BRPI0709369A2 - fluorescent dye, dye composition, process for staining keratin materials, multi-behavioral device and use of fluorescent dyes - Google Patents

Abstract

<B> FLUORESCENT DYE, DYE COMPOSITION, PROCESS FOR COLORING KERATIN MATERIALS, MULTICOMPARTMENT DEVICE AND USE OF FLUORESCENT DYES <D> The present invention relates to a dye composition comprising a fluorescent thiol dye! disulfide, which comprises an external cationic charge and a dyeing process that has a lightening effect on keratin materials, in particular on keratin fibers, in particular on human keratin fibers, such as hair, using said composition . It refers in a similar way to the new thiol / disinfectant fluorescent dyes and their uses in the keratin materials scoring. This composition makes it possible to obtain a visible and particularly resistant lightening effect on dark keratin fibers.

Description

"FLUORESCENT COLOR, COLOR COMPOSITION, PROCESS FOR COLORING KERATIN MATERIALS, MULTI-COMPARTMENT DEVICE AND USE OF FLUORESCENT COLORS"

Field of the Invention

The present invention relates to the staining of keratin materials using the thiol / disulfide fluorescent dyes comprising an external cationic charge.

Background of the Invention

It is common practice to dye keratin fibers, in particular human keratin fibers, by direct dyeing. The process conventionally used in direct dyeing comprises the application to keratin fibers of the direct dyes that are colored or dye molecules that have an affinity for the fibers, letting them diffuse and then rinsing the fibers.

Direct dyes that are conventionally used are, for example, nitrobenzene dyes, anthroquinone dyes, nitropyridine dyes, or azo, xanthene, acridine, azine or triarylmethane dyes.

The dyes that result from the use of direct dyes are temporary or semipermanent dyes, as the nature of the interactions that bind the direct dyes to the keratin fiber and its desorption from the fiber surface and / or core are responsible for its low power. dyeing and its low resistance to washing or perspiration operations.

Furthermore, staining of keratin fibers using conventional direct dyes does not make it possible to significantly lighten keratin fibers.

Lightening the color of keratin fibers, in particular from dark keratin fibers to lighter shades, by optionally modifying their shade, is an important demand.

Conventionally, in order to obtain a lighter coloration, a process for chemical discoloration is used. This process comprises the treatment of keratin materials, such as keratin fibers, in particular hair, with a strong oxidation system, generally hydrogen peroxide, possibly in combination with persals, in general. an alkaline medium.

This bleaching system has the disadvantage of damaging keratin materials, in particular keratin fibers, in particular human keratin fibers, such as hair, and of damaging their cosmetic properties in a harmful manner. In fact, fibers have a tendency to become rough, harder to detangle, and more fragile. Lastly, the bleaching or bleaching of keratin fibers using oxidizing agents is incompatible with treatments to modify the shape of said fibers, in particular in hair straightening treatments.

Another lightening technique comprises the application of direct fluorescent dyes to dark hair. This technique, described in particular in FR 2,830,189 and WO 2004/091473, makes it possible to retain the quality of keratin fiber during treatment, but the fluorescent dyes used do not exhibit satisfactory resistance to washing operations.

In order to increase the stability of direct dyes, it is a known practice to fix direct dyes by covalent bonding to the hair. For example, it is a known practice to react dyes comprising reactive groups with very numerous cystine or cysteine residues on keratin fibers; see, for example, Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91, 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509. In addition, it is a known practice to protect the thiol function (s) contained in a molecule to be grafted to the hair prior to application thereof to said hair, WO 99/51194. However, this application does not mention the use of fluorescent dyes for hair dyeing or lightening.

Other known disulfide dyes for dyeing keratin fibers are disulfide derivatives of aminothiophenol derivatives. Such dyes are described, for example, in FR 1,156,407. These dyes may be used under relatively mild conditions, in the presence of a slightly reducing medium or after a previous hair reducing treatment. However, these dyes can cause color changes during application.

Finally, WO 2005/097051 describes azoimidazole disulfide dyes for direct dyeing of keratin fibers.

Description of the Invention

The object of the present invention is to provide novel systems for dyeing keratin materials, in particular human keratin fibers, in particular hair, which do not have the disadvantages of existing bleaching processes. In particular, it is an object of the present invention to provide direct dyeing systems for obtaining bleaching effects, especially on naturally or artificially dark keratin fibers, which are resistant to successive washing operations which do not damage keratin fibers. and which do not adversely affect their cosmetic properties.

This object is achieved with the present invention, an object of which is a process for dyeing keratin materials, in particular keratin fibers, in particular human keratin fibers, such as hair, particularly dark hair. comprising the application of keratin materials of a dye composition comprising in a cosmetically acceptable medium at least one pyridinium fluorescent dye comprising an external cationic charge selected from the dyes of formula (I) or (II) below, down, beneath, underneath, downwards, downhill:

salts of organic or inorganic acid, their egeometric optical isomers, and solvates such as hydrates;

wherein in formula (I) or (II):

- Ra and R'a, which may be identical or different, represent a (C1-C4) arylalkyl group or a (C1-C6) alkyl group, optionally substituted by a hydroxyl, amino, (C1 -C4) alkylamino or (C1 -C4) dialkylamino group. -C4) 1 being possible for said alkyl radicals to form, with the nitrogen atom carrying them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom which may or may not be different from nitrogen; preferably Ra and / or R 'a represent a (C1-C3) alkyl group optionally substituted by a hydroxyl group or a benzyl group;

R'b and R'b, which may be identical or different, represent a hydrogen atom, an aryl (C1 -C4) alkyl group or an (C1 -C6) alkyl group which is optionally substituted; in particular, R'b and / or R'b represent a hydrogen atom or a (C1-C3) alkyl or benzyl group;

- R g, R'g, R "g and R" 'g, which may be identical or different, represent a hydrogen atom, an amino, (C1-C4) alkylamino (C1-C4) alkylamino or trifluoromethyl, a radical acylamino, (C1-C4) alkoxy, (C1-C4) alkylcarbonyloxy, (C1-C4) alkoxycarbonylamino (C1-C4) alkylcarbonylamino or (C1-C4) alkylsulfonylamino or a (C1-C3) alkyl radical;

-Rh, R'h, R "he R '" h, which may be identical or different, represent a hydrogen atom, a halogen atom, a (C1 -C4) dialkylamino or (C1 -C4) alkylcarbonylamino group. acylamino or C 1 -C 4 alkylsulfonylamino radical 1 or a C 1 -C 4 alkyl radical; in particular, R 1, R 1h, R "h and R '" h represent a hydrogen atom or a (C 1 -C 3) alkyl group;

- or two groups Rg and R'g; R "g and R" 'g; Rh and R'h; R "h and R" 'h, joined by two adjacent carbon atoms, together form a benzo ring or

indene, or a fused heterocycloalkyl or fused heteroaryl group; the benzo, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino, (C1 -C4) alkylamino (C1 -C4) dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl, acylamino, C1 -C4 alkoxy group , (C 2 -C 4) (poly) hydroxyalkoxy (C 1 -C 4) alkylcarbonyloxy 1 (C 1 -C 4) alkoxycarbonyl or (C 1 -C 4) alkylcarbonylamino 1 an acylamino, carbamoyl or C 1 -C 4 alkylsulfonylamino radical or an aminosulfonyl radical or a radical C1 -C16 alkyl optionally substituted by a group selected from C1 -C12 alkoxy, hydroxyl, cyano, carboxyl, amino, C1 -C4 alkylamino and C1 -C4 dialkylamino, or the other two alkyl radicals attached by amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical or different from that of the nitrogen atom; in particular Rg and R'g; R "g and R '" g together form a benzo group; - Ri, R ',; Rj "and R '" ,, which may be identical or different,

represent a hydrogen atom or a (C1 -C4) alkyl group; in particular a hydrogen atom;

- R 1, R 2, R 3, R 4 · R '1. R 2, R '3 and R 4, which may be identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl group in particular, R 1, R 2, R 3, R 4, R 1, R 2, R' 3 and R14 represents a hydrogen atom;

<formula> formula see original document page 7 </formula>

which may be present or absent represents a benzo group;

- Ta and Tb, which may be identical or different, represent:

(i) a covalent bond;

(ii) or a radical selected from -N (R) - and -N + (R) (Rc) -, wherein R and R0, which may be identical or different, represent a hydrogen atom, a C1-4 alkyl radical -C4 or C1-4 hydroxyalkyl or C1-4 arylalkyl;

(iii) or preferably a monocyclic, cationic or non-cationic, heterocycloalkyl or heteroaryl radical containing one or two heteroatoms, in particular two nitrogen atoms, and comprising in particular from 5 to 7 members, such as imidazole ; or a 6 member saturated heterocycle:

<formula> formula see original document page 7 </formula>

where A represents an oxygen or sulfur atom or a

group CH2 or NR01 wherein R0 is as defined above and An "represents an anionic counterion;

preferably Ta and Tb represent a covalent bond;

- m, m ', η and n', which may be identical or different, represent an integer between 0 and 6 inclusive, with m + n and m '+ n', which

can be identical or different, representing an integer between 1 and 10nclusive; in particular, the sum m + n = m '+ n' is an integer between 2 and 4 inclusive; preferably when Ta and Tb represent a covalent bond σ, m + n = m '+ n' is an integer equal to 2;

- when Ta represents a covalent bond σ, Y represents a group selected from:

- optionally substituted aryl such as phenyl,

dibenzosuberyl or 1,3,5-cycloheptatrienyl;

substituted, non-cationic or cationic, in particular aromatic heteroaryl, comprising from 1 to 4 heteroatoms, such as:

(i) monocyclic 5-, 6- or 7-membered heteroaryl such as furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or thienyl, pyrazolyl, oxazolyl,

oxazolium, isoxazolyl, isoxazolium, thiazolyl, thiazolium, isothiazolyl, isothiazolium, 1,2,4-triazolyl, 1,2,4-triazolium, 1,2,3-triazolyl, 1,2,3-triazolium, 1,2, 4-oxazolyl, 1,2,4-oxazolium, 1,2,4-thiadiazolyl, 1,2,4-thiadiazolium, pyryl, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine, azepinium, oxazepinyl, oxazepinium, tiepinil, tiepinium, imidazolyl, imidazole;

(ii) bicyclic heteroaryl comprising from 8 to 11 members, such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazole, thienocycloheptadienyls, or optionally monocyclic groups thereof; further groups such as (C1-C4) alkyl, for example methyl or (C1-C4) polyhaloalkyl, for example trifluoromethyl;

(iii) or the tricyclic heteroaryl ABC below:

wherein the two rings A, C optionally comprise a heteroatom, and ring B is a 5, 6 or 7 membered ring, in particular a 6 membered ring, and contains at least one heteroatom, for example piperidyl or pyranyl;

optionally cationic heterocycloalkyl, optionally substituted, the heterocycloalkyl group represents in particular a saturated or partially saturated 5, 6 or 7 membered monocyclic group comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / tetrahidrotiofenil, di / tetrahidropirrolil, di / tetrahydropyranyl, di / tetra / hexahidrotiopiranil, dihidropiridil, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydroazepinyl or di / tetrahydropyrimidinyl, these groups being optionally substituted by one or more groups such as (C1-C4) alkyl 1 oxo or thioxo; or the heterocycle represents the following groups:

<formula> formula see original document page 9 </formula>

wherein R'c, R'd, R'e, R'f, R'9 and R, h, which may be identical or different, represent a hydrogen atom or an alkyl group or two R'9 groups with R 'h, and / or R, and with R'f form an oxo or thioxo group, or R'9 with R'e together form a cycloalkyl; and ν represents an integer between 1 and 3 inclusive; preferably R'c to Rh represent a hydrogen atom; and An "represents an anionic counterion;

- optionally substituted (di) arylalkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted by one or more groups in particular selected from (C1 -C4) alkylC1 -C4 alkoxy such as methoxy hydroxyl, (C1 -C4) alkylcarbonyl and (di) (alkyl) amino (C1 -C4), for example dimethylamino;

- (di) heteroarylalkyl optionally substituted, the heteroaryl group is, in particular, cationic or non-cationic, monocyclic and comprises 5 or 6 members and from 1 to 4 heteroatoms selected from donitrogen, oxygen and sulfur, such as pyrrolyl, furanyl groups thiophenyl, pyridyl, pyridyl N-oxide, such as 4-pyridyl or 2-pyridyl N-oxide, pyryl, pyridinium or triazinyl, optionally substituted by one or more groups, such as (C1-C4) alkyl, particularly methyl, (di) heteroarylalkyl being advantageously (di) heteroarylmethyl or (di) heteroarylethyl;

- a sterically hindered cyclic group, such as the manada group;

- when Ta represents -N (R) -, -N + (R) (Rc) - or a cationic or non-cationic heterocycloalkyl or heteroaryl radical; Y represents a group selected from: (i) a hydrogen atom; (ii) a metal alkali; (iii) an alkaline earth metal; (iv) an ammonium group: N + RaRpRvR0 or a phosphonium group: P + RaRpRvR6 with Ra, Rp, Rv and Rc, which may be identical or different, representing a hydrogen atom or an alkyl group (Cr C4); or (v) a thiol function protection group; and

- M 'representing an anionic counterion;

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

Another object of the present invention is a dye composition comprising, in an acceptable cosmetic medium, at least one fluorescent dye selected from the dyes of formula (I) or (II) as defined above and, optionally, a reducing agent.

An object of the present invention is also novel fluorescent dyes of formula (I) or (II) as defined above. The dyeing process according to the present invention makes it possible to visibly color dark keratin materials, in particular the fibers of Dark human keratin, especially dark hair.

In addition, the process of the present invention makes it possible to obtain keratin materials, in particular human keratin fibers, in particular hair, without damaging that material which is persistent with respect to washing operations, common attacks (sunlight, perspiration) and other hair treatments. The process of the present invention also makes it possible to obtain lightening of keratin materials such as keratin fibers, preferably dark keratin fibers and more preferably dark hair.

For the purpose of the present invention, the term "dark keratin material" is intended to mean that it exhibits a brightness of L * measured in the C.I.E. L * a * b * less than or equal to 45 and preferably less than or equal to 40 since, in addition, L * = 0 is equivalent to black and L * = 100 is equivalent to white.

For the purpose of the present invention, the term "naturally or artificially dark hair" is intended to mean hair whose tone level is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (brownish brown).

Hair bleaching is assessed by variation in "tone level" before or after application of the compound of formula (I) or (II).

The notion of tone is based on the classification of natural tones, a tone separating each tone from the tone that immediately follows or precedes it. This definition and classification of natural hues is well known to hair stylists and is published in the book Science des traitements capillaires [Hair treatmentsciences] by Charles Zviak 1988, published by Masson1 pp. 215 and 278.

Tone levels range from 1 (black) to 10 (very light blonde), one unit corresponding to one tone; the bigger the picture, the brighter the tone.

Artificially colored hair is hair whose coloring has been modified by a dyeing treatment, for example, the pretense with direct dyes or oxidation dyes.

Preferably, the composition should, after application on hair, for example, on brownish brown hair, lead to the following results:

- interest is focused on hair performance performance levels when it is irradiated with visible light in the wavelength range of 400 to 700 nm;

reflectance curves as a function of wavelength, hair treated with the composition of the present invention and untreated hair are then compared;

- the curve corresponding to the treated hair must show a reflectance in the wavelength range of 500 to 700 nm which is greater than the curve corresponding to the untreated hair;

- this means that in the wavelength range 540 20 to 700 nm there is at least one interval where the reflectance curve

corresponding to the treated hair is larger than the reflectance curve corresponding to the untreated hair. The term "larger" is intended to mean a difference of at least 0.05% in reflectance, preferably at least 0.1%. Still, there may be, in the wavelength range from 540 to 700 nm, at least one interval where the reflectance curve corresponding to the treated hair is overlapping or less than the reflectance curve corresponding to the untreated hair.

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

For the purpose of the present invention, and unless otherwise indicated:

- "aryl" or "heteroaryl" radicals may be substituted by at least one carbon-borne substituent selected from:

- a C1-C16 alkyl radical, preferably CrCe;

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

- a hydroxyl group;

- a C1-C2 alkoxy radical;

- a C1-C2 alkylthio radical;

- a C2 -C4 (poly) hydroxyalkoxy radical;

- an amino radical;

- an amino radical substituted by one or two C1-C6 alkyl radicals, which may be identical or different, optionally bearing at least:

(i) a hydroxyl group,

(ii) an amino group,

- an acylamino radical (-NR-COR ') wherein the radical R is a hydrogen atom or a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the R' radical is a C1-C2 alkyl radical;

- a carbamoyl ((R) 2N-CO-) radical, wherein R radicals, which may or may not be identical, represent a hydrogen atom, or C1-C4 alkyl radical, optionally bearing at least one hydroxyl group;

- an alkylsulfonylamino radical (R'S02-NR-) wherein the radical R represents a hydrogen atom or a C1-C4 alkyl radical, optionally carrying at least one hydroxyl group, and the radical R 'represents a C1 alkyl radical -C4;

- an aminosulfonyl radical ((R) 2N-SO2-) wherein the R1 radicals which may or may not be identical represent a hydrogen atom or a C1-C4 alkyl radical, optionally bearing at least one hydroxyl group;

- a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium which is substituted or unsubstituted);

- a cyan group;

- a polyhaloalkyl group containing from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which may be identical or different; the polyhaloalkyl group is, for example, trifluoromethyl;

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

- hydroxyl;

C1 -C4 alkyl;

- C1 -C4 alkoxy;

- (poly) hydroxy C 2 -C 4 alkoxy;

- a C1-C2 alkylthio radical;

- RCO-NR'- wherein the radical R 'is a hydrogen atom or a C1-C4 alkyl radical, and the radical R is a hydrogen atom, a C1-C2 alkyl radical or an amino radical substituted by two alkyl groups Which may be identical or different, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle which is saturated or unsaturated, which is optionally and which comprises optionally at least one other heteroatom which may or may not be different from nitrogen,

- RCO-O- wherein the radical R is a C1-C4 alkyl radical or an amino radical substituted by one or two C1-C4 alkyl groups, which may be identical or different, said alkyl radicals possibly forming with the nitrogen atom at the same time. to which they are attached, a 5-7 membered saturated or unsaturated heterocycle which is optionally substituted and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen;

- RO-CO- wherein the radical R is a C1-C4 alkyl radical or an amino radical substituted by two C1-C4 alkyl groups, which may be identical or different, being possible for said alkyl radicals to form with the nitrogen atom to which they are attached, a 5- to 7-membered saturated or unsaturated heterocycle which is optionally substituted and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen;

an "aryl" radical represents a monocyclic or polycyclic group, condensed or non-condensed, containing from 6 to 22 carbon atoms, and at least one ring which is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;

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

- a "heteroaryl radical" represents a monocyclic or polycyclic, condensed or non-condensed, optionally cationic group comprising from 5 to 22 members and from 1 to 6 heteroatoms selected from one nitrogen, oxygen and sulfur atom, and at least one ring which is aromatic; preferably a heteroaryl radical is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, imidazopyridyl, oxidylimidazolyl, dihydrothiazolyl, benzhydrazolyl oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tiadiazolyl, thiazolyl, thiazolopyridinyl, thiazolylylthiazolylthiazolylthiazolylthiazolylthiazolylthiazolyl thiazolylthiazolyl thiazolylthiazolyl thiazolylthiazolyl thiazolylthiazolyl thiazolylazole;

- a "diheteroarylalkyl" radical represents a group comprising on the same carbon atom as an alkyl group, two heteroaryl groups, which may be identical or different, such as difurylmethyl, 1,1-difurylethyl, dipyrrolylmethyl or dithienylmethyl;

- a "cyclic" radical is a non-aromatic monocyclic or polycyclic cycloalkyl radical, condensed or non-condensed, containing from 5 to 22 carbon atoms, possibly comprising one or more unsaturation; in particular the cyclic radical is a cyclohexyl;

- a "sterically hindered cyclic" radical is a substituted or unsubstituted cyclic radical, aromatic or nonaromatic, hindered by steric effects or restrictions, comprising from 6 to 14 members, which may be punctuated; by sterically hindered radicals, mention may be made of bicyclo [1.1.0] butane, mesithiles such as 1,3,5-trimethylphenyl, 1,3,5-tri-tert-butylphenyl, 1,3,5 -isobutylphenyl, 1,3,5-trimethylsilylphenyl and adamantyl;

- a "heterocyclic radical" is a monocyclic or polycyclic condensed or non-condensed non-aromatic radical containing from 5 to 22 members, comprising from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium;

an "alkyl radical" is a C1-C16 hydrocarbon base radical, preferably C1-C8, straight or branched;

The term "optionally substituted" designated for the alkyl radical implies that said alkyl radical may be substituted by one or more radicals selected from the radicals: (i) hydroxyl; (ii) C1 -C4 alkoxy; (iii) acylamino; (iv) amino optionally substituted by one or two C1-C4 alkyl radicals, which may be identical or different, said alkyl radicals possibly form, with the nitrogen atom carrying them, a 5 to 7 membered heterocycle optionally comprising another heteroatom that may or may not be different from nitrogen;

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

- an "alkylthio radical" is an S-alkyl radical for which the radical

alkyl is a straight or branched C1 -C16 hydrocarbon base radical, preferably C1 -C6;

- The limits that delimit the range of values are included in this value range.

- an "organic or inorganic acid salt" is more particularly

selected from a salt derived from: (i) hydrochloric acid HCl; (ii) hydrobromic acid HBr; (iii) sulfuric acid H2 SO4; (iv) alkylsulfonic acids: Alq-S (0) 20H, such as methylsulfonic acid and ethylsulfonic acid; (v) arylsulfonic acids: Ar-S (0) 20H, such as benzenesulfonic acid and toluenesulfonic acid; (vi) citric acid; (vii) succinic acid; (viii) tartaric acid; (ix) lactic acid; (x) alkoxysulfinic acids: Alq-O-S (O) OH 1 such as methoxysulfinic acid and ethoxysulfinic acid; (xi) aryloxysulfinic acids, such as toluenoxysulfinic acid and phenoxysulfinic acid; (xii) phosphoric acid H3PO4; (xiii) acetic acid 25 CH 3 COOH; (xiv) CF3SO3H triflic acid and (xv) tetrafluoroboric acid HBF4;

- an "anionic counterion" is an anion or anionic group associated with the cationic charge of the dye; in particular, the anionic counterion is selected from: (i) halides, such as chloride or bromide; (ii) nitrates; (iii) sulfonates, including C1-C6 alkyl sulfonate: AIq-S (O) 2 O "such as methyl sulfonate or mesylate and ethyl sulfonate; (iv) aryl sulfonates: Ar-S (O) 2 O "such as benzene sulfonate and toluenesulfonate or tosylate; (v) citrate; (vi) succinate; (vii) tartrate; (viii) lactate; (ix) alkyl sulfates: AIq-OS (O) O "such as methyl sulfite and ethyl sulfite; (x) aryl sulfites: Ar-OS (O) O- such as benzenesulfite and toluenesulfite; (xi) alkyl sulfates; AIq-OS (O) 2 O ", such as methyl sulfate and ethyl sulfate; (xii) aryl sulfates: Ar-O-S (O) 2 O "; (xiii) phosphate; (xiv) acetate; (xv) triflate; and (xvi) borates, such as tetrafluoroborate.

Fluorescent dyes of formula (I) or (II) are capable of absorbing UV radiation or the visible range at an Xabs wavelength between 250 and 800 nm and capable of re-emitting within the visible range at an emission of the wavelength. wavelength between 400 and 800 nm.

Preferably, the fluorescent compounds of formula (I) or (II) are dyes capable of absorbing in the visible Xabs range between 400 and 800 nm and re-emitting in the visible Xe range between 400 and 800 nm. More preferably, fluorescent dyes are dyes capable of absorbing at a wavelength of Xabs between 420 nm and 550 nm and re-emitting within the visible range at a wavelength X ≤ 470 to 600 nm.

A specific embodiment relates to the dyes of formula (I) or (II) wherein Ta and Tb represent -N (R) -, -N + (R) (Rc) - or a cationic or non-cationic heterocycloalkyl or heteroaryl radical. More preferably, the thiol fluorescent dyes of formula (II) comprise a SY function, then comprise a group Y representing a hydrogen atom or an alkali metal; preferably Y represents a hydrogen atom.

According to another specific embodiment of the present invention, in the above mentioned formula (II) wherein Ta represents -N (R) - or -N + (R) (Rc) -Y is a protecting group and the protecting group is selected. from those known to those skilled in the art, for example those described in the books Protective Groups in Organic Synthesis, TW Greene1 Publisher John Willey & Sons, NY, 1981, pp. 193-217; Protecting Groups, P.

Kocienski, Thieme, 3rd ed., 2005, chap. 5

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

In particular, when Y represents a thiol function protecting group of the compound of formula (II), Y is selected from the following radicals:

C 1 -C 4 alkylcarbonyl;

C1 -C4 alkylthiocarbonyl;

- C1 -C4 alkoxycarbonyl;

- C1 -C4 alkoxythiocarbonyl;

C 1 -C 4 alkylthiothiocarbonyl;

- (di) (C1-4 alkyl) aminocarbonyl;

- (di) (alkyl) aminothiocarbonyl (C1-C4);

arylcarbonyl, such as a phenylcarbonyl;

aryloxycarbonyl;

aryl (C1-C4) alkoxycarbonyl;

(di) (C1 -C4) alkylcarbonyl such as dimethylaminocarbonyl;

- (C1-4 alkyl) arylaminocarbonyl;

carboxyl;

- SO3 "; M + wherein M + represents an alkali metal such as sodium or potassium, or M 'of formula (II) and M + are absent;

optionally substituted heteroaryl; including in particular the aromatic, cationic or non-cationic groups comprising from 1 to 4 heteroatoms below:

(i) monocyclics comprising 5, 6 or 7 members, such as furanyl or furyl, pyrrolyl or pyrril, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazole, isoxazolyl, isoxazolium, thiazolyl, isothiazolyl, isothiazole, 1,2, 4-triazolyl, 1,2,4-triazolium, 1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl, 1,2,4-oxazolium, 1,2,4- thiadiazolyl, 1,2,4-thiadiazolium, pyrillium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine, azepinium, oxazepinyl, oxazepinium, typinyl, tyrazidinium, imidazolium;

(ii) bicyclics comprising from 8 to 11 members, such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazole, pyridoimidazolyl, pyridoimidazole, thienocycloheptadienyl or these optionally monocyclic or monocyclic groups thereof groups such as alkyl, for example methyl or polyhaloalkyl, for example trifluoromethyl;

(iii) or the tricyclic ABC below:

wherein the two rings A, C optionally comprise a heteroatom, and ring B is a 5-, 6- or 7-membered ring, particularly 6-membered and contains at least one heteroatom, for example piperidyl or pyranyl;

optionally cationic heterocycloalkyl, optionally substituted, the heterocycloalkyl group represents in particular a saturated or partially saturated 5, 6 or 7 membered monocyclic group comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / tetrahidrotiofenil, di / tetrahidropirrolil, di / tetrahydropyranyl, di / tetra / hexahidrotiopiranil, dihidropiridil, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydroazepinyl or di / tetrahydropyrimidinyl, these groups being optionally substituted by one or more groups such as (C1-C4) alkyl, oxo or thioxo; or the heterocycle represents the following group:

<formula> formula see original document page 21 </formula>

wherein R, c, R, d, R'e, R'f, R'9 and R, h, which may be identical or different, represent a hydrogen atom or an alkyl group, or two R'9 groups having R'h, and / or R'e with R, f form an oxo or thioxo group, or R'9 with R'e together form a cycloalkyl; and ν represents an integer between 1 and 3 inclusive; preferably R'c to R'h represents a hydrogen atom; and An "represents a counterion;

isothiouronium -C (NR'cR'd) = N + R, eR'f; An "with R 'c, R, d, R, e and R' f, which may be identical or different, represents a hydrogen atom or an alkyl group; preferably R, ca R 'f represents a hydrogen atom; eAn "represents the counterion;

isothiourea -C (NR'cR'd) = NR, and with R, c, R, d, and R, and as defined above;

- optionally substituted (di) arylalkyl, such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted by one or more groups, in particular selected from alkyl, alkoxy, such as methoxy, hydroxyl, alkylcarbonyl and (di) (alkyl) ) amino, such as dimethylamino;

- optionally substituted (di) heteroarylalkyl, the heteroaryl group is, in particular, cationic or non-cationic, and monocyclic, comprising 5 or 6 members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl groups , furanyl, thiophenyl, pyridyl, pyridyl N-oxide, such as 4-pyridyl or 2-pyridyl N-oxide, pyryl, pyridinium or triazinyl, optionally substituted by one or more groups, such as alkyl, particularly methyl, advantageously (di) heteroarylalkyl is (di) heteroarylmethyl or (di) heteroarylethyl;

- CR1R2R3 with R11 R2 and R31 which may be identical or different, representing a halogen atom or a group selected from:

optionally substituted (C1-C4) alkyl, such as methyl or ethyl;

optionally substituted (C1 -C4) alkoxy, such as methoxy or oethoxy;

optionally substituted aryl such as phenyl optionally substituted by one or more groups such as alkyl; alkoxy or hydroxyl;

optionally substituted heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl or pyridyl optionally substituted by an alkyl group;

- P (Z1) Rm1Rm2R "3 with R" 1 and R "2, which may be identical or different, representing a hydroxyl, a C1 -C4 alkyl or alkoxy group;

representing a hydroxyl or alkoxy group; and Z 1 representing an oxygen or sulfur atom;

- a sterically hindered cyclic group; and

optionally substituted alkoxyalkyl, such as methoxymethyl (MOM), ethoxyethyl (EOM) or isobutoxymethyl.

In particular, the Y group of the fluorescent dye of formula (II) represents an alkali metal or a protecting group such as:

C 1 -C 4 alkylcarbonyl such as methylcarbonyl or aethylcarbonyl;

arylcarbonyl, such as phenylcarbonyl;

- C1 -C4 alkoxycarbonyl;

aryloxycarbonyl;

aryl (C1-C4) alkoxycarbonyl;

(di) (C1 -C4 alkyl) aminocarbonyl, such as dimethylaminocarbonyl;

- (C1-C4) (alkyl) arylaminocarbonyl;

optionally substituted aryl such as phenyl;

- 5- or 6-membered cationic monocyclic heteroaryl such as opium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium or imidazolium; these groups being optionally substituted by one or more identical or different (C1-C4) alkyl groups, such as methyl;

8 to 11 membered cationic bicyclic heteroaryl such as benzoimidazole or benzoxazolium; these groups being optionally

substituted by one or more identical or different (C1-C4) alkyl groups, such as methyl;

- cationic heterocycle of formula below:

<formula> formula see original document page 23 </formula>

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

- isothiurea -C (NH 2) = NH;

- SO3 ", M + with M + representing an alkali metal such as sodium or potassium, or M 'of formula (II) and M + are absent.

According to a specific embodiment, the protected thiol fluorescent dyes of formula (II) comprising a group Y (i) which is a cationic aromatic 5- or 6-membered monocyclic heteroaryl group comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazole, isothiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,4-oxazole, 1,2,4-thiadiazole, pyrillium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, tiepinyl, tiepinium or imidazolium; (ii) cationic 8 to 11 membered bicyclic heteroaryl group such as indolinium, benzoimidazole, benzoxazolium or benzothiazolium, these monocyclic or bicyclic heteroaryl groups being optionally substituted by one or more groups such as alkyl, for example methyl, or (C1 -C4) polyhaloalkyl for example trifluoromethyl (iii) or a heterocyclic group below:

<formula> formula see original document page 24 </formula>

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

According to another specific embodiment, when Ta and Tb represent a covalent bond, in particular, the protected thiol fluorescent dyes of formula (II) then comprise a group Y (i) which is a 5- or 6-membered monocyclic aromatic heteroaryl group , cationic, comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as oxazole, isoxazolium, thiazole, isothiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2, 4-oxazolium, 1,2,4-thiadiazolium, pyrilium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, tiepinyl, tiepinium or imidazolium; (ii) 8 to 11 cationic bicyclic heteroaryl group, such as indolinium, benzoimidazole, benzoxazole or benzothiazolium, these monocyclic or bicyclic heteroaryl groups being optionally substituted by one or more groups, such as alkyl, for example methyl, or polyhaloalkyl, for example trifluoromethyl (iii) or a heterocyclic group below:

<formula> formula see original document page 25 </formula>

wherein R'c and R'd, which may be identical or different, represent an alkyl group; preferably R'c to R'd represent an alkyl group; such as methyl; and An- represents an anionic counterion.

In particular, Y represents a group selected from oxazole, isoxazolium, thiazole, isothiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,4-oxazole, 1,2,4-thiadiazole pyrillium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium, benzoimidazole, benzoxazolium and benzothiazole, these groups being optionally substituted by one or more (C1 -C4) alkyl groups, in particular methyl.

In accordance with a specific embodiment of the present invention, the fluorescent dyes of the present invention are of formula (Ia), (IIa), (Ib), (IIb), (Ic) or (IIc), each having an ethylene group which has been substituted. attaches the pyridinium moiety to the phenyl moiety at the ortho or para positions at 4-4 ', 4-2', or 2-4 'positions at (Ia), (lia), (Ib) or (llb), or at the positions 4-5 'or 2-5' to (Ic) or (llc):

<formula> formula see original document page 25 </formula> <formula> formula see original document page 26 </formula>

in whose formula (Ia) or (lia):

R1a and R2a, which may be identical or different, represent a benzyl or alkyl group, optionally substituted by a hydroxyl group, such as methyl, ethyl or hydroxyethyl;

- R1b and R2b which may be identical or different, represent a hydrogen atom, a benzyl or alkyl group such as methyl or ethyl;

- T'a and T'b, which may be identical or different, represent a bond σ; or an -N + (R) (Rc) - group with R and R 0, which may be identical or different, representing an alkyl group such as methyl; or T1a and T'b represent an imidazolium group;

- Y 'represents a group selected from imidazole, thiazole; oxazole; 1,2,4-triazole; pyridinium; pyrimidine; benzoxazolium and benzothiazole; these groups being substituted by one or more alkyl groups which may be identical or different, such as methyl or ethyl;

- m, m ', η and n', which may be identical or different, represent an integer between 1 and 6 inclusive, with m + n = ητι '+ η' representing an integer between 2 and 6 inclusive, in particularly, when Ta and T'b represent a bond σ, then the sum m + n = m '+ n' is an integer equal to 2;

- M 'represents an anionic counterion; in whose formulas (Ib) or (llb):

- Ra, R1a, Rbi R'bi Ri> R'h R "i> R" Ri, R'i. R2, R2, R3, R3, R4, R'4, Ta, Tb, m, rrT, n, n 'and Y are as defined above;

- R g, R'g, R "g and R '" g, which may be identical or different, represent a hydrogen atom, a halogen atom, a group

amino, (C1-C4) alkylamino, (C1-C4) dialkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, an acylamino radical, (C1-C4) alkoxy, (poly) hydroxy C2-C4 alkoxycarbonyloxy, (C1-C4) alkoxycarbonyl or (C1-C4) alkylcarbonylamino, an acylamino, carbamoyl, (C1-C4) alkylsulfonylamino or aminosulfonyl group, or a (C1-C16) alkyl radical optionally substituted by a group selected from alkoxy ( C 1 -C 12), hydroxyl, cyano, carboxyl, amino, C 1 -C 4 alkylamino and C 1 -C 4 dialkylamino, or other of the two alkyl radicals attached by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical or different from that of the nitrogen atom; in particular Rg and R'g; R "g and R '" g represents a hydrogen or halogen atom or a (C1-C3) alkyl group, advantageously Rg and R'g; R "g and R '" g represents a hydrogen atom;

Rh and R'h; R "h and R '" h, joined by two adjacent carbon atoms, together form a benzo or indene ring, or a group

fused heterocycloalkyl or fused heteroaryl; the benzo, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino, (C1-C4) alkylamino, (C1-C4) dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl, acylamino, C1-C4 alkoxy group C 2 -C 4 (poly) hydroxyalkoxy, C 1 -C 4 alkylcarbonyloxy 1 C 1 -C 4 alkoxycarbonyl or C 1 -C 4 alkylcarbonylamino 1 an acylamino, carbamoyl or C 1 -C 4 alkylsulfonylamino radical or an aminosulfonyl radical or a radical (C1-C16) alkyl optionally substituted by a group selected from (C1-C12) alkoxy, hydroxyl, cyano, carboxyl, amino, (C1-C4) alkylamino and (C1-C4) dialkylamino, or the other two alkyl radicals attached by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical or different from that of the nitrogen atom; in particular Rh and R'h; R "h and R" 'h together form a benzo group; and

in which formula (Ic) or (llc):

- Ra, R 'a, Rb, R'b, Ri, R' i, Ri, R'i, R2, R'2, R3, R'3> R4, R'4, Ta, Tb, m, m ', n, n' and Y are as defined above;

-Rg, R'g, R "g, R" 'g, Rhl R'h, R "he R'" h, which may be identical or different, represent a hydrogen atom, a halogen atom, an amino group, C 1 -C 4 alkylamino, C 1 -C 4 dialkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C 1 -C 4 alkoxy, C 2 -C 4 (poly) hydroxyalkoxy, C 1 -C 4 alkylcarbonyloxy ) 1 (C1-C4) alkylcarbonylamino 1 an acylamino, carbamoyl, (C1-C4) alkylsulfonylamino radical or an aminosulfonyl group, or a (C1-C16) alkyl radical optionally substituted by a group selected from (C1-C12) alkoxy , hydroxyl, cyano, carboxyl, amino, (C1-C4) alkylamino and (C1-C4) dialkylamino 1 or other of the two alkyl radicals attached by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and, optionally, comprising another heteroatom identical or different from that of the nitrogen atom; in particular Rg and R'g; Rh and R'h represent a hydrogen or halogen atom or a (C1-C3) alkyl group; advantageously Rh and R'h represent a hydrogen atom, it being understood that when the compound of formula (Ia), (IIa), (Ib) 1 (IIb) 1 (Ic) or (IIc) contains other cationic moieties, It is associated with one or more counterions enabling formulas (Ia), (IIa), (Ib), (IIb), (Ic) or (IIc) to obtain electroneutrality.

Another specific embodiment of the present invention relates to the symmetric disulfide dyes of formula (I), that is, Ra, Rb, Rg, R'g, Rh, R'h, Ri, R'i, R1, R2, R3, R4, Ta, me and η are identical to R'a, R1bl R "g, R '" g. R "n, FTh, R" i. R "'i, R' 1, R 12, R '3, R' 4, Tbl m 'and n', respectively.

By way of example of the fluorescent dyes of the present invention, particular mention may be made of the following dyes:

<table> table see original document page 29 </column> </row> <table> <table> table see original document page 30 </column> </row> <table> <table> table see original document page 31 < / column> </row> <table> <table> table see original document page 32 </column> </row> <table> <table> table see original document page 33 </column> </row> <table> <table> table see original document page 34 </column> </row> <table> <table> table see original document page 35 </column> </row> <table> <table> table see original document page 36 < / column> </row> <table> <table> table see original document page 37 </column> </row> <table> <table> table see original document page 38 </column> </row> <table> <table> table see original document page 39 </column> </row> <table> <table> table see original document page 40 </column> </row> <table> <table> table see original document page 41 < / column> </row> <table> <table> table see original document page 42 </column> </row> <table> <table> table see original document page 43 </column> </row> <table> <table> table see original document page 44 </column> </row> <table> <table> table see original document page 45 </column> </row> <table> <table> table see original document page 46 </column> </row> < table> - with M 'and An ", which may be identical or different, representing an anionic counterion; and M + representing an alkali metal.

With An "and M ', which may be identical or different, representing an anionic counterion such as halides, for example chloride or bromide; nitrates; sulfonates, including C1-C6 alkylsulfonates: Alq-S (0 ) 20 ", such as methylsulfonate or mesylate and ethylsulfonate; arylsulfonates: Ar-S (O) 2O ", such as benzenesulfonate and toluenesulfonate or tosylate; citrate; succinate; tartrate; lactate; alkyl sulfates: AIq-OS (O) O", such as methyl sulfate and ethyl sulfate; aryl sulfates: Ar-O-S (O) O ", such as benzene sulfate and toluene sulfate; alkoxy sulfates: Alk-O-S (O) 2 O", such as methoxy sulfate and ethoxy sulfate; aryloxy sulfates: Ar-O-S (O) 2 O ", phosphate; acetate; triflate; and borates such as tetrafluoroborate.

Protected thiol dyes of formula (II ") may be synthesized in two stages. The first stage is the preparation of unprotected thiol dye (II") according to methods known to those skilled in the art, for example, Thiols and organic Sulfides , Thiocyanates and Isothiocyanates, organic, Ullmann's Encyclopaedia, Wiley-VCH, Weinheim, 2005. In addition, the second stage is the protection of thiol function according to conventional methods known to those skilled in the art for the production of thiol-protected dyes. formula (II). By way of example for the protection of thiol -SH function of the thiol dye, methods may be used in the Protective Groups in Organic Synthesis1 T.W. Greene, ed. John Willey & Sons, NY, 1981, pp. 193-217; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, chap. 5

This method can be illustrated by the method which consists of (i) producing thiol fluorescent dyes by reducing a bi-chromophore fluorescent dye carrying a disulfide function -SS- such as (Γ) and (ii) in protection according to with conventional methods, said thiol function of the compounds (ΙΓ) to obtain the protected thiol fluorescent dyes of formula (II ").

<formula> formula see original document page 48 </formula>

with R1, R2, R3, R4, Ra, Rb, Rg, R'g, Rh, R'h, Ri, R'i, Ta, m, η and M 'being as defined above and R representing a leaving group nucleophobic, for example mesylate, tosylate, triflate or halide.

According to another possibility, a thiol compound protected in (b) by a Y-protecting group as defined above, prepared according to one of the procedures described in the books mentioned above, said protected thiol compound comprising at least one nucleophilic function, may be reacted with a sufficiently preferably equimolar amount of a "reactive fluorescent chromophore" or a compound comprising such a "reactive fluorescent chromophore" (a). In other words, (a) comprises an electrophilic function to form a covalent bond, as can be seen schematically below:

<formula> formula see original document page 48 </formula> <formula> formula see original document page 49 </formula>

being as defined above; Nu represents an amino or heterocycloalkyl or heteroaryl nucleophilic group; And representing a nucleophobic group, such as, for example, mesylate, tosylate, triflate or halide, for example bromine, iodine or chlorine. Σ represents a radical selected from -N (R) - and -N + (R) (R °) wherein R and R0 as defined above, and heterocycloalkyl and heteroaryl, which may be cationic or noncationic.

Use may also be made of a thiol reagent Y-SH comprising a group Y, the nucleophilic SH function which may react with the carbon atom at the alpha position with respect to the halogen atom carried by the fluorescent chromophore (a ') of to provide the protected thiol fluorescent dye of formula (II):

<formula> formula see original document page 49 </formula>

with R1, R2, R3, R4, Ra, Rb, Rg, Rg, Rh, Rh, R, Ri, Ri, Ta, Y, m, n, and M'sendo as defined above; and Hal representing a nucleophobic halogen atom, such as bromine, iodine or chlorine.

A thioacid (a) (e.g. thioacetic acid) which will react with a halide attached to the fluorescent chromophore (a1) may also be used. <formula> formula see original document page 50 </formula>

with Ra> Rb, Rg, R'g, Rh> R'h, Ri, R'i, m, n, Hal and M 'being as defined above and R' representing a (C1-C6) alkyl group.

More particularly, a nucleophobic leaving group may be substituted by a thiourea group (S = C (NRR) NRR) to produce the isothiourons. For example, if the thiourea group is a thioimidazole (β), the reaction scheme is as follows: being as defined above.

A variation is to use, in place of the halide comprising the fluorescent chromophore (a '), a chromophore comprising another type of nucleophobe, such as tosylate or mesylate.

In another variation, it is possible to produce an imidazoline intermediate using the halide comprising the fluorescent chromophore (a ') and a thioimidazoline (b') so as to produce, upon alkylation with an R-Lg1 with R represented a group Alkyl is a leaving group such as halogen, for example chlorine, bromine, iodine, or a mesylate or tosylate group.

A nucleophobic leaving group may also be substituted by thiosulfate salts (eg sodium thiosulfate or potassium thiosulfate) to produce Bunte salts (-SSO3 ", Na + or K +):

<formula> formula see original document page 51 </formula>

with Ra, Rb, Rg1 Rgl Rh, R'h, Ri, R'i, m, n, Hal and M ', as defined above, and M + representing an alkali metal, such as sodium or potassium.

According to another possibility, certain protected thiol group (ΙΓ) fluorescent dyes can be obtained by reacting a protected thiol group compound by carrying a compound with a nucleofuge function (d) which is reacted with a flourishing chromophore carrying a nucleophilic function ( c) of primary or secondary amine of heterocycloalkyl or heteroaryl type:

With R1 R2, R3. R4, Ra, Rb, Rg1 R'g, Rh1 R'h, Ri, R'i, Ta, Yfm, η, M ', E, Nu and (II ") as defined above.

According to another possibility, the protected thiol fluorescent dyes of formula (II) may be obtained by reacting a compound comprising a protected group thiol with a group Y and a hydroxyl group 10 activated in advance to a nucleofugal leaving group (d ' ), for example mesylate, tosylate, triflate or halide, with a flourishing chromophore (c ') carrying a nucleophilic primary amine function where R b represents a hydrogen atom or a secondary amine.

<formula> formula see original document page 52 </formula>

With R1, R2, R3, R4, Ra, Rb, Rg, R'g, Rh, Rh1 Ri, R '', Ta, Y, m, n, M 'and E as defined above.

By way of example, a compound containing a protected thiol group contains an R-nucleofugal leaving group, for example mesylate, tosylate or triflate, which may be nucleophilically attacked by an aminas supported by a sterile flourishing chromophore:

Another alternative comes from the use of halides as nucleofuge leaving groups in a thiol compound that can be substituted with a secondary amine function, for example supported by a sterile flourishing chromophore:

<formula> formula see original document page 53 </formula>

According to another possibility, certain protected detiol fluorescent dyes (II) according to the present invention may be obtained by reacting a compound comprising a thiol group Y as defined above and an electrophilic group (f) with a compound comprising a nucleophilic group. As an example, an aldehyde or ketone when G represents an oxygen atom may be condensed with an "activated methylene" such as alkylpyridinium (e) to generate an ethylene bond.> C = C <This reaction is commonly known as condensation of "Knoevenagel". The term "activated methylenes" is intended to mean those mentioned, for example, in DE 19,951,134; particular mention may be made of 1,2-dialkylpyridinium, and in particular 1,2-dimethylpyridinium:

<formula> formula see original document page 53 </formula> with R1 R2, R3, R4, Ra, Rbl Rg, R'g, Rh, R'h, R'i, Ta, Y, m, η and M ' as defined above and G represents an oxygen or sulfur atom or an N (R) group with R representing a hydrogen atom or a (C1-C4) alkyl group.

Another variation of this reaction scheme is to carry out a "Knoevenagel" condensation reaction subsequently, that is, using intermediate (f), the amino group NR'R "can react with an equivalent of the Lg- (CR3R4) -Lg reagent. (i ') which may itself react with a protected thiol Y'SH to provide the aldehyde intermediate (j'). This intermediate may undergo the "Knoevenagel" condensation reaction with the alkylpyridinium (e) to to provide

the protected naphthyl thiol fluorescent dye (II ").

<formula> formula see original document page 54 </formula> with R ', R ", R1, R2, R3, R4, Ra, Rb, Rg, R'g, Rh, R'h, Ri, m, n, Y 'and M' as defined above, Lg represents a leaving group such as a halogen atom, in particular Br or I, or a tosylate, mesylate or triflate group, and Lg "represents the anionic counterion following the leaving of the leaving group Lg.

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

The formed thiol fluorescent dyes may be converted to the -S Y 'protected thiol fluorescent dyes by protecting the -SH thiol using conventional protecting groups. Thiol fluorescent dyes may also be metallized by also using conventional methods known to those skilled in the art, such as those described in Advanced Organic Chemistry, Reactions, Mechanisms and Structures, J. March, 4th ed. John Willey & Sons, NY 1992.

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

Starting reagents are commercially available or accessible by conventional methods known to those skilled in the art. By way of example, in order to synthesize the fluorescent dye of two phenyl / naphthyl chromophores carrying a disulfide function -SS (Γ), it is possible to start from a bifunctionalised naphthyl reagent (k), which comprises at position 2 a group nucleophobe GR with R representing a (C1-C4) alkyl, mesylate, tosylate or triflate group and G 'representing an oxygen or sulfur atom or an N (R) group with R representing a hydrogen atom or (C1-C4) alkyl group ), and comprising in position 6 an aldehyde or thioaldehyde electrophilic group. The two equivalents of this reagent may be reacted with diamine dialkyl disulfide (1) to provide, after condensation, the dialdehyde / thioaldehyde disulfate (m), which may condense with two equivalents of alkylpyridinium (e) to form compound (Γ).

<formula> formula see original document page 56 </formula>

Reference may be made to the book Advanced Organic Chemistry, J. March 14th ed. John Willey & Sons, 1992 or T.W. Greene Protective Groups in Organic Synthesis, for further details on the operant conditions used for the processes mentioned above.

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

<formula> formula see original document page 56 </formula> being Ra, R'a, Rb1 R't>. Rg> R'g. R "g. R '" g, Rh. R'h, R "h. R" 'hi Ri. R'i, R "i, R '" i, R1, R'i, R2, R'2, Rs. R'3, R4, R'4, m, m, n, n ', Ta, Tb and M' as defined above; Y 'represents a thiol function protecting group.

The composition of the present invention contains at least one fluorescent dye of formula (I) or (II). In addition to the presence of at least one fluorescent dye of formula (I) or (II), the composition of the present invention may also contain a reducing agent. This reducing agent may also be selected from thiols, for example cysteine, homocysteine or thiolactic acid, salts of these thiols, phosphines, bisulfide, sulfides, thioglycolic acid, and also their esters, in particular monothioglycolate and thioglycerol. This reducing agent may also be selected from borohydrides and their derivatives, for example borohydride, cyanoborohydride or triacetoxyborohydride or trimethoxyborohydride salts: sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-n-butylammonium or benzyltriethylammonium); Borane catechol.

The dye composition which may be used in the present invention generally contains an amount of fluorescent dye of formula (I) or (II) between 0.001% and 50% with respect to the total weight of the composition. Preferably, this amount is from 0.005% to 20% by weight, more preferably from 0.01% to 5% by weight, relative to the total weight of the composition.

The dye composition may also contain additional direct dyes. These direct dyes are, for example, selected from neutral, acidic or cationic nitrobenzene direct dyes, azo neutral, acidic or cationic direct dyes, tetraazopentametin dyes, neutral, acidic or cationic dyes, in particular, anthraquinone, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the natural direct dyes, mention may be made of lawsone, juglone, alizarin, glitter, carminic acid, kermesic acid, purpurogalin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenindin. Decoction extracts containing these natural dyes, and in particular poultices or henna extracts, may also be used.

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

Among the oxidation bases, mention may be made of para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, orfo-aminophenols, heterocyclic bases and their addition salts.

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

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

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

In general, the addition of salts of the oxidation bases and couplers which may be used in the context of the present invention are in particular selected from the addition of salts with an acid such as chlorides, bromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the addition salts with a base, such as alkali metal hydroxides such as sodium or potassium, aqueous ammonium, amines or alkanolamines.

A suitable dyeing medium, also called dye support, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. As an organic solvent, mention may be made, for example, of lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof .

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

The dye composition may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic polymers or mixtures, thickeners inorganic or organic compounds, and in particular anionic, cationic, nonionic associative polymeric thickeners, amphoters, antioxidants, penetrating agents, sequestering agents, fragrances, tampons, dispersing agents, conditioning agents such as modified or unmodified silicones, volatile or nonvolatile, such as amino silicones, film-forming agents, ceramides, preservatives, opacifiers or conductive polymers.

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

Of course, those skilled in the art will exercise care in selecting this or these possible additional compounds such that the advantageous properties intrinsically associated with the dye composition according to the present invention are not or are not substantially impaired by the subject (s). addition (s) contemplated.

The pH of the dye composition is generally from about 4 to 14, preferably from about 5 to 11. It can be adjusted to the desired value by acidifying or basifying agents commonly used in dyeing keratin fibers. or by conventional buffer systems.

Among the acidifying agents, mention may be made, for example, of organic or inorganic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for example acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.

Among the basifying agents, mention may be made, by way of example, of aqueous ammonia, alkaline carbonates, alkanolamines such as mono, di and triethanolamines, as well as derivatives thereof, sodium hydroxide or potassium hydroxide and the compounds of formula (Y) below:

<formula> formula see original document page 60 </formula>

wherein Wa is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; Ra ', Ra2, Ra3 and Ra4' which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a hydroxyalkyl radical.

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

The coloring process of the present invention consists in applying the composition of the present invention to keratin materials, in particular keratin fibers, in particular human keratin fibers such as hair, particularly dark hair, the composition The dye of the present invention comprises at least one fluorescent dye of formula (I) or (II).

According to a specific embodiment in the process of the present invention, a reducing agent may be applied as a pretreatment prior to application of the composition containing at least one fluorescent dye of formula (I) or (II).

This reducing agent may be selected from thiols, for example cysteine, homocysteine or thiolactic acid, salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid and also their esters, in particular, monothioglycolate. glyceryl and thioglycerol. This reducing agent may also be selected from borohydrides and their derivatives, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-n-butylammonium or benzyltriethylammonium); Borane catechol.

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

According to another process, the composition comprising at least one fluorescent dye of formula (I) or (II) also contains at least one reducing agent as defined above. When the thiol fluorescent dye of formula (II) comprises a thiol function protecting group Υ, the process of the present invention may be preceded by a deprotection step aimed at restoring SH function in situ. .

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

Table 1

<table> table see original document page 62 </column> </row> <table>

The deprotection step may also be carried out during a pre-hair treatment step, for example, the 1st hair reducing pre-treatment.

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

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

In the dyeing process, another variation is to apply the fluorescent dye of formula (I) or (II) at the same time as the reducing agent.

In another variation, the reducing agent is applied as a post-treatment after application of the composition containing at least one fluorescent dye of formula (I) or (II). The duration of posttreatment 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 specific embodiment, the reducing agent is a thiol or borohydrate type agent as described above.

A specific embodiment of the present invention relates to a process wherein the fluorescent dye of formula (I) or (II) may be applied directly to the hair without reducing agents, free from prior reduction treatment or after reduction treatment.

Treatment with an oxidizing agent may optionally be combined. Any type of conventional oxidant in the field may be used. Therefore, it can be selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates as well as enzymes, among which peroxidases, 2-electron oxidoreductases can be mentioned. such as uricases and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.

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

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

An object of the present invention is also a multicompartment device or staining kit wherein a first compartment contains a dye composition comprising at least one fluorescent dye of formula (I) or (II) and a second compartment contains a reducing agent capable of reducing the disulfide functions of the keratin materials and / or the disulfide function of the dye of formula (I).

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

The present invention also relates to a multi-compartment device wherein a first compartment contains a dye composition comprising at least one fluorescent dye of formula (I) or (II); or a second compartment contains a reducing agent capable of reducing the disulfide bonding of keratin materials; and a third compartment contains an oxidizing agent.

Another variation relates to a multicompartment staining device or staining kit comprising a first compartment containing a composition with at least one protected fluorescent dye of formula (II) and a second compartment comprising a composition containing a deprotecting agent, as a base.

Each of the aforementioned devices may be provided with means for providing the desired blend to the hair, for example, such as the devices described in FR 2,586,913.

The following examples serve to illustrate the present invention without limitation, however. The fluorescent dyes of the following examples were fully characterized by conventional spectroscopy and spectrometry methods.

Example 1

Synthesis of 1-Methyl-4 - {(E) -2- [4- (methyl {2 - [(1-methyl-1H-imidazol-2-yl) sulfanyl] ethyl} amino) phenyl] vinyl} pyridinium chloride [1]

<formula> formula see original document page 65 </formula>

Synthesis scheme.

<formula> formula see original document page 65 </formula>

Procedure:

Stages 1 ε 2: Synthesis of 4 - ((E) -2-l4-r (2-c0r0-ethyl) (methyl) amino1phenyl) vinyl) -1-methylpyridinium sulfate

4.99 g of 4-picoline diluted in 25 ml dichloromethane (CH 2 Cl 2) is stirred and heated to 40 ° C. 5 ml dimethyl sulfate diluted in 20 ml CH 2 Cl 2 is added dropwise to the reaction medium. The mixture is kept at 42 ° C for 30 minutes after addition and then 20 ml of isopropanol are added.

1.87 g of pyrrolidine diluted in 30 ml of isopropanol is added 5. The mixture is stirred and heated to 60 ° C for minutes. 10.5 g of 4 - [(2-chloroethyl) (methyl) amino] benzaldehyde are added. The mixture is stirred for 2 hours at 52 ° C, and then at room temperature for 48 hours. The reaction mixture is diluted in 50 ml of ethanol and then stored at -25 ° C for 12 hours. The precipitate obtained is filtered at room temperature, washed with 100 ml acetone and 3 times with 100 ml ethyl ether and dried in vacuo in the presence of P2O5.

15.1 g of light orange crystals are recovered. Analyzes indicate that the product is in compliance.

Stage 3: Synthesis of 1-μετιι_-4 - ((Ε) -2-Γ4- (μετιι. {2-Γ (1-μετιι.-1Η-imidazol-2-yl) sulfanyl1ethyl) amino) phenyl1vinyl> pyridinium chloride 4 - ((E) -2- {4 - [(2-chloroethyl) (methyl) amino] phenyl} vinyl) methylpyridinium methyl sulfate, 2.15 g of 2-mercapto-1-methylimidazole and 20 ml of Ethanol (EtOH) is stirred and heated at 70 ° C for 48 hours 2.15 g of 2-mercapto-1-methylimidazole diluted in 3 ml EtOH is added to the reaction mixture, the mixture is stirred at 72 ° C. For 72 hours 20 ml of isopropanol and 2 ml of water are added to the reaction mixture cooled to -10 ° C. The oil is separated from the supernatant, washed with ethyl acetate (EtOAc) 1 then solubilized in 100 ml of ethanol. and stored at -25 ° C for 48 hours.

The obtained crystals are filtered, washed with 20 ml ethanol and 25 times with 3 times 100 ml EtOAc, and then vacuum dried in the presence of P2O5. 5.79 g of brown powder is collected. Analyzes indicate that the product is in compliance. 1H NMR (400 MHz, ppm, DMSO-d6) 2.96 (s, 3 H), 3.51 (t, 2 H), 3.67 (s, 3 H), 3.68 (t, 2 H ), 4.20 (s, 3H), 6.75 (d, 2H), 7.20 (d, 1H), 7.57 (d, 2Η), 7.72 (1Η), 7, 76 (d, 1), 7.91 (d, 1), 8.07 (d, 2), 8.73 (d, 2).

Example 2

Synthesis of 4 - ((Ε) -2- (4-Κ2-ΓΜ.3-ρίμετΐί-1Η-imidazol-3-io-2-yl) sulfanyl1ethyl} (methyl) amino1phenyl) vinyl) -1 - sulfate / chloride methylpyridinium methyl [2]

Synthesis Scheme:

<formula> formula see original document page 67 </formula>

Procedure:

A solution of 1 g of 1-methyl-4 - {(E) -2- [4- (methyl {2 - [(1-methyl-1H-imidazol-2-yl) sulfanyl] ethyl} amino) phenyl chloride ] vinyl} pyridinium [1] in 2 ml of N-methylpyrrolidinone (NMP) and 8 ml of acetonitrile (ACN) is stirred at 70 ° C for 20 minutes. 500 μl of dimethyl sulfate is added to the mixture. Stirring and heating are maintained for 1 h 30 min. 500 mg of sodium acetate are added. After 4 hours, 1 ml of dimethyl sulfate is added and stirring is continued for 15 hours at room temperature. 50 ml of acetonitrile are added. The obtained precipitate is filtered off. 100 ml of acetone is introduced into the filtrate and the oil thus obtained is washed 3 times with 100 ml of acetone, then resolubilized in 50 ml of isopropanol and stored at -25 ° C for 48 hours. The precipitate formed is filtered, washed with 10 ml iPrOH and 3 times with 20 ml ethyl acetate and then vacuum dried in the presence of P2 O5. 1.11 g of brown powder is recovered. Analyzes indicate that the product is in the form of mixed chloride salts and methyl sulfate salts.

1H NMR (400 MHz1 ppm, MeOH-d6) 3.06 (s, 3 H), 3.35 (t, 2 H), 6.68 (s, 5.44 H, methyl sulfate), 3.77 ( t, 2 H), 3.79 (t, 6 H), 4.24 (s, 3 H), 6.82 (d, 2 H), 7.15 (d, 1 H), 7.64 ( d, 2 H), 7.75 (s, 2 H), 7.83 (d, 1 H), 8.00 (d, 2 H), 8.55 (d, 2 H).

Example 3

Synthesis of 2,2'-Phisulfan-diylbisretane-2,1-diyl (methylimino) -4.1-phenylene (E) -ethene-2,1-diylPbis (1-methylpyridinium) dichloride

<formula> formula see original document page 68 </formula>

Synthesis Scheme:

<formula> formula see original document page 68 </formula>

Procedure:

STAGE 1: 4,4'-DYSULFANODIILBISRETANE-2.1-DILLMETHYLIME)!) DIBENZALPEPE

82.3 g of phosphorus oxychloride are added to 500 ml of DMF at 0 ° C. After stirring for 30 min at 0 ° C, a solution of 47 g of N, N '- (disulfanidiyldietane-2,1-diyl) bis (N -methylaniline) is added dropwise. The mixture is stirred for 90 minutes at 0 ° C and then for 75 min at 10 ° C and 105 min at 40 ° C. It is then poured into 2.5 l of cold water and 700 ml of N 5 sodium hydroxide are added. The yellow precipitate obtained is filtered through celite and solubilized in 200 ml of dichloromethane and the obtained solution is washed with 200 ml of a saturated aqueous sodium chloride solution. After drying over magnesium sulfate and evaporation of dichloromethane, the yellow residue (80 g) is purified by silica gel chromatography. After drying, a light yellow powder is recovered. Analyzes indicate that the product conforms to the expected structure.

Stage 2: 2,2'-fDisuLFANODiiLBisrETAN-2.1-diyl (methylimino) -4,1-phenylene (E) etene-2,1-diyl1} bis (1-methylpyridinium dichloride) Γ31

25 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 is added to the mixture. The whole mixture is heated under stirring at 55 ° C for 11 h. Methanol is removed in vacuo at 40 ° C. The solid is mixed with 300 ml of isopropanol. After evaporative drying, 200 ml of isopropanol are introduced. The mixture becomes solid and is prolonged by the addition of 100 ml of isopropanol and torsion-dried over a sintered glass. The recovered solid is washed with isopropanol and then acetone, and then dried in vacuo. After drying, 36.7 g of orange powder is recovered. 27 g of a high purity orange red powder is recovered by recrystallization from isopropanol. Analyzes indicate that the product conforms to compound [3] and is pure.

1H NMR (400 MHz1 MeOH-d4) 2.99 (t, 4H), 3.81 (t, 4H), 4.31 (s, 6Η), 6.86 (d, 4H), 7.22 (d 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 4

SYNTHESIS OF 4,4'4DISULFANOPHL-BISrETAN-2,1-diyl (METHYLIMO) -4,1-5 phenyleneE) ethen-2,1-diyl1) bis (1-methylpyridinium) dimethoxysulfate [4]

<formula> formula see original document page 70 </formula>

Synthesis Scheme:

<formula> formula see original document page 70 </formula>

Procedure4,4'- | DISULFANODIILBISRETHANE-2,1-DIIL (METHYLIMIN) -4,1-PHENYLENE (E) ETENO-2,1-

3 ml of dimethyl sulfate is added to the solution, the temperature of which 5 increases at reflux (40 ° C). After stirring for 40 minutes, 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 is introduced into the mixture, followed by 4.99 g of 4 , 4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde. After stirring for 2 hours at 65 ° C, the reaction mixture is cooled to room temperature, and the precipitate formed is filtered and washed 3 times with 100 ml of isopropanol. The red paste thus obtained is brought to reflux and then cooled. The red precipitate formed is filtered off and then dried. 8.94 g of red powder is recovered. Analyzes indicate that the product conforms to the structure of [4] and pure. 1H NMR (400 MHz, DMSO-d6) 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).

SYNTHESIS OF 2,2 '- {DISULPHANOPYLIBISRETHANE-2.1-DIIL (METHYLIMINO) -4,1-DIYL) BIS (1-METHYLOPYRIDINE) dimethoxysulfate [4]

2.62 g of 4-picoline is diluted in 25 ml of dichloromethane and

Example 5

PHENYLENE (E) ETENO-2.1-PIILDBtsM-ETHYLOPYRIDINE) [5]

<formula> formula see original document page 71 </formula>

Synthesis scheme: <formula> formula see original document page 72 </formula>

Procedure:

SYNTHESIS OF 2,2 'DICHLORIDE - (DISULFANODIILBISRETANE-2.1-DIIL (METHYLIMIN) -4.1-PHENYLENE) ETHEEN-2.1-DIILUBIS (1-ETHYLPYRIDINE) Γ51

10 g of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]}

Ibenzaldehyde and 8.1 g of N-ethylpicolinium chloride are dissolved in 100 ml of isopropanol. 1.3 g of piperidine is added to the mixture. The entire mixture is refluxed for 5 hours under stirring. Isopropanol is removed in vacuo at 50 ° C. The obtained gum is triturated with acetone. 18 g of solid is recovered and treated with carbon black. 7.1 g of product are collected and 4 g are purified by liquid / water (BuOH) chromatography. After drying, 1.65 g of red powder is recovered. Analyzes indicate that the product conforms to the structure of the dye [5] and pure. 1H NMR (400 MHz, MeOH-C1-4) 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 β

synthesis of 4,4 '- (disulfanediylbisretane-2,1-diyl (methylimino) -4,1-phenylene (E) ethen0-2,1-dhl1) bis (1-ethylpyridinium) dibromide Γ6ΓSynthesis scheme:

<formula> formula see original document page 73 </formula>

Procedure

Synthesis of 4,4'-disulfanediylbisretane-2'-diyl (methylimino) -4.1-phenylene (E) etene-2.1-diyl1) bisM-ethylpyridinium) dibromide Γ6Ί

4.1 g of 4,4- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 400 ml of isopropanol and 0.86 ml of pyrrolidine are heated at 75 ° C for 20 minutes. 4.26 g of 1-trimethyl-4-methylpyridinium bromide is added to the reaction medium and the resulting mixture is stirred and heated for 5 h. 200 ml of acetone is introduced into the reaction mixture. The obtained precipitate is filtered off, washed with acetone and dried. 7.37 g of red powder is recovered. Analyzes indicate that the product is in compliance and pure. 1H NMR (400 MHz, DMSO-d6) 1.5 (t, 6 H), 2.98 (t, 4 H), 3.04 (s, 6 H), 3.74 (t, 4 H), 4.46 (q, 4 H), 6.84 (d, 4 H), 7.19 (d, 2 H), 7.61 (d, 4 H), 7.93 (d, 2 H), 8.08 (d, 4 Η), 8.82 (d, 4 Η).

Example 7

SYNTHESIS OF 4,4WDISULFANODIILBISRETHANE-2,1-DIYLPHYMETHYLIMIN) -4,1-PHENYLENEINE) ETENO-2,1-DIILl> BISRI- (2-HYDROXYETI-PYRIDINI)

<formula> formula see original document page 74 </formula>

Synthesis Scheme:

<formula> formula see original document page 74 </formula>

Procedure:

SUMMARY OF THE 4.4 '- (ρΐ8υίΡΑΝθΡΐΐίΒΐ3ΓΕΤΑΝθ-2,1-ριΐί (ΜΕΤιυινιΐΝθ) -4,1-FEN> LENO (E) ETENO-2,1-DHLl) Blsri- (2-HYDROXYETH) PYRIDINIUM Γ

4.1 g of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 40 ml of isopropanol and 0.86 ml of pyrrolidine are heated at 75 ° C for 1 hour. 4.6 g of 1- (2-hydroxyethyl) -4-methylpyridinium bromide is added to the reaction medium, and the resulting mixture is stirred and heated for 1 hour. 200 ml of acetone are introduced into the reaction mixture. The obtained gum is separated, filtered, washed 3 times with 150 ml isopropanol and dried. 6.59 g of powder is recovered. Analyzes indicate that the product is in compliance. 1H NMR (400 MHz1 MeOH-d) 2.97 (t, 4 H), 3.1 (s, 6 H), 3.78 (t, 4 H), 3.97 (t, 4 H), 4.51 (t, 4 H), 6.83 (d, 4 H), 7.09 (d, 2 H), 7.61 (d, 4 H), 7.83 (d, 2 H) , 7.98 (d, 4 H), 8.56 (d, 4 H).

Example 8

SYNTHESIS OF 4.4 '- {DISULPHANODIILBISRETHANE-2,1-DIIL (METHYLIMIN) -4,1-PHENYLENE (E) ETHENE-2,1-DIIL (BIS (BENZYLPYRIDINE) [8]

<formula> formula see original document page 75 </formula>

Synthesis Scheme:

<formula> formula see original document page 75 </formula>

Procedure: Stage 1: Synthesis of 4,4 '- {Pisulfanopiylbisretane-2,1-piyl (methylimino) -4.1-PhenylenOF) Ethene-2,1-diylbenzylpyridinium) dimethanesulfonate Γ81

4.1 g of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 40 ml of isopropanol and 0.86 ml of pyrrolidine are heated at 75 ° C for 20 minutes. 5.85 g of 1-benzyl-4-methylpyridinium bromide is added to the reaction medium, and the resulting mixture is stirred and heated for 5 hours. The reaction mixture is stirred at room temperature for 17 hours. The supernatant is filtered, the obtained black solid is separated, washed with 200 ml of isopropanol, filtered and then dried. 9.12 g of red powder is recovered. Analyzes indicate that the product is in compliance. 1H NMR (400 MHz, DMSO-d6) 2.98 (t, 4 H), 3.03 (s, 6 H), 3.78 (t, 4 H), 5.67 (s, 4 H), 6.82 (d, 4 H), 7.15 (d, 2 H), 7.40 (m, 5 H), 7.61 (d, 4 H), 7.90 (d, 2 H), 8.07 (d, 4 H), 8.90 (d, 4 H).

Example 9

Synthesis of 4.4 '- {pisulfanopiylbisretane-2,1-piyl (methylimino) -4.1-phenylene (E) etene-2,1-diyl1) bis (1-methylquinolinium) pimethyl sulfate Γ9Ί

<formula> formula see original document page 76 </formula>

Synthesis scheme: <formula> formula see original document page 77 </formula>

Procedure:

Synthesis P0 4,4'-fpisuLFAN0-piiLBisrETAN0-2,1-PiiL (METYLiMIN0) -4.1-PHENYLENE (E) ETEN0-2,1-PllLbisd-METHYLQUINOLIN) PIMETHYL SULPHATE Γ91

4.1 g of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 40 ml of isopropanol and 0.86 ml of pyrrolidine are heated at 75 ° C for 20 minutes. 5.9 g of 1,4-dimethylquinolinium bromide is added to the reaction medium, and the resulting mixture is stirred and heated for 5 hours. 200 ml of acetone is introduced into the reaction mixture. The obtained precipitate is separated, washed with 200 ml of acetone and then dried. 8.73 g of black powder is recovered. Analyzes indicate that the product is in compliance. LC-MS m / z 334, L max 524 nm

Example 10

SUMMARY PO 4.4 '- (PISULFAN-PIIL-BISRETANE-2.1-PYLIMETHYLIMIN) -4.1-PHENYLENE E) PROP-1-ENO-1.2-PIYLUBISRI- (2-HYPROXY-ETHYL) PYRIPINIOT PIBROMETO [original] formula see document page 78 </formula>

Synthesis Scheme:

<formula> formula see original document page 78 </formula>

Procedure:

Stage 1: Synthesis of 4.4 '- (DisuLFANODiiLBisrethane-2,1-DIILfMETILIMIN0) -4.1-FENLENOd E) prop-1-ENO-1.2-DIILl) BISn- (2-HYDROXYETH) pyridiniol [10]

4.1 g of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 40 ml of isopropanol and 0.86 ml of pyrrolidine are heated at 75 ° C for 20 minutes. 5.9 g of 4-ethyl-1- (2-hydroxyethyl) pyridinium bromide is added to the reaction medium, and the resulting mixture is stirred and heated for 5 hours. 200 ml of acetone is introduced into the reaction mixture. The precipitate obtained is filtered off, washed with 200 ml of acetone and then dried. 9.67 g of violet powder is recovered. Analyzes indicate that the product is in compliance and pure. 1H NMR (400 MHz, MeOH-c / 4) 2.38 (s; 6 H), 2.96 (t; 4 H), 3.06 (s; 6 Η), 3.76 (t; 4 Η) ), 3.99 (t; 4 '), 4.59 (t; 4'), 6.84 (d; 4 '), 7.49 (d; 4'), 7.52 (s; 2 ') ), 8.13 (d; 4 Η), 8.68 (d; 4 Η).

Example 11

Synthesis of 1-Ethyl-4- (fE) -244-r (17- (4-r (E) -2- (1-ETiLPiRiDINio-4-yl) vinylphenyl) -4.4,13,13-tetramethyl 8.9-dithio-17-azo-4.13-diazoniooctadec-1-yl) (methyl) aminolphenyl) vinyl) pyridinium [11]

<formula> formula see original document page 79 </formula>

Synthesis Scheme:

<formula> formula see original document page 79 </formula>

Procedure: Stage 1: Synthesis of 4-rr3- (dimethylamino) propill (methyl) aminolbenzaldehyde

10 g of 4-fluorobenzaldehyde and 12 g of potassium carbonate are mixed in 20 ml of N-methylpyrrolidinone (NMP) and brought to 50 ° C. 13 ml of N, N, N'-trimethyl-1,3-propanediamine are added and the mixture is brought to 80 ° C for 10 hours. After cooling, 100 ml of acetone is added. The obtained mixture is filtered and concentrated in vacuo. 21.85 oil containing the expected compound and 0.7 molar equivalents of MPN are recovered.

Stage 2: Synthesis of disulfanediildipropane-3,1-diyl dimethanesulfonate

9 g of 3,3'-disulfanodiildipropan-1-ol are diluted in 50 ml of ethyl acetate. 20 g of triethylamine is added, and the mixture is cooled to 0 ° C. 14.3 g of mesyl chloride is gradually added while keeping the temperature below 5 ° C. At the end of the addition, the mixture is stirred for one hour. at room temperature and then poured into 100 ml of a water / ice mixture. The product is extracted with 100 ml of ethyl acetate and washed with 2 x 100 ml of a molar solution of hydrochloric acid, 2 x 100 ml of water, 100 ml of a saturated sodium hydrogen carbonate solution and 2 x 100 ml of a saturated sodium chloride solution. The organic phase is dried over sodium sulfate and concentrated in vacuo. 6 g of a yellowish oil is recovered; Analyzes show that the product obtained is in compliance.

Stage 3: Synthesis of N.N '- (DisuLFANODiiLDiPROPANO-3.1-DiiL) Bis {3- (4-formylphenyl) (methyl) amino1-N.N-dimethylpropan-1-ammonium) dimethanesulfonate

2.2 g of 4 - [[3- (dimethylamino) propyl] (methyl) amino] benzaldehyde and 1.7 g of disulfanodiyldipropane-3,1-diyl dimethanesulfonate are mixed in 2 ml of N-methylpyrrolidinone at 80 ° C for 22 hours. After the reaction mixture has been cooled, 20 ml of ethanol are added. The solid obtained is filtered and is highly hygroscopic. Purification by trituration in dichloromethane results in the isolation of 232 mg of solid which conforms to the expected product.

Stage 4: Synthesis of 1-Ethyl-4 - ((E) -2-F4-r (17- (4-r (E) -2- (1-ETiLPiRiPIN-4-5 yl) vinylphenyl) -4) salt 4,13,13-tetraivethyl-8,9-dithio-17-azo-4,13-diazoniooctadec-1-yl) (methyl) amino] phenyl} vinyl) pyridinium [11]

230 mg of N1 N '- (disulfanediildipropane-3-dii-bisbisyl-4-formyl-phenyl-N-amino-N-dimethylpropan-1-ammonium dimethanesulfonate) and 163 mg of di-ethyl-4-methylpyridinium bromide are mixed in 5 ml of 53 μΙ of pyrolidine is added and the mixture is stirred at 70 ° C for 6 h and stirred at room temperature for 72 hours After cooling the mixture to -20 ° C the solid formed is filtered, collected in methanol and precipitated by the addition of 200 ml of tert-butyl methyl ether 118 mg of black solid is recovered The 15 analyzes indicate that the product conforms to the expected structure (MS (ESI +): mass peak m / z = 199).

Example 12

synthesis of 2,2 '- (disulfan-diylbisretane-2,1-dhlimino-4.1-FENLENOf E) ethylene-2.1-diylDbisM - (2-hydroxyethyl) pyridinium dibromide [12]

<formula> formula see original document page 81 </formula>

Synthesis scheme: <formula> formula see original document page 82 </formula>

Procedure:

STAGE 1: SYNTHESIS OF 4-R (2-HYDROX »ETHYL) AMINOLBENZALDEHYDE

1.24 g of 4-fluorobenzaldehyde, 10 ml of calcium hydride distilled DMSO, 1.16 g of sodium carbonate and a catalytic amount of 18-crown-6 ether (5 mol%) are mixed for 10 minutes under agitation. 1.2 ml of ethanolamine are slowly added to the reaction medium, which is kept under stirring and heated at 160 ° C for 52 hours. After cooling to 75 ° C, the reaction mixture is hydrolyzed with distilled water. The distilled hydrochloric acid solution is added to the mixture until a pH between 6 and 7 is obtained, and then the mixture is kept under stirring and heating at 40 ° C for 6 hours. The alcohol obtained is extracted with ethyl acetate. The organic phase is washed several times with distilled water and salified water, and then dried over magnesium sulfate. The mixture is concentrated in vacuo and purified by silica gel chromatography. 1.2 g of the brown solid is recovered. Analyzes show that the product conforms to the expected structure.

STAGE 2: SYNTHESIS OF 2-R (4-FORMYLPHENYL) AMINOLECTI METLL SULPHATE

0.4 g of 4 - [(2-hydroxyethyl) amino] benzaiadehyde and 10 ml of pyridine are mixed under stirring. The reaction medium is cooled in a dry ice and acetone bath. 0.18 ml of mesyl chloride is added dropwise at 0 ° C. The reaction mixture is stirred for 17 hours at a temperature between 0 and 5 ° C, and then ice water is introduced into the mixture. The formed solid is triturated, filtered, washed with distilled water and then vacuum dried. 550 mg of white powder is recovered. Analyzes indicate that the product is in compliance.

Stage 3: Synthesis of 4,4'-rDisuLFANODiiLBis (ethane-2,1-DIYLIMINOIDDIBENZALDEIDE)

0.5 g of 2 - [(4-formylphenyl) amino] ethyl methyl sulfate, 3 ml of a 1: 2 ethanol-water solution and 0.546 g of sodium thiosulfate are mixed at reflux for 2 hours with stirring . The obtained yellow solution is cooled, and then 2.8 ml of 35% sodium hydroxide is added dropwise. The mixture is kept under stirring at 75 ° C for 1 hour. After cooling, a light yellow solid is filtered off, washed with water and then vacuum dried. 237 mg of a yellow powder is recovered. Analyzes indicate that the product is compliant and pure. 1H NMR (400 MHz, CDCl3) 2.85 (t, 4H), 3.5 (m, 4 H), 4.61 (t, 2 H), 63.57 (d, 2 H), 7.63 (d, 4 H), 9.66 (s, 2 H).

Stage 4: Synthesis of 2,2'-fDisuLFANODHLBisrETAN-2,1-piilimino-4,1-phenylene (E) etenq-2,1-diylDbisM- (2-hydroxyethyl) pyridinyl dibromide [12] 200 mg of 1-bromide (2-Hydroxyethyl) -2-methylpyridinium and 260mg of 4,4 '- [disulfanediylbis (ethane-2,1-diylimino)] dibenzaldehyde are dispersed in 4 ml of isopropanol. 1 ml of a solution composed of 666 mg acetic acid, 790 mg pyrrolidine and 10 ml isopropanol are added to the suspension. The mixture is kept under stirring for 16 hours. 130 mg of 1- (2-hydroxyethyl) -2-methylpyridinium bromide is added and the mixture is heated at 60 ° C for 6 hours. The solid formed is filtered, triturated in 5 ml of isopropanol and 0.5 ml of water and then filtered and dried. 188 mg of black solid is recovered. Analyzes indicate that the product conforms to the expected structure. 1H NMR (400 MHz1 DMSOd6) 2.96 (t, 4H), 3.46 (m, 4 H), 3.84 (m, 4 H), 4.8 (t, 4 H), 5.22 ( t, 2 H), 6.70 (d, 4 H), 6.80 (t, 2 H), 7.28 (d, 2 H), 7.65 (d, 4 H), 7.72 ( dd, 2 H), 7.86 (d, 2 H), 8.35 (dd, 2 H), 8.45 (d, 2 H), 8.67 (d, 2 H).

Example 13

Synthesis of 2.2 '- {DisuLFANODiiLBisrethane-2,1-DiiLiMiNO-2,1-Phenylene (E) ETENO-2,1-DIlLllBlSd-Methylquinolinium Sulfate [13]

<formula> formula see original document page 84 </formula>

Synthesis scheme: <formula> formula see original document page 85 </formula>

Procedure:

Stage 1: Synthesis of 2-r (2-HiDRoxy EthiaminoIbenzaldehyde

1.24 g of 2-fluorobenzaldehyde, 10 ml of calcium hydride distilled DMSO, 1.16 g of sodium carbonate and a catalytic amount of 18-crown-6 ether (5 mol%) are mixed for 10 minutes under agitation. 1.3ml of ethanolamine are added. After stirring at 160 ° C for 3 hours, the mixture is brought back to 75 ° C and hydrolyzed with distilled water. The pH of the solution is lowered to 6 by the addition of dilute hydrochloric acid and the resulting mixture is kept under stirring and heating at 40 ° C for 18 hours. The alcohol obtained is extracted with ethyl acetate. The organic phase is washed several times with distilled water and salified water, and then dried over magnesium sulfate. The mixture is concentrated in vacuo and purified by silica gel chromatography. 1.2 g of the brown solid is recovered.

STAGE 2: SYNTHESIS OF 2 - [(2-FORMYLPHENYL) AMINO] ETHYLMETANOSULPHATE

0.5 g of 2 - [(2-hydroxyethyl) amino] benzaldehyde and 10 ml of distilled pyridine are mixed at 0 ° C under stirring. 0.23 ml of mesyl chloride is added dropwise. The reaction mixture is stirred for 17 hours at a temperature between 0 and 5 ° C, and then ice water is introduced into the mixture. The white solid obtained is filtered, rinsed with distilled water and then vacuum dried (650 mg). Analyzes indicate that the product is compliant and pure.

Stage 3: Synthesis of 2.2 '- [DisuLFAN0DiiLBis (ETAN0-2.1-DIILIMINO)] DIBENZALDEHYDE

0.5 g of 2 - [(2-formylphenyl) amino] ethyl methane sulfonate and 0.546 g of sodium thiosulfate pentahydrate are heated in 3 ml of an ethanol / water solution (1: 2) at 90 ° C for 15 g. The obtained solution is cooled, and then 2.8 ml of 35% sodium hydroxide is added and the mixture is stirred at 75 ° C for 1 hour. After cooling, a light yellow solid formed is filtered off, washed with distilled water and then vacuum dried. 222 mg of a powder is recovered. Analyzes indicate that the product conforms to expected product: 1H NMR (400 MHz1 CDCl3) 2.96 (t, 4 H), 3.63 (dt, 4 H), 6.74 (t, 2 H) 6.76 (d, 2 H), 7.41 (t, 2 H), 7.50 (d, 2 H), 8.54 (t, 2 H), 9.84 (s, 2 H) .

Stage 4: Synthesis of 2,2 '- (DisuLFANODiiLBisrethane-2,1-piiLiMiNO-2,1-phenylene (E) etene-2,1-diyl1) bis (1-methylquinolinium) dimethyl sulfate [13]

210 mg of 2,2 '- [disulfanediylbis (ethane-2) 1-diylimino)] dibenzaldehyde and 360 mg of 1,2-dimethyl quinolinium are dispersed in 4 ml of isopropanol. 1 ml of a solution composed of 790 ml of pyrrolidine, 666 mg of acetic acid and a sufficient amount of isopropanol to 10 ml are added. The mixture is stirred at room temperature for 10 days, 180 mg of quinolinium is added and stirring is continued for 3 days at room temperature. The mixture is filtered and the recovered solid is dried (214 mg). Analyzes indicate that the product conforms to the expected structure. LCMS (ESI +) 320, λmax 494 nm.

Coloring Example Example 1

Coloring Process - Compound [1]

A lock of 1g of Tone Level 4 hair is placed at the bottom of a container. 1 ml of a molar solution of ammonium thioglycolate at pH 8.5 is diluted with 9 ml of water. The solution thus obtained is applied to the rovings and allowed to act for 30 minutes. The locks are rinsed with running water and then placed back in a container. 10 ml of an aqueous solution containing 49 mg of compound [1] is applied for 30 minutes at room temperature (the locks are turned and re-impregnated after 15 minutes).

The locks are then rinsed with running water and dried. After staining, tone level 4 strand became visually lighter than untreated control strands.

Example 2

Coloring Process - Compound [2]

A lock of 1g of Tone Level 4 hair is placed at the bottom of a container. 1 ml of a molar solution of ammonium thioglycolate in pH 8.5 is diluted with 9 ml of water. The solution thus obtained is applied to the rovings and allowed to act for 30 minutes. The locks are rinsed with running water and then placed back in a container. 10 ml of an aqueous solution containing 63 mg of compound [2] is applied for 30 minutes at room temperature (the locks are turned and re-impregnated after 15 minutes).

The locks are then rinsed with running water and dried. After staining, tone level 4 strand became visually lighter than untreated control strands.

Example 3

Staining Process with Compounds [3] to [12]

Preparation of a composition A

<table> table see original document page 88 </column> </row> <table>

Preparation of a composition B

<table> table see original document page 88 </column> </row> <table>

At the time of use, compositions A (9 ml) and B (1 ml) are mixed, then the obtained mixture is applied to a 1 g dark hair lock (tone level 4) for 30 minutes at room temperature ( locks are turned over and reprinted after minutes).

After rinsing with running water and drying, the lightening of the hair thus treated is observed: the tone 4 level strand became visually lighter than the untreated control strands.

Remaining with respect to successive washing operations

The swabs thus treated are divided into two, half are subjected to 5 successive washing operations, according to a cycle comprising wetting the swabs with water, washing with a conventional shampoo, rinsing with water, followed by drying.

Visual Observations During the washing operations of examples [1], [2], [3], [4], [5], [7], [8], [9], [10] and [12] visible dye runoff, shampoo foam and rinse water are not colored.

The coloration observed in the strands is conserved and the whitening effect remains visible on tone level 4 hair, thus treated. Results in the L * a * b * system:

The staining of strands before and after 5 washes was evaluated in the L * a * b * system by means of a Konica Minolta® CM 2600D spectrophotometer (D65 illuminant).

In this system L * a * b *, L * represents the brightness, a * indicates the green / red axis and b * the blue / yellow axis. The higher the L value, the lighter or weaker the color, conversely, the lower the L value, the darker or stronger the color. The higher the value of a *, the redder the hue and the higher the value of b *, the yellower the hue.

The variation in color between dyed and washed hair strands ΤΗ4 (shade level 4) is measured by (ΔΕ) according to the following equation:

Δ E = - L0 *) 2 + (a * - a0 *) 2 + (b * - b0 *) 2 In this equation, L *, a * and b * represent the values measured after staining and L0 *, a0 * and bo * represent the values measured before staining (or washing).

The higher the value of ΔΕ, the greater the color difference between TH4 strands and colored streaks.

Table 2

<table> table see original document page 90 </column> </row> <table> The results in the Table show that the change in color is very small after 5 washing operations on originally TH4 strands stained with the dyes of the present invention. . Therefore, the coloring and bleaching effect of the hair remains virtually unchanged, which shows good wash resistance of the dyes of the present invention.

Results obtained on TH4.5 strands treated with compounds 3 to 5, followed by a series of 30 wash operations.

<table> table see original document page 91 </column> </row> <table>

The results in the Table show that the change in color is very small even after 30 wash operations on originally TH4.5 strands stained with the dyes of the present invention. Therefore, the coloring and bleaching effect of the hair remains virtually unchanged, which shows good wash resistance of the dyes of the present invention.

Reflectance Results

The lightening of the compositions according to the present invention and the remnant of said compositions in relation to the successive washing operations were expressed as a function of hair reflectance. These reflectances are compared to the reflectance of a TH4 tone level untreated strand of hair. The reflectance is measured by means of a Konica Minolta® CM 2600D spectrophotocolorimeter equipment and after irradiation of the hair with visible light in the range of 400 to 700 nm wave.

Reflectance of the Iocks treated with compounds 1 and 2 at application and after 5 shampooing operations

<table> table see original document page 92 </column> </row> <table> It is first observed that the reflectance of a lock of hair treated with a composition according to the present invention is greater than that of untreated hair . Therefore, the treated locks appear to be lighter.

In addition, the results show that the reflectance of the 4-level hair strands treated with the composition of the present invention changes very little after 5 washing operations. Therefore, the color and lightening effect on the hair remain virtually unchanged, which shows good resistance of the dyes of the present invention to shampooing operations.

Claims (23)

1. FLUORESCENT COLOR of formula (I) or (II) below: salts of organic or inorganic acid, their optical and geometric isomers, and solvates such as hydrates, wherein in formulas (I) and (II) Ra and R'a, which may be identical or different, represent a C 1 -C 4 arylalkyl group or a C 1 -C 6 alkyl group, optionally substituted by a hydroxyl, amino, C 1 -C 4 alkylamino or dialkylamino ( (C 1 -C 4), wherein it is possible for said alkyl radicals to form, with the nitrogen atom carrying them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom which may or may not be different from nitrogen; R'b, which may be identical or different, represent a hydrogen atom, a (C1 -C4) arylalkyl group or a (C1 -C6) alkyl group which is optionally substituted; R '"g, which may be identical or different, represent a hydrogen atom, an amino group, (C1 -C4) alkylamino, dialkyl. C 1 -C 4 lamino or trifluoromethyl, an acylamino, C 1 -C 4 alkoxy, C 1 -C 4 alkylcarbonyloxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonylamino or C 1 -C 4 alkylsulfonylamino radical, or an alkyl radical - Rh, R'h, R "he R" 'h, which may be identical or different, represent a hydrogen atom, a halogen atom, a (C1-C4) dialkylamino or alkylcarbonylamino ( C 1 -C 4), a C 1 -C 4 acylamino or C 1 -C 4 alkylsulfonylamino radical or a C 1 -C 4 alkyl radical; R "g and R '" g; Rh and R'h; R &lt; R &lt; &gt; linked by two adjacent carbon atoms together form a benzo or indene ring, or a fused heterocycloalkyl or fused heteroaryl group; the benzo, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino group, C 1 -C 4 alkylamino 1 C 1 -C 4 dialkylamino 1 cyano, carboxyl, hydroxyl or trifluoromethyl, acylamino, C 1 -C 4 alkoxy, C 2 -C 4 (poly) hydroxyoxyoxy 1 C 1 -C 4 alkoxycarbonyloxy C4) or (C1-C4) alkylcarbonylamino 1 an acylamino, carbamoyl or (C1-C4) alkylsulfonylamino radical, an aminosulfonyl radical or a (C1-C-16) alkyl radical optionally substituted by a group selected from (C1-4) alkoxy C12), hydroxyl, cyano, carboxyl, amino, (C1-C4) alkylamino and (C1-C4) dialkylamino, or other of the two alkyl radicals attached by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and, optionally comprising another heteroat atom identical or different from that of the nitrogen atom; R "and R '", which may be identical or different, represent a hydrogen atom or a (C1-C4) alkyl group; - R1, R2, R3, R4, R4, R'2, R * 3 and R4 , which may be identical or different, represent a hydrogen atom or a (C1-C4) alkyl group, <formula> which may be present or absent, represent a benzo group; - Ta and Tbl which may be identical or different, represent: (i) a covalent bond, (ii) or a radical selected from -N (R) - and -N + (R) (Rc) -, where R and R0, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl or C1-C4 hydroxyalkyl radical or a (C1-C4) arylalkyl, (iii) a cationic or non-cationic radical, heterocycloalkyl or heteroaryl; m, m ', η and n', which may be identical or different, represent an integer between 0 and 6 inclusive, with m + n and m '+ n \ which may be identical or different, representing an integer between 1 and 6. - when Ta represents a covalent bond σ, Y represents a group selected from: - optionally substituted aryl - optionally substituted heteroaryl - optionally substituted heterocycloalkyl - optionally substituted (di) arylalkyl - optionally substituted (di) heteroarylalkyl - a sterically hindered cyclic group; a represents -N (R) -, -N + (R) (Rc) - or a cationic or non-cationic heterocycloalkyl or heteroaryl radical; Y represents a group selected from: (i) a hydrogen atom; (ii) a metal alkali; (iii) an alkaline earth metal; (iv) an ammonium group: N + R0RpRvR0 or a phosphonium group: P + RaRpRvR0 with Ra, Rp, Rv and R6, which may be identical or different, representing a hydrogen atom or an alkyl group (Cr C4); or (v) a thiol function protection group; e - M 'representing an anionic counterion, 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 enabling formula (I) or (II) to obtain the electroneutrality. Fluorescent dye of formula (II) according to claim 1, wherein Ta represents -N (R) -, -N + (R) (Rc) - or a cationic or non-cationic heterocycloalkyl or heteroaryl radical; Y represents a hydrogen atom or an alkali metal. Fluorescent dye of formula (II) according to claim 1, wherein Ta represents -N (R) -, -N + (R) (Rc) - or a cationic or non-cationic heterocycloalkyl or heteroaryl radical; Y represents a thiol function protecting group below: - (C1-C4) alkylcarbonyl (C1-C4) alkylthiocarbonyl (C1-C4) alkoxycarbonyl (C1-C4) alkoxythiocarbonyl (C1-C4) alkylthiocarbonyl - (di) (C 1 -C 4 alkyl) aminocarbonyl - (di) (C 1 -C 4 alkyl) aminothiocarbonyl - arylcarbonyl such as phenylcarbonyl - aryloxycarbonyl - aryl (C 1 -C 4) alkoxycarbonyl - (( di) (C1 -C4 alkyl) aminocarbonyl; - (C1 -C4 alkyl) arylaminocarbonyl; - carboxyl; - SO3 "; M + where M + represents an alkali metal or M 'of formula (II) and M + are absent - optionally substituted aryl - optionally substituted heteroaryl - optionally substituted heterocycloalkyl - isothiouronium -C (NR, cR'd) = N + R'eR'f; An "with R'c, R, d, R'e and R, f, which may be identical or different, represents a hydrogen atom or an alkyl group - isothiourea -C (NR, cR'd) = NR, and with R'c, R'd, and R'e as defined above - optionally substituted (di) arylalkyl - optionally substituted (di) heteroarylalkyl CR1R2R3 with R11 R2 and R31 which may be identical or different, representing a halogen atom or a group selected from: - optionally substituted (C1 -C4) alkyl optionally substituted (C1 -C4) alkoxy; optionally substituted - optionally substituted heteroaryl - P (Z1) R "1 Rn2 R" 3 with R "1 and R" 2, which may be identical or different, representing a hydroxyl, an alkyl or alkoxy group; R 3 representing a hydroxyl or alkoxy group; and Z 1 representing an oxygen or sulfur atom; a sterically hindered cyclic group; optionally substituted e-alkoxyalkyl. Fluorescent dye of formula (II) according to one of claims 1 and 3, wherein when Ta represents -N (R) -, - N + (R) (Rc) - or a cationic heterocycloalkyl or heteroaryl radical or non-cationic; Y represents a protecting group selected from: - (C1-C4) alkylcarbonyl, - arylcarbonyl, - (C1-C4) alkoxycarbonyl, - aryloxycarbonyl, - (C1-C4) arylalkoxycarbonyl, - (di) (alkyl) aminocarbonyl ( (C 1 -C 4) - (C 1 -C 4) (alkyl) arylaminocarbonyl - optionally substituted aryl - 5 or 6 membered monocyclic heteroaryl - 8 to 11 membered cationic bicyclic heteroaryl - cationic heterocycle of the formula below: <formula> formula see original document page 99 </formula> - isothiouronium -C (NH2) = N + H2; An "; -isothiourea -C (NH 2) = NH; e-SO 3", M + with M + representing an alkali metal or M 'of formula (II) and M + are absent. Fluorescent dye of formula (II) according to claim 1, wherein when Ta represents a bond, Y represents a 5 or 6 membered aromatic, cationic monocyclic (i) heteroaryl comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen; (ii) an 8-11 membered bicyclic heteroaryl, cationic, these monocyclic or bicyclic groups being optionally substituted by one or more groups; (iii) or a heterocyclic group below: wherein R'c and R'd, which may be identical or different, represent hydrogen atom group or alkyl group; and An "represents a counterion. Fluorescent dye according to one of Claims 1 to 5, selected from the fluorescent dyes of formula (Ia), (lia), (Ib) 1 ( IIb) 1 (Ic) or (Mc) each having an ethylene group which binds the pyridinium moiety on the phenyl moiety at the ortho position or at the 4-4 ', 4-2', or 2-4 'positions for ( Ia), (IIa), (Ib) or (IIb), or at positions 4-5 'or 2-5' for (Ic) or (Ile): <formula> wherein (Ia) or (IIa): R1a and R2a, which may be identical or different, represent a benzyl or alkyl group, optionally substituted by a hydroxyl group, - R1b and R2bl which may be identical or different, represent a hydrogen atom, a benzyl or alkyl group T'a and T'b, which may be identical or different, represent a bond σ; or an -N + (R) (Rc) - group with R and R01 which may be identical or different, representing an alkyl group; or T'a and T'b represent an imidazolium group; -Y 'represents a group selected from imidazolium, thiazole; oxazole; 1,2,4-triazole; pyridinium; pyrimidine; benzoxazolium and benzothiazole; these groups being substituted by one or more alkyl groups, which may be identical or different, - m, m ', η and n', which may be identical or different, represent an integer between 1 and 6 inclusive, with m + n = m '+ n', representing an integer between 2 and 6 inclusive, - M 'represents an anionic counterion; in which formulas (Ib) or (11b): - Ra, R'a, Rbi R'b> R 1, R 'i, R "i, R" i> R-i. R'i. R2, R'2, R3> R'3> R4. R'4, Ta, Tb, m, m ', n, n' and Y are as defined in one of claims 1 to 5; -R9, R'g, R "g and R '" g, which may be identical. or different, represent a hydrogen atom, a halogen atom, an amino group, (C1-C4) alkylamino, (C1-C4) dialkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, an acylamino radical, (C1-4) alkoxy (C4), (C2 -C4) (poly) hydroxyalkoxy, (C1-C4) alkylcarbonyloxy, (C1-C4) alkoxycarbonyl or (C1-C4) alkylcarbonylamino, an acylamino, carbamoyl, (C1-C4) alkylsulfonylamino, or aminosulfonyl group, or a (C1-C16) alkyl radical optionally substituted by a group selected from (C1-C12) alkoxy, hydroxyl, cyano, carboxyl, amino, (C1-C4) alkylamino and (C1-C4) dialkylamino 1 or both of the two alkyl radicals linked by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical or different from that of the nitrogen atom; and R'h; R "h and R '" h, joined by two adjacent carbon atoms, together form a benzo or indene ring, or a fused heterocycloalkyl or fused heteroaryl group; the benzo, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino, (C1-C4) alkylamino, (C1-C4) dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl, acylamino, C1-C4 alkoxy group, (C 2 -C 4) (poly) hydroxyalkoxy, (C 1 -C 4) alkylcarbonyloxy, (C 1 -C 4) alkoxycarbonyl or (C 1 -C 4) alkylcarbonylamino a C 1 -C 4 acylamino, C 1 -C 4 alkylsulfonylamino radical, a C 1 -C 4 alkylamino radical or an aminosulfonyl radical Optionally substituted by a group selected from (C1-C12) alkoxy, hydroxyl, cyano, carboxyl, amino, (C1-C4) alkylamino and (C1-C4) dialkylamino, or other of the two alkyl radicals attached by the amino group nitrogen form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical or different from that of the nitrogen atom; and in whose formula (Ic) or (IIc): - Ra1 R1a. Rb. R'b. R1 R1, R1 R1 R21 R1 R1 R3 R4, R4 Ta, Tb, m, m, n, n and Y are as defined in one of the claims 1 - Rg1 R'g, R "g, R '" g, Rh, R'h, R "he R"' h, which may be identical or different, represent a hydrogen atom, a halogen atom, an amino group, (C1-C4) alkylamino, (C1-C4) dialkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C1-C4 alkoxy, (poly) hydroxy C 1-4 alkyloxycarbonyloxy (C1-C4) alkoxycarbonyl (C1-C4) 1 (C1-C4) alkylcarbonylamino 1 an acylamino, carbamoyl, (C1-C4) alkylsulfonylamino radical or an aminosulfonyl group, or a (C1-C16) alkyl radical optionally substituted by a group selected from alkoxy ( C 1 -C 12) 1 hydroxyl, cyano, carboxyl, amino, (C 1 -C 4) alkylamino and (C 1 -C 4) dialkylamino 1 or other of the two alkyl radicals attached by the amino group nitrogen atom form a 5 to 7 membered heterocycle comprising and optionally comprising another identical heteroatom or different from that of the nitrogen atom, it being understood that when the compound of formula (Ia), (IIa), (IIb), (Ic) or (IIc) contains other cationic parts, it is associated with a 5 or more counterions allowing formulas (Ia), (lla), (lb), (llb), (Ic) or (IIc) to obtain electroneutrality. Fluorescent dye of formula (I) according to one of claims 1 to 6, which is symmetrical. Fluorescent dye according to one of claims 1 to 7, selected from the following dyes: <table> table see original document page 104 </column> </row> <table> <table> table see original document page 105 </column> </row> <table> <table> table see original document page 106 </column> </row> <table> <table> table see original document page 107 </column> </row> <table> <table> table see original document page 108 </column> </row> <table> <table> table see original document page 109 </column> </row> <table> <table> table see original document page 110 </column> </row> <table> <table> table see original document page 111 </column> </row> <table> <table> table see original document page 112 </column> </row> <table> <table> table see original document page 113 </column> </row> <table> <table> table see original document page 114 </column> </row> <table> <table> table see original document page 115 </column> </row> <table> <table> table see original document page 116 </column> </row> <table> <table> table see original document pa ge 117 </column> </row> <table> <table> table see original document page 118 </column> </row> <table> - with M 'and An ", which may be identical or different, representing a anionic contraction; and M + representing an alkali metal. DYE COMPOSITION, which comprises in a cosmetically acceptable medium, a fluorescent dye of formula (I) or (II) as described in one of claims 1 to 8. DYE COMPOSITION, which comprises in a cosmetically acceptable medium, a fluorescent dye of formula (I) or (II) as described in one of claims 1 to 8 and at least one reducing agent. A dye composition according to claim 10, wherein the reducing agent is selected from cysteine, homocysteine, thiolactic acid, salts of these thiols, phosphines, bisulfide, sulfites, thioglycolic acid, and also esters thereof. , borohydrides and their derivatives, sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium salts and borane catechol. A process for staining keratin materials, wherein a dye composition comprising in a cosmetically acceptable medium at least one fluorescent dye of formula (I) or (II) as defined in one of claims 1 to 8; optionally in the presence of a reducing agent capable of reducing the disulfide bonds of keratin materials, it is applied to the materials. A staining process according to claim 12, wherein the uncle fluorescent dye is used. of formula (II) comprises a protecting group Y, the application is preceded by a deprotection step. Process for staining keratin materials according to one of claims 12 and 13, characterized in that the keratin materials are dark keratin fibers. A process according to any one of claims 12 to 14, wherein the reducing agent is applied before or after application of the fluorescent dye of formula (I) or (II). Coloring process according to one of claims 12 to 14, wherein the fluorescent dye of formula (I) or (II) is applied at the same time as the reducing agent. Process according to one of Claims 13 to 16, wherein the composition comprises an oxidizing agent. A process according to any one of claims 12 to 16, wherein it comprises an additional step of applying an oxidizing agent to the keratin fibers. A process according to any one of claims 12 to 18, wherein the fluorescent dye of formula (I) or (II) is present in an amount from 0.001% to 50% by weight with respect to the total weight of the composition. A multi-compartment device, wherein a first compartment contains a dye composition comprising a fluorescent dye as defined in claims 1 to 8, and a second compartment contains a reducing agent capable of reducing the disulfide bonds of keratin materials. A device according to claim 20 comprising a third compartment containing an oxidizing agent. Use of the fluorescent dyes of formula (!) Or (II) as defined in claims 1 to 8 to dye dark human keratin fibers, wherein the human keratin fibers are dark. Use according to claim 22 for lightening dark keratin fibers.