heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted with a (C1-C4) alkyl group; -P (Z ') R''R'2R'3 with R'1, and R'2 identical or different represent a hydroxyl group, (C1-C4) alkoxy or alkyl, R'3 represents a hydroxyl group or ( C 1 -C 4) alkoxy, and Z 'represents an oxygen or sulfur atom; sterically hindered cyclic such as adamantyl group; and optionally substituted (C 1 -C 4) alkoxyalkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.

  According to a particular embodiment, the protected thiol fluorescent dyes of formula (I) or (II) contain a group Y i) cationic aromatic 5- or 6-membered monocyclic heteroaryl 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, imidazolium; ii) cationic 8 to 11-membered bicyclic heteroaryl such as indolinium, benzoimidazolium, benzoxazolium, benzothiazolium, these mono or bicyclic heteroaryl groups being optionally substituted with one or more groups such as alkyl as methyl, or polyhalo (C 1 -C 4) alkyl as trifluoromethyl; iii) or heterocyclic according to: R '\

  N Rd An wherein R 'and R'd, identical or different, represent a hydrogen atom or a group (C, -C4) alkyl; preferentially R 'to R'd represent a (C 1 -C 4) alkyl group 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 (C1-C4) alkyl groups including methyl.

  In particular Y represents an alkali metal or a protective group such as: - (C1-C4) alkylcarbonyl such as methylcarbonyl or ethylcarbonyl; arylcarbonyl, such as phenylcarbonyl; - (C1-C4) alkoxycarbonyl; -aryloxycarbonyl; aryl (C1-C4) alkoxycarbonyl; - (di) (C1-C4) (alkyl) aminocarbonyl such as dimethylaminocarbonyl; - (C1-C4) (alkyl) arylaminocarbonyl; optionally substituted aryl such as phenyl; 5- or 6-membered monocyclic heteroaryl such as imidazolyl or cationic 5- to 6-membered monocyclic 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 the following formula: Me N N Me An-> isothiouronium -C (NH2) = N + H2; An; - isothiourea -C (NH 2) = NH; - SO3, W.

  By way of example of thiol fluorescent dyes, mention may be made in particular of the following compounds: O \ '. N ~ SH / N ~ / / NH SH M 'M' 1 2 N. ~ O vN ~ O \ NN \ NSH N ~ \ VHO, H SH M 'M' 3 4 o \ \ N Name \ ± NiSH N / , HH / '"ON ~ SM' OM '5 6 ON * NN O // H ~ O ~ HNO ~ M' M '7 8 oo OH SH \ .M' NOHN 2M '9 10 OO \ NN ~ \ N' + \. \ \ \ N Name \ / OH \ = / Ov 2M 'OHS ~ OM' 11 12 ~ IN + ~ ~ N + 1 HN ~ N ~ O ~ Ph HNOM 'ON' -N \ M '13 14 \ N + ~ NO N '~ HO v ~ NN) -N \ HNHS * ~ SN 2M' O 15 16 HO O \ N ~ NO HO HN ~ * SH N ~ SH O 17 18 With M ', same or different, representing a counter anionic ion. Synthesis of the dyestuffs of formula (I): The protected thiol dyes of formula (I ') and (I ") can be synthesized in two stages The first step of preparing the unprotected thiol dye (a) according to the known methods of 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 the conventional methods known to the skilled in the art to lead to protected thiol dyes of formula (I ') and (I "),. By way of example, to protect the thiol function of the thiol dye, the methods of Protective Groups in Organic Synthesis, T.W. Greene, John Willey & Sons, Ed., NY, 1981, pp.193-217; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, chap. 5. We can illustrate this method by the method consisting of i) generating thiol fluorescent dyes of formula d by reducing a fluorescent dye to two chromophores, naphthylimide, having a disulfide function -SS-such as IQ and ii) to protect according to conventional methods, said thiol function of j with the reagent Y 'R to access protected thiol fluorescent dyes of formula (II'). The thiol compound may also be metallized with an alkali metal or alkaline earth metal Met * to yield the thiolate fluorescent dye of formula (II ").

  HS 1930, Re-R, N Rb Rb Rf Re, Ta / SH Nu (CRI R2) m "(CR3R4) n N o iTa ~ / SùS / Ta ~ N Nu (CR R) (CRR) 12m34n (CR3R4 Another alternative for synthesis of naphthylimide thiol dye is to condense the reagent comprising the naphthylimide group (c) with a reagent bearing the thiol group protected by Y ', such as the reagent (d): ## STR2 ## Y'R -RH Rb \ O, T / SY '(N1 (CR1R2) m N (CR3R4) ## STR2 ## Metallization, T / SM and * a N (CR1R2) m N (CR3R4) # RbN / N Rf Re Rb ## STR2 ## For example, the covalent bonds E that can be generated are listed in FIG. table below from condensation of electrophiles with nucleophiles: Electrophiles E Nucleophiles Wu Covalent bonds E Activated esters * Amines Carboxamides Acyl azides ** Amines Carboxamides Acyl halides Amines Carboxamides Acyl halides Alcohols Esters Cyanides Acyl Alcohols Esters Acyl Cyanides Friend Carboxamides Alkyl halides Amines Alkylamines Alkali halides Carboxylic acids Esters Alkyl halides Thiols Thioesters Alkyl halides Alcohols Ethers Sulphonic acids and their Thiols Thioethers salts Sulphonic acids and their carboxylic acids Esters salts Sulphonic acids and their Alcohols Ethers salts Anhydrides Alcohols Esters Anhydrides Amines Carboxamides Aryl halides Thiols Thioethers Halides of aryl Amines Arylamines Aziridines Thiols Thioethers Carboxylic acids Amines Carboxamides Carboxylic acids Alcohols Esters Carbodiimides N-acylurea or anhydride carboxylic acids Diazoalkanes Carboxylic acids Esters Epoxides Thiols Thioethers Haloacetamides Thiols Thioethers Esters imidics Amines Amidines Isocyanates Amines Urea Isocyanates Alcohols Urethanes5 Isothiocyanates Amines Thioureas Maleimides Thiols Thioethers Sulphonic esters Amines Alkylamines Sulphonic esters Thiols Thioethers Sulphonyl esters Carboxylic acids Esters Sulphonic esters Alcohols Ethers Sulfonyl halides Amines Sulfonamides * Activated esters of the general formula ùCO-Part with Part representing a leaving group such as oxysuccinimidyl, oxybenzotriazolyl, optionally substituted aryloxy; The acyl azides can be rearranged to give the isocyanates We can illustrate the possible synthesis routes by the synthesis of the examples (g), (k) and (m) belonging to the general formula (I) from the reagents (e) and (f), (h) and (j), (h ') and (HSY') Rbb Rb •, HN ~ O H02Cu (CR3R4), SY 'R' R * O NùCOu (\ R3R4) n Rf Re ## STR5 ## wherein R 1 is CR 2 R 2, R 2, R (R), R (R), R (R), R (R), R (R), R (R (R)) ## STR3 ## (CR 1 R) m N / (CR 3 R 4) n H SY '-HGp, ùTa Ni (CR 1 R 2) m N (CR 3 R 4) n

  With Gp representing a leaving group such as a halogen such as chlorine, bromine, iodine or a particularly brominated or chlorinated mesylate or tosylate group. More particularly, a leaving group may be substituted by a thiourea group (S = C ( NRR) NRR) to generate the isothiouroniums. For example, if the thiourea group is a thioimidazolium ([3), the reaction scheme is as follows: R '/ - \ + An iRd T IS a (RIR22) (CR3R4) d ig1 Another variant is to use a thiolactone to generate a Ta amide bond as illustrated by the diagram below: Rb • RfRe .N * O ~ `-N _Rd Hal a / An RfRe

  N (R 1 R 2) m - (CRR) 0) 34 n O - H Hal RbN ~ N Rf Re SH R'c, R b N N - (N / Rb • Rf Re H / NùCO Nù (CRiR2) m \ 4CH2) 3 SY '(B) (b) Y'R - Y'H (B) H NùCO Nù (RiR2) m CH2) 3 I SY' metallation

  Rb • Rf Re H NùCO Nù (RiR2) \ CH2) 3

  An alternative is to start from a maleic derivative reagent (r) and generate the naphthylimide portion by amine derivatized nucleophilic condensation (s) comprising the protected thiol portion to yield the dye of the invention of formula (I). H2N, Tai / SY '(CR1R2) m (CR3R4) n -H2O NO, Ta / SY' N- (OR1R2), (CR3R4) n O (I ') A synthetic variant is to combine with In the first step, two equivalents of the nucleophilic reagent with a disulphide disulfide reagent Lt1 are produced so as to generate, after condensation, the dichromophoric disulfide product (1a), the latter being able to undergo a reduction to form the heterocyclic fluorescent thiol dye (a) which in turn can either to be protected to form the protected thiol fluorescent dye (I ') or to be metallized with an alkali metal to give the metallocured heterocyclic thiol dye (I ") / Nu Nu (CRI R2) m 2 OE ~ E (CR3R4) n LU (CR3R4) n LU ùS \ Nù (CR1R2) m N (CR3R4) n (CR3R4) n (CR1R2) ~ O ùTa / SH Nù (CR1R2) m ~ (CR3R4) n O (a) Rb \.-Ta ~ SY '(1) N N (CR1R2) m N (CR3R4) n O metallization ùTa / SMet * Nù (CR1R2) m ~ (CR3R4) n

  O ILD1 Y'R-RH10 Synthesis of the dyes of formula (II):

  The protected thiol dyes of formula (II) can be synthesized in two stages. The first step of preparing the unprotected thiol dye (a ') according to methods known to those skilled in the art such as 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 (II ') and (II "), by way of example to protect the The thiol function of the thiol dye can be used in the methods of Protective Groups in Organic Synthesis, TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217, Protecting Groups, P. Kocienski, Thieme, 3rd ed. (2005), chapter 5. (CR1R) "(CN) m (CRR) n (CR3R4) (CRR) m (IIa) reducer This method can be illustrated by the method consisting of i) generating thiol fluorescent dyes of formula j by reduction of a dye _ Ta, ûSH (CR1 R2) m "(CR3R4) n Ra N- a (CRIR2) m N (CR3R4) n (II ') metallation (CRgR2) m ~ (CR3R4) n Y'R-RH Rb Rb Ra N fluorescent with two chromophores, carrying a disulfide function -SS- such that and ii) to protect according to conventional methods said thiol function of Lj with the reagent Y'R to access protected thiol fluorescent dyes of formula (II '). The thiol compound may also be metallized with an alkali metal or alkaline earth metal Met * to yield the thiolate fluorescent dye of formula (II "), see the diagram above. For example more specifically it is possible to access the drifts of formula (II) with Ta representing a cationic heterocycle group as follows: ## STR1 ## Alternatively, it is possible to to carry out the synthesis of compounds of formula (II ') from halogenated naphthylimide reagent (e') on the naphthyl part of said reagent capable of undergoing the nucleophilic attack of the amino reactant (f ') carrying the nucleophilic group to arrive at the The reaction intermediate (g '), which can be condensed with a thiol derivative bearing an electrophilic group (h'), to give the fluorescent dye of formula (II '): Hal (f') Rb Nu (CR1R2) 7 5Vu Rg (e ') Ei (CR3R4) 7SY' (h ') Rg Wu representing a nucleophi group E representing an electrophilic group; and E the bond generated after nucleophilic attack on the electrophile. For the first step of this synthesis, this type of nucleophilic substitution is described in the literature. For example Dyes & Pigments, 45, (2000) 125-129; and J.Chem.Soc Perk Trans 2 (1990) 837-842.

  Another alternative is to use a thiolactone as follows from (g ') to lead to the dye (B), which itself can be protected or metallized: Rb (CR1R2) m \ (CR3R4) n (IIi) 10b (CR1R2) m 'COù (CH2) 3 (B) Rb N ~ NHRb (CR1 R2) m (b) Y'R - Y'H metallation (B) Rb ~ NRb SY' N '' (CRiR2) m CO ( The thiol fluorescent dyes formed can be converted to thiol dyes protected by the protection of the thiol by using conventional protecting groups. The thiol fluorescent dyes are metallated using also conventional methods known to those skilled in the art such as those described in Advanced Organic Chemistry, Reactions, Mechanisms and Structures, J. March, 4th Ed, John Willey & Sons, NY, 1992.

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

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

  The thiol fluorescent dyes formed can be converted to Y-protected thiols fluorescent dyes by the protection of the HSH thiol using conventional protecting groups. The thiol fluorescent dyes are metallated using also conventional methods known to those skilled in the art such as those described in Advanced Organic Chemistry, Reactions, Mechanisms and Structures, J. March, 4th Ed, John Willey & Sons, NY, 1992.

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

  The composition of the invention contains at least one thiol 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, 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); catechol borane. The dye composition useful in the invention generally contains an amount of thiol 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, mention may be made of para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%. The oxidation base (s) present in the dyeing composition are in general each present in an amount of between 0.001% and 10% by weight relative to the total weight of the dyeing composition, preferably between 0.005% and 6% by weight. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The solvents when present are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately. According to one variant, the invention contains a reducing agent capable of reducing the disulfide bonds 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 and amphoteric polymeric associative thickeners, 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 aminosilicones, film-forming agents, ceramides, preserving agents, 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 (y): R ~ 1 / Rat ~ N Wa N Ra4 \ Rai (Y) in which Wa is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra1, Ra2, Ra3 and Ra4, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

  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 process of the invention, a reducing agent may be applied as a pre-treatment before the application of the composition containing at least one thiol 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, in particular glycerol monothioglycolate, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra n-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 thiol 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. When the thiol fluorescent dye of formula (I) or (II) comprises a thiol-protecting group Y, 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 SY function with the protective group by adjusting the pH as follows: Y: alkylcarbonyl deprotecting protecting group, pH> 9 arylcarbonyl, pH> 9 alkoxycarbonyl, pH> 9 aryloxycarbonyl, pH> 9 arylalkoxycarbonyl pH > 95 (di) (alkyl) aminocarbonyl, pH> 9 (alkyl) arylaminocarbonyl pH> 9 aryl optionally substituted such pH> 9 as phenyl, monocyclic heteroaryl with 5, 6 or 7 pH> 9 members such as oxazolium; 8 to 11-membered bicyclic heteroaryl pH> 9-membered such as benzoimidazolium, or benzoxazolium 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 thiol fluorescent dye of formula (I) or (II) at the time of use. According to another method, the composition comprising at least one thiol 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 thiol 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 method in which the thiol fluorescent dye 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 thiol fluorescent dye of formula (I) or (II).

  The application of the dye composition according to the invention is generally carried out at room temperature. It can however be carried out at temperatures ranging from 20 to 180 C.

  The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one thiol fluorescent dye of formula (I) or (II) and a second compartment contains an agent reducing agent capable of reducing the disulfide functions of keratin materials. 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 thiol 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 (I) or (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 EXAMPLE OF SYNTHESIS Synthesis of 3 - {[1,3-dioxo-2- (2-sulfanylethyl) -2,3-dihydro-1H-benzo [de] isoquinolin-6-yl] amino} -N sulfate N, N, N-trimethylpropan-1-aminium [1] NOO,, SH 0.5 δ O [1] Synthesis Scheme Cl HZN NH 2 NMP DIPEA Cl Cl DMF N nn N / H HOOH EtOH HO SH HO [1] Step 1: Synthesis of 2,2 '- (disulfanediyldiethane-2,1-diyl) bis (6-chloro-1H-benzo [de] isoquinoline-1,3 (2H) -dione)

  9.30 g of 6-chloro-benzo [de] isochromene-1,3-dione previously purified by recrystallization from hot toluene, and oven-dried at 66 ° C., 4.46 g of cystamine hydrochloride and 50 ml of N-methylpyrrolidinone (NMP) are mixed, then 5.5 g of diisopropylamine (DIPEA) are added. The reaction mixture is heated at 120 ° C. for 2 hours. 50 ml of NMP are added to the mixture and heating is continued with stirring for 3 hours. Stirring is stopped for 7 days. 100 ml of water are added to the reaction mixture, the white precipitate obtained is filtered, washed with 3 times 100 ml of water and then dried in an oven. 9.01 g of white solid are collected.

Step 2: Synthesis of 2,2 '- (disulfanediyldiethane-2,1-diyl) bis [6 - {[3- (dimethylamino) propyl] amino} -1 H -benzo [de] isoquinoline-1,3 (2H) ) -dione] 4 g of 2,2 '- (disulfanediyldiethane-2,1-diyl) bis (6-chloro-1H-benzo [de] isoquinoline-1,3 (2H) -dione) and 40 mL of N, N-dimethylpropane-1,3-diamine are mixed with stirring and heating at 110 C for 18h and then at room temperature for 17h. The precipitate obtained is eliminated. 500 ml of an EtOH / H 2 O mixture (1/1) are added to the supernatant, then 200 ml of acetone are added to the precipitate, the gum obtained is washed with 3 times 100 ml of distilled water, dried in an oven at 66 C. 4.5 g of solid are collected.

Step 3: Synthesis of 3,3 '- {disulfanediylbis [ethane-2,1-diyl (1,3-dioxo-1H-benzo [de] isoquinoline-2,6 (3H) -diyl) imino} bis (N, N, N-trimethylpropan-laminate) [la]

4 g of 2,2 '- (disulfanediyldiethane-2,1-diyl) bis [6 - {[3- (dimethylamino) propyl] amino} -1H-benzo [de] isoquinoline-1,3 (2H) -dione] suspended in 50 ml of dimethylformamide (DMF) are stirred. 4 ml of dimethyl sulphate are introduced into the reaction medium, stirred for 4 hours at room temperature. The mixture is precipitated in 500 ml of ethyl acetate, the precipitate is filtered, washed with 4 times 100 ml of ethyl acetate and then dried under vacuum at 40 ° C. in the presence of P2O5. 5.91 g of yellow powder are collected. The analyzes indicate that the product is compliant.

  1H NMR (400MHz, DMSO-d6) 2.13 (m, 4H), 3.06 (m, 4H), 3.09 (s, 18H), 3.46 (m, 4H), 4.36 (m, 4H) , 6.85 (d, 2H), 7.71 (m, 2H), 7.82 (t, 2H), 8.28 (d, 2H), 8.29 (dd, 2H), 8.45 (dd, 2H).

Step 4: Synthesis of 3 - {[1,3-dioxo-2- (2-sulfanylethyl) -2,3-dihydro-1H-benzo [de] isoquinolin-6-yl] amino} -N, N salt , N-trimethylpropan-1-aminium [1]

  84 mg of the compound [la] are dissolved in 10 ml of 1: 1 water / ethanol mixture; 60 mg (2eq.) Of 3- [bis (2-carboxyethyl) 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 are added to the mixture. After stirring for 30 minutes at 40 ° C. under an inert atmosphere, the analyzes indicate that the mixture contains most of the expected product [1].

  LC-MS analysis: LC-DAD (400-700 nm) Column: Waters XTerra MS C18 5pm (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; 8 min 0/100 Flow rate: 1 mL / min. Detection: UV Diode array at = 400-700nm Retention time t = 3.8min. Relative purity> 95% MS (ESI +) m / z = 372 corresponds to the mass peak of the cation of the expected product [1] EXAMPLE OF COLORING Staining process

  10 ml of fresh solution of the compound [1] of the synthetic example are applied to a lock of 1 g of hair of pitch 4 arranged at the bottom of the same bowl for 30 minutes at room temperature (the locks are returned and re-treated 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 In shampoos, there is no visible bleeding, the shampoo foam and rinsing water are not colored The observed color is preserved and the lightening effect remains visible on the hair of height of tone 4 thus treated Results of Reflectance The lightening performance of the compositions according to the invention were expressed as a function of the reflectance of the hair. These reflectances are compared to the reflectance of a lock of untreated HT4 pitch hair.

  The reflectance is measured using a KONIKAMINOLTA spectrophotocolorimeter, CM 2600d and after irradiation of the hair with visible light in the wavelength range of 400 to 700 nanometers. Reflectance of the wicks treated with the compound 1 Wavelength (nm) ùreference ùCompound 1 6-5-4-3-2-1-025 It is found 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.

Claims (21)

  1. Thiol fluorescent dye of the following formula (I) or (II): ## STR1 ## N (CR3R4) n (I) O their organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates; formulas (I) and (II) in which: - Ra represents an aryl (C 1 -C 4) alkyl group or a (C 1 -C 6) alkyl group optionally substituted by a hydroxyl group, or (di) (C 1 -C 4) ) (alkyl) amino, said alkyl radicals being capable of forming, with the nitrogen atom bearing them, a 5- to 7-membered heterocyl, optionally comprising another heteroatom which is different from or different from nitrogen; Rb represents a hydrogen atom, an aryl (C 1 -C 4) alkyl group or an optionally substituted (C 1 -C 6) alkyl group; in particular Rb represents a hydrogen atom or a C1-C3 alkyl or benzyl group; - Re represents a (C 1 -C 6) alkylenyl hydrocarbon chain divalent, linear or branched, optionally unsaturated; Rf represents i) a quaternary ammonium group (R ") (R" ') (R "") N -, M' where R ", R" 'and R "", which may be identical or different, represent an atom of hydrogen or a (C 1 -C 4) alkyl group or (R ") (R" ') (R "") N -represents an optionally substituted cationic heteroaryl group, and M' represents an anionic counterion; ii) a hydroxyl group; iii) (C1-C6) (di) (alkyl) amino; or iv) optionally substituted non-cationic heteroaryl; - Rg represents a hydrogen, halogen, amino, (di) (C 1 -C 4) alkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, C 1 -C 4 alkoxy, (poly) hydroxyalkoxy group; C2-C4, (C1-C4) alkylcarbonyloxy (CIC4) alkoxycarbonyl, (C1-C4) alkylcarbonylamino, acylamino, carbamoyl, (C, -5C4) alkylsulfonylamino, amino-sulfonyl radical, or (C, - C16) alkyl optionally substituted with a group chosen from (C 1 -C 12) alkoxy, hydroxy, cyano, carboxy, amino, (di) (C 1 -C 4) alkylamino, or the two alkyl radicals borne by the atom nitrogen of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom; - R ,, R2, R3, R4, identical or different, represent a hydrogen atom or a group (C1-C4) alkyl, (C1-C4) alkoxy, hydroxy, cyano, carboxy, (di) (C1-C4) ) (alkyl) amino, said alkyl radicals being capable of forming, with the nitrogen atom which carries them, a 5- to 7-membered heterocyl, optionally comprising another heteroatom which may or may not be different from nitrogen; Ta is: i) either a covalent bond a, ii) or one or more radicals or combinations thereof selected from -SO2-, -06, -Siu, ùN (R) ù, ùN + (R) (R) ù, ùC ( Wherein R and R, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or aryl (C 1 -C 4) alkyl radical; iii) a heterocycloalkyl or heteroaryl radical, cationic or non-cationic; m and n, identical or different, represent an integer inclusive between 0 and 6 with m + n represents an integer inclusive between 1 and 10; and Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + RaRaRYR8 or a phosphonium group: P + RaRaRYR8 with Ra, Ra, R7 and R8, identical or different, representing a hydrogen atom or a (C 1 -C 4) alkyl group; or v) a thiol protecting group; it being understood that: when the compound of formula (I) or (II) contains one or more cationic parts, it is associated with one or more anionic counter-ions making it possible to reach the electroneutrality of formula (I) or (He).   2. Fluorescent dye of formulas (I) or (II) according to the preceding claim wherein Y represents a hydrogen atom, or an alkali metal.   3. Fluorescent dye of formulas (I) or (II) according to claim 1 wherein Y represents a protective group.   4. Fluorescent dye of formulas (I) or (II) according to the preceding claim wherein Y represents a protective group selected from the following radicals: - (C 1 -C 4) alkylcarbonyl; - (C1-C4) alkylthiocarbonyl; - (C1-C4) alkoxycarbonyl; - (C1-C4) alkoxythiocarbonyl; - (C1-C4) alkylthiothiocarbonyl; - (di) (C1-C4) (alkyl) aminocarbonyl; - (di) (C1-C4) (alkyl) aminothiocarbonyl; arylcarbonyl, such as phenylcarbonyl; aryloxycarbonyl; -aryl (C1-C4) alkoxycarbonyl; - (di) (C1-C4) (alkyl) aminocarbonyl; - (C1-C4) (alkyl) arylaminocarbonyl; carboxy; - SO3; M + with M + representing a metal or M + and M 'of the formula (I) are absent; optionally substituted aryl, - optionally substituted heteroaryl; optionally substituted heterocycloalkyl, optionally cationic; -isothiouronium -C (NR 'R'd) = N + R'eR'f; With R ', R'd, R'e and R'f, identical or different, represent a hydrogen atom or an alkyl group; preferentially R 'to R' f represent a hydrogen atom; and An- represents an anionic counterion; - isothiourea -C (NR 'R'd) = NR'e; with R ', R'd, R'e as defined above; - (di) arylalkyl optionally substituted; optionally substituted (di) heteroarylalkyl; - CR'1R'2R'3 with R'1, R'2 and R'3 identical or different, representing a halogen atom or a group selected from: alkyl; alkoxy; optionally substituted aryl; optionally substituted heteroaryl; - P (Z ') R "1R" 2R "3 with R" 1, and R "2 identical or different represent a hydroxyl, alkoxy or alkyl group, R" 3 represents a hydroxy or alkoxy group, and Z' represents a hydrogen atom; oxygen or sulfur; cyclic sterically hindered; - optionally substituted alkoxyalkyl.   A fluorescent dye according to any one of the preceding claims wherein Y represents an alkali metal or a protecting group selected from: - (C1-C4) alkylcarbonyl; arylcarbonyl; - (C1-C4) alkoxycarbonyl; aryloxycarbonyl; aryl (C1-C4) alkoxycarbonyl; - (di) (C1-C4) (alkyl) aminocarbonyl; - (C1-C4) (alkyl) arylaminocarbonyl; optionally substituted aryl; monocyclic 5- or 6-membered heteroaryl; 8 to 11-membered cationic bicyclic heteroaryl; cationic heterocycle of the following formula: Me N-An N-isothiouronium -C (NH 2) = N + H 2; An; -isothiourea -C (NH2) = NH; and - SO3; M +.   6. Heterocyclic thiol fluorescent dye according to any one of the preceding claims, chosen from the following dyes: ## STR2 ## ## STR2 ## ## STR5 ## ## STR1 ### * M ~ O ~ O ~ 7 8 oo \ * N + \ ~ SH \ N Name \ N = / + ~ ^ SO, HOHNM '2M' 9 10 oo N ^ S \ \ N * Name \ = / 'S, ## STR5 ## ## STR1 ## With M ', identical or different, representing an anionic counterion.   7. Dyeing composition comprising in a suitable cosmetic medium, a thiol fluorescent dye of formula (I) or (II) as defined in any one of claims 1 to 6.   8. dye composition comprising in a suitable cosmetic medium, at least one thiol fluorescent dye of formula (I) or (II) as defined in any one of claims 1 to 6 and at least one reducing agent.   9. 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, sodium, lithium, potassium, calcium and quaternary ammonium salts; catecholborane.   10. Composition according to any one of claims 7 to 9, wherein the thiol 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.   11. A method for dyeing keratinous materials, wherein is applied to the materials, a dye composition as defined in any one of claims 7 to 10, comprising in a suitable cosmetic medium, at least one thiol fluorescent dye of formula (I) or (II) as defined in any one of claims 1 to 6, optionally in the presence of a reducing agent capable of reducing the disulfide bonds of keratin materials.   12. The method of dyeing according to the preceding claim wherein when the thiol fluorescent dye of formula (I) or (II) comprises a protecting Y group, the application is preceded by a deprotection step.   13. A method of dyeing keratin materials according to any one of claims 11 or 12 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 11 to 13 wherein the reducing agent is applied before or after the application of the thiol fluorescent dye.   The process of any one of claims 11 to 14, wherein the composition comprises an oxidizing agent.   16. A method according to any one of claims 11 to 15 comprising a further step of applying to the keratin fibers an oxidizing agent.   17. A multi-compartment device in which a first compartment contains a dye composition comprising a thiol fluorescent dye as defined in claims 1 to 6 and a second compartment contains a reducing agent capable of reducing the disulfide bonds of keratin materials. 10   18. Device according to the preceding claim comprising a third compartment which contains an oxidizing agent.   19. Use of fluorescent dyes thiols as defined in claims 1 to 6 for dyeing dark human keratin fibers.   20. Use according to the preceding claim for lightening dark keratin fibers.   21. Use according to claims 19 or 20 characterized in that the keratin fibers have a pitch of less than 6.