BRPI0709369B1 - Fluorescent dye, dye compositions, process for staining keratin materials, multicompartment device and use of fluorescent dyes - Google Patents

Abstract

Fluorescent dye, dye composition, process for staining keratin materials, multicompartment device and use of fluorescent dyes The present invention relates to a dye composition comprising a thiol fluorescent dye. disulfide, which comprises an external cationic charge and a dyeing process which has 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 thiol / disulfide fluorescent dyes and their uses in the keratinization of keratin materials. This composition makes it possible to obtain a visible and particularly resistant whitening effect on dark keratin fibers.

Description

(54) Title: FLUORESCENT DYE, DYE COMPOSITIONS, PROCESS FOR COLORING KERATIN MATERIALS, MULTICOMPARTMENT DEVICE AND USE OF FLUORESCENT DYES (51) Int.CI .: C09B 23/14; C09B 49/12; A61Q 5/08 (30) Unionist Priority: 05/02/2007 FR 0753066, 12/02/2007 US 60 / 900,696, 19/04/2006 US 60 / 792,941, 24/03/2006 FR 0651035 (73) Holder ( es): LOREAL (72) Inventor (s): NICOLAS DAUBRESSE; ANDREWGREAVES

1/90 “FLUORESCENT DYE, DYE COMPOSITIONS, PROCESS FOR COLORING KERATIN MATERIALS, MULTICOMPARTMENT DEVICE AND USE OF FLUORESCENT DYES”

Field of the Invention [001] The present invention relates to the staining of keratin fibers using fluorescent thiol / disulfide dyes comprising an external cationic charge.

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 involves the application, in keratin fibers, of direct dyes that are colored or colored molecules that have 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, to the extent that the nature of the interactions that link 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.

[006] The lightening of the color of keratin fibers, in

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2/90, in particular, from dark keratin fibers to lighter shades, when optionally modifying its shade, constitutes 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 a medium alkali.

[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, difficult to untangle and 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 includes the application of direct fluorescent dyes to dark hair. This technique, described in particular in documents FR 2,830,189 and WO 2004/091473, makes it possible to retain the quality of the keratin fibers 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 that are very numerous in the keratin fibers; see, for example, Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91, 259-264 (1975); Journal of

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3/90

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 into the hair before applying it 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 the 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 direct dyeing of keratin fibers.

Brief Description of the Invention [014] The purpose of the present invention is to present new systems for coloring keratin materials, in particular human keratin fibers, especially 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 staining systems, in order to obtain the lightening 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 affect its cosmetic properties.

[015] This objective is achieved by the present invention, which has as its object a process of coloring keratin materials, in particular,

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4/90 of keratin fibers, especially human fibers, such as hair, particularly dark hair, which comprises the application in keratin materials, of a dye composition comprising, in a cosmetically acceptable medium, at least one fluorescent pyridinium dye comprising an external cationic charge, selected from the dyes of

R ''

R ^ SY ^a \ ./ ^ (C ^R 1 ^R 2) ^ (CR ₃ R ₄ ) n ^{g g}

^R 'g ^A = N ^gx R' M 'Ra ^{Ri R} ' h ^R b (II) its salts of organic or inorganic acid, its geometric optical isomers, and solvates, such as hydrates;

where in formula (I) or (II):

- Ra and R'a, which can be identical or different, represent an arylalkyl (C1-C4) group or an alkyl (C1-C6) group, optionally substituted by a hydroxy 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, Ra and / or R'a represent a (C1-C3) alkyl group optionally substituted by a hydroxyl group or a benzyl group;

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

- Rg, R'g, R ”g and R” ’g, which can be identical or different, represent a hydrogen atom, an amino group, (C1-C4) alkylamino,

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5/90 dialkylamino (C1-C4), trifluoromethyl, an acylamino radical, alkoxy (C1-C4), alkylcarbonyloxy (C1-C4), alkoxycarbonyl (C1-C4), alkylcarbonylamino (C1-C4) or alkylsulfonylamino (C1- C4), or a (C1-C3) alkyl radical;

- Rh, R'h, R''h and R ”'h, which can be identical or different, represent a hydrogen atom, a halogen atom, a dialkylamino group (C1-C4), alkylcarbonylamino (C1-C4), an acylamino or alkylsulfonylamino (C1-C4) radical, or a (C1-C4) alkyl radical; in particular, Rh, R’h, R ”h and R’ ’’ h represent a hydrogen atom or a (C1-C3) alkyl group;

- 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 benzo or indene ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, 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, acylamino, C1-C4 alkoxy group , C2-C4 (poly) hydroxyalkoxy, (C1-C4) alkylcarbonyloxy (C1-C4) alkoxy (C1-C4) alkylcarbonylamino (C1-C4), an acylamino, carbamoyl or alkylsulfonylamino (C1-C4) radical, an aminosulfonyl radical or alkyl radical (C1C16) optionally substituted by a group selected from the alkoxy (C1C12), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1C4), or else the two alkyl radicals linked by the nitrogen atom from the amino group they form a heterocycle comprising from 5 to 7 members and, optionally, comprising another heteroatom identical or different from that of the nitrogen atom; in particular, Rg and R’g; R’’g and R ’’ ’g together form a benzo group;

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

- R1, R2, R3, R4, R’1, R’2, R’3 and R’4, which can be identical or

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6/90 different represent a hydrogen atom or a (C1-C4) alkyl group, in particular, R1, R2, R3, R4, R'1, R'2, R'3 and R'4 represent a hydrogen atom ;

-, which may be present or absent, represents a benzo group;

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

(i) a covalent σ bond;

(ii) a radical selected from -N (R) - and -N + (R) (R °) -, where R and R ^o , which may be identical or different, represent a hydrogen atom, an alkyl radical C1-C4, C1-C4 hydroxyalkyl or an arylalkyl (C1C4);

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

\ An ^-

A where A represents an oxygen or sulfur atom or a CH2 or NR ^{o group} , where R ^o is as defined above and An ^- represents an anionic counterion;

- preferably, Ta and Tb represent a covalent bond;

- 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

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7/90 inclusive; preferably, when Ta and Tb represent a covalent bond σ, m + n = m '+ n' is an integer equal to 2;

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

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

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

(i) monocyclic heteroaryl 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, 1,2, isothiazolium, 1,2 , 4triazolyl, 1,2,4-triazolium, 1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl, 1,2,4oxazolium, 1,2,4-thiadiazolyl, 1 , 2,4-thiadiazolium, pyrillium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine, azepinium, oxazepinyl, iminoazide, tiepin;

(ii) bicyclic heteroaryl comprising from 8 to 11 members, such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazolyl, pyridoimidazole, or polyethylene groups more groups, such as (C1-C4) alkyl, for example methyl or polyhaloalkyl (C1C4), for example, trifluoromethyl;

(iii) or the tricyclic heteroaryl ABC below:

wherein the two rings A, C optionally comprise a

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8/90 heteroatom, and ring B is a 5-, 6- or 7-membered ring, in particular a 6-membered ring, and contains at least one heteroatom, for example, piperidyl or pyranyl;

- optionally cationic heterocycloalkyl, optionally substituted, the heterocycloalkyl group represents, in particular, a saturated or partially saturated 5, 6 or 7 membered monocyclic group comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / 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 groups:

N .d

An ^- where R ' ^c , R' ^d , R ' ^e , R' ^f , R ' ^g and R' ^h , which can be identical or different, represent a hydrogen atom or an alkyl group or two R ' ^g groups with R ' ^h , and / or R' ^and with R ' ^f , they form an oxo or thioxo group, or R' ^g with R ' ^and together they form a cycloalkyl; ev represents an integer between 1 and 3 inclusive; preferably, R ' ^c to R' ^h represent a hydrogen atom; and An ^- represents an anionic counterion;

- (di) arylalkyl optionally substituted, such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted by one or more groups, in particular, selected from alkyl (C1-C4), alkoxy (C1C4), such as methoxy, hydroxyl, alkylcarbonyl (C1-C4) and (di) (alkyl) amino (C1Petition 870180010020, of 02/05/2018, page 23/136

9/90

C4), for example, dimethylamino;

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

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

- when Ta represents -N (R) -, -N + (R) (R °) -, a heterocycloalkyl or heteroaryl radical, cationic or non-cationic; Y represents a group selected from: (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 (C1C4) alkyl group; or (v) a thiol function protection group; and

- M 'representing an anionic counterion;

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

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

[017] The present invention also has new fluorescent dyes of formula (I) or (II) as defined above.

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10/90 [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] In addition, the process of the present invention makes it possible to obtain a coloring of the keratin materials, in particular of the human keratin fibers, in particular the hair, without damaging this material, which is persistent with respect to washing operations, attacks common (sunlight, perspiration) and other hair treatments. The process of the present invention also makes it possible to obtain the lightening of keratin materials, such as keratin fibers, preferably dark keratin fibers and, most preferably, dark hair.

Brief Description of the Figures [020] Figure 1 shows the reflectance result of the locks treated by compounds 1 and 2 of the present invention, in the application and after 5 washes.

[021] Figure 2 shows the reflectance result of the locks treated by compounds 3, 4 and 5 of the present invention, in the application and after 5 washes.

[022] Figure 3 shows the reflectance result of the locks treated by compounds 10 and 12 of the present invention, in the application and after 5 washes.

Detailed Description of the Invention [023] For the purpose of the present invention, the term "dark keratin material" is intended to mean that it 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.

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11/90 [024] 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).

[025] 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) or (II).

[026] 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 classification of natural shades is well known to hair styling professionals and is published in the book Science des traitements capillaires [Hair treatment Sciences], by Charles Zviak 1988, published by Masson, pages 215 and 278.

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

[028] 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.

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

- 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 of the untreated hair, are then compared;

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12/90

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

- this means that, in the wavelength range from 540 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%. Even so, there may be, in the wavelength range, from 540 to 700 nm, at least one interval where the reflectance curve corresponding to the treated hair is superimposed or less than the reflectance curve corresponding to the untreated hair.

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

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

- the radicals "aryl" or "heteroaryl" can be replaced by at least one substituent charged with a carbon atom, selected from:

- a C1-C16 alkyl radical, preferably C1-C6;

- 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;

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13/90

- an amino radical substituted by one or two C 1 -C 6 alkyl radicals, which can be identical or different, optionally carrying at least:

(i) a hydroxyl group, (ii) an amino group,

- 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 radical R' is a C1-C2 alkyl radical;

- a carbamoyl radical ((R) 2N-CO-), wherein the radicals R, 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 radical R 'represents a C1 alkyl radical -C4;

- 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);

- 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 an atom of

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14/90 carbon, selected from the groups:

- hydroxyl;

- C1-C4 alkyl;

- C1-C4 alkoxy;

- C2-C4 (poly) hydroxyalkoxy;

- a C1-C2 alkylthio radical;

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

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

- 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, being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen;

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15/90

- 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 and sulfur atom, and at 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, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, triazyl, tyridyl and triazyl;

- 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, 1,1difurylethyl, 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 "cyclically sterically hindered radical" is a cyclic radical

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16/90 substituted or unsubstituted, aromatic or non-aromatic, prevented by steric effects or restrictions, comprising from 6 to 14 members, which can be dotted; by means of sterically hindered radicals, mention may be made of the bicyclo [1.1.0] butane, mesitylates, such as 1,3,5-trimethylphenyl, 1,3,5-tri-ferc-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 alkyl 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 possibly form, 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;

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

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

- 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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17/90 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 toluenoxysulfinic acid and phenoxysulfinic acid; (xii) phosphoric acid H3PO4; (xiii) CH3COOH acetic acid; (xiv) CF3SO3H triflic acid 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) tartrate; (viii) lactate; (ix) alkyl sulfates: Alq-O-S (O) O such as methyl sulfite and ethyl sulfite; (x) arylsulfites: Ar-O-S (O) O- such as benzenesulfite and toluenesulfite; (xi) alkyl sulfates: Alq-O-S (O) 2O^-, such as methyl sulfate and ethyl sulfate; (xii) aryl sulfates: Ar-O-S (O) 2O^-; (xiii) phosphate; (xiv) acetate; (xv) triflate; and (xvi) borates, such as tetrafluoroborate.

[032] Fluorescent dyes of formula (I) or (II) 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 in a emission of the wavelength at 400 to 800 nm.

[033] Preferably, the fluorescent compounds of formula (I) or (II) are dyes capable of absorbing in the visible range Àabs between 400 and 800 nm and re-emitting in the visible range Àem between 400 and 800 nm. Of greater

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18/90 Preferably, fluorescent dyes are dyes capable of absorbing at an Àabs wavelength between 420 nm and 550 nm and re-emitting in the visible range at an Àem wavelength between 470 and 600 nm.

[034] A specific embodiment refers to the dyes of formula (I) or (II) in which Ta and Tb represent -N (R) -, -N + (R) (R °) - or a heterocycloalkyl or heteroaryl, cationic radical or non-cationic. Most preferably, the fluorescent thiol dyes of formula (II) comprise a SY function, then comprise a group Y that represents a hydrogen atom or an alkali metal; preferably, Y represents a hydrogen atom.

[035] According to another specific embodiment of the present invention, in the formula mentioned above (II) where Ta represents -N (R) - or N ⁺ (R) (R °) - Y is a protecting group and the group protection is selected from those known to those skilled in the art, for example, those described in the books Protective Groups in Organic Synthesis, TW Greene, John Willey & Sons, NY, 1981, pp. 193 - 217; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, ch. 5.

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

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

- (C1-C4) alkylcarbonyl;

- (C1-C4) alkylthiocarbonyl;

- alkoxycarbonyl (C1-C4);

- alkoxycarbonyl (C1-C4);

- (C1-C4) alkylthiothiocarbonyl;

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19/90

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

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

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

(i) monocyclics 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, tetrazinil, tetrazinium, azepine, azepinium, oxazepinyl, oxazepin, iminoil, tiepin;

(ii) bicyclics 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 alkyl, for example, methyl or polyhaloalkyl, for example, trifluoromethyl;

(iii) or the tricyclic ABC below:

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20/90

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

- optionally cationic heterocycloalkyl, optionally substituted, the heterocycloalkyl group represents, in particular, a saturated or partially saturated 5, 6 or 7 membered monocyclic group comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / 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. (CR' ^and R ' ^f ).

.d

An ^- where R ' ^c , R' ^d , R ' ^e , R' ^f , R ' ^g and R' ^h , which can be identical or different, represent a hydrogen atom or an alkyl group, or two R 'groups ^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;

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- isothiouronium -C (NR ' ^c R' ^d ) = N + R ' ^and R'^f; An ^- with R ' ^c , R' ^d , R ' ^e and R' ^f , which can be identical or different, represents a hydrogen atom or an alkyl group; preferably, R ' ^c to R' ^f represents a hydrogen atom; and An ^- represents the counter ion;

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

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

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

- CR ' ¹ R' 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:

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

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

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

- optionally substituted heteroaryl, such as thiophenyl,

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22/90 furanyl, pyrrolyl, pyranyl or pyridyl, optionally substituted by an 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, alkyl or alkoxy; R ” ³ representing a hydroxyl or alkoxy group; and Z ¹ representing an oxygen or sulfur atom;

- a sterically hindered cyclic group; and

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

[038] In particular, the Y group of the fluorescent dye of formula (II) represents 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;

- optionally substituted aryl, such as phenyl;

- 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 (C1C4) 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

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23/90 as methyl;

- cationic heterocycle of the formula below: Me, NnV '/

N /

Me

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 (II) and M ⁺ are absent.

[039] According to a specific embodiment, fluorescent protected thiol dyes of formula (II) comprising a group Y (i) which is a 5- or 6-membered aromatic, cationic heteroaryl heteroaryl group, comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 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 indolinium, 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:

| 0 \

N //

N '

R '

An ^-

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24/90 where R ' ^c and R' ^d , which can be identical or different, represent 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.

[040] According to another specific embodiment, when Ta and Tb represent a covalent bond, in particular, the protected fluorescent thiol dyes of formula (II) then comprise a group Y (i) which is a monocyclic heteroaryl group of 5 or 6 aromatic, cationic members, comprising 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4triazolium, 1,2,3-triazolium, 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 indolinium, 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, for example, trifluoromethyl (iii) or a heterocyclic group below:

R ' ^d

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

[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, pyriline, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium, benzoimidazolium, benzoxazolium and benzothiazolium, these groups being optionally substituted by one or more alkyl groups (C1Petição 870180010020, from 02/05/2018, page 39/136

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C4), in particular, methyl.

[042] According to a specific embodiment of the present invention, the fluorescent dyes of the present invention are of formula (Ia), (IIa), (Ib), (IIb), (Ic) or (IIc), each having a ethylene group that binds the pyridinium part to the phenyl part in the ortho or para position, in the 4-4 ', 4-2', or 2-4 'positions for (Ia), (IIa), (Ib) or (IIb), or in positions 4-5 'or 2-5' for (Ic) or (IIc):

3 '2

4 '

^: N 1 \ ^N ( ^CH L »-I

R

-T ', S — S „' Wn

M '(Ia)

2 '3' (CH) ^{(CH) N 7/4;} _{? 1} 4

R ² /

N =? ² /

R b

b a

The

(IIb) g

M 'R (IIc) in whose formula (Ia) or (IIa):

- R ^{1 a} and R ² a, which may be identical or different, represent a benzyl or alkyl group, optionally substituted by a hydroxyl group,

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26/90 such as methyl, ethyl or hydroxyethyl;

- R ¹ b and R ² b, which can be identical or different, represent a hydrogen atom, a benzyl or alkyl group, such as methyl or ethyl;

- T'a and T'b, which can be identical or different, represent a bond σ; or a group -N + (R) (R °) - with R and R ^o , which can be identical or different, representing an alkyl group, such as methyl; or else T'a and T'b represent an imidazole group;

- Y 'represents a group selected from the imidazolium, thiazolium; oxazolium; 1,2,4-triazolium; pyridinium; pyrimidinium; benzoxazolium and benzothiazolium; these groups being replaced by one or more alkyl groups, which may be identical or different, such as methyl or ethyl;

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

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

- Ra, R'a, Rb, R'b, Ri, R'i, R''i, R '' 'i, R1, R'1, R2, R'2, R3, R'3, R4, R'4,

Ta, Tb, m, m ', n, n' and Y are as defined above;

- Rg, R'g, R''ge R '” _g , which can be identical or different, represent a hydrogen atom, a halogen atom, an amino group, alkylamino (C1-C4), dialkylamino (C1-C4 ), cyano, carboxyl, hydroxyl, trifluoromethyl, an acylamino radical, (C1-C4) alkoxy, C2-C4 (poly) hydroxyalkoxy, (C1-C4) alkylcarbonyloxy, (C1-C4) alkoxy (C1-C4) alkylcarbonylamino an acylamino, carbamoyl, alkylsulfonylamino (C1-C4) or aminosulfonyl group, or an alkyl (C1-C16) radical optionally substituted by a group selected from the (C1-C12) alkoxy, hydroxyl, cyano, carboxyl, amino,

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27/90 alkylamino (C1-C4) and dialkylamino (C1-C4), or 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 identical or different heteroatom that of the nitrogen atom; in particular, Rg and R’g; R’’g and R ’’ ’g represent a hydrogen or halogen atom or a (C1-C3) alkyl group, advantageously Rg and R’g; R’’g and R ’’ ’g represent a hydrogen atom;

- Rh and R’h; R’’h and R ’’ ’h, linked by two adjacent carbon atoms, together form a benzo or indene ring, or a fused heterocycloalkyl or fused heteroaryl group; the benzo, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino, alkylamino (C1-C4), dialkylamino (C1C4), cyano, carboxyl, hydroxyl or trifluoromethyl, acylamino, C1-C4 alkoxy group ( poly) hydroxyalkyl C2-C4, alkylcarbonyloxy (C1-C4), alkoxycarbonyl (C1-C4) or alkylcarbonylamino (C1-C4), an acylamino, carbamoyl or alkylsulfonylamino (C1-C4) radical, an aminosulfonyl radical or an alkyl radical (C1C16) optionally substituted by a group selected from the alkoxy (C1C12), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1C4), or else the two alkyl radicals linked by the nitrogen atom of amino groups form a heterocycle comprising from 5 to 7 members and, optionally, comprising another heteroatom identical or different from that of the nitrogen atom; in particular, Rh and R’h; R’’h and R ’’ ’h together form a benzo group; and whose formula (Ic) or (IIc):

- Ra, R'a, Rb, R'b, Ri, R''i, R1, R'1, R2, R'2, R3, R'3, R4, R'4, Ta, Tb, m, m ', n, n' and Y are as defined above;

- Rg, R’g, R’’g, R ’’ ’g, Rh, R’h, R’’h and R’ ’’ h, which can be identical or different, represent a hydrogen atom, an atom of

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28/90 halogen, an amino, alkylamino (C1-C4), dialkylamino (C1-C4), cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C1-C4 alkoxy, (poly) hydroxyalkoxy C2-C4, alkylcarbonyloxy (C1- C4), alkoxycarbonyl (C1-C4), alkylcarbonylamino (C1-C4), an acylamino radical, carbamoyl, alkylsulfonylamino (C1-C4) or an aminosulfonyl group, or an alkyl (C1-C16) radical optionally substituted by a group selected from the alkoxy (C1-C12), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1-C4), or else 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; in particular, Rg and R’g; Rh and R'h represent a hydrogen or halogen atom or a (C1-C3) alkyl group; advantageously, Rh and R’h represent a hydrogen atom;

it being understood that, when the compound of formula (Ia), (IIa), (Ib), (IIb), (Ic) or (IIc) contains other cationic parts, it is associated with one or more counterions allowing the formulas ( Ia), (IIa), (Ib), (IIb), (Ic) or (IIc) obtain electroneutrality.

[043] Another specific embodiment of the present invention relates to the symmetrical disulfide dyes of formula (I), that is, Ra, Rb, Rg, R'g, Rh, R'h, Ri, R'i, R1, R2, R3, R4, Ta, men are identical to R'a, R'b, R ”g, R” 'g. R’’h, R ’’ ’h, R’ i, R ’’ ’i, R’1, R’2, R’3, R’4, Tb, m’ and n ’, respectively.

[044] As an example of the fluorescent dyes of the present invention, a mention can be made, in. particular to the following dyes:

N ^ 'An ^- v '2An ^- 1 2

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_ / - ^f - ^r —C 4M ' 11 HO \ = _N + ^^ - ^s SS - «. ^{2M N} ^ ^{w H} - O OH ^J 12 (Ζ ^ · Λ_ / ^{Ν =} Ο HNN ^X SS / NH? _X O \ = / \ \ = / 2 ^X O ' ^S O O \ + ^Z 0 2An ^- 13 14 Q ^ A // - \ / ~ N \ \ = / \ An ^- ^ SO _N + q \ - \ \ = Z An ^- , M + 15 16 \ JV ^ A / ^ n + ^ - A ^ V ^ = ⁷ —y— NN ^ j N 3An ^- _ / SH An ^- 17 18 . ^ ~ N \ / / ⁺ ^ = ⁷ 2An ^- SH - N + -G N '\ An- 19 20 O - N + -G \ - N \ An- O - N + C / \ / \ _n \ An- 21 22

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^ = N + / V- NZ ^{7 +} \ \ = / \ 2An ^{- x} 2An ^- 23 24 N = \ fA A “W \ = N + / V- N ⁷ \ \ = / \ 2An ^- N = \ / ¼ y fí ~ X / / N ^ ^{Νχ = 7} 2An ^- 25 26 \ + r-TV * / \ = N ^{+ x} 2An ^- \ + = 7 '2An ^- 27 28 \ + fA _ AA- ⁵ \ = _N + _N / \ \ = / \ 2An ^- 2An ^- 29 30 \ + n-, _ AN ³ \ = N + í \ - N 1 \ \ = Z \ 2An ^- A z-cy r / VN ^N \ = / 2An ^- 31 32 \ + s-fÚ | 2An ^- \ + ^N z_s— / _ _{; í} . _n + i \ = y ~ \ 2An ^- 33 34 \ + N—, fA ΛΛ A ^ \ = N ⁺ V, - (/ Ά_Ν \ \ = / \ 2An ^- \ ₊ N * -. THE; r - / - ^Y “ ^N ^ A ^X 2An ^- 35 36

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^ = N ⁺ \ THE JT y_ \ \ + / An N / 2An ^- - N + JT \ = / - N \ \ + N-N sA h _ / Ní ! 2An ^- 37 38 \ + \ ₊ S— < N ^Y T S '' \ A ry S-- aa - N + - ¹ N / Γ X_ JT \ AA = / \ = N + \ = / 2An ^- \ 2An ^- 39 40 \ + N ^. Ύ N— S- Ή = N + ^N THE _r THE -N \ / y ~ N + y- AA AAA - N \ (THE / 2An ^- 2An ^- 41 42 Ύ N = \ N— ' \ + N ~~, S A J = N + \ THE _jr THE -N \ / GO _THE THE N / 2An ^- N A_A \ 2An ^- 43 44 \ + \ + TO THE THE / An sA jl J N ^ THE -N / HO— \ AA N / Ύ J / N \ GO <- / -N 2An ^- 2An ^- 45 46 THE O _.; THE) / /THE S- \ ₊ N ^. A j | s THE = N +> THE "THE - N \ y y ~ JT \ ^ j \ 2An ^- 2An ^- / 47 48

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N

\ </ _ \ = N + N 1 2An ^{- N} \ A \ 7 \ Af ^ ^{S_ <} ^ = ⁷ - \ _ / N ^N \ sssJ 3An 49 50 / iÍÇn \ = n ⁺ —ç yn ' ^xz \ 3An ^{- N} - N Y N = / (\ / ^{N + _} 2An ^- 51 52 X x = N ⁺ - / y — N oh 2An ^- Ν'-, * _ / S- ^ J ^ n ^^ PZPn>  'An- 53 54 ^< \ = N + \ —N / / ⁺ \ \ = / ^H 2An ^- \ = / ^H 2An ^- 55 56 N = \ Pa ZV \ = N + V, - / n / \ \ = 7 ^H 2An ^- N = \ / ^S ~ (\ 5) ^Νχ = / 2An ^- 57 58 \ + / / Λ— \ N / / \ _y / \ = / N '''n' ^X 2An ^- \ ₊ ^N = / 2An ^- 59 60

N

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2 M'

2 M'

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2 M'

S-S

2 M'

2 M'

2 M'

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2 M'

106

107

S-S

2 M'

108

109

2 M'

110

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representing an anionic counterion; and M + representing an alkali metal.

[045] With An ^- and M ', which can be identical or different, representing an anionic counterion, such as halides, for example, chloride or bromide; nitrates; sulfonates, including C1C6 alkylsulfonates: Alq-S (O) 2O ^- , such as methylsulfonate or mesylate and ethylsulfonate; arylsulfonates: Ar-S (O) 2O ^- , such as benzenesulfonate and toluenesulfonate or tosylate; citrate; succinate; tartrate; lactate; alkyl sulfates: Alq-OS (O) O ^- , such as methyl sulfate and ethyl sulfate; aryl sulfates: Ar-OS (O) O ^- , such as benzene sulfate and toluene sulfate; alkoxy sulfates: Alq-OS (O) 2O ^- , such as methoxy sulfate and ethoxy sulfate; aryloxy sulfates: Ar-OS (O) 2O ^- , phosphate; acetate; triflate; and borates, such as tetrafluoroborate.

[046] Protected thiol dyes of formula (II ”) can be synthesized in two stages. The first stage consists of the preparation of the unprotected thiol dye (II ”) 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 the conventional methods known to those skilled in the art for the production of the protected thiol dyes of formula (II). 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, T.W.

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Greene, ed. John Willey & Sons, NY, 1981, pages 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 thiol dyes by reducing a fluorescent bi-chromophore dye carrying a disulfide -SS- function such as (I ') and (ii) in protection, according to conventional methods, said thiol function of the compounds (II ') in order to obtain the protected thiol fluorescent dyes of formula (II' ').

R

^R g

RT = N ^g \ R '

M ' ^R a ⁱ

R ', S — Ss a. .

^N - (C ^R 1 ^R 2) _m (CR3RA ^ (C ^R 3 ^R 4) n ^(CR 1 ^R 2) m ^R , _π , R ' ^R ^ ^m ' ^h --- A z ⁿ > r ' ^R g '2'm ^R h (I')

Reducer

R b

^ T ^ / SH ii) 2Y-R

N ^{CR R.} CR R.. ' ^R b (II') a

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

[048] According to another possibility, a thiol compound protected in (b) by a protecting group Y as defined above, prepared according to one of the procedures described in the books mentioned above, said protected thiol compound comprising at least one function nucleophilic, 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 Σ bond, as can be seen schematically below:

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48/90

R

as defined above; Nu representing a nucleophilic amino or heterocycloalkyl or heteroaryl group; And representing a nucleophobic group, such as, for example, mesylate, tosylate, triflate or halide, for example, bromine, iodine or chlorine. Σ represents a radical selected from -N (R) - and -N + (R) (R ^o ) where R and R ^o as defined above, and heterocycloalkyl and heteroaryl, which can be cationic or non-cationic.

[049] A YSH thiol reagent comprising a group Y, the nucleophilic SH function, can also be used to react with the carbon atom in the alpha position with respect to the halogen atom carried by the fluorescent chromophore (a ') of in order to provide the protected thiol fluorescent dye of formula (II):

(01

N '(CR ^ -T-CR ^ X) - ^H a ^l b

(o! HS-Y (II)

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

[050] A thioacid (α) (for example, the

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49/90 thioacetic acid) which will react with a halide attached to the fluorescent chromophore (a ').

R

Hal

s

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

[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 is a thioimidazolium (β), the reaction scheme is as follows:

^R b

Hal

g with Ra, Rb, R'c, R'd, Rg, R'g, Rh, R'h, Ri, R'i, m, n, Hal, An ^- and M ', 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 nucleophobe, such as tosylate or mesylate.

[053] According to another variation, it is possible to produce a

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50/90 imidazoline intermediate using the halide comprising the fluorescent chromophore (a ') and a thioimidazoline (b') in order to produce, after alkylation with an R-Lg, with R represented an alkyl group and Lg a group of starting, such as halogen, for example, chlorine, bromine, iodine, or a mesylate or tosylate group.

Alkylation

R'd-Lg

[054] A nucleophobic leaving group can also be replaced with thiosulfate salts (for example, sodium thiosulfate or potassium thiosulfate) in order to produce the Bunte salts (-SSO3 ', Na ⁺ or K ⁺ ) :

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

[055] According to another possibility, certain dyes

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51/90 fluorescents with a protected thiol group (II ') can be obtained by reacting a compound with a protected thiol group carrying a compound with a nucleophile function (d) which is reacted with a flourishing chromophore carrying a nucleophilic function (c), of primary or secondary amine, of the heterocycloalkyl or heteroaryl type:

[057] With Ri, R2, R3, R4, Ra, Rb, R _g , R ' _g , Rh, R'h, Ri, R'i, T _a , Y, m, n, Μ', E, Nu and (II ”) as defined above.

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

[059] With R1, R2, R3, R4, Ra, Rb, R _g , R ' _g , Rh, R'h, Ri, R'i, T _a , Y, m, n, M' and E as defined above.

[060] By way of example, a compound containing a protected thiol group contains a nucleophile leaving group R, for example, mesylate, tosylate or triflate, which can undergo a nucleophilic attack by an amine supported by a flourishing chromophore:

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52/90

SY

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

[062] According to another possibility, certain fluorescent thiol dyes protected (II) 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 compound that comprises 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 alkylpyridinium (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 patent DE 19,951,134; mention may be made, in particular, of 1,2-dialkylpyridinium, and in particular 1,2-dimethylpyridinium:

[063] with Ri, R2, R3, R4,

Ra, Rb, Rg, R g, Rh, R h,

R’i, Ta, Y, m, n and

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53/90

M 'as defined above and G represents an oxygen or sulfur atom or an N (R) group with R representing a hydrogen atom or a (C1-C4) alkyl group.

[064] Another variation of this reaction scheme is to perform a condensation reaction “Knoevenagel” subsequently, that is, using the intermediate (f), the amino group NR'R ”can react with an equivalent of the reagent Lg- (CR3R4) -Lg in order to supply (i ') which can itself react with a protected Y'SH thiol to supply the aldehyde intermediate (j'). This intermediate can undergo the “Knoevenagel” condensation reaction with the alkylpyridinium (e) in order to provide the protected thiol naphthyl fluorescent dye (II ”).

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54/90 with R ', R ”, Ri, R2, R3, R4, Ra, Rb, Rg, R'g, Rh, R'h, Ri, m, n, Y' and M 'as defined above, Lg represents a leaving group, such as a halogen atom, in particular, Br or I, or a tosylate, mesylate or triflate group, and Lg ^- represents the anionic counterion following the departure of the leaving group Lg.

[065] can be made a reference to the book Advanced Organic Chemistry, Reactions, Mechanisms and Structures, 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.

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

[067] Protected thiol dyes can also be unprotected by conventional routes, such as those described in the books Protective Groups in Organic Synthesis, TW Greene, John Willey & Sons ed., NY, 1981; Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005.

[068] Starting reagents are either commercially available or accessible by conventional methods known to those skilled in the art. As an example, in order to synthesize the fluorescent dye of two phenyl / naphthyl chromophores that carries a disulfide function -SS (I '), it is possible to start from a bifunctionalized naphthyl reagent (k), which comprises in position 2 a nucleophobic group GR with R representing a (C1-C4) alkyl, mesylate, tosylate or triflate group and G 'representing an atom

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55/90 of oxygen or sulfur or an N (R) group with R representing a hydrogen atom or a (C1-C4) alkyl group, and comprising in position 6 an aldehyde or thioaldehyde electrophilic group. The two equivalents of this reagent can react with diamine-dialkyl-disulfide (1) to provide, after condensation, dialdehyde / thioaldehyde disulfate (m), which can condense with two equivalents of alkylpyridinium (e), to form the compound (I ').

T / ^s_s \ τ _D ^bXN - ( ^CRR 2) m ^ (CR3R4) n (CR ^ ^ (CRRJ-N ^

I I R (k)

RG'H (1)

R ^ (C ^R 1 ^R 2) P '(CR3R ₄ ) _n

H

R

T -s

Lm)

Knoevenagel

G ^R gg m ' ^ag (e) ^{2 R} ÃG ^N + R

H _r ^ ^(CR i ^R 2) m ^(CR 3 ^R 4) n ICRsRJn '(CRR) —N' ^x h

R y ^b

R

^R g ^R g

R

M (II ^R a ^ -N +

M + ^R g ¹¹ g ^ZR [069] 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.

[070] Dissimetric disulfide dyes of formula (I) can be synthesized in a single step by reacting an unshielded fluorescent thiol dye with a protected thiol fluorescent dye to form the dissimetric disulfide dye of formula ( I).

g g

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56/90 being Ra, R'a, Rb, R'b, Rg, R'g, R ”g, R” 'g, Rh, R'h, R ”h, R”' h, Ri, R ' i, R ”i, R” 'i, Ri, R'1, R2, R'2, R3, R'3, R4, R'4, m, m', n, n ', Ta, Tb and M 'as defined above; Y 'represents a group protecting the thiol function.

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

[072] The dye composition that can be used in the present invention generally contains an amount of fluorescent dye of formula (I) or (II) between 0.001% and 50% with respect to the total weight of the composition. Preferably, this amount is 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.

[073] The dye composition may 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, direct dyes of azine, direct dyes of

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57/90 triarylmethane, indoamine dyes and natural dyes.

[074] Among the natural direct dyes, mention may be made of lawsone, juglone, alizarin, glitter, carminic acid, kermésic 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.

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

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

[077] Among these couplers, particular mention can be made of half-phenylenediamines, half-aminophenols, half-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

[078] The coupler (s) 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% .

[079] The oxidation of the base (s) present in the dye composition is, 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.

[080] In general, the addition of salts of 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 addition salts with a base, as

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58/90 such as alkali metal hydroxides, such as sodium or potassium, aqueous ammonium, amines or alkanolamines.

[081] The appropriate medium for dyeing, also called dye support, is a cosmetic medium, in general, 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 polyether ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[082] 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 preferably, between about 5 % and 30% by weight.

[083] 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, amphoteric or zwitterionic 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.

[084] The above adjuvants are generally present in an amount, for each of them, between 0.01% and 20% by weight, with respect to

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59/90 weight of the composition.

[085] Obviously, those skilled in the art will take care when selecting 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 contemplated addition (s).

[086] 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 by means of acidifying or basifying agents normally used in dyeing keratin fibers or by conventional buffer systems.

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

[088] 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 compounds of formula (Y) below:

a2

N W-N

Ral ^to R 'where Wa is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; Rai, Ra2, Ra3 and Ra4, which can be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a hydroxyalkyl radical.

[089] The dye composition can be in several forms,

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60/90 such as in the form of a liquid, a cream or a gel, or in any other form suitable for dyeing keratin fibers and, in particular, hair.

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

[091] According to 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 fluorescent dye of formula (I) or (II).

[092] 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 also their 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.

[093] 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.

[094] According to another process, the composition comprising at least one fluorescent dye of formula (I) or (II) also contains at least one reducing agent as defined above. The composition

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61/90 is then applied to the hair.

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

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

Table 1

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 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

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

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

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

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62/90 [0100] In the dyeing process, another variation is to apply the fluorescent dye of formula (I) or (II) at the same time as the reducing agent.

[0101] 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) or (II). The duration of the post treatment with the reducing agent can be short, for example, from 0.1 seconds to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above. According to a specific embodiment, the reducing agent is a thiol or borohydrate type agent, as described above.

[0102] A specific embodiment of the present invention relates to a process in which the fluorescent dye of formula (I) or (II) can be applied directly to the hair without the reducing agents, free from the previous reduction treatment or after treatment reduction.

[0103] 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.

[0104] This oxidizing agent can be applied to fibers before or after application of the composition containing at least one fluorescent dye of formula (I) or (II).

[0105] The application of the dye composition according to the present invention is, in general, carried out at room temperature. However,

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63/90 it can be carried out at temperatures ranging from 20 to 180 ° C.

[0106] An object of the present invention is also a multi-compartment device or coloring kit in which a first compartment contains a dye composition comprising at least one fluorescent dye of formula (I) or (II) and a second compartment contains an agent reducing agent capable of reducing the disulfide functions of keratin materials and / or the disulfide function of the dye of formula (I).

[0107] One of these compartments can also contain one or more other dyes of the direct dye or oxidation dye type.

[0108] The present invention also relates to a multi-compartment device in which a first compartment contains a dye composition comprising at least one fluorescent dye of formula (I) or (II); or a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials; and a third compartment contains an oxidizing agent.

[0109] Another variation refers to a multi-compartment staining device or staining kit, which comprises a first compartment containing a composition with at least one fluorescent protected dye of formula (II) and a second compartment comprising a composition containing an agent deprotection, such as a base.

[0110] Each of the devices mentioned above can be equipped with means to provide the desired mixture to the hair, for example, such as the devices described in the FR 2,586,913 patent.

[0111] The following examples serve to illustrate the present invention without, however, being subject to limitation. The fluorescent dyes in the examples below have been fully characterized by conventional spectroscopy and spectrometry methods.

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64/90

Examples

Synthesis Examples

Example 1 [0112] Synthesis of 1-methyl-4 - {(E) -2- [4- (methyl {2 - [(1-methyl1H-imidazol-2-yl) sulfanyl] ethyl} amino) phenyl] chloride] vinyl} pyridinium [1] ^Cl + - N 7 — wr =

[1] [0113] Summary scheme:

oo 'O' ^S 'O'

CH ₂ Cl ₂

OO 'N' sl o ' ^s ' o ~

iPrOH

Cl

N--, ϊ-Ο

M «- * [1]

N [0114] Procedure:

Stages 1 and 2: sulfate synthesis of 4 - ((E) -2- {4 - [(2-chloroethyl) (methyl) amino] phenyl} vinyl) -1-methylpyridinium methyl [0115] 4.99 g of 4 -picolino diluted in 25 ml of dichloromethane

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65/90 (CH2Cl2) are stirred and heated to 40 ° C. 5 ml of dimethyl sulfate diluted in 20 ml of CH2Cl2 are added dropwise to the reaction medium. The mixture is kept at 42 ° C for 30 minutes after the addition and then 20 ml of isopropanol are added.

[0116] 1.87 g of pyrrolidine diluted in 30 ml of isopropanol are added. The mixture is stirred and heated to 60 ° C for 5 minutes. 10.5 g of 4 - [(2-chloroethyl) (methyl) -amino] benzaldehyde are added. The mixture is kept under stirring for 2 hours at 52 ° C, and then at room temperature for 48 hours. The reaction mixture is diluted in 50 ml of ethanol and then stored at 25 ° C for 12 hours. The precipitate obtained is filtered at room temperature, washed with 100 ml of acetone and 3 times with 100 ml of ethyl ether and dried in vacuo in the presence of P2O5.

[0117] 15.1 g of light orange crystals are recovered. The analyzes indicate that the product is in compliance.

Stage 3: synthesis of 1-METiL-4 - ((E) -2-r4- (METiL (2-r (1-METiL-1Himidazol-2-yl) sulfanyl1ethyl) amino) phenyl1vinyl) pyridinium chloride Í11 [0118] 5 g of methyl sulfate of 4 - ((E) -2- {4 - [(2chloroethyl) (methyl) amino] phenyl} vinyl) methylpyridinium, 2.15 g of 2-mercapto-1methylimidazole and 20 ml of ethanol (EtOH ) are stirred and heated to 70 ° C for 48 hours. 2.15 g of 2-mercapto-1-methylimidazole diluted in 3 ml of EtOH are added to the reaction mixture, the mixture is kept under stirring at 72 ° C for 72 hours. 20 ml of isopropanol and 2 ml of water are added to the reaction mixture cooled to -10 ° C. The oil is separated from the supernatant, washed with ethyl acetate (EtOAc), then solubilized in 100 ml of ethanol and stored at -25 °. C for 48 hours.

[0119] The obtained crystals are filtered, washed with 20 ml of ethanol and with 3 times 100 ml of EtOAc, and then vacuum dried in the presence of P2O5. 5.79 g of brown powder are collected. The analyzes indicate that the product

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66/90 is in compliance. 1H NMR (400 MHz, ppm, DMSO-Ó6) 2.96 (s, 3 H), 3.51 (t, 2 H), 3.67 (s, 3 H), 3.68 (t, 2 H ), 4.20 (s, 3H), 6.75 (d, 2 H), 7.20 (d, 1 H), 7.57 (d, 2 H), 7.72 (1 H), 7 , 76 (d, 1 H), 7.91 (d, 1 H), 8.07 (d, 2 H), 8.73 (d, 2 H).

Example 2

Synthesis of 4 - ((E) -2- (4-r (2-r (1,3-DiMETiL-1H-imidazol-3-io2-yl) sulfanyl1ethyl) (methyl) amino1phenyl) vinyl sulfate / chloride) - 1-methylpyridinium Γ21

[0120] Summary scheme:

Cl

Γ1]

Γ2]

[0121] Procedure:

[0122] A solution of 2 g of 1-methyl-4 - {(E) -2- [4 (methyl {2 - [(1-methyl-1H-imidazol-2-yl) sulfanyl] ethyl} amino] ) phenyl] vinyl} pyridinium [1] in 2 ml of N-methylpyrrolidinone (NMP) and 8 ml of acetonitrile (ACN) is stirred at 70 ° C for 20 minutes. 500 μΙ of dimethyl sulfate is added to the mixture. Stirring and heating are maintained for 1 h 30 min. 500 mg of sodium acetate is added. After 4 hours, 1 ml of dimethyl sulfate is added and stirring is continued for 15 hours at room temperature. 50 ml of acetonitrile is added. The precipitate obtained is filtered. 100 ml of acetone are introduced

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67/90 in the filtrate and the oil thus obtained is washed 3 times with 100 ml of acetone, then resolubilizing in 50 ml of isopropanol and kept at -25 ° C for 48 hours. The precipitate formed is filtered, washed with 10 ml of iPrOH and 3 times with 20 ml of ethyl acetate and then dried in vacuo in the presence of P2O5. 1.11 g of brown powder are recovered. The analyzes indicate that the product is in conformity, in the form of mixed chloride salts and methyl sulfate salts.

[0123] ¹ H NMR (400 MHz, ppm, MeOH-de) 3.06 (s, 3 H), 3.35 (t, 2 H), 6.68 (s, 5.44 H, methyl sulfate) , 3.77 (t, 2 H), 3.79 (t, 6 H), 4.24 (s, 3 H), 6.82 (d, 2 H), 7.15 (d, 1 H) , 7.64 (d, 2 H), 7.75 (s, 2 H), 7.83 (d, 1 H), 8.00 (d, 2 H), 8.55 (d, 2 H) .

Example 3

Synthesis of 2,2 'DICLORIDE - (DISULFANO-DIILBISrETANO-2,1-DIIL (METILIMINO) 4,1-phenylene (E) ethylene-2,1-diyl1) bis (1-methylpyridinium) Γ31

[3] [0124] Summary scheme:

[3] [0125] Procedure:

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68/90

Stage 1: 4 ₁ 4 '- (disulfanediylbisiethane-2 ₁ 1-diyl (methylimino) 1) dibenzaldehyde [0126] 82.3 g of phosphorus oxychloride are added to 500 ml of DMF at 0 ° C. After stirring for 30 min at 0 ° C, a solution of 47 g of N, N '(disulfanidiildietane-2,1-diyl) bis (N-methylaniline) is added in drops. The mixture is stirred for 90 minutes at 0 ^o C and then for 75 min at 10 ° C and 105 min at 40 ° C. It is then poured into 2.5 l of cold water and 700 ml of 5 N sodium hydroxide are added. The yellow precipitate obtained is filtered through celite and solubilized in 200 ml of dichloromethane and the solution obtained is washed with 200 ml of a saturated aqueous solution of sodium chloride. After drying over magnesium sulfate and evaporating dichloromethane, the yellow residue (80 g) is purified by chromatography on silica gel. After drying, a light yellow powder is recovered. The analyzes indicate that the product conforms to the expected structure.

Stage 2: 2,2 '- (DisuLFANODiiLBisrETANO-2,1-DiiL (METiLiMiNO) -4,1phenylene (E) ethylene-2,1-diyl1} bis (1-methylpyridinium dichloride) Γ31 [0127] 25 g of 4 , 4 '- {disulfanediilbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde and 18.5 g of N-methylpicolinium chloride are dissolved in 300 ml of methanol, 12.7 ml of piperidine are added to the mixture. The entire mixture is heated under stirring at 55 ° C for 11 h. Methanol is removed in vacuo at 40 ° C. The solid is mixed with 300 ml of isopropanol. After drying by evaporation, 200 ml of isopropanol is introduced. The mixture becomes solid and is prolonged by adding 100 ml of isopropanol and twist-dried over a sintered glass.The recovered solid is washed with isopropanol and then acetone, and then vacuum dried. After drying, 36.7 g of powder orange are recovered.27 g of a high purity orange red powder are recovered by recrystallization from isopropanol.The analyzes indicate that the product conforms to the compound [3] and pure.

[0128] ¹ H NMR (400 MHz, MeOH-d ₄ ) 2.99 (t, 4H), 3.81 (t, 4H),

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4.31 (s, 6H), 6.86 (d, 4H), 7.22 (d, 2H), 7.63 (m, 2H), 7.69 (d, 4H), 7.83 (d , 2H), 8.29 (m, 2H), 8.36 (m, 2H), 8.61 (m, 2H).

Example 4

SYNTHESIS OF 4,4 ’- {DISULFANODIIL-BISrETAN-2,1-DIIL (METHYLIMINE) -4,1phenylene (E) ethylene-2,1-diylDbis (1-methylpyridinium) dimethoxysulfate Γ41

A O— Λ

O O [4] [0129] Synthesis scheme:

-Q

O O

S.

'/ A-,

O o

O

s

The [4] [0130] Procedure:

4,4 '- {DISULFANODIILBISrETANO-2,1-DIIL (METHYLIMINE) -4,1-PHENYLENE (E) ETHENO-2,1diylRbis (I-methylpyridinium) dimethoxysulfate Γ41 [0131] 2.62 g of 4-picolino are diluted in 25 ml of dichloromethane and 3 ml of dimethyl sulfate are added to the solution, the temperature of which increases at reflux (40 ° C). After stirring for 40 minutes, 50 ml of isopropanol is added and the mixture is concentrated by distillation of dichloromethane (mixture

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70/90 heated to 60 ° C). 1.83 g of pyrrolidine are introduced into the mixture, followed by 4.99 g of 4.4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde. After stirring for 2 hours at 65 ° C, the reaction mixture is cooled to room temperature, and the precipitate formed is filtered and washed 3 times with 100 ml of isopropanol. The red paste thus obtained is brought to reflux and then cooled. The formed red precipitate is filtered and then dried. 8.94 g of red powder are recovered. The analyzes indicate that the product complies with the structure of [4] and pure. ¹ H NMR (400 MHz, DMSO-de) 2.96 (t, 4 H), 3.02 (s, 6 H), 3.36 (s, 6 H), 3.72 (t, 4 H) , 4.16 (s, 6 H), 6.81 (d, 4 H), 7.15 (d, 2 H), 7.57 (d, 4 H), 7.87 (d, 2 H) , 8.02 (d, 4 H), 8.66 (d, 4 H).

Example 5

SYNTHESIS OF 2,2 'DICLORIDE - {DISULFANODIYLBISrETHAN-2,1-DIYL (methylimino) -4,1phenylene (E) ethylene-2,1-diyl1} bis (1-ethylpyridinium) Γ51

Cl [5] [0132] Synthesis scheme:

O

H

Cl [5] [0133] Procedure:

Synthesis of 2,2 'DICLORIDE - {DISULFANODIILBISrETANO-2,1-DIIL (METHYLIMINE) -4,1phenylene (E) ethylene-2,1-diyl1} bis (1-ethylpyridinium) Γ51 [0134] 10 g of 4, 4 '- {disulfanodiilbis [ethane-2,1-diyl (methylimino)]}

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71/90 dibenzaldehyde and 8.1 g of N-ethylpicolinium chloride are dissolved in 100 ml of isopropanol. 1.3 g of piperidine is added to the mixture. The entire mixture is refluxed for 5 hours with stirring. Isopropanol is removed in vacuo at 50 ° C. The obtained gum is ground with acetone. 18 g of solid is recovered and treated with carbon black. 7.1 g of product are collected and 4 g are purified by liquid / liquid chromatography (water / BuOH). After drying, 1.65 g of red powder is recovered. The analyzes indicate that the product conforms to the structure of the dye [5] and is pure. ¹ H NMR (400 MHz, MeOH-c6) 1.57 (t, 6 H), 2.98 (t, 4 H), 3.11 (s, 6 H), 3.8 (t, 4 H) , 4.73 (q, 4 H), 6.85 (m, 4 H), 7.23 (d, 2 H), 7.69 (m, 6 H), 7.85 (d, 2 H) , 8.29 (m, 2 H), 8.38 (m, 2 H), 8.67 (m, 2 H).

Example 6

Synthesis of the 4,4 'DIBROMIDE - (DISULFANODIILBISrETANO-2,1-DIIL (METHYLIMINE) -4,1phenylene (E) ethylene-2,1-diylRbis (1-ethylpyridinium) Γ61

[6] [0135] Summary scheme:

iPrOH

2Br

[6] [0136] Procedure:

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4,4 'DIBROMIDE SYNTHESIS - (DISULFANODIYLBISrETHAN-2,1-DIYL (METHYLIMINE) -4,1phenylene (E) ethylene-2.1-diyl1) bis (1-ethylpyridinium) Γ6Ί [0137] 4.1 g of 4, 4 '- {disulfanodiilbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 400 ml of isopropanol and 0.86 ml of pyrrolidine are heated to 75 ° C for 20 minutes. 4.26 g of 1-ethyl-4-methylpyridinium bromide are added to the reaction medium and the resulting mixture is stirred and heated for 5 h. 200 ml of acetone is introduced into the reaction mixture. The precipitate obtained is filtered, washed with acetone and dried. 7.37 g of red powder are recovered. The analyzes indicate that the product is in conformity and pure. ¹ H NMR (400 MHz, DMSO-cfó) 1.5 (t, 6 H), 2.98 (t, 4 H), 3.04 (s, 6 H), 3.74 (t, 4 H) , 4.46 (q, 4 H), 6.84 (d, 4 H), 7.19 (d, 2 H), 7.61 (d, 4 H), 7.93 (d, 2 H) , 8.08 (d, 4 H), 8.82 (d, 4 H).

Example 7

SYNTHESIS OF DIBROMIDE 4,4 '- (DISULFANODIILBISrETANO-2,1-DIIL (METHYLIMINE) -4,1 ·

PHENYLENE (E) ETHENO-2,1-DIIL]} BISr1 - (2-HYDROXYETHYL) PYRIDINIUM] Γ7Ί

HO

Br

OH [7] [0138] Synthesis scheme:

HO

H iPrOH 8h at 75 ° C

HO

Br [7]

OH

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73/90 [0139] Procedure:

Synthesis of the 4,4 'dibromide - (DisuLFANODiiLBisrETANO-2,1DIIL (METILIMINO) -4,1-FENILENO (E) ETENO-2,1-DIILl) BISri- (2hydroxyethyl) pyridinium1 Γ71 [0140] 4.1 g of 4.4 '- {disulfanodiilbis [ethane-2,1diyl (methylimino)]} dibenzaldehyde, 40 ml of isopropanol and 0.86 ml of pyrrolidine are heated at 75 ° C for 1 hour. 4.6 g of 1- (2-hydroxyethyl) -4methylpyridinium bromide are added to the reaction medium, and the resulting mixture is stirred and heated for 1 hour. 200 ml of acetone is introduced into the reaction mixture. The obtained gum is separated, filtered, washed 3 times with 150 ml of isopropanol and dried. 6.59 g of powder are recovered. The analyzes indicate that the product is in compliance. ¹ H NMR (400 MHz, MeOHd4) 2.97 (t, 4 H), 3.1 (s, 6 H), 3.78 (t, 4 H), 3.97 (t, 4 H), 4 , 51 (t, 4 H), 6.83 (d, 4 H), 7.09 (d, 2 H), 7.61 (d, 4 H), 7.83 (d, 2 H), 7 , 98 (d, 4 H), 8.56 (d, 4 H).

Example 8

Synthesis of the 4,4 'DIBROMIDE - <DISULFANODIILBISrETANE-2,1-DIYL (METHYLIMINE) -4,1phenylene (E) ethene-2,1-diyl1) bis (1-benzylpyridinium) Γ81

[8]

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74/90 [0141] Summary scheme:

’7Q

Br

N ^^ ^S 'S'

O

N ^^ ^S 'S'

I

Br

[8] [0142] Procedure:

Stage 1: synthesis of 4,4 ’- (DisuLFANODiiLBisrETANO-2,1-DiiL (methylimino) -4,1-phenylene (E) ethylene-2,1-diyl1) bis (1-benzylpyridinium)

DIMETHANOSULPHONATE Γ8Ί [0143] 4.1 g of 4.4 '- {disulfanediilbis [ethane-2,1diyl (methylimino)]} dibenzaldehyde, 40 ml of isopropanol and 0.86 ml of pyrrolidine are heated at 75 ° C for 20 minutes . 5.85 g of 1-benzyl-4-methylpyridinium bromide are added to the reaction medium, and the resulting mixture is stirred and heated for 5 hours. The reaction mixture is stirred at room temperature for 17 hours. The supernatant is filtered, the black solid obtained is separated, washed with 200 ml of isopropanol, filtered and then dried. 9.12 g of red powder are recovered. The analyzes indicate that the product is in compliance. ¹ H NMR (400 MHz, DMSO-de) 2.98 (t, 4 H), 3.03 (s, 6 H), 3.78 (t, 4 H), 5.67 (s, 4 H) , 6.82 (d, 4 H), 7.15 (d, 2 H), 7.40 (m, 5 H), 7.61 (d, 4 H), 7.90 (d, 2 H) , 8.07 (d, 4 H), 8.90 (d, 4 H).

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75/90

Example 9

SYNTHESIS OF 4.4 '- (DISULFANODIILBISrETANO-2,1-DIIL (METHYLIMINE) -4,1 phenylene (E) ethylene-2,1-diyl1) bis (1-methylquinoline) dimethyl SULFATE F91

+ k

iPrOH 8h at 75 ° C

S., \ O 2 O-S

O O

[9] [0145] Procedure:

Synthesis of 4,4 '- {DISULFANO-DIILBISrETANO-2,1-DIIL (METILIMINO) -4,1phenylene (E) ethylene-2,1-diyl1} bis (1-methylquinoline) dimethyl SULFATE Γ91 [0146] 4.1 4.4 'g - {disulfanediilbis [ethane-2,1-diyl (methylimino)]}

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76/90 dibenzaldehyde, 40 ml of isopropanol and 0.86 ml of pyrrolidine are heated to 75 ° C for 20 minutes. 5.9 g of 1,4-dimethylquinoline bromide are added to the reaction medium, and the resulting mixture is stirred and heated for 5 hours. 200 ml of acetone is introduced into the reaction mixture. The precipitate obtained is separated, washed with 200 ml of acetone and then dried. 8.73 g of black powder are recovered. The analyzes indicate that the product is in compliance. LC-MS m / z 334, L max 524 nm.

Example 10

Synthesis of 4,4'-fDISULFANO-DIIL-BISrETANO-2,1-DIIL (METILIMINO) -4,1-FENILENO (1 E) PROP1-ENO-1,2-DIILl) BISri- (2-HYDROXY-ETHYL) PIRIDÍNIOl DIBROMETO Γ10]

[10] [0147] Summary scheme:

O

OH

Br

S _x

H / / 75 ° C 8h iPrOH

[10]

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77/90 [0148] Procedure:

Stage 1: Synthesis of the 4,4 'dibromide - (DisuLFANODiiLBisrETANO-2,1diyl (methylimino) -4,1-phenylene (1E) prop-1 -eno-1 ^ -diylUbisH - (2-hydroxyethyl)

PYRIDINIUM] Γ10Ί [0149] 4.1 g of 4.4 '- {disulfanediilbis [ethane-2,1diyl (methylimino)]} dibenzaldehyde, 40 ml of isopropanol and 0.86 ml of pyrrolidine are heated to 75 ° C for 20 minutes. 5.9 g of 4-ethyl-1- (2-hydroxyethyl) pyridinium bromide are added to the reaction medium, and the resulting mixture is stirred and heated for 5 hours. 200 ml of acetone is introduced into the reaction mixture. The precipitate obtained is filtered, washed with 200 ml of acetone and then dried. 9.67 g of violet powder are recovered. The analyzes indicate that the product is in conformity and pure. ¹ H NMR (400 MHz, MeOH-d ₄ ) 2.38 (s; 6 H), 2.96 (t; 4 H), 3.06 (s; 6 H), 3.76 (t; 4 H ), 3.99 (t; 4 H), 4.59 (t; 4 H), 6.84 (d; 4 H), 7.49 (d; 4 H), 7.52 (s; 2 H ), 8.13 (d; 4 H), 8.68 (d; 4 H).

Example 11

Synthesis of the salt of 1-ETiL-4 - ((E) -2-f4-K17-f4-KE) -2- (1-ethylpyridinium-4yl) vinyl1-phenyl) -4,4,13,13-tetramethyl-8, 9-dithio-17-azo-4,13-diazoniooctadec-1yl) (methyl) amino1phenyl) vinyl) pyridinium Γ11Ί

[11] [0150] Summary scheme:

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78/90

HO

S ^ -x ^ OH ff N \ -n ^z = / \

O

S-S \ + -N

^O O ² S ^O O .o '\ 2 .S [11] [0151] Procedure:

Stage 1: synthesis of 4-ΓΓ3 (dimethylamino) propyl1 (methyl) amino1benzaldehyde [0152] 10 g of 4-fluorobenzaldehyde and 12 g of potassium carbonate are mixed in 20 ml of N-methylpyrrolidinone (NMP) and brought to 50 ° C 13 ml of N, N, N'-trimethyl-1,3-propanediamine are added and the mixture is brought to 80 ° C for 10 hours. After cooling, 100 ml of acetone is added. The obtained mixture is filtered and concentrated in vacuo. 21.85 of oil, which contains the expected compound and 0.7 molar equivalents of PMN are recovered.

Stage 2: synthesis of disulfaneddihydropropane-3,1-diyl dimethanesulfonate [0153] 9 g of 3,3’-disulfanediildipropan-1-ol are diluted in 50 ml

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79/90 ethyl acetate. 20 g of triethylamine are added, and the mixture is cooled to 0 ^o C. 14.3 g of mesyl chloride are added gradually while maintaining the temperature below 5 ° C. At the end of the addition, the mixture is kept under stirring for one hour at room temperature and then poured into 100 ml of a water / ice mixture. The product is extracted with 100 ml of ethyl acetate and washed with 2 x 100 ml of a molar hydrochloric acid solution, 2 x 100 ml of water, 100 ml of a saturated solution of sodium hydrogen carbonate and 2 x 100 ml of a saturated sodium chloride solution. The organic phase is dried over sodium sulfate and concentrated in vacuo. 6 g of a yellowish oil are recovered; analyzes show that the product obtained is in compliance.

Stage 3: synthesis of N, N '- (DisuLFANODiiLDiPROPANO-3,1-DiiL) Bis (3-r (4formylphenyl) (methyl) amino1-N, N-dimethylpropan-1-ammonium) dimethanesulfonate [0154] 2.2 g 4 - [[3- (dimethylamino) propyl] (methyl) amino] benzaldehyde and 1.7 g of disulfaneddihydipropane-3,1-diyl dimethanesulfonate are mixed in 2 ml of N-methyl-pyrrolidinone at 80 ° C for 22 hours . After the reaction mixture has been cooled, 20 ml of ethanol is added. The obtained solid is filtered and is highly hygroscopic. Purification by trituration in dichloromethane results in the isolation of 232 mg of solid that conforms to the expected product.

Stage 4: salt synthesis of 1-ETiL-4 - ((E) -2- (4-r (17- (4-r (E) -2- (1-ETiLPiRiDinium-4yl) vinyl1-phenyl) -4,4 , 13,13-tetramethyl-8,9-dithio-17-azo-4,13-diazoniooctadec-1yl) (methyl) amino1phenyl) vinyl) pyridinium [111 [0155] 230 mg of N, N '- (disulfanediildipropane3) dimethanesulfonate , 1-diyl) bis {3 - [(4-formylphenyl) (methyl) amino] -N, N-dimethylpropan-1-ammonium} and 163 mg of 1-ethyl-4-methylpyridinium bromide are mixed in 5 ml of isopropanol . 53 μΙ of pyrolidine is added and the mixture is kept stirring at 70 ° C for 6 h and stirred at room temperature for 72 hours. After the mixture has cooled to 20 ° C, the solid formed is filtered, collected in methanol and re-precipitated by adding

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80/90 of 200 ml of ferc-butyl methyl ether. 118 mg of black solid are recovered. The analyzes indicate that the product conforms to the expected structure (MS (ESI +): peak mass m / z = 199).

Example 12

2,2 ’DIBROMIDE SYNTHESIS - {DISULFANO-DIILBISrETANO-2,1-DIILIMINO-4,1 ·

PHENYLENE (E) ETHENO-2,1-DIILRBISri- (2-HYDROXYETHIL) PYRIDINIUM Γ12Ί \ = / H

OH [0156] Synthesis scheme:

° ^ F

Na ₂ CO ₃ , DMSO

52h at 160 ° C 18C-6 -10%

MsCl

H N OH pyridine

Pyridine z% O ^r '· \ = / ^N O'O

1) Na ₂ S ₂ O ₃

2) NaOH

íf ^ ^S V ^ ^N “O ~ q

Hô

iPrOH

[0157] Procedure:

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81/90

STAGE 1: SYNTHESIS OF 4-K2-HYDROXYETHYL) AMINO1BENZALDEHYDE [0158] 1.24 g of 4-fluorobenzaldehyde, 10 ml of DMSO distilled in calcium hydride, 1.16 g of sodium carbonate and a catalytic amount of 18-crown-6 ether (5 mol%) are mixed for 10 minutes with stirring. 1.2 ml of ethanolamine is added slowly to the reaction medium, which is kept under stirring and heated to 160 ° C for 52 hours. After cooling to 75 ° C, the reaction mixture is hydrolyzed with distilled water. The distilled hydrochloric acid solution is added to the mixture until a pH between 6 and 7 is obtained, and then the mixture is kept under stirring and heating at 40 ° C for 6 hours. The alcohol obtained is extracted with ethyl acetate. The organic phase is washed several times with distilled water and salified water, and then dried over magnesium sulfate. The mixture is concentrated in vacuo and purified by chromatography on silica gel. 1.2 g of the brown solid are recovered. The analyzes show that the product conforms to the expected structure.

Stage 2: synthesis of 2-K4-formylphenyl) amino1ethyl methyl sulfate [0159] 0.4 g of 4 - [(2-hydroxyethyl) amino] benzaldehyde and 10 ml of pyridine are mixed with stirring. The reaction medium is cooled in a dry ice and acetone bath. 0.18 ml of mesyl chloride is added in drops at 0 ^o C. The reaction mixture is stirred for 17 hours at a temperature between 0 and 5 ° C, and then ice water is introduced into the mixture. The formed solid is crushed, filtered, washed with distilled water and then vacuum dried. 550 mg of white powder is recovered. The analyzes indicate that the product is in compliance.

Stage 3: synthesis of 4,4'-rDisuLFANODiiLBis (ETANO-2,1DIYLIMINO) lDIBENZALDEHYDE [0160] 0.5 g of methyl 2 - [(4-formylphenyl) amino] ethyl sulfate, 3 ml of an ethanol- water (1: 2) and 0.546 g of sodium thiosulfate are mixed at reflux for 2 hours with stirring. The yellow solution obtained is cooled, and then

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2.8 ml of 35% sodium hydroxide is added in drops. The mixture is kept under stirring at 75 ° C for 1 hour. After cooling, a light yellow solid is filtered, washed with water and then vacuum dried. 237 mg of a yellow powder are recovered. The analyzes indicate that the product is in compliance and is pure. ¹ H NMR (400 MHz, CDCla) 2.85 (t, 4H), 3.5 (m, 4 H), 4.61 (t, 2 H), 63.57 (d, 2 H), 7, 63 (d, 4 H), 9.66 (s, 2 H).

Stage 4: synthesis of the 2,2 'dibromide - (DisuLFANODiiLBisrETANO-2,1diilimino-4,1 -phenylene (E) eteno-2,1-diylPbisíI - (2-hydroxyethyl) pyridinium1

Γ121 [0161] 200 mg of 1- (2-hydroxyethyl) -2-methylpyridinium bromide and 260 mg of 4,4 '- [disulfanediilbis (ethane-2,1-diylimino)] dibenzaldehyde are dispersed in 4 ml of isopropanol. 1 ml of a solution composed of 666 mg of acetic acid, 790 mg of pyrrolidine and 10 ml of isopropanol are added to the suspension. The mixture is kept under stirring for 16 hours. 130 mg of 1- (2-hydroxyethyl) -2methylpyridinium bromide are added and the mixture is heated to 60 ° C for 6 hours. The solid formed is filtered, crushed in 5 ml of isopropanol and 0.5 ml of water and then filtered and dried. 188 mg of black solid is recovered. The analyzes indicate that the product conforms to the expected structure. ¹ H NMR (400 MHz, DMSOd6) 2.96 (t, 4H), 3.46 (m, 4 H), 3.84 (m, 4 H), 4.8 (t, 4 H), 5, 22 (t, 2 H), 6.70 (d, 4 H), 6.80 (t, 2 H), 7.28 (d, 2 H), 7.65 (d, 4 H), 7, 72 (dd, 2 H), 7.86 (d, 2 H), 8.35 (dd, 2 H), 8.45 (d, 2 H), 8.67 (d, 2 H).

Example 13

SYNTHESIS OF THE SULPHATE OF 2.2 ’- <DISULFANODIYLBISrETHANE-2,1-DIYLIMINE-2,1phenylene (E) ethylene-2,1-diyl1) bis (1-methylquinoline) dimethyl Γ131

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83/90 [0162] Synthesis scheme:

h ₂ n

OH

O

MsCl

O

DMSO 18 C6 -10% 160 ° C

OH

Pyridine ^Na 2 ^S 2 ^O 3

[13] [0163] Procedure:

Stage 1: synthesis of 2-r (2-HiDRõxi ethyl) amino] benzaldehyde [0164] 1.24 g of 2-fluorobenzaldehyde, 10 ml of DMSO

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84/90 distillates in calcium hydride, 1.16 g of sodium carbonate and a catalytic amount of 18-crown-6 ether (5 mol%) are mixed for 10 minutes with stirring. 1.3 ml of ethanolamine is added. After stirring at 160 ° C for 3 hours, the mixture is brought back to 75 ° C and hydrolyzed with distilled water. The pH of the solution is lowered to 6 by the addition of dilute hydrochloric acid and the resulting mixture is kept under stirring and heating at 40 ° C for 18 hours. The alcohol obtained is extracted with ethyl acetate. The organic phase is washed several times with distilled water and salified water, and then dried over magnesium sulfate. The mixture is concentrated in vacuo and purified by chromatography on silica gel. 1.2 g of the brown solid are recovered.

Stage 2: synthesis of 2-r (2-FORMiLFENiL) AMiNOlETiL methanesulfate [0165] 0.5 g of 2 - [(2-hydroxyethyl) amino] benzaldehyde and 10 ml of distilled pyridine are mixed at 0 ^o C with stirring. 0.23 ml of mesyl chloride is added in drops. The reaction mixture is stirred for 17 hours at a temperature between 0 and 5 ° C, and then ice water is introduced into the mixture. The white solid obtained is filtered, rinsed with distilled water and then vacuum dried (650 mg). The analyzes indicate that the product is in compliance and is pure.

Stage 3: synthesis of 2,2'-rDisuLFANODiiLBis (ETANO-2,1diilimino) 1dibenzaldehyde [0166] 0.5 g of 2 - [(2-formylphenyl) amino] ethyl methane sulfonate and 0.546 g of sodium thiosulfate pentahydrate they are heated in 3 ml of an ethanol / water solution (1: 2) at 90 ° C for 15 g. The obtained solution is cooled, and then 2.8 ml of 35% sodium hydroxide is added and the mixture is stirred at 75 ° C for 1 hour. After cooling, a light yellow solid formed is filtered, washed with distilled water and then vacuum dried. 222 mg of a powder are recovered. The analyzes indicate that the product is in

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85/90 conformity with the expected product: ¹ H NMR (400 MHz, CDCI3) 2.96 (t, 4 H), 3.63 (dt, 4 H), 6.74 (t, 2 H), 6, 76 (d, 2 H), 7.41 (t, 2 H), 7.50 (d, 2 H), 8.54 (t, 2 H), 9.84 (s, 2 H).

Stage 4: synthesis of 2,2'-fDisuLFANODiiLBisrETANO-2,1-DiiLiMiNO-2,1phenylene (E) ethylene-2.1-diyl1) bis (1-methylquinoline) dimethyl sulfate Γ13Ί [0167] 210 mg of 2,2'- [disulfanodiylbis (ethane-2,1diiIimino)] dibenzaIdehyde and 360 mg of 1,2-dimethyl-quinoIinium are dispersed in 4 ml of isopropanol. 1 ml of a solution composed of 790 ml of pyrrolidine, 666 mg of acetic acid and a sufficient amount of isopropanol for 10 ml are added. The mixture is kept under stirring at room temperature for 10 days, 180 mg of quinoline is added and the stirring is maintained for 3 days at room temperature. The mixture is filtered and the recovered solid is dried (214 mg). The analyzes indicate that the product conforms to the expected structure. LCMS (ESI +) 320, Àmax 494 nm.

Coloring Example

Example 1

Coloring Process - Compound Γ11 [0168] A 1 g lock of hair of tone level 4 is placed at the bottom of a container. 1 ml of a molar solution of ammonium thioglycolate at pH 8.5 is diluted with 9 ml of water. The solution thus obtained is applied to the locks and left to act for 30 minutes. The strands are rinsed with running water and then put back in a container. 10 ml of an aqueous solution containing 49 mg of the compound [1] are applied for 30 minutes at room temperature (the strands are turned and re-impregnated after 15 minutes).

[0169] The wicks are then rinsed under running water and dried. After staining, the tint of level 4 became visually lighter than the untreated control wicks.

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86/90

Example 2

Coloring Process - Compound Γ21 [0170] A 1 g lock of hair of tone level 4 is placed at the bottom of a container. 1 ml of a molar solution of ammonium thioglycolate at pH 8.5 is diluted with 9 ml of water. The solution thus obtained is applied to the locks and left to act for 30 minutes. The strands are rinsed with running water and then put back in a container. 10 ml of an aqueous solution containing 63 mg of the compound [2] are applied for 30 minutes at room temperature (the strands are turned and re-impregnated after 15 minutes).

[0171] The wicks are then rinsed with running water and dried. After staining, the tint of level 4 became visually lighter than the untreated control wicks.

Example 3

Coloring Process with Compounds Γ31 to Γ121 [0172] Preparation of composition A

Disulfite dye from [3] to [12] 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

[0173] Preparation of a composition B

Thioglycolic acid 1M Sodium hydroxide Qs pH 8.5 Demineralized water Qs 100 g

[0174] At the time of use, compositions A (9 ml) and B (1 ml) are mixed, then the obtained mixture is applied to a 1 g lock of dark hair (tone level 4) for 30 minutes at temperature environment (the wicks are turned and re-impregnated after 15 minutes).

[0175] After rinsing with running water and drying, the

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87/90 lightening of the hair thus treated is observed: the strand of the level of tone 4 has become visually lighter than the untreated control strands.

Remaining with respect to successive washing operations [0176] The strands treated in this way are divided in two, half are subjected to 5 successive washing operations, according to a cycle that comprises moistening the strands with water, washing with a conventional shampoo , rinse with water, followed by drying.

Visual Observations [0177] During the washing operations of examples [1], [2], [3], [4], [5], [7], [8], [9], [10] and [12 ] there is no visible flow of the dye, the foam of the shampoo and the rinse water are not colored.

[0178] The color observed in the locks is preserved and the lightening effect remains visible in the hair of the tone level 4, thus treated.

[0179] Results in the L * a * b * system:

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

[0180] In this system L * a * b *, L * represents the luminosity, a * indicates the axis of green / red color and b * the axis of blue / yellow color. The higher the L value, the lighter or weaker the color, conversely, the lower the L value, the darker or stronger the color. The higher the value of a *, the redder the hue and the higher the value of b *, the more yellow the hue.

[0181] The variation in coloring between the dyed and washed TH4 (tone level 4) strands of hair is measured by (AE) according to the following equation:

AE = / (L * - Lo *) ² + (a * - ao *) ² + (b * - bo *) ² [0182] In this equation, L *, a * and b *, represent the values

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88/90 measured after staining and Lo *, ao * and bo * represent the values measured before staining (or washing).

[0183] The higher the AE value, the greater the difference in color between the TH4 strands and the colored strands.

Table 2

Compound L * The* B* ΔΕ TH4 reference wicks 16.16 2.88 2.95 Compound 1 19.79 11.02 11.72 12.50 Compound 1 - 5 washing operations 21.45 11.36 12.87 14.08 Compound 2 20.76 8.65 14.18 13.44 Compound 2 - 5 washing operations 22.16 9.13 14.43 14.38 TH4 reference wicks 17.27 2.78 3.19 Compound 3 19.09 6.45 9.30 7.36 Compound 3 - 5 washing operations 18.75 5.41 8.02 5.70 Compound 4 17.94 9.33 9.24 8.95 Compound 4 - 5 washing operations 17.85 8.51 7.73 7.34 Compound 5 19.57 6.31 10.14 8.13 Compound 5 - 5 washing operations 19.02 5.84 9.31 7.06 7 17.76 7.76 7.65 6.71 Compound 7 - 5 washing operations 18.45 9.01 7.85 7.88 Compound 8 17.47 5.46 5.75 3.72 Compound 8 - 5 washing operations 17.89 6.82 6.99 5.59 Compound 9 16.91 4.67 2.15 2.19 Compound 9 - 5 washing operations 16.62 4.73 2.81 2.10 Compound 10 17.31 6.42 6.65 5.02 Compound 10 - 5 washing operations 18.55 6.47 6.82 5.34 Compound 12 20.06 3.66 9.15 6.64 Compound 12 - 5 washing operations 18.73 3.27 7.71 4.78

[0184] The results in the Table show that the change in color is very small after 5 washing operations on the strands originally of TH4 colored with the dyes of the present invention. Therefore, the coloring and lightening effect of the hair remains virtually unchanged, which shows good resistance to washing the dyes of the present invention.

[0185] Results obtained in the TH4.5 wicks treated with the

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89/90

compounds 3 to 5, followed by a series of 3 0 washing operations. L The* B* ΔΕ Reference wicks TH4,5 23.09 3.13 3.59 - Compound 3 25.49 10.56 9.96 10.08 Compound 3 after 30 washing operations 25.98 11.41 9.86 10.78 Compound 4 25.87 6.06 9.60 7.24 Compound 4 after 30 washing operations 24.38 5.86 9.20 6.37 Compound 5 25.08 1.19 7.51 4.81 Compound 5 after 30 washing operations 25.72 1.38 6.01 3.98

[0186] The results in the Table show that the change in color is very small even after 30 washing operations on the strands originally of TH4.5 colored with the dyes of the present invention. Therefore, the coloring and lightening effect of the hair remains virtually unchanged, which shows good resistance to washing the dyes of the present invention.

Reflectance Results [0187] The clarification of the compositions according to the present invention and the remnant of said compositions in relation to the successive washing operations were expressed as a function of the reflectance of the hair. These reflectances are compared to the reflectance of an untreated hair lock of tone level TH4.

[0188] The reflectance is measured using a Konica Minolta® CM 2600D spectrophotocolorimeter and after irradiating the hair with visible light in the wavelength range from 400 to 700 nm.

[0189] Firstly, it is observed that the reflectance of a strand of hair treated with a composition according to the present invention is greater than that of untreated hair. Therefore, the treated locks appear to be clearer.

[0190] In addition, the results, illustrated by figures 1, 2 and 3, show that the reflectance of the hair locks of tone level 4, treated

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90/90 with the composition of the present invention, changes very little after 5 washing operations. Therefore, the coloring and lightening effect on the hair remain virtually unchanged, which shows a good resistance of the dyes of the present invention to washing operations.

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1/30

1.

Claims (30)

Claims FLUORESCENT DYE, characterized by the fact that it presents the formula (I) or (II) below: R ^{g R} 'g ^X = N \ R' M 'R ⁱ , SS \ N- ( ^CR 1 ^R 2V (CR3R4) n '(CR ^^ CR' ^^ (I) ^{b R} 'h N ++ ^ R '„ R '' ' R ' M ' ^R ' h ^R b R ^R g ^R 'g ^{X =} N ^g ' R '_{M' R} ^{R '} i R'h ^R b N- ( ^CR 1 ^R 2) _m ZCR3R4) n zS Y (II) its salts of organic or inorganic acid, its optical and geometric isomers, and solvates, such as hydrates; where, in formulas (I) and (II): - Ra and R'a, which may be identical or different, represent an arylalkyl (C1-C4) group or an alkyl (C1-C6) group, optionally substituted by a hydroxy 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; - Rb and R'b, which can be identical or different, represent a hydrogen atom, an arylalkyl group (C1-C4) or an alkyl group (C1C6), which is optionally substituted; - Rg, R'g, R ”g and R” 'g, which can be identical or different, represent a hydrogen atom, an amino group, alkylamino (C1-C4), dialkylamino (C1-C4), trifluoromethyl, a radical acylamino, (C1-C4) alkoxy, (C1-C4) alkylcarbonyloxy (C1-C4) alkoxy, (C1-C4) alkylcarbonylamino, (C1-C4) alkylsulfonylamino, or (C1-C3) alkyl radical; - Rh, R’h, R’’h and R ’’ ’h, which can be identical or different, represent a hydrogen atom, a halogen atom, a group Petition 870180010020, of 02/05/2018, p. 106/136 2/30 dialkylamino (C1-C4), alkylcarbonylamino (C1-C4), an acylamino radical, alkylsulfonylamino (C1-C4), or an alkyl (C1-C4) radical; - 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 benzo, indene ring, a fused heterocycloalkyl group or fused heteroaryl; the benzo, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino, alkylamino (C1-C4), dialkylamino (C1-C4), cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C1-C4 alkoxy group , C2-C4 (poly) hydroxyalkoxy, (C1-C4) alkylcarbonyloxy (C1-C4) alkoxy (C1-C4) alkylcarbonylamino (C1-C4), an acylamino, carbamoyl, alkylsulfonylamino (C1-C4) radical, an aminosulfonyl radical, or an alkyl (C1C16) radical optionally substituted by a group selected from the alkoxy (C1C12), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1C4), or else the two alkyl radicals linked by the atom nitrogen 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; - Ri, R'i; Ri ”and R '’ ’i, which can 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 may be identical or different, represent a hydrogen atom or a (C1-C4) alkyl group, which may be present or absent, represents a benzo group; - Ta and Tb, which can be identical or different, represent: (i) a covalent σ bond; (ii) a radical selected from —N (R) - and -N + (R) (R °) -, where Petition 870180010020, of 02/05/2018, p. 107/136 3/30 R and R ^o , which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical, C1-C4 hydroxyalkyl or a (C1-C4) arylalkyl; (iii) a heterocycloalkyl or heteroaryl radical, cationic or non-cationic; - 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; - when Ta represents a covalent bond σ, Y represents a group selected from: - optionally substituted aryl; - optionally substituted heteroaryl; - optionally substituted heterocycloalkyl; - optionally substituted (di) arylalkyl; - optionally substituted (di) heteroarylalkyl; - a sterically hindered cyclic group; - when Ta represents —N (R) -, -N + (R) (R °) -, a heterocycloalkyl or heteroaryl radical, cationic or non-cationic; Y represents a group selected from: (i) a hydrogen atom; (ii) an alkali metal; (iii) an alkaline earth metal; (iv) an ammonium group: N + R ^to R ^and R ^Y R ^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 (C1C4) alkyl group; or (v) a thiol function protection group; and - M 'representing an anionic counterion; it being understood that when the compound of formula (I) or (II) contains other cationic parts, it is associated with one or more anionic counterions, allowing formula (I) or (II) to obtain electroneutrality. Petition 870180010020, of 02/05/2018, p. 108/136 4/30 2. FLUORESCENT DYE according to claim 1, characterized by the fact that it is of formula (II), in which when Ta represents -N (R) -, -N + (R) (R °) -, a heterocycloalkyl radical or heteroaryl, cationic or non-cationic, Y represents a hydrogen atom or an alkali metal. 3. FLUORESCENT DYE according to claim 1, characterized by the fact that it is of formula (II), in which when Ta represents -N (R) -, -N ⁺ (R) (R °) -, a heterocycloalkyl radical or heteroaryl, cationic or non-cationic, Y represents a protection group for thiol function below: - (C1-C4) alkylcarbonyl; - (C1-C4) alkylthiocarbonyl; - alkoxycarbonyl (C1-C4); - alkoxycarbonyl (C1-C4); - (C1-C4) alkylthio-thiocarbonyl; - (di) (alkyl) aminocarbonyl (C1-C4); - (di) (alkyl) aminothiocarbonyl (C1-C4); - arylcarbonyl, - aryloxycarbonyl; - arylalkoxycarbonyl (C1-C4); - (di) (alkyl) aminocarbonyl (C1-C4); - (C1-C4) (alkyl) arylaminocarbonyl; - carboxyl; - SO3 ^- ; M + where M + represents an alkali metal or M 'of formula (II), and M + are absent; - optionally substituted aryl; - optionally substituted heteroaryl; - optionally substituted heterocycloalkyl; Petition 870180010020, of 02/05/2018, p. 109/136 5/30 - isothiouronium -C (NR ' ^c R' ^d ) = N + R ' ^and R'^f; An ^- with R ' ^c , R' ^d , R ' ^e and R' ^f , which can be identical or different, representing a hydrogen atom or an alkyl group; - isothiourea -C (NR ' ^c R' ^d ) = NR ' ^e , with R' ^c , R ' ^d , and R' ^and as defined above; - optionally substituted (di) arylalkyl; - optionally substituted (di) heteroarylalkyl; - CR ' ¹ R' 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: - optionally substituted alkyl; - optionally substituted alkoxy; - 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, alkyl or alkoxy; R '' ³ representing a hydroxyl or alkoxy group; and Z ¹ representing an oxygen or sulfur atom; - a sterically hindered cyclic group; and - optionally substituted alkoxyalkyl. 4. FLUORESCENT DYE, according to one of claims 1 to 3, characterized by the fact that it is of formula (II), in which when Ta represents -N (R) -, -N + (R) (R °) -, a heterocycloalkyl or heteroaryl radical, cationic or non-cationic; Y represents a protection group selected from: - (C1-C4) alkylcarbonyl; - arylcarbonyl; - alkoxycarbonyl (C1-C4); Petition 870180010020, of 02/05/2018, p. 110/136 6/30 - aryloxycarbonyl; - arylalkoxycarbonyl (C1-C4); - (di) (alkyl) aminocarbonyl (C1-C4); - (C1-C4) (alkyl) arylaminocarbonyl; - optionally substituted aryl; - 5- or 6-membered monocyclic heteroaryl; - 8 to 11-membered cationic bicyclic heteroaryl; - cationic heterocycle of the formula below: Me ^Me An ^- - isothiouronium -C (NH2) = N + H2; An ^- ; - isothiourea -C (NH2) = NH; and - SO3 ^- , M + with M + representing an alkali metal or M 'of formula (II) and M + are absent. 5. FLUORESCENT DYE, according to claim 1, characterized by the fact that it is of formula (II), in which when Ta represents a bond, Y represents a 5 or 6 membered monocyclic heteroaryl (aromatic, cationic), comprising from 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen; (ii) an 8 to 11 membered bicyclic cationic heteroaryl, these monocyclic or bicyclic groups being optionally substituted by one or more groups; (iii) or a heterocyclic group below: An ^- Petition 870180010020, of 02/05/2018, p. 111/136 7/30 wherein R ' ^c and R' ^d , which may be identical or different, represent a hydrogen atom or an alkyl group; and An ^- represents a counterion. 6. FLUORESCENT DYE according to one of Claims 1 to 5, characterized in that it is selected from the fluorescent dyes of formula (Ia), (IIa), (Ib), (IIb), (Ic) or (IIc ), each having an ethylene group that binds the pyridinium part to the phenyl part, in the ortho or para position, in the 4-4 ', 4-2', or 2-4 'positions for (Ia), (IIa), ( Ib) or (IIb), or in positions 4-5 'or 2-5' for (Ic) or (IIc): 3 '2' -T ' 4 '/ + 2 ^ = / ¹ \! _T r ^ (CK _; ) .m (CH ..) ,. / ^S -S \ / X 2K C XfPU \ Yru A— M — A4 ' 2 M '(Ia) (cha ^Ch ^; · .vlyXV r ² : 1 \ 1 N? ² / b R a a (IIb) 4 3 R R ^g RA = n 1\ M 'R. 4 '3' ^R hr; ^R b / S — S τ / \ ^b x / \ J. ^{N (CR} ' ^R 2 ⁾ .m ^(CR 3 ^R 4) n (CR ^ n' ^N “(Ic) R „ R '' ^{3 4} R \ h3 '4' N + ^Z R / 1 R 'M', SY ^N ( ^CR , ^R :.). M '(CRsRJn 2 ^ X _R / ^R bg - n 4 '3' ^R h 1 \ ^{M Ra} (IIc) where, in formulas (Ia) or (IIa): Petition 870180010020, of 02/05/2018, p. 112/136 8/30 - R ^{1 a} and R ² a, which can be identical or different, represent a benzyl or alkyl group, optionally substituted by a hydroxyl group; - R ¹ b and R ² b, which can be identical or different, represent a hydrogen atom, a benzyl or alkyl group; - T'a and T'b, which can be identical or different, represent a bond σ; or a group -N + (R) (R °) - with R and R ^o , which can be identical or different, representing an alkyl group; or else T'a and T'b represent an imidazole group; - Y 'represents a group selected from the imidazolium, thiazolium; oxazolium; 1,2,4-triazolium; pyridinium; pyrimidinium; benzoxazolium and benzothiazolium; these groups being replaced by one or more alkyl groups, which can be identical or different; - m, m ', n and n', which can be identical or different, represent an integer between 1 and 6 inclusive, with m + n = m '+ n', representing an integer between 2 and 6 inclusive; - M 'represents an anionic counterion; where, in formulas (Ib) or (IIb): - Ra, R'a, Rb, R'b, Ri, R'i, R''i, R '' 'i, R1, R'1, R2, R'2, R3, R'3, R4, R'4, Ta, Tb, m, m ', n, n' and Y are as defined in one of claims 1 to 5; - Rg, R'g, R''ge R '' 'g, which can be identical or different, represent a hydrogen atom, a halogen atom, an amino group, alkylamino (C1-C4), dialkylamino (C1- C4), cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, (C1-C4) alkoxy, C2-C4 (poly) hydroxyalkoxy (C1-C4) alkylcarbonyloxy (C1-C4) alkoxy (C1-C4) alkylcarbonylamino , acylamino, carbamoyl, alkylsulfonylamino (C1-C4), aminosulfonyl, or an alkyl (C1-C16) radical optionally substituted by a group selected from the (C1-C12) alkoxy, hydroxyl, cyano, carboxyl, amino, (C1) alkylamino -C4) and Petition 870180010020, of 02/05/2018, p. 113/136 9/30 dialkylamino (C1-C4), or 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; - Rh and R'h; R "h and R '' '' h, linked by two adjacent carbon atoms, together form a benzo, indene ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indene, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino, alkylamino (C1-C4), dialkylamino (C1-C4), cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C1-C4 alkoxy group , C2-C4 (poly) hydroxyalkoxy, (C1-C4) alkylcarbonyloxy (C1-C4) alkoxy (C1-C4) alkylcarbonylamino (C1-C4), an acylamino, carbamoyl, alkylsulfonylamino (C1-C4) radical, an aminosulfonyl radical, or an alkyl (C1-C16) radical optionally substituted by a group selected from the alkoxy (C1-C12), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1-C4), or both 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; and where, in formulas (Ic) or (IIc): - Ra, R'a, Rb, R'b, Ri, R''i, R1, R'1, R2, R'2, R3, R'3, R4, R'4, Ta, Tb, m, m ', n, n' and Y are as defined in one of claims 1 to 5; - Rg, R'g, R''g, R '' 'g, Rh, R'h, R''he R' '' h, which can be identical or different, represent a hydrogen atom, an atom of halogen, an amino group, (C1-C4) alkylamino, (C1-C4) dialkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C1-C4 alkoxy, (C2-C4) hydroxyalkoxy, (C1-C4) alkylcarbonyloxy (C1-C4), alkoxycarbonyl (C1-C4), alkylcarbonylamino (C1-C4), acylamino, carbamoyl, alkylsulfonylamino (C1-C4), aminosulfonyl, or a (C1-C16) alkyl radical optionally substituted by a group selected from Petition 870180010020, of 02/05/2018, p. 114/136 10/30 alkoxy (C1-C12), hydroxyl, cyano, carboxyl, amino, alkylamino (C1-C4) and dialkylamino (C1-C4), or else 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; it being understood that when the compound of formula (Ia), (IIa), (Ib), (IIb), (Ic) or (IIc) contains other cationic parts, it is associated with one or more counterions allowing the formulas (Ia), (IIa), (Ib), (IIb), (Ic) or (IIc) obtain electroneutrality. 7. FLUORESCENT DYE according to one of claims 1 or 6, characterized by the fact that it is of formula (I), being symmetrical. 8. FLUORESCENT DYE, according to one of claims 1 to 7, characterized by the fact that it is selected from the Petition 870180010020, of 02/05/2018, p. 115/136 11/30 Petition 870180010020, of 02/05/2018, p. 116/136 12/30 _x O \ = / \ \ = / 2 O \ ₊ —N + ~ ^ - \ = / 2An ^- 13 14 Q HO ^^ _ 4 // - \ / ~ N \ \ = / \ An ^- ^^ SSO3- _N ^ A— / z \ - / ^N \ \ = / An ^- , M + 15 16 N ^ = ^{7 xv} - (! Vn '-n ι N''3An- _ / SH ^Z 0 An ^- 17 18 ^ = N + ^ ~ N \ ⁺ ^ = ⁷ 2An ^- SH - Ν '-G Υ- N '\ An- 19 20 ^N · ^N An- / ^Y A- ^N ' ^N An- 21 22 ^ = N + \ —NZ / ⁺ \ \ = / \ 2An ^- Ό «UçA a \ = / \ 2An ^- 23 24 N = \ Ν '\ = N + / V- N / \ \ = / \ 2An ^- N = \ / ¼ 77 ^{/ N Νχ} = ζ 2An ^- 25 26 Petition 870180010020, of 02/05/2018, p. 117/136 13/30 \ +, \ —N / \ = N + ^x 2An ^- \ + ^X 2An ^- 27 28 \ + N ^, \ = N + \ - N 1 \ \ = / \ 2An ^{- _n} ^^ V_ ^ A_n ^ \ = / \ 2An ^- 29 30 \ + N ···. \ = N + '/ V- N 1 \ \ = / \ 2An ^- <, · -Ο Y ~~ \ / - 1 ^N \ = / 2An ^- 31 32 \ + ^N \ \ = N ⁺ \ 2An ^- \ + ^N = Z 2An ^- 33 34 \ + N ^. Π-Λ ΛΛ r ^ ·· ⁵ \ = N + - / y— n \ \ = / \ 2An ^- \ + N ^, ji \ ^ 7 2A n ^- 35 36 \ + nn \ = N ++ / /> N 1 \ \ = / \ 2An ^- \ +, N'N _ / ^s_ jl ^Νχ = ^^ 2An ^- 37 38 Petition 870180010020, of 02/05/2018, p. 118/136 14/30 ^N \ 2An ^- \ + ^N \) ^X 2An ^- 39 40 p, pQ 2An ^- \ + N + \ = í \ / \ = J 2A n ^- 41 42 N = \ N / 2An ^- \ ₊ ~ ^ Nj! 2An ^- 43 44 \, çy ^ CAP ⁰ 2An ^- \ + N'N s — JJ H ° P f / - \ / N \ 1 2An ^- 45 46 \ ₊ \ = N + // ⁷ \ 1 2An ^- \ ₊ N + \ =) ~ \ 2An ^- 47 48 \ N-., Yy _ / ^S ^ Ç3 \ = N + N 1 2An ^- \ p / = w ^ ^s ^ y ^ = ⁷ '' —ρ n / 3An- 49 50 Petition 870180010020, of 02/05/2018, p. 119/136 15/30 / Çn \ = N ⁺ -fi y — N ^{x X 7 x} 3An ^- - N S N = / (\ / N ^{+ _} VA 2An ^- 51 52 ^OH 2An ^- N-, / SA J </ = \ N \ = N> N · '' An ^- 53 54 ^< \ = N + / V- N / / ⁺ \ \ = / ^H 2An ^- W ^H 2An ^- 55 56 N = \ \ = N + / V- N ⁷ \ \ = / ^H 2An ^- N = \ / ^s_ (\ 7) / ^{N Νχ} = ζ 2An ^- 57 58 \ + ^ NO z — λ í / - / N / // / // \ = / N \ = N + ⁷ 2An ^- \ + X 2An ^- 59 60 \ · N ^. ρ, „·. \ = _ν · fi \ - _N 1 \ \ = / ^H 2An ^- V N- ~ S — J t- \ / - ⁷ N ^ rfw ⁿ _N + ^^ V \ = / ^N \ = / 2An ^- 61 62 Petition 870180010020, of 02/05/2018, p. 120/136 16/30 Petition 870180010020, of 02/05/2018, p. 121/136 17/30 Petition 870180010020, of 02/05/2018, p. 122/136 18/30 Petition 870180010020, of 02/05/2018, p. 123/136 19/30 Petition 870180010020, of 02/05/2018, p. 124/136 20/30 Petition 870180010020, of 02/05/2018, p. 125/136 21/30 Petition 870180010020, of 02/05/2018, p. 126/136 22/30 Petition 870180010020, of 02/05/2018, p. 127/136 23/30 Petition 870180010020, of 02/05/2018, p. 128/136 24/30 Petition 870180010020, of 02/05/2018, p. 129/136 25/30 Petition 870180010020, of 02/05/2018, p. 130/136 26/30 Petition 870180010020, of 02/05/2018, p. 131/136 27/30 Petition 870180010020, of 02/05/2018, p. 132/136 28/30 N + \ \ ^N \ = / V_TA 2 M' 2 M' N i | 1 S-S N— / * + _x C | S-S_ / NH 147 148 Z_s— \ + N-—, <3 S ^ 2An ^- 149 - with M 'and An ^- , which can be identical or different, representing an anionic counterion; and M + representing an alkali metal. 9. DYE COMPOSITION, characterized in that it comprises, in a cosmetically acceptable medium, a fluorescent dye of formula (I) or (II), as described in one of claims 1 to 8. 10. DYE COMPOSITION, characterized in that it comprises, in a cosmetically acceptable medium, at least one fluorescent dye of formula (I) or (II), as described in one of claims 1 to 8, and at least one reducing agent . 11. DYE COMPOSITION, according to claim 10, characterized by the fact that the reducing agent is selected from cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, disulfide, sulfites, thioglycolic acid, and also its esters, borohydrides and their derivatives, the sodium, lithium, potassium, calcium, quaternary ammonium salts; the catecholborane. 12. PROCESS FOR COLORING KERATIN MATERIALS, characterized by the fact that a dye composition is applied to the materials, which comprises in a cosmetically acceptable medium, at least one fluorescent dye of formula (I) or (II), as defined in one of claims 1 to 8, optionally in the presence of a reducing agent Petition 870180010020, of 02/05/2018, p. 133/136 29/30 able to reduce the disulfide bonds of keratin materials. 13. PROCESS, according to claim 12, characterized in that when the fluorescent thiol dye of formula (II) comprises a protecting group Y, the application is preceded by a deprotection step. 14. PROCESS, according to one of claims 12 or 13, characterized in that the keratin materials are dark keratin fibers. 15. PROCESS according to one of claims 12 to 14, characterized in that the reducing agent is applied before or after the application of the fluorescent dye of formula (I) or (II). 16. PROCESS according to one of claims 12 to 14, characterized in that the fluorescent dye of formula (I) or (II) is applied at the same time as the reducing agent. 17. PROCESS according to one of claims 13 to 16, characterized in that the composition comprises an oxidizing agent. 18. PROCESS, according to one of claims 12 to 16, characterized by the fact that it comprises an additional step consisting of the application of an oxidizing agent to the keratin fibers. 19. PROCESS, according to one of claims 12 to 18, characterized in that the fluorescent dye of formula (I) or (II) is present in an amount between 0.001% and 50% by weight, in relation to the total weight of the composition. 20. MULTICOMPARTMENT DEVICE, characterized in that it comprises, in which a first compartment, a dye composition comprising a fluorescent dye as defined in claims 1 to 8, comprising, in a second compartment, a reducing agent capable of reducing bonds disulfide of keratin materials. Petition 870180010020, of 02/05/2018, p. 134/136 30/30 21. DEVICE, according to claim 20, characterized by the fact that it comprises a third compartment that contains an oxidizing agent. 22. USE OF FLUORESCENT DYES, of formula (I) or (II), as defined in claims 1 to 8, characterized by the fact that it is for dyeing human keratin fibers, in which human keratin fibers are dark. 23. USE, according to claim 22, characterized by the fact that it is used to lighten dark keratin fibers. Petition 870180010020, of 02/05/2018, p. 135/136 1/2 Reflection of the locks treated by compounds 1 and 2, on application and after 5 washes <5 rc Ό c -w φ 5 = Φ IX Compound Reference 1 Compound 1-5 washes Compound 2 Compound 2-5 washes