Method of dyeing and lightening keratin materials in the presence of a reducing agent comprising a fluorescent disulphide dye

0001The subject of the invention is a process for coloring and lightening keratin materials in the presence of a reducing agent.

0002It is known to dye keratin fibers, in particular human fibers, by direct coloring. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and coloring molecules having an affinity for the fibers, in letting them diffuse, then in rinsing the fibers.

0003The direct dyes which are conventionally used are, for example, dyes of the benzene nitro type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triarylmethane type.

0004The colorings which result from the use of direct dyes are temporary or semi-permanent dyes because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible. their low dye power and their poor resistance to washing or perspiration.

0005Furthermore, the coloring of keratin fibers from conventional direct dyes does not make it possible to lighten the keratin fibers significantly.

0006The lightening of the color of keratin fibers, more particularly dark towards lighter shades, possibly modifying the shade thereof, constitutes an important demand.

0007Conventionally, to obtain a lighter coloring, a chemical bleaching process is used. This method consists in treating keratin materials such as keratin fibers, in particular the hair, with a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, most often in an alkaline medium.

0008This bleaching system has the disadvantage of degrading the fibers and altering their cosmetic properties. The fibers tend to become rough, more difficult to disentangle and more fragile. Finally, the lightening or discoloration of keratin fibers from an oxidizing agent is incompatible with treatments for modifying the shape of said fibers, particularly in hair straightening treatments.

0009Another lightening technique is to apply fluorescent direct dyes to dark hair. This technique described in particular in the document<patcit id="pcit0001" dnum="FR2830189"><text>FR 2830189</text></patcit> respects the quality of the keratin fiber during the treatment, but the fluorescent dyes used do not have satisfactory resistance to shampooing.

0010To increase the toughness of 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 very numerous cystine or cysteine ​​residues in keratin fibers. Are thus described certain dyes carrying salt functions of Bunte and isothiuroniums, or other protective groups of thiols. However, obtaining the reactive form of the dye generally requires the use of strongly basic media. In addition, the thiol functions are generally generated in excess, which makes a post-neutralization step necessary after coloring.

0011Other disulfide dyes known for coloring keratin fibers are disulfide derivatives of aminothiophenol derivatives. Such dyes are described for example in the patent<patcit id="pcit0002" dnum="FR1156407"><text>FR 1156407</text></patcit>. These dyes can be used in relatively mild conditions, in the presence of a slightly reducing medium or after a reducing pretreatment of the hair. However, these dyes can cause color changes during application. In addition the document<patcit id="pcit0003" dnum="WO03028685A"><text>WO 03/028685</text></patcit> discloses direct fluorescent dyes used to lighten dark keratin fibers.

0012Finally, the document <patcit id="pcit0004" dnum="WO2005097051A"><text>WO 2005/097051</text></patcit> describes disulfide dyes azaimidazoliums for the direct dyeing of keratin fibers.

0013The object of the present invention is to provide new coloring systems with lightening effect of keratin materials, in particular human keratin fibers, especially the hair, which do not have the drawbacks of existing bleaching methods. In particular, one of the aims of the present invention is to provide direct coloring systems making it possible to obtain lightening effects in particular on naturally or artificially dark keratin fibers, tenacious in the face of successive shampoos and which do not degrade the keratin fibers and which do not alter their cosmetic properties.

0014This object is achieved with the present invention which relates to a process for coloring dark keratin materials, consisting in applying to the keratin materials, a dye composition, comprising in a suitable cosmetic medium, at least one fluorescent disulfide dye, for example chosen from the dyes of formulas (I) and (II) below:         A- (X)_p - VS_sat - SS - C '_sat - (X ')_p' - HAVE)         A- (X)_p - VS_sat - SS - C '_sat - (X ')_p'- D (II) their organic or mineral acid salts, optical isomers, geometric isomers, and solvates such as hydrates; formulas in which:<ul id="ul0001" list-style="bullet" compact="compact"><li>A, and A ', identical or different, represent a radical containing at least one cationic or non-cationic fluorescent chromophore;</li><li>X and X ', identical or different, represent a C hydrocarbon chain₁-VS₃₀, linear or branched, saturated or unsaturated, possibly interrupted and / or possibly terminated at one or two of its ends by one or more divalent groups or their combinations chosen from:<ul id="ul0002" list-style="dash" compact="compact"><li>-N (R) -, -N⁺(R) (R ') -, -O-, -S-, -CO-, -SO₂- with R, R ', identical or different, are chosen from hydrogen, a C 1 alkyl radical₁-VS₄, hydroxyalkyl and aminoalkyl</li><li>a radical (hetero), aromatic or unsaturated, saturated or unsaturated, condensed or not, optionally comprising one or more identical or not, heteroatoms, optionally substituted;</li></ul></li><li>the coefficient p, and p ', identical or different, represent an integer equal to 0 or 1;</li><li>VS_sat, VS'_sat, identical or different, represent a C alkylene chain₁-VS₁₈, linear or branched, optionally substituted, optionally cyclic;</li><li>D corresponds to a radical chosen from hydroxy, hydroxyalkyl, alkoxy, carboxylic, carboxylate, amino, alkylamino or dialkylamino radicals,</li></ul>this application is carried out in the presence of a reducing agent.

0015This reducing agent can be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid, as well as its esters, in particular the glycerol monothioglycolate, and thioglycerol.

0016This reducing agent can also be chosen from borohydrides and their derivatives, such as for example the salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxyborohydride: sodium salts, lithium, potassium, calcium, quaternary ammoniums (tetramethylammonium, tetraethylammonium, tetra n -butylammonium, benzyltriethylammonium); catecholborane.

0017The method of the invention makes it possible to obtain a lightening of dark keratin materials. In particular, the method of the invention makes it possible to obtain a lightening of keratin fibers such as the hair, very stubborn with shampoos, common aggressions (sun, perspiration), and other hair treatments without degrading the keratin fiber.

0018For the purposes of the invention, the term “dark keratinous material” is understood to mean that which has an luminescence L * encrypted in the CIE system 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.

0019For the purposes of the invention, the term “naturally or artificially dark hair” means hair whose pitch is less than or equal to 6 (dark blonde) and preferably less than or equal to 4 (chestnut).

0020The lightening of the hair is evaluated by the "height of tone" which characterizes the degree or the level of lightening. The notion "tone" is based on the classification of natural shades, a tone separating each shade from the one that immediately follows or precedes it. This definition and classification of natural shades is well known to hair professionals and published in the book "Science of hair treatments" by Charles ZVIAK 1988, Ed. Masson, p. 215 and 278.

0021The pitch of the tone ranges from 1 (black) to 10 (light light blonde), a unit corresponding to a tone; the higher the number, the lighter the shade.

0022An artificially colored hair is a hair whose color has been modified by a coloring treatment, for example coloring with direct dyes or oxidation dyes.

0023Preferably, the composition must, after application to hair, for example brown, lead to the results below.<ul id="ul0003" list-style="dash" compact="compact"><li>We are interested in the reflectance performance of hair when it is irradiated with visible light in the wavelength range from 400 to 700 nanometers.</li><li>The reflectance curves are then compared as a function of the wavelength, of hair treated with the composition of the invention and of untreated hair.</li><li>The curve corresponding to the treated hair must show a reflectance in the wavelength range from 450 to 700 nanometers greater than the curve corresponding to the untreated hair.</li><li>This means that, in the wavelength range from 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% of reflectance, and preferably of at least 0.1%. This does not prevent that it can exist in the wavelength range 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.</li></ul>

0024Preferably, the wavelength where the difference is maximum between the reflectance curve of the treated hair and that of the untreated hair, is in the wavelength range from 450 to 650 nanometers, and preferably in the wavelength range from 450 to 620 nanometers.

0025Within the meaning of the present invention, and unless a different indication is given:<ul id="ul0004" list-style="dash" compact="compact"><li>a fluorescent disulfide dye is a fluorescent compound comprising at least one fluorescent chromophore as defined below, and comprising one or more SS disulfide bonds between two carbon atoms, directly or indirectly linked to the fluorescent chromophore (s) of the compound, preferably the bond is capable of being reduced in a cosmetically acceptable medium;</li><li>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:<ul id="ul0005" list-style="bullet" compact="compact"><li>a C 1 alkyl radical₁-VS₁₆, preferably in C₁-VS₈, optionally substituted by one or more radicals chosen from hydroxy, C alkoxy radicals₁-VS₂, (poly) -hydroxyalkoxy in C₂-VS₄, acylamino, amino substituted by two alkyl radicals, identical or different, at C₁-VS₄ , 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 links, preferably from 5 to 6 links, optionally saturated or unsaturated substituted optionally comprising another heteroatom identical or different from nitrogen;</li><li>a halogen atom such as chlorine, fluorine or bromine;</li><li>a hydroxyl group;</li><li>a C alkoxy radical₁-VS₂ ; a (poly) -hydroxyalkoxy radical in C₂-VS₄ ;</li><li>an amino radical;</li><li>a 5- or 6-membered heterocycloalkyl radical;</li><li>an optionally cationic 5- or 6-membered heteroaryl radical, preferably imidazolium, and optionally substituted by a radical (C₁-VS₄) alkyl, preferably methyl;</li><li>an amino radical substituted by one or two identical or different C 1 alkyl radicals₁-VS₆ possibly carrying at least:<ol id="ol0001" compact="compact"><li>i) a hydroxyl group,</li><li>ii) an amino group optionally substituted by one or two C 1 alkyl radicals₁-VS₃ optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen,</li><li>iii) 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 alkyl group₁-VS₄; and M represents the counterion of the organic, mineral acid or of the corresponding halide,</li><li>iv) or a 5 or 6-membered heteroaryl radical optionally cationic, preferably imidazolium, and optionally substituted by a radical (C₁-VS₄) alkyl, preferably methyl;</li></ol></li></ul><ul id="ul0006" list-style="bullet" compact="compact"><li>an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C 1 alkyl radical₁-VS₄ optionally carrying at least one hydroxyl group and the radical R 'is a C 1 alkyl radical₁-VS₂ ; a carbamoyl radical ((R)₂N-CO-) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C 1 alkyl radical₁-VS₄ optionally carrying at least one hydroxyl group; an alkylsulfonylamino radical (R'SO₂-NR- in which the radical R represents a hydrogen atom, a C 1 alkyl radical₁-VS₄ optionally carrying at least one hydroxyl group and the radical R 'represents a C 1 alkyl radical₁-VS₄, a phenyl radical; an aminosulfonyl radical ((R)₂N-SO₂- in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C 1 alkyl radical₁-VS₄ optionally carrying at least one hydroxyl group,</li><li>a carboxylic radical in acid or salified form (preferably with an alkali metal or ammonium, substituted or not);</li><li>a cyano (CN) group;</li><li>a polyhaloalkyl group, preferably trifluoromethyl (CF₃) ;</li></ul></li><li>the cyclic or heterocyclic part of a non-aromatic radical can be substituted by at least one substituent carried by a carbon atom chosen from the groups:<ul id="ul0007" list-style="bullet" compact="compact"><li>hydroxyl,</li><li>C alkoxy₁-VS₄, (poly) hydroxyalkoxy in C₂-VS₄,</li><li>alkylcarbonylamino ((RCO-NR'-) in which the radical R 'is a hydrogen atom, a C 1 alkyl radical₁-VS₄ optionally carrying at least one hydroxyl group and the radical R is a C 1 alkyl radical₁-VS₂, amino substituted by two identical or different C alkyl groups₁-VS₄ optionally carrying at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other different heteroatom or not nitrogen;</li><li>alkylcarbonyloxy ((RCO-O-) in which the radical R is a C alkyl radical₁-VS₄, amino substituted by two identical or different C alkyl groups₁-VS₄ optionally carrying at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other different heteroatom or not nitrogen;</li><li>alkoxycarbonyl ((RO-CO-) in which the radical R is a C alkyl radical₁-VS₄, amino substituted by two identical or different C alkyl groups₁-VS₄ optionally carrying at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other different heteroatom or not nitrogen;</li></ul></li><li>a cyclic, heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, can also be substituted by one or more oxo groups;</li><li>a hydrocarbon chain is unsaturated when it has one or more double bonds and / or one or more triple bonds;</li><li>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;</li><li>a “heteroaryl radical” represents a mono or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 links, from 1 to 6 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atom, and of which at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl , phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyle, pyridyle, pyridinoimidazolyle, pyrrolyle, quinolyle, tétrazolyle, thiadiazolyle, thiazolyle, thiazolopyridinyle, thiazoylimidazolyle, thiopyrylyl, triazolyle, xanthylyl and its ammonium salt;</li><li>a “cyclic radical” is a non-aromatic, mono or polycyclic cycloalkyl radical, condensed or not, containing from 5 to 22 carbon atoms, which may contain from 1 to several unsaturations;</li><li>a “heterocyclic radical” is a mono or polycyclic nonaromatic radical, condensed or not, containing from 5 to 22 links, comprising from 1 to 6 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atom;</li><li>an “alkyl radical” is a C hydrocarbon radical₁-VS₁₆, linear or branched, preferably in C₁-VS₈,</li><li>the expression “optionally substituted” attributed to the alkyl radical means that said alkyl radical may be substituted by one or more radicals chosen from the i) hydroxy, ii) alkoxy radicals₁-VS₄, iii) acylamino, iv) amino optionally substituted by one or two identical or different C 1 alkyl radicals₁-VS₄, said alkyl radicals being able to form, with the nitrogen atom which carries them, a heterocyle comprising from 5 to 7 members, optionally comprising another heteroatom different or not 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 alkyl group₁-VS₄, or else -N⁺R'R "R" 'forms a heteroaryl such as imidazolium optionally substituted by a group C₁-VS₄ alkyl, and M represents the counterion of the organic, mineral acid or of the corresponding halide,</li><li>an “alkoxy radical” is an alkyloxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, at C₁-VS₁₆ preferably in C₁-VS₈ ; when the alkoxy group is optionally substituted, this means that the alkyl group is optionally substituted as defined above.</li></ul>

0026In addition, unless otherwise indicated, the limits delimiting the extent of a range of values ​​are included in this range of values.

0027According to the present invention, the term "fluorescent chromophore" means a radical derived from a fluorescent compound. A fluorescent compound is a compound which is capable of absorbing in UV or visible radiation at a wavelength λ_abs between 250 and 800 nm and capable of re-emitting in the visible range at an emission wavelength λ_em between 400 and 800 nm.

0028Preferably the fluorescent compounds are dyes capable of absorbing in the visible λ_abs between 400 and 800 nm and reemitting in the visible λ_em between 400 and 800 nm. More preferably, the fluorescent dyes are dyes capable of absorbing at a λ_abs between 420 nm and 550 nm and reemitting in the visible at a λ_em between 470 and 600 nm.

I

.

Dyes of formulas (I) and

(

II)

0029The radicals A and A 'of formulas (I) and (II) may contain one or more fluorescent chromophores, identical or different.

<u>I.1. Chromophores</u>

0030For the purposes of the present invention, the chromophores are said to be different when they differ in their chemical structure. Such chromophores can be chromophores from different families or from the same family provided that they have different chemical structures. For example, the chromophores can be chosen from the family of (poly) methine dyes but differ by the chemical structure of the radicals constituting it or by the respective position of these radicals.

0031Mention may be made, as fluorescent chromophores useful in the present invention, of the radicals derived from acridine dyes, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyranes, benzothiazoles, coumarins, difluoro {2 - [(2<i>H</i>-pyrrol-2-ylidene-kN) methyl] -1H-pyrrolato-kN} bores (BODIPY ®), dipyrrinones, dikétopyrrolopyrroles, fluorindines, (poly) méthines (in particular cyanines and styryles / hemicyanines), naphthalimides, naphthhanamine, naphthyl dansyles), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes / carotenoids, squaranes, stilbenes, xanthenes.

0032Mention may also be made of the fluorescent dyes described in the documents <patcit id="pcit0005" dnum="EP1133975A"><text>EP 1133975</text></patcit>, <patcit id="pcit0006" dnum="WO03029359A"><text>WO 03/029359</text></patcit>, <patcit id="pcit0007" dnum="EP860636A"><text>EP 860636</text></patcit>, <patcit id="pcit0008" dnum="WO9501772A"><text>WO 95/01772</text></patcit>, <patcit id="pcit0009" dnum="WO9515144A"><text>WO 95/15144</text></patcit>, <patcit id="pcit0010" dnum="EP714954A"><text>EP 714954</text></patcit> and those listed in the encyclopedia <i>"</i><nplcit id="ncit0001" npl-type="b"><text>The chemistry of synthetic dye "by K. VENKATARAMAN, 1952, Academic press vol 1 to 7</text></nplcit>, in the encyclopedia <i>"</i><nplcit id="ncit0002" npl-type="b"><text>Kirk Othme "" Chemical technology ", chapter" dyes and Dye intermediate ", 1993, Wiley and sons</text></nplcit>, and in various chapters of the encyclopedia <i>"</i><nplcit id="ncit0003" npl-type="b"><text>ULLMANN's ENCYCLOPEDIA of Industrial chemistry "7th edition, Wiley and sons</text></nplcit>, in <nplcit id="ncit0004" npl-type="s"><text>The Handbook - A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes / Invitrogen - Oregon 2005</text></nplcit> distributed via the Internet or in previous printed editions.

0033Preferably, the chromophores are chosen from those derived from coumarin, (poly) methine (especially cyanine and styryl / hemicyanine) and naphthalimide dyes.

0034According to a variant, the radicals A and A 'of formulas (I) or (II) contain at least one cationic radical carried by or included in at least one of the chromophores.

0035Preferably, the cationic radical is a quaternary ammonium.

0036These cationic radicals are, for example, an alkylammonium radical, acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolium, dihydrothiazolium, imidazolium, imidazolium naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

<u>I.1 C</u>_<u>sat</u><u>and C '</u>_<u>sat</u><u>:</u>

0037As indicated before, in formulas (I) or (II), C_sat and C '_sat, independently of one another, represent a C alkylene chain₁-VS₁₈, linear or branched, optionally substituted, optionally cyclic. As a substituent, mention may be made of amino groups, (C₁-VS₄) alkylamino, (C₁-VS₄) dialkylamino, or the group R^at-Z^at-C (Z^b) - (in which Z^at, Z^b, identical or different, represent an oxygen atom, a sulfur atom, or an NR group^at,, and R^at, represents an alkali metal, a hydrogen atom, or a group C₁-VS₄ alkyl and R^at, represents a hydrogen atom or a group C₁-VS₄ alkyl) preferably present on the carbon in beta or gamma position of the sulfur atoms.

0038Preferably, in the case of formulas (I) or (II), C_sat and C '_sat, represent a chain - (CH₂)_k- with k integer, inclusive between 1 and 8.

<u>1. 3. X and X ':</u>

0039According to a particular embodiment of the invention, in the above formulas (I) or (II), when p is equal to 1, X and X ', identical or different, represent the following sequence:         - (T)_t- (Z)_z- (T ')_you- said sequence being linked in formulas (I) or (II) symmetrically as follows:         - VS_sat (or C '_sat) - (T)_t- (Z)_z- (A or A '); in which<ul id="ul0008" list-style="none" compact="compact"><li><b>T</b> and <b>You,</b> identical or different, represent one or more radicals or their combinations chosen from: -SO₂- -O-; -S-; -N (R) -; -NOT⁺(R) (R °) -; -CO-; with R, R °, identical or different, representing a hydrogen atom, a C 1 alkyl radical₁-VS₄, C-hydroxyalkyl₁-VS₄ or an aryl (C₁-VS₄) alkyl; and a heterocycloalkyl or heteroaryl radical, cationic or not, preferably monocyclic, preferably containing two heteroatoms (more preferably two nitrogen atoms) and preferably comprising from 5 to 7 members, more preferentially imidazolium;</li><li>the clues <b>t</b> and <b>you,</b> identical or different, are 0 or 1;</li><li><b>Z</b> represented :<ul id="ul0009" list-style="dash" compact="compact"><li>- (CH₂)_m- with whole m between 1 and 8</li><li>- (CH₂CH₂O)_q- or - (OCH₂CH₂)_q- in which q is an integer between 1 and 15</li><li>an aryl, alkylaryl or arylalkyl radical in which the alkyl radical is C₁-VS₄ and the aryl radical is preferably C₆, being optionally substituted by at least one SO group₃M with M representing a hydrogen atom, an alkali metal or an ammonium ammonium group substituted by one or more alkyl radicals, identical or not, linear or branched, at C₁-VS₁₈ optionally carrying at least one hydroxyl</li></ul></li><li><b>z</b> is 0 or 1.</li></ul>

0040Furthermore, according to a particular embodiment of the invention, Z represents:<chemistry id="chem0001" num="0001"><img file="EP2004759B1_D0001.tif" /></chemistry>

<u>I.4. Disulfide fluorescent dyes:</u>

0041According to a preferred variant of the invention, the disulfide dye is a cationic fluorescent dye comprising at least one quaternary ammonium radical and such that, in formula (I) with p equal to 1:<ul id="ul0010" list-style="none" compact="compact"><li><b>AT</b> and <b>AT',</b> identical or different, more preferably identical, represent WC (R^vs) = C (R^d) -Ar- or -WC (R^vs) = C (R^d) -Ar, with W representing a heterocycle or a heteroaryl, comprising a quaternary ammonium; Ar represents a 5 or 6-membered (hetero) aryl radical of the phenyl or pyridium type, or an aromatic (hetero) bicycle of the naphthyl, benzopyrydinium, indolinyl, or benzoindolinyl type, optionally substituted by one or more halogen atoms, preferably chlorine, fluorine; by one or more alkyl groups, preferably C₁-VS₄ ; by one or more hydroxyl groups; by one or more alkoxy groups, by one or more hydroxyalkyl groups, by one or more amino or (di) alkylamino groups, preferably with the C alkyl part₁-VS₄, by one or more acylamino groups; by one or more heterocycloalkyl or heteroaryl groups with 5 or 6 members, preferably chosen from pyrrolidinyl, pyperazinyl, pyperidinyl and imidazolinyl; R^vs, R^d, identical or different, represent a hydrogen atom or a C alkyl group₁-VS₄.</li></ul>

0042According to a preferred variant p, p '= 1; z = 0; t '= 0 and t = 1 and T represents -N (R) -, preferably in the para position on Ar with respect to the olefin function -C (R^vs) = C (R^d)-.

0043According to another preferred variant p, p '= 1; z = 0; t, t '= 1; T represents - N (R) -, preferably in the para position on Ar with respect to the olefin function - C (R^vs) = C (R^d) - and T 'represents a group -N (R) -, -N⁺(R) (R °) - or an imidazolium.

0044Preferably, W is an imidazolium, pyridinium, benzopyridinium, benzimidazolium, quinolinium, and pyrazolium, optionally substituted by one or more alkyl radicals, identical or not, at C₁-VS₄.

0045According to another preferred variant, the disulfide dye is a cationic fluorescent dye comprising at least one quaternary ammonium radical and such that, in formula (I) with p equal to 1:<ul id="ul0011" list-style="none" compact="compact"><li>A representing a naphthalimidyl radical of formula:<chemistry id="chem0002" num="0002"><img file="EP2004759B1_D0002.tif" /></chemistry>with<img file="EP2004759B1_D0003.tif" /> representing the bond with the group X or X ', C_sat or C '_satin which R^e, R^f, R^g, and R^h, identical or different, represent a hydrogen atom or a C alkyl group₁-VS₆ possibly substituted.</li></ul>

0046More preferably, the disulfide dye is a fluorescent dye chosen from:<chemistry id="chem0003" num="0003"><img file="EP2004759B1_D0004.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP2004759B1_D0005.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP2004759B1_D0006.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP2004759B1_D0007.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP2004759B1_D0008.tif" /></chemistry><chemistry id="chem0008" num="0008"><img file="EP2004759B1_D0009.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP2004759B1_D0010.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP2004759B1_D0011.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP2004759B1_D0012.tif" /></chemistry>and<chemistry id="chem0012" num="0012"><img file="EP2004759B1_D0013.tif" /></chemistry>in which<ul id="ul0012" list-style="bullet" compact="compact"><li>G and G ', identical or different, represent a group -NR_vsR_d, -NR '_vsR '_d, or C₁-VS₆ optionally substituted alkoxy, preferably unsubstituted; preferably G and G 'represent a group -NR_vsR_d and-NR '_vsR '_d respectively ;</li><li>R_at and R '_at, identical or different, an aryl group (C₁-VS₄) alkyl or a group C₁-VS₆ alkyl optionally substituted by a hydroxyl or amino group, C₁-VS₄ alkylamino, C₁-VS₄ dialkylamino, said alkyl radicals being able to form, with the nitrogen atom which carries them, a heterocyle comprising from 5 to 7 members, optionally comprising another heteroatom different or not from nitrogen; preferably R_at and R '_at represent a group C₁-VS₃ alkyl optionally substituted by a hydroxy group, or a benzyl group;</li><li>R_b, R '_b, identical or different, represent a hydrogen atom, an aryl group (C₁-VS₄) alkyl or a group C₁-VS₆ optionally substituted alkyl; preferably R_b, R '_b represent a hydrogen atom or a group C₁-VS₃ alkyl or benzyl;</li><li>R_vs, R '_vs, R_d and R '_d, identical or different, represent a hydrogen atom, an aryl group (C₁-VS₄) alkyl, C₁-VS₆ alkoxy or a group C₁-VS₆ optionally substituted alkyl; R_vs, R '_vs, R_d and R '_d preferably represent a hydrogen atom, a hydroxy group, C₁-VS₃ alkoxy, amino, C₁-VS₃ (di) alkylamino, or a group C₁-VS₃ alkyl optionally substituted by i) a hydroxy group, ii) amino, iii) C₁-VS₃ (di) alkylamino, or iv) quaternary ammonium (R ") (R" ') (R "") N⁺-; or two adjacent radicals R_vs and R_d, R '_vs and R '_d carried by the same nitrogen atom together form a heterocyclic or heteroaryl group; preferably the heterocycle or heteroaryl is monocyclic and comprises between 5 and 7 links; more preferably, the groups are chosen from imidazolyl and pyrrolidinyl;</li><li>R_e and R '_e, identical or different, represent a C hydrocarbon chain₁-VS₆ divalent alkylenyl, linear or branched, optionally unsaturated;</li><li>R_f and R '_f, identical or different, represent a quaternary ammonium group (R ") (R" ') (R "") N⁺- where R ", R '" and R "", identical or different, represent a hydrogen atom or a group C₁-VS₄ alkyl or then (R ") (R" ') (R "") N⁺- represents a cationic heteroaryl group optionally substituted preferentially an imidazolinium group optionally substituted by a group C₁-VS₃ alkyl;</li><li>R_g, R '_g, R "_g, R '"_g R_h, R '_h, R "_h, and R "'_h, identical or different, represent a hydrogen atom, a halogen atom, an amino group, C₁-VS₄ alkylamino, C₁-VS₄ dialkylamino, cyano, carboxy, hydroxyl, trifluoromethyl, an acylamino radical, C alkoxy₁-VS₄, (poly) hydroxyalkoxy in C₂-VS₄, alkylcarbonyloxy alkoxycarbonyl, alkylcarbonylamino, an acylamino, carbamoyl, alkylsulfonylamino radical, an amino-sulfonyl radical, or a C radical₁-VS₁₆ alkyl optionally substituted by a group chosen from C₁-VS₁₂ alkoxy, hydroxy, cyano, carboxy, amino, C₁-VS₄ alkylamino and C₁-VS₄ dialkylamino, or else the two alkyl radicals carried by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical or different to that of the nitrogen atom; preferably R_g, R '_g, R "_g, R '"_g, R_h, R '_h, R "_h, and R "'_h represent a hydrogen atom, a halogen atom or a group C₁-VS₃ alkyl;</li><li>or two R groups_g and R '_g ; R "_g and R '"_g ; R_h, and R '_h ; R "_h and R "'_h carried by two adjacent carbon atoms, together form a benzo, indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino group, C₁-VS₄ alkylamino, C₁-VS₄ dialkylamino, nitro, cyano, carboxy, hydroxyl, trifluoromethyl, an acylamino, C alkoxy radical₁-VS₄, (poly) hydroxyalkoxy in C₂-VS₄, alkylcarbonyloxy alkoxycarbonyl, alkylcarbonylamino, an acylamino, carbamoyl, alkylsulfonylamino radical, an amino-sulfonyl radical, or a C radical₁-VS₁₆ alkyl optionally substituted by: a group chosen from C₁-VS₁₂ alkoxy, hydroxy, cyano, carboxy, amino, C₁-VS₄ alkylamino, C₁-VS₄ dialkylamino, or then the two alkyl radicals carried by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical or different to that of the nitrogen atom; preferably R_g and R '_g; R "_g and R '"_g together form a benzo group;</li><li>or when G represents -NR_vsR_d and G 'represents -NR'_vsR '_d two R groups_vs and R '_g ; R '_vs and R "_g ; R_d and R_g ; R '_d and R "'_g together form a saturated heteroaryl or heterocycle, optionally substituted by one or more group C₁-VS₆ alkyl, preferably a heterocycle containing one or two heteroatoms chosen from nitrogen and oxygen and comprising between 5 and 7 members; more preferably, the heterocycle is chosen from the morpholinyl, piperazinyl, pyperidinyl and pyrrolidinyl groups;</li><li>R_i, R '_i, R "_i, and R "'_i, identical or different, represent a hydrogen atom, or a group C₁-VS₄ alkyl;</li><li>R₁, R₂, R₃, R₄, R '₁, R '₂, R '₃, and R '₄, identical or different, represent a hydrogen atom or a group C₁-VS₄ alkyl, C₁-VS₁₂ alkoxy, hydroxy, cyano, carboxy, amino, C₁-VS₄ alkylamino, C₁-VS₄ dialkylamino, said alkyl radicals being able to form, with the nitrogen atom which carries them, a heterocyle comprising from 5 to 7 members, optionally comprising another heteroatom different or not from nitrogen; preferably R₁, R₂, R₃, R₄, R '₁, R '₂, R '₃, and R '₄ are hydrogen atoms or an amino group; more preferably R₁, R₂, R₃, R₄, R '₁, R '₂, R '₃, and R '₄ represent a hydrogen atom;</li><li>T_at, T_b, identical or different, represent i) either a covalent bond σ, ii) either one or more radicals or their combinations chosen from -SO₂- -O-, -S-, -N (R) -, -N⁺(R) (R °) -, -CO-, with R, R^o, identical or different, representing a hydrogen atom, a C 1 alkyl radical₁-VS₄, C-hydroxyalkyl₁-VS₄; or an aryl (C₁-VS₄) alkyl, preferably T_at is identical to T_b and represent a covalent bond σ or a group chosen from -N (R) -, -C (O) -N (R) -, - N (R) -C (O) -, -OC (O) -, - C (O) -O- and -N⁺(R) (R °) -, with R, R ° identical or different representing a hydrogen atom or a group C₁-VS₄ alkyl; more preferably T_at and T_b represent a σ bond; iii) either a heterocycloalkyl or heteroaryl radical, cationic or not, preferentially monocyclic, preferentially identical, preferentially containing two heteroatoms (more preferentially two nitrogen atoms) and preferably comprising from 5 to 7 members such as imidazolium;</li><li><chemistry id="chem0013" num="0013"><img file="EP2004759B1_D0014.tif" /></chemistry>identical or different, represent an optionally substituted heterocyclic group; preterentially the heterocycles are identical, monocyclic, saturated, and comprise in total two nitrogen atoms and from 5 to 8 chains;</li><li><chemistry id="chem0014" num="0014"><img file="EP2004759B1_D0015.tif" /></chemistry>represent an aryl or heteroaryl group fused to the phenyl ring; or is absent from the phenyl ring; preferably when the cycle is present the cycle is a benzo;</li><li>m, m ', n and n', identical or different, represent an integer inclusive between 0 and 6 with m + n, m '+ n', identical or different, represents an integer inclusive between 1 and 10; preferably m + n = m '+ n' = an integer inclusive between 2 and 4; more preferably m + n = m '+ n' = an integer equal to 2;</li></ul>

0047Representing me against ion or an organic or mineral acid salt.

0048By way of example of fluorescent disulfide dyes, mention may be made in particular of the following compounds:<chemistry id="chem0015" num="0015"><img file="EP2004759B1_D0016.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP2004759B1_D0017.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP2004759B1_D0018.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP2004759B1_D0019.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP2004759B1_D0020.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP2004759B1_D0021.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP2004759B1_D0022.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP2004759B1_D0023.tif" /></chemistry><chemistry id="chem0023" num="0023"><img file="EP2004759B1_D0024.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP2004759B1_D0025.tif" /></chemistry><chemistry id="chem0025" num="0025"><img file="EP2004759B1_D0026.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP2004759B1_D0027.tif" /></chemistry><chemistry id="chem0027" num="0027"><img file="EP2004759B1_D0028.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP2004759B1_D0029.tif" /></chemistry><chemistry id="chem0029" num="0029"><img file="EP2004759B1_D0030.tif" /></chemistry><chemistry id="chem0030" num="0030"><img file="EP2004759B1_D0031.tif" /></chemistry><chemistry id="chem0031" num="0031"><img file="EP2004759B1_D0032.tif" /></chemistry><chemistry id="chem0032" num="0032"><img file="EP2004759B1_D0033.tif" /></chemistry><chemistry id="chem0033" num="0033"><img file="EP2004759B1_D0034.tif" /></chemistry><chemistry id="chem0034" num="0034"><img file="EP2004759B1_D0035.tif" /></chemistry><chemistry id="chem0035" num="0035"><img file="EP2004759B1_D0036.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP2004759B1_D0037.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP2004759B1_D0038.tif" /></chemistry><chemistry id="chem0038" num="0038"><img file="EP2004759B1_D0039.tif" /></chemistry><chemistry id="chem0039" num="0039"><img file="EP2004759B1_D0040.tif" /></chemistry><chemistry id="chem0040" num="0040"><img file="EP2004759B1_D0041.tif" /></chemistry><chemistry id="chem0041" num="0041"><img file="EP2004759B1_D0042.tif" /></chemistry><chemistry id="chem0042" num="0042"><img file="EP2004759B1_D0043.tif" /></chemistry><chemistry id="chem0043" num="0043"><img file="EP2004759B1_D0044.tif" /></chemistry><chemistry id="chem0044" num="0044"><img file="EP2004759B1_D0045.tif" /></chemistry><chemistry id="chem0045" num="0045"><img file="EP2004759B1_D0046.tif" /></chemistry><chemistry id="chem0046" num="0046"><img file="EP2004759B1_D0047.tif" /></chemistry><chemistry id="chem0047" num="0047"><img file="EP2004759B1_D0048.tif" /></chemistry><chemistry id="chem0048" num="0048"><img file="EP2004759B1_D0049.tif" /></chemistry><chemistry id="chem0049" num="0049"><img file="EP2004759B1_D0050.tif" /></chemistry><chemistry id="chem0050" num="0050"><img file="EP2004759B1_D0051.tif" /></chemistry><chemistry id="chem0051" num="0051"><img file="EP2004759B1_D0052.tif" /></chemistry><chemistry id="chem0052" num="0052"><img file="EP2004759B1_D0053.tif" /></chemistry><chemistry id="chem0053" num="0053"><img file="EP2004759B1_D0054.tif" /></chemistry><chemistry id="chem0054" num="0054"><img file="EP2004759B1_D0055.tif" /></chemistry><chemistry id="chem0055" num="0055"><img file="EP2004759B1_D0056.tif" /></chemistry><chemistry id="chem0056" num="0056"><img file="EP2004759B1_D0057.tif" /></chemistry><chemistry id="chem0057" num="0057"><img file="EP2004759B1_D0058.tif" /></chemistry><chemistry id="chem0058" num="0058"><img file="EP2004759B1_D0059.tif" /></chemistry><chemistry id="chem0059" num="0059"><img file="EP2004759B1_D0060.tif" /></chemistry><chemistry id="chem0060" num="0060"><img file="EP2004759B1_D0061.tif" /></chemistry><chemistry id="chem0061" num="0061"><img file="EP2004759B1_D0062.tif" /></chemistry><chemistry id="chem0062" num="0062"><img file="EP2004759B1_D0063.tif" /></chemistry><chemistry id="chem0063" num="0063"><img file="EP2004759B1_D0064.tif" /></chemistry><chemistry id="chem0064" num="0064"><img file="EP2004759B1_D0065.tif" /></chemistry><chemistry id="chem0065" num="0065"><img file="EP2004759B1_D0066.tif" /></chemistry><chemistry id="chem0066" num="0066"><img file="EP2004759B1_D0067.tif" /></chemistry><chemistry id="chem0067" num="0067"><img file="EP2004759B1_D0068.tif" /></chemistry><chemistry id="chem0068" num="0068"><img file="EP2004759B1_D0069.tif" /></chemistry><chemistry id="chem0069" num="0069"><img file="EP2004759B1_D0070.tif" /></chemistry><chemistry id="chem0070" num="0070"><img file="EP2004759B1_D0071.tif" /></chemistry><chemistry id="chem0071" num="0071"><img file="EP2004759B1_D0072.tif" /></chemistry><chemistry id="chem0072" num="0072"><img file="EP2004759B1_D0073.tif" /></chemistry><chemistry id="chem0073" num="0073"><img file="EP2004759B1_D0074.tif" /></chemistry><chemistry id="chem0074" num="0074"><img file="EP2004759B1_D0075.tif" /></chemistry><chemistry id="chem0075" num="0075"><img file="EP2004759B1_D0076.tif" /></chemistry><chemistry id="chem0076" num="0076"><img file="EP2004759B1_D0077.tif" /></chemistry><chemistry id="chem0077" num="0077"><img file="EP2004759B1_D0078.tif" /></chemistry><chemistry id="chem0078" num="0078"><img file="EP2004759B1_D0079.tif" /></chemistry><chemistry id="chem0079" num="0079"><img file="EP2004759B1_D0080.tif" /></chemistry><chemistry id="chem0080" num="0080"><img file="EP2004759B1_D0081.tif" /></chemistry><chemistry id="chem0081" num="0081"><img file="EP2004759B1_D0082.tif" /></chemistry><chemistry id="chem0082" num="0082"><img file="EP2004759B1_D0083.tif" /></chemistry><chemistry id="chem0083" num="0083"><img file="EP2004759B1_D0084.tif" /></chemistry><chemistry id="chem0084" num="0084"><img file="EP2004759B1_D0085.tif" /></chemistry><chemistry id="chem0085" num="0085"><img file="EP2004759B1_D0086.tif" /></chemistry><chemistry id="chem0086" num="0086"><img file="EP2004759B1_D0087.tif" /></chemistry><chemistry id="chem0087" num="0087"><img file="EP2004759B1_D0088.tif" /></chemistry><chemistry id="chem0088" num="0088"><img file="EP2004759B1_D0089.tif" /></chemistry><chemistry id="chem0089" num="0089"><img file="EP2004759B1_D0090.tif" /></chemistry><chemistry id="chem0090" num="0090"><img file="EP2004759B1_D0091.tif" /></chemistry><chemistry id="chem0091" num="0091"><img file="EP2004759B1_D0092.tif" /></chemistry><chemistry id="chem0092" num="0092"><img file="EP2004759B1_D0093.tif" /></chemistry><chemistry id="chem0093" num="0093"><img file="EP2004759B1_D0094.tif" /></chemistry><chemistry id="chem0094" num="0094"><img file="EP2004759B1_D0095.tif" /></chemistry><chemistry id="chem0095" num="0095"><img file="EP2004759B1_D0096.tif" /></chemistry><chemistry id="chem0096" num="0096"><img file="EP2004759B1_D0097.tif" /></chemistry><chemistry id="chem0097" num="0097"><img file="EP2004759B1_D0098.tif" /></chemistry><chemistry id="chem0098" num="0098"><img file="EP2004759B1_D0099.tif" /></chemistry><chemistry id="chem0099" num="0099"><img file="EP2004759B1_D0100.tif" /></chemistry><chemistry id="chem0100" num="0100"><img file="EP2004759B1_D0101.tif" /></chemistry><chemistry id="chem0101" num="0101"><img file="EP2004759B1_D0102.tif" /></chemistry><chemistry id="chem0102" num="0102"><img file="EP2004759B1_D0103.tif" /></chemistry><chemistry id="chem0103" num="0103"><img file="EP2004759B1_D0104.tif" /></chemistry><chemistry id="chem0104" num="0104"><img file="EP2004759B1_D0105.tif" /></chemistry><chemistry id="chem0105" num="0105"><img file="EP2004759B1_D0106.tif" /></chemistry><chemistry id="chem0106" num="0106"><img file="EP2004759B1_D0107.tif" /></chemistry><chemistry id="chem0107" num="0107"><img file="EP2004759B1_D0108.tif" /></chemistry><chemistry id="chem0108" num="0108"><img file="EP2004759B1_D0109.tif" /></chemistry><chemistry id="chem0109" num="0109"><img file="EP2004759B1_D0110.tif" /></chemistry><chemistry id="chem0110" num="0110"><img file="EP2004759B1_D0111.tif" /></chemistry><chemistry id="chem0111" num="0111"><img file="EP2004759B1_D0112.tif" /></chemistry><chemistry id="chem0112" num="0112"><img file="EP2004759B1_D0113.tif" /></chemistry><chemistry id="chem0113" num="0113"><img file="EP2004759B1_D0114.tif" /></chemistry><chemistry id="chem0114" num="0114"><img file="EP2004759B1_D0115.tif" /></chemistry><chemistry id="chem0115" num="0115"><img file="EP2004759B1_D0116.tif" /></chemistry><chemistry id="chem0116" num="0116"><img file="EP2004759B1_D0117.tif" /></chemistry><chemistry id="chem0117" num="0117"><img file="EP2004759B1_D0118.tif" /></chemistry><chemistry id="chem0118" num="0118"><img file="EP2004759B1_D0119.tif" /></chemistry><chemistry id="chem0119" num="0119"><img file="EP2004759B1_D0120.tif" /></chemistry><chemistry id="chem0120" num="0120"><img file="EP2004759B1_D0121.tif" /></chemistry><chemistry id="chem0121" num="0121"><img file="EP2004759B1_D0122.tif" /></chemistry><chemistry id="chem0122" num="0122"><img file="EP2004759B1_D0123.tif" /></chemistry><chemistry id="chem0123" num="0123"><img file="EP2004759B1_D0124.tif" /></chemistry><chemistry id="chem0124" num="0124"><img file="EP2004759B1_D0125.tif" /></chemistry><chemistry id="chem0125" num="0125"><img file="EP2004759B1_D0126.tif" /></chemistry><chemistry id="chem0126" num="0126"><img file="EP2004759B1_D0127.tif" /></chemistry><chemistry id="chem0127" num="0127"><img file="EP2004759B1_D0128.tif" /></chemistry><chemistry id="chem0128" num="0128"><img file="EP2004759B1_D0129.tif" /></chemistry><chemistry id="chem0129" num="0129"><img file="EP2004759B1_D0130.tif" /></chemistry><chemistry id="chem0130" num="0130"><img file="EP2004759B1_D0131.tif" /></chemistry><chemistry id="chem0131" num="0131"><img file="EP2004759B1_D0132.tif" /></chemistry><chemistry id="chem0132" num="0132"><img file="EP2004759B1_D0133.tif" /></chemistry><chemistry id="chem0133" num="0133"><img file="EP2004759B1_D0134.tif" /></chemistry><chemistry id="chem0134" num="0134"><img file="EP2004759B1_D0135.tif" /></chemistry><chemistry id="chem0135" num="0135"><img file="EP2004759B1_D0136.tif" /></chemistry><chemistry id="chem0136" num="0136"><img file="EP2004759B1_D0137.tif" /></chemistry><chemistry id="chem0137" num="0137"><img file="EP2004759B1_D0138.tif" /></chemistry><chemistry id="chem0138" num="0138"><img file="EP2004759B1_D0139.tif" /></chemistry><chemistry id="chem0139" num="0139"><img file="EP2004759B1_D0140.tif" /></chemistry><chemistry id="chem0140" num="0140"><img file="EP2004759B1_D0141.tif" /></chemistry><chemistry id="chem0141" num="0141"><img file="EP2004759B1_D0142.tif" /></chemistry><chemistry id="chem0142" num="0142"><img file="EP2004759B1_D0143.tif" /></chemistry><chemistry id="chem0143" num="0143"><img file="EP2004759B1_D0144.tif" /></chemistry><chemistry id="chem0144" num="0144"><img file="EP2004759B1_D0145.tif" /></chemistry><chemistry id="chem0145" num="0145"><img file="EP2004759B1_D0146.tif" /></chemistry><chemistry id="chem0146" num="0146"><img file="EP2004759B1_D0147.tif" /></chemistry><chemistry id="chem0147" num="0147"><img file="EP2004759B1_D0148.tif" /></chemistry><chemistry id="chem0148" num="0148"><img file="EP2004759B1_D0149.tif" /></chemistry><chemistry id="chem0149" num="0149"><img file="EP2004759B1_D0150.tif" /></chemistry><chemistry id="chem0150" num="0150"><img file="EP2004759B1_D0151.tif" /></chemistry><chemistry id="chem0151" num="0151"><img file="EP2004759B1_D0152.tif" /></chemistry><chemistry id="chem0152" num="0152"><img file="EP2004759B1_D0153.tif" /></chemistry><chemistry id="chem0153" num="0153"><img file="EP2004759B1_D0154.tif" /></chemistry><chemistry id="chem0154" num="0154"><img file="EP2004759B1_D0155.tif" /></chemistry><chemistry id="chem0155" num="0155"><img file="EP2004759B1_D0156.tif" /></chemistry><chemistry id="chem0156" num="0156"><img file="EP2004759B1_D0157.tif" /></chemistry><chemistry id="chem0157" num="0157"><img file="EP2004759B1_D0158.tif" /></chemistry><chemistry id="chem0158" num="0158"><img file="EP2004759B1_D0159.tif" /></chemistry><chemistry id="chem0159" num="0159"><img file="EP2004759B1_D0160.tif" /></chemistry><chemistry id="chem0160" num="0160"><img file="EP2004759B1_D0161.tif" /></chemistry>with M 'an anionic counterion.

<u>I.5. Organic salt and counter-ion:</u>

0049A “salt of organic or inorganic acid” is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H₂SO₄, iv) alkylsulfonic 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-0-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) CF triflic acid₃SO₃H and xv) tetrafluoroboric acid HBF₄.

0050An “anionic counterion” is an anion or an anionic group associated with the cationic charge of the dye; more particularly the anionic counterion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates including C₁-VS₆ alkylsulfonates: Alk-S (O)₂O- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: ArS (O)₂O- such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfites: Alk-OS (O) O^- such as methysulfite and ethylsulfite; x) arylsulfites: Ar-OS (O) O^- such as benzenesulfite and toluenesulfite; xi) alkyl sulfates: Alk-OS (O)₂O^- such as methyl sulfate and ethyl sulfate; xii) arylsulfates: Ar-OS (O)₂O^-, xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

<u>I.6. Preparation of fluorescent disulfide dyes:</u>

0051The fluorescent disulfide dyes can be prepared according to methods known to those skilled in the art.

0052According to a first possibility, a disulfide compound comprising two amine functions, preferably primary or secondary, can be reacted with a sufficient quantity of a "reactive fluorescent chromophore" or of a compound comprising such a "reactive fluorescent chromophore", by d other terms comprising an electrophilic function.

0053Among the "reactive fluorescent chromophores" that may be mentioned are reactive dyes comprising in particular a vinylsulfone, sulfatoethylsulfone, monodi-chlorotriazine, monodi-chloro pyrimidine, difluoro chloro pyrimidine, dichloroquinoxaline, bromo-vinylsulfone function.

0054Also suitable, as reactive chromophores, are fluorescent chromophoric compounds comprising at least one group capable of reacting with an amine function to give a sulfonamide group (-SO₂-NR-) amide (-CO-NR-). For example, we can mention the -SO groups₃W ', -COOW' (with W 'representing a hydrogen atom, an alkali metal, such as sodium, potassium, an ammonium group, an ammonium group substituted by one or more alkyl groups, identical or not, linear or branched , in C₁-VS₁₀, optionally carrying at least one hydroxyl), which can be activated beforehand, according to known methods, respectively in -SO group₂Cl, -COCl.

0055It is thus conceivable to use, as reactive fluorescent chromophore, the acid dyes of the Color Index listed as such.

0056We can refer in particular to the book Advanced Organic Chemistry, March, 4^th Ed, to have more details on the operating conditions implemented.

0057Still within the framework of this first possibility, it is possible to use fluorescent chromophores comprising a labile group directly linked or not to the fluorescent chromophore and capable of being substituted by an amine group, such as Cl, Br, F, O-alkyl (e.g. O-Me), O-aryl, O-alkylaryl (e.g. O-benzyl).

0058The disulfide fluorescent dyes can also be obtained, within the framework of this possibility, by using chromophores having an acrylate function (-OCO-C = C-) on which an addition reaction is carried out.

0059According to another possibility, the disulfide fluorescent dyes can be obtained by reacting a disulfide compound with a compound carrying two carboxylic acid functions activated according to conventional methods (for example reaction with a carbodiimide or with thionyl chloride). The resulting product is then reacted with a fluorescent chromophore carrying a nucleophilic function, for example of primary or secondary amine type, or of aliphatic or aromatic alcohol type such as phenol.

0060Again, we can refer to the book Advanced Organic Chemistry, March, 4^th Ed, to have more details on the operating conditions implemented.

0061According to a third possibility, the disulfide fluorescent dyes can be obtained by reacting a compound comprising a disulfide group and two hydroxyl groups activated beforehand in leaving groups (for example mesylate, tosylate) with a fluorescent chromophore carrying a nucleophilic function, advantageously of primary, secondary or tertiary amine type, heteroaromatic or not, for example of the pyridine, imidazole, benzimidazole type.

0062In accordance with a fourth possibility, the disulfide fluorescent dyes can be obtained by gentle oxidation of dyes carrying an SH function.

0063According to a fifth possibility, and in particular for the preparation of the compounds corresponding to formula (II), the disulfide fluorescent dyes can be obtained by a variant of possibilities one, two or three described above, using a molar amount of reagent disulfide greater than or equal to the molar quantity of reagent containing the chromophore group.

0064The preparation of the disulfide fluorescent dyes corresponding to formula (I) for which A and A 'are identical is on the other hand facilitated by the use of a molar quantity of reagent containing the fluorescent chromophoric group preferably greater than or equal to twice the amount of disulfide reagents.

0065In accordance with a sixth possibility, and in particular for the preparation of the compounds corresponding to formula (I) and in which the two groups A, A 'on the one hand and X and X' on the other hand, are different, the disulfide compounds can be obtained from disulfide fluorescent compounds corresponding to formula (II).

<u>II. Dye composition:</u>

<u>II.1. Dyes:</u>

0066The dye composition useful in the invention generally contains an amount of fluorescent disulfide dye 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.

0067The dye composition may also contain additional direct dyes. These direct dyes are, for example, chosen from neutral, acidic or cationic benzene nitro direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, quinonic dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct azine dyes , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

0068Among the natural direct dyes, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine. One can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

0069The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin fibers.

0070Among 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

0071Among these couplers, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

0072The coupler (s) 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%.

0073The oxidation base (s) present in the dye composition are generally present each in an amount between 0.001 to 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6% by weight.

0074In general, the addition salts of the oxidation bases and of the couplers which can be used in the context of the invention are in particular chosen from addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as soda, potash, ammonia, amines or alkanolamines.

0075The medium suitable for dyeing, also called dye support, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. As organic solvent, mention may, for example, be made of lower C alkanols.₁-VS₄, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

0076The solvents when they are 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.

0077Alternatively, the invention contains a reducing agent capable of reducing the disulfide bonds. This reducing agent is as defined above.

<u>11.2. Adjuvants:</u>

0078The 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, zwitterionic polymers or their mixtures, mineral or organic thickening agents, and in particular associative anionic, cationic polymer thickeners, nonionic and amphoteric, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or not, such as silicones amines, film-forming agents, ceramides, preserving agents, opacifying agents, conductive polymers.

<u>Quantity of adjuvants:</u>

0079The above adjuvants are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.

0080Of course, those 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 dye composition according to the invention are not, or not substantially, affected by the or the additions envisaged.

<u>PH:</u>

0081The 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 by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.

0082Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

0083Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of following formula (a):<chemistry id="chem0161" num="0161"><img file="EP2004759B1_D0162.tif" /></chemistry>in which W_at is a propylene residue optionally substituted by a hydroxyl group or a C 1 alkyl radical₁-VS₄ ; R_a1, R_a2, R_a3 and R_a4, identical or different, represent a hydrogen atom, a C 1 alkyl radical₁-VS₄ or C hydroxyalkyl₁-VS₄.

<u>II.3. Types of composition:</u>

0084The dye composition may be in various forms, such as in the form of a liquid, cream, gel, or in any other form suitable for dyeing keratin fibers, and in particular hair.

<u>III. Coloring process:</u>

0085The application of the dye composition is generally carried out at room temperature. It can however be carried out at temperatures varying from 20 to 180 ° C.

0086In a particular coloring process of the invention, the application of the disulfide fluorescent dye on keratin materials is carried out at the same time as a reducing agent. The reducing agent is as defined above.

0087According to another variant, the reducing agent is added to the dye composition containing the disulfide fluorescent dyes (I) and (II) at the time of use.

0088According to another variant, the process of the invention can be implemented in the presence of an oxidizing agent in post-treatment when the composition already contains a reducing agent.

0089The oxidizing agent can be any oxidizing agent conventionally used in the field. Thus, it can be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, as well as the enzymes among which mention may be made of peroxidases, oxido- 2 electron reductases such as uricases and 4 electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.

0090This oxidizing agent can be applied to the fibers before or after the application of the composition containing the disulfide fluorescent dyes of formula (I) and (II).

<u>III. Dyeing device or "kit":</u>

0091The invention also relates to a device with several compartments or "kit" for dyeing in which a first compartment contains a dye composition comprising at least one fluorescent disulfide dye of formulas (I) or (II) and a second compartment contains an agent. reducing agent capable of reducing the disulfide bond of the dye and / or the disulfide functions of keratin materials.

0092One of these compartments may also contain one or more other dyes of the direct dye or oxidation dye type.

0093It also relates to a device with several compartments in which a first compartment contains a dye composition comprising at least one fluorescent disulfide dye of formulas (I) or (II); a second compartment contains a reducing agent capable of reducing the disulfide bond of the dye; a third compartment contains an oxidizing agent.

0094Each of the devices mentioned above can be equipped with a means enabling the desired mixture to be delivered to the hair, for example such as the devices described in the patent. <patcit id="pcit0011" dnum="FR2586913"><text>FR2 586 913</text></patcit>.

0095The examples which follow serve to illustrate the invention without, however, being limiting in nature. The disulfide fluorescent dyes of the examples below were fully characterized by conventional spectroscopic and spectrometric methods.

EXAMPLES

EXAMPLES OF SYNTHESIS

Example 1

0096<chemistry id="chem0162" num="0162"><img file="EP2004759B1_D0163.tif" /></chemistry>

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

0097A mixture of 56 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] ethane and 15 mL of <i>NOT</i> Methylpyrrolidone (NMP) is poured dropwise onto 35 g of 2-picoline with stirring, at 80 ° C. The mixture (white suspension) is kept stirred for 30 min at 80 ° C., 100 ml of acetonitrile are added, stirring is maintained at 80 ° C. for 90 min. After cooling, the solid obtained is filtered, washed with 100 ml of acetonitrile and then dried.

009856.2 g of brown powder are collected. 45 g of this powder are suspended in 300 ml of isopropanol, at reflux. Once the temperature has dropped to 40 ° C., the solid is filtered, washed with 3 times 100 ml of isopropanol and dried under vacuum. Light beige product, 40.56 g. Analysis in accordance with the expected structure.

Step 2: 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (2 - {(E) -2- [4- (dimethylamino) phenyl] vinyl} pyridinium) dibromide)

0099150 mg of pyrrolidine then 129 mg of acetic acid are added to a solution of 297 mg of 4-dimethylaminobenzaldehyde in 2 ml of methanol.

0100After 18 h of stirring at room temperature, 495 mg of 1 '- (disulfanediyldiethane-2,1-diyl) bis (2-methylpyridinium) dibromide are added to the mixture and stirring is maintained at room temperature for 7 days. After filtration, washing with methanol and drying under vacuum, 312 mg of orange powder are collected. Analysis in accordance with the expected structure. NMR¹H (400 MHz, MeOH-<i>d</i>₄): 3.02 (s, 6H), 3.22 (t, 2H), 5 (t, 2H), 6.72 (m, 2H), 7.19 (d, 1H), 7.63 (m, 3H), 7.76 (d, 1 H), 8.3 (m, 2H), 8.59 (m, 1H).

Example 2

0101<chemistry id="chem0163" num="0163"><img file="EP2004759B1_D0164.tif" /></chemistry>

Step 1: 4.4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde

010282.3 g of phosphorus oxychloride are added to 500 ml of DMF at 0 ° C. After 30 min of stirring at 0 ° C a solution of 47g of<i>NOT</i>,<i>NOT</i>'- (disulfanediyldiethane-2,1-diyl) bis (N-methylaniline) are added dropwise. The mixture is stirred for 90 min. at 0 ° C then 75 min. at 10 ° C and 105 min. at 40 ° C. It is then poured into 2.5 L of ice water, 700 mL of 5N sodium hydroxide are added. The yellow precipitate obtained is filtered through celite, dissolved in 200 ml of dichloromethane and the solution obtained is washed with 200 ml of saturated aqueous sodium chloride solution. After drying over magnesium sulphate and evaporation of the dichloromethane, the yellow residue (80 g) is purified by chromatography on silica gel.

0103After drying, a light yellow powder is collected. Analysis indicates that the product conforms to the expected structure.

Step 2: 2,2 'dichloride - {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-methylpyridinium)

010425 g of 4.4 ′ - {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde and 18.5 g of N-methylpicolinium chloride are dissolved in 300 ml of methanol. 12.7 mL of piperidine are added to the mixture. The whole is heated, with stirring at 55 ° C for 11 h. The methanol is removed in vacuo at 40 ° C. The solid is mixed with 300 ml of isopropanol. After a further drying by evaporation, 200 ml of isopropanol are introduced. The mixture solidifies, it is extended by addition of 100 ml of iospropanol and wrung on sintered glass. The solid collected is washed with isopropanol and then acetone, then dried under vacuum. After drying, 36.7 g of orange powder are collected. By recrystallization from isopropanol, 27 g of red orange powder of higher purity are collected. Analyzes indicate that the product is compliant and pure. NMR¹H (400 MHz, MeOH-<i>d</i>₄) 2.99 (t, 4H), 3.81 (t, 4H), 4.31 (s, 6H), 6.86 (d, 4H), 7.22 (d, 2H), 7.63 (m, 2H), 7.69 (d, 4H), 7.83 (d, 2H), 8.29 (m, 2H), 8.36 (m, 2H), 8.61 (m, 2H).

Example 3:

0105<chemistry id="chem0164" num="0164"><img file="EP2004759B1_D0165.tif" /></chemistry>

4.4 'dimethoxysulfate - {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-methylpyridinium)

01062.62 g of 4-picoline are diluted in 25 ml of dichloromethane, 3 ml of dimethyl sulfate are added to the solution, the temperature of which rises to reflux (40 ° C.). After 40 min. of stirring, 50 ml of isopropanol are added, and the mixture is concentrated by distillation of dichloromethane (mixture heated to 60 ° C). 1.83 g of pyrrolidine are introduced into the mixture followed by 4.99 g of 4.4 ′ - {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde. After 2 h of stirring at 65 ° C, the reaction mixture is cooled to room temperature, the precipitate formed is filtered, washed with 3 times 100 ml of isopropanol. The red paste obtained is dispersed in 200 ml of isopropanol, the mixture thus obtained is brought to reflux and then cooled. The red precipitate formed is filtered and then dried. 8.94 g of red powder are collected. Analyzes indicate that the product is compliant and pure. NMR¹H (400 MHz, DMSO-<i>d</i>₆) 2.96 (t, 4 H), 3.02 (s, 6 H), 3.36 (s, 6 H), 3.72 (t, 4 H), 4.16 (s, 6 H), 6.81 (d, 4 H), 7.15 (d, 2 H), 7.57 (d, 4 H), 7.87 (d, 2 H), 8.02 (d, 4 H), 8.66 (d, 4 H).

Example 4

0107<chemistry id="chem0165" num="0165"><img file="EP2004759B1_D0166.tif" /></chemistry>

2,2 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-ethylpyridinium) dichloride

010810 4.4 g - {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde and 8.1 g of N-ethylpicolinium chloride are dissolved in 100 ml of isopropanol. 1.3 g of piperidine are added to the mixture. The whole is heated, with stirring at reflux for 5 h. The isopropanol is removed under vacuum at 50 ° C. The gum obtained is triturated with acetone. 18 g of solid are collected and treated with carbon black. 7.1 g of product are collected and 4 g are purified by liquid liquid chromatography (water / BuOH). After drying 1.65 g of red powder are collected. Analyzes indicate that the product is compliant and pure. NMR¹H (400 MHz, MeOH-<i>d</i>₄) 1.57 (t, 6 H), 2.98 (t, 4 H), 3.11 (s, 6 H), 3.8 (t, 4 H), 4.73 (q, 4 H), 6.85 (m, 4 H), 7.23 (d, 2 H), 7.69 (m, 6 H), 7.85 (d, 2 H), 8.29 (m, 2 H), 8.38 (m, 2 H), 8.67 (m, 2 H).

Example

5

0109<chemistry id="chem0166" num="0166"><img file="EP2004759B1_D0167.tif" /></chemistry>

Step 1: 2.2 '- (disulfanediyldiethane-2,1-diyl) bis (6-chloro-1H-benzo [de] -isoquinoline-1,3 (2H) -dione)

01109.30 g of 6-chloro-1 H, 3H-benzo [de] isochromene-1,3-dione and 4.46 g of cystamine hydrochloride hydrochloride are suspended in 50 ml of N-methylpyrrolidone (NMP). 5.5 g of diisopropylethylamine are added and the mixture is heated, with stirring to 120 ° C. After two hours 50 ml of NMP are added and the mixture is kept stirred at 120 ° C. for 3 h. After cooling, the precipitated product is collected, the filtered solution is extended by adding 200 ml of water and a second precipitate is collected. The precipitates are washed with water and dried. 11.46 g of white powder are collected. Analysis shows that the product meets expectations

2nd step

:

2,2 '- (disulfanediyldiethane-2,1-diyl) bis [6 - {[3- (dimethylamino) propyl] -amino} -1H-benzo [de] isoquinoline-1,3 (2H) -dione]

01114 g of (6-chloro-2- (2 - {[2- (6-chloro-1,3-dioxo-1H-benzo [de] isoquinolin-2 (3H) -yl) ethyl] -disulfanyl} ethyl) - 1H-benzo [de] isoquinoline-1,3 (2H) -dione are suspended 40 ml of N, N-dimethylpropane-1,3-diamine The mixture is heated with stirring at 110 ° C for 12 h. cooling, a yellow precipitate is collected, 500 ml of ethanol / water mixture: 1/1 are added dropwise to the filtrate The yellow paste obtained is isolated and triturated with 200 ml of acetone. The solids obtained are washed with 300 ml of water and dried. 4.5 g of yellow powder are collected. Analysis shows that the product conforms to the expected.

Step 3: 3.3 'sulphate - {disulfanediylbis [ethane-2,1-diyl (1,3-dioxo-1H-benzo [de] isoquinoline-2,6 (3H) -diyl) imino)} bis (N , N, N-trimethylpropan-1-aminium)

01124 g of 6 - {[3- (dimethylamino) propyl] amino} -2- [2 - ({2- [6 - {[3- (dimethylamino) propyl] -amino} -1,3-dioxo-1H-benzo [de] isoquinolin-2 (3H) -yl] ethyl} disulfanyl) ethyl] -1H-benzo- [de] isoquinoline-1,3 (2H) -dione are suspended in 50 mL of dimethylformamide 4 mL of dimethylsulfate are added and the mixture is kept stirring at room temperature for 4 h. The reaction mixture is poured into 500 ml of ethyl acetate. The precipitate is filtered, washed with 4 times 100 ml of ethyl acetate and dried under vacuum. 5.9 g of yellow powder are collected. Analyzes indicate that the product conforms to the expected. NMR¹H (400 MHz, DMSO-<i>d</i>₆): 2.13 (m, 4 H), 3.06 (m, 4 H), 3.09 (s, 18 H), 3.46 (m, 4 H), 4.36 (m, 4 H), 6.85 (d, 2 H), 7.71 (m, 2 H), 7.82 (t, 2 H), 8.28 (d, 2 H), 8.29 (dd, 2 H), 8.45 (dd, 2 H).

Example 6

0113<chemistry id="chem0167" num="0167"><img file="EP2004759B1_D0168.tif" /></chemistry>

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

011467 g of 4-picoline are diluted in 100 ml of acetonitrile and the mixture is brought to 80 ° C. A mixture of 60 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] ethane and 15 mL of N-methylpyrrolidone (NMP) is added in 5 min. After 4 hours of stirring at 85 ° C., the mixture is cooled. The solid obtained is filtered, rinsed with 3 x 200 ml of acetonitrile and then dissolved in 800 ml of isopropanol (at reflux). After cooling, 1 L of ethyl ether is added. The precipitate formed is filtered, rinsed with 3 x 200 ml of ethyl ether and then dried. The off-white powder obtained (73.77 g) very largely contains (> 90%) the expected product which is used as it is for the next step.

Step 2: 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4 - {(E) -2- [4- (dimethylamino) phenyl] vinyl} pyridinium) dibromide)

011513.2 g of 4-dimethylaminobenzaldehyde are suspended in 100 ml of methanol. 6.2 g of pyrrolidine then 5.3 g of acetic acid diluted in 20 ml of methanol are added to the mixture (final pH 5/6). 20 g of 1.1 'dibromide - (disulfanediyldiethane-2,1-diyl) bis (4-methylpyridinium) obtained in the previous step, dissolved in 80 ml of methanol are introduced, then the reaction mixture is diluted by adding 100 mL of methanol. After 21 h of stirring at room temperature, a first precipitate is collected, washed with 3 x 100 ml of ethanol then 3 x 200 ml of ethyl acetate and dried (red powder, 7.4 g), then a second precipitate formed in the filtrate is also collected and dried (red powder, 11.44 g). Analyzes indicate that the two fractions conform to the expected structure. NMR¹H (400 MHz, MeOH-<i>d</i>₄): 3.02 (s, 12 H), 3.42 (t, 4 H), 4.74 (t, 4 H), 6.77 (d, 4 H), 7.19 (d, 2 H), 7.6 (d, 4 H), 7.97 (d, 2 H), 8.1 (d, 4 H), 8.79 (d, 4 H).

Example 7

0116<chemistry id="chem0168" num="0168"><img file="EP2004759B1_D0169.tif" /></chemistry><chemistry id="chem0169" num="0169"><img file="EP2004759B1_D0170.tif" /></chemistry><chemistry id="chem0170" num="0170"><img file="EP2004759B1_D0171.tif" /></chemistry>

Step 1: Synthesis of N, N '- (disulfanediyldiethane-2,1-diyl) bis (2-chloroacetamide)

011740.3 g of cystamine dihydrochloride are dissolved in 100 ml of water, 32 ml of 35% sodium hydroxide are added (pH 9.7) and the temperature is lowered to 5 ° C. 33.5 mL of chloroacetyl chloride are introduced dropwise, maintaining the temperature below 10 ° C and maintaining the pH between 7.9 and 9.3 by addition of sodium hydroxide. The medium is kept stirred at room temperature for 2 hours. The precipitate is filtered, washed with 5 x 150 ml of water and then dried under vacuum in the presence of P₂O₅. 35.3 g of white powder are collected. analyzes indicate that the product is compliant.

Step 2: Synthesis of 1,1 '- {disulfanediylbis [ethane-2,1-diylimino (2-oxoethane-2,1-diyl)]} bis (4-methylpyridinium) dichloride

01186.1 g N, N '- (disulfanediyldiethane-2,1-diyl) bis (2-chloroacetamide) and 4.5 g of 4-picoline are dissolved in 50 mL of NMP and brought to 80 ° C for 19 h. After cooling the mixture, by successive precipitation in acetone and drying under vacuum, 9.2 g of salts are collected. Analysis shows that the product is compliant. NMR¹H (400 MHz, D₂O): 2.61 (s, 6 H), 2.82 (t, 4 H), 3.56 (t, 4 H), 5.31 (s, 4 H), 7.85 (d, 4 H), 8.51 (d, 4 H) .

Step 3: Synthesis of 1,1 'dichloride - {disulfanediylbis [ethane-2,1-diylimino (2-oxoethane-2,1-diyl)]} bis {4 - [(E) -2- (3,4 , 5-trimethoxyphenyl) vinyl] pyridinium} [4]

0119785 mg of 3,4,5-trimethoxy-benzaldehyde, 328 µL of pyrrolidine, 232 µL of acetic acid and 490 mg of 1,1 'dichloride - {disulfanediylbis [ethane-2,1-diylimino (2-oxoethane-2 , 1-diyl)]} bis (4-methylpyridinium) are dissolved in 10 ml of isopropanol and kept stirred at room temperature for 3 h 30 min. The mixture is poured onto 50 ml of 1: 1 dichloromethane / acetone solution. A solid precipitates. It is filtered, washed with three times 20 ml of acetone and dried under vacuum. 509 mg of black powder are collected. The analyzes show that the product is compliant (LCMS: 100%; peak mass m / z = 388, corresponding to the indication).

COLORING EXAMPLES

Preparation of a composition <b>AT</b>

0120<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="75mm" /><colspec colnum="2" colname="col2" colwidth="19mm" /><tbody><row><entry valign="middle">Disulfide dye of formula (I) according to the invention</entry><entry align="right" valign="middle">10^-3 mol%</entry></row><row><entry valign="middle">Benzyl alcohol</entry><entry align="right" valign="middle">4 g</entry></row><row><entry valign="middle">Polyethylene glycol 6OE</entry><entry align="right" valign="middle">6 g</entry></row><row><entry valign="middle">Hydroxyethylcellulose</entry><entry align="right" valign="middle">0.7 g</entry></row><row><entry valign="middle">Alkylpolyglucoside in aqueous solution at 65% MA</entry><entry align="right" valign="middle">4.5g</entry></row><row><entry valign="middle">Demineralized Water</entry><entry align="right" valign="middle">qs 100g</entry></row></tbody></tgroup></table></tables>

Preparation of a composition <b>B</b>

0121<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="36mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><tbody><row><entry valign="middle">Thioglycolic acid</entry><entry align="right" valign="middle">1M</entry></row><row><entry valign="middle">Sodium hydroxide</entry><entry align="right" valign="middle">qs pH 8.5</entry></row><row><entry valign="middle">Demineralized Water</entry><entry align="right" valign="middle">qs 100g</entry></row></tbody></tgroup></table></tables>

0122At the time of use, the compositions are mixed <b>AT</b> (9 volumes) and <b>B</b> (1 volume), then apply the mixture obtained to dark hair (pitch 4) for 30 minutes at room temperature. After rinsing with water and drying, an optical lightening of the hair thus treated is observed.

0123The locks thus treated are subjected to 30 shampoos according to a cycle which comprises wetting the locks with water, washing with shampoos, rinsing with water followed by drying.

0124The lock is dried before applying the next shampoo.

0125The color of the locks before and after the 30 washes was evaluated in the L * a * b * system using a CM 2002 MINOLTA® spectrophotometer (Illuminant D65).

0126In the L * a * b * system, the three parameters respectively designate the intensity (L *), the hue (a *) and the saturation (b *). According to this system, the higher the value of L, the lighter or less intense the color. Conversely, the lower the value of L, the darker or very intense the color. a * and b * indicate two color axes, a * indicates the green / red color axis and b * the blue / yellow color axis.<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="53mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="14mm" /><colspec colnum="4" colname="col4" colwidth="14mm" /><thead><row><entry /><entry><b>L</b></entry><entry><b>at*</b></entry><entry><b>b *</b></entry></row></thead><tbody><row><entry valign="bottom">Compound 1</entry><entry align="center" valign="bottom">24,85</entry><entry align="center" valign="bottom">8,08</entry><entry align="center" valign="bottom">7,68</entry></row><row><entry valign="bottom">Compound 1 after 30 shampoos</entry><entry align="center" valign="bottom">24,78</entry><entry align="center" valign="bottom">7,83</entry><entry align="center" valign="bottom">7,56</entry></row><row><entry valign="bottom">Compound 2</entry><entry align="center" valign="bottom">26,32</entry><entry align="center" valign="bottom">6,38</entry><entry align="center" valign="bottom">10,01</entry></row><row><entry valign="bottom">Compound 2 after 30 shampoos</entry><entry align="center" valign="bottom">25,61</entry><entry align="center" valign="bottom">5,48</entry><entry align="center" valign="bottom">9,05</entry></row><row><entry valign="bottom">Compound 3</entry><entry align="center" valign="bottom">25,49</entry><entry align="center" valign="bottom">10,56</entry><entry align="center" valign="bottom">9,96</entry></row><row><entry valign="bottom">Compound 3 after 30 shampoos</entry><entry align="center" valign="bottom">25,98</entry><entry align="center" valign="bottom">11,41</entry><entry align="center" valign="bottom">9,86</entry></row><row><entry valign="bottom">Compound 4</entry><entry align="center" valign="bottom">25,87</entry><entry align="center" valign="bottom">6,06</entry><entry align="center" valign="bottom">9,60</entry></row><row><entry valign="bottom">Compound 4 after 30 shampoos</entry><entry align="center" valign="bottom">24,38</entry><entry align="center" valign="bottom">5,86</entry><entry align="center" valign="bottom">9,20</entry></row><row><entry valign="bottom">Compound 5</entry><entry align="center" valign="bottom">25,08</entry><entry align="center" valign="bottom">1,19</entry><entry align="center" valign="bottom">7,51</entry></row><row><entry valign="bottom">Compound 5 after 30 shampoos</entry><entry align="center" valign="bottom">25,72</entry><entry align="center" valign="bottom">1,38</entry><entry align="center" valign="bottom">6,01</entry></row></tbody></tgroup></table></tables>

0127The results in the table above show that the coloring changes very little even after 30 shampoos. Thus the coloring and the lightening effect on the hair remains almost unchanged, which shows very good resistance to shampooing of the dyes of the invention.