Dyeing composition containing a thiol/disulphide fluorescent colorant comprising amine groups and having an internal cationic charge, and method for lightening keratin materials using said colorant

Translation of description of equivalent WO 2007110537 A2

p0001DYE COMPOSITION CONTAINING A FLUORESCENT DYE THIOL / DISULPHIDE AMINO GROUPS AND INTERNAL CATIONIC CHARGE, AND METHOD OF CLARIFICATION OF CONTENTS Kerati N IQU ES FROM

p0002EC DYE The invention relates to the coloring of keratin materials using fluorescent dyes thiols / disulfides comprising one or more amino groups.

p0003It is known to dye keratin fibers, particularly human, by direct dyeing. The process conventionally used in direct dyeing comprises applying to the keratin fibers direct dyes, which are colored and coloring molecules that have affinity for the fibers, allowing them to diffuse and then rinsing the fibers.

p0004The direct dyes which are conventionally used are for example dyes of the nitrobenzene type, anthraquinone dyes, nitropyridine dyes of the azo, xanthene, acridine, azine or triaryl methane.

p0005The colorations resulting from the use of direct dyes are temporary or semi-permanent colorings since the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption from the surface and / or the heart of the fiber are responsible their low dyeing power and their poor resistance to washing or perspiration.

p0006Furthermore, the dyeing of keratinous fibers from conventional direct dyes does not allow to significantly lighten keratin fibers.

p0007The lightening of the color of keratin fibers, especially dark to lighter shades, by optionally modifying the shade thereof, constitutes an important demand.

p0008Conventionally, to obtain a lighter coloring implements a chemical bleaching process. This method comprises treating keratin materials such as keratin fibers, in particular hair, with a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, usually under alkaline conditions.

p0009This bleaching system has the disadvantage of degrading keratin materials, especially keratin fibers, especially human, such as hair and of impairing their cosmetic properties. The fibers have a tendency to become rough, more difficult to disentangle and more fragile. Finally, the lightening or bleaching of keratin fibers with oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in hair straightening treatments. Another lightening technique comprises applying dark hair fluorescent direct dyes. This technique, described in particular in documents FR 2830189 and WO 2004/091473 allows to respect the quality of the keratin fiber during the treatment, but the fluorescent dyes employed do not exhibit satisfactory resistance to shampoos. To increase the toughness of direct dyeing, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react with reactive groups in dyes residues cystine or cysteine ​​in many keratin fibers see for example the 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;

p0010Furthermore it is known to protect or thiol functions in one molecule to be grafted to the hair before applying said hair WO 99/51194. However, this application does not mention the use of fluorescent dyes for coloring or lighten hair. Other disulphide dyes known for coloring keratin fibers are disulphide derivatives of aminothiophenol derivatives. Such dyes are described for example in patent FR 1156407. These dyes may be used under relatively mild conditions in the presence of a slightly reducing medium or after a reducing pre-treatment of the hair. However, these dyes can cause colourshifts when applying.

p0011Finally, WO 2005/097051 describes the document disulfide dyes aza imidazoliums for the direct dyeing of keratin fibers.

p0012The object of the present invention is to provide new dyeing keratin materials systems in particular human keratin fibers, in particular hair, which do not present the drawbacks of the existing bleaching processes. In particular, an object of the present invention is to provide direct dyeing systems for obtaining lightening effects especially on naturally or artificially dark keratin fibers, stubborn face successive shampoos that do not degrade the fibers keratin and that do not alter their cosmetic properties.

p0013This object is achieved with the present invention which relates to a keratinous material dyeing process, in particular keratin fibers, especially human such as the hair, especially dark hair, consisting in applying to keratin materials, a dye composition comprising, in a suitable cosmetic medium, at least one thiol fluorescent dye selected from the dyes of formulas (I) and (II):

p0014<img id="imgf000004_0001" he="66" wi="142" file="imgf000004_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> the organic or mineral acid salts, optical isomers, geometrical isomers, and solvates such as hydrates; formulas (I) and (II) in which:

p0015> R and R ", identical or different, represent a hydroxyl, an amino group (NR_atR_b) Or ammonium (N⁺R_atR_bR_c), An^" ; with R_at, R_b and R_c, Identical or different, representing a hydrogen atom or a (C_rC₄) Alkyl; then two or alkyl R_at and R_b the amino or ammonium group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different than the nitrogen atom such as morpholinyl, piperazinyl, piperidinyl, pyrrolyl, morpholinium, piperazinium, piperidinium, pyrrolinium, and An^" representative against an anionic ion;

p0016> R 'and R ", identical or different, represent a hydrogen atom or a group as defined for R and R'" respectively;

p0017> R₉, R '_g, R "_g, R "_g, R_h, R '_h, R "_h and R " '_h, Identical or different, represent a hydrogen atom, halogen, amino, (di) (CrC₄) Alkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, alkoxy, -C₄(Poly) hydroxyalkoxy, C₂-C₄(Ci-C₄) Alkylcarbonyloxy, (Ci-C₄) Alkoxycarbonyl, (-C₄) Alkylcarbonylamino, acylamino, carbamoyl, (Ci-C₄) Alkylsulfonylamino, aminosulfonyl, or a (Ci-Ci₆) Alkyl optionally substituted by a group selected from (Ci-Ci₂) Alkoxy, hydroxy, cyano, carboxy, amino, (di) (Ci-C₄) Alkylamino, or else the two alkyl radicals borne by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different than the nitrogen atom; particularly R₉, R '_g, R "_g, R "_g, R_h, R '_h, R "_h and R " '_h represent a hydrogen atom or a (Ci-C₄) Alkyl;

p0018> R ', R "i, R'" i and R "" i, which are identical or different, represent a hydrogen atom or a (C_rC₄) Alkyl; particularly R'j, R ", R '" and R "" i represents a hydrogen atom;

p0019> M, m ', identical or different, represent an integer between and including 1 and 10; particularly an integer ranging between 2 and 4; preferably m and m 'are 2;

p0020> P, p ', q and q', same or different, represent an integer ranging between 1 and 6;

p0021> M¹ representative against an anionic ion; and> Y is i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N⁺R^αR^βR^γR^δ or a phosphonium group: P⁺R^αR^βR^γR^δ with R^α, R^β, R^γ and R^δ, Identical or different, representing a hydrogen atom or a (dC₄) Alkyl; or v) a protective group of thiol; it being understood that:

p0022- When the compound of formula (I) or (II) contains other cationic parts, it is associated with one or more anionic against ions to achieve electroneutrality of the formula (I) or (II).

p0023Another object 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 above, and a reducing agent.

p0024The invention also relates to novel fluorescent dyes of formula (I) or (II) as defined above.

p0025The dyeing process according to the invention allows to visibly color dark keratin materials, in particular dark human keratin fibers, especially dark hair. Furthermore, the process of the invention allows to obtain a dyeing of keratin materials, in particular human keratinous fibers, especially hair, without damaging said material, volatile vis-a-vis of shampoos, common attacks (sun, sweating) and other hair treatments. The method of the invention also provides a lightening of keratin materials such as keratin fibers, particularly dark keratin fibers and more particularly dark hair.

p0026Within the meaning of the invention, the term dark keratin material which exhibits a lightness L * in the CIEL L * a * b * less than or equal to 45 and preferably less than or equal to 40, given that, moreover L * = 0 is equivalent to black and L * = 100 to white.

p0027Within the meaning of the invention, the term hair naturally or artificially dark hair whose tone height is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut).

p0028The lightening of the hair is evaluated by the variation in "tone height" before and after application of the compound of formula (I) or (II).

p0029The notion of "tone" is based on the classification of natural shades, one tone separating each shade from the following or preceding immediately. This definition and classification of the natural shades are well known to hair styling professionals and published in the book "Science of hair treatment" Charles Zviak 1988 Ed. Masson, p. 215 and 278.

p0030The tone heights range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the number, the higher the grade is clear.

p0031An artificially colored hair is a hair whose color has been modified by for example a dyeing treatment, a dyeing with direct dyes or oxidation dyes.

p0032Preferably, the composition should, after application to the hair, for example chestnut, bring the results below.

p0033- We are interested in reflectance performance when hair is irradiated with visible light in the wavelength range from 400 to 700 nanometers.

p0034It then compares the reflectance curves as a function of wavelength, of hair treated with the composition of the invention and the untreated hair. The curve corresponding to the treated hair should show a reflectance in the range of wavelengths from 500 to 700 nanometers higher than the curve corresponding to the untreated hair.

p0035- This means that, in the wavelength range from 540 to 700 nanometers, there is at least a range where the reflectance curve corresponding to the treated hair is higher than the reflectance curve corresponding to the untreated hair. The term "higher" is a difference of at least 0.05% reflectance and preferably at least 0.1%. This does not exclude that there may be in the wavelength range from 540 to 700 nanometers, at least a range where the reflectance curve corresponding to the treated hair is superimposable or lower than the reflectance curve corresponding to untreated hair.

p0036Preferably, the wavelength at which the difference is between the maximum reflectance curve of the treated hair and of the untreated hair is in the wavelength range from 500 to 650 nanometers, and preferably in the wavelength range of 550-620 nanometers. Within the meaning of the present invention, and unless a different indication is given:

p0037- The radicals "aryl" or "heteroaryl" or the aryl or heteroaryl part of a radical may be substituted by at least one substituent on a carbon atom, selected from: • an alkyl radical Ci-Ci₆, Preferably -C₈Optionally substituted by one or more radicals chosen from hydroxyl, alkoxy, C₁-

p0038C₂(Poly) hydroxyalkoxy C₂-C₄, Acylamino, amino substituted with two alkyl radicals, identical or different C₁-C₄ , Optionally bearing at least one hydroxy group, or the two radicals to form, with the nitrogen atom to which they are attached, a heterocycle comprising

p00395 to 7 members, preferably 5 or 6 membered saturated or unsaturated optionally substituted optionally comprising another heteroatom identical to or different from nitrogen;

p0040• a halogen atom such as chlorine, fluorine or bromine; . a hydroxyl group;

p0041• an alkoxy radical C₁-C₂ ;

p0042. alkylthio -C₂ ;

p0043• a radical (poly) hydroxyalkoxy C₂-C₄ ; . an amino radical;

p0044• a heterocycloalkyl with 5 or 6 members;

p0045. a heteroaryl radical with 5 or 6 members optionally cationic, preferably imidazolium, optionally substituted with a (C₁-C₄) Alkyl, preferably methyl; • an amino radical substituted by one or two alkyl radicals, identical or different C₁-C₆ optionally bearing at least: i) hydroxy, ii) an amino group optionally substituted by one or two alkyl radicals C₁-C₃ optionally substituted, said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or may not be nitrogen,

p0046• -NR-COR 'in which the radical R is a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group and the radical R 'is alkyl C₁-C₂ ;

p0047. (R)₂N-CO- in which the R radicals, identical or not, represent a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group; • R¹SO₂-NR- Wherein the radical R represents a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group and the radical R 'represents an alkyl radical C₁-C₄A phenyl radical;

p0048• (R)₂N-SO₂- Wherein the radicals R, identical or different, represent a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group,

p0049• a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted);

p0050• a cyano group; . a polyhaloalkyl group having 1 to 6 carbon atoms and 1 to 6 halogen atoms, identical or different, the polyhaloalkyl group is for example trifluoromethyl;

p0051- The cyclic or heterocyclic part of a non aromatic radical may be substituted by at least one substituent on a carbon atom selected from the groups:. hydroxy,

p0052• alkoxy-C₄,

p0053. (Poly) hydroxyalkoxy, C₂-C₄, • an alkylthio radical -C₂ ;

p0054. RCO-NR'- wherein the radical R 'is a hydrogen atom, an alkyl radical C_rC₄ optionally bearing at least one hydroxyl group and the radical R is an alkyl radical Ci-C₂And amino substituted with two alkyl groups are identical or different C_rC₄ optionally bearing at least one hydroxyl group;

p0055. RCO-O- wherein the radical R is an alkyl radical dC₄, Amino substituted by one or two identical or different alkyl groups in d- C₄ optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or not nitrogen;

p0056• RO-CO- group wherein R is an alkyl radical Ci-C₄ 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 by one or more oxo or thioxo groups;

p0057- An "aryl" radical represents a monocyclic or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and at least one ring is aromatic; preferably the aryl is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;

p0058- A "diarylalkyl" radical represents a group having the same carbon atom of an alkyl group, two aryl groups, which are identical or different, such as diphenylmethyl or 1,1-diphenylethyl; - A "heteroaryl radical" represents a mono- or polycyclic group ∞ndensé or unsaturated, optionally cationic, comprising from 5 to 22 members and from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atom, and at least one ring 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, phénooxazolyle, pyrazinyl, pyrazolyl, pyrilyle, pyrazoyltriazyle, pyridyl, pyridinoimidazolyle, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyle, thiopyrylyle, triazolyl, xanthylyle and its ammonium salt;

p0059- A radical "diheteroarylalkyl" 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 dithienylmethyl;

p0060- A "cyclic group" is a non-aromatic cycloalkyl, mono- or polycyclic, condensed or not, containing from 5 to 22 carbon atoms, which may contain 1 or more unsaturations; particularly the cyclic radical is a cyclohexyl;

p0061- A radical "sterically hindered cyclic group" is a cyclic radical, aromatic or nonaromatic, substituted or unsubstituted, hindered by steric effect or stress, comprising 6 to 14 members, which may be bridged by way of sterically hindered radicals, bicyclo include [1.1.0] butane, the mésytyles such as 1, 3,5 triméthylpnényle, 1,3,5-triterbutylphényle, 1, 3,5-isobutylphenyl, the trimétylsillylphényle 1,3,5 and adamantyl ;

p0062- A "heterocycle or heterocyclic group" is a non-aromatic radical mono- or polycyclic, condensed or not, containing from 5 to 22 members and having from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium;

p0063- An "alkyl group" is a hydrocarbon radical CRCI₆Linear or branched, preferably Ci-Cs;

p0064- The expression "optionally substituted" assigned to the alkyl radical implies that said alkyl radical may be substituted by one or more radicals selected from radicals i) hydroxy, ii) -C alkoxy₄, Ni) acylamino, iv) amino optionally substituted by one or two alkyl radicals, identical or different, -C₄, Said alkyl radicals possibly forming with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom identical to or different from nitrogen; v) or a quaternary ammonium group

p0065-N R'R "R '" Mr.^" wherein R ', R ", R"', identical or different, represent a

p0066+ Hydrogen, or an alkyl group dC₄Or else -N R'R "R" 'forms a heteroaryl such as imidazolium optionally substituted by a group d- C₄ alkyl, and M represents the against-ion of the organic acid, mineral acid or the corresponding halide,

p0067- A "alkoxy radical" is an alkyl-oxy radical or alkyl-O- in which alkyl is a hydrocarbon radical, linear or branched C₁-C₁₆ preferentially;

p0068- A "alkylthio" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched C₁-C₁₆ preferably d-Cs; when the alkylthio group is optionally substituted, this means that the alkyl group is optionally substituted as defined above; - The limits delimiting the extent of a range of values ​​are included in this range; - An "organic or mineral acid salt" is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H₂SO₄, Iv) alkylsulfonic acids: AIk-S (O)₂OH such as methylsulphonic acid and ethylsulphonic acid; v) arylsulfonic acids: Ar-S (O)₂OH such as benzenesulfonic and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) of alcoxysulfiniques acids: Alk-OS (O) OH such as from methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulphinic acids such as tolueneoxysulphinic phenoxysulphinic acid and acid; xii) phosphoric acid H₃PO₄; xiii) of acetic acid CH₃COOH; xiv) of triflic acid CF₃SO₃H xv) tetrafluoroboric acid HBF₄ ; a "against anionic ion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly against the anionic ion is selected from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates including the -C₆ alkylsulphonates: Alk-S (O)₂O^" such as methyl sulfonate or mesylate and ethyl sulfonate; iv) arylsulfonates: Ar-S (O)₂O^" such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS (O)^" such as méthysulfate and ethyl sulfate; x) arylsulfates: Ar-OS (O)^" such as benzenesulfate and toluenesulfate; xi) alcoxysulfates: Alk-OS (O)₂O^" such as methoxy sulphate and ethoxy; xii) aryloxysulfates: Ar-OS (O)₂O^"Xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

p0069Fluorescent dyes of formula (I) or (II) are compounds capable of absorbing in the UV or visible radiation at a wavelength λ_abs between 250 and 800 nm and capable of réémettrent in the visible range at a transmission wavelength λ_em between 400 and 800 nm. Preferably fluorescent thiol compounds of the invention are dyes capable of absorbing in the visible λ_abs between 400 and 800 nm and re-emit 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 a λ_abs between 420 nm and 550 nm and re-emit in the visible range at a λ_em between 470 and 600 nm.

p0070The fluorescent compounds of formula (II) of the invention contain an SY function which may be in the covalent or ionic form -S -SY^" Y⁺ depending on the nature of Y and of the pH of the medium.

p0071A specific embodiment relates to fluorescent dyes to thiol group of formula (II) according to SY where Y is a hydrogen atom, or an alkali metal. Preferably Y is hydrogen.

p0072According to another embodiment of the invention, in formula (II) above, Y is a protecting group known in the art such as those described in the books "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed, NY, 1981, pp.193-217.

p0073"Protecting Groups" P. Kocienski, Thieme, 3^ΘmΘ ed., 2005, c. 5.

p0074Especially when Y represents a group protecting the thiol function, Y is selected from the following radicals: • (Ci-C₄) Alkylcarbonyl;

p0075• (Ci-C₄) Alkylthiocarbonyl;

p0076• (Ci-C₄) Alkoxycarbonyl;

p0077• (Ci-C₄) Alkoxythiocarbonyl; • (Ci-C₄) Alkylthio-thiocarbonyl;

p0078• (di) (-C₄) (Alkyl) aminocarbonyl;

p0079• (di) (C₁-C₄) (Alkyl) aminothiocarbonyl;

p0080• arylcarbonyl as phenylcarbonyl;

p0081• aryloxycarbonyl; • aryl (-C₄) Alkcoxycarbonyle;

p0082• (di) (C₁-C₄) (Alkyl) aminocarbonyl as dimethylaminocarbonyl;

p0083• (C₁-C₄) (Alkyl) arylaminocarbonyl;

p0084• carboxyl;

p0085• SO₃^" M⁺ with M⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (II) and M⁺ are absent;

p0086• optionally substituted aryl such as phenyl, dibenzosuberyl, or 1,3,5-cycloheptatrienyl,

p0087• optionally substituted heteroaryl; including the cationic or noncationic heteroaryl comprising from 1 to 4 heteroatoms: i) monocyclic 5-, 6- or 7-membered ring 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, tétrazinium, azepine , azépinium, oxazepinyl, oxazépinium, thiepinyl, thiépinium, imidazolyl, imidazolium; ii) bicyclic 8- to 11-membered ring such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyle, benzothiazolyl, benzothiazolium pyridoimidazolyle, pyridoimidazolium, thiénocycloheptadiényle, these monocyclic or bicyclic groups being optionally substituted by one or more groups such as (Ci-C₄) Alkyl such as methyl, or polyhalo (-C₄) Alkyl such as trifluoromethyl; iii) or tricyclic ABC:

p0088<img id="imgf000014_0001" he="17" wi="37" file="imgf000014_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein both rings A, G optionally comprises a heteroatom, and ring B is a 5-, 6 or 7-membered, particularly 6-membered and contains at least one heteroatom as piperidyl or pyranyl; optionally substituted heterocycloalkyl, optionally cationic, heterocycloalkyl particular group is a monocyclic saturated or partially saturated 5-, 6- or 7-membered ring comprising 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl , di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyle, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydroazepinyl di / tetrahydropyrimidinyl, these groups being optionally substituted by one or more groups such as ( C_rC₄) Alkyl, oxo or thioxo; or heterocycle represents the following group:

p0089<img id="imgf000014_0002" he="30" wi="38" file="imgf000014_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein R '^c, R '^d, R '^Θ, R '^f, R '⁹ and R '^h, Identical or different, represent a hydrogen atom or a (Ci-C₄) Alkyl, or else two groups R '⁹ R '^hAnd / or R '^Θ R '^f form an oxo or thioxo, or else R '⁹ R '^Θ together form a cycloalkyl; and v represents an integer ranging between 1 and 3; preferably, R '^c to R '^h represent a hydrogen atom; and An^" is against ion; • isothiouronium -C (NR '^cR '^d) = N⁺R '^ΘR '^f; An- R '^c, R '^d, R '^Θ and R '^fIdentical or different, represent a hydrogen atom or a (dC₄) Alkyl; preferably, R '^c to R '^f represent a hydrogen atom; and An^" is against ion;

p0090• isothiourea -C (NR '^cR '^d) = NR '^Θ; R '^c, R '^dAnd R '^Θ as defined above;

p0091• (di) aryl (-C₄) Alkyl optionally substituted such as 9-anthracenylmethyl, diphenylmethyl or phenylmethyl optionally substituted by one or more groups chosen in particular from (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy such as methoxy, hydroxy, (C_rC₄) Alkylcarbonyl, (di) (-C₄) (Alkyl) amino such as dimethylamino;

p0092• (di) heteroaryl (C_rC₄) Akyle optionally substituted, the heteroaryl group is in particular cationic or non monocyclic having 5 or 6 ring members and 1 to 4 heteroatoms selected 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 or triazinyl optionally substituted by one or more groups such as alkyl especially methyl, preferably (di) heteroaryl (Ci-C₄) Akyle is (di) heteroarylmethyl or (di) heteroarylethyl;

p0093• CR¹R²R³ with R¹, R² and R³ identical or different, representing a halogen atom or a group selected from:

p0094- (C₁-C₄) Alkyl;

p0095- (C₁-C₄) Alkoxy;

p0096- Aryl optionally substituted as phenyl optionally substituted with one or more groups such as (C_rC₄) Alkyl, (C_rC₄) Alkoxy, hydroxy;

p0097- Optionally substituted heteroaryl, such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted by a (C₁-OOaIkVIe;

p0098- P (Z¹ ) R ' ¹R¹²R '³ R '¹And R '² identical or different, representing a hydroxyl, (C₁-C₄JaIcOXy or alkyl, R '³ represents a hydroxy group or (C_rC₄) Alkoxy, and Z¹ represents an atom of oxygen or sulfur;

p0099• hindered cyclic such as adamantyl; and

p0100• alkoxy (-C₄) Alkyl optionally substituted such as methyl methoxy (MOM), ethoxyethyl (EOM) and isobutoxymethyl.

p0101According to a particular embodiment, the protected thiol fluorescent dyes of formula (II) comprise a group Y i) monocyclic heteroaryl of 5 or 6 membered aromatic, cationic 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, tétrazinium, oxazépinium, thiepinyl, thiépinium, imidazolium; ii) heteroaryl bicyclic 8- to 11-membered cationic such as indolinium, benzoimidazolium benzoxazolium, benzothiazolium, these monocyclic or bicyclic heteroaryl groups being optionally substituted by one or more groups such as alkyl like methyl, or polyhalo (Ci-C₄) Alkyl such as trifluoromethyl; iii) or heterocyclic:

p0102<img id="imgf000016_0001" he="30" wi="25" file="imgf000016_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein R '^c and R '^d, Identical or different, represent a hydrogen atom or a (dC₄) Alkyl; preferably, R '^c to R '^d represent a group

p0103(C_rC₄) Alkyl such as methyl; and An^" represents an against-ion.

p0104Y particularly represents a group selected from oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1, 2,3-triazolium, oxazolium 1,2,4, 1,2,4-thiadiazolium, pyrylium, pyridinium , pyrimidinium, pyrazinium, pyridazinium, imidazolium and triazinium, benzoimidazolium benzoxazolium, benzothiazolium, these groups being optionally substituted by one or more groups (-C₄) Alkyl especially methyl.

p0105In particular Y represents an alkali metal or a protecting group such as:

p0106> (C_rC₄) Alkylcarbonyl such as methylcarbonyl or ethylcarbonyl;

p0107> Arylcarbonyl as phenylcarbonyl;

p0108> (C_rC₄) Alkoxycarbonyl;

p0109> Aryloxycarbonyl; > Aryl (Ci-C₄) Alkoxycarbonyl;

p0110> (Di) (-C₄) (Alkyl) aminocarbonyl as dimethylaminocarbonyl;

p0111> (C_rC₄) (Alkyl) arylaminocarbonyl;

p0112> Aryl éve ntuellement substituted as phenyl; > Monocyclic 5- or 6-membered ring such as imidazolyl or pyridyl;

p0113> Cationic monocyclic heteroaryl of 5, 6-membered ring such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted by one or more identical or different groups (C_rC₄) Alkyl such as methyl; > Heteroaryl cationic bicyclic 8- to 11-membered ring such as benzoimidazolium or benzoxazolium; these groups being optionally substituted by one or more identical or different groups (dC₄) Alkyl such as methyl;

p0114> Cationic heterocycle of formula below:

p0115<img id="imgf000017_0001" he="26" wi="24" file="imgf000017_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> > Isothiouronium -C (NH₂) = N⁺H₂; Year^";

p0116> Isothiourea -C (NH₂) = NH; or

p0117> SO₃^" M⁺ with M⁺ with M⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (II) and M⁺ are absent;. In a particular embodiment of the invention, the dyes of the invention belong to the Formula (Ia) or (Ma) which have an ethylene group linking the pyridinium part to the phenyl ortho or para pyridinium either 2-4 ' , 4-2 ', 4-4':

p0118<img id="imgf000018_0001" he="69" wi="151" file="imgf000018_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> p, p ', q, q', Y and M 'are as defined above. particularly R_hj R "_h are ortho to the pyridinium group and R '_h, R "_h represent a hydrogen atom. Another aspect of the invention relates to dyes of formula (Ia) or (Ma) having groups R₉, R "_g 3 'and R'_g/ R "_g representing a hydrogen atom.

p0119Preferably the dye of formula (Ia) and (IIa) have their amino group: R '(CH₂)_p-N- (CH₂)_qR and / or R "(CH₂)_p.-N (CH₂)_q.-R "position in the.

p0120Examples of thiol fluorescent dyes, there may be mentioned the following compounds:

p0121<img id="imgf000018_0002" he="54" wi="122" file="imgf000018_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0122<img id="imgf000018_0003" he="17" wi="131" file="imgf000018_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> 2M ' <img id="imgf000019_0001" he="193" wi="159" file="imgf000019_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000020_0001" he="194" wi="159" file="imgf000020_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0123<img id="imgf000021_0001" he="203" wi="159" file="imgf000021_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /> M 'is an anionic ion-cons.

p0124Protected thiol dyes of formula (M ') can be synthesized in two steps. The first step of preparing the non-thiol dye (HH) according to known methods of skill 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 function thiol using conventional methods known in the art to give the protected thiol dyes of formula (II '). For example, to protect the thiol function -SH of the thiol dye methods of structures can be used "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; 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 comprising i) generating thiol fluorescent dyes of formula (HH) by reduction of a fluorescent dye two-chromophore bearing a disulfide function -SS- (I ') and ii) protect by conventional methods, said thiol function (CBM) with the reagent 7 Y'R to access the protected thiol fluorescent dyes of formula (M '). The thiol compound 6 can also be metallated with an alkali metal or alkaline earth metal Met * so as to thiolate fluorescent dye of formula (M ").

p0125<img id="imgf000023_0001" he="32" wi="145" file="imgf000023_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0126reducer

p0127<img id="imgf000023_0002" he="92" wi="150" file="imgf000023_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Y 'represents a protective group of thiol; Met * representing an alkali metal or an alkaline earth metal, particularly sodium or potassium, provided that when the metal is a alkalino earth metal thiolate-2 chromophores function S^" may be associated with 1 Metal²⁺ ;

p0128and R, R ', R₉, R '_g, R_h, R '_h, R ', R ", m, p, q and M' are as defined above; Y 'represents a protective group of thiol; and R Y'R represents a nucleofugic leaving group, for instance mesylate, tosylate, triflate or halide.

p0129Use may also be a thiol reagent Y'-SH comprising a Y 'group as defined above, the nucleophilic SH group can react on the carbon atom alpha to the halogen carried by the fluorescent chromophore atom (a ^ to yield the protected thiol fluorescent dye of formula (H '):

p0130<img id="imgf000024_0001" he="32" wi="107" file="imgf000024_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R, R ', R₉, R '_g, R_hj R '_hj R'j, R ", m, p, q, and M '(M') are as defined above, and Hal representing a halogen atom nucleofugic such as bromine, iodine or chlorine.

p0131More particularly may be substituted by a nucleofugic leaving group a thiourea group (S = C (NRR) NRR) for generating the isothiouroniums. For example, if the thiourea group is a thioimidazolinium (β), the reaction scheme is as follows:

p0132<img id="imgf000024_0002" he="34" wi="156" file="imgf000024_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R, R ', R₉, R '_g, R_h, R'H, R ', R ", m, p, q and M' are as defined above. An alternative is to use instead of the halide comprising the fluorescent chromophore (a ^ the chromophore including another type nucleofuge as tosylate, mesylate.

p0133By way of example a compound containing a protected thiol group, contains a nucleofugic leaving group R such as mesylate, tosylate, or triflate can undergo nucleophilic attack of the amine carried by the fluorescent chromophore styryl:

p0134<img id="imgf000024_0003" he="32" wi="156" file="imgf000024_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Another alternative arises from the use of halides as nucleofugic leaving group of a thiol compound which may be substituted by a primary amine function, for example carried by a fluorescent chromophore styryl: <img id="imgf000025_0001" he="34" wi="153" file="imgf000025_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0135According to another possibility, the thiol fluorescent dyes of formula (II) according to the invention can be obtained by reacting a compound comprising a thiol group Y as defined above and an electrophilic group (f) with a pyridinium compound comprising a nucleophilic group. For example, it is possible to condense an aldehyde, ketone or thioaldehyde, thioketone when G 'represents an oxygen atom or a sulfur with an "activated methylene" such as alkylpyridinium (e) for generating an ethylene bond> C = C <. This reaction is commonly known condensation "Knoevenagel". By "activated methylenes" is meant those in which preferably comprises 2 or 4 position of the pyridinium group a methylene group R-CH₂-:

p0136<img id="imgf000025_0002" he="31" wi="120" file="imgf000025_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R, R ', R₉, R '_g, R_h, R '_h, R'j, R ", m, p, q, Y and M 'as defined above and G' represents an oxygen or sulfur atom.

p0137Reference may be made to the book Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4^èmΘ Ed, John Willey &amp; Sons, 1992, or TW Greene "Protective Groups in Organic Synthesis" for more details on the operating conditions used in the processes mentioned above.

p0138The thiol fluorescent dyes formed can be converted into protected thiol fluorescent dyes -SY 'by the -SH thiol protection using standard 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 Willey &amp; Sons, NY, 1992. The protected thiol dyes can be deprotected by conventional routes such as those described in the books "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed, NY., 1981; "Protecting Groups" P. Kocienski, Thieme, 3^èmΘ ed., 2005. The departures reagents are commercially available or accessible by conventional methods known in the art. For example it is possible to synthesize the symmetrical thiol fluorescent dye (I) from 2 equivalents of pyridine derivative 1 and one equivalent of disulfide reagent comprising two leaving groups Gp to yield the dipyridinium salt disulfide 3 may condense in turn with two equivalents of aryl compound aldehyde group / thioaldehyde 4 to lead to (I ').

p0139<img id="imgf000026_0001" he="56" wi="148" file="imgf000026_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0140Knoevenagel - 2H₂G with Gp representing a nucleofugic leaving group, for instance mesylate, tosylate, triflate or halide. The against-ion GP compounds (I) above may be replaced with against-ion M 'other natures from methods known in the art including by ion-exchange resin.

p0141The unsymmetrical disulfide dyes of formula (I) can be synthesized in one step by reacting a thiol fluorescent dye unprotected with a protected thiol fluorescent dye with Y 'to form the disulphide dye of formula (I). <img id="imgf000027_0001" he="51" wi="150" file="imgf000027_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R, R ', R ", R'", R_g, R '_g, R "_g, R "_g, R_hj R '_hj R "_hj R " '_hj R₁, R¹,, R ", R" ', m, m', p, p ', q, q' and M 'are as defined above; Y 'represents a protective group of thiol. Reference may be made to the book Advanced Organic Chemistry, "Reactions,

p0142Mechanisms and Structures ", J. March, 4^èmΘ Ed, John Willey &amp; Sons, 1992, or TW Greene "Protective Groups in Organic Synthesis" for more details on the operating conditions used in the processes mentioned above.

p0143The thiol fluorescent dyes formed can be converted into protected thiol fluorescent dyes -SY 'by the -SH thiol protection using standard 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 Willey &amp; Sons, NY, 1992. The protected thiol dyes can be deprotected by conventional routes such as those described in the books "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed, NY., 1981; "Protecting Groups" P. Kocienski, Thieme, 3^èmΘ ed., 2005.

p0144The composition of the invention contains at least one fluorescent dye of formula (I) or (II). Furthermore the presence of at least one fluorescent dye of formula (I) or (II), the composition of the invention may also contain a reducing agent.

p0145This reducing agent may be chosen from thiols such as cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulphite, sulphites, thioglycolic acid and its esters, in particular glycerol monothioglycolate, and thioglycerol. This reducing agent may also be selected from borohydrides and derivatives thereof, such as salts of borohydride, cyanoborohydride, triacetoxyborohydride, the trimethoxyborohydride: sodium, lithium, potassium, calcium, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra n-butylammonium bromide, benzyltriethylammonium); catechol borane.

p0146The dye composition according to the invention generally contains an amount of fluorescent dye of formula (I) or (II) of between 0.001 and 50% based on the total weight of the composition. Preferably, this amount is between

p01470.005 to 20% by weight and even more preferably between 0.01 and 5% by weight relative to the total weight of the composition.

p0148The dye composition may also contain additional direct dyes. These direct dyes are chosen, for example nitrobenzene direct dyes, neutral, acidic or cationic neutral azo direct dyes, acid or cationic tetraazapentamethine dyes, quinone dyes and in particular anthraquinone, acidic or cationic, direct dyes, azine , triarylmethane direct dyes, direct dyes indoamine and natural direct dyes.

p0149Among the natural direct dyes include lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin. One can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

p0150The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin fibers.

p0151Among 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

p0152Among these couplers, mention may be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts. The coupler or couplers are each present in an amount between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

p0153The oxidation of bases present in the dye composition can be present in an amount ranging from 0.001 to 10% by weight of the weight of the total dyeing composition, preferably between 0.005 and 6% by weight.

p0154In general, the addition salts of the oxidation bases and couplers used in the context of the invention are chosen from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the addition salts with a base, such as hydroxides of alkali metal such as sodium, potassium, ammonia, amines or alkanolamines.

p0155The medium suitable for dyeing, also called dye support, is a cosmetic medium consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there can for example be made of lower alkanols dC₄, Such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, monomethyl ether of propylene glycol, monoethyl ether and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

p0156The 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.

p0157Alternatively, the invention contains a reducing agent capable of reducing the disulphide bonds of keratin and / or the dye of formula (I). This reducing agent is as defined above.

p0158The dye composition may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants, anionic, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, thickening agents, inorganic or organic, and associative thickeners anionic, cationic, nonionic and amphoteric polymers, antioxidants, penetrants, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as for example, volatile or nonvolatile silicones, modified or not, such as amino silicones, film-forming agents, ceramides, preservatives, opacifiers, or conductive polymers. The above adjuvants are generally present in an amount for each ranging from 0.01 to 20% by weight relative to the weight of the composition.

p0159Of course, the man of the art care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the dye composition according to the invention are not, or not substantially, impaired by the additions envisaged.

p0160The pH of the dye composition is generally between 3 and 14 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value using acidifying or alkalizing agents usually used for dyeing keratin fibers, or alternatively using standard buffer systems.

p0161Among the acidifying agents, mention may, for example, the inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulphonic acids. Among the alkalizing agents include, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium or potassium hydroxides and compounds formula (γ) below:

p0162^Raj _/^Ra2

p0163NW₃HSI

p0164^Ra4 ^Ra3 (_γ) Wherein W_at is a propylene residue optionally substituted with a hydroxyl group or an alkyl radical Ci-C₄ ; R_ati, R a2, R a3 and R_a4, Identical or different, represent a hydrogen atom, an alkyl radical -C₄ hydroxyalkyl or -C₄.

p0165The dye composition may be in various forms, such as in liquid, cream, gel, or in any other form suitable for dyeing keratin fibers, especially the hair.

p0166According to a particular embodiment in the method of the invention a reducing agent can be applied as a pretreatment before application of the composition containing at least one fluorescent dye of formula (I) or (II). This reducing agent may be chosen from thiols such as cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulphite, sulphites, thioglycolic acid and its esters, in particular glyceryl monothioglycolate, and thioglycerol. This reducing agent may also be selected from borohydrides and derivatives thereof, such as salts of borohydride, cyanoborohydride, triacetoxyborohydride of trimethoxyborohydride: sodium, lithium, potassium, calcium salts, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra-n butylammonium, benzyltriethylammonium); catecholborane.

p0167This pretreatment may be of short duration, in particular 0.1 second to 30 minutes, preferably 1 minute to 15 minutes with a reducing agent as mentioned previously.

p0168According 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.

p0169When the thiol fluorescent dye of formula (II) comprises a protecting group Y of the thiol function, the method of the invention may be preceded by a deprotection step aimed at restoring in-situ the SH function.

p0170For example it is possible to deprotect the SY function Y protecting group by adjusting the pH as follows:

p0171<img id="imgf000031_0001" he="96" wi="139" file="imgf000031_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0172The deprotection step can also be performed in the heart of a hair pretreatment step as for example, the reducing pretreatment hair.

p0173Alternatively, the reducing agent is added to the dye composition containing at least one fluorescent dye of formula (I) or (II) at the time of use. 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.

p0174According to another variant, the reducing agent is applied by post-treatment, after application of the composition containing at least one fluorescent dye of formula (I) or (II). The duration of post-treatment with the reducing agent may be short, for example from 0.1 second to 30 minutes, preferably 1 minute to 15 minutes, with a reducing agent as described above. In a particular embodiment the reducing agent is a thiol agent or borohydride as described above. A particular embodiment of the invention relates to a method wherein the fluorescent dye of formula (I) or (II) may be applied directly to the hair without reducing agents, free of reducing pretreatment or reducing aftertreatment.

p0175Treatment with an oxidizing agent may optionally be combined. We can use any type of conventional oxidizing agent in the field. Thus, it can be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes, among which mention may be made peroxidases, oxido 2-electron such as uricase and 4-electron oxygenases such as laccases.

p0176The use of hydrogen peroxide is particularly preferred. This oxidizing agent may be applied to the fibers before or after applying the composition containing at least one fluorescent dye of formula (I) or (II).

p0177The application of the dye composition according to the invention is generally carried out at room temperature. It may however be carried out at temperatures ranging from 20 to 180⁰C. The invention also relates to a multi-compartment device or "kit" 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 disulphide functions of keratin materials. One of these compartments may also contain one or more other dyes direct dye or oxidation dye.

p0178It 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 keratin materials; a third compartment contains an oxidizing agent.

p0179Alternatively, 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 free the thiol.

p0180Each of the devices mentioned above may be equipped with a means for applying to the hair the desired mixture, for example such as the devices described in patent FR 2 586 913. The examples which follow serve to illustrate the invention without limiting in nature. The thiol fluorescent dyes of the examples below were fully characterized by spectroscopic and spectrometric methods conventional.

EXAMPLES

SYNTHESIS EXAMPLES

p0183Example 1: Synthesis of dimethane sulfonate of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis [4 - ((E) -2- {4- [bis (2-hydroxyethyl) amino] phenyl} vinyl) pyridinium ] [1]

p0184<img id="imgf000034_0001" he="46" wi="109" file="imgf000034_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0185[1] Synthetic Scheme

p0186Sg ^ OH HO

TEA

p0188- AcOEt rcι

p0189<img id="imgf000035_0001" he="114" wi="113" file="imgf000035_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0190[1]

p0191Procedure Step 1: Synthesis of 2,1-diyl-disulfanediyldiéthane dimethanesulfonate

p019210 g of 2,2'-dithiodiéthanol and 14.44 g of triethylamine (TEA) are diluted in 100 ml of EtOAc. A 0⁰C, 16.35 g of methanesulfonyl chloride diluted in 35 ml of AcOEt are added dropwise to the reaction mixture with rapid stirring. 7.22 g of TEA are introduced, stirring is continued at room temperature for 4 h 30. 8.2 g of methanesulfonyl chloride are added dropwise at 15⁰C, then stirring is maintained at room temperature for 17 hours. The precipitate is filtered and washed 3 times with 50 ml of AcOEt. The organic phases are extracted with 100 mL of ice water; 100 mL of water, 3 times with 50 mL of a saturated solution of NaHCO>₃, With 2 times 20 mL of saturated NaCl, then dried over Na₂SO₄ anhydrous. L¹AcOEt is evaporated and 17.49 g of pale yellow translucent oil are recovered. The analyzes indicate that the product is compliant.

p0193Step 2: Synthesis dimethanesulfonate 1,1 '- (2,1 disulfanediyldiéthane-diyl) bis (4-methylpyridinium)

p01943.51 g of 4-picoline and 5 g of disulfanediyldiéthane-2,1-diyl dimethanesulfonate are diluted in 5 mL of N-methylpyrrolidinone (NMP) and heated to 80 ⁰C. under stirring for 2 hours. Stirring is maintained at room temperature for 17 h. The reaction medium is supplemented with 50 ml of EtOAc, then filtered, washed 3 times with 100 ml of EtOAc, and dried under vacuum in presence of P₂O₅. 7.29 g of brown powder are recovered. The analyzes indicate that the product complies and pure. NMR¹ H (400 MHz, DMSO-Of₆) 2.31 (s, 6H), 2.62 (s, 6H), 3.40 (t, 4H), 4.83 (t, 4H), 8.01 (d, 4H),

p01958.91 (d, 4H).

p0196Step 3: Synthesis of dimethane sulfonate of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis [4 - ((E) -2- {4- [bis (2-hydroxyethyl) amino] phenyl} vinyl) pyridinium ] [1] 4.32 g of 4- [bis- (2-hydroxy-ethyl) -amino] benzaldehyde, 10 mL of iPrOH, and 1.69 mL of pyrrolidine were mixed with stirring for 10 minutes. 1.18 mL of acetic acid is added and the mixture was 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. 8.56 g of powder are recovered. The analyzes indicate that the product complies and pure. NMR¹H (400 MHz, MeOH-c4) 2.71 (s, 6H), 3.35 (t, 4H), 3.64 (t, 8H), 3.76 (t, 8H), 4.74 (t, 4H), 6.83 (d, 4H), 7.04 (d, 2H), 7.58 (d, 4H), 7.81 (d, 2H), 7.96 (d, 4H), 8.56 (d, 4H).

p0197Example 2: Synthesis of dibromide of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis [4-

p0198((E) -2- {4- [ethyl (2-hydroxyethyl) amino] -2-methylphenyl} -1-methylvinyl) pyridinium]

p0199[2]

p0200<img id="imgf000037_0001" he="28" wi="108" file="imgf000037_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0201Synthetic Scheme

p0202Br-Br

-SS

p0204κ> NMP CH, CN

p0205<img id="imgf000037_0002" he="10" wi="54" file="imgf000037_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p02062 Br

p0207iPrOH <img id="imgf000037_0003" he="18" wi="50" file="imgf000037_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0208<img id="imgf000037_0004" he="18" wi="107" file="imgf000037_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p02092 Br

p0210Procedure Step 1: Synthesis of dibromide 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis (4 ethylpyridinium)

p021112. 9 g of 4-ethyl-pyridine dissolved in 4 mL of NMP and 15 mL of acetonitrile (ACN) were stirred and heated to 80 ⁰C. 15 g of 1-Bromo-2- (2-bromo-éthyldisulfanyl) -ethane diluted in 10 mL of ACN is added dropwise to the medium for 30 minutes. The reaction mixture was stirred and refluxed for 4 h, then at room temperature for 17 h. The green solid obtained are added 200 ml of acetone and the solid is broken, then filtered, washed with 50 mL of acetone and then dried. 23,32 g of green powder collected. The analyzes indicate that the product complies.

p0212Step 2: Synthesis of dibromide of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis [4 - ((E) - 2- {4- [ethyl (2-hydroxyethyl) amino] -2-methylphenyl} - 1-methylvinyl) pyridinium] [2] 5 g of 4- [ethyl- (2-hydroxy-ethyl) -amino] -2-methyl-benzaldehyde, 10 mL of iPrOH, and 1, 74 mL of pyrrolidine were mixed in stir for 10 min. 1, 21 ml_ of acetic acid are added and the mixture is stirred at room temperature for 20 min. 5 g dibromide 1.1^l- (Disulfanediyldiéthane-2,1-diyl) bis (4-ethyl pyridinium) suspended in 7 mL of iPrOH and 5 mL of methanol are added. The reaction mixture is stirred for 1 week at room temperature. The reaction mixture is kept at room temperature for 4 weeks. The reaction mixture was concentrated, the residue was extracted with a mixture of H₂OZCH₂THIS₂, Then the expected product is extracted with butanol and the organic phase is concentrated and the residue is taken up in ethyl acetate. The precipitate is filtered and dried. 810 mg of powder were recovered. The analyzes indicate that the product complies.

p0213Example 3: Synthesis of dimethane sulfonate of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis [4 - ((E) -2- {4 - [[3- (dimethylamino) propyl] (methyl) amino] phenyl} vinyl) - pyridinium] [3]

p0214<img id="imgf000038_0001" he="26" wi="114" file="imgf000038_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0215[3] Synthetic Scheme

p0216Roh <img id="imgf000039_0001" he="74" wi="74" file="imgf000039_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0217<img id="imgf000039_0002" he="27" wi="114" file="imgf000039_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0218[3]

p0219Procedure Step 1: Synthesis of 4 - [[3- (dimethylamino) propyl] (methyl) amino] benzaldehyde

p022010 g of 4-fluorobenzaldehyde, 12 g of K₂CO₃ , 20 mL of NMP was stirred and heated to 50 ⁰C. 13 mL of NNN'-trimethyl-I .S-propane are added dropwise in the middle stirred and heated to 80 ° C for 10 h. After cooling the reaction mixture to room temperature, 100 ml of acetone are added. The precipitate is filtered and the filtrate is evaporated to dryness and dried. 21.85 g of powder are recovered. The analyzes indicate that the product complies.

p0221Step 2: Synthesis of di methane sulfonate of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis [4 - ((E) -2- {4 - [[3- (dimethylamino) propyl] (methyl) amino ] phenyl} vinyl) - pyridinium] [3] 2 g of 4 - [(3-dimethylamino-propyl) -methyl-amino] benzaldehyde dissolved in 5 mL of iPrOH, to which are added 585 .mu.l of pyrrolidine are stirred at temperature ambient for 10 minutes. 408 .mu.l of acetic acid are added to the reaction medium stirred at room temperature for 20 minutes. 1, 71 g of di methanesulfonate of 1, 1 '- (disulfanediyldiéthane-2,1-diyl) bis (4-methyl pyridinium) previously dissolved in 3 mL of iPrOH and 1 mL of methanol are introduced into the stirred medium at 20 ° C for 4 days. 50 m L of diisopropyl ether are added to the cooled reaction mixture via a dry ice and acetone. The precipitate is filtered and dried. 2.21 g purple powder are recovered. The analyzes indicate that the product complies. NMR¹H (400 MHz, MeOH-α4) 1.84 (m 4H), 2.34 (s, 12H), 2.48 (t, 4H), 2.71 (s, 6H), 3.06 (s, 6H), 3.36 (t, 4H), 3.50 (t, 4H), 4.75 (t, 4H), 6.79 (d, 4H), 7.07 (d, 2H), 7.60 (d, 4H), 7.84 (d, 2H) , 7.98 (d, 4H), 8.57 (d, 4H).

p0222Example 4: Synthesis of 1,1 salt^l- (Disulfanediyldiéthane-2,1-diyl) bis {2 - [(E) -2- (4- {methyl [3- (trimethylammonio) propyl] amino} phenyl) vinyl] pyridinium} [4]

p0223<img id="imgf000040_0001" he="48" wi="61" file="imgf000040_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0224[4]

p0225Synthetic Scheme

p0226<img id="imgf000041_0001" he="122" wi="68" file="imgf000041_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0227[4]

p0228procedure

p0229Step 1: Synthesis of dibromide of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis (2-methyl-pyridinium)

p0230A mixture of 56 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] ethane, and 15 mL of N- methylpyrrolidone (NMP) is added dropwise to 35 g of 2-picoline under stirring at 80 ⁰C. The mixture (white suspension) is kept stirred for 30 minutes at 80 ⁰C, 100 mL of ACN are added, stirring is maintained at 80 ⁰C for 90 min. After cooling, the solid obtained is filtered, washed with 100 ml of ACN and dried. Collected 56.2 g of brown powder. 45 g of this powder are suspended in 300 ml of iPrOH, at reflux. Once the temperature lowered to 40⁰C, the solid is filtered, washed 3 times with 100 ml of iPrOH and dried under vacuum. beige product, 40.56 g. Analyzes in accordance with the expected structure. Step 2: Synthesis of methyl 3 - [(4-formylphenyl) (methyl) amino] -N, N, N-1-aminium triméthylpropan

p02315 g of - [[3- (dimethylamino) propyl] (methyl) amino] benzaldehyde are diluted in 15 mL of dichloromethane. 2.36 ml of dimethyl sulfate diluted in 10 ml of dichloromethane are progressively added. The mixture was heated to reflux for 4 h then cooled to room temperature and poured into 100 mL of ethyl acetate. The brown oil formed is decanted, washed with 100 mL of AcOEt in recovery

p0232200 mL of methanol and concentrated in vacuo. It was then dissolved in a saturated solution of sodium chloride and sodium bicarbonate and extracted with butanol. The butanol phase is concentrated under vacuum, dried under vacuum in the presence of

p0233P₂O₅Then the product is used for the next step.

p0234Step 3: Synthesis of salt of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis {2 - [(E) -2- (4- {methyl [3- (trimethylammonio) propyl] amino} phenyl) vinyl ] pyridinium} [4] 0.62 g of sulfate of 3 - [(4-formylphenyl) (methyl) amino] -N, N, N-triméthylpropan methyl-1- aminium chloride dissolved in 2 mL of iPrOH and 3 mL of methanol to which are added 0.15 mL of pyrrolidine were stirred at ambient temperature for 10 minutes. 0.11 mL of acetic acid are added to the reaction medium stirred at room temperature for 20 minutes. 0.41 g dibromide 1, 1^l- (Disulfanediyldiéthane-2,1-diyl) bis (2-methyl-pyridinium) predissolved in 2 mL of iPrOH and 2 mL of methanol are introduced into the medium agitated at 20 ⁰C for 17 h. The analyzes show the presence of the expected product.

p0235Example 5: Synthesis of 4 methanesulfonate - ((E) -2- {4- [bis (2-hydroxyethyl) - amino] -phenyl} vinyl) -1- (2-sulfanylethyl) pyridinium [5]

p0236<img id="imgf000042_0001" he="26" wi="67" file="imgf000042_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0237[5] Synthetic Scheme

p0238<img id="imgf000043_0001" he="87" wi="112" file="imgf000043_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0239[5]

p0240procedure

p0241Synthesis of the salt of 4 - ((E) -2- {4- [bis (2-hydroxyé ethyl) amino] phenyl} -vinyl) -1- (2- sulfanylethyl) pyridinium [5]

p024288 mg of compound [1] are dissolved in 10 mL of water / ethanol mixture (1/1); 60 mg

p0243(2 eq.) Of hydrate of 3- hydrochloride [bis (2-carboxy-ethyl) phosphino] propanoic acid dissolved in 1 ml of water and 21 mg (4 eq) of sodium bicarbonate dissolved in 1 mL of water was added to the mixture. After 30 minutes stirring at 40⁰C under an inert atmosphere, the analyzes indicate that the mixture contains very predominantly the expected product [5].

p0244LC-MS analysis: LC-DAD (400-700 nm)

p0245Column: Waters XTerra MS C18 5 .mu.m (4.6 x 50) mm

p0246Mobile phase: A: water + 0.1% formic acid / B: Acetonitrile

p0247linear gradient: T (min)% A / B%: 0 min 95/5; 8 min 0/100

p0248Flow rate: 1mL / min.

p0249Detection: UV LED Strip λ = 400-700nm

p0250Retention time t = 3.3 min Purity relative> 90%

p0251MS (ESI +) m / z = 345 corresponds to the mass peak of monocation the expected product [5] EXAMPLES OF COLOUR

p0252Example 1 - method for coloring the compounds [1] to [4]

p0253Preparation of a composition A

p0254Disulphide dye [1] to [4] 10^"3 mol%

p0255Benzyl Alcohol 4 g

p02566 g polyethylene glycol 6EO

p0257Hydroxyethylcellulose 0.7 g

p0258Alkylpolyglycoside in aqueous solution at 65% AS 4.5 g

p0259Demineralized water qs 100 g

p0260Preparing a composition B

p0261Thioglycolic acid 1M

p0262Sodium hydroxide qs pH 8.5

p0263Demineralized water qs 100 g

p0264At the time of use, mix compositions A (9 mL) and B (1 mL) and then apply the mixture to a lock of 1 g of dark hair (tone height 4) for 30 minutes at room temperature (the locks are turned over and reimpregnated after 15 minutes).

p0265After rinsing with running water and drying, there is a thinning of hair thus treated: the lock of tone height 4 has become visually lighter than untreated control locks.

p0266Example 2 - staining method with compound [5] 10 ml fresh solution of the compound [5] in the synthesis example are applied to a lock of 1 g hair of tone height 4 placed at the bottom of the same bowl for 30 minutes at room temperature (the locks are turned and reimpregnated after 15 minutes). The locks were then rinsed with running water and dried. After coloring the tone height 4 wick has become visually lighter than untreated control locks.

p0267Persistence vis-à-vis successive shampooing:

p0268The locks thus treated are divided into two, one half is subjected to 5 successive shampooing according to a cycle which includes the wetting of the locks with water, washing with a conventional shampoo, rinsing with water followed by drying.

p0269visual observations

p0270In shampoos, there is no visible bleeding, the shampoo foam and the rinsing water are not colored

p0271The color observed on the locks is preserved and the lightening effect remains visible on the hair thus treated

p0272Results in the L^*at^*b^* : The color of the locks before and after the 5 washes was evaluated in the L * a * b * using a spectrophotometer CM 2600D MINOLTA ®, (illuminant D65). In this L * a * b *, L * represents lightness, a * indicates the color axis red / green axis and b * the blue / yellow color. The higher the value of L, the higher the color lighter or less intense. Conversely, the more the value of L is small, the color is dark or intense. Over the a * value the higher the grade is red and the b * value is high more yellow the shade.

p0273The change in coloring between the strands of hair HT4, stained and washed are measured by (.DELTA.E) using the following equation:

p0274Δ E = V (L^* - L₀^*)² + (A^* - at₀^*)² + (B^* - b₀^*)²

p0275In this equation, L *, a * and b * represent the values ​​measured before dyeing, and L₀* Ao bo * and * represent the values ​​measured before coloring (or shampoo).

p0276Plus the value of .DELTA.E, the greater the difference in color between HT4 locks and dyed locks is important.

p0277Treatment with the fluorescent dye on the roving HT4 .DELTA.E <img id="imgf000046_0001" he="111" wi="152" file="imgf000046_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0278The results of the above table show that the color changes very little after 5 shampoos. Thus, the coloring and the lightening effect on the hair remains virtually unchanged, showing a very good resistance to shampoos dyes of the invention.

p0279Reflectance Results:

p0280lightening effectiveness of the compositions according to the invention and their vis-a-vis remanence successive shampoos were expressed in terms of the reflectance of the hair. These reflectances are compared to the untreated reflectance of a lock of hair of tone height TH4.

p0281The reflectance is measured using a MINOLTA spectrophotocolorimeter device KONIKA- ®, CM 260Od and after irradiation of the hair with visible light in the wavelength range from 400 to 700 nanometers. Reflectance of the locks treated with the compounds 1 and 2 to the application and after 5 shampoos

p0282Reference Compound 1

p0283Compound 1 -5 shampoos <img id="imgf000047_0001" he="41" wi="94" file="imgf000047_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> - * - Compound 2 Compound 2-5 shampoos oooooooooooooooc Δ

p0284Wavelength (nm)

p0285Reflectance of the locks treated with the compound 3 to the application and after 5 shampoos

p0286_^ 5

p0287S ⁴ Reference

p0288$ ³

p0289£ 2 Compound 3 * 1

p0290Compound 3-5 shampoos CMO o O o * o (D oO ooo o CMO "1 o &lt;D ooo oO CMO o * o &lt;D OOO cC

p0291Wavelength (nm)

p0292Reflectance of the locks treated with compound 5 to the application and after 5 shampoos

p0293• Reference

p0294- Compound 5

p0295<img id="imgf000047_0002" he="40" wi="94" file="imgf000047_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Compound 5-5 shampoos o O o CMO - ^ - Oco Oco IVCOs oO o-tf Oco Oco IVCOs oO o-st- Oco Oco gs.

p0296- * - * (C (CN

p0297Wavelength (nm)

p0298We first note that the reflectance of a lock of hair treated with a composition according to the invention is higher than that of untreated hair. The treated locks therefore appear brighter.

p0299In addition, the results show that the reflectance of the high hair strands of your 4 treated with the compositions of the invention change very little after 5 shampoos. Thus, the coloring and the lightening effect on the hair remains virtually unchanged, showing a very good resistance to shampoos dyes of the invention.