BRPI0709367B1 - FLUORESCENT DYE, DYE COMPOSITIONS, COLORING PROCESS OF KERATIN MATERIALS, MULTI-COMPARTMENT DEVICE AND USE OF FLUORESCENT DYES OF HETEROCYCLIC TIOL - Google Patents

Abstract

fluorescent dye, dye compositions, keratin material staining process, multi-compartment device and use of fluorescent dyes. the present invention relates to a dye composition comprising a fluorescent thiol dye! heterocyclic disulfide, and a dyeing process that has a lightening effect on keratin materials, in particular, keratin fibers, in particular, human keratin fibers, such as hair, using said composition. it refers in a similar way to the new heterocyclic thiol / disinfectant fluorescent dyes and their uses in the keratin materials bonding. this composition makes it possible to obtain a visible and particularly resistant lightening effect on dark keratin fibers.

Description

“FLUORESCENT DYE, DYE COMPOSITIONS, COLORING PROCESS OF KERATIN MATERIALS, MULTI-COMPARTMENT DEVICE AND USE OF FLUORESCENT DYES OF HETEROCYCLIC TIPS”

Field of the Invention [001] The present invention relates to the dyeing of keratin materials using thiol / disulfide fluorescent dyes comprising a heterocycloalkyl group.

Background of the Invention [002] It is a common practice to dye keratin fibers, in particular, human keratin fibers, by direct dyeing. The process conventionally used in direct dyeing comprises the application in the keratin fibers of the direct dyes that are colored or colored molecules having an affinity for the fibers, letting them diffuse and, then, rinsing the fibers.

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

[004] The dyes that result from the use of direct dyes are temporary or semi-permanent dyes as the nature of the interactions that bind direct dyes to the keratin fiber and their desorption from the surface and / or the fiber core are responsible for their low tinting power and low resistance to washing operations or perspiration.

[005] Furthermore, the coloring of keratin fibers using conventional direct dyes does not make it possible to significantly lighten keratin fibers.

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2/64 [006] Lightening the color of keratin fibers, in particular, from dark keratin fibers to lighter shades, by optionally modifying their shade, is an important demand.

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

[008] This whitening system has the disadvantage of damaging keratin materials, in particular keratin fibers, in particular human keratin fibers, such as hair, and of damaging its cosmetic properties. In reality, fibers have a tendency to become rough, more difficult to untangle and more fragile. Finally, 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.

[009] 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 the keratin fiber during treatment, but the fluorescent dyes used do not exhibit satisfactory resistance to washing operations.

[010] In order to increase the stability of direct dyes, it is a known practice to fix direct dyes by covalently bonding the hair. For example, it is a known practice to react the dyes that comprise the reactive groups with the cystine or cysteine residues very

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3/64 numerous in 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.

[011] In addition, it is a known practice to protect the thiol function (s) contained in a molecule to be grafted onto the hair prior to application of these to said hair, WO 99/51194. However, this application does not mention the use of fluorescent dyes for dyeing or lightening the hair.

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

[013] Finally, WO 2005/097051 describes azoimidazolium disulfide dyes for the direct dyeing of keratin fibers.

Description of the Invention [014] The purpose of the present invention is to present new systems for dyeing keratin materials, in particular, human keratin fibers, in particular hair, which does not have the disadvantages of existing bleaching processes. In particular, one of the objectives of the present invention is to provide direct dyeing systems to obtain the bleaching effects, in particular, on naturally or artificially dark keratin fibers, which are resistant to successive washing operations, which do not damage the keratin fibers. and that do not adversely affect its cosmetic properties.

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4/64 [015] This objective 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 the application of a dye composition to the keratin materials comprising, in a cosmetically acceptable medium, at least one fluorescent dye comprising a heterocyclic group, selected from the dyes of formula (I ), (II) or (III) below:

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

where in formulas (I), (II) or (III):

- Ra and R ' _a , which can be identical or different, represent an arylalkyl group (C1-C4) or an alkyl group (C1-C6), optionally substituted by a hydroxyl or amino, alkylamino (C1-C4) or dialkylamino group (C1-C4), it being possible for said alkyl radicals to form, with the nitrogen atom that carries them, a heterocycle that comprises from 5 to 7 members, optionally comprising another heteroatom that may or may not be different from nitrogen; preferably, R _a and R ' _a represent a (C 1 -C 3) alkyl group optionally substituted by a hydroxyl group, such as methyl or ethyl, or a benzyl group;

- R'c represents a hydrogen atom, an arylalkyl group (Ci-

C4) or a C1-C6 alkyl group which is optionally substituted;

- R _g , R ' _g , R ” _g , R'” _g , Rh, R'h, R ”he Rh '” which can be identical or

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6/64 different, represent a hydrogen atom, a halogen atom, a group an amino, alkylamino (C1-C4), dialkylamino (C1-C4), cyano, carboxyl, hydroxyl or trifluoromethyl, an acylamino radical, C1- alkoxy C4, 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 the (C1) alkoxy -C4), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1-C4), or others of the two alkyl radicals linked by the nitrogen 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’h, 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, linked by two adjacent carbon atoms, together form a benzene or indene ring, or a fused heterocycloalkyl or fused heteroaryl group; the benzene, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino, alkylamino (C1-C4), dialkylamino (C1-C4), cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino radical, C1 alkoxy -C4, 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 the (C1-) alkoxy C4), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1-C4), or others of the two alkyl radicals linked by the nitrogen 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 and R’g; R’’g and R ’’ ’g together form a benzo group;

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- Ri, R'i; Ri ”and R '’ ’i, which may be identical or different, represent a hydrogen atom or a (C1-C4) alkyl group; in particular, Ri, R’i, Ri ’’ and R ’’ ’i represent a hydrogen atom;

- R1, R2, R3, R4, R'1, R'2, R'3 and R'4, which can be identical or different, represent a hydrogen atom, an alkyl group (C1-C4), alkoxy (C1- C4), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) or dialkylamino (C1-C4), being possible for said radicals to form, with the nitrogen atom that carries them, a heterocycle that comprises from 5 to 7 limbs, optionally comprising another heteroatom that may or may not be different from nitrogen; in particular, R1, R2, R3, R4, R’1, R’2, R’3 and R’4 are hydrogen atoms or an amino group; in particular, R1, R2, R3 and R4 represent a hydrogen atom;

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

(i) a covalent σ bond, (ii) or one or more radicals or their combinations selected from -SO2-, -O-, -S-, -N (R) -, -N ⁺ (R) (R ^o ) -, -C (O) -, with R and R ^o , which can be identical or different, representing a hydrogen atom, an alkyl (C1-C4) or hydroxyalkyl (C1-C4) radical or an arylalkyl (C1 -C4); in particular, Ta and Tb represent a covalent bond σ 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) (R ^o ) -, with R and R ^o , which can 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 two heteroatoms, particularly two nitrogen atoms, and comprising in particular from 5 to 7 members, such as imidazolium, piperazinyl, piperazinium, homopiperazinyl or homopiperazinium, optionally substituted by

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8/64 a (C1-C4) alkyl group, such as methyl;

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

- m, m ', ne n', which can 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 10 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 σ, 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 ⁺ R ^to R ^p R ^Y R ^õ or a phosphonium group: P ⁺ R ^to R ^p R ^Y R ^õ with R ^a , R ^e , R ^Y and R ^õ , which can be identical or different, representing a hydrogen atom or a (C1-C4) alkyl group; or (v) a group with a thiol protection function;

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

[016] Another object of the present invention is a dye composition comprising, in an acceptable cosmetic medium, at least one

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9/64 fluorescent dye comprising a heterocyclic group of formula (I), (II) or (III) as defined above and, optionally, a reducing agent.

[017] An object of the present invention is also the new fluorescent dyes of formula (I), (II) or (III) as defined above.

[018] The coloring 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.

[019] Furthermore, the process of the present invention makes it possible to obtain the coloring of the keratin materials, in particular, the human keratin fibers, in particular the 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 the bleaching of keratin materials, such as keratin fibers, preferably dark keratin fibers and, most preferably, dark hair.

[020] For the purpose of the present invention, the term "dark keratin material" is intended to mean one that exhibits 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.

[021] 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) ).

[022] The lightening of the hair is evaluated by the variation in the “tone level” before or after the application of the compound of formula (I), (II) or (III).

[023] The notion of tone is based on the classification of natural shades, a shade separating each shade from the shade that immediately follows or precedes it. This definition and the classification of

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10/64 shades are well known to hair styling professionals and are published in the book Science des traitements capillaires [Hair treatment sciences], by Charles Zviak 1988, published by Masson, pages 215 and 278.

[024] The range of tone levels from 1 (black) to 10 (very light blond), one unit corresponding to a tone; the larger the figure, the lighter the tone.

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

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

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

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

- the curve corresponding to the treated hair should show a reflectance in the wavelength range from 450 to 700 nm which is greater than the curve corresponding to the untreated hair;

- this means that, in the wavelength range from 450 to 700 nm, there is at least one interval where the reflectance curve corresponding to treated hair is greater than the reflectance curve corresponding to untreated hair. The term "major" 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 range of the length of

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11/64 wave, from 450 to 700 nm, at least one interval where the reflectance curve corresponding to treated hair is superimposed or less than the reflectance curve corresponding to untreated hair.

[027] Preferably, the wavelength where the difference is at most between the reflectance curve of treated and untreated hair is within the wavelength range of 450 to 650 nm and preferably within the range wavelength from 450 to 620 nm.

[028] For the purpose of the present invention, and unless otherwise specified:

- the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical can be replaced by at least one substituent carried by a carbon atom, 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) C2-C4 hydroxyalkoxy, acylamino and amino substituted by two radicals C1-C4 alkyl, 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 5 to 6 members, which are saturated or unsaturated, which optionally comprises another heteroatom that can 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;

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

- an amino radical substituted by one or two C1C6 alkyl radicals, which can be identical or different, optionally carrying 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 heterocycle comprising from 5 to 7 limb, 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 ') in which 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 in which the R radicals, which may or may not be identical, represent a hydrogen atom or a C1-C4 alkyl radical optionally carrying at least one hydroxyl group; an alkylsulfonylamino radical (R'SO2-NR-) in which the radical R represents a hydrogen atom or a C1-C4 alkyl radical optionally carrying at least one hydroxyl group, and the R 'radical represents a C1-C4 alkyl radical or a phenyl radical; an aminosulfonyl radical ((R) 2N-SO2-) in which the R radicals, which may or may not be 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);

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- a cyan group;

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

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

- hydroxyl;

- C1-C4 alkoxy;

- C2-C4 (poly) hydroxyalkoxy;

- a C1-C2 alkylthio radical;

- alkylcarbonylamino (RCO-NR'-) in which the radical R 'is a hydrogen atom or a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R is a C1-C2 alkyl radical or an amino radical substituted by two C1-C4 alkyl groups, which can be identical or different, optionally carrying at least one hydroxyl group, it being possible for said radicals to 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 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 C1C4 alkyl groups, which may be identical or different, optionally carrying at least one hydroxyl group, said radicals alkyl possibly forming, with the 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;

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- alkoxycarbonyl (RO-CO-) where the radical R is a C1-C4 alkyl radical or an amino radical substituted by two C1-C4 alkyl groups, which can be identical or different, optionally carrying at least one hydroxyl group, being possible for said alkyl radicals to 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 or may not be different from nitrogen;

- a cyclic or heterocyclic radical or a non-aromatic part of an aryl or heteroaryl radical can also be replaced by one or more oxo or thioxo groups;

- 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 group, condensed or non-condensed, optionally cationic, comprising from 5 to 22 members and from 1 to 6 heteroatoms selected from a nitrogen, oxygen, sulfur and selenium atom, and by least one ring that is aromatic; preferably a heteroaryl radical is selected from the acridinila, benzimidazolyl, benzobistriazolil, benzopirazolil, benzopiridazinil, benzoquinolil, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihidrotiazolil, imidazopyridinyl, imidazolyl, indolyl, isoquimolil, naftoimidazolil, naftooxazolil, naftopirazolil, oxadiazolyl , oxazolyl, oxazolopyridyl, phenazinyl, fenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazil, pyridyl, pyridinoimidazolyl,

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15/64 pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopirylyl, triazolyl, xantilil and their ammonium salts;

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

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

- a "sterically hindered cyclic radical" is a substituted or unsubstituted cyclic radical, aromatic or non-aromatic, impeded by steric effects or restrictions, comprising from 6 to 14 members, which can be dotted; as a means of sterically hindered radicals, mention may be made of the [1.1.0] butane, mesityl bicycle 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 condensed or non-condensed, monocyclic or polycyclic non-aromatic radical containing 5 to 22 members, comprising 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium;

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

- the term "optionally substituted" designated for the alkyl radical implies that said radical can be replaced 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 form

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16/64 possibly, with the nitrogen atom that carries them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom that may or may not be different from nitrogen; (v) or a quaternary ammonium group -N + R'R''R ''', M ^- for which R', R ”, R ''', which can be identical or different, represents a hydrogen atom or a C1-C4 alkyl group or -N + R'R''R '''forms a heteroaryl, such as imidazole, optionally substituted by a C1-C4 alkyl group, and M ^- represents the counterion of the corresponding organic acid, inorganic acid or halide;

- an "alkylene chain" represents a divalent C1-C18 chain; particularly C1-C6, more preferably C1-C2, when the chain is linear; optionally substituted by one or more halogen atoms or groups, which can be identical or different, selected from hydroxyl, alkoxy, (di) (alkyl) amino (C1-C4), R ^a -Z ^to -C (Z ^b ) - with Z ^a and Z ^b , which can be identical or different, representing an oxygen or sulfur atom, or an NR ^a 'group, and R ^a representing an alkali metal, a hydrogen atom or an alkyl group and R ^a 'representing a hydrogen atom or an alkyl group;

- an "alkoxy radical" is an alkyloxy or alkyl-O- radical for which the alkyl radical is a straight or branched C1C16 hydrocarbon based radical, preferably C1-C8;

- an "alkylthio radical" is an S-alkyl radical for which the alkyl radical is a C1-C16 linear or branched hydrocarbon based 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 that limit the extension of the range of values are included in this range of values;

- an “organic or inorganic acid salt” is more particularly

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17/64 selected from a salt derived: (i) hydrochloric acid HCl; (ii) hydrobromic acid HBr; (iii) sulfuric acid H2SO4; (iv) alkylsulfonic acids: Alq-S (O) 2OH, such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alq-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as from toluenoxysulfinic acid and phenoxysulfinic acid; xii) H3PO4 phosphoric acid; xiii) CH3COOH acetic acid; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF4;

- an "anionic counterion" is an anion or an 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, among which are C1-C6 alkyl sulfonate: Alq-S (O) 2O- such as methyl sulfonate or mesylate and ethyl sulfonate; iv) aryl sulfonates: ArS (O) 2O- such as benzene sulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrato; viii) lactate; ix) alkyl sulfates: Alq-O-S (O) O- such as methyl sulfate and ethyl sulfate; x) arylsulfates: Ar-O-S (O) O- such as benzenesulfate and toluenesulfate; xi) alkoxysulfates: Alq-O-S (O) 2O- such as methoxy sulfate and ethoxy sulfate; xii) aryloxysulfates: Ar-O-S (O) 2O-; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

[029] Fluorescent dyes that comprise a heterocyclic group of formula (I), (II) or (III) are compounds capable of absorbing in UV radiation or in the visible range at an Aabs wavelength between 250 and 800 ° nm and capable of re-emitting in the visible range at an emission of the Àem wavelength between 400 and 800 ° nm.

[030] Preferably, the fluorescent compounds comprising a heterocyclic group of the present invention are dyes

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18/64 capable of absorbing in the visible range Àabs between 400 and 800 ° nm and of re-emitting in the visible range Àem between 400 and 800 ° nm. Most preferably, the fluorescent dyes of formula (I), (II) or (III) are dyes capable of absorbing in an Àabs between 420 ° nm and 550 ° nm and re-emitting in the visible range in an Àem between 470 and 600 ° nm.

[031] A specific embodiment of the present invention relates to fluorescent dyes that comprise a heterocyclic group of formula (I), (II) or (III), where m is 0.

[032] According to a specific embodiment of the present invention, the fluorescent dyes of the present invention, of which the heterocycle of formula:

group represent a cationic or non-cationic heterocyclic, optionally substituted

in particular, the heterocycle is monocyclic and saturated, comprises a total of two nitrogen atoms and is formed from 5 to 8 members.

[033] In particular, the heterocycle is selected from piperazinyl, homopiperazinyl, hexahydro-1,4-diazepinyl and piperazinium, homopiperazinium or hexahydro-1,4-diazepine optionally substituted by a (C1-C4) alkyl group.

[034] According to another embodiment, thiol fluorescent dyes comprise a heterocyclic group, of formula (I), (II) or (III), whose heterocyclic:

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or

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

[035] In particular, the heterocyclic group is selected from pyrrolidinyl, piperidyl and azepanyl.

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

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

[038] According to another specific embodiment of the present invention, in the formula mentioned above (III), Y is a protection group known to those skilled in the art, for example, those described in the books Protective Groups in Organic Synthesis, TW Greene, publisher John Willey & Sons, NY, 1981, pages 193-217; Protecting Groups, P. Kocienski, Thieme, 3rd ed.

2005, ch. 5.

[039] In particular, when Y represents a thiol protection group, Y is selected from the following radicals:

- (C1-C4) alkylcarbonyl;

- (C1-C4) alkylthiocarbonyl;

- alkoxycarbonyl (C1-C4);

- alkoxycarbonyl (C1-C4);

- (C1-C4) alkylthiothiocarbonyl;

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

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

- arylcarbonyl, such as a phenylcarbonyl;

- aryloxycarbonyl;

- arylalkoxycarbonyl (C1-C4);

- (di) (C1-C4) (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 1 to 4 heteroatoms below:

(i) monocyclic comprising 5, 6 or 7 members, 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, pyrillium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine, azepine, oxazepinil, oxazepinium, tiepinil, tiepinium, imidazolyl, imidazolium;

(ii) bicyclic comprising from 8 to 11 members, such as indolyl, indoline, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazole, optionally monocyclic or thienocyclic compounds groups, such as (C1-C4) alkyl, for example the

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21/64 methyl or polyhaloalkyl (C1-C4), 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 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, tetrahydrobenzyl, dihydrofluorohydride, dihydrofluorine groups, such as (C1-C4) alkyl, oxo or thioxo; or the heterocycle represents the following group:

^R '\ R' ^g

R ' ^h ' _n (CR'-R '·).

/

R ' ^d in nup R' ^c R ' ^d R' ^and R ' ^f R' ^g and R ' ^h which can be identical or ^ 111 quv i \, i \, ix, ix, ix ix, qu ^ puuv Ovi iuvi iliwx_ / ov / u different, represent a hydrogen atom or a (C1-C4) alkyl group

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22/64 or two groups R ' ^g with R' ^h , and / or R ' ^and with R' ^f , form an oxo or thioxo group, or R ' ^g with R' ^and together form a cycloalkyl; ev represents an integer between 1 and 3 inclusive; preferably, R ' ^c to R' ^h represents a hydrogen atom; and An ^- represents a counterion;

- irnnin -CVNR'cR'd \ —M + R'eR'f- Δη ^- γόπί R'c R'd R'e p R'f ni ip

- isolioui ui no -vz (inr ix) —in r Γχ; λάιι with lx, lx, lx and lx, which can 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;

- icpfipi irpip -P / NR'cR'd \ ₌ K | R'e R'c R'd p R'e ponfrtrmp

- isothiourea -c (inr r) = nr with r, R, and r as defined above;

- (di) arylalkyl (C1-C4) optionally substituted, such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted by one or more groups, in particular, selected from alkyl (C1-C4), alkoxy (CiC4), such as methoxy, hydroxyl, (C1-C4) alkylcarbonyl and (di) (alkyl) amino (C1-4) amino, such as dimethylamino;

- (di) heteroarylalkyl (C1-C4) optionally substituted, 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 the pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide groups, such as 4-pyridyl or 2-pyridyl N-oxide, pyrilium, pyridinium or triazinyl, optionally substituted by one or more groups, such as alkyl, particularly methyl, advantageously (di) heteroaryl (C1-C4) alkyl is (di) heteroarylmethyl or (di) heteroarylethyl;

- CR1R ² R ³ with R ¹ , R ² and R ³ , which can be identical or different, representing a halogen atom or a group selected from:

- (C1-C4) alkyl;

- (C1-C4) alkoxy;

- optionally substituted aryl, such as phenyl optionally

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23/64 replaced by one or more groups, such as (C1-C4) alkyl; alkoxy (C1-C4) or hydroxyl;

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

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

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

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

[040] According to a specific embodiment, the fluorescent protected thiol dyes comprise the heterocyclic groups of formula (III) comprising a group Y (i) which is a 5- or 6-membered aromatic, cationic monocyclic heteroaryl group, comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3triazolium, 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 membered cationic heteroaryl group, such as indoline, benzoimidazolium, benzoxazolium or benzothiazolium, these monocyclic or bicyclic heteroaryl groups being optionally substituted by one or more groups, such as alkyl, for example, methyl, or polyhaloalkyl (C1-C4), for example, trifluoromethyl (iii) or a heterocyclic group below:

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R ' ^d

Anem that R ' ^c and R' ^d , which can 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.

[041] In particular, Y represents a group selected from oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4oxazolium, 1,2,4- thiadiazolium, pyrillium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium, benzoimidazolium, benzoxazolium and benzothiazolium, these groups being optionally substituted by one or more alkyl groups (C1C4), in particular, methyl.

[042] In particular, the fluorescent dyes of formula (III) comprising a group Y represent an alkali metal or a protecting group, such as:

- (C1-C4) alkylcarbonyl, such as methylcarbonyl or ethylcarbonyl;

- arylcarbonyl, such as phenylcarbonyl;

- alkoxycarbonyl (C1-C4);

- aryloxycarbonyl;

- arylalkoxycarbonyl (C1-C4);

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

- (C1-C4) (alkyl) arylaminocarbonyl;

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- optionally substituted aryl, such as phenyl;

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

- 5- or 6-membered cationic monocyclic heteroaryl, such as pyrillium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium or imidazolium; these groups being optionally substituted by one or more identical or different (C 1 -C 4) alkyl groups, such as methyl;

- 8 to 11 membered cationic bicyclic heteroaryl, such as benzoimidazolium or benzoxazolium; these groups being optionally substituted by one or more identical or different (C1-C4) alkyl groups, such as methyl;

- cationic heterocycle of the formula below:

An ^-

- isothiouronium -C (NH2) = N + H2; An ^- ;

- isothiourea -C (NH2) = NH;

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

[043] 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 part in the phenyl in the ortho or para position is in position 4-4 ', 2-2', 4-2 'or 2-4'.

[044] Another specific embodiment of the present invention relates to the symmetrical fluorescent disulfide dyes of formula (I), that is, Ra, Rg,

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R'g. Rh, R'h, Ri, R'i, Ri, R2, R3, R4, T _a , men are identical to R ' _a , R ”g, R'” _g . R ”h, R” 'h, R ”i, R”' i, R'i, R'2, R'3, R'4, Tb, m 'and n', respectively.

[045] As an example of the fluorescent dyes of the present invention, a specific mention can be made of the following

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Anionic 33/64; and M ⁺ representing an alkali metal.

[046] Protected thiol dyes of formula (III ”) can be synthesized in two stages. The first stage consists of the preparation of the unprotected thiol dye (III ') according to the 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 consists of protecting the thiol function according to conventional methods known to those skilled in the art for the production of protected thiol dyes of formula (III ”). As an example to protect the thiol -SH function of the thiol dye, the methods can be used in the books Protective Groups in Organic Synthesis, TW Greene, John Willey & Sons ed., NY, 1981, page 193-217; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, ch. 5.

[047] This method can be illustrated by the method consisting of (i) the production of fluorescent heterocyclic thiol dyes of formula (III ') by the reduction of a heterocyclic bi-chromophore fluorescent dye carrying a -SS- disulfide function such as (lj and (ii) in protection, according to conventional methods, said thiol function of (III ') in order to obtain the protected thiol fluorescent dyes of formula (III ”).

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with Ri, R2, R3, R4, Ra, R _g , R'g, Rh, R'h, Ri, R'i, m, n, Het and M 'being as defined above; Y represents a protection group for thiol function; and R of Y'R represents a nucleophobic leaving group, for example, mesylate, tosylate, triflate or halide.

[048] 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 books mentioned above, said protective thiol compound comprising at least one nucleophilic function , can be reacted with a sufficient, 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 in order to form a covalent ligação bond, as can be seen schematically below:

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_ with Ri, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, m, n, Het, Y and M 'being as defined above; Nu representing a nucleophilic group; And representing an electrophilic group, and Σ the bond generated after the attack by the nucleophile on the electrophile.

As an example, the covalent bonds Σ that can be produced are listed in the Table below, based on the condensation of the electrophiles with the nucleophiles:

Table 1

Electrophiles E Naked Nucleophiles Covalent bonds Σ Activated esters * Amines Carboxamides Acyl azides ** Amines Carboxamides Acyl halides Amines Carboxamides Acyl halides Alcohols Esters Acyl cyanides Alcohols Esters Acyl cyanides Amines Carboxamides Alkyl halides Amines Alkylamines Alkyl halides Carboxylic acids Esters Alkyl halides Thiols Thioethers Alkyl halides Alcohols Ethers Sulfonic acids and their salts Thiols Thioethers Sulfonic acids and their salts Carboxylic acids Esters Sulfonic acids and their salts Alcohols Ethers Anhydrides Alcohols Esters Anhydrides Amines Carboxamides Aryl halides Thiols Thioethers Aryl halides Amines Arylamines Aziridines Uncle Thioethers

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Electrophiles E Naked Nucleophiles Covalent bonds Σ Carboxylic acids Amines Carboxamides Carboxylic acids Alcohols Esters Carbodiimides Carboxylic acids N-acylureas or anhydrides Diazoalkans Carboxylic acids Esters Epoxies Thiols Thioethers Haloacetamides Thiols Thioethers Imide esters Amines Amidines Isocyanates Amines Urea Isocyanates Alcohols Urethanes Isothiocyanates Amines Tioureas Maleimides Thiols Thioethers Sulfonic esters Amines Alkylamines Sulfonic esters Thiols Thioethers Sulfonic esters Carboxylic acids Esters Sulfonic esters Alcohols Ethers Sulphonyl halides Amines Sulphonamides

activated esters of the general formula -CO- part with part representing a starting group, such as oxysuccinimidyl, oxybenzotriazolyl, aryloxy which is optionally substituted;

** acyl azides can be rearranged to provide isocyanates.

[049] A variation of this process is the use of a fluorescent chromophore having an electrophilic acrylate function (-OCO-C = C-) in which an addition reaction is carried out that will produce a ligação bond.

[050] The use of a Y'SH thiol reagent comprising a group Y 'as defined above, the nucleophilic SH function can also be used, which can react with the carbon atom in the alpha position with respect to the halogen atom carried by the chromophore fluorescent (a) to provide the protected thiol fluorescent dye of formula (III ''):

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with Ri, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, m, n, Het, Y ', (III ”) and

M 'being as defined above; and Hal representing a nucleophobic halogen atom, such as bromine, iodine or chlorine.

[051] More particularly, a nucleophobic leaving group can be replaced by a thiourea group (S = C (NRR) NRR) in order to produce the isothiourons. For example, if the thiourea group formulates a thioimidazolium (β), the reaction scheme is as follows:

SH

with Ra, R'c, R'd, Rg, R'g, Rh, R'h, Ri, R'i, m, n, Het, Hal, An- and M 'being as defined above.

[052] A variation is to use, in place of the halide that comprises the fluorescent chromophore (a '), a chromophore that comprises another type of nucleophile, such as tosylate or mesylate.

[053] According to another possibility, certain protected heterocyclic thiol fluorescent dyes (III '' ') can be obtained

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38/64 by the reaction of a protected thiol compound with a compound that carries two carboxylic acid functions that are activated according to conventional methods (for example, the reaction with a carbodiimide or thionyl chloride). The resulting product (d) is subsequently reacted with a fluorescent heterocyclic chromophore that carries a nucleophilic function (c), for example, of the primary or secondary amine type, or of the aliphatic or aromatic alcohol type, such as phenol.

with Ri, R2, R3, R4, Ra, Rg, R'g, Rh, R’h, Ri, R’i, Het, Ta, Y ’, m, n, and

M ’, E, Nu and (III’ ’’) being as defined above.

[054] According to another possibility, the fluorescent heterocyclic thiol dyes protected from formula (III '' '' ') can be obtained by reacting a compound comprising a thiol group protected by a Y' group, and a hydroxyl group previously activated for a halide leaving group (d '), for example, mesylate, tosylate, triflate or halide, with a fluorescent chromophore (c') carrying an amino nucleophilic function in the heterocyclic part of Het.

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with Ri, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, Het, Ta, Y ', n, M', Σ and E are as defined above.

[055] As a means of example, a compound containing a protected thiol group containing a nucleophobic leaving group R, for example, mesylate, tosylate or triflate, which can undergo nucleophilic attack by the amine transported by the styrene fluorescent chromophore:

[056] Another alternative comes from the use of halides as a nucleophobic starting group in a thiol compound that can be replaced by a primary amine function, for example, carried by a fluorescent styrene chromophore:

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[057] According to another possibility, the fluorescent thiol dyes of formula (III) according to the present invention can be obtained by reacting a compound comprising a thiol group Y as defined above and an electrophilic group (f) with a pyridinium compound comprising a nucleophilic group. As an example, an aldehyde or ketone when G represents an oxygen atom, can be condensed with an "activated methylene", such as alkylpyrid (e) in order to generate an ethylene bond> C = C <. This reaction is commonly known as “Knoevenagel” condensation. 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:

with Ri, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, Het, Ta, m, n, 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

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41/64 is a (C1-C4) alkyl group.

[058] A variation of this process is to perform (i) a “Knoevenagel” condensation of an aldehyde or a ketone comprising a Het heterocycle comprising a nucleophilic amino group (g), with an “activated methylene”, such as alkylpyridinium (and ) in order to provide the heterocyclic styrene intermediate (h). The latter can subsequently (ii) be reacted in a cyclic monomer containing at least one thiolactam function, so as to provide, after opening the ring, the heterocyclic thiol fluorescent dye (IIIa ”” ”)

[059] With R1, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, Het, n and M 'as defined above, G and G' which can be identical or different, an oxygen or sulfur atom or an N (R) group with R representing a hydrogen atom or a (C1-C4) alkyl group.

[060] Alternatively, when the reagent (g ') comprises a Het group comprising an exocyclic amino group, the fluorescent dye comprising an amide, thioamide, guanidine or group

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42/64 amidine is obtained.

[061] With Ri, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, Het, n, M ', G and G', as defined above and R representing a hydrogen atom or an alkyl group. It is understood that the amide of the reactant (g) 'heterocycle that can be protected and then unprotected.

[062] Reference can be made to the book Advanced Organic

Chemistry, J. March, 4th ed. John Willey & Sons, 1992 or TW Greene

Protective Groups in Organic Synthesis, for more details on the operating conditions used for the processes mentioned above.

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

[064] Protected thiol dyes can be unprotected by conventional routes.

[065] The disulfide dyes of formula (I) can be

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43/64 synthesized in two stages. The first stage consists of preparing the unprotected thiol dye (III) according to the methods described above. In addition, the second stage consists of oxidizing the unprotected thiol dye (III) to form the symmetrical disulfide dye of formula (I '). The 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.

z— \ / ^SH Η O (HéÔ-ÍCR.R. ^ CCRgR ^ _(Γ) rr

[066] According to another possibility, an equivalent of a disulfide compound (b ") can 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 one “Reactive fluorescent chromophore” or a compound comprising such a “reactive fluorescent chromophore” (a), such as at least two equivalents. In other words, (a) comprises an electrophilic function in order to form a covalent bond Σ, in order to provide the disulfide dye of formula (I ”), as can be seen schematically below:

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+ JfríCRjR ^ -SS- (CR ₃ R ₄ ) _n -5 <w

· Ι. · ΊΜ <ιΙΙ (CR3R ₄ ) _n '' (CR ₃ R ₄ ) _fl

[067] With Ri, R2, R3, R4, Ra, Rg, R’g, Rh, R h, Ri, R’i, m, n, Het and M ', as defined above; Nu representing a nucleophilic group; And representing an electrophilic group, and Σ the bond generated after the attack by the nucleophile on the electrophile. As an example, the covalent bonds Σ that can be produced are listed in the Table above based on the condensation of the electrophiles with the nucleophiles.

[068] According to another possibility, certain fluorescent disulfide dyes (I ”) can be obtained by reacting at least two molar equivalents of a“ reactive fluorescent chromophore ”(c) comprising a nucleophilic part, with an equivalent of a compound dielectrophilic disulfide (d ”), in order to provide the disulfide dye (I”):

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a [069] [070] With Ri, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, Het, m, n, M ', E, Nu and ( I ”) as defined above.

[071] According to another possibility, the fluorescent heterocyclic disulfide dyes of formula (I '”) can be obtained by the reaction of a compound (d' ') comprising a disulfide group, and a hydroxyl group activated before a nucleophobic leaving group Lg, for example, with mesylate, tosylate, triflate or halide, with fluorescent chromophore (c ') carrying a nucleophilic function in the heterocyclic part of Het.

[072] With R1, R2, R3, R4, Ra, Rg, R’g, Rh, R’h, Ri, R’i, Het, n, M ’and Lg as defined above.

[073] By way of example, a compound containing a disulfide group contains a nucleophile leaving group R, for example, mesylate, tosylate

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46/64 or triflate, which can undergo nucleophilic attack by the amine transported by the fluorescent chromophore styrene, to provide the particular disulfide dye.

ísl

[074] Another alternative arises from the use of halides as a nucleophobic starting group in a disulfide compound that can be replaced by a secondary amine function, for example, carried by a fluorescent chromophore:

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47/64 [075] According to another possibility, the fluorescent disulfide dyes (I) according to the present invention, can be obtained by the reaction of a compound comprising a disulfide group as defined above and an electrophilic group (f ” ) with a compound comprising a nucleophilic group. For example, an aldehyde or ketone, when G represents an oxygen atom, can be condensed with an "activated methylene", such as alkylpyridinium (e) in order to produce an ethylene bond> C = C <. This reaction is commonly known as “Knoevenagel” condensation. The term "activated methylenes" is intended to mean those mentioned, for example, in DE 19,951,134; mention may be made, in particular, of 1,2dialkylpyridinium, and in particular 1,2-dimethylpyridinium:

with Ri, R2, R3, R4, Ra, Rg, R'g, Rh, R'h, Ri, R'i, Het, Ta, m, n, (I ') and M' are as defined above and G represents an oxygen or sulfur atom or an N (R) group with R representing an atom of

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48/64 hydrogen or a (C1-C4) alkyl group.

[076] can be made a reference to the book Advanced Organic Chemistry, J. March, 4th ed. John Willey & Sons, 1992 or TW Greene Protective Groups in Organic Synthesis, for more details on the operating conditions used for the processes mentioned above.

[077] The dissimetric disulfide dyes of formula (I) can be synthesized in a single stage by reacting an unshielded fluorescent thiol dye with a Y 'protected thiol fluorescent dye to form the disulfide dye formula (I).

with Ra, R'a, Rg, R'g, R''g, R '' 'g, Rh, R'h, R ”h, R”' h, Ri, R'i, R''i, R ”'i, m, m', n, n ', Ta, Tb, Het, Het', (I) and M 'as defined above; Y 'represents a thiol protection group.

[078] The dissimetric disulfide dyes of formula (II) can be synthesized in a single stage by the reaction of a dye

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49/64 fluorescent thiol protected with an unprotected thiol compound to form the disulfide dye of formula (i).

with Ra, R'a, Rg, R'g, R''g, R '' 'g, Rh, R'h, R ”h, R”' h, Ri, R'i, R''i, R ”'i,

R'c, m, m ', n, n', Ta, Tb, Het, Het ', (II) and M' as defined above; Y 'represents a thiol protection group.

[079] 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 composition of the present invention can also contain a reducing agent. This reducing agent can be selected from thiols, for example, cysteine, homocysteine or thiolactic acid, the salts of these thiols, phosphines, disulfides, sulfides, thioglycolic acid, and also their esters, in particular, monothioglycolate glycerol, and thioglycerol. This reducing agent can also be selected from borohydrides and their derivatives, for example, the borohydride, cyanoborohydride, or triacetoxyborohydride or trimethoxyborohydride salts: sodium salts, lithium salts, potassium salts, calcium salts, salts of quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-nPetition 870190108379, of 10/25/2019, page 58/174

50/64 butylammonium or benzyltriethylammonium); borane catechol.

[080] The dye composition that can be used in the present invention generally contains an amount 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 between 0.005% and 20% by weight, and more preferably between 0.01% and 5% by weight, with respect to the total weight of the composition.

[081] The dye composition can also contain additional direct dyes. These direct dyes are, for example, selected from direct dyes of neutral, acidic or cationic nitrobenzene, direct azo neutral, acidic or cationic dyes, tetraazopentamethine dyes, neutral, acidic or cationic dyes, in particular, dyes of anthraquinone, azine dyes, triarylmethane dyes, indoamine dyes and natural dyes.

[082] Among direct natural dyes, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermésico acid, purpurogalin, protocatechhaldehyde, indigo, isatin, curcumin, spinulosin and apigenindin. Decoction extracts containing these natural dyes and, in particular, poultices or henna extracts, can also be used.

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

[084] Among the oxidation bases, mention may be made of para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-paraaminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

[085] Among these couplers, particular mention can be made of half-phenylenediamines, half-aminophenols, half-diphenols,

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51/64 naphthalene couplers, heterocyclic couplers and their addition salts.

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

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

[088] In general, the addition of salts from the oxidation bases and couplers that can 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, aqueous ammonium, amines or alkanolamines.

[089] The appropriate medium for dyeing, also known as dye support, is a cosmetic medium consisting, in general, 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, as well as aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[090] The solvents, when they are present, are preferably in the proportions between preferably 1% and 40% by weight approximately, with respect to the total weight of the dye composition, and even more preferably between about 5 % and 30% by weight.

[091] According to a variation, the present invention contains

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52/64 a reducing agent capable of reducing keratin disulfide bonds. This reducing agents is as defined above.

[092] The dye composition may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants or their mixtures, anionic, cationic, non-ionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners and, in particular, anionic, cationic, non-ionic, non-ionic, amphoteric associative polymeric thickeners, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as, for example, modified silicones or unmodified, volatile or non-volatile, such as amino silicones, film-forming agents, ceramides, preservatives, opacifiers or conductive polymers.

[093] The above adjuvants are, in general, present in an amount, for each of them, between 0.01% and 20% by weight, with respect to the weight of the composition.

[094] Obviously, those skilled in the art will take care in selecting this or these additional possible compounds, in such a way that the advantageous properties intrinsically associated with the dye composition according to the present invention are not or are not substantially impaired by (s) contemplated addition (s).

[095] The pH of the dye composition is, in general, between about 4 and 14 and preferably between about 5 and 11. It can be adjusted to the desired value using acidifying or basifying agents normally used in dyeing the keratin fibers or by conventional buffer systems.

[096] Among acidifying agents, a mention can be made,

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as an example, to 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.

[097] Among the basifying agents, mention may be made, for example, of aqueous ammonia, alkaline carbonates, alkanolamines, such as mono, di and triethanolamines, and also their derivatives, sodium hydroxide or potassium hydroxide and the compounds of formula (Y) below:

^R a2

N WN to Ra ^Z 4 where Wa is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; Ra1, Ra2, Ra3 and Ra4, which can be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a hydroxyalkyl radical.

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

[099] In accordance with a specific embodiment in the process of the present invention, a reducing agent can be applied as a pretreatment before application of the composition containing at least one heterocyclic fluorescent dye of formula (I), (II) or (III) .

[0100] This reducing agent can be selected from thiols, for example, cysteine, homocysteine or thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid and

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54/64 also its esters, in particular, glyceryl monothioglycolate and thioglycerol. This reducing agent can also be selected from borohydrides and their derivatives, for example, the salts of borohydrides, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride: sodium salts, lithium salts, potassium salts, calcium salts, salts of quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-n-butylammonium or benzyltriethylammonium); borane catechol.

[0101] This pretreatment can 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.

[0102] When the heterocyclic thiol fluorescent dye (III) comprises a thiol Y protection group, the process of the present invention can be preceded by a deprotection step, which aims to restore the SH function in situ.

[0103] As an example, it is possible to unprotect the SY function with a protection group Y by adjusting the pH, as follows:

Table 2

Y: protection group Deprotection Alkylcarbonyl pH> 9 Arylcarbonyl pH> 9 Alkoxycarbonyl pH> 9 Aryloxycarbonyl pH> 9 Arylalkoxycarbonyl pH> 9 (di) (alkyl) aminocarbonyl pH> 9 (alkyl) arylaminocarbonyl pH> 9 Optionally substituted aryl, such as phenyl pH> 9

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5-, 6- or 7-membered monocyclic heteroaryl, such as oxazolium pH> 9 8- to 11-membered bicyclic heteroaryl, such as benzoimidazolium or benzoxazolium pH> 9

[0104] The deprotection step can also be performed during a pre-hair treatment step, for example, the pre-reducing hair treatment.

[0105] According to a 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.

[0106] 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.

[0107] According to 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 post-treatment with the reducing agent can 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.

[0108] In the staining process, another variation is to apply the fluorescent dye of formula (I), (II) or (III) at the same time with the reducing agent.

[0109] A specific embodiment of the present invention relates to a process in which the fluorescent dye of formula (I), (II) or

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56/64 (III) can be applied directly to the hair without the reducing agents, free from the previous reduction treatment or after reduction treatment.

[0110] Treatment with an oxidizing agent can be optionally combined. Any type of conventional oxidant in the field can be used. Therefore, it can be selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persals, such as perborates and persulfates and also enzymes, among which peroxidases, 2-electron oxidoreductases can be mentioned. , such as 4 electron uricases and oxygenases, such as laccases. The use of hydrogen peroxide is particularly preferred.

[0111] This oxidizing agent can be applied to fibers before or after application of the composition containing at least one fluorescent dye of formula (I), (II) or (III).

[0112] The application of the dye composition according to the present invention is, in general, carried out at room temperature. However, it can be performed at temperatures ranging from 20 to 180 ° C.

[0113] An object of the present invention is also a multi-compartment device or staining kit in which 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.

[0114] One of these compartments can also contain one or more other dyes of the direct dye or oxidation dye type.

[0115] The present invention also relates to a multi-compartment device in which a first compartment contains a

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57/64 dye composition comprising at least one fluorescent thiol dye of formula (I), (II) or (III); or a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials and / or the disulfide bond of the dyes of formula (I) or (II); and a third compartment contains an oxidizing agent.

[0116] 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 in order to release the thiol.

[0117] Each of the devices mentioned above can be equipped with means to deliver the desired mixture to the hair, for example, such as the devices described in the FR 2,586,913 patent.

[0118] The following examples serve to illustrate the present invention without, however, being subject to limitation. The fluorescent dyes in the examples below were fully characterized by conventional spectroscopy and spectrometry methods.

Examples

Synthesis Example

Example 1

2,1-diylpiperazine-4,1-diyl-4,1-phenylene (E) ethylene-2,1-diyl1} bis (1methylpyridinium) dimethyl sulfate [1]

[1]

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Synthesis scheme.

NMP

K ₂ CO ₃

H / iPrOH

AcOH

[1]

Stage 1: Synthesis of 4,4'-rDisuLFANODiiLBis (ETANO-2,1-DiiLPiPERAZiNA-4,1Diil) 1Dibenzaldehyde [0119] 2.5 g of 4-piperazin-1-ylbenzaldehyde, 1.37 g of 1-bromo- 2 [((2-bromoethyl) disulfanyl] ethane, 7.3 g of potassium carbonate (K2CO3), and 20 ml of N-methylpyrrolidinone (NMP) are mixed at 75 ° C for 55 h. The product is purified by chromatography on silica gel (eluent: 80/20 acetone / heptane then 90/10 dichloromethane / methanol 90/10). 469 mg of a yellow oil are recovered. The analyzes indicate that the product is in compliance.

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Stage 2: Synthesis of 4,4 '- {DisulfanodiilbisIEtane-2,1-Diylpiperazin-4,1Diyl-4,1-Phenylene (E) Ethene-2,1-Diyl1} Bis (1-Methylpyridinium) Dimethyl Sulfate IH [0120 ] 469 mg of 4.4 '- [disulfanediilbis (ethane-2,1-diyl-piperazin4,1-diyl)] dibenzaldehyde, 5 ml of isopropanol (iPrOH), 415 mg of 1,4-dimethylpyridinium methyl sulfate, 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 are added and the precipitate obtained is filtered, washed with 10 ml of isopropanol and then with 3 times 25 ml of acetone and dried. 610 mg of a red powder are recovered. The analyzes indicate that the product is in compliance.

[0121] NMR 1H (400 MHz, MeOH-d4) 2.68 (m, 8 H), 2.78 (t, 4 H), 2.95 (t, 4 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-I4- (2-sulfanylethyl) piperazin-1yl | phenyl} vinyl) pyridinium methyl sulfate I21

[2]

Synthesis scheme oOSPetição 870190108379, of 10/25/2019, p. 68/174

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H ₂ O

EtOH

Procedure [0122] Synthesis of the salt of 1-methyl-4 - ((E) -2- {4- [4- (2-sulfanylethyl) piperazin-1 -yl] phenyl} vinyl) pyridinium [2] [0123] 16 mg of compound [1] are dissolved in 10 ml of a water / ethanol mixture (v / v: 1/1). 60 mg (2 ^a eq.) Of 3 [bis (2-carboxyethyl) phosphine] propanoic acid hydrate in solution in 1 ml of water and 21 mg (4 ^a eq.) Of sodium bicarbonate in solution in 1 ml of water are added to the mixture. After stirring at 40 ° C for 30 minutes in an inert atmosphere, the analyzes indicate that the mixture contains predominantly the expected product [2].

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

Column: Waters XTerra MS C18 5 μm (4.6 x 50) mm

Mobile phase: A: water + 0.1% formic acid / B: acetonitrile

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

Flow speed: 1 ml / min

Detection: UV diode set λ = 400 - 700 nm

Retention time t = 3.0 min

Relative purity> 90%

MS (ESI +) m / z = 285 corresponds to the peak mass for the expected product monocation [2].

Coloring Example

Example 1

Coloring Process - Compound [1]

Preparation of composition A

Disulfite dye [1] 10-3 mol% Benzilic alcohol 4 g Polyethylene glycol 60 EO 6 g Hydroxyethylcellulose 0.7 g Alkylpolyglycoside in an aqueous medium solution containing 65% AM 4.5 g Demineralized water Qs100 g

Preparation of a composition B

Thioglycolic acid 1M Sodium hydroxide Qs pH 8.5 Demineralized water Qs100 g

[0124] At the time of use, compositions A (9 ml) and B (1 ml) are mixed, then the mixture obtained is applied to a tuft of 1 g of dark hair (tone level 4) for 30 minutes at temperature environment (the tufts are turned and re-impregnated after 15 minutes).

[0125] After rinsing with running water and drying, the whitening of the treated hair is observed: the tuft of the level of tone 4 has become visually lighter than the untreated control tufts.

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Example 2

Coloring Process with Compound [2] [0126] 10 ml of fresh solution of compound [2] from the synthesis example are applied to a tuft of 1 g of 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.

[0127] After drying, the tuft of tone level 4 became visually lighter than the untreated control tufts.

Remnant with respect to Successive Washing Operations:

[0128] The tufts so treated are divided in two, half are subjected to 5 successive washing operations, according to a cycle that includes moistening the tufts with water, washing with a conventional shampoo, rinsing with water, followed by drying.

Visual Observations [0129] During the washing operations, there is no visible flow of the dye, the foam of the shampoo and the rinse water are not colored.

[0130] The coloration observed in the tufts is preserved and the lightening effect remains visible in the hair of tone level 4, thus treated.

Results in the L * A * B * System:

[0131] The color of the tufts before and after 5 washes was evaluated in the L * a * b * system using a Konica Minolta ^® CM 2600D spectrophotometer, (D65 illuminant).

[0132] In this system L * a * b *, L * represents the color intensity, a * indicates the green / red color axis and b * the blue / yellow color 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 *,

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63/64 the redder the hue and the higher the b * value, the more yellow the hue.

[0133] The variation in coloring between tufts of hair TH4 (tone level 4) dyed and washed is measured by (AE) according to the following equation:

AE = J (L * - Lo *) 2 + (a * - a „*) ² + (b * - b _o *) 2 [0134] In this equation, L *, a * and b *, represent the values measured before of dyeing and L0 *, a0 * and b0 * represent the values measured after staining or after staining and washing operations.

[0135] The higher the AE value, the greater the difference in color between the TH4 tufts and the colored tufts.

Table 3

Treatment with the compound in the TH4 tufts ΔΕ After the application of compound 1 according to the present invention 8.84 After the application of compound 1 according to the present invention and 5 successive washing operations 7.38 After the application of compound 2 according to the present invention 4.22 After the application of compound 2 according to the present invention and 5 successive washing operations 5.24

[0136] The results in the Table show that there is no significant difference in color variation even after 5 washing operations. Therefore, the coloring and lightening effect of the hair remain virtually unchanged, which shows good resistance to washing the dyes of the present invention.

Reflection Results [0137] The clarification of the compositions according to the present invention and the remnant of said compositions in relation to the successive washing operations were also evaluated as a function of

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[0138] The reflectance is measured using a Konica Minolta® CM 2600D spectrophotocolorimeter equipment and after irradiating the hair with visible light in the wavelength range from 400 to 700 nm.

[0139] The reflectance results are illustrated in the graphs of Figures 1 and 2:

[0140] Firstly, it is observed that the reflectance of a tuft of hair treated with a composition according to the present invention is greater than that of untreated hair. Therefore, the tufts of treated hair appear to be noticeably lighter.

[0141] In addition, the results show that the reflectance of the tuft hairs of tone level 4, treated with the compositions of the present invention, changes very little after 5 washing operations. Therefore, the coloring and lightening effect on the hair remains virtually unchanged, which shows a good resistance of the dyes of the present invention to washing operations.

Claims (27)

Claims 1. FLUORESCENT DYE, characterized by being of formula (I), (II) or (III) below: Petition 870190108379, of 10/25/2019, p. 74/174 2/17 its salts of organic or mineral acid, its optical and geometric isomers, and solvates, such as hydrates; where in formulas (I), (II) or (III): - Ra and R ' _a , which can be identical or different, represent an arylalkyl group (C1-C4) or an alkyl group (C1-C6), optionally substituted with a hydroxyl or amino, alkylamino (C1-C4) or dialkylamino group (C1-C4), being possible for said alkyl radicals to form, with the nitrogen atom that carries them, a heterocycle that comprises from 5 to 7 members, optionally comprising another heteroatom that may or may not be different from nitrogen; - R'c represents a hydrogen atom, an arylalkyl (C1-C4) group or a C-i-Ce alkyl group that is optionally substituted; - R _g , R ' _g , R ” _g , R'” _g , Rh, R'h, R ”he Rh” 'which can be identical or different, represent a hydrogen atom, a halogen atom, a group one amino, alkylamino (C1-C4), dialkylamino (C1-C4), cyano, carboxyl, hydroxyl or trifluoromethyl, an acylamino radical, C1-4 alkoxy Petition 870190108379, of 10/25/2019, p. 75/174 3/17 C4, 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 with a group selected from the (C1) alkoxy -C4), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1-C4), or others of the two alkyl radicals linked by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally, comprising another heteroatom identical or different from that of the nitrogen atom; - or two groups Rg and R'g; R ”g and R '” _g ; Rh and R'h; R ”h and R '” h, linked by two adjacent carbon atoms, together form a benzene or indene ring, or a fused heterocycloalkyl or fused heteroaryl group; the benzene, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino, alkylamino (C1-C4), dialkylamino (C1-C4), cyano, carboxyl, hydroxyl, trifluoromethyl, a C1 alkoxy radical -C4, 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 with a group selected from the (C1C4) alkoxy , hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1-C4), or others of the two alkyl radicals linked by the nitrogen 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; - Ri, R'i; Ri '' and R '' 'i, which may be identical or different, represent a hydrogen atom or a (C1-C4) alkyl group; - R1, R2, R3, R4, R'1, R'2, R'3 and R'4, which can be identical or different, represent a hydrogen atom, a (C1-C4) alkyl group, Petition 870190108379, of 10/25/2019, p. 76/174 4/17 alkoxy (C1-C4), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) or dialkylamino (C1-C4), being possible for said radicals to form, with the nitrogen atom that carries them, a heterocycle comprising 5 to 7 members, optionally comprising another heteroatom that may or may not be different from nitrogen; - Ta or Tb, which can be identical or different, represent: (i) a covalent σ bond, (ii) or one or more radicals or their combinations selected from -SO2-, -O-, -S-, -N (R) -, -N + (R) (R ^o ) -, -C (O) -, with R and R ^o , which can be identical or different, representing a hydrogen atom, an alkyl (C1-C4) radical or hydroxyalkyl (C1-C4) radical or an arylalkyl (C1- C4); (iii) or, preferably, a monocyclic, cationic or non-cationic radical, heterocycloalkyl or heteroaryl radical containing one or two heteroatoms, particularly two nitrogen atoms, and comprising in particular from 5 to 7 members, -, which can be identical or different, represents an optionally substituted cationic or non-cationic heterocyclic group; - m, m ', ne n', which can 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 10 inclusive; - M 'represents an anionic counterion; and - Y represents: (i) a hydrogen atom; (ii) a metal Petition 870190108379, of 10/25/2019, p. 77/174 5/17 alkaline; (iii) an alkaline earth metal; (iv) an ammonium group: N + R ^to R ^and RYR ^õ or a phosphonium group: P ⁺ R ^to R ^and R ^Y R ^õ with R ^a , R ^e , R ^Y and R ^õ , which can be identical or different, representing a hydrogen atom or a (C1-C4) alkyl group; or (v) a thiol function protection group; it being understood that when the compound of formula (I), (II) or (III) contains other cationic parts, it is associated with one or more anionic counterions enabling formula (I), (II) or (III) to obtain electroneutrality . 2. FLUORESCENT DYE according to claim 1, characterized in that m and m 'are zero in formulas I, II and III or one of them. FLUORESCENT DYE, according to any one of claims 1 to 2, characterized by the heterocycle of formula: or represent a cationic or non-cationic heterocyclic group, optionally substituted: 4. FLUORESCENT DYE according to any one of claims 1 to 2, characterized by the heterocycle of the formula: Petition 870190108379, of 10/25/2019, p. 78/174 6/17 represent a monocyclic, saturated, heterocyclic group, comprising in total a single nitrogen atom, being formed from 5 to 7 members, in formulas I, II and III or one of them. 5. FLUORESCENT DYE, of formula (III), according to any one of claims 1 to 4, characterized in that Y represents a hydrogen atom or an alkali metal. 6. FLUORESCENT DYE, of formula (III), according to any one of claims 1 to 4, characterized in that Y represents a protecting group. 7. FLUORESCENT DYE, of formula (III), according to any one of claims 1 to 6, characterized in that Y represents a protection group selected from the following radicals: - (C1-C4) alkylcarbonyl; - (C1-C4) alkylthiocarbonyl; - alkoxycarbonyl (C1-C4); - alkoxycarbonyl (C1-C4); - (C1-C4) alkylthiothiocarbonyl; - (di) (alkyl) (C1-C4) aminocarbonyl; - (di) (alkyl) aminothiocarbonyl (C1-C4); - arylcarbonyl; - aryloxycarbonyl; - arylalkoxycarbonyl (C1-C4); - (di) (alkyl) (C1-C4) aminocarbonyl; Petition 870190108379, of 10/25/2019, p. 79/174 7/17 - (C1-C4) (alkyl) arylaminocarbonyl; - carboxyl; - SO3 ^- ; M + with M + representing an alkali metal, or M 'of formula (III) and M + are absent; - optionally substituted aryl; - optionally substituted heteroaryl; - isothiouronium -c (nr ^c r) = nr ^and R; An with r, r, r ^and er, which can be identical or different, represent a hydrogen atom or a (C1-C4) alkyl group; cd and c d e - isothiouiéia -c (nr r) = nr with r, r, and r conioime defined above; - (di) arylalkyl (C1-C4) optionally substituted; - (di) heteroaryl (C1-C4) optionally substituted; - CR1R2R ³ with R ¹ , R2 and R ³ , which can 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 (Z ¹ ) R ' ¹ R' ² R ' ³ with R' ¹ and R ' ² , which can be identical or different, representing a hydroxyl, an alkyl or alkoxy group (C1-C4); R ' ³ representing a hydroxyl or (C1-C4) alkoxy group; and Z ¹ representing an oxygen or sulfur atom; - a sterically hindered cyclic group; and - optionally substituted alkoxyalkyl (C1-C4). 8. FLUORESCENT DYE, of formula (III), according to any one of claims 1 to 7, characterized in that Y represents an alkali metal or a protection group selected from: Petition 870190108379, of 10/25/2019, p. 80/174 8/17 - (C1-C4) alkylcarbonyl; - arylcarbonyl; - alkoxycarbonyl (C1-C4); - aryloxycarbonyl; - arylalkoxycarbonyl (C1-C4); - (di) (alkyl) (C1-C4) aminocarbonyl; - (C1-C4) (alkyl) arylaminocarbonyl; - optionally substituted aryl; - 5- or 6-membered cationic monocyclic heteroaryl; - 8 to 11-membered cationic bicyclic heteroaryl; - cationic heterocycle of the formula below: - isothiouronium -C (NH2) = N + H2; An ^- ; - isothiourea -C (NH2) = NH; and - SO3 ^- , M + with M + representing an alkali metal or both M 'of formula (III) and M + are absent. 9. FLUORESCENT DYE, of formula (I), (II) or (III), according to any one of claims 1 to 8, characterized by having an ethylene group attached to the pyridinium part in the phenyl in the ortho- or para- , that is, in positions 4-4 ', 2-2', 2-4 '. 10. FLUORESCENT DYE, of formula (I), according to any one of claims 1 to 4 and 9, characterized by being symmetrical. Petition 870190108379, of 10/25/2019, p. 81/174 9/17 11. FLUORESCENT DYE, according to any one of claims 1 to 10, characterized in that it is selected from the dyes: Petition 870190108379, of 10/25/2019, p. 82/174 10/17 Petition 870190108379, of 10/25/2019, p. 83/174 11/17 Petition 870190108379, of 10/25/2019, p. 84/174 12/17 Petition 870190108379, of 10/25/2019, p. 85/174 13/17 Petition 870190108379, of 10/25/2019, p. 86/174 14/17 Petition 870190108379, of 10/25/2019, p. 87/174 15/17 with M ', and An; that they can be identical or different, representing an anionic counterion; and M ⁺ representing an alkali metal. 12. COLORING COMPOSITION, characterized in that it comprises, in an appropriate cosmetic medium, a heterocyclic fluorescent dye of formula (I), (II) or (III), as defined in any one of claims 1 to 11. 13. COLORING COMPOSITION, characterized in that it comprises in an appropriate cosmetic medium, at least one heterocyclic fluorescent dye of formula (I), (II) or (III), as defined in any one of claims 1 to 11, and at least one agent reducer. DYE COMPOSITION according to any one of claims 12 to 13, characterized in that the reducing agent is selected from cysteine, homocysteine or thiolactic acid, the salts of these thiols, phosphines, disulfides, sulphides, thioglycolic acid, and also its esters, borohydrides and their derivatives, sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium salts and borane catechol. COMPOSITION according to any one of claims 12 to 14, characterized in that the heterocyclic fluorescent dye of formula (I), (II) or (III) is present in an amount between 0.001% and Petition 870190108379, of 10/25/2019, p. 88/174 16/17 50% by weight, based on the total weight of the composition. 16. COLORING PROCESS OF KERATIN MATERIALS, characterized by a coloring composition, as defined in any one of claims 12 to 15, comprising in a cosmetically acceptable medium, at least one heterocyclic fluorescent dye of formula (I), (II) or (III), as defined in any one of claims 1 to 11, optionally in the presence of a reducing agent capable of reducing the disulfide bonds of the keratin materials, to be applied to the materials. COLORING PROCESS, according to claim 16, characterized in that when the heterocyclic fluorescent dye of formula (III) comprises a protecting group Y, the application is preceded by a deprotection step. COLORING PROCESS according to any one of claims 16 to 17, characterized in that the keratin materials are dark keratin fibers having a tone level less than or equal to 6, preferably less than or equal to 4. 19. COLORING PROCESS, according to any one of claims 16 to 18, characterized in that the reducing agent is applied before or after the application of the fluorescent thiol dye. 20. COLORING PROCESS, according to any one of claims 16 to 18, characterized in that the fluorescent dye of formula (I) or (II) is applied at the same time as the reducing agent. 21. COLORING PROCESS according to any one of claims 16 to 20, characterized in that the composition comprises an oxidizing agent. Petition 870190108379, of 10/25/2019, p. 89/174 17/17 22. COLORING PROCESS, according to any one of claims 16 to 20, characterized in that it comprises an additional step consisting of the application of an oxidizing agent to the keratin fibers. 23. MULTICOMPARTMENT DEVICE, characterized in that a first compartment contains a dye composition comprising a fluorescent dye of formula (I), (II) or (III), as defined in any one of claims 1 to 11, and a second compartment containing a reducing agent capable of reducing the disulfide bonds of keratin materials. 24. DEVICE, according to claim 23, characterized in that it comprises a third compartment containing an oxidizing agent. 25. USE OF HETEROCYCLIC FLUORESCENT TIOL DYES, as defined in any one of claims 1 to 11, characterized in that they are for dyeing dark human keratin fibers. 26. USE, according to claim 25, characterized in that it is used to lighten dark keratin fibers. 27. USE, in accordance with any of the claims 25 to 26, characterized by the keratin fibers having a tone level below 6.