Styryl tetrahydroquinolinium thiol/disulfide compound, process for lightening keratin materials using this dye

Compound styryl tetrahydroquinolinium thiol / disulfide, clarification process of keratin materials from this dye.

The invention relates to the coloration of keratin materials with the aid of fluorescent dyes styryl tetrahydroquinolinium thiols / disulfides.

It is known to dye keratin fibers, in particular human, by direct coloring. The procedure used classically in direct dyeing consists in applying direct dyes that are colored molecules and dyes that have an affinity for the fibers on the keratin fibers, in allowing them to diffuse, and then in clarifying the fibers.

The direct dyes used classically are, for example, benzene nitrated type dyes, anthraquinonic dyes, nitropyridines, azoic, xanthenic, acridine, azine or triaryl methane type dyes.

The coloring of the keratin fibers from these classic direct dyes does not make it possible to clarify keratin fibers remarkably.

The lightening of the color of the dark keratin fibers towards lighter shades, eventually modifying their hue, constitutes an important demand.

Classically, to obtain a clearer coloration, a chemical decolorization procedure is used. This procedure consists in treating the keratin fibers, such as the hair, by means of a strong oxidizing system, generally constituted by hydrogen peroxide associated or not with persales, most frequently in alkaline medium.

This discoloration system suffers from the inconvenience of degrading keratin fibers, and altering their cosmetic properties. Fibers tend to become rough, harder to untangle and more fragile. Finally, the clarification or discoloration of keratin fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in smoothing treatments.

Another technique of lightening consists of applying direct fluorescent dyes on dark hair. This technique described in particular in WO 03/028685, WO 2004/091473 and WO 2005/004822, allows to respect the quality of the keratin fiber during treatment. However, these direct fluorescent dyes do not have satisfactory toughness against external agents.

In order to increase the persistence of direct colorations, it is known to use disulphide dyes in particular dyes with imidazolium chromophore in patent applications WO 2005/097051 or EP 1 647 580, and dyes with pyridinium / indolinium-styryl chromophores in applications for WO 2006/134043 and WO 2006/136617.

The objective of the present invention is to provide new systems for coloring keratin materials, in particular human keratin fibers, in particular hair, which do not suffer from the drawbacks of existing bleaching processes.

Particularly, an object of the invention is to provide direct dyeing systems that allow to obtain lightening effects in particular on naturally or artificially darkened keratin fibers, tenacious against successive washes, which do not degrade keratin fibers and do not alter their cosmetic properties.

Another objective of the invention is to color chromatically and remotely in the face of external aggressions keratin materials. The invention also aims to provide compounds that color keratin fibers such as hair with a low color selectivity between the root and the tip, whether on natural or permanent fibers.

These objectives are achieved with the present invention which aims at a process of coloring keratin materials, in particular keratin fibers, in particular human such as hair, more particularly dark hair, which consists in applying a composition on the keratin materials dye, comprising in an appropriate cosmetic medium at least one fluorescent dye disulfide or thiol, selected from the following formula (I) and (II) dyes:

its salts of organic or mineral acid, optical isomers, geometric isomers and solvates such as hydrates;

formulas (I) and (II) in which:

<dl><dt>-</dt><dd /></dl>

represents an aryl, heterocycle or heteroaryl group operated on the phenyl cycle; or if it is not absent from the phenyl cycle; when the cycle is present, it represents in particular a benzo or indene cycle, more particularly benzo;

<dl><dt>-</dt><dd>G and G ', identical or different, represent a group -NRcRd or (C1-C6) optionally substituted alkoxy, in particular unsubstituted or else G or G' is absent; </dd></dl>

<dl><dt>-</dt><dd>Rc and Rd identical or different, represent a hydrogen atom, a (C1-C6) alkyl group optionally substituted, aryl (C1-C4) alkyl, (C1-C6) alkyl (C1-C6) alkyl, a group (C1 -C6) optionally substituted alkyl; </dd></dl>

Rc and Rd represent more particularly a hydrogen atom, a (C1-C3) alkyl group, or a (C1-C3) alkyl group substituted by i) a hydroxy group, ii) amino, iii) (di) (C1-C3 ) alkylamino, or iv) quaternary ammonium (R '') (R '' ') (R' '' ') N + -;

<dl><dt>-</dt><dd>or else the two radicals Rc and Rd supported by the same nitrogen atom together form a group </dd></dl>

fifteen heterocyclic or heteroaryl; particularly the heterocycle is monocyclic and comprises between 5 and 7 links and the heteroaryl is bicyclic and comprises 7 to 11 links; more particularly the groups are selected from piperidinyl, imidazolyl, pyrrolidinyl and indolyl; the heterocycle may be substituted by at least one hydroxy group;

<dl><dt>-</dt><dd>Rg, R'g, R''g, R '' 'g, Rh and R' '' h, identical or different, represent a hydrogen atom, a halogen, a group </dd></dl>

twenty amino, (di) (C1-C4) alkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, C1-C4 alkoxy, (poly) hydroxyalkoxy of C2-C4, (C1-C4) alkylcarbonyloxy, (C1-C4) alkoxycarbonyl , (C1-C4) alkylcarbonyl-amino, acylamino, carbamoyl, (C1-C4) alkylsulfonylamino, an amino-sulfonyl radical, or a (C1-C16) alkyl radical optionally substituted by a group selected from (C1-C12) alkoxy, hydroxy, cyano, carboxy, amino, (di) (C1-C4) alkylamino, or else the two alkyl radicals supported by the nitrogen atom of the amino group

25 they form a heterocycle comprising from 5 to 7 links and possibly comprising another heteroatom identical or different from that of the nitrogen atom; particularly, Rg, R'g, R''g, R '' 'g, Rh and R' '' h, represent a hydrogen atom;

or if not two groups Rg and R'g, R''g and R '' 'g, supported by two adjacent carbon atoms, together form a benzo, indene cycle, a fused heterocycloalkyl group or fused heteroaryl; the benzo, indene, heterocycloalkyl or heteroaryl cycle being optionally substituted by a halogen atom, (C1-C4) alkyl, an amino group, (C1-C4) alkylamino, (C1-C4) dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, an acylamino radical, C1-C4 alkoxy, (poly) hydroxyalkoxy of C2-C4, alkylcarbonyloxy alkoxycarbonyl, alkylcarbonylamino, an acylamino radical, carbamoyl, alkylsulfonylamino, an amino-sulfonyl radical, or a (C1-C16) alkyl radical optionally substituted by: a group selected from (C1-C12) alkoxy, hydroxy, cyano, carboxy, amino,

35 (C1-C4) alkylamino, (C1-C4) dialkylamino, or else the two alkyl radicals supported by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 links and possibly comprising another heteroatom identical or different from the one of the nitrogen atom; particularly Rg and R'g; R''gy R '' 'g together form a benzo group;

<dl><dt>-</dt><dd>or if not when G and / or G 'represent -NRcRd, two groups Rc and R'g, Rd and Rg and / or Rc and R "g, Rd and R"' g, together form a saturated heteroaryl or heterocycle, optionally substituted by one or more (C1-C6) alkyl groups; in particular the heterocycle or the heteroaryl contain one or two heteroatoms selected from nitrogen and oxygen, and the heterocycle comprises between 5 and 7 links, and the heteroaryl contains between 7 and 11 links; particularly, the heterocycle is selected from the groups morpholinyl, piperazinyl, piperidinyl, homopiperidinyl, pyrrolidinyl and the heteroaryl is an indolyl; </dd></dl>

<dl><dt>-</dt><dd>R'i and R '' 'i, identical or different, represent a hydrogen atom, or a (C1-C4) alkyl group; particularly, R'i and R '' 'i represent a hydrogen atom;</dd></dl>

<dl><dt>-</dt><dd>R'h with Ri and R''h with R''i form together with the carbon atoms that support them an optionally substituted C5-C7 cycloalkyl group, fused to the pyridinium group, particularly a cyclohexyl group; it being understood that the radical R'h or R''h and the styryl group that support the radical Ri or R''i are positioned on adjacent carbon atoms of the pyridinium groups; more particularly, they are positioned respectively on carbon atoms 3 and 4 of the pyridinium groups;</dd></dl>

<dl><dt>-</dt><dd> R1, R2, R3, R4, R'1, R'2, R'3 and R'4, identical or different, represent: </dd></dl>

<dl><dt>-</dt><dd> a hydrogen atom, </dd></dl>

<dl><dt>-</dt><dd> a (C1-C4) alkyl group, </dd></dl>

<dl><dt>-</dt><dd> (C1-C12) alkoxy, </dd></dl>

<dl><dt>-</dt><dd> hydroxy, </dd></dl>

<dl><dt>-</dt><dd> cyano, </dd></dl>

<dl><dt>-</dt><dd> -C (O) O-M +, representing M + an alkali metal or M + and An-are absent, </dd></dl>

<dl><dt>-</dt><dd> carboxy, </dd></dl>

<dl><dt>-</dt><dd>(di) (C1-C4) (alkyl) amino, said alkyl radicals being able to form with the nitrogen atom that supports them, a heterocycle comprising from 5 to 7 links, possibly comprising another heteroatom different or not from nitrogen; </dd></dl>

in particular, R1, R2, R3, R4, R'1, R'2, R'3 and R'4 are hydrogen atoms or a group -C (O) O-M +; particularly R1, R2, R3, R4, R'1, R'2, R'3 and R'4 represent a hydrogen atom;

<dl><dt>-</dt><dd> Ta, Tb, identical or different, represent: </dd></dl>

i) or a covalent bond!

ii) either one or more radicals or their combinations selected from -SO2-, -O-, -S-, -N (R) -, -N + (R) (R °) -, -C (O) -, R and R °, identical or different, represent a hydrogen atom, a C1-C4 alkyl radical, C1-C4 hydroxyalkyl or an aryl (C1-C4) alkyl; in particular Ta is identical to Tb and represents a covalent bond!, or a group selected from -N (R) -, -C (O) -, -C (O) -N (R) -, -N (R) -C (O) -, -C (O) -N (R) -C (O) -, -OC (O) -, -C (O) -Oy -N + (R) (R °) -, representing R, R °, identical or different, a hydrogen atom, a C1-C4alkyl group; particularly Ta and Tb represent -C (O) -N (R) -, -N (R) -C (O) -;

iii) either a heterocycloalkyl or heteroaryl radical, cationic or not, preferably monocyclic, containing in particular two heteroatoms, particularly two nitrogen atoms, and comprising in particular 5 to 7 links such as imidazolium, pyridinium or optionally substituted pyrrolidinium by a (C1-C4) alkyl group such as methyl;

<dl><dt>-</dt><dd>m, m ', n and n', identical or different, represent an integer included inclusive between 0 and 6, representing m + n, m '+ n', identical or different, an integer inclusive inclusive between 1 and 10; particularly the sum m + n = m '+ n' = an integer included inclusive between 2 and 4; preferably m + n = m '+ n' = 2;</dd></dl>

<dl><dt>-</dt><dd> An-represents an anionic counterion; and</dd></dl>

<dl><dt>-</dt><dd>Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + R∀R # R∃R% or a phosphonium group: P + R∀R # R∃R%, representing R∀, R #, R∃, R%, identical or different, a hydrogen atom or a (C1-C4) alkyl group; ov) a thiol protecting group;</dd></dl>

it being understood that when the compound of formula (I) or (II) contains other cationic parts, it is associated with one or more anionic counterions that allow the electroneutrality of formula (I) or (II) to be achieved.

Another object of the invention is a dyeing composition comprising, in a cosmetically appropriate medium, at least one disulfide fluorescent dye (I) or a thiol fluorescent dye of formula (II) such as those defined above, and possibly a reducing agent.

A subject of the invention is also new disulfide fluorescent dyes of formula (I) and thiols of formula (II).

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

10 In addition, the process of the invention makes it possible to obtain a coloration of keratin materials, in particular human keratin fibers, in particular hair, without degrading said matter, remaining in front of the washes, to the usual aggressions (Sun, perspiration), and other hair treatments. The process of the invention also makes it possible to obtain a lightening of keratin materials such as keratin fibers, particularly dark keratin fibers and more particularly dark hair.

fifteen The dyes of the invention are, on the other hand, stable against oxidants, and have a satisfactory solubility in the cosmetic dye media. These dyes extend the range of colors to yellows and oranges. The dyes of formula (I) or (II) color after application on the keratin fibers chromatically and remotely against external aggressions keratin materials with a low color selectivity between the root and the tip, and on different types of fibers.

twenty In the sense of the invention, dark keratin material is understood to mean that it has a 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 by another part that L * = 0 is equivalent to black and L * = 100 to white.

In the sense of the invention, natural or artificially dark hair is understood as hair whose tone height is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (brown).

25 Hair lightening is evaluated by varying the "pitch height" before and after the application of the compound of formula (I) or (II). The notion "tone" is based on the classification of natural nuances, separating a hue each hue from the immediately following or immediately preceding. This definition and classification of natural shades is well known by hairdressing professionals and is published in the work "Science des traitements capillaires" by Charles ZVIAK 1988, Ed. Masson, p. 215 and 278.

30 Tone heights range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; The higher the number, the clearer the nuance.

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

In the sense of the invention, it is understood as bleached hair, hair whose tone height is greater than 35 4 (brown) and preferably greater than 6 (dark blonde).

A means to measure the lightening effect provided to the hair after application of the fluorescent dyes of the invention is to use the phenomenon of hair reflectance.

Preferably, the composition should, after application on dark hair, lead to the following results.

40 - The reflective yields of the hair are interesting when they are irradiated with visible light in the range of wavelengths between 400 and 700 nanometers.

<dl><dt>-</dt><dd>The reflectance curves are then compared as a function of the wavelength of the hair treated with the composition of the invention and of the untreated hair. </dd></dl>

<dl><dt>-</dt><dd>The curve corresponding to the treated hair should show a reflectance in the wavelength range 45 between 500 and 700 nanometers greater than the curve corresponding to the untreated hair. </dd></dl>

<dl><dt>-</dt><dd>This means that, in the wavelength range between 540 and 700 nanometers, there is at least one interval in which the reflectance curve that corresponds to the treated hair is greater than the reflectance curve that corresponds to the untreated hair . "Greater than" means a difference of at least 0.05% reflectance, and preferably at least 0.1%. This does not prevent it from existing in the wavelength range between 540 and 700 nanometers, at least one interval in which the curve </dd></dl>

of reflectance that corresponds to treated hair is superimposable, or less than the reflectance curve that corresponds to untreated hair.

Preferably, the wavelength in which the separation is maximum between the reflectance curve of the treated hair and that of the untreated hair is in the wavelength range between 500 and 650 nanometers, and preferably in the wavelength range between 550 and 620 nanometers.

In the sense of the present invention, and unless a different indication is provided:

<dl><dt>-</dt><dd>the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent supported by a carbon atom, selected from: </dd></dl>

<dl><dt>* </dt><dd>a C1-C16 alkyl radical, preferably C1-C8, optionally substituted by one or more radicals selected from the hydroxy radicals, C1-C2 alkoxy, (poly) -hydroxyalkoxy radical of C2-C4, acylamino, amino substituted by two radicals C1-C4 alkyl, identical or different, optionally bearing at least one hydroxy group or, the two radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising 5 to 7 links, preferably 5 or 6 links, saturated or unsaturated, if necessary, optionally comprising another heteroatom identical or different from nitrogen; </dd></dl>

<dl><dt>* </dt><dd>a halogen atom such as chlorine, fluorine or bromine; </dd></dl>

<dl><dt>* </dt><dd>a hydroxy group; </dd></dl>

<dl><dt>* </dt><dd>a C1-C2 alkoxy radical; </dd></dl>

<dl><dt>* </dt><dd>a C1-C2 alkylthio radical; </dd></dl>

<dl><dt>* </dt><dd>a (poly) -hydroxyalkoxy radical of C2-C4; </dd></dl>

<dl><dt>* </dt><dd>an amino radical; </dd></dl>

<dl><dt>* </dt><dd>a heterocycloalkyl radical of 5 or 6 links; </dd></dl>

<dl><dt>* </dt><dd>a heteroaryl radical of 5 or 6 links, possibly cationic, preferably imidazolium, and optionally substituted by a (C1-C4) alkyl radical, preferably methyl; </dd></dl>

<dl><dt>* </dt><dd>an amino radical substituted by one or two alkyl radicals, identical or different, of C1-C6, possibly bearing at least: </dd></dl>

i) a hydroxy group,

ii) an amino group optionally substituted by one or two C1-C3 alkyl radicals that may be substituted, said radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 links, saturated or unsaturated, if substituted possibly comprises at least one other heteroatom different or not from nitrogen,

* -NR-COR 'in which the radical R is a hydrogen atom, a C1-C4 alkyl radical possibly bearing at least one hydroxy group and the radical R' is a C1-C2 alkyl radical;

<dl><dt>* </dt><dd>(R) 2-N-CO- in which the radicals R, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical, optionally bearing at least one hydroxy group; </dd></dl>

<dl><dt>* </dt><dd>R'SO2-NR- in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxy group and the radical R 'represents a C1-C4 alkyl radical, a phenyl radical ; </dd></dl>

<dl><dt>* </dt><dd>(R) 2N-SO2- in which the radicals R, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxy group, </dd></dl>

<dl><dt>* </dt><dd>a carboxylic radical in acidic or salified form (preferably with an alkali metal or an ammonium, substituted or not); </dd></dl>

<dl><dt>* </dt><dd>a cyano group; </dd></dl>

<dl><dt>* </dt><dd>a polyhalogenoalkyl group comprising from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, identical or different, the polyhalogenoalkyl group is for example trifluoromethyl; </dd></dl>

<dl><dt>-</dt><dd>The cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent selected from the groups: </dd></dl>

<dl><dt>* </dt><dd>hydroxy, </dd></dl>

<dl><dt>* </dt><dd>C1-C4 alkoxy, </dd></dl>

<dl><dt>* </dt><dd>C1-C4 alkyl, </dd></dl>

<dl><dt>* </dt><dd>C2-C4 (poly) hydroxyalkoxy, </dd></dl>

5 * a C1-C2 alkylthio radical,

* RCO-NR'- in which the radical R 'is a hydrogen atom, a C1-C4 alkyl radical, optionally bearing at least one hydroxy group, and the radical R is a C1-C2 alkyl radical, amino substituted by two identical or different C1-C4 alkyl groups, possibly bearing at least one hydroxy group;

10 * RCO-O- in which the radical R is a C1-C4 alkyl radical, amino substituted by one or two identical or different C1-C4 alkyl groups, possibly bearing at least one hydroxy group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 links, possibly saturated or unsaturated substituted, comprising at least one other heteroatom different or not from nitrogen;

fifteen * RO-CO- in which the radical R is a C1-C4 alkyl radical optionally bearing at least one hydroxy group;

<dl><dt>-</dt><dd>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; </dd></dl>

<dl><dt>-</dt><dd>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 cycle is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;</dd></dl>

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

<dl><dt>-</dt><dd> a "heteroaryl radical" represents a mono or polycyclic group, condensed or not, optionally cationic, </dd></dl>

25 comprising 5 to 22 links, 1 to 6 heteroatoms selected from the nitrogen, oxygen, sulfur and selenium atom, and of which at least one cycle is aromatic; preferably a heteroaryl radical is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrotiazolyl, imidazopyridyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyloxylazoyl naphthyloxylazoyloxylazoyl naphthaloxylazoyloxylazoyl naphthaloxylazoyloxylazoyloxylazoyl naphthaloxylazoyl naphthaloxylazoyloxylazoyl naphthaloxylazoyl naphthaloxylazoyl naphthaloxylazoyl naphthaloxylazoyloxylazoyloxylazoyl naphthaloxylazoylimidozolyl group

30 naftopirazolilo, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, fenooxazolilo, pyrazinyl, pyrazolyl, pirililo, pirazoiltriazilo, pyridyl, piridinoimidazolilo, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, tiazoilimidazolilo, tiopirililo, triazolyl, xantililo and its ammonium salt;

<dl><dt>-</dt><dd>a "diheteroarylalkyl" radical represents a group comprising on the same carbon atom of an alkyl group two heteroaryl groups, identical or different such as difurylmethyl, 1,1-difurylethyl, dipyrrolylmethyl, dithienylmethyl; </dd></dl>

<dl><dt>-</dt><dd>a "cyclic radical" is a non-aromatic, mono or polycyclic cycloalkyl radical, condensed or not, containing from 5 to 22 carbon atoms, may comprise from 1 to several unsaturations; particularly the cyclic radical is a cyclohexyl;</dd></dl>

<dl><dt>-</dt><dd> a "sterically congested cyclic radical" is a cyclic radical, aromatic or not, substituted or not, </dd></dl>

40 congested by steric effect or tension, which comprises 6 to 14 links, which may be bridged, as sterically congested radicals, the bicyclo [1.1.0] butane, mesityls such as 1,3,5- trimethylphenyl, 1,3,5-triterbutylphenyl, 1,3,5-isobutylphenyl, 1,3,5-trimethylsilylphenyl and adamantyl;

<dl><dt>-</dt><dd>a "heterocyclic radical or heterocycle" is a mono or polycyclic non-aromatic radical, condensed or not, containing from 5 to 22 links, comprising from 1 to 6 heteroatoms selected from the nitrogen, oxygen, sulfur and atom selenium; </dd></dl>

<dl><dt>-</dt><dd> an "alkyl radical" is a C1-C16 hydrocarbon radical, linear or branched, preferably C1-C8; </dd></dl>

<dl><dt>-</dt><dd>with the term "optionally substituted" attributed to the alkyl radical it is understood that said alkyl radical may be substituted by one or more radicals selected from the radicals i) hydroxy, ii) alkoxy of C1-C4, iii) acylamino, iv) amino, if necessary substituted by one or two identical or different alkyl radicals of C1-C4, said alkyl radicals being able to form with the nitrogen atom that supports them a heterocycle comprising from 5 to 7 links, which eventually comprises another heteroatom different or not from </dd></dl>

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 C1-C4 alkyl group , or else -N + R'R "R" 'form a heteroaryl such as imidazolium optionally substituted by a C1-C4 alkyl group, and M- represents the counterion of the corresponding organic, mineral or halide acid,

5 - an "alkoxy radical" is an alkyloxy or alkyl-O-radical for which the alkyl radical is a hydrocarbon radical, linear or branched, of C1-C16, preferably C1-C8;

<dl><dt>-</dt><dd>an "alkylthio radical" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, of C1-C16, preferably C1-C8; </dd></dl>

when the alkylthio group is optionally substituted, it is understood that the alkyl group is optionally substituted as defined above;

<dl><dt>-</dt><dd>the limits that delimit the extension of a range of values ​​are included in this range of values; </dd></dl>

<dl><dt>-</dt><dd>an "organic or mineral acid salt" is more particularly selected from a salt derived i) from HCI hydrochloric acid, ii) from HBr hydrobromic acid, iii) from H2SO4 sulfuric acid, iv) from alkylsulfonic acids: Alk-S (O ) 2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) of tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) of aryloxysulfinic acids such as toluenoxysulfinic acid and phenoxysulfinic acid; xii) H3PO4 phosphoric acid; xiii) acetic acid CH3COOH;</dd></dl>

twenty xiv) of triflic acid CF3SO3H and xv) of tetrafluoroboric acid HBF4;

<dl><dt>-</dt><dd>an "anionic counterion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly the anionic counterion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulphonates among which C1-C6 alkylsulfonates: Alk-S (O) 2O- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S (O) 2O- such as benzenesulfonate and</dd></dl>

25 toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS (O) O- such as methyl sulfate and ethyl sulfate; x) arylsulfates: Ar-OS (O) O- such as benzenesulfate and toluenesulfate; xi) alkoxysulfates: Alk-OS (O) 2O- such as methoxysulfate and ethoxy sulfate; xii) aryloxysulfates: Ar-OS (O) 2O-, xiii) phosphate; xiv) acetate; xv) the triflate; and xvi) borates such as tetrafluoroborate;

30 -The "solvates" represent hydrates as well as the association with linear or branched linear or branched C1-C4 alcohols such as ethanol, isopropanol, n-propanol.

The disulfide fluorescent dyes of formula (I) or thiols of formula (II) are compounds capable of absorbing in UV or visible radiation at a wavelength &amp; abs between 250 and 800 nm and capable of re-emitting in the visible domain at an emission wavelength between 400 and 800 nm.

35 Preferably, the fluorescent compounds of formula (I) or (II) of the invention are colorants capable of absorbing the visible &amp; abs between 400 and 800 nm and re-emitting the visible &amp; em between 400 and 800 nm. More preferably, the dyes of formulas (I) or (II) are dyes capable of absorbing at an &amp; abs between 420 nm and 550 nm and re-emitting the visible at a &amp; em between 470 and 600 nm.

The fluorescent compounds of the invention of formula (II) contain a SY function which can be found in covalent form -SY or ionic -S-Y + according to the nature of Y and the pH of the medium.

A particular mode refers to thiol fluorescent dyes of formula (II) with SY function in which Y represents a hydrogen atom, or an alkali metal. Advantageously, Y represents a hydrogen atom.

According to another particular embodiment of the invention, in the aforementioned formula (II), Y is a protective group known to those skilled in the art, such as those described in "Protective" documents

Four. Five Groups in Organic Synthesis ", TW Greene, John Willey &amp; Sons ed., NY, 1981, p.193-217;" Protecting Groups ", P. Kocienski, Thieme, 3rd ed., 2005, chap. 5. Understanding that Y as a protecting group, it cannot constitute a disulfide dye with the nitrogen atom that supports it, that is, it cannot constitute a compound of formula (I). The protecting group Y cannot represent in the formula (II) a group directly linked to the sulfur atom through another non-oxidized sulfur atom.

fifty Particularly, when Y represents a thiol protecting group, Y is selected from the following radicals:

<dl><dt>■</dt><dd>(C1-C4) alkylcarbonyl; </dd></dl>

<dl><dt>■</dt><dd>(C1-C4) alkylthiocarbonyl; </dd></dl>

<dl><dt>■</dt><dd>(C1-C4) alkoxycarbonyl; </dd></dl>

<dl><dt>■</dt><dd>(C1-C4) alkoxythiocarbonyl; </dd></dl>

<dl><dt>■</dt><dd>(C1-C4) alkylthio thiocarbonyl; </dd></dl>

<dl><dt>■ </dt><dd>(di) (C1-C4) (alkyl) aminocarbonyl; 5 ■ (di) (C1-C4) (alkyl) aminothiocarbonyl; </dd></dl>

<dl><dt>■ </dt><dd>arylcarbonyl as phenylcarbonyl; </dd></dl>

<dl><dt>■ </dt><dd>aryloxycarbonyl; </dd></dl>

<dl><dt>■ </dt><dd>aryl (C1-C4) alkoxycarbonyl; </dd></dl>

<dl><dt>■ </dt><dd>(di) (C1-C4) (alkyl) aminocarbonyl such as dimethylaminocarbonyl; 10 ■ (C1-C4) (alkyl) arylaminocarbonyl;</dd></dl>

<dl><dt>■ </dt><dd>carboxy; </dd></dl>

<dl><dt>■</dt><dd>SO3-; M + representing M + an alkali metal such as sodium or potassium, or else An- of the formula (Il) and M + are absent;</dd></dl>

<dl><dt>■ </dt><dd>optionally substituted aryl such as phenyl, dibenzosuberyl, or 1,3,5-cycloheptatrienyl, </dd></dl>

fifteen ■ possibly substituted heteroaryl; including in particular the cationic heteroaryl or not, comprising from 1 to 4 following heteroatoms:

i) monocyclic with 5, 6 or 7 links such as furanyl or furyl, pyrrolyl or pyrrile, 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,

twenty 1,2,4-thiadiazolyl, 1,2,4-thiadiazolium, pyrilio, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine, oxepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium, azepinium tiepinyl, tiepinium, imidazolyl, imidazolium;

ii) bicyclics with 8 to 11 links such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl,

25 pyridoimidazolium, thienocycloheptadienyl, these mono or bicyclic groups being optionally substituted by one or more groups such as (C1-C4) alkyl as methyl, or polyhalogen (C1-C4) alkyl as trifluoromethyl;

iii) or following tricyclic ABC:

30 in which the two cycles A, C eventually comprise a heteroatom, and cycle B is a cycle with 5, 6

or 7 links, particularly with 6 links and contains at least one heteroatom such as piperidyl, pyranyl;

■ optionally substituted heterocycloalkyl, optionally cationic, the heterocycloalkyl group represents in particular a saturated or partially saturated monocyclic group with 5, 6 or 7 links comprising

35 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl di / tetra / hexahydroazepinyl, di / tetrahydropyrimidinyl, these groups being eventually substituted by one or more groups such as (C1-C4) alkyl, oxo or thioxo; or the heterocycle represents the following group:

wherein R'c, R'd, R'e, R'f, R'g and R'h, identical or different represent a hydrogen atom or a (C1-C4) alkyl group, or if not two groups R'g with R'h, and / or R'e with R'f form an oxo or thioxo group, or else R'g with R'e together form a cycloalkyl; and v represents an integer included inclusive between 1 and 3; preferably R'c to R'h represent a hydrogen atom; and An'-represents an anionic counterion;

5 ■ isothiouronium;

■ -C (NR'cR'd) = N + R'eR'f; An-con R'c, R'd, R'e and R'f, identical or different, represent a hydrogen atom or a (C1-C4) alkyl group; preferably R'c to R'f represent a hydrogen atom; and An'- represents an anionic counterion;

■ isothiourea;

10 ■ -C (NR'cR'd) = NR'e; An-con R'c, R'd, R'e and An- are as defined above;

<dl><dt>■ </dt><dd>(di) aryl (C1-C4) alkyl optionally substituted, such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted by one or more groups selected in particular from (C1-C4) alkyl, (C1-C4) alkoxy such as methoxy, hydroxy, alkylcarbonyl, (di) (C1-C4) (alkyl) amino such as dimethylamino; </dd></dl>

<dl><dt>■ </dt><dd>(di) heteroaryl (C1-C4) alkyl optionally substituted, the heteroaryl group is in particular cationic or not, </dd></dl>

fifteen monocyclic, comprising 5 or 6 links and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide groups such as 4-pyridyl or 2-pyridyl -N-oxide, pyrilio, pyridinium, triazinyl, optionally substituted by one or more groups such as particularly methyl alkyl, advantageously the (di) heteroaryl (C1-C4) alkyl is (di) heteroarylmethyl or (di) heteroarylethyl;

twenty ■ -CR1R2R3, representing R1, R2 and R3, identical or different, a halogen atom or a group selected from:

i) (C1-C4) alkyl;

ii) (C1-C4) alkoxy;

iii) optionally substituted aryl such as phenyl optionally substituted by one or more groups such as (C1-C4) alkyl, (C1-C4) alkoxy, hydroxy;

iv) optionally substituted heteroaryl, such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted by a (C1-C4) alkyl group;

v) P (Z1) R'1R'2R'3, representing R'1 and R'2, identical or different, a hydroxy group, (C1-C4) alkoxy or alkyl, R'3 represents a hydroxy group or (C1 -C4) alkoxy, and Z1 represents an oxygen or sulfur atom;

30 ■ sterically congested cyclic; and

■ possibly substituted alkoxyalkyl, such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.

According to a particular embodiment, the protected thiol fluorescent dyes of formula (II) comprise a monocyclic heterocyl group Y i) with 5 or 6 aromatic links, comprising from 1 to 4 35 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, pyrilio, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, tiepinyl, tiepinium, imidazolium; ii) bicyclic heteroaryl with 8 to 11 cationic links such as indolinium, benzoimidazolium, benzoxazolium, benzothiazolium, these mono or bicyclic heteroaryl groups being optionally substituted by one or more groups such as alkyl as methyl, or

40 polyhalophene (C1-C4) alkyl as trifluoromethyl; iii) or following heterocyclic:

c

wherein R 'and R'd, identical or different, represent a hydrogen atom or a (C1-C4) alkyl group; preferably R'c to R'd represent a (C1-C4) alkyl group such as methyl; and An'- represents an anionic counterion.

Four. Five Particularly Y represents a group selected from oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrilium, pyridinium , pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium,

benzoimidazolium, benzoxazolium, benzothiazolium, these groups being eventually substituted by one or more (C1-C4) alkyl groups, in particular methyl. In particular Y represents an alkali metal or a protecting group such as: - (C1-C4) alkylcarbonyl such as methylcarbonyl or ethylcarbonyl; -arylcarbonyl as phenylcarbonyl; - (C1-C4) alkoxycarbonyl; -aryloxycarbonyl; - (C1-C4) alkoxycarbonyl; - (di) (C1-C4) (alkyl) aminocarbonyl such as dimethylaminocarbonyl; - (C1-C4) (alkyl) arylaminocarbonyl; - optionally substituted aryl such as phenyl; - monocyclic heteroaryl with 5 or 6 links such as imidazolyl or pyridyl;

<dl><dt>-</dt><dd>cationic monocyclic heteroaryl with 5.6 links such as pyrilium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted by one or several groups, identical or different, (C1-C4) alkyl groups such as methyl;</dd></dl>

<dl><dt>-</dt><dd>cationic bicyclic heteroaryl with 8 to 11 links such as benzoimidazolium, or benzoxazolium; these groups being optionally substituted by one or several groups, identical or different, (C1-C4) alkyl groups such as methyl;</dd></dl>

<dl><dt>-</dt><dd>cationic heterocycle of the following formula: </dd></dl>

-isothiouronium -C (NH2) = N + H2; An-; -isothiourea -C (NH2) = NH; -SO3-, M +, representing M + an alkali metal such as sodium or potassium, or otherwise An- of formula (Il) and M +

They are absent. According to a particular embodiment of the invention, the disulfide fluorescent dyes of the formula

(I) have an axis of symmetry C2 between the two sulfur atoms of the central disulfide radical.

According to a particular mode of the invention, the dyes of the invention belong to one of two formulas (la), (Ila) which possess the phenyl group that supports the amino group RcRdN-, preferably in para, or in position 1- 4, from the styryl group:

with, for formulas (la), (lla): -R3 and R4, identical or different, represent:

<dl><dt>-</dt><dd>a hydrogen atom, </dd></dl>

<dl><dt>-</dt><dd>a (C1-C4) alkyl group, </dd></dl>

<dl><dt>--</dt><dd>C (O) O-M + representing M + an alkali metal or M + and An-are absent, </dd></dl>

5 -Carboxi;

<dl><dt>-</dt><dd>Rg, R'g, and Rh, identical or different, represent a hydrogen atom, a halogen, a (di) (C1-C4) (alkyl) amino, hydroxy, acylamino, (C1-C4) alkoxy group, (C1 -C4) alkylcarbonylamino or a (C1-C6) alkyl radical; particularly Rg, R'g, and Rh, represent a hydrogen atom;</dd></dl>

<dl><dt>-</dt><dd>two groups Rc and R'g and / or Rd and Rg together form a saturated heterocycle or a heteroaryl, optionally substituted by one or more (C1-C6) alkyl groups, in particular a heterocycle and containing the heteroaryl one </dd></dl>

or two heteroatoms selected from nitrogen and oxygen, the heterocycle containing between 5 and 7 links and the heteroaryl containing between 7 and 11 links; particularly the heterocycle is selected from the groups morpholinyl, piperazinyl, piperidinyl and pyrrolidinyl, and the heteroaryl is an indolyl;

<dl><dt>-</dt><dd>Rc and Rd, identical or different, represent a hydrogen atom, a (C1-C6) alkyl group, if any </dd></dl>

fifteen substituted, aryl (C1-C4) alkyl, a (C1-C6) alkyl optionally substituted; Rc and Rd particularly represent a (C1-C4) alkyl group, or a (C1-C4) alkyl group substituted by i) a hydroxy group, ii) amino, iii) (di) (C1-C3) alkylamino, or iv) quaternary ammonium (R ") (R '' ') (R' '' ') N + -, more particularly substituted by the alkyl group substituted by a hydroxy group;

<dl><dt>-</dt><dd>or else the two radicals Rc and Rd supported by the same nitrogen atom together form a group </dd></dl>

twenty heterocyclic or heteroaryl; particularly the heterocycle is monocyclic and comprises between 5 and 7 links and is eventually substituted in particular by one or two groups, identical or different, hydroxy and / or (C1-C4) alkyl; more particularly the groups are selected from piperidino, pyrrolidino; said heterocyclic group being substituted, in particular, with 1 or 2 hydroxy substituents;

<dl><dt>-</dt><dd>Ta represents a covalent bond!, Or a group selected from: -N (R) -, -C (O) -N (R) -, -N (R) -C (O) -; Particularly -C (O) -N (R) -, -N (R) -C (O) -o a covalent bond;</dd></dl>

<dl><dt>-</dt><dd>myn, identical or different, represent an integer included inclusive between 1 and 6 representing the sum m + n an integer included inclusive between 2 and 6; preferably m = 1 and / on = 1, 2, or 3;</dd></dl>

<dl><dt>-</dt><dd>representing An-an anionic counterion; and</dd></dl>

30 - And it is as defined above;

it being understood that when the compounds of formulas (la) or (lla) contain other cationic parts, they are associated with one or more anionic counterions that allow the electroneutrality of the formula (la) or (lla) to be achieved.

By way of example, one can cite fluorescent dyes belonging to the following formulas (I) and (Il):

representing the An-, identical or different, an anionic counterion.

The protected thiol dyes of formula (II ') can be synthesized in two stages. The first step is to prepare the unprotected thiol dye (II '') according to the methods known to the person skilled in the art, 5 such as "Tiols and organic Sulfides", "Tiocyanates and Isotiocyanates, organic", Ullmann's Encyclopedia, Wiley-VCH, Weinheim, 2005. And the second stage, which consists in protecting the thiol function according to the classical methods known by the person skilled in the art to lead to the protected thiol dyes of formula (II '). As an example to protect the thiol -SH function of the thiol pendant, the methods of the "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed., NY, 1981, p.193-217 documents can be used ;

10 "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005, chap. 5.

This method can be illustrated by the method consisting of i) in generating thiol fluorescent dyes of formula (II '') by reducing a fluorescent dye with two chromophores, heterocyclic, which supports a disulfide -SS-function such as (I ' ) and ii) in protecting according to the classical methods said thiol function of (II '') with reagent 7 Y'R to access the protected thiol fluorescent dyes of the formula (II '). The thiol compound (II '')

fifteen it can also be metallized with an alkali metal or alkaline earth metal Met * to lead to the thiolate fluorescent dye of formula (II '' ').

Y 'representing a thiol protecting group; Met * representing an alkali metal or an alkaline earth metal, particularly sodium or potassium, it being understood that when the metal is an alkaline earth metal, 2 chromophores with thiolate-S-function can be associated with 1 metal2 +.

5 where R1, R2, R3, R4, Rg, R'g, Rh, R'h, Ri, R'i, m, n, G and Annals as defined above; Y 'represents a thiol protecting group; and R represents a nucleophilic leaving group, such as mesylate, tosylate, triflate or halide.

According to another possibility, a protected thiol compound (b) can be reacted by a protective group Y 'as defined above, prepared according to one of the procedures described in the cited documents

10 above, said thiol compound comprising at least one nucleophilic function comprising a sufficient, preferably equimolar, amount of a "reactive fluorescent chromophore" or a compound comprising said "reactive fluorescent chromophore" (a). In other words, (a) it comprises an electrophilic function to form a bonding group or a covalent bond ∋ as can be outlined below in the preparation of fluorescent dyes of formula (II '):

<dl><dt /><dd>being R 1, R2, R3, R4, Rg, R'g, Rh, R'h, R i, R'i, m, n, G and Annals as defined above; representing</dd></dl>

a nucleophile group; representing

<dl><dt /><dd>an electrophilic group; and ∋ the linkage group generated after the attack of the nucleophile on the electrophile, it being understood that ∋ is a subset of the definition of Ta as described in formulas (I) and (II).</dd></dl>

As an example, the covalent bonds ∋ that can be generated are classified in the following table, based on condensation of electrophiles with nucleophiles:

<dl><dt>Electrophiles </dt><dd>Nucleophiles Covalent bonds ∋ </dd></dl>

<dl><dt>Esters activated * </dt><dd>Amines Carboxamides </dd></dl>

<dl><dt>Acyl Azides ** </dt><dd>Amines Carboxamides </dd></dl>

<dl><dt>Acyl halides </dt><dd>Amines Carboxamides </dd></dl>

<dl><dt>Acyl halides </dt><dd>alcohols Esters </dd></dl>

<dl><dt>Acyl cyanides </dt><dd>Alcohols Esters </dd></dl>

<dl><dt>Acyan cyanides </dt><dd>Amines Carboxamides </dd></dl>

<dl><dt>Alkyl halides </dt><dd>Amines Alkylamines </dd></dl>

<dl><dt>Alkyl halides </dt><dd>Carboxylic acids Esters </dd></dl>

<dl><dt>Alkyl halides </dt><dd>Thiols Thioesters </dd></dl>

<dl><dt>Alkyl halides </dt><dd>Alcohols Ethers </dd></dl>

<dl><dt>Sulfonic acids and their salts </dt><dd>Thiols Thioethers </dd></dl>

<dl><dt>Sulfonic acids and their salts </dt><dd>Carboxylic acids Esters </dd></dl>

<dl><dt>Sulfonic acids and their salts</dt><dd>Alcohols Ethers </dd></dl>

<dl><dt>Anhydrides </dt><dd>Alcohols Esters </dd></dl>

<dl><dt>Anhydrides </dt><dd>Amines Carboxamides </dd></dl>

<dl><dt>Aryl halides </dt><dd>Thiols Thioethers </dd></dl>

<dl><dt>Aryl halides </dt><dd>Amines Arylamines </dd></dl>

<dl><dt>Aziridines </dt><dd>Thiols Thioethers </dd></dl>

<dl><dt>Carboxylic acids </dt><dd>Amines Carboxamides </dd></dl>

<dl><dt>Carboxylic acids </dt><dd>Alcohols Esters </dd></dl>

<dl><dt>Carbodiimides </dt><dd>Carboxylic acids N-acylureas </dd></dl>

<dl><dt>Diazoalkanes </dt><dd>Carboxylic acids Esters </dd></dl>

<dl><dt>Epoxides </dt><dd>Thiols Thioethers </dd></dl>

<dl><dt>Haloacetamides </dt><dd>Thiols Thioethers </dd></dl>

<dl><dt>Imidic esters </dt><dd>Amines Amidines </dd></dl>

<dl><dt>Isocyanates </dt><dd>Amines Ureas </dd></dl>

<dl><dt>Isocyanates </dt><dd>Alcohols Urethanes </dd></dl>

<dl><dt>Isothiocyanates </dt><dd>Amines Thioureas </dd></dl>

<dl><dt>Maleimides </dt><dd>Thiols Thioethers </dd></dl>

<dl><dt>Sulfonic esters </dt><dd>Amines Alkylamines </dd></dl>

<dl><dt>Sulfonic esters </dt><dd>Thiols Thioethers </dd></dl>

<dl><dt>Sulfonic esters </dt><dd>Carboxylic acids Esters </dd></dl>

<dl><dt>Sulfonic esters </dt><dd>Alcohols Ethers </dd></dl>

<dl><dt>Sulfonyl halides </dt><dd>Amines Sulfonamides </dd></dl>

* activated esters of the general formula -CO-Part, Part representing a leaving group such as oxisuccinimidyl, oxybenzotriazolyl, optionally substituted aryloxy;

** Acyl azides can be rearranged to provide isocyanates.

A variant of this procedure consists in using a fluorescent chromophore that has an electrophilic acrylate function (-OCO-C = C-) in which an addition reaction is carried out that generates a ∋ bond.

A thiol reagent (∀) may also be used: Y'-SH comprising a Y 'group as defined above, whose nucleophilic function SH can react on the alpha carbon atom of the halogen atom supported by a fluorescent chromophore to conduct to the protected thiol fluorescent dye of formula (II '):

where R1, R2, R3, R4, Rg, R'g, Rh, R'h, Ta, Ri, R'i, m, n, G, Y ', (II') and Annals as defined above, and Hal representing a nucleophilic halogen atom such as bromine, iodine or chlorine.

More particularly, a nucleophilic leaving group may be substituted by a derivative of a thiourea (S = C (NRR) NRR) or thiourea to generate isothiouroniums. For example, if the thiourea derivative is a thioimidazolinium (#), the reaction scheme is as follows:

where R'c, R'd, Rg, R'g, Rh, R'h, Ri, R'i, m, n, G, Hal, An-as defined above.

Another variant may allow access to compound (II '' '' sat) from a cyclic thiourea derivative of the imidazoline type (b '), followed by the alkylation of said imidazoline with the aid of R'd-Gp with Gp as leaving group 20 such as chloride, bromide, tosylate, mesylate:

where R'c, R'd, Rg, R'g, Rh, R'h, Ri, R'i, m, n, G, Hal, An-as defined above.

A variant consists in using instead of the halide comprising the fluorescent chromophore (a ') a chromophore comprising another type of nucleophage, such as tosylate, mesylate.

According to another possibility, certain protected thiol fluorescent dyes (II ') can be obtained by reacting a protected thiol compound, with a compound that supports two activated carboxylic acid functions according to the classical methods (for example reaction with a carbodiimide or with the chloride of thionyl). The resulting product (d) is then reacted with a fluorescent chromophore carrying a nucleophilic function.

(c) for example of primary or secondary amine type, or of aliphatic alcohol type.

R1, R2, R3, R4, Rg, R'g, Rh, R'h, Ri, R'i, G, Ta, Y ', m, n, AN-, and (Il') being as They have defined above.

Another variant is to use a thiolactone derivative as represented by the following scheme: R1, R2, Rg, R'g, Rh, R'h, Ri, R'i, G, Ta, Y ', Met * being , n, m, An-, as defined above, representing G 'an oxygen, sulfur atom or an NR' group, R 'representing a hydrogen atom or an alkyl radical, and R representing a hydrogen atom , a C1-C4 alkyl radical, C1-C4 hydroxyalkyl or a

5 aryl (C1-C4) alkyl. The thiolactone derivative is preferably selected with n = 3, and G 'represents an oxygen atom.

A synthesis variant consists in combining the above route with the first route, that is, from two equivalents of the nucleophilic reagent (c) with a dielectrophilic disulfide reagent (i), it is possible to generate the dichromophore diisulfide product (I) after condensation ''), the latter being able to undergo a reduction to form the thiol dye

10 heterocyclic fluorescent which in turn can either be protected to form the protected thiol fluorescent dye (II '), or be metalated by an alkali metal to lead to the metalated heterocyclic thiol fluorescent dye (II' '):

According to another possibility, the protected thiol fluorescent dyes of formula (II ') can be obtained by the reaction of a compound comprising a thiol group protected by a Y' group, and a hydroxy group previously activated in the nucleophage leaving group (d '), such as mesylate, tosylate, triflate or halide with a styrylpyridine chromophore (c').

where R1, R2, R3, R4, Rg, R'g, Rh, R'h, Ri, R'i, G, Ta, Y ', m, n, (II') and

as defined above.

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

Another alternative comes from the use of halides as a nucleophobic leaving group on a thiol compound that can be substituted by a primary amine function, for example supported by a styryl fluorescent chromophore:

According to another possibility, 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 which comprises a nucleophile group. As an example, an aldehyde or a thioaldehyde can be condensed when G 'represents an oxygen atom or a sulfur

10 with an "activated methylene" such as alkylpyridinium (e) to generate an ethylenic bond&gt; C = C &lt;. This reaction is commonly called "Knoevenagel" condensation. By "activated methylenes" means those which preferably comprise in position 2 or 4 of the pyridinium group a methylene group R1-CH2-:

where R1, R2, R3, R4, Ra, Rb, Rg, R'g, Rh, R'h, Ri, R'i, Ta, m, n, Y and An-, as defined above, and 15 representing G an oxygen or sulfur atom.

Reference may be made to the Advanced Organic Chemistry document, "Reactions, Mechanisms and Structures", J. March, 4th ed., John Willey &amp; Sons, 1992 or TW Greene "Protective Groups in Organic Synthesis", for more details on the conditions of performance used for the procedures mentioned above.

The thiols formed fluorescent dyes can be transformed into protected thiols fluorescent dyes

twenty -SY 'by thiol protection -SH using the classic protective groups. Thiol fluorescent dyes are also metalated using the classical methods known to those skilled in the art such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4th ed., John Willey &amp; Sons, NY, 1992.

Protected thiol dyes can be unprotected by classical routes such as those described in the

25 "Protective Groups in Organic Synthesis" documents, TW Greene, John Willey &amp; Sons ed., NY, 1981; "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005.

The starting reagents are marketed or accessible by the classical methods known to those skilled in the art. By way of example, it is possible to synthesize the reagent (I ') from 2 equivalents of pyridine derivative 1 and an equivalent of disulfide reagent comprising two leaving groups Gp, to lead to the salt of

30 dipyridinium disulfide 3 which in turn can be condensed with two equivalents of aryl compound with aldehyde / thioaldehyde group 4 to lead to 5.

Gp representing a nucleophilic leaving group, such as mesylate, tosylate, triflate or halide. The Gp-counterions of the above compounds (I ') can be replaced by An-counterions of other natures from methods known to the person skilled in the art, in particular by ion exchange resin.

Asymmetric disulfide dyes of formula (I) can be synthesized in one step by reacting an unprotected thiol fluorescent dye with a Y 'protected thiol fluorescent dye to form the disulfide dye of formula (I).

where Rg, R'g, R "g, R" 'g, Rh, R'h, R "h, R"' h, Ri, R'i, R'i, R "i, m, m ', n, n ', Ta, Tb, G, G', Het and Annals as defined above; Y 'represents a thiol protecting group.

The symmetrical fluorescent disulfide dyes of formula (I ') can be synthesized by oxidation of the thiol (II) hemicianine dyes.

The oxidation can be carried out with an oxidizing agent that can eventually be associated. Any type of classical oxidizing agent may be used in the field. Thus, it can be selected from hydrogen peroxide, the

fifteen urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, as well as enzymes among which peroxidases, oxido-reductases with 2 electrons such as uricases, and oxygenases with 4 electrons such as lacquers. The use of hydrogen peroxide is particularly preferred.

where Rg, R'g, R "g, R" 'g, Rh, R'h, R "h, R"' h, Ri, R'i, R "i, R" 'i, m, m' , n, n ', Ta, Tb, G, G' and Annals as defined above; Y 'represents a hydrogen atom or an alkali metal, possibly a thiol protecting group in the case where this group can be deprotected with an oxidizing agent or an alkaline agent (such as, by

5 example, acyl groups).

According to another possibility, a disulfide compound (b1) can be reacted, said disulfide compound comprising two nucleophilic functions with a sufficient amount, preferably two equivalents, of a chromophore (a1) styryl hemicianine, and comprising an electrophilic function to form a group covalent bonding ∋; see below the preparation of dyes of formula (I ').

where Rg, R'g, Rh, R'h, R'i, R "i, m, n, G, An--, ∋, ,and

as defined above, provided that ∋ represents a subset of Ta defined in formulas (I) and (II).

A variant of this procedure consists in using a styryl hemicianine chromophore that has an electrophilic acrylate function (-OCO-C = C-) on which an addition reaction is carried out that will generate a covalent bond

fifteen in a link group ∋.

compound (b2) comprising a disulfide group and two leaving groups mesylate, tosylate, triflate or halide with a chromophore (a2) styryl hemicianine bearing an X-group representing Rg , R'g, Rh, R'h, R'i, R "i, m, n, G, An--, ∋,

a hydrogen atom or an alkali metal, representing X- a hydrocarbon chain bearing a nucleophilic group capable of replacing the group

Gp, such as an amino or hydroxy function, always being understood that ∋ represents a subset of Ta 5 defined in formulas (I) and (II).

The starting reactive agents are marketed or accessible by the classical methods known to those skilled in the art.

Reference can be made to the Advanced Organic Chemistry document, "Reactions, Mechanisms and Structures", J. March, 4th ed., John Willey &amp; Sons, 1992 or TW Greene "Protective Groups in Organic Synthesis", for more

10 details about the conditions used for the procedures mentioned above.

The thiol fluorescent dyes formed can be transformed into thiol-protected thiol fluorescent dyes by protecting thiol -SH using the classic protecting groups. Thiol fluorescent dyes are also metalated using the classical methods known to those skilled in the art, such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4th ed., John Willey &amp;

fifteen Sons, NY, 1992.

Protected thiol dyes can be unprotected by classical routes such as those described in "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed., NY, 1981; "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005.

Another object of the invention relates to a dyeing composition for coloring the keratin materials it contains.

twenty at least one disulfide fluorescent dye of formula (I) or thiol of formula (II). In addition to the presence of at least one fluorescent dye of formula (I) or (II), the composition of the invention may also contain a reducing agent.

This reducing agent can be selected from thiols, for example cysteine, homocysteine, thiolactic acid, salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid, as well as their esters, in

25 particularly glycerol monothioglycolate, and thioglycerol. This reducing agent can also be selected from borohydrides and their derivatives, such as the salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxyborohydride: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra- n-butylammonium, benzyltriethylammonium); the catechol-borane.

The dye composition useful in the invention generally contains an amount of fluorescent dye of formula (I)

30 or (II) comprised between 0.001 and 50%, with respect 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 with respect to the total weight of the composition.

The dye composition may also contain additional direct dyes. These direct dyes are selected, for example, from the neutral benzene, acidic or cationic nitrated direct dyes, the

35 direct azoic neutral, acidic or cationic dyes, tetraazapentametin dyes, quinonic and in particular neutral anthraquinonic dyes, acidic or cationic dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the natural direct dyes, lawsona, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogaline, protocatecaldehyde, indigo, isatin, curcumin,

40 Spinulosin, apigenidine. Extracts or decoctions containing these natural dyes and in particular poultices or henna-based extracts can also be used.

The dye composition may contain one or several oxidation bases and / or one or more couplers conventionally used to dye keratin fibers.

Among the oxidation bases, para-phenylenediamines, bis-phenylalkylenediamines, para45 aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts can be mentioned.

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

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

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

In general, the addition salts of the oxidation bases and of the couplers usable within the scope of the invention are selected in particular from the addition salts with an acid such as hydrochlorides,

10 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.

The appropriate dye medium, also called dye support, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. By way of solvent

fifteen organic, for example, lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and ethers of polyols 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.

The solvents, when present, are preferably present in proportions preferably

twenty between 1 and 99% by weight approximately with respect to the total weight of the dyeing composition, and even more preferably between 5 and 95% by weight approximately.

According to a variant, the composition of the invention contains a reducing agent capable of reducing the disulfide bonds of the keratin and / or disulfide of the fluorescent dyes of formula (I). This reducing agent is as defined above.

25 The dyeing composition may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, non-ionic, amphoteric, zwitterionic polymers or their mixtures, mineral or organic thickeners, and in particular the cationic, nonionic and amphoteric anionic polymeric associative thickeners, some antioxidant agents, some penetrating agents, some

30 sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or not, such as aminated silicones, film-forming agents, ceramides, preservatives , opacifying agents, conductive polymers.

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

Obviously, the person skilled in the art will attempt to select this or these possible complementary compounds in such a way that the advantageous properties intrinsically linked to the dye composition according to the invention are not, or are not substantially, altered by the addition (s) considered.

The pH of the dye composition is generally between about 3 and 14, and preferably

40 between 5 and 11 approximately. It can be adjusted to the desired value by acidifying or alkalizing agents commonly used in the dyeing of keratin fibers or also with the help of classical buffer systems.

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

Four. Five Among the alkalizing agents, for example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines, as well as their derivatives, sodium or potassium hydroxides and compounds of formula ( ∃) following:

wherein Wa is a propylene moiety optionally substituted by a hydroxy group or a C1-C4 alkyl radical; 50 Ra1, Ra2, Ra3 and Ra4, identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl.

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

Another object of the invention is a process of coloring keratin matter which consists in applying on said materials a composition comprising at least one dye of formula (I) or (II). According to a particular embodiment, in the process of the invention, a reducing agent can also be applied as a pretreatment before application of the composition containing at least one fluorescent dye of formula (I)

or (II).

This reducing agent can be selected from thiols, for example cysteine, homocysteine, thiolactic acid, salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid, as well as their esters, in particular monothioglycolate. of glyceol, and thioglycerol. This reducing agent can also be selected from borohydrides and their derivatives, such as salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxyborohydride: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tera- tera- n-butylammonium, benzyltriethylammonium); The Catecholborane

This pretreatment can be of short duration, in particular from 0.1 seconds to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent such as that mentioned above.

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

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

As an example, it is possible to deprotect the SY function with Y as a protecting group by adjusting the pH in this way:

<dl><dt>Y: protective group </dt><dd>check out </dd></dl>

<dl><dt>alkylcarbonyl, </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>arylcarbonyl, </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>alkoxycarbonyl, </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>aryloxycarbonyl, </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>arylalkoxycarbonyl </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>(di) (alkyl) aminocarbonyl, </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>(alkyl) arylaminocarbonyl </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>optionally substituted aryl such as phenyl </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>monocyclic heteroaryl with 5, 6 or 7 links such as oxazolium </dt><dd>pH&gt; 9 </dd></dl>

<dl><dt>bicyclic heteroaryl with 8 to 11 links such as benzoimidazolium, or benzoxazolium </dt><dd>pH&gt; 9 </dd></dl>

The deprotection stage can also be carried out during a hair pre-treatment stage such as the hair reduction pre-treatment, for example.

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

According to another method, the composition comprising at least one fluorescent coloring agent of formula (I)

or (II) also contains at least one reducing agent as defined above. This composition is then applied to the hair.

According to another variant, the reducing agent is applied as 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 seconds to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above. According to a particular embodiment, the reducing agent is a thiol or borohydride type agent as described above.

A particular embodiment of the invention relates to a process in which the fluorescent dye of formula (I) or (II) can be applied directly to hair without reducers, free of pre-or post-reducing treatments.

A treatment with an oxidizing agent may eventually be associated. According to a particular embodiment of the invention, the process according to the invention comprises a supplementary step by application of an oxidizing agent on the keratin fibers. Any type of classical oxidizing agent may be used in the field. Thus, it is possible to select between hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, as well as enzymes among which peroxidases, oxidoreductases with 2 electrons can be mentioned such as uricases, and oxygen with 4 electrons like lacases. The use of hydrogen peroxide is particularly preferred.

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

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

A subject of the invention is also a device with several compartments or "dye kit" in which a first compartment contains a dyeing composition comprising at least one fluorescent dye of formula (I)

or (II) and a second compartment containing a reducing agent capable of reducing the disulfide functions of the keratin materials and / or of the disulfide fluorescent dye of formula (I).

One of these compartments may also contain another or other direct dyes or oxidation dyes.

It also refers to a device with several compartments in which a first compartment contains a dyeing composition comprising at least one fluorescent dye of formula (I) or (II); one second

fifteen compartment contains a reducing agent capable of reducing the disulfide bonds of keratin materials and / or of the disulfide fluorescent dye of formula (I); A third compartment contains an oxidizing agent.

Alternatively, the dye device contains a first compartment containing a dye composition comprising at least one protected thiol fluorescent dye of formula (II) and a second compartment containing an agent capable of deprotecting the protected thiol to release the thiol.

twenty Each of the aforementioned devices may be equipped with a means that allows the desired mixture to be supplied on the hair, for example, such as the devices described in FR 2 586 913.

The following examples serve to illustrate the invention without thereby presenting a limiting character. The thiol fluorescent dyes of the following examples have been fully characterized by spectroscopic methods

25 and classic spectrometers.

Synthesis Examples

Example 1: Synthesis of 2,2'- (disulfanodiildiethane-2,1-diiI) -bis {5- [4 (dimethylamino) benzylidene] -5,6,7,8-tetrahydroisoquinolinium} [1 ]

Synthesis Scheme

Stage 1: synthesis of 2,2'- (disulfanodiildietan-2,1-diyl) bis (5,6,7,8-tetrahydroisoquinolinium) di-methane sulfonate

3.2 g of 5,6,7,8-tetrahydroisoquinoline and 0.7 g of potassium carbonate in 3 ml of acetonitrile are mixed and taken

5 at 80 ° C. A solution of 3.4 g of disulfanodiildietan-2,1-diyl dimethanesulfonate in 3 ml of acetonitrile is added in 10 min. Stirring is maintained for 8h at 80 ° C and then the reaction medium is allowed to return to room temperature, filtered and concentrated under vacuum. 6 ml of dichloromethane are added and the solution is poured dropwise onto 500 ml of ethyl ether. The decanted oil is re-treated twice by dilution in 6 ml of methanol and addition in 500 ml of ethyl ether, one last time by dilution in 6 ml of dichloromethane and addition

10 in 500 m of ethyl ether. After drying under vacuum, 5.2 g of brown solid are collected. The analyzes conform to the expected structure.

Stage 2: 2,2'- (disulfanodiildiethane-2,1-diyl) bis {5- [4- (dimethylamino) benzylidene] -5,6,7,8-tetrahydroisoquinolinium} [1]

2.1 g of 2,2'- (disulfanodiildiethane-2,1-diyl) bis (5,6,7,8-tetrahydroisoquinolinium) di-methane sulfonate are mixed and

fifteen 1.1 g of dimethylaminobenzaldehyde in 6 ml of methanol. 130 (l of piperidine are added and the mixture is stirred for 8h at 21 ° C. 65 (l of piperidine are added and stirring is maintained for 48h. 130 (l of piperidine are added and the mixture is kept under stirring for 24h. The mixture obtained is poured dropwise onto 500 ml of methyl ether butyl ether under strong stirring, a viscous oil is decanted. This is separated from the supernatant, diluted in 20 ml of dichloromethane and poured dropwise onto 500 ml of methyl ether-butyl ether. The red precipitate is filtered

twenty Orange formed, rinsed by 50 ml of methyl ether-butyl ether, collected in 20 ml of dichloromethane and poured back into 500 ml of methyl ether-butyl ether, filtered, clarified and dried. 2.2 g of a red solid are obtained. The analyzes show that you are satisfied.

Example 2: Synthesis of the di-methanesulfonate 2,2 '- (disulfanodiildibutane-4,1-diyl) bis {5 - [(4-methyl-3,4-dihydro-2H1,4-benzoxazin-7-yl) methylene] -5,6,7,8-tetrahydroisoquinolinium} [2]

Stage 1: synthesis of 2,2'- (disulfanodiildibutane-4,1-diyl) bis (5,6,7,8-tetrahydroisoquinolinium) di-methane sulfonate

2.1 g of 5,6,7,8-tetrahydroisoquinoline and 0.5 g of potassium carbonate are mixed in 2 ml of acetonitrile and brought to 100 ° C. A solution of 2.7 g of disulfanodiildibutan-4,1-diyl dimethanesulfonate in 2 ml of acetonitrile is added in 5 min. Stirring is maintained for 3h at 100 ° C and then the reaction medium is allowed to return to the

10 room temperature and concentrated under vacuum. 10 ml of dichloromethane are added, and the solution is filtered and then poured onto 100 ml of ethyl ether dropwise. The decanted oil is treated again by dilution in 10 ml of dichloromethane and addition in 500 ml of ethyl ether. After drying under vacuum, 3.3 g of brown oil are collected. The analyzes conform to the expected structure.

Stage 2: 2,2'- (disulfanodiildibutane-4,1-diyl) bis {5 - [(4-methyl-3,4-dihydro-2H-1,4-benzoxazin-715 yl) di-methane sulfonate methylene] -5,6,7,8-tetrahydroisoquinolinium} [2]

2.8 g of 2,2'- (disulfanodiildibutane-4,1-diyl) bis (5,6,7,8-tetrahydroisoquinolinium) di-methanesulfonate and 2 g of 4-methyl-3,4-dihydro are mixed -2H-1,4-benzoxazine-7-carbaldehyde in 28 ml of isopropanol. 0.7 g of piperidine are added and the mixture is stirred for 10 hours at 80 ° C. The mixture is cooled and concentrated under vacuum, collected in 20 ml of dichloromethane and poured over 200 ml of ethyl ether. A solid and an oil are formed. These are separated (filtration of the supernatant with the solid), the oil is collected by 20 ml of dichloromethane and the mixture is poured onto 200 ml of ethyl ether. A new solid fraction is collected. The solid fractions obtained are each collected in 20 ml of dichloromethane and concentrated under high vacuum. 1.7 g of red solid are collected. The analyzes show that the product conforms to the expected structure.

Example 3: Synthesis of 2,2'- (disulfanodiildiethane-2,1-diyl) bis [5 - ({4- [bis (2-hydroxyethyl) amino] phenyl} methylidene) -5,6,7-bis-mesylate , 8-tetrahydroisoquinolinium] [3]

10 Synthesis Scheme

Stage 1: synthesis of 2,2 '- (disulfanodiildiethane-2,1-diyl) di-5,6,7,8-tetrahydroisoquinolinium bis-mesylate

50.12 g of disulfanodiildiethane-2,1-diyl dimethane sulfonate are solubilized in 90 ml of N-methylpyrrolidinone (NMP). The mixture is heated to 90 ° C and 46.49 g of tetraisoquinoline are added, followed by 50 ml in addition to NMP and 10 ml.

fifteen of acetonitrile. After 4h at 90 ° C, the reaction mixture is poured into 1.7 L of ethyl acetate (AcOEt) and cooled to -10 ° C. The supernatant is removed, and the organic phase is washed with 100 ml of isopropanol iPrOH and 300 ml of diethyl ether, and then several times with ethyl acetate until tetrahydroisoquinoline is no longer detected by thin layer chromatography (MCC). After drying, 77.5 g of oil are collected. The analyzes agree with the expected structure in stage 1.

Stage 2: Synthesis of 2,2'- (disulfanodiildiethane-2,1-diyl) bis [5 - ({4- [bis (2-hydroxyethyl) amino] phenyl} -methylidene) 5,6,7-bis-mesylate , 8-tetrahydroisoquinolinium]

5.12 ml of piperidine are added to a suspension of 45.6 g of 4- [bis- (2-hydroxy-ethyl) -amino] -benzaldehyde and 50 g of 2,2'-bis-mesylate - (disulfanodiildiethane- 2,1-diyl) di-5,6,7,8-tetrahydroisoquinolinium in 200 ml of methanol. After 28h of stirring at room temperature, the reaction mixture is poured into 1 l of ethyl acetate. The resulting sticky oil is washed several times with acetone and then dried. The analyzes agree with the structure of the compound [3].

LC / MS gradient ACONH4 20 mM-&gt; CH3CN 10 min. ESI +/- m / z = 385; &amp; max = 468 nm.

1H NMR (ppm): 1.91 (mH,, 4H), 2.69 (s, 6.7H-methylate), 2.92 (t, 4H), 2.98 (t, 4H), 3.36 (t, 4H), 3.63 (t, 8H), 3.76 (t, 8H), 4.74 (t, 4H), 6.84 (d, 4H), 7.51 (d, 4H) , 7.65 (s, 2H), 8.25 (d, 2H), 8.44 (d, 2H), 8.51 (d, 2H).

Coloring example Example 1: Coloring procedure - compounds [1] and [2]

Preparation of a composition A

<dl><dt>Compound [1] or [2] </dt><dd>5x10-4 mol% </dd></dl>

<dl><dt>Benzyl alcohol </dt><dd>4 g </dd></dl>

<dl><dt>60E polyethylene glycol </dt><dd>6 g </dd></dl>

<dl><dt>Hydroxyethyl cellulose </dt><dd>0.7 g </dd></dl>

<dl><dt>Alkyl polyglucoside in 65% aqueous solution MA </dt><dd>4.5 g </dd></dl>

<dl><dt>Demineralized water </dt><dd>csp 100 g </dd></dl>

Preparation of a composition B

<dl><dt>Thioglycolic acid </dt><dd>1M </dd></dl>

<dl><dt>Sodium hydroxide </dt><dd>csp pH 8.5 </dd></dl>

<dl><dt>Demineralized water </dt><dd>csp 100 g </dd></dl>

At the time of use, the compositions A (9 ml) and B (1 ml) are mixed, and then the formulas are applied on 90% white (BN), permanent white (BP) or brown-brown hair strands. tone height 4 (HT4). The resting time is 20 minutes at room temperature TA.

After rinsing with running water, a fixative (Duclia Vital II®) diluted by 10 with water is applied for 5 minutes at RT. After rinsing with running water and washing with shampoo, the wicks are air dried, a lightening of the dark hair thus treated is observed: the wick HT4 has become visually lighter than untreated control wicks. The wicks of gray hair are colored with intense shades.

Visual observations

During rinsing and shampooing of the colorations obtained with compounds [1] and [2], there is no visible color shift, the foam of the shampoos and the rinse water are practically not colored.

The color observed is preserved on the colored BN and BP, and the lightening effect remains visible in the soaped HT4 hair.

Reflectance results to assess clearance:

The lightening yields of the compositions according to the invention have been expressed as a function of the reflectance of the hair. These reflectances are compared with the reflectance of a wick of untreated hair of pitch height HT4.

The reflectance is measured by a KONIKA-MINOLTA TA® spectrophotocolorometric device, CM 3600d and after irradiation of the hair with visible light in the wavelength range between 400 and 700 nanometers.

First, it is found that the reflectance of a wick of hair treated with a composition according to the invention is superior to that of untreated hair. Very particularly, the reflectance of the wicks treated with the dyes [1] and [2] is clearly superior to that of the reference wick in the wavelength range

5 greater than 560 nm. The wicks treated by these two compounds therefore appear clearer.

Results in the L * a * b * system to evaluate the coloration of HT4, BN, BP:

The color of the wicks has been evaluated in the L * a * b * system by means of a CM 3600D MINOLTA® spectrum spectrum meter (Illuminant D65).

In this system L * a * b *, L * represents the brightness, a * indicates the green / red axis and b * the color axis

10 blue yellow. 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. The higher the value of a *, the redder the hue and the higher the value of b *, the more yellow the hue.

The variation of the coloration between the hair strands HT4, colored and washed is measured by () E) according to the following equation:

In this equation, L *, a * and b * represent the values ​​measured before coloring, and L0 *, a0 * and b0 * represent the values ​​measured before coloring (or shampooing).

The more important the value of) E, the more important the difference in color between the wicks HT4 and the colored wicks.

twenty On dark hair HT4:

<dl><dt>Compounds </dt><dd>L * (D65) to * (D65) b * (D65) )AND </dd></dl>

<dl><dt>Reference HT4 </dt><dd> 20 2,69 3,02 ----- </dd></dl>

<dl><dt>Compound 1 </dt><dd> 20,53 5,72 3,84 3,19 </dd></dl>

<dl><dt>Compound 2 </dt><dd> 20,12 4,92 3,7 2,34 </dd></dl>

The values ​​indicated in the table above show the effect of coloring with lightening obtained on dark hair (HT4) through the use of compounds 1 and 2.

About BN and BP hair: Permanent gray and gray hair are colored bright orange.

L * (D65) a * (D65) b * (D65)

Natural gray hair 60.5 1.5 16.1 Compound 1 39.1 37.9 33.3 Compound 2 35.5 36.9 29.7

Permanent gray hair 60.9 1.8 17.0 Compound 1 38.9 39.8 33.5 Compound 2 36.0 38.5 30.5

Remanence against successive shampooing:

The treated wicks are divided in two, one half is subjected to 5 successive shampoo washes according to a cycle that includes the humidification of the wicks with water, the washing with a classic shampoo, a rinse with water 5 followed by drying.

Visual observations

During shampooing, there is no visible color shift, shampoo foam and rinse water are not colored.

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

Remanence against the light:

A study of light tenacity has been carried out by exposure to Xenotest on the wicks of natural gray hairs and gray hairs remained for 3 hours. The exposure conditions are 90 W / m2, 60% relative humidity and with a chamber temperature of 35ºC.

fifteen After 3 hours of exposure to light, the natural gray hair BN and permanent gray hairs BP colored with the dyes 1 and 2 of the invention have hardly changed.