BRPI0709367A2 - fluorescent dye, dye compositions, keratin material staining process, multi-compartment device and use of fluorescent dyes - Google Patents

Abstract

FLUORESCENT COLOR, COMPOSITIONS COLOR, COLORING PROCESS OF KERATIN MATERIALS, MULTI - COMPARTMENT DEVICE AND USE OF FLUORESCENT COLORS. The present invention relates to a dye composition comprising a fluorescent thiol dye. heterocyclic disulfide, and a dyeing process having a lightening effect on keratin materials, in particular keratin fibers, in particular human keratin fibers, such as hair, using said composition. It similarly refers to novel heterocyclic fluorescent thiol / disulfide dyes and their uses in the curing of keratin materials. This composition makes it possible to obtain a visible and particularly resistant whitening effect on dark keratin fibers.

Description

"FLUORESCENT COLOR, COLOR COMPOSITIONS, DECORATING PROCESS OF KERATIN MATERIALS, DEVICEMULTICOMPARTIMENT AND USE OF FLUORESCENT COLORS"

Field of the Invention

The present invention relates to the dyeing of keratin materials using the thiol / disulfide fluorescent dyes comprising a heterocycloalkyl group.

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 involves applying keratin fibers to direct dyes that are colored molecules or decolorization having 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, denitropyridine dyes or azo, xanthene, acridine, azine or triarylmethane dyes.

The dyes that result from the use of direct dyes are temporary or semi-permanent dyes as the nature of the interactions that bind the direct dyes to the keratin fiber and its desorption to the fiber surface and / or core are responsible for its low detecting power and 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 shade, a process for discoloration is used. chemistry. 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 sprays, generally in 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 fact, the fibers have a tendency to become rough, harder to detangle and more fragile. Lastly, the bleaching or bleaching of keratin fibers using oxidation agents is incompatible with treatments for modifying the shape of said fibers, in particular in hair straightening treatments.

Another bleaching 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 the 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 in the 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.

Furthermore, it is a known practice to protect the thiol function (s) contained in a molecule to be grafted to the hair prior to its application to said hair, WO 99/51194. However, this application does not mention the use of fluorescent dyes for hair dyeing or bleaching.

Other known disulfide dyes for dyeing keratin fibers are disulfide derivatives of deaminothiophenol derivatives. Such dyes are described, for example, in FR1,156,407. 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 may 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 lightening effects, in particular on naturally or artificially dark keratin fibers, which are resistant to successful washing, do not damage keratin fibers and do not affect harmful demode its 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, which comprises applying keratin materials to a dye composition comprising, in a cosmetically acceptable medium, of at least one fluorescent dye comprising a heterocyclic group selected from the dyes of formula (I), (II) or (III) below:

salts of organic or mineral acid, their egeometric optical isomers, and solvates such as hydrates, wherein formula (I), (II) or (III):

- 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 or amine, (C1 -C4) alkylamino or (C1 -C4) alkylamino group. C4), wherein said alkyl radicals may form, with the nitrogen atom carrying them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom which may or may not be different from nitrogen; preferably Ra and R 'a represent a (C1-C3) alkyl group optionally substituted by a hydroxyl group such as amethyl or ethyl or a benzyl group;

R'c represents a hydrogen atom, a (C1-C4) arylalkyl group or a C1-C6 alkyl group which is optionally substituted;

- Rg1 R'g, R "g, R '", Rh, R'h, R "he Rh" "which may be identical or different, represents a hydrogen atom, a halogen atom, a (C1-C4) alkylamino group (C 1 -C 4) dialkylamino, cyano, carboxyl, hydroxylor trifluoromethyl, an acylamino radical, C 1 -C 4 alkoxy, C 2 -C 4 (poly) hydroxyalkoxy, alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino radical, an acylamino, carbamoylamino radical or alkylsulfonyl radical aminosulfonyl or a (C 1 -C 4) alkyl radical optionally substituted by a group selected from (C 1 -C 4) alkoxy, hydroxyl, cyano, carboxyl, amino, (C 1 -C 4) alkylamino (C 1 -C 4) alkylamino, or the other two radicals alkyl linked by the denitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom, in particular Rg, R'g, R "g, R '" g, Rh, R'hl R "h and R" 'h represent a hydrogen atom;

- or two groups Rg and R'g; R "g and R" 'g; Rh and R'h; R "h and R '" h, bonded by two adjacent carbon atoms, together form a benzo ouindene ring, or a fused heterocycloalkyl or fused heteroaryl group; Anelbenzo, indene, heterocycloalkyl or heteroaryl being optionally substituted by a halogen atom, an amino, (C1-C4) alkylamino, (C1-C4) dialkylamino, cyano, carboxyl, hydroxy or trifluoromethyl radical, a C1-C4 alkoxy radical, C2 -C4 (poly) hydroxyalkoxy, alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino, an acylamino, carbamoyl or alkylsulfonylamino radical, an aminosulfonyl radical or a (C1-C4) alkyl radical optionally substituted by a group selected from (C1-C4) alkoxy , 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 to or different from that of the nitrogen atom; in particular Rg and R'g; R "g and R" 'g together form a benzo group;

R1 R1; R1 "and R '", which may be identical or different, represent a hydrogen atom or a C1 -C4 alkyl group; in particular, R1, R1, R1 "and R '" represent a hydrogen atom;

- R 1, R 2, R 3, R 4, R 1, R 2, R 13 and R 4, which may be identical or

different represent a halogen atom, a (C1-C4) alkyl, (C1-C4) alkoxy, hydroxyl, cyano, carboxyl, amino, (C1 -C4) alkylamino or C1 -C4 alkylamino radical, and it is possible for such alkyl radicals to form with the nitrogen atom. carrying them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom which may or may not be other than nitrogen; in particular R1, R2, R3, R4, R1, R2-R3 and R14 are hydrogen atoms or an amino group; in particular R 1, R 2, R 3 and R 4 represent a hydrogen atom;

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

(i) a covalent bond,

(ii) or one or more radicals or combinations thereof selected from -SO 2 -, -O-, -S-, -N (R) -, -N + (R) (Rd) -, -C (O) -, with R and R01 which may be identical or different, representing a hydrogen atom, a (C1-C4) alkyl or hydroxy (C1-C4) alkyl or a (C1-C4) arylalkyl; in particular, Ta and Tb represent a covalent bond or a group selected from -N (R) -, -C (O) -, -C (O) -N (R) -, -N (R) -C (O) -, -C (O) -N (R) -C (O) -, -OC (O) -, - C (O) -O- and -N + (R) (Rq) -, with R and R01 which may be identical or different, representing a hydrogen atom or a (C1-C4) alkyl group; in particular, Ta or Tb represent a bond σ;

(iii) or preferably a monocyclic, cationic or non-cationic radical, heterocycloalkyl or heteroaryl radical containing one or doisheteroatoms, particularly two nitrogen atoms, and particularly comprising from 5 to 7 members, such as imidazole, piperazinyl, piperazinium homopiperazinyl or homopiperazine, optionally substituted by a (C1-C4) alkyl group, such as methyl;

which may be identical or different, represents an optionally substituted, cationic or non-cationic heterocyclic group; in particular, the heterocycle is monocyclic and saturated and has a total of one to two nitrogen atoms and 5 to 8 members;

- 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 e10 inclusive; 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, m + n = m '+ n' is an integer equal to 2;

- M 'represents an anionic counterion; and

Y represents: (i) a hydrogen atom; (ii) an alkali metal;

(iii) an alkaline earth metal; (iv) an ammonium group: N + R0RpRyR6 or a groupophosphonium: P + RaRpRvR6 with Ra, Rp1 Ry and R6, which may be identical or different, representing a hydrogen atom or a (C1 -C4) alkyl group;

or (v) a thiol protective group;

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

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

An object of the present invention are also novel fluorescent dyes of formula (I), (II) or (III) as defined above.

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

In addition, the process of the present invention makes it possible to obtain the coloring of keratin materials, in particular human keratin fibers, in particular hair, without damaging said 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 exhibiting a L * clarity 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 "hairy or artificially dark" 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 the "dotom level" before or after application of the compound of formula (I), (II) or (III).

The notion of tone is based on the classification of natural tones5, a tone separating each tone from the tone that immediately follows or precedes. This definition and shade classification is well known to hair stylists and is published in the book Science des traitements capillaires by Charles Zviak 1988, published by Masson1 pp. 215 and 278.

The range of tone levels from 1 (black) to 10 (very light blond), a unit corresponding to one tone; the bigger the picture, the clearer the tone.

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

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

-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 the round length, 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 450 to 700 nm which is greater than the curve corresponding to the untreated hair;

This means that in the wavelength range 450 to 700 nm there is at least one interval where the reflectance curve corresponding to the treated hair is greater 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%. All the same, there may be, in the wavelength range, from 450 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 450 to 650 nm and preferably within the wavelength range 450 to 650 nm. at 620 nm.

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

- "aryl" or "heteroaryl" radicals or the aryl or heteroaryl moiety of a radical may be substituted by at least one carbon-charged substituent selected from:

- a C1-C16 alkyl radical, preferably C1-C8, optionally substituted by one or more radicals selected from the radicals: hydroxyl, C1-C4 alkoxy, (poly) hydroxy C2-C4, acylamino and amino substituted by two C1-alkyl radicals -C4, which may be identical or different, optionally carrying at least one hydroxyl group, or the two radicals possibly forming, with the nitrogen atom to which it was attached, a heterocycle comprising from 5 to 7 members, preferably from 5 to 6 members, which are saturated or unsaturated, which optionally comprises another heteroatom which may be identical or different from nitrogen;

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

- a hydroxyl group;

a C1-C2 alkoxy radical, a C1-C2 alkylthio radical;

- a C2 -C4 (poly) hydroxyalkoxy radical;

- an amino radical;

- a 5- or 6-membered heterocycloalkyl radical;

- an optionally cationic 5- or 6-membered heteroaryl radical, preferably imidazole, optionally substituted by a C1-C4 alkyl radical, preferably methyl;

- 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 optionally substituted by one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle which is saturated or unsaturated, which is optionally substituted and optionally comprising at least one heteroatom which may or may not be different from nitrogen,

- an acylamino radical (-NR-COR ') wherein the radical R is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical is a C1-C2 alkyl radical; a carbamoyl radical ((R) 2N-CO-) wherein the R 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 alkylsulfonylamino (R 1 SO 2 -NR-) radical wherein the R radical represents a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group, and the R 'radical represents a C 1 -C 4 alkyl radical or a phenyl radical; an aminosulfonyl radical ((R) 2N-SO2-) wherein R radicals, whether or not identical, represent a hydrogen atom or a C1 -C4 alkyl radical optionally carrying at least one hydroxyl group,

- a carboxylic radical in the form of acid or salified (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; group polyhaloalkyl 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 alkoxy;

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

- a C1-C2 alkylthio radical;

- alkylcarbonylamino (RCO-NR'-) wherein the radical R 'is a hydrogen atom or a C1 -C4 alkyl radical which optionally carries at least one hydroxyl group and the radical R is a C1 -C2 alkyl radical or a radical substituted by two alkyl groups C 1 -C 4, which may be identical or different, optionally bearing at least one hydroxyl group, which is capable of said radicals forming, with the nitrogen atom to which they are attached, an optionally substituted, saturated or unsaturated heterocycle, comprising from 5 to 7 members, optionally comprising at least a heteroatom that may or may not be different from nitrogen,

alkylcarbonyloxy (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, optionally carrying at least one hydroxyl group, said alkyl radicals forming possibly, as a nitrogen atom to which they are attached, a 5 to 7 membered heterocycle which is saturated or unsaturated, optionally substituted and optionally comprising at least one other heteroatom which may or may not be different from nitrogen;

- alkoxycarbonyl (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, optionally carrying at least one hydroxyl group, being possible for such radicals alkyl form, with the nitrogen atom to which they are attached, an optionally substituted, saturated or unsaturated heterocycle, comprising from 5 to 7 members, optionally comprising at least one other heteroatom which may not be different from nitrogen;

- a cyclic or heterocyclic radical or a nonaromatic moiety of an aryl or heteroaryl radical may also be substituted by one or more oxo or thioxo groups;

- an aryl radical represents a monocyclic or polycyclic group,

condensed or non-condensing, 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, sulfur and selenium atom, and at least one ring. It is aromatic; preferably a heteroaryl radical is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, imidazopyridyl, oxydrazolyl, imidazopyridylazole, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrazolyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidylyl thiazopyridylthiazolylthiazolylthiazolyl thiazolylthiazolyl

- 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; As a means of sterically hindered radicals, mention may be made of bicyclo [1.1.0] butane, mesityl 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, non-aromatic, condensed or noncondensing radical containing from 5 to 22 members, comprising from 1 to 6 heteroatoms selected from donitrogen, 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 oradical alkyl implies that said 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 may form, with the nitrogen atom carrying them, a 5- to 7-membered heterocycle comprising, optionally, another heteroatom which may or may not be substituted. not be different from nitrogen; (v) or a quaternary ammonium group -N + R'R "R" \ M'for which R ', R ", R'", which may be identical or different, represents a hydrogen atom or a C1-C4 alkyl group or then -N + R'R "R '" forms a heteroaryl, such as imidazole, optionally substituted by a C1 -C4 alkyl group, and M "represents the corresponding organic acid octronion, inorganic acid or halide;

- "alkylene chain" represents a divalent C1 -C8 chain, particularly C1 -C6, more preferably C1 -C2, when the chain is straight, optionally substituted by one or more halogen atoms or groups, which may be identical or different, selected from hydroxyl, alkoxy, (di) (alkyl) amino (C1 -C4), Ra-Za-C (Zb) - with Za and Zb, which may be identical or different, representing an oxygen or sulfur atom, or a NRa 'group, and Ra' represents an alkali metal, a hydrogen atom or an alkyl group and Ra 'represents a hydrogen atom or an alkyl group;

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

when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above;

- the limits delimiting the range of values are included in this range;

- an "organic or inorganic acid salt" is more particularly selected from a salt derived from: (i) hydrochloric acid HCl; (ii) HBr hydrobromic acid; (iii) sulfuric acid H2SO4; (iv) alkylsulfonic acids: AIq-S (O) 2OH1 such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alq-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; (xi) aryloxysulfinic acids such as from toluenoxysulfinic acid and phenophenoxysulfinic acid; xii) phosphoric acid H3PO4; xiü) acetic acid CH3COOH, xiv) triflic acid CF3SO3H 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: Alk-O-S (O) O- such as methyl sulfate and ethyl sulfate; x) arylsulfates: Ar-O-S (O) O- such as obenzenesulfate and toluenesulfate; xi) alkoxysulfates: Alk-O-S (O) 2 O- such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-O-S (O) 2 O-; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

Fluorescent dyes comprising a heterocyclic group of formula (I), (II) or (III) are compounds capable of absorbing UV or visible range radiation at an Aabs wavelength between 250 and 800 ° nm and capable of re-emitting within the range. visible at an Aem wavelength emission between 400 and 800 ° nm.

Preferably, the fluorescent compounds comprising a heterocyclic group of the present invention are dyes capable of absorbing in the visible Aabs range between 400 and 800 ° nm and re-emitting in the visible range Aem between 400 and 800 ° nm. More preferably, the fluorescent dyes of formula (I), (II) or (III) are dyes capable of absorbing an Aabs between 420 ° nm and 550 ° nm and re-emitting in the visible range in an Aementre 470 and 600 ° nm. .

A specific embodiment of the present invention relates to fluorescent dyes comprising a heterocyclic group of formula (I), (II) or (III), in which it is 0.

According to a specific embodiment of the present invention, the fluorescent dyes of the present invention, of which the heterocycle defines:

<formula> formula see original document page 18 </formula>

represent a cationic or non-cationic heterocyclic group,

<formula> formula see original document page 18 </formula>

optionally substituted 1 ° U '' in particular, the heterocycle is monocyclic and saturated, and comprises in total two nitrogen atoms and is formed from 5 to 8 members.

In particular, the heterocycle is selected from piperazinyl, homopiperazinyl, hexahydro-1,4-diazepinyl and piperazinium, homopiperazinium or hexahydro-1,4-diazepinium optionally substituted by a (C 1 -C 4) alkyl group.

In another embodiment, the thiol fluorescent dyes comprise a heterocyclic group of formula (I), (II) or (III), whose heterocyclic:

or 1 represents a monocyclic saturated heterocyclic group comprising a total of a single nitrogen atom formed from 5 to 7 members.

In particular, the heterocyclic group is selected from dopyrrolidinyl, piperidyl and azepanyl.

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

A specific embodiment relates to thiol fluorescent dyes comprising a heterocyclic group of formula (III) which comprises a SY function where Y represents a hydrogen atom or an alkali metal. Advantageously, Y represents a hydrogen atom.

According to another specific embodiment of the present invention, in the above mentioned formula (III), Y is a protecting group known to those skilled in the art, for example those described in the books Protective Groups in Organic Synthesis, T.W. Greene1 Publisher John Willey & Sons, NY11981, pp 193-217; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, chap. 5

In particular, when Y represents a thiol function protecting group, Y is selected from the following radicals:

C1 -C4 alkylcarbonyl;

C1 -C4 alkylthiocarbonyl;

- C1 -C4 alkoxycarbonyl;

- C1 -C4 alkoxythiocarbonyl;

C 1 -C 4 alkylthiothiocarbonyl, (C 1 -C 4) di (alkyl) aminocarbonyl;

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

arylcarbonyl, such as a phenylcarbonyl;

aryloxycarbonyl;

aryl (C1-C4) alkoxycarbonyl;

(di) (C1-4 alkyl) aminocarbonyl, such as dimethylaminocarbonyl;

- (C1-C4) (alkyl) arylaminocarbonyl;

carboxyl;

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

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

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

(i) monocyclic comprising 5, 6 or 7 members, such as afuranyl or furyl, pyrrolyl or pyrril, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazolium, 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, pyrilium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine, azepinium, oxazepinyl, oxazepinium, tiepinidyl imidazole, typinidylazole ;

(ii) bicyclic comprising from 8 to 11 members, such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazole, pyridoimidazolyl, pyridoimidazole, thienocycloheptadienyl, or these optionally monocyclic groups or monocyclic groups , such as (C 1 -C 4) alkyl for example amethyl or (C 1 -C 4) polyhaloalkyl for example trifluoromethyl (iii) or 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;

substituted, the heterocycloalkyl group in particular represents a saturated or partially saturated 5-, 6- or 7-membered group comprising 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / tetrahydrothiophenyl, / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetrahydrohydropyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetrahydroazepinyl or di / tetrahydropyridyl, such groups being optionally substituted by groups such as C4-6-hydroxypyridyl; ), oxo or thioxo; or 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 a (C1 -C4) alkyl group or two R, g groups with 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 an optionally cationic, optionally hydrogen, heterocycloalkyl atom; and An "represents a counterion;

isothiouronium -C (NR'cR'd) = N + R, eR'f; An "with R'c, R, d, R, and e R'f, which may be identical or different, represents a hydrogen atom or a (C1-C4) alkyl group; preferably R'c to R'f represents a hydrogen atom; and An "represents a counterion;

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

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

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

- CR1R2R3 with R1, R2 and R3, which may be identical or different, representing a halogen atom or a group selected from:

C 1 -C 4 alkyl;

- C1 -C4 alkoxy;

optionally substituted aryl, such as optionally phenyl

substituted by one or more groups such as (C1-C4) alkyl; C1 -C4 alkoxy or hydroxyl;

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

- P (Z1) R'1 R'2R'3 with R'1 and R'2, which may be identical or different, representing a hydroxyl, a C1 -C4 alkyl or alkoxy group; R3 representing a hydroxyl or (C1-C4) alkoxy group; and Z1 representing an oxygen or sulfur atom;

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

optionally substituted (C1-C4) alkoxyalkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) or isobutoxymethyl.

According to a specific embodiment, the protected thiol fluorine dyes comprise the heterocyclic groups of formula (III) comprising a group Y (i) which is a cationic 5- or 6-membered aromatic heteroarylamonocyclic group comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as oxo-azole, isoxazole, thiazole, isothiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,4-oxazole, 1,2,4-thiadiazole, pyrilium, 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, benzoxazole or benzothiazolium, these heteroaryl ammonocyclic or bicyclic groups being optionally substituted by one or more groups, such as alkyl, for example methyl, or the (C1-C4) polyhaloalkyl, for example trifluoromethyl (iii) or a heterocyclic group below:

<formula> formula see original document page 23 </formula> wherein R'c and R'd, which may be identical or different, represent a hydrogen atom or a (C1-C4) alkyl group; preferably R, and R d represents a (C1-C4) alkyl group; such as methyl; and An "represents a 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 (C 1 -C 4) alkyl groups in particular, amethyl.

In particular, fluorescent dyes of formula (III) comprising a group Y represent an alkali metal or a group protector such as:

C1 -C4 alkylcarbonyl, such as methylcarbonyl or ethylcarbonyl;

arylcarbonyl, such as phenylcarbonyl;

- C1 -C4 alkoxycarbonyl;

aryloxycarbonyl;

aryl (C1-C4) alkoxycarbonyl;

- (di) (C1-4 alkyl) aminocarbonyl such as dimethylaminocarbonyl;

- (C1-C4) (alkyl) arylaminocarbonyl;

optionally substituted aryl such as phenyl;

monocyclic 5- or 6-membered heteroaryl such as imidazole or pyridyl;

- 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 obenzoimidazole 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 25 </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 (III) and M + are absent.

According to a specific embodiment of the present invention, the dyes of the present invention belonging to the formula (I), (II) or (III) have the ethylene group linking the pyridinium moiety on the phenyl ortho or para position, i.e. 4-4 ', 2-2', 4-2 'or 2-4'.

Another specific embodiment of the present invention relates to the symmetric disulfide fluorescent dyes of formula (I), that is, Ra, Rg, Rg-Rh, R'h, R1, R1, R1, R2, Rs, R4, Ta, Me η are identical to R'a, R "g, R '" g. R "h, R" 'h, R "i, Rmil R'i, R12, R'3, R'4, Tb, m' and n ', respectively.

As an example means of the fluorescent dyes of the present invention, specific mention may be made of the following compounds:

<formula> formula see original document page 25 </formula> <table> table see original document page 26 </column> </row> <table> <table> table see original document page 27 </column> </row> <table> <table> table see original document page 28 </column> </row> <table> <table> table see original document page 29 </column> </row> <table> <table> table see original document page 30 </column> </row> <table> - with M 'and Na ", which may be identical or different, representing an anionic counterion; and M + representing an alkali metal.

Protected thiol dyes of formula (III ") may be synthesized in two stages. The first stage consists of preparing the unprotected thiol dye (ΙΙΓ) according to methods known to those skilled in the art, for example, Thiols and organic Sulfides, Thiocyanates and Isothiocyanates, organic, UIImann1S 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 the protected thiol dyes of formula (III "). By way of example for the protection of thiol -SH function of the thiol dye, methods may be used in the ProtectiveGroups in Organic Synthesis, T.W. Greene, John Willey & Sons and NY, 1981, pp. 233-17; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, chap. 5

This method can be illustrated by the method consisting of (i) producing heterocyclic thiol fluorescent dyes of formula (ΙΙΓ) by reducing a heterocyclic bi-chromophore fluorescent dye carrying a disulfide -SS- function such as (I ') and (ii) in protection, according to conventional methods, said thiol function of (Ill ') to obtain the protected thiol fluorine dyes of formula (III ").

<formula> formula see original document page 31 </formula> with R1, R2, R3, R4, Ra, Rg, R'g. Rh, R'h, R1, R'i, m, n, Het and M 'send as defined above; Y 'represents a thiol function protecting group; and R deY1R represents a nucleophobic leaving group, for example mesylate, tosylate, triflate or halide.

According to another possibility, a thiol compound protected (b) by a protecting group Y 'as defined above, prepared according to one of the procedures described in the above mentioned books, thiol protecting ditocompound comprising at least one nucleophilic function, may be reacted. preferably sufficient equimolar 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 32 </formula>

with R1, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, m, n, Het, Y 'and M' as defined above; Nu representing a nucleophilic group; Representing an electrophilic group, it is the bond generated after the pelonucleophil attack on the electrophile.

By way of example, the covalent bonds that can be produced are listed in the Table below, based on the condensation of electrophiles with nucleophiles: Table 1

<table> table see original document page 33 </column> </row> <table> * activated esters of the general formula -CO- part with having a leaving group such as oxisuccinimidyl, oxybenzotriazolyl, aryloxy which is optionally substituted;

** Acyl azides may be rearranged to provide isocyanates.

A variation of this process is the use of a chromophorofluorescent having an electrophilic acrylate function (-OCO-C = C-) in which an addition reaction is performed which will produce a ligação bond.

Use may also be made of a thiol reagent Y-SH comprising a group Y 'as defined above, the nucleophilicized 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). provide the protected thiol fluorescent dye of formula (III "):

<formula> formula see original document page 34 </formula>

with R1, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, R1, R'i, rn, n, Het1 Y ', (III ") and M' being as defined above; and Hal representing a nucleophobic dehalogen atom, such as bromine, iodine or chlorine.

More particularly, a nucleophobic leaving group may be replaced by a thiourea group (S = C (NRR) NRR) to produce isothiourons. For example, if the thiourea group formulates a thioimidazole (β), the reaction scheme is as follows: with Ra, R1C R '<j, Rg1 Rgi Rh, R'h, Ri, Ri, rn, n, Het1 Hall An' and M'sendo as defined above.

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

According to another possibility, certain protected heterocyclic thiol fluorescent dyes (IIIm) can be obtained by reacting a protected thiol compound with a compound that carries two carboxylic acid functions which are activated according to conventional methods (e.g., the reaction carbodiimide or thionyl chloride). The resulting product (d) is subsequently reacted with a heterocyclic chromophorofluorescent that carries a nucleophilic (c) function, for example of the primary or secondary amine type, or of the aliphatic or aromatic alcohol type, such as phenol.

<formula> formula see original document page 35 </formula>

with R11 R2, R3, R4, Ra, Rg, R19, Rh, R'h, Ri, R'i, Het1 Ta, Y ', m, n, eM', E1 Nu and (ΙΙΠ) as defined above.

According to another possibility, the protected heterocyclic detiol fluorescent dyes of formula (III '' ') may be obtained by reacting a compound comprising a thiol group protected by a Y' group, and a previously activated hydroxyl group to a leaving group. halide (d '), for example mesylate, tosylate, triflate or halide, with a chromophorofluorescent (c') carrying an amino nucleophilic function in the heterocyclic part of Het. <formula> formula see original document page 36 </formula>

with R1, R2, R3, R4, Ra, Rg1 R'g, Rh, R'h. Ri, R'i, Het1 Ta, Y ', η, M', Σe E are as defined above.

By way of example, a thiol-protected group-containing compound containing an R1 nucleophobic leaving group, for example mesylate, tosylate or triflate, which may undergo nucleophilic attack of the amine carried by the sterile fluorescent chromophore:

<formula> formula see original document page 36 </formula>

Another alternative comes from the use of halides as a nucleophobic departed group in a thiol compound that can be replaced by a primary amine function, for example carried by a styryl chromophorofluorescent:

According to another possibility, the thiol fluorescent dyes of formula (III) according to the present invention may be obtained by combining a compound comprising a thiol group Y as defined above and a electrophilic group (f) with a pyridinium compound comprising a nucleophilic group. By way of example, an aldehyde or ketone when G represents an oxygen atom may be condensed with a "methylene activated" such as alkylpyride (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; a mention may be made in particular of 1,2-dialkylpyridinium, and in particular 1,2-dimethylpyridinium:

<formula> formula see original document page 37 </formula>

with R1, R2, R3, R4, Ra, Rg, R'g, Rh, R'n, Ri, R'i. Het1 Ta, m, η, Y and M 'are 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.

A variation of this process is to perform (i) a "Knoevenagel" condensation of an aldehyde or ketone comprising a Het heterocycle comprising a nucleophilic amino group (g) with an "activated methylene" such as alkylpyridinium (e) to provide the heterocyclic sterile intermediate (h). The latter may subsequently be (ii) reacted on a cyclic monomer containing at least one thiolactam function to provide, upon ring opening, the thiolheterocyclic fluorescent dye (IIIa "" ").

<formula> formula see original document page 38 </formula>

With R1, R2, R3, R4, Ra, Rg, R'g, Rh, R'n, Ri, R'i, Het1 η and M'as defined above, GeG 'which may be identical or different, an oxygen atom or sulfur or an N (R) group with R representing a hydrogen atom or a (C1-C4) alkyl group.

Alternatively, when reagent (g ') comprises a Het group comprising an exocyclic amino group, the fluorescent dye comprising an amide, thioamide, guanidine or amidine group is obtained.

<formula> formula see original document page 38 </formula> With R1, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, Het1 n, M ', G and G 'as defined above and R represents a hydrogen atom or an alkyl group. It is understood that the heterocycle amide of reagent (g) 'which can be protected and then unprotected.

Reference may be made to the book Advanced Organic Chemistry, J. March, 4th ed. John Wiiley & Sons, 1992 or T.W. GreeneProtective Groups in Organic Synthesis, for more details on the operating conditions used for the above mentioned processes.

The formed thiol fluorescent dyes can be converted to the -S Y 'protected thiol fluorescent preservatives by protecting the thiol-SH using conventional thiol protecting groups.

Protected thiol dyes may be unprotected by conventional pathways.

Disulfide dyes of formula (I) may be synthesized at two stages. The first stage is the preparation of the unprotected thiol dye (III) according to the methods described above. In addition, the second stage consists in the oxidation of the unprotected thiol dye (III) to form the symmetric disulfide dye of formula (Γ). Oxidation of a thiol to a disulfide is carried out according to conventional methods known to those skilled in the art, for example using hydrogen peroxide.

According to another possibility, an equivalent of a disulfide compound (b ") may be reacted according to one of the procedures described in the works mentioned above, said disulfide compound comprises two nucleophilic functions, with a sufficient amount of a" reactive fluorescent chromophore "or of a compound comprising such a "reactive fluorescent chromophore" (a) such as at least two equivalents In other words, (a) comprises an electrophilic function to form a covalent bond Σ to provide the disulfide dye of formula (I "), as can be seen schematically below:

R1, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, R1, R'i, m, n, Het and M 'as defined above; Nu representing a nucleophilic group; Representing an electrophilic group, it is the bond generated after the pelonucleophil attack on the electrophile. By way of example, the covalent bonds that can be produced are listed in the Table above based on the condensation of electrophiles with nucleophiles.

According to another possibility, certain disulfide fluorescent dyes (I ") may be obtained by reacting at least four molar equivalents of a" reactive fluorescent chromophore "(c) comprising a nucleophilic moiety with an equivalent of a dielectrophilic disulfide compound (d"). ) to provide the disulfide dye (I "): <formula> formula see original document page 41 </formula>

With R1, R2, R3, R4, Ra, Rg, R'g · Rh, R'h, Ri, R'i, Het1 m, n, M ', E1Nu and (I ") as defined above.

According to another possibility, the heterocyclic disulfide fluorescent dyes of formula (I '") may be obtained by the reaction of a compound (d") comprising a disulfide group, and a hydroxyl group previously activated to a Lg1 nucleophobic leaving group by for example with mesylate, tosylate, triflate or halide, with fluorescent chromophore (c ') carrying a nucleophilic function in the heterocyclic part of Het as defined above.

By way of example, a group-disulfide-containing compound contains an R-nucleofugal leaving group, for example, mesylate, tosylate or triflate, which may undergo nucleophilic attack of the amine carried by the stitile fluorescent chromophore to provide the disulfetoparticular dye.

With R1, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, Het, n, M 'and Lg <formula> formula see original document page 42 </formula>

Another alternative arises from the use of halides as a nucleophobic departed group in a disulfide compound that can be substituted for a secondary amine function, for example carried by a sterile chromophorofluorescent:

<formula> formula see original document page 42 </formula>

According to another possibility, the disulfide fluorescent dyes (I) according to the present invention may be obtained by reacting a compound comprising a disulfide group as defined above and an electrophilic group (f ") with a compound comprising a grouponucleophilic. By way of example, an aldehyde or ketone, when G represents an oxygen atom, may be condensed with an "activated methylene" such as alkylpyridinium (e) to produce 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, mention may be made in particular of 1,2-dialkylpyridinium, and in particular 1,2- dimethylpyridinium: <formula> formula see original document page 43 </formula>

with R1, R2, R3, R4, Ra, Rg, Rg, Rh, R'h, Ri, R'i, Het1 Ta, m, η, (Γ) and M 'are as defined above and G represents an atom of oxygen or sulfur or an N (R) group with R representing a hydrogen atom or a (C1-C4) alkyl group.

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

Disymmetric disulfide dyes of formula (I) may be synthesized at a single stage by reacting an unprotected fluorescent dye dye with a Y 'protected thiol fluorescent dye to form the disulphide dye of formula (I). Ra, R'a, Rg, Rg, R "g, R '" g, Rh, R'h, R "h. R"' h. Laugh R'i. R 'i. R' 'i · m, m', n, n ', Ta, Tbl Het, Het', (I) and M 'as defined above; Y 'represents a thiol function protection group.

Disymmetric disulfide dyes of formula (II) may be synthesized at a single stage by reaction of a fluorescently protected diol dye with an unprotected thiol compound to form the disulphide dye of formula (i).

<formula> formula see original document page 44 </formula>

with Ra, R'a, Rg, Rg-R "fl, R" 'g. Rh, R'h, R "h, R '" h, Ri, R-R "i. R'" i.R1c, m, m ', n, n, Ta, Tb, Het, Het', (II ) and M 'as defined above; Y'represents a thiol function protection group.

The composition of the present invention contains at least one heterocyclic fluorescent dye of formula (I), (II) or (III). In addition to the presence of at least one fluorescent dye of formula (I), (II) or (III), the present invention may also contain a reducing agent.

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

The dye composition which may be used in the present invention generally contains a quantity of heterocyclic fluorescent dye of formula (I), (II) or (III) 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 direct neutral, acidic or cationic nitrobenzene dyes, direct azo neutral, acidic or cationic dyes, tetraazopentametine, neutral quinone, acidic or cationic dyes, in particular deantraquinone dyes, dyes. azine direct, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the natural direct dyes, mention may be made of aolawsone, juglone, alizarin, glitter, carminic acid, kermesic acid, purpurogalin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and eapigenindin. 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 oxidizing 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-to-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. particularly to mepha-phenylenediamines, meta-aminophenols, mefa-diphenols, denaphthalene couplers, heterocyclic couplers and their addition salts.

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

The oxidation of the base (s) present in the dye composition is generally present in an amount from 0.001% to 10% by weight of the total weight of the dye composition, preferably from 0.005% to 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 of salts with a base such as alkali metal hydroxides such as sodium or potassium, ammonium aqueous, amines or alkanolamines.

The suitable dyeing medium, also called decorating 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 monomethyl 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 of preferably from 1% to 40% by weight, about the total weight of the dye composition, and preferably preferably from 5% to 30% by weight. .

According to one variation, the present invention contains a reducing agent capable of reducing keratin disulfide bonds. Reducers are as defined above.

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 thereof, inorganic or inorganic thickeners and in particular anionic, cationic, nonionic associative polymeric thickeners, amphoters, antioxidants, penetrating agents, sequestering agents, fragrances, tampons, dispersing agents, conditioning agents such as, for example, modified or non-modified, volatile or non-volatile silicones, 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, between 0.01% and 20% by weight, with respect to the opioid composition.

Of course, those skilled in the art will take care to select this or these additional possible 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 addition (s). contemplated.

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

Among the basifying agents, mention may be made, for example, of aqueous ammonia, alkaline carbonates, alkanolamines such as ammonium, 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 48 </formula>

wherein Wa is a propylene residue optionally substituted by a hydroxyl group or a C1 -C4 alkyl radical; Rai, 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 a liquid, a cream or a gel, or in any other form suitable for dyeing keratin fibers and, in particular, hair.

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

This reducing agent may be selected from thiols, for example cysteine, homocysteine or thiolactic acid, salts of these thiols, asphosphines, bisulfite, sulfites, thioglycolic acid and also their esters, in particular glyceryl monothioglycolate 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, decalcium salts, quaternary ammonium (tetrammonium salts) tetraethylammonium, tetra-n-butylammonium or benzyltriethylammonium); Borane catechol.

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

When the heterocyclic thiol fluorescent dye (III) comprises a thiol function protection group Υ, the process of the present invention may be preceded by a deprotection step which aims to restore 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 2

<table> table see original document page 49 </column> </row> <table>

The deprotection step may also be performed during a pre-treatment stage of the hair, for example pre-treatment of hair reduct.

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

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

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), (II) or (III). The duration of posttreatment with the reducing agent may be short, for example, from 0.1 seconds to 30 minutes, preferably from 1 minutes 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.

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

A specific embodiment of the present invention relates to a process wherein the fluorescent dye of formula (I), (II) or (III) 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 oxidizer in the camp can be used. Therefore, it can be selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perperborates and persulfates as well as enzymes, among which peroxidases, 2-electron oxidoreductases such as asuricases 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), (II) or (III).

Application of the dye composition according to the present invention is generally performed 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 multi-compartment device or staining kit wherein a first compartment contains a dye composition comprising at least one heterocyclic fluorescent dye of formula (I), (II) or (III) and a second compartment contains a reducing agent capable of reducing the disulfide functions of keratin materials.

One such compartment 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 detiol fluorescent dye of formula (I), (II) or (III); or a second compartment contains a reducing agent capable of reducing the disulfide bonding of keratin materials and / or disulfide bonding of the dyes of formula (I) or (II); and a third compartment contains an oxidizing agent.

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

Each of the aforementioned devices may be equipped 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.

Examples

Synthesis Example

Example 1

2,1-diylpiperazine-4,1-diyl-4,1-phenylene (E) etene-2,1-diyl]} bis (1-methylpyridinium) dimethyl sulfate [1]

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

Synthesis scheme.

<formula> formula see original document page 52 </formula> Stage 1: Synthesis of 4.4 '- [DisuLFAN0DiiLBis (ETAN0-2.1-DiiLPiPERAZiNA-4,1-Diyl)] Dibenzaldehyde

2.5 bromoethyl) disulfanyl] ethane, 7.3 g potassium carbonate (K 2 CO 3) 1 and 20 ml N-methylpyrrolidinone (NMP) are mixed at 75 ° C for 55 h. The product is purified by silica gel chromatography (eluent: 80/20 acetone / heptano then 90/10 dichloromethane / methanol 90/10). 469 mg of yellow oil are recovered. Analyzes indicate that the product is in compliance.

Stage 2: Synthesis of 4.4 '- [DisuLFANODiiLBis [ETANO-2.1-DiiLPiPERAZiN-4.1-Diyl-4.1-Phenylene (E) Ethyl-2.1-PiiL]} Bis (1-Methylpyridinium) Dimethyl Sulfate [1]

4,4 '- [Disulfanediylbis (ethane-2,1-diyl-piperazin-4,1-diyl)] dibenzaldehyde 469 mg, isopropanol (iPrOH) 5 ml, 1,4-dimethylpyridinomethyl sulfate 415 mg, 80 mg of pyrrolidine, 56 mg of acetic acid and 5 ml of dichloromethane are mixed at room temperature for 24 h and then at 40 ° C for 24 h. After cooling the mixture, 20 ml of acetone is added and the precipitate obtained is filtered off, washed with 10 ml of isopropanol and then 25 ml of acetone and dried. 610 mg of a red powder is recovered. Analyzes indicate that the product is in compliance.

1H NMR (400 MHz1 MeOH-d4) 2.68 (m, 8 H), 2.78 (t, 4 H), 2.95 (t4 H), 3.37 (m, 8 H), 3.68 (s, 6 H), 4.24 (s, 6 H), 7 (d, 4 H), 7.16 (d, 2 H), 7.62 (d, 4 H), 7.82 (d , 2 H), 8.01 (d, 4 H), 8.56 (d, 4 H).

Example 2

Synthesis of 1-methyl-4 - ((E) -2- {4- [4- (2-sulfanylethyl) piperazin-1-yl] phenyl} vinyl) pyridinium methyl sulfate [2]

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

2.5 g 4-piperazin-1-ylbenzaldehyde, 1.37 g 1-bromo-2 - [(2-Synthesis Scheme

<formula> formula see original document page 54 </formula>

Procedure

Synthesis of 1-Methyl-4 - ((E) -2- {4- [4- (2-sulfanyl-ethyl) piperazin-1-yl] phenyl} vinyl) pyridinium salt [2]

16 mg of compound [1] is dissolved in 10 ml of a water / ethanol mixture (v / v: 1/1). 60 mg (2a eq.) 3- [bis (2-carboxyethyl) phosphino] propanoic acid chloride hydrate in solution in 1 ml water and 21 mg (4a eq.) Sodium bicarbonate solution in 1 ml water are added to the mixture.

After stirring at 40 ° C for 30 minutes in an inert atmosphere, analyzes indicate that the mixture predominantly contains the expected product [2].

LC-MS Analysis: LC-DAD (400 - 700 nm) Column: Waters XTerra MS C18 5 μηι (4,6 χ 50) mmPhase: A: water + 0.1% formic acid / B: acetonitrileLinear gradient: T (min) A% / B%: 0 min 95/5; 8 min 0 / 100Flow speed: 1 ml / minDetection: UV diode assembly λ = 400 - 700 nmRetention time t = 3.0 minRelative hardness> 90% MS (ESI +) m / z = 285 corresponds to mass peak for expected product recognition [2].

Coloring Example

Example 1

Coloring Process - Compound [1]

<formula> formula see original document page 55 </formula>

At the time of use, compositions A (9 ml) and B (1 ml) are mixed, so the obtained mixture is applied to a 1 g dark hair tuft (tone level 4) for 30 minutes at room temperature (the tufts are turned and reimpregnated after 15 minutes).

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

Example 2

Staining Process with Compound 2

10 ml fresh solution of Synthesis Example Compound [2] is applied to a tuft of 1 g tone level 4 hair placed in the bottom of a container for 30 minutes at room temperature (the tufts are turned and re-impregnated after 15 minutes). The tufts are subsequently rinsed with running water and dried.

After drying, tone level 4 tuft became visually lighter than untreated control tufts.

Remaining Regarding Successive Washing Operations:

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

Visual Observations

During washing operations, there is no visible docent flow, shampoo foam and rinse water are not colored.

The coloration observed in the tufts is conserved and the dyeing effect remains visible in the tone level 4 hair thus treated.

L * A * B * System Results:

Tuft coloration 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 color intensity, 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 L1 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 TH4 (tone level) tufts of hair is measured by (ΔΕ) according to the following equation: ΔΕ = V (L * -L0 *) 2 + (a * -a0 *) 2 + (b * -b0 *) *

In this equation, L *, a * and b * represent values measured before dyeing and L0 *, a0 * and b0 * represent values measured after staining or after staining and washing operations.

The higher the value of ΔΕ, the greater the color difference between TH4 tufts and colored tufts.Table 3

Tufted Compound Treatment TH4 ΔΕ

<formula> formula see original document page 57 </formula>

The results in the Table show that there are no significant differences in color variation even after 5 wash operations. Therefore, the color and lightening effect of the hair remain 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 with respect to successive washing operations were also evaluated as a function of hair diversity. These reflectances are compared to the reflectance of a tuff level TH4 untreated hair.

Reflectance is measured by means of a Konica Minolta® CM 2600D spectrophotocolorimeter and after irradiation of the hair with visible light in the wavelength range 400 to 700 nm.

<formula> formula see original document page 57 </formula> Reflection of the Iocks treated with compound 2at application and after 5 shampooing operations

<table> table see original document page 58 </column> </row> <table>

First, it is observed that the reflectance of a tuft-treated tuft with a composition according to the present invention is greater than that of untreated hair. Therefore, the tufts of treated hair seem to be noticeably lighter.

In addition, the results show that the reflectance of Tone level 4 hair tufts treated with the compositions of the present invention changes very little after 5 wash operations. Therefore, the coloring and bleaching effect on the hair remain virtually unchanged, which shows good resistance of the dyes of the present invention to shampooing operations.

Claims (27)

1. FLUORESCENT COLOR of formula (I), (II) or (III) below: <formula> formula see original document page 59 </formula> salts of organic or mineral acid, their egeometric optical isomers, and solvates, such as hydrates: wherein formula (I), (II) or (III): - Ra and R'a, which may be identical or different, represent a group (C1-C4) arylalkyl or a (C1-C6) alkyl group optionally substituted by a hydroxyl or amine, (C1-C4) alkylamino or (C1-C4) alkylamino group, being possible for said alkyl radicals to form with nitrogen atom bears them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom which may or may not be other than nitrogen: - R1c represents a hydrogen atom, a (C1-C4) arylalkyl group or a C1-C6 alkyl group which is optionally - Rg, R'g, R "g, R" ', Rh, R'h, R "he Rh'" which may be identical or different, representing to a hydrogen atom, a halogen atom, a (C1-C4) aminoalkylamino, (C1-C4) dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino radical, C1-C4 alkoxy, (C2-C4) (poly) hydroxyalkoxy, alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino, an acylamino, carbamoyl or alkylsulfonylamino radical, an aminosulfonyl radical or a (C1-C4) alkyl radical optionally substituted by a group selected from (C1-C4) alkoxy, hydroxyl, cyano, carboxyl, amino, (C1-C4) alkylamino (C1-C4) alkylamino, or other of the two alkyl radicals attached by the denitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom; - or two groups Rg and R'g; R "g and R '" g; Rh and R'h; R 'and FTh1 bound 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, C1-6 alkylamino group (C4) dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl, a radical acylamino, C1-C4 alkoxy, (poly) hydroxyC2 -C4 alkyloxycarbonyl, alkoxycarbonyl or alkylcarbonylamino, an acylamino, carbamoylamino or carbamoylamino radical, an aminosulfonyl radical or a (C1-C4) alkyl radical optionally substituted by a group selected from (C1-C4) 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 atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of nitrogen atom; R1 "and R '", which may be identical or different, represent a hydrogen atom or a (C1 -C4) alkyl group; - R1, R2, R3, R4, R1, R'2, R's and R14, which may be identical or different, represent a halogen atom, a (C1 -C4) alkyl, a (C1 -C4) alkoxy, hydroxy, cyano, carboxyl, amino, (C1 -C4) alkylamino or (C1 -C4) alkylamino radical, and it is possible for such alkyl radicals to form , with the nitrogen atom carrying them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom which may or may not be different from nitrogen: - Ta or Tb, which may be identical or different, represent: (i) a bond σ (ii) or one or more radicals or combinations thereof selected from -SO 2 -, -O-, -S-, -N (R) -, -N + (R) (Rc) -, -C (O) - with R and R0, which may be identical or different, representing a hydrogen atom, a C1 -C4 alkyl or hydroxy C1 -C4 alkyl or a C1 -C4 arylalkyl, or preferably a radical; monocyclic, cationic or non-cationic, heterocycloalkyl or heteroaryl radical containing one or doisheteroatoms, particularly two nitrogen atoms, and particularly comprising from 5 to 7 members, which may be identical or different, represents an optionally substituted, cationic or non-cationic heterocyclic group ; - 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 -10 inclusive; - M 'represents an anionic counterion; and Y represents: (i) a hydrogen atom; (ii) a metal alkali; (iii) an alkaline earth metal; (iv) an ammonium group: N + RaRpRvR0or a phosphonium group: P + RaRpRvR0 with Ra1 Rp, Rv and R61 which may be seridentic or different, representing a hydrogen atom or a C1 -C4 alkyl group; or (v) a group having a thiol protecting function, it being understood that when the compound of formula (I), (II) or (III) contains other cationic moieties, it is associated with one or more anionic coupling enabling formula (I), (II) or (III) obtain the electroneutrality. Fluorescent dye of formula (I), (II) or (III) according to claim 1, wherein m and m 'are zero. Fluorescent dye of formula (I), (II) or (III) according to claims 1 and 2, wherein the heterocycle of formula: <formula> formula see original document page 62 </formula> represents a group cationic or non-cationic heterocyclic, optionally substituted <formula> formula see original document page 62 </formula> Fluorescent dye of formula (I), (II) or (III) according to claims 1 and 2, wherein the heterocycle of formula: <formula> formula see original document page 62 </formula> represents a group Monocyclic, saturated, heterocyclic and in total comprises a single nitrogen atom and is formed from 5 to 7 members. Fluorescent dye of formula (III) according to one of the preceding claims, wherein Y represents a hydrogen atom or an alkali metal. Fluorescent dye of formula (III) according to any one of claims 1 to 4, wherein Y represents a protecting group. Fluorescent dye of formula (III) according to any one of the preceding claims, wherein Y represents a protecting group selected from the following radicals: - (C 1 -C 4) alkylcarbonyl (C 1 -C 4) alkylthiocarbonyl; (C 1 -C 4) - (C 1 -C 4) alkoxythiocarbonyl - (C 1 -C 4) alkylthiothiocarbonyl - (C 1 -C 4) (di) (alkyl) aminocarbonyl - (C 1 -C 4) (di) (alkyl) aminothiocarbonyl; - arylcarbonyl; - aryloxycarbonyl; - (C 1 -C 4) arylalkoxycarbonyl; - (C 1 -C 4) (di) (alkyl) aminocarbonyl; - (C 1 -C 4) alkyl arylaminocarbonyl; - carboxyl; - SO 3 "; M + with M + representing an alkali metal such as sodium or potassium or M 'of formula (III) and M + are absent - optionally substituted aryl - optionally substituted heteroaryl - isothiouronium -C (NR, cR'd) = N + R'eR An "with R, c, R'd, R, and and R, f, which may be identical or different, represents a hydrogen atom or a (C1-C4) alkyl group; - isothiourea -C (NR'cR, d) = NR'e with R'0, R'd, and R'e conformed - (di) optionally substituted (di) aryl (C1-C4) alkyl - optionally substituted (di) heteroaryl (C1-C4) alkyl - CR1R2R3 with R1, R2 and R3, which may be identical or different, representing a halogen atom or a group selected from (i) (C1-C4) alkyl; (ii) C1 -C4 alkoxy; (iii) optionally substituted aryl - optionally substituted heteroaryl - P (Z1) R'1R'2R'3 with R'1 and R'2, which may be identical or different, representing a hydroxyl, C1-6 alkyl or alkoxy group -C4); R is a hydroxyl or (C1-C4) alkoxy group; and Z 1 representing an oxygen or sulfur atom: a sterically hindered cyclic group; optionally substituted (C1-C4) alkoxyalkyl. Fluorescent dye of formula (III) according to any one of the preceding claims, wherein Y represents an alkali metal or a protecting group selected from: - (C 1 -C 4) alkylcarbonyl, - arylcarbonyl; - (aryloxycarbonyl) - (C1-C4) aryloxycarbonyl - ((C1-C4) (di) (alkyl) aminocarbonyl) - (C1-C4) (alkyl) arylaminocarbonyl - optionally substituted aryl - monocyclic heteroaryl of 5 or 6 membered - 8 to 11 membered cationic bicyclic heteroaryl - cationic heterocycle of formula below: <formula> formula see original document page 65 </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 (III) and M + are absent. FLUORESCENT COLOR of formula (I), (II) or (III) according to one of the preceding claims, which has a pyridinium ethylene group attached to the phenyl in the ortho or para position, that is, in the A-4 positions ', 2-2', 2-4 '. Fluorescent dye of formula (I) according to one of claims 1 to 4 and 9 which is symmetrical. 11. FLUORESCENT COLOR, according to one of the preceding claims, selected from the colors: <table> table see original document page 65 </column> </row> <table> <table> table see original document page 66 </ column > </row> <table> <table> table see original document page 67 </column> </row> <table> <table> table see original document page 68 </column> </row> <table> <table > table see original document page 69 </column> </row> <table> <table> table see original document page 70 </column> </row> <table> - with M 'and An ", which may be identical or different, representing an anionic counterion, and M + representing a metal alkali. DYE COMPOSITION, which comprises in a suitable meocosocosmetic, a heterocyclic fluorescent dye of formula (I), (II) or (III) as defined in one of claims 1 to 11. DYE COMPOSITION, which comprises in a suitable meocosocosmetic, at least one heterocyclic fluorescent dye of formula (I), (II) or (III) as defined in one of claims 1 to 11 and at least one reducing agent. DYE COMPOSITION according to one of the preceding claims, wherein the reducing agent is selected from cysteine, homocysteine or thiolactic acid, the salts of these thiols, phosphines, obisulfide, sulfides, thioglycolic acid, and also their esters, borohydride and their derivatives, sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium salts and borane catechol. A composition according to any one of claims 11 to 14, wherein the heterocyclic fluorescent dye of formula (I), (II) or (III) is present in an amount between 0.001% and 50% by weight, with respect to the total weight of the product. composition. A dyeing material coloring process, wherein a dye composition as defined in any one of claims 11 to 15 comprises in a cosmetically acceptable medium at least one heterocyclic fluorescent dye of formula (I), (II) or (III) as as defined in one of claims 1 to 11, optionally in the presence of a reducing agent capable of reducing keratin material disulfide bonds, is applied to the materials. A coloring process according to one of the preceding claims, wherein when the heterocyclic fluorescent dye of formula (III) comprises a protecting group Y, the application is preceded by a deprotection step. Process for staining the quaternary materials according to claim 16 or 17, characterized in that the keratin materials are dark keratin sheets having a tone level of less than or equal to 6, preferably less than or equal to 4. A process according to one of claims 16 to 18, wherein the reducing agent is applied before or after the application of thiol fluorescent dyeing agent. A staining process according to any one of claims 16 to 18, 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 16 to 20, wherein the composition comprises an oxidizing agent. Process according to one of Claims 16 to 20, comprising an additional step of applying an oxidizing agent to the keratin fibers. A multi-compartment device, wherein a first compartment contains a dye composition comprising a fluorescent dye of the formula (I), (II) or (III) as defined in claims 1 to 11, and a second compartment containing reducing agent capable of reducing the bonds. disulfide of keratin materials. A device according to claim 23 comprising a third compartment containing an oxidizing agent. Use of the fluorophilic thiolheterocyclic dyes as defined in claims 1 to 11 to dye dark human keratin fibers. Use according to the preceding claim for lightening dark keratin fibers. Use according to claims 25 and 26, characterized in that the keratin fibers have a tone level of less than